Photovoltaic materials,history, status and outlook

This paper reviews the history, the present status and possible future developments of photovoltaic (PV) materials for terrestrial applications. After a brief history and introduction of the photovoltaic effect theoretical requirements for the optimal performance of materials for pn-junction solar cells are discussed. Most important are efficiency, long-term stability and, not to be neglected, lowest possible cost. Today the market is dominated by crystalline silicon in its multicrystalline and monocrystalline form. The physical and technical limitations of this material are discussed. Although crystalline silicon is not the optimal material from a solid state physics point of view it dominates the market and will continue to do this for the next 5–10 years. Because of its importance a considerable part of this review deals with materials aspects of crystalline silicon. For reasons of cost only multicrystalline silicon and monocrystalline Czochralski (Cz) crystals are used in practical cells. Light induced instability in this Cz-material has recently been investigated and ways to eliminate this effect have been devised. For future large scale production of crystalline silicon solar cells development of a special solar grade silicon appears necessary. Ribbon growth is a possibility to avoid the costly sawing process. A very vivid R&D area is thin-film crystalline silicon (about 5–30 μm active layer thickness) which would avoid the crystal growing and sawing processes. The problems arising for this material are: assuring adequate light absorption, assuring good crystal quality and purity of the films, and finding a substrate that fulfills all requirements. Three approaches have emerged: high-temperature, low-temperature and transfer technique. Genuine thin-film materials are characterized by a direct band structure which gives them very high light absorption. Therefore, these materials have a thickness of only one micron or less. The oldest such material is amorphous silicon which is the second most important material today. It is mainly used in consumer products but is on the verge to also penetrate the power market. Other strong contenders are chalcogenides like copper indium diselenide (CIS) and cadmium telluride. The interest has expanded from CuInSe₂, to CuGaSe₂, CuInS₂ and their multinary alloys Cu(In,Ga)(S,Se)₂. The two deposition techniques are either separate deposition of the components followed by annealing on one hand or coevaporation. Laboratory efficiencies for small area devices are approaching 19% and large area modules have reached 12%. Pilot production of CIS-modules has started in the US and Germany. Cadmium telluride solar cells also offer great promise. They have only slightly lower efficiency and are also at the start of production. In the future other materials and concepts can be expected to come into play. Some of these are: dye sensitized cells, organic solar cells and various concentrating systems including III/V-tandem cells. Theoretical materials that have not yet been realized are Auger generation material and intermediate metallic band material.     

A Grain Orientation-Independent Single-Step Saw Damage Gettering/Wet texturing Process for Efficient Silicon Solar Cells

Improving electrical and optical properties is important in manufacturing high-efficiency solar cells. Previous studies focused on individual gettering and texturing methods to improve solar cell material quality and reduce reflection loss, respectively. This study presents a novel method called saw damage gettering with texturing that effectively combines both methods for multicrystalline silicon (mc-Si) wafers manufactured using the diamond wire sawing (DWS) method. Although mc-Si is not the Si material currently used in photovoltaic products, the applicability of this method using the mc-Si wafers as it contains all grain orientations is demonstrated. It utilizes saw damage sites on the wafer surfaces for gettering metal impurities during annealing. Additionally, it can crystallize amorphous silicon on wafer surfaces generated during the sawing process to allow conventional acid-based wet texturing. This texturing method and annealing for 10 min allow for the removal of metal impurities and effectively forms a textured DWS Si wafer. The results show that the open-circuit voltage (ΔV_oc = +29 mV), short-circuit current density (ΔJ_sc = +2.5 mA cm⁻²), and efficiency (Δη = +2.1%) improved in the p-type passivated emitter and rear cells (p-PERC) manufactured using this novel method, as compared to those in the reference solar cells.     

Anlagen für die Solarzellen‐Schichterzeugung benötigen hervorragend ausgelegte Vakuumsysteme

Vacuum pumps are an enabling technology for solar power because all modules require vacuum processing at various stages of production. Specially engineered products that are helping to make solar modules more affordable by reducing equipment downtime and improving process performance are essential to become a successful partner for the solar industry. The processes used for thin film technology are extremely demanding. Pump performance for high flows of light gases must be achieved and in parallel safety aspects must be considered carefully. The pump solutions must be extreme reliable in order to guarantee maximum tool up‐time which is mandatory for a production line in order to be cost competitive. Design and performance of such solutions must be qualified in close collaboration between pump supplier and the equipment producer together wi^th the user of the equipment. Experience and know how from industries using similar processes like semiconductor, large area coating or FPD production can be applied for solar production lines which can help to reduce time to market. The article will outline the specific needs for thin film solar cells based on amorphous silicon and CdTe.     

High voltage Cu(In,Ga)S2 solar modules

Sulfurcell (SC) has been running a pilot production for thin-film solar modules using CuInS₂-chalcopyrite (CIS) as absorber material since 2004. Since then production technology has been constantly improved with module power values exceeding 64 W, corresponding to an aperture area efficiency level of about 9%. Small area (0.5 cm2) cells cut out of such CIS modules reach maximum efficiencies close to 11%. Strong efforts have been made to develop a new sequential Cu(In,Ga)S₂ (CIGS) process suitable for production of large-scale CIGS solar modules thereby enabling module efficiencies above 10%. CIGS-based solar cells are—quite similar to CIS-based modules—prepared from sputtered metals subsequently sulfurized using rapid thermal processing in sulfur vapor. Such Cu(In,Ga)S₂ solar cells reach material record efficiencies about 13%. The cells are characterized by high open-circuit voltages up to 890 mV. Based on the results of the “Helmholtz Zentrum Berlin” (HZB), Sulfurcell has successfully scaled this process to our typical module size of 125 cm × 65 cm and is currently piloting the process for mass production. This paper will give an overview of electrical and structural parameters of world's first large-scale CIGS modules. CIGS module and cell parameters will be compared with standard CIS module and cell parameters and measured CIGS efficiency temperature coefficients will be compared with typical temperature coefficients of modules based on established PV technologies.     

Crystalline Silicon Thin‐Film Solar Cells on Silicon Nitride Ceramic Substrates

Photovoltaics—the generation of electricity from sunlight—is a technically challenging but environmentally benign technology to generate electricity with a large economical potential. However, the major hurdle for its widespread usage is its present high cost. Various thin‐film solar cell technologies are investigated to bring down the total cost to an economic value. One of them, the crystalline silicon thin‐film (CSiTF) solar cell combines the advantages of conventional wafer‐based silicon solar cells such as high efficiency and non‐toxicity with the benefits of thin‐film technologies such as serial interconnection and large area deposition. This paper reports for the first time the preparation of CSiTF solar cells on specially developed Si₃N₄ ceramic substrates. Three different types of Si₃N₄ ceramic wafers were single‐sided coated with 10μm of microcrystalline silicon, which was recrystallized by a zone melting step and subsequently thickened to approx. 30 μm. Optical analysis of the layer surface and cross sections was done to determine the crystallographic properties of the silicon layers, as well as mass spectroscopy to measure the concentration of transition metal impurities. A one‐side contacted solar cell process was applied on non‐conducting Si₃N₄ substrates. The best 1 cm² cells achieved an efficiency of 8.0 % with an excellent fill factor of 74 % and an open circuit voltage of 554 mV. The solar cell characterization was complemented by measurements of dark current–voltage characteristics, spectrally resolved light beam induced current mapping, and external quantum efficiency.     

Low‐Temperature Soft‐Cover Deposition of Uniform Large‐Scale Perovskite Films for High‐Performance Solar Cells

Large‐scale high‐quality perovskite thin films are crucial to produce high‐performance perovskite solar cells. However, for perovskite films fabricated by solvent‐rich processes, film uniformity can be prevented by convection during thermal evaporation of the solvent. Here, a scalable low‐temperature soft‐cover deposition (LT‐SCD) method is presented, where the thermal convection‐induced defects in perovskite films are eliminated through a strategy of surface tension relaxation. Compact, homogeneous, and convection‐induced‐defects‐free perovskite films are obtained on an area of 12 cm², which enables a power conversion efficiency (PCE) of 15.5% on a solar cell with an area of 5 cm². This is the highest efficiency at this large cell area. A PCE of 15.3% is also obtained on a flexible perovskite solar cell deposited on the polyethylene terephthalate substrate owing to the advantage of presented low‐temperature processing. Hence, the present LT‐SCD technology provides a new non‐spin‐coating route to the deposition of large‐area uniform perovskite films for both rigid and flexible perovskite devices.     

Low‐Temperature and Rapid Growth of Large Single‐Crystalline Graphene with Ethane

Future applications of graphene rely highly on the production of large‐area high‐quality graphene, especially large single‐crystalline graphene, due to the reduction of defects caused by grain boundaries. However, current large single‐crystalline graphene growing methodologies are suffering from low growth rate and as a result, industrial graphene production is always confronted by high energy consumption, which is primarily caused by high growth temperature and long growth time. Herein, a new growth condition achieved via ethane being the carbon feedstock to achieve low‐temperature yet rapid growth of large single‐crystalline graphene is reported. Ethane condition gives a growth rate about four times faster than methane, achieving about 420 µm min^?1 for the growth of sub‐centimeter graphene single crystals at temperature about 1000 °C. In addition, the temperature threshold to obtain graphene using ethane can be reduced to 750 °C, lower than the general growth temperature threshold (about 1000 °C) with methane on copper foil. Meanwhile ethane always keeps higher graphene growth rate than methane under the same growth temperature. This study demonstrates that ethane is indeed a potential carbon source for efficient growth of large single‐crystalline graphene, thus paves the way for graphene in high‐end electronical and optoelectronical applications.     

溶液法CH3NH3PbCl3单晶的生长与性能研究

分别采用蒸发结晶法和逆温结晶法生长尺寸约为4 mm×3 mm×3 mm的CH₃NH₃PbCl₃单晶。对两种方法生长的单晶粉体的XRD分析结果显示, 单晶具有立方晶系结构, 其晶格常数分别为0.56833、0.56891 nm。实验测量了CH₃NH₃PbCl₃单晶的红外光谱(FT-IR)和拉曼光谱, 并对谱峰进行了指认; 使用UV-VIS-NIR分光光度计、荧光光度计对CH₃NH₃PbCl₃单晶的光学性能进行了测试。结果表明: CH₃NH₃PbCl₃晶体的吸收边约为423 nm, 光致发光峰为433 nm, 带隙值为2.97 eV, 与CH₃NH₃PbCl₃薄膜的光学特性相比, CH₃NH₃PbCl₃单晶更具潜在的应用前景。最后, 结合第一性原理研究了CH₃NH₃PbCl₃晶体的能带结构, 计算得出带隙值2.428 eV, 与实验值吻合较好。     

Fracture Strength of Photovoltaic Silicon Wafers Evaluated Using a Controlled Flaw Method

Propagation of pre‐existing micro cracks and their associated residual contact stresses, generated from the wafer sawing process, is the leading cause for photovoltaic (PV) silicon wafer/cell breakage during handling and processing. In the current work, the impact of a single micro crack on the fracture strength of PV silicon wafer is investigated based on a controlled flaw method. Radial/median cracks with controllable scales are introduced through microindentation at the center of a PV silicon sample to simulate micro cracks resulting from wafer sawing, handling, or thermal processing. Results indicate that the fracture strength of PV silicon wafer decreases linearly with the increasing of the microindentation load (radial crack scale). In addition, it is found that the impurity carbon plays an important role in the contact cracking‐fracture process. The fracture strength increased ≈21% when the substitutional carbon concentration is increased from 1.2 × 10¹⁸ to 6.4 × 10¹⁸ cm^?3.     

Epitaxially grown crystalline silicon thin-film solar cells reaching 16.5% efficiency with basic cell process

We report about the current performance of crystalline silicon thin-film (cSiTF) solar cells that are a very attractive alternative to conventional wafer-based silicon solar cells if sufficiently high cell efficiencies are achieved at acceptable cost of production. Applying a standard cell process (diffused POCl₃ emitter, front contacts by photolithography, no surface texture) to thin-films deposited with a lab-type reactor, specifically designed for high-throughput photovoltaic applications, on highly-doped Cz substrates we routinely obtain efficiencies above 16%. On 1 Ω cm FZ material substrates we reach efficiencies up to 18.0%, which is among the highest thin-film efficiencies ever reported. Additionally, a comparison to microelectronic-grade epitaxially grown cSiTF material underlines the excellent electrical quality of the epitaxial layers deposited.     

Improvement of a-Si:H solar cell performance by SiH4 purging treatment

Amorphous silicon (a-Si:H) thin film solar cells were prepared in a single chamber large area plasma enhanced chemical vapor deposition (PECVD) system. A purging process using silane (SiH₄) gas was developed to remove the residual contaminations in the reactor after a nitrogen trifluoride (NF₃) plasma dry cleaning process. Such a purging treatment leads to a clear improvement in initial fill factor (FF) and in efficiency of as-prepared a-Si:H solar cells. Secondary ion mass spectroscopy (SIMS) results demonstrate that fluorine impurity concentration [F] at the p-layer as well as p/i interface of solar cells reduces by more than one order of magnitude after this purging process. Additionally, high [F] is accompanied with high oxygen impurity concentration [O] which plays a great role in the solar cell performance. Low degradation rate of open circuit voltage (V_oc) and fill factor (FF) of solar cells after a purging process after a 1000 h light soaking further illustrates an improvement in the material properties. Implanting such a purging process in the practical production line, about 2 W in power for a-Si:H solar modules (1.1 m × 1.3 m) are gained and meanwhile the champion solar module (1.1 m × 1.3 m) of stabilized power of 113 W with 160 nm thick intrinsic layer has been achieved.     

制备硅薄膜太阳能电池的先进技术与实验研究

介绍了Si薄膜太阳能电池的材料与结构,重点介绍了几种叠层薄膜太阳能电池,详细阐述了近年发展的用于制备低成本、高效率Si薄膜太阳能电池的技术与最新的实验研究成果,其中高温沉积法、低温沉积法、层转移法尤为重要,展望了Si薄膜太阳能电池未来的技术发展和科研方向.三叠层薄膜太阳能电池是有发展前景的产品之一,更多叠层的薄膜太阳能电池与量子点叠层薄膜太阳能电池将长期作为实验研究的热门课题.     

Non-aqueous preparation of anatase TiO2 hollow microspheres for efficient dye-sensitized solar cells

TiO₂ hollow spheres are fabricated by a facile and template-free approach, which is efficient, cost-saving and favorable for large scale production. The as-prepared TiO₂ hollow spheres with diameters ranging from 1 to 1.5 μm and a shell thickness of 150 nm are formed by the self-assembly of nanoparticles with a size of about 12 nm. The mesoporous TiO₂ hollow spheres possess a high specific surface area up to 166.2 m² g⁻¹. TiO₂ hollow spheres show superior light trapping characteristics and significantly improve the light scattering ability. The formation of hollow structure is interpreted by the Ostwald ripening mechanism. By employing a double-layered photoanode made of the as-prepared TiO₂ hollow spheres as the overlayer and P25 as the bottom layer, the dye-sensitized solar cell achieved a power conversion efficiency of 7.90%, which is ascribed to the enhanced dye loading and light scattering ability of TiO₂ hollow spheres.     

Large area dye-sensitized solar cells with titanium based counter electrode

Construction of dye-sensitized solar cell of large area using platinum sputtered titanium metal counter electrode is demonstrated. An impressive increase in the fill factor and consequently the efficiency compared to the conventional platinized conducting glass based counter electrodes result from very low sheet resistance of the titanium plate and a cell of active area 151 cm² with parallel silver collecting grids delivered an efficiency of 7.4%. The possibility of using this technique for commercial production of dye-sensitized solar cells was discussed giving details of fabrication procedure.     

Improvement of magnetic induction-wire sawing process using a magnetic system

Magnetic induction-free abrasive wire sawing is a hybrid process that applies a homogeneous magnetic field to transport more abrasives into the sawing channel. This causes the performance of wire sawing significantly improved. Magnetic field strength is a key factor in determining the magnetic force acting on the magnetic abrasives, then affecting the quantity of abrasives adsorbed on the saw wire surface. However, the background magnetic induction strength produced by two permanent magnets is limited in this process. To further investigate the influence of magnetic field strength on the wire sawing performance, a magnetic system, which is based on the magnetic circuit design principle and the structure of single-wire sawing machine, is designed and fabricated. The magnetic field characteristics of the designed magnetic system are investigated both by numerical simulations and experiments. An experimental setup that installs the fabricated magnetic system on the single-wire sawing machine is built to conduct the magnetic induction-wire sawing experiments. The results show that the optimal magnetic induction strength is about B₀?=?135?mT. In this case, the kerf loss is decreased by 10% compared to the free abrasive wire sawing technology without a magnetic field.     

Manufacturing of CdTe thin film photovoltaic modules

The technology to fabricate CdTe/CdS thin film solar cells can be considered mature for a large-scale production of CdTe-based modules. Several reasons contribute to demonstrate this assertion: a stable efficiency of 16.5% has been demonstrated for 1 cm² laboratory cell and it is expected that an efficiency of 12% can be obtained for 0.6 × 1.2 m² modules; low cost soda lime float glass can be used as a substrate; the amount of source material is at least 100 times less than that used for single crystal modules and is a negligible part of the overall cost. The fabrication process can be completely automated and a production yield of one module every 2 min can be obtained, which implies a production cost substantially less than 1€/W_P. A further cost reduction will render this kind of energy production competitive with the energy obtained from fossil fuels by approaching the so-called grid-parity. Some new companies have recently announced the start of production or plan to do so in the near future. Many of these plants are located in Germany, some in the USA. In Italy, a new company has been constituted in 2008, with the aim of building a factory with a capacity of 18 MW/year. In this article, we will describe and compare the basic principles of CdTe solar cells and modules. We will include an overview of the potentials of these technologies and of the R&D issues under investigation. This paper describes how the large-area mass production of CdTe solar modules is realized in the Italian factory and presents a worldwide overview of the current production activities.     

An Interfacial Solar‐Driven Atmospheric Water Generator Based on a Liquid Sorbent with Simultaneous Adsorption–Desorption

Water scarcity is one of the greatest challenges facing human society. Because of the abundant amount of water present in the atmosphere, there are significant efforts to harvest water from air. Particularly, solar‐driven atmospheric water generators based on sequential adsorption–desorption processes are attracting much attention. However, incomplete daytime desorption is the limiting factor for final water production, as the rate of water desorption typically decreases very quickly with decreased water content in the sorbents. Hereby combining tailored interfacial solar absorbers with an ionic‐liquid‐based sorbent, an atmospheric water generator with a simultaneous adsorption–desorption process is generated. With enhanced desorption capability and stabilized water content in the sorbent, this interfacial solar‐driven atmospheric water generator enables a high rate of water production (≈0.5 L m^?2 h^?1) and 2.8 L m^?2 d^?1 for the outdoor environment. It is expected that this interfacial solar‐driven atmospheric water generator, based on the liquid sorbent with a simultaneous adsorption–desorption process opens up a promising pathway to effectively harvest water from air.     

2D Porous TiO2 Single‐Crystalline Nanostructure Demonstrating High Photo‐Electrochemical Water Splitting Performance

Porous single crystals are promising candidates for solar fuel production owing to their long range charge diffusion length, structural coherence, and sufficient reactive sites. Here, a simple template‐free method of growing a selectively branched, 2D anatase TiO₂ porous single crystalline nanostructure (PSN) on fluorine‐doped tin oxide substrate is demonstrated. An innovative ion exchange–induced pore‐forming process is designed to successfully create high porosity in the single‐crystalline nanostructure with retention of excellent charge mobility and no detriment to crystal structure. PSN TiO₂ film delivers a photocurrent of 1.02 mA cm^?2 at a very low potential of 0.4 V versus reversible hydrogen electrode (RHE) for photo‐electrochemical water splitting, closing to the theoretical value of TiO₂ (1.12 mA cm^?2). Moreover, the current–potential curve featuring a small potential window from 0.1 to 0.4 V versus RHE under one‐sun illumination has a near‐ideal shape predicted by the Gartner Model, revealing that the charge separation and surface reaction on the PSN TiO₂ photoanode are very efficient. The photo‐electrochemical water splitting performance of the films indicates that the ion exchange–assisted synthesis strategy is effective in creating large surface area and single‐crystalline porous photoelectrodes for efficient solar energy conversion.     

Enhancing Performance of Large‐Area Organic Solar Cells with Thick Film via Ternary Strategy

Large‐scale fabrication of organic solar cells requires an active layer with high thickness tolerability and the use of environment‐friendly solvents. Thick films with high‐performance can be achieved via a ternary strategy studied herein. The ternary system consists of one polymer donor, one small molecule donor, and one fullerene acceptor. The small molecule enhances the crystallinity and face‐on orientation of the active layer, leading to improved thickness tolerability compared with that of a polymer‐fullerene binary system. An active layer with 270 nm thickness exhibits an average power conversion efficiency (PCE) of 10.78%, while the PCE is less than 8% with such thick film for binary system. Furthermore, large‐area devices are successfully fabricated using polyethylene terephthalate (PET)/Silver gride or indium tin oxide (ITO)‐based transparent flexible substrates. The product shows a high PCE of 8.28% with an area of 1.25 cm² for a single cell and 5.18% for a 20 cm² module. This study demonstrates that ternary organic solar cells exhibit great potential for large‐scale fabrication and future applications.     

Silicon sawing waste treatment by electrophoresis and gravitational settling

In silicon wafer manufacturing for solar cells, a great amount of hazardous sawing waste with tiny Si particles is produced, resulting in serious environmental problems. Recycling Si and abrasives from the waste is regarded as an effective solution. Based on the view of recycling, Al(2)O(3) might be good abrasives for cutting Si ingot due to its larger density and higher isoelectric point than SiC. This study reports the separation of Si/SiC and Si/Al(2)O(3) mixtures by electrophoresis and gravitational settling. At pH 9, nearly uncharged Al(2)O(3) settled quickly and the negatively charged Si moved toward the anode, leading to an obvious Si distribution on the cell bottom. The experimental results show the separation performance of Si and Al(2)O(3) at pH 9 was better than at pH 2.5, and the performance was higher than that between Si and SiC. The minimum and maximum Al(2)O(3) contents remaining in Si/Al(2)O(3) mixture were 9 wt% and 90 wt% after applying 1 V/cm for 24h at pH 9. The recovered material with high Si content can be considered as a new Si source for solar cell, and the abrasives can be reused in the sawing process.