Thin-film photovoltaic devices based on chalcopyrite Cu(In,Ga)Se2 (CIGS) absorber layers show excellent light-to-power conversion efficiencies exceeding 20%. This high performance level requires a small amount of alkaline metals incorporated into the CIGS layer, naturally provided by soda lime glass substrates used for processing of champion devices. The use of flexible substrates requires distinct incorporation of the alkaline metals, and so far mainly Na was believed to be the most favourable element, whereas other alkaline metals have resulted in significantly inferior device performance. Here we present a new sequential post-deposition treatment of the CIGS layer with sodium and potassium fluoride that enables fabrication of flexible photovoltaic devices with a remarkable conversion efficiency due to modified interface properties and mitigation of optical losses in the CdS buffer layer. The described treatment leads to a significant depletion of Cu and Ga concentrations in the CIGS near-surface region and enables a significant thickness reduction of the CdS buffer layer without the commonly observed losses in photovoltaic parameters. Ion exchange processes, well known in other research areas, are proposed as underlying mechanisms responsible for the changes in chemical composition of the deposited CIGS layer and interface properties of the heterojunction.

The introduction of a KF post-deposition treatment (KF PDT) of Cu(In,Ga)Se 2 (CIGS) thin films has led to the achievement of several consecutive new world record efficiencies up to 21.7% for the CIGS solar cell technology. The beneficial effect of the KF PDT on the photovoltaic parameters was observed by several groups in spite of differing growth methods of the CIGS layer. For CIGS evaporated at lower temperature on alkali-free, flexible plastic substrates, a postdeposition treatment to add Na was already successfully applied. However with the introduction of additional KF under comparable conditions, distinctly different influences on the final absorber alkali content as well as surface properties are observed. In this work we discuss in more details the intrinsically different role of both alkali-treatments by combining several microstructural and compositional analysis methods. The ion exchange of Na by K in the bulk of the absorber is carefully analyzed, and further evidences for the formation of a K-containing layer on the CIGS surface with increased surface reactivity are given. These results shall serve as a basis for the further understanding of the effects of alkali PDT on CIGS and help identifying research needs to achieve even higher efficiencies.

In this work, a systematic study of the effect of electron dose rate, solute concentration, imaging mode (broad beam vs scanning probe mode), and liquid cell setup (static vs flow mode) on the growth mechanism and the ultimate morphology of Au nanoparticles (NPs) was performed in chloroauric acid (HAuCl4) aqueous solutions using in situ liquid-cell TEM (LC-TEM). It was found that a diffusion limited growth dominates at high dose rates, especially for the solution with the lowest concentration (1 mM), resulting in formation of dendritic NPs. Growth of 2D Au plates driven by a reaction limited mechanism was only observed at low dose rates for the 1 mM solution. For the 5 mM and 20 mM solutions, reaction limited growth can still be induced at higher dose rates, due to abundance of the precursor available in the solutions, leading to formation of 2D plates or 3D faceted NPs. As a proof-of-concept, an Au nanostructure with a 3D faceted particle core and a dendritic shell can be in situ produced by simply tuning the electron dose in the 1 mM solution irradiated in a flow cell setup in the STEM mode. This work paves the way to study the growth of complex heteronanostructures composed of multiple elements in LC-TEM.

Large-grained CuInSe 2 absorber layers are synthesized using a non-vacuum process based on nanoparticle ink precursors and selenization by rapid thermal processing (RTP). The use of hydroxide-based particles in organic solvents allows for the conversion with elemental selenium without the need to employ explosive and/or toxic H 2 or H 2 Se gasses. Lateral grain sizes up to 4 μm are obtained through a novel RTP route, overcoming the inherently high layer porosity for previous nanoparticle processes. Morphological and elemental characterization at interrupted selenization steps suggests that liquid selenium can play a beneficial role in promoting layer densification and grain growth. Long carrier collection lengths in CuInSe 2 enable notable conversion efficiencies, despite the low minority carrier lifetimes of below 1 ns. Record efficiencies up to 8.73% highlight the potential of low-cost, non-vacuum deposition of chalcopyrite absorber layers with safe and simple precursors and processing routes.