Two-photon excitation provides a means of activating chemical or physical processes with high spatial resolution in three dimensions and has made possible the development of three-dimensional fluorescence imaging, optical data storage, and lithographic microfabrication. These applications take advantage of the fact that the two-photon absorption probability depends quadratically on intensity, so under tight-focusing conditions, the absorption is confined at the focus to a volume of order λ3 (where λ is the laser wavelength). Any subsequent process, such as fluorescence or a photoinduced chemical reaction, is also localized in this small volume. Although three-dimensional data storage and microfabrication have been illustrated using two-photon-initiated polymerization of resins incorporating conventional ultraviolet-absorbing initiators, such photopolymer systems exhibit low photosensitivity as the initiators have small two-photon absorption cross-sections (δ). Consequently, this approach requires high laser power, and its widespread use remains impractical. Here we report on a class of π;-conjugated compounds that exhibit large δ (as high as 1, 250 × 10−50 cm4 s per photon) and enhanced two-photon sensitivity relative to ultraviolet initiators. Two-photon excitable resins based on these new initiators have been developed and used to demonstrate a scheme for three-dimensional data storage which permits fluorescent and refractive read-out, and the fabrication of three-dimensional micro-optical and micromechanical structures, including photonic-bandgap-type structures.

Two-photon polymerization initiators for three-dimensional optical data storage and microfabrication

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Graphene quantum dots (GQDs) that are flat 0D nanomaterials have attracted increasing interest because of their exceptional chemicophysical properties and novel applications in energy conversion and storage, electro/photo/chemical catalysis, flexible devices, sensing, display, imaging, and theranostics. The significant advances in the recent years are summarized with comparative and balanced discussion. The differences between GQDs and other nanomaterials, including their nanocarbon cousins, are emphasized, and the unique advantages of GQDs for specific applications are highlighted. The current challenges and outlook of this growing field are also discussed.

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Recent Advances on Graphene Quantum Dots: From Chemistry and Physics to Applications

Scattering of electromagnetic waves by subwavelength objects is accompanied by the excitation of electric and magnetic Mie resonances that may modify substantially the scattering intensity and radiation pattern. Scattered fields can be decomposed into electric and magnetic multipoles, and the magnetic multipoles define magnetic response of structured materials underpinning the new field of all-dielectric resonant meta-optics. Here we review the recent developments in meta-optics and nanophotonics and demonstrate that the Mie resonances can play a crucial role offering novel ways for the enhancement of many optical effects near magnetic and electric multipolar resonances, as well as driving a variety of interference phenomena which govern recently discovered novel effects in nanophotonics. We further discuss the frontiers of all-dielectric meta-optics for flexible and advanced control of light with full phase and amplitude engineering, including nonlinear nanophotonics, anapole nanolasers, quantum optics, ...

Functional Meta-Optics and Nanophotonics Govern by Mie Resonances

The emergence of carbon dots (CDs) has opened up an exciting new field in the science and technology of carbon nanomaterials and has attracted increasing interest in recent years. Due to their diverse physicochemical properties and favourable attributes, such as quantum confinement effects and abundant surface defects, CDs and their derived hybrids have shown exciting and indispensable prospects in the energy conversion and storage fields. Considering the latest developments, in this review, we comprehensively summarize the classification and structure of CDs. Three strategies for structural engineering of CDs are presented and analyzed, in terms of the tuning of size and crystallinity, and the methodologies for surface modification and heteroatom doping, with a focus on the relationship among the synthesis methods, structure and properties of the concerned CDs. More importantly, the recent advances in energy-oriented applications of CDs, including photo- and electro-catalysis, light-emitting diodes, photovoltaic cells, lithium/sodium ion batteries and supercapacitors, will be systematically highlighted. Finally, we discuss and outline the remaining major challenges and opportunities for CDs in the future.

Design and fabrication of carbon dots for energy conversion and storage

Nitrogen-functionalized graphene quantum dots (NGQDs) with tailorable optical properties are prepared by a versatile technique, which allows the highest occupied molecular orbital/lowest unoccupied molecular orbital energy levels and energy gaps to be continuously varied. The integration of NGQD layers into the structures significantly improves the performance of optoelectronic devices.

Molecularly Designed, Nitrogen-Functionalized Graphene Quantum Dots for Optoelectronic Devices.

Due to the presence of strong magnetic resonances, high refractive index dielectric nanoantennnas have shown the ability to expand the methods available for controlling electromagnetic waves in the subwavelength region. In this work, we experimentally demonstrate that an asymmetric dielectric dimer made of silicon can lead to highly directional scattering depending on the excitation wavelength, due to the interference of the excited magnetic resonances. A back focal plane imaging system combined with a prism coupling technique enables us to explore the scattering profile parallel to the substrate. The directivity of scattering along the substrate is high enough to produce selective guiding of light along the substrate. These results showing tunable control of directional scattering will encourage the realization of novel optical applications, such as optical nanocircuitry.

Experimental Demonstration of Tunable Directional Scattering of Visible Light from All-Dielectric Asymmetric Dimers

An ultrahigh-aspect-ratio, 0.06-µ m-diameter, 2-µ m-deep contact hole pattern of SiO2 was successfully fabricated using a poly-Si mask and a magnetically enhanced reactive-ion-etching (RIE) system in a mixture of CHF3/CO gas. In this dimensional area, processing for vertical profiles is extremely difficult, and problems in the form of bowing at the sidewalls of the holes can occur. Furthermore, it is possible that ion flux and energy are significantly reduced when ions pass through the poly-Si mask, rather than through the SiO2 hole. The bowing is associated with bending of the incident ion trajectories, where the first stage of the trajectory change occurs at the mask, and subsequent multiple scattering of ions at the sidewall of the hole can occur. Other factors include sidewall protection by redeposited Si sputtered from the poly-Si mask and/or the deposited fluorocarbon polymers, and the effects of ion energy and flux bombarding these deposited materials.

https://iopscience.iop.org/article/10.1143/JJAP.36.2470/pdf

Characteristics of Very High-Aspect-Ratio Contact Hole Etching

Dielectric guided mode resonant gratings exhibit a sharp spectral and angular response of high reflectivity for propagation wave, and strong evanescent waves are excited. We show that in such a resonant grating positioned above the silicon carbide (SiC) plate, incident light is absorbed in the SiC plate via the evanescent wave coupling when the lateral wavenumber of a guided mode of the grating coincides with that of surface phonon polaritons on the SiC plate. This coupling scheme using the thermally transparent grating enables a sharp spectral and angular emission in the infrared region with capabilities of emissivity modulation and spatially asymmetric emissivity. Thermally transparent subwavelength structures electromagnetically coupled to polar material thermal bodies are crucial in enabling components for thermal emission control.

Thermal emission control by evanescent wave coupling between guided mode of resonant grating and surface phonon polariton on silicon carbide plate

We investigate titanium nitride (TiN) thin film coatings on silicon for CMOS-compatible sub-bandgap charge separation upon incident illumination, which is a key feature in the vast field of on-chip photodetection and related integrated photonic devices. Titanium nitride of tunable oxidation distributions serves as an adjustable broadband light absorber with high mechanical robustness and strong chemical resistivity. Backside-illuminated TiN on p-type Si (pSi) constitutes a self-powered and refractory alternative for photodetection, providing a photoresponsivity of about ∼1 mA/W at 1250 nm and zero bias while outperforming conventional metal coatings such as gold (Au). Our study discloses that the enhanced photoresponse of TiN/pSi in the near-infrared spectral range is directly linked to trap states in an ultrathin TiO2–x interfacial interlayer that forms between TiN and Si. We show that a pSi substrate in conjunction with a few nanometer thick amorphous TiO2–x film can serve as a platform for photocurrent...

Takayuki Matsui

Papers

Molecularly Designed, Nitrogen-Functionalized Graphene Quantum Dots for Optoelectronic Devices.

Experimental Demonstration of Tunable Directional Scattering of Visible Light from All-Dielectric Asymmetric Dimers

Characteristics of Very High-Aspect-Ratio Contact Hole Etching

Thermal emission control by evanescent wave coupling between guided mode of resonant grating and surface phonon polariton on silicon carbide plate

TiO2–x-Enhanced IR Hot Carrier Based Photodetection in Metal Thin Film–Si Junctions