(Invited) Phase Stable and Less-Defect Perovskite Quantum Dots: Optical Property, Photoexcited Carrier Dynamics, and Application to Solar Cells

Abstract

Perovskite quantum dots (QDs) as a new type of colloidal nanocrystals have gained significant attention for both fundamental research and commercial applications owing to their appealing optoelectronic properties and excellent chemical processability.1 For their wide range of potential applications, synthesizing colloidal QDs with high crystal quality is of crucial importance. However, like most common QD systems, those reported perovskite QDs still suffer from a certain density of trapping defects, giving rise to detrimental non-radiative recombination centers and thus low photoluminescence quantum yield (PL QY). Halide vacancy in perovskites has been widely accepted to be the main factor preventing near-unity PL QY by creating uncoordinated Pb octahedra and the subsequent localized deep trap states.2 Very recently, we have succeeded in synthesis of phase-stable and less-defect perovskite QDs, including FAPbI3 QDs, CsPbI3 QDs and Sn-Pb alloyed QDs.3-6 We have demonstrated that a high room-temperature PL QY of up to 100% can be obtained in FAPbI3 and CsPbI3 perovskite QDs, signifying the achievement of almost complete elimination of the trapping defects. This is realized by the modulation of halide precursor involved in the synthesis, in which trioctylphosphine (TOP) is used to dissolve halide salts, allowing sufficient releasing of halide ions as well as improved surface passivation. Ultrafast kinetic analysis with time-resolved transient absorption spectroscopy evidences the negligible electron or hole trapping pathways in our QDs, which explains such a high quantum efficiency. For Sn-Pb alloyed QDs, although the alloyed QDs possess much improved structural stability than that of the pure Pb- and Sn-based one, they still suffer from an extremely low PL QY of ~0.3%, indicative of the severe charge trapping in these Sn-containing perovskites. Such low PL QY is believed to result from the widely known facile oxidation of Sn2+ to Sn4+. To address this issue, we have demonstrated very recently that the deep-level trap states in Sn-based perovskites can be well suppressed by Na+ doping, which gives rise to a dramatically improved PL QY of ~28% without alerting their favorable electronic structure.7 X-ray photoelectron spectroscopy (XPS) studies suggest the formation of a stronger chemical interaction between I- and Sn2+ ions upon Na doping, which is in line with the results obtained by DFT calculations. On the other hand, though the reported TOP-based route has demonstrated efficacy in producing CsSnxPb1-xI3 QDs (x = 0~0.6) with superior structural stability, such synthetic protocol can only find success in making these I-related QDs, preparing those pure Cl- and Br-based analogues remains challenging because of the insufficient solubility of PbBr2 and PbCl2 in TOP. Therefore, by taking advantage of the strong coordinating ability of trioctylphosphine oxide (TOPO), we have recently reported the first synthesis of ASnxPb1-xX3 QDs (A = Cs, FA, MA) with excellent tunability in both Sn/Pb ratio and a full range of halide covering. The ability to generate all possible, unique combinations has offered great material versatility for the perovskite QD family. Further, by employing ultrafast spectroscopic techniques, we have resolved the fundamental photoexcited charge carrier dynamics in these alloyed QDs including trapping states-involved recombination, hot carrier relaxation, and charge transfer dynamics, which shall pave the way for future study for enhancing their usefulness in optoelectronic applications.8 In addition, photoexcited hot and cold carrier dynamics as well as charge transfer at the heterojunction of QD/metal oxide were systematically investigated.9 Solar cells based on these high-quality perovskite QDs exhibit power conversion efficiency of over 12%, showing great promise for practical application. We expect the successful synthesis of the “ideal” perovskite QDs will exert profound influence on their applications to both QD-based light-harvesting and -emitting devices in the near future. References Swarnkar, A. et al., Science 2016, Vol. 354, pp. 92-95.Alivisatos et al., J. Am. Chem. Soc. 2018, Vol. 140, pp. 17760F. Liu and Q. Shen et al., ACS Nano , Vol. 11, No. 10, pp. 10373-10383, 2017.F. Liu and Q. Shen et al., J. Am. Chem. Soc. , Vol. 139, No. 46, pp. 16708-16719, 2017.F. Liu and Q. Shen et al., J. Phys. Chem. Lett. , Vol. 9, No. 2, pp. 294-297, 2018.F. Liu and Q. Shen et al., Chem. Mater. , Vol. 31, No. 3, pp. 798-807, 2019.F. Liu and Q. Shen et al., Angew. Chem. Int. Ed. , Vol. 59, pp. 1-5, 2020.F. Liu and Q. Shen et al., Chem. Mater. , Vol. 32, No. 3, pp. 1089-1100, 2020.C. Ding and Q. Shen et al., Nano Energy 2020, 67, 104267.