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Shiro Nishiwaki

Bio: Shiro Nishiwaki is an academic researcher from Swiss Federal Laboratories for Materials Science and Technology. The author has contributed to research in topics: Copper indium gallium selenide solar cells & Thin film. The author has an hindex of 27, co-authored 76 publications receiving 4607 citations. Previous affiliations of Shiro Nishiwaki include École Polytechnique Fédérale de Lausanne.


Papers
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Journal ArticleDOI
TL;DR: A new sequential post-deposition treatment of the CIGS layer with sodium and potassium fluoride is presented that enables fabrication of flexible photovoltaic devices with a remarkable conversion efficiency due to modified interface properties and mitigation of optical losses in the CdS buffer layer.
Abstract: Thin-film photovoltaic devices based on chalcopyrite Cu(In,Ga)Se2 (CIGS) absorber layers show excellent light-to-power conversion efficiencies exceeding 20%. This high performance level requires a small amount of alkaline metals incorporated into the CIGS layer, naturally provided by soda lime glass substrates used for processing of champion devices. The use of flexible substrates requires distinct incorporation of the alkaline metals, and so far mainly Na was believed to be the most favourable element, whereas other alkaline metals have resulted in significantly inferior device performance. Here we present a new sequential post-deposition treatment of the CIGS layer with sodium and potassium fluoride that enables fabrication of flexible photovoltaic devices with a remarkable conversion efficiency due to modified interface properties and mitigation of optical losses in the CdS buffer layer. The described treatment leads to a significant depletion of Cu and Ga concentrations in the CIGS near-surface region and enables a significant thickness reduction of the CdS buffer layer without the commonly observed losses in photovoltaic parameters. Ion exchange processes, well known in other research areas, are proposed as underlying mechanisms responsible for the changes in chemical composition of the deposited CIGS layer and interface properties of the heterojunction.

1,124 citations

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TL;DR: A strong composition gradient in the absorber layer is identified as the main reason for inferior performance and it is shown that, by adjusting it appropriately, very high efficiencies can be obtained.
Abstract: Solar cells based on polycrystalline Cu(In,Ga)Se(2) absorber layers have yielded the highest conversion efficiency among all thin-film technologies, and the use of flexible polymer films as substrates offers several advantages in lowering manufacturing costs. However, given that conversion efficiency is crucial for cost-competitiveness, it is necessary to develop devices on flexible substrates that perform as well as those obtained on rigid substrates. Such comparable performance has not previously been achieved, primarily because polymer films require much lower substrate temperatures during absorber deposition, generally resulting in much lower efficiencies. Here we identify a strong composition gradient in the absorber layer as the main reason for inferior performance and show that, by adjusting it appropriately, very high efficiencies can be obtained. This implies that future manufacturing of highly efficient flexible solar cells could lower the cost of solar electricity and thus become a significant branch of the photovoltaic industry.

810 citations

Journal ArticleDOI
TL;DR: It is concluded that a model based on a secondary diode at the CIGS/Mo interface can best explain these features such as the position of the N1 signal in admittance spectroscopy and the roll-over of the J-V curve at low temperature.
Abstract: Thin film solar cells with a Cu(In,Ga)Se2 (CIGS) absorber layer achieved efficiencies above 20%. In order to achieve such high performance the absorber layer of the device has to be doped with alkaline material. One possibility to incorporate alkaline material is a post deposition treatment (PDT), where a thin layer of NaF and/or KF is deposited onto the completely grown CIGS layer. In this paper we discuss the effects of PDT with different alkaline elements (Na and K) on the electronic properties of CIGS solar cells. We demonstrate that whereas Na is more effective in increasing the hole concentration in CIGS, K significantly improves the pn-junction quality. The beneficial role of K in improving the PV performance is attributed to reduced recombination at the CdS/CIGS interface, as revealed by temperature dependent J–V measurements, due to a stronger electronically inverted CIGS surface region. Computer simulations with the software SCAPS are used to verify this model. Furthermore, we show that PDT with either KF or NaF has also a distinct influence on other electronic properties of the device such as the position of the N1 signal in admittance spectroscopy and the roll-over of the J–V curve at low temperature. In view of the presented results we conclude that a model based on a secondary diode at the CIGS/Mo interface can best explain these features.

284 citations

Journal ArticleDOI
TL;DR: This work introduces an innovative concept for the controlled doping of the CdTe layer in the inverted device structure by means of evaporation of sub-monolayer amounts of Cu and subsequent annealing, which enables breakthrough efficiencies up to 13.6%.
Abstract: Roll-to-roll manufacturing of CdTe solar cells on flexible metal foil substrates is one of the most attractive options for low-cost photovoltaic module production. However, various efforts to grow CdTe solar cells on metal foil have resulted in low efficiencies. This is caused by the fact that the conventional device structure must be inverted, which imposes severe restrictions on device processing and consequently limits the electronic quality of the CdTe layer. Here we introduce an innovative concept for the controlled doping of the CdTe layer in the inverted device structure by means of evaporation of sub-monolayer amounts of Cu and subsequent annealing, which enables breakthrough efficiencies up to 13.6%. For the first time, CdTe solar cells on metal foil exceed the 10% efficiency threshold for industrialization. The controlled doping of CdTe with Cu leads to increased hole density, enhanced carrier lifetime and improved carrier collection in the solar cell. Our results offer new research directions for solving persistent challenges of CdTe photovoltaics.

232 citations

Journal ArticleDOI
TL;DR: In this article, a solution-deposited earth-abundant precursors are used to enhance the surface chemisorption of selenium molecules and promote the formation of liquid Na2Sex phases during reactive annealing of the precursor.
Abstract: Cu2ZnSn(S,Se)4 thin layers processed from solution-deposited earth-abundant precursors emerge as absorber materials for low-cost thin film solar cells. A frequently observed drawback of the chemical solution processing—poor crystallinity of the chalcogenide absorber—can be overcome by employing a sodium-containing reactive agent. We demonstrate a massive improvement in grain growth in the presence of sodium. It enhances the surface chemisorption of selenium molecules and can promote the formation of liquid Na2Sex phases during reactive annealing of the precursor. The sodium is also incorporated into the semiconductor absorber and significantly modifies its electronic properties. By adjusting the sodium precursor quantity, it is possible to tune doping levels and gradients to maximize the collection of photogenerated carriers in thin film Cu2ZnSn(S,Se)4 solar cells. The presented approach can be extended to other solution-processed metal chalcogenides to enhance their structural and electronic properties, ...

191 citations


Cited by
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Journal ArticleDOI
TL;DR: In this paper, the bulk absorber layer of CH3NH3PbI3−xClx perovskite solar cells was reduced from 500 to <150 °C and achieved power conversion efficiency up to 12.3%.
Abstract: We have reduced the processing temperature of the bulk absorber layer in CH3NH3PbI3−xClx perovskite solar cells from 500 to <150 °C and achieved power conversion efficiencies up to 12.3%. Remarkably, we find that devices with planar thin-film architecture, where the ambipolar perovskite transports both holes and electrons, convert the absorbed photons into collected charge with close to 100% efficiency.

1,524 citations

Journal ArticleDOI
TL;DR: In this article, the authors presented flexible organic solar cells that are less than 2 μm thick, have very low specific weight and maintain their photovoltaic performance under repeated mechanical deformation.
Abstract: Organic solar cells are promising for technological applications, as they are lightweight and mechanically robust. This study presents flexible organic solar cells that are less than 2 μm thick, have very low specific weight and maintain their photovoltaic performance under repeated mechanical deformation.

1,451 citations

Journal ArticleDOI
TL;DR: In this article, the effect of different alkali elements in the post deposition treatment of CIGS solar cells was investigated and a diode analysis revealed an improved diode quality for cells treated-ed with heavier alkalis.
Abstract: We report on the use and effect of the alkali elements rubidium and caesium in the place of sodium and potassium in the alkali post deposition treatment (PDT) as applied to Cu(In,Ga)Se2 (CIGS) solar cell absorbers. In order to study the effects of the different alkali elements, we have produced a large number of CIGS solar cells with high efficiencies resulting in a good experimental resolution to detect even small differences in performance. We examine the electrical device parameters of these fully functional devices and observe a positive trend in the I –V parameters when moving from devices without PDT to KF-, RbF-, and eventually to CsF-PDT. A diode analysis reveals an improved diode quality for cells treat-ed with heavier alkalis. Furthermore, secondary ion mass spectrometry (SIMS) measurements reveal a competitive mechanism induced within the class of alkali elements in the CIGS absorber induced by the alkali post deposition treatment. (© 2016 WILEY-VCH Verlag GmbH &Co. KGaA, Weinheim)

1,264 citations

Journal ArticleDOI
TL;DR: Kelvin probe force microscopy (KPFM) is a tool that enables nanometer-scale imaging of the surface potential on a broad range of materials as discussed by the authors, including metallic nanostructures, semiconductor materials, and electrical devices.

1,242 citations

Journal ArticleDOI
TL;DR: The calculated properties explain the experimental observation that Cu poor and Zn rich conditions 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.
Abstract: 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.

1,139 citations