聚合物发光器件中激子的解离与复合效率

对聚合物发光器件中极化子激子的形成与解离过程进行了详细探讨,提出了极化子激子解离的理论模型及解离概率的解析式,分析了激子解离后正、负极化子的输运过程,认为是极化子的链间跃迁实现了聚合物的电导,计算并讨论了内量子效率随外加电场、温度及杂质浓度的变化关系.该模型较好地解释了有关实验现象. 关键词： 聚合物发光器件 极化子激子 激子解离 内量子效率     

基态非简并聚合物中的极化子和双极化子动力学

研究了极化子和双极化子在基态非简并聚合物中的动力学.弱电场下，发现载流子为带电极 化子或双极化子，它们的晶格态与电荷态始终耦合在一起同步运动.极化子比双极化子的运 动速度快，存在饱和速度，且它们的饱和速度随聚合物非简并度的增加而降低；强电场下， 元激发的电荷态将脱离晶格态的束缚而快速运动，参与导电的不再是极化子或双极化子，而 是电子直接导电. 关键词： 极化子 双极化子 动力学模拟     

二维链间扩展的极化子动力学研究

基于扩展的SSH模型,研究了有序耦合聚合物链系统中的极化子动力学,包括极化子的形成过程及其在外场下的输运.发现,当聚合物链间的耦合较强时,注入到系统中的电子会诱发二维链间扩展的极化子态,分布在多条聚合物链上.另外,动力学模拟表明,与一维链内定域极化子相比,在相同的电场强度下二维极化子具有更大的运动速度,这与实验结果一致. 关键词： 链间扩展极化子 链间耦合     

链间耦合对聚合物中双激子态反向极化的影响

从紧束缚模型出发，研究了链间相互作用对双激子态反向极化的影响.结果发现：加链间耦合后，双激子态仍主要局域在一条链中.当简并破缺较小时，反向极化程度随耦合强度的增加大幅提高；当简并破缺较大时，反向极化程度随耦合强度的增加基本不变. 关键词： 反向极化 双激子态 链间耦合     

有机共轭高聚物的分子链间耦合局域态

有机共轭高分子中,孤子、极化子及激子都是基本的元激发,对解释有机聚合材料的导电发光特性起着主导作用.孤子、极化子以及激子等在晶格位形上都是各具特征的空间局域状态.本文将讨论在有机共轭高分子中存在着另一种局域态——链间耦合局域态,这种局域态是由于分子链间的相互作用所导致,在相互作用分子链端附近形成势阱,可有效束缚电子和空穴等带电粒子.     

高聚物中极化子和三重态激子的碰撞过程研究

采用一维紧束缚近似的SSH模型,计算了不同强度的电场下高聚物中一个负电极化子和一个三重态激子的碰撞过程.结果表明,碰撞后体系仍保持为极化子和三重态激子状态的几率最大,束缚在极化子缺陷中的电子有较大的几率被激发到导带形成自由电子,另外,三重态激子有一定的几率被极化子湮灭形成极化子激发态.极化子和激子的碰撞对极化子的稳定性有影响,还会使能隙中出现新的能级.由于极化子激发态可以通过辐射跃迁回到基态,因此碰撞会对高聚物的电致发光效率产生一定影响.研究结果对于理解高聚物中极化子的输运性质和高聚物的发光性质具有一定的 关键词： 极化子 激子 高聚物     

链间耦合对聚乙炔多链体系中电子极化子再激发态的影响

采用拓展紧束缚Su-Schrieffer-Heeger(SSH)模型,研究了链间耦合对反式聚乙炔多链体系中电子极化子再激发态的晶格位形、净电荷密度、局域能级波函数和态密度的影响.结果发现:对于两条链体系,当链间耦合很小(t⊥≤0.01 e V)时,注入到系统中的电子只会在第一条链上诱发产生一个晶格缺陷,形成电子极化子再激发态,这和单链体系是一致,而第二条链仍是二聚化基态.随着链间耦合的增大,第一条链上缺陷的局域度减少而第二条链上的缺陷局域度相应增加,直至两条链上的位形相同;对于多条链(5条链和6条链)体系,当耦合很小(t⊥≤0.05 e V)时,电子极化子再激发态也只会存在于一条链上,当链间耦合较强时,极化子再激发态会在链间层次性地扩展开来,并不会出现多条链位形相同;从两条链的能级图上可以看到随着链间耦合t⊥的增大,体系的带隙不断的增大和电子态密度显示的是完全吻合的,体系的导电性减弱.通过分析两条链体系在t⊥=0 e V和t⊥=0.1 e V的能级态密度,发现链间耦合越强,则中间局域能级的态密度越小,最后没有中间局域态.     

链间耦合对聚乙炔多链体系中电子极化子再激发态的影响

从拓展紧束缚模型出发,研究了链间耦合对反式聚乙炔多链体系中电子极化子再激发态的晶格位形、净电荷密度、局域能级波函数和态密度的影响。结果发现：对于两条链体系,当链间耦合很小（eV）时,注入到系统中的电子只会在第一条链上诱发产生一个晶格缺陷,形成电子极化子再激发态,这和单链体系是一致,而第二条链仍是二聚化基态。随着链间耦合的增大,第一条链上缺陷的局域度减少而第二条链上的缺陷局域度相应增加,直至两条链上的位形相同。对于多条链（5条链和6条链）体系,当耦合很小（0.05eV）时,电子极化子再激发态也只会存在于一条链上,当链间耦合较强时,极化子再激发态会在链间层次性地扩展开来,并不会出现多条链位形相同。从两条链的能级图上可以看到随着链间耦合的增大,体系的带隙不断的增大和电子态密度显示的是完全吻合的,体系的导电性减弱。通过分析两条链体系在eV和eV的能级态密度,发现链间耦合越强,则中间局域能级的态密度越小,最后没有中间局域态。     

导电聚合物P3MT的光调制反射谱

本文报道了导电聚合物光调制反射光谱的研究工作。实验观察到聚三甲基噻吩的带间跃迁和与双极化子态有关的跃迁,并且观察了谱结构随掺杂浓度、温度以及调制光强度的变化。实验结果证明,光子能量大于禁带宽度E_g的光可在聚合物分子链中诱导产生双极化子。虽然双极化子可以由光诱导产生,也可以由杂质诱导产生,但它本身是不依赖于诱导方式的聚合物分子链的本征元激发态。荷电的双极化子可受离化杂质的库仑吸引,产生钉扎效应,并使禁闭参数变大。 关键词：     

基态非简并聚合物中的极化子和双极化子的动力学(Ⅱ)--强电场下研究

本文模拟了基态非简并聚合物中的极化子和双极化子在强电场中的运动 ,研究了在不同简并参数的系统中极化子和双极化子的动力学稳定性,发现在强场下简并参数对极化子的稳定性影响不大,极化子晶格畸变的运动滞后于电子的运动,价带上的电子在强电场的激发下参与导电.双极化子在简并参数大的系统中较为稳定.     

Inelastic scattering of oppositely charged polarons in conjugated polymers

Within an one-dimensional tight-binding model, we investigate the inelastic scattering processes of oppositely charged polarons in conjugated polymers under the influence of an external electric field, by using a nonadiabatic evolution method. It is found that the polaron pair does not necessarily scatter into an entity(neutral exciton), but a mixed state composed of both polarons and excitons. The yield of the neutral exciton depends sensitively on the strength of applied fields. Additionally, effects of interchain coupling on the scattering processes are also discussed, which shows that the interchain coupling is of fundamental importance and facilitates the formation of the polaron-exciton.     

Dynamics of photogenerated polarons in conjugated polymers

Within a tight-binding electron-phonon interacting model, we investigate the dynamics of photoexcitations to address the generation mechanism of charged polarons in conjugated polymers by using a nonadiabatic evolution method. Besides the neutral polaron exciton which is well known, we identify a novel product of lattice dynamic relaxation from the photoexcited states in a few hundreds of femtoseconds, which is a mixed state composed of both charged polarons and neutral excitons. Our results show that the charged polarons are generated directly with a yield of about 25%, which is independent of the excitation energies, in good agreement with results from experiments. Effects of the conjugation length are also discussed.     

有机高分子中光生极化子的物理机制

有机聚合物中光生载流子（荷电极化子）产生的物理机制是一个非常重要的物理问题，但一直存在争议，文章介绍了作者对此问题的最新研究结果：荷电极化子和中性激子一样，是由光激发直接产生的，而不是激子解体的结果，其生成时间在100fs的量级．荷电极化子的量子产率约为25％，并且与激发能量无关，与实验观测的结果一致．     

Optically detected magnetic resonance studies of luminescence‐quenching processes in π‐conjugated materials and organic light‐emitting devices

It is widely recognized that nonradiative quenching of excitons by other excitons and polarons become the dominant decay mechanism of these excitons at high excitation densities. These quenching processes cause the roll‐off in the efficiency of organic light‐emitting devices (OLEDs) and prevent lasing at high injection current densities. This review presents the optically‐detected magnetic resonance (ODMR) evidence for these photoluminescence‐ and electroluminescence‐quenching processes. And while it provides such evidence for quenching of singlet excitons by polarons and triplet excitons, it reveals the central role of the strongly spin‐dependent annihilation of triplet excitons by polarons, since under normal excitation conditions the steady‐state polaron and triplet exciton populations are 100–10⁴ times the singlet exciton population. In addition, it also suggests that quenching of singlet excitons by bipolarons, likely stabilized by a counterpolaron or countercharge at specific sites, may also be a significant quenching mechanism that also affects the charge transport properties.     

Polaronic exciton in quantum wells wires and nanotubes

We investigate the effect of the longitudinal-optical phonon field on the binding energies of excitons in quantum wells, well-wires and nanotubes based on ionic semiconductors. We take into account the exciton-phonon interaction by using the Aldrich-Bajaj effective potential for Wannier excitons in a polarizable medium. We extend the fractional-dimensional method developed previously for neutral and negatively charged donors to calculate the exciton binding energies in these heterostructures. In this method, the exciton wave function is taken as a product of the ground state functions of the electron polaron and hole polaron with a correlation function that depends only on the electron-hole separation. Starting from the variational principle we derive a one-dimensional differential equation, which is solved numerically by using the trigonometric sweep method. We find that the potential that takes into account polaronic effects always give rise to larger exciton binding energies than those obtained using a Coulomb potential screened by a static dielectric constant. This enhancement of the binding energy is more considerable in quantum wires and nanotubes than in quantum wells. Our results for quantum wells are in a good agreement with previous variational calculations. Also, we present novel curves of the exciton binding energies as a function of the wire and nanotubes radii for different models of the confinement potential.     

The effect of interface hopping on inelastic scattering of oppositely charged polarons in polymers

The inelastic scattering of oppositely charge polarons in polymer heterojunctions is believed to be of fundamental importance for the light-emitting and transport properties of conjugated polymers. Based on the tight-binding SSH model, and by using a nonadiabatic molecular dynamic method, we investigate the effects of interface hopping on inelastic scattering of oppositely charged polarons in a polymer heterojunction. It is found that the scattering processes of the charge and lattice defect depend sensitively on the hopping integrals at the polymer/polymer interface when the interface potential barrier and applied electric field strength are constant. In particular, at an intermediate electric field, when the interface hopping integral of the polymer/polymer heterojunction material is increased beyond a critical value, two polarons can combine to become a lattice deformation in one of the two polymer chains, with the electron and the hole bound together, i.e., a self-trapped polaron-exciton. The yield of excitons then increases to a peak value. These results show that interface hopping is of fundamental importance and facilitates the formation of polaron-excitons.     

电子关联对聚乙炔中激子类型的影响

在SSH哈密顿基础上引进电子关联,对反式聚乙炔链中光致激子的产生和演化过程实施分子动力学模拟。弱关联强度U取值0～1.250 eV,V =U/2取值0～0.625 eV .计算结果表明,关联强度的大小影响链中元激发类型,U＜0.555eV时产生的元激发为孤子-反孤子对,U ＞0.555eV 时产生的元激发为正负荷电极化子对。为进一步讨论该类型一维系统中不同类型激子的产生、输运、衰减等动态过程,关联强度U的选择提供参考。     

Spin Physics of Excitons in Colloidal Nanocrystals

We present a review of spin-dependent properties of excitons in semiconductor colloidal nanocrystals. The photoluminescences (PL) properties of neutral and charged excitons (trions) are compared. The mechanisms and the polarization of radiative recombination of a “dark” (spin-forbidden) exciton that determines the low-temperature PL of colloidal nanocrystals are discussed in detail. The radiative recombination of a dark exciton becomes possible as a result of simultaneous flips of the surface spin and electron spin in a dark exciton that leads to admixture of bright exciton states. This recombination mechanism is effective in the case of a disordered state of the spin system and is suppressed if the polaron ferromagnetic state forms. The conditions and various mechanisms of formation of the spin polaron state and possibilities of its experimental detection are discussed. The experimental and theoretical studies of magnetic field-induced circular polarization of PL in ensembles of colloidal nanocrystals are reviewed.     

Stark effect of negatively and positively charged excitons in semiconductor quantum wells

We study the effect of an electric field applied normal to the layers on the binding energy of charged excitons (or trions) in GaAs quantum wells. We find that, in contrast to the neutral exciton, their binding energy is sharply reduced by modest electric fields. The effect is stronger for the positively charged exciton than the negatively charged one. The ionisation of the excess carrier is explained by the field-induced polarisation of the electron and hole subband wave functions.