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AbstractA new apparatus was built to rapidly cool molten salts in liquid argon to prevent contamination during quenching and enable new insight into the structure in the liquid state. To test the applicability of the apparatus, several industrially relevant chloride salt compositions were first melted, rapidly solidified, and then characterized. The design proved applicable for the rapid quenching of molten salt. Furthermore, the structure of the apparatus prevented exposure of the rapidly quenched salt to impurities (humidity, oxygen, etc.). X-ray diffraction of salt specimens cooled with and without liquid argon showed differences including a structure further from the expected stoichiometric equilibrium with rapid cooling. Of particular interest is the chemical state of metallic impurities, and this may be probed using electron paramagnetic resonance.

Nanomaterials are naturally metastable with respect to bulk solids. This raises the very important fundamental problem of their morphological stability, especially when nanoscale crystallites are touching or nearly touching each other, such as in thin-film devices. In some cases, nanostructuring must be preserved under operational conditions (e.g., in quantum dot LEDs, lasers, photodetectors, and nanogranular thermoelectric devices). In other cases, we use nanocrystalline particles as precursors to a material with large crystalline grains and aim to sinter them as efficiently as possible (e.g., in polycrystalline thin-film solar cells). We carried out a systematic study of sintering and grain growth in materials composed of various sub-10 nm semiconductor grains. The boundaries between individual semiconductor grains have been chemically engineered using inorganic surface ligands. We found that the early stages of sintering and grain growth of nanocrystalline semiconductors are controlled by the ion mobility at the nanocrystal surfaces, while the late stages of grain growth are controlled by the mobility of the grain boundaries. This appears to be a general phenomenon for semiconductor nanocrystals, and it leads to several interesting and counterintuitive trends. For example, III–V InAs nanocrystals are generally much more resilient against sintering and grain growth compared to II–VI CdSe nanocrystals even though bulk CdSe has significantly higher melting point temperature than InAs (1268 °C vs 942 °C). Grain growth can be dramatically accelerated when coupled to solid−solid phase transitions. These findings expand our toolbox for rational design of nanocrystal materials for different applications.

Roll-to-roll (R2R) device fabrication using solution-processed materials is a cheap and versatile approach that has attracted widespread interest over the past 2 decades. Here, we systematically introduce and investigate R2R-friendly modifications in the fabrication of ultrathin, sintered CdTe nanocrystal (NC) solar cells. These include (1) scalable deposition techniques such as spray-coating and doctor-blading, (2) a bath-free, controllable sintering of CdTe NCs by quantitative addition of a sintering agent, and (3) radiative heating with an infrared lamp. The impact of each modification on the CdTe nanostructure and solar cell performance was first independently studied and compared to the standard, non-R2R-friendly procedure involving spin-coating the NCs, soaking in a CdCl2bath, and annealing on a hot plate. The R2R-friendly techniques were then combined into a single, integrated process, yielding devices that reach 10.4% power conversion efficiency with a Voc, Jsc, and FF of 697 mV, 22.2 mA/cm2, and 67%, respectively, after current/light soaking. These advances reduce the barrier for large-scale manufacturing of solution-processed, ultralow-cost solar cells on flexible or curved substrates.