Sensitivity improvement of a single-NV diamond magnetometer using a chiral waveguide.

A single nitrogen-vacancy (NV) center in diamond is utilized to perform nanoscale magnetic measurements. However, the low contrast and poor collection efficiency of spin-dependent emitted photons limited the instrument sensitivity to approximately several nT/Hz. Here, we design a diamond magnetometer based on a chiral waveguide. We numerically demonstrate that the proposed device achieves a sensitivity of 170 pT/Hz owing to near-unity contrast and efficient photon collection. We also confirm that the device sensitivity is robust against position misalignment and dipole misorientation of an NV center. The proposed approach will enable the construction of a highly-sensitive magnetometer with high spatial resolution.

Variations in the Photoexcitation Mechanism of an Adsorbed Molecule on a Gold Nanocluster Governed by Interfacial Contact.

We performed first-principles calculations on the optical response of a Au147-azobenzene complex to elucidate the role of the interfacial contact between Au147 and azobenzene. Our calculations of photoexcited electron dynamics for different configurations of azobenzene adsorbed on the Au147 nanocluster revealed that the optical properties of the azobenzene moiety change markedly by the interfacial contact, even if the electronic structure in the ground state is almost unchanged. The optical absorption measured for isolated azobenzene weakens when the Au147-azobenzene interaction increases, while the absorption measured using the light field along the Au147-azobenzene alignment strengthens. The electronic excitation analysis showed that the mechanism of the charge-transfer excitation between Au147 and azobenzene changes remarkably depending on the strength of the interfacial interaction. We revealed that the optical property can be governed by the atomic-scale difference in the adsorption structure of azobenzene on a Au147 nanocluster. This study affords novel insights that could enable the photoexcitation mechanism to be controlled by designing the interface between a metal nanoparticle and a molecule.

Synthesis of silver nanostructure on gold nanoparticle using near field assisted second harmonic generation.

By using gold (Au) nanoparticles (NPs) as an optical near-field source under far-field illumination in combination with a silver (Ag) ion solution containing a photoinitiator, we coated Ag on Au NPs using a near-field (NF)-assisted process. We evaluated the change in the size of the NPs using transmission electron microscopy. Evaluation of the synthesized Ag volume over illumination power confirmed the squared power dependence of the NP volume with illumination using 808 nm light, i.e., a wavelength longer than the absorption edge wavelength of the photoinitiator molecules. The rate of volume increase was much lower than the plasmonic field enhancement effect. Therefore, the squared power dependency of the volume increase using a wavelength longer than the absorption edge wavelength originated from NF-assisted second-harmonic generation and the resulting excitation.

Magnetometer with nitrogen-vacancy center in a bulk diamond for detecting magnetic nanoparticles in biomedical applications.

We developed a novel magnetometer that employs negatively charged nitrogen-vacancy (NV-) centers in diamond, to detect the magnetic field generated by magnetic nanoparticles (MNPs) for biomedical applications. The compact probe system is integrated into a fiber-optics platform allowing for a compact design. To detect signals from the MNPs effectively, we demonstrated, for the first time, the application of an alternating current (AC) magnetic field generated by the excitation coil of several hundred microteslas for the magnetization of MNPs in diamond quantum sensing. In the lock-in detection system, the minimum detectable AC magnetic field (at a frequency of 1.025 kHz) was approximately 57.6 nT for one second measurement time. We were able to detect the micromolar concentration of MNPs at distances of a few millimeters. These results indicate that the magnetometer with the NV- centers can detect the tiny amounts of MNPs, thereby offering potential for future biomedical applications.

Visible light-induced thymine dimerisation based on large localised field gradient by non-uniform optical near-field.

The localised excitations of several molecular reactions utilising optical irradiation have been studied in the field of molecular physics. In particular, deoxyribonucleic acid (DNA) strands organise the genetic information of all living matter. Therefore, artificial methods for freely controlling reactions using only light irradiation are highly desirable for reactions of these strands; this in regard with artificial protein synthesis, regional genetic curing, and stochastic analysis of several genetic expressions. Generally, DNA strands have strong absorption features in the deep ultra-violet (DUV) region, which are related to the degradation and reconstruction of the strand bonding structures. However, irradiation by DUV light unavoidably induces unintended molecular reactions which can damage and break the DNA strands. In this paper, we report a photo-induced molecular reaction initiated by the irradiation of DNA strands with visible light. We utilised photo-dissociation from the vibrational levels induced by non-uniform optical near-fields surrounding nanometric Au particles to which DNA strands were attached. The results were experimentally observed by a reduction in the DUV absorbance of the DNA strands during irradiation. There was a much higher yield of molecular reactions than expected due to the absorbance of visible light, and no defects were caused in the DNA strands.

Realization of red shift of absorption spectra using optical near-field effect.

In many applications such as CO2 reduction and water splitting, high-energy photons in the ultraviolet region are required to complete the chemical reactions. However, to realize sustainable development, the photon energies utilized must be lower than the absorption edge of the materials including the metal complex for CO2 reduction, the electrodes for water splitting, because of the huge amount of lower energy than the visible region received from the sun. In the previous works, we had demonstrated that optical near-fields (ONFs) could realize chemical reactions, by utilizing photon energies much lower than the absorption edge because of the spatial non-uniformity of the electric field. In this paper, we demonstrate that an ONF can realize the red shift of the absorption spectra of the metal-complex material for photocatalytic reduction. By attaching the metal complex to ZnO nano-crystalline aggregates with nano-scale protrusions, the absorption spectra by using diffuse reflection of the metal complex can be shifted to a longer wavelength by 10.6 nm. The results of computational studies based on a first-principles computational program including the ONF effect provide proof of the increase in the absorption of the metal complex at lower photon energies. Since the near-field assisted field increase improves the carrier excitation in the metal-complex materials, this effect may be universal and it could applicable to CO2 reduction using the other metal-complex materials, as well as to the other photo excitation process including water splitting.

Angstrom-scale flatness using selective nanoscale etching.

The realization of flat surfaces on the angstrom scale is required in advanced devices to avoid loss due to carrier (electron and/or photon) scattering. In this work, we have developed a new surface flattening method that involves near-field etching, where optical near-fields (ONFs) act to dissociate the molecules. ONFs selectively generated at the apex of protrusions on the surface selectively etch the protrusions. To confirm the selective etching of the nanoscale structure, we compared near-field etching using both gas molecules and ions in liquid phase. Using two-dimensional Fourier analysis, we found that near-field etching is an effective way to etch on the scale of less than 10 nm for both wet and dry etching techniques. In addition, near-field dry etching may be effective for the selective etching of nanoscale structures with large mean free path values.

Surface improvement of organic photoresists using a near-field-dependent etching method.

Surface flattening techniques are extremely important for the development of future electrical and/or optical devices because carrier-scattering losses due to surface roughness severely limit the performance of nanoscale devices. To address the problem, we have developed a near-field etching technique that provides selective etching of surface protrusions, resulting in an atomically flat surface. To achieve finer control, we examine the importance of the wavelength of the near-field etching laser. Using light sources at wavelengths of 325 and 405 nm, which are beyond the absorption edge of the photoresist (310 nm), we compare the resulting cross-sectional etching volumes. The volumes were larger when 325 nm light was employed, i.e., closer to the absorption edge. Although 405 nm light did not cause structural change in the photoresist, a higher reduction of the surface roughness was observed as compared to the 325 nm light. These results indicate that even wavelengths above 325 nm can cause surface roughness improvements without notably changing the structure of the photoresist.

Optically controlled magnetic-field etching on the nano-scale.

Electric and magnetic fields play an important role in both chemical and physical reactions. However, since the coupling efficiency between magnetic fields and electrons is low in comparison with that between electric fields and electrons in the visible wavelength region, the magnetic field is negligible in photo-induced reactions. Here, we performed photo-etching of ZrO2 nano-stripe structures, and identified an etching-property polarisation dependence. Specifically, the etching rate and etched profiles depend on the structure width. To evaluate this polarisation-dependent etching, we performed numerical calculations using a finite-difference time-domain method. Remarkably, the numerical results revealed that the polarisation-dependent etching properties were determined by the magnetic field distributions, rather than the electric field distributions. As nano-scale structures induce a localised magnetic field, the discovery of this etching dependence on the magnetic field is expected to introduce a new perspective on advanced nano-scale structure fabrication.

Controlling the optical and structural properties of ZnS-AgInS2 nanocrystals by using a photo-induced process.

ZnS-AgInS2 (ZAIS) solid-solution nanocrystals are promising materials for nanophotonic devices in the visible region because of their low toxicity and good emission properties. We developed a technique of photo-induced synthesis to control the size and composition of the ZAIS nanocrystals. This method successfully decreased the defect levels, as well as the size and size variation of ZAIS nanocrystals by controlling the excitation wavelength during synthesis. Detailed analysis of transmission electron microscope images confirmed that the photo-induced synthesis yielded a high crystallinity of the ZAIS nanocrystals with small variations in size and content.

Observation and analysis of structural changes in fused silica by continuous irradiation with femtosecond laser light having an energy density below the laser-induced damage threshold.

The laser-induced damage threshold (LIDT) is widely used as an index for evaluating an optical component's resistance to laser light. However, a degradation in the performance of an optical component is also caused by continuous irradiation with laser light having an energy density below the LIDT. Therefore, here we focused on the degradation in performance of an optical component caused by continuous irradiation with femtosecond laser light having a low energy density, i.e., laser-induced degradation. We performed an in situ observation and analysis of an increase in scattering light intensity in fused silica substrates. In experiments conducted using a pulsed laser with a wavelength of 800 nm, a pulse width of 160 fs and pulse repetition rate of 1 kHz, we found that the scattered light intensity increased starting from a specific accumulated fluence, namely, that the laser-induced degradation had a threshold. We evaluated the threshold fluence F t as 6.27 J/cm(2) and 9.21 J/cm(2) for the fused silica substrates with surface roughnesses of 0.20 nm and 0.13 nm in R a value, respectively, showing that the threshold decreased as the surface roughness increased. In addition, we found that the reflected light spectrum changed as degradation proceeded. We analyzed the details of the degradation by measuring instantaneous reflectance changes with a pump-probe method; we observed an increase in the generation probability of photogenerated carriers in a degraded silica substrate and a damaged silica substrate and observed a Raman signal originating from a specific molecular structure of silica. From these findings, we concluded that compositional changes in the molecular structure occurred during degradation due to femtosecond laser irradiation having an energy density below the LIDT.

Dressed-photon-phonon (DPP)-assisted visible- and infrared-light water splitting.

A dressed-phonon-phonon (DPP) assisted photocatalyst reaction was carried out to increase the visible light responsibility, where the photon energy of the radiation, which ranged from visible to infrared light is less than band gap energy of the photocatalyst (ZnO, 3.3 eV). The dependence of the photocurrent on excitation power indicated that two-step excitation occurred in DPP-assisted process. A cathodoluminescence measurement also supported the conclusion that the visible- and infrared-light excitation originated from DPP excitation, not from defect states in the ZnO nanorod photocatalyst.

Challenges in realizing ultraflat materials surfaces.

Ultraflat surface substrates are required to achieve an optimal performance of future optical, electronic, or optoelectronic devices for various applications, because such surfaces reduce the scattering loss of photons, electrons, or both at the surfaces and interfaces. In this paper, we review recent progress toward the realization of ultraflat materials surfaces. First, we review the development of surface-flattening techniques. Second, we briefly review the dressed photon-phonon (DPP), a nanometric quasiparticle that describes the coupled state of a photon, an electron, and a multimode-coherent phonon. Then, we review several recent developments based on DPP-photochemical etching and desorption processes, which have resulted in angstrom-scale flat surfaces. To confirm that the superior flatness of these surfaces that originated from the DPP process, we also review a simplified mathematical model that describes the scale-dependent effects of optical near-fields. Finally, we present the future outlook for these technologies.

CO2 phonon mode renormalization using phonon-assisted energy up-conversion.

Molecular dissociation under incident light whose energy is lower than the bond dissociation energy has been achieved through multi step excitation using a coupled state of a photon, electron, and multimode-coherent phonon as known as the dressed photon phonon (DPP). Here, we have investigated the effects of the DPP on CO2, a very stable molecule with high absorption and dissociation energies, by introducing ZnO nanorods to generate the DPP. Then, the changes in CO2 absorption bands were evaluated using light with a wavelength longer than the absorption wavelength, which confirmed the DPP-assisted energy up-conversion. To evaluate the specific CO2 modes related to this process, we measured the CO2 vibration-rotation spectra in the near-infrared region. Detailed analysis of the 3ν3 vibrational band when a DPP source is present showed that DPP causes a significant increase in the intensity of certain absorption bands, especially those that require higher energies to activate.

Demonstration of modulatable optical near-field interactions between dispersed resonant quantum dots.

We experimentally demonstrated the basic concept of modulatable optical near-field interactions by utilizing energy transfer between closely positioned resonant CdSe/ZnS quantum dot (QD) pairs dispersed on a flexible substrate. Modulation by physical flexion of the substrate changes the distances between quantum dots to control the magnitude of the coupling strength. The modulation capability was qualitatively confirmed as a change of the emission spectrum. We defined two kinds of modulatability for quantitative evaluation of the capability, and an evident difference was revealed between resonant and non-resonant QDs.

Site-selective deposition of gold nanoparticles using non-adiabatic reaction induced by optical near-fields.

In this paper, we report on site-selective deposition of metal nanoparticles using a non-adiabatic photochemical reaction. Photoreduction of gold was performed in a silica gel membrane containing tetrachloroaurate (AuCl(4)( - )) ions, using ZnO nanorods as the sources of optical near-field light, resulting in deposition of gold nanoparticles with an average diameter of 17.7 nm. The distribution of distances between the gold nanoparticles and nanorod traces revealed that the gold nanoparticles were deposited adjacent to the ZnO nanorods, reflecting the attenuation of the optical near-fields in the vicinity of the ZnO nanorods. We found that the emission wavelength from the ZnO nanorods was longer than the absorption edge wavelength of the tetrachloroaurate. Additionally, from the intensity distribution obtained by a finite-difference time-domain method, the gold deposited around the ZnO nanorods was found to be due to a non-adiabatic photochemical reaction.

Nanophotonic code embedded in embossed hologram for hierarchical information retrieval.

A hierarchical hologram works in both optical far-fields and near-fields, the former being associated with conventional holographic images, and the latter being associated with the optical intensity distribution based on a nanometric structure that is accessible only via optical near-fields. We propose embedding a nanophotonic code, which is retrievable via optical near-field interactions involving nanometric structures, within an embossed hologram. Due to the one-dimensional grid structure of the hologram, evident polarization dependence appears in retrieving the code. Here we describe the basic concepts, numerical simulations, and experimental results in fabrication of a prototype hierarchical hologram and describe its optical characterization.

Quadrupole-dipole transform based on optical near-field interactions in engineered nanostructures.

Nanophotonics has the potential to provide novel devices and systems with unique functions based on optical near-field interactions. Here we experimentally demonstrate, for the first time, what we call a quadrupole-dipole transform achieved by optical near-field interactions between engineered nanostructures. We describe its principles, the nanostructure design, fabrication of one- and two-layer gold nanostructures, an experimental demonstration, and optical characterization and analysis.

Hierarchical hologram based on optical near- and far-field responses.

A "hierarchical hologram" and experiments using it are described. This type of hologram works both in optical far-fields and near-fields.We exploit the physical difference between the propagating light and optical near-field, where the former is associated with conventional holographic patterns obtained in optical far-fields, whereas the latter is associated with nanometric structure accessible only via optical near-fields. We also describe an experimental demonstration of the basic principles with our prototype optical elements.

Self-assembly of size- and position-controlled ultralong nanodot chains using near-field optical desorption.

We report the self-assembly of a size- and position-controlled ultralong nanodot chain using a novel effect of near-field optical desorption. A sub-100-nm dot chain with a deviation of 5 nm forms at a size based on plasmon resonance, depending on the photon energy; the resulting structure forms a high-transmission-efficiency nanoscale waveguide. Using this method with simple lithographically patterned substrates allows one to increase the throughput of the production of nanoscale structures dramatically at all scales.