Effect of Alkali Metal Atom Doping on the CuInSe2-Based Solar Cell Absorber

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School of Science | A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
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Volume 121, Issue 29, The Journal of Physical Chemistry Part C
The efficiency of Cu(In,Ga)Se_2 (CIGS)-based solar cells can bemarkedly improved by controlled introduction of alkali metal (AM) atomsusing post-deposition treatment (PDT) after CIGS growth. Previous studieshave indicated that AM atoms may act as impurities or agglomerate intosecondary phases. To enable further progress, understanding of atomic levelprocesses responsible for these improvements is required. To this end, we haveinvestigated theoretically the effects of the AM elements Li, Na, K, Rb, and Cson the properties of the parent material CuInSe_2 . First, the effects of the AMimpurities in CuInSe_2 have been investigated in terms of formation energies,charge transition levels, and migration energy barriers. We found that AM atoms preferentially substitute for Cu atoms at theneutral charge state. Under In-poor conditions, AM atoms at the In site also show low formation energies and are acceptors. Themigration energy barriers show that the interstitial diffusion mechanism may be relevant only for Li, Na, and K, whereas all theAM atoms can diffuse with the help of Cu vacancies. The competition between these two mechanisms strongly depends on theconcentration of Cu vacancies. We also discuss how AM atoms can contribute to increasing Cu-depleted regions. Second, AMatoms can form secondary phases with Se and In atoms. We suggest a mechanism for the secondary phase formation followingthe PDT process. On the basis of the calculated reaction enthalpies and migration considerations, we find that mixed phases aremore likely in the case of LiInSe_2 and NaInSe_2 , whereas formation of secondary phases is expected for KInSe_2 , RbInSe_2 , andCsInSe_2 . We discuss our findings in the light of experimental results obtained for AM treatments. The secondary phases havelarge energy band gaps and improve the morphology of the buffer surface by enabling a favorable band alignment, which canimprove the electrical properties of the device. Moreover, they can also passivate the surface by forming a diffusion barrier.Overall, our work points to different roles played by the light and heavy AM atoms and suggests that both types may be neededto maximize their benefits on the solar cell performance.
solar cell, alkali, CIGS, DFT
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Malitckaya, M. & Komsa, H.-P. & Havu, V. & Puska, M. J. 2017. Effect of Alkali Metal Atom Doping on the CuInSe2-Based Solar Cell Absorber. The Journal of Physical Chemistry Part C. Volume 121, Issue 29. 15516-15528. DOI: 10.1021/acs.jpcc.7b03083.