GW/BSE级别下的非绝热动力学模拟揭示桥连化学键对调控酞菁锌-富勒烯给体-受体复合物激发态弛豫过程的重要作用（英文）

本文采用基于多体格林函数方法和Bethe-Salpeter方程(GW/BSE)的电子结构计算方法和非绝热动力学模拟研究了两种不同桥连化学键构型(5-6构型和6-6构型)的酞菁锌-富勒烯(ZnPc-C_(60))给受体复合物的激发态性质及其弛豫过程.对于6-6构型,ZnPc-C_(60)的最低激发态S_1态为光谱明态,即ZnPc的局域激发(LE)态,因此,6-6构型的ZnPc-C_(60)在光激发之后几乎不会发生电荷分离过程.相比之下,5-6构型的ZnPc-C_(60)的S_1态是C_(60)的LE态,为光谱暗态,而作为光谱明态的ZnPc的LE态的能量更高.而且,在ZnPc和C_(60)的LE态之间还存在若干电荷转移(CT)态.因此,电荷转移会在从高能的ZnPc的LE态到低能的C_(60)的LE态的弛豫过程中发生.GW/BSE级别的非绝热动力学模拟结果进一步验证了电子结构计算的结论,并给出了相关过程的时间尺度:从ZnPc到C_(60)的超快激发态能量转移过程在前200 fs完成;随后发生的是由C_(60)到ZnPc的超快空穴转移过程.本工作表明不同的桥连化学键模式(即5-6和6-6构型)可用于调节ZnPcC_(60)给体-受体复合物的激发态性质及其光电性质.与此同时,本工作证明了GW/BSE级别的非绝热动力学方法是探索非周期性给体-受体复合物、有机金属配合物、量子点、纳米团簇等复杂体系的光诱导动力学的可靠工具.     

GW/BSE级别下的非绝热动力学模拟揭示桥连化学键对调控酞菁锌-富勒烯给体-受体复合物激发态弛豫过程的重要作用

本文采用基于多体格林函数方法和Bethe-Salpeter方程(GW/BSE)的电子结构计算方法和非绝热动力学模拟研究了两种不同桥连化学键构型(5-6构型和6-6构型)的酞菁锌-富勒烯(ZnPc-C₆₀)给受体复合物的激发态性质及其弛豫过程. 对于6-6构型,ZnPc-C₆₀的最低激发态S₁态为光谱明态,即ZnPc的局域激发(LE)态,因此,6-6构型的ZnPc-C₆₀在光激发之后几乎不会发生电荷分离过程. 相比之下,5-6构型的ZnPc-C₆₀的S₁态是C₆₀的LE态,为光谱暗态,而作为光谱明态的ZnPc的LE态的能量更高. 而且,在ZnPc和C₆₀的LE态之间还存在若干电荷转移(CT)态. 因此,电荷转移会在从高能的ZnPc的LE态到低能的C₆₀的LE态的弛豫过程中发生. GW/BSE级别的非绝热动力学模拟结果进一步验证了电子结构计算的结论,并给出了相关过程的时间尺度：从ZnPc到C₆₀的超快激发态能量转移过程在前200 fs完成;随后发生的是由C₆₀到ZnPc的超快空穴转移过程. 本工作表明不同的桥连化学键模式(即5-6和6-6构型)可用于调节ZnPc-C₆₀给体-受体复合物的激发态性质及其光电性质. 与此同时,本工作证明了GW/BSE级别的非绝热动力学方法是探索非周期性给体-受体复合物、有机金属配合物、量子点、纳米团簇等复杂体系的光诱导动力学的可靠工具.     

通过飞秒泵浦探测技术研究PbS纳米颗粒的激发态瞬态动力学过程

利用飞秒泵浦探测技术研究了PbS半导体纳米颗粒复合的SiO₂溶胶凝胶薄膜的瞬态动力学过程。通过改变激发探测波长和激发光强度,研究引起PbS半导体纳米颗粒的非线性吸收的两种机制。当激发探测波长选在激子吸收峰附近(620nm)时,由于激子的饱和吸收引起的光致漂白,当激发波长选在激子能态的低能侧(753,800nm),同时观察到激子的饱和吸收和双激子效应引起的光致吸收。研究了激子的饱和吸收和双激子效应引起的激发态吸收随激发态电子-空穴对浓度的变化关系,表明双激子效应与载流子浓度有很大关系。在高激发强度下,双激子效应引起的诱导吸收远远大于激子跃迁引起的光致漂白,双激子效应在非线性吸收中起着决定性作用。     

一锅法合成四芳基吡咯并[3,2-b]吡咯空穴传输材料及其在无掺杂倒置钙钛矿太阳电池的应用（英文）

本文采用一锅法合成了四芳基吡咯并[3,2-b]吡咯有机空穴输运材料(D41、D42、D43和D44),制备出无掺杂的倒置型平面钙钛矿太阳电池.材料D41的芳环上含有甲基,具有供体-π-给体-π-供体结构;而D42、D43和D44具有受体-π-给体-π-受体结构,其中,芳环上分别含有氰基、氟和三氟甲基.研究表明,芳环上取代基对其分子表面电荷分布和空穴输运层薄膜形貌有显著影响,钙钛矿晶体颗粒的大小与空穴输运材料分子结构有关,含有氰基的材料D42最有利于形成较大的钙钛矿晶粒,这主要是由于吡咯并[3,2-b]吡咯结构具有丰富的电子性质的缘故.D42制备的倒置型平面钙钛矿太阳电池光电转换效率为17.3%,在黑暗条件下22天后,仍保留了初始效率的55%.吡咯并[3,2-b]吡咯结构具有良好的给电子特性,可作为高效钙钛矿薄膜的空穴传输材料.     

使用超快拉曼光谱技术研究四极矩给体-受体-给体分子的激发态动力学

具有对称结构和四极矩性质的给体-受体-给体分子在激发态通常展现出从离域的电荷转移态向局域的电荷转移态转化的电荷重分布过程，该现象已被多种超快时间分辨光谱技术进行了大量研究. 飞秒受激拉曼光谱是一种常用的超快时间分辨光谱，该光谱可以通过检测分子内特定的振动模来研究分子激发态动力学. 本研究采用的4，4''-(1，3-丁二炔-1，4-二基)双(N，N-二(4-甲氧苯基)苯胺)含有位于中间位置的两个相邻炔基(电子受体)和对称分布在分子两侧的N，N-二(4-甲氧苯基)苯胺(电子给体). 研究发现，飞秒受激拉曼光谱能够实时观测该分子在溶剂中发生的激发态电荷重分布过程. 该结果将有助于深入研究具有相邻特征官能团的对称四极矩分子光致电荷局域/离域动力学.     

共轭高分子中激子演化过程的非绝热动力学研究

有机共轭高分子受光激发或被电荷掺杂后可能会产生各种激发状态的激子,激子的演化过程对有机发光光谱有着至关重要的影响.通过非绝热动力学演化的方法模拟了受光激发后有机高分子中激子驰豫的动力学过程,结果表明高激发态激子不稳定,由于电声耦合作用,高激发态激子会持续向低激发态激子演化,同时,低激发态激子的复合发光会发生红移.稳定的激子复合发光光谱中,基态激子发光强度最大,可高达70-80%;第一激发态激子及其它激发态激子发光强度的总和不超过20%.     

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.     

聚合物中产生双激子的新通道

由于聚合物中的双激子能产生新奇的光致极化反转现象,如何在聚合物中产生双激子变成为一个重要的研究课题.在现在已知的产生双激子的通道以外,提出了一条新的通道:双电子激发,并用动力学方法研究了此通道产生双激子的弛豫过程(包括键结构畸变和电子态的方面),确定了双激子形成和极化反转所需要的时间. 关键词： 聚合物 双激子 通道     

分子聚集体中激子-激子湮灭过程

分子的激发能量转移和电荷转移是提高光伏电池和发光二极管效率的关键问题,其中分子聚集体中的激子-激子湮灭过程是影响分子激发能量转移的重要方面,细致研究激子-激子湮灭的动力学过程并与相关的瞬间吸收谱信号对比对相关的理论和实验都有重要意义.本文在分子间弱耦合近似下,用经典的率方程,应用方酸分子的基本参数对激子-激子湮灭过程做...     

一锅法合成四芳基吡咯并[3,2-b]吡咯空穴传输材料及其在无掺杂倒置钙钛矿太阳电池的应用

本文采用一锅法合成了四芳基吡咯并[3,2-b]吡咯有机空穴输运材料(D41、D42、D43和D44),制备出无掺杂的倒置型平面钙钛矿太阳电池. 材料D41的芳环上含有甲基,具有供体-π-给体-π-供体结构;而D42、D43和D44具有受体-π-给体-π-受体结构,其中,芳环上分别含有氰基、氟和三氟甲基. 研究表明,芳环上取代基对其分子表面电荷分布和空穴输运层薄膜形貌有显著影响,钙钛矿晶体颗粒的大小与空穴输运材料分子结构有关,含有氰基的材料D42最有利于形成较大的钙钛矿晶粒,这主要是由于吡咯并[3,2-b]吡咯结构具有丰富的电子性质的缘故. D42制备的倒置型平面钙钛矿太阳电池光电转换效率为17.3%,在黑暗条件下22天后,仍保留了初始效率的55%. 吡咯并[3,2-b]吡咯结构具有良好的给电子特性,可作为高效钙钛矿薄膜的空穴传输材料.     

Synthesis and fluorescence properties of carbazole and fluorene-based compounds

Three donor-acceptor (D-A) conjugated compounds consisted of carbazole and fluorene (Scheme 1) were synthesized via Wittig-Horner, Ullmann or Sonogashira reaction. Their photoluminescence properties were investigated in solution and solid state, respectively. Luminescence in various solvents revealed the intramolecular charge transfer (ICT) process exists in these D-A molecules. Correlation between the Stokes’ shifts and solvent polarity parameters indicated that moderate large dipole moments exist in the excited states.     

Initial-Condition Sensitivity and Nonlinear Relaxation in Photo-Induced Ionic-to-Neutral Phase Transition in Tetrathiafulvalen- p -Chloranil Crystals

Recent experimental results of the photoinduced ionic-to-neutral (NI) phase transition in tetrathiafulvalen- p -chloranil (TTF-CA) crystals are reviewed with emphasis on the state-sensitive features and nonlinear properties. Frenkel-type and charge transfer (CT)-type excited states can induce the NI transition but with different characteristics; the transition can be induced only above threshold-excitation intensities in the case of CT excitation, whereas it is induced without any threshold for Frenkel-type excitation. The threshold that implies nonlinear processes of CT excited states is strongly state-dependent and temperature-dependent. Femtosecond time-resolved studies have resolved three distinctive sequential steps in the dynamics; formation of the precursor of N-phase domains, the local proliferation of photoinduced changes, and the process of forming N-phase orders. Origin of the nonlinear processes and the mechanism of the NI transition have been discussed based on these results.     

电场对ZnCdSe-ZnSe应变超晶格光致发光的影响

n=1重空穴激子和施主-受主(D-A)对的光致发光在常压MOCVD生长的Zn0.85Cd0.15Se-ZnSe应变超晶格中被观测到了.激子和施主-受主对发光峰值位置随着增加正向偏置电压都相继产生蓝移和红移.这是由量子限制斯塔克效应引起的,究竟是蓝移还是红移则取决于由肖特基势垒引起的内部自建电场与外加正向电压引起的外电场之间的竞争.     

吩噻嗪衍生物的分子内电荷转移激发态的特性

合成了一系列的N-10位取代的吩噻嗪给体受体化合物,这些受体包括苯、苯甲醚、吡啶、萘、苯乙酮和苯乙腈.研究了不同极性溶剂中这些化合物的分子内的光诱导电荷转移现象.稳态荧光的溶剂化效应和较大的Stokes位移清楚表明,仅仅后四种吩噻嗪衍生物的激发态存在着分子内的电荷转移,而苯和苯甲醚取代吩噻嗪因为受体部分氧化电势低,所以不具有这种特性.修正过的Lippert-Mataga公式被用来分析Stokes位移值,从而获得激发态偶极矩.较大的激发态偶极矩说明在激发态时这四种给体受体化合物体系内发生了完全的电子转移.氧化还原电势的数据表明基态时这四种衍生物给体受体部分的作用比较弱.分析荧光光谱获得的结果说明伴随着电荷转移这四种衍生物的激发态构型变化比较小,给体和受体间的扭转角在电荷转移后的激发态与在基态时相似.     

Experimental and Theoretical Studies of the Spectroscopic Properties of Chalcone Derivatives

Newly synthesized, differently substituted chalcones (1,3-diaryl-2-propen-1-ones) have been studied using steady-state and time-resolved techniques combined with quantum-chemical modelling. To explore spectroscopic structure - property relationships the substituent (acceptor moiety) was chosen according to systematic variation in the Hammett parameter. It was shown that photophysical properties of the studied donor-acceptor (D-A) molecules can be predicted in terms of a simple model from the properties of individual chromophores (composite-model of decoupled moieties: donor (D) and acceptor (A)). The results of spectroscopic measurements also indicate that for investigated D-A fluorophores in medium-polar solvent, the initially populated, locally excited (LE) state (where the fundamental role plays donor moiety (D*-A)) reacts further to produce intramolecular charge transfer (ICT) state. Additionally, the experimental absorption (M _ge ) and fluorescence (M _eg ) transition dipole moments were calculated on the basis of spectroscopic data and compared with results of our quantum-chemical calculations. The absorption transition dipole moment was found to vary linearly with the Hammett substituent coefficient (σ).     

Theory for photoinduced structural phase transitions

A general concept for photoinduced structural phase transitions is developed in terms of the hidden multistability of the ground state and the proliferations of optically excited states. Taking the ionic→neutral (I - N) phase transition in the organic charge transfer crystal, TTF—CA, as a typical example for this type of transition, we, at first, theoretically show an adiabatic path of this transition, which starts from a single charge transfer exciton in the ionic phase, but finally reaches a neutral domain with a macroscopic size. In connection with this I—N transition, the concept of the initial condition sensitivity is also developed so as to clarify experimentally observed nonlinear characteristics of this material. In the next, using a more simplified model for the many-exciton system, we theoretically study the early time quantum dynamics of the exciton proliferation, which finally results in the domain formation of a large number of ex-citons. For this purpose, we derive a stepwise iterative equation to describe the exciton proliferation, and clarify the origin of the initial condition sensitivity.     

Nondoped blue fluorescent OLED based on cyanophenanthrimidazole‐styryl‐triphenylamine/carbazole materials

New 2‐(4′‐9H‐carbazole‐9‐yl)‐styryl‐1H‐phenathro[9,10‐d]imidazole‐1‐yl)benzonitrile (SPICN‐Cz) and 4‐(2‐(4‐(diphenylamino)phenyl‐styryl‐1H‐phenathro[9,10‐d]imidazole‐1‐yl)benzonitrile (SPICN‐TPA) have been synthesised, and their photophysical, electrochemical, and electroluminescent properties were analysed in comparison with their cyano‐free parent compounds, SPI‐Cz, and SPI‐TPA. Solvatochromic effects show the transformation of an excited state character from locally excited (LE) state to charge transfer (CT) state. Using time‐dependent density functional theory calculation, the excited state properties of these donor‐acceptor blue emissive materials have been analysed. Their excited state properties have been tuned by replacing the strong donor triphenylamine to weak donor carbazole to achieve the combination of high photoluminance efficiency locally excited (LE) component and high exciton‐utilizing CT component in one excited state. Hybridization processes between LE and CT components of SPICN‐Cz and SPICN‐TPA in the emissive state have been discussed. The nondoped organic light emitting diode device based on SPICN‐Cz exhibit better electroluminescent performances than those of SPICN‐TPA–based device: high external quantum efficiency of 2.58 %, current efficiency of 2.90 cd A^‐1, and power efficiency of 2.26 lm W^‐1 with Commission Internationale de l'Éclairage (CIE) coordinates of (0.15, 0.12). The excited state modulation and the composition of LE and CT states in the donor‐acceptor system could be useful to design low‐cost, high‐efficiency fluorescent organic light emitting diode materials.