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.     

Growth of large-grain CuInSe2 thin films by flash-evaporation and sputtering

Thin films of (112) oriented CuInSe₂, with an average grain size larger than 50 μm, have been grown by flash-evaporation and sputtering. Platelets of Corning glass 7059, 1 in² in size, covered by a layer of lead 2 μm thick, have been used as substrates. The lead layer is prepared by a new method which allows one to obtain (111) oriented films with a grain size ranging between 30 and 500 μm. This method is now being patented. Solar cells sing CuInSe₂/CdS thin films, prepared by flash-evaporating low resistivity CdS thin films on top of CuInSe₂, have so far exhibited high photocurrents close to 40 mA cm⁻² at 100 mW cm⁻² solar illumination, and a maximum efficiency of about 4%.     

Contribution of silicon substrates to the efficiencies of silicon thin layer solar cells

Although silicon solar cells based on layers less than 50 μm thick have become very popular, little attention has been paid to the role of the underlying silicon substrate. This treatment uses the device simulation program PC-1D and the ray tracing program SUNRAYS to examine the role of the substrate in contributing to the current and efficiency of textured and non-textured thin layer solar cells. For the case of a heavily doped silicon substrate, substrate contributions can be significant for cells with sufficiently thin base layers. For example, for the case of a silicon thin layer cell with a base layer thickness of 20 μm and a substrate doping of 6 × 10¹⁸ cm⁻³, the substrate contributes no more than 4% of the total short-circuit current. However, decreasing the base width to 5 μm results in an increase in this substrate contribution to 20%. Light trapping tends to alleviate the substrate contribution by increasing the effective path length in the base. Examination of the current components under forward bias reveals that for a thin layer cell with a high quality base and good front surface passivation, back diffusion of electrons into the substrate limits cell performance.     

Fabrication of microcrystalline silicon solar cells on a SnO2 coated substrate using seed layer insertion

We fabricated hydrogenated microcrystalline silicon (μc-Si:H) solar cells on SnO₂ coated glass using a seed layer insertion technique. Since rich hydrogen atoms from the μc-Si:H deposition process degrade the SnO₂ layer, we applied p-type hydrogenated amorphous silicon (p-a-Si:H) as a window layer. To grow the μc-Si:H layer on the p-a-Si:H window layer, we developed a seed layer insertion method. We inserted the seed layer between the p-a-Si:H layer and intrinsic bulk μc-Si:H. This seed layer consists of a thin hydrogen diluted silicon buffer layer and a naturally hydrogen profiled layer. We compared the characteristics of solar cells with and without the seed layer. When the seed layer was not applied, the fabricated cell showed the characteristics of a-Si:H solar cell whose spectral response was in a range of 400-800 nm. Using the seed layer, we achieved a μc-Si:H solar cell with performance of V_oc=0.535 V, J_sc=16.0 mA/cm², FF=0.667, and conversion efficiency=5.7% without any back reflector. The spectral response was in the range of 400-1100 nm. Also, the fabricated device has little substrate dependence, because a-Si:H has weaker substrate selectivity than μc-Si:H.     

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.     

Au/Porous silicon‐based sodium borohydride fuel cells

The Au/Porous silicon structure (Au/PS) was developed as hydrogen fuel cell. The use of a porous silicon filled with hydrochloric acid as a proton‐conducting membrane and thin gold film as a catalyst in Au/PS/Si fuel cell is demonstrated. The devices were fabricated by first creating 10–20 µm thick porous silicon layer by anodization etching in a standard silicon wafer and then depositing the gold catalyst film onto the porous silicon. Using sodium borohydride (NaBH₄) solution as the fuel, generation of the open‐circuit voltage of 0.55 V and the fuel cell peak power density of 13 mW cm⁻² at room temperature was achieved. Moreover production of hydrogen by evolution (out‐diffusion) of hydrogen from solid sodium borohydride during thermal annealing at 30–120°C was investigated. Data on the effective diffusion coefficient of the hydrogen in NaBH₄ were determined from intensity changes of infrared vibration peaks of B–H bond (2280 and 3280 cm⁻¹), as a result of thermal annealing of NaBH₄ samples. The relatively high values of the diffusion coefficient of hydrogen, increasing from 1×10⁻⁶ cm² s⁻¹ to 2×10⁻⁴ cm² s⁻¹ suggest that a thermo‐stimulated evolution process can be used for producing hydrogen from NaBH₄. Copyright © 2010 John Wiley & Sons, Ltd.     

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.     

Liquid phase epitaxial growth and electrical characterization of CuInSe2

A CuInSe₂ layer was grown on a ZnSe substrate by the liquid phase epitaxy (LPE) method from a Bi solution. The optimum growth conditions, namely a maximum temperature of 600°C and a cooling rate of 0.5°C min⁻¹, resulted in the over-growth layer being of thickness 6 μm and the mixed crystal layer of thickness 4.5 μm. The flatness and crystalline quality of the layer decreased in the order of the orientations (111)_Se, (100), (111)_Zn and (110). The electrical properties of the layer were measured by the Hall effect after heat treatment in either Se or Zn atmospheres. The LPE wafer was fabricated into p-CuInSe₂/n-ZnSe and n-CuInSe₂/n-ZnSe heterodiodes, which were characterized using I–V and C–V characteristics, photoresponse and electron beam induced current measurements. The n-CuInSe₂/n-ZnSe heterodiode in particular showed a high photoresponse. The effects of diffusion of the component elements Cu, In and Bi into the substrate and the CuInSe₂ layer were investigated by means of cathodoluminescence, Hall-effect measurements and electron-acoustic microscopy. Bi diffused in CuInSe₂ acts as a high mobility donor.     

Maximum light trapping for the random back-reflective silicon film solar cell with omnidirectional light transmission characteristics

The light trapping characteristics in the wavelength range of 0.5−1.2 μm for the random back-reflective silicon film with omnidirectional top anti-reflection are numerically analyzed based on the simplified probability method. The spectrum averaged maximum external quantum efficiency (EQE) for the 5 μm thick silicon film is evaluated with an increase of 10.6% compared with the best bulk planar silicon solar cell—suggesting that an efficiency higher than those of the best bulk planar cell can be obtained for thin film silicon solar cells several microns thick. The light absorption curves drop slowly with increased back absorption, exhibiting that the performance of the thin film silicon solar cell with light trapping is tolerant of back absorption.     

Development of n-μc-SiOx:H as cost effective back reflector and its application to thin film amorphous silicon solar cells

Development of doped silicon oxide based microcrystalline material as a potential candidate for cost-effective and reliable back reflector layer (BRL) for single junction solar cells is discussed in this article. Phosphorus doped μc-SiO_x:H layers with a refractive index ∼2 and with suitable electrical properties were fabricated by radio frequency plasma enhanced chemical vapor deposition (RF-PECVD) technique, using the conventional capacitively coupled reactors. Optoelectronic properties of these layers were controlled by varying the oxygen content within the film. The performance of these layers as BRL have been investigated by incorporating them in a single junction amorphous silicon solar cell and compared with the conventional ZnO:Al based reflector layer. Single junction thin film a-Si solar cells with efficiency ∼9.12% have been successfully demonstrated by using doped SiO:H based material as a back reflector. It is found that the oxide based back reflector shows analogous performance to that of conventional ZnO:Al BRL layer. The main advantage with this technology is that, it can avoid the ex-situ deposition of ZnO:Al, by using doped μc-SiO:H based material grown in the same reactor and with the same process gases as used for thin-film silicon solar cells.     

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.     

Nanostructured Zn-Fe2O3 thin film modified by Fe-TiO2 for photoelectrochemical generation of hydrogen

Nanostructured semiconductor thin films of Zn-Fe₂O₃ modified with underlying layer of Fe-TiO₂ have been synthesized and studied as photoelectrode in photoelectrochemical (PEC) cell for generation of hydrogen through water splitting. The Zn-Fe₂O₃ thin film photoelectrodes were designed for best performance by tailoring thickness of the Fe-TiO₂ film. A maximum photocurrent density of 748 μA/cm² at 0.95 V/SCE and solar to hydrogen conversion efficiency of 0.47% was observed for 0.89 μm thick modified photoelectrode in 1 M NaOH as electrolyte and under 1.5 AM solar simulator. To analyse the PEC results the films were characterized for various physical and semiconducting properties using XRD, SEM, EDX and UV–Visible spectrophotometer. Zn-Fe₂O₃ thin films modified with Fe-TiO₂ exhibited improved visible light absorption. A noticeable change in surface morphology of the modified Zn-Fe₂O₃ film was observed as compared to the pristine Zn-Fe₂O₃ film. Flatband potential values calculated from Mott–Schottky curves also supported the PEC response.     

Photoelectrochemical decomposition of water using modified monolithic tandem cells

Photovoltaic tandem cells, consisting of a gallium indium phosphide (GaInP₂) homojunction grown epitaxially on a gallium arsenide (GaAs) homojunction with a Ga Astunnel diode interconnect, were modified with an additional top p-layer of GaInP₂. These cells were used as electrodes to photoelectrochemically decompose water into hydrogen and oxygen in 1M, 5M and 11M KOH electrolyte solutions. The hydrogen reaction was catalyzed at the semiconductor surface with a photoelectrochemically deposited thin layer of platinum and ruthenium. Gas chromatography and electrochemical experiments demonstrate that the modified tandem cells produce hydrogen and oxygen with a light-to-hydrogen conversion efficiency of up to 6%. Both the efficiency and the stability of these cells are discussed. © 1999 International Association for Hydrogen Energy. Published by Elsevier Science Ltd. All rights reserved.     

Hall effect analysis of liquid phase epitaxy silicon for thin film solar cells

We use variable temperature Hall effect measurements to determine the doping concentration, impurity compensation, and mobility of n- and p-type liquid phase epitaxy (LPE) silicon layers that are grown from indium solutions onto silicon substrates. Our theoretical analysis of carrier concentration versus temperature data considers temperature-dependent effective masses, Fermi-Dirac statistics, multiple majority impurity levels, excited impurity states, and the temperature dependence of the Hall scattering factor. The measured Hall mobilities and computed compensation ratios in these LPE silicon thin films are within the range of values that have been measured in bulk silicon crystals. Such LPE layers are therefore suitable for the fabrication of high efficiency silicon thin film solar cells.     

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.     

Effect of Ti sublayer on the ORR catalytic efficiency of dc magnetron sputtered thin Pt films

A series of thin Pt films were deposited by dc magnetron sputtering directly on a commercial hydrophobic carbon paper substrate having a thin microporous Vulcan-XC72 layer or upon a thin Ti sublayer sputtered on the top of the microporous carbon film. The electrocatalytic properties of the sputtered Pt films toward the oxygen reduction reaction were investigated in 0.5 M H₂SO₄ solution and in a hydrogen PEM fuel cell. The catalyst with ultralow Pt loading of 22 μg cm⁻² deposited on a 33 Å thick Ti sublayer is robust, mechanically stable, possesses highly developed surface area and improved catalytic efficiency. Its performance as a MEA cathode in a single hydrogen PEM fuel cell (577 mA cm⁻² at 0.4 V cell voltages and a maximum power of 0.954 W) proved to be much superior compared to that of MEA with the same cathode Pt loading but without Ti sublayer (173 mA cm⁻² at 0.4 V, 0.231 W, respectively).     

Development of thin film amorphous silicon oxide/microcrystalline silicon double-junction solar cells and their temperature dependence

We have developed thin film silicon double-junction solar cells by using micromorph structure. Wide bandgap hydrogenated amorphous silicon oxide (a-SiO:H) film was used as an absorber layer of top cell in order to obtain solar cells with high open circuit voltage (V_oc), which are attractive for the use in high temperature environment. All p, i and n layers were deposited on transparent conductive oxide (TCO) coated glass substrate by a 60 MHz-very-high-frequency plasma enhanced chemical vapor deposition (VHF-PECVD) technique. The p-i-n-p-i-n double-junction solar cells were fabricated by varying the CO₂ and H₂ flow rate of i top layer in order to obtain the wide bandgap with good quality material, which deposited near the phase boundary between a-SiO:H and hydrogenated microcrystalline silicon oxide (μc-SiO:H), where the high V_oc can be expected. The typical a-SiO:H/μc-Si:H solar cell showed the highest initial cell efficiency of 10.5%. The temperature coefficient (TC) of solar cells indicated that the values of TC for conversion efficiency (η) of the double-junction solar cells were inversely proportional to the initial V_oc, which corresponds to the bandgap of the top cells. The TC for η of typical a-SiO:H/μc-Si:H was −0.32%/ °C, lower than the value of conventional a-Si:H/μc-Si:H solar cell. Both the a-SiO:H/μc-Si:H solar cell and the conventional solar cell showed the same light induced degradation ratio of about 20%. We concluded that the solar cells using wide bandgap a-SiO:H film in the top cells are promising for the use in high temperature regions.     

Development of high efficiency p-i-n amorphous silicon solar cells with the p-μc-Si:H/p-a-SiC:H double window layer

A structure is developed to help improve the TCO/p contact and efficiency of the solar cell. A p-i-n amorphous silicon (a-Si:H) solar cell with high-conversion efficiency is presented via use of a double p-type window layer composed of microcrystalline silicon and amorphous silicon carbide. The best efficiency is obtained for a glass/textured TCO/p-μc-Si:H/p-a-SiC:H/buffer/i-a-Si:H/n-μc-Si:H/GZO/Ag structure. Using a SnO₂/GZO bi-layer and a p-type hydrogenated microcrystalline silicon (p-μc-Si:H) layer between the TCO/p-a-SiC:H interface improves the photovoltaic performance due to reduction of the surface potential barrier. Layer thickness, B₂H₆/SiH₄ ratio and hydrogen dilution ratio of the p-μc-Si:H layer are studied experimentally. It is clearly shown that the double window layer can improve solar cell efficiency. An initial conversion efficiency of 10.63% is achieved for the a-Si:H solar cell.     

A high efficiency thin film silicon solar cell and module

A photoelectric conversion efficiency of over 10% has been achieved in thin-film microcrystalline silicon solar cells which consist of a 2 μm thick layer of polycrystalline silicon. It was found that an adequate current can be extracted even from a thin film due to the very effective light trapping effect of silicon with a low absorption coefficient. As a result, this technology may eventually lead to the development of low-cost solar cells. Also, an initial aperture efficiency as high as 13.5% has been achieved with a large area (91 cm × 45 cm) tandem solar cell module of microcrystalline silicon and amorphous silicon (thin film Si hybrid solar cell). An even greater initial efficiency of 14.7% has been achieved in devices with a small size (area of 1 cm²), and further increases of efficiency can be expected.     

High efficiency silicon solar cells by plasma-CVD method

We have succeeded in obtaining excellent Back Surface Field (BSF) structures by depositing a highly doped silicon layer on the back side of the substrate even though the textured wafer is used. The substantial increase of the spectral response in longer wavelength has been observed and an increase of V_oc has also been found. The BSF formation technology, together with the low temperature grown thin a-Si emitter layer with appropriate bandgap, has enabled us to obtain a very high J_sc of 40.5 mA/cm², thus a high active area conversion efficiency of 18.9 % (V_oc = 0.592 V, FF = 0..789).