A review is given on the diffusion, solubility and electrical activity of 3d transition metals in silicon. Transition elements (especially, Cr, Mn, Fe, Co, Ni, and Cu) diffuse interstitially and stay in the interstitial site in thermal equilibrium at the diffusion temperature. The parameters of the liquidus curves are identical for the Si:Ti — Si:Ni melts, indicating comparable silicon-metal interaction for all these elements. Only Cr, Mn, and Fe could be identified in undisturbed interstitial sites after quenching, the others precipitated or formed complexes. The 3d elements can be divided into two groups according to the respective enthalpy of formation of the solid solution. The distinction can arise from different charge states of these impurities at the diffusion temperature. For the interstitial 3d atoms remaining after quenching, reliable energy levels are established from the literature and compared with recent calculations.

Transition metals in silicon

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 CuInSe 2 , to CuGaSe 2 , CuInS 2 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.

Photovoltaic materials, history, status and outlook

With a global market share of about 90%, crystalline silicon is by far the most important photovoltaic technology today. This article reviews the dynamic field of crystalline silicon photovoltaics from a device-engineering perspective. First, it discusses key factors responsible for the success of the classic dopant-diffused silicon homojunction solar cell. Next it analyzes two archetypal high-efficiency device architectures – the interdigitated back-contact silicon cell and the silicon heterojunction cell – both of which have demonstrated power conversion efficiencies greater than 25%. Last, it gives an up-to-date summary of promising recent pathways for further efficiency improvements and cost reduction employing novel carrier-selective passivating contact schemes, as well as tandem multi-junction architectures, in particular those that combine silicon absorbers with organic–inorganic perovskite materials.

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High-efficiency crystalline silicon solar cells: status and perspectives

The emergence of methyl-ammonium lead halide (MAPbX3) perovskites motivates the identification of unique properties giving rise to exceptional bulk transport properties, and identifying future materials with similar properties. Here, we propose that this “defect tolerance” emerges from fundamental electronic-structure properties, including the orbital character of the conduction and valence band extrema, the chargecarrier effective masses, and the static dielectric constant. We use MaterialsProject.org searches and detailed electronic-structure calculations to demonstrate these properties in other materials than MAPbX3. This framework of materials discovery may be applied more broadly, to accelerate discovery of new semiconductors based on emerging understanding of recent successes.

Identifying defect-tolerant semiconductors with high minority-carrier lifetimes: beyond hybrid lead halide perovskites

A review of the properties of hydrogen in crystalline semiconductors is presented. The equilibrium lattice positions of the various states of hydrogen are detailed, together with the reactions of atomic hydrogen with shallow and deep level impurities that passivate their electrical activity. Evidence for several charge states of mobile hydrogen provides a consistent picture for both the temperature dependence of its diffusivity and the chemical reactions with shallow level dopants. The electrical and optical characteristics of hydrogen-related defects in both elemental and compound semiconductors are discussed, along with the surface damage caused by hydrogen bombardment. The bonding configurations of hydrogen on semiconductor surfaces and the prevalence of its incorporation during many benign processing steps are reviewed. We conclude by identifying the most important areas for future effort.

Hydrogen in crystalline semiconductors

The effects of various metallic impurities, both singly and in combinations, on the performance of silicon solar cells have been studied. Czochralski crystals were grown with controlled additions of secondary impurities. The primary dopants were boron and phosphorus while the secondaires were: A1, B, C, Ca, Co, Cr, Cu, Fe, Mg, Mn, Mo, Nb, P, Pd, Ta, Ti, V, W, Zn, and Zr. Impurity concentrations ranged from 1010to 1017/cm3. Solar cells were made using a conventional diffusion process and were characterized by computer reduction of I-V data. The collected data indicated that impurity-induced performance loss was primarily due to reduction of the base diffusion length. Based on this observation, an analytic model was developed which predicts cell performance as a function of the secondary impurity concentrations. The calculated performance parameters are in good agreement with measured values except for Cu, Ni, and Fe, which at higher concentrations, degrade the cell substantially by means of junction mechanisms. This behavior can be distinguished from base diffusion length effects by careful analysis of the I-V data. The effects of impurities in n-base and p-base devices differ in degree but submit to the same modeling analysis. A comparison of calculated and measured performance for multiple impurities indicates a limited interaction between impurities, e.g., copper appears to improve titanium-doped cells.

Impurities in silicon solar cells

Deep level transient spectroscopy coupled with dark and lighted I–V measurements were used to study the electrical properties of silicon crystals and solar cells purposely contaminated with controlled amounts of molybdenum. Mo severely degrades minority carrier lifetime, and hence solar cell performance, by inducing a recombination center at EV + 0.30 eV. Neither HCl nor POCl3 gettering at temperatures as high as 1100°C and times up to five hours mitigate the effects of Mo. Because the Mo segregation coefficient is small, 4.5 × 10−8, impurity contamination of silicon during crystal growth can be kept below the levels for which electrical properties are affected.

The impact of molybdenum on silicon and silicon solar cell performance

The object of the program has been to investigate the effects of various processes, metal contaminants, and contaminant-process interactions on the properties of silicon and on the performance of terrestrial silicon solar cells. The study has encompassed topics such as thermochemical (gettering) treatments, base-doping concentration, base-doping type (n vs. p), grain boundary-impurity interaction in polycrystalline devices, and long-term effects of impurities and impurity impacts on high-efficiency cells, as well as a preliminary evaluation of some potential low-cost silicon materials. The effects have been studied of various metallic impurities, introduced singly or in combination into Czochralski, float zone, and polycrystalline silicon ingots and into silicon ribbons grown by the dendritic web process. The solar cell data indicate that impurity-induced performance loss is caused primarily by a reduction in base diffusion length. An analytical model based on this observation has been developed and verified experimentally for both n- and p-base material. Studies of polycrystalline ingots containing impurities indicate that solar cell behavior is species sensitive and that a fraction of the impurities are segregated to the grain boundaries. HCl and POCl gettering improve the performance of single-crystal solar cells containing Fe, Cr, and Ti. In contrast Mo-doped material is barely affected. Themore » efficiencies of solar cells fabricated on impurity-doped wafers is lower when the front junction is formed by ion implantation than when conventional diffusion techniques are used. For most impurity-doped solar cells stability is expected for projected times beyond 20 years. Feedstock impurity concentrations below one part per million for elements like V, or 100 parts per million for more benign impurities like Cu or Ni, will be required.« less

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Silicon materials task of the low-cost solar-array project. Effect of impurities and processing on silicon solar cells. Final report

The effects of impurities, various thermochemical processes, and any impurity-process interactions upon the performance of terrestrial solar cells are defined. The results form a basis for silicon producers, wafer manufacturers, and cell fabricators to develop appropriate cost benefit relationships for the use of less pure, less costly solar grade silicon.

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Silicon materials task of the Low Cost Solar Array Project: Effect of impurities and processing on silicon solar cells

Results of the 14th quarterly report are presented for a program designed to assess the effects of impurities, thermochemical processes and any impurity process interactions on the performance of terrestrial silicon solar cells The Phase 3 effort encompasses: (1) potential interactions between impurities and thermochemical processing of silicon; (2) impurity-cell performance relationships in n-base silicon; (3) effect of contaminants introduced during silicon production, refining or crystal growth on cell performance; (4) effects of nonuniform impurity distributions in large area silicon wafers; and (5) a preliminary study of the permanence of impurity effects in silicon solar cells

H.C. Mollenkopf

Papers

Impurities in silicon solar cells

The impact of molybdenum on silicon and silicon solar cell performance

Silicon materials task of the low-cost solar-array project. Effect of impurities and processing on silicon solar cells. Final report

Silicon materials task of the Low Cost Solar Array Project: Effect of impurities and processing on silicon solar cells

Effects of Impurities and Processing on Silicon Solar Cells, Phase 3