Dynamic Plasmonic Metasurface Regulated by Drude‐Like Active Spacers

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.

In this Letter, we present a theoretical study based on the Lorentz function and harmonic oscillator model to explore temporal dynamics of charge transfer plasmon (CTP) resonances. By fitting scattering curves and near-field oscillations, we determine the dephasing time of CTP modes in conductively connected gold nanodisk dimers. We show that, compared with the well-known particle plasmon and dimer plasmon modes, the CTP mode has a narrow spectral width and longer lifetime. Moreover, quantitative analysis of optical near-fields reveals that CTP modes oscillate completely out-of-phase with the particle plasmon and dimer plasmon modes. The dephasing time, near-field decay rate and charge transfer time of the CTP mode are found to be on a few femtosecond timescales, implying that conductively connected plasmonic nanoparticles hold great promise as channels for ultrafast transfer of information in all-optical computing and optoelectronic devices.

Charge transfer plasmon (CTP) refers to the direct transfer of charge between nanoparticles across a conductive gap, offering advantages in achieving near-infrared (NIR) plasmon resonance and modulating charge transfer in metallic nanoparticles. However, CTP is normally formed on the chip-based substrate, while the formation of CTP in colloids remains challenging due to the stringent requirement for a metallic nanobridge, limiting its exploration and applications. In this study, we demonstrated that the growth of silver nanoparticles on gold nanoparticles can be controlled by solvent polarity to create a conductive nanobridge between the particles, facilitating CTP formation. This solvent polarity-induced CTP was established as a universal strategy and successfully realized in nanospheres, nanorods, and nanostars. Furthermore, leveraging this scalable fabrication method and the unique charge transfer properties of CTP, we demonstrated its superior ability to enhance near-field effects, such as surface-enhanced Raman scattering (SERS), compared to conventional plasmon dipole modes. This approach provides a universal strategy for large-scale CTP formation while offering deeper insights into its underlying principles and potential applications.

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.

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.

The optical resonances of plasmonic metasurfaces can have a significant impact on the ability to control the light properties. In particular, resonant plasmonic metasurfaces exhibit photonic topological transitions, leading to sharp transformations in the topology of the isofrequency contours in reciprocal lattice space. For instance, elliptical contours can transform into hyperbolic ones, and vice versa, significantly altering the wavefront and properties of the propagating light. This transition is accompanied by the flat isofrequency contours corresponding to the canalization regime, which means the divergenceless and high-directional wave propagation. In this work, we investigate the formation and engineering of the photonic topological transitions and the related effects in the plasmonic metasurfaces based on gold nanopatches via the continuous transformation from isotropic to anisotropic cases. We study the impact of the induced anisotropy on the spectral positions and amplitudes of the surface conductivity resonances describing the metasurfaces leading to the emergence of hyperbolicity, near-field hot-spots and plasmon canalization. Particular attention is paid to a comparative analysis of the two anisotropy-inducing strategies, stretching the meta-atoms and stretching the lattice, in terms of functionality and fabrication of plasmonic resonant metasurfaces. Our findings emphasize the importance of using anisotropic resonant nanostructures for a plethora of photonic applications, especially in the area of the in-plane light management.

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 directly on a purely dielectric substrate. The results of this work serve to advance our understanding of the interaction between metallic nanoparticles and metallic films, as well as provide a method for creating more robust plasmonic platforms that are less affected by changes in the size of individual 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.

Summary form only given. A plasmon resonant mode is the collective oscillation of free electrons in a structure stimulated by incident light. 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 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sup> . 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. For instance, a plasmonic gap field of 1010 V/m (or an incident power of 3×10 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">10</sup> W/cm <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sup> ) is needed when the gap length is 0.8 nm. 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, such as high speed switches and modulators.

For two-dimensional (2D) polar semiconductors with out-of-plane polarization, as the number of stacked layers increases, the electronic properties could change from single-layer semiconductor to multi-layer metal. The metallic characteristic manifests as the formation of 2D conductive electron and hole gas on the surfaces. In this study, we investigate the mechanism behind the formation of a two-dimensional electron gas (hole gas) on the surface and interlayer directional charge transfer process of polar quintuple-layers (QLs)-Al2O3 through first-principles calculations. The accumulated polarized electric field acts as the thermodynamic driving force for directional charge transfer between QL-Al2O3 layers, involving all Al and O atoms in the charge transfer process. However, the point defects in 2QLs-Al2O3, including different effective charge, significantly influence the dynamic process of directional interlayer charge transfer. The presence of unsaturated oxygen atoms at the interface contributes to the formation of interface trapped charges in 2QLs-Al2O3.

Functional and reversible plasmonic resonances across the visible and near-infrared spectrum have opened new avenues for developing advanced next-generation nanophotonic devices. In this study, by using optothermally controlled phase-change material (PCM) for plasmonic nanostructures, we successfully induced highly tunable charge transfer plasmon (CTP) resonance modes. To this end, we have chosen a two-member dimer assembly consisting of gold cores and Ge2Sb2Te5 (GST) shells in distant, touching, and overlapping regimes. We show that switching between amorphous (dielectric) and crystalline (conductive) phases of GST allows for achieving tunable dipolar and CTP resonances and enables an effective interplay between these modes along the near-infrared spectrum. By analyzing electromagnetically calculated spectral responses for the dimer antenna in tunneling and direct charge transfer regimes, we confirmed that the induced CTPs in touching and overlapping regimes are highly controllable and pronounced in comparison to the quantum tunneling regime. We also use the precise, fast, and controllable switching between dipolar and CTP resonant modes to develop a telecommunication switch based on a simple metallodielectric dimer. The proposed structures can help designing optothermally controlled devices without morphological variations in the geometry of the design, and having strong potential for advanced plasmon modulation and fast data routing.

We investigate optical properties of wire-bridged plasmonic nanoantennas. Here we found two spectral features: a dipolar plasmon in the visible and a Charge Transfer Plasmon (CTP) in the infrared. The CTP depends sensitively on the conductance of the junction wire, offering a controllable way for tuning the plasmon resonance to the desired wavelength regime via junction geometries. Here we use single-particle dark field spectroscopy from UV, visible to IR to identify plasmonic modes in different spectrum regimes. The simulations using Finite-difference time-domain (FDTD) method are in good agreement with experiment: Increasing the junction wire width and concurrently the junction conductance blue shifts resonance positions, and simultaneously modifies scattering strengths, the linewidth of CTP and dipolar plasmon. We notice that CTP in a much longer wavelength regime and preserving a narrow line width, an important implication for designing IR plasmons with a high quality factor for enhanced spectroscopy and sensing applications. We also extend the CTP to the IR regime by increasing the wire length to create IR plasmon while keeping the line width of the resonance. Our work offers a way for studying the charge transfer properties in plasmonic nanostructures. Not only it adds another degree in understanding the charge transfer properties in plasmonic nanostructures but also offers an optical platform for studying molecules transport at optical frequencies and related applications.

Angle and polarization dependent coupling of surface plasmon and gap modes in plasmonic gap metasurfaces

Graphene has promising applications for novel optoelectronic devices. However, graphene-based photodetectors have two major drawbacks that need attention. The first is how to preserve graphene’s original high carrier mobility, and the second is how to enhance graphene’s absorption to improve its performance. Hexagonal boron nitride (hBN)/graphene van der Waals (vdW) heterostructure-based plasmonic metasurfaces (PMs) are proposed for wavelength-selective infrared (IR) photodetectors. hBN preserves graphene’s high carrier mobility, and PMs enhance graphene’s absorption. Numerical calculations demonstrate sufficient wavelength-selective absorption in the broadband IR wavelength range. Such optical properties are realized by coupling the localized surface plasmon resonance (SPR) of PMs and propagating SPR of graphene. The proposed vdW heterostructure-based PMs could be used for high-performance multi-spectral IR photodetectors.

Realization of the direct charge transfer at metal–semiconductor interfaces is a long-standing goal of both fundamental and technological significance. Here we report the synthesis of a colloidal Sb2Se3–Au core–shell nanorod as a model system to demonstrate an efficient direct charge transfer from an Au shell to Sb2Se3 core when the metal is selectively excited at the plasmonic wavelength. In our experiments, direct charge transfer by the Landau damping of the plasmons of metal shell significantly enhances the excited state population that results in an unprecedented ultrafast third-order nonlinear optical response as a function of the plasmon-excitation detuning wavelength. The single step photo-induced charge transfer analogous to the intramolecular electronic transition in molecules is probed by ultrafast transient absorption, which reveals that the electrons are directly transferred from the Fermi level of Au to the unoccupied levels of Sb2Se3 in less than 150 fs. First principles density functional theory calculations indicate that the hybridized eigenstates of the strongly coupled system are delocalized across the metal–semiconductor interfaces. By formulating the theoretical models, we connect our experimental results to the theory.