Surface Exciton Research Articles

A Semiclassical Model for Plasmon-Exciton Interaction From Weak to Strong Coupling Regime

Exploitation of strong light-matter interactions in plasmonic systems is vital for both fundamental studies and the development of new applications, which enables exceptional physical phenomena and promotes potential applications in nanophotonics, information communication, and quantum information processing. Here, we present an analytic model of the interaction between localized surface plasmon resonances and excitons, where a semiclassical method is utilized. Two kinds of metal nanoparticles (nanosphere and nanoellipsoid) are considered in our study. We derive the relations between the plasmon-exciton coupling strength and the geometry and material parameters of the coupled systems when the nanoparticles are put in an excitonic medium, which give an important guide to achieve strong plasmon-exciton coupling. Rabi splittings and anticrossing behavior are also demonstrated in the calculated extinction spectra. Furthermore, we propose an analytic model to describe the strong coupling between excitons and plasmon in a core-shell nanorod structure which is widely used in experiments. Our study provides a simple yet rigorous prescription to both analyze and design plexcitonic systems aiming at strong light-matter interactions.

Understanding radiative transitions and relaxation pathways in plexcitons

Summary Molecular aggregates on plasmonic nanoparticles have emerged as attractive systems for the studies of polaritonic light-matter states, called plexcitons. Such systems are tunable, scalable, easy to synthesize, and offer sub-wavelength confinement, all while giving access to the ultrastrong light-matter coupling regime, promising a plethora of applications. However, the complexity of these materials prevented the understanding of their excitation and relaxation phenomena. Here, we follow the relaxation pathways in plexcitons and conclude that while the metal destroys the optical coherence, the molecular aggregate coupled to surface processes significantly contributes to the energy dissipation. We use two-dimensional electronic spectroscopy with theoretical modeling to assign the different relaxation processes to either molecules or metal nanoparticle. We show that the dynamics beyond a few femtoseconds has to be considered in the language of hot electron distributions instead of the accepted lower and upper polariton branches and establish the framework for further understanding.

A Review of Many-Body Interactions in Linear and Nonlinear Plasmonic Nanohybrids

In this review article, we discuss the many-body interactions in plasmonic nanohybrids made of an ensemble of quantum emitters and metallic nanoparticles. A theory of the linear and nonlinear optical emission intensity was developed by using the many-body quantum mechanical density matrix method. The ensemble of quantum emitters and metallic nanoparticles interact with each other via the dipole-dipole interaction. Surfaces plasmon polaritons are located near to the surface of the metallic nanoparticles. We showed that the nonlinear Kerr intensity enhances due to the weak dipole-dipole coupling limits. On the other hand, in the strong dipole-dipole coupling limit, the single peak in the Kerr intensity splits into two peaks. The splitting of the Kerr spectrum is due to the creation of dressed states in the plasmonic nanohybrids within the strong dipole-dipole interaction. Further, we found that the Kerr nonlinearity is also enhanced due to the interaction between the surface plasmon polaritons and excitons of the quantum emitters. Next, we predicted the spontaneous decay rates are enhanced due to the dipole-dipole coupling. The enhancement of the Kerr intensity due to the surface plasmon polaritons can be used to fabricate nanosensors. The splitting of one peak (ON) two peaks (OFF) can be used to fabricate the nanoswitches for nanotechnology and nanomedical applications.

Tailoring surface plasmon-exciton polariton for high-performance refractive index monitoring

We report coupling between surface plasmon polariton (SPP) and surface exciton polariton (SEP) as hybrid mode; surface plasmon exciton polariton (SPEP) that can be utilized for highly sensitive and accurate refractive index monitoring. The proposed structure comprises of a thin layer of organic semiconductor; J-aggregate cyanine dye (5,5′,6,6′-tetrachloro-1,10-diethyl-3, 30-di(4-sulfobutyl) benzimidazolo-carbocyanine (TDBC)) having, strong dipole moment resulting from linear chain-like structure, over plasmon active metal coated on prism. It is found that due to SPEP excitation, the sensitivity of the proposed refractometer is ∼84% higher as compared to that of conventional plasmonic sensor at λ = 532 nm and has high tolerance towards 10 nm of metal thickness. The wavelength dependent performance analysis of SPEP modes reveals that for high energy SPEP (mode-1 at λ = 532 nm), sensitivity as well as figure of merit (FOM) of the proposed refractometer is ∼80% and ∼200% respectively higher than low energy SPEP (mode-2 at λ = 633 nm). We believe that the study will open a new window for a diverse range of biochemical and gaseous sensing applications.

Study on mode shifts of localized surface plasmon cavity in Ag nanowire tetramer

The interaction between noble metal nanowires can induce the local surface plasmonic resonance effect, thereby enhancing the distribution of electric field in the nanostructures, which is of very important significance in improving the fluorescence characteristics and enhancing the sensitivity of sensors. In this study, we design several types of tetramers based on precious metals Ag nanostructures, including cylindrical and prismatic Ag tetramers, and by changing the arrangement and the rotation angle of prism nanowires, we simulate the rotation-angle dependent electric field distribution and electric field intensity of <i>X</i> component , and also discuss the physical mechanism of the relationship between the resonant peak position of absorption spectrum and the change of mode volume. The results show that in the Ag nanowires tetramer structure, the electric field in the cylindrical structure is not enhanced obviously, but the electric field in the prismatic structure is greatly enhanced, and an electric dipole resonance mode is produced in the gap between tetramers. The polarization of plasma resonant cavity revels that the morphology plays a decisive role in generating the hot spots, After changing both the combination mode of tetramer nanowires and the rotation angle of the four-prism, the local surface exciton resonance of the unrotated asymmetric tetramer structure is most ideal and has resonance intensity higher than the that of symmetrical four-prism structure. Therefore, our results provide a structural model and theoretical parameters for the enhancement of electric field intensity by local surface plasmon resonance effect.

An “on-off-super on” photoelectrochemical sensor based on quenching by Cu-induced surface exciton trapping and signal amplification of copper sulfide/porous carbon nitride heterojunction

In this work, we report an “on-off-super on” photoelectrochemical sensor for probing hydrogen sulfide due to its toxicity in water environment by using porous carbon nitride as photoelectric transducers. Synthesized by an alkaline-assisted hydrothermal method, the porous carbon nitride photoanode exhibited a remarkable photocurrent on the initial “on” state. Cu2+ immobilized on the surfaces of porous carbon nitride could significantly decrease the charge transfer efficiency and quench the photoelectrochemical signal in the “off” state. In addition, the introduction of S2− ions could eliminate the influence of Cu-induced surface exciton trapping and amplify the photoelectrochemical signal due to the formation of carbon nitride/copper sulfide heterojunction, thus leading to the achievement of the ‘‘super on’’ state and subsequently detection of hydrogen sulfide. More importantly, this photoelectrochemical sensor shows the excellent performance for probing hydrogen sulfide in terms of stability, selectivity, sensitivity and fabrication cost. Enabled by a unique “on-off-super on” strategy, it could serve as a reference for developing the new class of photoelectrochemical sensor.

Relativistic structural characterization of molybdenum and tungsten disulfide materials

AbstractThe advent of two‐dimensional transition metal dichalcogenides has triggered an interest in exploring a new class of high‐performance materials with intriguing physicochemical attributes. Molybdenum and tungsten disulfides have attracted significant attention due to surface excitons and trions and the large spin‐orbit effects of these compounds. Moreover, WS2 is especially intriguing due to large relativistic effects, which result in bound excitons at the edge and biexciton formation in the bilayers. Hence, we present a relativistic topological model for the characterization of these two types of metal disulfides. We have employed relativistically weighted graph‐theoretical methods for obtaining structural descriptors of these compounds through the inclusion of different shapes on the boundaries and employing the topological cut techniques.

Unraveling the electronic structures in different phases of gadolinium sesquioxides performed by electron energy loss spectroscopy

The gadolinium sesquioxide (Gd2O3) with its bandgap of ∼5.4 eV and high dielectric permittivity and refractive index has been used widely in optics, magnetic resonance imaging, and high k dielectrics. Electron energy loss spectroscopy (EELS) reveals spectral features at 13.5 eV and 15 eV, which can be interpreted as surface and volume plasmons, respectively. The unusual surface exciton polariton, with surface resonances associated with excitonic onsets, was also observed at ∼7.5 eV. Because of the differences in electronic structures between the cubic and the monoclinic phases of Gd2O3, it is straightforward to distinguish the two phases using the low-loss regime and O K-edge as a fingerprint. We further successfully performed EELS and electron diffraction to identify the crystalline phase of a single-crystal Gd2O3 film epitaxially grown on a Si(111) substrate.

Numerical simulations on strong coupling of Bloch surface waves and excitons in dielectric-semiconductor multilayers

Simulations on Bloch surface waves and Bloch surface wave–exciton–polaritons based on the transfer matrix method were performed using only the layer thicknesses and refractive indices of the materials. We demonstrate that the incorporation of the influence of active layer is necessary to accurately determine the Bloch surface wave dispersion. Furthermore, the mode splitting that gives rise to the lower and upper polariton branches can be simulated by including the full dispersive refractive index of the active layer in the transfer matrix calculation. We show the dependence of coupling strength on active layer and truncation layer thicknesses, which implies that the Bloch surface wave–exciton interaction strength can be tuned just by changing these structural parameters. Furthermore, we calculate the area inside the dips corresponding to the lower and upper polariton modes, which can serve as an indicator of mode visibility. We find that in the Kretschmann–Raether configuration, a tradeoff between high Rabi splitting and good mode visibility must be taken into account in designing multilayer structures for Bloch surface wave–exciton–polaritons. Angle-resolved reflectivity maps were also calculated to illustrate how these results can be observed in an experimental set-up. This work serves as a guide map in the design and potential optimization of multilayer structures for the study of two-dimensional polaritonic systems.

Supramolecular Porous Organic Nanocomposites for Heterogeneous Photocatalysis of a Sulfur Mustard Simulant.

Efficient heterogeneous photosensitizing materials require both large accessible surface areas and excitons of suitable energies and with well-defined spin structures. Confinement of the tetracationic cyclophane (ExBox4+ ) within a nonporous anionic polystyrene sulfonate (PSS) matrix leads to a surface area increase of up to 225 m2 g-1 in ExBox•PSS. Efficient intersystem crossing is achieved by combining the spin-orbit coupling associated to Br heavy atoms in 1,3,5,8-tetrabromopyrene (TBP), and the photoinduced electron transfer in a TBP⊂ExBox4+ supramolecular dyad. The TBP⊂ExBox4+ complex displays a charge transfer band at 450 nm and an exciplex emission at 520 nm, indicating the formation of new mixed-electronic states. The lowest triplet state (T1 , 1.89 eV) is localized on the TBP and is close in energy with the charge separated state (CT, 2.14 eV). The homogeneous and heterogeneous photocatalytic activities of the TBP⊂ExBox4+ , for the elimination of a sulfur mustard simulant, has proved to be significantly more efficient than TBP and ExBox+4 , confirming the importance of the newly formed excited-state manifold in TBP⊂ExBox4+ for the population of the low-lying T1 state. The high stability, facile preparation, and high performance of the TBP⊂ExBox•PSS nanocomposites augur well for the future development of new supramolecular heterogeneous photosensitizers using host-guest chemistry.

A regenerative photoelectrochemical sensor based on functional porous carbon nitride for Cu2+ detection

In the work, carbon nitride with porous structure and abundant surface functional groups was successfully prepared through an alkaline hydrothermal treatment. Functional porous carbon nitride could serve as the excellent photoelectric transducer substrate and also act as the anchor site for capturing target Cu2+. As a result, a photoelectrochemical (PEC) sensor based on the functional porous carbon nitride was proposed for sensitive detection of Cu2+. Under visible light irradiation, Cu2+-induced surface exciton trapping was appeared on the photoanode sensors, greatly suppressing the transfer of photogenerated charge, which was different from the previous PEC system. Meanwhile, the PEC sensors show satisfactory performance in the detection of Cu2+ with high sensitivity and low detection limit. More importantly, using EDTA, we realized the regeneration of photoanode sensors for probing Cu2+. This work provides a reference for development of the regenerative PEC sensor in the area of commercial determination.

Principle and Applications of the Coupling of Surface Plasmons and Excitons

Surface plasmons have been attracting increasing attention and have been studied extensively in recent decades because of their half-light and half-material polarized properties. On the one hand, the tightly confined surface plasmonic mode may reduce the size of integrated optical devices beyond the diffraction limit; on the other hand, it provides an approach toward enhancement of the interactions between light and matter. In recent experiments, researchers have realized promising applications for surface plasmons in quantum information processing, ultra-low-power lasers, and micro-nano processing devices by using plasmonic structures, which have demonstrated their superiority over traditional optics structures. In this paper, we introduce the theoretical principle of surface plasmons and review the research work related to the interactions between plasmons and excitons. Some perspectives with regard to the future development of plasmonic coupling are also outlined.

Strong plasmon-exciton coupling between lithographically defined single metal nanoparticles and monolayer WSe2.

Strong coupling between surface plasmons and excitons leads to the formation of plexcitons with new energy states, providing a versatile platform for a range of frontier research subjects. Single plasmonic nanoparticles have recently attracted much attention for realizing strong coupling due to their small mode volume. However, the usually used chemically synthesized metal nanoparticles are unfavorable for accurately tailoring the surface plasmon resonances and adverse to the implementation of on-chip integration. Here, we report for the first time the realization of strong coupling between monolayer WSe2 and lithographically defined single metal nanoparticles. Focusing on gold nanobowties, the large Rabi splitting of 187 meV is achieved. The excitons around the nanogaps in the nanobowties contribute dominantly to the coupling strength, and the coupling strength is larger for smaller nanobowties due to the smaller mode volume. Moreover, the hybrid systems of monolayer WSe2 and gold nanoparticle monomers of nanorods, nanotriangles, and nanodisks are found to closely satisfy the criterion of strong coupling. The strong plasmon-exciton coupling realized by single plasmonic nanostructures fabricated by advanced nanofabrication techniques and monolayer semiconductors can provide new opportunities for manipulating strong light-matter interactions at the nanoscale and facilitate the development of plexciton-based nanodevices with ultrasmall footprints.

Polarizability of germanium quantum dots with spatially separated electrons and holes

In the framework of dipole approximation, it is shown that the quantities (the oscillator strengths of transitions, the dipole moments for transitions, and the polarizability) describing optical absorption on surface exciton states with spatially separated electrons and holes (the hole moves in the germanium quantum dot and the electron is localized over the spherical interface of the silicon quantum dot matrix) assume giant values considerably exceeding the typical values of the corresponding quantities for semiconductors under the action of low-intensity light.

Near-field analysis of strong coupling between localized surface plasmons and excitons

We simulate the near-field effects of strong coupling between molecular excitons and localized surface plasmons, supported by aluminum nanodisks. The simulations are done using a simple model of a two-level system, implemented in a commercial electromagnetic finite-difference time-domain solver. While the Rabi splitting is present in the near-field, its spectral gap is seen to be smaller than the one obtained in the far-field, although it follows a clear square root dependence on the molecular density as expected. Moreover, the energy exchange between the plasmonic mode and the excitonic material is evident in 'beats' within the electromagnetic near-field, which are out of phase with respect to the exciton population. Our results explicitly demonstrate the collective nature of strong coupling, which is expressed by the synchronized population oscillations at the collective Rabi frequency set by the number of molecules interacting with the plasmonic mode. This analysis sheds light on strong coupling effects in the near-field region using a versatile model, which provides a powerful tool to study strong coupling, near-field effects, and light-matter interactions in general.

Band‐Edge Exciton Fine Structure and Exciton Recombination Dynamics in Single Crystals of Layered Hybrid Perovskites

Abstract2D perovskite materials have recently reattracted intense research interest for applications in photovoltaics and optoelectronics. As a consequence of the dielectric and quantum confinement effect, they show strongly bound and stable excitons at room temperature. Here, the band‐edge exciton fine structure and in particular its exciton and biexciton dynamics in high quality crystals of (PEA)2PbI4 are investigated. A comparison of bulk and surface exciton lifetimes yields a room temperature surface recombination velocity of 2 × 103 cm s−1 and an intrinsic lifetime of 185 ns. Biexciton emission is evidenced at room temperature, with a binding energy of ≈45 meV and a lifetime of 80 ps. At low temperature, exciton state splitting is observed, which is caused by the electron–hole exchange interaction. Transient photoluminescence resolves the low‐lying dark exciton state, with a bright/dark splitting energy estimated to be 10 meV. This work contributes to the understanding of the complex scenario of the elementary photoexcitations in 2D perovskites.

Polarizability of germanium quantum dots with spatially separated electrons and holes in Ge/Si heterostructures

ABSTRACTIn the framework of dipole approximation, it is shown that the quantities (the oscillator strengths of transitions, the dipole moments for transitions, and the polarizability) describing optical absorption on surface exciton states with spatially separated electrons and holes (the hole moves in the germanium quantum dot and the electron is localised over the spherical interface of the silicon quantum dot matrix) assume giant values considerably exceeding the typical values of the corresponding quantities for semiconductors under the action of low-intensity light.

Surface Exciton Polaritons: A Promising Mechanism for Refractive-Index Sensing

The possibility of constructing a surface exciton polariton (SEP) based sensor at room temperature is explored. The proposed SEP sensor is based on the Kretschmann-Raether configuration of conventional surface plasmon resonance (SPR) sensor, where the metal thin film was replaced by the J-aggregate cyanine dye film. The excitation of SEP results in a strong electric field at the interface of TDBC and analyte, and exponentially decaying into the analyte, which is sensitive to the refractive index variations of analyte. The sensitivity of 118.1818 $^\circ/\text{RIU}$ (140.4286 $^\circ/\text{RIU}$) was achieved for the proposed SEP sensor within the refractive index range 1.0-1.001 (1.33-1.36) of gaseous analyte (aqueous solutions), which is about 2 (3.5) times higher than that of conventional gold-based SPR sensor. The significant superiority of the SEP sensor in sensitivity revealing SEP as a new promising mechanism for sensing applications.

2D semiconductor nonlinear plasmonic modulators

A plasmonic modulator is a device that controls the amplitude or phase of propagating plasmons. In a pure plasmonic modulator, the presence or absence of a plasmonic pump wave controls the amplitude of a plasmonic probe wave through a channel. This control has to be mediated by an interaction between disparate plasmonic waves, typically requiring the integration of a nonlinear material. In this work, we demonstrate a 2D semiconductor nonlinear plasmonic modulator based on a WSe2 monolayer integrated on top of a lithographically defined metallic waveguide. We utilize the strong interaction between the surface plasmon polaritons (SPPs) and excitons in the WSe2 to give a 73 % change in transmission through the device. We demonstrate control of the propagating SPPs using both optical and SPP pumps, realizing a 2D semiconductor nonlinear plasmonic modulator, with an ultrafast response time of 290 fs.

Unveiling the Stimulated Robust Carrier Lifetime of Surface‐Bound Excitons and Their Photoresponse in InSe

AbstractIn contrast to zero‐bandgap metallic graphene, the binary semiconducting compound, InSe, possesses a tunable bandgap. Herein, a range of particle sizes of β‐InSe from bulk to few‐layer nanosheets and quantum dots are carefully prepared. The size‐dependent bandgap variation and photon‐induced carrier dynamics of InSe are systemically investigated. In contrast to the normal size‐dependent carrier lifetime trend observed at 700 nm, anomalous size‐independent carrier decay is observed at 500 nm. Through time‐dependent density functional theory calculations, the normal carrier lifetimes at lower probe photon energies are attributed to in‐plane excitons, whereas the abnormal size‐independent carrier lifetimes at higher probe photon energies are found to be stimulated by surface‐bound excitons. In view of the robust surface exciton, this suggests that InSe may possess an outstanding optoelectronic performance in the shorter wavelength range. Through photoelectrochemical detection experiments, it is confirmed that InSe features a high photocurrent density and stability and, in particular, a more distinct photoresponse at short wavelengths than at longer ones. Comprehending and quantifying the role of the surface‐bound excitons in InSe across a broad range of semiconductor nanostructures and their fundamental properties may play an important role in understanding the physical properties of 2D III–VI compound materials.