Comparative study of different approaches of multicrystalline silicon texturing for solar cell fabrication

Alkali etchant cannot produce uniformly textured surface to generate satisfactory open circuit voltage as well as the efficiency of the multi-crystalline silicon (mc-Si) solar cell due to the unavoidable grain boundary delineation with higher steps formed between successive grains of different orientations during alkali etching of mc-Si. Acid textured surface formed by using chemicals with HNO₃–HF–CH₃COOH combination generally helps to improve the open circuit voltage but always gives lower short circuit current due to high reflectivity. Texturing mc-Si surface without grain boundary delineation is the present key issue of mc-Si research. We report the isotropic texturing with HF–HNO₃–H₂O solution as an easy and reliable process for mc-Si texturing. Isotropic etching with acidic solution includes the formation of meso- and macro-porous structures on mc-Si that helps to minimize the grain-boundary delineation and also lowers the reflectivity of etched surface. The study of surface morphology and reflectivity of different mc-Si etched surfaces has been discussed in this paper. Using our best chemical recipe, we are able to fabricate mc-Si solar cell of 14% conversion efficiency with PECVD AR coating of silicon nitride film. The isotropic texturing approach can be instrumental to achieve high efficiency in mass production using relatively low-cost silicon wafers as starting material with the proper optimization of the fabrication steps.     

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.     

Efficiency improved by acid texturization for multi-crystalline silicon solar cells

In this paper, we will show that efficiency of multi-crystalline silicon (mc-Si) solar cells may be improved by acid texturization. In order to enhance overall efficiency of mc-Si for solar-cell applications, the surface treatment of texturization with wet etching using appropriate solutions can improve incident light into the cell. Alkali etchant cannot produce uniformly textured surface to generate enough open circuit voltage (V_OC) and high efficiency of the mc-Si due to the unavoidable grain randomly oriented with higher steps formed during etching process. Optimized acid etching conditions can be obtained by decreasing the reflectance (R) for mc-Si substrate below levels generated by alkali etching. Short-circuit current (I_SC) measurements on acid textured cells reveal that current gain can be significantly enhanced by reducing reflection. The optimal acid etching ratio HF:HNO₃:H₂O = 15:1:2.5 with etching time of 60 s and lowering 42.7% of the R value can improve 112.4% of the conversion efficiency (η) of the developed solar cell. In order to obtain more detailed information of different defect region, high-resolution light beam induced current (LBIC) is applied to measure the internal quantum efficiency (IQE) and the lifetime of minority carriers. Thus, the acid texturing approach is instrumental to achieve high efficiency in mass production using relatively low-cost mc-Si as starting material with proper optimization of the fabrication steps.     

Damage-free reactive ion etch for high-efficiency large-area multi-crystalline silicon solar cells

Texturing of silicon (Si) wafer surface is a key to enhance light absorption and improve the solar cell performance. While alkaline texturing of single-crystalline Si (sc-Si) wafers was well established, no chemical solution has been successfully developed for multi-crystalline Si (mc-Si) wafers. Reactive-ion-etch (RIE) is a promising technique for effective texturing of both sc-Si and mc-Si wafers, regardless of crystallographic characteristics, and more suitable for thin wafers. However, due to the use of plasma source generated by high power, the wafer surface gets a physical damage during the processing, which requires an additional subsequent damage-removal wet processing. In this work, we developed a damage-free RIE texturing for mc-Si solar cells. An improved self-masking RIE texturing process, developed in this study, produced ∼0.7% absolute efficiency gain on 156×156 mm² mc-Si cells, where the gas ratio and the plasma power density were keys to mitigate the plasma-induced-damage during the RIE processing while maintaining decent surface reflectance. In the self-masking RIE texturing, a mixture of SF₆/Cl₂/O₂ gases was found to significantly affect the surface morphology uniformity and reflectance, where an optimal etch depth was found to be 200-400 nm. We achieved J_sc gain of ∼1.3 mA/cm² while maintaining decent FFs of ∼0.78 without a V_oc loss after optimization of firing conditions.     

Texturization of multicrystalline silicon wafers for solar cells by chemical treatment using metallic catalyst

A new etching method for texturing multicrystalline p-type Si wafers for solar cells was developed. In this method, we used platinum or silver particles as the catalysts, which were loaded on the wafers by means of the electroless-plating technique. After deposition of the catalysts, the wafers were etched and textured in HF solution, to which in some cases chemical oxidants were added. The solar cells (4 cm²) manufactured from the textured wafers showed efficiency as high as 16.6%, which was about 1% (absolute) higher than that of the cells made from the wafers treated by the conventional alkaline method.     

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.     

Investigation of surface features using reactive ion etching method for the enhanced performance of multi-crystalline silicon solar cells

Maskless, random RIE texturing with a gas mixture of SF₆/O₂ (SO) and SF₆/O₂/Cl₂ (SOC) was investigated to achieve higher efficiency for mc-Si solar cells. Cone structure with aspect ratio of 3.7 was highly effective for reducing surface reflectance particularly for wavelength from 310 to 700 nm and triangular pyramid structure with aspect ratio of 2 revealed rather uniform reduction of reflectance with respect to the optimized wet texturing for whole wavelength range of 310–1100 nm. On the contrary to results of reflectance, performances of fabricated cell were much better for triangular pyramid structure than cone structure. The degradation of cell performances for the cone structure was assigned both to the poor e-h pair generation efficiency relevant to the formation of highly defective surface layer with high density recombination centers, and ohmic shunt. The efficiency enhancement by 0.6% in mc-Si solar cells with triangular pyramid structures was assigned also to the slightly enhanced e-h pair generation efficiency with respect to the reference cell.     

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.     

Novel approaches for tri-crystalline silicon surface texturing

Tri-crystalline silicon (Tri-Si) is a promising candidate to reduce the cost of solar cells fabrication because it can be made by a low-cost, fast process with a better mechanical strength, and needs a thinner wafer. One of the key parameters in improving the efficiency of the Tri-Si solar cells is the reflectance, which can be lowered by etching methods. However, Tri-Si is a crystal compound consisting of three mutually tilted monocrystalline silicon grains. In all grains boundaries the surface is (1 1 0)-oriented. A standard surface texture of etched random pyramids using an anisotropic etchant, such as NaOH, is not achievable here. In this paper, for the first time, a novel texturing method has been attempted, which consisted of two steps—HF:HNO₃:DI (2.5:2.5:5) etching was followed by exposure to the vapors to generate fine holes and an etching depth of 2.5 μm had been reached. A best result of 12.3% has been achieved for surface reflectance, which is about 10% lower than that using normal acidic texturing. Nanoporous structures were formed and the size of the porous structure varied from 5 to 10 nm. An antireflection coating of SiN_x SLAR was used to optimize the reflectance. A fill factor of 0.78 has been reached with an efficiency of 16.2% in 12.5 cm×12.5 cm. This high efficiency is mainly due to an increased short-circuit current density of 34 mA/cm².     

Wafer thickness, texture and performance of multi-crystalline silicon solar cells

The influence of wafer thickness and surface texturing of silicon solar cells on cell results has been investigated using neighbouring multi-crystalline silicon wafers with thickness ranging from 150 to 350 μm and isotropic NaOH or acid etched. It was found experimentally that V_oc decreases nearly 1.5% and J_sc decreases nearly 3%, resulting in a 4% relative decrease in efficiency, in halving the wafer thickness. These trends are independent of the front surface texturing.Front surface texturing, however, results in a 6% increase of J_sc and a nearly 6% increase in efficiency independent of the wafer thickness.     

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.     

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.     

Concentrator silicon solar cells from silicon industry rejects

Two types of silicon (Si) substrates (40 n-type with uniform base doping and 40 n/n⁺ epitaxial wafers) from the silicon industry rejects were chosen as the starting material for low-cost concentrator solar cells. They were divided into four groups, each consisting of 20 substrates: 10 are n/n⁺ and 10 are n substrates, and the solar cells were prepared for different diffusion times (45, 60, 75 and 90 min). The fabricated solar cells on n/n⁺ substrates (prepared with a diffusion time of 75 min) showed better parameters. In order to improve their performances, particularly the fill factor, 20 new solar cells on n/n⁺ substrates were fabricated using the same procedure (the diffusion time was 75 min)—but with four new front contact patterns. Investigation of current–voltage (I–V) characteristics under AM 1.5 showed that the parameters of these 20 new solar cells have improved in comparison to previous solar cells' parameters, and were as follows: open-circuit voltage (V_OC=0.57 V); short circuit current (I_SC=910 mA), and efficiency (η=9.1%). Their fill factor has increased about 33%. The I–V characteristics of these solar cells were also investigated under different concentration ratios (X), and they exhibited the following parameters (under X=100 suns): V_OC=0.62 V and I_SC=36 A.     

Effect of porous silicon on the performances of silicon solar cells during the porous silicon-based gettering procedure

In this work we analyse the effect of porous silicon on the performances of multicrystalline silicon (mc-Si) solar cells during the porous silicon-based gettering procedure. This procedure consists of forming PS layers on both front and back sides of the mc-Si wafers followed by an annealing in an infrared furnace under a controlled atmosphere at different temperatures. Three sets of samples (A, B and C) have been prepared; for samples A and B, the PS films were removed before and after annealing, respectively. In order to optimize the annealing temperature, we measure the defect density at a selected grain boundary (GB) using the dark current–voltage (I–V) characteristics across the GB itself. The annealing temperature was optimized to 1000 °C. The effect of these treatments on the performances of mc-Si solar cells was studied by means of the current–voltage characteristic (at AM 1.5) and the internal quantum efficiency (IQE). The results obtained for cell A and cell B were compared to those obtained on a reference cell (C).     

Properties of an n-C:P/p-Si carbon-based photovoltaic cell grown by radio frequency plasma-enhanced chemical vapor deposition at room temperature

The phosphorus-doped amorphous carbon (n-C:P) films were grown by radiofrequency (RF) power-assisted plasma-enhanced chemical vapor deposition (PECVD) at room temperature using a solid phosphorus target. The influence of phosphorus doping on the material properties of n-C:P based on the results of simultaneous characterization are reported. Moreover, solar cell properties such as series resistance, short-circuit current density, open-circuit current voltage, fill factor and conversion efficiency along with the spectral response are reported for the fabricated carbon-based n-C:P/p-Si heterojunction solar cells by standard measurement technique. The cells’ performances have been given in the dark I–V rectifying curve and I–V working curve under illumination when exposed to AM 1.5 illumination condition (100 mW/cm², 25 °C). The maximum open-circuit voltage (V_oc) and short-circuit current density (J_sc) for the cells are observed to be approximately 236 V and 7.34 mA/cm², respectively, for the n-C:P/p-Si cell grown at a lower RF power of 100 W. The highest energy conversion efficiency (η) and fill factor (FF) were found to be approximately 0.84% and 49%, respectively. We have observed that the rectifying nature of the heterojunction structures is due to the nature of n-C:P films.     

The effect of front pyramid heights on the efficiency of homogeneously textured inline-diffused screen-printed monocrystalline silicon wafer solar cells

The majority of industrial monocrystalline silicon (c-Si) wafer solar cells are alkaline textured (at least the illuminated surface) to reduce reflection and increase absorption of incident light. Therefore, understanding the influence of front pyramid heights on the solar cell parameters is essential for further improving cell efficiency. In this work we report the impact of pyramid height on the performance of inline-diffused c-Si solar cells. Three alkaline texture processes with potassium silicate additives are optimised to result in homogeneous coverage of pyramids. By modifying the process, surface textures with small (∼5 μm maximum), medium (∼6 μm maximum) and large (∼8 μm maximum) pyramid heights are formed. The impact of pyramid size on cell parameters is experimentally studied using industrial-grade 156-mm pseudo-square p-type Czochralski wafers. It is found that within the pyramid size range studied here, there is no significant variation in effective minority carrier lifetime, reflectance, open-circuit voltage or short-circuit current. However, fill factor and hence efficiency is significantly impacted by pyramid size. While cells in all three groups demonstrate high fill factor (>79%), it is shown that an average fill factor gain of up to 1% absolute can be achieved by using the best-suited texture process.     

On-wafer investigation of SiC and Si3N4 inclusions in multicrystalline Si grown by directional solidification

Commercial multicrystalline Si (mc-Si) wafers containing SiC and Si₃N₄ inclusions and wire-sawing defects on their surfaces were collected from an mc-Si wafer manufacturer. The mc-Si, used for solar cells, was grown using industrial directional solidification systems. The technique of controlled etching was applied to these mc-Si wafers to dissolve a certain amount of silicon from the surface of each wafer and to partially expose SiC and Si₃N₄ inclusions inside these wafers to allow for direct observation. The physical presence and morphologies of the SiC and Si₃N₄ inclusions within the mc-Si wafers were investigated using scanning electron microscopy. SiC inclusions were composed of SiC particles of different sizes, and they were usually present as clusters embedded within the mc-Si wafers. Si₃N₄ inclusions were present as rods distributed within the mc-Si wafers. It has been shown that the presence of SiC particles is responsible for the formation of the wire-sawing defects, while Si₃N₄ particles are readily sawed across without introducing wire-sawing defects during the wire-sawing process. This work will provide an important base-line for further investigation on how these inclusions affect the photovoltaic performance of mc-Si solar cells.     

Substrate to substrate aluminized bonding of 10 cm round silicon substrates for application in solar photovoltaics

Large area silicon solar cells with screen printed contacts have been realized for the first time on 10 cm diameter, p-type, Cz silicon wafers which were bonded to silicon substrates by alloying of a suitably thick screen printed layer of Al on them. In cells made on 300 μm thick wafers without texturization, antireflection coating and passivation of the front surface, the values of the open-circuit voltage (V_oc), the short-circuit current density (J_sc), curve factor (CF) and the efficiency (η) were found to be in the range 572–579 mV, 16–19.2 mA cm⁻², 0.53–0.61 and 5.5–5.89%, respectively, under simulated tungsten halogen light of 100 mW cm⁻² intensity. Using thinner wafers and having optical confinement, surface passivation and effective back surface field, the cell performance would be substantially improved. In fact, an efficiency close to 18% (AM1.5) would be realizable with this approach. Another attractive feature of this approach is that a low-cost silicon substrate could be used at the bottom that would act as support for the thin top surface without disadvantage to the cell performance. In this paper only the principle has been demonstrated experimentally. Possible improvements have been shown by computer simulation.     

Characterization of N, N′-bis-2-(1-hydoxy-4-methylpentyl)-3, 4, 9, 10-perylene bis (dicarboximide) sensitized nanocrystalline TiO2 solar cells with polythiophene hole conductors

We have fabricated solid-state, dye-sensitized nanocrystalline TiO₂ solar cells (DSSC) based on perylene derivative dye, N,N′-bis-2-(1-hydoxy-4-methylpentyl)-3,4,9,10-perylene bis (dicarboximide) (HMPER) with two different polythiophenes as hole conductors; i.e. poly (3-octyl thiophene) (P3OT) and poly (3-hexyl thiophene) (P3HT), respectively. HMPER adsorbs strongly to the surface of nanocrystalline TiO₂ and inject electrons into TiO₂ conduction band upon absorption of light. Polythiophene derivatives are well-known materials as hole conductors in solid-state dye-sensitized solar cells. We obtained quite similar results with P3OT and P3HT yielding a short-circuit current density of around 80 μA/cm² and open-circuit voltage of around 0.7 V at 80 mW/cm² AM 1.5 light intensity. The results are compared with Ru-535 TBA-sensitized nc-TiO₂ cells prepared by using the same polythiophene derivatives.     

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

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