Heterovalent CsPbBr doping with Bi results in a significant red shift of the optical absorption of both single-crystal and powdered samples. The results of low-temperature (3.6 K) photoluminescence studies of perovskite single crystals indicate that the position of the excitonic luminescence peak remains unaffected by Bi doping that, in turn, infers that the band gap of Bi-doped perovskite is not changed as well. The position and state density distribution of the valence band and Fermi level of single-crystal perovskites were determined by another direct method of ultraviolet photoelectron spectroscopy. The obtained results show that Bi doping causes no changes in the valence band structure but an increase in the Fermi level by 0.6 eV. The summary of the obtained results directly demonstrates that the concept of the band-gap engineering in Bi-doped CsPbBr halide perovskite is not valid.

We present optical study of MAPbBr 3 single crystals grown from solution by inverse temperature crystallization method. Photoluminescence temperature dependence of narrow and isolated exciton resonance showed encouragingly low inhomogeneous broadening Γ ≈ 0.5 meV, which is comparable to those of MBE-grown III-V heterostructures, indicating high quality of the solution-grown perovskite. Excitonic origin of the resonance was proved by its superlinear pump intensity dependence in contrast to the linear behavior of the defect-assisted recombination bands. In addition, for the first time phonon replicas were resolved in MAPbBr 3 photoluminescence spectra and attributed to the known lattice vibrational modes by comparison with Raman scattering spectra.

The Vuoriyarvi Devonian carbonatite–ijolite–pyroxenite–olivinite complex comprises several carbonatite fields: Neske Vara, Tukhta-Vara, and Petyayan-Vara. The most common carbonatites in the Tukhta-Vara and Neske-Vara fields are calciocarbonatites, which host several P, Fe, Nb, and Ta deposits. This paper focuses on the Petyayan-Vara field, in which the primary magmatic carbonatites are magnesian. The least altered magnesiocarbonatites are composed of dolomite with burbankite and are rich in REE (up to 2.0 wt. %), Sr (up to 1.2 wt. %), and Ba (up to 0.8 wt. %). These carbonatites underwent several stages of metasomatism. Each metasomatic event produced a new rock type with specific mineralization. The introduction of K, Si, Al, Fe, Ti, and Nb by a F-rich fluid (or fluid-saturated melt) resulted in the formation of high-Ti magnesiocarbonatites and silicocarbonatites, composed of dolomite, microcline, Ti-rich phlogopite, and Fe–Ti oxides. Alteration by a phosphate–fluoride fluid caused the crystallization of apatite in the carbonatites. A sulfate-rich Ba–Sr–rare-earth elements (REE) fluid (probably brine-melt) promoted the massive precipitation of ancylite and baryte and, to a lesser extent, strontianite, bastnäsite, and synchysite. Varieties of carbonatite that contain the highest concentrations of REE are ancylite-dominant. The influence of sulfate-rich Ba-Sr-REE fluid on the apatite-bearing rocks resulted in the dissolution and reprecipitation of apatite in situ. The newly formed apatite generation is rich in HREE, Sr, and S. During late-stage transformations, breccias of magnesiocarbonatites with quartz-bastnäsite matrixes were formed. Simultaneously, strontianite, quartz, calcite, monazite, HREE-rich thorite, and Fe-hydroxides were deposited. Breccias with quartz-bastnäsite matrix are poorer in REE (up to 4.5 wt. % total REE) than the ancylite-dominant rocks (up to 11 wt. % total REE).

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