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SIMS Study of the Penetration of Metallic Secondary Impurities in Screen-Printed Silicon Solar Cells

M. Van Craen,J-$ L. Frissonfi and F. C. Adamst


t University of Antwerp (UIA), Department of Chemistry, Universiteitsplein 1, B-2610 Wilrijk, Belgium 0 SA Fabricable NV, Photon Technology, B- 15 1 I Huizingen, Belgium

The penetration of metallic B, Ti, Fe, Cu and Ag in silicon solar cells was studied. They were prepared using the screen printing process for metallization. The level and depth of penetration were determined using secondary ion mass spectrometry (SIMS). Quantitative SIMS depth profile analysis was performed using ion implanted substrates as standard materials. The influence of different production parameters, such as silicon crystal orientation, metallization temperature, composition of the Ag-paste and the presence of an anti-reflective TiO, coating on the silicon cells were determined. The penetration of some metallic species has considerable influence on the solar cell characteristics and its efficiency. The penetration levels can not be explained by diffusion but are probably related to more reactive interactions.

INTRODUCTION
Spurred on mainly by the potential use of solar cells' for large scale terrestrial solar energy applications, research and development has grown considerably in the past few years. Photovoltaic conversion of solar energy to electricity is already known for many years. It is intensively used in space technology for electrical supply of satellites. The problems associated with the large scale applications are mainly economical. The silicon cells studied in this work are prepared using the screen printing process for metallization.2 The characteristics of cells produced by this metallization technique are comparable with other, more expensive ones. The process uses thick film technology and lends itself much more easily to automation than the conventional vacuum operation techniques. Indeed, the evaporation is a hand-operated batch process and the vacuum process involves high facility costs. The screen printing technique on the other hand, avoids the disadvantages with almost the same final efficiency. It is easy to fully automate, with fabrication cost reduction of processing by 60 to 80%. The major difference with evaporation technology is that the front metallization pattern is screened on a anti-reflective TiO, coating instead of using evaporation, directly onto the silicon wafer. A glass containing silverpaste to which a few percent of Ti is added, is screen printed on the front side of the silicon wafer using a grid configuration. The Si is heated at a temperature of ca. 860C to minimise the contact resistance. An aluminium paste is then screen printed on the back side to produce an ohmic back surface contact after A 1 diffusion. The A1 paste is heated in the air between 660 to 720C. An Ag based paste is screen printed on top of the A1 contact to obtain a solderable contact. Fig. 1 presents a cross sectional view of a Si cell.
$ Present address: Bell Telephone Manufacturing Company, R & D Labs, B-9000 Gent, Belgium.

Sintering temperatures are considerably higher in the screen printing process than in the evaporation technology. Hence, the penetration of metallic impurities into the cell may be of considerable importance here. Metallization products and impurities must be prevented from penetrating the p n junctions being situated at shallow depth (ca. 0.5 pm), thus affecting the junction. The choice of suitable metallization and substrate materials, the cleanliness of working conditions and the use of an adequate temperature treatment, is hence important. Surface-sensitive analytical methods are needed to study the level and depth of penetration of different metallic species into the solar cell surface. Secondary ion mass spectrometry (SIMS) with a ion microscope was chosen for this purpose owing to its low detection limits, its surface-sensitivity and the inherent possibility of the method to perform depth profiling. Quantitative penetration profiles were obtained with SJMS using suitable ion implanted standards as reference materials. The most important elements, which can penetrate into the silicon from the Ag metallization and from the TiO, antireflective coating are B, Ti, Fe, Cu and Ag. Other elements already present in the silicon wafer at its fabrication need not be taken into account because their concentration is very low (semiconductor grade silicon) and therefore are of no influence on the cells characteristics.

////////lllllllllm,////u

Al

Figure 1. Cross section of a screen-printed, TiO, coated monocrystalline Si solar cell (ARC=anti-reflective coating).

CCC-0142-242 1/84/0006-0257 $02.00


@ Wiley Heyden Ltd, 1984

SURFACE AND INTERFACE ANALYSIS, VOL, 6, NO. 6, 1984 257

M. VAN CRAEN. L. FRISSON A N D F. C. ADAMS

INSTRUMENTATION
Secondary ion mass spectrometry Measurements were performed on a CAMECA IMS-300 ion microscope/ion analyser.3 The apparatus was equipped with an electrostatic sector analyser for energy discrimination of the secondary ions and automated data acquisition and p r o ~ e s s i n g .The duoplasmatron ion ~ source was operated with argon gas at a working pressure of 2 ~ l O - ~ T o r r . The samples were bombarded with 5.5 keV primary ions, while oxygen gas was continuously flooded over the surface until a pressure of about 5 x 10-6Torr was attained. Also, in order to avoid edgeeffects during depth profiling, the primary ion beam was rastered over a 400 x 400 pm area while a 55 pm diameter mechanical aperture, located in the immersion lens system, was used to restrict the area viewed by the detector. The primary ion current density was approximately 100 pA cm-2, yielding erosion rates of several A s-' for Si. Secondary ion intensities in an energy band width of SeV, centered around the maximum of Al+, were measured. Positive aluminium ions were chosen as a reference for tuning off the spectrometer because their energy distribution is very well known. Standardization

of view of the ions collected within the rastered crater. By proper choice of diaphragms in the immersion lens system this can limit significantly instrumentallyinduced tailing effects for ion-implanted depth profi~ing.~ Samples Five solar cells labelled A to E were prepared, using different production parameters: A: normal case, metallization temperature T = 810 "C, p ( 1 1 1)Si substrate, metallization paste 'A', anti-reflectively coated before metallization. B: identical to A, except T = 860 "C. C: identical to A, except p(1OO)Si substrate. D: identical to A, Except metallization paste D. E: identical to A, except that the metallization is done directly on the Si wafer.

RESULTS
Figure 2 presents, as an example, the SIMS depth profile of lo9Ag+ obtained for the ion-implanted standard materials. The elemental sensitivity factors for Ti, Fe, Cu and Ag were obtained from this and similar profiles. For B the sensitivity was directly available from the homogeneously doped standard wafer. The uncertainty of the elemental sensitivities in the Si matrix, determined using the ion-implanted profiles is of the order of 10 to 15% relative error. The authentic depth scales for the profiles measured on the silicon solar cells were established using Tallystep crater depth measurements. Impurity concentration profiles, obtained for Ti and Cu, are represented in Fig. 3. From these profiles the actual concentration levels of secondary impurities at the surface and at the junction can be derived (Table I). The accuracy of these values is of the order of 50%, taken into account all contributing sources of error.

For B a p-type Si wafer was used with known concentration of 5 x 10l6 at cm-3 as deduced from resistivity measurements. The other reference materials were prepared by ion implantation6in pure silicon using a known amount of 48Ti, s4Fe, 63Cu and '"Ag. With an acceleration energy of 70 keV, 3 x lOI3 at cm7* were implanted. For the determination of the ion-implantation profiles of the substrates, 30Si+was taken as a reference signal in order to eliminate possible fluctuation of the primary ion current density during the measurements. The optical system used in the Cameca instrument defines the field

sl

10-3

50 100 Sputtering depth InmJ

150

Figure 2. SIMS profile of Ag implanted in Si (=70keV, 3 x 1013at cm-').

Hill et d 8investigated the effect of certain secondary impurities (C, 0, Na, Mg, Al, Ti, V, Cr, Mn, Fe, Ni, Cu and Zr) on the degradation of conventional solar cell performance. Ti, V and Zr appeared to be the most harmful secondary impurities. The tolerable impurity concentrations, defined as the maximum level which provides a 10% efficiency solar cell is 0.8 x 10I6at cm-3 for B in Czochralsky Si and 1 X I O l 7 for B in a float zone Si. For Ti, Fe and Cu these levels are 4 x 1013, 1 x 10" and 1 x 10" at ~ m - respectively. These data can not be ~ , expected to be more accurate than a factor of 10. From a comparison of these tolerable concentrations with Table 1, we derive the following: (a) The boron impurity level for all cells is well below 1 x 10l6at cm-3 at the junction, consequently it can be expected that this level is due to the base doping of the silicon slice and does not proceed from the metallization; however for reasons which could not be elucidated, in some cases the measured values were even lower than the expected base doping level (8 x 10" at cm-').

258 SURFACE A N 0 INTERFACE ANALYSIS, VOL. 6, NO. 6,1984

SIMS STUDY OF THE PENETRATION OF METALLIC SECONDARY IMPURITIES

Ti

CU

0
C

500 Depth ( nrn)

1000

500 Depth (nml

1000

Figure 3. Depth profile of Ti (a) and Cu (b) impurities in Si solar cells, the labels refer to the samples prepared using different production parameters, described in the text.

(b) The iron concentrations are of the order of the acceptable impurity levkl both at the surface and at larger depths, while the measured Fe levels are about 2 orders of magnitude higher than expected from solid state diffusion. This can be due to a partial uptake of Fe by the glass phase in the Ag metallization paste. This phase, enriched in Fe, then probably penetrates into the Si cell. (c) The copper concentrations, also, are of the same order as the tolerable levels in samples A, B and E. For the sample D and to a lesser extent also for sample C the surface levels are somewhat too high. (d) For silver, Hill et a/.*have not given information. However, if we take into account the segregation

we can assume coefficient for Ag in silicon (1.7 x that a concentration in the order of l o i 4at cm-3 may be tolerable. Then, for several of the investigated solar cells the high Ag content could become a problem. (e) For titanium, however, the concentrations found both at the surface and at the p-n junction are much higher than the tolerable levels. All cells have a surface concentration higher than 3 x 1015at cmp3, even up to 3 x 10 at cmp2 for cell C. At the junction, all cells contain more than 3 x lOI4at cmP3,but most pronounced Ti levels are found for cells A, C and D (up to 5 x l o i 6at cm-3 for cell c). The higher metallization temperature used for cell B does not give rise to much higher impurity

Table 1. Impurity levels at the surface and p-n junction measured under the Ag metallization as determined with SIMS
Boron impurity concentration (atcm Surface Junction
Iron impurity concentration (at cm-) Surface Junction Silver impurity concentration (at ~ m - ~ ) Cell type Surface Junction

Cell type

Cell type

A B C D E

6 x 1015 1.5 x 10 <6 x 1015 1.2 x 10 -1 ~ 1 0 ~ 1 . 8 ~ 1 0 ~ 8 ~ 1 0 ~ 2x10 <l XlOl5 4.4x10l6


Titanium impurity concentration (at cm 3, Surface Junction

A
B C

D E

2.8 x10l5 5.8 x 1 015 1.5 x 1015 1.9 x 1015 2.6 X 1015

2.8 x loi5 5.8 x 1 Oi5 1.5 x 1015 3 x 1015 4.6 X 1015

A B C D E

- 1 x1015 - 8 x 1015 -1 ~ 1 0 5 1 ~ 1 0 ~ 1.8 x 1015

5.8~10~ 5.8 x 1014 5.1 ~ 1 0 1 ~ 2.8~10~ 1 x10i5

Cell type

Cell type

Copper impurity concentration (at ern-') Surface Junction

A B C D E

6 ~ 1 0 ~ 1.3~10~ 1~ 1 0 ~ 3.6~10~ 2.8 x 1017 4.6 x 1 O I 6 1.4 x 1015 1.4 x 10l6 3.3 x 1014 2.8 x 1015

A B C

1.7 x 1015 -1 xi015 5.8 x 1015 1.5 x 1015 1.5 x 1015

7.6 x 1014 -1 ~ 1 0 ~ 1.7 x 1015 1 x10i5 1.5 x 1015

SURFACE AND INTERFACE ANALYSIS, VOL, 6, NO. 6, 1984 259

M. V A N CRAEN. L. FRISSON A N D F. C. ADAMS

"
u

210'6 I

c 0 +
c

e
c
Y

c
+
3 L

:d 75 a

I---

E -

'

10

L
( %)

11

12

Cell e f f i c i e n c y

10
( O h )

11

12

Figure 4. Measured impurityconcentration of Cu at the n-p junction for different Si cells. No correlation is found with tQe efficiency of the solar cell.

Cell efficiency

Figure 5. Influence of the Ag concentration at the n-p junction on the solar cell efficiency.

concentrations. The use of a Si (100) substrate instead to the normally used p ( 1 1 1) led to an increase of the Ti and Cu concentration (by a factor of about 4 and 2, respectively), to a decrease of the B and Fe level (by a factor of 3 and 2, respectively) and has no perceptable effect on the Ag concentration level. No correlation was found between the B, Fe and Cu secondary impurity concentration and the solar cell efficiency as is demonstrated in Fig. 4 for Cu, as an example. Hence of the metallic impurities determined, only titanium and silver can influence the electrical efficiency. Even if the metallization is applied directly on the Si cell, i.e. without first coating it with antireflective titanium oxide (sample E), Ti levels are still higher than the tolerable concentrations. Yet, the levels of this cell (E) are a factor up to 140 lower than for the other cells. The increased Ag concentration in cell D

could be traced to an inferior quality of the metallization paste. The relation between the cell efficiency and the measured Ag concentration at the junction depth is presented in Fig. 5. Both the use of the defective silver paste (cell D) and the application of the TiO, layer after metallization (cell E) influence negatively the efficiency. For cell E this is most probably due to the absence of a penetration barrier for Ag. In addition, the high Ag level observed for all cells are too high to be explained by normal diffusion processes. Acknowledgement
M.V.C. i s indebted to the Belgian IWONL for financial support. T h i s work was carried out under research grant 80-85/ 10 of the Interministrial Commission for Science Policy, Belgium.

REFERENCES
1. H. Fischer and K. Roy, lnstitute of Physics Conference Series No. 53, p. 55 (1970). 2. L. Frisson, Ph. Lauwers, R. Mertens, R. Van Overstraeten and R. Govaerts, Electrocomponent Sci. Techno/. 7, 107 (1980). 3. G. Morrison and G. Slodzian. Anat. Chem. 47, 933A (1975). 4. M. Van Craen, P. Van Espen and F. Adams, Rev. Sci. lnstrum. 53, 1007 (1982). 5. S. Hoffman, Surf. Interface Anal. 2 148 (1980). 6. D. Leta and G. H. Morrison, Anal. Chem. 52, 277 (1980); D. Leta, G. H. Morrison, G. Harris and C. Lee, lnt J. Mass Spectrom. /on Phys. 34 147 (1980). 7. C. Magee. W. Harrington and R. Honig, Rev. Sci. Instrum. 49,477 (1978). 8. D. Hill, H. Gutsche, M. Wang, K. Gupta, W. Tucker, J. Dowdy and R. Crepin, lEEE Photovoltaic Specialists Conference 1976, p. 112 9. B. R. Bathey and M. C. Cretalla, J. Mat. Sci. 17, 3077 (1982).

Received 1 August 1983; accepted 26 March 1984

260 SURFACE AND INTERFACE ANALYSIS, VOL. 6, NO. 6, 1984

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