Abstract
Cu(In, Ga)$Se_2$ (CIGS) precursor films were electrodeposited on Mo/glass substrates in acidic solutions containing $Cu^{2+}$, $In^{3+}$, $Ga^{3+}$, and $Se^{4+}$ ions at -0.6 V (SCE) and pH. 1.8. In order to induce recrystallization, the electrodeposited $Cu_{1.00}In_{0.81}Ga_{0.09}Se_{2.08}$ (25.0 at.% Cu + 20.2 at.% In + 2.2 at.% Ga + 52.0 at.% Se) precursor films were annealed under a high Se gas atmosphere for 15, 30, 45, and 60 min, respectively, at $500^{\circ}C$. The Se amount in the film increased from 52 at.% to 62 at.%, whereas the In amount in the film decreased from 20.8 at.% to 9.1 at.% as the annealing time increased from 0 (asdeposited state) to 60 min. These results were attributed to the Se introduced from the furnace atmosphere and reacted with the In present in the precursor films, resulting in the formation of the volatile $In_2Se$. CIGS precursor grains with a cauliflower shape grew as larger grains with the $CuSe_2$ and/or $Cu_{2-x}Se$ faceted phases as the annealing times increased. These faceted phases resulted in rough surface morphologies of the CIGS films. Furthermore, the CIGS layers were not dense because the empty spaces between the grains were not removed via annealing. Uniform thicknesses of the $MoSe_2$ layers occurred at the 45 and 60 min annealing time. This implies that there was a stable reaction between the Mo back electrode and the Se diffused through the CIGS film. The results obtained in the present research were sufficiently different from comparable studies where the recrystallization annealing was performed under an atmosphere of Ar gas only or a low Se gas pressure.
