2D/3D钙钛矿异质结中多重量子阱的形成使声子瓶颈效应失效

声子瓶颈效应对有机-无机杂化钙钛矿光电性能的重要性已经广为认知.虽然在2D/3D异质结构中经常产生随机分布的多重量子阱结构,但人们对2D/3D钙钛矿异质结构中多重量子阱的形成对声子瓶颈效应的影响知之甚少.本文使用2D有机-无机杂化钙钛矿(NH_(3)(CH_(2))_(8)NH_(3)PbI_(4))去钝化3D有机-无机杂化钙钛矿,构建了2D/3D钙钛矿异质结构,并通过光致发光光谱和飞秒光泵浦太赫兹探测光谱研究了其激子和载流子动力学.观察到了多重量子阱结构的形成,并建立了激子形成时间、热载流子冷却速率和有效电荷载流子迁移率之间的结构-动力学-性能的构效关系.多重量子阱结构的形成可使声子瓶颈效应失效,并且调控2D/3D钙钛矿异质结的光电性能.该工作为构建2D/3D钙钛矿异质结构策略中认识能带排列和声子瓶颈效应的重要性提供有价值的信息.

Film Thickness and Surface Plasmon Tune the Contribution of SFG Signals from Buried Interface and Air Surface

Sum frequency generation vibrational spectroscopy(SFG-VS)is a powerful technique for determining molecular structures at both buried interface and air surface.Distinguishing the contribution of SFG signals from buried interface and air surface is crucial to the applications in devices such as microelectronics and bio-tips.Here we demonstrate that the SFG spectra from buried interface and air surface can be differentiated by controlling the film thickness and employment of surface-plasmon enhancement.Using substrate-supported PMMA(poly(methyl methacrylate))films as a model,we have visualized the variations in the contribution of SFG signals from buried interface and air surface.By monitoring carbonyl and C-H stretching groups,we found that SFG signals are dominated by the moieties(-CH2,-CH3,-OCH3 and C=O)segregated at the PMMA/air surface for the thin films while they are mainly contributed by the groups(-OCH3 and C=O)at the substrate/PMMA buried interface for the thick films.At the buried interface,the tilt angle of C=O decreases from65°to 43°as the film preparation concentration increases;in contrast,the angles at the air surface fall in the range from 38°to 21°.Surface plasmon generated by gold nanorods can largely enhance SFG signals,particularly the signals from the buried interface.

Sum Frequency Generation Vibrational Spectra of Perovskite Nanocrystals at the Single-Nanocrystal and Ensemble Levels

Determination of molecular structures of organicinorganic hybrid perovskite(OIHP)nanocrystals at the single-nanocrystal and ensemble levels is essential to understanding the mechanisms responsible for their size-dependent optoelectronic properties and the nanocrystal assembling process,but its detection is still a bit challenging.In this study,we demonstrate that femtosecond sum frequency generation(SFG)vibrational spectroscopy can provide a highly sensitive tool for probing the molecular structures of nanocrystals with a size comparable to the Bohr diameter(∼10 nm)at the single-nanocrystal level.The SFG signals are monitored using the spectral features of the phenyl group in(RMBA)PbBr_(3) and(R-MBA)_(2)PbI_(4) nanocrystals(MBA:methyl-benzyl-ammonium).It is found that the SFG spectra exhibit a strong resonant peak at 3067±3 cm^(−1)(ν2 mode)and a weak shoulder peak at 3045±4 cm^(−1)(ν_(7a) mode)at the ensemble level,whereas a peak of theν2 mode and a peak at 3025±3 cm^(−1)(ν20b mode)at the single-nanocrystal level.The nanocrystals at the single-nanocrystal level tend to lie down on the surface,but stand up as the ensemble number and the averaged sizes increase.This finding may provide valuable information on the structural origins for size-dependent photo-physical properties and photoluminescence blinking dynamics in nanocrystals.

Real-Time Observation of Protein Transport across Membranes by Femtosecond Sum Frequency Generation Vibrational Spectroscopy

Characterization of conformation kinetics of proteins at the interfaces is crucial for understanding the biornolecular functions and the mechanisms of interfacial biological action. But it requires to capture the dynamic structures of proteins at the interfaces with suffi- cient structural and temporal resolutions. Here, we demonstrate that a ferntosecond sum frequency generation vibrational spectroscopy （SFG-VS） system developed by our group provides a powerful tool for monitoring the real-tirne peptide transport across the membranes with time resolution of less than one second. By probing the real-time SFG signals in the arnide I and arnide A bands as WALP23 interacts with DMPG lipid bilayer, it is found that WALP23 is initially absorbed at the gel-phase DMPG bilayer with a random coil structure. The absorption of WALP23 on the surface leads to the surface charge reversal and thus changes the orientation of rnembrane-bound water. As the DMPG bilayer changes from gel phase into fluid phase, WALP23 inserts into the fluid-phase bilayer with its N-terminal end moving across the membrane, which causes the membrane dehydration and the transition of WALP23 conformation from random coil to mixed helix/loop structure and then to pure α-helical structure. The established system is ready to be employed in characterizing other interracial fast processes, which will be certainly helpful for providing a clear physical picture of the interracial phenomena.

Laboratory study on high-temperature adsorption of HCI by dry-injection of Ca（OH）2 in a dual-layer granular bed filter

Combustion-generated hydrogen chloride （HCl） is considered to be a very hazardous acid gaseous pollutant. This paper presents a laboratory study on the dry adsorption of HCl. The experiments were conducted in a dual-layer granular bed filter, at gas temperatures of 500℃-700℃ and n（Ca）/n（Cl）molar ratios of 1.0-5.0 using the silver nitrate titration method by dry adsorbent powders Ca（OH）2. Mainly, the adsorption efficiency of HCI and utilization efficiency of Calcium were studied, by varying relevant factors including n（Ca）/n（Cl）, tempera- ture, feeding method, water vapor and CO2. With a relatively higher HCl concentration of 1000ppm, the experimental results revealed that 600℃ may be the optimum temperature for HCl adsorption when optimum n （Ca）/n（Cl） was 2.5 in our tests. The results also demonstrated that the feeding at a constant pressure was more effective, and the HCl adsorption efficiency could rapidly reach over 90% with n（Ca）/n（Cl） = 2.5 at 600℃. Furthermore, the HCl adsorption efficiency was found to be slightly promoted by water vapor, while could be impeded by CO2, and the utilization efficiency of calcium could be up to 74.4% without CO2, while was only 36.8% with CO2 when n（Ca）/n（Cl） was 2.5 at 600℃.