Hydrogen passivation of defects in EFG ribbon silicon

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

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.     

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

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

Potential cost reduction of buried-contact solar cells through the use of titanium dioxide thin films

This paper explores the potential of applying titanium dioxide (TiO₂) thin films to the buried-contact (BC) solar cell. The aim is to develop a lower-cost BC technology that can be applied to multicrystalline silicon (mc-Si) wafers, the predominant substrate of the photovoltaics (PV) industry. The original BC solar cell used a thick, thermally grown, silicon dioxide (SiO₂) layer as the front surface dielectric coating. Upon commercialisation of the BC technology, BP Solar replaced this layer with silicon nitride (Si₃N₄), which exhibits improved optical properties. It is anticipated that production costs can be further reduced by using a low temperature deposited front surface dielectric coating, such as TiO₂, thereby reducing the number of lengthy high temperature processing steps, and developing a process such that it can be applied to mc-Si wafers. TiO₂ is chosen because of its optimal optical properties for glass-encapsulated silicon solar cells and familiarity of PV manufacturers with this material. The results presented resolve the issue of surface passivation with TiO₂ and demonstrate that TiO₂/SiO₂ stacks, achieved during a brief high-temperature oxidation process after TiO₂ thin film deposition, are compatible with high-efficiency solar cells. However, TiO₂ cannot perform all the necessary functions of the thick SiO₂ or Si₃N₄ layer, due to its inability to act as a phosphorus diffusion barrier. In light of these results, three alternate BC solar cell fabrication sequences are presented, and an initial conversion efficiency of 11.5% has been achieved from the first batch of solar cells in a non-optimised processes.     

Phosphorous emitter etch back and bulk hydrogenation by means of an ECR-hydrogen plasma applied to form a selective emitter structure on mc-Si

In this paper, we study the effect of hydrogen-electron cyclotron resonance plasma (ECR plasma) on the phosphorous-doped emitter of a solar cell based on multicrystalline silicon (POLIX^®). The purpose of this experiment is to realise a selective emitter structure, using the front metal contacts as a mask. We show that hydrogen plasma etches the surface of the emitter away, and simultaneously diffuses into the silicon and increase the bulk lifetime. Both minority carrier lifetime and etch rate depend on the grain orientation. Hydrogen diffusion is hindered by the high phosphorous concentration of the emitter, as shown on the SIMS profiles. Besides, SIMS profiles are revealing an anomalous behaviour of phosphorous, which diffuses into the silicon at temperatures as low as 350°C on (1 0 0) oriented grains.     

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.     

Highly reflective nanotextured sputtered silver back reflector for flexible high-efficiency n-i-p thin-film silicon solar cells

High reflectivity is essential when a metal is used as back contact and reflector in thin-film silicon solar cells. We show that thermal annealing at 150 °C improves the reflectivity of silver films deposited by sputtering at room temperature on nanotextured substrates. The annealing provokes two interlinked effects: rearrangement of the silver layer with a modification of its morphology and an increase of up to 42% in the grain size of the polycrystalline film for the preferential orientation as measured by X-ray diffraction. The main consequence of these two mechanisms is a large increase in the reflectivity of silver when measured in air. This reflectivity increase is also noticeable in devices: amorphous silicon thin-film solar cells grown on annealed silver films yield higher internal and external quantum efficiencies compared to cells grown on as-deposited silver. The morphology modification smoothes down the substrate, which is revealed by a clear increase of the open-circuit voltage and fill factor of the cells grown on top. An amorphous silicon cell with a 200 nm nominally thick i-layer fabricated on a flexible plastic substrate yielded an initial efficiency close to 10% with 15.9 mA/cm² of short-circuit current using highly reflective annealed textured silver. We also propose, for industrial purpose, the sputtering of thin silver layer (120 nm) under moderate substrate temperature (∼150 °C) to increase the layer reflectivity, which avoids lengthening of the back reflector fabrication.     

The effect of baking conditions on the effective contact areas of screen-printed silver layer on silicon substrate

In this paper, Ag-based paste was screen-printed on the polished as well as on the textured p-type (100) single crystalline silicon wafers. Three types of baking processes were studied: the tube furnace, the belt furnace and the hot plate baking. The effective contact areas of Ag/Si system were measured with a novel method, namely metal insulator semiconductor structure measurement. The results show that after baking on the hot plate at 400°C for 5 min, the size and number of pores in the Ag film layer as well as at the interface between silver layer and silicon decreases significantly, the effective contact area also increases about 20%, particularly on the textured silicon substrate.     

Impact of thermal processes on multi-crystalline silicon

Fabrication of modern multi-crystalline silicon solar cells involves multiple processes that are thermally intensive. These include emitter diffusion, thermal oxidation and firing of the metal contacts. This paper illustrates the variation and potential effects upon recombination in the wafers due to these thermal processes. The use of light emitter diffusions more compatible with selective emitter designs had a more detrimental effect on the bulk lifetime of the silicon than that of heavier diffusions compatible with a homogenous emitter design and screen-printed contacts. This was primarily due to a reduced effectiveness of gettering for the light emitter. This reduction in lifetime could be mitigated through the use of a dedicated gettering process applied before emitter diffusion. Thermal oxidations could greatly improve surface passivation in the intragrain regions, with the higher temperatures yielding the highest quality surface passivation. However, the higher temperatures also led to an increase in bulk recombination either due to a reduced effectiveness of gettering, or due to the presence of a thicker oxide layer, which may interrupt hydrogen passivation. The effects of fast firing were separated into thermal effects and hydrogenation effects. While hydrogen can passivate defects hence improving the performance, thermal effects during fast firing can dissolve precipitating impurities such as iron or de-getter impurities hence lower the performance, leading to a poisoning of the intra-grain regions.     

Testing of materials for solar power space applications

This paper summarizes the results of a program initiated at the Naval Research Laboratory to test conventional and state-of-the-art solar power space systems by flying them aboard satellites. The program (approximately nine years in duration) confirmed the practicality of improvements in advanced silicon solar cells such as textured surfaces, shallow junctions, back surface field and back surface reflector techniques, as well as novel methods of bonding coverslips to conventional cells. In addition, the performance of gallium aluminum arsenide solar cells first tested in a space environment and demonstrated to be satisfactory. Finally, advanced silicon cells such as lithium-diffused and vertical junction cells, which were reported to be radiation resistant on the basis of measurements in the laboratory, were found unsuitable for extended space application.     

Comparison between SiNx:H and hydrogen passivation of electromagnetically casted multicrystalline silicon material

This work intends to compare two different passivation methods for electromagnetically continuous pulling silicon (EMCP): remote plasma hydrogenation and remote plasma enhanced CVD of SiN followed by high-temperature sintering. All experiments are carried out on textured and non-textured EMCP samples from the same ingot. To check the effect of high-temperature diffusion on EMCP, a n⁺-emitter is formed on one group of the samples using POCl₃ diffusion. Passivation capabilities of both techniques are checked using measurements of minority carrier lifetime by means of microwave photoconductance decay mapping. Solar cells are made to compare lifetime measurement with cell parameters.     

A simple technology to improve crystalline-silicon solar cell efficiency

The manufacturing of high-efficiency crystalline-silicon (c-Si) solar cells involves advanced technologies and sophisticated equipment not available in third-world country laboratories. This paper shows that conversion efficiencies in the 15–16% range can be achieved with a simple laboratory process. The main steps, which only require the use of analytic grade chemicals, are: (a) diffusion of a phosphorus-doped emitter layer on a textured surface; (b) deposition of narrow top metal contacts using a ph otolithography process; (c) Al alloyed back surface field, and d) a chemically sprayed tin dioxide antireflective coating.     

Design of textured Al electrode for a hydrogenated amorphous silicon solar cell

Textured surface of metal electrodes formed on a polymer film have been studied to take advantage of an optical confinement effect for hydrogenated amorphous silicon (a-Si:H) solar cell. Theoretical considerations and simulated experiments show that an inclination angle of the textured shape larger than 30° causes an optical confinement effect. The suitable textured Al surface was formed by controlling the crystallization of Al in a sputter-deposition process and adopted for back-side electrodes of stainless steel/Al/polymer. Consequently, the short-circuit current (J_sc) was improved by about 10% by using a textured Al layer with homogeneous roughness of 200–400 nm in size. For further enhancement of J_sc, this textured layer was adopted for multilayer electrodes such as Ti/Ag/Ti/Al, and ITO/p-i-n type solar cells formed on this multilayer electrode showed a high conversion efficiency of 11.28%.     

High-quality narrow gap (1.52 eV) a-Si:H with improved stability fabricated by excited inert gas treatment

Narrow band gap (1.5 eV) hydrogenated amorphous silicon (a-Si:H) were fabricated by a chemical annealing technique using noble gases (Ar, He, Ne). Although hydrogen content in the film was reduced to 1 atm% and band gap was decreased to 1.52 eV, high photoconductivity and large mobility–lifetime products were maintained and no marked changes in the short-range structure was found. Using these narrow band gap a-Si:H for photoactive layer in n-i-p solar cells, reasonable photovoltaic performances were obtained, i.e., open-circuit voltage of 0.71 V and fill factor of 57%. Also enhanced red response was observed with the 1.58 eV band gap i-layer solar cell prepared on textured substrate.     

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).     

16.4% efficient, thin active layer silicon solar cell grown by liquid phase epitaxy

An energy conversion efficiency of 16.4% is reported for a silicon solar cell of 4.11 cm² total area with a thin active layer of 32 μm grown by liquid phase epitaxy (LPE). This is the highest ever total area efficiency for a cell of this type and is due to a number of improvements over earlier reported results. The thin active layer was grown by LPE on an inactive silicon substrate from an indium solution in a 20% hydrogen/argon forming gas mixture ambient rather than pure hydrogen. Higher current density and efficiency than previously reported for similar cell structures have been achieved by employing microgroove texturing of the front surface, a very shallow (0.25 μm) and high sheet resistivity (220 Ω□) top surface phosphorus diffusion, an optimized ZnS/MgF₂ double layer antireflection coating on top of a 200Å thick, high quality passivation SiO₂ layer, a large aspect ratio (0.45) for the metal contacts, and a graded doping level within the 32 μm thick LPE active layer. The effect of the improved techniques on the cell performance and the properties of the thin active layers are discussed.     

High-efficiency drift-field thin-film silicon solar cells grown on electronically inactive substrates

A drift-field in the base region of a solar cell can enhance the effective minority-carrier diffusion length, thus increasing the long-wavelength spectral response and energy-conversion efficiency. Silicon thin-films of 20–32 μm thickness as a cell base layer were grown by liquid-phase epitaxy (LPE) on electronically inactive heavily doped p⁺⁺-type CZ silicon substrates. Growth was performed from In/Ga solutions, and in a purified Ar/4%H₂ forming gas ambient, rather than pure H₂. The Ga dopant concentration was tailored throughout the p-type film to create a drift-field in the base layer of the solar cell. An independently confirmed efficiency of 16.4% was achieved on such an LPE drift-field thin-film silicon solar cell with a total cell area of 4.11 cm². Substrate thinning, combined with light trapping which is encouraged by the textured front surface and a highly reflective aluminium rear surface, is demonstrated to improve the long-wavelength response and thus, increase cell efficiency by a factor of up to 23.7% when thinned to a total cell thickness of 30 μm.     

CF4/O2 dry etching of textured crystalline silicon surface in a-Si:H/c-Si heterojunction for photovoltaic applications

We investigated a dry cleaning procedure of the crystalline substrate, both mono- and multi crystalline silicon, to leave an uncontaminated surface using an etching process involving CF₄/O₂ mixture. A detailed investigation was performed to find compatibility and optimisation of amorphous layer depositions both on flat and textured silicon by changing the plasma process parameters. We found evidence that plasma etching acts by removing the native oxide and the damages of textured silicon and by leaving an active layer on silicon surface suitable for the emitter deposition. SEM analysis confirmed that it is possible to find plasma process conditions where no appreciable damages and change in surface morphology are induced. By using this process we achieved on amorphous crystalline heterostructure a photovoltaic conversion efficiency of 13% on 51 cm² and 14.5% on 1.26 cm² active area. We also investigated compatibility of the process with industrial production of large area devices.     

On the electrochemistry of an anode stack for all-solid-state 3D-integrated batteries

This paper will report on the electrochemical and material characterization of a potential planar anode stack for all-solid-state 3D-integrated batteries. The first element of the stack is the silicon substrate. On top of silicon, a Li diffusion barrier layer material is deposited in order to effectively shield the substrate from the battery stack. Several materials are investigated with conventional electrochemical techniques. The best candidates, sputtered and atomic layer deposited (ALD) TiN, are studied in more detail with ex situ X-ray diffraction (XRD) and the reaction mechanism of these materials with Li is discussed. The third element of the stack is the active anode material. Thin films of poly-Si are studied towards their thermodynamic and kinetic properties. Moreover, the growth of SEI layers on top of poly-Si anodes cycled in two liquid electrolytes has been investigated by means of ex situ SEM. Strikingly, when poly-Si is covered with a solid-state electrolyte, prolonged lifetime is found, enabling future 3D-integrated all-solid-state batteries.     

Novel low-cost approach for removal of surface contamination before texturization of commercial monocrystalline silicon solar cells

This paper reports a novel approach on the surface treatment of monocrystalline silicon solar cells using an inorganic chemical, sodium hypochlorite (NaOCl) that has some remarkable properties. The treatment of contaminated crystalline silicon wafer with hot NaOCl helps the removal of organic contaminants due to its oxidizing properties. The objective of this paper is to establish the effectiveness of this treatment using hot NaOCl solution before the saw damage removal step of the conventional NaOH texturing approach. A comparative study of surface morphology and FTIR analyses of textured monocrystalline silicon surfaces with and without NaOCl pre-treatment is also reported. The process could result in a significant low cost approach viable for cleaning silicon wafers on a mass production scale.