Unmasking electronic energy transfer of conjugated polymers by suppression of O(2) quenching

The photochemistry of poly[2-methoxy, 5-(2'-ethyl-hexyloxy)-p-phenylene-vinylene] (MEH-PPV) has been found to be highly dependent on the presence of O(2), which increases singlet exciton quenching dramatically. Spectroscopy on isolated single molecules of MEH-PPV in polycarbonate films that exclude O(2) reveals two distinct polymer conformations with fluorescence maxima near 555 and 580 nanometers wavelength, respectively. Time-resolved single-molecule data demonstrate that the 580-nanometer conformation exhibits a "landscape" for intramolecular electronic energy relaxation with a "funnel" that contains a 580-nanometer singlet exciton trap at the bottom. The exciton traps can be converted to exciton quenchers by reaction with O(2). Conformationally induced, directed-energy transfer is arguably a critical dynamical process that is responsible for many of the distinctive photophysical properties of conjugated polymers.     

Phase diagram of degenerate exciton systems

Degenerate exciton systems have been produced in quasi-two-dimensional confined areas in semiconductor coupled quantum well structures. We observed contractions of clouds containing tens of thousands of excitons within areas as small as (10 micron)2 near 10 kelvin. The spatial and energy distributions of optically active excitons were determined by measuring photoluminescence as a function of temperature and laser excitation and were used as thermodynamic quantities to construct the phase diagram of the exciton system, which demonstrates the existence of distinct phases. Understanding the formation mechanisms of these degenerate exciton systems can open new opportunities for the realization of Bose-Einstein condensation in the solid state.     

Multiple exciton collection in a sensitized photovoltaic system

Multiple exciton generation, the creation of two electron-hole pairs from one high-energy photon, is well established in bulk semiconductors, but assessments of the efficiency of this effect remain controversial in quantum-confined systems like semiconductor nanocrystals. We used a photoelectrochemical system composed of PbS nanocrystals chemically bound to TiO(2) single crystals to demonstrate the collection of photocurrents with quantum yields greater than one electron per photon. The strong electronic coupling and favorable energy level alignment between PbS nanocrystals and bulk TiO(2) facilitate extraction of multiple excitons more quickly than they recombine, as well as collection of hot electrons from higher quantum dot excited states. Our results have implications for increasing the efficiency of photovoltaic devices by avoiding losses resulting from the thermalization of photogenerated carriers.     

Stepwise quenching of exciton fluorescence in carbon nanotubes by single-molecule reactions

Single-molecule chemical reactions with individual single-walled carbon nanotubes were observed through near-infrared photoluminescence microscopy. The emission intensity within distinct submicrometer segments of single nanotubes changed in discrete steps after exposure to acid, base, or diazonium reactants. The steps were uncorrelated in space and time and reflected the quenching of mobile excitons at localized sites of reversible or irreversible chemical attack. Analysis of step amplitudes revealed an exciton diffusional range of about 90 nanometers, independent of nanotube structure. Each exciton visited about 10,000 atomic sites during its lifetime, providing highly efficient sensing of local chemical and physical perturbations.     

Control of exciton fluxes in an excitonic integrated circuit

Efficient signal communication uses photons. Signal processing, however, uses an optically inactive medium, electrons. Therefore, an interconnection between electronic signal processing and optical communication is required at the integrated circuit level. We demonstrated control of exciton fluxes in an excitonic integrated circuit. The circuit consists of three exciton optoelectronic transistors and performs operations with exciton fluxes, such as directional switching and merging. Photons transform into excitons at the circuit input, and the excitons transform into photons at the circuit output. The exciton flux from the input to the output is controlled by a pattern of the electrode voltages. The direct coupling of photons, used in communication, to excitons, used as the device-operation medium, may lead to the development of efficient exciton-based optoelectronic devices.     

Control of energy transfer in oriented conjugated polymer-mesoporous silica composites

Nanoscale architecture was used to control energy transfer in semiconducting polymers embedded in the channels of oriented, hexagonal nanoporous silica. Polarized femtosecond spectroscopies show that excitations migrate unidirectionally from aggregated, randomly oriented polymer segments outside the pores to isolated, aligned polymer chains within the pores. Energy migration along the conjugated polymer backbone occurred more slowly than Forster energy transfer between polymer chains. The different intrachain and interchain energy transfer time scales explain the behavior of conjugated polymers in a range of solution environments. The results provide insights for optimizing nanostructured materials for use in optoelectronic devices.     

基态非简并的共聚物的掺杂机制

根据共聚物掺后电导及光学性质的改变，提出了基态非简并的共聚物的掺杂机制。沿链是极化子和双极化子态，而链间是由于双极化子的跳跃；较好地解释了有关实验事实。     

Excimers and exciplexes of conjugated polymers

Observations of intermolecular excimers in several pi-conjugated polymers and exciplexes of these polymers with tris(p-tolyl) amine are reported. It is shown that the luminescence of conjugated polymer thin films originates from excimer emission and that the generally low quantum yield is the result of self-quenching. Thus, in sufficiently dilute solution, the "single-chain" emission has a quantum yield of unity. Exciplex luminescence and exciplex-mediated charge photogeneration have much higher quantum yields than the excimer-mediated photophysical processes. These results provide a basis for understanding and controlling the photophysics of conjugated polymers in terms of supramolecular structure and morphology.     

Integrated optoelectronic devices based on conjugated polymers

An all-polymer semiconductor integrated device is demonstrated with a high-mobility conjugated polymer field-effect transistor (FET) driving a polymer light-emitting diode (LED) of similar size. The FET uses regioregular poly(hexylthiophene). Its performance approaches that of inorganic amorphous silicon FETs, with field-effect mobilities of 0.05 to 0.1 square centimeters per volt second and ON-OFF current ratios of >10(6). The high mobility is attributed to the formation of extended polaron states as a result of local self-organization, in contrast to the variable-range hopping of self-localized polarons found in more disordered polymers. The FET-LED device represents a step toward all-polymer optoelectronic integrated circuits such as active-matrix polymer LED displays.     

Two-dimensional electronic excitations in self-assembled conjugated polymer nanocrystals

Several spectroscopic methods were applied to study the characteristic properties of the electronic excitations in thin films of regioregular and regiorandom polythiophene polymers. In the regioregular polymers, which form two-dimensional lamellar structures, increased interchain coupling strongly influences the traditional one-dimensional electronic properties of the polymer chains. The photogenerated charge excitations (polarons) show two-dimensional delocalization that results in a relatively small polaronic energy, multiple absorption bands in the gap where the lowest energy band becomes dominant, and associated infrared active vibrations with reverse absorption bands caused by electron-vibration interferences. The relatively weak absorption bands of the delocalized polaron in the visible and near-infrared spectral ranges may help to achieve laser action in nanocrystalline polymer devices using current injection.     

北京地区大叶黄杨越冬进程中光系统Ⅱ的行为特征

利用PAM2100调制式叶绿素荧光仪与氧电极技术,监测常绿阔叶植物大叶黄杨在北京地区越冬进程中光系统Ⅱ(PSⅡ)行为特征的转变。结果表明:随着越冬进程的推进,光合放氧速率和PSⅡ光化学效率相继降低,阳生叶降低的幅度均比阴生叶大。深冬,阳生叶的荧光诱导曲线的动力学变化完全消失,而阴生叶能保持一定的荧光动力学变化。同时,植物采取多种防御措施相互配合,保护PSⅡ反应中心:首先,初始荧光(Fo)与最大PSⅡ光化学效率(FV/Fm)同步降低,表明植物通过减小捕光天线系统的方式减少过多光能对PSⅡ反应中心的激发压;其次,光化学猝灭(qP)始终较高,表明PSⅡ通过保持较高的开放程度,减少激发能在PSⅡ供体侧的积累;最后,非线性电子传递与天线系统之外的热耗散是大叶黄杨越冬进程重要的光保护机制。     

利用瞬态荧光技术研究单重态激子裂变的电荷转移模型

有机材料中单重态激子的裂变过程,由于其在有机光伏器件中的潜在应用而成为一个科学研究的热点.传统的观点采用电荷转移模型来解释激子裂变过程,即认为2个参与裂变的分子之间通过两次的电荷转移来实现分子状态的改变.而在电荷转移的物理图像中,又包括双空穴转移方式和双电子转移方式两种可能性.为了检验电荷转移模型的合理性,将能够发生激子裂变过程的红荧烯分子分别混合于其他4种有机分子中,这4种有机分子被当作间隔分子,用来分离混合膜中掺杂的红荧烯分子.对红荧烯分子与间隔分子,二者间HOMO能级的能量差构成空穴转移的隧穿势垒,而二者间LUMO能级的能量差构成电子转移的隧穿势垒.对4个样品发光衰减曲线的测量与分析表明,激子裂变的速率与电子隧穿势垒的高度具有明显的关联,这从实验角度首次印证了双电子转移模型而否定了双空穴转移模型.     

Observation of charge transport by negatively charged excitons

We report transport of electron-hole complexes in semiconductor quantum wells under applied electric fields. Negatively charged excitons (X-), created by laser excitation of a high electron mobility transistor, are observed to drift upon applying a voltage between the source and drain. In contrast, neutral excitons do not drift under similar conditions. The X- mobility is found to be as high as 6.5 x 10(4) cm2 V-1 s-1. The results demonstrate that X- exists as a free particle in the best-quality samples and suggest that light emission from opto-electronic devices can be manipulated through exciton drift under applied electric fields.     

Architecture of a charge-transfer state regulating light harvesting in a plant antenna protein

Energy-dependent quenching of excess absorbed light energy (qE) is a vital mechanism for regulating photosynthetic light harvesting in higher plants. All of the physiological characteristics of qE have been positively correlated with charge transfer between coupled chlorophyll and zeaxanthin molecules in the light-harvesting antenna of photosystem II (PSII). We found evidence for charge-transfer quenching in all three of the individual minor antenna complexes of PSII (CP29, CP26, and CP24), and we conclude that charge-transfer quenching in CP29 involves a delocalized state of an excitonically coupled chlorophyll dimer. We propose that reversible conformational changes in CP29 can "tune" the electronic coupling between the chlorophylls in this dimer, thereby modulating the energy of the chlorophyll-zeaxanthin charge-transfer state and switching on and off the charge-transfer quenching during qE.     

聚丁二炔甲苯硫胺中的振子强度和激子的斯塔克（Stark）移动

本文利用量子近似计算了聚丁二炔甲硫胺中基态与最低激发态之间的振子强度和激子的斯塔克移动，讨论了支配其非线性光学响应的机理。     

Quantum coherence in an optical modulator

Semiconductor quantum well electroabsorption modulators are widely used to modulate near-infrared (NIR) radiation at frequencies below 0.1 terahertz (THz). Here, the NIR absorption of undoped quantum wells was modulated by strong electric fields with frequencies between 1.5 and 3.9 THz. The THz field coupled two excited states (excitons) of the quantum wells, as manifested by a new THz frequency- and power-dependent NIR absorption line. Nonperturbative theory and experiment indicate that the THz field generated a coherent quantum superposition of an absorbing and a nonabsorbing exciton. This quantum coherence may yield new applications for quantum well modulators in optical communications.     

The effect of alumina on the electrical conductivity of silicate perovskite

Measurements of the electrical conductivity of silicate perovskite at 25 gigapascals and 1400 degrees to 1600 degreesC show that the conductivity of (Mg,Fe)SiO3 perovskite containing 2.89 weight percent Al2O3 is about 3.5 times greater than that of aluminum-free (Mg0.915Fe0.085)SiO3 perovskite. The conduction mechanism in perovskite between 1400 degrees and 1600 degreesC is most likely by polarons, because Mossbauer studies show that the aluminum-bearing perovskite has about 3.5 times the amount of Fe3+ as the aluminum-free sample. A conductivity-depth profile from 660 to 2900 kilometers based on aluminum-bearing perovskite is consistent with geophysical models.     

A tunable diode based on an inorganic Semiconductor&cjs3539;Conjugated polymer interface

Although in principle semiconductor-metal (Schottky) diodes should be tunable by changing the work function of the metal, such flexibility cannot be achieved in a single device and in practice is often limited by interfacial states that cause Fermi-level pinning. A tunable diode is reported based on a hybrid inorganic-organic, n-indium phosphide&cjs3539;poly- (pyrrole)&cjs3539;nonaqueous electrolyte architecture. By electrochemically manipulating the work function of the conjugated polymer poly(pyrrole), the turn-on voltage (more precisely, the forward bias potential required to pass a particular current) of the diode can be continuously and actively tuned by more than 0.6 volt. The work highlights a distinguishing feature of conjugated polymers relative to more traditional semiconductor materials, namely, the ability of dopant ions to permeate conjugated polymers, thereby enabling electrochemical manipulation.     

含共轭三键的聚合物的掺杂机理和导电特性的研究

以聚丁（对甲苯硫酸）－２，４－己炔－１，６－二醇酯（ＰＤＡ－ＴＳ）为例，探讨了含共轭三键的聚合物的掺杂和导电特性的研究，对其微观掺杂机制，在比较现有的掺杂模型的基础上，提出了新的掺杂模型。     

Shape and temperature memory of nanocomposites with broadened glass transition

Shape-memory polymers can revert to their original shape when they are reheated. The stress generated by shape recovery is a growing function of the energy absorbed during deformation at a high temperature; thus, high energy to failure is a necessary condition for strong shape-memory materials. We report on the properties of composite nanotube fibers that exhibit this particular feature. We observed that these composites can generate a stress upon shape recovery up to two orders of magnitude greater than that generated by conventional polymers. In addition, the nanoparticles induce a broadening of the glass transition and a temperature memory with a peak of recovery stress at the temperature of their initial deformation.