Abstract:
Single crystals of Cu2ZnGeSe4 and Cu2ZnGeS4 solid solutions were developed and successfully
obtained using the chemical vapor transfer method, with iodine acting as a transporter. The
structure, compositional dependences of lattice parameters, pycnometric and X-ray densities and
microhardness were determined. The chemical composition determined by the X-ray microanalysis satisfactorily corresponds to the nominal one with a tolerance of ±5 %. The XRD analysis
showed that all the obtained compounds and their solid solutions have unit cell described by
tetragonal symmetry. The attice parameters were found to be а = 5.342 ± 0.005 Å, с = 10.51 ±
0.01 Å for the Сu2ZnGeS4 compound and а = 5.607 ± 0.005 Å, с = 11.04 ± 0.01 Å for the
Cu2ZnGeSe4, respectively. Structural studies confirmed the validity of the Vegard’s law in relation
to the obtained samples. The pycnometric densities of ~4.28 g/cm3 for the Cu2ZnGeS4 and
~5.46 g/cm3 for the Cu2ZnGeSe4 were found to be slightly less than their X-ray densities of
~4.32 g/cm3 and ~5.52 g/cm3
, respectively. The maximum microhardness of ~398 kg/mm2 for
these solid solutions corresponds to x = 0.60. The melt point of the solid solutions increases from
~1180 ◦C for the Сu2ZnGeSe4 up to ~1400 ◦C for the Сu2ZnGeS4. Based on X-ray fluorescence
analysis and DTA data, the phase diagram of the Cu2ZnGeSe4-Cu2ZnGeS4 system was constructed.
Analysis of the obtained diagram indicates its first type according to Rozbom’s classification.
