A morphotropic phase boundary driven by epitaxial strain has been observed in lead‐free multiferroic BiFeO3 thin films and the strain‐driven phase transitions have been widely reported as iso‐symmetric Cc‐Cc by recent works. In this paper, it is suggested that the tetragonal‐like BiFeO3 phase identified in epitaxial films on (001) LaAlO3 single crystal substrates is monoclinic MC. This MC phase is different from the MA type monoclinic phase reported in BiFeO3 films grown on low mismatch substrates, such as SrTiO3. This is confirmed not only by synchrotron X‐ray studies but also by piezoresponse force microscopy measurements. The polarization vectors of the tetragonal‐like phase lie in the (100) plane, not the (110) plane as previously reported. A phenomenological analysis is proposed to explain the formation of MC Phase. Such a low‐symmetry MC phase, with its linkage to MA phase and the multiphase coexistence open an avenue for large piezoelectric response in BiFeO3 films and shed light on a complete understanding of possible polarization rotation paths and enhanced multiferroicity in BiFeO3 films mediated by epitaxial strain. This work may also aid the understanding of developing new lead‐free strain‐driven morphotropic phase boundary in other ferroic systems.
Growing oxide shells on seed nanoparticles requires the control of several processes: (a) the nucleation and growth of the shell material; (b) the "wetting" of the shell material on the seeds; and (c) the aggregation of the nanoparticles. These processes are influenced by a number of factors, many of which are related. Without understanding the interdependence of these contributing factors, it is difficult to circumvent problems and achieve rational synthesis. We first did a case study on encapsulating Au nanoparticles with ZnO to understand the multiple roles of polyvinylpyrrolidone (PVP) and their dependence on other factors. We developed a general method for coating ZnO on a variety of seeds, including metals, oxides, polymer nanoparticles, graphene oxide, and carbon nanotube. This method can be further extended to include Fe3O4, MnO, Co2O3, TiO2, Eu2O3, Tb2O3, Gd2O3, β-Ni(OH)2, ZnS, and CdS as the shell materials. The understanding obtained in this systematic study will aid rational design and synthesis of other core-shell nanostructures.
Iron pyrite has been the material of interest in the solar community due to its optical properties and abundance. However, the progress is marred due to the lack of control on the surface and intrinsic chemistry of pyrite. In this report, we show iron pyrite as an efficient counter electrode (CE) material alternative to the conventional Pt and poly(3,4-ethylenedioxythiophene (PEDOT) CEs in dye-sensitized solar cells (DSSCs). Pyrite film CEs prepared by spray pyrolysis are utilized in I3(-)/I(-) and Co(III)/Co(II) electrolyte-mediated DSSCs. From cyclic voltammetry and impedance spectroscopy studies, the catalytic activity is found to be comparable with that of Pt and PEDOT in I3(-)/I(-) and Co(III)/Co(II) electrolyte, respectively. With the I3(-)/I(-) electrolyte, photoconversion efficiency is found to be 8.0% for the pyrite CE and 7.5% for Pt, whereas with Co(III)/Co(II) redox DSSCs, efficiency is found to be the same for both pyrite and PEDOT (6.3%). The excellent performance of the pyrite CE in both the systems makes it a distinctive choice among the various CE materials studied.
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