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.     

Improvement of the efficiency of triple junction n-i-p solar cells with hot-wire CVD proto- and microcrystalline silicon absorber layers

Hot-wire chemical vapour deposition (HWCVD) was applied for the deposition of intrinsic protocrystalline (proto-Si:H) and microcrystalline silicon (μc-Si:H) absorber layers in thin film solar cells. For a single junction μc-Si:H n-i-p cell on a Ag/ZnO textured back reflector (TBR) with a 2.0 μm i-layer, an 8.5% efficiency was obtained, which showed to be stable after 750 h of light-soaking. The short-circuit current density (J_sc) of this cell was 23.4 mA/cm², with a high open-circuit voltage (V_oc) and fill factor (FF) of 0.545 V and 0.67.Triple junction n-i-p cells were deposited using proto-Si:H, plasma-deposited proto-SiGe:H and μc-Si:H as top, middle and bottom cell absorber layers. With Ag/ZnO TBR's from our lab and United Solar Ovonic LLC, respective initial efficiencies of 10.45% (2.030 V, 7.8 mA/cm², 0.66) and 10.50% (2.113 V, 7.4 mA/cm², 0.67) were achieved.     

High efficiency microcrystalline silicon solar cells with Hot-Wire CVD buffer layer

Microcrystalline silicon (μc-Si:H) solar cells with i-layers deposited by hot wire chemical vapor deposition (HWCVD) exhibit higher open circuit voltage and fill factor than the cells with i-layers deposited by plasma enhanced (PE)-CVD. Inserting an intrinsic μc-Si:H p/i buffer layer prepared by HWCVD into PECVD cells nearly eliminates these differences. The influence of buffer layer properties on the performance of μc-Si:H solar cells was investigated. Using such buffer layers allows to apply high deposition rate processes for the μc-Si:H i-layer material yielding a high efficiency of 10.3% for a single junction μc-Si:H solar cell.     

Improvement of μc-Si:H n-i-p cell efficiency with an i-layer made by hot-wire CVD by reverse H2-profiling

The technique of maintaining a proper crystalline ratio in microcrystalline silicon (μc-Si:H) layers along the thickness direction by decreasing the H₂ dilution ratio during deposition (H₂ profiling) was introduced by several laboratories while optimizing either n-i-p or p-i-n μc-Si:H cells made by PECVD. With this technique a great increase in the energy conversion efficiency was obtained. Compared to the PECVD technique, the unique characteristics of HWCVD, such as the catalytic reactions, the absence of ion bombardment, the substrate heating by the filaments and filament aging effects, necessitate a different strategy for device optimization. We report in this paper the result of our method of using a reverse H₂ profiling technique, i.e. increasing the H₂ dilution ratio instead of decreasing it, to improve the performance of μc-Si:H n-i-p cells with an i-layer made by HWCVD. The principle behind this technique is thought to be a compensation effect for the influence of progressing silicidation of the filaments during the growth of μc-Si:H, if the filament current is held constant during growth. The dependence of the material crystallinity on thickness with and without H₂ profiling is discussed and solar cell J-V parameters are presented. Thus far, the best efficiency of μc-Si:H n-i-p cells made on a stainless steel substrate with an Ag/ZnO textured back reflector made in house has been improved to 8.5%, which is the highest known efficiency obtained for n-i-p cells with a hot-wire μc-Si:H i-layer.     

Deposition of device quality silicon nitride with ultra high deposition rate (> 7 nm/s) using hot-wire CVD

The application of hot-wire (HW) CVD deposited silicon nitride (SiN_x) as passivating anti-reflection coating on multicrystalline silicon (mc-Si) solar cells is investigated. The highest efficiency reached is 15.7% for SiN_x layers with an N/Si ratio of 1.20 and a high mass density of 2.9 g/cm³. These cell efficiencies are comparable to the reference cells with optimized plasma enhanced (PE) CVD SiN_x even though a very high deposition rate of 3 nm/s is used. Layer characterization showed that the N/Si ratio in the layers determines the structure of the deposited films. And since the volume concentration of Si-atoms in the deposited films is found to be independent of the N/Si ratio the structure of the films is determined by the quantity of incorporated nitrogen. It is found that the process pressure greatly enhances the efficiency of the ammonia decomposition, presumably caused by the higher partial pressure of atomic hydrogen. With this knowledge we increased the deposition rate to a very high 7 nm/s for device quality SiN_x films, much faster than commercial deposition techniques offer [S. von Aichberger, Photon Int. 3 (2004) 40].     

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.     

Annealing optimization of silicon nitride film for solar cell application

Hydrogenated films of silicon nitride (SiNx:H) is commonly used as an antireflection coating as well as passivation layer in crystalline silicon solar cell. SiNx:H films deposited at different conditions in Plasma Enhanced Chemical Vapor Deposition (PECVD) reactor were investigated by varying annealing condition in infrared (IR) heated belt furnace to find the optimized condition for the application in silicon solar cells. By varying the gases ratio (R = NH₃/SiH₄ + NH₃) during deposition, the SiNx:H films of refractive indices 1.85-2.45 were obtained. Despite the poor deposition rate, the silicon wafer with SiNx:H film deposited at 450 °C showed the best effective minority carrier lifetime. The film deposited with the gases ratio of 0.57 shows the best peak of carrier lifetime at the annealing temperature of 800 °C. The single crystalline silicon solar cells fabricated in conventional industrial production line applying the optimized film deposition and annealing conditions on large area substrates (125 mm × 125 mm) were found to have the conversion efficiencies as high as 17.05 %. Low cost and high efficiency single crystalline silicon solar cells fabrication sequence employed in this study has also been reported in this paper.     

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.     

Double layer SiNx:H films for passivation and anti-reflection coating of c-Si solar cells

In this report, we present a cost effective simple innovative approach to fabricate double layer anti-reflection (DLAR) coatings using a single material which can provide high qualities of passivation and anti-reflection property. Two layers of SiN_x:H films with different refractive indices were deposited onto p-type c-Si wafer using plasma enhanced chemical vapor deposition reactor by controlling the NH₃ and SiH₄ gas ratio. Refractive indices of top and bottom layers were chosen as 1.9 and 2.3 respectively. The effect of passivation at the interface was investigated by effective carrier lifetime, hydrogen concentration and interface trapped density (D_it) measurements. The optical characteristic was analyzed by reflectance and transmittance measurements. A superior efficiency of 17.61% was obtained for solar cells fabricated with DLAR coating when compared to an efficiency of 17.24% for cells with SLAR coating. Further, J_sc and V_oc of solar cell with DLAR coating is increased by a value of ~ 1 mA/cm² and 4 mV respectively than cell with SLAR coating.     

Enhancement of microcrystalline n-i-p solar cell performance via use of pre-covering layers and H2 treatment

We study the effects of a-Si:H and μc-Si:H covering layers and an H₂ treatment on the characteristics of μc-Si:H thin film solar cells deposited in open single chamber very high frequency plasma enhanced chemical vapor deposition systems. Secondary ion mass spectrometry is used to evaluate the phosphor concentration in the μc-Si:H material. Compared to use of an a-Si:H covering layer, use of a μc-Si:H covering layer reduces dopant contamination by a relative 50%, and improves efficiency by a relative 6%, and use of an H₂ treatment reduces dopant contamination by a relative 64%, and improves efficiency by a relative 17%.     

Assortment of technological terms for silicon-germanium thin films in gradient configuration

Phase diagrams have been studied to describe the RF PECVD process for intrinsic-hydrogenated silicon Si:H and silicon-low germanium alloy a-Si_1−xGe_x:H thin films using textured Al substrates that have been overdeposited with n-type amorphous Si:H (n⁺ a-Si:H). UV, vis, IR, atomic force microscopy (AFM), Raman spectroscopy, small angle X-ray and cross-section transmission electron microscopy (TEM) are used to establish the phase diagram. The a-Si:H, a-Si_1−xGe_x and μc-Si:H processes are applied for optimization of triple-junction thin silicon-based n-i-p solar cells.     

Plasma deposition of n-SiOx nanocrystalline thin film for enhancing the performance of silicon thin film solar cells

In this paper, we firstly optimized the properties of n-SiO_x nanocrystalline thin film through tuning deposition parameters by plasma enhanced chemical vapor deposition, so that we can actively control the properties of materials obtained. Secondly, we proposed using n-SiO_x/Al as back reflector for amorphous silicon (a-Si:H) solar cells. Compared to Al single-layer as back reflector, adding an n-SiO_x layer into the back reflector could improve the solar cell performance, which not only enhances the short circuit current density by an improvement of spectral response in the wavelength range of 550-750 nm, but also improves the open circuit voltage. With an optimized n-SiO_x/Al back reflector, a-Si:H solar cells with an intrinsic layer thickness of 270 nm show 13.1% enhancement in efficiency. In addition, a-Si:H/μc-Si:H tandem solar cells with n-SiO_x as intermediate reflector were also researched. As a result, it evidently balanced the current matching between top and bottom cell.     

Tungsten filament effect on electronic properties of hot-wire CVD silicon films for heterojunction solar cell application

In this study, we describe the correlation between cell efficiency and wire aging during hot-wire chemical vapor deposition in detail. The new and aged tungsten (W) filaments were used to deposit the n-type microcrystalline silicon (μc-Si) films for heterojunction (HJ) Si solar cell applications. Tungsten silicide (WSi_x) was coated on the W catalyzer surface (center and end regions) after each deposition, and which was investigated and determined by scanning electron microscopy and electron probe microanalysis. The wire age has an effect on the resulting electronic properties of the grown film, thought to be related to differences in dark conductivity with aged versus new wires. It was found that the aging process is related to the formation of a silicide at the surface. A limited amount of silicon was observed in the bulk of catalyzer, suggesting that silicon diffusion into the wire has occurred. The original single-side HJ solar cell with efficiency of 15.3% has been fabricated using the new wires. The quality of n-type μc-Si films and efficiency of HJ solar cells were reduced when the aged W filament was employed. The quality of silicon films and the efficiency of HJ solar cell could be improved after regeneration process.     

Characterization of SiNx/a-Si:H crystalline silicon surface passivation under UV light exposure

One of the most promising solution for crystalline silicon surface passivation in solar cell fabrication consists in a low temperature (< 400 °C) Plasma Enhanced Chemical Vapor Deposition of a double layer composed by intrinsic hydrogenated amorphous silicon (a-Si:H) and hydrogenated amorphous silicon nitride (SiN_x). Due to the high amount of hydrogen in the gas mixture during the double layer deposition, the passivation process results particularly useful in case of multi-crystalline silicon substrates in which hydrogenation of grain boundaries is very needed. In turn the presence of hydrogen inside both amorphous layers can induce metastability effects. To evaluate these effects we have investigated the stability of the silicon surface passivation obtained by the double layer under ultraviolet light exposure. In particular we have verified that this double layer is effective to passivate both p- and n-type crystalline silicon surface by measuring minority carrier high lifetime, via photoconductance-decay. To get better inside the passivation mechanisms, strongly connected to the charge laying inside the SiN_x layer, we have collected the Infrared spectra of the SiN_x/a-Si:H/c-Si structures and we have monitored the capacitance-voltage profiles of Al/SiN_x/a-Si:H/c-Si Metal Insulator Semiconductor structures at different stages of UltraViolet (UV) light exposure. Finally we have verified the stability of the double passivation layer applied to the front side of solar cell devices by measuring their photovoltaic parameters during the UV light exposure.     

Amorphous silicon thin film solar cells deposited entirely by hot-wire chemical vapour deposition at low temperature (< 150 °C)

Amorphous silicon n-i-p solar cells have been fabricated entirely by Hot-Wire Chemical Vapour Deposition (HW-CVD) at low process temperature < 150 °C. A textured-Ag/ZnO back reflector deposited on Corning 1737F by rf magnetron sputtering was used as the substrate. Doped layers with very good conductivity and a very less defective intrinsic a-Si:H layer were used for the cell fabrication. A double n-layer (µc-Si:H/a-Si:H) and µc-Si:H p-layer were used for the cell. In this paper, we report the characterization of these layers and the integration of these layers in a solar cell fabricated at low temperature. An initial efficiency of 4.62% has been achieved for the n-i-p cell deposited at temperatures below 150 °C over glass/Ag/ZnO textured back reflector.     

Fabrication of selective-emitter silicon heterojunction solar cells using hot-wire chemical vapor deposition and laser doping

The Si heterojunction (HJ) solar cells were fabricated on the textured p-type mono-crystalline Si (c-Si) substrates using hot-wire chemical vapor deposition (HWCVD). In view of the potential for the bottom cell in a hybrid junction structure, the microcrystalline Si (μc-Si) film was used as the emitter with various PH₃ dilution ratios. Prior to the n-μc-Si emitter deposition, a 5 nm-thick intrinsic amorphous Si layer (i-a-Si) was grown to passivate the c-Si surface. In order to improve the indium-tin oxide (ITO)/emitter front contact without using the higher PH₃ doping concentration, a laser doping technique was employed to improve the ITO/n-μc-Si contact via the formation of the selective emitter structure. For a cell structure of Ag grid/ITO/n-μc-Si emitter/i-a-Si/textured p-c-Si/Al-electrode, the conversion efficiency (AM1.5) can be improved from 13.25% to 14.31% (cell area: 2 cm × 2 cm) via a suitable selective laser doping process.     

Surface passivation of silicon by rf magnetron-sputtered silicon nitride films

Si-rich silicon nitride (SiN_x(:H)) films are deposited on single crystalline p-type silicon to investigate their properties as a passivation and antireflection coating for solar cells. The SiN_x(:H) films were reactively sputtered from an intrinsic Si-target in an Ar/N₂/H₂ rf (13.56 MHz) magnetron plasma at substrate temperatures from 150°C to 350°C. The optical band gap of Si-rich SiN_x(:H) becomes lower than 3 eV which was determined from spectral data of the complex refractive index. Infrared spectra show a strong Si–H band in Si-rich films. The effective surface recombination velocity (SRV) was calculated from the effective life time in SiN_x(:H) covered p-Si wafers by the microwave detected photoconductivity decay (MW PCD) technique. Very low values for the effective SRV of about 60 cm/s were determined. The low values of the effective SRV are due to field-effect passivation. The field-effect passivation of the SiN_x(:H)/Si contact is explained with the model of a hetero junction.     

Amorphous Si1−xCx:H films prepared by hot-wire CVD using SiH3CH3 and SiH4 mixture gas and its application to window layer for silicon thin film solar cells

B-doped hydrogenated amorphous silicon carbon (a-Si_1−xC_x:H) films have been prepared by hot-wire CVD (HWCVD) using SiH₃CH₃ as the carbon source gas. The optical bandgap energy and dark conductivity of the film are about 1.94 eV and 2 × 10^− 9 S/cm, respectively. Using this film as a window layer, we have demonstrated the fabrication of solar cells having a structure of the textured SnO₂(Asahi-U)/a-Si_1−xC_x:H(p)/a-Si_1−xC_x:H(buffer)/a-Si:H(i)/μc-Si:H(n)/Al. The conversion efficiency of the cell is found to be 7.0%.     

High efficiency a-Si:H/a-Si:H solar cell with a tunnel recombination junction and a n-type μc-Si:H layer

In this paper, a-Si:H/a-Si:H tandem solar cells have been fabricated using a plasma enhanced chemical vapor deposition. The solar cell has a structure of glass/textured-SnO₂/p-a-SiC:H/i-a-Si:H/n-μc-Si:H/p-μc-Si:H/p-a-SiC:H/i-a-Si:H/n-μc-Si:H/gallium-doped zinc oxide/Ag. Higher efficiency in a-Si:H/a-Si:H tandem solar cells can be achieved by use of a good tunnel recombination junction (TRJ) and current matching. Accordingly, solar cells with a n-μc-Si:H/p-μc-Si:H TRJ are investigated. This paper studies the influence of the thickness of the top intrinsic amorphous silicon (i-a-Si:H) layer with regard to short circuit current density and current matching between the top and the bottom cells. Experimental results with lab-fabricated samples show that the optimal thickness of the i-a-Si:H layer in the top and bottom cells is 60 and 250 nm, respectively. An initial conversion efficiency of 10.29% is achieved for the optimized a-Si:H/a-Si:H tandem solar cell. Light-induced degradation of the solar cells is about 17%.