A novel low cost texturization method for large area commercial mono-crystalline silicon solar cells

Texturization of mono-crystalline silicon for solar cell fabrication is still a key issue due to consumption of large amount of costly isopropyl alcohol (IPA) in conventional NaOH/KOH solution. The need of IPA arises due to the improvement in the uniformity of pyramidal structures and elimination of spots caused by bubbles sticking on the wafer surface during the texturization process. We investigated a new texturization technique for mono-crystalline silicon solar cells with tribasic sodium phosphate (Na₃PO₄, 12H₂O) solution with much less amount of IPA. The proposed texturization method of this paper is cost effective due to reduction in the consumption of expensive IPA. The cost comparison of our novel texturization approach with conventional NaOH texturization has also been reported in this paper. We are reporting for the first time such a novel approach of using tribasic sodium phosphate for texturization of mono-crystalline silicon surface with which solar cells of efficiency 14–14.8% are fabricated with more than 90% yield.     

Low-cost texturization of large-area crystalline silicon solar cells using hydrazine mono-hydrate for industrial use

Reduction in optical losses in mono-crystalline silicon solar cells by surface texturing is one of the important issues of modern silicon photovoltaics. In order to achieve good uniformity in pyramidal structures on the silicon surface, a mixture of sodium hydroxide (NaOH) or potassium hydroxide (KOH) and isopropyl alcohol (IPA) is generally used during texturization of mono-crystalline silicon solar cell. However, due to the high cost of IPA, there is always a search for alternate chemical which plays the same role as IPA during texturization for industrial solar cell production. For a better texturization, the interfacial energy between silicon and ionized electrolyte of chemical solution should be reduced to achieve sufficient wettability of the silicon surface, which will enhance the pyramid nucleation. In this work, we have investigated the role of hydrazine mono-hydrate as a surface-active additive, which supplies OH⁻ ions after its dissociation. Our process cuts down the IPA consumption during texturing without any loss in uniformity of textured pyramids. We are the first to report the novel idea to add hydrazine mono-hydrate in NaOH solution for texturing mono-crystalline silicon surface to fabricate solar cells with more than 85% yield in the efficiency range of 14.5–15.3%.     

Investigation of texturization for monocrystalline silicon solar cells with different kinds of alkaline

In this paper, monocrystalline silicon was textured with different kind of etchants for solar cells, respectively. It was found that, only with sodium hydroxide (NaOH) or sodium acetate anhydrous (CH₃COONa) solution, the textural results were very weak, resulting in high reflectance of silicon surface. However, if using the mixture solution of NaOH and CH₃COONa, the reflectance was noticeably decreased. Moreover, the dependence of reflectance on the etching time showed that longer etching time was necessary for texturization in the NaOH+CH₃COONa+H₂O system. And it was also found that the addition of isopropyl alcohol (IPA) to this mixture solution had a detrimental effect on the texturization. All these results suggested that acetate (CH₃COO⁻) plays a similar role as IPA for alkaline texturization, but they cannot coexist. Finally, the mechanisms of texturization with different kinds of etchant were discussed in detail.     

Role of hydrazine monohydrate during texturization of large-area crystalline silicon solar cell fabrication

Reduction of optical losses in monocrystalline silicon solar cells by surface texturing is one of the important issues of modern silicon photovoltaic. For texturization during commercial monocrystalline silicon solar cell fabrication, a mixture of NaOH or KOH and isopropyl alcohol (IPA) is generally used in order to achieve good uniformity of pyramidal structure on the silicon surface. The interfacial energy between silicon and electrolyte should be reduced in order to achieve sufficient wettability for the silicon surface which in turn will enhance the pyramid nucleation. In this work, we have investigated the role of hydrazine monohydrate as a surface-active additive, which supplies OH⁻ ions after dissociation. This cuts down the IPA consumption during texturing without any loss of uniformity of textured pyramid. We are probably the first group to report such a novel idea of using hydrazine monohydrate addition in NaOH solution for texturization of solar cell. We were able to fabricate monocrystalline silicon solar cells with more than 85% yield in the range of 14–15% efficiency.     

Impact of surface roughness on the electrical parameters of industrial high efficiency NaOH-NaOCl textured multicrystalline silicon solar cell

Sodium hydroxide (NaOH) and sodium hypochlorite (NaOCl) solution (1:1 ratio by volume) based texturization process at 80-82 °C is an easy, low cost and comparatively new and convenient option for fabrication of any multicrystalline silicon (mC-Si) solar cell. In the present study atomic force microscope is used to observe the intragrain surface in a miniscule area (3 μm × 3 μm) of NaOH-NaOCl textured surface by two and three dimensional analysis, roughness analysis and section analysis. The r.m.s value of the surface parameter of 7.0 nm ascertains the smoothness of the textured surface and further the surface reflectivity is minimized to 4-6% in the 500-1000 nm wavelength range by a proper silicon nitride anti-reflection coating. Comparing with the standard HF-HNO₃-CH₃COOH acid textured cell, the NaOH-NaOCl textured cell shows a comparatively lower value of series resistance of 7.17 mΩ, higher value of shunt resistance of 18.4 Ω to yield a fill factor of 0.766 leading to more than 15% cell efficiency in the industrial cell processing line. This AFM study yields different surface roughness parameters for the NaOH-NaOCl textured wafers which can be used as a reference standard for optimized texturing.     

Multicrystalline silicon solar cells with porous silicon emitter

A review of the application of porous silicon (PS) in multicrystalline silicon solar cell processes is given. The different PS formation processes, structural and optical properties of PS are discussed from the viewpoint of photovoltaics. Special attention is given to the use of PS as an antireflection coating in simplified processing schemes and for simple selective emitter processes as well as to its light trapping and surface passivating capabilities. The optimization of a PS selective emitter formation results in a 14.1% efficiency mc-Si cell processed without texturization, surface passivation or additional ARC deposition. The implementation of a PS selective emitter into an industrially compatible screenprinted solar cell process is made by both the chemical and electrochemical method of PS formation. Different kinds of multicrystalline silicon materials and solar cell processes are used. An efficiency of 13.2% is achieved on a 25 cm² mc-Si solar cell using the electrochemical technique while the efficiencies in between 12% and 13% are reached for very large (100–164 cm²) commercial mc-Si cells with a PS emitter formed by chemical method.     

Optimization of sodium carbonate texturization on large-area crystalline silicon solar cells

This work describes a texturization method for monocrystalline silicon solar cells based on a mixture of sodium carbonate and sodium hydrogen carbonate solutions. A specific solution has been found that results in an optimal etching rate, the lowest surface reflectance and a homogeneous density of pyramidal structures on the silicon surface. The subsequent phosphorus diffusion with rapid thermal processes has been modified in order to drastically reduce the process time and, simultaneously, to obtain a high homogeneity of the sheet resistance values and improved photocarriers lifetimes. 100×100 mm solar cells with an efficiency of 15.8% have been obtained compared to an efficiency of 14.7% for the reference cell.     

烧结曲线对多晶PERC太阳电池光致衰减效应的影响

针对多晶PERC太阳电池其较大的光衰效应会影响功率输出的问题,研究烧结曲线对多晶PERC太阳电池光致衰减效应的影响。在常规烧结曲线1的基础上通过改变烧结曲线峰值温度位置得到优化烧结曲线2和优化烧结曲线3,然后将双面沉积Al2O3/SiNx叠层钝化膜的寿命片和丝网印刷后的多晶PERC电池分别采用不同烧结曲线热处理,最后将样品在70℃、800 W/m2环境下进行45 h光衰处理。结果发现经过烧结曲线1~曲线3处理后的寿命片少子寿命衰减率分别为63%、42%和23%,多晶PERC太阳电池转换效率的衰减率分别为6.46%、3.55%和2.30%,光衰处理后的多晶PERC电池的EL测试结果显示烧结曲线1亮度最小,曲线2次之,曲线3最大。以上结果表明,仅通过烧结炉的烧结曲线优化就可以很明显地减小多晶PERC太阳电池的光致衰减幅度,可为探究抑制多晶PERC太阳电池光致衰减效应的方法提供一种全新的思路。     

Application of phosphorus diffusion gettering process on upgraded metallurgical grade Si wafers and solar cells

Although phosphorus (P) diffusion gettering process has been wildly used to improve the performance of Si solar cells in photovoltaic technology, it is a new attempt to apply P diffusion gettering process to upgraded metallurgical grade silicon (UMG-Si) wafers with the purity of 99.999%. In this paper, improvements on the electrical properties of UMG-Si wafers and solar cells were investigated with the application of P diffusion gettering process. To enhance the improvements, the gettering parameters were optimized on the aspects of gettering temperature, gettering duration and POCl₃ flow rate, respectively. As we expected, the electrical properties of both multicrystalline Si (multi-Si) and monocrystalline Si (mono-Si) wafers were significantly improved. The average minority carrier lifetime increased from 0.35 μs to nearly about 2.7 μs for multi-Si wafers and from 4.21 μs to 5.75 μs for mono-Si wafers, respectively. Accordingly, the average conversion efficiency of the UMG-Si solar cells increased from 5.69% to 7.03% for multi-Si solar cells (without surface texturization) and from 13.55% to 14.55% for mono-Si solar cells, respectively. The impurity concentrations of as-grown and P-gettered UMG-Si wafers were determined quantitively so that the mechanism of P diffusion gettering process on UMG-Si wafers and solar cells could be further understood. The results show that application of P diffusion gettering process has a great potential to improve the electrical properties of UMG-Si wafers and thus the conversion efficiencies of UMG-Si solar cells.     

Large-area multicrystalline silicon solar cell fabrication using reactive ion etching (RIE)

Surface texturing of crystalline silicon wafer improves the conversion efficiency of solar cells by the enhancement in antireflection property and light trapping. Compared to antireflection coating, it is a more permanent and effective scheme. Wet texturing with the chemicals such as alkali (NaOH, KOH) or acid (HF, HNO₃, CH₃COOH) is too difficult for thinner wafer to apply due to a large amount of silicon loss. However, Plasma surface texturing using Reactive Ion Etching (RIE) can be effective in reducing the surface reflectance with low silicon loss. In this study, we have fabricated a large-area (156×156 mm) multicrystalline silicon (mc-Si) solar cell by mask less surface texturing using a SF₆/O₂ reactive ion etching. We have accomplished texturing with RIE by reducing silicon loss by almost half of that in wet texturing process. By optimizing the processing steps, we achieved conversion efficiency, open circuit voltage, short circuit current density, and fill factor as high as 16.1%, 619 mV, 33.5 mA/cm², and 77.7%, respectively. This study establishes that it is possible to fabricate the thin multicrystalline silicon solar cells of low cost and high efficiency using surface texturing by RIE.     

On the texturization of monocrystalline silicon with sodium carbonate solutions

The texturization of monocrystalline silicon wafers using sodium carbonate solution has been investigated. This etching process has been evaluated in terms of the surface morphology and the reflectance value. The results show that for low concentration of sodium carbonate the increase of texturing time decreases the reflectance value because of the change in morphology from hillocks to pyramidal; on the contrary for intermediate and high concentrations the increase of time has a detrimental effect on texturization because it increases both the pyramid sizes and their non-uniform distribution. However, a good cell performance could be obtained by etching at high concentrations and short times.     

Pyramidal texturing of silicon solar cell with TMAH chemical anisotropic etching

High-efficiency silicon solar cells need a textured front surface to reduce reflectance and to improve light trapping. Texturing of monocrystalline silicon is usually done in alkaline solutions. These solutions are cheaper, but are pollutants of silicon technologies. In this paper, we investigate an alternative solution containing tetramethyl ammonium hydroxide ((CH₃)₄NOH, TMAH ). This study shows the influence of different parameters (concentration, agitation, duration and temperature), to obtain uniform and reliable pyramidal texturization on different silicon surfaces (as cut, etched and polished). Under optimized conditions, TMAH-textured surface led to an average weighted reflectance of 13%, without any antireflection coating independent of the initial silicon surface. Unlike potassium hydroxide (KOH) texturing solution, characterization of silicon oxide layer contamination after TMAH texturing process revealed no pollution, and passivation is less affected by TMAH than by KOH texturization.     

Antireflective porous layer formation on multicrystalline silicon by metal particle enhanced HF etching

Antireflection of silicon (Si) surface is one key technology for the manufacture of efficient solar cells. Metal particle enhanced HF etching is applied to produce uniform antireflecting porous layer on multicrystalline Si wafers that cannot be uniformly texturized by anisotropic etching with an alkaline solution. Fine platinum (Pt) particles are deposited on multicrystalline n-Si wafers by electroless displacement reaction in a hexachloroplatinic acid solution containing HF. Both macroporous and luminescent microporous layers are uniformly formed by immersing the Pt-particle-deposited multicrystalline Si wafers in a HF solution. The reflectance of the wafers is reduced from 30% to 6% by the formation of porous layer. The photocurrent density of photoelectrochemical solar cells using porous multicrystalline n-Si has a 25% higher value than non-porous Si cells.     

Texturisation of multicrystalline silicon solar cells by RIE and plasma etching

Texturing by reactive ion etching (RIE) is demonstrated as an attractive technical solution for lowering of reflectance of multicrystalline silicon solar cells. A suitable sequence of processes is developed to combine the advantage of reactive ion etching with “natural lithography” based on colloidal masks. The RIE single-wafer texturisation is driven to an industrial applicable batch process by plasma etching with a gain in efficiency of 0.3% absolute.     

A cost-effective alkaline multicrystalline silicon surface polishing solution with improved smoothness

In the present paper, intragain surface morphology of multicrystalline silicon (mC-Si) wafer surface of area 3 μm×3 μm polished by the acid-based solution comprising of hydrofluoric (HF), nitric (HNO₃) and acetic (CH₃COOH) acids and new alkaline solution containing sodium hydroxide (NaOH) and sodium hypochlorite (NaOCl) has been studied using an atomic force microscope (AFM). From the roughness and section analysis study of the intergrain surface by the AFM, it is revealed that the NaOH–NaOCl polishing process is quite superior to the existing acid polishing one. Quantitative measurements indicate better smoothness of polished silicon surface after the NaOH–NaOCl treatment as compared with acid polishing. Also process cost per wafer involved in the NaOH–NaOCl polishing process is far lower than that by the acid polishing process along with additional advantageous features of high productivity, environment friendliness and safety. All these factors finally contribute to make the NaOH–NaOCl solution a better polisher for mC-Si surface.     

Recovery of minority carrier lifetime in low-cost multicrystalline silicon

Lifetime of minority carriers has been widely identified to be the key material parameter determining the conversion efficiency of pn-junction silicon solar cells. Impurities and defects in the silicon crystal lattice reduce the charge carrier lifetime and thus limit the performance of the solar cells. Removal of impurities by silicon material purification is often contradictory with low cost production of photovoltaic devices. In this paper, we present experimental results of an efficient gettering technique which can be applied to low cost processing of multicrystalline silicon solar cells without any additional process steps or compromises with optimal device design parameters. This technique is based on well-known phosphorous gettering. We have discovered that if the silicon wafers are kept in the furnace after the emitter diffusion at the 700°C, significant improvement in the lifetime will take place. At this temperature the properties of the pn-junction remain unaffected meanwhile many lifetime killers are still mobile. The time needed for this temperature program can be easily modified in order to respond to the material quality variations in substrates originating from different parts of multicrystalline ingot. Better control of lifetime can lead to higher degree of starting material utilization.     

Surface and bulk-passivated large area multicrystalline silicon solar cells

We have investigated the surface and bulk passivation technique on large-area multicrystalline silicon solar cells, a large open-circuit voltage has been obtained for cells oxidized to passivate the surface and hydrogen annealed after deposition of silicon nitride film on both surfaces by plasma CVD method (P---SiN) to passivate the bulk. The texture surface like pyramid structure on multicrystalline silicon surface has been obtained uniformly using reactive ion etching (RIE) method. Combining these RIE method and passivation schemes, the conversion efficiency of 17.1% is obtained on 15 cm × 15 cm multicrystalline silicon solar cell. Phosphorus diffusion, BSF formation, passivation technique and contact metallization for low-cost process sequence are also described in this paper.     

Reduced light reflection of textured multicrystalline silicon via NPD for solar cells applications

Texturing by negative potential dissolution (NPD) process of p-type multicrystalline silicon for solar cells application is reported. The effect of the negative potential, KOH concentration, and texturing time of cast multicrystalline silicon was studied. Rapid texturing of multicrystalline silicon was achieved in a time-frame of 2 min with the application of negative potential of −30 V and the use of optimal alkaline concentration of 32 wt%. While texturing process in these optimal NPD conditions results in a step-free morphology, necessary in solar cells contacts printing, light reflection was reduced to minimal values, as well.     

Investigation of texturization for crystalline silicon solar cells with sodium carbonate solutions

We investigate a new texturization technique for crystalline silicon solar cells with sodium carbonate (Na₂CO₃) solutions. We show the dependence of the hemispherical surface reflectance on solution temperature, the etching time and the Na₂CO₃ concentration. Furthermore, we investigate what element in Na₂CO₃ solution influences the texturing for reducing the texturing time. As a result of experiments, we find it possible to get low reflectance in a shorter texturing time by the addition of NaHCO₃. The size of texture becomes smaller by the addition of NaHCO₃ but the etching rate does not change. We conclude carbonic ion and/or its compound seems to play an important role as the initiator of pyramidal structure. This texturing method is cost effective because there is no need of expensive IPA, and the surface reflectance is reduced sufficiently in a short time. This method is promising for a large-scale production of crystalline silicon 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.