First-principles study on alkali-metal effect of Li, Na, and K in CuInSe2 and CuGaSe2

The substitution energies and migration energies of the alkali metal atoms of Li, Na, and K in CuInSe2 (CIS) and CuGaSe2 (CGS) were investigated by first-principles calculations. The substitution energies of Li, Na, and K atoms in CIS and CGS were calculated for two different cationic atom positions of Cu and In/Ga in the chalcopyrite unit cell. In CIS and CGS, the substitution energies of NaCu are much lower than those of NaIn and NaGa. The substitution energies of the LiCu atoms in CIS and CGS are lower than those of NaCu, while the substitution energies of KCu atoms in CIS and CGS are much higher than those of NaCu. Therefore, it is difficult to form KCu in CIS and CGS. The migration energies of Li, Na, and K atoms in CIS and CGS are obtained by a combination of the linear and quadratic synchronous transit (LST/QST) methods and the nudged elastic band (NEB) method. The theoretical migration energies of a Na atom at the Cu site to the nearest Cu vacancy (Na-Cu -> V-Cu) in CIS and CGS are much lower than those of (Cu-Cu -> V-Cu) in CIS and CGS. The mechanism underlying the alkali metal effect of Li, Na, and K in the CIGS film during the post-deposition treatment of LiF, NaF, and KF is discussed on the basis of the calculated substitution and migration energies. (C) 2015 The Japan Society of Applied Physics