共轭高分子中激子形成的非绝热动力学研究

有机共轭高分子被光激发后,其电子结构会发生明显的变化,通过非绝热数值计算的方法模拟了受光激发后有机高分子中激子生成的动力学过程.结果表明,激子的生成一般需要数十飞秒时间,激子的生成周期随分子链长度的增大而增大.高激发态激子可以根据生成周期分为两类,第一类激子的生成周期在数十到上百飞秒之间,第二类激子的生成周期可达上千飞秒.对于超过200个碳原子的高分子,第二类激子的生成周期可达5000飞秒以上.这个计算结果说明,相比于有机高分子,有机小分子中更容易观测到激子.     

有机高分子链内的场致激子解离

基于SSH(Su-Schrieffer-Heeger)模型,采用静态及动力学自洽算法模拟了有机高分子链内激子在光激发及外电场作用下的形成与解离过程。结果表明,受光激发后,有机高分子链内激子的生成与解离密切依赖于施加外电场的时机,当外电场与光激发同时发生时,激子能否生成完全取决于电场强度的大小;而当外电场在光激发后的一段时间(通常为皮秒量级)之后被引入,则在有机高分子链内能够形成稳定的激子,且该激子只有在强外电场(超过1MV/cm)的作用下,才会发生解离,临界场强量级与实验结果相符合。     

电场中高分子的发光和激子的解离

研究了电场对高分子的发光及激子的影响.1.在强电场中，激子会解离成正负极化子对，这可定量解释最近观察到的实验：(1)电场超过1.5MV/cm时，PPP衍生物的发光强度很快减弱；(2)电场对4.5MV/cm时，发光强度减为24%；(3)电场使发光光谱向蓝色移动.2.高分子中π电子具有“离域性”，易于极化.算得高分子中激子具有很大的极化率，比氢原子大三个数量级以上. 关键词：     

高低温条件下氟化锂材料的离子激发发光光谱分析

在北京师范大学GIC4117串列加速器原有离子激发发光(ion beam induced luminescence,IBIL)分析靶室基础上,安装了可实现80—900 K温度范围内精确控温的冷热样品台,实现高低温条件下IBIL光谱的测量.添加金硅面垒探测器,在离子辐照材料样品过程中同步采集背散射离子的计数,实现束流的在线监测.在不同温度下,利用2 MeV H~+束轰击氟化锂样品,获得的IBIL光谱中可明显观察到温度对不同发光中心发光效果的影响:激子峰和杂质峰发光在低温条件下更为清晰;高温时各类型F色心的发光强度在较小的注量下即可达到饱和值或开始衰减.辐照初期受扰激子峰(296 nm)发光强度的上升过程表明不能排除受扰激子峰与点缺陷发光中心相关的可能性,激子峰强度的上升源自低注量时核弹性碰撞产生的应变键;温度对空位迁徙速率及非辐射复合的影响是造成发光强度随注量演变差异的重要原因.     

CdSe/ZnSe复合结构非对称量子阱的发光特性

利用MOCVD技术在GaAs衬底上外延生长了非对称量子阱结构CdSe/ZnSe材料,通过对其稳态变温光谱及变激发功率光谱,研究了其发光特性。稳态光谱表明:在82～141K时,观测到的两个发光峰来源于不同阱层厚度的量子阱激子发光,用对比实验验证了高能侧发光的来源。宽阱发光强度先增加后减小,将其归结为激子隧穿与激子热离化相互竞争的结果。通过Arrhenius拟合,对宽阱激子热激活能进行了计算。82K时变激发功率PL光谱表明:由于激子隧穿的存在,使得窄阱发光峰位不随激发功率变化而变化,宽阱发光峰位随激发功率增加发生了蓝移,并对激子隧穿进行了实验验证。     

共轭聚合物中受激吸收与受激辐射的量子动力学研究

基于扩展的一维SSH紧束缚模型结合非绝热的分子动力学方法,理论研究了共轭聚合物分子(PPV)在光脉冲作用下受激吸收和受激辐射的量子动力学过程.首先,设定分子初始处于基态,讨论了受激吸收过程中不同的电子受激跃迁模式与光激发脉冲的关系.通过对终态的分析,发现分子受激后只能产生电子-空穴的束缚态,包括:激子、双激子和高能激子.计算了各种激发态的产率,特别是,给出了各种激发态产率与光激发能量的定量关系.此外,基于实验,分别讨论了光激发强度对高能激子和双激子产率的影响,并与实验结果进行了比较.最后,设定分子初始分别处于激子和双激子态,研究了分子内定域能级之间的受激辐射过程,并简单讨论了激子和双激子受激辐射与光激发能量及强度的关系.     

MEH-PPV/SiO_2异质结发光机理和非晶SiO_2二次特性的研究

在薄膜电致发光中采用有机聚合物MEH-PPV和无机半导体SiO_2复合制成异质结发光器件,利用SiO_2的加速、倍增和离化的二次特性,实现了固态阴极射线发光.结构为ITO/SiO_2/MEH-PPV/SiO_2/Al的发光器件,其电致发光光谱的显著特征是有两个发光谱带.光谱中除了波长较长(峰值为583 nm)的MEH-PPV的激子发光谱外,还观察到了波长较短(峰值为403 nm)的蓝色发光谱,并且长短波的发光强度随着电压的不同而变化.电压较低时,只有长波光发射.当电压较高时,只有短波光存在.这种有两个谱带的发光是固态阴极射线发光的独特标志,它是一种全新的激发方式,引发出发光学中一些新而重要的问题.固态阴极射线发光理论的重要方面之一就足SiO_2的二次特性.文章研究了固态阴极射线发光动力学问题,高电场下SO_2二次特性及厚度对二次特性的影响.     

神经网络法研究多溴代二苯胺热力学性质

通过时间分辨光谱技术详细地研究了ZnCuInS/ZnSe/ZnS量子点的激子弛豫动力学. 基于速率分布模型,波长依赖的发射动力学表明本征激子、界面缺陷态中的激子、给-受体对态中的激子都会参与量子点的发光过程,整个发光过程主要依赖于给-受体对态发射. 瞬态吸收数据表明激发后本征激子和界面缺陷物种可能会同时出现,在高激发光强下,光强依赖的俄歇复合过程也存在于量子点中     

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。     

有机发光材料中的三重激发态（英文）

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。     

Room-temperature exciton storage in elongated semiconductor nanocrystals

The excited state of colloidal nanoheterostructures consisting of a spherical CdSe nanocrystal with an epitaxially attached CdS rod can be perturbed effectively by electric fields. Field-induced fluorescence quenching coincides with a conversion of the excited state species from the bright exciton to a metastable trapped state (dark exciton) characterized by a power-law luminescence decay. The conversion is reversible so that up to 10% of quenched excitons recombine radiatively post turn-off of a 1 micro s field pulse, increasing the delayed luminescence by a factor of 80. Excitons can be stored for up to 10(5) times the natural lifetime, opening up applications in optical memory elements.     

Luminescence spectra produced by exciton relaxation at local magnetization fluctuations in semimagnetic semiconductors

An analysis is made of the exciton angular-momentum alignment along a fluctuation in local magnetization, which is the first stage in evolution of the localized-exciton spin state in a semimagnetic semiconductor. It is shown that spin relaxation of localized excitons subjected to resonant optical excitation is accompanied by their relaxation in energy. When excited by polarized light, this process gives rise to an anisotropic angular-momentum distribution in the spectrum of final exciton states and, hence, to polarization of the secondary luminescence. Luminescence spectra of a cubic crystal are calculated, and the possibility of their experimental observation discussed. Fiz. Tverd. Tela (St. Petersburg) 40, 2156–2160 (December 1998)     

共轭高聚物双分子结构中激子电致解离的动力学研究

通过绝热动力学方法，研究了共轭高聚物双分子结构中激子对外加电场的响应.当外电场强度超过某个临界值时，激子会被解离成一对自由的电子与空穴.对于双分子结构中的激子，其临界解离电场除了受电子与电子相互作用以及电声相互作用影响之外，还受分子间相互作用的影响.由动力学演化的计算得到，激子临界解离电场强度随分子间相互作用强度的增大而呈非线性降低；随电子与电子相互作用强度的增大呈非线性减小的变化；但是，随电声耦合强度的增大却呈现出线性增大的变化.     

Magneto-optical properties and exciton dynamics in diluted magnetic semiconductor nanostructures

Nanostructures of diluted magnetic semiconductors were fabricated to study novel magneto-optical properties that are derived from quantum confined band electrons interacting with magnetic ions. Quantum dots (QDs) of Cd_0.97Mn_0.03Se were grown by the self-organization on a ZnSe substrate layer. QDs of Zn_0.69Cd_0.23Mn_0.08Se and quantum wires (QWRs) of Cd_0.92Mn_0.08Se and Zn_0.69Cd_0.23Mn_0.08Se were fabricated by the electron beam lithography. A single quantum well (QW) of ZnTe/Zn_0.97Mn_0.03Te and double QWs of Cd_0.95Mn_0.05Te–CdTe were grown by molecular beam epitaxy. Magneto-optical properties and the formation and relaxation dynamics of excitons were investigated by ultrafast time-resolved photoluminescence (PL) spectroscopy. Excitons in these nanostructures were affected by the low-dimensional confinement effects and the interaction with magnetic ion spins. The exciton luminescence of the Cd_0.97Mn_0.03Se QDs shows the confined exciton energy due to the dot size of 4–6 nm and also shows marked increase of the exciton lifetime with increasing the magnetic field. The QDs of Zn_0.69Cd_0.23Mn_0.08Se fabricated by the electron beam lithography display narrow exciton PL spectrum due to the uniform shape of the dots. The exciton luminescence from the QWRs of Cd_0.92Mn_0.08Se and Zn_0.69Cd_0.23Mn_0.08Se shows the influence of the one-dimensional confinement effect for the exciton energy and the luminescence is linearly polarized parallel to the wire direction. The transient PL from the ZnTe/Zn_0.97Mn_0.03Te QWs displays, by the magnetic field, the level crossing of the exciton spin states of the nonmagnetic and magnetic layers and the spatial spin separation for the excitons. Cd_0.95Mn_0.05Te–CdTe double QWs show the injection of the spin polarized excitons from the magnetic well to the nonmagnetic QW.     

Effect of heteroboundary spreading on the properties of exciton states in Zn(Cd)Se/ZnMgSSe quantum wells

Exciton states in Zn(Cd)Se/ZnMgSSe quantum wells with different diffusion spreading of interfaces are studied by optical spectroscopy methods. It is shown that the emission spectrum of quantum wells at low temperatures is determined by free excitons and bound excitons on neutral donors. The nonlinear dependence of the stationary photoluminescence intensity on the excitation power density and the biexponential luminescence decay are explained by the neutralization of charged defects upon photoexcitation of heterostructures. With the stationary illumination on, durable (about 40 min) reversible changes in the reflection coefficient near the exciton resonances of quantum wells are observed. It is shown that, along with the shift of exciton levels, the spreading of heteroboundaries leads to three effects: an increase in the excitonphonon interaction, an increase in the energy shift between the emission lines of free and bound excitons, and a decrease in the decay time of exciton luminescence in a broad temperature range. The main reasons for these effects are discussed.     

Tunneling and reflection of an exciton incident upon a quantum heterostructure barrier

We investigate, in one spatial dimension, the quantum mechanical tunneling of an exciton incident upon a heterostructure barrier. We model the relative motion eigenstates of the exciton using a form of the one-dimensional hydrogen atom which avoids difficulties previously associated with 1D hydrogenic states. We obtain probabilities of reflection and transmission using the method of variable transmission and reflection amplitudes. Our calculations may be broadly divided into two sets. In the first set, we consider general qualitative aspects of exciton tunneling, such as the effect of different effective masses for electrons and holes and a relative difference in electron and hole barrier strengths. The second set models the tunneling of an exciton in a GaAs/Al(x)Ga(1-x)As heterostructure. In these calculations we find that, for energies such that the two lowest exciton states are coupled, the probability spectrum for transition from the ground state to the first excited state is identical to that for transition from the first excited state to the ground state. In addition, narrow peaks in the probability spectrum for transition are observed across this energy range for low dopant concentration x. Other interesting phenomena correlated with these peaks in the transition probability are reported.     

Triplet exciton states in ammonium tetraphenylborate crystals

In the study of spontaneous exciting luminescence of polycrystalline BPh₄NH₄ structures, it was shown that observed luminescence is caused by triplet exciton states which are stable at low temperatures under dark conditions. Triplet excitons are formed when an electron is transferred from the anionic part of complexes to cations of neighboring complexes. The ATPB crystal structure makes it possible to switch ∼2% of complexes from states with S = 0 to the state with S = 1, i.e., to provide high density of data recording. Information is read when luminescence is excited and is erased when a structure is heated to room temperatures. Switching of ATPB states from S = 0 to S = 1 by light should be of interest for spintronics.     

Anomalous energy transfer dynamics due to torsional relaxation in a conjugated polymer

In isolated conjugated polymers two explanations are in discussion for the redshift of the emission on a picosecond time scale-exciton energy transfer (EET) between conjugated segments along the chains and conformational changes of these segments themselves, i.e., torsional relaxation. In order to resolve this question we perform femtosecond time-resolved transient absorption measurements of the energy relaxation of poly[3-(2,5-dioctylphenyl)thiophene] in toluene solution. We show that torsional relaxation can be distinguished from EET by site-selectively exciting low-energy conjugated segments. We present a unified model that integrates EET and torsional dynamics. In particular, comparison to ultrafast depolarization measurements shows that torsional dynamics cannot be neglected when analyzing EET dynamics and furthermore reveals that the exciton extends itself by about 2 monomer units during torsional relaxation.     

共轭高聚物双分子链中激子生成的动力学研究

通过对耦合共轭高分子双链中激子生成的动力学研究,讨论了受到光激发后,激子在分子内或分子间生成的制约因素.激子的生成除了受分子链间耦合强度的制约,还受到光激发模式的影响.结果表明,激子既可以在分子内生成,也可以在耦合分子间生成.增大分子之间的相互作用强度,可以增大在分子之间生成激子的概率.