有机发光材料中的三重激发态

有机发光材料有望广泛应用于新一代柔性光电子器件。由于自旋多重性,有机分子发光材料 中单重激发态和三重激发态转换较慢,限制有机发光器件特别是电注入荧光器件的效率。我们介绍 下近年来通过分子设计操控激发不同时间尺度三重态的动力学来突破这一限制的策略,通过控制激 发单重态和激发三线态之间的电子耦合,利用热激子系间窜越、反向系间窜越、激发三重态稳定化 等过程能够有效提高有机发光材料的发光效率。在此基础上实现的热活化延迟荧光、有机长余辉发 光等在有机发光二极管、传感器、生物成像等领域有重要潜在应用价值。     

Laser-Induced Fluorescence Molecular Beam Investigation of New Singlet and Triplet Electronic States of Yttrium Monohydride

The yttrium monohydride spectrum in the range 12 500-25 000 cm⁻¹ has been studied by various laser-induced fluorescence (LIF) techniques. YH (YD) molecules have been produced in a free jet molecular beam apparatus by a laser vaporizing yttrium metal in the presence of He doped with H₂ (D₂) or NH₃ (ND₃). Low-resolution (∼0.04 cm⁻¹) excitation spectra have been recorded in the entire studied range. Four green bands (19 300-19 900 cm⁻¹) of the YH isotopomer have been studied in more detail: (1) high-resolution (∼120 MHz, ∼0.004 cm⁻¹) excitation spectra have been recorded, (2) dispersed fluorescence spectra have been obtained, and (3) lifetimes of the selected rotational levels of the upper states have been measured. Our observations have confirmed that the ground state of yttrium monohydride has ¹Σ⁺ symmetry and have provided a link between the singlet and triplet manifolds. The upper states of the observed transitions have been tentatively assigned to five electronic states, d0⁺, f³Π, f′1, D¹Π, E0⁺, and Fl. The low-energy excited electronic state observed in the dispersed fluorescence experiment has been assigned as the a³Δ state.     

溶解有机质的三维荧光光谱特征研究

利用三维荧光光谱研究了河流、湖泊等不同来源溶解有机质(DOM)的荧光光谱特性。河流DOM的三维荧光光谱图中含有类富里酸荧光峰A和C以及类蛋白荧光峰B和D,一般而言,类富里酸荧光峰强度比较大,或者只有类富里酸荧光,但是受人类活动污染河流DOM的三维荧光光谱图中具有极强的类蛋白荧光。同样,红枫湖DOM可以由陆源输入,还可以由水体内微生物活动产生,具有4个荧光峰,受人类活动影响比较显著的百花湖DOM则表现出强的类蛋白荧光。贵阳市地下水中DOM含量相对较低,一般只含有类富里酸荧光峰,但是若受生产生活污水污染,也可检测出强的类蛋白荧光峰。考察DOM含量(以DOC表示)与类富里酸荧光强度(peak C)以及在254 nm处紫外吸收光谱强度的关系时发现它们都具有良好的线性相关关系(r2＝0.82和0.95),而紫外区类富里酸荧光与可见区类富里酸荧光之间也存在良好的线性相关关系(r2＝0.96)。此外,pH对DOM的三维荧光光谱具有显著影响,并且类富里酸荧光峰A和C的pH值效应基本一致,荧光强度最大值出现在pH 10左右,类蛋白荧光峰B的pH值效应与之略有区别,荧光强度最大值出现pH 8.5左右。     

拉曼激发激光诱导电子荧光流场测量系统中标记过程的研究

研制了一套拉曼激光发激光诱导电子荧光空气流场测速系统,利用Nd:YAG激光器的二次谐波及其抽运的氧气受激拉曼散射作为标记光源,以ArF准分子激光作为荧光再现光源,并用像增强CCD摄像机（ICCD）记录荧光图像,成功地获得了纯氧及空气中的标记线的荧光图像,并进行了氧气喷流速度测量的初步研究。     

134Ba核的高激发态能级结构研究

在中国原子能科学研究院H-13串列加速器上, 通过重离子核反应¹³⁰Te(⁹Be,5n)与在束γ谱的实验技术, 对A=130缺中子核区的¹³⁴Ba核的高自旋态进行了研究, 建立了¹³⁴Ba核的新的能级纲图, 最高自旋态扩展到20h. 除验证了以前报道的大部分能级与跃迁外, 将基带的能级扩展到10⁺, 同时发现了基于10⁺同质异能态以上的众多的能级与跃迁. 对实验结果的系统学分析表明, 10⁺同质异能态为yrast陷阱, 起源于两中子组态, 可能具有γ≈－120°的长椭形状, 在其以上的能级表现出很强的单粒子性，具有复杂的结构. 基带中观测到明显的集体回弯现象, 推转壳模型的计算表明, 此集体回弯是由一对中子的顺排所致, TRS计算表明, 随着转动频率的增加, 核的形状发生明显的变化, 基带中在中子顺排后核具有γ≈－60°的扁椭形状.     

Thermally Activated Delayed Fluorescence Triplet State Excitons for High-Performance Organic Photodetectors: A Novel Strategy

Photoinduced charge-trapping is a promising strategy for boosting the photosensitivity of organic photodetectors at the expense of their response time. In addition, they have a low carrier extraction yield due to the formation of low-energy triplet excitons through the recombination of a photogenerated hole–electron pair. Materials with thermally activated delayed fluorescence (TADF) exhibit a long-lived (≈µs) excited spin-triplet nearly iso-energetically aligned with that of an excited spin-singlet, which results in suppressed exciton losses and is widely used in organic light-emitting diodes. The extraction and population of triplet state excitons in TADFs is a sought-after but underexplored aspect of photoinduced gating in photodetectors. A 1,2,3,5-tetrakis(carbazol-9-yl)4,6-Dicyanobenzene (4CzIPN) TADF blend with a high-mobility Poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT-C₁₄) polymer via bulk type-II offset can increase free carrier extraction yield (fast response) and retain trapped electrons in TADF triplet states (high gain). The PBTTT-C₁₄/4CzIPN ultraviolet photodetector device maintains a trade-off between high photogain (≈10³) and fast response time (79 ms) at 300 nm while operating at a shallow dark current (≈pA). Furthermore, the device shows high external quantum efficiency (≈10⁴ %) and detectivity (≈10¹¹ Jones) for low light power (<pW). The innovative application of TADF material can lead to exciting new developments in organic-based high-performance photodetection.     

Structural and Electronic (Absorption and Fluorescence) Properties of a Stable Triplet Diphenylcarbene: A DFT Study

A triplet diphenylcarbene, bis[3-bromo-5-(trifluoromethyl)[1,1'-biphenyl]-4-yl]methylidene (B3B), with exceptional stability was discovered by chemists from Japan's Mie University. To investigate its different quantum chemical features, a theoretical analysis was predicated on Density Functional Theory (DFT) and Time Dependent-DFT (TD-DFT) based technique. According to the findings, the singlet–triplet energy gap (ES-T), as well as HOMO–LUMO energy bandgap (E_H-L), was found to be diminished when nucleophilicity (N) rose. We looked at the geometrical dimensions, molecular orbitals (MOs), electronic spectra, electrostatic potential, molecular surfaces, reactivity characteristics, and thermodynamics features of the title carbene (B3B). Its electronic spectra in different solvents were calculated using TD-DFT and Polarizable Continuum Model (PCM) framework. The estimated absorption maxima of B3B were seen between 327 and 340 nm, relying on the solvents, and were attributed to the S⁰?→?S¹ transition. Estimated fluorescence spectral peaks were found around 389 and 407 nm with the S¹ and S⁰ transitions being identified. Its fluorescence/absorption intensities revealed a blue shift change when the solvent polarity was increased. The least exciting state has been discovered to be the π?→?π^* charge-transfer (CT) phase. According to the Natural Bonding Orbital (NBO) exploration, ICT offers a significant role in chemical system destabilization. Furthermore, several hybrid features were used to determine the NLO (nonlinear optical) features (polarizability, first-order hyperpolarizability, and dipole moment). The calculated values suggest that B3B is a promising candidate for further research into nonlinear optical properties.

Graphical Abstract

     

Features of Emission and Absorption of Indotricarbocyanine Dyes on Excitation to Higher Electronic States

The manifestation of ion pairs in the absorption and emission of fluorescence by symmetric indotricarbocyanine dyes with the same cation and anions Br, I, and BF₄ in ethanol, methylene chloride, and dichlorobenzene has been investigated. It is shown that the formation of ion pairs on passing to low-polarity solvents, along with the changes in the electronic absorption and emission spectra, manifests itself in the polarization and fluorescence excitation spectra. We were the first to establish that the presence of an equilibrium mixture of contact ion pairs and free ions in solutions has an effect on the position and probabilities of transitions not only for the first but also for higher excited singlet states of the molecules of polymethine dyes. The formation of ion pairs manifests itself more clearly when the spectral-luminescence properties of compounds in the shortwave spectral region are analyzed. It has been established that marked changes arise in the absorption, excitation, emission, and polarization fluorescence spectra, as well as in the lifetime and quantum yield of fluorescence in this spectral region when the solvent is changed.     

煤矿区水体溶解有机质三维荧光光谱特征

应用三维荧光光谱对煤矿区水体溶解有机质进行分析测定,探讨特殊环境条件下水体溶解有机质光谱特征。类富里酸荧光峰(峰Ⅰ)和类腐殖酸荧光峰(峰Ⅱ)最为显著,类蛋白荧光峰(峰Ⅳ)强度较弱。地下水体溶解有机质荧光峰强度普遍低于地表水水体同类荧光峰。受人类活动的影响,炼焦区域和采煤区水体荧光峰强于污灌区域和农业区域水体同类荧光峰。矿区人类活动剧烈,煤矿开采加工活动容易把煤中的大量烃类物质分散到周围环境中去,地表水体接受矿井排水、洗煤废水及生活污水等,地下水体则相对不容易受到污染。整个石龙区水体溶解有机质荧光集团来源较多,峰强度受pH影响不大,但在某种程度上受到水体中Ca2+含量的影响。     

Photophysical Processes in the Gas Phase at High Levels of Vibrational Excitation of Triplet Molecules of Benzophenone and Fluorenone

By the delayed fluorescence activated by direct multiphoton excitation of triplet molecules by CO₂–laser radiation we have studied the prevailing deactivation pathways of triplet molecules with a high store of vibrational energy E _vib. The dependences of the kinetic characteristics of delayed fluorescence on the presence of vapors and foreign gases have been used to estimate the rates and efficiencies of intermolecular vibrational relaxation in the vibrational quasi–continuum of the triplet state T ₁. By the changes in the intensities and decay rates over a wide range of vibrational energies we have established the E _vib dependences of reversible intercombination conversion between the states T ₁ and S ₁ and interconversion from T ₁ to the ground electronic state S ₀ for both the case of isolated excited molecules and at a steady vibrational temperature. It is shown that at high vibrational temperatures the radiationless transition from the T ₁ state to S ₀ has an activation character and is accomplished through the energy barrier. The conditions for going to an exponential dependence have been determined. It has been found that the obtained dependences are in good agreement with the known experimental results. The influence of molecular and environmental characteristics on the decay rate of triplet molecules is compared.     

Excitation of Autoionization States and Electronic Stopping Powers at Collisions of Slow Ions with a Solid

It has been shown that the excitation of autoionization states at collisions of keV ions with a solid is decisive for inelastic energy loss and, correspondingly, the electronic stopping power dE/dx. It has been proposed to estimate the electronic stopping power dE/dx using the relation of cross sections for the excitation of autoionization states to ionization cross sections. When ionization cross sections are unknown, scaling is used to calculate ionization cross sections at the excitation of the L and M shells. A threshold dependence of the electronic stopping power dE/dx on the energy of bombarding ions has been predicted.     

常规净水工艺去除有机物效果的三维荧光光谱分析法

有机物的荧光特性被广泛用来解析其在水体中的来源与分布。荧光光谱技术具有灵敏度高、选择性好、且不破坏样品结构的优点,非常适合用来研究有机物的化学和物理性质。运用三维荧光光谱分析技术对常规净水工艺中有机物的去除效果进行了研究。实验结果表明,三维荧光光谱技术能有效地揭示净水工艺中有机物的变化过程。在整个净水过程中,没有完全消除类富里酸荧光物质,也没有产生新的荧光物质。就类富里酸荧光物质的去除效果而言,混凝沉淀基本没有去除作用,过滤作用的去除率在5%～15%之间。     

High Efficiency and Stable Organic Light-Emitting Diodes Based on Thermally Activated Delayed Fluorescence Emitter

High efficiency,stable organic light-emitting diodes(OLEDs)based on 2-pheyl-4'-carbazole-9-H-Thioxanthen-9-one-10,10-dioxide(TXO-PhCz)with different doping concentration are constructed.The stability of the encapsulated devices are investigated in detail.The devices with the 10wt% doped TXO-PhCz emitter layer(EML)show the best performance with a current efficiency of 52.1 cd/A,a power efficiency of 32.7lm/W,and an external quantum efficiency(EQE)of 17.7%.The devices based on the 10wt%-doped TXO-PhCz EML show the best operational stability with a half-life time(LT50)of 80 h,which is 8h longer than that of the reference devices based on fac-tris(2-phenylpyridinato)iridium(Ⅲ)(fr(ppy)_3).These indicate excellent stability of TXO-PhCz for redox and oxidation processes under electrical excitation and TXO-PhCz can be potentially used as the emitters for OLEDs with high efficiency and excellent stability.The high-performance device based on TXO-PhCz with high stability can be further improved by the optimization of the encapsulation technology and the development of a new host for TXO-PhCz.     

Relaxation Processes at High Levels of Vibrational Excitation of Polyatomic Molecules in the Ground Electronic State

By the spectral and kinetic characteristics of the luminescence of vapors of polyatomic molecules (anthracene, anthraquinone, fluorenone) initiated by selective IR multiphoton excitation (IR MPE) of molecules in the ground electronic state S ₀ the relaxation processes proceeding under vibrational excitation of molecules to energies exceeding the energies of the lower excited electronic states have been investigated. The changes in the spectral and kinetic characteristics with increasing CO₂ laser energy density and vapor P _v and foreign gas pressure P _FG are analyzed. They are similar to the characteristics obtained for normal fluorescence of these molecules with changing vibrational energy E _vib content. On the basis of experimental data and model calculations it has been concluded that at the laser radiation densities used in the case of IR MPE the molecules reach energies considerably exceeding the energies of the electronic levels. It is shown that a nonadiabatic connection between the electronic states leads to the population of mixed electronic states isoenergetic to the vibrational levels of the ground electronic state and to emission of delayed luminescence spectrally identical to the normal luminescence of these molecules. It has been found that when high vibrational levels are populated, new relaxation channels, such as reverse electron relaxation, emission from high vibrational levels of the ground electronic state, and multiquantum vibrational energy transfer at collisions leading to a rapid establishment of vibrational equilibrium become important.     

Influence of Temperature on the Fluorescence Duration and Electronic Spectra of Metal-Free Tetrapyrroles in an Organic Polymer

Journal of Applied Spectroscopy - Spectral and luminescent characteristics and the duration of fluorescence were measured for a series of metal-free tetrapyrroles in polyvinylbutyral solid films at...     

800nm激发下AlF3基氟化物玻璃中高掺杂Er3+的上转换光谱性质

在８００ｎｍ激光二极管激发下,研究高掺杂Ｅｒ＾３＋（摩尔比大于３％）的ＡｌＦ３基（ＡＹＦ、ＡＺＦ）玻璃的红外－可见上转换发光性质。在ＡＹＦ玻璃中,５５０ｎｍ绿光上转换最佳Ｅｒ＾３＋掺杂摩尔比为６％,而在ＡＺＦ玻璃中为１２％。随着Ｅｒ＾３＋掺杂量的增加,红光与绿光上转换发光强度比（Ｉｒ／Ｉｓ）增加。这被认为与两个Ｅｒ＾３＋离子（一个在４Ｉ０／２态、另一个在＾４Ｓ３／２）的交叉弛豫过程有关。同时由于此     

Cs(8S)态的碰撞转移和高位原子态的激发

在Cs蒸气中,二步激发Cs原子至8S态,研究了其碰撞转移和高位原子态的产生过程.在1016～1017 cm-3密度范围内,测量了碰撞激发转移8S 6S→6D 6S的速率系数.由测得的荧光强度随密度的变化关系,得到k6D=(2.4±0.5)×10-10 cm3·s-1.同时研究了碰撞能量合并过程5D 5D→nL 6S(nL=9D,11S,7F),5D态是由8S→7P→5D的辐射跃迁产生的.由以前测量过的6P 5D 6S 7D的转移速率系数以及6P态的原子密度,结合荧光强度比得到碰撞能量合并过程的速率系数,对于9D,11S和7F各态,其平均值分别为(6.4±3.2)×10-10,(1.0±0.5)×10-10和(8.4±4.2)×10-10 cm3·s-1.     

空心阴极灯激发的微波等离子体炬原子/离子荧光光谱研究--钙的原子/离子荧光光谱

用强短脉冲供电技术的空心阴极灯作激发源、微波等离子体炬作原子／离子化器，建立了原子／离子荧光光谱实验装置。详细研究了微波等离子体功率、观察高度、空心阴极灯电流等因素对原子／离子荧光信号强度的影响，测量了系统对Ca的原子／离子荧光光谱的检出限。     

Determination of Interatomic Potentials for the X0(+), A0(+), and B1 States of HgKr from Fluorescence and Excitation Spectra

We present an analysis of the A0(+)(6(3)P(1))-->X0(+)(6(1)S(0)) bound-bound and bound-free fluorescence spectrum, and of the A0(+)(6(3)P(1))<--X0(+)(6(1)S(0)) and B1(6(3)P(1))<--X0(+)(6(1)S(0)) bound-bound excitation spectrum of the HgKr van der Waals molecule. The A-->X fluorescence spectrum, which was observed for the first time, as well as the excitation spectra were recorded using a pulsed supersonic molecular beam crossed with a pulsed dye laser beam. An analysis of the A(v')<--X(v"), B(v')<--X(v"), and A(v'=8)-->X(v") bound-bound bands indicates that a Morse function combined with a long-range approximation represents the interatomic potential energy curve of the A, B, and X states below the dissociation limit. In the simulation of the A(v'=8)-->X bound-free spectrum the Morse, Lennard-Jones (n-6), and Maitland-Smith (n(0), n(1)) functions were tested, and the Maitland-Smith (11.39, 10.50) potential was found to be a good representation of the repulsive part of the X-state PE curve above the dissociation limit, over the internuclear separation range R=2.85-3.55 ?. The spectroscopic characteristics for the A, B, and X states obtained in this work are compared with other available experimental and theoretical results. Copyright 2001 Academic Press.