The work is devoted to the solving of the actual problem of searching and studying of the crystalline dielectrics properties for their use in classical optical devices and different fields of modern optoelectronics and sensorics; to the development of methods for prediction and synthesis of materials with predetermined, controlled and stable refractive properties possessing points of birefringence sign inversion (BSI) in a wide temperature and spectral ranges. The work contains results of experimental studies of the refractive properties of dielectric crystals of the АВSO4 (where А, В = Li, К, Na, Rb, NH4) sulfates group and А2ZnCl4 (where А = К, Rb) chlorozincates group, as well as doped crystals of triglycine sulfate; their temperature-spectral-baric changes and theoretical calculations of the band-energy structure, on the basis of which spectra of the optical constants of these crystals are analyzed.
It is established that the increase of the refractive indices of crystals due to the isomorphic cationic-anionic substitution is caused by the increase of their average ionic radius and the density of the crystal, which causes an increase in the polarization action of the cations and anionsThe isotropic points at the temperature of 300 K and λ0 ≈ 683 nm (α-LiNH4SO4 crystal), and in the short-wavelength spectrum region (β-LiNH4SO4 crystal) are revealed.
The nature of the baric changes of the refractive indices ni and birefringence ni in a wide temperature (77–1000 K) and spectral (300–800 nm) ranges is elucidated. It is shown that uniaxial compression increases refraction R and polarizability i of crystals. Baric growth of refractive indices of crystals is caused by the decrease in the effective power of the ultraviolet oscillator and a slight increase in the power of the infrared oscillator caused by the decrease in the band gap Eg and shift of the UV absorption band maximum towards lower frequencies, as well as by change in effective oscillators density of crystals. The factor characterizing the change in the dispersion frequency (change in the type of chemical bond), ie the polarizability itself in comparison with the geometric factor (compression of the sample) is dominant in the total baric increment of refraction R, and, therefore, in the change of refractive index.
It is established that the uniaxial pressures can induce the "pseudoisotropic" states in crystals, shift isotropic points along spectral and temperature ranges, and change the temperature interval of existence of the intermediate phase of the K2SO4 crystal. The disappearance of incommensurate phase and the occurrence of paraelectric-ferroelectric PT ("triple point") in chlorozincate crystals under the action of uniaxial pressure is revealed. The mechanism of influence of uniaxial pressures of different geometry on temperature points of PT is presented. The effect of uniaxial pressures on the mechanism of structural phase transitions in ferroics of the sulfate and chlorozincate groups, which consists in various variants of ordering the orientations of tetrahedral groups, is elucidated, and the infrared (IR) reflection spectra of mechanically free and uniaxially loaded crystals are analyzed.
Calculations of the band-energy structure of single crystals, as well as the total and partial densities of electronic states and the nature of the main energy groups are confirmed by studies of X-ray photoelectron spectra (XPS) and X-ray emission spectra (XES) of their electronic structure.
The method of calculation of spectral dependences of the refractive indices n(λ), birefringence Δn(λ) and absorption k(E) of crystals using Kramers–Kronig dispersion ratios on the basis of the dependences of the real and imaginary part of the complex dielectric function, obtained from band-energy structure and experimental IR reflection spectra, was tested. The qualitative correlation of experimental and calculated curves is revealed. This gives grounds for the use of theoretical methods for calculating optical functions, primarily in spectral regions that are difficult to access for the experiment.
Based on the temperature-spectral-baric diagrams of the uniaxial state of α-LiNH4SO4, (NH4)2SO4 and K2SO4 crystals, it is proposed to use them as piezo-optic and thermo-optic elements for crystal-optic pressure and temperature sensors. For experimental optical measurements of the refractive parameters, the device for investigation of the optical quality of single crystals was proposed.
Key words: dispersion, refractive index, birefringence, birefringence sign inversion (isotropic point), phase transitions, temperature-spectral-baric diagrams, uniaxial mechanical pressures, IR reflection spectra, piezo-optic coefficients, band-energy structure, density of states, dielectric function, X-ray photoelectron and X-ray emission spectra.
