Near-field Optical Excitation Research Articles

Order recognition by Schubert polynomials generated by optical near-field statistics via nanometre-scale photochromism

Irregular spatial distribution of photon transmission through a photochromic crystal photoisomerized by a local optical near-field excitation was previously reported, which manifested complex branching processes via the interplay of material deformation and near-field photon transfer therein. Furthermore, by combining such naturally constructed complex photon transmission with a simple photon detection protocol, Schubert polynomials, the foundation of versatile permutation operations in mathematics, have been generated. In this study, we demonstrated an order recognition algorithm inspired by Schubert calculus using optical near-field statistics via nanometre-scale photochromism. More specifically, by utilizing Schubert polynomials generated via optical near-field patterns, we showed that the order of slot machines with initially unknown reward probability was successfully recognized. We emphasized that, unlike conventional algorithms, the proposed principle does not estimate the reward probabilities but exploits the inversion relations contained in the Schubert polynomials. To quantitatively evaluate the impact of Schubert polynomials generated from an optical near-field pattern, order recognition performances were compared with uniformly distributed and spatially strongly skewed probability distributions, where the optical near-field pattern outperformed the others. We found that the number of singularities contained in Schubert polynomials and that of the given problem or considered environment exhibited a clear correspondence, indicating that superior order recognition is attained when the singularity of the given situations is presupposed. This study paves way for physical computing through the interplay of complex natural processes and mathematical insights gained by Schubert calculus.

Generation of Schubert polynomial series via nanometre-scale photoisomerization in photochromic single crystal and double-probe optical near-field measurements

Generation of irregular time series based on physical processes is indispensable in computing and artificial intelligence. In this report, we propose and demonstrate the generation of Schubert polynomials, which are the foundation of versatile permutations in mathematics, via optical near-field processes introduced in a photochromic crystal of diarylethene combined with a simple photon detection protocol. Optical near-field excitation on the surface of a photochromic single crystal yields a chain of local photoisomerization, forming a complex pattern on the opposite side of the crystal. The incoming photon travels through the nanostructured photochromic crystal, and the exit position of the photon exhibits a versatile pattern. We emulated trains of photons based on the optical pattern experimentally observed through double-probe optical near-field microscopy, where the detection position was determined based on a simple protocol, leading to Schubert matrices corresponding to Schubert polynomials. The versatility and correlations of the generated Schubert matrices could be reconfigured in either a soft or hard manner by adjusting the photon detection sensitivity. This is the first study of Schubert polynomial generation via physical processes or nanophotonics, paving the way for future nano-scale intelligence devices and systems.

Self-assembly of fluorescent nanospheres on nanostructured azo molecular thin films and optical near-field excitation

We demonstrate self-assembly of fluorescent polymer nanospheres on a nanostructured azobenzene molecular thin film, and evaluate optical near-field excitation of aligned nanospheres. Nanogratings on azo thin film optically fabricated utilizing standing evanescent waves were used for an alignment layer of nanospheres. After dropping and air-drying a solution of nanospheres, the nanospheres were aligned along the grooves of nanograting. The variations in distribution of nanospheres were observed for a choice of grating shape and dispersing solvent of nanospheres. The size ordered alignment of nanospheres was found by using spin coating. To evaluate the fundamental processes of optical near-field excitation of the nanospheres, the emission light from the fluorescent nanospheres periodically aligned on azo grating was observed. The angular distribution of emission lights at a prism side of the angles larger than critical angle was confirmed, which correspond to the near-field optical excitation mediated by evanescent waves radiated near nanospheres.

Enhanced photo-sensitivity in a Si photodetector using a near-field assisted excitation

Silicon is an indispensable material in electric device technology. However, Si is an indirect bandgap material; therefore, its excitation efficiency, which requires phonon assistance, is low under propagating far-field light. To improve the excitation efficiency, herein we performed optical near-field excitation, which is confined in a nano-scale, where the interband transitions between different wave numbers are excited according to the uncertainty principle; thus, optical near-field can directly excite the carrier in the indirect bandgap. To evaluate the effect of optical near-field confined in a nano-scale, we fabricate the lateral Si p–n junction with Au nanoparticles as sources to generate the field confinement. We observed a 47.0% increase in the photo-sensitivity rate. In addition, by using the thin lateral p–n junction, which eliminates the far-field excitation, we confirmed a 42.3% increase in the photo-sensitivity rate.

Near-Field Enhanced Photochemistry of Single Molecules in a Scanning Tunneling Microscope Junction.

Optical near-field excitation of metallic nanostructures can be used to enhance photochemical reactions. The enhancement under visible light illumination is of particular interest because it can facilitate the use of sunlight to promote photocatalytic chemical and energy conversion. However, few studies have yet addressed optical near-field induced chemistry, in particular at the single-molecule level. In this Letter, we report the near-field enhanced tautomerization of porphycene on a Cu(111) surface in a scanning tunneling microscope (STM) junction. The light-induced tautomerization is mediated by photogenerated carriers in the Cu substrate. It is revealed that the reaction cross section is significantly enhanced in the presence of a Au tip compared to the far-field induced process. The strong enhancement occurs in the red and near-infrared spectral range for Au tips, whereas a W tip shows a much weaker enhancement, suggesting that excitation of the localized plasmon resonance contributes to the process. Additionally, using the precise tip-surface distance control of the STM, the near-field enhanced tautomerization is examined in and out of the tunneling regime. Our results suggest that the enhancement is attributed to the increased carrier generation rate via decay of the excited near-field in the STM junction. Additionally, optically excited tunneling electrons also contribute to the process in the tunneling regime.

Plasmonically Induced Transparency in Graphene Oxide Quantum Dots with Dressed Phonon States

The absorption in quantum dots (QDs) embedded within a semiconductor matrix can be manipulated by resonant optical excitation of phonons. The far-field interaction of the light leading to dressed phonon states within reduced graphene oxide quantum dots has been coherently modified by a near-field optical driving field at the nanoscale limit. The near-field optical excitation was introduced by resonant excitation of localized plasmons in metal nanoparticles coupled to QDs for ultrafast light manipulation. The coherent interaction of photons due to localized plasmon induced a change in the transient absorption of graphene oxide quantum dots conjugated to silver nanoparticles. Resonant pumping of plasmons and phonons with 400 nm pump photons induces a coherent change in excitonic absorption within QDs which results in phonon-assisted plasmon induced transparency at room temperature. This novel effect can be related to the appearance of the coherent effects such as forming dark states and coherent population ...

Nano-optical functionality based on local photoisomerization in photochromic single crystal

Towards the construction of functional devices and systems using optical near-field processes, we demonstrate the multivalent features in the path-branching phenomena in a photochromic single crystal observed in optical phase change between colorless (1o) and blue-colored (1c) phases that transmits in subwavelength scale over a macroscopic spatial range associated with local mechanical distortions induced. To observe the near-field optical processes of transmission path branching, we have developed a top-to-bottom double-probe scanning near-field optical microscope capable of nanometer-scale correlation measurements by two individually position-controlled probes that face each other sandwiching the photochromic material. We have experimentally confirmed that a local near-field optical excitation applied to one side of the photochromic crystal by a probe tip resulted in characteristic structures of subwavelength scale around 100 nm or less that are observed by the other probe tip located on the opposite side. The structures are different from those resulting from far-field excitations that are quantitively evaluated by autocorrelations. The results suggest that the mechanical distortion caused by the local phase change in the photochromic crystal suppresses the phase change of the neighboring molecules. This new type of optical-near-field-induced local photoisomerization has the potential to allow the construction of functional devices with multivalent properties for natural intelligence.

Nonlinear optical response induced by a second-harmonic electric-field component concomitant with optical near-field excitation

Electron dynamics excited by an optical near field (ONF) in a two-dimensional quantum dot model was investigated by solving a time-dependent Schr\"odinger equation. It was found that the ONF excitation of the electron caused two characteristic phenomena: a two-photon absorption and an induction of a magnetic dipole moment with a strong third-harmonic component. By analyzing the interaction dynamics of the ONF and the electron, we explained that the physical mechanism underlying these phenomena was the second-harmonic electric-field component concomitant with the near-field excitation originating from the nonuniformity of the ONF. Despite a $y$-polarized ONF source, the second-harmonic component of an $x$-polarized electric field was inherently generated. The effect of the second-harmonic electric-field component is not due to usual second-order nonlinear response but appears only when we explicitly consider the electron dynamics interacting with the ONF beyond the conventional optical response assuming the dipole approximation.

Near-field optical control of doughnut-shaped nanostructures

The application of a local near-field optical excitation with a control of the illumination time can be used to manage step-by-step the reshape of individual doughnut-shaped azopolymer nano-objects demonstrating their performances as a promising functional nano-objects. The possibility to provide a photoinduced reshaping opens a way to the fundamental study of size-dependent scaling laws of optical properties, photoinduced reshaping efficiency and possible nanoreactor or nanoresonator behaviors at nanometer scales. As an example the created nano-object is used to self-assembly polystyrene nanospheres in a supraball.

Demonstration of Controlling the Spatiotemporal Dynamics of Optical Near-Field Excitation Transfer in Y-Junction Structure Consisting of Randomly Distributed Quantum Dots

Solution searching devices that operate on the basis of controlling the spatiotemporal dynamics of excitation transfer via dressed photon interactions between quantum dots have been proposed. Long-range excitation transfer based on dressed photon interactions between randomly distributed quantum dots is considered to be effective in realizing such devices. Here, we successfully controlled the spatiotemporal dynamics of excitation transfer using a Y-junction structure consisting of randomly dispersed CdSe/ZnS core-shell quantum dots. This Y-junction structure has two “output ends” and one “tap end.” By exciting one output end with control light, we observed increased excitation transfer to the other output end via a state-filling effect. Conversely, we observed reduced excitation transfer to the output ends by irradiating the tap end with control light, due to excitation of defect levels in the tap end. These results show the possibility of controlling the optical excitation transfer dynamics between multiple quantum dots.

Optical near-field excitation at commercial scanning probe microscopy tips: a theoretical and experimental investigation

A systematic study of the influence of the excitation angle, the light polarization and the coating thickness of commercial SPM tips on the field enhancement in an apertureless scanning near-field optical microscope is presented. A new method to optimize the alignment of the electric field vector along the major tip axis by measuring the resonance frequency was developed. The simulations were performed with a MNPBEM toolbox based on the Boundary Element Method (BEM). The influence of the coating thickness was investigated for the first time. Coatings below 40 nm showed a drastic influence both on the resonance wavelength and the enhancement. A shift to higher angles of incidence for the maximum enhancement could be observed for greater tip radii.

Optical near-field excitation using liquid crystals on nanostructured photoreactive molecular thin films

Optical near-field excitations were investigated on the basis of molecular alignment control of liquid crystals (LCs) on an optically rewritable nanostructure of photoreactive molecular thin films. Twisted nematic (TN) cells of LC molecules were constructed utilizing ITO substrates with 260 nm gratings of an azobenzene molecular thin film, fabricated using standing evanescent waves. The polarization changes of light transmitted through the TN cells, which were due to the alignment changes of LC molecules locally rubbed by the azobenzene nanogratings, were observed. Furthermore, we demonstrated local plasmon excitation of Au nanowires deposited on the azobenzene nanogratings using oblique vacuum evaporation, a phenomenon that produced strong anti-optical absorption spectra. The modulation of the local plasmon resonance in metallic nanowires decorated with LC molecules was confirmed.

Excitation of gap modes in a metal particle-surface system for sub-30 nm plasmonic lithography

In this Letter, a near-field optical excitation of gap modes in a metal particle-surface system for patterning periodic nanostructure is proposed and numerically demonstrated using the finite-difference time-domain method. It is observed that high-density sub-30 nm periodic structures were achievable by employing an aluminium nanosphere-silver surface system. A 2D resist profile cross section using the modified cellular automata model, which was obtained through this proposed configuration, is also presented.

Excitation of nonradiative surface-plasmon-polariton beams in nanoparticle arrays

Gaussian beams of surface-plasmon polaritons in suitably designed two-dimensional square-lattice arrays of noncontacting noble-metal nanoparticles can be produced upon near-field optical excitation. Both positive- and negative-refraction effects are possible in the same structure and can be accessed simply by switching the polarization.

Field-Induced Photoluminescence Modulation of MEH−PPV under Near-Field Optical Excitation

Electric field-induced modulation of the near-field photoluminescence of thin films of the conjugated polymer MEH−PPV was measured. A voltage bias applied between the near-field probe and the substrate results in a highly spatially confined electric field. The near-field photoluminescence intensity decreases when the sample bias is positive with respect to the probe while the intensity increases when the sample bias is negative. The modulation of photoluminescence intensity provides a sensitive measure of changes in the local carrier density induced by the applied electric field. Experiments performed with a blocking layer indicate that carriers are generated by photoexcitation in the bulk of the polymer film. On the basis of the modulation results, we estimate the concentration of holes under optical and electrical excitation to be 1017 cm-3. The temporal response of the fluorescence upon the application of voltage is described in terms of the carrier mobility and electric field.

Analysis of individual (macro)molecules and proteins using near-field optics

Recent achievements in single molecule detection using near-field optical excitation are presented. By proper control of technology, distinct advantages of near-field optics are exploited: (i) the nanometric excitation/emission volume (104–105 nm3), which provides high spatial resolution, localization of a single molecule within a few nm, and reduced background; (ii) the sensitivity for single molecule orientation in all three dimensions; (iii) the high local brightness, allowing real-time single molecule detection down to μs resolution; (iv) the simultaneous colocalization with nanometric surface topography. Real-time quantum jumps between singlet and triplet state of an individual molecule are observed. Distributions for triplet state lifetime and crossing yield are determined. Both triplet state lifetime and crossing yield of a single molecule appear to vary in time, due to the local heterogeneity. Individual dendritic molecules containing a single fluorescent core are investigated. The dendritic assemblies are discriminated from free fluorescent cores on the basis of accurate simultaneous localization of both the fluorescent core and the topography of the surrounding dendritic shell. Intramolecular rotational motion of the fluorescent core is observed. Individual green fluorescent proteins are visualized, both in fluorescence and topography. Photoinduced conformational changes to a nonemissive form of the protein are observed, leading to long dark intervals of several seconds.

Optical near-field excitation at the semiconductor band edge: Field distributions, anisotropic transitions and quadrupole enhancement

The optical near-field response of a three dimensional subwavelength aperture-semiconductor system is analyzed within a finite difference time domain scheme for Maxwell’s and excitonic material equations. The analysis includes the field modification due to the high refractive index environment and the excitonic response to a near-field distribution. The resonant optical response is illustrated for anisotropic dipole transitions in quantum wells and the enhancement of the quadrupole transition in materials with dipole forbidden interband transitions.

Pressure-induced modulation of the confinement in self-organized quantum dots produced and detected by a near-field optical probe

Near-field optical probing, or nanoprobing, achieves spatial resolution that surpasses the diffraction limit of light and makes possible the luminescence imaging and spectroscopy of single quantum dots in dense arrays of dots. We use optical nanoprobing to study self-organized InGaAs quantum dots grown on (311)B oriented GaAs substrates. Here, we emphasize a new feature of nanoprobing: pressure-induced strain modulation near the surface. Operating in near-field optical excitation–collection mode, the probe makes contact with the surface and exerts direct pressure whose main effect is a compressive uniaxial strain under the probe. By adjusting the applied pressure, we modulate the local strain environment in and around a quantum dot, but still preserve the capability to capture its near-field luminescence. Nanoprobe pressure effects modify the confinement potential and radiative emission of single quantum dots, and the coupling strength between dots. This opens new possibilities for the study and control of the optical and electronic properties of single- and coupled-quantum dots.

Spatial Imaging of Singlet Energy Migration in Perylene Bis(phenethylimide) Thin Films

The migration length of singlet electronic energy excitations (excitons) in thin films of perylene bis(phenethylimide) (PPEI) has been measured by an imaging technique that incorporates near-field optical excitation and far-field fluorescence imaging. The observed energy migration lengths fall in the range of ≤50 to ∼500 nm depending on sample morphologies. Sample morphology was controlled by “solvent annealing” and characterized by fluorescence NSOM and scanning force microscopy. The potential role of sample morphology in singlet energy migration is discussed. Additionally, the results reported herein are compared with a previous determination of singlet energy migration in PPEI.

Near-field dynamics of excitonic wave packets in semiconductor quantum wells

A model study of the near-field optical excitation and spatiotemporal dynamics of excitons in semiconductor quantum wells is presented. It is shown that the spatially and temporally localized excitation results in the interference of radiative and nonradiative excitonic contributions, which form a propagating wave packet. The influence of excitation conditions, boundaries, and surface roughness on the wave packet are discussed. The experimentally measurable optical far-field emission of the wave packet is calculated.