Thin-film solar cells based on Cu(In,Ga)Se 2 (CIGS) absorbers have achieved conversion efficiencies close to 23%. Such a high performance could be reached by incorporating heavy alkali elements into the CIGS absorber using an alkali fluoride post-deposition treatment (PDT). In order to improve the understanding of the effect of the PDT, we investigated a highly efficient CIGS solar cell whose absorber was subjected to a RbF-PDT. By applying synchrotron-based X-ray fluorescence analysis in combination with scanning transmission electron microscopy and electron backscatter diffraction to a cross-sectional lamella of the whole device, we were able to correlate the local composition of the absorber with its microstructure. The incorporated Rb accumulates at grain boundaries, with a random misorientation of the adjacent grains, at the p−n junction, and at the interface between the absorber and the MoSe 2 layer. The accumulation of Rb at the grain boundaries is accompanied by a reduced Cu concentration and slightly increased In and Se concentrations. Additionally, variations in the local composition of the absorber at the p−n junction indicate the formation of a secondary phase, which exhibits a laterally inhomogeneous distribution. The improved solar cell performance due to RbF-PDT can thus be expected to originate from a favorable modification of the back contact interface, the random grain boundaries, the p−n junction, or a combination of these effects.
Example of an advanced characterization study of a complex system (thin film solar cell) that may serve as an instructive handbook to help building up the full picture of multilayer-based devices for a broad spectrum of readers and researchers.
The presence of Ge during the synthesis of thin film
kesterite
Cu2ZnSnSe4 (CZTSe) solar cell absorbers boosts
their power conversion efficiency, especially due to an improved open
circuit voltage. The mechanism underlying this beneficial effect of
Ge is still under debate. We gained deep insights into the role of
Ge by applying advanced synchrotron nanoprobe-based X-ray fluorescence
spectroscopy and X-ray absorption near-edge structure spectroscopy
to cross-sectional lamellas taken from high efficiency devices. We
observe that Ge remains in the CZTSe absorber layer after the synthesis
process with a specific heterogeneous distribution. Different grains
contain different Ge concentrations. Moreover, Ge depletion exists
at random grain boundaries but not at symmetric Σ3-boundaries,
leading to different band alignments. The incorporated Ge occupies
Sn lattice sites in the CZTSe crystal structure; however, the concentration
is only 0.1 to 0.5 at %. Also Ge aggregates in nanoscale inclusions,
which we could identify to be GeO2 that likely lessen the
beneficial effect of Ge on the photovoltaic performance.
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