Texturisation of multicrystalline silicon wafers for solar cells by reactive ion etching through colloidal masks

Texturing of multicrystalline silicon solar cells by reactive ion etching (RIE) is demonstrated as an attractive solution for lowering of reflectance. A suitable sequence of processes is developed to exploit the advantage of RIE in combination with “natural lithography” based on colloidal masks. A homogeneous particle coverage on 4 in. monocrystalline wafers and on 100×100 mm² multicrystalline wafers (Baysix) has been achieved. Finally, texture is obtained by RIE patterning. Data of optical properties are presented. A significant lowering of the reflection of textured wafers compared to untexture is achieved for all states of solar cell production.     

Mono- and tri-crystalline Si for PV application

Crystalline silicon wafers are by far the dominant absorber materials for today's production of solar cells and modules due to their good price/performance relation and their proven environmental stability. These wafers are mainly produced either by a solar-optimized Czochralski (Cz)-growth method yielding crystalline silicon with low defect density (c-Si) or by a directional solidification or a ribbon growth method yielding large grained multi-crystalline (mc-Si) wafers with higher defect density. To further improve the price/performance relation of Cz solar cells, tri-crystalline silicon (tri-Si) is being developed as a high-quality wafer material that combines both the high diffusion length of minority carriers of up to 1300 μm of c-Si and the productivity of mc-Si. More than 1000 μm LID free diffusion length could be reached with specially doped tri-crystals. Due to an increased mechanical stability tri-Si allows both quasi-continuous pulling and thin slicing with higher mechanical yields. This paper reviews the structural, electronic, and mechanical properties of tri-crystalline silicon wafers with respect to c-Si wafers for solar applications. Actual non-textured solar cells processed with a simple cost effective fabrication process exhibit the same cell efficiencies up to 15.9% for both tri-silicon and mono-silicon wafers. With an improved process, up to 18% cell efficiency can be obtained with textured mono-Si.     

Texturing of large area multi-crystalline silicon wafers through different chemical approaches for solar cell fabrication

Surface texturing of silicon can reduce the reflectance of incident light and hence increase the conversion efficiency of solar cells. Comparatively lesser concentrated (10%) standard alkaline (NaOH/KOH) solution does not give good textured multi-crystalline silicon (mc-Si) surface, which could give satisfactory open-circuit voltage. This is due to grain-boundary delineation with steps formed between successive grains of different orientations. In this work an attempt has been made to obtain a well-textured mc-Si surface through three different approaches. The first two are with two different types of acid solutions and the third with concentrated alkaline NaOH. Solutions of HF–HNO₃–CH₃COOH/H₂O system with different concentrations of HF and HNO₃ were used for texturing. The results on the effect of texturing of these three solutions on the surface morphology of very large area (125 mm×125 mm) mc-Si wafer as well as on the performance parameters of solar cell are presented in this paper. Attempts have been made to study extensively the surface morphologies of mc-Si wafers in two effective regions of the isoetch curves of the HF:HNO₃:diluent's system. Also we studied the reflectance, uniformity, spectral response, short-circuit current, open-circuit voltage, fill factor and dark current–voltage of the cells fabricated using wafers textured with the three different methods. Short-circuit current of the solar cells fabricated using acid-textured wafers were measured to be in the range of 4.93 A. This value is 0.37 and 0.14 A higher than the short-circuit current values measured in the cells fabricated with isotextured and alkaline-textured wafers, respectively.     

Effectiveness of anisotropic etching of silicon in aqueous alkaline solutions

Optical effectiveness of anisotropic etching of (1 0 0) silicon in inorganic alkaline solution has been studied from the view point of its application in commercial silicon solar cells. The damage caused by ID saw or wire saw during slicing of the wafer is required to be removed for fabrication of solar cells. The etch rates for removal of the surface damages for boron doped Czochralski wafers of 1–2 Ω cm resistivity in 20% NaOH solution at 80°C was measured and was found to be 1.4 μm/min. After the damage removal, texturisation was obtained in 2% NaOH solution buffered with isopropyl alcohol at 80°C. An optical effectiveness parameter f_eff,λ was defined and its value was estimated from the study of reflectivity and topography of the wafers textured for different durations of time. The kinetics of anisotropic etching was studied which indicated that growth of pyramids begins at preferential sites which may arise due to crystalline defects or wetting. Silicon solar cells have been realized by standard process involving phosphorous diffusion and vacuum evaporated front and back contacts. The value of optical effectiveness parameter is found to have a direct correlation with the improvement in short circuit current density of the textured cells.     

Optimisation of NaOH texturisation process of silicon wafers for heterojunction solar-cells applications

The formation of a pyramidal structure on the surface of 〈1 0 0〉-oriented monocrystalline-silicon wafers is an effective and well known method to reduce reflection losses from the front surface of both silicon solar cells and silicon-heterojunction solar cells (SHJs). The consequence of this texturisation is an important optical gain, with a subsequent increase of the short-circuit current density (J_sc) and thus of the conversion efficiency of the devices. On the other hand, silicon-heterojunction solar cells are critically affected by the surface quality of the c-Si substrates, so the right combination of optimum texturisation- and cleaning steps previous to emitter (a-Si:H) deposition are indispensable in the fabrication process. The main goal of this work has been to perform a systematic and comprehensive analysis aimed at optimising the texturisation process based on the use of alkali solutions of NaOH with de-ionised water (DIW) and isopropyl alcohol (IPA) in different types of monocrystalline-silicon wafers for silicon-heterojunction solar-cell (a-Si:H/c-Si) applications. Three types of 〈1 0 0〉 silicon substrates have been used: polished float-zone (FZ) wafers and rough- (as-cut) and polished Czochralski (CZ) wafers. The texturisation process has been evaluated from images obtained by Scanning Electron Microscopy (SEM) and from hemispherical-reflectance spectra. Different etching times, temperatures and NaOH concentrations of the solutions as well as cleaning treatments of the wafers prior to the texturisation process have been analysed. Results show different conditions of the optimum texturisation process for each type of silicon wafers. An effective texturisation of FZ and CZ substrates has been achieved. Finally, SHJ solar cells have been obtained from FZ and CZ silicon wafers textured by the chemical processes optimised in this work.     

Electrochemical fabrication of p-poly(3-methylthiophene)/n-silicon solar cells

Solar cells with p-poly(3-methylthiophene)/n-silicon heterojunctions have been fabricated by one-step electrodeposition of 3-methylthiophene onto textured n-Si wafers. The devices deliver a 2.0 mA cm⁻² short current density and 0.26 V open-circuit voltage with a 0.42% power conversion efficiency under an AM1.5 simulated solar intensity of 30 mW cm⁻². The devices with neutral poly(3-methylthiophene) show much lower performance.     

Solar cell materials based on scarp Si wafers

A method to select, process and control Si wafers, scrapped from the production of integrated circuits and designed to be used as solar cell material has been described. The control for establishing defectless samples (constant etching rate and constant surface photovoltage) is carried out for check wafers in order to determine the time to process the batch. Data has been presented for solar cells, prepared from such material with a maximum area of 25 cm², scribed from wafers with a diameter of 76 mm.     

Screen printed titanium oxide and PECVD silicon nitride as antireflection coating on silicon solar cells

Silicon nitride and titanium oxide coatings have been used to reduce the reflection losses from silicon solar cells. Both 100-mm-diameter circular and 100 × 100 mm pseudo-square single crystalline silicon solar cells have been used in the present studies. More than 27% enhancement in the short circuit current has been demonstrated in polished cells using screen printed titanium oxide antireflection coating. Solar cells made from textured silicon wafers were used for plasma enhanced CVD grown silicon nitride antireflection coating on them. In these cells more than 23% enhancement in short-circuit current has been observed after silicon nitride antireflection coating.     

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-size multi-crystalline silicon solar cells with honeycomb textured surface and point-contacted rear toward industrial production

In this paper, we present a multi-crystalline solar cell with hexagonally aligned hemispherical concaves, which is known as honeycomb textured structure, for an anti-reflecting structure. The emitter and the rear surface were passivated by silicon nitride, which is known as passivated emitter and rear (PERC) structure. The texture was fabricated by laser-patterning of silicon nitride film on a wafer and wet chemical etching of the wafer beneath the silicon nitride film through the patterned holes. This process succeeded in substituting the lithographic process usually used for fabricating honeycomb textured structure in small area. After the texturing process, solar cells were fabricated by utilizing conventional fabrication techniques, i.e. phosphorus diffusion in tube furnace, deposition of anti-reflection film and rear passivation film by chemical vapor deposition, front and rear electrodes formation by screen printing, and contact formation by furnace. By adding relatively small complicating process to conventional production process, conversion efficiency of 19.1% was achieved with mc-Si solar cells of over 200 cm² in size. The efficiency was independently confirmed by National Institute of Advanced Industrial Science and Technology (AIST).     

A new technique for boosting efficiency of silicon solar cells

A new type of photovoltaic system with higher generation power density has been studied in detail. The feature of the system is a V-shaped module (VSM) with two tilted monocrystalline solar cells. Compared to solar cells in a flat orientation, the VSM enhances external quantum efficiency and leads to an increase of 31% in power conversion efficiency. Due to the VSM technique, short-circuit current density was raised from 24.94 to 33.7 mA/cm², but both fill factor and open-circuit voltage were approximately unchanged. For the VSM similar results (about 30% increase) were obtained for solar cells fabricated by using mono-crystalline silicon wafers with only conventional background impurities.     

Progress in emitter wrap-through solar cell fabrication on boron doped Czochralski-grown silicon

We report on RISE-EWT (Rear Interdigitated Single Evaporation-Emitter Wrap-Through) solar cells on full area (12.5×12.5 cm²) pseudo square boron doped Czochralski-grown silicon wafers. We investigate the main efficiency optimisation factors of these cells by investigating the dependence of RISE-EWT cell parameters on the base dopant concentration N_A. We furthermore detail the effects of large feature sizes in base and emitter regions at the rear of the solar cell and investigate these effects with particular attention to the edge regions. EWT solar cells typically exhibit rather low fill factors. However, our results show that the improved fill factors can be achieved by increasing N_A, which in return leads to optimised efficiency values. For our RISE-EWT solar cells made from boron doped Cz-Si wafers, this benefit is maintained even after light-induced degradation. Our investigation of edge area related effects shows the importance of proper cell design in these areas, leading to a further 2.8% absolute improvement in the fill factor. Combining increased base dopant concentration with optimised edge design, we achieve 19.0% efficiency on (12.5×12.5 cm²) boron doped Cz silicon wafers before light-induced degradation, resulting in 18.1% efficiency in the light-degraded state.     

Easy-to-fabricate 20% efficient large-area silicon solar cells

Recently, an innovative silicon solar cell structure has been developed at ISFH which is capable of achieving very high cell efficiencies on industrial-size wafers with a simple photolithography-free processing sequence. As the corresponding solar cells essentially rely on the application of obliquely evaporated contacts they are denoted as OECO cells. In this paper the successful up-scaling of the novel OECO process from 21% efficient 4 cm² laboratory devices to the fabrication of large-area (100 cm²) silicon solar cells is described, and independently confirmed total area efficiencies of 20% are reported for 10×10 cm² OECO-type solar cells fabricated on p-type float-zone silicon.     

Reactive ion etching (RIE) technique for application in crystalline silicon solar cells

Saw damage removal (SDR) and texturing by conventional wet chemical processes with alkali solution etch about 20 micron of silicon wafer on both sides, resulting in thin wafers with which solar cell processing is difficult. Reactive ion etching (RIE) for silicon surface texturing is very effective in reducing surface reflectance of thin crystalline silicon wafers by trapping the light of longer wavelength. High efficiency solar cells were fabricated during this study using optimized RIE. Saw damage removal (SDR) with acidic mixture followed by RIE-texturing showed the decrease in silicon loss by ∼67% and ∼70% compared to conventional SDR and texturing by alkaline solution. Also, the crystalline silicon solar cells fabricated by using RIE-texturing showed conversion efficiency as high as 16.7% and 16.1% compared with 16.2%, which was obtained in the case of the cell fabricated with SDR and texturing with NaOH solution.     

Defect passivation on cast-mono crystalline screen-printed cells

Cast-mono crystalline silicon wafers contain crystallographic defects, which can severely impact the electrical performance of solar cells. This paper demonstrates that applying hydrogenation processes at moderate temperatures to finished screen print cells can passivate dislocation clusters within the cast-mono crystalline silicon wafers far better than the hydrogenation received during standard commercial firing conditions. Efficiency enhancements of up to 2% absolute are demonstrated on wafers with high dislocation densities. The impact of illumination to manipulate the charge state of hydrogen during annealing is investigated and found to not be significant on the wafers used in this study. This finding is contrary to a previous study on similar wafers that concluded increased H^– or H⁰ from laser illumination was responsible for the further passivation of positively charged dangling bonds within the dislocation clusters.     

Formation of porous silicon for large-area silicon solar cells: A new method

Luminescent porous silicon (PS) was prepared for the first time using a spraying set-up, which can diffuse in a homogeneous manner HF solutions, on textured or untextured (1 0 0) oriented monocrystalline silicon substrate. This new method allows us to apply PS onto the front-side surface of silicon solar cells, by supplying very fine HF drops. The front side of N⁺/P monocrystalline silicon solar cells may be treated for long periods without altering the front grid metallic contact. The monocrystalline silicon solar cells (N⁺/P, 78.5 cm²) which has undergone the HF-spraying were made with a very simple and low-cost method, allowing front-side Al contamination. A poor but expected 7.5% conversion efficiency was obtained under AM1 illumination. It was shown that under optimised HF concentration, HF-spraying time and flow HF-spraying rate, Al contamination favours the formation of a thin and homogeneous hydrogen-rich PS layer. It was found that under optimised HF-spraying conditions, the hydrogen-rich PS layer decreases the surface reflectivity up to 3% (i.e., increase light absorption), improves the short circuit current (I_sc), and the fill factor (FF) (i.e., decreases the series resistance), allowing to reach a 12.5% conversion efficiency. The dramatic improvement of the latter is discussed throughout the influence of HF concentration and spraying time on the I–V characteristics and on solar cells parameters. Despite the fact that the thin surfae PS layer acts as a good anti-reflection coating (ARC), it improves the spectral response of the cells, especially in the blue-side of the solar spectrum, where absorption becomes greater, owing to surface band gap widening and conversion of a part of UV and blue light into longer wavelengths (that are more suitable for conversion in a Si cell) throughout quantum confinement into the PS layer.     

Crystalline Si solar cells based on solar grade silicon materials

A new method named Chemical Physics (CP) method was developed to produce solar grade silicon feedstock at a company in China. In this paper the characteristic of the solar grade silicon made by CP method was analysed. The results show that the purity of solar grade silicon is above 5 N and most of impurities are below 0.0001 wt.%. Crystalline silicon solar cells were prepared using solar grade silicon wafers based on CP method. Average efficiency of the solar cells is about 15.05%, and the highest efficiency is 15.60% under AM1.5 illumination conditions. The light-induced degradation of the solar cells was examined. Degradation by up to 15% of the initial efficiency of the solar cells is detected. The solar cell results and light-induced characteristic show that the solar cells based on CP methods have desired performance and thus have the potential for large scale production.     

TMAH-textured, a-Si/c-Si, heterojunction solar cells with 10% reflectance

Single-polished c-Si (1 0 0) wafers were textured in aqueous solutions with varying concentrations of tetra-methyl ammonium hydroxide (TMAH). The resulting surface reflectance and morphology were examined as a function of etching time and temperature, TMAH concentration, and addition of isopropyl alcohol to the solution.The lowest reflectance, 9.8% at a 600-nm wavelength with 0.3% scattering over a 4″ wafer surface, was obtained after 40 min of etching in a 2% TMAH solution at 80 °C under 700 rpm magnetic stirring. Upon adding isopropyl alcohol to the solution, the resulting pyramids were round-edged, and 12% sample reflectance was obtained.The results are interpreted in terms of micro-masking formation and temperature-dependent crystallographic selectivity.The compatibility of the treatment with photovoltaic applications was evaluated by studying the performance of heterojunction solar cells, which are particularly sensitive to surface quality. A degradation of the open circuit voltage was observed in devices fabricated on surfaces featuring crooked pyramid sides. Optimised process conditions led to smooth pyramid sides and no degradation of the open circuit voltage, which indicates no sign of increased surface recombination-centre concentration. The reduced reflectance resulted in a 16% increase of the short circuit current of the solar cell device.     

Porous silicon Bragg mirrors on single- and multi-crystalline silicon for solar cells

Porous silicon Bragg mirrors at back-side of single crystalline and multicrystalline silicon solar cell were numerically simulated by transfer matrix method. It allows to choose the optimal parameters of porous stack of bi-layers (indexes of refraction, number of bi-layers) when the increase of photon absorption in 900–1050 nm spectral region is achieved. Application of Bragg mirrors at back-side of single crystalline solar cell can improve the efficiency on more than 0.8% in absolute for 200 μm both-side textured thickness wafer. The simulated results were compared with characteristics of Bragg mirrors fabricated by electrochemical etching of single- and multi-crystalline silicon. It is shown that despite the natural crystallites disorientation the efficient Bragg mirrors can be fabricated on multicrystalline silicon wafers in such way. Maximum measured reflectivity for Bragg mirrors on multicrystalline substrate achieves approximately 62%, whereas for single crystalline silicon the reflectivity in maximum is more than 90%.     

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.