Highest-quality surface passivation of low-resistivity p-type silicon using stoichiometric PECVD silicon nitride

The surface passivation properties of silicon nitride (SiN) films fabricated by high-frequency direct plasma-enhanced chemical vapour deposition (PECVD) on low-resistivity (1 Ω cm) p-type silicon solar cell substrates have been investigated. The process gases used were ammonia and a mixture of silane and nitrogen. In order to find the optimum set of SiN deposition parameters, a large number of carrier lifetime test structures were prepared under different deposition conditions. The optimised deposition parameters resulted in outstandingly low surface recombination velocities (SRVs) below 10 cm/s. Interestingly, we find the lowest SRVs for stoichiometric SiN films, as indicated by a refractive index of 1.9. In former studies similarly low SRVs had only been obtained for silicon-rich SiN films. The fundamentally different passivation behaviour of our SiN films is attributed to the addition of nitrogen to the process gases.     

Silicon nitride film for solar cells

In this work, our aim was to determine the deposition parameters leading to optimal optical properties of Silicon nitride (SiN) film for photovoltaic application. The deposition was performed in an industrial pulsed direct-PECVD using a gas mixture of NH₃/SiH₄.After defining the optimum deposition parameters, we have chemically evaluated the film quality in BOE solution. Plasma removal of the optimized SiN films from multicrystalline 4-in solar cells allows highlighting and estimating the emitter passivation and ARC effects on the solar cell electrical performance.     

Angle-dependent XPS analysis of silicon nitride film deposited on screen-printed crystalline silicon solar cell

In this work silicon nitride (Si₃N₄) film was deposited as an antireflection coating (ARC) on crystalline silicon solar cell (cell?A) using plasma-enhanced chemical vapor deposition (PECVD). Two solar cells XA and XB of approximately equal area were diced from cell#A and characterized by angle-dependent X-ray photoelectron spectroscopy (XPS). The XPS profiling shows the presence of silicon (Si), nitrogen (N), carbon (C) and oxygen (O) in the Si₃N₄ film. The presence of C and O indicates that organic substances, involved in processing steps were not released completely from the surface and may diffuse in Si₃N₄ ARC during deposition. The XPS spectra corresponding to Si2p, N1s, C1s and O1s were recorded at angles 0° (normal to the surface), 30° and 45°, as angle increases spectra becomes more surface sensitive. Peak positions in Si2p and N1s spectra explain the oxygen contamination in the Si₃N₄ film. The shift in the peak positions of C1s and O1s as angle increases from 0° to 45° explains the surface contamination of carbon and oxygen. The atomic composition of elements Si, N, C and O show more carbon, oxygen concentration and smaller N/Si ratio than stoichiometry, i.e. Si₃N₄ in cell XB. However, cell XA not only show better photovoltaic performance in terms of parameters open-circuit voltage (V_oc), short-circuit current density (J_sc), fill factor (FF) and efficiency (η) but also have more uniform texturization and regular pyramids on the surface as revealed by scanning electron microscopy (SEM). The presence of higher concentration of impurities (carbon and oxygen), non-uniformity in texturization and in the Si₃N₄ film as well could be responsible for less satisfactory photovoltaic performance of cell XB.     

Study on hydrogenated silicon nitride for application of high efficiency crystalline silicon solar cells

The hydrogenated silicon nitride films (SiN_x:H) deposited by plasma enhanced chemical vapor deposition (PECVD) technique is commonly used as an antireflection coating as well as surface passivating layer of crystalline silicon solar cells. The refractive indices of SiN_x:H films could be changed by varying the growth gas ratio R(=NH₃/SiH₄+NH₃) and annealing temperature. For optimum SiN_x:H film, the optical and chemical characterization tools by varying the film deposition and annealing condition were employed in this study. Metal-insulator-semiconductor (MIS) devices were fabricated using SiN_x:H as an insulator layer and they were subjected to capacitance-voltage (C-V) and current-voltage (I-V) measurements for electrical characterization. The effect of rapid thermal annealing (RTA) on the surface passivation as well as antireflection properties of the SiN_x:H films deposited at various process conditions were also investigated for the fabrication of low cost and high efficiency silicon solar cells.     

Overview on SiN surface passivation of crystalline silicon solar cells

Silicon nitride (SiN) fabricated by plasma-enhanced chemical vapour deposition (PECVD) is increasingly used within the crystalline silicon (c-Si) photovoltaic industry as it offers the possibility to fabricate a surface and bulk passivating antireflection coating at low temperature (450°C). This article presents an overview on the present status of SiN for industrial as well as laboratory-type c-Si solar cells. Topics covered include the fundamentals of the PECVD technology, the present status of high-throughput PECVD machines for the deposition of SiN onto c-Si wafers, and a review of the fundamental properties of Si–SiN interfaces fabricated by PECVD.     

Study of the composition of hydrogenated silicon nitride SiNx:H for efficient surface and bulk passivation of silicon

This work is a contribution towards the understanding of the properties of hydrogenated silicon nitride (SiN_x:H) that lead to efficient surface and bulk passivation of the silicon substrate. Considering the deposition system used (low-frequency plasma-enhanced chemical vapour deposition (PECVD)), we report very low values of surface recombination velocity S_eff. As-deposited Si-rich SiN_x:H leads to the best results (n-type Si: S_eff=4 cm/s - p-type Si: S_eff=14 cm/s). After annealing, the surface passivation quality is drastically deteriorated for Si-rich SiN_x:H whereas it is lightly improved for low refractive index SiN_x:H (n∼2-2.1). The chemical analysis of the layers highlighted a high hydrogen concentration, regardless the SiN_x:H stoichiometry. However, the involved H-bond types as well as the hydrogen desorption kinetics are strongly dependent on the SiN_x:H composition. Furthermore, “N-rich” SiN_x:H appears to be denser and thermally more stable than Si-rich SiN_x:H. When subjected to a high-temperature treatment, such a layer is believed to induce the release of hydrogen in its atomic form, which consequently leads to an efficient passivation of surface and bulk defects of the Si substrate. The results are discussed and compared with the literature data reported for the different configurations of PECVD reactors.     

The use of silicon nitride in buried contact solar cells

Silicon nitride offers many potential benefits to the family of buried contact fabrication sequences including improved design flexibility and efficiency. The main device structures of the buried contact family comprise the standard buried contact, the simplified buried contact and the double-sided buried contact cells. The physical properties of silicon nitride allow it to be used for surface passivation, as an anti-reflection coating, as a diffusion source material and as a masking dielectric. The use of silicon nitride in each buried contact fabrication sequence is described in this work.     

Design and simulation of antireflection coating for application to silicon solar cells

Phosphorous silicate glass (PSG) was formed at the temperature range 800–900°C during diffusion of phosphorous (P) into Si wafers from liquid POCl₃ source in ambient atmosphere of N₂ and O₂. The thickness and refractive indices were measured by an ellipsometer. The refractive index increased with the temperature of formation upto 875°C and then became constant at which point PSG is saturated with P. From the growth rate data at different temperatures, the linear and parabolic activation energies were determined as 0.79 and 1.43 eV for parabolic and linear rate constants, respectively. Therefore, growth rate of PSG is higher than thermal SiO₂. The PSG films were found to have refractive indices 1.85, 1.78, 1.74 and 1.71 for forming temperature 800°C, 825°C, 850°C and 875°C, respectively. Reflectivity varied from 2.5% to 7.5% in the wavelength range 450–700 nm. SIMS depth profiling suggests that there has been a pile up of P on the Si side at the Si/SiO₂ (PSG) interface.     

Low temperature silicon oxide and nitride for surface passivation of silicon solar cells

Surface passivation at low processing temperature becomes an important topic for crystalline and multicrystalline silicon solar cells. In this work, silicon oxide (250°C) and silicon nitride (300°C) have been developed by Photo-CVD and PECVD technique respectively. Effects of deposition parameters on the optoelectronic and structural properties of the films have been investigated. Interface-trap density (D_it) and fixed charge density (Qf) have been estimated by high frequency (1 MHz) capacitance-voltage measurement on Metal–Insulator–Silicon structure (CV-MIS). The effect of silicon oxide and silicon nitride on the performance of c-Si solar cells have been studied.     

Design and simulation of antireflection coating systems for optoelectronic devices: Application to silicon solar cells

Reflectance calculation for various single-, double- and triple-layer Antireflection coatings (ARCs) on silicon substrate are presented. A calculation program is developed to determine the optimum thickness and the refractive index of each layer at a single wavelength for optoelectronic applications and through the visible spectrum for photovoltaic applications.Ta₂O₅, ZnS, Al₂O₃ single layer, MgF₂/Zns double layer and MgF₂/Al₂O₃/ZnS triple layer ARC systems are deposited on silicon substrate using electron beam and thermal evaporation as deposition techniques. The reflectance as a function of the wavelength of AR coating systems on silicon substrate is measured. All curves show good accordance between the theoretical and the experimental reflectance. As application in the photovoltaic field, a ZnS single-layer AR coating is evaporated on concentrator silicon solar cells. Spectral response and current–voltage characteristics are measured before and after ZnS ARC deposition to estimate the improvement of the cell performances. Short-circuit current and cell efficiency are increased by about 31% and 29.4%, respectively.     

Plasma-enhanced chemical vapour-deposited silicon nitride films; The effect of annealing on optical properties and etch rates

The optical properties and etch rates of silicon nitride (SiN_x:H) deposited by plasma-enhanced chemical vapour deposition (PECVD) and their correlation with bond concentrations have been studied. By varying the silane-to-total gas ratio, films with refractive index (n) between 1.92 and 3.00 were deposited. Higher n films had increased absorption and decreased etch rates. Annealing the samples at different temperatures revealed that all films were thermally stable up to 750 °C, above which all experienced a rise in n, attributed mainly to mass densification. The etch rate correlated well the N–H bond concentration for both annealed and as-deposited films.     

High-density inductively coupled plasma chemical vapor deposition of silicon nitride for solar cell application

The silicon nitride films were deposited by means of high-density inductively coupled plasma chemical vapor deposition in a planar coil reactor. The process gases used were pure nitrogen and a mixture of silane and helium. Passivated by silicon nitride, solar cells show efficiency above 13%. Strong H-atom release from the growing SiN film and Si–N bond healing are responsible for the improved electrical and passivation properties of SiN film. This paper presents the optimal refractive index of SiN for single layer antireflection coating as well as double layer antireflection coating in solar cell applications.     

UVCVD silicon nitride passivation and ARC layers for multicrystalline solar cells

This work intends to investigate the effectiveness of silicon nitride layers (SiN_x : H) deposited by photochemical vapor deposition (UVCVD) for antireflection and passivation purposes when applied to electromagnetically casted silicon solar cells (EMC). Effective reflectivity of 10.8% is achieved, as well as 66% increase of minority carrier lifetime.     

Silicon solar cells with antireflection diamond-like carbon and silicon carbide films

Optical properties of diamond-like carbon and silicon carbide (SiC) films in dependence on deposition conditions were investigated. It was established that the films having refractive index from 1.6 to 2.3 may be obtained. The film optical bandgap and hardness may be changed from 1.5 to 4 eV and from 1 to 20 GPa, correspondingly. The films were deposited onto the front side of silicon solar cells (SCs). It has been shown that deposition of single- or two-layer diamond-like carbon antireflection (AR) coatings enables the SCs efficiency to be improved 1.35–1.5 times. The improvement is connected with decreasing of reflection losses and passivation of recombination active centers. SiC AR coatings improve the solar cell efficiency up to 1.3 times.     

Fabrication of silicon nanowire arrays based solar cell with improved performance

We report fabrication of solar cell (n⁺-p-p⁺ structure) on black silicon substrates consisting of silicon nanowire (SiNW) arrays prepared by Ag induced wet chemical etching process in aqueous HF-AgNO₃ solution. SiNW arrays surface has low reflectivity (<5%) in the entire spectral range (400-1100 nm) of interest for solar cells. The solar cells were fabricated by conventional cell fabrication protocol. Performance of three types of cells, namely cell with SiNW over the entire front surface, cell with SiNW only in the active device area and control cell (on planar surface), has been compared. It was found that cell based on selectively grown shorter length SiNW arrays has the best cell performance.     

The effects of the band gap and defects in silicon nitride on the carrier lifetime and the transmittance in c-Si solar cells

In this paper, silicon nitride thin films with different silane and ammonia gas ratios were deposited and characterized for the antireflection and passivation layer of high efficiency single crystalline silicon solar cells. An increase in the transmittance and a recombination decrease using an effective antireflection and passivation layer can be enhanced by an optimized SiN_x film in order to attain higher solar cell efficiencies. As the flow rate of the ammonia gas increased, the refractive index decreased and the band gap increased. Consequently, the transmittance increased due to the higher band gap and the decrease of the defect states, which existed for the 1.68 and 1.80 eV in the SiN_x films. The interface trap density found in silicon can be reduced down to 1.0×10¹⁰ cm⁻² eV⁻¹ for the SiN_x layer deposited under the optimized silane to ammonia gas ratio. Reduction in the carrier lifetime of the SiN_x films deposited using a higher NH₃/SiH₄ flow ratio was caused by the increase of the interface traps and the defect states in/on the interface between the SiN_x and the silicon wafer. Silicon and nitrogen rich films are not suitable for generating both higher carrier lifetimes and transmittance. An improvement in the single c-Si solar cell parameters was observed for the cells with an optimal SiN_x layer, as compared to those with non-optimal SiN_x layers. These results indicate that the band gap and the defect states of the SiN_x films should be carefully controlled in order to obtain the maximum efficiency for c-Si solar cells.     

Defect passivation of industrial multicrystalline solar cells based on PECVD silicon nitride

Low surface recombination velocity and significant improvements in bulk quality are key issues for efficiency improvements of solar cells based on a large variety of multicrystalline silicon materials. It has been proven that PECVD silicon nitride layers provide excellent surface and bulk passivation and their deposition processes can be executed with a high throughput as required by the PV industry. The paper discusses the various deposition techniques of PECVD silicon nitride layers and also gives results on material and device properties characterisation. Furthermore the paper focuses on the benefits achieved from the passivation properties of PECVD SiN_x layers on the multi-Si solar cells performance. This paper takes a closer look at the interaction between bulk passivation of multi-Si by PECVD SiN_x and the alloying process when forming an Al-BSF layer. Experiments on state-of-the-art multicrystalline silicon solar cells have shown an enhanced passivation effect if the creation of the alloy and the sintering of a silicon nitride layer (to free hydrogen from its bonds) happen simultaneously. The enhanced passivation is very beneficial for multicrystalline silicon, especially if the defect density is high, but it poses processing problems when considering thin (<200 μm) cells.     

Deposition of thin film silicon using the pulsed PECVD and HWCVD techniques

We report on the use of pulsed plasma-enhanced chemical vapor deposition (P-PECVD) technique and show that “state-of-the-art” amorphous silicon (a-Si:H) materials and solar cells can be produced at a deposition rate of up to 15 Å/s using a modulation frequency in the range 1–100 kHz. The approach has also been developed to deposit materials and devices onto large area, 30 cm×40 cm, substrates with thickness uniformity (<5%), and gas utilization rate (>25%). We have developed a new “hot wire” chemical vapor deposition (HWCVD) method and report that our new filament material, graphite, has so far shown no appreciable degradation even after deposition of 500 μm of amorphous silicon. We report that this technique can produce “state-of-the-art” a-Si:H and that a solar cell of p/i/n configuration exhibited an initial efficiency approaching 9%. The use of microcrystalline silicon (μc-Si) materials to produce low-cost stable solar cells is gaining considerable attention. We show that both of these techniques can produce thin film μc-Si, dependent on process conditions, with 1 1 1 and/or 2 2 0 orientations and with a grain size of approx. 500 A. Inclusion of these types of materials into a solar cell configuration will be discussed.     

Recycling of solar cell silicon scraps through filtration, Part I: Experimental investigation

This study investigated the removal of SiC and Si₃N₄ inclusions from top-cut solar cell silicon scraps by filtration with foam filters. Laboratory experiments tested various models for the removal mechanism of inclusions and the efficiency of ceramic foam filters. Inclusions in solar cell silicon top-cut scraps were mainly needle-like Si₃N₄ particles and lumpy SiC inclusions. SiC and Si₃N₄ inclusions sometimes agglomerated as clusters. Si₃N₄ inclusions were usually more than 500 μm long with diameters of ∼20 μm, and SiC inclusions were usually smaller than 500 μm. After filtration, no Si₃N₄ inclusions were found. The remaining inclusions were mainly SiC inclusions smaller than 10 μm. Filters with smaller pores improved the removal of inclusions. It was discovered that contamination of the silicon may occur from components of the filters themselves, especially from binders. The crucible was also a source of contamination. A filtration process that does not produce contamination of its own should be developed before being used in real industrial processes. Mechanisms for the removal of inclusions from silicon through filtration are as follows: (1) cake filtration, for the removal of large Si₃N₄ rods and large SiC inclusions; (2) deep-bed filtration of smaller Si₃N₄ inclusions and most SiC particles; (3) formation of large SiC clusters and bridges across pores, and (4) silicon dissolution into carbon filters, and a subsequent reaction to form layers of SiC.     

Fundamental understanding and implementation of Al-enhanced PECVD SiNx hydrogenation in silicon ribbons

A low-cost, manufacturable defect gettering and passivation treatment, involving simultaneous anneal of a PECVD SiN_x film and a screen-printed Al layer, is found to improve the lifetime in Si ribbon materials from 1–10 μs to over 20 μs. Our results indicate that the optimum anneal temperature for SiN_x-induced hydrogenation is 700°C for EFG and increases to 825°C when Al is present on the back of the sample. This not only improves the degree of hydrogenation, but also forms an effective back surface field. We propose a three-step physical model, based on our results, in which defect passivation is governed by the release of hydrogen from the SiN_x film due to annealing, the generation of vacancies during Al–Si alloying, and the retention of hydrogen at defect sites due to rapid cooling. Controlled rapid cooling was implemented after the hydrogenation anneal to improve the retention of hydrogen at defect sites by incorporating an RTP contact firing scheme. RTP contact firing improved the performance of ribbon solar cells by 1.3–1.5% absolute when compared to slow, belt furnace contact firing. This enhancement was due to improved back surface recombination velocity, fill factor, and bulk lifetime. Enhanced hydrogenation and rapid heating and cooling resulted in screen-printed Si ribbon cell efficiencies approaching 15%.