Electrochemical Formation of Divalent Samarium Cation and Its Characteristics in LiCl-KCl Melt.

The electrochemical reduction of trivalent samarium in a LiCl-KCl eutectic melt produced highly stable divalent samarium, whose electrochemical properties and electronic structure in the molten salt were investigated using cyclic voltammetry, UV-vis absorption spectroscopy, laser-induced emission spectroscopy, and density functional theory (DFT) calculations. Diffusion coefficients of Sm2+ and Sm3+ were electrochemically measured to be 0.92 × 10-5 and 1.10 × 10-5 cm2/s, respectively, and the standard apparent potential of the Sm2+/3+ couple was estimated to be -0.82 V vs Ag|Ag+ at 450 °C. The spectroelectrochemical study demonstrated that the redox behavior of the samarium cations obeys the Nernst equation ( E°' = -0.83 V, n = 1) and the trivalent samarium cation was successfully converted to the divalent cation having characteristic absorption bands at 380 and 530 nm with molar absorptivity values of 1470 and 810 M-1 cm-1, respectively. Density function theory calculations for the divalent samarium complex revealed that the absorption signals originated from the 4f6 to 4f55d1 transitions. Additionally, laser-induced emission measurements for the Sm cations in the LiCl-KCl matrix showed that the Sm3+ ion in the LiCl-KCl melt at 450 °C emitted an orange color of fluorescence, whereas a red colored emission was observed from the Sm2+ ion in the solidified LCl-KCl salt at room temperature.

Effect of multi-armed triphenylamine-based hole transporting materials for high performance perovskite solar cells.

A series of hole-transporting materials (HTMs) based on [2,2]paracyclophane and triphenyl-amine (TPA) was synthesized. We studied the effect of the chemical structure of the HTM on the photovoltaic performance of perovskite solar cells by varying the number of TPA charge transporting components in the HTM. Tetra-TPA, in which four TPAs are incorporated into the [2,2]paracyclophane core, exhibited better hole transport properties than di-TPA and tri-TPA, which contain two and three TPAs, respectively. In particular, incorporation of the TPA group with a multi-armed structure effectively enhanced the conductivity of the HTM layer in the out-of-plane direction in the solar cell device. Due to the improved charge transport and appropriate molecular energy levels of tetra-TPA, the perovskite solar cell based on the tetra-TPA HTM achieved higher Jsc and FF values than the devices based on di-TPA and tri-TPA HTMs, with a high solar cell efficiency (17.9%).