Hydrogen passivation of defects in EFG ribbon silicon

To enhance the bulk lifetime of multicrystalline silicon material, gettering of impurities and hydrogen passivation of defects are investigated. In edge-defined film-fed grown (EFG) ribbon silicon, an aluminium-enhanced hydrogenation of defects by silicon nitride has been reported. On thin wafers, the formation of a full area aluminium back surface field will lead to wafer bending due to different thermal expansion coefficients of aluminium and silicon. To circumvent this problem, remote plasma-enhanced chemical vapour deposited (PECVD) silicon nitride (SiN_x) as passivation scheme for the front and rear surface is proposed. In this work, the bulk passivation by hydrogenation is investigated using two different hydrogen passivation techniques: (i) passivation in a remote hydrogen plasma and (ii) passivation due to a post-deposition anneal of remote PECVD-SiN_x in a lamp-heated conveyor belt furnace. Measurements of the bulk lifetime show that the lifetime improvement due to remote hydrogen plasma passivation degrades under illumination with white light. In contrast, the hydrogen passivation by a post-deposition SiN_x anneal is only effective if a phosphorous-doped emitter is present below the SiN_x layer during the hydrogenation. This lifetime improvement is stable under illumination.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Modeling effective carrier lifetimes of passivated macroporous silicon layers

We derive and apply a model that determines the effective minority carrier lifetime of macroporous crystalline silicon samples as a function of bulk lifetime, surface passivation and pore morphology. Two cases are considered: A layer of periodic macropores at the surface of a silicon wafer and a free standing macroporous silicon layer. We compare the model with experimental lifetime measurements for samples with randomly positioned macropores with a length of 10-40 μm. The pores have an average pore diameter of 2.4 μm and an average pore distance of 5.2 μm. The surface is passivated by thermal oxidation. The model agrees with the measurements if we assume an average surface recombination velocity S=24 cm/s at the pore surface.     

Angle-resolved characteristics of silicon photovoltaics with passivated conical-frustum nanostructures

Passivation plays a critical role in silicon photovoltaics, yet how a passivation layer affects the optical characteristics of nano-patterned surfaces has rarely been discussed. In this paper, we demonstrate conical-frustum nanostructures fabricated on silicon solar cells using polystyrene colloidal lithography with various silicon-nitride (SiN_x) passivation thicknesses. The omnidirectional and broadband antireflective characteristics were determined by utilizing angle-resolved reflectance spectroscopy. The conical-frustum arrays with a height of 550 nm and a SiN_x thickness of 80 nm effectively suppressed the Fresnel reflection in the wavelength range from 400 to 1000 nm, up to an incidence angle of 60°. As a result, the power conversion efficiency achieved was 13.39%, which showed a 9.13% enhancement compared to that of a conventional KOH-textured silicon cell. The external quantum efficiency measurements confirmed that the photocurrent was mostly contributed by the increased optical absorption in the near-infrared. The angular cell efficiencies were estimated and showed improvements over large angles of incidence.     

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%.     

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.     

Application of rapid thermal processing on SiNx thin film to solar cells

Rapid thermal processing (RTP) of SiN _x thin films from PECVD with low temperature was investigated. A special processing condition of this technique which could greatly increase the minority lifetime was found in the experiments. The processing mechanism and the application of the technique to silicon solar cells fabrication were discussed. A main achievement is an increase of the minority lifetime in silicon wafer with SiN _x thin film by about 200% after the RTP was reached. PC-1Dsimulation results exhibit an enhancement of the efficiency of the solar cell by 0.42% coming from the minority lifetime improvement. The same experiment was also conducted with P-diffusion silicon wafers, but the increment of minority lifetime is just about 55%. It could be expected to improve the solar cell efficiency if it would be used in silicon solar cells fabrication with the combination of laser firing contact technique. __________ Translated from Journal of Shanghai Jiaotong University, 2008, 42(1): 152–155 [译自: 上海交通大学学报]     

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.     

SiO2 passivation layer grown by liquid phase deposition for silicon solar cell application

Surface passivation is one of the primary requirements for high efficient silicon solar cells. Though the current existed passivation techniques are effective, expensive equipments are required. In this paper, a comprehensive understanding of the SiO₂ passivation layer grown by liquid phase deposition (LPD) was presented, which was cost-effective and very simple. It was found that the post-annealing process could significantly enhance the passivation effect of the LPD SiO₂ film. Besides, it was revealed that both chemical passivation and field-effect passivation mechanisms played important roles in outstanding passivation effect of the LPD SiO₂ film through analyzing the minority carrier lifetime and the surface recombination velocity of n-type and p-type silicon wafers. Although the deposition parameters had little influence on the passivation effect, they affected the deposition rate. Therefore, appropriate deposition parameters should be carefully chosen based on the compromise of the deposition rate and fabrication cost. By utilizing the LPD SiO₂ film as surface passivation layer, a 19.5%-efficient silicon solar cell on a large-scale wafer (156 mm × 156 mm) was fabricated.     

Vanadium-based antireflection coated on multicrystalline silicon acting as a passivating layer

In this paper, we present important experimental results of a new efficient (ARC), leading to an efficient surface passivation that have not been reported before. Vanadium pentoxide V₂O₅ powder was thermally evaporated onto the front surface of mc-Si substrates, followed by a short annealing duration at 600 °C, 700 °C and 800 °C under an O₂ atmosphere. The chemical composition of the deposited vanadium oxide thin films was analyzed by means of Fourier Transform Infrared Spectroscopy (FTIR). Surface and cross-section morphology were determined by a scanning electron microscope (SEM). The effect of the deposited thin film on the electrical properties was evaluated by means of the internal quantum efficiency (IQE), minority carrier lifetime measurements which have been made using a WTC-120 photoconductance lifetime tester and we used dark current–voltage (I–V) characteristic to measure the defect density at a selected grain boundary (GB) in all samples and compared to an untreated wafer. The results show that the deposited thin film single layer gives the possibility of combining, in one processing step, an antireflection coating deposition along with efficient surface state passivation, as compared to a reference wafer.     

Effect of hydrogen passivation on electrical transport in polycrystalline silicon

Hydrogen passivation of grain boundaries in polycrystalline silicon is shown to improve the efficiencies of devices fabricated from these materials. We have carried out hydrogen plasma passivation of polycrystalline silicon in RF discharge and have studied the variation in room temperature resistivity of the polysilicon wafer after H plasma treatment. In order to study intergrain changes in the polysilicon wafer after optimum H plasma treatment, we have carried out J(V,T) measurement in the temperature range 130 to 330 K. It is shown that after optimum hydrogenation, the temperature range over which thermionic emission occurs extrapolates to a much lower temperature value which is due to reduction of the grain boundary potential barrier after H passivation.     

Influence of hydrogen passivation on majority and minority charge carrier mobilities in ribbon silicon

Multicrystalline silicon materials and ribbons in particular contain a higher amount of defects as compared to monocrystalline silicon, which have to be passivated during solar cell processing in order to reach satisfactory cell efficiencies. Within the solar cell process, this is usually carried out via the deposition of a hydrogen-rich SiN_x layer and a following firing step. During passivation, the electronic properties of the materials (conductivity, mobility) can change which might have an influence on the optimised parameters like emitter sheet resistance and grid geometry. This paper deals with the impact of hydrogen passivation on the electronic properties of majority and minority charge carriers in ribbon silicon materials. Majority charge carrier mobilities resulting from Hall measurements are strongly increasing after hydrogenation especially at temperatures below 300 K. Even at room temperature, changes in mobility up to a factor of 2 have been observed. For the determination of minority charge carrier mobilities in processed solar cells, a new method is presented based on spatially resolved internal quantum efficiency and lifetime measurements. It allows the calculation of mapped mobilities especially in materials showing small diffusion lengths. The same reductions in mobility of a factor 2–3 as compared to monocrystalline silicon for both majority and minority charge carriers could be detected in RGS silicon.     

Theoretical investigation on the absorption enhancement of the crystalline silicon solar cells by pyramid texture coated with SiNx:H layer

The absorption enhancement of the crystalline silicon (c-Si) solar cells by pyramid texture coated with SiN_x:H layer was investigated by theoretical simulation via rigorous coupled-wave analysis (RCWA). It was found that in order to maximize the spectrally weighted absorptance of the solar cells for the Air Mass 1.5 (AM1.5) solar spectrum (A_AM1.5), the required pyramid size (d) was dependent on the thickness of the c-Si substrate. The thinner the c-Si substrate is, the larger the pyramids should be. Pyramids with d > 0.5 μm can make A_AM1.5 maximal if the c-Si substrate thickness is larger than 50 μm. But d > 1.0 μm is needed when the c-Si substrate thickness is less than 25 μm. If the c-Si substrate is thinner than 5 μm, even d > 4.0 μm is required. The underlying mechanism was analyzed according to the diffraction theory. The pyramid texture acts as not only an antireflective (AR) component, but also a light trapping element. Then, the optimized refractive index and the thickness of SiN_x:H layer to further enhance the absorption were given out. The potential solar cell efficiency was also estimated.