Publishing type：Research paper (international conference proceedings)   Publisher：IOP Publishing  

Abstract

The coarsening of austenite grains produced through a massive-like transformation from the ferrite to the austenite phase during/after solidification in Fe–0.45mass%C steel was examined through time-resolved X-ray diffraction measurements using time-resolved computed tomography. The δ phase solidification resulted in a single δ grain in the observation region (0.6 mm in diameter, 0.1 mm in height). The massive-like transformation produced multiple γ grains, and coarsening immediately followed the transformation. The coarsening in the observation region was completed even within 200 s. A correlation of crystallographic orientation between the γ grains was found in the γ grain structure. The massive-like transformation frequently produced fcc (111) twinned grains, and the twinned austenite grains tended to remain during coarsening because the twin interface energy is lower than the grain boundary energy. The massive-like transformation following the solidification contributed to the texture formation in the γ grain structure.

DOI： 10.1088/1757-899x/1274/1/012055

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Other Link： https://iopscience.iop.org/article/10.1088/1757-899X/1274/1/012055/pdf

Publishing type：Research paper (international conference proceedings)   Publisher：IOP Publishing  

Abstract

A technique combining time-resolved computed tomography (4D-CT) and three-dimensional X-ray diffraction (3DXRD) was employed to investigate semisolid deformation in an Al-10mass%Cu alloy with the equiaxed grain structure. The diffraction patterns and reconstructed 3D images were used to quantitatively analyse the translational and rotational motions of solid grains in the semisolid alloy. Finally, the motion of solid grains and the expansion of porosity during the compression tests are discussed on the basis of in situ observations.

DOI： 10.1088/1757-899x/1274/1/012053

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Other Link： https://iopscience.iop.org/article/10.1088/1757-899X/1274/1/012053/pdf

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Informa {UK} Limited  

DOI： 10.1080/27660400.2022.2076548

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Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Walter de Gruyter GmbH  

<title>Abstract</title>
Exploration of suitable partner materials (so-called buffer layer or n-type emitter) for each light-absorbing material is essential to practicalize various emerging photovoltaic devices. Motivated by our recent discovery of a partner material, Mg(Mg_{<italic>x</italic>}Zn_{1−<italic>x</italic>})₂P₂, in Mg/Zn₃P₂ solar cells, the related series of materials <italic>M</italic>Zn₂P₂ (<italic>M</italic> = Ca, Sr, Ba) is of interest to the application in pnictide-based solar cells. In this study, we synthesize these materials to evaluate the optoelectronic properties concerning photovoltaic applications. To deal with the difficulties of the high vapor pressure and reactivity of the constituent elements, we utilized Sn as a solvent to reduce their activities during heat treatments. Powders that are mainly composed of <italic>M</italic>Zn₂P₂ were obtained by crushing the samples after solution growth, although single-phase crystals of <italic>M</italic>Zn₂P₂ could not be obtained in this study. The optical bandgap and the ionization potential of each <italic>M</italic>Zn₂P₂ were evaluated through the diffuse reflectance and the photoelectron yield spectroscopy measurements of the powder. As a result, we found that CaZn₂P₂ would be a promising partner material in photovoltaics based on Zn₃P₂ and ZnSnP₂.

DOI： 10.1515/htmp-2022-0019

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Other Link： https://www.degruyter.com/document/doi/10.1515/htmp-2022-0019/pdf

Language：English   Publishing type：Research paper (scientific journal)   Publisher：The Japan Society of Applied Physics  

In this article, we introduce our studies on the application of chalcopyrite phosphides to solar cells, including bulk crystal growth based on the phase diagram, and thin film deposition through chemical potential diagram. A phase diagram is a useful tool for the fabrication of multi-component materials, while the chemical potential diagram, which is a kind of phase diagram with chemical potentials as axes, is well suited for discussing vapor growth. As another example of using the chemical potential diagram, the stability of a hetero-interface is presented. In addition, bandgap control through order-disorder phenomena is described.

DOI： 10.11470/jsaprev.220411

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Elsevier BV  

DOI： 10.1016/j.scriptamat.2021.114335

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：IOP Publishing Ltd  

ZnSnP2, an emerging inorganic material for solar cells, was characterized by deep level transient spectroscopy (DLTS) and photoluminescence (PL). Acceptor- and donor-like traps with shallow energy levels were detected by DLTS analysis. The previous study based on first-principle calculation also suggested such traps were due to antisite defects of Zn and Sn. PL measurements also revealed sub-gap transitions related to these trap levels. Additionally, DLTS found a trap with a deep level in ZnSnP2. A short lifetime of minority carrier in previous work might be due to such trap, coming from phosphorus vacancies and/or zinc interstitials suggested by the first-principle study.

DOI： 10.35848/1347-4065/ac468a

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DOI： 10.1021/acsomega.1c05232

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Elsevier BV  

In this study, we investigated reactive diffusion at the interface between a Cu back electrode and a ZnSnP2 absorber, at which ohmic behavior was previously confirmed by appropriate annealing. Cross-sectional observation of the Cu/ZnSnP2 interface revealed that Cu3P was formed along the ZnSnP2 surface after annealing. It was also found that Cu3P was epitaxially formed beside ZnSnP2 with a lattice-mismatch of less than 0.5% by electron diffraction around the Cu3P/ZnSnP2 interface and consideration of atomic arrangements, particularly the phosphorus sublattice, in both phosphides. In addition, photoelectron yield spectroscopy revealed that the work function of Cu3P and ionization potential of ZnSnP2 are both about 5.2 eV, suggesting that the potential barrier against hole transport is small at the Cu3P/ZnSnP2 interface. The formation of Cu3P at the interface leads to higher current density and no roll-over of J-V curves in ZnSnP2 solar cells. Consequently, the highest efficiency of ZnSnP2 solar cells of 3.87% was achieved by intentionally prepared Cu3P using sputtering. It is concluded that Cu3P is a promising back buffer material for ZnSnP2 solar cells due to the alignment with ZnSnP2 from the viewpoints of band and lattice structures.

DOI： 10.1016/j.solmat.2020.110891

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Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER INST PHYSICS  

Acceptor doping CdTe with group-V elements is promising for increasing the power conversion efficiency of CdTe photovoltaic devices via an increased hole concentration and open circuit voltage (V-OC). In past work, we have investigated doping with As in Cd-rich CdTe single crystals grown using the Cd-solvent traveling heater method we have developed. In this study, we compare the doping parameters and stability of hole concentration in the light and dark for P, As, and Sb dopants in crystals cooled very slowly from the growth temperature to approximate thermal equilibrium. In contrast to older reports of a high acceptor ionization energy for Sb, our temperature dependent Hall effect experiments reveal an acceptor ionization energy slightly above 90meV for Sb doping in the mid 10(16) cm(-3) range. Room temperature hole concentrations above 10(16) cm(-3) are observed for P, As, and Sb with each dopant type exhibiting only small changes in hole concentrations over 2 years' time at room temperature. Crystals doped with P, As, or Sb exhibit increased conductivity after above-gap illumination, which decays over periods of minutes to hours depending on temperature. Analysis of the photoconductivity decay reveals a barrier attributed to hole capture of 190-280meV for the series P, As, and Sb.

DOI： 10.1063/5.0004883

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Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry (RSC)  

<p>Sunlight-induced photoelectrochemical H₂ evolution was achived by using a photocathode based on a chalcopyrite CuGaSe₂ single crystal.</p>

DOI： 10.1039/d0ra07904a

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Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：ACADEMIC PRESS INC ELSEVIER SCIENCE  

Mg(MgxZn1-x)(2)P-2 was found to be a key material in Zn3P2-based solar cells, which have attracted attention as an earth-abundant photovoltaic technology. However, Mg(MgxZn1-x)(2)P-2 has not been investigated as a functional material thus far, and even the single-phase range in the Mg-P-Zn equilibrium phase diagram is currently unknown. Thus, in this work, we investigate the phase equilibria around Mg(MgxZn1-x)(2)P-2 in the Mg-P-Zn system using Sn as a flux for equilibrium experiments. We find that Mg(MgxZn1-x)(2)P(2)exists as a single phase with a trigonal P (3) over bar m1 structure from x = 0 to x = 0.55 based on our XRD and the SEM-EDS analyses. The lattice parameters, a and c, monotonically increase with increase in the Mg content. In addition, the Mg(MgxZn1-x)(2)P-2 phase can equilibrate with Zn3P2 only in the case of x = 0 (MgZn2P2) despite the wide composition range available. The lattice mismatch between MgZn2P2 and Zn3P2 is about 0.5%, which is consistent with our previous results of an electron diffraction study on Mg(MgxZn1-x)(2)P-2/Zn3P2 interfaces. We also find that the interface between Mg and Mg(MgxZn1-x)(2)P-2 is unstable and that the interface reaction is expected to result in the formation of the Mg-rich phosphide phase, which is air- and water-sensitive. The instability of the reaction product in the atmosphere can degrade the device via the formation of voids around the interface, which was observed in our previous work. Therefore, we deduce that Mg is not suitable as the surface electrode of Mg(MgxZn1-x)(2)P-2/Zn3P2 solar cells. The phase equilibria established in this study can aid in redesigning the device structure of Zn3P2-based solar cells and in further investigation of the physical properties of Mg(MgxZn1-x)(2)P-2.

DOI： 10.1016/j.jssc.2019.120983

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Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1021/acsaelm.9b00084

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Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：IEEE  

One of the main issues for the improvement of solar cells is to develop Ohmic contacts with low contact resistance on absorbers, such as CIGS/MoSe2/Mo. In the case of ZnSnP2 (ZTP)-based solar cells, Cu is used as a back electrode. At the Cu/ZTP interface, Cu3P is formed epitaxially on ZTP due to interdiffusion through annealing process and contributes to the improvement of the carrier transport property across the junction. However, the interdiffusion also causes degradation of electrodes and hence the increase in the series resistance. In this study, we adopt DC sputtering of a Cu3P target on the ZTP wafers before the deposition of Cu electrodes to prepare uniform Cu/Cu3P electrodes. As a result, the degradation of electrodes was suppressed and the low series resistance was obtained in the annealing time range from 5 to 30 min. The Cu/Cu3P stacked electrodes could therefore be a robust Ohmic contact for ZTP.

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Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1021/acsami.8b11423

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Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：IEEE  

DOI： 10.1109/pvsc.2018.8547932

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Authorship：Lead author   Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：IEEE  

DOI： 10.1109/pvsc.2017.8366757

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Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

Orientation of solar absorber is an important factor to achieve high efficiency of thin film solar cells. In the case of Zn3P2 which is a promising absorber of low-cost and high-efficiency solar cells, (110)/(001) orientation was only reported in previous studies. We have successfully prepared (101)-oriented Zn3P2 films by phosphidation of (0001)-oriented Zn films at 350 degrees C. The phosphidation mechanism of Zn is discussed through STEM observations on the partially-reacted sample and the consideration of the relationship between the crystal structures of Zn and Zn3P2. We revealed that (0001)-oriented Zn led to nucleation of (101)-oriented Zn3P2 due to the similarity in atomic arrangement between Zn and Zn3P2. The electrical resistivity of the (101)-oriented Zn3P2 film was lower than those of (110)/(001)-oriented films, which is an advantage of the phosphidation technique to the growth processes in previous works. The results in this study demonstrated that well-conductive Zn3P2 films could be obtained by controlling orientations of crystal grains, and provide a guiding principle for microstructure control in absorber materials.

DOI： 10.1016/j.jcrysgro.2016.11.040

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Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry  

Carrier transport across a metal/semiconductor interface plays a key role in electronic devices. It is generally affected by some interactions at interfaces, such as atomic interdiffusion and formation of intermediate compounds
however, it is hard to consider all possible chemical reactions at the interface. In this work, we adopted a chemical potential diagram for comprehensive discussions on chemical reactions at the interfaces between the metal (M) and p-type zinc phosphide (p-Zn3P2), which is a promising candidate as an absorber in thin-film solar cells. We revealed that Schottky or Ohmic behavior depended on the reaction at the interfaces through the investigations in Al/p-Zn3P2 and Ag/p-Zn3P2 junctions. The interdiffusion was observed at the interface of Al/p-Zn3P2, while the interfacial structure in Ag/p-Zn3P2 was not changed by annealing. Such behaviors were thermodynamically expected from the chemical potential diagrams and determined the transport characteristics considering the similar work functions of Al and Ag. Furthermore, the discussions on other M-P-Zn (M = Au, In, Mn, Cu) systems based on chemical potential diagrams clarified that phosphide semiconductors as intermediate compounds were formed in the M/p-Zn3P2 junctions, which show Schottky behavior, and that Ohmic M/p-Zn3P2 junctions are stable. Therefore, it is concluded that we should discuss the band structures in heterojunctions under the considerations on reactivity at the interfaces, which is comprehensively understood using chemical potential diagrams.

DOI： 10.1039/c7tc01047h

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Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：IOP PUBLISHING LTD  

In this paper, we report the crystal growth of indium-doped zinc phosphide bulk crystals to obtain n-type conduction. The crystal growth experiments were carried out by unidirectional solidification from In-Zn-P ternary solution, and n-type Zn3P2 bulk crystals were successfully obtained. It was also revealed that the electrical properties of indium-doped Zn3P2 crystals could be controlled by heat treatment under controlled partial pressure of phosphorus or zinc. The relationship between the electron concentration and the partial pressure of zinc or phosphorus even in indium-doped Zn3P2 can be understood on the basis of defect equilibria, as in the case of undoped Zn3P2. However, the controllable range of the electron concentration was 10(10)-10(13)cm(-3), which was too low in terms of the concentration of doped indium. This is due to the low formation energy of the intrinsic acceptor, interstitial phosphorus, and carrier compensation should be discussed. According to recent reports on ab initio calculation, a weakly n-type Zn3P2 is expected to be formed under extremely Zn-rich growth conditions. The results obtained in this study coincide with the prediction based on calculations, and provide useful knowledge for the formation of the p-n junction of Zn3P2. (C) 2016 The Japan Society of Applied Physics

DOI： 10.7567/JJAP.55.041201

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

High-quality Cu(2)ZriSn(SxSe1-x)(4)(CZTS(x)Se(1-x)) single crystals were grown by the traveling heater method (THN1), which is an example of a solution growth process. The CZTS(x)Se(1-x) solute-Sn solvent pseudobinary system was investigated and the ranges of growth temperature and quantity of solvent were determined for THN1 growth. The CZTS(x)Se(1-x) Sel single crystals were obtained from a 70-80 mol% CZTS(x)Se(1-x), solution at growth temperature 900 degrees C and speed 4-5 mmiclay. The structural and compositional analyses of the grown single crystals were carried out by powder X-ray diffraction, Raman spectroscopy and electron probe microanalysis. The grown crystals were kesterite and nearly stoichiometric with slightly Cu poor and Zn-rich despite the excess Sn used as the solvent. As the sulfur content x increases, the carrier concentration increases slightly but systematically between 2 x 10(17) and 3 x 10(17) cm(-3) while the mobility decreases from 35.1 to 104 cm(2) V-1 s(-1). These data provide references for the results of characterization on thin film samples as well as giving insight into the defect equilibrium and resulting quantities such as doping and mobility affecting device performance. Published by Elsevier B.V.

DOI： 10.1016/j.jcrysgro.2015.04.012

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