Synthesis, XPS and NEXAFS spectroscopy study of Zn, Cr codoped bismuth tantalate pyrochlores

Abstract

The study investigated the formation of inhomophase ceramics through Zn doping in Bi2СrTa2O9.5–Δ. It was found that all Bi2ZnxCr1–xTa2O9.5–Δ (0.3 ≤ x ≤ 0.7) investigated samples crystallized in the pyrochlore structural type (sp. Gr. Fd-3m) and contained an admixture of triclinic β-BiTaO4 (up to 24 wt %, sp. gr. P-1), with the admixture concentration proportional to the degree of zinc doping. It was shown that impurities in the samples could be eliminated by creating a defective bismuth sublattice proportional to the impurity content, resulting in single-phase Bi2–yZnxCr1–xTa2O9.5–Δ (y ≤ 0.5, 0.3 ≤ x ≤ 0.7) samples with the pyrochlore structure. The unit cell parameter of pyrochlore increased with an increase in zinc ion content in the samples from 10.4493 Å (x = 0.3) to 10.4976 Å (x = 0.7). The microstructure of ceramics was represented by individual slightly melted grains 0.5–2 μm in size, which increased in size and fuse with each other with an increase in zinc content. The near edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS) data showed that zinc doping did not change the oxidation degree of bismuth and tantalum in pyrochlore, with the ions in charge states Bi(+3), Zn(+2) and Ta(+5). The study also observed an energy shift of the absorption band in the Ta 4f spectrum toward lower energies (ΔE = 0.55 eV) characteristic of tantalum ions with an effective charge (+5–δ) and a shift of the Bi 4f7/2 and Bi 4f5/2 bands shift to lower energies with increase in x(Zn), due to the distribution of some Zn(II) ions in the bismuth position. The oxidation degree of chromium ions in the samples was mainly (+3), with some chromium ions oxidized and having an oxidation degree close to (+6) according to NEXAFS data. The studied ceramics showed promise as dielectrics for multilayer ceramic capacitors and devices for microwave applications due to their low sintering temperature and high porosity.