Perovskite Light-Emitting Devices Based on Solid-State Diffusion In Situ Dynamic Thermal Crystallization.

Due to the excellent photonic and electrical properties of metal halide perovskite materials, perovskite light-emitting devices have the potential to replace OLED devices as the next-generation of commercial light-emitting devices. In this article, we controlled the surface morphology of PbBr2 using an in situ dynamic thermal crystallization process, which increased the specific surface area of the films and promoted the solid-state diffusion rate. The CsPbBr3 PeLEDs prepared using this method achieved a maximum current efficiency of 7.1 cd/A at the voltage of 5 V, which was 200% higher than devices prepared using traditional spin-coating processes. These results proved that the in situ thermal dynamic crystallization process effectively improved the film quality of perovskite materials.

Photo- and Thermal-Induced Ion Migration and Phase Separation in Mn-Doped Two-Dimensional PEA2PbX4 Perovskite.

Ion migration and phase separation in perovskite materials have negatively affected the solid-state lighting and display. Studying photo- and thermal-induced degradation is considered as a promising approach to understanding the luminescence mechanism and promoting practical applications. Herein, the Mn-doped two-dimensional PEA2PbX4 (X = Cl, Br, I) microcrystals with changing halogen composition were synthesized by an acid-assisted post-processing strategy. Then, photo- and thermal-induced degradation was studied by using steady-state and time-resolved photoluminescence (PL) spectroscopy. The band edge exciton PL peak of Mn-doped 2D PEA2PbX4 microcrystals was adjusted from 397 to 500 nm. The reduced Mn PL lifetime (1.37 to 0.21 ms) was monitored under ion exchange from Cl to Br to I. The degradation mechanism could be divided into two cases: (i) The halide ion migration in Mn-doped 2D perovskite under continuous illumination was revealed, suggesting that the migration of Cl ions was more accessible than that of Br and I. (ii) The PL redshift and lifetime reduction were observed after annealing at 420 K, which means that thermally induced aggregation of Mn ions resulted in the formation of Mn2+-Mn2+ dimers. In addition, the experimental results indicated that the induced B-site phase separation at high temperature annealing made the mixed perovskite phase of Pb and Mn ultimately transform into pure PEA2PbBr4 and PEA2MnBr4.

Near-unity blue-orange dual-emitting Mn-doped perovskite nanocrystals with metal alloying for efficient white light-emitting diodes.

The tunable dual-color emitting Mn2+ doped CsPbCl3-xBrx nanocrystals (NCs) with near-unity photoluminescence quantum yield (PL QY) were synthesized through post-treatment of metal bromide at room temperature for fabrication of efficient warm white light-emitting diodes (WLEDs). Especially, the CdBr2 treated blue-orange emitting Mn doped NCs with various Mn/Pb molar feed ratios exhibit higher PL QY of 97% and longer Mn2+ PL lifetime of 0.9 ms. It is surprisingly found that the X-ray diffraction peak at 31.9° is almost not changed with increasing Br composition, meaning formation of metal alloying due to incorporation of amount of divalent cation in NCs. The strong and stable Mn2+ PL at temperature ranging from 80 K to 360 K are revealed and the temperature-dependent energy transfer efficiencies in Mn2+ doped CsPbCl1.5Br1.5 NCs are obtained. The enhancement mechanism of Mn2+ PL QY was attributed to improved energy transfer from exciton to Mn2+ d-d transition and suppressed defect state density after post-treatment. The efficient warm WLEDs with color rendering index of 90 and luminous efficacy of 92 lm/W at 10 mA were fabricated by combining blue-orange dual-emitting Mn2+ doped CsPbCl3-xBrx@SiO2 and green emissive CsPbBr3@SiO2 NCs with violet GaN chips.

Near-Unity Red Mn2+ Photoluminescence Quantum Yield of Doped CsPbCl3 Nanocrystals with Cd Incorporation.

Although Mn2+ doping in semiconductor nanocrystals (NCs) has been studied for nearly three decades, the near 100% photoluminescence (PL) quantum yield (QY) of Mn2+ emission has never been realized so far. Herein, greatly improved PL QYs of Mn2+ emissions are reported in Mn2+-doped CsPbCl3 NCs with various Mn2+ doping concentrations after CdCl2 post-treatment at room temperature. Specifically, the near-unity QY and near single-exponential decay of red Mn2+ emission peaking at 627 nm in doped CsPbCl3 NCs are obtained for the first time. The temperature dependence of steady-state and time-resolved PL spectra reveals that the CdCl2 post-treatment significantly reduces the nonradiative defect states and enhances the energy transfer from host to Mn2+ ions. Moreover, the Mn2+:CsPbCl3 NCs after CdCl2 post-treatment exhibit robust stability and high PL QYs after multipurification. The results will provide an effective route to obtain doped perovskite NCs with high performance for white lighting emitting diodes.

Tunable photoluminescence and an enhanced photoelectric response of Mn2+-doped CsPbCl3 perovskite nanocrystals via pressure-induced structure evolution.

Mn2+:CsPbCl3 nanocrystals (NCs) were synthesized using a modified one-pot injection method, which exhibits significantly improved thermal stability. For the first time, the pressure-treated optical and structural properties of synthetic Mn2+:CsPbCl3 NCs were further investigated, and their associated intriguing electrical and photoelectric properties were revealed from impedance spectra and photocurrent measurements under compression. The pressure-dependent photoluminescence experienced an initial redshift before 1.7 GPa followed by a continuous blueshift, as evidenced by the bandgap shifts. High-pressure XRD spectra uncovered a cubic-to-orthorhombic structural transition at about 1.1 GPa and subsequent amorphization upon further compression, which was fully reversible. Furthermore, the sample annealing from 340 K drove grain growth and decreased grain boundary resistance at ambient pressure. The compression further decreased the grain boundary barrier and improved the electrical conductivity (up to ∼10-2Ω-1 cm-1) of the thermally annealed Mn2+:CsPbCl3 NC surface. Simultaneous photocurrent enhancement of thermally annealed NCs was also achieved as expected, and reached optimal performance at 0.7 GPa. Strikingly, after the pressure cycling (loading-releasing), the results show that thermally annealed Mn2+:CsPbCl3 NCs gained preservable higher electrical conductivity (∼10 times increase) and an improved photoelectric response compared to the ambient state before compression. This work proves that high pressure is useful for opening the versatility in the structure and properties of metal-halide perovskite nanocrystals leading to a promising way for superior optoelectronic materials-by-design.