Intrinsic polarization of ferroelectrics (FE) helps separate photon-generated charge carriers thus enhances photovoltaic effects. However, traditional FE with transition-metal cations (M) of d0 electron in MO6 network typically has a band gap (Eg) exceeding 3.0 eV. Although a smaller Eg (2.6 eV) can be obtained in multiferroic BiFeO3, the value is still too high for optimal solar energy applications. Computational “materials genome” searches have predicted several exotic MO6 FE with Eg < 2.0 eV, all thus far unconfirmed because of synthesis difficulties. Here we report a new FE compound with MO4 tetrahedral network, KBiFe2O5, which features narrow Eg (1.6 eV), high Curie temperature (Tc ~ 780 K) and robust magnetic and photoelectric activities. The high photovoltage (8.8 V) and photocurrent density (15 μA/cm2) were obtained, which is comparable to the reported BiFeO3. This finding may open a new avenue to discovering and designing optimal FE compounds for solar energy applications.

With the addition of oxygen into the chain-like bismuth sulfide of Bi2S3, there are two interesting functional compounds of Bi2O2S (photoelectric) and Bi4O4S3 (superconducting) containing the PbO-like [Bi2O2] layers. Nanoscale Bi2O2S crystals with an indirect band gap of 1.12 eV are synthesized via a facile hydrothermal method. This semiconductor shows excellent photoelectric response under the irradiation of visible light lamp at room temperature. Theoretical calculations and packing factor model both indicate that the loosely packed Bi2O2S is an excellent photoelectric material. When the Bi2O2S phase was annealed at 500 °C in an evacuated quartz tube, nanocrystals of Bi4O4S3 were obtained. The powder X-ray diffraction and electron microscope analyses (SEM, TEM, EDX) confirmed the thermal decomposition from orthorhombic Bi2O2S to tetragonal Bi4O4S3. The superconducting transition temperature of Bi4O4S3 was observed to be 4.6 K from the temperature-dependence measurements of electrical resistivity and magnetic susceptibility. Our results also provide a new method utilizing thermal decomposition to prepare a new phase without high temperature reaction.

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[Bi2O2]-containing tetragonal compounds have received enormous attention due to unique functions including ferroelectricity, photocatalysis, and superconductivity. Here, a new layered compound Bi9O7.5S6 was synthesized via a facile hydrothermal route. The compound, belonging to a new structure type crystallizes in a rhombohedral system with space group R3̅m (a = 4.0685(1) Å, c = 31.029(5) Å, V = 444.8(1) Å(3), Z = 1). The overall crystal structure consists of alternatively packed unique [Bi2O2] and [BiS2] layers along [001] which are combined with each other by van der Waals interaction. The phase purity of the product is confirmed by powder X-ray diffraction. XPS analyses indicate +3 for Bi and -2 for S atoms. The temperature dependence of resistivity ρ(T) indicates that the semiconducting sample follows the mechanisms of variable range hopping (VRH) and adiabatic small polaron hopping (SPH). The direct-transition band gap, Eg = 1.27 eV derived from optical absorption spectrum, falls in the optimal region of solar absorber materials. Accordingly, the photoelectric measurement demonstrates the potential for applications for photovoltaic devices.

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By applying hydrostatic pressure, a structural evolution from 2D layered to 3D network structure has been realized in bismuth oxysulfide Bi9O7.5S6, resulting in giant enhancements in electric conductivity and photoelectric current.

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Enhanced solar light absorption and photocatalytic and photoelectrochemical properties have been achieved in black BaTiO with a unique core/shell structure (crystalline BaTiO@amorphous BaTiO) using an Al-reduction method. This finding may open a new avenue to tune the inert ferroelectric materials toward excellent photocatalysts for advanced applications.