J. Mater. Sci. Technol. ›› 2021, Vol. 76: 111-121.DOI: 10.1016/j.jmst.2020.10.026

• Research Article • Previous Articles     Next Articles

Negative thermal expansion in one-dimension of a new double sulfate AgHo(SO4)2 with isolated SO4 tetrahedra

Yuriy G. Denisenkoa,b,c, Victor V. Atuchind,e,f,*(), Maxim S. Molokeevg,h,i, Naizheng Wangj, Xingxing Jiangj, Aleksandr S. Aleksandrovskyk,l, Alexander S. Krylovm, Aleksandr S. Oreshonkovh,j, Alexander E. Sedykhb,h, Svetlana S. Volkovaa, Zheshuai Linj,o, Oleg V. Andreeva,p, Klaus Müller-Buschbaumb,n   

  1. a Institute of Chemistry, Tyumen State University, Tyumen, 625003, Russia
    b Institute of Inorganic and Analytical Chemistry, Justus-Liebig-University of Giessen, 35392, Giessen, Germany
    c Department of General and Special Chemistry, Industrial University of Tyumen, Tyumen, 625000, Russia
    d Laboratory of Optical Materials and Structures, Institute of Semiconductor Physics, SB RAS, Novosibirsk, 630090, Russia
    e Laboratory of Semiconductor and Dielectric Materials, Novosibirsk State University, Novosibirsk, 630090, Russia
    f Research and Development Department, Kemerovo State University, Kemerovo, 650000, Russia
    g Laboratory of Crystal Physics, Kirensky Institute of Physics, Federal Research Center KSC SB RAS, Krasnoyarsk, 660036, Russia
    h Siberian Federal University, Krasnoyarsk, 660041, Russia
    i Department of Physics, Far Eastern State Transport University, Khabarovsk, 680021, Russia
    j Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190, China
    k Laboratory of Coherent Optics, Kirensky Institute of Physics, Federal Research Center KSC SB RAS, Krasnoyarsk, 660036, Russia
    l Institute of Nanotechnology, Spectroscopy and Quantum Chemistry, Siberian Federal University, Krasnoyarsk, 660041, Russia
    m Laboratory of Molecular Spectroscopy, Kirensky Institute of Physics, Federal Research Center KSC SB RAS, Krasnoyarsk, 660036, Russia
    n Center for Materials Research (LaMa), Justus-Liebig-University Giessen, Giessen, 35392, Germany
    o University of the Chinese Academy of Sciences, Beijing, 100049, China
    p Laboratory of the Chemistry of Rare Earth Compounds, Institute of Solid State Chemistry, UB RAS, Ekaterinburg, 620137, Russia
  • Received:2020-06-26 Revised:2020-08-03 Accepted:2020-08-15 Published:2021-06-20 Online:2020-10-27
  • Contact: Victor V. Atuchin
  • About author:*Laboratory of Optical Materials and Structures, Insti-tute of Semiconductor Physics, SB RAS, Novosibirsk, 630090, Russia.E-mail address: atuchin@isp.nsc.ru (V.V. Atuchin).

Abstract:

A double holmium-silver sulfate was obtained for the first time. The temperature intervals for the formation and stability of the compound were determined by differential scanning calorimetry. The crystal structure of AgHo(SO4)2 was determined by Rietveld method. The X-ray diffraction (XRD) analysis showed that the compound crystallizes in the monoclinic syngony, space group P21/m, with the unit cell parameters a = 4.71751 (4) Å, b = 6.84940 (6) Å and c = 9.89528 (9) Å, β = 95.1466 (4)°, V = 318.448 (5) Å3, Z = 2, RB = 1.55 %, T = 303 K. Two types of sulfate tetrahedra were found in the structure, which significantly affected the spectral properties in the infrared range. In the temperature range of 143-703 K, a negative thermal expansion along the b direction accompanied by a positive thermal expansion along the a and c directions was observed. It was established that negative thermal expansion is the result of the deformation of sulfate tetrahedra, which is affected by the movement of holmium and silver atoms. The excitation in the blue spectral range (457.9 nm) produces a luminescence in light blue (489 nm), green (545 nm) and red (654 nm) spectral ranges, and the latter two were of comparable intensity that is favorable for WLED sources. The observed luminescent band distribution is ascribed to the specific crystal field at Ho3+ ion sites rather than a variation of radiationless probability.

Key words: Sulfate, Crystal structure, Thermal expansion, Raman, Photoluminescence, Band structure