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.     

A review of thin-film crystalline silicon for solar cell applications. Part 2: Foreign substrates

One of the most promising ways to reduce the cost of photovoltaics is thin-film crystalline silicon solar cells. This paper, together with part 1, reviews the current state of research in thin-film crystalline silicon solar cells. Deposition on silicon, novel techniques which use a high-quality, reusable silicon substrate and light trapping have been described in part 1 of this paper. This paper describes deposition on glass and ceramics and discusses cell designs for thin-film crystalline silicon solar cells.     

Advanced cost-effective crystalline silicon solar cell technologies

An overview is given concerning current industrial technologies, near future improvements and medium-term developments in the field of industrially viable crystalline silicon terrestrial solar cell fabrication (without concentration).     

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.     

Laser structuring of crystalline silicon thin-film solar cells on opaque foreign substrates

Crystalline silicon thin-film solar cells were fabricated on graphite substrates. A laser ablation process was developed for edge isolation of the thin-film cells. The shunt resistance was comparable to otherwise identical cells isolated by plasma etching, while the reproducibility of the laser isolation process was higher. The solar cells were characterized by current-voltage and light beam induced current measurements (LBiC). No interference was detected along the ablated edges. Spatial variations of the minority carrier lifetime are attributed to the grain structure of the seeding layer obtained by the zone melting recrystallization (ZMR).     

Characterization of crystalline silicon grown by plasma-enhanced CVD for thin-film solar cells

High growth-rate Si epitaxy by plasma-enhanced chemical vapor deposition (PECVD) has been investigated for a thin-film solar cell application. A high growth rate of 50 μm/h was obtained at 1050°C with plasma which is 50% larger than that by the conventional CVD without plasma. The electrical properties are almost the same for epitaxial layers with and without plasma. For undoped n-type layers, the Hall mobility and carrier density were about 600 cm²/V s and low 10¹⁵ cm⁻³, respectively. The electron diffusion length in doped p-type layers was about 20 μm. These electrical properties for the layer with plasma, in spite of higher growth rate, are comparable or better than those without plasma.     

Crystalline silicon thin-film solar cells on ZrSiO4 ceramic substrates

The development of a low-cost substrate is one of the major technological challenges for crystalline Si thin-film solar cells. Zirconium silicate (ZrSiO₄) ceramics is a material which can meet the demanding physical requirements as well as the cost goals. Thin microcrystalline Si films were deposited by atmospheric pressure CVD on ZrSiO₄-based ceramic substrates coated with barrier layers. The Si film was transferred into a multicrystalline grain structure by zone-melting recrystallization (ZMR). Film growth was analyzed in situ and correlated with substrate and barrier layer properties. Thin-film solar cells were fabricated from selected coarse-grained films. The best solar cell achieved an efficiency of 8.3% with a short circuit current density of 26.7 mA/cm². The effective diffusion length obtained from internal quantum efficiency measurements was about 25 μm.     

New processes for the production of solar-grade polycrystalline silicon: A review

The global energy consumption is predicted to grow dramatically every year. Higher energy prices and public awareness for the global warming problem have opened up the market for solar cells. The generation of electricity with solar cells is considered to be one of the key technologies of the new century. The impressive growth is mainly based on solar cells made from polycrystalline silicon. This paper reviews the recent advances in chemical and metallurgical routes for photovoltaic (PV) silicon production.     

Porous silicon as an intermediate layer for thin-film solar cell

The potential of porous silicon (PS) with dual porosity structure as an intermediate layer for ultra-thin film solar cells is described. It is shown that a double-layered PS with a porosity of % allows to grow epitaxial Si film at medium temperature (725°–800°C) and at the same time serves as a gettering/diffusion barrier for impurities from potentially contaminated low-cost substrate. A 3.5 μm thin-film cell with reasonable efficiency is realized using such a PS intermediate layer.     

Hydrogen in polycrystalline silicon solar cell material: Its role and characteristics

The role and the characteristics of hydrogen in different polycrystalline silicon material are studied in this paper. The hydrogen diffusion through the grains and the grain boundaries, and its diffusion coefficient, are investigated. Moreover, the influence of the oxygen and the carbon contents on the diffusion mechanism of hydrogen in silicon is addressed. Also, it is found that the minority carrier diffusion length of polycrystalline silicon wafers considerably improves when annealed in hydrogen at high temperatures (>1000°C). Consequently, a significant amount of oxygen is out-diffused from the bulk of the wafers.     

Latest results on semitransparent POWER silicon solar cells

The paper presents the latest results of the polycrystalline wafer engineering result (POWER) silicon solar cell research (G. Willeke, P. Fath, The POWER silicon solar cell, Proceedings of the 12th EPVSEC, Amsterdam, 1994, pp. 766–768). Mono – as well as bifacially active semitransparent silicon solar cells have been created by forming perpendicularly overlapping grooves on the front and the rear side of a silicon wafer resulting in a regular pattern of holes. The developed very simple manufacturing process is fully compatible with an industrial production and uses POCl₃-tube diffusion, PECVD silicon nitride as single ARC and screen-printing metallization. Maximum efficiencies of η=11.2% for monofacial POWER cells on 0.4 Ω cm Cz material with a transparency of 18.2% and η=12.9% for bifacial cells on 1 Ω cm Cz material with a transparency of 16% have been obtained. Results for multicrystalline (mc) semitransparent mono- and bifacially active silicon solar cells are also presented.     

Formation of porous silicon for large-area silicon solar cells: A new method

Luminescent porous silicon (PS) was prepared for the first time using a spraying set-up, which can diffuse in a homogeneous manner HF solutions, on textured or untextured (1 0 0) oriented monocrystalline silicon substrate. This new method allows us to apply PS onto the front-side surface of silicon solar cells, by supplying very fine HF drops. The front side of N⁺/P monocrystalline silicon solar cells may be treated for long periods without altering the front grid metallic contact. The monocrystalline silicon solar cells (N⁺/P, 78.5 cm²) which has undergone the HF-spraying were made with a very simple and low-cost method, allowing front-side Al contamination. A poor but expected 7.5% conversion efficiency was obtained under AM1 illumination. It was shown that under optimised HF concentration, HF-spraying time and flow HF-spraying rate, Al contamination favours the formation of a thin and homogeneous hydrogen-rich PS layer. It was found that under optimised HF-spraying conditions, the hydrogen-rich PS layer decreases the surface reflectivity up to 3% (i.e., increase light absorption), improves the short circuit current (I_sc), and the fill factor (FF) (i.e., decreases the series resistance), allowing to reach a 12.5% conversion efficiency. The dramatic improvement of the latter is discussed throughout the influence of HF concentration and spraying time on the I–V characteristics and on solar cells parameters. Despite the fact that the thin surfae PS layer acts as a good anti-reflection coating (ARC), it improves the spectral response of the cells, especially in the blue-side of the solar spectrum, where absorption becomes greater, owing to surface band gap widening and conversion of a part of UV and blue light into longer wavelengths (that are more suitable for conversion in a Si cell) throughout quantum confinement into the PS layer.     

Pulsed KrF excimer laser annealing of silicon solar cell

The pulsed KrF excimer laser annealing of silicon films for solar cell with EBEP-CVD and LP-CVD was studied theoretically and experimentally. Three-dimensional thermal diffusion equation for microcrystalline and amorphous silicon was solved by using the finite difference methods. The results of our heat-flow simulation of laser re-crystallization in a laser irradiation with 50 ns pulse duration almost agree with the experimental results in re-crystallization depth of 0.7 μm for microcrystalline silicon (EBEP-CVD) and 0.4 μm for amorphous silicon (LP-CVD) in a single pulse excimer laser annealing.     

Crystalline silicon on glass (CSG) thin-film solar cell modules

Crystalline silicon on glass (CSG) solar cell technology was developed to address the difficulty that silicon wafer-based technology has in reaching the very low costs required for large-scale photovoltaic applications as well as the perceived fundamental difficulties with other thin-film technologies. The aim was to combine the advantages of standard silicon wafer-based technology, namely ruggedness, durability, good electronic properties and environmental soundness with the advantages of thin-films, specifically low material use, large monolithic construction and a desirable glass superstrate configuration. The challenge has been to match the different preferred processing temperatures of silicon and glass and to obtain strong solar absorption in notoriously weakly-absorbing silicon of only 1.4 μm thickness, the thinnest active layer of the key thin-film contenders. A rugged, durable silicon thin-film technology has been developed arguably with the lowest likely manufacturing cost of these contenders and confirmed efficiency for small pilot line modules already in the 8–9% energy conversion efficiency range, on the path to 12–13%.     

Effects of grain boundaries in polycrystalline silicon thin-film solar cells based on the two-dimensional model

The two-dimensional calculation for polycrystalline Si thin-film solar cells was performed. Two models, “stripe structure” and “columnar structure”, were applied for the solar cells composed of grains. For the stripe structure of 20 μm active layer, to keep the efficiency distribution within 5% for individual unit cells, the stripe width requires more than 500 μm for a minority-carrier lifetime of 1×10⁻⁵ s and recombination velocity at the grain boundary of 1×10⁴ cm/s. For the columnar structure of 10 μm active layer, to keep the efficiency independent of grain size, the recombination velocity should be kept less than 1×10³ cm/s. If imperfect passivation of a grain boundary is given, the way of decreasing carrier concentration to 10¹⁴ cm⁻³ in an active layer may realize insusceptible output. An appropriate device modeling is needed in the two-dimensional calculation for polycrystalline Si thin films with an electron diffusion length close to or more than grain size and with a poorly passivated grain boundary. The calculated efficiency using bad model will include an error of about 1% as overestimation.     

Present status and future of crystalline silicon solar cells in Japan

Crystalline silicon solar cells show promise for further improvement of cell efficiency and cost reduction by developing process technologies for large-area, thin and high-efficiency cells and manufacturing technologies for cells and modules with high yield and high productivity.In this paper, Japanese activities on crystalline Si wafers and solar cells are presented. Based on our research results from crystalline Si materials and solar cells, key issues for further development of crystalline Si materials and solar cells will be discussed together with recent progress in the field. According to the Japanese PV2030 road map, by the year 2030 we will have to realize efficiencies of 22% for module and 25% for cell technologies into industrial mass production, to reduce the wafer thickness to 50–100 μm, and to reduce electricity cost from 50 Japanese Yen/kWh to 7 Yen/kWh in order to increase the market size by another 100–1000 times.     

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.     

Characterisation of direct epitaxial silicon thin film solar cells on a low-cost substrate

Direct epitaxial crystalline silicon thin film (CSiTF) solar cells on low-cost silicon sheets from powder (SSP) ribbons have been prepared using rapid thermal chemical vapour deposition (CVD) growth. The characterisation of CSiTF solar cells was investigated by electron and spectrally resolved light beam induced current (EBIC and SR-LBIC, respectively). All EBIC measurements were performed on both the front-side surface as well as on the cross-section of CSiTF solar cells. The electrical recombination was detected by EBIC and compared with their morphologies. The results of EBIC scan show that recombination centres are situated at grain boundaries (GBs); higher the density of grain, higher the recombination activities (higher contrast). Recombination of different intensity (strong and weak) takes place at vertical GBs. Compared with the high recombination at GBs, the contrast in intragrain is low. The dark contrast of the GBs and intragrain defects is clearly reduced near the surface due to the passivation by hydrogen, which indicates that the minority carrier diffusion length decreases gradually with the depth perpendicular to the surface. The diffusion length was determined by SR-LBIC. The results show that the diffusion length distribution is quite inhomogeneous over the whole cell area. A maximum L_eff of about 25 μm and mean values around 15 μm are calculated for the best solar cell.     

Two- and three-dimensional optical carrier generation determination in crystalline silicon solar cells

Two- and three-dimensional analyses of the distribution of optically generated charge carriers in textured crystalline silicon solar cells of arbitrary geometry have been performed. The simulation algorithm, developed for that purpose, is based on geometrical optics and ray tracing. It determines the dominant contributions to the optical generation within textured silicon exactly. The contribution of weakly absorbed long-wavelength photons is calculated using a Monte-Carlo simulation. The presented algorithm is fast and accurate and can also be used to calculate reflectance and transmittance spectra in excellent agreement with measurements. Two- and three-dimensional generation profiles in single- and double-sided textured solar cells are presented and discussed in detail. Examples for applications are given. Finally, the presented algorithm is compared with a pure Monte-Carlo algorithm.     

The influence of porous silicon on junction formation in silicon solar cells

In this work the results of a structural investigation by SEM of porous silicon (PS) before and after diffusion processes are reported. The formation of PS n⁺/p structures were carried out on PS p/p silicon wafers with two methods: from POCl₃ in a conventional furnace and from a phosphorous doped paste in an infrared furnace. Sheet resistance was found to be a strong function of PS structure. Further details on sheet resistance distribution are reported. The electrical contacts in prepared solar cells were obtained by screen printing process, with a Du Ponte photovoltaic silver paste for front contacts and home-prepared silver with 3% aluminium paste for the back ones. Metallization was done in the infrared furnace. Solar cell current–voltage characteristics were measured under an AM 1.5 global spectrum sun simulator. The average results for multi-crystalline silicon solar cells without antireflection coating are: I_sc=720 (mA), V_oc=560 (mV), FF=69%, Eff=10.6% (area 25 cm²).