Observation and enhancement through alkali metal doping of p-type conductivity in the layered oxyselenides Sr₂ZnO₂Cu₂Se₂ and Ba₂Zn_1−xO_2−xCu₂Se₂

The optoelectronic properties of two layered copper oxyselenide compounds, with nominal composition Sr2ZnO2Cu2Se2 and Ba2ZnO2Cu2Se2, have been investigated to determine their suitability as p-type conductors. The structure, band gaps and electrical conductivity of pristine and alkali-metal-doped samples have been determined. We find that the strontium-containing compound, Sr2ZnO2Cu2Se2, adopts the expected tetragonal Sr2Mn3SbO2 structure with I4/mmm symmetry, and has a band gap of 2.16 eV, and a room temperature conductivity of 4.8 × 10−1 S cm−1. The conductivity of the compound could be increased to 4.2 S cm−1 when sodium doped to a nominal composition of Na0.1Sr1.9ZnO2Cu2Se2. In contrast, the barium containing material was found to have a small zinc oxide deficiency, with a sample dependent compositional range of Ba2Zn1−xO2−xCu2Se2 where 0.01 < x < 0.06, as determined by single crystal X-ray diffraction and powder neutron diffraction. The barium-containing structure could also be modelled using the tetragonal I4/mmm structure, but significant elongation of the oxygen displacement ellipsoid along the Zn–O bonds in the average structure was observed. This indicated that the oxide ion position was better modelled as a disordered split site with a displacement to change the local zinc coordination from square planar to linear. Electron diffraction data confirmed that the oxide site in Ba2Zn1−xO2−xCu2Se2 does not adopt a long range ordered arrangement, but also that the idealised I4/mmm structure with an unsplit oxide site was not consistent with the extra reflections observed in the electron diffractograms. The band gap and conductivity of Ba2Zn1−xO2−xCu2Se2 were determined to be 2.22 eV and 2.0 × 10−3 S cm−1 respectively. The conductivity could be increased to 1.5 × 10−1 S cm−1 with potassium doping in K0.1Ba1.9Zn1−xO2−xCu2Se2. Hall measurements confirmed that both materials were p-type conductors with holes as the dominant charge carriers

Distorted magnetic orders and electronic structures of tetragonal FeSe from first-principles

We use the state-of-the-arts density-functional-theory method to study various magnetic orders and their effects on the electronic structures of the FeSe. Our calculated results show that, for the spins of the single Fe layer, the striped antiferromagnetic orders with distortion are more favorable in total energy than the checkerboard antiferromagnetic orders with tetragonal symmetry, which is consistent with known experimental data, and the inter-layer magnetic interaction is very weak. We investigate the electronic structures and magnetic property of the distorted phases. We also present our calculated spin coupling constants and discuss the reduction of the Fe magnetic moment by quantum many-body effects. These results are useful to understand the structural, magnetic, and electronic properties of FeSe, and may have some helpful implications to other FeAs-based materials

The synthesis and characterisation of complex oxychalcogenides and oxypnictides

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