Structural studies of mechano-chemically synthesized CuIn1−xGaxSe2 nanoparticles

CuInGaSe2 is a I–III–VI2 semiconducting material of tetragonal chalcopyrite structure. It is a very prominent absorber layer for photovoltaic devices. Particle-based coating process for CIGS is considered to be promising technique with relatively simple procedures and low initial investment. In the present work CIGS nanoparticle precursors suitable for screen-printing ink has been prepared by ball milling. High purity elemental copper granules, selenium and indium powders and fine chips of gallium were used as starting materials. First the ball milling was carried out for CuIn1−xGaxSe2 (x = 0.5) with (i) 10 ml of ethyl alcohol (ii) 5 ml of tetra ethylene glycol (wet) and (iii) 1 ml of ethylene diamine (semi-dry) for a milling time of 3 h and the results are not stoichiometric. In order to obtain an improved stoichiometric composition dry ball milling of elemental sources for three different compositions of CuIn1−xGaxSe2 (x = 0.25, 0.5 and 0.75) has been carried out. X-ray diffraction analysis revealed the presence of (1 1 2), (2 2 0)/(2 0 4), (3 1 2)/(1 1 6), (4 0 0) and (3 3 2) reflections for all the milled powders. These reflections correspond to chalcopyrite structure of CIGS. Shift in peaks towards higher value of 2θ is observed with the increase in Ga composition. Average grain size calculated by Scherrer's formula is found to be around 13 nm for the dry samples milled for 1.5 h and 7–8 nm for the samples wet milled for 3 h. Lattice constants ‘a’ and ‘c’ are found to decrease with the increase in concentration of Gallium. FESEM analysis revealed a strong agglomeration of the particles and the particle size varied from 11 to 30 nm for the dry-milled samples. Composition of milled powders has been studied by energy dispersive X-ray analysis. TEM analysis revealed the presence of nanocrystalline particles and SAED pattern corresponds to (1 1 2), (2 2 0)/(2 0 4), (5 1 2)/(4 1 7) and (6 2 0)/(6 0 4) diffraction peaks of CIGS. From the HRTEM analysis the d-spacing values were evaluated and found to be 1.06, 3.33, 2.03 and 0.906 Å corresponding to the diffraction pattern. Also the planes corresponding to the nanoparticles have been simulated and matched with the HRTEM pattern. Raman spectra show the intense peak at 168–172 cm−1, which corresponds to the chalcopyrite structure.