Solubility of Copper in Silicons

I
Characterization of the Cu-Si System and

Utilization of Metallurgical Techniques in Silicon
Refining for Solar Cell Applications
by
Aleksandar Mitrainovi
A thesis submitted in conformity with the requirements
for the degree of Doctor of Philosophy
Department of Materials Science and Engineering
University of Toronto
Copyright by Aleksandar Mitrainovi 2010

II

Characterization of the Cu-Si System and Utilization of
Metallurgical Techniques in Silicon Refining for Solar Cell
Applications
Aleksandar Mitrainovi
Doctor of Philosophy
Department of Materials Science and Engineering
University of Toronto
2010

Abstract

Two methods for refining metallurgical grade silicon to solar grade silicon have been
investigated. The first method involved the reduction of impurities from metallurgical
grade silicon by high temperature vacuum refining. The concentrations of analyzed
elements were reduced several times. The main steps in the second refining method
include alloying with copper, solidification, grinding and heavy media separation. A
metallographic study of the Si-Cu alloy showed the presence of only two
microconstituents, mainly pure silicon dendrites and the Cu
3
Si intermetallic. SEM
analysis showed a distinct boundary between the silicon and the Cu
3
Si phases, with a
large concentration of microcracks along the boundary, which allowed for efficient
separation. After alloying and grinding, a heavy media liquid was used to separate the

III
light silicon phase from the heavier Cu
3
Si phase. Cu
3
Si residues together with the
remaining impurities were found to be located at the surface of the pure silicon particles,
and should be efficiently removed by acid leaching. Thirty elements were analyzed by
the Inductively Coupled Plasma Mass Spectrometry (ICP) chemical analysis technique.
ICP revealed a several times higher impurity level in the Cu
3
Si intermetallic than in the
pure silicon; furthermore, the amounts of 22 elements in the refined silicon were reduced
below the detection limit where the concentrations of 7 elements were below 1ppm
w
and
6 elements were below 2ppm
w
. The results showed that the suggested method is efficient
in removing impurities from metallurgical grade silicon with great potential for further
development.
IV
Content

1 Introduction.........................................................................................1
1.1 Conversion Efficiency of Silicon Solar Cells...........................................................................5
1.2 Energy Payback for Silicon Solar Cells....................................................................................7
1.3 Future of Silicon Solar Cells.......................................................................................................8
1.4 MGS as Possible Primary Resource in SGS Production.......................................................9
1.5 Objectives................................................................................................................................... 11
2 Silicon Production and Refining ....................................................... 12
2.1 MGS Production....................................................................................................................... 13
2.2 SGS Production - Conventional Processes............................................................................ 15
2.2.1 Siemens Process ................................................................................... 17
2.2.2 Union Carbide Process.......................................................................... 20
2.2.3 Ethyl Corporation Process..................................................................... 21
2.3 Metallurgical Techniques......................................................................................................... 23
2.3.1 Acid Leaching ...................................................................................... 23
2.3.2 Alloying ............................................................................................... 23
2.3.3 Directional Solidification...................................................................... 24
2.3.4 Reactive Gas Blowing........................................................................... 26
2.3.5 Slagging ............................................................................................... 26
2.3.6 High Temperature Vacuum Refining .................................................... 27
2.4 Refractory Material for Si Refining........................................................................................ 27
2.4.1 Mullite.................................................................................................. 28
2.4.2 Graphite................................................................................................ 30
2.4.3 Glass..................................................................................................... 30
2.4.4 Silicon Carbide ..................................................................................... 31
3 Impurity Detection in High Purity Silicon......................................... 33
3.1 Inductively Coupled Plasma Mass Spectrometry (ICP) ..................................................... 34
3.2 Atomic Absorption Spectrophotometry (AAS) ................................................................... 35
3.3 Standard Titration Technique (STT)...................................................................................... 36
3.4 Glow Discharge Mass Spectrometry (GDMS).................................................................... 36
3.5 LECO - Combustion Techniques........................................................................................... 37
3.6 Recommended Analytical Techniques for Cu-Si Alloys.................................................... 37
4 Vacuum Refining............................................................................... 38
4.1 Material Balance of Silicon Refining By Vacuum Technique .......................................... 40
4.2 Experimental Investigation of Impurity Reduction in Silicon by the Vacuum Technique
...................................................................................................................................................... 43
4.3 Vacuum Technique - Experimental Procedure.................................................................... 44
4.4 Impurity Reduction in Metallurgical Grade Silicon............................................................. 50
4.5 Influence of the Holding Temperature on Impurity Reduction During Vacuum
Treatment.................................................................................................................................... 51
4.6 Impurity Reduction During Vacuum Treatment.................................................................. 54
4.7 Vacuum Refining Results........................................................................................................ 56
V
5 Properties of the Cu-Si System.......................................................... 59
5.1 Copper Diffusivity in Silicon................................................................................................... 62
5.2 Copper Solubility in Silicon..................................................................................................... 65
5.3 Copper Distribution Sites in Silicon....................................................................................... 66
5.4 Impurities in Cu-Si Alloys....................................................................................................... 69
6 Metallurgical Refining of MGS......................................................... 71
6.1 Chemical Composition of Starting Copper and Silicon...................................................... 73
6.2 Apparatus.................................................................................................................................... 74
6.3 Alloying...................................................................................................................................... 76
6.4 Cooling Rates............................................................................................................................. 76
6.5 Generation of Size Fractions.................................................................................................... 77
6.6 Heavy Media Separation.......................................................................................................... 80
6.7 Chemical Analysis.................................................................................................................... 84
7 Metallographic Analysis .................................................................... 85
7.1 Oxidation Behavior................................................................................................................... 85
7.2 Microscopy Findings................................................................................................................ 86
7.2.1 Micro-constituents Analysis.................................................................. 87
7.2.2 Phase Boundary Condition.................................................................... 89
7.2.3 Dendrite Thickness Measurements........................................................ 90
7.2.4 SEM Analysis....................................................................................... 93
7.2.5 EDX Analysis....................................................................................... 96
7.3 Image Analysis.......................................................................................................................... 99
7.3.1 Area Fraction Determination............................................................... 100
7.3.2 Homogeneous Particles....................................................................... 102
7.4 Silicon Dendrite Origin..........................................................................................................105
7.4.1 Temperature Regime Influence on Solidification Characteristics......... 106
7.4.2 Silicon Dendrite Formation................................................................. 107
8 Characterization of the Cu-Si System.............................................. 113
8.1 DTA Experimental Procedure ..............................................................................................113
8.2 DTA Results ............................................................................................................................116
8.3 XRD Analysis..........................................................................................................................129
9 Impurity Contents ............................................................................ 132
9.1 Copper Chemical Analysis....................................................................................................133
9.2 Impurity Contents....................................................................................................................141
9.3 Elemental Concentrations in Light and Heavy Media ......................................................143
9.4 Silicon Recovery.....................................................................................................................155
9.5 Recovery of Silicon and Driving Forces for HLMS..........................................................160
9.6 Copper Removal .....................................................................................................................162
9.7 Impurity Removal...................................................................................................................164
9.8 Optimal Particle Size ..............................................................................................................166
9.9 Distribution Ratio....................................................................................................................167
9.10 Maximum Distribution Ratio................................................................................................169

VI
10. Summary and Conclusions .............................................................. 171
10.1 High Temperature Vacuum Refining..................................................................................171
10.2 Copper Impurity Collection Method....................................................................................172
10.3 New Findings...........................................................................................................................174
11. Proposed Final Refining Steps ........................................................ 175
11.1 Acid Leaching..........................................................................................................................175
11.2 Directional Solidification.......................................................................................................176
11.3 Proposed Process Improvements..........................................................................................177
References .............................................................................................. 180
Appendices.............................................................................................. 192
Appendix 01: Equipment used in the experiments..........................................................................192
Appendix 02: Equipment Calibration................................................................................................193
Appendix 03: Thermodynamic Data.................................................................................................194
Appendix 04: DTA Curves .................................................................................................................199
Appendix 05: Various Shift Intensities for Cu-Si Compounds......................................................204
Appendix 06: ImageJ Figures .............................................................................................................206
Appendix 07: Chemical Analysis.......................................................................................................209
Appendix 08: Temperature Controller Setup....................................................................................216
Appendix 09: Silicon Refining Plant Layout....................................................................................217

VII

Table of Figures

Figure 1.1. Annual demand and availability of silicon feedstock [1-2] ...................... 1
Figure 1.2. Price of the silicon based solar module in U.S. [1-3] ............................... 2
Figure 1.3. Cost breakdown of silicon solar cell components. [1-6]........................... 4
Figure 1.4. Energy efficiency improvement in silicon solar cells measured under the
global AM1.5 spectrum (1000w/m
2
) at a cell temperature of 25
o
C. [1-12]
............................................................................................................... 5
Figure 1.5. Relationship between purity and the cost of silicon. .............................. 10
Figure 2.1. Schematic representation of a furnace for production of metallurgical
grade silicon [2-5]................................................................................. 15
Figure 2.2. Schematic representation of the traditional Siemens reactor [2-8] and
positioning of the Si rods inside the reactor [2-9]. ................................. 18
Figure 2.3. A schematic representation of a fluidized bed reactor for polysilicon
production [2-11]. ................................................................................. 22
Figure 2.4. Al
2
O
3
-SiO
2
phase diagram where mullite is an intermediate compound
with ideal stoichiometry 3Al
2
O
3
-2SiO
2
. [2-25]...................................... 29
Figure 3.1. An approximate detection limit for the ICP technique used at the
University of Toronto [3-19]................................................................. 34
Figure 3.2. Elements determined by the AAS [3-20]............................................... 35
Figure 4.1. Vapor pressure of various elements and same oxides. ........................... 38
Figure 4.2. Relationship between vapor pressure (Pa) and temperature (K) for
phosphorus and silicon [4-18]. .............................................................. 39
Figure 4.3. Flow chart of the suggested Vacuum Route. Steps in highlighted fields
were tested in current project. ............................................................... 43
Figure 4.4. Experimental setup of the vacuum refining trials................................... 44
Figure 4.5. Cross section of the furnace used in the vacuum experiments................ 45
Figure 4.6. Temperature regime for the vacuum experiments.................................. 46
Figure 4.7. Lance position during vacuum experiments........................................... 49
Figure 4.8. Impurity path during purging with argon during vacuum refining
experiments. ......................................................................................... 49
Figure 4.9. Mo, Pb and Zn in MGS before and after vacuum treatment (24h).......... 51
Figure 4.10. Co, Cr, W and Zr in MGS before and after vacuum treatment (24h)...... 52
Figure 4.11. Mn, Ni, Cu and V in MGS before and after vacuum treatment (24h). .... 52
Figure 4.12. Al, Fe and Mg in MGS before and after vacuum treatment (24h). ......... 53
Figure 4.13. Cu reduction from MGS during vacuum experiments after holding
for 24h. ................................................................................................ 54
Figure 4.14. Zn and Zr reduction from the MGS during vacuum experiments after
holding for 24h. .................................................................................... 55
Figure 4.15. Al, Fe and Mg reduction from the MGS during vacuum experiments after
holding for 24h. .................................................................................... 55
Figure 5.1. Copper-silicon binary phase diagram [5-5]............................................ 61
Figure 5.2. Diffusivity of copper in silicon [5-11]. .................................................. 63
VIII
Figure 5.3. Solubility of copper in silicon for various temperatures......................... 65
Figure 5.4. Possible copper distribution sites in a silicon sample. 1) Lattice defect, 2)
Grain Boundary, 3) Sample surface, 4) Precipitation into Cu
3
Si. ........... 66
Figure 5.5. Characteristic microconstituents distribution in 50wt%Cu-Si alloy
solidified under (a) slow cooling regime and (b)fast cooling regime.
Dark fields are Si dendrites while bright fields are Cu
3
Si intermetallic. . 67
Figure 5.6. Formation of the Cu-silicides around point defect and its growth in bulk
Si . Si lattice constant 5.43; Cu lattice constant 3.61 ; Si atomic radius
1.46 ; and Cu atomic radius 1.57 . ................................................... 68
Figure 5.11. Proposed refining techniques in order to purify metallurgical silicon to
solar grade silicon. ................................................................................ 70
Figure 6.1. Flow chart of the proposed metallurgical route...................................... 71
Figure 6.2. Experimental setup for alloying silicon with copper. ............................. 74
Figure 6.3. Reaction tube during alloying. .............................................................. 75
Figure 6.4. Heating-cooling regime......................................................................... 77
Figure 6.5. Fraction generation. .............................................................................. 78
Figure 6.6. Sample collection: A view of the specimen after removing from the
furnace (upper figure), collected fractions from section B after crushing
and screening (bottom-left) and middle cross segment from section C
(bottom-right). ...................................................................................... 79
Figure 6.7. Three distinctive layers formed after heavy media separation. ............... 80
Figure 6.8. Heavy media separation procedure........................................................ 83
Figure 7.1. Weight gain of fine grinded Si-50wt%Cu alloy (size less than 38m) in
laboratory air at room temperature. ....................................................... 86
Figure 7.2. Secondary electron images with the two microconstituents phases present
in 50Cu-Si hypereutectic alloy. a) close to the wall, b) region between the
edge and the center of the sample and c) central part of the sample. ...... 87
Figure 7.3. Secondary electron image with a number of loose fractions at the edge of
the Si and Cu
x
Si phases......................................................................... 88
Figure 7.4. Secondary electron image with a number of microcracks along the
microconstituents boundary in the Si-50%wtCu alloy; carbon coated,
20kV [7-3]. ........................................................................................... 89
Figure 7.5. The middle cross section of the as is solidified specimen. ..................... 91
Figure 7.6. Average dendrite thickness calculation procedure. I ) part of the sample,
II ) straitening the circle and III ) counting Si and thickness measurement.
............................................................................................................. 92
Figure 7.7. Loose Si particles after gravity separation mounted onto the SEM sample
stand [7-3]. ........................................................................................... 93
Figure 7.8. Loose silicon rich particle after gravity separation with Cu
x
Si residues at
the surface [7-3].................................................................................... 94
Figure 7.9. Loose silicon rich particles after gravity separation with Cu
x
Si residues at
the surface with corresponding EDX analyses in Figure 7.10 [7-3]........ 95
Figure 7.10. EDX analysis of the loose silicon rich particles after gravity separation
with Cu
x
Si residues at the surface. ........................................................ 95
Figure 7.11. Si-50wt%Cu alloy fraction prior to crushing and gravity separation
prepared for EDX analysis, mounted in epoxy. ..................................... 96
IX
Figure 7.12. EDX analysis of the Si-50wt%Cu alloy fraction prior to gravity
separation. Upper diagram is related to point 1 in Figure 7.11 and bottom
diagram is related to point 2 in Figure 7.11. .......................................... 97
Figure 7.13. SEM figures of different size silicon-copper alloy particles before heavy
media separation. a) Particle size is 106-500m; b) particle size is 500-
1000m, and c) particle size is above 1000m. ..................................... 99
Figure 7.14. Mixed particle used to determine total area, Si area and Cu
3
Si area. .... 100
Figure 7.15. Homogeneous and mixed particles in the 50Cu-Si alloy. ..................... 103
Figure 7.16. Area fractions of homogeneous particles and Si particles with up to 1%
Cu
x
Si prior to gravity separation. ........................................................ 104
Figure 7.17. Temperature regime during solidification............................................ 107
Figure 7.18. Solidification of the Cu-Si system. a) Forces present in Cu-Si system and
heat flow, b) mass flow, c-e) Si dendrites formation, growth and path of
the Si particles. ................................................................................... 108
Figure 7.19. A view of the sample after removal from the furnace, method by which
the sample was sectioned, up-right surface prepared for metallographic
analysis. .............................................................................................. 109
Figure 7.20. Morphology of the Cu-Si alloy sample with three regions (i, ii and iii)
and four layers (1, 2, 3 and 4).............................................................. 110
Figure 7.21. Angle and length of the Si dendrites throughout the 50Cu-Si sample
measured from the bottom................................................................... 111
Figure 7.22. Angle and length of Si dendrites throughout the 70Cu-Si sample
measured from the bottom................................................................... 112
Figure 8.1. Selected chemical compositions for 4 alloys generated for DTA analysis.
........................................................................................................... 115
Figure 8.2. Characteristic DTA curves for pure silicon and pure copper................ 117
Figure 8.3. DTA curves as a function of temperature. ........................................... 118
Figure 8.4. DTA curves for the solidus region for 4 Cu-Si alloys. ......................... 119
Figure 8.5. DTA curves for the 50wt%Cu-Si and 70wt%Cu-Si alloys. .................. 120
Figure 8.6. DTA curves for the 83wt%Cu-Si and 87wt%Cu-Si alloys. .................. 121
Figure 8.7. DTA curves with respect to temperature for samples generated from the
light and heavy media. ........................................................................ 124
Figure 8.8. DTA curves for solar grade silicon and light media fraction samples... 125
Figure 8.9. DTA curves for a 50Cu alloy and a mixture of light and heavy media
fraction samples. ................................................................................. 126
Figure 8.10. DTA curves for 83Cu alloy and heavy media fraction samples............ 127
Figure 8.11. Shape of the DTA curves for a) transformation in solid, b) solidus and c-
d) liquidus. 50wt%Cu, 70wt%Cu and mixture of light and heavy media
samples. .............................................................................................. 128
Figure 8.12. XRD of the 50wt%Cu-Si light and heavy media particles. .................. 129
Figure 8.13. XRD of the non-oxidized samples with 50wt%Cu, 70wt%Cu and
83wt%Cu chemical composition alloys. .............................................. 130
Figure 8.14. XRD of the light and heavy media sample a with possible SiO
2
peaks. 131
Figure 9.1. Recommended chemical analysis methods for Cu-Si alloys samples. ICP
- Inductively Coupled Plasma, AAS - Atomic Absorption Spectrometry
and STT - Standard Titration Technique ............................................. 132
X
Figure 9.2. Cu content in the light fraction after gravity separation for the 50Cu-Si
alloy (Specimens #1-#4) and average Cu content with standard deviation
bars. .................................................................................................... 134
Figure 9.3. Amount of Cu in the light fraction after gravity separation for the 50Cu-
Si and 70Cu-Si alloys.......................................................................... 135
Figure 9.4. Amount of Cu in the heavy fraction after gravity separation for the 50Cu-
Si alloy (Specimens #1-#4). ................................................................ 139
Figure 9.5. Amount of Cu in the heavy fraction after gravity separation for the 70Cu-
Si alloy. .............................................................................................. 140
Figure 9.7. Concentrations of selected impurities after gravity separation of the Si-
50Cu alloy. ......................................................................................... 141
Figure 9.8. Concentrations of Al, Ca, Cr, Fe and Zn after gravity separation in the Si-
50Cu alloy. ......................................................................................... 142
Figure 9.10. Concentration of Al in the light and heavy media. ............................... 144
Figure 9.11. Concentration of Ag in the light and heavy media. .............................. 144
Figure 9.12. Concentration of Ba in the light and heavy media. .............................. 145
Figure 9.13. Concentration of Bi in the light and heavy media. ............................... 145
Figure 9.14. Concentration of Ca in the light and heavy media. .............................. 146
Figure 9.15. Concentration of Cd in the light and heavy media. .............................. 146
Figure 9.16. Concentration of Co in the light and heavy media. .............................. 147
Figure 9.17. Concentration of Cr in the light and heavy media. ............................... 147
Figure 9.18. Concentration of La in the light and heavy media................................ 148
Figure 9.19. Concentration of Fe in the light and heavy media. ............................... 148
Figure 9.20. Concentration of Mn in the light and heavy media. ............................. 149
Figure 9.21. Concentration of Mo in the light and heavy media. ............................. 149
Figure 9.22. Concentration of Ni in the light and heavy media. ............................... 150
Figure 9.23. Concentration of Pb in the light and heavy media................................ 150
Figure 9.24. Concentration of Sc in the light and heavy media. ............................... 151
Figure 9.25. Concentration of Sr in the light and heavy media. ............................... 151
Figure 9.26. Concentration of Ti in the light and heavy media. ............................... 152
Figure 9.27. Concentration of Tl in the light and heavy media. ............................... 152
Figure 9.28. Concentration of Zn in the light and heavy media. .............................. 153
Figure 9.29. Concentration of Zr in the light and heavy media. ............................... 153
Figure 9.30. Concentration of V in the light and heavy media. ................................ 154
Figure 9.31. Concentration of W in the light and heavy media. ............................... 154
Figure 9.32. Fashion which samples were prepared and weighed for recovery analysis.
........................................................................................................... 155
Figure 9.33. Apparent silicon recovery in the 50Cu-Si alloy for 4 specimens. ......... 156
Figure 9.34. Silicon recovery from the 50Cu-Si alloy for 4 specimens. ................... 158
Figure 9.35. Forces present in the system during gravity separation. ....................... 160
Figure 9.36. Cu removal from the 50Cu-Si alloy..................................................... 163
Figure 9.37. Removal of the impurities after gravity separation in the 50Cu-Si. .......... 164
Figure 9.38. Removal of Al, Ba, Cr, Pb, Sr and Zn after gravity separation in the
50Cu-Si alloy...................................................................................... 165
Figure 9.39. Removal of Cu for different particle size derived from the ICP chemical
analyzes. ............................................................................................. 166
XI
Figure 9.40. Distribution ratio of impurities in heavy over light fraction in the 50Cu-Si
alloy after gravity separation [7-3]. ..................................................... 167
Figure 9.41 Distribution ratio for Al, Ca, Cr, Pb and Zn in heavy over light fraction in
the 50Cu-Si alloy after gravity separation [7-3]................................... 168
Figure 9.42. Maximum distribution ratio of impurities in 50Cu-Si alloy after gravity separation.
........................................................................................................... 170
........................................................................................................... 170
Figure 11.1. Suggested experimental setup for vacuum solidification investigation
using modified PoDFA unit. ............................................................... 178
Figure A1. The equipment used during mixing and melting of metallurgical silicon
and copper: 1. Argon gas; 2. Mass flow controller; 3. Copper getter
furnace; 4. Lance; 5. Reaction tube; 6. Electric furnace; 7. Temperature
controller. ........................................................................................... 192
Figure A2. Equipment used for screening Cu-Si alloys. Tyler Canada, FH Brass Pan
type screens. ....................................................................................... 192
Figure A3. Equipment used for gravity separation of the Cu-Si alloys. .................. 192
Figure A4. Analytical balance used for weighting samples. ................................... 192
Figure A5. Furnace chamber temperature measured with controller thermocouple
sited at the edge of the crucible and R-type thermocouple placed in the
middle of the crucible. ........................................................................ 193
Figure A6. Time required for furnace chamber temperature (measured with R-type
thermocouple placed in the middle of the crucible) to reach controller
given temperature (measured at the edge of the crucible). ................... 193
Figure A7. Vapor Pressure of Elements ................................................................ 194
Figure A8. Standard Free Energies of Formation, Ellingham Diagram................. 196
Figure A9. Standard Free Energies of Formation of chlorides. .............................. 197
Figure A10. DTA curves for non-oxidized samples. ............................................... 199
Figure A11. DTA curve for non-oxidized solar grade sample. ................................ 199
Figure A12. DTA curve for non-oxidized 50wt%Cu-Si sample. ............................. 200
Figure A16. DTA curve for non-oxidized electronic copper sample........................ 202
Figure A17. DTA curve for light media sample. ..................................................... 202
Figure A18. DTA curve for heavy media sample. ................................................... 203
Figure A19. DTA curves for light and heavy media samples. ................................. 203
Figure A20. Shift intensities for Si, Cu and Cu
3
Si phases. ...................................... 204
Figure A21. Shift intensities for SiO
2
. .................................................................... 205
Figure A22. SEM figure for 38-106m particle size before heavy media separation for
50wt%Cu-Si alloy............................................................................... 206
Figure A23. Counting the number of particles in 38-106m particle size sample before
heavy media separation (50wt%Cu-Si alloy). ...................................... 206
Figure A24. SEM figure for the 106-500m particle size before heavy media
separation for 50wt%Cu-Si alloy. ....................................................... 207
XII
Figure A25. Count of the particles in 106-500m particle size sample before heavy
media separation (50wt%Cu-Si alloy). ................................................ 207
Figure A26. SEM figure for the 1000+m particle size before heavy media separation
for 50wt%Cu-Si alloy. ........................................................................ 208
Figure A27. Count of the particles in 1000+m particle size sample before heavy
media separation (50wt%Cu-Si alloy). ................................................ 208

XIII

List of Tables

Table 2.1. Segregation coefficients for various impurities in silicon [2-21]............ 25
Table 2.2. Typical physical and mechanical properties of some refractory material.
............................................................................................................. 28
Table 2.3. Typical physical and mechanical properties of the mullite..................... 28
Table 2.4. Typical physical and mechanical properties of graphite [2-26]. ............. 30
Table 2.5. Typical physical and mechanical properties of the carbide. ................... 31
Table 3.1. Most suitable measurement techniques for trace amounts of impurities in
pure silicon [3-18]................................................................................. 33
Table 4.1: Parameters for impurity reduction c from liquid silicon......................... 40
Table 4.2. Experimental design for the Vacuum Route procedure. ......................... 47
Table 4.3. Chemical composition (ppm
w
) of the metallurgical grade silicon (MGS)
used in the experiments......................................................................... 48
Table 4.4. Impurity concentration in ppm
w
in metallurgical grade silicon before and
after vacuum refining. ........................................................................... 56
Table 4.5. Impurity Reduction Factor after vacuum refining. ................................. 57
Table 5.1. Atomic structure and physical properties of the copper and silicon........ 59
Table 5.2. Copper diffusivity in silicon.................................................................. 62
w
) of the electrolytic copper (EC) and
metallurgical grade silicon (MGS) used in experiments......................... 73
Table 6.2. Different size fractions used in the experiments. ................................... 78
Table 7.1. Weight gain of Si-50wt%Cu alloy fraction with size less than 38m. .... 85
Table 7.2. Local thickness of the dendrites in the middle cross-section of the
specimen............................................................................................... 92
Table 7.3. EDX analysis of mixed particle close to the phase boundary with
respective standard deviation for silicon in the bright field. ................... 98
Table 7.4. Number of particles and total analyzed area for samples prior to
separation. .......................................................................................... 100
Table 7.5. Area fraction of silicon prior to and after gravity separation for 50Cu-Si
alloy*.................................................................................................. 101
Table 7.6. Number of homogeneous particles in 50Cu-Si alloy. ........................... 102
Table 7.7. Characteristic parameters for hypereutectic Cu-Si alloys calculated by
FactSage Chemical Thermodynamics Application. ............................. 106
Table 8.1. Weight of the DTA samples used in experiments. ............................... 114
Table 8.2. Characteristic temperatures during heating for non-oxidized samples.. 116
Table 8.3. Characteristic temperatures during cooling for non-oxidized samples. 116
Table 8.4: Weight and approximate chemical composition of the light and heavy
media samples. ................................................................................... 122
Table 8.5. Characteristic temperatures during heating for light and heavy media
samples. .............................................................................................. 122
XIV
Table 8.6. Characteristic temperatures during cooling for light and heavy media
samples. .............................................................................................. 123
Table 9.1. ICP and AAS results for light media sample, 50wt%Cu-Si.................. 136
Table 9.2. Average copper concentration in different fractions for 50wt%Cu-Si alloy
with standard deviation**: .................................................................. 137
Table 9.3. Polynomial coefficients of the concentration curve in the light media for
the 50Cu-Si and 70Cu-Si alloys. ......................................................... 138
Table 9.4. Weights of the light and heavy fractions after heavy media separation:159
Table 11.1. Tolerable impurity concentration before directional solidification and
achieved concentration in current project (ppm
w
). ............................... 176

1
1 Introduction

Our planet receives approximately 1.210
17
W of solar power, while the rate of current
worldwide energy consumption is approximately 10,000 times smaller at around
1.310
13
W [1-1]. This indicates that the earth receives more solar energy in an hour
than the total energy consumed by humans in an entire year. Solar energy alone has the
potential capacity to meet the planets entire energy needs in the future. Additionally, an
increase in global energy consumption, higher energy prices and public awareness of
global warming has unlocked the solar cell market. In 2003, the photovoltaic (PV)
industry had a growth rate of more than 30%, a situation that many other industries can
only dream about [1-2]. Meanwhile, the most recent analysis of the silicon solar cell
market [1-3] shows a growth rate of 110% in 2008 in installations and with $37.1 billion
in global revenues. The majority of solar cells are made of silicon, and experts believe
that it will take at least a decade before other photovoltaic technologies based on other
materials could be competitive.

Figure 1.1. Annual demand and availability of silicon feedstock [1-2]

2
The remarkable growth of the photovoltaic industry has caused a shortage of Solar
Grade Silicon (SGS), or silicon with the required chemical purity for photovoltaic
applications, (Fig. 1.1). The primary source of solar grade silicon has been silicon
rejected from the electronic industry. Presently, the production cost for solar grade
silicon, via the labor and energy intensive chemical vapor deposition technique, is a
limiting factor for environmentally friendly solar energy to become one of the major
energy sources (Fig 1.2).

Figure 1.2. Price of the silicon based solar module in U.S. [1-3]

Most solar cells and modules are made of either single crystal or polycrystalline silicon,
which are converted into large wafers of purified silicon. The other major costs
involved in photovoltaic components are modules, panels, arrays, mounting equipment,
wiring, inverters, grid connection equipment, service and labor to assemble,
management and administration costs and costs of permits etc. A summarized cost
breakdown of a silicon solar cell is given in Figure 1.3, where it can be seen that the
3
solar grade silicon contributes to about 50% of the cost of the solar cell module (Figure
1.3,a). Furthermore, module cost contributes into the final system setup with about 55%
(Figure 1.3,b) bringing the cost of the silicon in the final cost to 25-30%. In addition,
looking at the energy required for different parts production and system installation,
shows that silicon contributes far more than any other component, about 59% (Figure
1.3,c). This leads to the conclusion that the greatest avenue for price per Watt
reduction is in the silicon refining process where price per watt is a measure of the cost
of the solar panel expressed as a ratio between the price of the panel and the nominal
number of watts. Implementing new production and refining techniques for solar grade
silicon could reduce the price of a silicon module to $3 per Watt, which some
economists denote as a critical barrier for the transition of the solar cell industry from
small contractor businesses into larger companies. Involvement of larger companies
will result in significant cost reduction in other major aspects involved in photovoltaic
systems that can initiate a further cost reduction to $1 per Watt [1-4]. Reaching this
benchmark will be the turning point from which markets will emerge and grow without
any government aid and that could be the transition point for the solar cell industry from
the alternative source to a reliable, economical source of energy [1-5]. The greatest
limitations for silicon based photovoltaic systems are the efficiency and price of the
silicon solar cells.

4

Figure 1.3. Cost breakdown of silicon solar cell components. [1-6]

a)
b)
c)
5
1.1 Conversion Efficiency of Silicon Solar Cells

Henri Becquerel discovered in 1836 the photovoltaic effect or the capacity of some
material systems to generate a voltage when illuminated. Pearson, Chapman, and Fuller
from the Bell Laboratories, first reported the modern silicon solar cell in 1954
demonstrating a 5 to 6% efficiency [1-7]. In the 1960s, solar cells were successfully
developed primarily for powering satellites. Such cells were too expensive for almost
all other applications. Considerable technical progress and cost reductions were gained
from government-funded R&D programs during the energy crisis of the 1970s.
Nowadays, the efficiency of silicon solar cells in laboratory conditions is approaching
the theoretical limit of 29%. Figure 1.4 shows the rise in efficiency of laboratory
produced solar cell's from the 1950s up today.

Figure 1.4. Energy efficiency improvement in silicon solar cells measured under
the global AM1.5 spectrum (1000w/m
2
) at a cell temperature of 25
o
C. [1-12]

6
Basically, the different semiconductor materials or combinations are suited only for
specific spectral ranges. Particularly, silicon transforms 1.1eV of photons
electromagnetic energy into electrical energy. Therefore a specific portion of the radiant
energy cannot be used, because some photons do not have enough energy to activate the
charge carriers, e.g photons below 1.1eV in silicon based solar cells. On the other hand,
surplus photon energy is transformed into heat rather than into electrical energy. In
addition to that, there are optical losses, reflections of incoming rays, electrical
resistance losses, disrupting influences of material contamination, surface effects and
crystal defects, etc. Single loss mechanisms cannot be further improved because of
inherent physical limits imposed by the materials themselves. This leads to a theoretical
maximum level of efficiency, i.e. approximately 29% for crystal silicon.

Research results have demonstrated efficiencies close to 25%, while industrially
produced solar cells have efficiencies ranging from 12% to 18%. Closing the gap
between laboratory and factory efficiencies depends on materials-processing
innovations, composition and purity of the silicon, thermodynamics, phase
transformation, kinetics, heat and mass transfer, hydrodynamics, solid-state physics,
thin-film technology, process control, etc.

To provide some sense of the capabilities of silicon based solar cells, the required area
of solar cells needed to meet the average consumption of an U.S. residence has been
calculated. Under noontime sunshine on a clear summer day, a typical (12% efficient)
silicon solar-cell module with an area of 1m
2
would produce about 100W of direct-
current power. On average over the year, this output could be sustained for about six
hours per day, for a daily yield of about 600Wh of energy per square meter of installed
solar cells. The typical U.S. household consumes about 25kWh of electricity per day,
and solar cells comprising about 42m
2
would be required to provide sufficient power.

7
1.2 Energy Payback for Silicon Solar Cells

In Figure 1.3, it can be seen that the major cost in the production of a solar module is
producing the solar grade silicon (SGS). Furthermore, purifying and crystallizing the
silicon is the most energy consuming part of the solar cell manufacturing process.
Advantages of producing electricity with photovoltaic devices are zero emissions and no
fossil fuel consumption. These are great environmental benefits, however the
production of pure silicon also consumes energy. The period required for a solar cell to
produce the same amount of energy that was used to create it, is called the Payback
Time. Due to the many factors influencing quality and lifetime of solar cells, the
economy of the solar cells is usually expressed in the Payback Time rather than in the
cost of the solar cell.

An analysis of the Payback Time for solar grade silicon that had originally been rejected
from electronic grade silicon consumers was performed by Erik Alsema [1-13]. His best
estimates of energy used to make frameless PV were 600 kWh/m
2
for single crystal
silicon modules and 420 kWh/m
2
for polycrystalline silicon. Assuming a 12%
conversion efficiency (standard conditions) and 1700 kWh/m
2
per year of available
sunlight energy (the U.S. average is 1800), the calculated payback time is about four
years for contemporary polycrystalline silicon photovoltaic systems. Projecting
improvements 10 years into the future, where the author assumes a constant supply of
solar grade silicon feedstock by conventional processes and 14% efficiency, energy
payback is reduced to about two years. Replacing the conventional Siemens process
with a direct metallurgical route can reduce payback time to one year. Furthermore,
silicon treatment by a direct metallurgical route for production of SGS can be five times
more energy efficient than the conventional/commercial processes that use more than
200kWh for 1kg silicon produced [1-14].

The U.S. Department of Energy Photovoltaics Program [1-15] estimates that an average
U.S. household producing 1000 kWh of electricity with solar power reduces emissions
by nearly 8 pounds of sulfur dioxide, 5 pounds of nitrogen oxides, and more than 1,400
8
pounds of carbon dioxide. During its projected 28 years of clean energy production, a
rooftop system with 2-year payback and meeting half of a households electricity use
would avoid conventional electrical plant emissions of more than half a ton of sulfur
dioxide, one-third a ton of nitrogen oxides, and 100 tons of carbon dioxide, giving great
environmental benefits.

1.3 Future of Silicon Solar Cells

For some time now, due to the limited theoretical efficiency, it has been thought that
monocrystalline or polycrystalline silicon solar cells would be made obsolete by the
eventual introduction of very inexpensive alternative solar cells based on thin films of
semiconductors such as cadmium telluride (CdTe), copper-indium diselenide (CIS),
amorphous silicon (-silicon) or organic photovoltaic material. This may happen, but so
far on the basis of cost, reliability, performance, and lifetime, none of these alternatives
appear to be in a position to challenge silicon solar cells.

Indeed, recent reports about silicon properties and photovoltaic capacities at the nano
level seem to have positioned silicon at the forefront as a major future component for
photovoltaic applications. A typical solar cell generates one electron per photon of
incoming sunlight. Conversely, some materials are capable of producing multiple
electrons per photon, but for the first time this effect have been seen in silicon at the
National Renewable Energy Laboratory (NREL), in Golden, CO. Results have shown
that silicon nanocrystals can produce two or three electrons per photon of high-energy
sunlight [1-16]. In most silicon solar cells, the extra energy in blue and ultraviolet light
is wasted as heat. The small size of nanoscale crystals, called quantum dots [1-17, 1-
18], leads to novel quantum-mechanical effects that convert this energy into electrons.
The effect can lead to a new type of solar cell that utilizs the same feedstock as
9
commercial solar cells but that are more than twice as efficient as today's typical silicon
based photovoltaic. Arthur Nozik [1-19] claims that by generating multiple electrons
from high-energy photons, solar cells made of silicon nanocrystals could theoretically
convert more than 40 percent of the energy in light into electrical power. Furthermore,
concentrating sunlight with mirrors or lenses could raise that figure to well over 60
percent. New technology not only gains from the advantages of efficiency inherent in
producing different numbers of electrons based on the amount of energy in the striking
photon, but a manufacturer does not incur the expensive pure-silicon-crystal-growth
processes. Such situation can make silicon produced by affordable, high capacity,
entirely metallurgical refined a perfect product.

1.4 MGS as Possible Primary Resource in SGS Production

Due to the strong demand for silicon photovoltaic applications, manufacturers of silicon
solar cells and producers of metallurgical grade silicon have the same interest. For
metallurgical grade silicon producers, the increase and inconsistency in energy prices are
a challenge and it is necessary to find products with higher value and stable demand for
which the energy input contributes less to the fixed costs. At the same time, solar cell
manufacturers are looking for reliable, high capacity and economically viable sources of
solar grade silicon. Under the given conditions, it appears that metallurgical grade
silicon is a prefect starting material for silicon solar cells (Figure 1.5). However, with
the demand for extremely high purity products and the necessity to develop complete
new processes, the introduction of this new product into the market involves a great deal
of research and the development of new silicon treatment techniques.

10

AGS AGS AGS AGS -Alloy Grade Si
MGS MGS MGS MGS-Metallurgical Grade Si
EGS EGS EGS EGS -Electronic Grade Si

Figure 1.5. Relationship between purity and the cost of silicon.

11
1.5 Objectives

The aim of the current project is to investigate a set of the low cost metallurgical
techniques for refining Metallurgical Grade Silicon (MGS) to Solar Grade Silicon
(SGS), consequently reducing the cost for solar cell production.

With the purpose of advancing the knowledge of silicon refining, particularly in alloying
with copper, separation from solvent metal and surface treatment with the possibility of
creating a new set of process steps, the overall objective was to develop new silicon
refining processes, including:

Determine optimal process parameters for high temperature vacuum treatment
and a copper impurity collection method.
Determine effect of vacuum treatment on impurities removal from the
metallurgical grade silicon.
Determine the feasibility of the newly developed copper impurity collection
method to reduce the amount of impurities in the metallurgical grade silicon.
Determine the mechanisms of the silicon dendrite formation and optimal
solidification conditions for a Cu-Si alloy in order to form clean and large silicon
dendrites.
Determine the recovery of refined silicon after separation.
Determine the copper content in the silicon after refining process.
Remove all impurity elements to solar grade requirements.
Investigate the industrial potential of purifying silicon by copper alloying and
heavy media separation in order to achieve solar grade requirements.
12
2 Silicon Production and Refining

Silicon is a metalloid, one of only a very few elements that have characteristics of both
metals and non-metals. The melting point of silicon is 1414C (2574F) and the boiling
point is 2355C (4270F). Its density is 2.33 grams per cubic centimeter, and it forms a
face-centered cubic structure with a lattice spacing of 5.43 [5-1]. Silicon is a relatively
inactive element and does not combine with oxygen or most other elements at room
temperature while at higher temperatures, silicon becomes much more reactive. Also,
water, steam, and most acids have very little effect on silicon. Information on the health
effects of silicon is limited. Overall, silicon probably has no positive or negative effects
on human health unless silicon is ground up into a very fine powder that can cause
silicosis [5-2, 5-3].

Silicon, like carbon and other group IV elements, form a face-centered diamond cubic
crystal structure. Silicon, in particular, forms a face-centered cubic structure with a
lattice spacing of 0.5430710nm.

Silicon Applications
Silicon, in the form of SiO
2
, is vital to the construction industry as a principal constituent
of natural stone, glass, concrete and cement. Silicon's greatest impact on the modern
world's economy and lifestyle has resulted from silicon wafers used in the manufacture
of electronic devices such as power transistors, and integrated circuits such as computer
chips.

Silicon Alloys
The largest application of metallurgical grade silicon, representing more than 50% of the
world consumption, is in the manufacture of aluminium-silicon alloys to produce cast
parts, mainly for the automotive industry. Silicon is an important constituent of steel,
modifying its resistivity and ferromagnetic properties. Silicon is added to molten cast
13
iron as ferrosilicon to improve its performance in casting thin sections, and to prevent
the formation of cementite at the surface.

2.1 MGS Production

Silicon is the second most abundant element in the Earth's crust (about 28%), exceeded
only by oxygen. Many rocks and minerals contain silicon. Examples include sand,
quartz, clays, flint, amethyst, opal, mica, feldspar, garnet, tourmaline, asbestos, talc,
zircon, emerald, and aquamarine. Silicon never occurs as a free element but as silicon
dioxide, known as silicates. Silicon is commercially produced from its minerals by the
reaction of high-purity silica with coal in an electric arc furnace using carbon electrodes.
This process is named Carbothermic Reduction of Silica and the silicon produced via
this process is called Metallurgical Grade Silicon (MGS). Metallurgical grade silicon
has a purity of at least 95%. Reduction of silicon is accomplished by the carbothermic
reduction of silica where the main chemical reaction is:

SiO
2
(s) + 2 C (s) = Si (l) + 2 CO (g) (2.1)

Source of the carbon is coal together with woodchips and coke. Quartz and carbon are
carefully selected in order to maximize furnace performance and to reduce emissions of
the SO
2
and NO
X
gases. The mixture of the raw material is heated by an intense electric
arc located between the tips of three submerged electrodes and the electrical ground of
the furnace. The quality of the carbon electrodes is an important factor of the MGS
production. A prepared mixture of the raw materials is charged from the top of the
furnace and liquid silicon is collected from the bottom side. The temperature in the
upper zone is below 1900C and the main reactions are:

SiO
2
(s) + 2 C (s) = Si (l) + 2 CO (g) (2.1)
14

SiO (g) + 2 C (s) = SiC (s) + CO (g) (2.2)

2 SiO (g) = Si (l) + SiO
2
(s) (2.3)

Silicon is produced in the inner zone where the temperature is between 1900 to 2100C.
The main reactions in inner zone are:

2 SiO
2
(l) + SiC (s) = 3 SiO (g) + CO (g) (2.4)

SiO (g) + SiC (s) = 2 Si (l) + CO (g) (2.5)

A schematic description of the furnace is given in Figure 2.1. Raw materials are fed in
small batches with frequent intervals and are distributed on top of the charge. Liquid
silicon is at frequent intervals, drained out from the bottom of the furnace. The silica
fumes, which consist mainly of very fine particles of amorphous silica less than 1 m,
are passed through filter cloths installed in large bag-house systems adjacent to the
furnaces. The collected amorphous silica finds applications as additives in concrete and
refractories. Depending on the quality of the raw materials used and the operational
strategy, the silicon yield as metallurgical silicon ranges from 80 to 90%, the balance
resulting in silica fume [2-4].

The liquid crude silicon contains normally less than 3% impurities depending on the raw
materials and the type of electrodes. The main impurities are Fe: 0.21%, Al: 0.40.7%,
Ca: 0.20.6%, Ti: 0.10.02%, C: 0.10.15%

15

Figure 2.1. Schematic representation of a furnace for production of metallurgical
grade silicon [2-5].

2.2 SGS Production - Conventional Processes

Impurities in the ppb
(a)
range are required for the electronic grade silicon supplied to the
semiconductor industry. The ultra-high purity is needed to ensure rigorous
semiconductor properties in the silicon crystals.

Many processes to produce polysilicon have been tested, patented and a few operated for
many years. Only three large commercial processes are currently active:

1. The most popular process is based on the thermal decomposition of trichlorosilane
(SiHCl
3
) at 1100C on a heated silicon rod placed inside a deposition chamber.
16
This process, which was developed in the late fifties, is commonly referred to as
the Siemens process with reference to the company that carried out its early
development.

2. In a more recent process developed by Union Carbide Chemicals in the United
States of America, the trichlorosilane has been replaced by monosilane (SiH
4
), but
the principle of decomposition on a heated silicon rod inside a closed deposition
chamber is maintained. This process, presently run by the company Advanced
Silicon Materials, LLC. The Union Carbide process has gained a significant
market acceptance in the past 15 years.

3. Finally, in the third process, also making use of monosilane SiH
4
, the heated
silicon rod in the closed reaction chamber has been replaced by a heated fluidized
bed containing silicon particles. The particles act as seeds on which SiH
4
is
continuously decomposed to larger granules of hyper-pure silicon. Unlike
Siemens or Union Carbide, this process is a continuous one. This process is
known as the Ethyl Corporation process, after the name of the US chemical
company that developed it and presently is run by the US corporation MEMC in
Pasadena, Texas.

The respective features, advantages and disadvantages of these different routes are
described in the following sections.

17
2.2.1 Siemens Process

Trichlorosilane (HSiCl
3
) is prepared by hydrochlorination of metallurgical grade silicon
in a fluidised bed reactor [2-6, 2-7, 2-8]:

Si (s) + 3 HCl = HSiCl
3
+ H
2
(2.6)

This reaction occurs at 350C normally without a catalyst. A competing reaction is
contributing to the formation of unsuitable tetrachlorosilane in molar proportion of 10 to
20%:

Si (s) + 4 HCl = SiCl
4
+ 2 H
2
(2.7)

Trichlorosilane is chosen because of its high deposition rate, its low boiling point
(31.8C) and its comparatively high volatility and hence the ease of purification with
respect to boron and phosphorus down to the ppb level. The suitable trichlorosilane
undergoes a double purification through fractional distillation, the first step removing
the heaviest components resulting from the direct synthesis and the second step
eliminating the components lighter than trichlorosilane, also called volatiles. High-
purity trichlorosilane is then vaporised, diluted with high-purity hydrogen and
introduced into the deposition reactors. The gas is decomposed onto the surface of
heated silicon seed rods, electrically heated to about 1100C, and growing large rods of
hyperpure silicon. The main reactions are:

H
2
+ HSiCl
3
= Si + 3 HCl (2.8)
2 SiHCl
3
= SiH
2
Cl
2
+ SiCl
4
(2.9)
SiH2Cl
2
= Si + 2 HCl (2.10)
HCl + HSiCl
3
= SiCl
4
+ H
2
(2.11)

The stream of reaction by-products, which leaves the reactor, contains H
2
, HCl, SiHCl
3
,
SiCl
4
and SiH
2
Cl
2
.
18

A schematic representation of the Siemens reactor is given in Figure 2.2. The Siemens
process is highly energy consuming, a major part of the energy being dispersed and lost.
To avoid deposition on the inner surfaces of the reaction chamber, they have to be
cooled. The decomposition chamber consists of a steel bell jar where 30 or more
inverted U-rods are placed in each reactor [2-7].

Figure 2.2. Schematic representation of the traditional Siemens reactor [2-8] and
positioning of the Si rods inside the reactor [2-9].

As reactions and equilibriums (2.8) to (2.11) show, the deposition process generates by-
products. Unfortunately, for each mole of Si converted to polysilicon, 3 to 4 moles are
converted to SiCl
4
, binding large amounts of chlorine and valuable silicon. With
polysilicon production growing much faster than silicones and pyrogenic silica, the
question is whether to eliminate or recycle the tetrachlorosilane. Recycling the by-
product back to the valuable starting material is generally a preferred solution. There are
two basic chemical processes applicable to reconvert SiCl
4
to SiHCl
3
:

19
1. The high temperature reduction of silicon tetrachloride with hydrogen:

SiCl
4
+ H
2
= SiHCl
3
+ HCl (2.12)

At about 1000C, a 1:1 molar mixture of SiCl
4
and H
2
produces approximately
20 to 25% molar SiHCl
3
in the gaseous mixture. This process requires a fair
amount of electrical energy but has a distinct advantage that the trichlorosilane
produced is of very high quality because both reactants, silicon tetrachloride and
hydrogen, are basically electronic grade when produced by equations (2.8) and
(2.11).

2. The hydrogenation of silicon tetrachloride in a mass bed of metallurgical
silicon:

3SiCl
4
+ 2H
2
+ Si = 4SiHCl
3
(2.13)

This hydrogenation reaction produces approximately 20% trichlorosilane at
500C and 35 bar with a 1:1 ratio of SiCl
4
to H
2
in one pass through
metallurgical grade silicon in a fluidized bed reactor.

In spite of its widespread and dominant position in the industry, the Siemens process as
described above suffers from the following disadvantages:
- High energy consumption, over 90% of the input power is lost to the cold walls
of the reactor.
- Two power supplies and preheating of the seed rods are normally required
because the high-resistivity (~230,000 ohm cm) seed rods require very high
power supplies and high initial power rates to heat the rods.
- Hot spot formation and filament burn out may occur.
- The process is operated batchwise.
- Large amount of by-products need to be handled or recycled.
20
2.2.2 Union Carbide Process

The main steps for the union carbide process are as follows:
1) The hydrogenation of tetrachlorosilane through a mass bed of silicon metal is
carried out in a fluidised bed reactor as already described by equation (2.13).
2) The trichlorosilane is separated by distillation while the unreacted
tetrachlorosilane is recycled back to the hydrogenation reactor.

The purified trichlorosilane is then treated in two separate steps:

2 HSiCl
3
= H
2
SiCl
2
+ SiCl
4
(2.14)

3 H
2
SiCl
2
= SiH
4
+ 2 HSiCl
3
(2.15)

Products of (2.14) and (2.15) are separated by distillation. Tetrachlorosilane and
trichlorosilane are recycled to the hydrogenation (2.13) reactor and the first step (2.14),
respectively. Silane is further purified by distillation and then pyrolysed to produce
polysilicon onto heated silicon seed rods mounted in a metal bell-jar reactor:

SiH
4
= 2 H
2
+ Si (2.16)

With hydrogen and chlorine recycled, the only raw material requirement is metallurgical
grade silicon in granular form designed for fluidisation. Since equations (2.13) to (2.15)
yield low fractions of suitable products, and the intermediates tri- and tetrachlorosilane
are distilled, recycled and purified many times before conversion to silane. This results
in an extremely high purity for the silane and the subsequent polysilicon. It is operated
as a closed-loop process [2-5]. Advantages of using SiH
4
are that the pyrolysis may be
operated at significantly lower temperature, the decomposition is complete, conversion
efficiency is higher and no corrosive compounds are formed. Uniform, large-diameter,
long, dense, void-free cylindrical rods of polysilicon produced this way are particularly
21
suitable for single-crystal manufacturing by the floating zone (FZ) method. The
disadvantage of the monosilane-based process is the high cost since additional steps are
required to convert trichlorosilane to monosilane. Each recycling of unsuitable
chlorosilanes yields only a small percentage of the suitable silane.

2.2.3 Ethyl Corporation Process

The Ethyl Corporation process is, by comparison with the Siemens and the Union
Carbide processes, revolutionary in all aspects except for the concept of purifying and
decomposing a volatile silicon compound by pyrolysis. The first radical change was the
choice not to use metallurgical grade silicon as the primary raw material for silane. The
idea was to make use of silicon fluoride, which is a waste by-product of the huge
fertilizer industry. Tens of thousands of tones of silicon fluoride every year are
available. This is potentially a very low-cost starting material. Silicon fluoride is
hydrogenated to monosilane by metal hydrides such as lithium aluminium hydride or
sodium aluminium hydride.

2 H
2
+ M+ Al = AlMH
4
, M being Na or Li (2.17)

SiF
4
+ AlMH
4
= SiH
4
+ AlMF
4
(2.18)

After distillation, monosilane SiH
4
is thermally decomposed to polysilicon as described
by (2.16) while AlMF
4
is believed to find application in the aluminium industry, making
it a valuable saleable product. However, to realize this process, Ethyl Corporation
introduced a second radical change, not using static silicon seed rods in a bell-jar reactor
but dynamic silicon seed spheres in a fluidised bed sustained by a gas stream of silane
and hydrogen. A schematic representation of a fluidised bed reactor is given in Figure
2.3. The fluidised bed reactor offers significant advantages compared to the bell-jar
reactor. Most of the shortcomings identified for the Siemens process are then
22
eliminated. The energy losses and hence the energy consumption are considerably
reduced because the decomposition takes place at a lower temperature. Another
advantage is that large reactors may be constructed and operated continuously, reducing
further the capital and operating costs [2-10]. The end products are small granules of
polysilicon that may present some advantages (e.g. when continuous feeding in customer
process is requested) or disadvantages (e.g. not usable for direct float zone
crystallisation). A disadvantage of the process is the generation of powder due to
homogeneous decomposition of SiH
4
in the free reactor space and the hydrogen
absorption into the polysilicon deposition layer.

Figure 2.3. A schematic representation of a fluidized bed reactor for polysilicon
production [2-11].

All mentioned processes have several common properties. All present processes for
production of pure silicon are energy intensive, involve toxic chemicals and are
relatively low capacity that increases cost per kg for produced pure silicon.
23

2.3 Metallurgical Techniques

The disadvantages present in current processes for the production of pure silicon could
be overcome by implementation of a set of metallurgical techniques. The most
recommended metallurgical techniques for silicon refining are acid leaching, alloying,
directional solidification, reactive gas blowing, high temperature vacuum treatment or
slagging.

2.3.1 Acid Leaching

Most of the impurities in silicon lie in the inter-crystalline boundaries or areas with grain
defects [2-12, 2-13]. An efficient route of removing the majority of the impurities is to
crush the silicon and treat the resulting powder. The particle size of the silicon prepared
for acid leaching is from 50 to 70m. The dissolution rate of the silicon itself is very
low in most of the leaching reactants [2-14]. Various acids like HCl, HF, H
2
SO
4
and
HNO
3
or their combinations are used to dissolve silicon. Acids dissolve impurities such
as silicides of iron, calcium and magnesium as well as other impurities. The extent of
impurities removal depends on the particle size of the silicon and the duration of acid
leaching. However there are no reports about efficient removal of boron, phosphorous
and copper by the acid leaching technique.

2.3.2 Alloying

Very little work is being done in alloying metallurgical silicon in order to increase its
purity. Some attempts have been made with aluminum as the alloying element [2-15, 2-
16]. Work conducted on impurity elimination by alloying with Al proved to be partially
successful, especially for boron removal [2-15, 2-17]. However, Al is one of the most
24
efficient electron donors and is detrimental for Si solar cells. Furthermore, Si retrieval
from the Al-Si alloy is expected to be difficult because of the relative high segregation
coefficient of Al in Si, and leaching of Al is difficult due to formation of the Al-oxide or
Al-hydrates that inhibit further dissolution. Also, the low density difference between Si
and Al makes gravity separation unfeasible. Iron is another potential Si purifier due to
the high-density difference between Si and Fe. However, Fe effective ionic radius is
higher than Cu and this reduces the Fe mobility in solid Si.

Recent discoveries show that Cu can be efficiently used as an alloying agent in the route
to Si purification. An interesting finding is the diffusion coefficient of Cu in Si [2-18].
The data shows that Cu is the fastest diffusing foreign atom in solid Si. Cu diffuses an
order of magnitude faster than B, Al or P, and this difference is even higher at lower
temperatures. Also, Cu properties like low activity coefficient in silicon for most
impurity elements, low effective ionic radius and low cost indicate high potential of
inheriting impurities from the silicon.

2.3.3 Directional Solidification

The solid solubility in silicon is extremely small for most elements; therefore directional
solidification is an efficient refining technique [2-19]. The effectiveness of directional
solidification can be estimated by the segregation coefficient value. The segregation
coefficient gives the relation between the concentration of the impurity atom in the
growing crystal and that of the melt. Values of the segregation coefficient are usually
much below one because impurity atoms usually stay in the melt. In other words, the
solubility of impurity atoms in the melt is larger than in the solid. Solid silicon shows a
very low solubility for most of the elements, much lower than liquid silicon, resulting in
a strong segregation of these elements at freezing [2-20]. A typical example is iron that
shows a segregation coefficient of 8x10
-6
. Segregation coefficients for various
impurities in silicon are given in Table 2.1.

25

Table 2.1. Segregation coefficients for various impurities in silicon [2-21]
Impurity
Segregation
coefficient
Impurity
Segregation
coefficient
Aluminium 2.0 x 10
-3
Molybdenum 4.5 x 10
-8

Antimony 2.3 x 10
-2
Nickel 1.0 x 10
-4

Arsenic 3.0 x 10
-1
Niobium 4.4 x 10
-7

Bismuth 7.0 x 10
-4
Palladium 5.0 x 10
-5

Boron 8.0 x 10
-1
Phosphorus 3.5 x 10
-1

Carbon 5.0 x 10
-2
Silver 1.7 x 10
-5

Chromium 1.1 x 10
-5
Tantalum 2.1 X 10
-8

Cobalt 2.0 x 10
-5
Tin 1.6 X 10
-2

Copper 4.0 x 10
-4
Titanium 2.0 X 10
-6

Gallium 8.0 x 10
-3
Tungsten 1.7 X 10
-8

Indium 4.0 x 10
-4
Vanadium 4.0 X 10
-6

Iron 8.0 x 10
-6
Zinc 1.0 X 10
-5

Magnesium 3.2 x 10
-6
Zirconium 1.6 X 10
-8

Manganese 1.3 x 10
-5

So far only the Czochralski, float-zone and heat exchange methods have been
experimentally tried to achieve efficient SGS from MGS. The success of refining by
directional solidification techniques depends on the initial chemical composition of the
MGS. Higher concentration of elements with high segregation coefficient reduces the
efficiency of the directional solidification process. Particularly, boron, phosphorous and
aluminum have high segregation coefficients; therefore, they are not easily removed
from the silicon. At the same time, they are considered as dopants in silicon for
electronic devices and an increased amount of these impurities significantly decrease the
photovoltaic properties of the silicon based solar cells. Currently, a combination of
purification processes by chemical methods and directional solidification has provided
the best results. Repeating the refining processes increases the purity but trades off in the
final costs for silicon.
26

2.3.4 Reactive Gas Blowing

Reactive Gas Blowing is one of the common techniques practiced by the silicon refining
industry to obtain a purity level of at least 99.99% [2-22] where can only be used to
refine elements that are more reactive than silicon, such as Al, Ca, Mg, Na... The
method could be used in combination with other refining techniques, either as the first
step of refining or before directional solidification. The gases used in silicon refining
industry are Cl
2
, O
2
, SiCl
4
, wet hydrogen and CO
2
or their combinations, usually diluted
with an inert gas. Cl
2
and wet hydrogen form low boiling point compounds with various
elements that are easily volatilized.

2.3.5 Slagging

A slagging technique is used to remove elements less noble than silicon. There have
been many attempts utilizing CaCO
3
, BaO, MgO, Al/SiO
2
, CaO/SiO
2
or CaF
2
/SiO
2
to
make a refining slag. The amount of the artificial slag is usually 1-5% of the amount of
silicon. Elements like Al, Ca and Mg are oxidized at a high rate. The degree of refining
is determined by the distribution equilibrium of the respective reaction (equations 2.19
to 2.22).

4 Al + 3 SiO
2

(SLAG)
= 3 Si
(LIQUID)
+ 2 Al
2
O
3

(SLAG)
(2.19)
2 Ca + SiO
2
= Si
(LIQUID)
+ 2 CaO
(SLAG)
(2.20)
2 Mg + SiO
2
= Si
(LIQUID)
+ 2 MgO
(SLAG)
(2.21)
Si
(LIQUID)
+ O
2
= SiO
2

(SLAG)
(2.22)

The impurity level reduction for some of the elements such as Ti, Mn, V and Al are
about one order of magnitude.
27

2.3.6 High Temperature Vacuum Refining

Vacuum refining is a technique used to purify and separate one liquid from another. It is
based on chemical volatility or the relative ease of which the molecules leave the surface
of a liquid. The successful application of vacuum refining techniques depends on
several factors such as the difference in boiling points of chemicals present, the size of
the sample and type of refining apparatus. Several reports claim success in removing
boron and phosphorous by vacuum refining at temperatures above the melting point of
silicon. However, the feasibility is limited due to requirements for temperatures above
1500
o
C and vacuum at a level below 0.05atm [2-23, 2-24].

2.4 Refractory Material for Si Refining

One of the important items in refining metallurgical grade silicon is the refractory
material. It has to withstand the refining temperature at about 1550
o
C, minimize
contribution of impurities to the molten silicon, be compatible with silicon and type of
heating system, and be low cost. Since all these characteristics are important, a task of
the investigation was to evaluate crucible materials that can be used for refining
metallurgical grade silicon. Table 2.2 gives physical characteristics for several
commonly used refractory materials. The types of crucible materials taken into
consideration were mullite, alumina, silicon carbide, magnesia, graphite and glass.

28
Table 2.2. Typical physical and mechanical properties of some refractory
material.

Mullite
3Al
2
O
3
:2Si
O
2

Alumina

Al
2
O
3

Silicon
Carbide
Si-SiC
Magnesia

MgO
Graphite

C
Glass
SiO
2
:Al
2
O
3
:
BaO:MgO
Thermal
Expansion,
10
-6
K
-1

4.5-5.6 7.2 3-6 40-50 1.2-8.2 5.9
Contamination
LOW MEDIUM MEDIUM HIGH HIGH LOW
Cost
LOW LOW MEDIUM LOW LOW HIGH
Max
Operating
Temp.,
o
C
1725 1750 1600
2200-air
1600-vcm
- -

2.4.1 Mullite

Mullite is a mineral of long interlocking needle-like crystal structure that is very
resistant to thermal shock failure (has a low thermal expansion coefficient). Typical
physical properties of the mullite are given in the Table 2.3. It is also has a low thermal
conductivity and is very refractory. Mullite is rarely found in nature but it can be
synthesized by calcining kyanite, bauxite or alumina/kaolin mixtures.

Table 2.3. Typical physical and mechanical properties of the mullite.
Property
Density (g/cm
3
) 3.03
Youngs Modulus (GPa) 130
Fracture Toughness (MPa.m
-1/2
) 2-4
Thermal Expansion Coefficient (x10
-6
/C) 4.5-5.6
Thermal Conductivity (W/m.K) 4.0-6.0 (100-1400C)
29

Mullite has long been used as a refractory material. Its properties include:
- Good high temperature strength.
- Good thermal shock resistance.
- Excellent thermal stability.
- It has excellent stability in acid slags and is insoluble in most acids.
- Resistance to oxidation and furnace atmospheres.
- Resistance to abrasion.
- Good electrical resistivity.
The approximate limiting temperatures of use are 1725
o
C in air and 1600
o
C in vacuum.

The binary phase diagram of Al
2
O
3
and SiO
2
is given in Figure 2.4.

Figure 2.4. Al
2
O
3
-SiO
2
phase diagram where mullite is an intermediate compound
with ideal stoichiometry 3Al
2
O
3
-2SiO
2
. [2-25]

30
2.4.2 Graphite

Due to its high temperature stability and chemical inertness graphite has been used for a
refractory material in the refining metallurgical silicon. Graphite is used in the
production of refractory bricks, crucibles, ladles and moulds for containing molten
metals. Graphite is one of the most common materials used in the production of
functional refractories for the continuous casting of steel and also to form a part of the
lining of blast furnaces. Typical physical properties of the graphite are given in the
Table 2.4 Its structural strength at high temperature, thermal shock resistance, high
thermal conductivity, low thermal expansion and good chemical resistance are of
paramount importance for material used for refractory purposes. The electrodes used in
many electrical metallurgical furnaces are manufactured from graphite such as the
electric arc furnaces.

Table 2.4. Typical physical and mechanical properties of graphite [2-26].
Property
Density (g/cm
3
) 1.3-2.23
Youngs Modulus (GPa) 9.2-20
-1/2
) 1.7
-6
C) 1.2-8.2
Thermal conductivity (W/m.K) 25-470
Porosity (%) 0.7-53

2.4.3 Glass

There are no fixed properties for glasses as their compositions and use are so varied.
Perhaps the most important characteristics for the glasses are their thermal properties.
The coefficient of thermal expansion varies strongly with composition e.g. from quartz
glass 3.2 x 10
-6
/
o
C to heavy lead flint 8.0 x 10
-6
/
o
C.
31

2.4.4 Silicon Carbide

Silicon carbide was originally produced by a high temperature electro-chemical reaction
of sand and carbon. Silicon carbide is composed of tetrahedra of carbon and silicon
atoms with strong bonds in the crystal lattice. This produces a very hard and strong
material. Up to 800C, silicon carbide is not attacked by any acids or alkalis or molten
salts. In air, silicon carbide forms a protective silicon oxide coating at 1200C. The
high thermal conductivity coupled with low thermal expansion and high strength gives
this material exceptional thermal shock resistant qualities. Silicon carbide can also be
used as an electrical conductor and has applications in resistance heating, flame igniters
and electronic components.

Table 2.5. Typical physical and mechanical properties of the carbide.
Property
Density (g/cm
3
) 3.21
Youngs Modulus (GPa) 207-483
-1/2
) 3-5
-6
/C) 4.3-5.6
Thermal Conductivity (W/m.K) 33-155

Silicon carbide chemical purity, resistance to chemical attack at temperature, and
strength retention at high temperatures has made this material very popular as wafer tray
supports and paddles in semiconductor furnaces where with little or no grain boundary
impurities maintains strength to very high temperatures, approaching 1600C with no
strength loss. The most beneficial properties of silicon carbide are:
High hardness (second only to diamond).
Low density.
Low porosity.
32
Good wear resistance in sliding and abrasive environments.
Excellent corrosion resistance in most chemical environments.
Low thermal expansion and high thermal conductivity leading to excellent
thermal shock resistance.

However, the high price and possible carbon contamination puts this material below
mullite as a possible refractory material for metallurgical silicon refining.
33
3 Impurity Detection in High Purity Silicon

There are a number of techniques for chemical composition measurements of pure
silicon such as Inductively Coupled Plasma - Mass Spectrometry (ICP-MS) and
Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) [3-1:4],
Atomic Absorption Spectrophotometry (AAS), Standard Titration technique (STT) [3-
5:8], Glow Discharge Mass Spectrometry (GDMS) [3-9:13], LECO-Combustion
Techniques [3-15:17], etc.

An effective technique for impurity detection in pure silicon is Inductively Coupled
Plasma (ICP). However, ICP is limited in that it is not capable of measuring carbon or
oxygen. In addition, the measurement resolution is not sensitive enough to detect the
lower limit of detrimental elements like titanium, calcium, boron and phosphorus. In
order to provide a full analysis of silicon, the use of other measurement techniques such
as Glow Discharge Mass Spectroscopy (GDMS) and nitrogen/oxygen determination
(carried out on LECO Corporation equipment) is necessary. Table 3.1 shows
recommended techniques in order to determine exact chemical composition in pure
silicon.

Table 3.1. Most suitable measurement techniques for trace amounts of impurities
in pure silicon [3-18].
Element Impurity Measurement
Calcium GDMS
Copper ICP-OES
Phosphorous GDMS
Boron GDMS
Iron ICP-OES
Carbon LECO C-200
Oxygen LECO TC-436
Aluminum ICP-OES
Nickel ICP-OES
Titanium GDMS

34
3.1 Inductively Coupled Plasma Mass Spectrometry (ICP)

ICP is a comprehensive technique able to analyze most elements from lithium through
uranium. It is an extremely sensitive technique with detection limits in the parts per
trillion (ppt) ranges for many elements in aqueous solutions. An approximate detection
limit for the ICP technique used at the University of Toronto is given in Figure 3.1. Its
high level of relative accuracy (1 to 2%) coupled with its sensitivity allows the analyst to
cover more than nine orders of magnitude in concentration. This has eliminated the
need to use several techniques to obtain a complete analysis. Recent technological
advances in Cool Plasma ICP have helped eliminate or reduce interferences caused by
the argon plasma thus allowing lower detection levels for Li, Na, K, Ca and Fe.

Approximate
Detection Limit:

Figure 3.1. An approximate detection limit for the ICP technique used at the
University of Toronto [3-19].

35
3.2 Atomic Absorption Spectrophotometry (AAS)

This is a technique for elemental analysis in liquids. Metallic species can be determined
in both organic and inorganic samples. It is a sensitive technique that can measure the
concentration of most elements at part - per - million (ppm) levels. If lower detection
limits are required, then a graphite furnace is used as the excitation source (GFAAS),
replacing the standard flame. GFAAS is utilized for ultra-trace analysis. It has detection
limits that exceed the conventional flame by several orders of magnitude. Figure 3.2
shows elements that can be detected by the atomic absorption spectrophotometry
technique.

Through the use of calibration curves, prepared from suitable standards, a high level of
accuracy and precision (1 to 3 %) is achieved for the flame AAS technique. Most
spectral interferences and matrix effects are overcome by utilizing well characterized
conditions and matrix matching of samples and standards. AAS has an average
accuracy which is suitable for reporting at the ultra-trace impurity level.

Figure 3.2. Elements determined by the AAS [3-20]

36
3.3 Standard Titration Technique (STT)

Titration is a common laboratory method of quantitative chemical analysis that can be
used to determine the concentration of a known reactant. Because volume measurements
play a key role in titration, it is also known as volumetric analysis. A reagent, called the
titrant, of known concentration (a standard solution) and volume is used to react with a
solution of the analyte, whose concentration is not known in advance. Using a calibrated
burette to add the titrant, it is possible to determine the exact amount that has been
consumed when the endpoint is reached. The endpoint is the point at which the titration
is complete, as determined by an indicator. Standard titration technique is the most
suitable for analysis of the copper in Cu-Si alloys.

3.4 Glow Discharge Mass Spectrometry (GDMS)

In Glow-Discharge Mass Spectrometry (GDMS), the sample to be analyzed forms the
cathode in a low pressure (~ 100 Pa) gas discharge or plasma. Argon is typically used as
the discharge gas. Argon positive ions are accelerated towards the cathode (sample)
surface with energies from hundreds to thousands of eV resulting in erosion and
atomization of the upper atomic layers of the sample. Only the sputtered neutral species
are capable of escaping the cathode surface and diffusing into the plasma where they are
subsequently ionized. The atomization and ionization processes are thus separated in
space and time, which appears to be a keystone for simplified calibration, quantification
and the near matrix independence of this technique. Strengths of GDMS Analysis is full
periodic table coverage (except H), sub-ppb to ppt detection, minimal matrix effects and
linear and simple calibration. However, GDMS technique is very expensive.

37
3.5 LECO - Combustion Techniques

Combustion techniques are used to determine the concentration of carbon, nitrogen,
oxygen and sulphur in inorganic samples. The techniques are extremely useful for the
determination of these elements over a wide concentration range. This range can be six
orders of magnitude (sub-ppm to tens of percent). The level of accuracy and precision
makes this technique suitable for many applications. Although the LECO technique was
not used in the current research its is recommended for accurate detection of oxygen and
carbon in silicon before and after treatment.

3.6 Recommended Analytical Techniques for Cu-Si Alloys

Specific properties of silicon and high purity demand for SGS makes obtaining accurate
results extremely difficult. The considered impurities are highly diluted in the analyzed
silicon. Analysis of a small area can lead to inaccurate conclusions. At the same time
silicon is difficult to dissolve in most known reagents. The most efficient reagent for
dissolving silicon is combination of the HCl, HF, H
2
SO
4
and HNO
3
. In this research a
combination of techniques are used. For the determination of the trace elements in the
silicon rich granules of the alloy, the ICP method is used while for copper determination
the AAS method is used. For determination of copper in the copper rich granules the
STT method is used.
38
4 Vacuum Refining

A most recommended and exploited method for refining metallurgical grade silicon to
solar grade quality is the vacuum technique. It is based on molecular transportation
across the interface between liquid and gaseous phases due to differences in vapor
pressures [4-1]. Silicon has lower vapor pressure than most of the impurity elements
(Figure 4.1). Therefore, it should be possible to refine the liquid silicon by the vacuum
technique.

Figure 4.1. Vapor pressure of various elements and same oxides.
39

The vacuum refining principle is mostly recommended for phosphorous reduction from
the silicon melt [4-1:18]. Phosphorus is an impurity in silicon that has a maximum limit
of 1 ppm
w
in solar grade silicon. Unfortunately, the segregation coefficient of
phosphorus in silicon is large (0.35), so it is difficult to remove phosphorus by
directional solidification refining. Therefore, vacuum refining may be a good
alternative. Besides theoretical analysis of potential phosphorous removal, the aim in
this chapter is to systemically investigate the theoretical, literature and experimental
potential of reducing various impurities in silicon using vacuum refining.

Metal vacuum refining relies on differences in the respective metallic vapor pressure of
each metal at different temperatures. Figure 4.2 presents the relationship between
saturated pressure (lg p* ) and temperature (T) for phosphorus and silicon. As shown in
Figure 4.2, the saturation pressure of phosphorus is much higher than that of silicon. As
a result, vacuum refining can theoretically separate phosphorus from silicon.

Figure 4.2. Relationship between vapor pressure (Pa) and temperature (K) for
phosphorus and silicon [4-18].

40
4.1 Material Balance of Silicon Refining By Vacuum Technique

From a set of reports providing excellent results for boron and phosphorous removal [4-
14:16, 4-21:30], the most favorable conditions were chosen for further investigation. A
virtual experimental setup, based on the parameters given in Table 4.1, is analyzed:

Table 4.1: Parameters for impurity reduction c from liquid silicon.
Ref.
Reaction P
2
2P [4-15]
Sample weight 3g [4-14]
Argon flow rate
1 l*min
-1
at atmospheric
pressure and 25
o
C
[4-14]
Pressure 0.05atm [4-15]
Time 50min [4-14]
Temperature 1800K [4-16]
Concentration at
the beginning
C
Phosphorus(t=0)
=9.4ppm
w
[4-15]
Concentration at
the end
C
Phosphorus(t=50min)
=3.2ppm
w
[4-15]

From the conditions given in Table 4.1, the amount of argon gas to reduce the
phosphorus level from 9.4 to 3.2ppm can be deduced where the first step is to calculate
the argon gas flow:

RT
PQ
n RT n PV
Argon Argon
= =

41
[ ]
[ ]
[ ]
[ ] K
Kmol
J
s
m
Pa
K
Kmol
J
l
atm
n
Argon
298 * 314 . 8
06 . 0 * 10 * 013 . 1
298 * 314 . 8
min
1 * 0 . 1
3
5
(
(
(
=
(
s
mol
n
Argon
4
10 * 79 . 6 @ 1800K, 1 l*min
-1
and 0.05atm

With the given flow in 50 minutes the amount of used argon will be:

[ ] s
s
mol
Time n Argon
Argon
60 * 50 * 10 * 79 . 6 *
4
(
= =

[ ] mol Argon 05 . 2 =

which shows that 60 mols of argon gas is required to remove 6.2ppm phosphorus (from
9.4 to 3.2ppm)

Considering that 6.2ppm phosphorus is removed from 3g silicon sample, the amount of
phosphorus in the silicon could be calculated:
(g) M
3g(Si)
g 10 * 6.2
1g(Si)
Theor P,
6 -
= M
P,Theor
(g) = 1.86*10
-5
g (P)

or transferring in mols gives:

( )
g 10 * 1.86
(mol) X
P 31g
1mol(Si)
5 -
Theor P,
= X
P,Theor
(mol) = 6*10
-7
mol (P)

Thus, 50 liters of argon gas (1l per minute in 50 minutes) will remove 1.86x10
-5
g or
6x10
-7
mol phosphorus.

42
Assuming laboratory conditions for experiments explained in the following sections we
can calculate the time required to remove phosphorus from the liquid silicon. Laboratory
conditions were as follows: Sample weight 70g, C
Phosphorus(t=0)
=20ppm. Therefore, the
amount of phosphorus in 70g silicon sample can be calculated:

M
70g(Si)

g(P) 10 * 20
1g(Si)
Exp P,
6 -
= M
P,Exp
= 1.40*10
-3
g (P)

Finally, we can calculate required amount of argon gas to reduce phosphorus in the
70g(Si) sample to 3.2ppm:

V(Ar)
(P) g 10 * 1.40

(Ar) 50l
(P) g 10 * 1.86
-3 -5
= V(Ar) = 3,763 l

For our experimental setup, using 1 liter per minute we need about 2.6 days to reach
satisfactory level of phosphorus in solar grade silicon. From a practical point of view or
industrial implementation, the vacuum refining technique has time and energy
limitations in removing impurities from the metallurgical grade silicon in order to satisfy
solar grade silicon requirements. Nevertheless, initial experiments were performed in
order to investigate the level of impurity reduction by the vacuum technique.

43
4.2 Experimental Investigation of Impurity Reduction in
Silicon by the Vacuum Technique

A flow diagram of the experimental procedure used in the current project is given in
Figure 4.3 where experiments in the highlighted fields were executed and white fields
are recommended for further investigation.

MGS
Oxidation Refining
Blowing with H
2
O(Humid Air)
Vacuum Treatment
Reduced Pressure down to 5kPa
Directional Solidification
SGS
Gas Purging
Blowing with Argon

Figure 4.3. Flow chart of the suggested Vacuum Route. Steps in highlighted
fields were tested in current project.

Due to the relatively easy formation of highly volatile boron-hydrides, oxidation refining
procedure is recommended for boron removal. Carbon could also be refined at an
increased rate by adding oxidizing reagents. P, O, Ca, Al have a relatively high partial
pressure above liquid silicon and oxidation refining is recommended. Beside the
44
removal of boron, other impurities are expected to be removed at different rates during
vacuum treatment.

4.3 Vacuum Technique - Experimental Procedure

The experimental setup is given in Figure 4.4 where vacuum refining took place in a
high temperature furnace (Figure 4.5). A reaction tube with a 50 mm inside diameter is
placed inside the furnace. A high temperature resistant brick was sculptured and placed
to fit the closed end of the reaction tube. After that, the MgO crucible with the MGS
silicon was positioned and secured on top of the high temperature resistant brick.
Afterwards, a high temperature resistant insulation brick is placed between the MgO
crucible and the top of the reaction tube. The top of the reaction tube is sealed with a
specially designed water cooled brass cap.

Figure 4.4. Experimental setup of the vacuum refining trials.
45

The water-cooled brass cap allows for the experiments to take place under a controlled
atmosphere. There are three openings at the top of the cap. The central opening is for
the argon and the other two openings are for a vacuum pump, pressure transducer and a
thermocouple. Through the central opening, the ceramic lance (Figure 4.5) is inserted
into the MgO crucible. Later, argon is provided through the ceramic lance.

Figure 4.5. Cross section of the furnace used in the vacuum experiments.

The heating cycle for the vacuum refining experiments is presented in Figure 4.6. A
heating rate of 5.5
o
C/min is applied from room temperature to 110
o
C. The temperature
is kept constant for 10 minutes, therefore any humidity is removed from the system.
Heating is continued at a rate of 32
o
C/min up to 750
o
C. Because of the thermal shock
properties of the refractory materials, after 750
o
C the heating rate is reduced to 7
o
C/min.
The heating rate is then kept constant until the targeted experimental temperature is
46
reached. Once the experiment is over, the cooling rate is maintaned at 7
o
C/min in order
to protect the ceramic and refractory materials from thermal shock.

Figure 4.6. Temperature regime for the vacuum experiments

Details of the performed experiments are presented in Table 4.2. Experiments number
03, 11, 31, 44, 51 and 52 (gray fields in Table 4.1) were chosen for chemical analysis
and further investigations.

47
Table 4.2. Experimental design for the Vacuum Route procedure.
Temp,
(
o
C)
Time
(h)
Lance
Position
Applied
Pressure
Experiment
#
5 kPa 01
Above melt
101 kPa 02
5 kPa 03
1
Immersed
101 kPa 04
5 kPa 09
Above melt
101 kPa 10
5 kPa 11
1450
24
Immersed
101 kPa 12

Temp,
(
o
C)
Time
(h)
Lance
Position
Applied
Pressure
Experiment
#
5 kPa 21
Above melt
101 kPa 22
5 kPa 23
1
Immersed
101 kPa 24
5 kPa 29
Above melt
101 kPa 30
5 kPa 31
1500
24
Immersed
101 kPa 32

Temp,
(
o
C)
Time
(h)
Lance
Position
Applied
Pressure
Experiment
#
5 kPa 41
Above melt
101 kPa 42
5 kPa 43
1
Immersed
101 kPa 44
5 kPa 49
Above melt
101 kPa 50
5 kPa 51
1550
24
Immersed
101 kPa 52

The initial chemical composition of the metallurgical grade silicon (MGS) is given in
Table 4.3. Concentration of the several elements were below the detection limit of the
chemical analysis technique used in this investigation (Inductively Coupled Plasma
Mass Spectrometry).

48

w
) of the metallurgical grade silicon (MGS)
used in the experiments.
Element ppm
w
Element ppm
w

Ag <1.00 Mn 171.5
Al 2650 Ni 175.5
As <5.0 P 16.0
B 18.00 Pb 9.5
Bi <2.0 Sb <5.0
Ca 100 Si Major
Cu 247 Ti 550
Co 11.5 V 504
Cr 9.5 W 31.4
Fe 3300 Zn 3.0
K <100 Zr 31.6
Sign < denotes concentration below detection limit.

During the heating cycle the ceramic lance was held above the silicon while the gas flow
rate was kept constant at 30 standard cubic centimeters per minute (Figure 4.7). Once
the silicon melted, the flow rate was increased to 100 standard cc/min. The ceramic
lance was immersed into the liquid and thus preheated argon gas was used as purging
media. During cooling as the temperature reached 1414
o
C, the freezing point of silicon,
the ceramic lance was raised above the melt and the gas flow was reduced to 30 standard
standard cc/min.

49

Figure 4.7. Lance position during vacuum experiments.

Argon bubbles facilitated stirring and created a large surface area for the evaporation of
impurities.

Figure 4.8. Impurity path during purging with argon during vacuum refining
experiments.

After solidification, the cast silicon was detached from the crucible. Without breaking
the silicon sample, any (semi)-loose material was removed by air jets. Later, the sample
50
was crushed into particles below 500m size and prepared for chemical analysis. These
crushed particles were mixed and 2g were randomly selected for chemical analysis from
the formed bath of the crushed silicon sample. Hence, all parts of the sample were
equally analyzed and chemical analysis outcomes presented an average chemical
composition of the purified sample.

4.4 Impurity Reduction in Metallurgical Grade Silicon

The chemical analysis revealed that the concentration of almost all elements was
reduced after vacuum treatment. Only Mg was elevated because parts of the MgO
crucible were physically attached to the solidified silicon sample. Experiments were
done at three holding temperatures, 1450
o
C, 1500
o
C and 1550
o
C. Figures 4.9 to 4.12
show the concentration of the impurity elements in the silicon with respect to holding
temperature after keeping the liquid silicon under 5kPa pressure for 24h. The lowest
amount of impurities was observed for the highest holding temperature at 1550
o
C.
While the reduction of elements with a low vapor pressure point is expected, removal of
Ti, V, Zr, Mo and W requires further clarification. Ti has a similar boiling point and
vapor pressure values like Si but may have formed TiO
2
. Mo and W easily form volatile
oxides [4-31] and will follow the same path as B removal that is well explained in the
literature. Also, some reports show high volatility of the V oxide.

51
4.5 Influence of the Holding Temperature on Impurity
Reduction During Vacuum Treatment

The results show that the holding temperature has a great influence on the removal of
impurities. Figures 4.9-4.12 show the reduction of the impurity elements in silicon with
respect to holding temperature.

Figure 4.9. Mo, Pb and Zn in MGS before and after vacuum treatment (24h).

52

Figure 4.10. Co, Cr, W and Zr in MGS before and after vacuum treatment (24h).

Figure 4.11. Mn, Ni, Cu and V in MGS before and after vacuum treatment (24h).
53

Figure 4.12. Al, Fe and Mg in MGS before and after vacuum treatment (24h).

54

4.6 Impurity Reduction During Vacuum Treatment

Figures 4.13 to 4.15 show the reduction of the impurity elements after holding for 1h
and 24h at 1450
o
C and 1550
o
C. It can be seen that 24h holding time improves impurity
reduction. Figure 4.15 shows the reduction of elements that have the highest
concentration in MGS and as such require more attention.

Figure 4.13. Cu reduction from MGS during vacuum experiments after
holding for 24h.
55

Figure 4.14. Zn and Zr reduction from the MGS during vacuum experiments after
holding for 24h.

Figure 4.15. Al, Fe and Mg reduction from the MGS during vacuum experiments
after holding for 24h.
56
4.7 Vacuum Refining Results

The result showed that the vacuum technique can be used for purification of
metallurgical silicon. The element with the lowest reduction factor was Ti where its
concentration was reduced 1.83 times. Most elements with lower boiling point had
higher reduction factor. An analysis of the reduction factor data showed that most
elements achieved constant evaporation rate at holding temperatures below 1600
o
C.

Tables 4.4 and 4.5 show how vacuum refining can lower concentration of impurities
compared to that of the standing metallurgical grade silicon. Impurity concentration
ratio is expressed as ratio between the amount of impurity before and after vacuum
refining.

Table 4.4. Impurity concentration in ppm
w
in metallurgical grade silicon before
and after vacuum refining.
Temperature,
o
C
Element Before 1450 1500 1550
Al 2650 1200 1500 900
Co 11.5 8.0 6.0 5.0
Cr 10.5 10.0 7.5 3.0
Cu 248 194 117 88.0
Fe 3300 1800 1100 1200
Mn 172 70.0 25.0 51.0
Mo 5.0 4.0 2.0 2.0
Ni 176 121 57.0 81.0
Pb 9.5 5.0 8.0 <0.2
Sc 2.0 1.0 1.0 1.0
Ti 550 300 <100 300
V 504 286 <100 273
W 31.4 30.0 20.0 13.0
Zn 3.0 2.0 2.0 <1.0
Zr 31.6 17.0 7.0 15.0
* Sign < denotes concentration below detection limit.
57

Table 4.5. Impurity Reduction Factor after vacuum refining.
Concentration Ratio
Element 1450
o
C 1500
o
C 1550
o
C
Al 2.2 1.8 3.0
Co 1.4 1.9 2.3
Cr 1.1 1.4 3.5
Cu 1.3 2.1 2.8
Fe 1.8 3.0 2.8
Mn 2.5 6.9 3.4
Mo 1.3 2.5 2.5
Ni 1.5 3.1 2.2
Pb 1.9 1.2 <4.8
Sc 2.0 2.0 2.0
Ti 1.8 <5.5 1.8
V 1.8 <5.0 1.9
W 1.1 1.6 2.4
Zn 1.5 1.5 <3.0
Zr 1.9 4.5 2.1

Elements with a low boiling point like Pb, Mn, Zn or Al had high reduction factor. The
reduction factor of Al is important since the concentration of Al in metallurgical grade
silicon is usually very high. Also, the segregation coefficient of Al in Si is relatively
high therefore it is important to find a technique other than zone refining capable to
remove Al from silicon. 3d elements like Cu, Cr, Sc, Fe, Ni or Co had satisfactory
reduction factor. Similar to Al, the concentration of Fe in metallurgical grade silicon is
often very high. Similar to Cu, Fe is an element that can be used as alloying agent in a
58
process of refining Si. Elements with lower vapor pressure than silicon showed reduced
amount in refined silicon. Elements such as V, W or Zr had reduction factors from 1.9
to 2.1 for 1550
o
C holding temperature. The lowest reduction factor was for titanium.

The possible reason for removal of low vapor pressure elements is the formation of
respective oxides with vapor pressure higher than silicon. Since the mullite or alumina
reaction tubes allow some diffusion of gases at very high temperature, vacuum treatment
led to same diffusion of air into the reaction tube [4-32, 4-33]. The oxygen entering the
tube would react with the various elements in the silicon, allowing for the formation of
various oxides. Some could separate into a slag phase and some could volatilize.

59
5 Properties of the Cu-Si System

Copper has an atomic mass more than two times higher than silicon and almost four
times higher density. The atomic structure and physical properties of the copper
compounds with silicon are given in Table 5.1. Unlike silicon, copper has a weakly
bonded electron in the outer orbital and considerably higher electrical and thermal
conductivities.

Table 5.1. Atomic structure and physical properties of the copper and silicon.
Atomic Structure
of Copper
Atomic Structure
of Silicon
Atomic Radius 1.57 1.46
Atomic Volume 7.1 cm
3
mol
-1
12.1 cm
3
mol
-1

Covalent Radius 1.17 n/a
Crystal Structure Cubic face centered Cubic Face Centered
Electron Configuration 1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
1
1s
2
2s
2
2p
6
3s
2
3p
2

Physical Properties
of Copper
Physical Properties
of Silicon
Atomic Mass 63.546 28.0855
Density 8.96g cm
-3
@ 300K 2.329 g cm
-3
@ 293K
Melting Point 1358 K (1085
o
C) 1687 K (1414
o
C)
Boiling Point 2833 K (2560C) 2628 K (2355C)
Coefficient of Linear
Thermal Expansion
16.5x10
-6
K
-1
3.0x10
-6
K
-1
@ 293K
Electrical Conductivity 60.7 10
6
S cm
-1
@ 300K 1.2x10
-5
S cm
-1
@ 293K
Thermal Conductivity 401 W cm
-1
K
-1
149 W cm
-1
K
-1

It is known that an element with lower valence is more likely to have a greater solubility
than an element with higher valence. In the Cu-Si system, copper has a valence of one
and silicon a valence of four. Therefore, the solid solubility of copper in silicon will be
very low. In addition, the silicon atom has four valence electrons in the outer orbital
60
where each silicon atom has four nearest neighbors in its crystal lattice. Thus,
completing all outer electrons shells by forming four sets of paired bonds silicon forms
very stable covalent bonds. Eventual substitution of a silicon atom with copper in the
silicon lattice disrupts the covalent sharing of the four electrons from the silicon because
a copper atom can contribute only one electron. Thus, the presence of copper atoms in
the silicon lattice causes a situation in which the bonding of its nearest neighboring
silicon ions is incomplete, bringing the overall system into a higher energy state.

Increasing the number of substitutional copper atoms replacing silicon atoms in silicon
lattice significantly increase the internal energy of the system. Hence, copper will not fill
the Si lattice as substitutional atom and the solid solubility of copper atoms in a silicon
lattice will be very low (see Figure 5.3, solubility of Cu in Si).

The binary phase diagram (Figure 5.1) of the Copper-Silicon system, with its
thermodynamic properties, is fairly well established with some uncertainty related to the
high temperature copper rich intermetallics [5-1:5]. There are three stable intermetallic
phases at room temperature in the Cu-Si system. In the literature these phases are
mostly named with greek letters: (Cu
3
Si), (Cu
15
Si
4
) and (Cu
5
Si). Cu
3
Si phase has two
high temperature modifications (556-802
o
C) and (467-556
o
C) beside the room
temperature stable intermetallic (stable below 467
o
C).

61

Figure 5.1. Copper-silicon binary phase diagram [5-5].

62
5.1 Copper Diffusivity in Silicon

Copper, unlike other d elements, has a weakly bonded single electron in the 4s orbital.
Such configuration allows copper to easily give away 4s
1
electron and significantly
reduces its ionic radii [5-6] allowing copper to diffuse through the silicon lattice as a
positively charged ion. After loosing the electron from the 4s orbital, the farthest orbital
in the copper atom is 3d. Furthermore, the next two electrons suborbitals (3p
6
and 3d
10
)
have cylindrical shape rather than spherical. While in the literature the bigger radius is
considered as copper ionic radius, smaller radius of such ion should be considered as
effective-copper-ionic-radius. Furthermore, the opposite positioned orbitals are capable
of bending, allowing Cu ions even faster movement through the Si lattice [5-7]. Such
configuration makes Cu by an order of magnitude the fastest moving foreign element in
the Si lattice except hydrogen (Figure 5.2, diffusivity of Cu in Si).

Due to the small effective ionic radius, copper diffuses as interstitial ion rather than
substitutional atom. The diffusivity of interstitial copper in silicon can be estimated with
the following equation [5-8]:

( )
|
\
|
=
kT
eV
x D
m
01 . 0 18 . 0
exp * 10 % 10 0 . 3
4
m
[cm
2
s
-1
] (5.1)
where T is the temperature in (K) and k is Boltzmanns constant (m
2
kg s
-2
K
-1
).

Table 5.2 shows calculated copper diffusivities for some characteristic temperatures in
Cu-Si alloys.

Table 5.2. Copper diffusivity in silicon.
Temperature, (K) 300 800 1075 1687
Diffusivity, (cm
2
s
-1
) 2.8*10
-7
2.2*10
-5
4.3*10
-5
8.7*10
-5

63
Further, Bracht [5-9] compared the copper diffusivity in silicon with the diffusivity of
other elements as seen in Figure 5.4. Figure 5.4 reveals that copper interstitial ion has a
diffusivity similar to hydrogen and significantly higher than any other element [5-10].
The dashed lines in Figure 5.2 represent interstitial diffusion mechanism while solid
lines correspond to substitutional diffusion mechanism.

Figure 5.2. Diffusivity of copper in silicon [5-11].
64

Copper diffuses through the silicon lattice as a positively charged ion, which makes it
susceptible to acceptor type inclusions. In the presence of acceptor type elements such
as elements in the third group in periodic table, copper will form electron donor-acceptor
pairs and its diffusivity will be lower. The effective diffusivity of the copper in silicon
could be expressed with following equation [5-12]

|
\
|
|
\
|
+
|
\
|
T
N
T
x
T
x
D
a
Eff
4990
exp 10 584 . 2 1
2090
exp 10 3
20
4
[cm
2
s
-1
] (6.2)
where N
a
is concentration of the acceptor elements (atoms/cm
3
)

The presence of the acceptor type elements slightly decreases diffusivity of the copper in
silicon. However, solving this equation we get similar values as in Table 5.2

65
5.2 Copper Solubility in Silicon

Copper has a fairly low solubility in solid silicon that is expressed via the following
equation [5-13]:

|
\
|
=
kT
eV
x S
Cu
49 . 1
4 . 2 exp 10 5
22
(atoms/cm
3
) (5.3)

Unlike diffusivity, the solubility changes significantly at different temperatures. Figure
5.3 shows the solubility as a function of temperature reported by different authors. The
highest solubility of copper in silicon is around 1300
o
C. Solubility rapidly decreases as
temperature falls. The solubility of copper in silicon decreases with decreasing
temperature and drops below 1ppm
w
at temperature below 1100
o
C.

Figure 5.3. Solubility of copper in silicon for various temperatures.

66
5.3 Copper Distribution Sites in Silicon

The solubility of copper in silicon at room temperature is negligible (Figure 5.3)
meaning that with sufficient time all copper trapped in the silicon will move to the
surface of the sample or will precipitate into the Cu
3
Si phase. Possible distribution sites
for trapped copper are (Figure 5.4):
1) Lattice defects such as dislocations or partial dislocations,
2) Grain boundaries,
3) Sample surface, or
4) Precipitation of the copper into Cu-silicides, most likely at the lattice defects or
grain boundaries.

Figure 5.4. Possible copper distribution sites in a silicon sample. 1) Lattice defect,
2) Grain Boundary, 3) Sample surface, 4) Precipitation into Cu
3
Si.

If slow cooling is provided, copper will agglomerate at lattice defect sites with lower
activation energy and later will move towards grain boundaries. With enough time,
copper will follow grain boundaries to the surface. On the other hand, during rapid
cooling the copper atom has not enough time to diffuse to nearest grain boundary or
1
2
3
4
67
surface of the sample. As a result, copper atoms will most likely start to agglomerate
around lattice defects and precipitate into Cu-silicide. Later, copper atoms will move
toward the already formed Cu-silicide precipitate inside the silicon grain.

The only stable Cu-silicide in hypereutectic Cu-Si alloys at room temperature is Cu
3
Si.
The molecular volume of the Cu
3
Si is 46
3
[5-17]. This volume is considerably higher
than the molecular volume of silicon that is 20
3
causing a significant increase in
internal stresses during Cu
3
Si formation and growth. The formation of the Cu
3
Si inside
silicon dendrites is highly unlikely even at high cooling rates because difference in
density between silicon and Cu-intermetallics. Furthermore, in the presence of the
lattice defects, copper atoms will rather accommulate on them than form intemetallics
[5-18]. Figure 5.5 shows characteristic microconstituents distribution in a 50Cu-Si
alloy, solidified under slow and fast cooling regimes.

Figure 5.5. Characteristic microconstituents distribution in 50wt%Cu-Si alloy
solidified under (a) slow cooling regime and (b)fast cooling regime. Dark fields are
Si dendrites while bright fields are Cu
3
Si intermetallic.

a
a
b
b
68
Figure 5.6 shows a schematics of the growth of copper precipitates in bulk silicon.
Copper atoms will occupy regions around lattice defects. When the transition barrier is
reached, agglomerated copper atoms will form the Cu-Si intemetallic. Initially, formed
intermetallic will have disc-plate shape. The size of the disc-plated copper precipitates
depends on the amount of copper and the cooling rate. Horanyi [5-19] reported the
presence of such phases in silicon containing less than 10
13
/cm
3
copper atoms.
Additional copper atoms will agglomerate around the newly formed phase and will
eventually build spherical micro constituents inside the silicon grain. The spherical
shape is thermodynamically the most stable shape in final stages of precipitation of
diluted elements, forming intermetallics with major element, in the bulk sample.

Figure 5.6. Formation of the Cu-silicides around point defect and its growth in
bulk Si . Si lattice constant 5.43; Cu lattice constant 3.61 ; Si atomic radius 1.46
; and Cu atomic radius 1.57 .

Due to the significant volume change involved in Cu
3
Si formation (
Si Si Cu
xV V 3 . 2
3
)
precipitation of Cu atoms is possible only near point defects such as dislocations, voids,
stacking faults, grain boundaries or surface. Hsiu-Wu Guo gave the free energy of
formation of a spherical shaped defect [5-20]. In addition, nucleation and growth of Cu-
silicide in a silicon crystal requires a higher driving force than most other silicides.
69
Therefore, in the presence of lattice defects, copper will be the last to accumulate around
them or form a silicide precipitate around the lattice defect. High diffusivity and the
improbability of forming silicides enables copper to approach thermodynamical
equilibrium more easily than any other element. Unlike other elements, out-diffusion
(diffusion to the surface) of copper is a realistic and significant factor that has to be
considered.

An important factor for copper out diffusion is the initial quality of the silicon crystal. A
perfect crystal, with low amount of defects as spots for heterogenous nucleation, will
have fewer sites for copper agglomeration or further silicide formation. Under such
conditions copper atoms will, most likely, follow the out-diffusion path. Furthermore,
Nakahara [5-21] suggests that continuous polishing of the surface of the sample will
improve copper removal from the silicon sample. Given enough time, copper will reach
the surface and will achieve an equilibrium composition in the silicon.

5.4 Impurities in Cu-Si Alloys

Most elements have low solubility and segregation coefficient in solid silicon.
However, copper has a high affinity for a wide range of elements, low activity
coefficient, stable intermetallics and low effective ionic radius. This further reduces the
segregation coefficient for most elements in silicon in the presence of Cu. During
solidification of the liquid alloy, pure silicon crystallizes first while the remaining
solvent together with the impurity elements, solidifies in the gaps between the silicon
dendrites. With slow cooling, the impurity elements with low solubility in solid silicon
(Au, Co, Cu, Fe, Mn, Ni, Ti, Zr) are retained in the solvent or are deposited at grain
boundaries of the alloy. Homogeneous nucleation requires a higher driving force than
heterogeneous nucleation [5-22] and the most expected site for the silicides-
heterogeneous-nucleation is at the grain boundaries, lattice defects or the other impurity
70
rich regions. Such sites are the weakest areas in the alloy and most likely will be
exposed in case of alloy crushing. Importantly, due to the lack of homogeneous
nucleation, an impurity micro dispersion in the Si particles is not expected.

Lattice defects, grain boundaries or surface of the sample are easily exposed after
sample crushing and any exposed inclusions can be removed with a surface related
technique like acid leaching. The following treatments are suggested in order to remove
impurities from metallurgical grade silicon (Figure 5.11):
Alloying Si with Cu Impurities tend to enrich in the Cu-Si phase, along grain
boundaries or at the surface of the sample.
Solidified alloy is crushed Physical separation is used to try to produce pure Si
dendrites and remove the Cu-Si bulk phase together with trapped impurities.
Cu-Si intermetallics are separated from the Si by gravity separation Pure silicon
is separated from the heavy Cu-silicides and other impurities heavier than
silicon.

Figure 5.11. Proposed refining techniques in order to purify metallurgical silicon to
solar grade silicon.
71
6 Metallurgical Refining of MGS

In order to study the purifying capability of copper in silicon, a set of experiments using
different metallurgical techniques were used:

Alloying metallurgical grade silicon with copper;
Prolonged solidification of the mixture;
Crushing and screening of the solidified Cu-Si alloy and
Cu-Si intermetallics separation from the Si by heavy media separation.

A flow diagram of the suggested experimental procedure is presented in Figure 6.1. The
scope of our testing did not include leaching and directional solidification.

Figure 6.1. Flow chart of the proposed metallurgical route.
72

The most important factors that may improve silicon purity and recovery are the
chemical composition of the alloy, shape of the casting (height to diameter ratio), heat
removal direction (unidirectional), free surface to volume ratio, purging/protecting gas
flow rate, crushed particle size and viscosity of the HLMS. In the current research, the
casting had a cylindrical shape with a height to diameter ratio of 3:1. Change of
diameter can change as cast structure. Silicon dendrites grow perpendicular to crucible
wall deep into the middle of the sample. Higher diameter will allow longer dendrite
growth. Due to the shape of the casting with good insulation at the top and bottom of
the chamber, heat removal was considered mainly radial-unidirectional.

A detailed description of the sample generation, preparation, experimental setup and
critical analysis is given in the following sections.

73
6.1 Chemical Composition of Starting Copper and Silicon

The chemical composition of the metallurgical grade Si (Table 6.1), received from Arise
Technology Corporation, was attained by inductively coupled spectrometry (ICP) while
the composition of the electrolytic grade Cu was obtained by the glow discharge (GD)
method. ICP analysis was done by International Plasma Labs Ltd., Richmond, BC
(www.ipl.com) while GD analysis was done by Northern Analytical Laboratory Inc.,
Londonderry, NH (www.northernanalytical.com).

w
) of the electrolytic copper (EC) and
metallurgical grade silicon (MGS) used in experiments.
EC MGS

EC MGS
Element GD ICP

Element GD ICP
Ag 15 <1.00 Mg 0.005 100
Al 0.008 2650 Mn 0.2 171.5
As 0.24 <5.00 Ni 1.5 175.5
B <0.01 18.0 P 1.2 16.0
Bi 0.23 <2.00 Pb 0.38 9.5
Ca 0.028 100 Sb 0.7 <5.00
Cu Major 247 Si 0.007 Major
Co 0.001 11.5 Ti 0.002 550
Cr 0.27 9.5 Zn 0.034 3
Fe 1.7 3300 Zr <0.01 <100
K 0.026 <100 V <0.01 504

74
6.2 Apparatus

A schematic of the equipment used in the alloying experiments is given in Figure 6.2.
An electrical furnace designed and assembled at the University of Toronto was used in
alloying silicon with copper.

Figure 6.2. Experimental setup for alloying silicon with copper.

A mullite closed-end reaction tube with 50mm inside diameter was placed inside the
furnace and the top was sealed with a brass cap. The mixture was protected with argon
gas provided through a ceramic lance. Also, argon gas was used as a purging/mixing
media. A Copper Getter Furnace at about 500
o
C (Fig. 6.2, CG Furnace) was used for
the elimination of the oxygen traces from the argon gas. Before argon gas was provided,
the copper getter furnace was flushed with a mixture of hydrogen and nitrogen gas.
Therefore, the copper strips inside the furnace were left with clean surfaces capable of
picking up any oxygen residues in the argon. Mass flow controller Omega FMA-5605
controlled the argon gas flow. A ST-1600-High Temperature Controller from Sentro
75
Tech Corp controlled the temperature inside the furnace. The chamber temperature was
measured with a thermocouple attached to the wall of the crucible while the temperature
of the melt was monitored with periodic insertion of an additional thermocouple into the
melt. Photographs of the equipment used in all the experiments are given in Appendix
1.

Figure 6.3 gives a detailed view of the furnace setup during the experiments. A mullite
closed-end reaction tube was filled with 500g of metallurgical silicon lumps and 500g of
copper plates, respectively. The reaction tube was closed off with an insulation brick.
The insulation brick had one opening for thermocouple insertion, the second opening
provided opening for gas removal while a ceramic lance was threaded through the
middle of the insulation brick.

Figure 6.3. Reaction tube during alloying.

76
6.3 Alloying

The Cu-Si melt was held at 1450
o
C for one hour to assure complete melting and mixing.
A B type thermocouple, connected to the temperature controller, was used to control the
temperature during heating and subsequent controlled cooling. During heating, the gas
flow was maintained at 30 standard cm
3
min
-1
in order to protect the melt from contact
with the air. A ceramic lance was placed through the middle of the crucible. After the
mixture had melted, the ceramic lance was lowered to the bottom of the crucible and the
gas flow was raised to 100 standard cm
3
min
-1
; therefore, argon gas was used as the
stirring agent as well as for protection from oxidation. During cooling, after the mixture
reached the liquidus temperature, the lance was raised and the gas flow was reduced to
30 standard cm
3
min
-1
, again. After reaching room temperature, the solidified specimen
was removed from the furnace and cut into several sections. The chemical composition
of the C-Si alloy prepared at the University of Toronto was 50.8wt% Cu and 68.1wt%
Cu for the 50Cu-Si and 70Cu-Si, respectively.

6.4 Cooling Rates

The mixture was heated to 1450
o
C and kept at this temperature for one hour to ensure
complete melting. After one hour at 1450
o
C, a slow cooling rate (0.66
o
C min
-1
) was
employed, which was applied down to 810
o
C (Figure 6.4). The eutectic temperature of
the Cu-Si binary system is 802
o
C. The temperature was kept slightly above the eutectic
temperature for several hours to increase segregation between Si and Cu as well as to
maintain high diffusion coefficients of the contamination elements in the solidified Si.
In addition, the alloy had enough time for silicon dendrite growth and for impurities to
move along the solid/liquid boundary. After the mixture reached room temperature the
alloy was removed from the furnace.

77

Figure 6.4. Heating-cooling regime.

6.5 Generation of Size Fractions

A total of four 50Cu-Si and one 70Cu-Si specimens were prepared for removal and
chemical analysis. The specimens were crushed in mullite mortars (Fig. 6, crushing
stage), and sieved (Fig. 6.5, Sieving Stage) in brass screens, and the resulting fractions
were collected by the different particle sizes. Tyler Canada, FH Brass Pan type screens
were used. The Sieves were washed, dried and cleaned before each experimental trial,
therefore the demand for ultra clean equipment was satisfied.

78

Figure 6.5. Fraction generation.

Four screens were used in the sieving stage and consequently five different particle size
fractions were collected (Fig. 6.5). The size fractions and average particle size used in
the current work are given in Table 6.2.

Table 6.2. Different size fractions used in the experiments.

79

Fig. 6.6 shows the fashion in which each specimen was sectioned. Four 50Cu-Si and
one 70Cu-Si specimens were collected for further metallographic and chemical analysis.
Most of the specimen was crushed, and the consequently created fractions are screened
and collected by particle size (Fig. 6.6-B). A middle cross section (Fig. 6.6-C) of the
specimen was prepared for metallographic analysis while the bottom and upper parts
(Fig. 6.6-A) were removed due to possible contamination.

Figure 6.6. Sample collection: A view of the specimen after removing from the
furnace (upper figure), collected fractions from section B after crushing and
screening (bottom-left) and middle cross segment from section C (bottom-right).

80

6.6 Heavy Media Separation

Due to high capacity, adaptability and low cost, the lack of hazardous materials or high
temperature requirements; gravity separation is an effective method for separating
species with significant difference in one of the gravity parameters such as density,
particle size or shape [6-1, 6-2].

In general, gravity separation is most efficient when there is a large difference in the
density of the components to be separated, the particle size is similar and not excessively
fine, and the particle shape is round. Heavy media separation leads to a three layer
system where the denser media settles to the bottom, the light floats to the top, and the
heavy media separator remains in the middle partitioning the two newly formed species.
Formation of the three different layers in heavy media separation is given in Figure 6.7.

Figure 6.7. Three distinctive layers formed after heavy media separation.

81
Heavy liquids are dense fluids or solutions used to separate materials of different density
through their buoyancy. Materials with a density greater than the heavy liquid will sink,
while materials with a density less than the heavy liquid will float on the surface. In the
analysis of mineral samples, separation based on mineral density is an important step in
many sectors of the mining industry. On a plant scale the methods used include jigs,
spirals, riffle tables and heavy medium separation. On a laboratory scale, heavy liquids
are commonly used where heavy liquid separations result in two components, the heavy
fraction (or sinks) and the light fraction (or floats). In industry it is usually the heavy
fraction of a mineral suite which contains the valuable component, and which is
separated from sand (silica) and other components having a density less than 2.7 g/mL.
The solution density used for this type of separation is about 2.85 g/mL, nearly three
times the density of water. Since our product is pure silicon we are interested in the
light fraction more than in the heavy fraction. HLMS used in the current experiments is
lithium metatungstate with the tungsten anion [H
2
W
12
O
40
]
6-
which belong to a class of
structures known in the literature as the 'Keggin' species.

The density, viscosity and amount of the HLMS were kept constant throughout the
experiments. The amount of the light media could be correlated to the Density Factor
(DF) of the HLMS where the density factor could be calculated from the density of the
Si, Cu
3
Si and HLMS using the following equation:

Si Si Cu
Si HLMS
DF

=
3

A value for DF of zero refers to the density of the HLMS close to the density of the Si,
while HLMS with similar density to the Cu
3
Si will have a DF value close to one. The
densities of the Si, Cu
3
Si and HLMS are 2.33 g*cm
-3
, ~6 g*cm
-3
and 2.85 g*cm
-3
,
respectively. Therefore, the used HLMS has a low value of DF 0.14 and will give a high
ratio of pure Si particles and further purification will be easier but at the same time
recovery would be significantly reduced. On the other hand, a higher density of the
82
HLMS will increase the amount of the mostly Si particles but more mixed (Si-Cu
3
Si)
particles will also be recovered, decreasing the purity of the silicon.

The light, mostly pure silicon particles were separated from the heavy Cu-intemetallic
particles by the heavy media separation technique. A Heavy Liquid for Mineral
Separations (HLMS), with a density of 2.85g cm
-3
was used as the media separator.
HLMS is a concentrated solution of lithium heteropolytungstates in water and can reach
a density up to 2.95 g/mL at 25 C, and a density of 3.6 g/mL at elevated temperatures.
At its optimal working density at 2.85 g/mL, LST heavy liquid has a viscosity of 10 cP.
Heavy Liquid solids contain heteropolytungstates in the form of extremely soluble,
colourless, hydrated crystals. Concentrated aqueous solutions of LST Heavy Liquid
form colourless or pale yellow heavy liquids. LST Heavy Liquid is normally used as an
aqueous solution. However, the LST Heavy Liquid crystals are also highly soluble in
acetone and alcohols, and can form dense liquids in these organic solvents. These
provide a range of methods for the use and recycling of LST heavy liquids.

Solutions of HLMS have been found to be stable up to 140C for at least two weeks. No
decomposition, or loss of maximum density was observed during this time. This means
that solutions of HLMS that have been diluted by washing etc. can easily be
reconcentrated by heating to boiling when evaporating off excess water. The media
separator was chemically stable and does not interact with Cu or Si, and neither with any
of the trace elements present in the system. The heavy media separation procedure is
illustrated in Figure 6.8.
83

Figure 6.8. Heavy media separation procedure.

The separatory funnel was filled with 30ml of the HLMS followed by 20g of the Cu-Si
alloy. The suspension was stirred several times to provide better mixing so that any
trapped light particles in the bottom of the funnel were liberated. The suspension was
left to sediment until three distinctive layers were recognized (Fig. 6.8, Separation).
Once completely settled, the stopcock under the separatory funnel was opened and the
bottom layer flowed out into a beaker (Fig. 6.8, Particle Collection). The stopcock was
closed once the entire bottom layer consisting mainly of Cu
3
Si was collected.
Subsequently, the beaker below the separatory funnel was changed and the procedure
was repeated until the middle section was collected. Finally, the top layer of mainly
silicon grains was collected following the previously mentioned procedure. Once the
heavy and light fractions were gathered, washing of the HLMS, drying and weighting
were performed. After heavy media separation, the different size fraction samples
(Table 6.2) were separated into light (Si) and heavy media (Cu
3
Si). Figure 6.7 shows a
detailed look at the separatory funnel after separation but before particle collection. The
approximate sedimentation time varies with each specimen, whereas smaller particles
demand longer time for sedimentation. After heavy media separation, the particles were
rinsed with deionized water while the liquid media separator was collected for
subsequent trials.

84
6.7 Chemical Analysis

Chemical analysis for the Cu in the light fraction was done by Atomic Absorption
Spectrophotometry (AAS) as it is the most suitable technique for samples with less than
10 wt% Cu. The chemical analyses of the starting alloys and heavy fraction samples
were done by the Titration (TT) technique that is suitable for samples with more than 10
wt% Cu. The concentration of the different impurity elements, which are below 2wt%
in light and heavy fraction before and after heavy media separation, was investigated by
Inductively Coupled Plasma Mass Spectrometry (ICP) that gives results at the ppm
wt

85
7 Metallographic Analysis

Metallurgical refining outcomes are organized by techniques that were implemented in
the current investigation. Sections 7.2 and 7.3 are related to metallography and image
analysis results, where the main goal was first to recognize and characterize the
microconstituents present in the Cu-Si alloys. Section 7.4 is focused on understanding
of Si dendrite formation and growth.

7.1 Oxidation Behavior

After crushing of the Si-50wt%Cu alloy, 10g of the finest particles were placed on an
analytical balance and examined for oxidation at room temperature. This was done to
ensure that the particles did not change during storage and handling. Table 7.1 shows
the weight gain of the sample for extended time periods for particles less than 38m.
After 24h, there is no further increase in weight, showing a 3.94x10
-5
% gain. Therefore,
if this mass gain is due to oxidation of the alloy, the rate is very low and does not show
significant influence on the parameters that will be examined. This also shows that the
samples do not absorb any noticeable amount of moisture. It was therefore concluded
that the samples could be handheld in air without any risk of the sample either being
oxidized or affected by the humidity in air.

Table 7.1. Weight gain of Si-50wt%Cu alloy fraction with size less than 38m.
Time, (h) 0 4 12 24 48
Gain, (%) 0 1.97x10
-3
2.95x10
-3
3.94x10
-3
3.94x10
-3

86

0.0E+00
5.0E-04
1.0E-03
1.5E-03
2.0E-03
2.5E-03
3.0E-03
3.5E-03
4.0E-03
4.5E-03
0 10 20 30 40 50 60
Time, (Hours)
W
e
i
g
h
t

G
a
i
n
,

(
%
)

Figure 7.1. Weight gain of fine grinded Si-50wt%Cu alloy (size less than 38m)
in laboratory air at room temperature.

7.2 Microscopy Findings

Particles of five different sizes (0-38, 38-106, 106-500, 500-1000 and above 1000m)
were mounted in resin for polishing and subsequent microscopic analysis. Also, loose
particles were embedded into a nonmagnetic tape for surface residues analysis. Images
are acquired by a SEM microscope. The microscope was operated at 20kV while the
samples were carbon-coated. For image analysis purposes, low magnification was used
to maximize the observed area and to increase the number of analyzed particles, while
for detailed analysis of the phase boundaries, high magnification was used. For each
size fraction, three kinds of samples were analyzed:
87
- Sample prior to gravity separation,
- Light fraction particles after gravity separation,
- Heavy fraction particles after gravity separation

7.2.1 Micro-constituents Analysis

Figure 7.2 depicts shape and size of the formed Si dendrites in the 50Cu-Si alloy
solidified at 0.66
o
C/min cooling rate. The region close to the sample wall is
characterized by long straight Si dendrites such as D1 or D2 in Figure 7.2a. Moving into
the middle of the sample, the Si dendrites remain long with curved edges such as D3 and
D4 in Figure 7.2b. The upper central part of the sample is rich with short irregular shape
Si particles mostly like D5 or D6 in Figure 7.2c.

Figure 7.2. Secondary electron images with the two microconstituents phases
present in 50Cu-Si hypereutectic alloy. a) close to the wall, b) region between the
edge and the center of the sample and c) central part of the sample.

88
Both phases, Si and Cu
x
Si are very brittle. Figure 7.3 shows broken edges of the present
microconstituents and the fashion that the phases are broken. It can be seen that the
particles are generally broken along phase boundaries. The morphology shown in
Figure 7.3 is characteristic for zone 4 explained in Section 7.4.2, or the last solidified
segment of the sample. Such segment is rich with broken Si dendrite parts and dendrites
with trapped Cu
3
Si phase in the middle. This segment has the highest area-boundary
ratio, therefore has the highest internal residual stresses. Thus, the numbers of small
particles are easily detached from the specimen surface even during sample preparation
as seen in Figure 7.3.

Figure 7.3. Secondary electron image with a number of loose fractions at the edge
of the Si and Cu
x
Si phases.

89
Si is a more brittle constituent than the nearby Cu
x
Si. Thus, most microcracks are
parallel to the phase boundary with the highest density in the Si phase, behind the phase
boundary where the internal residual stresses are the highest. Such microcracks
distribution gives a clean Si particle surface after crushing, while any impurities from
the phase boundaries will easily be removed during rinsing after gravity separation.

7.2.2 Phase Boundary Condition

Figure 7.4 gives closer analysis of the Si and Cu-rich-silicides (Cu
x
Si) boundary as well
as a closer look into a number of microcracks present in the Cu-Si alloy. The darker
field in Figure 7.4 is silicon and the brighter field is Cu-intermetallic. The boundary
between Si and Cu
x
Si is several microns thick without transitional intermetallics or a
solute rich solid solution.

Figure 7.4. Secondary electron image with a number of microcracks along the
microconstituents boundary in the Si-50%wtCu alloy; carbon coated, 20kV [7-3].
90

The strain in the material due to volume changes causes the formation of microcracks in
the silicon and the Cu
3
Si phase. Although the crystal structure of the low temperature
silicides (Cu
3
Si, Cu
15
Si
4
and Cu
5
Si) is not known [7-1], a significant change in volume
is recognized during Cu
3
Si formation [7-2] and may result in the high density of
microcracks observed on the SEM micrograph presented in Figure 7.4. The subsequent
separation of the pure silicon from the Cu
3
Si is greatly improved by the formation of
these microcracks. These properties make copper a good silicon purifier not only
during solidification, but also during eventual heat treatment or solid-state mechanical
treatments.

7.2.3 Dendrite Thickness Measurements

The middle cross section of the formed specimen (Fig. 7.5) is analyzed using an optical
microscope to determine the average dendrite size. Long silicon dendrites are expected
due to the slow solidification conditions and furthermore some of the dendrites are
longer than the diameter of the samples cross section. Such long dendrites prevented
dendrite thickness analysis in the middle of the sample. The characteristic eutectic
morphology is found neither in the middle part of the cross section nor at the edge.

91

Figure 7.5. The middle cross section of the as is solidified specimen.

The first step in the local dendrite thickness investigation was the implementation of
concentric circles. The circles center was in the center of the cross section (Figure 7.5).
Then, each circle was extracted and straightened using image analysis software (Figure
7.6, I). After the circle was straightened, the total length covered by Si along each circle
was measured and divided by the number of Si dendrites intersecting each circle.

92

Figure 7.6. Average dendrite thickness calculation procedure. I ) part of the
sample, II ) straitening the circle and III ) counting Si and thickness measurement.

The average dendrite thickness results for three circles at 10, 15 and 20mm are given in
Table 7.2. The outcome of this analysis is in good correlation with the optimal particle
size (Section 9.7) for the efficient separation between pure silicon and Cu-Si
intermetallics. However, the results for the dendrite thickness should be taken with some
reserve because of the relatively small ratio between the sample size and dendrite length,
as well as dendrite orientation.

Table 7.2. Local thickness of the dendrites in the middle cross-section of the
specimen

Distance from
the Center,
Average Dendrite
Thickness,
(mm) (m)
R1 10.0 96
R2 15.0 146
R3 20.0 167

I
II
III
93
7.2.4 SEM Analysis

Preparation of the loose particles required special attention due to the small size of the
particles and the high magnetic force inside the SEM microscope chamber. In order to
avoid Si particles being moved by the strong magnets, the particles were embedded into
a double-sided nonmagnetic tape. One side of the tape was glued to the disk holder
while the other side of the tape contained loose Si particles. Sample mounting for the
loose particles examination is shown in Figure 7.7a.

Figure 7.7. Loose Si particles after gravity separation mounted onto the SEM
sample stand [7-3].

F
i
g
u
r
e

7
.
8

94
A SEM micrograph of the loose particles taken with the secondary electron technique is
shown in Figure 7.8, where the surface of the light fraction particles after gravity
separation can be observed. The Si particles surface is coarse with a low amount of
impurities. Cu
x
Si residues are trapped in the crevices of the Si particles surface and
weakly bonded to the Si. Cu
x
Si residues are recognised at the Si surface as the film
shape with only a couple of microns in thickness (Figure 7.8c).

Figure 7.8. Loose silicon rich particle after gravity separation with Cu
x
Si residues
at the surface [7-3].

Semi-quantitative EDX analysis detected only Cu and Si in the examined particles,
where the dark clean surface in Figure 7.9e (point 1) is pure silicon, while the light
waffle like surface is Cu
x
Si (point 2). The other elements could not be detected by EDX
due to their low concentration; therefore ICP chemical analysis was used for trace
element determinations.
S Si il li ic co on n
G Gr ra ai in n
C Cu u
3 3
S Si i
R Re es si id du ue e
95

Figure 7.9. Loose silicon rich particles after gravity separation with Cu
x
Si residues
at the surface with corresponding EDX analyses in Figure 7.10 [7-3].

1 2

Figure 7.10. EDX analysis of the loose silicon rich particles after gravity separation
with Cu
x
Si residues at the surface.

1
2

96

7.2.5 EDX Analysis

Figure 7.11 shows a characteristic particle containing Si and Cu
x
Si intermetallic phases.
EDX analysis of the fraction prior to gravity separation shows that the main phase in the
Si-50wt%Cu alloy is pure silicon, while pure Cu is not found. However, Cu is detected
only in the form of Cu-silicides, where EDX results included in Figure 7.12 show
intermetallics with a copper atomic ratio close to 3 times higher than silicon which
allows for concluding that the Cu
3
Si intermetallic is formed as a result of the alloying.

Figure 7.11. Si-50wt%Cu alloy fraction prior to crushing and gravity separation
prepared for EDX analysis, mounted in epoxy.

Based on the EDX results, the chemical formula for the Cu intermetallics in the
investigated alloy is Cu
3
Si (Figure 7.12). The SEM analysis of the Cu rich residues at
1 (Si)
2 (Cu
3
Si)
97
the surface of the Si particles shows the presence of the small/thin Cu rich phases,
however they are indiscriminate and EDX analysis gives a Cu concentration below
75at%Cu (Figure 7.9e). Thus, Cu
3
Si at the surface of the pure Si is thin and should be
relative easy to remove with acid leaching or any other surface related technique.

.
Figure 7.12. EDX analysis of the Si-50wt%Cu alloy fraction prior to gravity
separation. Upper diagram is related to point 1 in Figure 7.11 and bottom diagram is
related to point 2 in Figure 7.11.

1
2
98

Ten consecutive measurements were made in the direction perpendicular from the phase
boundary on a characteristic Si-50wt%Cu alloy particle before separation. The distance
between each measurement was 20m. The resulting EDX chemical analysis is given in
Table 7.3.

Table 7.3. EDX analysis of mixed particle close to the phase boundary with
respective standard deviation for silicon in the bright field.
Distance from B r i g h t F i e l d D a r k F i e l d
Spot # the Boundary,
(m)
Si,
at%
Cu,
at%
Si,
at%
Cu,
at%
1 10 22.16 77.84 100.00 0.00
2 30 22.93 77.07 100.00 0.00
3 50 23.68 76.32 100.00 0.00
4 70 24.05 75.95 100.00 0.00
5 90 25.03 74.97 100.00 0.00
6 110 25.09 74.91 100.00 0.00
7 130 24.89 75.11 100.00 0.00
8 150 24.36 75.64 100.00 0.00
9 170 22.66 77.34 100.00 0.00
Standard
Deviation
1.09 1.09

The thickness of the selected Cu
3
Si microconstituent was 180m, therefore the last
measurement went into the adjacent Si dendrite. Average copper concentration for nine
measurements were 76.12at%Cu. Slightly higher copper concentration was at the edges
of the Cu-intermetallic.

99

7.3 Image Analysis

Several secondary electron images of each size fraction (0-38, 38-106, 106-500, 500-
1000 and above 1000m) were connected together, uploaded into the ImageJ software
and prepared for image analysis.

Figure 7.13. SEM figures of different size silicon-copper alloy particles before
heavy media separation. a) Particle size is 106-500m; b) particle size is 500-
1000m, and c) particle size is above 1000m.

The black area in Figure 7.13 is epoxy, the dark grey area is pure silicon and the light
area is Cu
3
Si intermetallic. Several SEM images of each particle size samples are
connected and used for further analysis. A large picture with connected images is given
in Appendix 06 together with the ImageJ software processed image.

100
7.3.1 Area Fraction Determination

A large number of particles were analyzed in order to reduce statistical errors. Table 7.4
shows how many particles were analyzed as well as the area covered with Si and Cu
3
Si.
The size range 0-38m could not be mounted into epoxy and properly polished, and
therefore was not analyzed.

Table 7.4. Number of particles and total analyzed area for samples prior to
separation.
Particle Size, Particles Area Analyzed
(m) Analyzed mm
2

38 - 106 960 34.77
106 - 500 927 68.86
5001000 129 72.86
1000+ 51 110.84

Furthermore, each particle is analyzed for its total area as well as for its area and
percentage of Si and Cu
x
Si intermetallic. Figure 7.14 shows the method how a selected
particle was evaluated.

Figure 7.14. Mixed particle used to determine total area, Si area and Cu
3
Si area.
101

The outcome of image analysis (Table 7.5) of the fractions prior to gravity separation
shows similar amounts of Si and Cu
3
Si intermetallics in the analyzed samples; however
samples after gravity separation have an increased amount of silicon in the light fraction.
The silicon area fraction increases with lower particle size, reaching 97.1% silicon for
particles size 38-106m range.

Table 7.5. Area fraction of silicon prior to and after gravity separation for 50Cu-Si
alloy*.
Particle Size, Before Sep., After Sep.,
(m) ( % ) ( % )
38 - 106 71.3 97.1
106 - 500 68.3 97.0
5001000 68.2 84.4
1000+ 68.2 76.7
*Analyses for 0-38m could not be completed due to difficult
sample preparation.

The higher value for 38-106m particle size could be due to the software calibration.
Smaller particles have a longer total border between the particle and the epoxy, and
between different phases inside each particle that makes them more sensitive to the
contrast adjustments in the image analysis software.

102

7.3.2 Homogeneous Particles

After crushing, the fractions consist of 3 particle types:
- refined or homogeneous Si,
- homogeneous Cu
3
Si and
- mixed particles containing both Si and Cu
3
Si microconstituents.

The number of the particles that were analyzed is given in Table 7.6. For the particle
size range 38-106m, 565 particles were pure Si without traces of Cu-intermetallics
neither in the middle of the particle (difficult to remove) nor at the edge (easy to remove
with acid leaching). At the same time there was 163 single-phase Cu
3
Si particles
without traces of Si. For that size range, the sum of 565 and 163 gives the total number
of homogeneous particles bringing the amount of homogeneous particles to 68.1% out of
all analyzed particles.

Table 7.6. Number of homogeneous particles in 50Cu-Si alloy.
Particle Size, Homogeneous Homogeneous Homogeneous
(m) Si Cu
3
Si Total
38 - 106 565 163 728
106 - 500 437 106 543
5001000 31 10 41
1000+ 4 3 7

Figure 7.15 shows homogeneous Si, mixed Si-Cu
3
Si and homogeneous Cu
3
Si particles.
The area fraction and number of the nearly pure Si particles with up to 1% Cu
3
Si was
also investigated. If possible, only homogeneous particles should be formed because
homogeneous Si particles do not require any further treatment while homogeneous
Cu
3
Si particles could be brought back to the alloying stage and recycled. Mixed
103
particles, containing Si and Cu
3
Si, require either additional crushing or some surface
treatment. The total area fractions of the homogeneous Si and Cu
3
Si are the highest for
the 38-106m particle range.

Figure 7.15. Homogeneous and mixed particles in the 50Cu-Si alloy.

Analysis of the particles after crushing but before gravity separation showed a high
number of homogeneous particles (Fig. 7.16). The highest area fraction of homogenous
silicon particles is in the 38-106m particle range reaching 58.9% while the area fraction
of the homogeneous Si and Cu
3
Si particles together is 68.1%. In addition, a high
percentage of nearly pure Si particles is observed. Such particles are easy to liberate
from the mostly surface attached impurities residues. The analysis shows an area
fraction of the 17.0% for the nearly pure Si particles with only 1% Cu-intermetallics
attached, for the 38-106m particle size range. With increased particle size, the area and
number of homogeneous particles rapidly decreases.
104

0
10
20
30
40
50
60
70
38-106 106-500 500-1000 1000+
Particle Size, m
H
o
m
o
g
e
n
o
u
s

P
a
r
t
i
c
l
e
s
,

%
Si
Si+1%Cu3Si

Figure 7.16. Area fractions of homogeneous particles and Si particles with up to
1% Cu
x
Si prior to gravity separation.

105

7.4 Silicon Dendrite Origin

During solidification of Cu-Si alloys, as long as the Cu concentration is below 83wt%,
pure Si will be the first to solidify (See Cu-Si binary phase diagram in Figure 7.17).
Consequently, the remaining liquid will be enriched with Cu up to the moment when the
amount of Cu reaches 68.3at% where the eutectic temperature is reached and complete
solidification is expected.

The solubility of Cu in solid Si decreases with decreasing temperature. Therefore,
solidifying Cu-Si alloy at the lowest possible temperature and holding the alloy at the
given temperature throughout the solidification process will give the lowest
concentration of Cu in the Si dendrites. Due to the high density difference between Si
and Cu, a complex system is formed during solidification. The liquid phase becomes
enriched in copper, leading to increasing density and a downward flow tendency at the
solidification interface. A comprehensive understanding of the solidification conditions
of the Cu-Si alloy is important for reaching high Si recovery and high impurity removal.
Thus, the temperature regime and dendrite formation are investigated.

Characteristic thermodynamic parameters for the two examined hypereutectic alloys are
given in Table 7.7 together with properties of pure Si and the alloy with eutectic
composition. Liquidus temperature of the two synthetic alloys is significantly lower
than melting of pure Si. The liquidus temperatures for 50Cu-Si and 70Cu-Si alloys are
204
o
C and 394
o
C lower than the melting point of pure Si (1414
o
C). The solidus
temperature for both alloys is at 802
o
C, which is 612
o
C lower than the melting point of
pure Si. Cu-Si molar ratios for 50Cu-Si and 70Cu-Si alloys are 0.43 and 1.33,
respectively; while the molar ratio between Cu and Si for the eutectic composition is
2.15.

106

Table 7.7. Characteristic parameters for hypereutectic Cu-Si alloys calculated by
FactSage Chemical Thermodynamics Application.
Alloy
Liquidus,
(
o
C)
Solidus, (
o
C)
Mol Fraction
Cu
Weight
Fraction Cu
Pure Si 1414 1414 - -
50Cu-Si 1210 802 0.301 0.494
70Cu-Si 1020 802 0.570 0.750
Eutectic 802 802 0.683 0.830

7.4.1 Temperature Regime Influence on Solidification
Characteristics

Figure 7.17 illustrates three characteristic periods during Cu-Si hypereutectic alloy
solidification related to the temperature range. The first period is related to the
temperature above the liquidus where only a liquid phase exists (Figure 7.17, bright
field). The second period starts at the liquidus temperature when the first solid Si grains
are formed. With decreased temperature the Si grains grow into long, coarse dendrites
while the liquid phase is progressively richer in Cu (Figure 7.17, gray field). Finally, the
third period starts at the eutectic temperature when the remaining liquid solidifies among
the formed Si dendrites (Figure 7.17, dark field).

107

Figure 7.17. Temperature regime during solidification.

7.4.2 Silicon Dendrite Formation

The first grains are formed at the wall of the crucible due to uni-radial heat loss through
the walls (Figure 7.18). Si grains with direction normal to the crucible wall will grow at
the beginning. The remaining liquid rich in Cu is significantly heavier than Si and a
mass flow is expected. Broken Si dendrites will be pushed down by the flow of the
heavy liquid, turning into the middle of the crucible and due to the buoyancy force will
start to move upward. Finally, the broken Si dendrites will settle at the top of the
sample.

108

a) b) c) d) e)
Figure 7.18. Solidification of the Cu-Si system. a) Forces present in Cu-Si system
and heat flow, b) mass flow, c-e) Si dendrites formation, growth and path of the Si
particles.

After the initially formed Si dendrites are broken (dendrites perpendicular to the wall),
Si dendrites exposed to the lowest metalostatic pressure will freely grow into the liquid.
In order to investigate the suggested solidification path, the samples formed were cut
longitudinally and prepared for metallographic observation. Figure 7.19 shows a sample
after solidification and the method by which the samples were cut. Half of the sample
was prepared for up-right directional analysis, while the other half was cut perpendicular
for horizontal metallographic observation.

109

Figure 7.19. A view of the sample after removal from the furnace, method by
which the sample was sectioned, up-right surface prepared for metallographic
analysis.

Figure 7.20 shows characteristic regions recognized in the upright and longitudinally cut
samples. The analysis of the upright cross section revealed three characteristic regions
in the solidified sample. The region adjacent to the wall at the periphery of the sample is
rich with Si dendrites (i). The bottom-central region of the sample contains
predominantly Cu
3
Si intemetallic (ii) and upper-central region (iii) with crushed Si
dendrites embedded into the Cu
3
Si matrix.

110

Figure 7.20. Morphology of the Cu-Si alloy sample with three regions (i, ii and iii)
and four layers (1, 2, 3 and 4).

Metallographic analysis of the longitudinally cut samples revealed different
morphologies in different zones of the sample. The bottom of the sample has long
vertical Si dendrites. Such dendrites had sustained the highest metalostatic pressure;
however, the total pressure was directed parallel from the tip of the dendrites and the
total momentum force was zero, therefore the dendrites were allowed to grow.

The upright cross section in the region around layer 3 in Figure 7.20 had long Si
dendrites at the edge (i) and silicon free central zone (ii). Longitudinal cross section
(Figure 7.20, Layer 3) showed only short Si bars instead of long dendrites because the
longest Si dendrites were at 2 to 25
o
angles with respect to the cutting direction
(perpendicular to the sample edge).

Finally, the upright cross section in the region around layer 2 had long Si dendrites at the
wall along the crucible (i). The central zone had a mixture of irregular Si chunks
surrounded with Cu
3
Si intemetallic matrix (iii).

111
Figure 7.21 gives the angle of the formed dendrites with respect to the position of the
sample (distance from the bottom) for the 50Cu-Si alloy sample. Dendrites growth
angle indicates presence of the high metallostatic pressure and high difference in density
between solidified dendrites and the remaining liquid. From Figure 7.21 it can be
observed that the 50Cu-Si sample has simple concave dependence for angle and length
with a maximum at a height of 40mm. The bottom part of the sample becomes enriched
with Cu
3
Si due to its high density. Also, the metalostatic pressure on Si at the bottom
part of the sample is higher; therefore the Si dendrites cannot grow very long. The
middle part of the sample endures less metalostatic pressure; therefore the Si dendrites
are allowed to grow freely. The upper part solidifies last, therefore has the lowest
amount of Si. Also, the upper part endures the highest internal residues stresses that
results in shorter Si dendrites.

0
5
10
15
20
25
30
0 10 20 30 40 50 60 70 80 90 100
Distance, (mm)
A
n
g
l
e
0
5
10
15
20
25
30
D
e
n
d
r
i
t
e

L
e
n
g
t
h
,

(
m
m
)
Angle
Dendrite Length
50wt%Cu-Si

Figure 7.21. Angle and length of the Si dendrites throughout the 50Cu-Si sample
measured from the bottom.

112
The 70Cu-Si sample has a more complex outcome with two maxima for angle and
length at 15 and 70mm (Figure 7.22). The 70Cu-Si alloy sample has significantly more
Cu than the 50Cu-Si sample. The higher amount of the Cu gives significantly bigger
volume of the ii zone (Figure 7.20). Wider ii zone prevents the Si dendrite to grow at
the bottom and middle of the sample. Hence, Si dendrites in the 70Cu-Si alloy exhibit a
minimum elongation at the distance 40-50mm from the bottom of the sample.

0
5
10
15
20
25
30
0 10 20 30 40 50 60 70 80 90 100
Distance, (mm)
A
n
g
l
e
0
5
10
15
20
25
30
D
e
n
d
r
i
t
e

L
e
n
g
t
h
,

(
m
m
) Angle
Dendrite Length
75wt%Cu-Si

Figure 7.22. Angle and length of Si dendrites throughout the 70Cu-Si sample
measured from the bottom.

70wt%Cu-Si
113
8 Characterization of the Cu-Si System

In order to investigate the phases present in the various alloys, Differential Thermal
Analysis (DTA) was employed. DTA detects the release or absorption of heat, which is
associated with chemical and physical changes in materials as they are heated or cooled.
During DTA, the examined specimen and an inert reference material such as Al
2
O
3
are
heated concurrently at a linear rate. The thermal-energy changes provide information
about melting, freezing, crystal transitions, material purity, solidus, liquidus, eutectic or
other phase transformation, etc. The purpose of our DTA tests was to better understand
the solidification process of our Cu and Si alloys. Also, determination of characteristic
transformation temperatures can indicate the number of phases present in light and
heavy media samples as well as difference between equilibrium system and our systems

8.1 DTA Experimental Procedure

Alloys used in the experiments were prepared by mixing metallurgical grade silicon and
electric grade copper and melted in mullite crucibles. After melting and solidifying,
each alloy was crushed into grain size around 100m which is an appropriate size for
charging the DTA crucibles. The procedure used to prepare the alloys was identical to
that in Chapter 6 except that the sample height was 3cm with diameter 2.54cm and a
ceramic lance was used to stir the sample throughout the whole experiment. In this way,
the produced samples were comparable with light and heavy media fractions produced
following the procedure in Chapter 6 and at the same time a uniform structure was
preserved all through the samples.

114
Four casting were made with 50wt%Cu, 70wt%Cu, 83wt%Cu and 87wt%Cu chemical
compositions. These compositions are superimposed on the phase diagram shown in
Figure 8.1. Two hypereutectic alloys were matching previously investigated 50wt%Cu-
Si and 70wt%Cu-Si alloys. 83wt%Cu is the eutectic composition for the Cu-Si system
while 87wt%Cu corresponds to the maximum of the congruent transformation between
two eutectics, which also corresponds closely to single Cu
3
Si phase at room temperature.
Table 8.1 gives the composition and weight of the samples. Also, a pure solar grade
sample and electronic copper with high purity, were used for controlling and calibration
trials.

Table 8.1. Weight of the DTA samples used in experiments.
Exp # Sample ID Crucible, mg Al
2
O
3
, mg Alloy, mg
5 50Cu 256 100 97
6 70Cu 244 100 99
7 83Cu 256 100 103
8 SolSi 255 100 100
9 87Cu 256 100 98
10 100Cu 256 100 101

115

Figure 8.1. Selected chemical compositions for 4 alloys generated for DTA
analysis.

The equipment used is a SETRAM 92-16.18 DTA/TGA analyzer [8-1, 8-2]. Crucibles
with reference and investigated sample were placed on the sample holder. Two
thermocouples were placed beneath the crucibles. The stand with the crucibles was
lowered into the analyzer chamber. The chamber was evacuated and filled with argon
gas to create an inert atmosphere during the experiments. The gas flow rate of
100ml/min was kept constant. The SETARAM CS92 temperature controller monitored
the temperature while the acquired results were stored. All measurements were set to
begin and end at 100
o
C. A heating and cooling rate of 15
o
C/min was used in all
experiments. The sensitivity range for the B-type thermocouple is from 500
o
C up to
1800
o
C. Therefore, the B-type thermocouple shows irregular reading for temperatures
below about 500
o
C for heating cycles.

116

8.2 DTA Results

Tables 8.2 and 8.3 show characteristic temperatures for the prepared samples.

Table 8.2. Characteristic temperatures during heating for non-oxidized samples.
Heating
Transformation
in Solid
Eutectic
(Solidus)
Liquidus

start peak start peak start peak start peak
Sol Si - - - - 1410 1446
50Cu 551 563 795 824 - 1235
70Cu 552 563 802 834 - -
83Cu 553 563 800 837 - -
87Cu 551 565 803 841 - -
100Cu - - - - 1084 1105

Table 8.3. Characteristic temperatures during cooling for non-oxidized samples.
Cooling
Transformation
in Solid
Eutectic
(Solidus)
Liquidus

Sol Si - - - - 1364 1355
50Cu 532 522 776 764 1223 1201
70Cu 533 522 779 757 950 937
83Cu 530 523 780 756 - -
87Cu 529 522 774 753 821 805 - -
100Cu - - - - 1002 1000

Initial trials were made with electronic grade silicon and electronic copper. Figure 8.2
shows characteristic points of the DTA curve for the silicon and copper. The first peak
117
recognized at 1084
o
C is the melting of copper, while melting of silicon occurred at
1410
o
C. Due to the fairly high heating rate (15
o
C/min), transformations occurred over a
temperature range as given by the furnace thermocouple. Therefore, slightly higher
temperatures than nominal values for melting point of the copper and silicon were
recognized. During the cooling cycle, solidification for silicon and copper started at
1364
o
C and 1002
o
C, respectively. This difference is due to the relatively high cooling
rate where supercooling phenomenon commonly occur.

-40
-30
-20
-10
0
10
20
30
40
400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Temperature, (
o
C)
H
e
a
t

F
l
u
x
,

(
V
)
SolSi
100Cu
Melting of Copper
Melting of Silicon
Silicon Freezing
Copper Freezing

Figure 8.2. Characteristic DTA curves for pure silicon and pure copper.

Tests were carried out for the various alloys. Six DTA curves with respect to
temperature are shown in Figure 8.3. As seen in Figure 8.3 the first transformation
during heating is recognized at 551
o
C where Cu
3
Si intermetallic has a phase
transformation. At 800
o
C, a eutectic reaction is observed which correlates to
transformation of the Cu
3
Si microconstituent formed during sample making. 50wt%Cu
118
alloy revealed liquidus reactions at around 1200
o
C while pure silicon did not go under
any transition until 1410
o
C (its melting point).

-80
-60
-40
-20
0
20
40
60
80
400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Temperature, (
o
C)
H
e
a
t

F
l
u
x
,

(
V
)
SolSi
50Cu
70Cu
83Cu
87Cu

Figure 8.3. DTA curves as a function of temperature.

Figure 8.4 depicts detailed look at the solidus transformation. Pure silicon and copper
samples did not show any reaction besides melting at 1410
o
C and 1084
o
C, respectively.
Four Cu-Si alloys showed distinctive solidus reactions at around 800
o
C (Figure 8.4).
The higher peaks and increased area below the peaks refer to higher enthalpy of melting
and solidification.

119

All alloy samples observe start of melting just about 800
o
C, which during cooling
solidification starts at about 780
o
Cfor all alloy samples. The heating data fit perfectly to
that expected by the phase diagram. The approximate 20
o
C undercooling is typical for
such tests.

-140
-120
-100
-80
-60
-40
-20
0
20
40
60
80
700 720 740 760 780 800 820 840 860 880 900
Temperature, (
o
C)
H
e
a
t

F
l
u
x
,

(
V
)
SolSi
50Cu
70Cu
83Cu
87Cu
100Cu
Solidus

Figure 8.4. DTA curves for the solidus region for 4 Cu-Si alloys.

Characteristic transformation temperatures for 50wt%Cu-Si and 70wt%Cu-Si alloys are
compared in Figure 8.5. During the heating cycle, the eutectic transformation is
observed in both alloys. The liquidus transformation is clearly revealed for 50wt%Cu
while the 70wt%Cu alloy has slight displacement from the base line without any
distinguishable peak. During the cooling cycle both transformations, liquidus and
solidus are recognized.

120

-60
-40
-20
0
20
40
60
400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Temperature, (
o
C)
H
e
a
t

F
l
u
x
,

(
V
)
50Cu
70Cu
Eutectic transformation,
(50Cu, 70Cu)
Liquidus transformation,
(70Cu Alloy)
(50Cu Alloy)
Eutectic transformation
(50Cu, 70Cu)
Cu
3
Si transf. in solid
(50Cu, 70Cu)
Heating
Cooling
(50Cu Alloy)
Cu
3
Si transf. in solid,
(50Cu, 70Cu)

Figure 8.5. DTA curves for the 50wt%Cu-Si and 70wt%Cu-Si alloys.

Characteristic transformation temperatures for 70wt%, 83wt%Cu-Si and 87wt%Cu-Si
alloys that are close to eutectic composition are given in Figure 8.6. During the heating
cycle, only the eutectic transformation is observed. . Since three analyzed alloys
consist mostly of Cu
3
Si intermetallic, alloys were completely melted at the eutectic
temperature and liquidus or congruent transformations did not occur. Remained silicon
were dissolved into the liquid, it is only a gradual and almost steady process, so hard to
detect at the DTA curve. During the cooling cycle, the liquidus transformation is found
for the 70wt%Cu-Si alloy while the 83wt%Cu alloy did not show any transformation
until the eutectic. The tip of the curve at 809
o
C for 87wt%Cu-Si alloy corresponds to
the congruent transformation.

121

-80
-60
-40
-20
0
20
40
60
80
400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Temperature, (
o
C)
H
e
a
t

F
l
u
x
,

(
V
)
70Cu
83Cu
87Cu
Cu
3
Si transf. in solid,
(all alloys)
Eutectic transformation,
(all alloys)
Congruent transformation,
(87Cu Alloy)
Eutectic transformation
(all alloys)
Cu
3
Si transf. in solid
(all alloys)
Heating
Cooling
No transformation,
(83Cu Alloy)
(70Cu Alloy)

Figure 8.6. DTA curves for the 83wt%Cu-Si and 87wt%Cu-Si alloys.

To understand better the light and heavy fractions, DTA analysis of samples with
particle size 38-106m was conducted and the obtained results were compared with the
above analyzed alloys (Table 8.4, experiments 1 and 4). In addition, for experiments 2
and 3, light and heavy media particles used for experiments 1 and 4 are physically mixed
together to match the approximate chemical composition of the 50wt%Cu and 70wt%Cu
(Table 8.4, experiments 2 and 3).

Table 8.4 shows weight and approximate chemical composition of the light and heavy
media samples used for DTA analysis while Figure 8.7 shows DTA curves of the light
and heavy media with respect to time and temperature. During heating, light media
sample did not show phase transformation at 800
o
C while solidification started at around
1350
o
C. Solidification of the heavy media sample begun at 800
o
C while liquidus
transformation is not identified. Both samples had distinguished transformation at
122
1030
o
C that is related to decomposition of the copper oxides. During heating light and
heavy media samples performed similar to equilibrium behavior.

Table 8.4: Weight and approximate chemical composition of the light and heavy
media samples.
Exp # Sample ID Crucible, mg Al
2
O
3
, mg Alloy, mg
1 Light Media 251 100 119
2
~50Cu
Mixture
238 100 126
3
~70Cu
Mixture
238 100 126
4 Heavy Media 243 100 121

Characteristic transformation points recognized at the heating/cooling curves are given
in Tables 8.5 and 8.6.

Table 8.5. Characteristic temperatures during heating for light and heavy media
samples.
Heating
Transformation
in Solid
Eutectic
(Solidus)
Liquidus

Light
Media
- - - - 1034 1062 1384 1433
~50Cu
Mixture
- - 799 811 1073 1080 n/a n/a
~70Cu
Mixture
- - 865 880 1085 1114 1293 1403
Heavy
Media
800 812 1012 1057 n/a n/a

123

Table 8.6. Characteristic temperatures during cooling for light and heavy media
samples.
Cooling
Transformation
in Solid
Eutectic
(Solidus)
Liquidus

Light
Media
- - - - - - 1378 1365
~50Cu
Mixture
532 524 779 772 - - 1310 1305
~70Cu
Mixture
531 524 770 764 - - 1283 1277
Heavy
Media
531 524 774 766 - - 1235 1227

Figure 8.7 shows the explicit solidus reaction at 800
o
C and a jagged curve from the
solidus up to liquidus. The obtained results reveal the existence of a complex system
rather than a simple two-component system. Such behavior is likely due to an oxide
layer at the surface of the particles that prevents immediate transformation of all
particles. During heating, there is a transformation reaction detected at 1034
o
C and
1012
o
C for light and heavy media, respectively.

124
-80
-60
-40
-20
0
20
40
60
80
400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Temperature, (
o
C)
H
e
a
t

F
l
u
x
,

(
V
)
Light Media
Heavy Media

Figure 8.7. DTA curves with respect to temperature for samples generated from
the light and heavy media.

Figures 8.8 to 8.10 show the DTA curves for matching samples generated for the DTA
analysis and samples generated from the light and heavy fractions. Characteristic
transformation points for clean alloys are more exposed than their matching samples
generated from the light and heavy fractions.

Figure 8.8 shows a comparison between solar grade silicon and light media particles
where solar grade silicon can be considered as pure silicon. Melting temperature of
solar grade silicon was at 1410
o
C while solidification occurred at 1364
o
C. The
difference in freezing and solidification of the solar grade silicon indicates high heating
and cooling rate (15
o
C/min). The DTA curve of the solar grade silicon had almost a
straight shape with only one exothermic reaction. Surface of the light media particles
were covered with thin layer of silicon and copper oxides. Although the formed oxides
contributed less than 1% in total weight their fine dispersion along the surface had
recognizable influence on the DTA curve shape. During the heating, an exothermic
125
reaction is recognized at 1034
o
C that indicates a complex reaction between silicon,
copper and oxygen resulting in formation of Si-Cu oxides (Eq 8.1).

2Cu
2
O + Si = 4 Cu + SiO
2
(8.1)

The liquidus temperature for light media is seen to be around 1384
o
C. Solidus
transformations were not recorded either for the heating or for the cooling cycle.
Liquidus temperatures during heating could not be clearly deduced due to presence of
fine Si-Cu oxides at the surface of silicon grains and due to the presence Cu-Si
intermetallic residues. However, the liquidus transformation is clearly distinguished at
1378
o
C during cooling. The lack of a solidus transformation during cooling indicates
that almost clean silicon is present in the light media without significant presence of the
second element. The exothermic reaction detected at 1034
o
C most likely corresponds to
a reaction between copper oxides and silicon where copper oxide reacts with silicon
forming elemental copper and silicon oxide.

-80
-60
-40
-20
0
20
40
60
80
400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Temperature, (
o
C)
H
e
a
t

F
l
u
x
,

(
V
)
SolSi
Light Media
Melting of Silicon
Silicon Freezing

Figure 8.8. DTA curves for solar grade silicon and light media fraction samples.
126

Figure 8.9 shows a comparison between a non-oxidized alloy with 50wt% Cu
composition and a matching mixture of light and heavy media. During heating, the
eutectic transformation for a mixture of light and heavy media has a lower peak and
smaller area below the peak, indicating that light particles were not involved in the
transformation. Indistinguishable liquidus temperature during the heating cycle
indicated the presence of an oxide layer on the surface of light and heavy media
particles. A notable liquidus transformation for light/heavy media sample is recorded at
1310
o
C during the cooling cycle.

-80
-60
-40
-20
0
20
40
60
80
400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Temperature, (
o
C)
H
e
a
t

F
l
u
x
,

(
V
)
50Cu
~50%Cu Mixture
Eutectic
transformation
Liquidus
transformation
Eutectic
transformation
Liquidus
transformation

Figure 8.9. DTA curves for a 50Cu alloy and a mixture of light and heavy media
fraction samples.

The heavy media sample in Figure 8.10 had similar eutectic transformation shape like
the mixed light and heavy media sample in Figure 8.9. However, an exothermic reaction
127
is recognized at 1012
o
C that indicates a complex reaction between silicon, copper and
oxygen resulting in the formation of Si-Cu oxides, similar to light media sample in
Figure 8.8 and equation 8.1. The lack of a liquidus transformation during heating
implies that there was no significant amount of free silicon in the heavy media.
However, during cooling the liqudius is recorded at 1235
o
C. Further, the difference in
heavy media DTA curves for heating and cooling cycle refers that the silicon in the
heavy media was dissolved in the copper intermetallic. The endothermic reaction at
1012
o
C most likely corresponds to the melting of copper oxides.

-80
-60
-40
-20
0
20
40
60
80
400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Temperature, (
o
C)
H
e
a
t

F
l
u
x
,

(
V
)
83Cu
Heavy Media
Eutectic
transformation
Eutectic
transformation
Liquidus
transformation

Figure 8.10. DTA curves for 83Cu alloy and heavy media fraction samples.

The observed differences between non-oxidized samples and light and heavy media
samples are more pronounced for heating than for the cooling cycle. Figure 8.11 shows
the effect of oxides layer in light and heavy media samples on the shape of the DTA
curves. Both alloys, 50wt%Cu and 70wt%Cu, are hypereutectic meaning they should
128
have two characteristic transformations at solidus and liquidus temperatures. Figure
8.11 emphasize different shapes of the DTA curves originated from the fresh samples
and light/heavy media samples for several characteristic points during melting and
solidification. The transformation in the solid at 550
o
C is not clear in the light/heavy
fraction samples while in non-oxidized samples, the solid transformation of the Cu
3
Si is
clearly recognized (Fig. 8.11a). Although all samples have the same solidus
temperature, the non-oxidized samples have a larger area below the solidus peak (Fig.
8.11b). Furthermore, light/heavy fraction samples have two peaks unlike the non-
oxidized samples. The highest difference in DTA curves is observed in the liquidus
region during heating Fig. 8.11c and d). Liquidus transformations during heating occur
at a range of temperatures while during cooling liquidus temperature occur at a specific
temperature.

Figure 8.11. Shape of the DTA curves for a) transformation in solid, b) solidus and
c-d) liquidus. 50wt%Cu, 70wt%Cu and mixture of light and heavy media samples.

a)
b) c)
d)
129
8.3 XRD Analysis

In order to characterize the microconstituents formed during solidification and their
susceptibility to oxidation during a prolonged time period, the XRD technique was
employed. Light and heavy media particles were milled and prepared for analysis.
Also, non-oxidized samples made from recently melted alloys with a chemical
composition of 50wt%Cu, 70wt%Cu and 83wt%Cu were prepared and analyzed.

Figure 8.12 shows XRD analysis of the 50wt%Cu-Si light and heavy media samples.
The light media sample shows pure silicon crystallography with weak peaks related to
the Cu
3
Si intemetallic. The heavy media sample shows strong Cu
3
Si related peaks with
the presence of pure silicon. Also, weak peaks for pure copper are detected.

Figure 8.12. XRD of the 50wt%Cu-Si light and heavy media particles.

130
Alloys with 50wt%Cu and 70wt%Cu showed similar crystallography where silicon
peaks had the highest intensity (Figure 8.13). 70wt%Cu sample had peaks that indicated
the presence of pure copper as well. However, the 83wt%Cu alloy showed the highest
peak for Cu
3
Si intermetallic while the presence of silicon and copper was detected.

Figure 8.13. XRD of the non-oxidized samples with 50wt%Cu, 70wt%Cu and
83wt%Cu chemical composition alloys.

In order to detect the presence of different oxides, additional tests were run in the range
from 20 to 28 degree where SiO
2
has the strongest peaks. Angle sensitivity was setup at
0.4
o
/step. Light and Heavy media samples were compared to the baseline of fresh
83wt%Cu sample. Figure 8.14 shows weak peaks at 20.32
o
and 26.52
o
that indicate a
small amount of SiO
2
.

131
0
20
40
60
80
100
120
20 20.5 21 21.5 22 22.5 23 23.5 24 24.5 25 25.5 26 26.5 27 27.5 28
2
I
n
t
e
n
s
i
t
y
,

(
a
.
u
)
Light Media
Heavy Media
Fresh 83wt%Cu
SiO
2
SiO
2

Figure 8.14. XRD of the light and heavy media sample a with possible SiO
2
peaks.

XRD analysis indicated that the light media samples have the highest peak related to
silicon. Heavy media sample had the highest intensity peak for the Cu
3
Si intermetallic.
Also, weak peaks related to pure copper are detected in the heavy media sample. A
comparison between the light/heavy media samples and non-oxidized samples revealed
a number of weak peaks in the light/heavy media samples probably related to oxides or
Si-Cu-O complex compounds, formed at the surface of the particles after extended time
periods.

132
9 Impurity Contents

Figure 9.1 shows recommended chemical analysis methods with respect to the expected
concentrations of copper and impurities in the examined samples. Inductively Coupled
Plasma (ICP) technique is an economical impurity detection method and more than 25
trace elements can be detected. However, the ICP technique becomes inaccurate for
most elements when the concentration exceeds 2wt% such as for copper in many of our
samples. Furthemore, the ICP technique is inadequate for detection of boron and
phosphorus in the low ppm level. For accurate assessment of boron and phosphorus,
Glow Discharge Mass Spectroscopy (GDMS) is recommended.

Figure 9.1. Recommended chemical analysis methods for Cu-Si alloys samples.
ICP - Inductively Coupled Plasma, AAS - Atomic Absorption Spectrometry and
STT - Standard Titration Technique

133

The light media mostly consists of pure silicon; therefore the amounts of Cu and other
impurities were expected to be below 2wt%. Under such conditions, ICP is an excellent
technique for the detection of most elements. In order to provide an accurate Cu
chemical analysis of the samples, Atomic Absorption Spectrometry (AAS) was
employed for the light media samples where the Cu concentration was below 10wt%.
Standard Titration Technique (STT) examined the amounts of Cu in the samples before
separation and in the heavy media samples because the amount of Cu is very high.

9.1 Copper Chemical Analysis

Chemical analysis showed that the copper concentration in the mixture before separation
was 50.78wt% Cu and 68.11wt% Cu for the 50Cu-Si and 70Cu-Si alloys, respectively.
The concentration of copper in the light and heavy fractions after separation for different
particle sizes is given in Figures 9.2 and 9.3. The lowest Cu concentration is observed in
the 50Cu-Si alloy for the 75m average particle size. As seen in Figure 9.3, the amount
of Cu in the 50Cu-Si alloy for the smaller particles, is lower than in the 70Cu-Si alloy
where the Si dendrites are coarser and longer.

134

0
1
2
3
4
5
6
7
8
9
10
11
12
0 100 200 300 400 500 600 700 800
Average Particle Size, (m)
C
u
,

(
w
t
%
)
Specimen #1, AAS
Specimen #2, AAS
Specimen #3, AAS
Specimen #4, AAS
Specimen #1, ICP
Specimen #2, ICP
Specimen #3, ICP
Specimen #4, ICP
LIGHT MEDIA
0
2
4
6
8
10
12
0 100 200 300 400 500 600 700 800
C
o
p
p
e
r
,

(
w
t
%
)
Average, AAS

Figure 9.2. Cu content in the light fraction after gravity separation for the 50Cu-Si
alloy (Specimens #1-#4) and average Cu content with standard deviation bars.

The results showed that the different techniques provide similar results for particles
below 400m. As Figure 9.4 and Table 9.1 depict, ICP and AAS analysis do not show
any significant scatter, consequently only ICP analysis was done for the 70Cu-Si alloy
(Figure 9.3) since it lowers cost and shortens the analysis time.

135

0
1
2
3
4
5
6
7
8
9
10
0 100 200 300 400 500 600 700 800
C
u
,

(
w
t
%
)
70wt%Cu-Si, ICP
50wt%Cu-Si(Avg), AAS
LIGHT MEDIA

Figure 9.3. Amount of Cu in the light fraction after gravity separation for the
50Cu-Si and 70Cu-Si alloys.

Due to the low concentration of impurities from a mass point of view, it is assumed that
besides Cu the rest is Si. Therefore, retrieval of the silicon in the light fraction after
gravity separation is up to 98.75wt% for the 75m average particle size. The Cu
concentration in the mixture before gravity separation is 50.78wt%. The average
concentrations of Cu in the light and heavy fractions after gravity separation from the 4
samples are given in Table 9.2.

136

Table 9.1. ICP and AAS results for light media sample, 50wt%Cu-Si.

Average
Particle Size,
( m )
ICP,
(wt% Cu)
AAS
(wt% Cu)
19 3.85 3.71
75 1.77 1.75
303 2.97 2.89
750 6.76 6.42
S
a
m
p
l
e

#
1

1500 5.95 5.6
19 - -
75 1.19 1.13
303 4.99 4.79
750 11.90 12.07
S
a
m
p
l
e

#
2

1500 16.82 16.85
19 1.71 1.71
75 0.70 0.68
303 2.90 2.77
750 7.70 7.67
S
a
m
p
l
e

#
3

1500 13.27 13.43
19 4.21 4.07
75 1.47 1.46
303 3.63 3.51
750 10.80 10.64
S
a
m
p
l
e

#
4

1500 22.65 21.56
19 3.26 3.16
75 1.28 1.25
303 3.62 3.49
750 9.29 9.20
A
v
e
r
a
g
e

1500 14.67 14.36

Similar to the 50Cu-Si alloy, the lowest Cu concentration in the 70Cu-Si alloy is
observed for 53-150m average particle size range (Figure 9.3). However, the 70Cu-Si
alloy is closer to the eutectic composition and consequently it is more difficult to
separate the two existing microconstituents (Si and Cu
3
Si).

137

Table 9.2. Average copper concentration in different fractions for 50wt%Cu-Si
alloy with standard deviation**:
Particle
Size,
(m)
Light
Fraction,
(wt%)
Standard
Deviation

Heavy
Fraction,
(wt%)
Standard
Deviation
0-38 3.3 1.4 41.6 21.3
38- 106 1.3 0.5 52.2 11.9
106-500 3.6 1.0 64.4 4.3
500-1000 9.3 2.5 64.6 4.6
1000+ 14.7 7.0 65.2 3.3
**ICP analysis is recommended at the ppm
w
level up to 2wt%, so Cu concentration is rounded to
1/100wt%.

A surprising result is that lower amounts of Cu are found in the largest particle size
range of the light media for the 70Cu-Si alloy than for the 50Cu-Si alloy. A reason for
this could be that the 70Cu-Si alloy has more copper. Therefore, during solidification
more silicon will be consumed for formation of the Cu
3
Si microconstituent.
Consequently, less silicon is available during the late phase of solidification when most
of the heavy media is formed, therefore bigger particles in the 70Cu-Si alloy have less Si
dendrites and the amount of light media is low but silicon dendrites are cleaner with less
Cu
3
Si residues. Furthermore, due to the lower amount of larger particles in the light
media, there are fewer crevices or irregular spots at the Si dendrite surface where Cu
3
Si
residues could be trapped.

Based on experimental values in Figure 9.3, a concentration curve, valid from 50 to
750m particle size, could be constructed. Such a curve can approximate copper
138
concentration for any average particle size between 50 and 750m. The following
polynomial form can approximate the concentration curve in the light fraction:

Cu
wt%
Light
= A +B x + C x
2
+ D x
3
(9.1)

where Cu
wt%
Light
is the copper concentration in the light media,
x is average particle size of the light media particles expressed in m and,
A, B, C and D are polynomial coefficients determined by the mathematical
regression analysis.

Polynomial coefficients for the predicted concentration curve in the two synthetic alloys
are given in Table 9.3.

Table 9.3. Polynomial coefficients of the concentration curve in the light media
for the 50Cu-Si and 70Cu-Si alloys.
Alloy
A
B C D
50Cu-Si 2.60 5.67 x 10
-3
3.00 x 10
-5
-1.39 x 10
-8

70Cu-Si 3.45 -1.31 x 10
-2
5.00 x 10
-5
-3.00 x 10
-8

In the heavy media, the amount of the Cu is considerably higher for the 70Cu-Si alloy
(Figure 9.5) than for the 50Cu-Si alloy for all particle sizes (Figure 9.4).

139

52
54
56
58
60
62
64
66
68
70
72
74
76
78
0 100 200 300 400 500 600 700 800
C
u
,

(
w
t
%
)
Specimen #1, TT
Specimen #2, TT
Specimen #3, TT
Specimen #4, TT
Specimen #1, ICP
Specimen #2, ICP
Specimen #3, ICP
Specimen #4, ICP
HEAVY
MEDIA

Figure 9.4. Amount of Cu in the heavy fraction after gravity separation for the
50Cu-Si alloy (Specimens #1-#4).

The difference in the results obtained from the various chemical analysis techniques
becomes higher for the heavy media than for the light media. Furthermore, the scatter
becomes higher for higher average particle sizes (Figs 9.2 and 9.4). For this reason, ICP
results should be considered as semi quantitative for compositional comparison of the
Cu in heavy media samples.

140

52
54
56
58
60
62
64
66
68
70
72
74
76
78
0 100 200 300 400 500 600 700 800
C
u
,

(
w
t
%
)
70wt%Cu-Si, ICP
HEAVY
MEDIA

Figure 9.5. Amount of Cu in the heavy fraction after gravity separation for the
70Cu-Si alloy.

141

9.2 Impurity Contents

The chemical compositions of the light and heavy fractions obtained from gravity
separation were analyzed by Inductively Coupled Plasma Mass Spectrometry (ICP).
The concentrations of selected impurities are given in Figs. 9.7 and 9.8 (due to large
number of data detailed amounts of each element are given in Section 9.3).

Figure 9.7. Concentrations of selected impurities after gravity separation of the Si-
50Cu alloy.

142

Figure 9.8. Concentrations of Al, Ca, Cr, Fe and Zn after gravity separation in the
Si-50Cu alloy.

The majority of the impurities show a higher concentration in the heavier fraction than
in the lighter fraction (Figs. 9.7 and 9.8). The concentrations of 10 elements in the 50Cu
Si alloy were below 2 ppm
w
. Such elements are Ag, Ba, Bi, Cd, Co, La, Mo, Sr, Tl and
Zr. Furthermore, most of the elements with a high segregation coefficient in Si had
significantly reduced concentrations in the light media. Although the amounts of
elements like Fe and Ti are reduced to below 100 ppm
w
, further examination is required
due to the relatively high detection limit of the ICP method.

Impurities with the highest concentration in the heavy media are Al, Ca, Cr and Fe
(Figure 9.8). Such an outcome is expected due to their initial high amounts in
143
metallurgical silicon. These elements all belong to the substitutional type and these
require the longest time for diffusion. However, the amount of impurities in the light
media is reduced to a fairly low level, where further treatment can reduce their amounts
down to solar grade quality. Chapter 11 gives detailed recommendation for further
treatment of the light fraction after heavy media separation.

9.3 Elemental Concentrations in Light and Heavy Media

The following section gives detailed diagrams for each element detected in the system.
The amounts of each element in light and heavy media are given in separate graphs. The
amount of each element in the 50Cu-Si alloy is taken as the average value for four
samples. The dashed line depicts the detection limit of the ICP measurements. Also, the
minimum detection limit is marked at the right hand side above the dashed line.

The impurity concentration outcome for the 50Cu-Si alloy is given in light green color
while the impurity concentration for the 70Cu-Si is given in dark blue color.
Furthermore, impurity concentrations in the light and heavy media for 50Cu-Si and
75Cu-Si alloy are given with different symbols:
Concentration of the impurity in the light fraction in the 50Cu-Si alloy.
Concentration of the impurity in the light fraction in the 70Cu-Si alloy.
Concentration of the impurity in the heavy fraction in the 50Cu-Si alloy.
Concentration of the impurity in the heavy fraction in the 70Cu-Si alloy.

The elements are classified in alphabetical order.
144

0
200
400
600
800
1000
1200
0 200 400 600 800 1000 1200 1400 1600
Average Particle Size, m
p
p
m
w
50Cu-Si
70Cu-Si
Al
100ppm
w
LIGHT MEDIA

0
200
400
600
800
1000
1200
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Al
100ppm
w
HEAVY MEDIA

Figure 9.10. Concentration of Al in the light and heavy media.

0.0
1.0
2.0
3.0
4.0
5.0
6.0
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Ag
0.5 ppm
w
LIGHT MEDIA

0
2
4
6
8
10
12
14
16
18
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Ag
0.5 ppm
w
HEAVY MEDIA

Figure 9.11. Concentration of Ag in the light and heavy media.
145

0
2
4
6
8
10
12
14
16
18
20
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Ba
2 ppm
w
LIGHT MEDIA

0
10
20
30
40
50
60
70
80
90
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Ba
2 ppm
w
HEAVY MEDIA

Figure 9.12. Concentration of Ba in the light and heavy media.

0
10
20
30
40
50
60
70
80
90
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Bi
2 ppm
w
LIGHT MEDIA

0
200
400
600
800
1000
1200
1400
1600
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Bi
2 ppm
w
HEAVY MEDIA

Figure 9.13. Concentration of Bi in the light and heavy media.
146

0
50
100
150
200
250
300
350
400
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Ca
100 ppm
w
LIGHT MEDIA

0
100
200
300
400
500
600
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Ca
100 ppm
w
HEAVY MEDIA

Figure 9.14. Concentration of Ca in the light and heavy media.

0.0
0.5
1.0
1.5
2.0
2.5
3.0
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Cd
0.2 ppm
w
LIGHT MEDIA

0
2
4
6
8
10
12
14
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Cd
0.2 ppm
w
HEAVY MEDIA

Figure 9.15. Concentration of Cd in the light and heavy media.
147

0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Co
1 ppm
w
LIGHT MEDIA

0
1
2
3
4
5
6
7
8
9
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Co
1 ppm
w
HEAVY MEDIA

Figure 9.16. Concentration of Co in the light and heavy media.

0
2
4
6
8
10
12
14
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Cr
1 ppm
w
LIGHT MEDIA

0
5
10
15
20
25
30
35
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Cr
1 ppm
w
HEAVY MEDIA

Figure 9.17. Concentration of Cr in the light and heavy media.
148

0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
La
2 ppm
w
LIGHT MEDIA

0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
La
2 ppm
w
HEAVY MEDIA

Figure 9.18. Concentration of La in the light and heavy media.

0
100
200
300
400
500
600
700
800
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Fe
100 ppm
w
LIGHT MEDIA

0
200
400
600
800
1000
1200
1400
1600
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Fe
100 ppm
w
HEAVY MEDIA

Figure 9.19. Concentration of Fe in the light and heavy media.
149

0
5
10
15
20
25
30
35
40
45
50
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Mn
1 ppm
w
LIGHT MEDIA

35
40
45
50
55
60
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Mn
HEAVY MEDIA

Figure 9.20. Concentration of Mn in the light and heavy media.

0
2
4
6
8
10
12
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Mo
1 ppm
w
LIGHT MEDIA

0.0
1.0
2.0
3.0
4.0
5.0
6.0
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Mo
1 ppm
w
HEAVY MEDIA

Figure 9.21. Concentration of Mo in the light and heavy media.
150

0
5
10
15
20
25
30
35
40
45
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Ni
1 ppm
w
LIGHT MEDIA

0
20
40
60
80
100
120
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Ni
1 ppm
w
HEAVY MEDIA

Figure 9.22. Concentration of Ni in the light and heavy media.

0
10
20
30
40
50
60
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Pb
2 ppm
w
LIGHT MEDIA

0
50
100
150
200
250
300
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Pb
2 ppm
w
HEAVY MEDIA

Figure 9.23. Concentration of Pb in the light and heavy media.
151

0
5
10
15
20
25
30
35
40
45
50
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Sc
1 ppm
w
LIGHT MEDIA

0
10
20
30
40
50
60
70
80
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Sc
1 ppm
w
HEAVY MEDIA

Figure 9.24. Concentration of Sc in the light and heavy media.

0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Sr
1 ppm
w
LIGHT MEDIA

0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Sr
HEAVY MEDIA
1 ppm
w

Figure 9.25. Concentration of Sr in the light and heavy media.
152

0
50
100
150
200
250
300
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Ti
LIGHT MEDIA

0
50
100
150
200
250
300
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Ti
100 ppm
w
HEAVY MEDIA

Figure 9.26. Concentration of Ti in the light and heavy media.

0
5
10
15
20
25
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Tl
2 ppm
w
LIGHT MEDIA

0
20
40
60
80
100
120
140
160
180
200
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Tl
2 ppm
w
HEAVY MEDIA

Figure 9.27. Concentration of Tl in the light and heavy media.
153

0
20
40
60
80
100
120
140
160
180
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Zn
1 ppm
w
LIGHT MEDIA

0
200
400
600
800
1000
1200
1400
1600
1800
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Zn
HEAVY MEDIA

Figure 9.28. Concentration of Zn in the light and heavy media.

0
1
2
3
4
5
6
7
8
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Zr
1 ppm
w
LIGHT MEDIA

0
2
4
6
8
10
12
14
16
18
20
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
Zr
1 ppm
w
HEAVY MEDIA

Figure 9.29. Concentration of Zr in the light and heavy media.
154

0
10
20
30
40
50
60
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
V
1 ppm
w
LIGHT MEDIA

0
50
100
150
200
250
0 200 400 600 800 1000 1200 1400 1600
p
p
m
50Cu-Si
70Cu-Si
V
1 ppm
w
HEAVY MEDIA

Figure 9.30. Concentration of V in the light and heavy media.

1
10
100
1000
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
W
5 ppm
w
LIGHT MEDIA

1
10
100
1000
10000
100000
0 200 400 600 800 1000 1200 1400 1600
p
p
m
w
50Cu-Si
70Cu-Si
W
5 ppm
w

Figure 9.31. Concentration of W in the light and heavy media.
155

9.4 Silicon Recovery

Light and heavy fractions are weighed after heavy media separation and the mass
balance is calculated. Twenty grams of each particle size (0-38, 38-106, 106-500, 500-
1000 and 1000+m) were separated and collected into light and heavy fractions (Figure
9.32).

Figure 9.32. Fashion which samples were prepared and weighed for recovery
analysis.

The apparent silicon recovery is calculated by dividing the weight of the light media by
the weight of light plus heavy media as given by Equation 9.2.

HeavyMedia LightMedia
LightMedia ery
Apparent
M M
M
Si
+
=
cov Re
[wt%] (9.2)

where M
LightMedia
and M
HeavyMedia
are weights of the light and heavy fractions after heavy
media separation. The weights of the light and heavy fractions after heavy media
separation are given in Table 9.4.
156

Figure 9.33 shows the apparent silicon recovery from the 50Cu-Si alloy after heavy
media separation.

Figure 9.33. Apparent silicon recovery in the 50Cu-Si alloy for 4 specimens.

The lower size particles had more light media and therefore more pure silicon. The
largest size did not show significant amounts of the light particles. Considering that the
density of the liquid heavy media was close to the density of silicon, a high amount of
the light fraction for big particles is not expected because even a small amount of the
Cu-intermetallic will increase the particle density above that of the liquid heavy media.
157

The theoretical amount of Si in each alloy, for the equilibrium condition, could be
obtained from the Cu-Si binary phase diagram. At room temperature, two stable micro
constituents are recognized in two hypoeutectic alloys used in the experiments,
particularly pure Si and Cu
3
Si intermetallic. Since the solid solubility of Cu in Si at
room temperature is very low, C
Si
is rounded to 100wt%. Therefore, concentrations of
the respective phases at room temperature are 100wt% for Si (C
Si
) and 12.50wt% for
Cu
3
Si (C
Cu3Si
). Using the Lever rule, the following equation could be derived in order to
establish the theoretical amount of Si in any hypereutectic Cu-Si alloy:

Si Cu Si
Alloy Si Si
ery
l Theoretica
C C
C C
Si
3
,
cov Re
*
= [wt%] (9.3)

where C
Si,Alloy
is 50.78wt% Cu for 50Cu-Si. Due to the low cooling rate of 0.66
o
C min
-1

the alloy formed should be close to an equilibrium composition. From the equilibrium
phase diagram the theoretical limit for the Si in 50Cu-Si alloy should be 59.52wt%
(equation 9.3). Furthermore, the apparent recovery (Figure 9.33) obtained in the current
experiments can be compared with theoretical limit in order to determine the recovery of
pure Si in the current experiments (Eq. 9.4). Figure 9.34 shows the results for Si
recovery of the 20g batch samples in 50Cu-Si alloy for different fraction sizes.

100 *
cov Re
cov Re
cov Re
ery
l Theoretica
ery
Apparent
ery
Si
Si
Si = (%) (9.4)

158

Figure 9.34. Silicon recovery from the 50Cu-Si alloy for 4 specimens.

The results show that smaller particles are close to the theoretical limit. However,
reaching the theoretical limit is not feasible for large particles that are more mixed with
Cu, and denser and will settle through the heavy media. In addition, smaller particles
show lower scatter in the collected light and heavy media due to increased number of
analyzed particles, and better separation between Si and Cu
3
Si. The outcome for 19m
will be explained in more details.

159
Table 9.4. Weights of the light and heavy fractions after heavy media separation:
Specimen
Particle
Size,
(m)
Light
Media,
(g)
Heavy
Media,
(g)
Total,
(g)
-38 3.03 1.97 5.00*
#1 38- 106 10.12 9.88 20.00
106-500 5.15 14.85 20.00
500-1000 2.49 17.51 20.00
1000+ 1.30 18.70 20.00
-38 3.02 1.98 5.00
#2 38- 106 10.05 9.95 20.00
106-500 5.65 14.35 20.00
500-1000 3.60 16.40 20.00
1000+ 1.83 18.17 20.00
-38 2.71 2.29 5.00
#3 38- 106 9.64 10.36 20.00
106-500 5.37 14.63 20.00
500-1000 3.96 16.04 20.00
1000+ 3.24 16.76 20.00
-38 2.79 2.21 5.00
#4 38- 106 10.10 9.90 20.00
106-500 5.46 14.54 20.00
500-1000 4.78 15.22 20.00
1000+ 4.30 15.70 20.00
*For -38um fraction only 5g is used for separation.

160
9.5 Recovery of Silicon and Driving Forces for HLMS

Recovery analysis reported in Section 8.6 shows that bigger particles are not completely
liberated; therefore, most of these particles remain in the heavy media due to the high
amounts of Cu and higher density. A reduction of the particle size should increase the Si
recovery. However, the drag force exerted by the HLMS and flocculation between
particles can become very influential for fine particles. Consequently, smaller particles
require longer time for separation and collection. Figure 9.35 shows the force balance
on a Si particle as it rises up through the HLMS during gravity separation of the Si and
Cu
3
Si particles. The particle motion in the HLMS is affected by the gravitational force
(F
Gravity
), buoyancy force (F
Buoyant
), drag force (F
drag
) and interaction force among
particles (F
CPI
).

Figure 9.35. Forces present in the system during gravity separation.

F
Buoyant
is caused by the HLMS and is directed upward; while F
drag
always acts in the
opposite direction to that of the motion of the particle and in this case for Si particle is
161
directed downward as along with F
Gravity
which is always acting downward. F
CPI

encompasses several forces that play a role in the interaction between colloidal particles
and its neighbors. Due to a number of factors and forces present in colloidal system,
F
CPI
will not be discussed in detail; nevertheless, with reduction in particle size F
CPI

takes a greater role. Therefore, a force balance can be expressed by the following
equation:

CPI Gravity Drag Bouyancy
F F F F + + =

and by substituting in expressions for each of these forces, we have:

CPI Particle Particle HLMS
F g R RV g R + + =
3 3
3
4
6
3
4

where denotes density and is the viscosity of the HLMS while V
Particle
is the velocity
of the particle. By solving the above equation for V
Particle
we arrive at:

( )
R
F
R
g
V
CPI
Particle HLMS Particle

6 9
2
2
=

where , and g are constant throughout the experiments. From this formula it can be
seen that the velocity (V
Particle
) is lower for smaller particles. Therefore V
Particle
of a large
particle is greater than that for a small particle of the same material while at the same
time F
CPI
is significantly higher for smaller particle. Once the value of F
CPI
overcomes
the density difference factor, V
Particle
approaches zero and gravity separation becomes
inefficient for the given particle size. The outcome in Section 8.6, found for the 19m
average particle size, indicates incomplete separation between pure Si and particles
containing Cu-intermetallics. Removal results indicated that besides the existence of an
upper limit, a lower limit for optimal particle size has to be established.

162
Reduced recovery of the small particles is in agreement with literature data where it is
recognized a downward trend of the gravity separation technique for small particles with
different densities [9-1]. Work by A. Falconer [9-2] discussed the specifics of operating
small particles, while examining the different gravity separation techniques in mining
operations where particle sizes are significantly higher than in Cu-Si alloys separation.

9.6 Copper Removal

Removal analysis characterizes the amount of solute element removed from the silicon
in the light fraction. Taking into consideration the amount of the light and heavy
fractions and concentrations of the impurity element inside each fraction, the Impurity
Removal (IR) from the silicon can be calculated with the following equation:

IR =
ion HeavyFract ion HeavyFract ion LightFract ion LightFract
ion HeavyFract ion HeavyFract
M C M C
M C
* *
*
+

where C is solute element concentration,
M is weight of the fraction (Table 9.4).

Removal of Cu from the 50Cu-Si alloy is given in Figure 9.36, where the average
concentration of the 4 specimens is taken as C
LightFraction
and C
HeavyFraction
. Each analyzed
batch had a predetermined average particle size and weighed 20g before gravity
separation.

163

Figure 9.36. Cu removal from the 50Cu-Si alloy.

In Fig. 9.36 four regions of removal efficiency can be recognized. Cu particles above
750m size exponentially approaching the 50% removal line and further increase in the
particle size does not influence the removal efficiency (Region IV). By reducing the
particle size from 750m, the Cu removal is significantly increased. For particles
between 750 and 200m the removal curve has a sharper slope and exhibits significant
improvement in the removal of Cu (Reg. III). At 200m the removal reaches a plateau,
approaching the maximum value and further reduction in the particle size does not
improve the removal efficiency (Reg. II). Copper removal for zero average particle size
should be 50%. Therefore, after reaching a maximum the removal efficiency most likely
quickly decreases in which case the removal curve rapidly approaches the 50% removal
value (Reg. I).

164

9.7 Impurity Removal

Following the same procedure as for Cu, each impurity removal can be calculated. Fig.
9.37 shows the results from the removal analysis for trace elements present in the 50Cu-
Si alloy where the average concentration of the 4 specimens is taken as C
LightFraction
and
C
HeavyFraction
for the analyzed solute element concentration. The detection limit of the
ICP technique for most elements is higher than the required amount for Si solar cell
applications, therefore 100% removal for elements such Bi, Ca, Co, Sc, Sr, Ti, Mo, Zr
implies that their concentration has been reduced to below the detection limit.

Figure 9.37. Removal of the impurities after gravity separation in the 50Cu-Si.

165
The majority of the impurities show a higher concentration in the heavy fraction than in
the light fraction (Figs. 9.7 and 9.8), therefore the overall removal outcome is high.
Impurities with the lowest removal percentage are Al, Cr and Pb (Figure 9.38).

Figure 9.38. Removal of Al, Ba, Cr, Pb, Sr and Zn after gravity separation in the
50Cu-Si alloy.

166
9.8 Optimal Particle Size

Recognizing the fact that the effectiveness of gravity separation and impurity removal
depends on particle size, not just density, an analytical approach to identify an optimal
particle size for a given media separator has been derived. A removal curve, valid for 50
to 800m particle size range, has been deduced using mathematical regression from data
given in Figures 9.2 to 9.5. A fourth order homogeneous exponential equation (Fig.
9.39) has been derived from the ICP and AAS/TTS chemical analyzes for the Cu
removal with respect to the average particle size (Figure 9.39).

Figure 9.39. Removal of Cu for different particle size derived from the ICP
chemical analyzes.

167
From the given removal curve the first derivative can be subtracted, where a zero value
for the first derivative gives the maximum removal percentage. Assigning this value to
find the corresponding optimal particle size for a given solute element in a given alloy
could be estimated. Such average particle size represents the optimal particle size for
which the highest removal is expected. Optimal particle size requires further
examination and narrowing analysis between 40 and 500m.

9.9 Distribution Ratio

The ratio between the amount of impurities in the heavy and light fractions
(C
HeavyFraction
/C
LightFraction
) can be expressed as the Distribution Ratio. The Distribution
ratio gives the Cu purifying capacity for each element or the quantitative result for the
amount of impurities removed from silicon by mixing with copper. The Distribution
Ratio results for selected elements are given in Figures 9.40 and 9.41.

Figure 9.40. Distribution ratio of impurities in heavy over light fraction in the
50Cu-Si alloy after gravity separation [7-3].
168

Impurities with a value for the distribution ratio above one, tend to enrich in the heavy
Cu-Si intermetallics. Impurities with a higher distribution ratio will be removed more
easily than impurities with a lower distribution ratio. The highest distribution ratio for
most elements is in the 38-106m range, followed by the 106-500m particle size (Figs.
9.40 and 9.41).

Figure 9.41 Distribution ratio for Al, Ca, Cr, Pb and Zn in heavy over light fraction
in the 50Cu-Si alloy after gravity separation [7-3].

The chemical analyses of the smallest particles below 38m show a significant drop in
the distribution ratio due to coagulation and increased separation time. The aforesaid
problems lead to a lower distribution ratio and a decreased removal of the smaller
particles. Particles with a size above 500m are not fully divided between silicon and
Cu
x
Si intermetallics, as a consequence the distribution ratio is poor. Large particles
could be ground finer in order to liberate trapped Si, or remelted and used as a source of
Cu.
169
9.10 Maximum Distribution Ratio

The distribution ratio results showed that the Cu collected most of the impurities from
the metallurgical Si. Most trace elements had several time higher concentrations in the
Cu
3
Si phase than in the Si. Thirty elements were analyzed by ICP where 22 elements
were below the detection limit. The concentration of elements such as Ag, Cd, Co, Mo,
Sc, Sr and Zr were below 1 ppm
w
while the concentrations of Ba, Bi, La, Ni, Tl and V
were below 2 ppm
w
. Furthermore, most of the elements with a high segregation
coefficient in Si have a high distribution ratio; thus, the suggested method is an excellent
accompaniment to directional solidification as the most practiced technique for silicon
refining, which is inefficient for impurity distribution with a high segregation
coefficient. Therefore, the implementation of either acid leaching treatment or
directional solidification, as the last step in the purification route, makes the proposed
process cost effective and environmentally friendly.

Extrapolating the distribution ratio curve with respect to average particle size and taking
the value at the optimal particle size, a maximum distribution ratio number can be
obtained. The maximum distribution ratio is a dimensionless number, taking into
account the amount of the impurity element, Si particle size, distribution between
heavy/light media and giving quantitative value of how many times is concentration of
the given element could be higher in the heavy than in light media. Furthermore, the
maximum distribution ratio gives the purifying efficiency of the given alloy for a given
element and by knowing the starting amount of the impurity, a final concentration of the
impurity element could be estimated. The maximum distribution ratio for the selected
impurity elements is given in Figures 9.42 and 9.43 where impurities with distribution
ratio above 1 tend to collect in the heavy Cu-Si intermetallics. Impurities with a higher
distribution ratio will be removed easier than impurities with a lower distribution ratio.
Concentrations of elements such as As, Co, Hg, La, Mo, Sb, Sr and Ti were below the
detection limit of the ICP technique therefore their maximum distribution ratio could be
expressed as only as infinite number.

170



171
10. Summary and Conclusions

In an era of ultra pure materials, the logical question that arises is: what is the most
efficient way to extract trace levels of impurities from metallic silicon? One way to
refine silicon could be high temperature vacuum refining while another option could be
to utilize the copper impurity collection method. Therefore, these two metallurgical
techniques were investigated and compared.

10.1 High Temperature Vacuum Refining

Molten silicon has a very low vapor pressure making it possible to remove certain
elements by selective evaporation. The amount of all elements with higher vapor
pressure than silicon may be reduced at temperatures above the melting point of silicon
and under low pressure.

1. It was found that for most elements, the concentration was decreased 2 to 6 times
relative to their initial concentrations in the metallurgical grade silicon.
2. Elements with higher vapor pressure and lower boiling point had higher removal
ratios.
3. It was found that some elements were removed due to the formation of respective
oxides with high vapor pressure.
4. An analysis of the reduction factor showed that most elements achieved
maximum evaporation at holding temperatures below 1600
o
C.

172
10.2 Copper Impurity Collection Method

Due to its chemical and physical properties, copper can extract trace elements from
metallic silicon. In addition it is fairly cheap, plentiful and can be readily recycled. The
first introduction of Cu as an ultra pure metal refiner could be in the fast growing silicon
solar cell industry where Cu is mixed with inexpensive but less pure metallurgical grade
silicon (see Chapter 6). Cu diffuses an order of magnitude faster than any other element
through the Si face centered lattice. Due to a large volume difference between the Cu-
silicides and the original Si lattice (V
Cu-Si
/V
Si
=2.3) the formation of Cu intermetallics
inside Si dendrites is highly unlikely. In such conditions, Cu has no other option than to
move through the Si lattice until it reaches a grain boundary or surface that is
thermodynamically stable.

Cu-Si hypereutectic alloys, with a Cu concentration below 87 wt%, create structures
with two microconstituents at room temperature, namely pure Si and the Cu
3
Si
intermetallic. If a mixture of Cu and at least 13 wt% Si is fully melted and left to slowly
solidify, long dendrites of pure Si form, while Cu becomes enriched between the Si
dendrites into the remaining liquid phase (see Chapter 7). The interdendritic liquid
becomes enriched with Cu until the atomic ratio between Cu and Si reaches 3 to 1
forming Cu
3
Si. This Cu rich liquid also became enriched in various other impurities.
Later, the solidified alloy is crushed and pure Si is separated from the Cu
3
Si using a
heavy media. Selected outcomes from the present tests are:

Chemical analysis of the pure Si and Cu
3
Si phases showed that most of the
impurities concentrated in the Cu
3
Si phase rather than in the Si phase.
After extraction with Cu, the concentrations of 22 elements (30 elements
analyzed) were below the detection limit of the ICP technique where the
concentration of 7 elements were below 1 ppm
w
and another 6 elements were
below 2 ppm
w
in the Si product.
The amount of the other elements decreased several times in the refined Si,
compared to that in the initial metallurgical Si (see Chapter 9).
173
Copper alloying and heavy media separation techniques were demonstrated to be
reliable technologies to remove a large fraction of most of the impurities from
the metallurgical grade silicon.
Metallographic analysis showed complete separation between Si and Cu
3
Si
intermetallic phase at the microscopic level.
Sharp edges and high density of microcracks along microconstituents boundaries
allowed for efficient Si separation from the Cu
3
Si.
Chemical analysis revealed that the amount of most impurities is reduced to an
acceptable level for solar grade silicon.
The optimal particle size for heavy media separation was found to be in the range
of 75 to 125m.
Most of the elements with a high segregation coefficient in Si have a high
distribution ratio.

The suggested method seems to be an excellent accompaniment to directional
solidification, which by itself is inefficient for impurity distribution for elements with
high segregation coefficient.

Environmental and economical benefits from this new method could be enormous.
Using this novel energy efficient method instead of conventional chemical deposition
processes, could reduce the payback time for silicon solar cells from 5-10 years
(currently) to 1 year (see Chapter 1). This could in turn move silicon based solar cells
from an alternative source of energy to a reliable, self-efficient and economical source of
energy, finally independent of fossil fuels.

174
10.3 New Findings

This work gathered new data for two metallurgical techniques applied to the refining of
silicon. New experimental values are given for impurity concentrations in silicon before
and after high temperature vacuum treatment. Also, valuable experimental data are
provided for various steps in the copper impurity collection route. Beside experimental
contributions, this research created several novel contributions in the field of metallurgy,
characterization, refining and process development:

This research is the first in the world that investigated copper as refining tool in
combination with heavy media separation.

The phase boundary between pure silicon dendrites and copper intermetallic is
described in detail using advanced microscopy and analytical methods.

The Cu-Si system is better characterized.

Heavy media separation was shown to be an efficient method for physical
separation between pure silicon and impurity enriched copper intermetallics.

A new method for impurity prediction for refining silicon is suggested.

A new process for silicon refining has been tested.

175
11. Proposed Final Refining Steps

The scope of the present investigation was to carry out Cu-Si alloying, crushing,
grinding and heavy media separation to produce fairly pure silicon dendrites. It was not
the scope to carry out further refining steps such as leaching and remelting. In the
following a brief outline of subsequent possible refining steps is added.

General requirements for solar silicon have been set at 120ppm for total amount of
impurities [11-1], while requirements for silicon purity before directional solidification
is set in the range from 1 to 1000ppm for different elements [11-2]. Although an exact
recommendation for the level of impurities in solar grade silicon does not exist, some
suggestions have been established. Table 11.1 gives an acceptable level of a particular
impurity element before directional solidification, together with the achieved impurity
reduction in the current investigation.

11.1 Acid Leaching

Cu
3
Si at the surface of the pure Si is very thin and should be relatively easy to remove
with a surface related technique such as acid leaching. The calculated Eh-pH diagram
for the Si-Cu-H
2
O system at room temperature allows for the conclusion that in an acid
solution up to pH=3, copper will be dissolved as Cu
2+
[11-3, 11-4, 11-5]. The formed
H
2
SiO
4
will be washed away together with the acid reactant.

176

11.2 Directional Solidification

Directional solidification can also be used as a subsequent purification process. Since
most impurities will be more soluble in the liquid than in the solid phase during
solidification, impurities will be "pushed" by the solidification front, causing much of
the finished casting to have a lower concentration of impurities than the initial material,
while the last solidified portion will be enriched with impurities. This last part of the
metal can be removed or recycled. The suitability of directional solidification in
removing a specific impurity from a certain metal depends on the partition coefficient of
the impurity in the metal. Directional solidification is frequently employed as a
purification step in the production of multicrystalline silicon for solar cell. The tolerable
impurity concentration before directional solidification from different sources together
with the achieved impurity concentrations in the current project is given in Table 11.1.

Table 11.1. Tolerable impurity concentration before directional solidification and
achieved concentration in current project (ppm
w
).
Al Ba Ca Cr Fe Mg Mn Ni Sc Zn Zr
[11-6] 25 - 53 72 186 - 76 66 - - <100
[11-7] 4944 - 2772 - 4300 60 - - - - -
[11-8] 374 - 49.7 - 615 14 - - - - -
[11-9] 750 4 305 15 2800 6.3 135 16 49 80 11
Current
project
<100 1 <100 7.5 <100 <10 5 7.2 4.2 18.5 0.5
< indicates concentration below detection limit.

177
11.3 Proposed Process Improvements

The author of this report had a unique opportunity to be the first student in the world to
investigate the possibility of refining Si by Cu alloying followed by physical separation.
Encouraging results created a great deal of excitement and satisfaction. Several
outcomes have lead to new questions that engender new possible research avenues. The
current project should be continued with acid leaching and directional solidification
analysis in order to conclude all suggested process steps. Furthermore, in depth analysis
of boron and phosphorus partitioning between Si and Cu-inteemetallics should be
conducted. Due to discrepancies in the literature regarding enthalpy of formation of the
Cu
3
Si intermetallic, calorimetric analysis of the Cu-Si alloys will be valuable to carry
out. Specifically, the calculated thermo-dynamical models of the Cu-Si binary system
gives positive values for the enthalpy of formation of the Cu
3
Si intermetallic while it is
clear that such intermetallic is stable at the room temperature [11-10, 11-11, 11-12].
Also, modeling of the Cu-Si system including specific conditions used in the current
project could be performed using FACT thermodynamics modeling system.

Several investigations requiring a new experimental setup could be performed. Such
experiments can involve:
- One-step alloying/directional solidification refining,
- Vacuum solidification,
- Centrifugal and/or jet flow separation or,
- Ti addition.

One step alloying-directional solidification refining:
The current research was focused on the purifying capabilities of Cu, where
solidification parameters were adjusted in such a way that the purifying effect of
directional solidification was eliminated. Consequently, a new set of experiments can be
designed to investigate the combined positive effects of Cu purifying potential and
directional solidification technique together. Samples can be melted with high
elongation-diameter ratio, followed by very slow solidification. Considering the low
178
solid solubility of Cu in Si at room temperature and the high diffusion coefficient, the
first solidified Si dendrites should be free of impurities.

Vacuum Solidification:

In Al alloys, a great improvement in impurity removal is observed if the liquid metal is
solidified under reduced pressure [11-13]. Vacuum solidification of the alloyed Si could
be added to the one step alloying-directional solidification refining process. The widely
used Alcans PoDFA unit could be used in such experiments [11-14]. Figure 11.1
shows the suggested experimental setup. Several benefits should be presumably gained
from the suggested setup. The metal will solidify under a controlled atmosphere.
Further, due to the formation of small droplets, the presence of oxygen and other
unavoidable gases in the solidified samples will be eliminated. Impurities will more
easily reach the surface of the droplet that is thermodynamically the most stable site.
Droplets formed at the bottom of the vacuum chamber will have the preferred shape and
size for eventual hydrometallurgical treatment. The PoDFA filter will bring an
additional purifying step in the Si refining process.

Figure 11.1. Suggested experimental setup for vacuum solidification investigation
using modified PoDFA unit.

179
Centrifugal or jet flow separation:

When considering possible industrial implementation, heavy media separation is the
biggest downward stage. A heavy liquid is expensive and difficult to maintain and
recycle in a closed circle. Therefore, the introduction of the centrifugal separation [11-
15] or jet stream separation [11-16] is worth considering.

Ti addition:

Although the bonding mechanism of Ti is not clear, it is observed that Ti tends to bond
strongly with many impurity elements and later provides sites for crystallization. This
property is widely utilized in the grain refining process for the Al alloys. Expecting a
similar result, a small amount of the Ti could be added to Si alloy. The addition of Ti
could be particularly beneficial in removing boron because of early formation of the
stable intermetallics (Ti
3
B and Ti
5
B) [11-17, 11-18] that could be separated later.

180
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192
Appendices

Appendix 01: Equipment used in the experiments

1000 1000 m m
500 500 m m
200 200 m m
106 106 m m
38 38 m m

Figure A1. The equipment used
during mixing and melting of
metallurgical silicon and copper: 1.
Argon gas; 2. Mass flow controller;
3. Copper getter furnace; 4. Lance;
5. Reaction tube; 6. Electric furnace;
7. Temperature controller.
Figure A2. Equipment used for
screening Cu-Si alloys. Tyler
Canada, FH Brass Pan type screens.

Figure A3. Equipment used for
gravity separation of the Cu-Si
alloys.

Figure A4. Analytical balance used
for weighting samples.

193
Appendix 02: Equipment Calibration

Furnace Temperature Calibration.
C
o
n
t
r
o
l
e
r
M
i
d
d
l
e

T
C
D
i
f
f
e
r
e
n
c
e
oC mV Cor. mV oC oC
1350 14.9 0.2 15.1 1335 15
1400 15.6 0.2 15.8 1383 17
1450 16.3 0.2 16.5 1433 17
1500 17 0.2 17.2 1483 17
1550 17.7 0.2 17.9 1532 18
1600 18.2 0.2 18.4 1568
1300
1350
1400
1450
1500
1550
1600
1650
1 2 3 4 5 6
T
e
m
p
e
r
a
t
u
r
e
,

(
o
C
)
Controler
Middle TC
Controller B type Thermocouple
Middle TC K type Thermocouple

Figure A5. Furnace chamber temperature measured with controller thermocouple
sited at the edge of the crucible and R-type thermocouple placed in the middle of
the crucible.

Time required for furnace to reach steady state temperature.
15
17
19
21
23
25
27
-5 0 5 10 15
Time, (minutes)
T
e
m
p
.

D
i
f
f
e
r
e
n
c
e
,

(
o
C
)
1550 oC
1500 oC
1450 oC
T
i
m
e

A
f
t
e
r

R
e
a
c
h
i
n
g

H
o
l
d
i
n
g

T
e
m
p
e
r
a
t
u
r
T
a
r
g
e
t
e
d

H
o
l
d
i
n
g

T
e
m
p
e
r
a
t
u
r
eT
C

T
e
m
p
e
r
a
t
u
r
eD
i
f
f
e
r
e
n
c
e
min oC oC oC
0 1450 1427 23
2 1450 1433 17
5 1450 1433 17
10 1450 1433 17
0 1500 1476 24
2 1500 1483 17
5 1500 1483 17
10 1500 1483 17
0 1550 1525 25
2 1550 1532 18
5 1550 1532 18
10 1550 1532 18
.

Figure A6. Time required for furnace chamber temperature (measured with R-type
thermocouple placed in the middle of the crucible) to reach controller given
temperature (measured at the edge of the crucible).
R

194
Appendix 03: Thermodynamic Data

Figure A7. Vapor Pressure of Elements

195

continuation

196

Figure A8. Standard Free Energies of Formation, Ellingham Diagram

197

Figure A9. Standard Free Energies of Formation of chlorides.

J. Kr. Tuset, in proceeding of International seminar on refining and alloying of liquid aluminum and ferro-
alloys, August 1985, Trondheim, Norway, pp. 48-69.

198

Vapor pressure of oxides relative to corresponding metals.

Vapor Pressure of Oxides in kPa
oC 800 1000 1200 1400 1600 1800 2000
B
2
O
3
=B
2
O
3
(g) 7.61E-09 7.70E-06 1.10E-03 4.56E-02 8.20E-01 8.19E+00 5.32E+01
Mo+O
2
(g)=MoO
2
(g) 4.11E+02 2.77E+02 2.03E+02 1.57E+02 1.26E+02 1.04E+02 8.66E+01
4/3Ti+O
2
(g)=
2/3Ti
2
O
3

4.76E+41 1.06E+34 2.90E+28 1.76E+24 8.73E+20 1.77E+18 1.36E+16
VO
2
=VO
2
(g) 2.86E-12 8.74E-09 2.82E-06 2.16E-04 5.61E-03 5.68E-02 3.64E-01
W
3
O
8
(g)=W
3
O
8
(g) 8.03E+61 1.07E+49 4.74E+39 3.76E+32 1.00E+27 3.22E+22 6.43E+18

Vapor Pressure of Elements in kPa
oC 800 1000 1200 1400 1600 1800 2000
B=B(g) 2.01E-18 4.16E-14 5.72E-11 1.38E-08 1.02E-06 3.24E-05 0.000556
Mo=Mo(g) 7.33E-23 7.12E-18 2.99E-14 1.67E-11 2.38E-09 1.28E-07 3.35E-06
Ti=Ti(g) 4.21E-14 1.49E-10 5.50E-08 4.83E-06 1.60E-04 2.50E-03 2.29E-02
V=V(g) 4.72E-16 4.04E-12 2.90E-09 4.25E-07 2.11E-05 4.82E-04 5.97E-03
W=W(g) 1.02E-32 3.67E-26 2.26E-21 1.01E-17 7.57E-15 1.58E-12 1.29E-10

199
Appendix 04: DTA Curves
-350
-300
-250
-200
-150
-100
-50
0
50
100
150
200
400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Temperature, (
o
C)
H
e
a
t

F
l
u
x
,

(
V
)
SolSi
50Cu
70Cu
83Cu
87Cu
100Cu

Figure A10. DTA curves for non-oxidized samples.
-300
-250
-200
-150
-100
-50
0
50
100
150
200
400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Temperature, (
o
C)
H
e
a
t

F
l
u
x
,

(
V
)
SolSi

Figure A11. DTA curve for non-oxidized solar grade sample.
200
-60
-50
-40
-30
-20
-10
0
10
20
30
40
400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Temperature, (
o
C)
H
e
a
t

F
l
u
x
,

(
V
)
50Cu
Heating
Cooling

Figure A12. DTA curve for non-oxidized 50wt%Cu-Si sample.

-130
-110
-90
-70
-50
-30
-10
10
30
50
70
400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Temperature, (
o
C)
H
e
a
t

F
l
u
x
,

(
V
)
70Cu
Heating
Cooling

201
-140
-120
-100
-80
-60
-40
-20
0
20
40
60
400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Temperature, (
o
C)
H
e
a
t

F
l
u
x
,

(
V
)
83Cu
Heating
Cooling


-140
-120
-100
-80
-60
-40
-20
0
20
40
60
80
400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Temperature, (
o
C)
H
e
a
t

F
l
u
x
,

(
V
)
87Cu
Heating
Cooling

202
-350
-300
-250
-200
-150
-100
-50
0
50
400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Temperature, (
o
C)
H
e
a
t

F
l
u
x
,

(
V
)
100Cu

Figure A16. DTA curve for non-oxidized electronic copper sample.

-250
-200
-150
-100
-50
0
50
100
150
400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Temperature, (
o
C)
H
e
a
t

F
l
u
x
,

(
V
)
Light Media
Heating
Cooling

Figure A17. DTA curve for light media sample.
203
-30
-25
-20
-15
-10
-5
0
5
10
400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Temperature, (
o
C)
H
e
a
t

F
l
u
x
,

(
V
)
Heavy Media
Heating
Cooling

Figure A18. DTA curve for heavy media sample.

-350
-300
-250
-200
-150
-100
-50
0
50
100
150
200
400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Temperature, (
o
C)
H
e
a
t

F
l
u
x
,

(
V
)
Light Media
~50%Cu Mixture
Heavy Media

Figure A19. DTA curves for light and heavy media samples.
204
Appendix 05: Various Shift Intensities for Cu-Si Compounds

Figure A20. Shift intensities for Si, Cu and Cu
3
Si phases.
205

..continuation

Figure A21. Shift intensities for SiO
2
.
206
Appendix 06: ImageJ Figures

Figure A22. SEM figure for 38-106m particle size before heavy media separation
for 50wt%Cu-Si alloy.

Figure A23. Counting the number of particles in 38-106m particle size sample
before heavy media separation (50wt%Cu-Si alloy).

207

Figure A24. SEM figure for the 106-500m particle size before heavy media
separation for 50wt%Cu-Si alloy.

Figure A25. Count of the particles in 106-500m particle size sample before heavy
media separation (50wt%Cu-Si alloy).
208

Figure A26. SEM figure for the 1000+m particle size before heavy media
separation for 50wt%Cu-Si alloy.

Figure A27. Count of the particles in 1000+m particle size sample before heavy
media separation (50wt%Cu-Si alloy).

209
Appendix 07: Chemical Analysis

Sample Marking:
ICP+AA ICP+T ICP
1 UT-LM-01-A 21 UT-HM-01-A 43 UT-V-01
2 UT-LM-01-B 22 UT-HM-01-B 44 UT-V-02
3 UT-LM-01-C 23 UT-HM-01-C 45 UT-V-06
4 UT-LM-01-D 24 UT-HM-01-D 46 UT-V-10
5 UT-LM-01-E 25 UT-HM-01-E 47 UT-V-27
6 UT-LM-02-A 26 UT-HM-02-A 48 UT-MGS-01
7 UT-LM-02-B 27 UT-HM-02-B 49 UT-MGS-02
8 UT-LM-02-C 28 UT-HM-02-C
9 UT-LM-02-D 29 UT-HM-02-D
10 UT-LM-02-E 30 UT-HM-02-E
11 UT-LM-03-A 31 UT-HM-03-A
12 UT-LM-03-B 32 UT-HM-03-B
13 UT-LM-03-C 33 UT-HM-03-C
14 UT-LM-03-D 34 UT-HM-03-D
15 UT-LM-03-E 35 UT-HM-03-E
16 UT-LM-04-A 36 UT-HM-04-A
17 UT-LM-04-B 37 UT-HM-04-B
18 UT-LM-04-C 38 UT-HM-04-C
19 UT-LM-04-D 39 UT-HM-04-D
20 UT-LM-04-E 40 UT-HM-04-E
41 UT-M-03
42 UT-M-04
UT-LM-01-D University of Toronto
UT-LM-01-D Light Media
UT-HM-01-D Heavy Media
UT-LM-01-D Casting Number
UT-LM-01-D Particle Size for samples #11
A 0-38m A 0-53m
B 38-106m B 53-150m
C 106-500m C150-212m
D 500-1000m D 212-500m
E 1000+m E 500-600m
UT-M-01 Mixed Media (before heavy media separation)
UT-V-01 Vacuum Experiments
UT-MGS-01 MGS Grade Silicon
C
a
s
t
i
n
g

1
C
a
s
t
i
n
g

2
C
a
s
t
i
n
g

3
C
a
s
t
i
n
g

4

210

Copper amount in light fraction samples in 50wt%Cu-Si alloy. Copper concentration is
determined by Atomic Absorption Spectrophotometry (AAS) technique:

211

Copper amount in light fraction samples in 50wt%Cu-Si alloy. Copper concentration is
determined by Standard Titration Technique (STT) technique:

212
Chemical analyses of the Si-50wt%Cu alloy by Inductively Coupled Plasma Mass
Spectrometry (ICPMS):

213

continuation

214
Chemical analyses of the Si-70wt%Cu alloy by Inductively Coupled Plasma Mass
Spectrometry (ICPMS):

215
Chemical Composition of the Metallurgical Grade Silicon Given by Supplier:

Silicon #1 Silicon #2
Element ppmw Elem ppmw Element ppmw Elem ppmw
H Zn 4.5 H Zn 0.13
Li 0.033 Ge 1.6 Li 0.027 Ge 0.45
Be As 0.065 Be As 0.15
B 18 Se <0.3 B 7.2 Se <0.3
C Sr 0.23 C Sr 0.26
N Y 0.11 N Y 0.062
O Zr 7 O Zr 4.7
F 0.1 Nb 0.17 F 0.1 Nb 0.29
Na 0.1 Mo 0.71 Na 0.01 Mo 0.54
Mg 0.7 Ag <0.3 Mg 0.31 Ag <0.3
Al 335 Cd <0.3 Al 220 Cd <0.3
Si Major In <0.1 Si Major In <0.1
P 16 Sn <0.1 P 12 Sn <0.1
S 0.069 Sb <0.1 S 5.8 Sb <0.1
Cl 0.31 Te <0.3 Cl 0.37 Te <0.3
K 0.072 La 0.52 K 0.025 La 0.11
Ca 5.6 Ce 1.3 Ca 0.88 Ce 0.38
Sc Pr 0.2 Sc Pr 0.077
Ti 35 Nd 1.2 Ti 55 Nd 0.33
V 1.7 Ta <5 V 45 Ta <5
Cr 8.7 W 0.2 Cr 1.4 W 0.31
Mn 55 Au Mn 18 Au
Fe 2800 Pb <0.05 Fe 560 Pb <0.05
Co 1.3 Bi <0.05 Co 1.7 Bi <0.05
Ni 7.1 Th 0.039 Ni 34 Th 0.056
Cu 24 U 0.035 Cu 26 U 0.1

Chemical Composition of the Electrolytic Copper Given by Supplier:

216
Appendix 08: Temperature Controller Setup
(ST-1600-High Temperature Furnace Controller)

217
Appendix 09: Silicon Refining Plant Layout

Solubility of Copper in Silicons

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Solubility of Copper in Silicons

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Characterization of the Cu-Si System and

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