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.     

Low temperature surface passivation for silicon solar cells

Surface passivation at low processing temperatures becomes an important topic for cheap solar cell processing. In this study, we first give a broad overview of the state of the art in this field. Subsequently, the results of a series of mutually related experiments are given about surface passivation with direct Plasma Enhanced Chemical Vapour Deposition (PECVD) of silicon oxide (Si-oxide) and silicon nitride (Si-nitride). Results of harmonically modulated microwave reflection experiments are combined with Capacitance-Voltage measurements on Metal-Insulator-Silicon structures (CV-MIS), accelerated degradation tests and with Secondary Ion Mass Spectrometry (SIMS) and Elastic Recoil Detection (ERD) measurements of hydrogen and deuterium concentrations in the passivating layers. A large positive fixed charge density at the interface is very important for the achieved low surface recombination velocities S. The density of interface states D_it is strongly reduced by post deposition anneals. The lowest values of S are obtained with PECVD of Si-nitride. The surface passivation obtained with Si-nitride is stable under typical operating conditions for solar cells. By using deuterium as a tracer it is shown that hydrogen in the ambient of the post deposition anneal does not play a role in the passivation by Si-nitride. Finally, the results of CV-MIS measurements (Capacitance-Voltage measurements on Metal-Insulator-Silicon structures) on deposited Si-nitride layers are used to calculate effective recombination velocities as a function of the injection level at the surface, using a model that is able to predict the surface recombination velocity S at thermally oxidized silicon surfaces. These results are not in agreement with the measured increase of S at low injection levels.     

Surface passivation of crystalline silicon wafer via hydrogen plasma pre-treatment for solar cells

The carrier lifetime of crystalline silicon wafers that were passivated with hydrogenated silicon nitride (SiN_x:H) films using plasma enhanced chemical vapor deposition was investigated in order to study the effects of hydrogen plasma pre-treatment on passivation. The decrease in the native oxide, the dangling bonds and the contamination on the silicon wafer led to an increase in the minority carrier lifetime. The silicon wafer was treated using a wet process, and the SiN_x:H film was deposited on the back surface. Hydrogen plasma was applied to the front surface of the wafer, and the SiN_x:H film was deposited on the hydrogen plasma treated surface using an in-situ process. The SiN_x:H film deposition was carried out at a low temperature (<350 °C) in a direct plasma reactor operated at 13.6 MHz. The surface recombination velocity measurement after the hydrogen plasma pre-treatment and the comparison with the ammonia plasma pre-treatment were made using Fourier transform infrared spectroscopy and secondary ion mass spectrometry measurements. The passivation qualities were measured using quasi-steady-state photoconductance. The hydrogen atom concentration increased at the SiN_x:H/Si interface, and the minority carrier lifetime increased from 36.6 to 75.2 μs. The carbon concentration decreased at the SiN_x:H/Si interfacial region after the hydrogen plasma pre-treatment.     

Surface passivation in high efficiency silicon solar cells

Surface passivation for crystalline silicon solar cells is particularly important for devices with open-circuit voltages in excess of 650 mV. Thick passivating thermal oxides, originally developed for use with buried contact solar cells, are shown to produce the most effective and stable surface passivation particularly in conjunction with lightly phosphorus diffused surfaces. However, for improved optical performance, antireflection coatings are only effective with surface oxide thicknesses reduced to 100–200 Å. Thinner passivating oxides cause significant voltage loss, most of which can be recovered through hydrogen passivation. Throughout this study, variation in surface passivation approaches has produced open-circuit voltages ranging from 620 mV to record voltages of 720 mV.     

Hydrogen passivation of defects in multicrystalline silicon solar cells

The knowledge of how hydrogen interacts with defects and impurities in silicon is crucial for the understanding of device performance, especially for solar cells made from disordered silicon wafers. Hydrogen can be introduced in silicon by several techniques, but this paper will be focused on hydrogenation by means of plasma enhanced chemical vapor deposition of hydrogen-rich silicon nitride layer on the surface of the wafer. Passivation effects are observed after annealing and evaluated using minority carrier diffusion length measurements and light-beam-induced current scan maps.It was found that individual intragrain defects are well passivated, while deep levels are transformed into poorly recombining shallow levels at grain boundaries and dislocation clusters. In solar cells, the stability of the hydrogen passivation is much higher with this technique than with other hydrogenation techniques. This is probably due to an encapsulation of hydrogen by the frontwall silicon nitride coating layers and by the backside aluminum film.     

Ribbon growth on substrate (RGS) silicon solar cells with microwave-induced remote hydrogen plasma passivation and efficiencies exceeding 11%

For the first time efficiencies above 11% for solar cells (4 cm²) based on Bayer ribbon growth on substrate (RGS) crystalline silicon have been demonstrated including mechanical V-structuring of the front surface, aluminum-gettering, microwave-induced remote hydrogen plasma (MIRHP) passivation and PECVD SiN/SiO₂ double-layer antireflection coating. MIRHP alone resulted in absolute improvements in the open-circuit voltage of 27 mV, in the short-circuit current density of 2.8 mA cm⁻² and in the cell efficiency of 1.9% leading to an open-circuit voltage of 538 mV and an efficiency of 11.1%.     

Wet-chemical passivation and characterization of silicon interfaces for solar cell applications

The interface properties of silicon solar cell structures were characterized by the two non-destructive and highly surface-sensitive spectroscopic techniques: surface photovoltage and spectroscopic ellipsometry. The resulting charge and density of interface states as well as the microscopic surface roughness and oxide coverage were investigated during silicon wafer preparation and during sample storage in air. The surface state density of hydrogen-terminated silicon surfaces as well as the long-time stability of the hydrogen termination were found to primarily depend on the surface morphology resulting from the wet-chemical oxidation procedures applied before. The smallest interface state densities were obtained by NH₄F treatment subsequent to oxidation in ultra-pure water at 80°C. Surfaces prepared using this procedure are found to be much more stable upon exposition to clean-room air than those prepared by conventionally prepared H-terminated surfaces.The successful application of the new passivation procedures in photovoltaics is shown for selected examples of different solar cell concepts.     

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.     

Silicon nitride passivated bifacial Cz-silicon solar cells

A new process for all silicon nitride passivated silicon solar cells with screen printed contacts is analysed in detail. Since the contacts are fired through the silicon nitride layers on both sides, the process is easy to adapt to industrial production. The potential and limits of the presented bifacial design are simulated and discussed. The effectiveness of the presented process depends strongly on the base doping of the substrate, but only the open circuit voltage is affected. The current is mainly determined by the rear surface passivation properties. Thus, using a low resistivity base material higher efficiencies compared to an aluminium back surface field can be achieved.     

Surface passivation at a SiO2/n-layer interface

Effects of surface passivation at a SiO₂/phosphorus-doped layer (n⁺-layer) front interface were investigated. Two kinds of cells with different surface concentration were fabricated. Surface potential at the interface was changed by applying bias voltage (V_F). Both open-circuit voltage and short-circuit current of the cell with n⁺-layer concentration of 3 × 10¹⁸ cm⁻³ depended on V_F. Internal quantum efficiency of this cell in short- and medium-wavelength range was changed by applying V_F. It was shown that cell performance was improved by the accumulation of electrons at the interface. To consider the work function difference between a material on the SiO₂ film and the n⁺-layer is important, and cell performance can be further improved by applying V_F to passivate the SiO₂/n⁺-layer interface.     

Effect of hydrogen radical annealing on SiN passivated solar cells

Remote plasma was used for PE-CVD of SiN films and it was found that hydrogen radical (H^* ) annealing of c-Si cells with SiN films improved the efficiency of the cells. Cell efficiency of 21.8% was obtained by applying a SiN/SiO₂ double-layer structure on the emitter of a PERL-type solar cell. It was found that the H^* annealing has two effects: it reduces surface recombination velocity (SRV); and it degrades bulk-lifetime of p-type c-Si. To apply SiN practically, it is effective to use a rear n-floating or a triode structure. Reducing the exposed area of the p-type substrate by using n-type diffused layer increases the efficiency of solar cells.     

Low temperature passivation of silicon surfaces by polymer films

A novel surface passivation method for silicon carrier lifetime measurements and solar cells using a polymer film is introduced. It is easy to apply, no special pre-treatment, e.g. no hydrofluoric acid (HF)-treatment, is necessary. The surfaces to be passivated are covered with the polymer solution, dried at 90°C and encapsulated. Surface recombination velocities (S) as low as S=30 cm/s for various doping concentrations have been observed, nearly independent of the bulk injection level. The passivation is stable for at least 6 h. For a polymer-passivated rear contact solar cell the same open circuit voltage is achieved as for a cell with thermally grown oxide.     

Comparing improved state-of-the-art to former EFG Si-ribbons with respect to solar cell processing and hydrogen passivation

Recently, the ASE Company succeeded in enhancing the material quality of their octagon edge-defined film-fed growth (EFG) silicon ribbons resulting in a higher average cell efficiency in the manufacturing line of ASE Americas. In order to quantify and characterize these improvements in material quality, lifetime measurements have been performed on state-of-the-art and, for comparison reasons, also on older EFG material. Moreover, these wafers were subjected to a laboratory solar cell process. Consequently, it has been possible to perform laser beam induced current (LBIC) mappings and to compare the resulting internal quantum efficiency (IQE) mappings to the lifetime measurements performed before cell processing. As a result we found typical, different distributions of lifetime and IQE for the two materials. Further on, the solar cells have been hydrogen passivated using a microwave-induced hydrogen plasma and characterized again so that the impact of this passivation technique on the materials in different states of development could have been investigated. In this way, an appropriate hydrogen defect passivation turned out to reduce the differences between the different kinds of EFG ribbons.     

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.     

太阳能电池背表面钝化的研究

利用PC1D模拟不同少子寿命的电池效率与背表面复合速率的关系,采用氮化硅和及其与二氧化硅薄膜的叠加层作为背面钝化膜,通过丝网印刷的方法形成条形局域背接触和局域背面点接触,条形接触的面积为背表面的25%,背面点接触孔径为250μm,间距2mm。经过RTP处理之后,两种不同的接触方式存在相同的问题,串联电阻大,并联电阻小,而利用腐蚀浆料的方法形成背面点接触,在电性能参数有少许改善。结果表明,在正常的烧结状态下,常规铝浆很难完全穿透氮化硅薄膜及其叠加层背面钝化层。而利用腐蚀浆料的方法形成背面点接触,在电性能参数有少许改善。     

Hydrogen passivation of defects in polycrystalline silicon solar cells

The investigations of hydrogen passivation of defects in polycrystalline silicon produced by the Czochralski method have been carried on. The results presented give evidence that it is advisable to use this material to create cheap effective solar cells.     

Experimental evidence of very high open-circuit voltages of inversion–layer silicon solar cells

In this paper the first experimental evidence of the high V_oc-potential of inversion-layer silicon solar cells is given. Minority-carrier lifetime measurements on inversion-layer emitters have been performed and the diffused p–n contact of PN-IL silicon solar cells has been optimized for high open-circuit voltages. PN-IL silicon solar cells with open-circuit voltages of 693 mV have been fabricated on 0.2 and 0.5-Ω cm FZ p-Silicon wafers. These values are the highest ever reported V_oc's for inversion-layer silicon solar cells on p-Silicon. This demonstrates that inversion-layer silicon solar cells exhibit a similar potential for achieving high open-circuit voltages as silicon solar cells with a diffused p–n junction.     

Effect of hydrogen producing mixed culture on performance of microbial fuel cells

This study examined the influence of H₂-producing mixed cultures on improving power generation using air-cathode microbial fuel cells (MFCs) inoculated with heat-treated anaerobic sludge. The MFCs installed with graphite brush anode generated higher power than the MFCs with carbon cloth anode, regardless heat treatment of anaerobic sludge. When the graphite brush anode-MFCs were inoculated selectively with H₂-producing bacteria by heat treatment, power production was not improved (about 490 mW/m²) in batch mode operation, but for slightly increased in carbon cloth anode-MFCs (from 0.16 to 2.0 mW/m²). Although H⁺/H₂ produced from H₂-producing bacteria can contribute to the performance of MFCs, suspended biomass did not affect the power density or potential, but the Coulombic efficiency (CE) increased. A batch test shows that propionate and acetate were used effectively for electricity generation, whereas butyrate made a minor contribution. H₂-producing mixed cultures do not affect the improvement in power generation and seed sludge, regardless of the pretreatment, can be used directly for the MFC performance.     

A new back surface passivation stack for thin crystalline silicon solar cells with screen-printed back contacts

In order to manufacture high-efficiency Si solar cells with a passivated rear surface and local contacts, it is necessary to develop both an excellent rear-passivation scheme compatible with screen-printing technology and a robust patterning technique for local contact formation. In this work, we have fabricated Si solar cells on ∼130 μm thick substrates using manufacturable processing, where rear side was passivated with a plasma-enhanced chemical vapor deposited SiO_x/SiN_x/SiO_xN_y stack and local back contacts using laser. As a result of both the rear surface passivation stack and the laser-fired local contacts, cell efficiencies of up to 17.6% on a 148.6 cm² Float-zone Si wafer and 17.2% for a 156.8 cm² multicrystalline Si wafer were achieved. PC-1D calculations revealed that the cells had a back surface recombination velocity (BSRV) of ∼400 cm/s and a back surface reflectance (BSR) of over 90%, as opposed to standard full Al-BSF cells having a BSRV of ∼800 cm/s and a 70% BSR. This result clearly indicates that the new technique of the passivation scheme and the patterning using laser developed in this study are promising for manufacturing high-efficiency PERC-type thin Si solar cells.     

Surface passivation for germanium photovoltaic cells

Passivation of a germanium surface has proved to be challenging. Various materials have been examined for this purpose, like for example silicon nitride and amorphous silicon. In this work the optimisation of PECVD amorphous silicon and the influence of the preliminary surface treatment for passivation purposes are described. Furthermore, experiments done to extract the surface recombination velocity and the bulk lifetime of a germanium substrate will be presented. Optimisation of the deposition parameters, in combination with a pre-deposition in situ hydrogen plasma, results in a surface recombination velocity of 17 cm/s on a lowly doped germanium substrate.