ABSTRACT
The semiconductor Cu2ZnSnSe4 (CZTSe) is a promising candidate for both thermoelectric and photovoltaic energy harvesting applications due to a combination of features such as direct band gap, high absorption coefficient, and low thermal conductivity. We report the solid-state synthesis and characterization of Mn-doped Cu2Zn1-xMnxSnSe4 (x = 0, 0.05, 0.10, and 0.15) in an attempt to explore the effect of isovalent substitution at the Zn site. X-ray diffraction and Raman spectroscopy of all specimens confirmed the formation of a single-phase tetragonal kesterite structure (space group I4Ì ). The band gap obtained by UV-visible diffuse reflectance measurements was 1.42 eV for all compositions. Thermoelectric properties were measured in the range 300-785 K. Electrical resistivity was metallic and reduced on Mn doping, while the Seebeck coefficient exhibited a p-type semiconducting behavior that enhanced on Mn doping, with associated enhancement of the power factor. Lattice thermal conductivity showed a 1/T behavior, falling from about 1.9-2.7 W m-1 K-1 at 300 K to 0.51-0.9 W m-1 K-1 above 750 K. The combined effect of enhanced power factor and reduced lattice thermal conductivity resulted in a figure of merit ZT in the range of 0.19-0.42 above 750 K. Thin-film photovoltaic devices with a CZTSe absorber and an SnSe electron transport layer gave 3.2% efficiency.
ABSTRACT
A number of Dzyaloshinskii-Moriya interaction (DMI) driven canted antiferromagnets or weak ferromagnets (WFM) including hematite exhibit two distinct time scales in magnetization relaxation measurements, one of which is ultra-slow. This leads to the observation of a part of remanence that is time-stable in character. In this work, our endeavor is to optimize the magnitude of this time-stable remanence for the hematite, a room temperature WFM, as a function of shape size and morphology. A substantial enhancement in the magnitude of this unique remanence is observed in porous hematite, consisting of ultra-small nano particles, as compared to crystallites grown in regular morphology, such as cuboids or hexagonal plates. This time-stable remanence exhibits a peak-like pattern with magnetic field, which is significantly sharper in porous sample. Experimental data suggest that the extent and the magnitude of the spin canting associated with the WFM phase can be best gauged by the presence of this remanence and its unusual magnetic field dependence. Temperature variation of lattice parameters bring out correlations between strain effects that alter the bond length and bond angle associated with primary super exchange paths, which in-turn systematically alter the magnitude of the time-stable remanence. This study provides insights regarding a long standing problems of anomalies in the magnitude of magnetization on repeated cooling in case of hematite. Our data caps on these anomalies, which we argue, arise due to spontaneous spin canting associated with WFM phase. Our results also elucidate on why thermal cycling protocols during bulk magnetization measurements are even more crucial for hematite which exhibits both canted as well as pure antiferromgnetic phase.