Organometal trihalide perovskite based solar cells have exhibited the highest efficiencies to-date when incorporated into mesostructured composites. However, thin solid films of a perovskite absorber should be capable of operating at the highest efficiency in a simple planar heterojunction configuration. Here, it is shown that film morphology is a critical issue in planar heterojunction CH3NH3PbI3-xCl x solar cells. The morphology is carefully controlled by varying processing conditions, and it is demonstrated that the highest photocurrents are attainable only with the highest perovskite surface coverages. With optimized solution based film formation, power conversion efficiencies of up to 11.4% are achieved, the first report of efficiencies above 10% in fully thin-film solution processed perovskite solar cells with no mesoporous layer. © 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim.

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Morphological control for high performance, solution-processed planar heterojunction perovskite solar cells

Organic-inorganic metal halide perovskites have recently emerged as a top contender to be used as an absorber material in highly efficient, low-cost photovoltaic devices. Solution-processed semiconductors tend to have a high density of defect states and exhibit a large degree of electronic disorder. Perovskites appear to go against this trend, and despite relatively little knowledge of the impact of electronic defects, certified solar-to-electrical power conversion efficiencies of up to 17.9% have been achieved. Here, through treatment of the crystal surfaces with the Lewis bases thiophene and pyridine, we demonstrate significantly reduced nonradiative electron-hole recombination within the CH(3)NH(3)PbI(3-x)Cl(x) perovskite, achieving photoluminescence lifetimes which are enhanced by nearly an order of magnitude, up to 2 μs. We propose that this is due to the electronic passivation of under-coordinated Pb atoms within the crystal. Through this method of Lewis base passivation, we achieve power conversion efficiencies for solution-processed planar heterojunction solar cells enhanced from 13% for the untreated solar cells to 15.3% and 16.5% for the thiophene and pyridine-treated solar cells, respectively.

Enhanced photoluminescence and solar cell performance via Lewis base passivation of organic-inorganic lead halide perovskites.

The path towards a high-performance solution-processed kesterite solar cell ☆

The kesterite-structured semiconductors Cu2ZnSnS4 and Cu2ZnSnSe4 are drawing considerable attention recently as the active layers in earth-abundant low-cost thin-film solar cells. The additional number of elements in these quaternary compounds, relative to binary and ternary semiconductors, results in increased flexibility in the material properties. Conversely, a large variety of intrinsic lattice defects can also be formed, which have important influence on their optical and electrical properties, and hence their photovoltaic performance. Experimental identification of these defects is currently limited due to poor sample quality. Here recent theoretical research on defect formation and ionization in kesterite materials is reviewed based on new systematic calculations, and compared with the better studied chalcopyrite materials CuGaSe2 and CuInSe2 . Four features are revealed and highlighted: (i) the strong phase-competition between the kesterites and the coexisting secondary compounds; (ii) the intrinsic p-type conductivity determined by the high population of acceptor CuZn antisites and Cu vacancies, and their dependence on the Cu/(Zn+Sn) and Zn/Sn ratio; (iii) the role of charge-compensated defect clusters such as [2CuZn +SnZn ], [VCu +ZnCu ] and [ZnSn +2ZnCu ] and their contribution to non-stoichiometry; (iv) the electron-trapping effect of the abundant [2CuZn +SnZn ] clusters, especially in Cu2ZnSnS4. The calculated properties explain the experimental observation that Cu poor and Zn rich conditions (Cu/(Zn+Sn) ≈ 0.8 and Zn/Sn ≈ 1.2) result in the highest solar cell efficiency, as well as suggesting an efficiency limitation in Cu2ZnSn(S,Se)4 cells when the S composition is high.

Classification of lattice defects in the kesterite Cu2ZnSnS4 and Cu2ZnSnSe4 earth-abundant solar cell absorbers.

Using vacuum process, we fabricated Cu2ZnSnS4 solar cells with 8.4% efficiency, a number independently certified by an external, accredited laboratory. This is the highest efficiency reported for pure sulfide Cu2ZnSnS4 prepared by any method. Consistent with literature, the optimal composition is Cu-poor and Zn-rich despite the precipitation of secondary phases (e.g., ZnS). Despite a very thin absorber thickness (~600 nm), a reasonably good short-circuit current was obtained. Time-resolved photoluminescence measurements suggest a minority carrier-diffusion length on the order of several hundreds of nanometers and relatively good collection of photo-carriers across the entire absorber thickness. Copyright © 2011 John Wiley & Sons, Ltd.

Thin film solar cell with 8.4% power conversion efficiency using an earth‐abundant Cu2ZnSnS4 absorber

High efficiency Cu2ZnSnS4 solar cells have been fabricated on glass substrates by thermal evaporation of Cu, Zn, Sn, and S. Solar cells with up to 6.8% efficiency were obtained with absorber layer thicknesses less than 1 μm and annealing times in the minutes. Detailed electrical analysis of the devices indicate that the performance of the devices is limited by high series resistance, a “double diode” behavior of the current voltage characteristics, and an open circuit voltage that is limited by a carrier recombination process with an activation energy below the band gap of the material.

Thermally evaporated Cu2ZnSnS4 solar cells

We have carried out detailed microstructural studies of phase separation and grain boundary composition in Cu2ZnSnS4 based solar cells. The absorber layer was fabricated by thermal evaporation followed by post high temperature annealing on hot plate. We show that inter-reactions between the bottom molybdenum and the Cu2ZnSnS4, besides triggering the formation of interfacial MoSx, results in the out-diffusion of Cu from the Cu2ZnSnS4 layer. Phase separation of Cu2ZnSnS4 into ZnS and a Cu–Sn–S compound is observed at the molybdenum-Cu2ZnSnS4 interface, perhaps as a result of the compositional out-diffusion. Additionally, grain boundaries within the thermally evaporated absorber layer are found to be either Cu-rich or at the expected bulk composition. Such interfacial compound formation and grain boundary chemistry likely contributes to the lower than expected open circuit voltages observed for the Cu2ZnSnS4 devices.

Structural and elemental characterization of high efficiency Cu2ZnSnS4 solar cells

Techniques for fabricating nanowire/microwire-based solar cells are provided. In one, a method for fabricating a solar cell is provided. The method includes the following steps. A doped substrate is provided. A monolayer of spheres is deposited onto the substrate. The spheres include nanospheres, microspheres or a combination thereof. The spheres are trimmed to introduce space between individual spheres in the monolayer. The trimmed spheres are used as a mask to pattern wires in the substrate. The wires include nanowires, microwires or a combination thereof. A doped emitter layer is formed on the patterned wires. A top contact electrode is deposited over the emitter layer. A bottom contact electrode is deposited on a side of the substrate opposite the wires.

Nano/Microwire Solar Cell Fabricated by Nano/Microsphere Lithography

Techniques for fabricating thin film solar cells are provided. In one aspect, a method of fabricating a solar cell includes the following steps. A molybdenum (Mo)-coated substrate is provided. Absorber layer constituent components, two of which are sulfur (S) and selenium (Se), are deposited on the Mo-coated substrate. The S and Se are deposited on the Mo-coated substrate using thermal evaporation in a vapor chamber. Controlled amounts of the S and Se are introduced into the vapor chamber to regulate a ratio of the S and Se provided for deposition. The constituent components are annealed to form an absorber layer on the Mo-coated substrate. A buffer layer is formed on the absorber layer. A transparent conductive electrode is formed on the buffer layer.

Kejia Wang

Papers

The path towards a high-performance solution-processed kesterite solar cell ☆

Thermally evaporated Cu2ZnSnS4 solar cells

Structural and elemental characterization of high efficiency Cu2ZnSnS4 solar cells

Nano/Microwire Solar Cell Fabricated by Nano/Microsphere Lithography

Fabrication of CuZnSn(S,Se) Thin Film Solar Cell with Valve Controlled S and Se