Potential of VHF-plasmas for low-cost production of a-Si: H solar cells

Compared to the use of the standard glow discharge technique the production of amorphous silicon solar cells by the very high frequency glow discharge (VHF-GD) bears yet additional cost reduction potentials:Using VHF-GD at excitation frequencies higher than 13.56 MHz, a more efficient dissociation of silane gas is obtained; thus, higher deposition rates are achieved; this reduces considerably the deposition time for intrinsic amorphous and microcrystalline silicon layers.Furthermore, by itself and even more so, in combination with argon dilution, VHF-GD technique improves silane utilisation and leads, thus, to further cost reduction.Finally, by combining the VHF-GD technique and the “micromorph” concept “real” tandem cells (i.e. a superposition of two cells with distinctly different band gaps) can be deposited at low temperatures without the use of expensive germane gas.     

Microcrystalline silicon and the impact on micromorph tandem solar cells

Intrinsic microcrystalline silicon opens up new ways for silicon thin-film multi-junction solar cells, the most promising being the “micromorph” tandem concept. The microstructure of entirely microcrystalline p–i–n solar cells is investigated by transmission electron microscopy. By applying low pressure chemical vapor deposition ZnO as front TCO in p–i–n configurated micromorph tandems, a remarkable reduction of the microcrystalline bottom cell thickness is achieved. Micromorph tandem cells with high open circuit voltages of 1.413 V could be accomplished. A stabilized efficiency of around 11% is estimated for micromorph tandems consisting of 2 μm thick bottom cells. Applying the monolithic series connection, a micromorph module (23.3 cm²) of 9.1% stabilized efficiency could be obtained.     

Deposition pressure effects on material structure and performance of micromorph tandem solar cells

Tandem solar cells represent an elegant way of overcoming the efficiency limits of single-junction solar cells and reducing the light-induced degradation of amorphous silicon films. Stacked structures consisting of an amorphous silicon top cell and a microcrystalline silicon bottom cell allow a good utilization of the solar spectrum due to the band gap values of the two materials. These devices, firstly introduced by the IMT research group, were designated as “micromorph” tandem solar cells. To better exploit this concept, it is important to tune parameters like the band gaps and the short-circuit currents.In this work, we have realized micromorph tandem solar cells on Asahi U-type TCO-covered glass substrates. The intrinsic layer of both the amorphous top cell and the microcrystalline bottom cell is grown by very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD) at 100 MHz at low substrate temperature (150 °C). Finally, a ZnO reflector and a metal contact complete the structure. No intermediate optical mirror between the two cells is used at this stage. Undiluted a-Si:H, with reduced band gap when compared to H₂-diluted amorphous silicon, is used as absorber layer in the top cell. As for the bottom cell, the high-pressure–high-power regime (up to 267 Pa–80 W) has been explored aiming at growing high-quality microcrystalline silicon at large deposition rates. The effect of the structural composition of the microcrystalline absorber layer on the current–voltage characteristic and spectral response of tandem devices has been investigated. An efficiency of 11.3% has been obtained with short-circuit current densities around 13 mA/cm², open-circuit voltages 1.34 V and fill factors 66%.     

Microcrystalline/micromorph silicon thin-film solar cells prepared by VHF-GD technique

Hydrogenated microcrystalline silicon prepared at low temperatures by the glow discharge technique is examined here with respect to its role as a new thin-film photovoltaic absorber material. XRD and TEM characterisations reveal that microcrystalline silicon is a semiconductor with a very complex morphology. Microcrystalline p–i–n cells with open-circuit voltages of up to 560–580 mV could be prepared. “Micromorph” tandem solar cells show under outdoor conditions higher short-circuit currents due to the enhanced blue spectra of real sun light and therefore higher efficiencies than under AM1.5 solar simulator conditions. Furthermore, a weak air mass dependence of the short-circuit current density could be observed for such micromorph tandem solar cells. By applying the monolithic series connection based on laser patterning a first micromorph mini-module (total area of 23.6 cm²) with 9% cell conversion efficiency could be fabricated.     

Towards high-efficiency thin-film silicon solar cells with the “micromorph” concept

Tandem solar cells with a microcrystalline silicon bottom cell (1 eV gap) and an amorphous-silicon top cell (1.7 eV gap) have recently been introduced by the authors; they were designated as “micromorph” tandem cells. As of now, stabilised efficiencies of 11.2% have been achieved for micromorph tandem cells, whereas a 10.7% cell is confirmed by ISE Freiburg. Micromorph cells show a rather low relative temperature coefficient of 0.27%/K. Applying the grain-boundary trapping model so far developed for CVD polysilicon to hydrogenated microcrystalline silicon deposited by VHF plasma, an upper limit for the average defect density of around 2 × 10¹⁶/cm³ could be deduced; this fact suggests a rather effective hydrogen passivation of the grain-boundaries. First TEM investigations on μc-Si : H p-i-n cells support earlier findings of a pronounced columnar grain structure. Using Ar dilution, deposition rates of up to 9 Å/s for microcrystalline silicon could be achieved.     

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.     

Microcrystalline silicon films and solar cells deposited by PECVD and HWCVD

The application of microcrystalline silicon (μc-Si:H) in thin-film solar cells is addressed in the present paper. Results of different technologies for the preparation of μc-Si:H are presented, including plasma enhanced chemical vapour deposition (PECVD) using 13.56 MHz (radio frequency, rf) and 94.7 MHz (very high frequency, vhf) and hot-wire chemical vapour deposition (HWCVD). The influence of the silane concentration (SC) on the material and solar cell parameters is studied for the different techniques as the variation of SC allows to optimise the solar cell performance in each deposition regime. The best performance of μc-Si:H solar cells is always observed near the transition to amorphous growth. The highest efficiency obtained so far at a deposition rate of 5 Å/s is 9.4%, achieved with rf-PECVD in a deposition regime of using high pressure and high discharge power. High deposition rates and solar cell efficiencies could be also achieved by vhf-PECVD. An alternative approach represents the HWCVD which also demonstrated high deposition rates for μc-Si:H. However, good material quality and solar cell performance could only be achieved at low substrate temperatures and, consequently, low deposition rates. The μc-Si:H solar cells prepared by HWCVD exhibit comparably high efficiencies up to 9.4% and exceptionally high open circuit voltages up to 600 mV but at lower deposition rates (≈1 Å/s). The properties of PECVD and HWCVD solar cells are carefully compared.     

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.     

A novel route to a polycrystalline silicon thin-film solar cell

An alternative approach is described for the fabrication of a polycrystalline silicon thin-film solar cell on inexpensive substrates. In a first step amorphous silicon is recrystallized in an aluminum-induced crystallization process forming a large-grained polycrystalline silicon layer on glass or metal substrates. In a second step this layer is used as a template for epitaxial growth of the absorber layer (2–3 μm thick) at T<600 °C using ion-assisted deposition techniques. The third step consists of the formation of an a-Si:H/c-Si heterojunction by depositing an a-Si:H emitter from the gas phase. It will be shown that each of these steps has been successfully developed and can now be implemented in a solar cell process.     

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.     

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%.     

Preparation of microcrystalline single junction and amorphous–microcrystalline tandem silicon solar cells entirely by hot-wire CVD

The hot-wire chemical vapour deposition (HWCVD) has been used to prepare highly conducting p- and n-doped microcrystalline silicon thin layers as well as highly photoconducting, low defect density intrinsic microcrystalline silicon films. These films were incorporated in all-HWCVD, all-microcrystalline nip and pin solar cells, achieving conversion efficiencies of η=5.4% and 4.5%, respectively. At present, only the nip-structures are found to be stable against light-induced degradation. Furthermore, microcrystalline nip and pin structures have been successfully incorporated as bottom cells in all-hot-wire amorphous–microcrystalline nipnip- and pinpin-tandem solar cells for the first time. So far, the highest conversion efficiencies of the “micromorph” tandem structures are η=5.7% for pinpin-solar cells and 7.0% for nipnip solar cells.     

High-Ts amorphous top cells for increased top cell currents in micromorph tandem cells

In the present paper, the authors discuss the application of amorphous p–i–n solar cells containing i-layers which are deposited at high substrate temperatures as top cells in amorphous silicon/microcrystalline silicon tandem (“micromorph”) solar cells. Increasing the substrate temperature for the deposition of intrinsic a-Si : H results in a reduced optical gap. The optical absorption is enhanced and thereby the current generation. A high-current generation within a relatively thin amorphous top cell is very interesting in the context of micromorph tandem cells, where the amorphous top cell should contribute a current of at least 13 mA/cm² for a total cell current density of 26 mA/cm². A detailed study of the intrinsic material deposited by VHF-GD at 70 MHz at substrate temperatures between 220°C and 360°C is presented, including samples deposited from hydrogen-diluted silane plasmas. The stability of the films against light soaking is investigated employing the μ₀τ₀ parameter, which has been shown to be directly correlated to the cell performance. The paper discusses in detail the technological problems arising from the insertion of i-layers deposited at high substrate temperatures into solar cells. These problems are specially pronounced in the case of cells in the p–i–n (superstrate) structure. The authors demonstrate that an appropriate interface layer at the p/i-interface can largely reduce the detrimental effects of i-layer deposition at high temperatures. Finally, the application of such optimized high-temperature amorphous cells as top cells in micromorph tandem cells is discussed. Current densities of 13 mA/cm² in the top cell are available with a top cell i-layer thickness of only 250 nm.     

TCO and light trapping in silicon thin film solar cells

For thin film silicon solar cells and modules incorporating amorphous (a-Si:H) or microcrystalline (μc-Si:H) silicon as absorber materials, light trapping, i.e. increasing the path length of incoming light, plays a decisive role for device performance. This paper discusses ways to realize efficient light trapping schemes by using textured transparent conductive oxides (TCOs) as light scattering, highly conductive and transparent front contact in silicon p–i–n (superstrate) solar cells. Focus is on the concept of applying aluminum-doped zinc oxide (ZnO:Al) films, which are prepared by magnetron sputtering and subsequently textured by a wet-chemical etching step. The influence of electrical, optical and light scattering properties of the ZnO:Al front contact and the role of the back reflector are studied in experimentally prepared a-Si:H and μc-Si:H solar cells. Furthermore, a model is presented which allows to analyze optical losses in the individual layers of a solar cell structure. The model is applied to develop a roadmap for achieving a stable cell efficiency up to 15% in an amorphous/microcrystalline tandem cell. To realize this, necessary prerequisites are the incorporation of an efficient intermediate reflector between a-Si:H top and μc-Si:H bottom cell, the use of a front TCO with very low absorbance and ideal light scattering properties and a low-loss highly reflective back contact. Finally, the mid-frequency reactive sputtering technique is presented as a promising and potentially cost-effective way to up-scale the ZnO front contact preparation to industrial size substrate areas.     

In-situ transmission measurements as process control for thin-film silicon solar cells

In this work, in-situ transmission measurements using plasma as light source are presented for the determination of growth rate and crystallinity during silicon thin-film growth. The intensity of distinct plasma emission lines was measured at the backside of the transparent substrates on which silicon films, ranging from amorphous to microcrystalline, were deposited. Using this configuration, the growth rate of thin-films was determined with high accuracy. In addition, we show that the crystallinity of the films can be monitored in the most critical range (between 40% and 80%) for microcrystalline silicon solar cells by evaluating the intensity ratio of two transmitted wavelengths in-situ. The gradual change in the absorption behaviour of the films during the phase transition is reflected by this ratio of two wavelengths as demonstrated by the good correlation with the crystallinity fraction determined by ex-situ Raman spectroscopy. This approach of in-situ transmission spectroscopy provides an easy-to-implement monitoring and control system for the industrial deposition of thin-film silicon solar cells, as critical material properties can be determined real-time during the deposition process even on rough substrates that are optimized for light trapping in solar 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.     

Deposition of thin film silicon using the pulsed PECVD and HWCVD techniques

We report on the use of pulsed plasma-enhanced chemical vapor deposition (P-PECVD) technique and show that “state-of-the-art” amorphous silicon (a-Si:H) materials and solar cells can be produced at a deposition rate of up to 15 Å/s using a modulation frequency in the range 1–100 kHz. The approach has also been developed to deposit materials and devices onto large area, 30 cm×40 cm, substrates with thickness uniformity (<5%), and gas utilization rate (>25%). We have developed a new “hot wire” chemical vapor deposition (HWCVD) method and report that our new filament material, graphite, has so far shown no appreciable degradation even after deposition of 500 μm of amorphous silicon. We report that this technique can produce “state-of-the-art” a-Si:H and that a solar cell of p/i/n configuration exhibited an initial efficiency approaching 9%. The use of microcrystalline silicon (μc-Si) materials to produce low-cost stable solar cells is gaining considerable attention. We show that both of these techniques can produce thin film μc-Si, dependent on process conditions, with 1 1 1 and/or 2 2 0 orientations and with a grain size of approx. 500 A. Inclusion of these types of materials into a solar cell configuration will be discussed.     

Multicrystalline silicon solar cells with porous silicon emitter

A review of the application of porous silicon (PS) in multicrystalline silicon solar cell processes is given. The different PS formation processes, structural and optical properties of PS are discussed from the viewpoint of photovoltaics. Special attention is given to the use of PS as an antireflection coating in simplified processing schemes and for simple selective emitter processes as well as to its light trapping and surface passivating capabilities. The optimization of a PS selective emitter formation results in a 14.1% efficiency mc-Si cell processed without texturization, surface passivation or additional ARC deposition. The implementation of a PS selective emitter into an industrially compatible screenprinted solar cell process is made by both the chemical and electrochemical method of PS formation. Different kinds of multicrystalline silicon materials and solar cell processes are used. An efficiency of 13.2% is achieved on a 25 cm² mc-Si solar cell using the electrochemical technique while the efficiencies in between 12% and 13% are reached for very large (100–164 cm²) commercial mc-Si cells with a PS emitter formed by chemical method.     

Silicon-based thin-film solar cells fabricated near the phase boundary by VHF PECVD technique

The light-soaked and annealing behaviors for silicon (Si)-based thin-film single-junction solar cells fabricated near the phase boundary using a very-high-frequency plasma-enhanced chemical vapor deposition (VHF PECVD) technique are investigated. The hydrogen dilution ratio is changed in order to achieve wide band gap hydrogenated amorphous Si (a-Si:H) and narrow band gap hydrogenated microcrystalline Si (μc-Si:H) absorbers. Just below the a-Si:H-to-μc-Si:H transition, highly hydrogen-diluted a-Si:H solar cells with a good stability against light-soaking and fast annealing behavior are obtained. In contrast, the solar cell fabricated at the onset of the μc-Si:H growth is very unstable and its annealing behavior is slow. In the case of μc-Si:H solar cells with the crystal volume fraction of 43–53%, they show the lowest light-induced degradation among the fabricated solar cells. However, it is very difficult to recover the degraded μc-Si:H solar cells via thermal annealing.     

Microcrystalline silicon solar cells fabricated by VHF plasma CVD method

A series of systematic investigations on microcrystalline silicon (μc-Si:H) solar cells at high deposition rates has been studied. The effect of high deposition pressure and narrow cathode-substrate (CS) distance on the deposition rate and quality of microcrystalline silicon is discussed. The microcrystalline silicon solar cell is adopted as middle cell and bottom cell in a three-stacked junction solar cell. The characteristics of large area three-stacked junction solar cells, whose area is 801.6 cm² including grid electrode areas, are studied in various deposition rates from 1 to 3 nm/s of microcrystalline silicon. An initial efficiency of 13.1% is demonstrated in the three-stacked junction solar cell with microcrystalline silicon deposited at 3 nm/s.