Colloidal Synthesis and Charge-Carrier Dynamics of Cs2 AgSb1-y Biy X6 (X: Br, Cl; 0 ≤y ≤1) Double Perovskite Nanocrystals.

A series of lead-free double perovskite nanocrystals (NCs) Cs2 AgSb1-y Biy X6 (X: Br, Cl; 0≤y≤1) is synthesized. In particular, the Cs2 AgSbBr6 NCs is a new double perovskite material that has not been reported for the bulk form. Mixed Ag-Sb/Bi NCs exhibit enhanced stability in colloidal solution compared to Ag-Bi or Ag-Sb NCs. Femtosecond transient absorption studies indicate the presence of two prominent fast trapping processes in the charge-carrier relaxation. The two fast trapping processes are dominated by intrinsic self-trapping (ca. 1-2 ps) arising from giant exciton-phonon coupling and surface-defect trapping (ca. 50-100 ps). Slow hot-carrier relaxation is observed at high pump fluence, and the possible mechanisms for the slow hot-carrier relaxation are also discussed.

Lead-Free Direct Band Gap Double-Perovskite Nanocrystals with Bright Dual-Color Emission.

Lead-free double-perovskite nanocrystals (NCs), that is, Cs2AgIn xBi1- xCl6 ( x = 0, 0.25, 0.5, 0.75, and 0.9), that can be tuned from indirect band gap ( x = 0, 0.25, and 0.5) to direct band gap ( x = 0.75 and 0.9) are designed. Direct band gap NCs exhibit 3 times greater absorption cross section, lower sub-band gap trap states, and >5 times photoluminescence quantum efficiency (PLQE) compared to those observed for indirect band gap NCs (Cs2AgBiCl6). A PLQE of 36.6% for direct band gap NCs is comparable to those observed for lead perovskite NCs in the violet region. Besides the band edge violet emission, the direct band gap NCs exhibit bright orange (570 nm) emission. Density functional theory calculations suggesting forbidden transition is responsible for the orange emission, which is supported by time-resolved PL and PL excitation spectra. The successful design of lead-free direct band gap perovskite NCs with superior optical properties opens the door for high-performance lead-free perovskite optoelectronic devices.

Method to improve the resolution of a non-parallel Fabry-Perot etalon.

A new method to improve the resolution of a slightly non-parallel solid etalon is proposed. The method is aimed to reduce the spectrum broadening caused by non-parallel surfaces; it contains a theoretical formula for adjusting image distances, and an algorithm for processing the corresponding fringe patterns. Theoretical consideration, computer simulation, experimental results, and application demonstration are given. The fringe patterns captured by a CCD showed good agreement with the computer simulation, and the resolution of a λ/10-wavefront-error etalon was improved from 3.1 GHz to 0.51 GHz. In comparison with other methods, this new method is convenient and economical.

Direct bleaching of a Cr4+:YAG saturable absorber in a passively Q-switched Nd:YAG laser.

In this work, the anisotropy of nonlinear absorption in a crystal Q-switch was considered when we established coupled rate equations of a passively Q-switched laser. A [100]-cut Cr4+:YAG crystal, with initial transmission T0=40%, was used as the Q-switch to evaluate the theoretical model, and the results of the simulation were in good accordance with the experiment. In order to control timing jitter of the passively Q-switched laser, an actively Q-switched Nd:YAG laser was applied to directly bleach the [100]-cut Cr4+:YAG crystal. The timing jitter was more than 1 µs without bleaching light. While there was a bleaching light, the time lag between the laser pulse and the bleaching light was less than 100 ns, which meant the timing jitter decreased. The pulse width of the passively Q-switched laser was found to decrease from 45 to 35 ns due to the existing of bleaching light. As the peak power of bleaching light was increased, the laser pulse energy increased from 18.2 to 24.6 mJ, which meant a 35% increment in the pulse energy. The increase in pulse energy can be explained by the increase of α coefficient, and the results of simulation agreed well with the experiment.

Energy-Transfer Kinetics Driven by Midinfrared Amplified Spontaneous Emission after Two-Photon Excitation from Xe (s0) to the Xe (6p[1/2]0) State.

In optically pumped laser systems, rare gas lasers (RGLs) are a field of great interest for researchers. Gas laser regimes with metastable Ne, Ar, and Kr atoms have been investigated, while studies of RGLs based on metastable Xe are sparse. In this work, when a strong excitation laser (2.92 mJ/pulse, 7.44 × 105 W/cm2) was applied to excite Xe atoms from the ground state to the 6p[1/2]0 state, an interesting phenomenon emerged: An intense fluorescence of 980 nm (6p[1/2]1-6s[3/2]2) was produced. However, when the energy of excitation laser was decreased to 0.50 mJ/pulse (1.27 × 105 W/cm2), the fluorescence of 980 nm became very weak. Besides, lifetime and decay rate constant of the 6p[1/2]0 state under the condition of E = 2.92 mJ are significantly different from either those measured by other groups or those of E = 0.50 mJ. These phenomena indicate that the high energy of excitation laser should trigger some new kinetic mechanisms. Further works identified that the new kinetic mechanism is the MIR ASE of 3408 nm (6p[1/2]0-6s'[1/2]1). The mechanisms are proposed as follows. Substantial 6p[1/2]0 atoms are produced by laser excitation. Then, the ASE of 3408 nm (6p[1/2]0-6s'[1/2]1) is quickly produced to populate substantial 6s'[1/2]1 atoms. The 6s'[1/2]1 atoms can readily arrive at the 6p[1/2]1 states through collision by virtue of the small energy difference (84 cm-1) and high collision rate constant of the transition from the 6s'[1/2]1 state to the 6p[1/2]1 state. As a result, the intense fluorescence of 980 nm is generated.

Ultrasensitive Optical Thermometry via Inhibiting the Energy Transfer in Zero-Dimensional Lead-Free Metal Halide Single Crystals.

Self-referencing optical thermometry based on the fluorescence intensity ratio (FIR) have drawn extensive attention as a result of their high sensitivity and non-invasively fast response to temperature. However, it is a great challenge for luminescent materials to achieve simultaneously high absolute and relative temperature sensitivity based on the FIR technique. Herein, we developed a novel optical thermometer by designing hybrid lead-free metal halide (TTPhP)2MnCl4:Sb3+ (TTPhP+ = tetraphenylphosphonium cation) single crystals with multimodal photoluminescence (PL). The large TTPhP+ organic chain resulted in isolated [MnCl4]2- and [SbCl5]2- in the single crystal, which leads to a negligible energy trasfer process within them. Therefore, the two PL bands (band 1 from [MnCl4]2-) with a peak at 518 nm and band 2 (from [SbCl5]2) with a peak at 640 nm exhibit different thermal-quenching effects, which resulted in excellent temperature sensitivity, with the maximum absolute and relative sensitivities reaching 0.236 K-1 and 3.77% K-1 in a temperature range from 300 to 400 K. Both the absolute and relative sensitivities are among the highest values for luminescence thermometry.

Organo-Metal Halide Scintillator with Weak Thermal Quenching Up to 200 °C.

The prominent thermal quenching (TQ) effect of organic-inorganic metal halides limits their applications for lighting and imaging. Herein, we report an organo-metal halide scintillator (TTPhP)2MnCl4 (TTPhP+ = tetraphenylphosphonium cation), which exhibits a weak TQ effect up to 200 °C under ultraviolet-visible light (efficiency loss of 5.5%) and X-ray radiation (efficiency loss of 37%). The light yield of the (TTPhP)2MnCl4 scintillator (37 000 photons MeV-1 at 200 °C) under X-ray radiation is >2 times that of the commercial scintillator LuAG:Ce (15 000 photons MeV-1 at 200 °C). The microscopic mechanism of the weak TQ effect is demonstrated to be the scintillator having the ability to compensate for the emission losses from trapped charges and the large Mn-Mn distance (10.233 Å) suppressing nonradiative recombination at high temperatures. We further demonstrate the applications of (TTPhP)2MnCl4 as high-power white-light-emitting diodes operated at currents of ≤300 mA and X-ray imaging at 200 °C with a high spatial resolution.

Ultrasensitive and Fast All-Inorganic Perovskite-Based Photodetector via Fast Carrier Diffusion.

Low trap-state density, high carrier mobility, and efficient charge carrier collection are key parameters for photodetectors with high sensitivity and fast response time. This study demonstrates a simple solution growth method to prepare CsPbBr3 microcrystals (MCs) with low trap-state density. Time-dependent photoluminescence study with one-photon excitation (OPE) and two-photon excitation (TPE) indicates that CsPbBr3 MCs exhibit fast carrier diffusion with carrier mobility over 100 cm2 V-1 S-1 . Furthermore, CsPbBr3 MC-based photodetectors with high charge carriers' collection efficiency are fabricated. Such photodetectors show ultrahigh responsivity (R) up to 6 × 104 A W-1 with OPE and high R up to 6 A W-1 with TPE. The R for OPE is over one order of magnitude higher (the R for TPE is three orders of magnitude higher) than that of previously reported all-inorganic perovskite-based photodetectors. Moreover, the photodetectors exhibit fast response time of ≈1 ms, which corresponds to a gain ≈105 and a gain- bandwidth product of 108 Hz for OPE (a gain ≈103 and a gain-bandwidth product of 106 Hz for TPE).