硅烯量子点二聚物的等离激元激发

基于含时密度泛函理论,研究了随着间距改变时硅烯量子点二聚物的等离激元激发特性。沿垂直于硅烯所在平面方向激发时,在一定间距范围内,硅烯量子点二聚物中形成了长程电荷转移激发模式。参与长程电荷转移激发的π电子主要在两个量子点之间运动。该等离激元模式随着间隙的减小发生蓝移。此外,在不同间距时,体系中还有两个等离激元共振带,分别位于7和15 eV附近。沿平行于硅烯所在平面方向激发时,由于两个量子点之间的耦合,在低能     

氮掺杂六角石墨烯纳米结构的近红外等离激元研究

基于含时密度泛函理论研究了氮掺杂六角石墨烯纳米结构的近红外等离激元.沿一定的激发方向,边长为1 nm的氮掺杂六角石墨烯纳米结构在整个近红外光谱区都有强度较大的等离激元共振.参与这种近红外等离激元模式共振的电子在六角纳米结构的中心和边缘区域之间来回振荡.近红外等离激元共振模式的形成依赖于氮掺杂的位置和纳米结构的尺度大小.只有当氮掺杂在靠近边界区域时体系才会在近红外光谱区形成等离激元共振模式.对于边长小于1 nm的六角石墨烯纳米结构,氮掺杂后体系不能在近红外光谱区形成等离激元共振模式.     

等离激元表面晶格共振研究进展

当金属纳米粒子排列成有序阵列结构时,沿阵列平面内传播的衍射波与单粒子局域等离激元共振耦合,将导致等离激元共振急剧窄化,光谱宽度降至2 nm以下.与共振宽度在80 nm以上的常规单粒子共振相比,这种具有高品质因子的衍射耦合等离激元共振称为等离激元表面晶格共振.近年来,关于表面晶格共振研究已成为纳米光子学领域的研究热点,在发光、激光、光伏、通讯、存储以及传感等领域显示出巨大的应用前景.本文主要综述等离激元表面晶格共振的基本原理和性质,包括共振宽度、共振品质、电场增强,探讨了表面晶格共振的测试方法、影响因素以及纳米光学应用.     

反胶束法合成Cd1-xMnxS量子点及其发光性能研究

应用反胶束法制备了稀磁半导体Cd1-xMnxS量子点.量子点的大小可通过改变ωo值(wo=[水]/[表面活性剂])来控制.高分辨透射电镜的分析结果表明,量子点呈单分散性,是几乎没有缺陷的单晶体.量子点的大小约为4.8～6nm,随wo值增大而增大.电子能谱(EDS)测定结果表明,Mn2+离子在量子点中的摩尔分数为1.5%.由电子自旋共振(ESR)分析确定一部分Mn2+离子取代Cd2+离子位置而位于晶格,另一部分Mn2+离子位于Cd1-xMnxS的表面或间隙位置.吸收光谱显示,随着量子点变小,吸收带边发生蓝移,显示明显的量子尺寸效应.光致荧光光谱分析表明,发光峰属于Mn2+的4T1-6A1跃迁,而且随着ωo和粒径的增大,发光峰从2.26,2.10,2.05eV红移到1.88eV;其发光峰偏离2.12eV,主要是由于Mn2+离子位于扭曲的四面体晶体场所致.     

基于量子点的荧光共振能量转移

研究了具有相反电荷的两种量子点间的荧光共振能量转移.分别以巯基乙酸(TGA)和十六烷基三甲基溴化胺(CTMAB)修饰发射绿色和红色荧光的CdSe/ZnS量子点,使其由油溶性变为水溶性,且表面带相反的电荷,并对修饰后的水相量子点进行琼脂糖凝胶电泳、荧光成像、量子产率等系列表征.对两种量子点间的荧光共振能量转移现象进行研究.结果表明: 在激发波长为400 nm时,两种量子点在磷酸盐缓冲溶液(pH 7.5)中具有较好的荧光共振能量转移效率(猝灭效率0.54,增强效率0.27).     

可调控且稳定的SrMoO4等离激元共振用于增强的可见光驱动的氮还原

光催化固氮是最具潜力的人工光合过程之一,也是有望取代工业Haber-Bosch方法实现氨的绿色合成的清洁能源技术之一.由于氮气分子还原为氨需要较高的还原电位,导致大部分常规的半导体材料的导带能级不能满足固氮反应的热力学要求.同时,固氮光催化剂普遍存在光响应波段窄、表面催化活性低、太阳光向氨的转化效率低等问题.缺陷工程是目前制备高效固氮光催化剂的最有效的途径之一.在催化剂中引入缺陷可以带来两个方面的好处:(1)促进氮气分子在缺陷位点上的化学吸附和活化,从而降低反应能垒;(2)拓宽催化剂的太阳光响应波段,提高对太阳光的利用效率.等离激元效应来自于自由载流子的集体振荡,广泛存在于金属纳米结构中.尽管金属等离激元纳米材料在光催化中也有广泛的应用,可以通过等离激元增强的光吸收和散射、热载流子传输以及等离激元共振能量传递等机理提高太阳能转化效率,但其能量转化效率仍有限,多用于弥补半导体材料的弱点.研究发现,一些半导体纳米材料在可见光和近红外光范围表现出优异的等离激元共振吸收.相比等离激元金属纳米材料,这些半导体的等离激元共振效应的调控手段更加丰富.等离激元半导体材料普遍具有较高的缺陷浓度、非常宽的光响应波段,因而是理想的固氮光催化剂.本文利用具有还原性的气氛处理溶剂热法制备的SrMoO4,通过引入高浓度的氧空位,实现了可调控的稳定的等离激元共振吸收.制备的SrMoO4在可见光和近红外光范围具有强的等离激元吸收,其共振吸收峰的中心位置可从520调到815 nm,显著拓宽了SrMoO4的光响应波段,而样品的本征吸收边仍然位于310 nm.研究发现,氢气还原没有改变Sr的氧化态,而是将Mo6+还原成Mo5+.紫外光电子能谱分析结果表明,高温氢气处理没有改变SrMoO4样品的导带和价带能级.电子顺磁共振研究结果表明,氢气处理在SrMoO4中形成了大量的氧空位.Mott-Schottky测试结果发现,氢气处理后的样品的载流子浓度高达～2.0×1020 cm-3.具有等离激元效应的SrMoO4表现出优异的可见光固氮性能,相比不具有等离激元效应的SrMoO4,在入射光波长大于420 nm的可见光照射下,在氢气气氛中处理10 min,3,6和8h的SrMoO4样品的氨的产率分别为41.2,36.3,24.5和20.8 μg gcat-1 h-1.其增强光催化活性主要来源于更宽的太阳光吸收波段、等离激元激发产生的热载流子和丰富的缺陷活性位点.一方面,SrMoO4具有较高的导带能级,本征激发形成的导带电子能在热力学上将氮气分子还原为氨;另一方面,等离激元激发产生的热载流子具有较高的能量,能够越过固液界面的肖特基能垒,将吸附在催化剂表面缺陷处的氮气分子还原为氨.但是,尽管缺陷在光催化固氮中展现出多方面的优点,其在半导体中的浓度仍需进一步的优化.     

电场强度对等离激元诱导热电子的影响

等离激元纳米结构因其通过改变纳米结构的尺寸、形貌和组成成分,可以在紫外-可见-近红外范围内实现对光的操控从而提高能量利用率而受到人们的广泛关注.在光的激发下,等离激元纳米结构可以产生高能热电子,并驱动光化学反应,但其利用效率较低.因此,如何提升热电子的激发效率成为了一个亟待解决的关键问题.本工作制备了三维壳层隔绝银纳米粒子载金（3D Ag SHINs-Au）超结构,以对巯基苯胺（pATP）为探针分子,结合原位表面增强拉曼光谱技术和三维有限时域差分法研究不同电场强度对等离激元诱导的热电子激发效率的影响.实验结果显示电场强度越强,热电子激发效率越高,pATP催化速率越快.此外,带内跃迁比带间跃迁更有利于热电子的激发.本研究有助于人们理解电场强度如何影响热电子的激发效率.     

应用表面等离激元提高有机发光器件效率的研究进展

表面等离激元（SPP）存在于金属和介质界面,是光场和金属表面自由电子相互作用而产生的电子集体振荡行为.一方面,由于在金属纳米颗粒表面会形成局域的SPP震荡（LSP）,可以调控金属表面附近分子的发光性质,因此,很多研究者尝试在有机电致发光器件（OLED）中引入金属纳米颗粒,利用LSP改善OLED器件性能;另一方面,在传统发光器件中,由于金属表面等离激元的波矢量和自由光波的波矢量不匹配,无法辐射成自由光波,最终只能以热能的形式耗散掉.通过改变金属表面形貌,如附加光栅结构等方法,使得SPP的能量能够耦合成自由光,从而提高发光器件的外量子效率.利用SPP来提高有机发光器件的效率,已经引起广泛的关注,本文着重综述以下两个方面的工作：一是采用金属纳米颗粒的LSP提高荧光分子辐射跃迁的几率,从而提升发光器件的内量子效率;二是利用有序或无序光栅结构使得SPP与自由光的波矢匹配来提高器件的耦合出光,从而提升外量子效率.     

可调控且稳定的SrMoO_4等离激元共振用于增强的可见光驱动的氮还原（英文）

光催化固氮是最具潜力的人工光合过程之一,也是有望取代工业Haber-Bosch方法实现氨的绿色合成的清洁能源技术之一.由于氮气分子还原为氨需要较高的还原电位,导致大部分常规的半导体材料的导带能级不能满足固氮反应的热力学要求.同时,固氮光催化剂普遍存在光响应波段窄、表面催化活性低、太阳光向氨的转化效率低等问题.缺陷工程是目前制备高效固氮光催化剂的最有效的途径之一.在催化剂中引入缺陷可以带来两个方面的好处:(1)促进氮气分子在缺陷位点上的化学吸附和活化,从而降低反应能垒;(2)拓宽催化剂的太阳光响应波段,提高对太阳光的利用效率.等离激元效应来自于自由载流子的集体振荡,广泛存在于金属纳米结构中.尽管金属等离激元纳米材料在光催化中也有广泛的应用,可以通过等离激元增强的光吸收和散射、热载流子传输以及等离激元共振能量传递等机理提高太阳能转化效率,但其能量转化效率仍有限,多用于弥补半导体材料的弱点.研究发现,一些半导体纳米材料在可见光和近红外光范围表现出优异的等离激元共振吸收.相比等离激元金属纳米材料,这些半导体的等离激元共振效应的调控手段更加丰富.等离激元半导体材料普遍具有较高的缺陷浓度、非常宽的光响应波段,因而是理想的固氮光催化剂.本文利用具有还原性的气氛处理溶剂热法制备的SrMoO_4,通过引入高浓度的氧空位,实现了可调控的稳定的等离激元共振吸收.制备的SrMoO_4在可见光和近红外光范围具有强的等离激元吸收,其共振吸收峰的中心位置可从520调到815nm,显著拓宽了SrMoO_4的光响应波段,而样品的本征吸收边仍然位于310 nm.研究发现,氢气还原没有改变Sr的氧化态,而是将Mo~(6+)还原成Mo~(5+).紫外光电子能谱分析结果表明,高温氢气处理没有改变SrMoO_4样品的导带和价带能级.电子顺磁共振研究结果表明,氢气处理在SrMoO_4中形成了大量的氧空位.Mott-Schottky测试结果发现,氢气处理后的样品的载流子浓度高达～2.0×10~(20) cm~(-3).具有等离激元效应的SrMoO_4表现出优异的可见光固氮性能,相比不具有等离激元效应的Sr Mo O_4,在入射光波长大于420 nm的可见光照射下,在氢气气氛中处理10 min,3,6和8 h的SrMoO_4样品的氨的产率分别为41.2,36.3,24.5和20.8μg g~(-1)_(cat) h~(-1).其增强光催化活性主要来源于更宽的太阳光吸收波段、等离激元激发产生的热载流子和丰富的缺陷活性位点.一方面,SrMoO_4具有较高的导带能级,本征激发形成的导带电子能在热力学上将氮气分子还原为氨;另一方面,等离激元激发产生的热载流子具有较高的能量,能够越过固液界面的肖特基能垒,将吸附在催化剂表面缺陷处的氮气分子还原为氨.但是,尽管缺陷在光催化固氮中展现出多方面的优点,其在半导体中的浓度仍需进一步的优化.     

金/铜纳米异质界面的电荷转移等离激元调控

金属纳米结构由于其独特的局域表面等离激元共振现象而倍受关注,对催化、传感、纳米医学以及光学器件等具有重要意义.电荷转移等离激元共振强烈依赖于纳米单元间的导电结点,可产生频率连续可调的共振光吸收和光散射,为获得高度局域化的增强光磁场和光热效应提供了可能.然而,受制于已有构筑手段和有限的结构种类,相关研究仍处于初级阶段.针对此,本工作发展了一种十分简单、有效的Au/Cu纳米异质结点调控策略,利用廉价易得的天然DNA分子在金纳米粒子“种子”表面发生非特异性吸附,有效控制铜在金表面发生异相成核时的相间接触面积,得到导电结点宽度连续可调的电荷转移纳米粒子二聚体.实验光谱和理论模拟显示,结点宽度、铜和金纳米粒子的尺寸是决定电荷转移等离激元性质的重要参数,其分别可由DNA吸附量、Cu²⁺加入量和金纳米粒子尺寸加以控制,进而实现共振波长在可见至近红外区的宽广调节.通过与其它吸附分子对比证明了DNA吸附调控模式的独特性.这种具有可调控导电结点的双金属纳米异质界面为实现电荷转移等离激元共振与催化和传感等功能的集成以及相关应用探索奠定了重要基础.     

Light trapping and guidance in plasmonic nanocrystals

We illustrate the possibility of light trapping and funneling in periodic arrays of metallic nanoparticles. A controllable minimum in the transmission spectra of such constructs arises from a collective plasmon resonance phenomenon, where an incident plane wave sharply localizes in the vertical direction, remaining delocalized in the direction parallel to the crystal plane. Using hybrid arrays of different structures or different materials, we apply the trapping effect to structure the eigenmode spectrum, introduce overlapping resonances, and hence direct the light in space in a wavelength-sensitive fashion.     

Strong polarized enhanced raman scattering via optical tunneling through random parallel nanostructures in Au thin films

Random parallel nanostructures (ridges and channels) were created by scratching gold thin films deposited on glass slides. Atomic force microscope (AFM) images showed that the width of the substructures within the scratches were of the order of a few hundred nanometers. These nanometric gold features can then support localized surface plasmon resonances in the direction perpendicular to the propagation of the scratches. This surface plasmon excitation led to a remarkable dependence of the intensity of the surface-enhanced resonance Raman scattering (SERRS) on the polarization direction of the incident light relative to the orientation of the scratch. The maximum SERRS intensities for oxazine 720 (a common laser dye) adsorbed on these nanostructures were obtained when the polarization of the light field was perpendicular to the direction of the substructures. The SERRS intensities followed a squared dependence on the polarization direction of the incident field.     

Enhanced Photochromism of Diarylethene Induced by Excitation of Localized Surface Plasmon Resonance on Regular Arrays of Gold Nanoparticles

Localized surface plasmon resonance (LSPR) excitation on the photochromic reaction of a diarylethene derivative (DE) was studied by surface enhanced Raman scattering (SERS). UV and visible light irradiations transform reversibly DE between open-form (OF) and closed-form (CF) isomers, respectively. A mixture of PMMA and DE (either OF or CF isomer) was spin-coated onto gold nanorods (GNRs) arrays, designed by electron beam lithography, with two localized surface plasmon resonances (LSPR) at distinct wavelengths, due to their anisotropy. The photochromic reaction rates from CF to OF isomers, under LSPR excitation, were monitored from SERS spectral changes under different polarizations, on the same GNR substrate to compare the effect of LSPR field strength. It appears that the photoisomerization rate was faster when LSPR was excited with the polarization parallel to the GNR long axis. The present results highlight a potential genuine mechanism, from near field LSPR excitation, involved in the photochromic enhancement of diarylethene photochromes.     

On the excited state dynamics of vibronic transitions. High-resolution electronic spectra of acenaphthene and its argon van der Waals complex in the gas phase

Rotationally resolved fluorescence excitation spectroscopy has been used to study the dynamics, electronic distribution, and the relative orientation of the transition moment vector in several vibronic transitions of acenaphthene (ACN) and in its Ar van der Waals (vdW) complex. The 0(0)(0) band of the S(1) ← S(0) transition of ACN exhibits a transition moment orientation parallel to its a-inertial axis. However, some of the vibronic bands exhibit a transition moment orientation parallel to the b-inertial axis, suggesting a Herzberg-Teller coupling with the S(2) state. Additionally, some other vibronic bands exhibit anomalous intensity patterns in several of their rotational transitions. A Fermi resonance involving two near degenerate vibrations has been proposed to explain this behavior. The high-resolution electronic spectrum of the ACN-Ar vdW complex has also been obtained and fully analyzed. The results indicate that the weakly attached argon atom is located on top of the plane of the bare molecule at ~3.48 ? away from its center of mass in the S(0) electronic state.     

Electron Energy Spectroscopic Mapping of Surface Plasmon by Parallel Scanning Method

In this work, electron energy spectroscopic mapping of surface plasmon of Ag nanostructures on highly oriented pyrolytic graphite is reported. Benefitting from the angular dispersive feature of the present scanning probe electron energy spectrometer, a multi-channel detection mode is developed. By scanning along one direction, the two-dimensional intensity distribution of Ag surface plasmon excitation due to the collision of electron emitted from the tip can be obtained in parallel. The spectroscopic spatial resolution is determined to be around 80 nm.     

Pure surface plasmon resonance enhancement of the first hyperpolarizability of gold core-silver shell nanoparticles

We report the optical second harmonic (SH) response from gold core-silver shell nanoparticles supported at a liquid-liquid interface in the spectral region where the second harmonic generation (SHG) frequency is resonant with the surface plasmon (SP) resonance excitation of the nanoparticles. We compare these results with that obtained by classical linear optical absorption spectroscopy and show that the nonlinear optical response is dominated by the SP resonance enhancement with negligible contributions from the interband transitions. As a result, the SH spectrum exhibits two clear SP resonance bands attributed to the two SP resonances of the composite nanostructure formed by the gold core-silver shell nanoparticles. Absolute values of the hyperpolarizabilities are measured by hyper Rayleigh scattering (HRS) and compared that of pure gold nanoparticles. The hyperpolarizability measured at a harmonic energy of 3.0 eV, enhanced through excitation of the high energy SP resonance of the nanoparticle, increases with the silver content whereas the hyperpolarizability measured at a harmonic energy of 2.4 eV, enhanced through the excitation of the low energy SP resonance of the nanoparticle, decreases because of the shift of this resonance away from the harmonic frequency. The hyperpolarizability determined by HRS and the square root of the SHG intensities, scaling with the nanoparticle hyperpolarizability, have similar trends with respect to the silver content indicative of closely related adsorption properties yielding similar surface concentrations at the liquid-liquid interface.     

Narrow plasmonic/photonic extinction and scattering line shapes for one and two dimensional silver nanoparticle arrays

The interaction of light with silver nanoparticle arrays can in some cases produce mixed plasmonic/photonic bands that have extremely narrow (<1 meV) line shapes in extinction and scattering. In this paper we extend computational electrodynamics results of a recent communication [S. Zou, N. Janel, and G. C. Schatz, J. Chem. Phys. 120, 10871 (2004)] where this effect was first described to study how these narrow bands are influenced by a number of structural factors, and to determine how useful these arrays might be for sensing applications. Included are studies of the effect of disorder in the array structure on plasmon intensity and width, of the effect of orientation of the array relative to the polarization and propagation direction of the incident light, and of the effect of particle shape (comparing results for silver spheres and cylindrical disks). Our results show that the narrow lines are remarkably robust to array disorder, but vacancy defects can easily destroy the effect. The narrowest lines are associated with one dimensional arrays in which both polarization and wave vectors are perpendicular to the array axis. For two dimensional arrays, the narrowest lines are associated with the wave vector perpendicular to the plane of the array and polarization in the plane. Arrays composed of oblate cylinders generate more intense and more redshifted plasmon/photonic peaks than do prolate or spherical particles under comparable conditions. Finally, for sensing applications in which analyte binding is determined by the plasmon wavelength shift associated with change in the surface refractive index, we show that the arrays have greater sensitivity than isolated nanoparticles.     

In situ measurements of emission transition dipole moment of individual ordered microdomain of diprotonated tetraphenylporphine aggregate formed at dodecane/aqueous H<Subscript>2</Subscript>SO<Subscript>4</Subscript> interface

Rhombic-ordered microdomains of diprotonated 5,10,15,20-tetraphenylporphine aggregate, whose sizes were 10–200 μm, were formed at dodecane/aqueous H₂SO₄ interfaces. The light excitation of their two absorption bands (410 and 473 nm for H- and J-bands, respectively) led to one fluorescence band at longer wavelength (723 nm). The direction of the emission transition dipole moment (μ _e) of individual rhombic microdomains, determined with an in situ optical microscope and a linear polarizer, was almost parallel to the major axis, which was also almost parallel to the direction of the absorption transition dipole moment of their J-bands. Their absorption and emission transition scheme was proposed.     

Two-layered metallic film-induced surface plasmon polariton for fluorescence emission enhancement in on-chip waveguide

We demonstrate an enhancement of fluorescence emission due to bimetallic silver-gold film-induced surface plasmon wave extension. Rhodamine B (RhB) dyes were excited by the evanescent wave field produced from surface plasmon polaritons excited on metal-deposited sections along an embedded strip waveguide. Various silver-gold combinations were used to quantify for the evanescent field enhancement. The underlying silver yields better evanescent field enhancement, while the overlying gold ensures that the stability of the sensing surface is not compromised. In comparison to the conventional single gold film surface plasmon resonance (SPR) configuration, the two-layered metallic structure is capable of enhancing the surface plasmon polariton (SPP) evanescent field considerably, as verified experimentally by the ca. 4.0 times improvement in the RhB fluorescence emission. The compact waveguide structure and improved electric field probing depth can potentially be exploited for on-chip SPR--fluorescence excitation of less concentrated fluorophore-labelled biological and chemical analytes, with a capability of massively parallel processing for high throughput screening.