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Available online at www.sciencedirect.com Thin Solid Films 516 (2008) 6989 – 6993 www.elsevier.com/locate/tsf

Available online at www.sciencedirect.com

Available online at www.sciencedirect.com Thin Solid Films 516 (2008) 6989 – 6993 www.elsevier.com/locate/tsf

Thin Solid Films 516 (2008) 6989 6993

Thin Solid Films 516 (2008) 6989 – 6993 www.elsevier.com/locate/tsf Structural and electrical

www.elsevier.com/locate/tsf

Structural and electrical properties of epitaxial Si layers prepared by E-beam evaporation

P. Dogan , E. Rudigier, F. Fenske, K.Y. Lee, B. Gorka, B. Rau, E. Conrad, S. Gall

Hahn-Meitner-Institut Berlin, Kekuléstr. 5, 12489 Berlin, Germany

Available online 15 December 2007

Abstract

In this work, we present structural and electrical properties of thin Si films which are homoepitaxially grown at low substrate temperatures ( T s = 450700 °C) by high-rate electron beam evaporation. As substrates, monocrystalline Si wafers with (100) and (111) orientations and polycrystalline Si (poly-Si) seed layers on glass were used. Applying Secco etching, films grown on Si(111) wafers exhibit a decreasing etch pit density with increasing T s . The best structural quality of the films was obtained on Si(100) wafers. Defect etching on epitaxially grown poly-Si absorbers reveal regions with different crystalline quality. Solar cells have been prepared on both wafers and seed layers. Applying Rapid Thermal Annealing (RTA) and Hydrogen plasma passivation an open circuit voltage of 570 mV for wafer based and 346 mV for seed layer based solar cells have been reached. © 2007 Elsevier B.V. All rights reserved.

Keywords: Crystalline silicon; Secco etching; Extended defects; Low temperature epitaxy

1. Introduction

Large grained polycrystalline silicon (poly-Si) on glass is a potential candidate for high efficiency, low cost Si thin film solar cells. One approach to realise such solar cells is based on the epitaxial thickening of a poly-Si seed layer (template) pre- pared by Aluminum Induced Crystallisation (AIC) of a-Si. [1]. Due to the thermal requirements of glass substrate, the epitaxial growth needs to be applied with low thermal budget processes, which still remains as an important challenge. Epitaxial thick- ening of a seed layer at such low temperatures was obtained by Electron Cyclotron Resonance Chemical Vapour Deposition (ECRCVD) [2] , Ion Assisted Deposition (IAD) [3] and Layered Laser Crystallization (LLC) [4]. This paper deals with the investigation of epitaxially grown Si films prepared by high-rate electron beam evaporation under non-ultra high vacuum conditions. The effects of the deposition parameters are mainly investigated on epitaxial Si films grown on Si wafers (ideal seed layers).

Corresponding author. Tel.: +49 30 8062 1392; fax: +49 30 8062 1333. E-mail address: pinar.dogan@hmi.de (P. Dogan).

0040-6090/$ - see front matter © 2007 Elsevier B.V. All rights reserved.

2. Experimental procedure

As substrates, monocrystalline Si(100) and Si(111) wafers and poly-Si seed layers on glass have been used. The 200 nm thick p + -type poly-Si seed layers have been grown on Borofloat glass substrates (0.7 mm) by using the AIC process [5]. Prior to the absorber layer growth, the substrates have been cleaned by a standard RCA procedure and finally the native silicon oxide is removed by 2% HF (30 s). The absorber layers were grown by evaporating high purity (FZ quality) Si with an e-gun at rates of 60 150 nm/min to a film thickness of 1.5 2 μ m. The p-type doping was realized by coevaporation of boron from a high temperature effusion cell. The base pressure was in the range of 10 6 Pa and the residual gas pressure during deposition was around 10 4 Pa. No additional post ionization stage has been used, and the substrates were held at ground potential. The substrate temperature has been varied in the range of T s = 450 700 °C. For the extended defect analysis, Si films have been Secco- etched for 10 s and then investigated by a Scanning Electron Microscopy (SEM) [6] . For the Raman measurements a micro- Raman spectrometer DILOR/ISA LabRAM 010 in back-

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scattering configuration equipped with an unpolarized HeNe laser for excitation (wavelength 632.82 nm, spectral resolution 1 cm 1 ) was used. With this wavelength the epi-layer as well as the highly doped wafer will have a contribution to the Raman signal. For Hall effect measurements performed at room temperature, p-type Si layers have been grown on n-type Si (100) ( N 3 k Ω cm) wafers. Ohmic contacts were prepared by thermal evaporation of gold (300 nm). Two types of solar cells in the substrate configuration have been prepared with the following structure (Fig. 1 (a)): p + -Si (100) wafer (2 mΩ cm) or (b) 200 nm thick p + -type poly-Si seed layer on glass/epitaxially grown p-type Si absorber (1500 2000 nm) / n + -type a-Si:H emitter (10 nm)/TCO (80 nm ZnO:

Al)/Al contacts. For the deposition of the a-Si:H emitter Plasma Enhanced Chemical Vapour Deposition (PECVD) was used. The ZnO:Al films were deposited by sputtering. Prior to the emitter deposition, Rapid Thermal Annealing (RTA) and hydrogen plasma passivation have been applied. First, the samples were annealed at 850 °C for 100 s under nitrogen atmosphere. Later, the hydrogen plasma passivation has been performed in a vacuum chamber equipped with a hollow- cathode plasma source and a lamp radiation heater. The samples were treated at 520 °C for 10 min using a plasma power density of 0.1 W/cm 2 . The total area of the solar cells was 4 mm × 4 mm with a mesa or an interdigitated contacting scheme for wafer based and seed layer based solar cells, respectively. For the solar cell characteristics active areas were used. The active areas were 10.65 mm 2 (mesa), and 7.44 mm 2 (interdigitated), respectively. For the measurement of glass based solar cells a white back reflector is used. The solar cells were characterized by current- voltage measurements under AM 1.5 illumination, 100 mW/ cm 2 , 25 °C.

under AM 1.5 illumination, 100 mW/ cm 2 , 25 °C. Fig. 1. Schemes of (a)

Fig. 1. Schemes of (a) Si (100) wafer based and (b) large grained poly-Si seed layer (on glass) based solar cells that have been used in this study.

3. Results and discussion

In this section, the results of the variation of T s on the epita- xially grown Si layers are presented as structural properties, electrical properties and solar cell characteristics.

3.1. Structural properties

The epitaxial Si layers have been grown on monocrystalline Si(100) and Si (111) wafers at T s = 450 700 °C. Secco etch was used to reveal the extended defects in the epitaxially grown layers. The films grown on Si(100) wafers exhibit no charac- teristic etch pits, indicating the good quality epitaxial growth on these substrates (not shown here). However in our previous work characteristic etch pits on films grown on Si(110) and Si (111) wafers have been reported, and the strong influence of underlying crystallographic orientation of the substrate on the extended defect density have been discussed [7] . In this work, to investigate the effect of T s on the extended defect density, films grown on Si(111) wafers have been analysed. The results are illustrated in Fig. 2 . The etch pits in the form of triangles are caused by stacking faults [8] . The stacking faults are formed along the (111) planes resulting in an inverted equilateral triangular pyramid in the epitaxial layers. These triangles on the sample surface correspond to the base plane of this tetrahedron. From the length of these triangles, it is analysed that most of the defects are created at the substrate/epitaxial film interface. The strong influence of T s on the etch pit density is also clearly visible. The etch pit density decreases by increasing T s , which corresponds to an enhancement of the structural quality of the films. At T s 550 °C, the etch pit density is above 10 8 cm 2 , meaning that not enough thermal energy has been supplied for high quality epitaxial growth. However the etch pit density decreases dramatically for T s 600 °C. In contrast to our pre- vious report [7] , the etch pit density could be further decreased at elevated temperatures of 650 700 °C. We attribute this to a better conditioning of the system prior to the deposition. In conclusion, the lowest etch pit density is observed at highest T s values, meaning that the best epitaxial growth is obtained at these temperatures. In addition, some micro roughness of the sample surface has been observed at these high temperatures, but the reason is not yet understood. The Raman spectra have been recorded for the epitaxial silicon layers grown on Si(100) wafers at T s = 450 700 °C. As an example in Fig. 3 a the spectra for the samples grown at T s = 500 and 650 °C together with a crystalline Si wafer (reference) are plotted. The measured intensities are normalised. The posi- tion of the dominant Raman peak for crystalline Si, the LO TO phonon mode, is at around 520 cm 1 . The spectra of the films exhibit the same peak position and the curve shape that is characteristic for crystalline Si. This confirms the epitaxial film growth. In Fig. 3 b the Full Width at Half Maximum (FWHM) of the Raman spectra is plotted as a function of T s . To determine the FWHM of the phonon line a Lorentzian has been used as fitting procedure. The spectral width is interpreted in terms of phonon confinement, i.e., it is a measure for the density of defects in the films, as these determine the unperturbated pho-

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et al. / Thin Solid Films 516 (2008) 6989 – 6993 6991 Fig. 2. SEM images

Fig. 2. SEM images of Secco-etched surfaces of the Si films grown on Si(111) wafers at T s = 450700 °C. The Si films grown on (100) oriented Si wafers have shown no etch pits in this temperature range.

non propagation. No clear correlation between the FWHM and T s has been obtained. However, FWHM values of between 3.7 and 3.9 cm 1 have been calculated for the whole temperature

− 1 have been calculated for the whole temperature Fig. 3. Raman spectra of the Si

Fig. 3. Raman spectra of the Si films grown on Si(100) wafers at T s = 500 and 650 °C together with reference c-Si wafer (a) and their corresponding FWHM for T s = 450700 °C (b).

range. The FWHM value of a bare Si wafer is around 3.0 cm 1 , which is still much lower than the obtained values for the films. Even though no etch pits could be observed on films grown on Si (100) wafers after Secco etching in the SEM images, it can be concluded from the Raman measurements that the structural properties of the films are perturbated. An SEM image of the film grown at T s = 600 °C on a seed layer after Secco etching is shown in Fig. 4 a and b. Fig. 4 b is the image of grain 1 marked in Fig. 4 a in a bigger magnification. From the first figure it is seen that while some of the grains exhibit better quality epitaxial growth, some other grains exhibit a more defective growth. The area of the more defectively grown grains corresponds to about 40% of the total area of the sample surface analysed by the optical light microscope. From Electron Backscattering Deflection (EBSD) analysis on our poly-Si seed layers [9], we know that about 60% of the grains feature a preferential (100) orientation, which is favourable for epitaxial thickening at low temperatures. This means that the more defective regions (40% of the total area) are probably related to underlying grains with orientations towards (110) and (111). From Fig. 4 b it is also seen that even less defectively grown grains exhibit dislocations (circular pits in the figure). These circular etch pits are characteristic of Si(100) dislocations. These defects indicate that the intra grain defects which are already present in the seed layer, at the seed layer/epitaxial film interface or the defects generated in the bulk of epitaxial layer can lead to a defective epitaxial growth.

3.2. Electrical properties

Fig. 5 shows the free carrier concentration (circles) and the mobility of majority carriers (triangles) determined by Hall effect measurements as a function of T s in the p-type Si films grown on Si (100) wafers at T s = 450700 °C . The free carrier concentration is about 68× 10 16 cm 3 at T s 600 °C. Below T s =600 °C, the free carrier concentration drops down to 3× 10 16 cm 3 . In a previous

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P. Dogan et al. / Thin Solid Films 516 (2008) 6989 – 6993 Fig. 4. SEM

Fig. 4. SEM image of a Secco-etched Si film grown on a poly-Si seed layer at T s = 550 °C (a), and grain 1 marked in Fig. 4 a in a bigger magnification (b).

report [10], we measured the atomic concentration of boron in the epitaxial layers by Secondary Ion Mass Spectroscopy (SIMS) and the free carrier concentration by Hall effect and CapacitanceVoltage (CV) measurements for T s = 600 °C. There it has been shown that at T s =600 °C the doping efficiency is almost unity, meaning that all the incorporated boron was fully electrically activated. From this result we can conclude, that in this work, at lower T s , the free carrier concentration decreases because of a less incorporation of boron on lattice sites. The fluctuations of the free carrier concentration at higher temperatures can be attributed to slight variations of the deposition rate.

be attributed to slight variations of the deposition rate. Fig. 5. Free carrier concentration (circles) and

Fig. 5. Free carrier concentration (circles) and Hall mobility of holes (triangles) as a function of T s in the range 450700 °C measured on the films grown on Si (100) wafers.

The majority carrier mobility is also plotted as a function of T s in Fig. 5 . The mobility of holes is below 160 cm 2 /Vs for the low temperature regime (T s = 450 °C). For T s 500 °C, the mobility increases to about 200 cm 2 /Vs and stays constant for the higher temperature regime. The small fluctuations of mo- bility are attributed to the changes in the deposition rate and so in the free carrier concentration. This value of mobility is still too less compared to a theoretical value of 300 cm 2 /Vs of a perfect crystalline Si within the dopand impurity concentration range of the samples and indicates scattering by defect centers present in the films [11] .

3.3. Solar cells

The solar cells have been prepared on both Si(100) wafers and poly-Si seed layers on glass. To improve the quality of the epi-Si absorber layer post deposition treatments (RTA and Hydrogen plasma passivation) have been applied. Fig. 6 shows the solar cell efficiency as a function of T s (on Si(100) wafer substrates). As it is seen the solar cell efficiency increases with increasing T s , which is in agreement with the structural and electrical measurements that have been investigated. The effi- ciency increases from 4.4% at T s = 450 °C to about 5.8% at T s = 650 700 °C. Fig. 7 illustrates the current-voltage characteristics of a wafer based solar cell deposited at T s = 650 °C with an absorber layer thickness of 1.8 µm (with mesa contacting scheme) together with the best Si thin-film solar cell on glass (of this invest- igation) deposited at T s = 550 °C with an absorber layer thick- ness of 2 µm (with interdigitated contacting scheme). Due to the softening point of glass substrate at 600 °C, no solar cells on glass could be prepared for the temperatures of 650 and 700 °C. The best cell is obtained at 550 °C instead of 600 °C mainly due to thicker absorber that affects the short circuit density and so the efficiency. The wafer based solar cell is the best solar cell so far obtained on Si(100) wafer. The efficiency of 5.86% has been reached with an open circuit voltage of 570 mV, a short circuit current density of 13.28 mA/cm 2 and a fill factor of 75.92%. On the

of 13.28 mA/cm 2 and a fill factor of 75.92%. On the Fig. 6. Active area

Fig. 6. Active area solar cell efficiency as a function of T s in the range 450 700 °C measured on the films grown on Si(100) wafers.

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et al. / Thin Solid Films 516 (2008) 6989 – 6993 6993 Fig. 7. Active area

Fig. 7. Active area current density versus voltage of solar cells (a) with an epi-Si film thickness of 1.8 µm on Si(100) wafer grown at T s = 650 °C (solid line), (b) with an epi-Si film thickness of 2 µm on poly-Si seed layer on glass grown at T s = 550 °C (dashed line).

same sample measured from a 10 × 10 mm 2 cell, similar results have been also obtained. This result indicates that material quality is homogeneous over the total sample surface. The seed layer based solar cell features an efficiency of 2.28%, an open circuit voltage of 346 mV, a short circuit current density of 11.49 mA/cm 2 , and a fill factor of 57.58%. The short circuit current density of poly-Si solar cell of about 11 mA/cm 2 is almost 70% of the theoretical limit of about 16 mA/cm 2 (without light trapping) for a 2 µm thick absorber layer [12] . However, the open circuit voltage of 346 mV of poly-Si solar cell is still much lower compared to 570 mV of Si(100) wafer based solar cell. Similarly, comparison of 57.58% fill factor of poly-Si solar cell to 75.92% fill factor of Si (100) wafer based solar cell shows the difference in the material quality. These results show that the material quality of poly-Si sample needs to be further improved by tuning the deposition parameters and by optimising the post deposition treatments.

4. Conclusions

Using electron beam evaporation, the effect of substrate temperature on the structural and electrical properties of the epitaxially grown Si films on ideal seed layers (Si (100) and Si (111) wafers) and on poly-Si seed layers on glass have been investigated. The best structural quality has been obtained for the films grown on Si (100) wafers. No extended defects have been observed for these films at T s = 450 700 °C. However, the films grown on Si (111) wafers have shown typical etch pits. It is found that the extended defect density decreases as the subs- trate temperature increases. From the Raman measurements, it has been seen that the epitaxially grown Si films exhibit pertur- bation of the crystal structure. The films grown on poly-Si seed layers on glass have shown that about 60% preferentially (100)

oriented grains exhibit a good quality epitaxial growth, where as the rest 40% shows a more defective growth. Also the intra grain defects have been observed. These results show that the substrate temperature and the underlying crystallographic orientation play a crucial role on the low temperature epitaxy. Hall effect measurements on the epitaxially grown p-type Si films have shown that the free carrier concentration decreases at T s b 600 °C, meaning that not all the incorporated boron is electrically activated. The mobility of the majority carriers is limited to 200 cm 2 /Vs, probably due to scattering by defect centers present in the films. Finally solar cells have been pre- pared. The efficiencies of 5.86% and 2.28% have been reached for solar cells on Si(100) wafers and on poly-Si seed layers on glass, respectively, (after applying RTA and H passivation). E- beam evaporation can be a promising method for producing thin film solar cells on poly-Si seed layers at low temperatures. However, the seed layer properties and the epitaxial growth parameters need to be improved to make the growth of device grade solar cells possible.

Acknowledgements

The authors would like to thank S. Common, M. Muske, L. Scheller, K. Jakob and C. Klimm from HMI for the sample preparation and technical support. This work has been support- ed by the FP6 research project ATHLET (Contract No. 019670- FP6-IST-IP) and by the company Von ARDENNE Anlagen- technik GmbH.

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