杂质对柱形量子点系统束缚能的影响

在有效质量近似和变分原理的基础上,考虑内建电场(BEF)效应和量子点的三维约束效应.研究了纤锌矿结构的GaN/AlxGa1xN单量子点中杂质体系的基态能量与杂质电荷的关系,讨论了杂质电子的束缚能随量子点的主要结构参数(量子点高度L和量子点半径R)以及杂质在量子点中不同位置的变化规律,并研究了考虑量子点内外电子有效质量失配对杂质电子束缚能的影响.     

量子环上双电子激发态的研究

研究外加电场以及荷电杂质电场对量子环上双电子激发态的影响.结果表明:激发态对含有双电子的量子环中的能谱和持续电流具有控制作用,在某些情况下相邻能级和持续电流的振幅可增至几个数量级.该结论对于设计和研制微器件具有指导意义.     

镧系荧光探针DATTA-Eu~(3+)光诱导电子转移机理的理论计算

含有镧系金属铕的DATTA-Eu~(3+)络合物是基于光诱导电子转移(PET)的荧光探针分子,能够高灵敏、高选择性地监控一氧化氮.应用含时密度泛函理论计算方法研究该探针分子的荧光开-关效应和PET机理.结果表明:联三吡啶分子作为配体和荧光母体,受光激发后发生HOMO到LUMO的电子跃迁,由于与其共价相连的邻二氨基苯氧基团的HOMO轨道能级高于联三吡啶HOMO轨道能级,能够将电子转移到单电子占据的联三吡啶HOMO轨道,使激发态电子无法正常回落,阻断了能量向中心Eu~(3+)离子的转移,无法产生铕的特征荧光.当邻二氨基苯氧基团与NO反应生成苯并三唑后,其HOMO轨道能级降低,PET过程被阻断,联三吡啶返回基态时将能量转移到Eu~(3+)离子而产生铕的特征荧光.     

基于位阻效应调控的D- A-π- A型三苯胺敏化染料的设计与性能研究

纯有机敏化染料分子结构，特别是染料分子的平面性变化能够有效调控分子的多种性能.将具有不同位阻效应的甲氧基和羟基基团分别引入到染料分子中，合成了具有D-A-π-A结构的敏化染料CS-75和CS-76,并对其结构和性能进行了深入研究.结果表明，具有较小位阻效应基团的CS-76的平面性更强，其产生较强的H-聚集导致荧光寿命和电子注入效率均低于CS-75,基于CS-76的电池器件的光电转换效率也较低.这项工作为纯有机敏化染料的分子设计提供参考.     

麦芽糖在CdS量子点表面吸附的荧光光谱

用巯基丙酸作稳定剂,合成了水溶性好、单分散的Cd S量子点,利用麦芽糖对Cd S量子点的荧光猝灭效应,研究了麦芽糖在Cd S量子点表面的吸附行为.结果表明:量子点的荧光猝灭效应受到p H值和量子点浓度的显著影响,并且与吸附在量子点表面的麦芽糖分子数有关,麦芽糖分子在Cd S量子点表面吸附符合Langmuir等温吸附方程.c/ΔF与浓度c成很好的直线关系,浓度的变化范围达到3个数量级.根据Langmuir等温吸附方程式,在较低的浓度范围内,ΔF与浓度c也成很好的直线关系,利用这种直线关系可以建立麦芽糖的定量分析方法,检出限达到nmol级.     

单自旋量子精密测量——基于钻石量子传感器的微观磁共振

量子精密测量作为基于量子力学原理发展起来的精密测量技术,正成为各学科发展的重要推动力.此处所谓的单自旋量子精密测量一层含义是指以金刚石中的一类点缺陷——氮-空位色心单自旋为量子信息载体,通过光探测磁共振方式对其进行检测;另一层面是指通过微波射频的操控将氮-空位色心单自旋制备成量子传感器,实现高灵敏度高空间分辨率的微观磁共振,甚至可以达到对单电子/单核自旋检测的水平.这一技术用量子传感代替电学探测模式,将传统磁共振的检测能力在空间上从毫米推进到纳米尺度,分子数从数十亿推进到单个分子水平.基于氮-空位色心的量子精密测量技术仍处于快速发展阶段,其正在被应用于二维材料磁性研究、超导、单分子结构、单细胞磁检测等方向,有望为物理、化学、生命科学甚至医学等领域的发展提供重要支撑.本文首先介绍单自旋量子精密测量的基本概念和原理,接着着重介绍本课题组近年基于氮-空位色心的量子精密测量相关实验研究,包括单分子顺磁共振、纳米核磁共振、基础物理等方面的相关进展及未来研究展望.     

单分子二极管整流特性的第一性原理计算

在分子电子学领域中, 设计分子的结构可以实现特定的功能. 单分子二极管的整流行为是极具吸引力的器件功能之一. 研究了对称分子和非对称分子结的电子输运, 分别对应为四苯基和二嘧啶基二苯基单分子结, 二者均是共价结合到两金属电极. 与其同源对称嵌段相比, 非对称二嵌段分子表现出明显的整流行为, 且电子输运方向是从二苯基流向二嘧啶基. 利用密度泛函理论(density functional theory, DFT)和非平衡格林函数(non-equilibrium Green's function, NEGF)结合的第一性原理方法研究了单分子结的电子结构及其量子输运. 电流-电压 ($I$-$V$)曲线的非对称性可以用非对称分子二嵌段在偏压下由于电子态的局域性带来的非平衡效应进行解释. 本理论计算定性上符合其他小组的实验结果, 且尝试了不同的末端接触. 结果发现, 实验中的扫描隧道显微镜(scanning tunneling microscope, STM)针尖接触结构会一定程度地抵消非对称分子的整流效应, 而 STM 针尖接触结构的结果分析也符合之前的理论预测.     

菁染料增感溴化银体系时间分辨荧光动力学研究

利用皮秒时间分辨条纹相机技术检测了3种不同染料在立方体和T-颗粒溴化银上吸附后形成聚集体的荧光光谱, 分析了不同染料在不同浓度下对染料聚集体到溴化银导带的超快电子转移过程的影响, 进而分析其对增感效率的影响关系, 并探讨了增感过程的微观机理. 实验结果表明, 荧光衰减的动力学曲线与双指数函数拟合得相当好, 存在一快一慢衰减成分, 快衰减成分占拟合较大比例, 认为其源于与荧光衰减相竞争的从激发态染料聚集体到AgBr导带的电子转移. 光致电子转移的速率及增感效率随着染料相对浓度的变化而改变, 不同染料增感的乳剂, 其变化趋势不同.     

双量子点系统单态三重态传输诱导的散粒噪声

基于有效粒子数分辨的量子主方程和全计数统计,研究了耦合双量子点系统电子输运性质,讨论了源极和漏极的极化程度、电子在量子点中的自旋交换作用对平均电流、散粒噪声的影响,给出了平均电流和散粒噪声在不同的交换耦合下随电极极化率的变化特征,分析了自旋单态和三重态在电子输运过程中对平均电流和散粒噪声的贡献,并借助于自旋阻塞引起的聚束效应解释了超泊松散粒噪声的形成。     

准一维多嵌段共聚物有机量子阱和超晶格特征

在紧束缚模型的基础上, 研究了由聚乙炔(PA)和聚对苯撑(PPP)组成的准一维多嵌段共聚物系列材料的电子特性, 发现它们具有量子阱或超晶格特征. 各单体的尺度、单体间界面耦合以及电子-声子相互作用的强弱对共聚物的电子性质都有显著的影响, 与传统半导体量子阱和超晶格相似, 沿链方向外加电场的作用, 可导致量子隧穿的发生以及Franz-Keldysh效应和量子约束效应的出现.     

电场对脉冲激光沉积纳米Si晶粒尺寸和面密度分布的影响

为了研究外加电场对脉冲激光沉积纳米Si晶粒的影响,采用XeCl准分子激光器,烧蚀高阻抗单晶Si靶,在10 Pa氩气环境下,调整外加电压的强度,沉积制备了一系列Si薄膜.X线衍射(XRD)谱仪、拉曼(Raman)谱、扫描电子显微镜(SEM)图像均显示纳米Si晶粒已经形成,随着靶衬间距的增加,所形成的纳米Si晶粒的平均尺寸...     

Attosecond control of electrons emitted from a nanoscale metal tip

Attosecond science is based on steering electrons with the electric field of well controlled femtosecond laser pulses. It has led to the generation of extreme-ultraviolet pulses with a duration of less than 100 attoseconds (ref. 3; 1 as = 10(-18) s), to the measurement of intramolecular dynamics (by diffraction of an electron taken from the molecule under scrutiny) and to ultrafast electron holography. All these effects have been observed with atoms or molecules in the gas phase. Electrons liberated from solids by few-cycle laser pulses are also predicted to show a strong light-phase sensitivity, but only very small effects have been observed. Here we report that the spectra of electrons undergoing photoemission from a nanometre-scale tungsten tip show a dependence on the carrier-envelope phase of the laser, with a current modulation of up to 100 per cent. Depending on the carrier-envelope phase, electrons are emitted either from a single sub-500-attosecond interval of the 6-femtosecond laser pulse, or from two such intervals; the latter case leads to spectral interference. We also show that coherent elastic re-scattering of liberated electrons takes place at the metal surface. Owing to field enhancement at the tip, a simple laser oscillator reaches the peak electric field strengths required for attosecond experiments at 100-megahertz repetition rates, rendering complex amplified laser systems dispensable. Practically, this work represents a simple, extremely sensitive carrier-envelope phase sensor, which could be shrunk in volume to about one cubic centimetre. Our results indicate that the attosecond techniques developed with (and for) atoms and molecules can also be used with solids. In particular, we foresee subfemtosecond, subnanometre probing of collective electron dynamics (such as plasmon polaritons) in solid-state systems ranging in scale from mesoscopic solids to clusters and to single protruding atoms.     

LB膜和SA膜中的分子取向研究

LB(Langmuir-Blodgett）膜技术是一项有近70多年历史的技术，由于技术条件的限制，发展一直较慢，近10年来，随着纳米技术的飞速发展，日益显示出LB膜技术在纳米材料应用方面的优越性。LB膜分子间具有规整的排列和各向异性，可以实现能量转移及电子转移。通过LB膜技术可以控制分子尺度；设计成膜技术可以组装分子可以组装分子取向，进行有序分子组装，得到大面积单分子层。SA（Self-Assembly）膜技术提供了在分子水平上构造理想界面的方便手段，由于得到的膜具有传统LB膜的均一性和稳定性，近年来也成为研究的热点。     

Experimental evidence for sub-3-fs charge transfer from an aromatic adsorbate to a semiconductor

The ultrafast timescale of electron transfer processes is crucial to their role in many biological systems and technological devices. In dye-sensitized solar cells, the electron transfer from photo-excited dye molecules to nanostructured semiconductor substrates needs to be sufficiently fast to compete effectively against loss processes and thus achieve high solar energy conversion efficiencies. Time-resolved laser techniques indicate an upper limit of 20 to 100 femtoseconds for the time needed to inject an electron from a dye into a semiconductor, which corresponds to the timescale on which competing processes such as charge redistribution and intramolecular thermalization of excited states occur. Here we use resonant photoemission spectroscopy, which has previously been used to monitor electron transfer in simple systems with an order-of-magnitude improvement in time resolution, to show that electron transfer from an aromatic adsorbate to a TiO(2) semiconductor surface can occur in less than 3 fs. These results directly confirm that electronic coupling of the aromatic molecule to its substrate is sufficiently strong to suppress competing processes.     

Internal motions of a quasiparticle governing its ultrafast nonlinear response

A charged particle modifies the structure of the surrounding medium: examples include a proton in ice, an ion in a DNA molecule, an electron at an interface, or an electron in an organic or inorganic crystal. In turn, the medium acts back on the particle. In a polar or ionic solid, a free electron distorts the crystal lattice, displacing the atoms from their equilibrium positions. The electron, when considered together with its surrounding lattice distortion, is a single quasiparticle, known as the Fr?hlich polaron. The basic properties of polarons and their drift motion in a weak electric field are well known. However, their nonlinear high-field properties--relevant for transport on nanometre length and ultrashort timescales--are not understood. Here we show that a high electric field in the terahertz range drives the polaron in a GaAs crystal into a highly nonlinear regime where, in addition to the drift motion, the electron is impulsively moved away from the centre of the surrounding lattice distortion. In this way, coherent lattice vibrations (phonons) and concomitant drift velocity oscillations are induced that persist for several hundred femtoseconds. They modulate the optical response at infrared frequencies between absorption and stimulated emission. Such quantum coherent processes directly affect high-frequency transport in nanostructures and may be exploited in novel terahertz-driven optical modulators and switches.     

酮戊二酸接枝壳聚糖-纳米金粒子复合物固定漆酶基电极的催化氧还原性能

以α－酮戊二酸接枝壳聚糖和纳米金溶胶共混所得复合物为固定漆酶的载体,将固酶复合物滴涂在裸玻碳电极表面干燥后,得到固定漆酶基阴极。文章考察了此电极在不含底物的电解质溶液中的直接电化学行为,同时还考察了其在扩散型电子中介体存在时的异相电子迁移动力学,同时研究了此电极对氧气还原反应的催化性能（中介体存在时）。在此基础上进一步考察了此电极作为氧气电化学传感器的性能。研究结果表明：α－酮戊二酸接枝壳聚糖一纳米金溶胶复合物固定漆酶修饰电极在无电子中介体时不能实现漆酶活性中心与电极之间的直接电子迁移,也不具备催化氧还原的性能。在扩散型电子中介体存在时,该电极能在较高的电位（催化氧还原的起始电位：790mV）下实现氧气的电还原,而且对氧气浓度较为敏感。这种漆酶基电极的在生理pH值时仍具有一定的催化活力。这种电极对氧的传感性能良好：检测限低达0．5×10－6mol／L、灵敏度高达35．6×10-6AL／mmol和良好的对氧亲和力（KM=89．9×10mol／L）。     

Direct measurement of hole transport dynamics in DNA

Our understanding of oxidative damage to double helical DNA and the design of DNA-based devices for molecular electronics is crucially dependent upon elucidation of the mechanism and dynamics of electron and hole transport in DNA. Electrons and holes can migrate from the locus of formation to trap sites, and such migration can occur through either a single-step "superexchange" mechanism or a multistep charge transport "hopping" mechanism. The rates of single-step charge separation and charge recombination processes are found to decrease rapidly with increasing transfer distances, whereas multistep hole transport processes are only weakly distance dependent. However, the dynamics of hole transport has not yet been directly determined. Here we report spectroscopic measurements of photoinduced electron transfer in synthetic DNA that yield rate constants of approximately 5 x 10(7) s(-1) and 5 x 10(6) s(-1), respectively, for the forward and return hole transport from a single guanine base to a double guanine base step across a single adenine. These rates are faster than processes leading to strand cleavage, such as the reaction of guanine cation radical with water, thus permitting holes to migrate over long distances in DNA. However, they are too slow to compete with charge recombination in contact ion pairs, a process which protects DNA from photochemical damage.     

Electron dynamics in collisionless magnetic reconnection with a PIC simulation

Two-dimensional particle-in-cell (PIC) simulation is used to investigate electron dynamics in collisionless magnetic reconnection, and the proton/electron mass ratio is taken to be m _i /m _e = 256. The results show that the presence of a strong initial guide field will change the direction of the electron flow. The electron density cavities and the parallel electric field can be found in the electron inflow region along the separatrix, and the electron inflow and density cavities only appear in the second and fourth quadrants. What is different from the results with a smaller mass ratio is that new structures appear in the diffusion region near the X line: (1) Narrow regions of density enhancement and density cavities can be found synchronously in this region; and (2) corresponding to the electron density changes near the X line, the strong parallel electric fields are found to occur in the first and third quadrants. These electric fields perhaps play a more important role in acceleration and heating electrons than those fields located in the density cavities. Supported by National Natural Science Foundation of China (Grant No. 40725013) and Open Research Program Foundation of State Key Laboratory for Space Weather, Chinese Academy Sciences     

Visualizing single-molecule diffusion in mesoporous materials

Periodic mesoporous materials formed through the cooperative self-assembly of surfactants and framework building blocks can assume a variety of structures, and their widely tuneable properties make them attractive hosts for numerous applications. Because the molecular movement in the pore system is the most important and defining characteristic of porous materials, it is of interest to learn about this behaviour as a function of local structure. Generally, individual fluorescent dye molecules can be used as molecular beacons with which to explore the structure of--and the dynamics within--these porous hosts, and single-molecule fluorescence techniques provide detailed insights into the dynamics of various processes, ranging from biology to heterogeneous catalysis. However, optical microscopy methods cannot directly image the mesoporous structure of the host system accommodating the diffusing molecules, whereas transmission electron microscopy provides detailed images of the porous structure, but no dynamic information. It has therefore not been possible to 'see' how molecules diffuse in a real nanoscale pore structure. Here we present a combination of electron microscopic mapping and optical single-molecule tracking experiments to reveal how a single luminescent dye molecule travels through linear or strongly curved sections of a mesoporous channel system. In our approach we directly correlate porous structures detected by transmission electron microscopy with the diffusion dynamics of single molecules detected by optical microscopy. This opens up new ways of understanding the interactions of host and guest.     

外电场作用下水分子结构和电子光谱

采用密度泛函B3P86方法在aug—cc—pvqz基组水平上优化得到了在不同外电场（-0．06-0．05a．u．）作用下,水分子的基态电子状态、几何结构、电偶极矩和分子总能量。在优化构型下利用杂化CIS-DFT方法（CIS-B3P86）研究了同样外电场条件下对水分子的激发能和振子强度的影响。计算结果表明,基态分子几何构型与电场大小呈现强烈的依赖关系,分子偶极矩m随电场的增加而减小。分子总能量随着电场增加而降低。无论是正向还是反向外电场作用下,激发能随电场增加而减小,表明在外电场作用下,分子易于激发和离解。