Junsheng Chen

Photo-stability of CsPbBr3 perovskite quantum dots for optoelectronic application

Due to their superior photoluminescence (PL) quantum yield (QY) and tunable optical band gap, all-inorganic CsPbBr3 perovskite quantum dots (QDs) have attracted intensive attention for the application in solar cells, light emitting diodes (LED), photodetectors and laser devices. In this scenario, the stability of such materials becomes a critical factor to be revealed. We hereby investigated the long-termstability of as-synthesized CsPbBr3 QDs suspended in toluene at various environmental conditions. We found light illumination would induce drastic photo-degradation of CsPbBr3QDs. The steady-state spectroscopy, transmission electron microscopy (TEM), and X-ray diffraction (XRD) verified that CsPbBr3 QDs tend to aggregate to form larger particles under continuous light soaking. In addition, decreasing PL QY of the QDs during light soaking indicates the formation of trap sites. Our work reveals that the main origin of instability in CsPbBr3 QDs and provides reference to engineer such QDs towards optimal device application.摘要全无机CsPbBr3钙钛矿量子点因其优异的发光性能, 而在太阳能电池、发光二极管、光探头和激光器件等应用研究领域受到广泛关注. 基于此, 我们研究了CsPbBr3钙钛矿量子点在不同光照、气氛和温度条件下的稳定性. 光照下, 量子点表面缺陷态的产生和量子点的聚集促使量子点的发光效率降低, 吸收和发光光谱发生红移. 透射电子显微镜和X-光单晶衍射实验结果表明, 在光照下量子点发生了聚集进而形成了大尺寸的晶体. 我们的工作表明光照是影响CsPbBr3钙钛矿量子点稳定性的决定性因素, 因此需要改善其光稳定性从而优化CsPbBr3钙钛矿量子点光电器件性能.

Lead‐Free, Air‐Stable All‐Inorganic Cesium Bismuth Halide Perovskite Nanocrystals

Lead-based perovskite nanocrystals (NCs) have outstanding optical properties and cheap synthesis conferring them a tremendous potential in the field of optoelectronic devices. However, two critical problems are still unresolved and hindering their commercial applications: one is the fact of being lead-based and the other is the poor stability. Lead-free all-inorganic perovskite Cs3 Bi2 X9 (X=Cl, Br, I) NCs are synthesized with emission wavelength ranging from 400 to 560 nm synthesized by a facile room temperature reaction. The ligand-free Cs3 Bi2 Br9 NCs exhibit blue emission with photoluminescence quantum efficiency (PLQE) about 0.2 %. The PLQE can be increased to 4.5 % when extra surfactant (oleic acid) is added during the synthesis processes. This improvement stems from passivation of the fast trapping process (2-20 ps). Notably, the trap states can also be passivated under humid conditions, and the NCs exhibited high stability towards air exposure exceeding 30 days.

Sensing Mechanism for Biothiols Chemosensor DCO: Roles of Excited-State Hydrogen-Bonding and Intramolecular Charge Transfer

The biothiols sensing mechanism of (E)-7-(diethylamino)-3-(2-nitrovinyl)-2H-chromen-2-one (DCO) has been investigated using the density functional theory (DFT) and time-dependent DFT methods. The theoretical results indicate that the excited-state intermolecular hydrogen bonding (H-B) plays an important role for the biothiols sensing mechanism of the fluorescence sensor DCO. Multiple H-B interaction sites exist in DCO and in its Michael addition product DCOT, which then induce the formation of the H-B complexes with water molecules, DCOH2 and DCOTH4. In the first excited state, the intermolecular H-Bs between water molecule and DCO in DCOH2 are cooperatively and generally strengthened and thus induced the weak fluorescence emission of DCO, while the cooperative H-Bs between water molecule and DCOT in DCOTH4 are overall weakened and thus responsible for the enhanced fluorescence emission of DCOT. Moreover, the theoretical results suggest that the blue shift of the UV-Vis absorption spectrum of DCOT can be attributed to the relatively weak excited-state intramolecular charge transfer in DCOT compared to DCO.

Lead-Free Silver-Bismuth Halide Double Perovskite Nanocrystals

Lead-free perovskite nanocrystals (NCs) were obtained mainly by substituting a Pb2+ cation with a divalent cation or substituting three Pb2+ cations with two trivalent cations. The substitution of two Pb2+ cations with one monovalent Ag+ and one trivalent Bi3+ cations was used to synthesize Cs2 AgBiX6 (X=Cl, Br, I) double perovskite NCs. Using femtosecond transient absorption spectroscopy, the charge carrier relaxation mechanism was elucidated in the double perovskite NCs. The Cs2 AgBiBr6 NCs exhibit ultrafast hot-carrier cooling (<1 ps), which competes with the carrier trapping processes (mainly originate from the surface defects). Notably, the photoluminescence can be increased by 100 times with surfactant (oleic acid) added to passivate the defects in Cs2 AgBiCl6 NCs. These results suggest that the double perovskite NCs could be potential materials for optoelectronic applications by better controlling the surface defects.

Enhanced Size Selection in Two-Photon Excitation for CsPbBr3 Perovskite Nanocrystals

Cesium lead bromide (CsPbBr3) perovskite nanocrystals (NCs), with large two-photon absorption (TPA) cross-section and bright photoluminescence (PL), have been demonstrated as stable two-photon-pumped lasing medium. With two-photon excitation, red-shifted PL spectrum and increased PL lifetime is observed compared with one-photon excitation. We have investigated the origin of such difference using time-resolved laser spectroscopies. We ascribe the difference to the enhanced size selection of NCs by two-photon excitation. Because of inherent nonlinearity, the size dependence of absorption cross-section under TPA is stronger. Consequently, larger size NCs are preferably excited, leading to longer excited-state lifetime and red-shifted PL emission. In a broad view, the enhanced size selection in two-photon excitation of CsPbBr3 NCs is likely a general feature of the perovskite NCs and can be tuned via NC size distribution to influence their performance within NC-based nonlinear optical materials and devices.

Photostability and photodegradation processes in colloidal CsPbI3 perovskite quantum dots

All-inorganic CsPbI3 perovskite quantum dots (QDs) have attracted intense attention for their successful application in photovoltaics (PVs) and optoelectronics that are enabled by their superior absorption capability and great photoluminescence (PL) properties. However, their photostability remains a practical bottleneck and further optimization is highly desirable. Here, we studied the photostability of as-obtained colloidal CsPbI3 QDs suspended in hexane. We found that light illumination does induce photodegradation of CsPbI3 QDs. Steady-state spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and transient absorption spectroscopy verified that light illumination leads to detachment of the capping agent, collapse of the CsPbI3 QD surface, and finally aggregation of surface Pb0. Both dangling bonds containing surface and Pb0 serve as trap states causing PL quenching with a dramatic decrease of PL quantum yield. Our work provides a detailed insight about the correlation between the structural and photophysical consequences of the photodegradation process in CsPbI3 QDs and may lead to the optimization of such QDs toward device applications.