压力诱导发光 未来可期

科技创新的根源是基于基础科学研究的提升,而“从0到1”的突破是需要长期的积累和灵感的。本文讲述了发现压力诱导发光这一新现象的思想和材料设计。     

Shedding Light on the Origin of Solid-State Luminescence Enhancement in Butterfly Molecules

Different molecular strategies have been carefully evaluated to produce solid-state luminescence enhancement (SLE) in compounds that show dark states in solution. A set of α-phenylstyrylarene derivatives with a butterfly shape have been designed and synthesised, for the first time, with the aim of improving the solid-state fluorescence emission of their parent styrylarene compounds. Although these butterfly molecules are not fluorescent in solution, one of them (1,2,4,5-tetra(α-phenylstyryl)benzene) exhibits a fluorescence quantum yield as high as 68 % in a drop-cast sample and 31 % in its crystalline form. In contrast, 1,3,5-tris(α-phenylstyryl)benzene and 4,6-bis(α-phenylstyryl)pyrimidine do not show SLE. A range of fluorescence spectroscopy experiments and DFT calculations were carried out to unravel the origin of different photophysical behaviour of these compounds in the solid state. The results indicate that a rational strategy to control the SLE effect in luminogens depends on a delicate balance between molecular properties and inter-/intramolecular interactions in the solid state.     

The Role of Torsional Dynamics on Hole and Exciton Stabilization in π‐Stacked Assemblies: Design of Rigid Torsionomers of a Cofacial Bifluorene

Exciton and charge delocalization across π‐stacked assemblies is of importance in biological systems and functional polymeric materials. To examine the requirements for exciton and hole stabilization, cofacial bifluorene ( F 2) torsionomers were designed, synthesized, and characterized: unhindered (model) ^Me F 2, sterically hindered ^tBu F 2, and cyclophane‐like ^C F 2, where fluorenes are locked in a perfect sandwich orientation via two methylene linkers. This set of bichromophores with varied torsional rigidity and orbital overlap shows that exciton stabilization requires a perfect sandwich‐like arrangement, as seen by strong excimeric‐like emission only in ^C F 2 and ^Me F 2. In contrast, hole delocalization is less geometrically restrictive and occurs even in sterically hindered ^tBu F 2, as judged by 160 mV hole stabilization and a near‐IR band in the spectrum of its cation radical. These findings underscore the diverse requirements for charge and energy delocalization across π‐stacked assemblies.     

Evidence for the Cyclodextrin Mediated Aggregation of Cyanine Dyes into Oligomers

Based on the analysis of UV/Vis-and CD spectra of several cyanine dyes in - and -cyclodextrin a case is made for the aggregation of the dyes into oligomers. The criteria for this new type of aggregates are: (i) the appearance of a concentration and temperature dependent shoulder on the high energy side of the dimer band in the UV/Vis-spectra; (ii) two oppositely signed high intensity CD absorptions, one centered at the shoulder, the other at about the energy of the monomer absorption. Calculations based on coupled-oscillator theory support the contention that chiral dye aggregates are formed in the presence of cyclodextrins, most probably trimers and tetramers. From UV/Vis- and CD-data a helically twisted sandwich structure is suggested for these aggregates. In contrast to the reported inclusion complexes these aggregates must form — at least partly — outside the chiral host.     

ZnCdSe/ZnSe非对称双量子阱中的光学特性研究

用LP-MOCVD技术在GaAs衬底上外延生长了ZnCdSe/ZnSe非对称双量子阱(ADQW)结构。通过ps时间分辨光谱、吸收光谱、发射光谱等的研究得到了如下的结果:在弱激发下,观测到ADQW结构中的激子隧穿现象;在强激发下,在ADQW结构中发现了一个内建电场,它将影响激子隧穿;首次观测到由激子隧穿引起的在一定温度范围内宽阱的发光强度随温度上升而增加的现象;首次观测到该ADQW结构中来自宽阱的光泵受激发射。     

Exciton lifetime in quantum well with vicinal high-density excitons

Radiative lifetime of an exciton in a GaAs quantum well (QW) is controlled by high-density excitons, which restrict the exciton coherence through scattering. In order to circumvent the phase space filling effect of high-density excitons, we have prepared a QW structure in such a way that a reservoir for high-density excitons is separated from the QW. The lifetime increases (up to 30%) with the exciton density in the reservoir and saturates at 1×10¹⁷/cm³. The upper bound lifetime is determined by the excitonic relative motion.     

Problems of the electronic structure of nonmetals in a wide energy region of fundamental absorption (review)

The article surveys the main unsolved problems of the electronic structure of nonmetals in a wide energy region of fundamental absorption. Udmurtia State University, 71, Krasnogeroiskaya Str., Izhevsk, 426034, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 3, pp. 299–315, May–June, 1999.     

Exciton reflection of ZnSe single crystals with account for the effect of the surface electric field

The mechanism of formation of an exciton reflection band is analyzed using a multilayer model of the near-surface region of ZnSe single crystals. It is shown that the appearance of a fine structure (a spike) in the reflection spectra at large damping parameters of the exciton is due to the surface electric field and the Stark exciton effect. The exciton-resonance energies and the damping parameters of free excitons for temperatures ranging from 12 to 100 K are determined by comparing experimental and predicted contours of the reflection spectrum. The surface concentration of charged centers and the characteristics of the space-charge region are evaluated within the framework of the model employed. Brest Polytechnic Institute, 267, Moskovskaya Str., Brest, 224017, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 3, pp. 401–407, May–June, 1999.     

中子诱发12C反应的理论计算与分析

利用统一的Hauser–Feshbach理论和角动量相关的激子模型,以中子诱发¹²C反应为例,研究了轻核反应的反应机制和轻核反应的特点,并进行了理论计算,同时与实验数据进行了比较.     

高分子中激子和双激子的极化率(解析计算)

高分子的电致发光是载流子在电场中的输运和复合,为了阐明它的机理,需要研究高分子中激子的极化性质,首先求得了激子和双激子的解析解,然后用线性响应的Green函数方法计 算了两者的极化率,解析地证明了一个重要的结论：激子的极化率为正,双激子的极化率为负.从激子跃迁至双激子,高分子的电偶极矩要反转方向. 关键词： 激子 双激子 解析解 负极化率