Hydrogen passivation and junction formation on APIVT-deposited thin-layer silicon by hot-wire CVD

The hot-wire chemical vapor deposition (HWCVD) technique was employed to deposit μc-Si emitters and a-SiN_x:H passivation/antireflection films, and to hydrogenate silicon thin layers grown by atmospheric-pressure iodine vapor transport (APIVT). Photovoltaic devices with HWCVD μc-Si emitters on APIVT epitaxial silicon exhibit greater than 8% efficiency, similar to those made with diffused junctions. On polycrystalline APIVT-Si layers, a HWCVD-deposited μc-Si emitter reduces open-circuit voltage loss caused by grain boundaries. Hot-wire hydrogenation improves Hall mobility by approximately 50%. HWCVD a-SiN_x:H films improve minority-carrier lifetime significantly after thermal annealing at temperatures up to 500 °C.     

Structural changes studies of a-Si:H films deposited by PECVD under different hydrogen dilutions using various experimental techniques

Plasma enhanced chemical vapour deposition (PECVD) has been used to prepare hydrogenated amorphous silicon (a-Si:H) thin films at different hydrogen dilution of silane source gas. The films were deposited on Corning glass 1737 substrate and on (100) oriented c-Si wafers and characterized by XRD diffraction, micro-Raman and FTIR spectrometry. Experimental data show evolution from amorphous to nanocrystalline silicon and contain the medium-range order (MRO) with varying hydrogen dilution during deposition. From X-ray diffraction and Raman analysis, it is found that the presence of crystalline phase depends on the kind of substrate and on the dilution scale.     

Microstructure characterization of microcrystalline silicon thin films deposited by very high frequency plasma-enhanced chemical vapor deposition by spectroscopic ellipsometry

We applied ex situ spectroscopic ellipsometry (SE) on silicon thin films across the a-Si:H/μc-Si:H transition deposited using different hydrogen dilutions at a high pressure by very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD). The optical models were based on effective medium approximation (EMA) and effective to estimate the thickness of the amorphous incubation layer and the volume fractions of amorphous, microcrystalline phase and void in μc-Si:H thin films. We obtained an acceptable data fit and the SE results were consistent with that from Raman spectroscopy and atomic force microscopy (AFM). We found a thick incubation layer in μc-Si:H thin films deposited at a high rate of ~ 5 Å/s and this microstructure strongly affected their conductivity.     

Effects of dilution ratio and seed layer on the crystallinity of microcrystalline silicon thin films deposited by hot-wire chemical vapor deposition

We deposited microcrystalline silicon (μc-Si) by hot-wire chemical vapor deposition (HWCVD) at different thickness and dilution ratio, with and without seed layer. As the dilution ratio increased, we observed an increase in the amount of microcrystalline phase in the film, a change in the structure of the grains and a loss of the (220) preferential orientation. The films deposited over a seed layer had a larger fraction of crystalline phase than films deposited with the same parameters but without a seed layer. For high dilution ratios (R=100), most of the film grows epitaxially at the interface with the Si substrate, but a microcrystalline film slowly replaces the single-crystal phase. For low dilution ratios (R=14), the film starts growing mostly amorphously, but the amount of crystalline phase increases with thickness.     

Interpretation of the hydrogen evolution during deposition of microcrystalline silicon by chemical transport

Hydrogen diffusion is a crucial step in film growth by chemical vapor deposition of both hydrogenated amorphous silicon (a-Si:H) and hydrogenated microcrystalline silicon (µ-Si:H) materials. To gain an insight into the correlation between hydrogen diffusion and the amorphous to microcrystalline transition, we have exposed freshly deposited intrinsic, boron- and phosphorus-doped a-Si:H thin films to hydrogen (or deuterium) plasma in conditions of µc-Si:H deposition by chemical transport. Using both in-situ and ex-situ characterizations techniques, we examined the kinetics of hydrogen excess evolution during the plasma exposure. Solution of the partial differential equation for the diffusion of mobile H atoms with a specific boundary condition that accounts for the reduction of atomic H flux with the growth of the µc-Si:H layer supports the theory that the out-diffusion is a consequence of the growth of the µc-Si:H layer.     

Microcrystalline silicon films fabricated by bias-assisted hot-wire chemical vapor deposition

Microcrystalline silicon films (μc-Si:H) were deposited on stainless steel substrates by bias-assisted hot-wire chemical vapor deposition. The effect of substrate bias and substrate temperature on the crystallinity of μc-Si:H films was studied by Raman spectroscopy, X-ray diffraction and scanning electron microscopy. The results show that both the Raman peak position and the crystalline fraction of the μc-Si:H films deposited at 200 °C were obviously improved by introducing ?800 V substrate bias. The films deposited at 200 °C with ?800 V substrate bias show strongly sharpened Si (111) peak together with Si (220) and Si (311) peaks, which was different from a weak Si (111) peak for those deposited without substrate bias. By increasing the substrate temperature from 200 to 300 °C, while keeping the substrate bias at ?800 V, the crystallinity of the silicon films was further improved, and μc-Si:H films with crystalline fraction of 74 % was obtained.     

Cat-CVD-prepared oxygen-rich μc-Si:H for wide-bandgap material

Microcrystalline phase-involved oxygen-rich a-Si:H (hydrogenated amorphous silicon) films have been obtained using catalytic chemical vapor deposition (Cat-CVD) process. Pure SiH₄ (silane), H₂ (hydrogen), and O₂ (oxygen) gases were introduced in the chamber by maintaining a pressure of 0.1 Torr. A tungsten catalyzer was fixed at temperatures of 1750 and 1950 °C for film deposition on glass and crystalline silicon substrates at 200 °C. As revealed from X-ray diffraction spectra, the microcrystalline phase appears for oxygen-rich a-Si:H samples deposited at a catalyzer temperature of 1950 °C. However, this microcrystalline phase tends to disappear for further oxygen incorporation. The oxygen content in the deposited films was corroborated by FTIR analysis revealing SiOSi bonds and typical SiH bonding structures. The optical bandgap of the sample increases from 2.0 to 2.7 eV with oxygen gas flow and oxygen incorporation to the deposited films. In the present thin film deposition conditions, no strong tungsten filament degradation was observed after a number of sample preparations.     

Intrinsic microcrystalline silicon prepared by hot-wire chemical vapour deposition for thin film solar cells

Microcrystalline silicon (μc-Si:H) prepared by hot-wire chemical vapour deposition (HWCVD) at low substrate temperature T_S and low deposition pressure exhibits excellent material quality and performance in solar cells. Prepared at T_S below 250 °C, μc-Si:H has very low spin densities, low optical absorption below the band gap, high photosensitivities, high hydrogen content and a compact structure, as evidenced by the low oxygen content and the weak 2100 cm⁻¹ IR absorption mode. Similar to PECVD material, solar cells prepared with HWCVD i-layers show increasing open circuit voltages V_oc with increasing silane concentration. The best performance is achieved near the transition to amorphous growth, and such solar cells exhibit very high V_oc up to 600 mV. The structural analysis by Raman spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM) shows considerable amorphous volume fractions in the cells with high V_oc. Raman spectra show a continuously increasing amorphous peak with increasing V_oc. Crystalline fractions X_C ranging from 50% for the highest V_oc to 95% for the lowest V_oc were obtained by XRD. XRD-measurements with different incident beam angles, TEM images and electron diffraction patterns indicate a homogeneous distribution of the amorphous material across the i-layer. Nearly no light induced degradation was observed in the cell with the highest X_C, but solar cells with high amorphous volume fractions exhibit up to 10% degradation of the cell efficiency.     

氢稀释比与衬底温度对硅基薄膜相变及其光电性能影响的研究

采用热丝辅助微波电子回旋共振化学气相沉积法(HWAMWECR-CVD),通过改变衬底温度及氢稀释比制备了系列硅基薄膜,研究了衬底温度及氢稀释比对薄膜由非晶相转晶相相变及其光电性能的影响。研究结果表明,当采用低温制备硅基薄膜时,衬底温度和氢稀释比的提高都有利于非晶相向晶相的转变,但提高氢稀释比对相变的影响更为显著;晶化比越高并不代表薄膜光电性能越好,95%氢稀释比条件下制备的微晶硅薄膜具有优良的光电性能。     

沉积条件对硅基薄膜非晶转微晶相变、沉积速率及其光电性能的影响(英文)

本文采用HWA-MWECR-CVD系统制备了微晶硅薄膜。研究了氢稀释比、反应压强以及微波功率对微晶硅薄膜非晶转微晶相变及其相关性能的影响。实验结果表明:当氢稀释比为94%、反应压强为1.5Pa以及微波功率为500W时,高质量的微晶硅薄膜可以被获得,如2.86*104的高光敏性,1nm左右的沉积速率以及8.9%的光致衰退速率等。     

Enhancement of thermal conductivity of hydrogenated silicon film by microcrystalline structure growth

Hydrogenated silicon film is fabricated by plasma enhanced chemical vapor deposition method, and the enhancement of thermal conductivity of hydrogenated silicon film by microcrystalline structure growth is investigated. The thermal conductivity of films is measured based on Fourier thermal transmitting law by using platinum electrode. Raman spectroscopy characterization reveals the crystalline volume fraction (X _c) of microcrystalline silicon (μc-Si:H) and demonstrates it is embedded with nanocrystals. Spectroscopic ellipsometry with Forouhi–Bloomer model is used to obtain the thickness of films. The measurement results show that the thermal conductivity of μc-Si:H is much higher than amorphous silicon (a-Si:H).     

High quality microcrystalline Si films by hydrogen dilution profile

Novel hydrogen dilution profiling (HDP) technique was developed to improve the uniformity in the growth direction of μc-Si:H thin films prepared by hot wire chemical vapor deposition (HWCVD). It was found that the high H dilution ratio reduces the incubation layer from 30 nm to less than 10 nm. A proper design of hydrogen dilution profiling improves the uniformity of crystalline content, X_c, in the growth direction and restrains the formation of micro-voids as well. As a result the compactness of μc-Si:H films with a high crystalline content is enhanced and the stability of μc-Si:H thin film against the oxygen diffusion is much improved. Meanwhile the HDP μc-Si:H films exhibit the low defect states. The high nucleation density from high hydrogen dilution at early stage is a critical parameter to improve the quality of μc-Si:H films.     

Effect of hydrogen radical on growth of μc-Si in hetero-structured SiCx alloy films

The changes of the crystallinity of μc-Si phase are studied in samples deposited with hydrogen dilution ratio, H₂/SiH₄, from 9.0 to 19.0 by hot-wire CVD (Cat-CVD). In the samples deposited at filament temperature, T_f, of 1850 °C, the crystalline fraction and the crystallite size of μc-Si phase increased with increasing the H₂/SiH₄. The carbon content, C/(Si+C), was almost constant. In the XRD patterns, the intensity of Si(1 1 1) peak decreased and that of Si(2 2 0) peak increased with increasing the H₂/SiH₄. In the samples deposited at T_f of 2100 °C with H₂/SiH₄ over 11.4, the μc-Si phase was not formed and the C/(Si+C) increased. The growth mechanism of μc-Si in hetero-structured SiC_x alloy films is discussed.     

Suppression of crystalline growth in silicon films deposited from hydrogen diluted silane using a layer-by-layer approach

Si:H films with a thickness of approximately 450 nm have been deposited with rf-PECVD using a plasma of silane diluted with hydrogen. The aim was to grow heterogeneous films without an amorphous to microcrystalline phase transition. A layer-by-layer scheme was applied in which thin interlayers deposited from pure silane are included with the intention to interrupt the crystalline growth that is characteristic to the deposition with hydrogen dilution of silane. Raman spectroscopy and TEM imaging have confirmed that the application of the amorphous interlayers results in a decrease of the crystalline fraction of the layer-by-layer films compared to films grown with continuous hydrogen dilution. Absorption coefficient spectra of the films before and after light soaking have been investigated.     

Hydrogenated microcrystalline silicon films prepared by VHF-PECVD and single junction solar cell

Intrinsic microcrystalline silicon films have been prepared with very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD) from silane/hydrogen mixture at 180°C. The effect of silane concentration and discharge power on the growth of silicon films was investigated. Samples were investigated by Fourier transform infrared spectroscopy, Raman scattering and X-ray diffraction. The Raman spectrum shows that the morphological transition from microcrystalline to amorphous occurs under conditions of high silane concentration and low discharge power. X-ray diffraction spectra indicate a preferential growth direction of all microcrystalline silicon films in the (111) plane. In addition, a solar cell with an efficiency of 5.1% has been obtained with the intrinsic microcrystalline layer prepared at 10W.     

Hot-wire deposition of amorphous and microcrystalline silicon using different gas excitations by a coiled filament

Microcrystalline silicon (μc-Si:H) and amorphous silicon (a-Si:H) films were deposited using a hot-wire CVD (HWCVD) system that employs a coiled filament. Process gasses, H₂ and Si₂H₆, could be directed into the deposition chamber via different gas inlets, either through a coiled filament for efficient dissociation or into the chamber away from the filament, but near the substrates. We found that at low deposition pressure (e.g. 20 mTorr) the structure of the films depends on the way gases are introduced into the hot-wire chamber. However, at higher pressure (e.g. 50 mTorr), Raman measurement shows similar results for films deposited with different gas inlets.     

Highly conductive microcrystalline silicon carbide films deposited by the hot wire cell method and its application to amorphous silicon solar cells

Microcrystalline silicon carbide (μc-Si_1−xC_x) films were successfully deposited by the hot wire cell method using a gas mixture of SiH₄, H₂ and C₂H₂. It was confirmed by Fourier transform infrared and X-ray diffraction analyses that the films consisted of μc-Si grains embedded in a-Si_1−xC_x tissue. The p-type μc-Si_1−xC_x films were deposited using B₂H₆ as a doping gas. A dark conductivity of 0.2 S/cm and an activation energy of 0.067 eV were obtained. The p-type μc-Si_1−xC_x was used as a window layer of a-Si solar cells, in which the intrinsic layer was deposited by photo-chemical vapor deposition, and an initial conversion efficiency of 10.2% was obtained.     

The silicon neighborhood across the a-Si:H to μc-Si transition by X-ray absorption spectroscopy (XAS)

We report a synchrotron X-ray absorption spectroscopy study of the average neighborhood of Si near the transition from a-Si:H to μc-Si on wedge-shaped samples prepared by hot-wire CVD in a chamber using a movable shutter. The thickness of the wedge varies from 30 to 160 nm. Nucleation of μc-Si occurs at a critical thickness of approximately 100 nm. X-Ray absorption was measured at the Si K-edge (1.84 keV) by total electron photoemission yield. The absorption oscillations in the EXAFS region are very similar to all along the wedge. Analysis indicates an average tetrahedral first neighbor shell with radial disorder decreasing with crystallization. In the near-edge (XANES) region multiple scattering effects appear at the onset of crystallinity. Unlike single crystal silicon, these effects involve only double scattering within the first neighbor shell, indicating an ill-formed second shell in μc-Si.     

A simple tool for quality evaluation of the microcrystalline silicon prepared at high growth rate

Silicon thin films were grown by plasma enhanced chemical vapor deposition at high-pressure (700 Pa), high-power (4– W/cm²) depletion regime using multi-hole cathode. Series of samples were deposited by varying hydrogen/silane ratio or plasma power to study evolution of film structure and transport properties near a-Si:H/μc-Si:H transition. We suggest a simple “μc-Si:H layer quality factor” based on the ratio of subgap optical absorption (1.4 eV)/ (1 eV) measured by constant photocurrent method. This ratio correlates well with the values of ambipolar diffusion lengths measured by surface photovoltage method perpendicularly to the substrate, i.e., in the direction of the collection of the photogenerated carriers in solar cells.     

Microwave power dependence of the optical and structural properties of boron and phosphorus-doped SiC:H films prepared using ECR-CVD

Hydrogenated silicon carbide films (SiC:H) were deposited using the electron cyclotron resonance chemical vapour deposition (ECR-CVD) technique from a mixture of methane, silane and hydrogen, and using diborane and phosphine as doping gases. The effects of changes in the microwave power on the deposition rate and optical bandgap were investigated, and variations in the photo- and dark-conductivities were studied in conjunction with film analysis using the Raman scattering technique. In the case of boron-doped samples, the conductivity increased rapidly to a maximum, followed by rapid reduction at high microwave powers. The ratio of the photo- to dark-conductivity (σ_ph/σ_d) peaked at microwave power of 600 W. Under conditions of high microwave power, Raman scattering analysis showed evidence of the formation and increase in the silicon microcrystalline and diamond-like phases in the films, the former of which could account for the rapid increase and the latter the subsequent decrease in the conductivity. In the case of phosphorus-doped SiC:H samples, it was found that increase in the microwave power has the effect of enhancing the formation of the silicon microcrystalline phase in the films which occurred in correspondence to a rapid increase in the conductivity. The conductivity increase stabilised in samples deposited at microwave powers exceeding 500 W probably as a result of dopant saturation. Results from Raman scattering measurements also showed that phosphorus doping has the effect of enhancing the formation of the silicon microcrystals in the film whereas the presence of boron has the effect of preserving the amorphous structure.