纳腔等离激元对分子上和分子旁边的隧穿电子诱导发光的作用研究（英文）

本文使用含时量子主方程,从理论上计算了当分子或者等离激元分别被激发的情形下等离激元-分子耦合体系发光特性的时间和光谱演化,并在此基础上讨论了纳腔等离激元在扫描隧道显微镜(STM)诱导发光中发挥的不同作用.当STM针尖在分子上方,隧穿电子可以直接激发分子时,纳腔等离激元的主要作用是通过提高分子的辐射速率来增强其发光,此时耦合体系表现出具有分子特征的尖锐发光峰.另一方面,当STM针尖非常靠近分子边缘但没有载流子注入直接激发分子时,等离激元-分子之间的相干耦合会在这两个量子客体之间产生相消干涉,导致在分子激子能量附近出现法诺共振,使我们观察到具有法诺凹谷特征的等离激元发光光谱.     

单分子尺度的光量子态调控与单分子电致发光研究

分子尺度上的光电相互作用研究可以为发展未来信息和能源技术提供科学基础.扫描隧道显微镜不仅可以用来观察和操纵纳米世界中的原子和分子,而且其高度局域化的隧穿电流还可以被用来激发隧道结中的分子,使之发光,以研究局域场下的分子光电特性.本文综述了中国科学技术大学单分子光电研究组近期在锌酞菁分子电致发光方面取得的科学进展,包括：1）利用有效的电子脱耦合与纳腔等离激元调控技术,实现了隧穿电子激发下的单个锌酞菁分子的电致荧光,并通过发展相关的光子发射统计测量方法,表征了单个分子在隧穿电子激发下的电致荧光具有单光子发射特性;2）发展了具有亚纳米空间分辨的荧光光谱成像技术,实现了对酞菁分子间相干偶极相互作用特征的实空间观察;3）对分子与纳腔等离激元之间的相干耦合作用进行了亚纳米精度的操控,在单分子水平上观察到了法诺共振和兰姆位移效应.这些研究结果不仅为研发基于有机分子的电泵纳米光源与单光子光源等分子光电器件提供了新的思路,而且为在单分子尺度上研究分子光电特性、分子间能量转移以及场与物质之间的相互作用规律等提供了新的表征方法.     

扫描隧道显微镜诱导单分子发光热荧光现象的全量子理论

使用量子主方程方法从理论上研究了STM诱导分子电致发光现象,并特别考虑了分子和量子化等离激元相互作用对于单分子光学性质的影响. 分子-等离激元相互作用大大增加了分子的自发辐射速率和分子发光的的强度,而且当分子自发辐射速率和振动弛豫速率可比拟的时候,将会出现热荧光现象.     

钠原子连接的C_(60)富勒烯二聚物的等离激元激发

基于含时密度泛函理论,研究了钠原子连接的C60富勒烯二聚物的等离激元激发。由于碱金属钠原子和C60分子之间的耦合,在红外光谱区,钠原子连接的C60富勒烯二聚物出现了等离激元共振激发。随着C60分子之间间隙的逐渐减小,红外光谱区的等离激元先发生红移,之后发生了蓝移。在间隙较大,C60分子间电容性相互作用时,中红外光谱区的等离激元是一种多极共振模式。在间隙较小时,由于电子的隧穿,中红外光谱区的等离激元逐渐演化为近红外光谱区的另外一种等离激元共振模式,该等离激元共振模式是长程电荷转移激发模式和多极共振模式的耦合。     

二维方形量子点体系等离激元的量子化

量子点体系等离激元的研究是光电子学领域的热点.为进一步加深和完善对等离激元的量子效应的认识,本文利用紧束缚近似和线性响应理论研究了二维方形量子点体系对外场的集体响应.结果表明,当外场频率等于等离激元的频率时,量子点体系会有强烈的电荷振荡,并伴随着能量的极大吸收和近场的增强.在量子点中,等离子体存在分立的元激发.等离子体元激发的个数将随着量子点尺寸和电子个数的增加而增加.随量子点尺寸的增加,分立的等离激元将逐步呈现准连续的特性,即过渡为经典连续的等离激元,其频谱曲线演化为经典的色散曲线.结果还表明:随量子点尺寸的增加,等离激元的频率会红移,等离激元的激发强度会增大;随量子点中电子数的增加,等离激元的频率会蓝移,等离激元的激发强度会增大.     

光激发作用下分子与多金属纳米粒子间的电荷转移研究

金属纳米粒子在光激发作用下的增强作用是纳米科学领域的一个研究热点. 针对分子和多个不同位形下的金属纳米粒子在光激发下的相互作用展开了理论研究. 应用密度矩阵理论描述分子和金属纳米粒子同时激发产生表面等离激元后的电荷输运过程. 研究发现, 表面等离激元增强效应与分子和各个金属纳米粒子的相对位置有密切关系. 详细分析了金属纳米粒子间的耦合强度、分子和金属纳米粒子间的耦合强度、表面等离激元能级杂化、分子激发能和外场频率对表面等离激元增强效应的影响.     

Ag(100)表面α-6T分子的自组装和STM诱导发光

利用扫描隧道显微镜诱导发光技术, 对有机分子α-6T在Ag(100)表面的自组装和光子发射特性进行了研究. 发现在极低的覆盖率下,α-6T分子以四个分子形成一种独特的风车形状的异构体. 随着覆盖率的增加,α-6T分子倾向于肩并肩紧密排列形成条纹状结构. 进一步增加覆盖率时,分子以低层分子的条纹结构作为模板,一层一层往上生长. 在五层分子厚度的样品上,利用光致方法可以获得分子荧光,这说明顶层分子已经被有效脱耦合. 然而在同样的样品上,STM诱导发光光谱却只展现出类似等离激元的发射特性. 在这种情况下,分子荧     

表面等离激元“热点”的可控激发及近场增强光谱学

金属纳米结构中特定表面等离激元模式的光学激发及其相互作用是发展高分辨、高灵敏、高精度界面光谱学的物理基础.本文综述了我们研究组近期在表面等离激元共振的光学激发、分类识别、近场增强及在界面光谱学中的应用等方面的进展,主要内容包括:1)利用时域有限差分法,分析了金属粒子-基底体系中SPR"热点"产生的物理机制及影响因素,讨论了电模式和磁模式下界面"热点"的可控激发及"热点"转移的影响因素; 2)利用粒子-金膜体系,实现了可见光频率的表面等离激元磁共振,并利用其形成的"热点"进行了表面增强拉曼光谱实验,获得了比常规电模式更高的拉曼增强; 3)通过界面SPR"热点"增强二次谐波的实验和理论研究,提出并实现了空间分辨率达到1 nm的等离激元增强二次谐波纳米尺; 4)讨论了针尖增强拉曼光谱及针尖增强荧光体系中的空间分辨率、定向发射等关键共性问题的解决方案.相关研究成果可为界面SPR"热点"的可控激发及进一步发展表面增强拉曼、针尖增强拉曼、表面等离激元增强二次谐波等各类高灵敏度,高空间分辨率的界面光谱学方法提供新的思路.     

基于表面等离激元场的分子反射镜的理论研究

本文提出了一种基于微纳金属膜结构激发的表面等离激元场的分子反射镜新方案,利用中性分子与金属表面垂直方向上蓝失谐消逝波光场之间的偶极力相互作用,实现入射分子束的表面反射.理论计算了表面等离激元场的空间分布,用蒙特卡洛方法模拟了分子在该场中运动的动力学过程,得到了分子反射镜的反射率与相互作用时间和入射光强之间的关系.结果表明:当入射激光脉宽为10 ns,光强为I=1.0×109W/cm2时,纵向温度为10 mK,横向温度为1 mK的碘分子束反射效率达到55.89%,而且反射率随着入射光强的增大而增大.     

分子激发中的表面等离激元增强效应

金属纳米粒子的表面等离激元增强效应是纳米科学领域的一个研究热点.针对染料分子与金属纳米粒子的耦合系统,应用偶极-偶极近似计算分子与金属纳米粒子的库仑相互作用,并应用密度矩阵理论描述在不同极化方向的电场作用下的电荷输运过程,分析了分子与金属纳米粒子在不同相对位置下分子激发态的动力学过程,发现表面等离激元的增强效应与分子和金属钠米粒子的相对位置以及等离激元的耗散系数有密切关系,详细讨论了分子与金属纳米粒子间的耦合强度、外场的极化方向、等离激元的寿命及共振激发条件对分子激发态及表面等离激元增强的影响,分析了分子-金属纳米粒子耦合系统中表面等离激元增强效应的物理本质.     

Nonlocal dissociative chemistry of adsorbed molecules induced by localized electron injection into metal surfaces

We present a novel approach to surface chemistry studies using scanning tunneling microscopy (STM), where dissociation of molecules adsorbed on metal surfaces is induced nonlocally in a 10-100 nm radius around the STM tip by hot electrons that originate from the STM tip and transport on the surface. Nonlocal molecular excitation eliminates the influence of the STM tip on the outcome of the electron-induced chemical reaction. The spatial attenuation of the nonlocal reaction is used as a direct measure of hot-electron transport on the surface.     

Spatially resolved STM light emission spectra of cleaved (1 1 0) AlGaAs/GaAs heterostructures

We have measured the spectra of light emitted from individual single GaAs quantum wells of cleaved (1 1 0) AlGaAs/GaAs heterostructures using the STM (scanning tunneling microscope) tip as a local electron injection source. The cross-sectional STM images of the quantum wells were obtained, and the light emission spectra were measured by locating the STM tip over individual quantum wells of interest. Single emission peaks were observed to shift to the high-energy side with decreasing well width. The peak positions agree with the calculated transition energies for the corresponding well width. The thermalization length of the injected electron was estimated by observing the change in the emission intensity as the tip is moved at different distances from a given well.     

Vibration-induced structures in scanning tunneling microscope light emission spectra of Ni(1 1 0)-streaky (1 × 2)-H

We have measured the scanning tunneling microscope (STM) light emission spectra of Ni(1 1 0)-streaky (1 × 2) surfaces. When the tip was fixed over atomic hydrogen adsorbed on the surfaces, two types of vibration-induced structure were observed in the STM light emission spectra. One is the periodic fine structures that were already reported in our previous paper [Y. Uehara, S. Ushioda, Phys. Rev. Lett. 92 (2004) 066102] and the other newly found in the present experiments is a stepwise structure that is located at the vibrational energy of hydrogen below the cutoff energy of the STM light emission. They are ascribed to different excitation mechanisms of the vibration in the STM light emission process; the periodic fine structures appear when the vibrating motion is directly excited by the electrons injected from the tip. Conversely, the stepwise structure is observed when it is excited by the electromagnetic fields confined in the tip-sample gap, i.e., by localized surface plasmons.     

Photon mapping of MgO thin films with an STM

The light emission from an STM junction consisting of an MgO thin film on Mo(0 0 1) and an Au tip is analyzed with respect to its spatial distribution for various excitation conditions. The spectral characteristic of the light is compatible with an emission mechanism mediated by tip-induced plasmons that are excited by inelastic electron tunneling involving field-emission resonances in the tip-sample gap. The dependence of field-emission resonances on the MgO work function allows the controlled stimulation of differently thick oxide islands in the photon maps by changing the sample bias.     

STM tip-enhanced photoluminescence from porphyrin film

Tunneling electrons-induced molecular fluorescence in organic film is enhanced by the surface plasmons. The plasmon enhancement can be expected not only by the plasmons of the substrate but also by the noble metal tip of scanning tunneling microscope (STM). In this report we investigate the tip effect in photoluminescence of meso-tetrakis(3,5-di-tertiarybutyl-phenyl)porphyrin (H₂TBPP) film on indium tin oxide (ITO) combined with a STM. The experimental result shows the PL of molecules is enhanced by an Ag tip. This enhancement factor is evaluated larger than 2000.     

Relaxation of excited states of an emitter near a metal nanoparticle: An analysis based on superradiance theory

Methods of superradiance theory are employed for determining the relaxation rate of the excited state of a resonant emitter (atom, molecule, or quantum dot) near a metal nanoparticle under resonant excitation of plasmons in it, viz., modes of spatially uniform (dipole) harmonic oscillations of the electron density. Detuning from resonance and nonradiative loss suppressing radiation from the emitter near the nanoparticle surface are taken into account. The results are used to estimate the threshold conditions for generating a plasmon (“dipole”) nanolaser. It is shown that the threshold conditions of induced (laser) generation of plasmons for the emitter at a distance of 5–40 nm from an ellipsoidal nanoparticle are satisfied for relatively low emitter pumping rates (on the order of the rate of spontaneous emission of the emitter into the free space).     

Carrier-diffusion-limited remote optical addressing of single quantum dots

We present a scheme for remotely addressing single quantum dots (QDs) by means of near-field optical microscopy that simply makes use of the polarization of light. A structure containing self-assembled CdTe QDs is covered with a thin metal film presenting sub-wavelength holes. When the optical tip is positioned some distance away from a hole, surface plasmons in the metal coating are generated which, by turning the polarization plane of the excitation light, transfer the excitation towards a chosen hole and induce emission from the underlying dots. In addition, our procedure gives valuable insight into the diffusion of photo-excited carriers in the QD plane that can put limits to the addressing scheme.     

STM-induced photon emission spectroscopy of granular gold surfaces in air

Light emission has been detected under ambient conditions in the tip–sample region of a scanning tunneling microscope (STM) consisting of an etched gold tip and a granular gold film. The photon yield as a function of surface geometry (photon mapping) has been studied. By means of STM, it was possible to measure photon emission spectra locally. We have studied the effect of grain size and applied bias voltage on the spectrum. We found that the peak position in the photon emission spectrum shifts to a shorter wavelength when increasing the bias voltage and shifts to a longer wavelength when tunneling to larger grains. These effects can be understood in a simple model which considers tunneling electrons exciting localized surface plasmons which decay by emitting photons.     

Time-resolved STM light emission from an evaporated Au film

STM (scanning tunneling microscope) light emission from an evaporated Au film irradiated by pico second laser pulses has been investigated for various bias voltages of the STM. The observed emission consists of two components. The first component that has the same duration as the incident laser pulse is excited by laser induced tunneling electrons. The second component that has a longer duration than that of the laser pulse is emitted from surface polariton plasmons excited non-linearly by the laser pulse.