Journal of Electronic Materials, Vol. 11, No.

5, 1982

EFFECTS OF MONOCHLOROSILANE ON THE PROPERTIES OF PLASMA DEPOSITED HYDROGENATED AMORPHOUS SILICON*

A.E. Delahoy, 1 R . W . Grifflth, 2 F.J. Kampas and P.E. Vanier Division of Metallurgy and Materials Science Brookhaven National Laboratory Upton, New York 11973

(Received October 23,

1981)

Concentrations of monochlorosilane (SiH3CI) of the order of 2500 ppm have been detected in some commercial tanks of silane by mass spectrometry and optical emission spectroscopy (OES). This impurity is shown to depress the position of the Fermi level in a-Si:H, resulting in lower photoconductlvity and solar cell efficiency. Key words: Amorphous silicon, monochlorosilane, optical emission spectroscopy, mass spectrometry, photoconductlvity, solar cells. ipresent address: Chronar Corporation 330 Bakers B a s i n Rd. Trenton, NJ 08638 2present address: U.S. ARO Electronics Division P.O. Box 12211 Research Triangle Park, NC 27709

*This research was performed under the auspices of the U.S. Department of Energy under Contract No. DE-ACO276CH00016.
869
0361-5235/82/1105-86953.00 1982 AIME

870

Delahoy, Griffith, Kampasand Vanier

Introduction

The study of hydrogenated amorphous silicon has been hampered for a long time by the variability of the properties of samples produced in different laboratories. Even when comparisons are made only between samples produced by a particular deposition method (for instance, rf glow discharge in silane) the properties of films described by different groups cover a wide range. Some of the differences between samples can be attributed to controllable deposition parameters such as substrate temperature, total rf power, gas pressure and flow rate. Other variations may arise in more subtle ways from the detailed geometry of the deposition chamber, which determines the characteristic gas flow patterns and the distribution of rf power density. Even when all these parameters are kept constant, we have observed large differences in electronic properties between films prepared from different tanks of silane. In this paper we will show that such variations in film properties can be caused by differences in concentration of monochlorosilane (SiH3CI) w h i c h sometimes is present as an impurity in silane. The presence of this impurity in one particular silane tank was first indicated when a peak at 281 nm in the glow-dlscharge emission spectrum was tentatively attributed to the species SiCl (i). The assignment was reasonable, since silane is often synthesized by reduction of chlorlne-contalnlng compounds. It was also noticed immediately that the films prepared from this tank showed photoconductive behavior that was significantly different from previous depositions. Wlth improvements in the optical system, this emission peak was resolved into two components expected for SIC1 and found to occur, but with lower intensity, when several other tanks of silane were employed (2). Furthermore, the amount of chlorine in the deposited film, as measured by secondary ion mass spectrometry (SIMS), was found to correlate with the intensity of the SiCl emission. We have now completely established that the emitting species is SIC1, identified the parent compound as monochlorosilane (SIH3CI), and studied the effects of this impurity upon the properties of a-Si:H films and solar cells.

Effects of Monochlorosilane on Amorphous Silicon Experimental

871

The optical emission spectrometer consists of a Spex 0.75-m monochromator, a cooled Hamamatsu R 9 5 5 P photomultiplier tube, and a Spex PC-I p h o t o n counter. The m o n o chromator has a dispersion of i.i nm/mm and was operated with 0.5-mm slits. The parent compound of the SiCI emission was identified as SiH3CI using a m o d e l IO0-C UTI quadrupole mass spectrometer operated at an ionization energy of 70 eV. With no rf power applied, the deposition system was used as a controllable source of silane and was set at a pressure of 1.0 Tort. A Veeco PV-10 piezo-electric valve was used to modulate the gas flow between the deposition system and the mass spectrometer, which was diffusion pumped. The output of the mass spectrometer was detected by an Ithaco 3 9 7 E 0 lock-in amplifier. Dark conductivity and photoconductivity measurements were performed on coplanar ~amples in which the elec5 trodes, consisting of a 300 X layer of Cr and a I000 A layer of Mo, were first evaporated onto Corning 7059 glass substrates leaving a 1.6 ~m gap. The a-Si:H was then deposited in an rf capacitatlve system as a 0.4 ~m thick layer bridging the gap and forming ohmic contacts with the Mo. The rf power was set at the lowest level at which a discharge could be maintained, which in this system was 15 W. The silane flow rate was I00 sccm at a pressure of I00 m T o r r and the substrate temperature was 225C. Depositions were carried out both with and without a proprietary chlorosilane filter provided by Matheson Gas Company. A Keithley 616 electrometer was used for dc measurements, and the Ithaco lock-in amplifier was used for modulated photoconductivlty experiments. Monochromatic light with a wavelength of 600 nm and an intensity of 1014 photons cm-2s -I was chopped at 7 Hz in the latter case. The applied voltage for both dark conductivity and photoconductivity measurements was i00 V. Further details on the deposition system and measurement techniques can be found in a previous publication (3). The Cl concentration in the a-Si:H films was determined by secondary-lon mass spectrometry (SIMS) of 35CI using a Cs+ primary beam (4). In order to study the effect of SiH3CI on devices, diagnostic solar cells were fabricated in the p-i-n

872

Delahoy, Griffith, Kampas and Vanier

configuration from the same tank of silane both with and without the chlorosilane filter. The a-Si:H was deposited to a nominal thickness of 6000 A on stainless steel substrates held at 180C. J ~ e p- and n-type layers were respectively I00 ~ and 4 4 v = in thickness, and were prepared using gas phase concentrations of i000 ppm B2H6 and 150 ppm PH3, respectively. Cells 2 ~ 2 in area were defined u%ing as a top contact either a metallic film (e.g. 65 A Pd) or a q~arter-wave transparent conducting oxide layer (e.g. 660 A In203). The latter layer was e-beam evaporated from a slntered source of In203 using a low gun voltage (4 kV) to avoid damaging the a-Si:H. The deposition was performed with a partial pressure of dry oxygen of 5 x 10-4 Torr, a substrate temperature of 140C, and at a rate of 0.3 ~ s-I. The current-voltage (J-V) characteristics of the cells were determined under approximately AMI illumination provided by a Xenon lamp solar simulator. The J-V data were acquired automatically using 12 bit A/D and D/A converters controlled by a Tektronix 4051 graphics computer. Since the In203 layers were often found to have non-abrupt edges, the J-V data were obtained using a mask placed in contact with the cell to accurately define the illuminated area and to prevent peripheral collection. For this purpose the In203 deposition mask itself was used. Results Emission Spectroscopy a n d Mass Spectrometry

An emission spectrum of a deposition using the silane tank with the highest chlorosilane content is shown in Fig. i. The silane pressure was i00 m T o r r and an rf power of 15 W was employed. Emission from two different electronic transitions (B'2A-~ X2~ and B 2 E + ' ~ X 2 H ) of SIC1 is identified (5). The state X2R is the electronic ground state of SIC1. The pairs of numbers in parenthesis in Fig. i give the vibrational quantum numbers of the excited and ground states, respectively. The symbols QI' PI' and P2 give the branch of the spectrum, which is determined by the change in rotational quantum number. Also shown is emission from atomic silicon, transiI and UV 43 (6). The emission line UV 43 is the

tions

Effects of Monochlorosilane on Amorphous Silicon

I
2000 SiCI

873
: r

T-~

Si uv43

500 t~m SLITS 5 nm/ rnin I seclC SiC1 A2]~.~X2 H

e' 2A*x2n
"6 QI I P2

iz IOOC

SiI . _ ~ j ~ u ~

-z

(~

(LO) I~,o)

(i,

~o,o1

,i,,,,,2)i /I

oyJ~

(o,2)

V \~V,Jv p ~,2)/(o,4) ~ A I/UI# , /

[

W, EE G3 Into) / V L N 1~ e

Fig. i. Emission spectrum showing SIC1 and Si lines.

from an rf discharge in silane See text for conditions.

strongest in the sllane glow discharge spectrum and had an intensity of approximately 1.5 x 105 counts s-I for the spectrum shown. The mass spectrum of the silane from the tank with the largest SlCl emission had peaks at m/e values of 63, 64, 65, and 66 (e.g. 28Si35CIIHx or 28Si37CIIHx, x=O,l) with amplitudes in the approximate ratios of 2: I0: 2: 3. The mass spectrum of a tank with no detectable SiCI emission did not have these peaks. The signal-to-nolse ratio for the peak at m/e of 66 was approximately five. Peaks at m/e values of 67 and 68 (e.g. 28S137CIIHx, x=2,3) were either not present (implying H 2 is split off in the ionizer), or were too weak to be detected. The strongest peak (at m/e of 64) had an amplitude of approximately 1/400 of the principal peak from silane (at m/e of 30). Since the detector efficlencles of these species are not known, we can only estimate the concentration of SiH3CI to be i in 400, i.e. 2500 ppm, within an order of magnitude. No peaks were seen for m/e values of 98-103, as would be expected for dl-, tri-, and tetrachlorosilane (7). As a check, the mass spectrum of a mixture of 1% dichlorosilane in argon was measured and the peaks at m/e of 98-103 were detected. Furthermore, no SICI emission was observed when I000 ppm of dlchlorosilane was added to a high purity silane discharge. These results establish conclusively that the parent compound of the SiCI emission is monochlorosilane.

874

Delahoy, Griffith, Kampas and Vanier

Dark Conductivity and Photoconductlvlty Arrhenius plots of the dark conductlvlties od of two films are shown in Fig. 2. The dashed llne represents a film prepared from a silane tank w h i c h was found to contain SIH3CI. The activation energy for the straight section of the plot above r o o m temperature is EG = 0.96 eV. Another estimate of the room temperature Fermi energy E F relative to the mobility edge is given by AE = kT in (Go/Gd(T)) = 0.78 eV (at T = 300 K), where the minimum metallic conductivity is assumed to be GO = 200 ~ - I cm -I. The solid llne represents a film prepared from the same tank of silane under identical deposition conditions except that the silane was first passed through the filter for removing chlorosilanes. (OES measurements showed that the filter was effective in reducing the SiCl peaks b e l o w the level of detectability.) In this case, the two estim a t e s of the Fermi level position were E~ = 0.75 eV and AE = 0.55 eV. By either method of estimating EF, the removal of SIH3CI from the gas stream results in an upward shift of EF by about 0.22 eV in the films deposited. In Fig. 3 the photoconductlvlties GD of the same two films are plotted against reciprocal temperature. There are two striking differences between these curves. First, the filtered silane produces a film with a room temperature photoconductivlty three orders of magnitude higher than is obtained using unfiltered silane. Second, the film produced with the filter exhibits a single valley in the photoconductlvity plot whereas the film deposited from unfiltered silane shows a more complicated temperature dependence, with two valleys. By adding various amounts of B2H6 to silane from a tank w h i c h contains no SiH3CI , we found that 1 ppm B2H 6 in the silane produces a-Si:H films whose dark conductivity and photoconductivity is very similar to the films deposited from the silane containing 2500 ppm SiH3CI.

Effects

of SIHBCI on Devices

We turn now to the effects of SIH3Cl on device performance. In Fig. 4 we compare the illuminated J-V c h a r acteristics of two In203/P-l-n solar cells, deposited with and without the chlorosilane filter. The illumination

Effects of M o n o c h l o r o s i l a n e o n A m o r p h o u s S i l i c o n

875

-3 -4 -~ -" -5

T b

-6

~ -8
-9
-IO 1

\ ~,---Wl T H O U T F I L T E R
I 3 \ I I 4 I

I O 0 0 / T (K -I)

Fig. 2. Arrhenius plots of od for two films grown from the same tank of silane under identical reactor conditions. Solid line - silane was filtered to remove chlorosilanes. Broken line - without filter.

-3

'

-4 -" 'E T b -5 -6

-9
I I I I I I I I

"~
I

-102

6 7' 8 9 I O 0 0 / T (K-I) "

I0

II

12

Fig. 3. Arrhenius plots of ap for the same two films s h o w n in Fig. 2. Photon flux fi 1014 cm-2 s-l; X fi 600 nm. f f

876

Delahoy, Griffith, Kampasand Vanier

J (mAcrn 2) 12.0 In203/p-i-n/ss 15W, IOOmTorr, 180=C

/
./ / / / / / WITH FILTER~ l.OV

-I.0

WITHOUT FILTER ~ ' ~

-120

Fig. 4. Illuminated J-V characteristics of In203/P-i-n solar cells a and d in Table I, showing the effect of monochlorosllane. intensities were 99.2 mW cm-2 and 97.6 mW cm-2, respectively. The photovoltalc parameters of these cells are given in T a b l e I (cells a and d). Short-clrcult current densities (Jsc'S) are normalized to exactly I00 mW cm-2 incident intensity. We see that the cell deposited from unfiltered sllane exhibited a poor fill factor (0.340) and a somewhat low current density (6.96 mA cm-2). Upon flltering out the SiH3CI , however, the flll factor FF increased dramatically to 0.539 and Jsc increased to 7.46 m A c m -2, resulting in an increase of conversion efficiency from 1.90% to 3.34%. (The In203 was deposited onto cells a, c, and d simultaneously, so differences between these cells cannot be attributed to variations In the transmission or resistivity of thls layer; the In203 on cell b was deposited separately, although under the same conditions.) Similar results regarding Jsc and FF were found for Pd/p-i-n cells (8). The respective Jsc'S of In203 and Pd cells deposited from filtered sllane were typical of cells deposited from tanks of sllane that produced no detectable SiCI emission. In those cells, SIMS analysis of the a-Si:H indicated a CI concentration of the order of 2 ppm. In cell d, deposited from the unfiltered sllane, 400-600 ppm CI was found.

Effects of Monochiorosilane on Amorphous Silicon TABLE I.

877

Parameters of In203/P-i-n a-Si:H Solar Cells as a Function of SIH3CI Concentration in the Plasma a-Si :H Thick- Av. Dep. hess Rate Voc (X) ( ~ s-11 (V) 6000 7400 0.48 0.73 0.830 0.826

Cell

Silane

Dep. Time (rain) 210 170

Jsc (mAcro-21 7.46 8,81

FF

~] (%) 3.34 3.83

a b

Filtered Partially Filtered Partially Filtered Unfiltered

0.539 0.526

210

9300

0.74

0.816

9.77

0.423

3.37

210

9600

0.76

0.804

6.96

0.340

1.90

At some point during the deposition of the a-SI:H for c e l l s b and c, SiCI emission appeared. By the end of the run the intensity had slowly increased to about that found for unfiltered silane, thus signalling saturation of the filter. (A freshly charged filter was used for cell a.) It is estimated that the CI concentration in these cells is graded in some fashion from <I0 ppm at the back of the cell to 400 ppm at the front. Interestingly enough, the Jsc'S of these Cl-graded cells were 8.81 mA cm-2 and 9.77 mA cm-2, i.e. higher than those of cells a and d. For cell b the increase In Jsc resulted In an efficiency of 3.83%. For cell c the considerable Increase in Jsc was offset by a reduced fill factor (see Table I), The effect of the monochlorosilane impurity upon the film deposition rate can be ~een from Table I. The average depositiono rate is 0.48 A s-I for filtered silane but rises to 0.76 A s-I for unfiltered silane. Discussion The dark conductivity data clearly show that small concentrations of monochlorosllane depress the Fermi level significantly. However, monochlorosilane is only a weak ptype dopant since 2500 ppm SiH3CI has about the same effect

878

Delahoy, Griffith, Kampasand Vanier

as i ppm B2H 6. Monochlorosilane also increases the film deposition rate, like diborane (9). This result implies that the position of the growing film F e r m i level affects the deposition rate, since it is unlikely that B2H 6 and SiHsCI have any catalytic properties in common. The lower photoconductlvity of a-Si:H films deposited from unfiltered silane is a consequence of the lower Fermi level position (3). The valley in the temperature dependence of Gp (with filter) is largely a result of competition between two distinct types of recombination centers. A schematic of the density of states in the gap needed to explain this type of data as well as the related phenomenon of infrared quenching (I0) is shown in Fig. 5. In addition to exponential band tails there are two different types of states in the gap labeled I and 2. States 2 have a larger electron capture cross-section than states i. A lower Fermi level results in a higher concentration of holes in states 2. The resulting higher recombination rate then lowers the photoconductivity. The origin of the second valley in Gp (without filter) is not clear without further experiments (ii). A simple explanation of the device results shown in Fig. 4 is that the lowered photoconductivity of films made from unfiltered silane results in a large series resistance (4100 ~ cm2) in the device. However, spectral response studies have shown that the situation is more complicated (8). As far as the variations in Jsc for the cells of T a b l e I are concerned we conclude the following. The increase in Jsc in passing from cell a to b to c is due to enhanced light absorption (for ~ > 600 nm) resulting from the increased cell thickness. In competition with this trend is the progressive reduction in zero-bias quantum efficiency for % < 600 nm with increasing SiHsCI concentration in the plasma. Eventually this effect dominates and accounts for the lower Jsc of cell d. The progressive reduction in FF for cells a-d is due to the progressive reduction in quantum efficiency for ~ < 600 nm when a forward bias is applied. These reductions in quantum efficiency in p-i-n cells are caused by increased electron recombination (8) as indicated by the decreased photoconductlvity. Finally we remark that in the case of n-i-p cells (light incident on the n layer) it is possible that a lowered Fermi level would improve hole transport to the back of the cell. In that case the presence of SiH3CI may be beneficial.

Effects of Monochlorosilane on Amorphous Silicon

879

\\ - \ \\\\ \ I

1!6

112

OI

0.4

0.0

AE[eV)

Fig. 5. Schematic of proposed density of states in hydrogenated amorphous silicon. All of our results can be explained by the weak ptype doping caused by monochlorosilane. However, the mechanism by which this occurs is unclear. We considered the possibility that a CI containing species in the plasma etched the AI electrodes thereby introducing AI into the films. However, SIMS analyses of a-Si:H films deposited from various tanks of silane revealed no correlation between SiH3CI concentration in the silane and AI concentration in the film (which ranged from roughly 2 ppb to 2 ppm). A study of the properties of a-Si:(H,CI) deposited from SiC14 + H 2 (12) is not useful in understanding the effects we report here. Those films contained 1.5 to 8% chlorine and had activation energies ranging from 0.3 to 0.8 eV. (It was apparently assumed that the films were n-type.) In the same study a-Si=H films were prepared from silane in a different deposition system. The differences in deposition systems, starting gases, and deposition parameters make it impossible to deduce the effects of Cl as an impurity in a-Si:H from those results.

880

Delahoy, Griffith, Kampas and Vanier

An effect of chlorosllane impurities in disilane on a-Si:H film photoconductivlty was reported by Scott et al. (13). They also found that films containing small amounts of chlorine have lower photoconductivity than films with no detectable chlorine. The low doping efficiency of SiH3CI indicates that only a small fraction of the chlorine atoms can be acting as acceptors. It may also be that the doping mechanism is indirect and that the presence of SiH3CI in the discharge alters the concentrations of non-chlorlne containing defects, thus moving the Fermi level. The fact that SiH3CI is not available commercially raises a large obstacle to further investigation. Conclusion The effects of monochlorosilane impurity on glow discharge deposited a-Si:H films can largely be understood in terms of its p-type dopant properties. The detection of this impurity in several commercial tanks of silane and the deleterious effect it has on solar cell efficiency would indicate a need for care on the part of the silane user as well as the silane manufacturer. Two analytical techniques, mass spectrometry and glow discharge optical emission spectroscopy, are adequate in sensitivity. Acknowledgments We should like to thank Dr. Zvl Ovadyahu for advice concerning the deposition of In203 and Mr. Robert Gremme for technical assistance.

Effects of Monochlorosilane on Amorphous Silicon

881

References (i) R. W. Griffith, F. J. Kampas, P. E. Vanier, and M. D. Hirsch, J. Non-Cryst. Solids 35/36, 391 (1980). F. J. Kampas and R. W. Griffith, Solar Cells 2, 385

(2)

(1980).
(3) P. E. Vanier, A. E. Delahoy, and R. W. Appl. Phys. 52, 5235 (1981). SIMS analyses were performed Associates, San Mateo, CA. by Grlffith, J.

(4)

Charles

Evans

and

(5)

R. W. B. Pearse and A. G. Gaydon, The Identification of Molecular Spectra, Chapman and Hall, London, 4th edn., 1976. C. E. Moore, Selected Tables of Atomic Spectra Si I, NSRDS-NBS 3, Section 2, Reference Data Series, National Bureau of Standards, Washington, DC, 1967. V. S. Ban, Mat. Res. Bull. IO, 81 (1975).

(6)

(7) (8)

A. E. Delahoy and R. W. Griffith, in Proc. 15th IEEE PhotoVoltaic Specialists Conference, Kissimmee, FL (IEEE, New York, 1981), pp. 704-712. J. C. Knights, (1980). J. Non-Cryst. Solids 35/36, 159

(9)

(lO)

P. E. Vanier, A. E. Delahoy, and R. W. Griffith, in Tetrahedrally Bonded Amorphous Semiconductors, AIP Conference Proceedings, Number 73, edited by R. A. Street, D. K. Biegelsen, J. C. Knights (ALP, New York, 1981), pp. 227-232. Recent photothermoelectric power measurements indicate that the appearance of the third peak in photoconductivity near room temperature is associated with hole conduction (see Fig. 3, and A. E. Delahoy and P. E. Vanier, Bull. Am. Phys. Soc. 27(3), 268

(Ii)

(1982)).

882
(12)

Delahoy, Griffith, Kampasand Vanier

W. W. Kruehler, R. D. Plaettner, M. Moeller, B. Rauscher, and W. Stetter, J. Non-Cryst. Solids

35/36, 333 (1980).

(13) B. A. Scott, M. H. Brodsky, D. C. Green, P. B. Kirby, R. M. Plecenik, and E. E. Simonyi, Appl. Phys. Lett. 37, 725 (1980).