Deep-blue emissive Cs3Cu2I5 perovskites nanocrystals with 96.6% quantum yield via InI3-assisted synthesis for light-emitting device and fluorescent ink applications. (July 2022) - Gao, Fei
Abstract: Lead-free metal halide perovskites are promising materials for future optoelectronic application, which have recently attracted great attention for their environmental-friendliness and excellent light emission properties. However, the development of deep-blue emission lead-free halide perovskite nanocrystal is still far behind in performance in comparison with its red/green counterparts. Herein, the lead-free Cs3 Cu2 I5 nanocrystals are prepared via a modified hot-injection strategy. By adding InI3 as precursor, the synthesized Cs3 Cu2 I5 single-phase nanocrystals show a bright deep-blue emission peaked at ~440 nm, with a record high photoluminescence quantum yield (PL QY) up to 96.6% at an optimized InI3 content of 0.15 mmol. The InI3 additive contributes to the high PL QY through both iodide vacancy reparation of I - ions and size-controlled growth of In 3+ ions. First principle calculations reveal that the broadband blue emission originates from self-trapped excitons in Cs3 Cu2 I5, which are formed due to the excited-state lattice expansion and Cu-I bond lengthening of [Cu2 I5 ] 3- cluster under light excitation. The good stabilities of these Cs3 Cu2 I5 nanocrystals against heat, water, UV irradiation and environmental storage are also investigated experimentally and theoretically in detail. For application demonstration, light-emitting devices are manufactured by using these Cs3 Cu2 I5 nanocrystals powder as phosphor, which exhibit good working stability with a half-lifetime over 300 h. Besides, the Cs3 Cu2 I5 nanocrystals solution is also utilized as fluorescent ink, and the printed patterns can maintain anti-counterfeiting features even after treatment by heating and long-term environmental storage, indicating the robustness of these Cs3 Cu2 I5 nanocrystals for potential anti-counterfeiting application. Graphical Abstract: Lead-free Cs 3 Cu 2 I 5 NCs with single-phase purity and record-high PLQY of 96.6%, have been synthesized by employing InI3 as precursor in a modified hot-injection strategy. A series of characterizations and calculations prove the high crystal quality, STE emission mechanism and good stability of the Cs3 Cu2 I5 NCs. Promising application prospects of these Cs3 Cu2 I5 NCs are further demonstrated in terms of light-emitting devices and anti-counterfeiting fluorescent inks. ga1 Highlights: Single-phase deep-blue emission Cs3 Cu2 I5 NCs with a record high PL QY of 96.6% are prepared using InI3 -assisted hot-injection route. By optimizing the InI3 additive amount, the high-quality NCs were obtained by repairing iodide vacancies and controlling growth size. The high-efficiency blue emission is from radiative recombination of self-trapped excitons caused by photo-induced excited-state lattice expansion. These Cs3 Cu2 I5 NCs exhibit good stabilities against heat, water, UV irradiation and environmental storage. LEDs with long half-lifetime and anti-counterfeiting fluorescent inks with good environmental robustness are manufactured by these Cs3 Cu2 I5 NCs.