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.     

Technological process for a new silicon solar cell structure with honeycomb textured front surface

This paper presents a new silicon solar-cell structure improved by texturisation of the front surface using silicon micromachining technologies. A ‘honeycomb’-textured front surface has been obtained through a photolithographical process to generate patterns (disc holes) on the front surface followed by isotropic etching (in HNO₃: HF: CH₃COOH) until the wells joined together.For front-surface loss characterisation, the spectral dependence of the front-surface reflectivity has been investigated by spectrophotometrical measurements. The surface reflectivity was lowered under 10% and this value was a good one compared to the reflectivity of silicon monocrystalline wafer untextured surface. The p–n junction made by phosphorous diffusion at 0.8 μm follows the honeycomb profile. In order to obtain low series resistance, a p+ boron diffusion on the back of the structure was made. The fabrication process was completed with an ohmic contact (Al on top and on the back surface).     

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.     

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.     

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.     

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.     

Direct patterned etching of silicon dioxide and silicon nitride dielectric layers by inkjet printing

An inkjet method for the direct patterned etching of silicon dioxide and silicon nitride dielectric is described. The method involves fewer steps, lower chemical usage and generates less hazardous chemical waste than existing resist-based patterning methods (e.g., photolithography), which employ immersion etching. Holes of diameter 40–50 μm and grooves 50–60 μm wide were etched in 300 nm silicon dioxide layers. Grooves were also etched in 75 nm silicon nitride layers formed on textured silicon surfaces. The resulting patterned dielectric layers were used to facilitate masked etching, local diffusions and metal contacting of underlying silicon for solar cell applications.     

The enhancement of homogeneity in the textured structure of silicon crystal by using ultrasonic wave in the caustic etching process

The presence of the ultrasonic wave in the caustic etching process enhances the etching rate and results in a finer, and more homogeneous, textured structure. The silicon solar cell, texture etched for 20 min at 60°C in the caustic solution with ultrasonic wave, gives higher cell performance than the cell texture etched for 40 min at 70°C without ultrasonic wave. This comparison indicates a strong possibility of lowering the texturing cost of the silicon crystal by saving time and expensive chemicals normally employed in the texturisation of the crystalline silicon.     

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).     

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.     

Texturing industrial multicrystalline silicon solar cells

Three potential techniques for texturing commercial multicrystalline silicon solar cells are compared on the basis of reflectance measurements. Wet acidic texturing, which would be the least costly to implement, produces a modest improvement in reflection before antireflection coating and encapsulation, whereas maskless reactive-ion etching texturing, and especially masked reactive-ion etched ‘pyramids’, generate a larger gain in absorption. After antireflection coating and encapsulation however, the differences between the methods are reduced. Short-circuit current measurements on wet acidic textured cells reveal that there is a significant additional current gain above that expected from the reduced reflection. This is attributed to both light-trapping and oblique coupling of incident light into the cell, resulting in generation closer to the junction.     

An optimized texturing process for silicon solar cell substrates using TMAH

Random pyramidal texturing of silicon solar cell substrates allows to increase the short-circuit current of the device, and it is usually achieved, in commercial solar cells, by chemical anisotropic etching using a potassium hydroxide and isopropyl alcohol solution. Due to some drawbacks of these chemicals, alternative chemical etching solutions are required. Our successful results on the tetramethyl ammonium hydroxide (TMAH), (CH₃)₄NOH, solution for silicon random texturing are reported. Heterojunction solar cells were deposited on textured substrates, indicating the feasibility of TMAH texturing for solar cell fabrication.     

Study of electrical properties of oxidized porous silicon for back surface passivation of silicon solar cells

Back surface passivation becomes a key issue for the silicon solar cells made with thin wafers. The high surface recombination due to the metal contacts can be lowered by reducing the back contact area and forming local back surface field (LBSF) in conjunction with the passivation with dielectric layer. About 3×10^-7 m thick porous silicon (PS) layer with pore diameter mostly of 1×10^-8–5×10^-8 m was formed by chemical etching of silicon using the acidic solution containing hydrofluoric acid (HF), nitric acid (HNO₃) and De-ionized water in the volume ratio 1:3:5 at 298 K for which etching time was kept constant for 360 s. Electrical properties of oxidized PS was studied through the current–voltage (I–V) and capacitance–voltage (C–V) characteristics of the metal–insulator–semiconductor (MIS) device in which the oxidized PS was used as an insulating layer and the results were further analyzed. The C–V curves of all the studies MIS devices showed the negative flatband voltage varying from -2 to , confirming that the oxidized layer of PS has fixed positive charge.     

Optimization of front surface texturing processes for high-efficiency silicon solar cells

This paper presents the results of an experimental study regarding the increase in the efficiency of the silicon solar cells by texturing the front surface. Designing, patterning and surface etching processes led to refined structures with very low losses of the incident optical radiation. Photolithography has been used to generate patterns (disc hole) through the silicon dioxide layer grown at the beginning on silicon wafers. The holes (4 μm in diameter) have been uniformly distributed on the entire surface (2×2) cm² and the distance between the hole centres was determined to be 20 μm. Semispherical walls have been defined in holes by isotropic etching up to join together of the wells.     

Anodic and optical characterisation of stain-etched porous silicon antireflection coatings

Porous silicon (PS) antireflection coatings have been obtained by stain etching of crystalline Si in HF:HNO₃:H₂O solutions at different etching times and HNO₃ concentrations. The morphology of the PS samples was characterised by anodic oxidation and revealed the increase of the porous surface area with the HNO₃ concentration. Upon a certain critical concentration of HNO₃, the surface of crystalline Si immersed in the solution becomes polished, and a decrease of its surface area is observed. The samples were also characterised by a spectrophotometer in the range 300–900 nm, showing an effective reflectance below 4% in most of the spectral range for samples obtained in an etching solution, where the HNO₃ is below its critical concentration. Anodic oxidation after etching can be used as an useful tool for the qualitative and quantitative analysis of porous surface areas.     

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.     

Improvement on surface texturing of single crystalline silicon for solar cells by saw-damage etching using an acidic solution

Texturing the surfaces of silicon wafer is one of the most important ways of increasing their efficiencies. The texturing process reduces the surface reflection loss through photon trapping, thereby increasing the short circuit current of the solar cell. The texturing of crystalline silicon was carried out using alkaline solutions. Such solutions resulted in anisotropic etching that leads to the formation of random pyramids. Before the texturing process was carried out, saw-damage etching was performed in order to remove the surface defects and damage caused by wire sawing. In general, potassium hydroxide (KOH) solution has been used for saw-damage etching. This etching results in a fairly flat surface. The results from this study showed that the outcome of the surface texturing is related to the original surface morphology of the silicon. It was found that saw-damage etching using an acidic solution improved the effects of the texturing. In this case, regular and small pyramids were formed on the surface of the silicon. This reduced the reflectance of the surface, thereby increased the short circuit current and the conversion efficiency of the solar cell.     

Structural, electrical and photovoltaic characterization of Si nanocrystals embedded SiC matrix and Si nanocrystals/c-Si heterojunction devices

Thin films of Si nanocrystals (Si NCs) embedded in a silicon carbide (SiC) matrix (Si-NC:SiC) were prepared by alternating deposition of Si-rich silicon carbide (Si_1−xC_x) and near-stoichiometric SiC mutilayers (Si_1−xC_x/SiC) using magnetron cosputtering followed by a post-deposition anneal. Transmission electron microscopy and Raman spectroscopy revealed that the Si NCs were clearly established, with sizes in the range of 3–5 nm. Optical studies showed an increase in the optical band gap after annealing from 1.4 eV (as-deposited) to 2.0 eV (annealed at 1100 °C). P-type Si-NC:SiC/n-type crystalline silicon (c-Si) heterojunction (HJ) devices were fabricated and their electrical and photovoltaic properties were characterized. The diode showed a good rectification ratio of 1.0×10⁴ at the bias voltage of ±1.0 V at 298 K. The diode ideality factor and junction built-in potential deduced from current–voltage and capacitance–voltage plots are 1.24 and 0.72 V, respectively. Illuminated I–V properties showed that the 1-sun open-circuit voltage, short-circuit current density and fill factor of a typical HJ solar cell were 463 mV, 19 mA/cm² and 53%, respectively. The external quantum efficiency and internal quantum efficiency showed a higher blue response than that of a conventional c-Si homojunction solar cell. Factors limiting the cell's performance are discussed.     

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.     

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.