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.     

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.     

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

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.     

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.     

表面等离激元共振生物传感分析及应用

基于物理中发生在金属表面的表面等离激元现象 ,阐述表面等离激元共振生物传感分析原理 ;进而建立表面等离激元共振生物传感成像。给出应用表面等离激元共振研究生物单元相互作用的实例。     

等离激元共振能量转移与增强光催化研究进展

等离激元共振能量转移指表面等离激元将俘获的能量通过偶极-偶极相互作用转移到邻近的半导体或分子等激子体系中,它是等离激元非辐射弛豫的一个通道,也可作为获取和利用等离激元共振能量的一种方式.此外,等离激元能量还可以通过热电子弛豫(非辐射)和光散射(辐射)等方式耗散.等离激元各个弛豫通道之间存在着很强的关联,相关的能量转移和电荷转移过程可以将等离激元耗散的能量输送到其他体系或转换为其他能量形式.本文主要介绍了等离激元共振能量转移和与其相关的能量和电荷转移过程(包括等离激元近场增强及耦合、远场散射、热电子弛豫等)的物理机制和动力学性质,并详细介绍了这些机制在增强光催化研究领域的最新进展.     

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。     

表面等离激元量子信息应用研究进展

近年来表面等离激元得到了越来越多的关注和研究,得益于其能把电磁场束缚在金属-介质界面附近的亚波长尺度范围内.本文回顾了近年来表面等离激元在量子信息领域中的理论和实验研究,包括表面等离激元的基本量子性质、表面等离激元量子回路、在量子尺度下与物质的相互作用及其潜在应用.量子表面等离激元开辟了对表面等离激元基本物理性质研究的新方向,可以应用于高度集成化的量子集成光学回路,同时也可以用来增强光与量子发光体的相互作用.     

金属基底上光学偶极纳米天线的自发辐射宽带增强:表面等离激元直观模型

本文提出一种具有宽波段自发辐射增强性能的金属基底上光学偶极纳米天线,实现的总辐射速率与远场辐射速率增强因子分别达到5454和1041,在近红外波段,自发辐射增强(Purcell因子超过1000)波长范围达到260 nm,并且能够实现远场定向辐射.为了阐明天线性能背后的物理机制,本文考虑天线臂上表面等离激元激发和多重散射的直观物理过程,基于Maxwell方程组第一性原理,建立了一个半解析模型,能够全面复现天线的辐射特性,包括总辐射速率、远场辐射速率、远场辐射方向图等.该模型提供了一个直观的物理图像,即在模型导出的两个相位匹配条件下,表面等离激元在天线臂上形成了一对Fabry-Perot共振获得增强,然后传播到纳米间隙内点辐射源位置和散射到自由空间,由此分别提高了总辐射速率和远场辐射速率.并且,这一对Fabry-Perot共振产生了一对相互靠近的谐振峰,由此形成了宽波段自发辐射增强.本文提出的偶极纳米天线可以应用于荧光增强、拉曼散射增强及高速、高亮度纳米光源等领域,所提出的模型可用于光学天线的物理理解和直观设计.     

表面等离激元调控化学反应

表面等离激元是金属与介质表面自由电子的集体振荡,能够突破衍射极限,将光束缚在纳米结构表面附近极小的空间内,为纳米尺度的光操控提供可能.利用表面等离激元共振,不仅可以增强局域表面电磁场强度,实现对表面附近分子荧光和拉曼信号的极大增强,而且等离激元弛豫诱导的热电子还可以调控表面分子的化学反应,提高反应速率和选择性,即等离激元调控(催化)化学反应.作为一种新型催化体系,等离激元催化已经实现了多种传统光催化中难以发生的化学反应,是表面等离激元领域的前沿热点问题.由于等离激元催化反应的复杂性与多样性,其反应动力学过程的完全表征和反应机理的揭示仍然是一个巨大的挑战.精确表征催化反应的中间及最终产物,获取反应动力学过程中更多的细节信息,对于探索等离激元催化机理,以及设计更为合理高效的催化体系极为重要.本文围绕等离激元催化的最新研究进展,总结并探讨等离激元催化中所使用的各种表征技术.首先,简单介绍了等离激元催化的基本概念和催化机理.其次,综述了拉曼光谱(包括表面/针尖增强拉曼光谱),在等离激元催化原位监测中的应用,并进一步详细介绍了气相色谱法、气相色谱-质谱联用、高效液相色谱法、扫描透射电子显微镜、扫描隧道显微镜、扫描电化学显微镜、紫外可见吸收光谱等技术在等离激元催化反应研究中的重要作用.最后,探讨了这些表征技术在等离激元催化动力学过程研究和催化机理探索中的特点与优势,并展望了等离激元催化及相关表征技术的发展与挑战.     

Surface plasmon amplification by stimulated emission of radiation: quantum generation of coherent surface plasmons in nanosystems

We make a step towards quantum nanoplasmonics: surface plasmon fields of a nanosystem are quantized and their stimulated emission is considered. We introduce a quantum generator for surface plasmon quanta and consider the phenomenon of surface plasmon amplification by stimulated emission of radiation (spaser). Spaser generates temporally coherent high-intensity fields of selected surface plasmon modes that can be strongly localized on the nanoscale, including dark modes that do not couple to far-zone electromagnetic fields. Applications and related phenomena are discussed.     

Au表面等离子体激元激发的扫描探针电子能谱

结合扫描隧道显微镜（STM）与电子能谱仪是实现表面微区元素分析的途径之一．我们将环形电子能量分析器和三维扫描探针系统相结合,建立了一台扫描探针电子能谱仪(SPEES)．通过测量针尖近场发射束流激发的Au表面能量损失谱,我们用研究了Au原子的等离子体激元激发现象．进一步通过改变针尖－样品距离,我们研究了Au等离子体激元峰与弹性散射峰的强度比随针尖－样品距离变化的关系．研究结果发现该强度比与针尖－样品距离的关系并不是单调变化,而是在一个特定位置存在极大．     

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.     

Model calculations of STM imaging and manipulation of oxygen on Pt(111)

We study tip-adsorbate–substrate interactions in scanning tunneling microscopy (STM) manipulation and imaging, and the influence of impurities on the images. Thence, we perform molecular dynamics simulations and calculate qualitative STM images for oxygen on Pt(1 1 1) surface. The adsorption site of the oxygen molecule is found to be in accordance with ab initio calculations. The calculated STM image has a good resemblance to the experimental ones. The contamination of the tip by oxygen or water alters the STM image strongly. Molecular dynamics simulations on manipulations of oxygen on the surface reveal several mechanisms of how molecular oxygen can be either produced or decomposed with STM tip. Finally, we find out that transfer of oxygen from the surface to an STM tip is not very probable.     

Scanning tunneling microscopy and molecular orbital calculation of pentacene molecules adsorbed on the Si(100)2×1 surface

Adsorption of the organic molecule pentacene on Si(100)2×1 surfaces was imaged using scanning tunneling microscopy (STM). The molecular images exhibit distinct shapes corresponding to the expected shapes for adsorption configurations. Semi-empirical molecular orbital (MO) calculations reveal a local surface density of states for the adsorbed pentacene on the Si surface. In the cases where the pentacene molecule is adsorbed on an Si dimer row, the calculated MOs are in good agreement with the molecular images observed in STM. In the case of pentacene adsorbed on two or three Si-dimer rows, however, the MOs of the pentacene do not correlate directly with the observed STM images. It is thus considered that the STM images are produced by a combination of Si dimer states and MO.     

Silver nanowires for photonics applications

Although silver nanowires as plasmonic components have been investigated extensively in both theoretical and experimental studies, a systematic study is still lacking. In this work, a review is given to explain some basic features of experimentally prepared nanowires and their optical properties in different situations, such as waveguides, resonators, and antennas. The review also lists several possible applications of nanowires for enhanced light‐emitting, photonic device fabrication, sensors, lasers, and nonlinear optics. Combined with the merits of both nanowires and surface plasmon polaritons, silver nanowires are certain to show their potential in photonics in the near future.     

Plasmonic Enhancement of Single-Molecule Fluorescence Near a Silver Nanoparticle

In this short paper, we reported the enhanced fluorescence from a single fluorophore bound to a 50nm silver nanoparticle. We found that on average the Cy5 molecules bound to metal nanoparticles are approximately 15-fold brighter than that of free dyes, and that single molecule lifetimes are shorter as compared to free fluorophores. The increased emission rate is primarily the result of local plasmon enhancement. These results demonstrate that the use of fluorophore-metal interactions can increase the brightness and photostability of fluorophores for single molecule detection.     

STM and chemistry: a qualitative molecular orbital understanding of the image of CO on a Pt surface

Theoretical calculations of STM images for isolated carbon monoxide on Pt(111) have been performed. These simulations are directly comparable to experimental data from Eigler's group. They also confirm a strong site dependence of the STM molecular contrast and assign the two experimental STM forms of CO with two distinct binding sites (the top and the bridge sites) which have already been well-characterised by other surface techniques. Moreover, the approach used here allows a detailed understanding of the electronic origin of the STM molecular pattern. Hence, we demonstrate that the CO STM pattern results from the superposition, with interference effects, of two current contributions. The direct through space tunneling process between the tip and the metal surface is decreased by the presence of the adsorbate molecule, but this depression in the current is more or less compensated, depending on the binding site, by the tunnel current mediated by the molecular levels of the adsorbate. The frontier π orbitals of CO have a small contribution to the current and the σ framework has the major influence with the 5σ lone pair (HOMO of CO) and also the low-lying 3σ. These two MO contributions, however, show a destructive interference effect, and this, together with the absence of π current, is responsible for the weak amplitude of the CO STM image.     

Photon emission from adsorbed C60 molecules with sub-nanometer lateral resolution

We present the first experimental demonstration of spatially resolved photon emission of individual molecules on a surface. A scanning tunneling microscope (STM) was used as a local electron source to excite photon emission from hexagonal arrays of C₆₀ molecules on Au(110) surfaces. Specifically, we show that in maps of photon emission intensities, C₆₀ fullerenes appear as arrays of individual light emitters 4 Å in diameter and separated by 10 Å. Comparison with simultaneously recorded STM images reveals, that most intense emission is detected when the STM tip is centered above a molecule. The results demonstrate the highest spatial resolution of light emission to date using a scanning probe technique.