THE QUATERNARY CHALCOGENIDE COMPOUND Ag2FeGeSe4: A REVISION OF THEIR CRYSTAL STRUCTURE AND MAGNETIC PROPERTIES

Abstract

Background: Quaternary compounds bellowing to the I2-II-IV-VI4 system are of considerable technological interest due to their possible use in the preparation of solar cell and thermoelectric materials devices. In recent years, considerable attention has been focused on the detailed study of quaternary chalcogenide compounds related to the chalcopyrite compounds, particularly AgInSe2, which has emerged as a leading material for the preparation of photovoltaic devices due to their potential applications in solar cell technology. Aims: This work focuses on synthesis, chemical analysis, thermal study, magnetism measurement, and crystal structural characterization of the quaternary semiconductor Ag2FeGeSe4, an essential member of the family I2-II-IV-VI4. Methods: This material was synthesized by the melt and anneal technique. The chemical analysis was carried out by scanning electron microscopy (SEM) and differential thermal analysis (DTA). Magnetic susceptibility () as a function of temperature and magnetization as a function of the magnetic field were also performed, and crystal structure analysis was made employing the Rietveld method with powder X-ray diffraction data. Results and Discussion: The preparation confirms the formation of the quaternary compound with stoichiometric 2:1:1:4 according to the chemical analysis. This quaternary compound melt at 1015 K, and show an antiferromagnetic behavior with Neel temperature TN of 240 K. The Debye temperature (D) estimated for this compound was 194 K. The quaternary chalcogenide compound Ag2FeGeSe4 crystallizes in the orthorhombic space group Pmn21, Z = 4, with unit cell parameters: a = 7.6478(1) Å, b = 6.5071(1) Å, c = 6.4260(1) Å, and V = 319.79(1) Å3, in a wurtzite-stannite arrangement with a Cu2CdGeS4-type structure, which is characterized by a three-dimensional arrangement of slightly distorted AgSe4, FeSe4, and GeSe4 tetrahedra connected by corners. In this structure, each Se atom is coordinated by four cations located at the corners of a slightly distorted tetrahedron, and each cation is tetrahedrally bonded to four anions. Conclusions: The melt and anneal method remains effective for preparing compounds chalcogenides as the quaternary Ag2FeGeSe4, a new member of I2-II-IV-VI4 family of semiconductors, which crystallizes in the non-centrosymmetric space group Pmn21 with diamond-like structure. The crystal structure information of this compound allows explaining their magnetic properties, which in combination with its semiconductor properties make this material a potential aspirant for different applications, mainly in solar cells.