UA119942C2 - METHOD OF GROWING SINGLE CRYSTAL SINGLE CRYSTALS OF COMPOSITION (Cu _1-X Ag _X) ₇ SiS ₅ I METHOD MELT-SOLUTION - Google Patents

Abstract

The invention relates to the field of inorganic chemistry. A method of growing single crystals of solid solutions of the composition (Cu1-xAgx) 7SiS5I (x = 0.25, 0.5, 0.75) by the method of directional crystallization from a melt-solution, which includes stepwise heating of vacuum quartz ampoules at a rate of 100 K / h. to a temperature of 1023 K and exposure at the same temperature for 24 hours and subsequent cultivation of single crystals. Moreover, pre-synthesized halogen chalcogenides Cu7SiS5I and Ag7SiS5I, taken in stoichiometric ratios, are used, heating is carried out at a rate of 50 K / h. to a maximum temperature of 1220-1390 K and holding at this temperature for 72 hours, the cultivation of single crystals is carried out by the method of directional crystallization from the melt-solution at a rate of 0.4-0.5 mm / h in evacuated quartz ampoules, after which the single crystal is cooled to room temperature at a rate of 5 K / h. The proposed method is convenient, fast and provides a superionic material with high cationic conductivity.

Description

The proposed method is convenient, fast and ensures the production of a superionic material with high cationic conductivity.

The invention belongs to the field of inorganic chemistry and inorganic materials science, in particular to the technology of growing single crystals of tetrarhalogen sulfides, some of which are promising superionic materials with high cationic conductivity in the solid state.

The closest to the proposed method is the method of growing solid solutions of the composition (Sci-Adh);/evvi by the method of directed crystallization from melt-solution (11.

The task of the invention is to obtain a new superionic material with high cationic conductivity in the solid state.

The task is solved in such a way that the method of growing single crystals of solid solutions of the composition (Si:i-xAdh);bievI (x-0.25, 0.5, 0.75) by the method of directional crystallization from melt-solution, which includes step heating, is proposed vacuumed quartz ampoules at a rate of 100 K/h. to a temperature of 1023 K and exposure at the same temperature for 24 hours. and further growth of single crystals, which is distinguished by the fact that pre-synthesized halogen chalcogenides Si75ib5I and Ad7bi5b5iI are used, taken in stoichiometric ratios, heating is carried out at a rate of 50 K/h. to the maximum temperature of 1220-1390 K and holding at this temperature for 72 hours, the growth of single crystals is carried out by the method of directed crystallization from the melt-solution at a speed of 0.4-0.5 mm/h. in vacuumed quartz ampoules, after which the single crystal is cooled to room temperature at a rate of 5 K/h.

The method is implemented as follows.

The synthesis of solid solutions of the composition (Syz-xAdh)75iZ5I to obtain single crystals was carried out from the previously synthesized tetrarhalogenides Si?bibbI and AdbisbviI, taken in stoichiometric ratios in vacuumed quartz ampoules.

The synthesis mode included step heating at a rate of 100 K/h. up to 1023 K with exposure at this temperature for 24 h, further temperature increase at a rate of 50

K/hour to a value 50 K higher than the melting temperature and holding at this temperature for 72 hours. Cooling was carried out with the furnace turned off.

The growth of single crystals of solid solutions of the composition (Sshc1-xAdh);5ibv5I by crystallization from a melt solution was carried out in a vertical two-zone tubular resistance furnace using

From a quartz container of a special configuration. The technological conditions for growing single crystals are given in Table.

Table of melt, K of annealing, K

In order to homogenize the melt, the ampoule was kept in the melt zone for 24 hours.

The growth of a single crystal consists of the formation of a nucleus in the lower cone-shaped part of the container by the collective recrystallization method within 48 hours. and crystal growth on the formed nucleus. The optimal speed of movement of the crystallization front was 0.4-0.5 mm/hour, the cooling rate to room temperature was 5 K/hour. According to this method, single crystals of solid solutions of the composition (Syt-xAax)75ibv5I (x-0.25, 0.5, 0.75) of dark gray color with a metallic luster of 30-40 mm in length and 10-15 mm in diameter were obtained.

The powders of the obtained single crystals |2| were studied using the X-ray phase analysis method and it was established that compounds and solid solutions based on them crystallize in cubic syngonia, space group E-43t, 7-4. With the help of the BISMOI 04 |Z, 4) program, the corresponding values of the lattice parameters were calculated. The concentration dependence of the lattice period (drawing) is subject to Vegard's rule and has a monotonic character with a positive deviation from the linear one, which is associated with the disordering (distortion) of the anionic sublattice due to the difference in the crystal chemical radii of Ad" and C" and the change in the ratio of occupancy of equivalent positions during cationic substitution.

The invention can be used to obtain a patent-protected superionic material with high cationic conductivity at room temperature.

Sources:

1. Pat. 120661 Ukraine IPC SZOV 9/00, SZOV 13/00, SZOV 13/04 (2006.01). The method of growing solid solutions of the composition (Sc-xAdh);/syezZ»5I by the method of directed crystallization from melt-solution / Pogodin A.I., Kokhan O.P., Solomon A.M., Izai V.Yu., Studeniak I. P.; applicant and owner of the patent "UzhNU" DVNZ. - MO 120661; y201705597, application 06.06.17.; published 10.11.17., Bull.

Mo 21. - Prototype. 2. Kovba L.M. Radiography in inorganic chemistry / L.M. Kovba. - M.: Moscow State University Publishing House, 1991. - 256 p.

Z. Gotseg 0. Ipdehipud m/yp She 5issezvime aispoiotu teyiyoi, BISMOI 04. // MaietiiaIe Bigisishige. 2004, 11(2), 79. 4. Y osheg Y. Roughdeg racet ipdehipd apa (Zhe dispoiyutu aidogiyt. // 27. KgiviaPyodg. Zirri. 2007,

Claims (1)

26, 191-196. FORMULA OF THE INVENTION The method of growing single crystals of solid solutions of the composition (Си:-хАдх)75иЕвИ (х-0.25, 0.5, 0.75) by the method of directed crystallization from the melt-solution, which includes stepwise heating of vacuumed quartz ampoules at a rate of 100 K/ hours to a temperature of 1023 K and exposure at the same temperature for 24 hours. and further growth of single crystals, which is distinguished by the fact that pre-synthesized halogen chalcogenides Si?5i5vi and Ad5bib5i are used, taken in stoichiometric ratios, heating is carried out at a rate of 50 K/h. to the maximum temperature of 1220-1390 K and holding at this temperature for 72 hours, the growth of single crystals is carried out by the method of directed crystallization from the melt-solution at a speed of 0.4-0.5 mm/h. in vacuumed quartz ampoules, after which the single crystal is cooled to room temperature at a rate of 5 K/h. V. their Knowledge of winter: mini mini zni min pn min nn znih NK g Y Mono ; Mez! ее ШЕ а эн ш 3 - ХА . and Wow! about « and what about | вх ж - I V, I: o - od me pan nn nn A NK shi V BI vo SCHO p me syu AGE Si,