A review of thin-film crystalline silicon for solar cell applications. Part 1: Native substrates

Approximately half the cost of a finished crystalline silicon solar module is due to the silicon itself. Combining this fact with a high-efficiency potential makes thin-film crystalline silicon solar cells a growing research area. This paper, written in two parts, aims to outline world-wide research on this topic. The subject has been divided into techniques which use native substrates and techniques which use foreign substrates. Light trapping, vapour- and liquid-phase deposition techniques, cell fabrication and some general considerations are also discussed with reference to thin-film cells.     

Crystalline silicon thin-film solar cells—recent results at Fraunhofer ISE

Crystalline silicon thin-film solar cells combine the advantages of the stability and high-efficiency potential of crystalline silicon solar cell technology with the low material utilization of the thin-film solar cell technology. At Fraunhofer ISE the wafer equivalent concept is currently pursued. Within this concept, the active silicon layers are deposited on high-temperature stable substrates. The resulting substrate/layer sandwich can be processed into a solar cell using the same techniques that are used in conventional crystalline silicon wafer solar cell processing, hence the name wafer equivalent. In the present paper we report on how we realized wafer equivalents and explain in detail our development work on processors for both large-area silicon deposition and for zone melting recrystallization. An overview is given on the solar cell results achieved in this area.     

Zone melting recrystallization of silicon films for crystalline silicon thin-film solar cells

Coarse-grained silicon films for crystalline silicon thin-film solar cells have been prepared by zone melting recrystallization. A zone melting heater was modified to obtain better temperature homogeneity of the sample and higher reproducibility of the melt process. Various substrate materials of different purity and surface roughness have been tested concerning their suitability for, silicon deposition, zone melting and solar cell process. Solar cell efficiencies up to 10.5% could be achieved on silicon sheets from powder, capped by an intermediate layer. Silicon films on SiAlON ceramics were successfully processed to solar cells by a completely dry solar cell process.     

Amorphous solar cells, the micromorph concept and the role of VHF-GD deposition technique

During the last two decades, the Institute of Microtechnology (IMT) has contributed in two important fields to future thin-film silicon solar cell processing and design:

(1) In 1987, IMT introduced the so-called “very high frequency glow discharge (VHF-GD)” technique, a method that leads to a considerable enhancement in the deposition rate of amorphous and microcrystalline silicon layers. As a direct consequence of reduced plasma impedances at higher plasma excitation frequencies, silane dissociation is enhanced and the maximum energy of ions bombarding the growing surface is reduced. Due to softer ion bombardment on the growing surface, the VHF process also favours the formation of microcrystalline silicon. Based on these beneficial properties of VHF plasmas, for the growth of thin silicon films, plasma excitation frequencies f_exc in the range 30–300 MHz, i.e. clearly higher than the standard 13.56 MHz, are indeed scheduled to play an important role in future production equipment.

(2) In 1994, IMT pioneered a novel thin-film solar cell, the microcrystalline silicon solar cell. This new type of thin-film absorber material––a form of crystalline silicon––opens up the way for a new concept, the so-called “micromorph” tandem solar cell concept. This term stands for the combination of a microcrystalline silicon bottom cell and an amorphous silicon top cell. Thanks to the lower band gap and to the stability of microcrystalline silicon solar cells, a better use of the full solar spectrum is possible, leading, thereby, to higher efficiencies than those obtained with solar cells based solely on amorphous silicon.

Both the VHF-GD deposition technique and the “micromorph” tandem solar cell concept are considered to be essential for future thin-film PV modules, as they bear the potential for combining high-efficiency devices with low-cost manufacturing processes.     

Crystalline and thin-film silicon solar cells: state of the art and future potential

Bulk crystalline silicon solar cells have been the workhorse of the photovoltaic industry over the past decades. Recent major investments in new manufacturing facilities for monocrystalline and multicrystalline wafer-based cells, as well as for closely related silicon ribbon and sheet approaches, ensure this role will continue well into the future. Such investments suggest that the silicon wafer-based approach has successfully withstood the challenge mounted by thin-film chalcogenide-based cells, in the form of polycrystalline films of CdTe and CuInSe₂, as well as that mounted by thin-film cells based on amorphous silicon and its alloys with germanium. The encumbent now faces a fresh challenge by a new wave of thin-film technologies developed in the 1990s, more closely related to the bulk approach and with some advantages over the earlier contenders. One new approach is based on a stack of two silicon thin-film cells, one cell using amorphous silicon and the other mixed-phase microcrystalline silicon. The second uses silicon thin-films in polycrystalline form deposited onto glass, even more directly capturing the strengths of the wafer-based approach.     

Commercial white paint as back surface reflector for thin-film solar cells

In this work, commercially available white paint is applied as a pigmented diffuse reflector (PDR) on the rear surface of thin-film crystalline silicon (c-Si) solar cells with a silicon thickness in the 1–2 μm range. We show that white paint increases the short-circuit current density of the solar cells enormously, with a boost of 41% observed for very thin planar solar cells illuminated with the global AM1.5 solar spectrum. We also show that white paint is a better back surface reflector (BSR) than aluminium, air, a transparent conductive oxide (TCO)/aluminium stack, and even a detached aluminium mirror. While previous studies have investigated the influence of PDRs on silicon solar cells with thicknesses of over 27 μm, this work closes the gap that has existed for much thinner cells.     

Thin-film silicon solar cells: A review and selected trends

A case is developed for considering silicon as the prime medium-term candidate for semiconductor photovoltaic cells; the argumentation is based on other materials not being abundantly available, highly toxic and/or very expensive. Crystalline silicon solar cells have excellent efficiencies, however, according to data presented by the authors on material fluxes and energy consumption there are serious bottlenecks for this technique with respect to future large-scale applications both from an economical as well as from an ecological point of view. Thus, the authors consider thin-film silicon solar cells as the main option for large-scale energy applications in the foreseeable future. Thin-film silicon solar cells are either polycrystalline or amorphous. The first category is gaining in interest at this moment, but major technological problems remain unresolved, e.g., growth of a high-quality crystalline structure on foreign (low-cost) substrates, reduction of deposition temperature and increase of deposition rate. The second category has so far yielded only limited stable efficiencies, although progress has been recently achieved in improving the stability of solar cells using stacked or tandem/triple structures. Novel approaches to further improve the stable efficiencies, such as using low-level doping profiles within the i-layer of the p-i-n solar cell, are listed. Entirely microcrystalline p-i-n solar cells that are stable and can be deposited at low temperatures (220° C) with rates up to 1 å/s by the VHF plasma deposition technique are described as further, recent contribution to thin-film silicon photovoltaic technology.     

Improving thin-film crystalline silicon solar cell efficiency with back surface field layer and blaze diffractive grating

Both 2D electromagnetic and electrical semiconductor simulations are performed sequentially in this study in order to better understand the structural principles of thin-film crystalline solar cells with back surface field and blaze diffractive grating. In the absence of adequate approximations for blazed gratings, we simulate silicon solar cells electromagnetically and electrically in order to deal with the geometrical complexity produced by the blazed grating with a BSF on top of it. Thin-film crystalline silicon solar cells (TF-c-Si SCs) typically exhibit poor quantum efficiency both at shorter wavelengths and longer wavelengths with sharp drops in spectral response. Longer wavelength spectral response (from 0.6 μm to 1.2 μm) is addressed here first by considering the influence of blaze gratings on the enhancement of effective optical absorption in thin-film crystalline silicon (TF-c-Si) solar cells. The effect of the back surface field layer (BSF) in terms of improving minority carrier collection is also taken into account. In the 2D electromagnetic simulation, polarization dependent two-dimensional (2D) numerical simulations based on rigorous coupled wave analysis (RCWA) and finite element method (FEM) are implemented for the optimization of optical absorption of the solar cell structure. A rather large tolerance in design parameters of the optimized blaze grating structure was found. The optimized blaze grating structures help in improving the cell efficiency, especially for weak absorption thin cell structures. The enhancement of equivalent optical path length reveals the efficient light trapping effect caused by the diffractions of the blaze grating structures, especially in the longer wavelength range. In the electrical semiconductor simulation, the BSF, which arises from the heavy acceptor doping that creates the concentration gradient, is set atop the blaze grating in order to provide an extra small drift field for the collection of minority electrons. Incorporating the optimized antireflection coating along with a BSF layer and a blaze-grating in the 2 μm cell doubles cell efficiency. The use of blazed gratings in thin-film solar cells, which can be performed upon silicon by means of lithography and ion-beam etching, is promising for low cost and high-efficient solar cell applications.     

基于柔性晶体硅电池的光伏瓦研究

光伏瓦作为一种建筑材料,可替代屋顶陶瓦建材,且增加了发电功能,以薄膜电池为主的柔性光伏瓦具有质量轻和可弯曲的特性,但存在转换效率低、使用寿命短的问题。采用柔性晶体硅太阳电池,通过固化炉加气压釜的新型层压工艺,克服了层压过程中气泡、脱层等工艺问题,实现了基于晶体硅电池效率的柔性光伏瓦。     

Fabrication and characterisation of parallel multijunction thin film silicon solar cells

The parallel multijunction solar cell design offers the exciting possibility of high efficiency at low cost. To date, there has been no detailed report on the experimental characteristics of these devices. This paper reports on the beginnings of a detailed experimental investigation of the parallel multijunction solar cell. Progress is reported on the fabrication of parallel multijunction thin-film silicon solar cells (on inert single-crystal silicon substrates), specifically designed and fabricated to serve as experimental test-beds for the detailed study of cell performance limiting mechanisms. Of particular interest is the importance of junction space-charge-region recombination in heavily defected parallel multijunction cells.     

Thin-film c-Si solar cells prepared by metal-induced crystallization

We prepared a thin-film polycrystalline silicon solar cell using metal-induced crystallization (MIC) of an amorphous silicon film and a thin Ni layer. The MIC using a 0.6-nm-thick Ni layer produced a highly activated n-type crystalline layer at a 550°C annealing temperature. The Ni concentration in the i-layer of a solar cell prepared by successively depositing i- and p-layers on an MIC n-layer using plasma-enhanced CVD was lower than 1×10¹⁶/cm³. This solar cell was highly responsive in the long-wavelength region of its quantum efficiency, indicating that the n/i interface and i-layer region near the n-layer were of high quality.     

Photovoltaic materials, past, present, future

This paper traces briefly the history of this photovoltaic materials and it tries to look at possible future scenarios. A large part of the paper is concerned with silicon although from solid-state physics we know that silicon is not the ideal material for photovoltaic conversion. From the first solar cell developed at Bell Laboratories in 1954 photovoltaics was dominated by silicon. The reasons for this dominating position are investigated. Crystalline silicon today has a market share of 86% which is almost equally distributed between single crystal and cast silicon. Amorphous silicon has another 13%. The main endeavor is to reduce cost. Present trends in the crystalline field are reviewed. The conventional technology still has significant potential for cost reduction but this comes only with increasing volume. A problem to be solved is the supply of solar-grade silicon material. Other future possibilities include thin film crystalline silicon on different substrates. Because of the low absorption coefficient of silicon light trapping is required. True thin film materials need only 1–2 μm of material. Amorphous silicon, copper indium diselenide (CIS) and CdTe are hopeful approaches for very cost-effective solar cells. Some other, more speculative materials and concepts are described at the end of this paper     

Thin film silicon solar cells for space applications: Study of proton irradiation and thermal annealing effects on the characteristics of solar cells and individual layers

The paper reports on the effects of a proton irradiation campaign on a series of thin-film silicon solar cells (single- and double-junction). The effect of subsequent thermal annealing on solar cells degraded by proton irradiation is investigated. A low-temperature annealing behaviour can be observed (at temperatures around 100 to 160°C) for microcrystalline silicon solar cells. To further explore this effect, a second proton irradiation campaign has been carried out, but this time on microcrystalline silicon layers. The effect of proton irradiation and subsequent thermal annealing on the optical and electronic properties of microcrystalline silicon is, thus, thoroughly investigated.     

Recent advances of high-efficiency single crystalline silicon solar cells in processing technologies and substrate materials

Single crystalline silicon solar cells have demonstrated high-energy conversion efficiencies up to 24.7% in a laboratory environment. One of the recent trends in high-efficiency silicon solar cells is to fabricate these cells on different silicon substrates. Some silicon wafer suppliers are also involved in such development. Another recent trend is the increased production of high-efficiency silicon cells, some of them with low-cost structures. This paper will discuss the progress at the University of New South Wales, and these trends in other organisations.     

Rough ZnO layers by LP-CVD process and their effect in improving performances of amorphous and microcrystalline silicon solar cells

Doped ZnO layers deposited by low-pressure chemical vapour deposition technique have been studied for their use as transparent contact layers for thin-film silicon solar cells.Surface roughness of these ZnO layers is related to their light-scattering capability; this is shown to be of prime importance to enhance the current generation in thin-film silicon solar cells. Surface roughness has been tuned over a large range of values, by varying thickness and/or doping concentration of the ZnO layers.A method is proposed to optimize the light-scattering capacity of ZnO layers, and the incorporation of these layers as front transparent conductive oxides for p–i–n thin-film microcrystalline silicon solar cells is studied.     

硅太阳电池稳步走向薄膜化

考察了硅太阳电池在光伏产业中所处的地位,分析了薄膜硅太阳电池的发展趋势。指出硅太阳电池在未来15a仍将保持优势地位,并继续沿着晶硅电池和薄膜硅电池两个方向发展。在此发展过程中,两个发展方向的主流很可能会汇合到一起,共同促使低成本、高效率、高可靠薄膜晶硅电池的诞生和产业化,从而继续保持硅太阳电池的优势地位。     

Material constraints for thin-film solar cells

Harnessing solar energy by using photovoltaic cells has the potential to become a major CO₂-free energy source. Materials requirements for the solar cells based on four types of thin-film photovoltaics have been estimated and compared with global reserves, resources and annual refining. The use of solar cells based on Cd, Ga, Ge, In, Ru, Se and Te as a major energy-supply technology has severe resource constraints. Other systems such as a-Si without Ge and crystalline silicon do not involve such constraints. For some of these metals, there is the risk of enhanced, environmentally deleterious concentrations in the ecosphere due to leakage from manufacturing, use or waste handling.     

弱光下晶体硅太阳电池的开路电压

讨论了弱光下影响晶体硅太阳电池开路电压的主要因素。要提高弱光下开路电压主要应提高太阳电池的并联电阻。     

Aluminium BSF in silicon solar cells

The purpose of this work is to develop a back surface field (BSF) for industrial crystalline silicon solar cells and thin-film solar cells applications. Screen-printed and sputtered BSFs have been realised on structures which already have a n⁺p back junction due to the diffusion of the phosphorus in both faces of the wafer during solar cell emitter elaboration. Rapid thermal annealing temperatures from 700°C to 1000°C have been used. Thickness of the BSF has been measured by SIMS and confronted to the theoretical expected value and simulations. Electrical and optical measurements have been done in order to characterise the BSF. For 250 μm thick industrial solar cells, 6% relative increase in photocurrent has been reached.     

An optimum design of antireflection coating for spherical silicon solar cells

Antireflection (AR) coatings for spherical crystalline silicon solar cells are theoretically optimized from the viewpoint of achieving the largest photon densities in the spherical crystalline silicon solar cells. Because the AR film thickness is optimized with regard to the photon densities in the spherical crystalline silicon solar cells, tolerance in the film thickness can be evaluated. Also, the optimized AR film thicknesses for the spherical crystalline silicon solar cells and planar crystalline silicon solar cells are compared, and analytic expressions for the optimized AR film thicknesses are derived as a function of a quarter-wavelength film thickness.