Near Room Temperature Solvothermal Growth of Ferroelectric CsPbBr3 Nanoplatelets with Ultralow Dark Current.

CsPbBr3 exhibits outstanding optoelectronic properties and thermal stability, making it a coveted material for detectors, light-emitting diodes, and solar cells. Despite observations of ferroelectricity in CsPbBr3 quantum dots, synthesizing bulk ferroelectric CsPbBr3 crystals has remained elusive, hindering its potential in next-generation optoelectronic devices like optical switches and ferroelectric photovoltaics. Here, a breakthrough is reported: a novel solvothermal technique enabling the growth of ferroelectric CsPbBr3 nanoplatelets with lateral dimensions in the tens of micrometers. This represents a significant step toward achieving large-area ferroelectric CsPbBr3 crystals. Unlike traditional methods, this approach allows for growth and crystallization of CsPbBr3 in alcohol solutions by enhancing precursor solubility. This study confirms the ferroelectric nature of these nanoplatelets using second harmonic generation, electrical characterizations, and piezoresponse force microscopy. This work paves the way for utilizing ferroelectric CsPbBr3 in novel optoelectronic devices, significantly expanding the potential of this material and opening doors for further exploration in this exciting field.

Improving the optoelectronic properties of monolayer MoS2field effect transistor through dielectric engineering.

The reduced dielectric screening in atomically thin two-dimensional materials makes them very sensitive to the surrounding environment, which can be modulated to tune their optoelectronic properties. In this study, we significantly improved the optoelectronic properties of monolayer MoS2by varying the surrounding environment using different liquid dielectrics, each with a specific dielectric constant ranging from 1.89 to 18. Liquid mediums offer the possibility of environment tunability on the same device. For a back-gated field effect transistor, the field effect mobility exhibited more than two-order enhancement when exposed to a high dielectric constant medium. Further investigation into the effect of the dielectric environment on the optoelectronic properties demonstrated a variation in photoresponse relaxation time with the dielectric medium. The rise and decay times were observed to increase and decrease, respectively, with an increase in the dielectric constant of the medium. These results can be attributed to the dielectric screening provided by the surrounding medium, which strongly modifies the charged impurity scattering, the band gap, and defect levels of monolayer MoS2. These findings have important implications for the design of biological and chemical sensors, particularly those operating in a liquid environment. By leveraging the tunability of the dielectric medium, we can optimize the performance of such sensors and enhance their detection capabilities.

Single Molecule Surface Enhanced Raman Scattering in a Single Gold Nanoparticle-Driven Thermoplasmonic Tweezer.

Surface enhanced Raman scattering (SERS) is optically sensitive and chemically specific to detect single-molecule spectroscopic signatures. Facilitating this capability in optically trapped nanoparticles at low laser power remains a significant challenge. In this letter, we show single molecule SERS signatures in reversible assemblies of trapped plasmonic nanoparticles using a single laser excitation (633 nm). Importantly, this trap is facilitated by the thermoplasmonic field of a single gold nanoparticle dropcasted on a glass surface. We employ the bianalyte SERS technique to ascertain the single molecule statistical signatures and identify the critical parameters of the thermoplasmonic tweezer that provide this sensitivity. Furthermore, we show the utility of this low power (≈ 0.1 mW/µm2) tweezer platform to trap a single gold nanoparticle and transport assembly of nanoparticles. Given that our configuration is based on a dropcasted gold nanoparticle, we envisage its utility to create reconfigurable plasmonic metafluids in physiological and catalytic environments and to be potentially adapted as an in vivo plasmonic tweezer.

Optothermal pulling, trapping, and assembly of colloids using nanowire plasmons.

Optical excitation of colloids can be harnessed to realize soft matter systems that are out of equilibrium. In this paper, we present our experimental studies on the dynamics of silica colloids in the vicinity of a silver nanowire propagating surface plasmon polaritons (SPPs). Due to the optothermal interaction, the colloids are directionally pulled towards the excitation point of the nanowire. Having reached this point, they are spatio-temporally trapped around the excitation location. By increasing the concentration of colloids in the system, we observe multi-particle assembly around the nanowire. This process is thermophoretically driven and assisted by the SPPs. Furthermore, we find such an assembly to be sensitive to the excitation polarization at the input of the nanowire. Numerically-simulated temperature distribution around an illuminated nanowire corroborates sensitivity to the excitation polarization. Our study will find relevance in exploration of SPP-assisted optothermal pulling, trapping and assembly of colloids, and can serve as a test-bed of plasmon-driven active matter.

Beaming Elastic and SERS Emission from Bent-Plasmonic Nanowire on a Mirror Cavity.

We report on the experimental observation of beaming elastic and surface enhanced Raman scattering (SERS) emission from a bent-nanowire on a mirror (B-NWoM) cavity. The system was probed with polarization resolved Fourier plane and energy-momentum imaging to study the spectral and angular signature of the emission wavevectors. The out-coupled elastically scattered light from the kink occupies a narrow angular spread. We used a self-assembled monolayer of molecules with a well-defined molecular orientation to utilize the out-of-plane electric field in the cavity for enhancing Raman emission from the molecules and in achieving beaming SERS emission. Calculated directionality for elastic scattering and SERS emission was found to be 16.2 and 12.5 dB, respectively. The experimental data were corroborated with three-dimensional numerical finite element and finite difference time domain based numerical simulations. The results presented here may find relevance in understanding coupling of emitters with elongated plasmonic cavities and in designing on-chip optical antennas.

Modal and wavelength conversions in plasmonic nanowires.

We show that plasmonic nanowire-nanoparticle systems can perform nonlinear wavelength and modal conversions and potentially serve as building blocks for signal multiplexing and novel trafficking modalities. When a surface plasmon excited by a pulsed laser beam propagates in a nanowire, it generates a localized broadband nonlinear continuum at the nanowire surface as well as at active locations defined by sites where nanoparticles are absorbed (enhancement sites). The local response may couple to new sets of propagating modes enabling a complex routing of optical signals through modal and spectral conversions. Different aspects influencing the optical signal conversions are presented, including the parameters defining the local formation of the continuum and the subsequent modal routing in the nanowire.

Observation of photonic spin-momentum locking due to coupling of achiral metamaterials and quantum dots.

Chiral interfaces provide a new platform to execute quantum control of light-matter interactions. One phenomenon which has emerged from engineering such nanophotonic interfaces is spin-momentum locking akin to similar reports in electronic topological materials and phases. While there are reports of spin-momentum locking with combination of chiral emitters and/or chiral metamaterials with directional far field excitation it is not readily observable with both achiral emitters and metamaterials. Here, we report the observation of photonic spin-momentum locking in the form of directional and chiral emission from achiral quantum dots (QDs) evanescently coupled to achiral hyperbolic metamaterials (HMM). Efficient coupling between QDs and the metamaterial leads to emergence of these photonic topological modes which can be detected in the far field. We provide theoretical explanation for the emergence of spin-momentum locking through rigorous modeling based on photon Green's function where pseudo spin of light arises from coupling of QDs to evanescent modes of HMM.

Self-Assembled Helical Arrays for the Stabilization of the Triplet State.

Room-temperature phosphorescence of metal and heavy atom-free organic molecules has emerged as an area of great potential in recent years. A rational design played a critical role in controlling the molecular ordering to impart efficient intersystem crossing and stabilize the triplet state to achieve room-temperature ultralong phosphorescence. However, in most cases, the strategies to strengthen phosphorescence efficiency have resulted in a reduced lifetime, and the available nearly degenerate singlet-triplet energy levels impart a natural competition between delayed fluorescence and phosphorescence, with the former one having the advantage. Herein, an organic helical assembly supports the exhibition of an ultralong phosphorescence lifetime. In contrary to other molecules, 3,6-phenylmethanone functionalized 9-hexylcarbazole exhibits a remarkable improvement in phosphorescence lifetime (>4.1 s) and quantum yield (11 %) owing to an efficient molecular packing in the crystal state. A right-handed helical molecular array act as a trap and exhibits triplet exciton migration to support the exceptionally longer phosphorescence lifetime.

Large-scale optothermal assembly of colloids mediated by a gold microplate.

Light-activated colloidal assembly and swarming can act as model systems to explore non-equilibrium state of matter. In this context, creating new experimental platforms to facilitate and control two-dimensional assembly of colloidal crystals are of contemporary interest. In this paper, we present an experimental study of assembly of colloidal silica microparticles in the vicinity of a single-crystalline gold microplate evanescently excited by a 532 nm laser beam. The gold microplate acts as a source of heat and establishes a thermal gradient in the system. The created optothermal potential assembles colloids to form a two-dimensional poly-crystal, and we quantify the coordination number and hexagonal packing order of the assembly in such a driven system. Our experimental investigation shows that for a given particle size, the variation in assembly can be tuned as a function of excitation-polarization and surface to volume ratio of the gold microplates. Furthermore, we observe that the assembly is dependent on size of the particle and its material composition. Specifically, silica colloids assemble but polystyrene colloids do not, indicating an intricate behaviour of the forces under play. Our work highlights a promising direction in utilizing metallic microstructures that can be harnessed for optothermal colloidal crystal assembly and swarming studies. Our experimental system can be utilized to explore optically driven matter and photophoretic interactions in soft-matter including biological systems such as cells and micro organisms.

Directional second-harmonic generation controlled by sub-wavelength facets of an organic mesowire.

Directional harmonic generation is an important property characterizing the ability of nonlinear optical antennas to diffuse the signal in a well-defined region of space. Herein, we show how sub-wavelength facets of an organic molecular mesowire crystal can be utilized to systematically vary the directionality of second-harmonic generation (SHG) in the forward-scattering geometry. We demonstrate this capability on crystalline diamonoanthraquinone (DAAQ) mesowires with sub-wavelength facets. We observed that the radial angles of the SHG emission can be tuned over a range of 130 deg. This angular variation arises due to spatially distributed nonlinear dipoles in the focal volume of the excitation as well as the geometrical cross section and facet orientation of the mesowire. Numerical simulations of the near-field excitation profile corroborate the role of the mesowire geometry in localizing the electric field. In addition to directional SHG from the mesowire, we experimentally observe optical waveguiding of the nonlinear two-photon excited fluorescence (TPEF). Interestingly, we observed that for a given pump excitation, the TPEF signal is isotropic and delocalized, whereas the SHG emission is directional and localized at the location of excitation. All the observed effects have direct implications not only in active nonlinear optical antennas but also in nonlinear signal processing.

Spin-Hall effect in the scattering of structured light from plasmonic nanowire.

Spin-orbit interactions are subwavelength phenomena that can potentially lead to numerous device-related applications in nanophotonics. Here, we report the spin-Hall effect in the forward scattering of Hermite-Gaussian (HG) and Gaussian beams from a plasmonic nanowire. Asymmetric scattered radiation distribution was observed for circularly polarized beams. Asymmetry in the scattered radiation distribution changes the sign when the polarization handedness inverts. We found a significant enhancement in the spin-Hall effect for a HG beam compared to a Gaussian beam for constant input power. The difference between scattered powers perpendicular to the long axis of the plasmonic nanowire was used to quantify the enhancement. In addition, the nodal line of the HG beam acts as the marker for the spin-Hall shift. Numerical calculations corroborate experimental observations and suggest that the spin flow component of the Poynting vector associated with the circular polarization is responsible for the spin-Hall effect and its enhancement.

Doughnut-shaped emission from vertical organic nanowire coupled to thin plasmonic film.

Vertical nanowires facilitate an innovative mechanism to channel the optical field in the orthogonal direction and act as a nanoscale light source. Subwavelength, vertically oriented nanowire platforms, both of plasmonic and semiconducting variety, can facilitate interesting far-field emission profiles and potentially carry orbital angular momentum states. Motivated by these prospects, in this Letter, we show how a hybrid plasmonic-organic platform can be harnessed to engineer far-field radiation. The system that we have employed is an organic nanowire made of diaminoanthroquinone grown on a plasmonic gold film. We experimentally and numerically studied angular distribution of surface plasmon polariton mediated emission from a single, vertical organic nanowire by utilizing evanescent excitation and Fourier plane microscopy. Photoluminescence and elastic scattering from a single nanowire was analyzed individually in terms of inplane momentum states of the outcoupled photons. We found that the emission is doughnut-shaped in both photoluminescence and elastic scattering regimes. We anticipate that the discussed results can be relevant in designing efficient, polariton-mediated nanoscale photon sources that can carry orbital angular momentum states.

Differential Wavevector Distribution of Surface-Enhanced Raman Scattering and Fluorescence in a Film-Coupled Plasmonic Nanowire Cavity.

We report on the experimental observation of differential wavevector distribution of surface-enhanced Raman scattering (SERS) and fluorescence from dye molecules confined to a gap between plasmonic silver nanowire and a thin, gold mirror. The fluorescence was mainly confined to higher values of in-plane wavevectors, whereas SERS signal was uniformly distributed along all the wavevectors. The optical energy-momentum spectra from the distal end of the nanowire revealed strong polarization dependence of this differentiation. All these observations were corroborated by full-wave three-dimensional numerical simulations, which further revealed an interesting connection between out-coupled wavevectors and parameters such as hybridized modes in the gap-plasmon cavity, and orientation and location of molecular dipoles in the geometry. Our results reveal a new prospect of discriminating electronic and vibrational transitions in resonant dye molecules using a subwavelength gap plasmonic cavity in the continuous-wave excitation limit, and can be further harnessed to engineer molecular radiative relaxation processes in momentum space.

Exciton Emission Intensity Modulation of Monolayer MoS2 via Au Plasmon Coupling.

Modulation of photoluminescence of atomically thin transition metal dichalcogenide two-dimensional materials is critical for their integration in optoelectronic and photonic device applications. By coupling with different plasmonic array geometries, we have shown that the photoluminescence intensity can be enhanced and quenched in comparison with pristine monolayer MoS2. The enhanced exciton emission intensity can be further tuned by varying the angle of polarized incident excitation. Through controlled variation of the structural parameters of the plasmonic array in our experiment, we demonstrate modulation of the photoluminescence intensity from nearly fourfold quenching to approximately threefold enhancement. Our data indicates that the plasmonic resonance couples to optical fields at both, excitation and emission bands, and increases the spontaneous emission rate in a double spacing plasmonic array structure as compared with an equal spacing array structure. Furthermore our experimental results are supported by numerical as well as full electromagnetic wave simulations. This study can facilitate the incorporation of plasmon-enhanced transition metal dichalcogenide structures in photodetector, sensor and light emitter applications.

Plasmon-controlled excitonic emission from vertically-tapered organic nanowires.

Organic molecular nanophotonics has emerged as an important avenue to harness molecular aggregation and crystallization on various functional platforms to obtain nano-optical devices. To this end, there is growing interest to combine organic molecular nanostructures with plasmonic surfaces and interfaces. Motivated by this, herein we introduce a unique geometry: vertically-tapered organic nanowires grown on a plasmonic thin film. A polarization-sensitive plasmon-polariton on a gold thin-film was harnessed to control the exciton-polariton propagation and subsequent photoluminescence from an organic nanowire made of diaminoanthraquinone (DAAQ) molecules. We show that the exciton-polariton emission from individual DAAQ nanowires can be modulated up to a factor of 6 by varying the excitation polarization state of surface plasmons. Our observations were corroborated with full-wave three-dimensional finite-difference time-domain calculations performed on vertically-tapered nanowire geometry. Our work introduces a new optical platform to study coupling between propagating plasmons and propagating excitons, and may have implications in emerging fields such as hybrid-polariton based light emitting devices and vertical-cavity nano-optomechanics.

Large-scale dynamic assembly of metal nanostructures in plasmofluidic field.

We discuss two aspects of the plasmofluidic assembly of plasmonic nanostructures at the metal-fluid interface. First, we experimentally show how three and four spot evanescent-wave excitation can lead to unconventional assembly of plasmonic nanoparticles at the metal-fluid interface. We observed that the pattern of assembly was mainly governed by the plasmon interference pattern at the metal-fluid interface, and further led to interesting dynamic effects within the assembly. The interference patterns were corroborated by 3D finite-difference time-domain simulations. Secondly, we show how anisotropic geometry, such as Ag nanowires, can be assembled and aligned in unstructured and structured plasmofluidic fields. We found that by structuring the metal-film, Ag nanowires can be aligned at the metal-fluid interface with a single evanescent-wave excitation, thus highlighting the prospect of assembling plasmonic circuits in a fluid. An interesting aspect of our method is that we obtain the assembly at locations away from the excitation points, thus leading to remote assembly of nanostructures. The results discussed herein may have implications in realizing a platform for reconfigurable plasmonic metamaterials, and a test-bed to understand the effect of plasmon interference on assembly of nanostructures in fluids.

Plasmofluidic single-molecule surface-enhanced Raman scattering from dynamic assembly of plasmonic nanoparticles.

Single-molecule surface-enhanced Raman scattering (SM-SERS) is one of the vital applications of plasmonic nanoparticles. The SM-SERS sensitivity critically depends on plasmonic hot-spots created at the vicinity of such nanoparticles. In conventional fluid-phase SM-SERS experiments, plasmonic hot-spots are facilitated by chemical aggregation of nanoparticles. Such aggregation is usually irreversible, and hence, nanoparticles cannot be re-dispersed in the fluid for further use. Here, we show how to combine SM-SERS with plasmon polariton-assisted, reversible assembly of plasmonic nanoparticles at an unstructured metal-fluid interface. One of the unique features of our method is that we use a single evanescent-wave optical excitation for nanoparticle assembly, manipulation and SM-SERS measurements. Furthermore, by utilizing dual excitation of plasmons at metal-fluid interface, we create interacting assemblies of metal nanoparticles, which may be further harnessed in dynamic lithography of dispersed nanostructures. Our work will have implications in realizing optically addressable, plasmofluidic, single-molecule detection platforms.

Analysis of protein acetyltransferase structure-function relation by surface-enhanced raman scattering (SERS): a tool to screen and characterize small molecule modulators.

Among the different posttranslational modifications (PTMs) that significantly regulate the protein function, lysine acetylation has become the major focus, especially to understand the epigenetic role of the acetyltransferases, in cellular physiology. Furthermore, dysfunction of these acetyltransferases is well documented under pathophysiological conditions. Therefore, it is important to understand the dynamic structure-function relationship of acetyltransferases in a relatively less complicated and faster method, which could be efficiently exploited to design and synthesis of small molecule modulators (activators/inhibitors) of these enzymes for in vivo functional analysis and therapeutic purposes. We have developed surface-enhanced Raman scattering (SERS) method, for acetyltransferases towards this goal. By employing SERS, we have not only demonstrated the autoacetylation induced structural changes of p300 enzyme but also could use this technique to characterize and design potent, specific inhibitors as well as activators of the p300. In this chapter we shall describe the methods in detail which could be highly useful for other classes of HATs and PTM enzymes.