Charge Transfer Plasmon Mode Research Articles

Nanoengineering of conductively coupled metallic nanoparticles towards selective resonance modes within the near-infrared regime

In this work, the mode transition effect of different plasmonic resonances in linked dimers by a conductive junction is numerically investigated.Without the junction, the dimer supports a single dipolar bonding plasmon mode, while two new resonance modes, a screened bonding dipolar mode and a low energy charge transfer plasmon mode, emerge when two nanoparticles are linked via a bridge. Such effect is proved to be unrelated to the shape of the nanoparticles, whether sphere, core-shell or nanoegg. However, it was found that the status of each specific resonance mode is profoundly influenced by the shape of nanoparticles. Furthermore, a detailed discussion of mechanisms of controlling plasmon modes, specially charge transfer mode, and tuning their corresponding spectra in bridged nanoparticles as functions of nanoparticle parameters and junction conductance is presented. These results show that the optical response of the dimer is highly sensitive to changes in the inter-particle gap. While the capacitive dimer provides a strong hotstop, the conductive dimer leads to highly controllable low energy plasmon mode at the mid-infrared region appropriate for novel applications. These findings may serve as an important guide for optical properties of linked nanoparticles as well as understanding the transition between the capacitive and conductive coupling.

Functional Charge Transfer Plasmon Metadevices.

Reducing the capacitive opening between subwavelength metallic objects down to atomic scales or bridging the gap by a conductive path reveals new plasmonic spectral features, known as charge transfer plasmon (CTP). We review the origin, properties, and trending applications of this modes and show how they can be well-understood by classical electrodynamics and quantum mechanics principles. Particularly important is the excitation mechanisms and practical approaches of such a unique resonance in tailoring high-response and efficient extreme-subwavelength hybrid nanophotonic devices. While the quantum tunneling-induced CTP mode possesses the ability to turn on and off the charge transition by varying the intensity of an external light source, the excited CTP in conductively bridged plasmonic systems suffers from the lack of tunability. To address this, the integration of bulk plasmonic nanostructures with optothermally and optoelectronically controllable components has been introduced as promising techniques for developing multifunctional and high-performance CTP-resonant tools. Ultimate tunable plasmonic devices such as metamodulators and metafilters are thus in prospect.

Hollow Porous Gold Nanoshells with Controlled Nanojunctions for Highly Tunable Plasmon Resonances and Intense Field Enhancements for Surface-Enhanced Raman Scattering.

Plasmonic metal nanostructures with nanogaps have attracted great interest owing to their controllable optical properties and intense electromagnetic fields that can be useful for a variety of applications, but precise and reliable control of nanogaps in three-dimensional nanostructures remains a great challenge. Here, we report the control of nanojunctions of hollow porous gold nanoshell (HPAuNS) structures by a facile oxygen plasma-etching process and the influence of changes in nanocrevices of the interparticle junction on the optical and sensing characteristics of HPAuNSs. We demonstrate a high tunability of the localized surface plasmon resonance (LSPR) peaks and surface-enhanced Raman scattering (SERS) detection of rhodamine 6G (R6G) using HPAuNS structures with different nanojunctions by varying the degree of gold sintering. As the neck region of the nanojunction is further sintered, the main LSPR peak shifts from 785 to 1350 nm with broadening because the charge transfer plasmon mode becomes more dominant than the dipolar plasmon mode, resulting from the increase of conductance at the interparticle junctions. In addition, it is demonstrated that an increase in the sharpness of the nanojunction neck can enhance the SERS enhancement factor of the HPAuNS by up to 4.8-fold. This enhancement can be ascribed to the more intense local electromagnetic fields at the sharper nanocrevices of interparticle junctions. The delicate change of nanojunction structures in HPAuNSs can significantly affect their optical spectrum and electromagnetic field intensity, which are critical for their practical use in a SERS-based analytical sensor as well as multiple-wavelength compatible applications.

Understanding plasmon coupling in nanoparticle dimers using molecular orbitals and configuration interaction.

We perform a theoretical investigation of the electronic structure and optical properties of atomic nanowire and nanorod dimers using DFT and TDDFT. In both systems at separation distances larger than 0.75 nm, optical spectra show a single feature that resembles the bonding dipole plasmon (BDP) mode. A configuration interaction (CI) analysis shows that the BDP mode arises from constructive coupling of transitions, whereas the destructive coupling does not produce significant oscillator strength for such separation distances. At shorter separation distances, both constructive and destructive coupling produce oscillator strength due to wave-function overlap, which results in multiple features in the calculated spectra. Our analysis shows that a charge-transfer plasmon (CTP) mode arises from destructive coupling of transitions, whereas the BDP results from constructive coupling of the same transitions at shorter separation distances. Furthermore, the coupling elements between these transitions are shown to depend heavily on the amount of exact Hartree-Fock exchange (HFX) in the functional, which affects the splitting of CTP and BDP modes. With 50% HFX or more, the CTP and BDP modes mainly merge into a single feature in the spectra. These findings suggest that the effects of exact exchange must be assessed during the prediction of CTP modes in plasmonic systems.

Molecular Tunnel Junction-Controlled High-Order Charge Transfer Plasmon and Fano Resonances.

Quantum tunneling plays an important role in coupled plasmonic nanocavities with ultrasmall gap distances. It can lead to intriguing applications such as plasmon mode excitation, hot carrier generation, and construction of ultracompact electro-optic devices. Molecular junctions bridging plasmonic nanocavities can provide a tunneling channel at moderate gap distances and therefore allow for the facile fabrication of quantum plasmonic devices. Herein we report on the large-scale bottom-up fabrication of molecular junction-bridged plasmonic nanocavities formed from Au nanoplate-Au nanosphere heterodimers. When the molecular junction turns from insulating to conductive, a distinct spectral change is observed, together with the emergence of a high-order charge transfer plasmon mode. The evolution of the electron tunneling-induced plasmon mode also greatly affects the Fano resonance feature in the scattering spectrum of the individual heterodimers. The molecular conductance at optical frequencies is estimated. The molecular junction-assisted electron tunneling is further verified by the reduced surface-enhanced Raman intensities of the molecules in the plasmonic nanocavity. We believe that our results provide an interesting system that can boost the investigation on the use of molecular junctions to modulate quantum plasmon resonances and construct molecular plasmonic devices.

Robust Charge Transfer Plasmons in Metallic Particle–Film Systems

Understanding how the plasmonic response of a metallic nanoparticle is modified by its coupling with a metallic film is a fundamental research problem relevant for many applications including sensing, solar energy harvesting, spectroscopy, and photochemistry. Despite significant research effort on this topic, the nature of the interaction between colloidal nanoparticles and metallic films is not fully understood. Here, we investigate, both experimentally and theoretically, the optical response of surface ligand-coated gold nanorods interacting with gold films. We find that the scattering cross section of these systems is dominated by a charge transfer plasmon mode, for which charge flows between the particle and the film. The properties of this mode are dictated by the characteristics of the particle–film junction, which makes the frequency of this charge transfer plasmon far less sensitive to the nanoparticle size and geometry than a typical dipolar plasmon mode excited in similar nanorods placed directl...

Tunable multiband plasmonic response of indium antimonide touching microrings in the terahertz range.

In this paper, we propose a terahertz (THz) plasmonic structure that supports three resonance modes, including the charge transfer plasmon (CTP), the bonding dipole-dipole plasmon, and the antibonding dipole-dipole plasmon, which can be strongly tuned by geometrical parameters, passively, and the temperature, actively. The structure exhibits a considerable thermal sensitivity of more than 0.01THz/K. The introduced multiband and tunable THz plasmonic structures offer important applications in thermal switches, thermo-optical modulators, broadband filters, design of multifunctional molecules originating from the multiband specification of the proposed structure, and improvement in plasmonic sensor applications stemming from a detailed study of the CTP mode.

Screened bonding, antibonding and charge transfer plasmon modes in conductively connected nanorod heterodimer

Screened bonding (SB), screened antibonding (SA) and charge transfer plasmon (CTP) modes in the conductively connected nanorod heterodimer are studied in detail by simulation. All of the SB, SA and CTP modes can be observed in the extinction spectra of the conductively connected nanorod heterodimer. Also, the amplitudes of the three modes can be tuned by changing the radius of the cylinder conductive connection. Even the amplitude of the SA mode can be tuned to be higher than that of the SB mode, which is difficult to achieve in an unconnected nanorod heterodimer. Furthermore, the wavelengths of the three plasmon modes can be adjusted with a high degree of freedom, since the wavelength of the SB mode mainly depends on the length of the longer nanorod, the wavelength of the SA mode mainly depends on the length of the shorter nanorod and the wavelength of the CTP mode mainly depends on the total length of the nanorod heterodimer. Our study will be helpful for the design of plasmon enhancement devices, such as surface enhanced Raman scattering (SERS), plasmon enhanced fluorescence, plasmon rulers and so on.

Optical Switching Using Transition from Dipolar to Charge Transfer Plasmon Modes in Ge2Sb2Te5 Bridged Metallodielectric Dimers

Capacitive coupling and direct shuttling of charges in nanoscale plasmonic components across a dielectric spacer and through a conductive junction lead to excitation of significantly different dipolar and charge transfer plasmon (CTP) resonances, respectively. Here, we demonstrate the excitation of dipolar and CTP resonant modes in metallic nanodimers bridged by phase-change material (PCM) sections, material and electrical characteristics of which can be controlled by external stimuli. Ultrafast switching (in the range of a few nanoseconds) between amorphous and crystalline phases of the PCM section (here Ge2Sb2Te5 (GST)) allows for designing a tunable plasmonic switch for optical communication applications with significant modulation depth (up to 88%). Judiciously selecting the geometrical parameters and taking advantage of the electrical properties of the amorphous phase of the GST section we adjusted the extinction peak of the dipolar mode at the telecommunication band (λ~1.55 μm), which is considered as the OFF state. Changing the GST phase to crystalline via optical heating allows for direct transfer of charges through the junction between nanodisks and formation of a distinct CTP peak at longer wavelengths (λ~1.85 μm) far from the telecommunication wavelength, which constitutes the ON state.

Gap plasmonics of silver nanocube dimers

We theoretically investigate gap plasmons for two silver nanocubes coupled through a molecular tunnel junction. In absence of tunneling, the red-shift of the bonding mode saturates with decreasing gap distance. Tunneling at small gap distances leads to a damping and slight blue-shift of the bonding mode, but no low-energy charge transfer plasmon mode appears in the spectra. This finding is in stark contrast to recent work of Tan et al. [Science 343, 1496 (2014)].

Gradual plasmon evolution and huge infrared near-field enhancement of metallic bridged nanoparticle dimers.

By three-dimensional (3D) finite element method (FEM) plasmon mapping, gradual plasmon evolutions of both bonding dipole plasmon (BDP) and charge transfer plasmon (CTP) modes are visualized. In particular, the evolved BDP mode provides a physical insight into the rapid degeneration of electromagnetic hot spots in practical applications, while the rising CTP mode enables a huge near-field enhancement for potential plasmonic devices at infrared wavelengths.

Broadband Mid-Infrared Super-Resolution Imaging with Metallic Nanorod-Bridged Dimer Array

We propose a broadband mid-infrared super-resolution imaging system comprising a metallic nanorod-bridged dimer array. The imaging array enables super-resolution imaging of shaped dipole sources in the near field. A charge transfer plasmon (CTP) appears in a metallic nanorod-bridged dimer. By varying the radius of the junction, the plasmon resonance wavelength of CTP mode can be tuned into the mid-infrared region. Here, we investigate the broadband super-resolution imaging of the incoherent and coherent dipole sources at mid-infrared wavelengths. With the array pitch varying, we calculate the cross-sectional field intensity distributions at the source plane and the image plane by using the finite element method. The simulation results indicate that the broadband incoherent and coherent super-resolution imaging can be realized at mid-infrared wavelengths with the imaging array. The image quality is sensitively dependent on the source coherent, the array pitch, and the distance from the image plane to the array. In the same structural parameters, the image quality of coherent source of in-phase is lower than that of incoherent source. Increasing the array pitch improves the image quality but it also increases the size of the array. By reasonably choosing the array pitch of the array, the spatial resolution of ∼λ/109 and ∼λ/73 is obtained corresponding to the incoherent imaging case and coherent imaging case at the mid-infrared wavelength of 4390 nm. Moreover, the larger image-array distance results in the lower image quality.

Plasmon excitation in C60 fullerene dimers

Plasmon resonances in C60 fullerene dimers are investigated using time-dependent density functional theory. Owing to larger separation between molecules, there exist capacitive coupling plasmon modes in fullerene dimers. With the decrease of the gap distance, low-energy capacitive coupling plasmon modes show red shift. When the gap distance further decreases, because of the electrons tunneling across the dimer junction, plasmon resonance modes of C60 fullerene dimers are significantly modified, and the charge transfer plasmon modes occur. C60 fullerene dimer is different from metallic nanostructures dimmer. As the gap distance is again reduced, the charge transfer plasmon modes are not blue-shifted, but they are further red-shifted. In the range of the visible spectrum, C60 fullerene dimmers have strong absorption peaks.

Coexistence of classical and quantum plasmonics in large plasmonic structures with subnanometer gaps

Large metal nanostructures with subnanometer interparticle separations (gaps) can provide extremely high local fields and are of particular interest in surface enhanced spectroscopy, as well as for basic understanding of plasmonics. In this experimental electron energy loss study, we monitor the transition of plasmonic dimers from a classical to a quantum system by decreasing gaps to dimensions when tunneling occurs and a conductive nanobridge evolves. Our studies show that silver dimers with atomic scale gaps can exhibit a regime, in which charge transfer plasmon modes, as a hallmark of a quantum nature, and “classical” bright and dark dipolar plasmon modes can be seen simultaneously.

Plasmon resonances and the plasmon-induced field enhancement in nanoring dimers

Plasmon resonances and the plasmon-induced field enhancement (FE) in sodium nanoring dimers are investigated by time-dependent density functional theory. For larger separations, the optical absorption, the induced charge response and the frequency dependent current demonstrate that there are two capacitive coupling plasmon modes. One feature of FE is that, in the surface region of the nanoring, it has a very large maximum. Another feature of FE is that, along the perpendicular bisector of the line segment joining the two nanoring center points in the middle region of the nanoring dimers, it has maxima. With the decrease of the gap distance, because of the electrons tunneling across the dimer junction and screening, collective excitation modes are changed, and the charge transfer plasmon modes emerge in the nanoring dimers. FE induced by any plasmon modes decreases in the gap region. Moreover, corresponding to different gap distances, the high-energy plasmon resonance peak almost does not shift, because this plasmon mode is mainly the collective excitation as a result of interactions among degenerate individual electronic states.

Fowler–Nordheim Tunneling Induced Charge Transfer Plasmons between Nearly Touching Nanoparticles

Reducing the gap between two metal nanoparticles down to atomic dimensions uncovers novel plasmon resonant modes. Of particular interest is a mode known as the charge transfer plasmon (CTP). This mode has been experimentally observed in touching nanoparticles, where charges can shuttle between the nanoparticles via a conductive path. However, the CTP mode for nearly touching nanoparticles has only been predicted theoretically to occur via direct tunneling when the gap is reduced to ~0.4 nm. Because of challenges in fabricating and characterizing gaps at these dimensions, experiments have been unable to provide evidence for this plasmon mode that is supported by tunneling. In this work, we consider an alternative tunneling process, that is, the well-known Fowler-Nordheim (FN) tunneling that occurs at high electric fields, and apply it for the first time in the theoretical investigation of plasmon resonances between nearly touching nanoparticles. This new approach relaxes the requirements on gap dimensions, and intuitively suggests that with a sufficiently high-intensity irradiation, the CTP can be excited via FN tunneling for a range of subnanometer gaps. The unique feature of FN tunneling induced CTP is the ability to turn on and off the charge transfer by varying the intensity of an external light source, and this could inspire the development of novel quantum devices.

Quantum mechanical study of plasmonic coupling in sodium nanoring dimers

In sodium nanoring dimers, plasmon resonances and the plasmon-induced field enhancement are investigated by time-dependent density functional theory. The optical absorption, the induced charge response, and the frequency dependent current demonstrate that the main plasmon resonance modes are the charge transfer plasmon mode and the bonding dimer plasmon mode (BDP). Moreover, there are also two small hybridized plasmon modes. The induced field enhancement of each spatial region depends on the gap distance and the plasmon mode. For the narrow gap, the field enhancement at different positions of the straight line segments between two nanorings is almost uniformly distributed. However, for large separations, along the axial direction, the field enhancement gradually decreases in the region within the radius of the sodium atom. Then, the change of the field enhancement is nonlinear. For different plasmon modes, there is a different number of field enhancement extrema. The largest extreme value is located in the middle region. These findings are expected to play an important role in designing plasmonic nanostructures for practical applications that require coupled metallic nanoparticles with enhanced electric fields.

Optical characterization of charge transfer and bonding dimer plasmons in linked interparticle gaps

We present a theoretical study of the optical properties of nanoparticle dimers connected by conductive gap linkers. The geometrical and conductive properties of the linker modify strongly the optical response of the linked metallic cavity. Two plasmonic modes are responsible for the main spectral features of the cavity: a bonding dimer plasmon (BDP) and a charge transfer plasmon (CTP). We first explore how these two modes are modified as a function of the geometry and the conductance through the cavity, identifying the spatial distribution of the linking current densities. Furthermore, we introduce a resonant feature in the conductivity of the linker, where we observe a complex splitting of the plasmon modes. We also study the capabilities of the BDP and CTP modes in localized surface plasmon resonance (LSPR) sensing.

Quantum mechanical study of the coupling of plasmon excitations to atomic-scale electron transport

The coupling of optical excitation and electron transport through a sodium atom in a plasmonic dimer junction is investigated using time-dependent density functional theory. The optical absorption and dynamic conductance is determined as a function of gap size. Surface plasmons are found to couple to atomic-scale transport through several different channels including dipolar, multipolar, and charge transfer plasmon modes. These findings provide insight into subnanoscale couplings of plasmons and atoms, a subject of general interest in plasmonics and molecular electronics.