Plasmon-exciton Interaction Research Articles

Host-Guest Interaction Mediated Perovskite@Metal-Organic Framework Z-Scheme Heterojunction Enabled Paper-Based Photoelectrochemical Sensing.

Exploring the high-performance photoelectronic properties of perovskite quantum dots (QDs) is desirable for paper-based photoelectrochemical (PEC) sensing;however, challenges remain in improving their stability and fundamental performance. Herein, a novel Z-scheme heterostructure with host-guest interaction by the confinement of CH3NH3PbBr3 QDs within Cu3(BTC)2 metal-organic framework (MOF) crystal (MAPbBr3@Cu3(BTC)2) is successfully constructed on the paper-based PEC device for ultrasensitive detection of Ochratoxin A (OTA), with the assistance of the exciton-plasmon interaction (EPI) effect. The host-guest interaction is estabilished by encapsulating MAPbBr3 QDs as guests within Cu3(BTC)2 MOF as a host, which prevents MAPbBr3 QDs from being damaged in the polar system, offering access to long-term stability with high-performance PEC properties. Benefiting from the precise alignment of energy levels, the photogenerated charge carriers can migrate according to the Z-scheme charge-transfer pathway under the driving force of the internal electric field, achieving a high photoelectric conversion efficiency. Upon OTA recognition, the EPI effect is activated to modulate the exciton response in MAPbBr3 QDs by accelerating radiative decay, finally achieving sensitive OTA sensing with a detection limit of 0.017 pg mL-1. We believe this work renders new insight into designing host-guest Z-scheme heterojunctions in constructing the paper-based PEC sensing platforms for environmental monitoring.

Plasmon-Exciton Interaction at the Nanoscale: Silver Is More "Precious" than Gold!

Predictive understanding of factors affecting plasmon-exciton coupling is crucial for the successful realization of the exciting potentials of plexcitonic nanostructures. Here, we systematically investigate the role of plasmonic metals in controlling the plasmon-exciton coupling strength. We use gold and silver nanoprisms, having identical LSPR maxima, as the plasmonic components and form two plexciton hybrids with the J-aggregates of a cyanine dye. Single-particle spectroscopy is employed to study and compare the abilities of gold and silver in influencing plasmon-exciton interaction at the nanoscale. Despite much faster plasmon dephasing than its gold counterpart, the silver nanoprism exhibits greater Rabi splitting. We reveal that the smaller plasmon mode-volume despite having larger physical volume, superior local electric-field enhancement, and smaller Ohmic losses compared to gold, enables the silver nanoprism to defy the pronounced plasmon decoherence effects and to show stronger plasmon-exciton coupling. These findings suggest that silver nanostructures should be the unequivocal choice over gold when "strong coupling" is desired for any application.

Enhanced trapping properties of coupled plasmonic tweezers via plasmon-exciton interaction

Excited plasmonic nanoantennas enable the manipulation of photons coupled with quantum emitters or the trapping of particles as plasmonic tweezers, leveraging the strong evanescent gradient fields at the nanoscale. However, the ohmic loss of metals presents a significant challenge for the stable and high-precision manipulation of nanoparticles without causing damage. In this study, we investigated the enhanced trapping properties induced by plasmon-exciton interaction for coupled plasmonic tweezers. Through the coupling between plasmons and excitons, dynamic particle trapping is achievable under low excitation power conditions of 0.45 mW, with the trapping stiffness increasing by nearly 20 times. Furthermore, the trapping stiffness can be fine-tuned by modulating the quantity of excitons to regulate the coupling strength. Coupled plasmonic tweezers offer an effective strategy to mitigate the influence of ohmic loss on trapping performance, by manipulating particles with minimal laser power. These findings provide insights into enhancing trapping performance through plasmon-exciton coupling, with potential applications in biomedicine and quantum information science.

Rough Fe3O4/gold nanostructure enhanced fluorescence of quantum dots for Salmonella typhimurium detection in cabbage

Salmonella typhimurium (S. typhimurium) is a leading biological factor of foodborne diseases. A sensitive detection for S. typhimurium is crucial to controlling fresh vegetable-related outbreaks. Here, fluorescence-based S. typhimurium detection in fresh cabbage samples has been reported which capitalizes on the plasmon-exciton interaction between non-spherical gold nanoparticles-covered iron oxide nanoparticles (Fe3O4@Au NPs) and gold quantum dots (Au QDs). Firstly, new synthesis methods for non-spherical Fe3O4@Au NPs and Au QDs are reported. Then, a two-fold emission enhancement and shortening of the lifetime were achieved from urchin-like NPs compared with those of spherical NPs. This finding was utilized for the detection of S. typhimurium. Results revealed that the changes in fluorescence emission were linearly correlated with the concentration of S. typhimurium within the range of 100–1000 colony forming unit per milliliter (CFU mL−1) and the limit of detection was 32 CFU mL−1 in fresh cabbage.

Plasmon-exciton interactions in ZnO/AuNPs heterostructure film for high photoconductivity

This study investigatesplasmon-exciton interactions within ZnO/AuNPs heterostructure films. Elemental, structural, and morphological analyses validate the successful formation of these films. The observed shift in the plasmonic resonance band and absorption edge otowards the red region the red region is attributed to strong surface plasmon damping influenced by exciton interactions within ZnO. Irradiation with blue light induces plasmonic electrons, generation in the ZnO/AuNPs film, enhancing electrical conductivity through interaction with ZnO excitonic states. UV light irradiating generates the electron-hole pair in the ZnO film and interacts with the free electrons in AuNPs. The ZnO/AuNPs heterostructure films hold promise for applications such as high-performance UV-photodetectors, photoactive layers in solar cells, light-emitting diodes, and energy storage devices.

Multiphoton emission of single CdZnSe/ZnS quantum dots coupled with plasmonic Au nanoparticles.

The fluorescence blinking and low multiphoton emission of quantum dots (QDs) have limited their application in lasing, light-emitting diodes, and so on. Coupling of single QDs to plasmonic nanostructures is an effective approach to control the photon properties. Here plasmon-exciton systems including Au nanoparticles and CdZnSe/ZnS QDs were investigated at the single particle level. With the modulation of the local electromagnetic field, the fluorescence intensity of single QDs is increased, accompanied by a significant suppression in blinking behavior, and the lifetime is shortened from 15 ns to 2 ns. Moreover, the second-order photon intensity correlation at zero lag time g2(0) of coupled single QDs is larger than 0.5, indicating an increased probability of multiphoton emission. The enhancement factors of radiative and nonradiative decay rates of QDs coupled with Au nanoparticles are calculated. The sharply increased radiative decay rate can be comparable to the nonradiative Auger rate, leading to dominated multiple exciton radiative recombination with PL intensity enhancement, suppressed blinking, lifetime shortening, and multiphoton emission. The results of the exciton decay dynamics and emission properties of single QDs in this work are helpful in exploring the mechanism of plasmon-exciton interaction and optoelectronic application of single QDs.

Magnetic-assisted exciton-plasmon interactions modulated Bi2S3 nanorods@MoS2 nanosheets heterojunction: towards a split-type photoelectrochemical sensing of profenofos.

A split-type photoelectrochemical (PEC) sensor was designed for the detection of profenofos (PFF) depending on the magnetic-assisted exciton-plasmon interactions (EPI) between the semiconductor substrate and Au NPs. The core-shell Bi2S3 nanorods@MoS2 nanosheets (Bi2S3 NRs@MoS2 NSs) heterostructure nanomaterial with fascinating performance was synthesized and used as the photovoltaic conversion substrate and signal molecules absorption platform. The PEC sensor is operated by co-incubating with the released Au NPs-cDNA from the surface of magnetic beads, originating from the target-triggered DNA double-stranded structure opening event. Due to the strong EPI effects, the photocurrent of Bi2S3 NRs@MoS2 NSs decreased and varied with the PFF concentrations. The proposed PEC sensor exhibited outstanding analytical performances, including a wide linear range (1.0 pg mL-1~1.0 μg mL-1), low detection limitation (0.23 pg mL-1, at 3 σ/m), excellent specificity, high stability, and applicability. Overall, this work provides a new signal strategy for PEC biosensors and extends its application in environmental analysis.

Quantum Kinetics of the Electronic Energy Transformation in Molecular Nanostructures

A quantum theory of electronic energy transfer in a layered nanostructure with molecular J-aggregates of polymethine dyes was proposed. An expression for the exciton-plasmon bond energy depending on various parameters of the system was given. The rate of non-radiative Fὄrster resonance energy transfer (FRET) from surface plasmon polaritons (SPPs) of a metal substrate to Frenkel excitons of J-aggregates was determined and dispersion dependences for hybrid states were obtained. It was established that the energy transfer rate can reach values of 1012–1013 s–1, and the value of the Rabi splitting is up to 100 MeV. The kinetics of the process under strong exciton-plasmon interaction was investigated. The time dependence of the energy exchange between the system components had the form of damped oscillations depending on the relaxation parameters, the Rabi frequency, and the response to resonance. In addition, the exciton FRET between two parallel monolayers of J-aggregates of polymethine dyes separated by a nanometer-thick metal film was investigated. It was found that the presence of the metal layer increases the FRET rate. The spin evolution of a pair of two triplet (T) molecules localized in the nano-cell region under the over-barrier jumps regime in a magnetic field was studied. The influence of the parameters of the two-dimensional potential on the frequency of inter-dimensional motions and the population of triplets was considered. The spin dynamics of molecular T-T pairs in the magnetic field of a ferromagnetic globular nanoparticle under free surface diffusion of a spin-carrying molecule was investigated.

Plasmon-exciton coupling in Au nanosphere/carbocyanine J-aggregate hybrids assessed by magnetic circular dichroism (MCD) spectroscopy

In this study, we evaluate plasmon-exciton coupling in Au nanosphere/carbocyanine J-aggregate hybrids by magnetic circular dichroism (MCD) spectroscopy. The carbocyanine dye we used is JC-1, which adsorbs onto Au nanospheres to form J-aggregates. The hybrids exhibit a double-peaked extinction spectrum, and a shallow dip appears at the resonance position of the native J-aggregates, indicating the presence of plasmon-exciton interactions. MCD spectra of the hybrids show a derivative-like profile originated from the surface plasmon resonance of Au nanospheres accompanied by an additional distinct dip (or bump) caused by the exciton resonance of the adsorbed J-aggregates. Importantly, the MCD dip (or bump) position does not correspond to that of the observed new extinction peak, but agrees well with the extinction dip. Moreover, we find that the linewidths of the MCD dip (or bump) are narrow and comparable to that of the J-band of the dye aggregates. All the results suggest that the present hybrid systems are categorized in a weak-coupling regime. Hence we believe that MCD will be a useful spectroscopic method to effectively assess the plasmon-exciton interactions in various kinds of plasmonic-excitonic nanohybrid systems.

Subtle Structural Change in the Exciton-Forming Dye Drives Plasmon–Exciton Interaction Involving Gold Nanorods into the Strong Coupling Regime: Implications for Enhanced Optical Processes

Subtle Structural Change in the Exciton-Forming Dye Drives Plasmon–Exciton Interaction Involving Gold Nanorods into the Strong Coupling Regime: Implications for Enhanced Optical Processes

Formation of plasmon-exciton nanostructures based on quantum dots and metal nanoparticles with a nonlinear optical response

The establishment of the conditions for the formation of nanostructures with plasmon-exciton interaction based onquantum dots and plasmonic nanoparticles that provide unique nonlinear optical properties is an urgent task. The study demonstrates the formation of plasmon-exciton nanostructures based on hydrophilic colloidal Zn0.5Cd0.5S, Ag2S quantum dots and metal nanoparticles. Transmission electron microscopy and optical absorption and luminescence spectroscopy were used to substantiate the formation of plasmon-exciton hybrid nanostructures. The phase composition of the studied samples was determined by X-ray diffraction. The results obtained using ARLX’TRA diffractometer (Switzerland) indicated a cubic crystal structure (F43m) of synthesised Zn0.5Cd0.5S quantum dots and monoclinic (P21/C) crystal lattice of Ag2S. Transmission electron microscopy revealed that plasmonic nanoparticles are adsorption centres for quantum dots. The average sizes of the studied samples were determined: colloidal Ag2S quantum dots (2.6 nm), Zn0.5Cd0.5S(2.0 nm) and metal nanoparticles: silvernanospheres (10 nm) and gold nanorods (4x25 nm). The transformation of the extinction spectra of the light and the luminescence quenching of quantum dots have been established in mixtures of quantum dots and plasmonic nanoparticles. The nonlinear optical parameters of the studied samples were determined using the Z-scanning method at wavelengths of 355 and 532 nm in the field of nanosecond laser pulses. The conditions for the formation of hybrid nanostructures that provide an increase of the coefficient of nonlinear absorption of laser pulses (355 and 532 nm) up to 9 times with a duration of 10 ns due to the reverse saturable absorption occurring due to cascade two-quantum transitions in the intrinsic and local states of colloidal quantum dots and the suppression of nonlinear refraction, were determined. The observed changes were explained by the manifestation of the Purcell effect on the states of quantum dots in the presence of nanoresonators (gold nanorods and silver nanospheres). The results of these studies create new opportunities for the development of original systems for controlling the intensity of laser radiation, as well as quantum sensors of a new generation

Giant Out-of-Plane Exciton Emission Enhancement in Two-Dimensional Indium Selenide via a Plasmonic Nanocavity

Out-of-plane (OP) exciton-based emitters in two-dimensional semiconductor materials are attractive candidates for novel photonic applications, such as radially polarized sources, integrated photonic chips, and quantum communications. However, their low quantum efficiency resulting from forbidden transitions limits their practicality. In this work, we achieve a giant enhancement of up to 34000 for OP exciton emission in indium selenide (InSe) via a designed Ag nanocube-over-Au film plasmonic nanocavity. The large photoluminescence enhancement factor (PLEF) is attributed to the induced OP local electric field (Ez) within the nanocavity, which facilitates effective OP exciton-plasmon interaction and subsequent tremendous enhancement. Moreover, the nanoantenna effect resulting from the effective interaction improves the directivity of spontaneous radiation. Our results not only reveal an effective photoluminescence enhancement approach for OP excitons but also present an avenue for designing on-chip photonic devices with an OP dipole orientation.

Plasmon–Exciton Strong Coupling Effects of the Chiral Hybrid Nanostructures Based on the Plexcitonic Born–Kuhn Model

A deep understanding of the optical properties of the chiral plexcitonic systems not only adds a new dimension to the exploration of the strong plasmon–exciton interaction but also provides a new method to design chiroptical devices. We develop a plexcitonic Born–Kuhn model to explore the strong coupling dynamics of the chiral hybrid nanostructures made of corner-stacked nanorod dimers and molecules from the chiroptical perspective. As a consequence of strong interaction between plasmons and excitons, double normal mode splittings/Rabi splittings and an anti-crossing phenomenon appear in circular dichroism (CD) spectroscopy. The character of dual plexciton (symmetric and anti-symmetric plexciton) and associated chiroptical properties have been demonstrated. The interplay between mirror symmetry breaking and plasmon–plasmon/plasmon–exciton interaction leads to an optimal configuration with the maximal chiroptical response. Moreover, chirality (of incident light) selective excitation of plexcitonic modes has been achieved by structural design. Finally, we verify our theory experimentally by synthesizing chiral plasmonic nanodimers and coating these structures with J-aggregate dye molecules.

Hairpin DNAs conformational changes inducing opposite-polarity photoelectric signals recovery for simultaneous monitoring of dual microRNAs

Building flexible and reliable photoelectrochemical (PEC) sensors capable of measuring multiple miRNAs simultaneously still suffers from a challenge. In this protocol, a unique multiplexed PEC biosensor for miRNA-141 and miRNA-155 was developed by Fe3O4 @SiO2 @CdS-HP1-Ag2S NPs and CdTe QDs-HP2-Au NPs nanobioprobes polarity switching mode. HP1 and HP2 can be simultaneously unfolded by the two targets. The corresponding rigid DNA double-strand structure makes the distance between CdS shells and Ag2S NPs even greater, exposing more photoactive sites of CdS shells and thus the enhanced photoanode current. Similarly, the exciton-plasmon interaction (EPI) between the CdTe QDs and the Au NPs is disrupted, resulting in the photocurrent recovery of the CdTe QDs. Through external magnetic force, the one-step electrode modification of each above nanobioprobe was realized and the photocurrent polarity switching was also achieved. The linearity range of the designed multiplexed PEC biosensor was from 50 fM to 10 nM, and the detection limits reached 40.8 fM and 37.5 fM, respectively, without using any bioamplification technology. In addition, the manufactured PEC biosensor has significant advantages in compactness, short signal acquisition time, cost-effectiveness, as well as stability and replicability. The unique design provides a new perspective for monitoring multiple miRNAs simultaneously.

Strong coupling of multiple plasmon modes and excitons with excitation light controlled active tuning

Abstract While the strong coupling between cavity modes and quantum emitters has been investigated in various systems, multiple surface plasmon modes in single nanostructures strongly coupling with excitons are rarely explored. Here, we investigate the strong coupling between three surface plasmon modes in silver nanowires and excitons in monolayer WSe2 at room temperature. Four plasmon-exciton polariton (plexciton) states are observed in the scattering spectra. The photoluminescence (PL) spectra of the hybrid system show clear splitting due to strong coupling, and the energies of the emission corresponding to the two lower plexciton states agree with that of the scattering very well. In addition, we show that the plasmon-exciton interaction in this system can be efficiently tuned by controlling the excitation power. These results reveal the fundamental properties of strong coupling between multiple plasmon modes and excitons, deepen the understanding of the correlation between scattering and PL spectra of plasmon-exciton strong coupling systems, and open up a new way to actively control the coupling between plasmonic nanostructures and two-dimensional semiconductors.

How to Obtain the Correct Rabi Splitting in a Subwavelength Interacting System.

We unambiguously extract the individual decay channels of a coupled plasmon-exciton system by using correlated single-particle absorption and scattering measurements. A remarkable difference in the two channels is present─clear Rabi splitting in the plasmon channel but no Rabi splitting in the exciton channel. Discordance in the absorption and scattering spectra are mainly originated from the distinct contributions of plasmon and exciton channels in the absorption and scattering process. Our findings provide insights into plasmon-exciton interaction in an open cavity and can impact the design of plexcitonic devices for ultrafast nonlinear nanophotonics.

Observation of Multi-Directional Energy Transfer in a Hybrid Plasmonic-Excitonic Nanostructure.

Hybrid plasmonic devices involve a nanostructured metal supporting localized surface plasmons to amplify light-matter interaction, and a non-plasmonic material to functionalize charge excitations. Application-relevant epitaxial heterostructures, however, give rise to ballistic ultrafast dynamics that challenge the conventional semiclassical understanding of unidirectional nanometal-to-substrate energy transfer. Epitaxial Au nanoislands are studied on WSe2 with time- and angle-resolved photoemission spectroscopy and femtosecond electron diffraction: this combination of techniques resolves material, energy, and momentum of charge-carriers and phonons excited in the heterostructure. A strong non-linear plasmon-exciton interaction that transfers the energy of sub-bandgap photons very efficiently to the semiconductor is observed, leaving the metal cold until non-radiative exciton recombination heats the nanoparticles on hundreds of femtoseconds timescales. The results resolve a multi-directional energy exchange on timescales shorter than the electronic thermalization of the nanometal. Electron-phonon coupling and diffusive charge-transfer determine the subsequent energy flow. This complex dynamics opens perspectives for optoelectronic and photocatalytic applications, while providing a constraining experimental testbed for state-of-the-artmodelling.

Tuning nanoscale plasmon-exciton coupling via chemical interface damping.

Understanding the exact role of each plasmon decay channel in the plasmon-exciton interaction is essential for realizing the translational potential of nanoscale plexciton hybrids. Here, using single-particle spectroscopy, we demonstrate how a particular decay channel, chemical interface damping (CID), influences the nanoscale plasmon-exciton coupling. We investigate the interaction between cyanine dye J-aggregates and gold nanorods in the presence and absence of CID. The CID effect is introduced via surface modification of the nanorods with 4-nitrothiophenol. The relative contribution of CID is systematically tuned by varying the diameter of the nanorods, while maintaining the aspect ratio constant. We show that the incorporation of the CID channel, in addition to other plasmon decay channels, reduces the plasmon-exciton coupling strength. Nanorods' diameter-dependency measurements reveal that in the absence of CID contribution, the plasmon mode-volume factor gradually dominates over the plasmon decoherence effects as the diameter of the nanorods decreases, resulting in an increase in the plasmon-exciton coupling strength. However, the situation is entirely different when the CID channel is active: plasmon dephasing determines the plasmon-exciton coupling strength by outweighing the influence of even a very small plasmon mode-volume. Most importantly, our findings indicate that CID can be used to controllably tune the plasmon-exciton coupling strength for a given plexciton system by modifying the nanoparticle's surface with suitable adsorbates without the need for altering either the plasmonic or excitonic systems. Thus, judicious exploitation of CID can be tremendously beneficial in tailoring the optical characteristics of plexciton hybrid systems to suit any targeted application.

Plexcitonics: plasmon-exciton coupling for enhancing spectroscopy, optical chirality, and nonlinearity.

Plexcitonics is a rapidly developing interdisciplinary field that holds immense potential for the creation of innovative optical technologies and devices. This field focuses on investigating the interactions between plasmons and excitons in hybrid systems. In this review, we provide an overview of the fundamental principles of plasmonics and plexcitonics and discuss the latest advancements in plexcitonics. Specifically, we highlight the ability to manipulate plasmon-exciton interactions, the emerging field of tip-enhanced spectroscopy, and advancements in optical chirality and nonlinearity. These recent developments have spurred further research in the field of plexcitonics and offer inspiration for the design of advanced materials and devices with enhanced optical properties and functionalities.

Ultra-confined Propagating Exciton–Plasmon Polaritons Enabled by Cavity-Free Strong Coupling: Beating Plasmonic Trade-Offs

Hybrid coupling systems consisting of transition metal dichalcogenides (TMD) and plasmonic nanostructures have emerged as a promising platform to explore exciton–plasmon polaritons. However, the requisite cavity/resonator for strong coupling introduces extra complexities and challenges for waveguiding applications. Alternatively, plasmonic nano-waveguides can also be utilized to provide a non-resonant approach for strong coupling, while their utility is limited by the plasmonic confinement-loss and confinement-momentum trade-offs. Here, based on a cavity-free approach, we overcome these constraints by theoretically strong coupling of a monolayer TMD to a single metal nanowire, generating ultra-confined propagating exciton–plasmon polaritons (PEPPs) that beat the plasmonic trade-offs. By leveraging strong-coupling-induced reformations in energy distribution and combining favorable properties of surface plasmon polaritons (SPPs) and excitons, the generated PEPPs feature ultra-deep subwavelength confinement (down to 1-nm level with mode areas ~ 10–4 of λ2), long propagation length (up to ~ 60 µm), tunable dispersion with versatile mode characters (SPP- and exciton-like mode characters), and small momentum mismatch to free-space photons. With the capability to overcome the trade-offs of SPPs and the compatibility for waveguiding applications, our theoretical results suggest an attractive guided-wave platform to manipulate exciton–plasmon interactions at the ultra-deep subwavelength scale, opening new horizons for waveguiding nano-polaritonic components and devices.