Field effect surface passivation of SiO2/Si interfaces by heat treatment with high-pressure H2O vapor

We investigated a simple field effect passivation of the silicon surfaces using the high-pressure H₂O vapor heating. Heat treatment with 2.1×10⁶ Pa H₂O vapor at 260°C for 3 h reduced the surface recombination velocity from 405 cm/s (before the heat treatment) to 38 cm/s for the thermally evaporated SiO_x film/Si. Additional deposition of 140 nm-SiO_x films (x<2) with a high density of fixed positive charges on the SiO₂/Si samples further decreased the surface recombination velocity to 22 cm/s. We also demonstrated the field effect passivation for n-type silicon wafer coated with thermally grown SiO₂. Additional deposition of 210 nm SiO_x films on both the front and rear surfaces increased the effective lifetime from 1.4 to 4.6 ms. Combination of thermal evaporation of SiO_x film and the heat treatment with high-pressure H₂O vapor is effective for low-temperature passivation of the silicon surface.     

Potential cost reduction of buried-contact solar cells through the use of titanium dioxide thin films

This paper explores the potential of applying titanium dioxide (TiO₂) thin films to the buried-contact (BC) solar cell. The aim is to develop a lower-cost BC technology that can be applied to multicrystalline silicon (mc-Si) wafers, the predominant substrate of the photovoltaics (PV) industry. The original BC solar cell used a thick, thermally grown, silicon dioxide (SiO₂) layer as the front surface dielectric coating. Upon commercialisation of the BC technology, BP Solar replaced this layer with silicon nitride (Si₃N₄), which exhibits improved optical properties. It is anticipated that production costs can be further reduced by using a low temperature deposited front surface dielectric coating, such as TiO₂, thereby reducing the number of lengthy high temperature processing steps, and developing a process such that it can be applied to mc-Si wafers. TiO₂ is chosen because of its optimal optical properties for glass-encapsulated silicon solar cells and familiarity of PV manufacturers with this material. The results presented resolve the issue of surface passivation with TiO₂ and demonstrate that TiO₂/SiO₂ stacks, achieved during a brief high-temperature oxidation process after TiO₂ thin film deposition, are compatible with high-efficiency solar cells. However, TiO₂ cannot perform all the necessary functions of the thick SiO₂ or Si₃N₄ layer, due to its inability to act as a phosphorus diffusion barrier. In light of these results, three alternate BC solar cell fabrication sequences are presented, and an initial conversion efficiency of 11.5% has been achieved from the first batch of solar cells in a non-optimised processes.     

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.     

Characteristics of vapor-liquid-solid grown silicon nanowire solar cells

We report fabrication and characterization of solar cells based on vapor-liquid-solid (VLS) grown silicon nanowires (NWs) that form core-shell radial p-n junction structures. We observe efficiency enhancement due to the presence of the NWs that increase the light trapping within the device, while the use of gold as VLS catalyst results in increased carrier recombination within the wires. From the spectral efficiency data, we identify that the surface recombination effect becomes more significant in the large surface area NW cells. To remedy this issue we demonstrate the efficacy of a highly conformal Al₂O₃ film grown by atomic layer deposition to serve as surface passivation layer. This work highlights the key issues confronted by NW-based solar cells grown by VLS technique.     

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.     

Effect of hydrogen dilution on intrinsic a-Si:H layer between emitter and Si wafer in silicon heterojunction solar cell

In silicon heterojunction solar cells, a thin intrinsic amorphous-silicon (a-Si:H) buffer layer between a doped emitter and a c-Si wafer is essential to minimize carrier recombination. This study examines the effect of H₂ dilution on the properties of the intrinsic a-Si:H layers deposited on Si wafers by plasma-enhanced chemical vapor deposition. A H₂/SiH₄ ratio of 24 led to improvements in the quality of intrinsic a-Si:H films and in the performance of passivation compared to a-Si:H film without H₂ dilution. A high H₂-dilution ratio, however, degraded the passivation of the a-Si:H film. The Si heterojunction solar cells with an optimal intrinsic a-Si:H layer showed an efficiency of 12.3%.     

Plasma enhanced chemical vapor deposition of excellent a-Si:H passivation layers for a-Si:H/c-Si heterojunction solar cells at high pressure and high power

The intrinsic a-Si:H passivation layer inserted between the doped a-Si:H layer and the c-Si substrate is very crucial for improving the performance of the a-Si:H/c-Si heterojunction (SHJ) solar cell. The passivation performance of the a-Si:H layer is strongly dependent on its microstructure. Usually, the compact a-Si:H deposited near the transition from the amorphous phase to the nanocrystalline phase by plasma enhanced chemical vapor deposition (PECVD) can provide excellent passivation. However, at the low deposition pressure and low deposition power, such an a-Si:H layer can be only prepared in a narrow region. The deposition condition must be controlled very carefully. In this paper, intrinsic a-Si:H layers were prepared on n-type Cz c-Si substrates by 27.12 MHz PECVD at a high deposition pressure and high deposition power. The corresponding passivation performance on c-Si was investigated by minority carrier lifetime measurement. It was found that an excellent a-Si:H passivation layer could be obtained in a very wide deposition pressure and power region. Such wide process window would be very beneficial for improving the uniformity and the yield for the solar cell fabrication. The a-Si:H layer microstructure was further investigated by Raman and Fourier transform infrared (FTIR) spectroscopy characterization. The correlation between the microstructure and the passivation performance was revealed. According to the above findings, the a-Si:H passivation performance was optimized more elaborately. Finally, a large-area SHJ solar cell with an efficiency of 22.25% was fabricated on the commercial 156 mm pseudo-square n-type Cz c-Si substrate with the opencircuit voltage (V_oc) of up to 0.732 V.     

I-V characteristics of a-Si-c-Si hetero-junction diodes made by hot wire CVD

p-Type hydrogenated amorphous silicon (a-Si:H) was deposited on n-type crystalline silicon (c-Si) substrates to obtain hetero-junction diodes. Additionally, a thin intrinsic a-Si:H layer was inserted between both the p-type film and the n-type substrate to study its passivation effect on the c-Si surface. The amorphous films were obtained by the hot wire chemical vapor deposition (HWCVD) technique, using a tungsten filament and silane (SiH₄), hydrogen (H₂) and diborane (B₂H₆) gases, where the deposition parameters such as gas flow, substrate temperature and filament temperature were varied. Optical band gap, deposition rate and conductivity were measured for all the films. We studied the influence of the quality of the amorphous films upon the performance of the hetero-junction diodes. In particular, the diode ideality factor (n) and the saturation current density (J₀) were determined by measuring the current-voltage characteristics in dark conditions. It is shown that the presence of the intrinsic layer is fundamental for making good diodes, since devices made without this film cause the diodes to have high saturation current density and ideality factor (J₀>10×10⁻⁶ A/cm², n>4) as compared to diodes with a good intrinsic layer (J₀=5×10⁻⁹ A/cm², n=1.39). The results obtained are encouraging, but the quality of the intrinsic films still should be improved for applying them to HIT solar cells.     

Passivation and etching of fine-grained polycrystalline silicon films by hydrogen treatment

Here we investigated the effects of hydrogen treatment on highly defected polycrystalline silicon solar cells in terms of defects passivation and surface etching. The poly-Si films were formed by high-temperature chemical vapour deposition. The hydrogen treatment was carried out through deposition of a-SiN_x:H layer followed by a thermal treatment or by direct hydrogen plasma. The deposition of silicon nitride layers on polysilicon cells led to a slight increase in the open-circuit voltage without damage to the surface. In contrast, after plasma hydrogenation, the results revealed an etching process of the emitter simultaneously with an important increase of the measured open-circuit voltage by a factor 2, reaching 420 mV.     

Requirements of PECVD SiNx:H layers for bulk passivation of mc-Si

Optimization of plasma enhanced chemical vapor deposited hydrogenated silicon nitride (SiN_x:H) towards bulk passivation of multi-crystalline silicon cells has been carried out for both low and high frequency (HF) plasma deposition. Experimental results showed that bulk passivation is not caused by hydrogen incorporation in the top silicon layer during deposition and subsequent diffusion towards the bulk during firing, but that it is released from the SiN_x:H film. We demonstrate that the amount of passivation depends on the SiN_x:H density and its resistance against etching in HF. Optimization of the density, varying deposition temperature and using hydrogen dilution resulted in an optimized passivation.     

Crystalline silicon surface passivation by amorphous silicon carbide films

This article reviews the surface passivation of n- and p-type crystalline silicon by hydrogenated amorphous silicon carbide films, which provide surface recombination velocities in the range of 10 cm s⁻¹. Films are deposited by plasma-enhanced chemical vapor deposition from a silane/methane plasma. We determine the passivation quality measuring the injection level (Δn)-dependent lifetime (τ_eff(Δn)) by the quasi-steady-state photoconductance technique. We analyze the experimental τ_eff(Δn)-curves using a physical model based on an insulator/semiconductor structure and an automatic fitting routine to calculate physical parameters like the fundamental recombination velocities of electrons and holes and the fixed charge created in the film. In this way, we get a deeper insight into the effect of the deposition temperature, the gas flow ratio, the doping density of the substrate and the film thickness on surface passivation quality.     

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.     

16.4% efficient, thin active layer silicon solar cell grown by liquid phase epitaxy

An energy conversion efficiency of 16.4% is reported for a silicon solar cell of 4.11 cm² total area with a thin active layer of 32 μm grown by liquid phase epitaxy (LPE). This is the highest ever total area efficiency for a cell of this type and is due to a number of improvements over earlier reported results. The thin active layer was grown by LPE on an inactive silicon substrate from an indium solution in a 20% hydrogen/argon forming gas mixture ambient rather than pure hydrogen. Higher current density and efficiency than previously reported for similar cell structures have been achieved by employing microgroove texturing of the front surface, a very shallow (0.25 μm) and high sheet resistivity (220 Ω□) top surface phosphorus diffusion, an optimized ZnS/MgF₂ double layer antireflection coating on top of a 200Å thick, high quality passivation SiO₂ layer, a large aspect ratio (0.45) for the metal contacts, and a graded doping level within the 32 μm thick LPE active layer. The effect of the improved techniques on the cell performance and the properties of the thin active layers are discussed.     

Silicon lifetime enhancement by SiNx:H anti-reflective coating deposed by PECVD using SiH4 and N2 reactive gas

Hydrogenated films of silicon nitride SiN_x:H are largely used as antireflective coating as well as passivation layer for industrial crystalline and multicrystalline silicon solar cells. In this work, we present a low cost plasma enhanced chemical vapor deposition (PECVD) of this thin layer by using SiH₄ and N₂ as a reactive gases. A study was carried out on the variation effect of the ratio silane (SiH₄) to nitrogen (N₂) and time deposition on chemical composition, morphologies, reflectivity and carrier lifetime. The thickness was varied, in order to obtain a homogeneous antireflective layer. The Fourier transmission infrared spectroscopy (FTIR) shows the existence of Si–N and Si–H bonds. The morphologies of the sample were studied by Atomic Force Microscopy (AFM). The resulting surface of the SiN_x:H shows low-reflectivity less than 5% in wavelength range 400–1200 nm. As a result, an improvement in minority carrier lifetime has been achieved to about 15 μs.     

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.     

Investigation of various surface passivation schemes for silicon solar cells

In this work, we have investigated three different surface passivation technologies: classical thermal oxidation (CTO), rapid thermal oxidation (RTO) and silicon nitride by plasma enhanced chemical vapor deposition (PECVD). Eight different passivation properties including SiO₂/SiN_x stacks on phosphorus diffused (100 and 40 Ω/Sq) and non-diffused 1 Ω cm FZ silicon were compared. Both types of SiO₂ layers, CTO and RTO, yield a higher effective lifetime on the emitter surface than on the non-diffused surface. For the SiN_x layers the situation is reverted. On the other hand, with SiO₂/SiN_x stacks high lifetimes are obtained not only non-diffused surface but also on the diffused surface. Thus, we have chosen the RTO/SiN_x stack layers as front and rear surface passivation in solar cells, which passivate relatively good on the surface and has very low-weighted reflection. On planar cells passivated with RTO/SiN_x a very high V_oc of 675.6 mV and a J_sc of 35.1 mA/cm² was achieved. Compared to a planar cell using CTO the efficiency of RTO/SiN_x cell is 0.8% higher (4.5% relative). It can be concluded that the RTO/SiN_x layers are the optimal passivation for the front and rear surface. On the other hand, for textured cells, the J_sc and FF of RTO/SiN_x cells are lower than those of CTO cells. The main reasons of these J_sc and FF losses were also discussed systematically.     

Carrier transport in high-efficiency ZnO/SiO2/Si solar cells

Carrier transport in ZnO/SiO₂/n-Si solar cell has been theoretically analyzed with a consideration that the photo-carrier transport from silicon to ZnO layer through the barrier is dominated by quantum mechanical tunneling process of minority carrier. It was found that the highest efficiency of the cell could be achieved at SiO₂ layer thickness of around 20 Å. The efficiency of the cells decreases as the surface states density Q_ss becomes higher. Moreover, the efficiency increases as the electron concentration of ZnO layer is increased due to the decrease of work function of ZnO. It was also found that the lower transmittance of the high carrier concentration ZnO due to the free-carrier absorption at infrared wavelength region does not give any significant effect to the cell performance. The efficiency of higher than 25% is achievable by optimizing the involved device parameters.     

Improvement of characteristics of new-type solar cells, having a “transparent conductor/thin Si02 layer with ultrafine metal particles as conductive channels/n-Si” junction

New-type solar cells, having a structure “transparent conductor/thin Si0₂ layer with ultrafine metal islands as conductive channels/n-Si” have been prepared by forming a very thin (< 1.0 nm) silicon oxide (Si0₂) layer as well as platinum (Pt) islands (5–50 nm in size) embedded in it on a single crystal n-type silicon (n-Si) wafer, followed by the deposition of an indium tin oxide (ITO) film (200 nm thick) by the electron-beam evaporation method. The open-circuit photovoltages (V_oc) of the solar cells of the above structure were relatively low, 0.25–0.47 V, but they increased very much to 0.50–0.59 V if a thin (3–10 nm) layer of an organic compound such as copper phthalocyanine (CuPc) was pre-deposited on the Pt-island modified n-Si wafer before the ITO deposition. The reason for the beneficial effect of the pre-deposition of the thin CuPc layer was investigated in detail, and it has been found that certain crystal defects are formed in n-Si near the n-Si/Si0₂ interface during the ITO deposition in the absence of the CuPc layer. The formation of such defects is prevented in the presence of the CuPc layer, which leads to a decrease in surface carrier recombination and hence to the increase in V_oc.     

A simple and efficient process for fabricating high efficiency polycrystalline silicon ribbon solar cells

The aim of this work is to clarify the potential of the low cost polycrystalline silicon String Ribbon for fabricating high efficiency solar cells with gettering and passivation techniques. The application of P and Al gettering as well as SiO₂ and H passivation schemes enhanced the material quality and boosted the efficiency of the solar cells. A cell efficiency above 15% has been achieved using a simple fabrication process.     

Recent developments in rear-surface passivation at Fraunhofer ISE

Fraunhofer ISE has a long experience in the field of surface passivation for crystalline silicon wafers. Novel rear-surface passivation layer systems have led to excellent results. Using a low-temperature passivation stack of hydrogenated amorphous silicon and plasma-enhanced chemical vapor deposition (PECVD) silicon oxide an efficiency of up to 21.7% has been achieved. Thermally stable passivation can be proven with all-PECVD stacks of silicon oxide, silicon nitride, and silicon oxide (PECVD-ONO), i.e. after contact firing. Solar cell efficiencies of up to 20.0% have been reached with PECVD-ONO. In parallel, Fraunhofer ISE is working on silicon carbide (SiC_x) layers, which provide excellent and thermally stable passivation, as well deposited by PECVD. Solar cells with SiC_x layers as rear passivation led to efficiencies of up to 20.2%.