Solar Energy Materials & Solar Cells 71 (2002) 153167

Inuence of silane ow on structural, optical and electrical properties of a-Si:H thin lms deposited by hot wire chemical vapor deposition (HW-CVD) technique
S.R. Jadkara, Jaydeep V. Salia, D.V. Musaleb, S.T. Kshirsagarb, M.G. Takwalea,*
b a School of Energy Studies, University of Pune, Ganeshkhind, Pune 411 007, India Physical and Materials Chemistry Division, NCL, Pashan Road, Pune 411 007, India

Received 20 September 2000

Abstract The electrical, structural and optical properties of hydrogenated amorphous silicon (a-Si:H) lms deposited from pure silane (SiH4) using hot wire chemical vapor deposition (HW-CVD) technique are systematically studied as a function of silane ow rate FSiH4 between 5 and 30 sccm. We found that the properties are greatly aected by the silane ow rate over the range we studied. The device quality a-Si:H lms with a photosensitivity >105 were ( deposited by HW-CVD at a deposition rate >10 A s1 using low silane ow rate. However, aSi:H lms deposited at higher silane ow rate and/or higher deposition rates show degradation in their structural and electrical properties. The FTIR studies indicate that the hydrogen bonding in a-Si:H lms shifts from mono-hydrogen (SiH) to di-hydrogen (SiH2) and (SiH2)n complexes when lms were deposited at higher silane ow rate. The hydrogen content in the a-Si:H lms increases with increase in silane ow rate and was found to be less than 10 at.%. The Raman spectra show increase in disorder and the Rayleigh scattering with increase in silane ow rate. The optical band gap also shows an increasing trend with silane ow rate. Therefore, only the hydrogen content cannot be accounted for the increase in the optical band gap. We think that the increase in the optical band gap may be due to the increase in the voids. These voids reduce the eective density of material and increase the average SiSi distance, which is responsible for the increase in the band gap. Silane ow rate of 5 sccm, appears to be an optimum ow rate for the growth of mono-hydrogen (SiH) bonded species having low hydrogen content (B4.25 at%) in a-Si:H lms at high deposition rate

*Corresponding author. Tel.: +91-20-565-5201; fax: +91-20-565-5201. E-mail address: mgt@physics.unipune.ernet.in (M.G. Takwale). 0927-0248/02/$ - see front matter r 2002 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 7 - 0 2 4 8 ( 0 1 ) 0 0 0 5 1 - 4

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( (B12.5 A s1), high photosensitivity (B105) and small structural disorder. r 2002 Elsevier Science B.V. All rights reserved.
Keywords: Hydrogenated amorphous silicon; HW-CVD; Electrical properties; Structural properties; Raman spectra; Optical properties

1. Introduction The hot wire chemical vapor deposition (HW-CVD) technique was introduced in 1979 by Wiesmaan et al. [1]. They found that the silicon lms could be formed by the thermal decomposition of silane from a hot tungsten or carbon foil. However, their attempt was not successful due to poor photoconductivity and photosensitivity of a-Si:H lms compared to those obtained by plasma chemical vapor deposition (PCVD) technique. Only in 1986, Mastumura et al. [2] obtained high quality hydrogenated amorphous silicon lms. He showed that the dissociation of SiH4 on a heated lament is a catalytic process and called this method as Cat-CVD. In 1988, Doyle et al. [3], also succeeded in obtaining high quality a-Si:H lms by same technique and called the method evaporative surface decomposition (ESD) method. Mahan et al. [4] in 1991, reported on the development of device quality lms of a-Si:H at low hydrogen content and called this method as Hot Wire Chemical Vapor Deposition (HW-CVD). Since then HW-CVD gained considerable interest from many research groups for the deposition of device quality a-Si:H lms at deposition rates much higher than those achieved with conventional PCVD. ( The advantage of HW-CVD technique is that high deposition rate >10 A s1 can be achieved without deteriorating the device quality of a-Si:H lm which is an order of magnitude faster than that obtained using PCVD [5]. The degradation of a-Si:H due to well-known StaeblerWronski eect is related to hydrogen content CH in the lm. For CH o10%, the HW-CVD grown lms are superior both structurally and electronically to PCVD lms. The HW-CVD grown lms with hydrogen content as low as 0.07 at% have device quality electronic properties [6]. This hydrogen content is sucient to passivate the dangling bonds and demonstrates that the excess H is not necessary [7]. Therefore, it is concluded that the HW-CVD grown material could lead to a more stable solar cell in comparison with PCVD grown material [8]. The process parameters play a crucial role in determining the lm properties in HW-CVD. These parameters aect the lm properties in dierent ways and in order to obtain desired lm properties an optimum set of parameters need to be selected. In this paper, we present the details of investigation of electrical, optical and structural properties of a-Si:H lms deposited by HW-CVD as a function of the silane ow rate. Some groups have previously studied the eect of silane ow rate on a-Si:H thin lms by HW-CVD. Dusane et al. [9] reported synthesis of hydrogenated microcrystalline mc-Si:H) lms at low silane ow rates (5 sccm) and low lament temperature (Tfil 14001C) without hydrogen dilution. They have also reported that the lms deposited with higher ow rates are completely amorphous in nature.

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Naota Tsuji et al. [10] suggested that the deposition rate of a-Si:H lms can be controlled by the surface area of hot wire and silane ow rate at high silane depletion. Recently, Feenstra et al. [11] reported that the structure factor (R) of a-Si:H thin lms strongly depends on the silane ow rate. In this paper, an attempt has been made to investigate the role of silane ow rate on electrical, optical and structural properties of a-Si:H. We have observed that these properties are greatly aected by the silane ow rate. In the present study we have demonstrated that device quality a-Si:H lms with higher photosensitivity (B105), low hydrogen contents (o10 at.%) and high growth rate ( ( (29 A s1ordo12 A s1) can be achieved by HW-CVD method.

2. Experimental 2.1. Film preparation The HW-CVD reactor used in the present study was described elsewhere [12]. The apparatus consists of a stainless steel chamber coupled with a turbo molecular pump, which yields a base pressure of 5 107 Torr. The pressure during deposition was kept constant by using manual throttle valve. A tungsten wire of 0.5 mm diameter was used as the lament. Two straight laments each of length 5 cm are kept parallel and 3 cm apart. The gas was decomposed over the laments, which was thoroughly degassed under high vacuum. The direction of ow of the source gas inlet into the deposition chamber was parallel to the plane of the lament. The substrate temperature was held constant using a thermocouple and temperature controller. The lament temperature was determined by optical pyrometer (Chino Corporation, Japan). Pure silane (SiH4) Matheson semiconductor grade was used as the source gas. All lms were deposited at the lament temperature 19001C, because lower lament temperature (o17001C) lead to tungsten silicide formation on the wires, thus reducing the catalytic action of the hot lament and higher temperatures (>20001C) lead to evaporation of the tungsten wire itself and subsequent detectable tungsten incorporation in the lm [5]. The deposition conditions for all samples used in the present study are listed in Table 1. The silane ow rate was varied from 5 to 30 sccm at an interval of 5 sccm. In order to study the optical and electrical properties, the lms were deposited on corning #7059 glass. Structural properties of the lms were studied using the lms deposited on a single crystal silicon (1 1 1) wafers. During the deposition, slight increase in the substrate temperature (B51C) was observed due to radiation from the hot lament. To remove any water vapor absorbed on the substrate, the substrate holder and the deposition chamber were baked for two hours at 2001C. After that the temperature was brought to desired value by appropriately setting the temperature controller. The deposition was carried out for the desired amount of time and lms were allowed to cool to room temperature in vacuum. Then lms were taken out for characterization.

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Table 1 Deposition conditions for a-Si:H lms Substrate temperature (Tsub) Filament temperature (Tl) Chamber pressure (P) Silane ow rate FSiH4 Substrate to lament distance (dsf) Deposition time (t) 2001C 19001C 21 mTorr 530 sccm 8 cm 10 min

2.2. Film characterization The lms of dimensions 3 cm 1 cm deposited on glass substrate were taken and Al electrodes 0.5 mm apart were deposited on it by vacuum evaporation. The measurements were carried out at room temperature and atmospheric pressure. A voltage of 64.5 V was applied to the electrodes and current passing through the lm was measured by an electrometer (Keithley, model 614). The lm was then illuminated by a tungsten halogen lamp, with an intensity of 100 mW cm2, which was calibrated using a standard c-Si solar cell. The measurements were taken at the interval of 10 s after the light was put on. The values of dark conductivity (s dark ) and photoconductivity (sphoto ) were calculated using the relation s 1 Vto=Il ; where V is the applied voltage (V), I is the current (A), t is the thickness (cm), o is the width (cm) and l is the distance between the electrodes (cm). The optical absorption coecient (a) was determined from the transmission % T and reection % R measurements using double beam Hitachi UVVisible spectrophotometer. The optical energy band gaps (Eopt) of the lms were determined from the relation aE 1=3 B E Eopt ; where E hu is the photon energy. The extrapolation of ahu1=3 versus hu plot yields Eopt : Total hydrogen content (CH ) was determined from Fourier transform infrared (FTIR) spectroscopy. CH was calculated using CH NH =NSi ; where NSi is the density of silicon atoms and NH is the density of bonded hydrogen atoms calculated from the integrated absorption coecient of SiH wagging mode centered about R 618 cm1, using the relation, NH AW o ao=o do; where Aw =1.6 1019 cm2 [13]. Raman spectra were recorded with SPEX 1403 reection grating type double spectrometer. The scattering measurements were performed in the frequency range 50700 cm1. The SPEX 1442 third monochromator, slaved in tandem to the double monochromator was used to reduce the Rayleigh light and other background eects. The data were collected in the photon counting mode using RCA C31034 GaAs photomultiplier detector system and SPEX DMI DATAMATE spectrometer controller and data processor. The radiation of wavelength 514.5 nm from the Argon-ion laser (Spectra Physics model 165-B) ltered through the SPEX Lasermate, was allowed to fall on the sample in a line focus geometry (approximately 1 cm 0.005 cm area) achieved with the help of a cylindrical lens. The intensity of the

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radiation incident on the sample was 250 mW. The scattered radiation was collected and focused onto the spectrometer using a Minolta camera lens (55 mm, f/1.2). The polarization of the incident radiation was kept in the horizontal plane. The actual position, intensities and the width of the various Raman bands were measured after a light smoothing of the raw data by using the in-built software of DM 1 processor. The ultimate resolution at the wide exit slit was better than 72 cm1. The thickness of lms were determined by Talystep prolometer (Taylor Hobson).

3. Results and discussion In HW-CVD, the silane ow rate is an important parameter because of high deposition rate a-Si:H thin lms. If the silane ow is too low, the environment near the hot lament becomes depleted of silane which reduces the catalytic reaction due to limited supply of silane and hence deposition rate decreases. If the silane ow rate is too high, there is possibility of radicalradical reaction, which leads to a deterioration of lm properties. Thus, optimum supply of silane is necessary to obtain device quality a-Si:H lms at high deposition rate by HW-CVD technique. 3.1. Variation of the deposition rate The variation of deposition rate (rd) plotted as a function of silane ow rate FSiH4 is shown in Fig. 1. All lms were deposited for a xed period of time, i.e. 10 min. The deposition rate was then calculated by thickness measurements. As seen ( from the gure, the deposition rate increases from 12 to 29 A s1 as silane ow rate increases from 5 to 30 sccm. The increase in deposition rate with increase in silane ow rate is due to following reasons: With increase in silane ow rate, the silane partial pressure and hence density of SiH4 molecules in the deposition chamber increases. This increases the impingement of SiH4 molecules on the hot lament and as a result the SiH4 decomposition increases. This increases the number of lm forming radicals. So, deposition rate increases with increase in the silane ow rate. The density of SiH4 molecules can also be increased by increasing the deposition pressure. Hence, we have deposited several lms with dierent chamber pressure keeping the silane ow rate constant. The variation of deposition rate as a function of chamber pressure is as shown in the inset of Fig. 1. The deposition rate continuously increases with increase in chamber pressure. This is clearly due to the increase of SiH4 molecules in the chamber. This supports the above interpretation. Thus, with increase in silane ow rate, the density of SiH4 molecules and hence the deposition rate increases. 2. Increase in the silane ow rate increases the dwell time of the radicals and as a result the mean free path of the lm forming radicals decreases. This increases 1.

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Fig. 1. Variation of deposition rate rd as a function of silane ow rate FSiH4 : The inset shows the variation of deposition rate as a function of chamber pressure.

the number of secondary gas phase reactions and reaction products. The atomic H generated from the hot lament is depleted through secondary gas phase reactions. As a result, the concentration of atomic H decreases. This reduces the etching eect of growing material and hence, overall deposition rate increases with increase in silane ow rate. The increase in deposition rate with silane ow rate in a-Si:H lms deposited by HWCVD has been observed earlier by other groups [9,10]. 3.2. Variation of hydrogen content The Fourier transform infrared (FTIR) spectra of a-Si:H lms deposited by HW-CVD at dierent silane ow rate FSiH4 is shown in Fig. 2. As seen from the spectra, the lm deposited at FSiH4 =5 sccm has major IR absorption bands near

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Fig. 2. H-related features of the FTIR spectra for a-Si:H lms deposited at dierent silane ow rates FSiH4 :

2000 and 618 cm1 which correspond, respectively, to stretching and wagging modes of local vibrations of mono-hydrogen (SiH) bonded species [14]. However, a-Si:H lms deposited at higher silane ow rates FSiH4 > 5 sccm show similar bands with additional vibrational bands near 2080 and 880 cm1 which correspond, respectively, to stretching and bending vibrational modes of di-hydrogen (SiH2) bonded species and (SiH2)n complexes (isolated or coupled) [15]. Also, as seen from the FTIR spectra the absorption of 2080 and 880 cm1 bands enhances with increasing the silane ow rate. Therefore, it is clear that the di-hydrogen (SiH2) bonded species in a-Si:H lms deposited by HW-CVD increases with increase in silane ow rate. Thus, it is concluded that the hydrogen bonding in HW-CVD deposited a-Si:H lms shifts from mono-hydrogen (SiH) to di-hydrogen (SiH2) and (SiH2)n complexes, when the lms are deposited at higher silane ow rate or deposited at higher deposition rate. Silane ow rate of 5 sccm appears to be an optimum ow rate for the growth of mono-hydrogen (SiH) bonded species in hydrogenated amorphous silicon at high ( deposition rate (12 A s1).

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Fig. 3. Variation of hydrogen content CH ) for a-Si:H lms deposited at dierent silane ow rates FSiH4 :

Fig.(3) shows the variation of total hydrogen content (CH ) with silane ow rate FSiH4 : The CH in all lms is found to be less than 10 at% over the range of silane ow rate studied. It monotonically increases from 4.25 to 9.21 at.% as FSiH4 increases from 5 to 30 sccm. For the deposition of a-Si : H thin lms by HW-CVD, we used a low pressure (20 mTorr) of SiH4 and lament temperature of 19001C. At this temperature, SiH4 can be very eectively decomposed into atomic silicon and atomic hydrogen. One SiH4 molecule when decomposed on the hot lament produces one Si and four H atoms via reaction [8], SiH4 Hot wire Tfil 19001C-Si 4H: These radicals are primary radicals available for the lm growth. Hence, only monohydrogen (SiH) bonding conguration is expected for low silane ow rate. However, with increasing silane ow rate, these primary radicals reach the substrate

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with the probability of gas phase collision with ambient SiH4 molecule [7]. Since Si and H are highly reactive SiH4 [11], they react with the ambient of SiH4 molecules forming secondary long lived, hydrogen rich species like SiH2, SiH3 etc., which further contribute to the lm growth [1618]. As mentioned earlier, with increasing silane ow rate, the probability of radicalradical reaction will also enhance. The radicalradical reaction products will also contribute to higher silane species like Si2H6 [19] and consequently HSiSiH3+H2 or SiH2+SiH4 [20] to the lm growth. Therefore, increasing the silane ow rate increases the total hydrogen content in the lm. 3.3. Raman spectroscopic studies Fig.4 shows the Raman spectra of lms deposited at dierent silane ow rate FSiH4 by HW-CVD. The Raman spectra are characteristic of a-Si:H over the entire range of silane ow rates studied. The increase in the silane ow rate is found to modify TA vibrational region of the Raman spectra. The Raman spectra indicate increase in the Rayleigh scattering with increase in silane ow rate. The increase in the Rayleigh scattering can be attributed to increase in void size and void density in

Fig. 4. The Raman spectra of a-Si:H lms deposited at dierent silane ow rates FSiH4 :

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the lm [21]. The FWHM of TO peak is a measure of bond angle distribution and therefore allows a quantitative measure of disorder in the lm [22]. It is estimated from doubling the value measured from the peak to the half intensity at high frequency side of TO band, which is free from the intensity of LO band. The variation of TO peak position oTO and its full width at half maximum GTO are plotted as a function of silane ow rates FSiH4 in Fig. 5a and 5b, respectively. The TO peak position shifts from 480 to lower frequency 466 cm1 and GTO increase from 55.5 to 69.0 cm1 as silane ow rates increase from 5 to 30 sccm. Variation of bond angle Dy as a function of silane ow rate FSiH4 is shown in Fig. 5c. It is seen that Dy also increases from 6.751 to 9.001 as FSiH4 increases from 5 to 30 sccm. These results show that the structural disorder Dy in the lms increases with increase in silane ow rate. As mentioned earlier, the hydrogen bonding conguration in a-Si:H lms deposited by HW-CVD shifts from mono to di-hydrogen with increase in silane ow rate which increases the void size as well as density of voids in the lm [21]. These voids are expected to enhance the Rayleigh scattering, which is seen to overlap with TA band positioned at 100150 cm1. The increase in silane ow rate increases the size of the void and shifting of hydrogen bonding from mono-hydrogen to dihydrogen which is expected to modify the ring structure of the a-Si:H aecting the LALO scattering [22,23]. Thus, increase in silane ow rate changes ring statistics as well as increases the structural disorder Dy which induces increased strain in a-Si:H lms. Therefore, it is concluded that a-Si:H lms deposited at higher silane ow rates or higher deposition rates by HW-CVD show increase in structural disorder and density of voids. 3.4. Variation in the optical band gap The optical band gap Eopt for a-Si:H produced at dierent silane ow rates FSiH4 is shown in Fig. 6. The optical band gap increases with increase in silane ow rate. It is minimum B1.62 eV for ow rate FSiH4 =5 sccm which increases to B1.75 eV for ow rate FSiH4 =30 sccm. We attribute increase in Eopt to increase in the CH in the lms (see Fig. 3) and increase in the density of voids due to the Rayleigh scattering (see Fig. 5). The incorporation of hydrogen in a-Si network aects the band gap in two ways. Firstly, increase in hydrogen content causes a chemical shift of the valance band states to the lower state. This widens the band gap. In PCVD, almost linear relationship between total hydrogen content CH and band gap Eopt has been reported by Cody et al. [24]. Secondly, the incorporation of hydrogen in a-Si network relieves the strain and improves the structural order [25]. This reduces the tail state density, resulting in widening the band gap [26]. However, we observed increase in structural disorder with increase in the silane ow rate or increase in the hydrogen content in the lm. Hence, we suggest only number of SiH bonds cannot account for increase in band gap. We think that the increase in the Eopt may be due to the increase in the voids. As seen from the Raman spectra (Fig. 5), the Rayleigh scattering increases with increase in the silane ow rate. The increase in the Rayleigh scattering is due to increase in void size and void density in the lm [21]. The voids reduce the eective density of material and increases the average SiSi

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Fig. 5. Variation of: (a) TO peak position oTO ), (b) full width at half maximum of TO peak GTO ); and (c) bond angle deviation Dy as a function of silane ow rates FSiH4 :

distance, which is responsible for increase in the band gap [7]. The SAXS measurements by Mahan et al. [27] and recently NMR experiments by Wu et al. [28] have shown that HW-CVD grown material has a higher void fraction than PCVD grown materials.

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Fig. 6. Variation of band gap Eopt ) of a-Si:H lms deposited at dierent silane ow rates FSiH4 :

3.5. Variation in dark conductivity and photoconductivity The variation of the dark conductivity sDark and photoconductivity sPhoto ) are shown as a function of silane ow rate FSiH4 in Fig. 7. As seen from the gure, the dark conductivity increase by more than two orders of magnitude (5.7 1010 S cm1osDark o1.4 108 S cm1) when silane ow rate increases from 5 to 30 sccm. The photoconductivity shows a decreasing trend (2.3 104 S cm o sPhoto o 3.6 105 S cm1) with increase in silane ow rate. These results suggest that the defect density in the forbidden gap increases with increase in silane ow rate. As a result, the photosensitivity decreases from 4.03 105 to 2.57 103, when FSiH4 increased from 5 to 30 sccm. Variation of photosensitivity with silane ow rate is shown in Fig. 8. As FSiH4 increases, the number of gas phase reactions and products also increase. By gas phase reactions, more mobile gas species are created. The increase in the dark conductivity with increase in saline ow rate can be attributed to

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Fig. 7. Variation of dark conductivity sdark ) and photoconductivity sPhoto ) as a function of silane ow rates FSiH4 :

this eect. From the FTIR spectra (Fig. 2), it is seen that with increase in silane ow rate the hydrogen incorporated in a-Si:H lms is predominantly in di-hydrogen conguration. As a result, the large number of dangling bonds remain unsaturated. These dangling bonds act as ecient trapping or recombination centers. Consequently, the photoconductivity decreases. Also, at higher silane ow rate, the probability of radicalradical reaction increases which deteriorates the lm properties and hampers the photoconductivity.

4. Conclusions An attempt has been made to ascertain the role of the silane ow rate on the electrical, optical and structural properties of a-Si:H lms deposited by HW-CVD.

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Fig. 8. Variation of photoconductivity (sPhoto= sdark ) as a function of silane ow rates FSiH4 :

We have demonstrated that device quality a-Si:H lms with low hydrogen contents and high growth rate can be achieved by HW-CVD method. The device quality a-Si:H lms with a photosensitivity >105 were deposited by ( HW-CVD at a deposition rate >10 A s1 using low silane ow rates. However, a-Si:H lms deposited at higher silane ow rate and/or higher deposition rates show degradation in their structural and electrical properties. The hydrogen bonding in a Si:H lms shifts from mono-hydrogen (SiH) to di-hydrogen FSiH4 conguration when the lms deposited at higher silane ow rate or deposited at higher deposition rate. The hydrogen content in the a-Si:H lms deposited at dierent silane ow rates were found to be less than 10 at.%. The Raman spectra show increase in disorder and the Rayleigh scattering with increase in silane ow rate. The increase in the Rayleigh scattering is an indication of increase in void size and void density in the aSi:H lms. The optical band gap also shows an increasing trend with silane ow rate. Therefore, only hydrogen content cannot account for the increase in the optical band gap. We think that the increase in the optical band gap may be due to the increase in the voids. These voids reduce the eective density of material and increase the average SiSi distance, which is responsible for the increase in the band gap. The a-Si : H lms deposited at higher silane ow rates show degradation of electrical properties. Silane ow rate of 5 sccm appears to be an optimum ow rate for the growth of mono-hydrogen (SiH) bonded species having low hydrogen content (B4.25 at.%) ( in a-Si:H lms at high deposition rate (B12.5 A s1), high photosensitivity (B105) and small structural disorder.

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Acknowledgements The authors gratefully acknowledge Dr. B.R. Marathe for useful discussions. The author SRJ acknowledges nancial support from University Grants Commission, Govt. of India, for teacher fellowship under IX plan. DVM acknowledges nancial support from Council for Scientic and Industrial Research (CSIR), Govt. of India.

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