Investigation of silicon contamination of Ta filaments used for thin film silicon deposition

After extensive utilisation of tantalum (Ta) catalyst filaments for hot wire chemical vapor deposition (HWCVD) of thin silicon films a strong degradation takes place. A high concentration of silicon was found not only on the surface but also in the bulk of the tantalum filament. Visual microscopic investigations, Secondary Ion Mass Spectrometry (SIMS), X-ray Diffraction (XRD) and Energy Dispersive X-ray Analysis (EDX) indicate appearance of various silicides and formation of thick silicon layer (> 50 μm) on the filament surface. The high-power backscattered scanning electron microscopy (SEM BSE) and optical microscopic analysis of the filament cross section reveal a complicated, non-uniform structure of filaments after use. By XRD a recrystallisation of tantalum kernel was detected. The EDX analysis indicates that silicides on the filament surface have the highest concentration of Si.     

Effect of ammonia on Ta filaments in the hot wire CVD process

The exposure of Ta filaments to a pure NH₃ ambient in a hot wire chemical vapour deposition (HWCVD) reactor affects the resistance of the wires. For filament temperatures below 1950 °C the resistance increases over time, which is probably caused by in-diffusion of N atoms. Using the filaments in a mixed SiH₄ and NH₃ atmosphere (under SiN_x deposition conditions) the filaments are hardly affected. Only at the “cold” parts near the electrical contact SiN_x deposition on the Ta filaments is observed. X-ray diffraction patterns and cross-section microscope images reveal that in a CH₄, H₂ and NH₃ ambient the TaC_0.275N_0.218 phase is formed on the surface of the filament. Annealing of these filaments at 2000 °C causes the TaC0.275N0.218 structure to separate into Ta and Ta₂C phases.     

Silicidation and carburization of the tungsten filament in HWCVD with silacyclobutane precursor gases

Study of the tungsten filament alloying processes with different precursor molecules shows that silicidation occurs when using silacycobutane (SCB) and carburization with 1,1,3,3-tetramethyl-1,3-disilacyclobutane (TMDSCB). The difference in the decomposition chemistry with the two molecules is responsible for the observation. Comparison of the depth profile and temperature distribution of the Si or C content in the alloyed filament illustrates the interplay among the Si or C deposition onto, evaporation from, and diffusion into the filament. Examination of the time distribution of key products from secondary gas-phase reactions at various filament temperatures demonstrates that gas-phase reactions dominate only at low temperatures. Silicidation or carburization is the dominant process at high temperatures, which contributes to a large consumption rate of precursor gas and a reduction in formation rate of the gas-phase reaction products.     

Degradation and silicidation of Ta- and W-filaments for different filament temperatures

Using typical conditions for hot wire chemical vapour deposition (HWCVD) of high quality thin silicon films in a UHV deposition chamber, we studied the silicidation of different filaments mainly varying the filament temperatures between 1700 °C and 2130 °C. The experiments were done with constant current, running the filament for 5 to 8 h and even longer. The changes of filament resistance and filament temperature with time will be shown and discussed. We investigated the material changes over the whole filament by Scanning Electron microscopy (SEM), especially the thickness of the formed silicide layers. The change of filament resistance depending on the filament temperature was also monitored, pointing out the different behaviour of tungsten and tantalum filaments. As a result, optimum temperature regimes for tantalum and tungsten filaments could be derived with respect to the filament degradation reducing the filament lifetime. Using a specially developed protection for the cold ends, a tungsten filament could be run for more than 139 h under silane with a filament temperature of T_fil ≈ 2000 °C.     

The effect of composition on the bond structure and refractive index of silicon nitride deposited by HWCVD and PECVD

Silicon nitride (SiN_x) is a material with many applications and can be deposited with various deposition techniques. Series of SiN_x films were deposited with HWCVD, RF PECVD, MW PECVD and LF PECVD. The atomic densities are quantified using RBS and ERD. The influence of the atomic densities on the Si-N and Si-Si bond structure is studied. The density of N-N bonds is found to be negligible. New Si-N FTIR proportionality factors are determined which increase with increasing N/Si ratio from 1.2 · 10¹⁹ cm^− 1 for Si rich films (N/Si = 0.2) to 2.4 · 10¹⁹ cm^− 1 for N rich films (N/Si = 1.5). The peak position of the Si-H stretching mode in the FTIR spectrum is discussed using the chemical induction model. It is shown that especially for Si-rich films the hydrogen content affects the Si-H peak position. The influence of the composition on the refractive index of the films is discussed on the basis of the Lorentz-Lorenz equation and the Kramers-Kronig relation. The decreasing refractive index with increasing N/Si ratio is primarily caused by an increase of the band gap.     

A direct correlation between film structure and solar cell efficiency for HWCVD amorphous silicon germanium alloys

The film structure and H bonding of high deposition rate a-SiGe:H i-layers, deposited by HWCVD and containing ~ 40 at.% Ge, have been investigated using deposition conditions which replicate those used in n-i-p solar cell devices. Increasing the germane source gas depletion in HWCVD causes not only a decrease in solar cell efficiency from 8.64% to less than 7.0%, but also an increase in both the i-layer H preferential attachment ratio (PA) and the film microstructure fraction (R?). Measurements of the XRD medium range order over a wide range of germane depletion indicate that this order is already optimum for the HWCVD i-layers, suggesting that energetic bombardment of a-SiGe:H films may not always be necessary to achieve well ordered films. Preliminary structural comparisons are also made between HWCVD and PECVD device layers.     

Effect of filament temperature and deposition time on the formation of tungsten silicide with silane

The effect of filament temperature and deposition time on the formation of tungsten silicide upon exposure to the SiH₄ gas in a hot wire chemical vapor deposition process was studied using the techniques of cross-sectional scanning electron microscopy and Auger electron spectroscopy. At a relatively low temperature of 1500 °C, the decomposition of WSi₂ phase and the diffusion of Si towards the silicide/W interface produce a thick W₅Si₃ layer. The diffusional nature leads to a parabolic rate law for silicide growth. An exponential decrease of silicide thickness with temperature between 1600 and 2000 °C illustrates the dominance of Si evaporation at higher temperatures (T ≥ 1600 °C) over the silicide formation.     

Applications of microcrystalline hydrogenated cubic silicon carbide for amorphous silicon thin film solar cells

We demonstrated the fabrication of n-i-p type amorphous silicon (a-Si:H) thin film solar cells using phosphorus doped microcrystalline cubic silicon carbide (μc-3C-SiC:H) films as a window layer. The Hot-wire CVD method and a covering technique of titanium dioxide TiO₂ on TCO was utilized for the cell fabrication. The cell configuration is TCO/TiO₂/n-type μc-3C-SiC:H/intrinsic a-Si:H/p-type μc- SiC_x (a-SiC_x:H including μc-Si:H phase)/Al. Approximately 4.5% efficiency with a V_oc of 0.953 V was obtained for AM-1.5 light irradiation. We also prepared a cell with the undoped a-Si_1−xC_x:H film as a buffer layer to improve the n/i interface. A maximum V_oc of 0.966 V was obtained.     

Optimization of organized silicon nanowires growth inside porous anodic alumina template using hot wire chemical vapor deposition process

A Hot Wire assisted Chemical Vapor Deposition (HWCVD) process has been developed for producing high-density arrays of parallel, straight and organized silicon nanowires (SiNWs) inside vertical Porous Anodic Alumina (PAA) templates, exploring temperatures ranging from 430 °C to 600 °C, and pressures varying between 2.5 and 7.5 mbar. In order to prevent parasitic amorphous silicon (a-Si) deposit and to promote the crystalline SiNWs growth, we used a tungsten hot wire to partially crack H₂ into atomic hydrogen, which acts like a selective etchant regarding a-Si. Here we describe the optimization route we followed to limit the deposit of a-Si onto the surface of the porous membrane and on the walls of the pores, which led to the possibility to grow SiNWs inside the PAA membranes. Such an approach has high potentialities for device realization, like PIN junctions, FETs or electrodes for Li-ion batteries.     

Microcrystalline silicon carbide alloys prepared with HWCVD as highly transparent and conductive window layers for thin film solar cells

Crystalline silicon carbide alloys have a very high potential as transparent conductive window layers in thin-film solar cells provided they can be prepared in thin-film form and at compatible deposition temperatures. The low-temperature deposition of such material in microcrystalline form (µc-Si:C:H) was realized by use of monomethylsilane precursor gas diluted in hydrogen with the Hot-Wire Chemical Vapor Deposition process. A wide range of deposition parameters has been investigated and the structural, electronic and optical properties of the µc-SiC:H thin films have been studied. The material, which is strongly n-type from unintentional doping, has been used as window layer in n-side illuminated microcrystalline silicon solar cells. High short-circuit current densities are obtained due to the high transparency of the material resulting in a maximum solar cell conversion efficiency of 9.2%.     

Electronic properties of low temperature epitaxial silicon thin film photovoltaic devices grown by HWCVD

This study addresses the correlation of the electrical, surface, and structural evolution of HWCVD crystalline Si thin films with temperature, thickness, and hydrogen dilution. Scanning electron microscopy and atomic force microscopy reveal an increase with surface roughness with hydrogen dilution, as expected, while showing increasing surface roughness with substrate temperature, in contrast to previous studies of crystalline Si growth. This suggests that H desorption enables more contaminant absorption of the growing surface with increasing temperature, in turn increasing roughness. The open-circuit voltage of these films is shown to increase significantly over time, ∼ 50 mV over one week, due to the decrease in surface recombination velocity associated with the growth of a native oxide layer. This indicates the importance of post-deposition treatments for surface passivation.     

Comparison of surface passivation of crystalline silicon by a-Si:H with and without atomic hydrogen treatment using hot-wire chemical vapor deposition

We compared surface passivation of c-Si by a-Si:H with and without atomic hydrogen treatment prior to a-Si:H deposition. The atomic hydrogen is produced by hot-wire chemical vapor deposition (HWCVD). For this purpose, we deposited a-Si:H layers onto both sides of n-type FZ c-Si wafers and measured the minority carrier effective lifetime and implied V_OC for different H treatment times ranging from 5 s to 30 s prior to a-Si:H deposition. We found that increasing hydrogen treatment times led to lower effective lifetimes and implied V_OC values for the used conditions. The treatments have been performed in a new virgin chamber to exclude Si deposition from the chamber walls. Our results show that a short atomic hydrogen pretreatment is already detrimental for the passivation quality which might be due to the creation of defects in the c-Si. AFM measurements do not show any change in the surface roughness of the different samples.     

Problem of catalyst ageing during the hot-wire chemical vapour deposition of thin silicon films

The filament in a hot-wire chemical vapour deposition (HWCVD) reactor is an important component. When tantalum (Ta) filaments are used for the deposition of thin silicon films, strong degradation takes place: there is a large amount of silicon not only at the surface but also in the bulk of the tantalum catalyst. Ta-Si phases form on the filament surface and in the bulk, which can lead to a porous structure of the catalyst filament. Filament contamination (silicide formation and thick silicon deposits (TSDs)) is the reason for the changes in filament resistance. It also reduces filament lifetime, which is a serious concern for HWCVD deposition technology. A cleaning procedure for the filament at high-temperatures in a vacuum (about 2000 °C) can neither remove the thick silicon deposits nor fully restore the filament surface properties. In order to decrease the silicon content in the tantalum catalyst and suppress TSD formations on the filament surface, we use radio-frequency alternating current (RF, 13.5 MHz) instead of direct current (DC) to heat the filament. The skin effect of the RF current reduces the formation of TSDs on the surface and silicon diffusion into the filament. We show that it is possible to clean the filament surface of TSDs by means of a high-frequency current. Combined RF + DC filament heating allows us to increase the lifetime of the catalyst (almost twofold) and to improve HWCVD process reproducibility without any deterioration in the quality of the deposited film.     

Development of microcrystalline silicon carbide window layers by hot-wire CVD and their applications in microcrystalline silicon thin film solar cells

Microcrystalline silicon carbide (μc-SiC:H) thin films in stoichiometric form were deposited from the gas mixture of monomethylsilane (MMS) and hydrogen by Hot-Wire Chemical Vapor Deposition (HWCVD). These films are highly conductive n-type. The optical gap E₀₄ is about 3.0-3.2 eV. Such μc-SiC:H window layers were successfully applied in n-side illuminated n-i-p microcrystalline silicon thin film solar cells. By increasing the absorber layer thickness from 1 to 2.5 μm, the short circuit current density (j_SC) increases from 23 to 26 mA/cm² with Ag back contacts. By applying highly reflective ZnO/Ag back contacts, j_SC = 29.6 mA/cm² and η = 9.6% were achieved in a cell with a 2-μm-thick absorber layer.     

Preliminary results on a-SiC:H based thin film light emitting diode by hot wire CVD

Preliminary results on the first hot wire deposited a-SiC:H based thin film light emitting p–i–n diode having the structure glass/TCO(SnO₂:F)/p-a-SiC:H/i-SiC:H/n-a-SiC:H/Al are reported. The paper discusses the results of our attempts to optimize the p-, i- and the n-layers for the desired electrical and optical properties. The optimized p-layers have a bandgap E_g2 eV and conductivity a little lower than 10⁻⁵ (Ω cm)⁻¹. On the other hand, the optimized n-type a-SiC:H show a conductivity of 10⁻⁴ (Ω cm)⁻¹ with bandgap 2.06 eV. The highest bandgap of the intrinsic layer is approximately 3.4 eV and shows room temperature photoluminescence peak at approximately 2.21 eV. Thin film p–i–n diodes having i-layers with E_g from 2.7 to 3.4 eV show white light emission at room temperature under forward bias of >5 V. However, the 50-nm thick devices show appreciable reverse leakage current and a low emission intensity, which we attribute to the contamination across the p–i interface since these devices are made in a single chamber with the same filament.     

Microstructure of highly crystalline silicon carbide thin films grown by HWCVD technique

Highly crystalline silicon carbide films were synthesised by HWCVD technique. Raman spectroscopic studies show that the SiC films contain crystalline SiC and also carbon phases. Carbon is graphitic at higher chamber pressures (≥ 50 Pa) and resembles diamond-like carbon at low pressure (5 Pa). Cross-section TEM results show a columnar morphology of the crystallites with typical column diameters up to ∼ 50 nm. Transmission electron diffraction patterns reveal SiC in its cubic and hexagonal SiC phases and the C diamond phase at low pressure. Annealing at 1000 °C for 1 h results in enhancement of crystallite size without nucleation of new phases.     

Ultrafast deposition of silicon nitride and semiconductor silicon thin films by hot wire chemical vapor deposition

The technology of Hot Wire Chemical Vapor Deposition (HWCVD) or Catalytic Chemical Vapor Deposition (Cat-CVD) has made great progress during the last couple of years. This review discusses examples of significant progress. Specifically, silicon nitride deposition by HWCVD (HW-SiN_x) is highlighted, as well as thin film silicon single junction and multijunction junction solar cells. The application of HW-SiN_x at a deposition rate of 3 nm/s to polycrystalline Si wafer solar cells has led to cells with 15.7% efficiency and preliminary tests of our transparent and dense material obtained at record high deposition rates of 7.3 nm/s yielded 14.9% efficiency. We also present recent progress on Hot-Wire deposited thin film solar cells. The cell efficiency reached for (nanocrystalline) nc-Si:H n-i-p solar cells on textured Ag/ZnO presently is 8.6%. Such cells, used in triple junction cells together with Hot-Wire deposited proto-Si:H and plasma-deposited SiGe:H, have reached 10.9% efficiency. Further, in our research on utilizing the HWCVD technology for roll-to-roll production of flexible thin film solar cells we recently achieved experimental laboratory scale tandem modules with HWCVD active layers with initial efficiencies of 7.4% at an aperture area of 25 cm².     

Comparison of growth mechanisms of silicon thin films prepared by HWCVD with PECVD

Hot-wire chemical vapor deposition (HWCVD) and plasma-enhanced chemical vapor deposition (PECVD) of Si thin films show different growth kinetic processes. According to the fractal analysis, the root-mean-square surface roughness δ and the film thickness d have the relation of δ ∼ d^β, where β is the dynamic scaling exponent related to the film growth mechanism. It was found that β is 0.44 for Si films prepared by HWCVD and 0.24 by PECVD. The former refers to a stochastic deposition while the latter corresponds to the finite diffusion of the radicals. Monte Carlo simulations indicate that the sticking process of growth radicals play an important role in determining the morphology of Si films.     

Low temperature (< 100 °C) fabrication of thin film silicon solar cells by HWCVD

Amorphous silicon films have been made by HWCVD at a very low substrate temperature of ≤ 100 °C (in a dynamic substrate heating mode) without artificial substrate cooling, through a substantial increase of the filament-substrate distance (∼ 80 mm) and using one straight tantalum filament. The material is made at a reasonable deposition rate of 0.11 nm/s. Optimized films made this way have device quality, as confirmed by the photosensitivity of > 10⁵. Furthermore, they possess a low structural disorder, manifested by the small Γ/2 value (half width at half maximum) of the transverse optic (TO) Si-Si vibration peak (at 480 cm^− 1) in the Raman spectrum of ∼ 30.4 cm^− 1, which translates into a bond angle variation of only ∼ 6.4°. The evidence gathered from the studies on the structure of the HWCVD grown film by three different techniques, Raman spectroscopy, spectroscopic ellipsometry and transmission electron microscopy, indicate that we have been able to make a photosensitive material with a structural disorder that is smaller than that expected at such a low deposition temperature.Tested in a p-i-n solar cell on Asahi SnO₂:F coated glass (without ZnO at the back reflector), this i-layer gave an efficiency of 3.4%. To our knowledge, this is the first report of a HWCVD thin film silicon solar cell made at such a low temperature.     

Microcrystalline silicon carbide thin films grown by HWCVD at different filament temperatures and their application in n-i-p microcrystalline silicon solar cells

To optimize the performance of microcrystalline silicon carbide (µc-SiC:H) window layers in n-i-p type microcrystalline silicon (µc-Si:H) solar cells, the influence of the rhenium filament temperature in the hot wire chemical vapor deposition process on the properties of µc-SiC:H films and corresponding solar cells were studied. The filament temperature T_F has a strong effect on the structure and optical properties of µc-SiC:H films. Using these µc-SiC:H films prepared in the range of T_F = 1800-2000 °C as window layers in n-side illuminated µc-Si:H solar cells, cell efficiencies of above 8.0% were achieved with 1 µm thick µc-Si:H absorber layer and Ag back reflector.