The beneficial effects of heavy alkali metals such as K, Rb, and Cs in enhancing Cu(In,Ga)Se2 (CIGS) photovoltaic efficiencies are widely known, though the detailed mechanism is still open for discussion. In the present work, the effects of the lightest alkali metal, Li, on CIGS thin-film and device properties are focused upon and compared to the effects of heavy alkali metals. Till date, the beneficial effects of elemental Li on Cu2ZnSnS4 photovoltaic devices in enhancing efficiencies have been reported. On the other hand, it is shown in the present work that the beneficial effects of Li on CIGS are not so significant. In contrast to the effects of Na or Rb in enhancing CIGS(112) growth orientation, Li was revealed not to affect CIGS growth orientation. The most distinctive feature observed between Li and other alkali metals was the elemental depth profile in CIGS films. Namely, Na and heavier alkali metals show a concentration peak near the surface (relatively Cu-poor) region of CIGS films, whereas elemental Li showed no such trend, suggesting that Li has no significant effect on CIGS surface modification. Nonetheless, Li was found to have some effect in enhancing the PL peak intensity and photovoltaic performance of CIGS, though the effect is relatively small in comparison to that obtained with other alkali metals.
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