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

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.Peer reviewe

The fox and the hound:in-depth and in-grain Na doping and Ga grading in Cu(In,Ga)Se₂ solar cells

Abstract Cu(In,Ga)(S,Se)₂ (CIGS) thin film solar cells require appropriate depth and lateral distributions of alkali metal dopants and gallium to attain world record photovoltaic energy conversion. The two requirements are interdependent because sodium is known to hamper In/Ga interdiffusion in polycrystalline films. However, such a fact is challenged by recent findings where sodium appears to enhance In/Ga interdiffusion in monocrystalline films. This contribution reviews closely the two cases to the benefits of grain boundary engineering in CIGS. A computational model reveals why Na induces In accumulation at CIGS grain boundaries, confining Ga to grain interiors. The positive technological implications for wider gap chalcopyrites are stressed

Heavy Alkali Treatment of Cu In,Ga Se2 Solar Cells Surface versus Bulk Effects

International audienc

Chemical instability at chalcogenide surfaces impacts chalcopyrite devices well beyond the surface

The electrical and optoelectronic properties of materials are determined by the chemical potentials of their constituents. The relative density of point defects is thus controlled, allowing to craft microstructure, trap densities and doping levels. Here, we show that the chemical potentials of chalcogenide materials near the edge of their existence region are not only determined during growth but also at room temperature by post-processing. In particular, we study the generation of anion vacancies, which are critical defects in chalcogenide semiconductors and topological insulators. The example of CuInSe2 photovoltaic semiconductor reveals that single phase material crosses the phase boundary and forms surface secondary phases upon oxidation, thereby creating anion vacancies. The arising metastable point defect population explains a common root cause of performance losses. This study shows how selective defect annihilation is attained with tailored chemical treatments that mitigate anion vacancy formation and improve the performance of CuInSe2 solar cells