Synthesis, structural, electronic and linear electro-optical features of new quaternary Ag{sub 2}Ga{sub 2}SiS{sub 6} compound
For the first time phase equilibria and phase diagram of the AgGaS{sub 2}–SiS{sub 2} system were successfully explored by differential thermal and X-ray phase analysis methods. Crystal structure of low-temperature (LT) modification of Ag{sub 2}Ga{sub 2}SiS{sub 6} (LÐ Ñž- Ag{sub 2}Ga{sub 2}SiS{sub 6}) was studied by X-ray powder method and it belongs to tetragonal space group I-42d, with unit cell parameters a=5.7164(4) Å, c=9.8023(7) Å, V=320.32(7) Å{sup 3}. Additional details regarding the crystal structure exploration are available at the web page Fachinformationszentrum Karlsruhe. X-ray photoelectron core-level and valence-band spectra were measured for pristine LÐ Ñž- Ag{sub 2}Ga{sub 2}SiS{sub 6} crystal surface. In addition, the X-ray photoelectron valence-band spectrum of LÐ Ñž-Ag{sub 2}Ga{sub 2}SiS{sub 6} was matched on a common energy scale with the X-ray emission S Kβ{sub 1,3} and Ga Kβ{sub 2} bands, which give information on the energy distribution of the S 3p and Ga 4p states, respectively. The presented X-ray spectroscopy results indicate that the valence S p and Ga p atomic states contribute mainly to the upper and central parts of the valence band of LÐ Ñž-Ag{sub 2}Ga{sub 2}SiS{sub 6}, respectively, with a less significant contribution also to other valence-band regions. Band gap energy was estimated by measuring the quantum energy in the spectral range of the fundamental absorption. We have found that energy gap Eg is equal to 2.35 eV at 300 K. LT-Ag{sub 2}Ga{sub 2}SiS{sub 6} is a photosensitive material and reveals two spectral maxima on the curve of spectral photoconductivity spectra at λ{sub max1} =590 nm and λ{sub max2} =860 nm. Additionally, linear electro-optical effect of LT-Ag{sub 2}Ga{sub 2}SiS{sub 6} for the wavelengths of a cw He-Ne laser at 1150 nm was explored. - Graphical abstract: Manuscript present the technology of growth and investigation of properties a new quaternary compound Ag{sub 2}Ga{sub 2}SiS{sub 6} including the detailed study of the phase equilibria in the AgGaS{sub 2}–SiS{sub 2} system to determine the physico-chemical conditions of its formation. We examined crystal structure of the compound by X-ray powder method, its electronic structure by XPS method. Finally we have found these crystals like promising material for nonlinear optical, electrooptical and piezoelectric applications. - Highlights: • Phase diagram of the AgGaS{sub 2}–SiS{sub 2} system was successfully described at first time. • Crystal Ag{sub 2}Ga{sub 2}SiS{sub 6} was grown and its structure was determined. • Electronic structure and chemical bonding of the Ag{sub 2}Ga{sub 2}SiS{sub 6} crystal were examined by. • X-ray photoelectron spectroscopy (XPS) and X-ray emission spectroscopy (XES) methods. • Optical and photoelectrical properties were investigated.