Growing crystals and studying structure and electronic properties of Cu2ZnGe(SÑ Se1-x)4 compositions.

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.

Magnetotransport and conductivity mechanisms in Cu2ZnSnxGe1-xS4 single crystals.

Resistivity, ρ(T), and magnetoresistance (MR) are investigated in the Cu2ZnSnxGe1-xS4 single crystals, obtained by the chemical vapor transport method, between x = 0-0.70, in the temperature range of T ~ 50-300 K in pulsed magnetic field of B up to 20 T. The Mott variable-range hopping (VRH) conductivity is observed within broad temperature intervals, lying inside that of T ~ 80-180 K for different x. The nearest-neighbor hopping conductivity and the charge transfer, connected to activation of holes into the delocalized states of the acceptor band, are identified above and below the Mott VRH conduction domain, respectively. The microscopic electronic parameters, including width of the acceptor band, the localization radius and the density of the localized states at the Fermi level, as well as the acceptor concentration and the critical concentration of the metal-insulator transition, are obtained with the analysis of the ρ(T) and MR data. All the parameters above exhibit extremums near x = 0.13, which are attributable mainly to the transition from the stannite crystal structure at x = 0 to the kesterite-like structure near x = 0.13. The detailed analysis of the activation energy in the low-temperature interval permitted estimations of contributions from different crystal phases of the border compounds into the alloy structure at different compositions.

RF Electromagnetic Field Treatment of Tetragonal Kesterite CZTSSe Light Absorbers.

In this work, we propose a method to improve electro-optical and structural parameters of light-absorbing kesterite materials. It relies on the application of weak power hydrogen plasma discharges using electromagnetic field of radio frequency range, which improves homogeneity of the samples. The method allows to reduce strain of light absorbers and is suitable for designing solar cells based on multilayered thin film structures. Structural characteristics of tetragonal kesterite Cu2ZnSn(S, Se)4 structures and their optical properties were studied by Raman, infrared, and reflectance spectroscopies. They revealed a reduction of the sample reflectivity after RF treatment and a modification of the energy band structure.

Polarized Raman scattering study of kesterite type Cu2ZnSnS4 single crystals.

A non-destructive Raman spectroscopy has been widely used as a complimentary method to X-ray diffraction characterization of Cu2ZnSnS4 (CZTS) thin films, yet our knowledge of the Raman active fundamental modes in this material is far from complete. Focusing on polarized Raman spectroscopy provides important information about the relationship between Raman modes and CZTS crystal structure. In this framework the zone-center optical phonons of CZTS, which is most usually examined in active layers of the CZTS based solar cells, are studied by polarized resonant and non-resonant Raman spectroscopy in the range from 60 to 500 cm(-1) on an oriented single crystal. The phonon mode symmetry of 20 modes from the 27 possible vibrational modes of the kesterite structure is experimentally determined. From in-plane angular dependences of the phonon modes intensities Raman tensor elements are also derived. Whereas a strong intensity enhancement of the polar E and B symmetry modes is induced under resonance conditions, no mode intensity dependence on the incident and scattered light polarization configurations was found in these conditions. Finally, Lyddane-Sachs-Teller relations are applied to estimate the ratios of the static to high-frequency optic dielectric constants parallel and perpendicular to c-optical axis.