Confined Plasmons in Nanofabricated Single Silver Particle Pairs:  Experimental Observations of Strong Interparticle Interactions

Gunnarsson, Linda; Rindzevicius, Tomas; Prikulis, Juris; Kasemo, Bengt Herbert; Käll, Mikael; Zou, Shengli; Schatz, George C.

doi:10.1021/jp049084e

Cited by 500 publications

(631 citation statements)

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“…By doing so, we are able to relate the results of the optical response from different approximations and predict the influence of nonlocality in the limit of subnanometric distances where nonlocal effects are pronounced. In elucidating the major physics behind the nonlocal response in plasmonic nanoparticle dimer, we find a robust plasmon ruler [18][19][20][21][22] that unambiguously determines the spectral position of surface plasmon resonances in strongly coupled systems forming subnanometric plasmonic cavities.To implement the TDDFT calculations, a cylindrical jellium model is adopted to describe the electronic structure of the infinite metallic nanowire. This model captures the collective plasmonic modes of conduction electrons and is perfectly suited to address nonlocal effects derived from the interactions between these electrons, such as the dynamical screening of the external field [1,4,5] and tunneling [23][24][25][26][27] as discussed below.…”

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confidence: 95%

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confidence: 95%

“…The use of the plasmon ruler relies on the universal dependence of the DP frequency on the scaled separation [18,21]. In Fig.…”

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Robust Subnanometric Plasmon Ruler by Rescaling of the Nonlocal Optical Response

et al. 2013

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We present the optical response of two interacting metallic nanowires calculated for separation distances down to angstrom range. State-of-the-art local and nonlocal approaches are compared with full quantum time-dependent density functional theory calculations that give an exact account of nonlocal and tunneling effects. We find that the quantum results are equivalent to those from classical approaches when the nanoparticle separation is defined as the separation between centroids of the screening charges. This establishes a universal plasmon ruler for subnanometric distances. Such a ruler not only impacts the basis of many applications of plasmonics, but also provides a robust rule for subnanometric metrology. DOI: 10.1103/PhysRevLett.110.263901 PACS numbers: 42.25.Bs, 36.40.Gk, 73.20.Mf, 78.67.Bf The exact calculation of the optical response of a nanosystems is a challenging task. In metallic nanostructures the complex nonlocal interactions between conduction electrons modify the standard local classical response, typically characterized by the presence of surface plasmon resonances [1]. This effect is more pronounced in small particles and in strongly coupled systems where the nonlocal nature of electronic interactions is emphasized. To establish an exact and accurate model to describe the spectral features of plasmonic resonances in such systems is thus of paramount importance from both fundamental and practical points of view [2,3]. A variety of theoretical approaches that incorporate different levels of sophistication have been adopted to address the optical response, but certain lack of unification still persists. In particular, the community of surface physics has elaborated accurate nonlocal treatments to address the surface response of conduction electrons of metal surfaces and small metallic objects [1,[4][5][6][7][8][9], whereas the community of nano-optics has focused on developing practical local and nonlocal treatments where the emphasis is placed on the geometrical aspects of the metal boundaries rather than on the actual response of the electrons [2,3,[10][11][12][13][14][15][16]. This Letter bridges both fields, providing a unified and practical picture of the optical response in coupled metallic nanoparticles located at subnanometric proximity.We calculate the optical response of two interacting metallic nanowires in vacuum using a full quantum timedependent density functional theory (TDDFT) approach [17] as well as using macroscopic theory based on solution of classical Maxwell equations with local and nonlocal descriptions of the system. The comparison between quantum and classical results on coupled nanowires provides a perfect basis to unravel the limitations, tendencies, and physics of the optical response under different levels of approximation. By doing so, we are able to relate the results of the optical response from different approximations and predict the influence of nonlocality in the limit of subnanometric distances where nonlocal effects are pronounced. In elucidating the m...

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Robust Subnanometric Plasmon Ruler by Rescaling of the Nonlocal Optical Response

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“…HGN aggregates are also known to exhibit both hybridized plasmon modes, which are the result of surface plasmon interactions with cavity plasmon modes, and collective charge transfer resonances [296][297][298]. However, even when not in direct contact with one another there is an intensification of the dipole charge at the interparticle gap of nanoparticle aggregates in near field proximity [8,[299][300][301]. For example, Xu et al observed that the junction between two nanoparticles 1 nm apart exhibited an EM field enhancement of 10 10 compared to an individual particle [302].…”

Section: Plasmon Coupling In Aggregates For Sersmentioning

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Controllable Cobalt Oxide/Au Hierarchically Nanostructured Electrode for Nonenzymatic Glucose Sensing

2016

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By electrodeposition and galvanic replacement reaction, we developed a facile, time-saving, cost-effective, and environmentally friendly, two-step synthesis route to obtain a controllable cobalt oxide/Au hierarchically nanostructured electrode for glucose sensing. The nanomaterials were characterized by transmission electron microscopy, scanning electron microscopy, Raman spectroscopy, energy-dispersive spectrometry, and X-ray photoelectron spectroscopy, meanwhile, the sensing performance was investigated by cyclic voltammetry and amperometric response. The results revealed that this novel electrode exhibited excellent electrocatalytic performance toward glucose oxidation, with a wide double-linear range from 0.2 μM to 20 mM and a low detection limit of 0.1 μM based on a signal-to-noise ratio of 3, which was mainly attributed to the ability of loading a small amount of Au with good electron conductivity on the surface of cobalt oxide nanosheets with large active surface area and synergistic electrocatalytic activity of Au and cobalt oxide toward glucose electrooxidation. This facile, sensitive, and selective glucose sensor is also proven to be suitable for the detection of glucose in human serum.

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“…Mais recentemente eles obtiveram experimentalmente o espectro do plasmon de superfícies de pares isolados de nanodiscos de Ag, utilizando um microscópio óptico no modo "dark field", e mostraram que, quando a polarização da radiação incidente é paralela ao eixo interpartículas, é possível observarem-se efeitos de confinamento de plasmon e desvio da banda para o vermelho 48 . Este efeito, que corresponde ao surgimento de um campo elétrico muito intenso no espaço entre as duas partículas metálicas, tornase maior quanto menor for a distância entre elas, indicando um maior acoplamento entre seus plasmons.…”

Section: Plasmon De Superfície E Espectros De Extinçãounclassified

O efeito SERS na análise de traços: o papel das superfícies nanoestruturadas

Sant’Ana¹,

Cório²,

Temperini³

2006

Quím. Nova

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Recebido em 20/7/05; aceito em 13/9/05; publicado na web em 6/3/06 THE SERS EFFECT IN TRACE ANALYSIS: THE ROLE OF NANOSTRUCTURED SURFACES. Surface-Enhanced Raman Scattering -SERS -underwent huge advances since a single-molecule Raman spectrum was obtained in 1997. New theoretical and experimental approaches emerged since then leading to a better understanding of the enhancement mechanisms and to a significant improvement in the Raman signal. This review presents the current status of the SERS effect and the promising ways of designing and preparing high performance SERS-active substrates.Keywords: SERS; metallic surface; nanostructure. INTRODUÇÃOAvanços na tecnologia da instrumentação dos espectrômetros Raman têm levado esta técnica a uma posição de destaque dentre as disponíveis para aplicações em problemas de interesse químico. Como exemplos podem ser citados o desenvolvimento de detectores multicanal (CCD), o uso de microscópio óptico acoplado ao espectrômetro e o desenvolvimento de equipamentos de baixo custo, com laser de estado sólido e fibra óptica para transporte da luz incidente e espalhada.A intensidade do espalhamento Raman depende, entre outras coisas, do número de espalhadores e, dessa forma, tais avanços, são insuficientes para a investigação de fenômenos de interface, nos quais as espécies de interesse estão geralmente presentes como submonocamadas. A espectroscopia Raman ordinária possui baixa secção de choque 1 (ca. 10 -30 cm 2 molécula -1 sr -1 ), o que a torna pouco sensível, quando comparada, por ex., à absorção no infravermelho ou à fluorescência, que possuem secções de choque superiores em mais de 10 ordens de grandeza 2,3 .Existem, apesar disso, efeitos de intensificação que melhoram o desempenho da técnica como o efeito Raman ressonante (RR) e o efeito de intensificação de espalhamento por meio de superfície (SERS). O efeito Raman ressonante é um acoplamento vibrônico que ocorre quando a energia da radiação excitante se aproxima ou coincide com uma banda de transição eletrônica permitida da espé-cie em estudo, fazendo com que haja um aumento substancial na intensidade das bandas das vibrações envolvidas com o grupo cromofórico 4 . Já o efeito SERS, é observado quando uma espécie química está próxima ou adsorvida sobre uma superfície metálica rugosa, permitindo um aumento significativo da intensidade Raman. Ganho ainda maior pode ser obtido em espectros SERS quando a espécie interagindo com a superfície possui transição eletrônica com energia em ressonância com a radiação excitante utilizada. Neste caso, além do efeito SERS, ocorre intensificação por RR e a este efeito denomina-se SERRS ("Surface-Enhanced Resonance Raman Scattering").A partir do momento em que a intensificação foi caracterizada como um novo efeito e não como decorrente do aumento da área superficial do metal foram publicados inúmeros trabalhos que levaram a espectroscopia SERS a se tornar uma técnica de análise de superfícies, através da qual é possível determinar a identidade, a orientação e os sítios de interação dos ads...

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Confined Plasmons in Nanofabricated Single Silver Particle Pairs: Experimental Observations of Strong Interparticle Interactions

Cited by 500 publications

References 49 publications

Robust Subnanometric Plasmon Ruler by Rescaling of the Nonlocal Optical Response

Robust Subnanometric Plasmon Ruler by Rescaling of the Nonlocal Optical Response

Controllable Cobalt Oxide/Au Hierarchically Nanostructured Electrode for Nonenzymatic Glucose Sensing

O efeito SERS na análise de traços: o papel das superfícies nanoestruturadas

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