Publication database

Localized surface plasmon resonance (LSPR)-induced hot-carrier transfer is a key mechanism for achieving artificial photosynthesis using the whole solar spectrum, even including the infrared (IR) region. In contrast to the explosive development of photocatalysts based on the plasmon-induced hot electron transfer, the hole transfer system is still quite immature regardless of its importance, because the mechanism of plasmon-induced hole transfer has remained unclear. Herein, we elucidate LSPR-induced hot hole transfer in CdS/CuS heterostructured nanocrystals (HNCs) using time-resolved IR (TR-IR) spectroscopy. TR-IR spectroscopy enables the direct observation of carrier in a LSPR-excited CdS/CuS HNC. The spectroscopic results provide insight into the novel hole transfer mechanism, named plasmon-induced transit carrier transfer (PITCT), with high quantum yields (19%) and long-lived charge separations (9.2 μs). As an ultrafast charge recombination is a major drawback of all plasmonic energy conversion systems, we anticipate that PITCT will break the limit of conventional plasmon-induced energy conversion.

New types of air filter technologies are being called because air pollution by particulate matters (PMs) and volatile organic compounds has raised serious concerns for public health. Conventional air filters have limited application and poor degradability and they become non-disposable wastes after use. Here, we report a highly efficient, eco-friendly, translucent, and multifunctional air purification filter that is highly effective for reducing air pollution, protecting the environment, and detecting hazardous chemical vapors encountered in everyday life. Uniform silk protein nanofibers were directly generated on a window screen by an electrospinning process. Optical properties (translucence and scattering) of the silk nanofibrous air filters (SNAFs) are advantageous for achieving viewability and controlling the room temperature. Air filtration efficiencies of the fabricated SNAFs could reach up to 90% and 97% for PMs with sizes under 2.5 and 10 μm, respectively, exceeding the performances of commercial semi-high-efficiency particulate air (semi-HEPA) filters. After use, the SNAFs could be naturally degraded. Furthermore, we demonstrate the ability of SNAFs impregnated with organic dyes to sense hazardous and volatile vapors encountered in everyday life.

We evaluate the performance of a mid-infrared emission spectrometer operating at wavelengths between 1.5 and 6 μm based on an amorphous tungsten silicide (a-WSi) superconducting nanowire single-photon detector (SNSPD). We performed laser induced fluorescence spectroscopy of surface adsorbates with sub-monolayer sensitivity and sub-nanosecond temporal resolution. We discuss possible future improvements of the SNSPD-based infrared emission spectrometer and its potential applications in molecular science.

High-throughput laser micro-machining demands precise control of the laser beam position to achieve optimal efficiency, but existing methods can be both time-consuming and cost-prohibitive. In this paper, we demonstrate a new high-throughput micro-machining technique based on rapidly scanning the laser focal point along the optical axis using an acoustically driven variable focal length lens. Our results show that this scanning method enables higher machining rates over a range of defocus distances and that the effect becomes more significant as the laser energy is increased. In a specific example of silicon, we achieve a nearly threefold increase in the machining rate, while maintaining sharp side walls and a small spot size. This method has great potential for improving the micro-machining efficiency of conventional systems and also opens the door to applying laser machining to workpieces with uneven topography that have been traditionally difficult to process.

Long-lived excitons formed upon visible light absorption play an essential role in photovoltaics, photocatalysis, and even in high-density information storage. Here, we describe a self-assembled two-dimensional metal-organic crystal, composed of graphene-supported macrocycles, each hosting a single FeN₄ center, where a single carbon monoxide molecule can adsorb. In this heme-like biomimetic model system, excitons are generated by visible laser light upon a spin transition associated with the layer 2D crystallinity, and are simultaneously detected via the carbon monoxide ligand stretching mode at room temperature and near-ambient pressure. The proposed mechanism is supported by the results of infrared and time-resolved pump-probe spectroscopies, and by ab initio theoretical methods, opening a path towards the handling of exciton dynamics on 2D biomimetic crystals.

Molecular scale information about the structure of surfactants at interfaces underlies their application in consumer products. In this study the non-linear optical technique of Sum Frequency Generation (SFG) vibrational spectroscopy has been used to investigate the structure and temporal behaviour of two cationic surfactants used frequently in hair conditioners. SFG spectra of films of behenyltrimethylammonium methosulfate (BTMS) and behenyltrimethylammonium chloride (BTAC) were recorded at the air/water interface and on glass slides following Langmuir Blodgett (LB) deposition. The assignment of the BTMS and BTAC spectral features (resonances) to the C---H stretching modes of the surfactants was consolidated by comparison with the SFG spectrum of deuterated cetyltrimethylammonium bromide (d-CTAB) and by recording spectra on D₂O as well as on water. The C---H resonances arise from the methylene and methyl groups of the tail and head-groups of the surfactants. A slow collapse mechanism was observed following film compression of both BTAC and BTMS. The change in molecular structure of the films undergoing this slow collapse was followed by recording sequential SFG spectra in the C---H region, and by monitoring the SFG intensity at specific wavenumbers over time. Additionally, LB deposition onto glass was used to capture the state of the film during the slow collapse, and these SFG spectra showed close similarity to the corresponding spectra on water. Complementary Atomic Force Microscopy (AFM) was used to elucidate the layering of the compressed and relaxed films deposited onto mica by LB deposition.

Here we present the excited state dynamics of jet-cooled 6-thioguanine (6-TG), using resonance-enhanced multiphoton ionization (REMPI), IR–UV double resonance spectroscopy, and pump–probe spectroscopy in the nanosecond and picosecond time domains. We report data on two thiol tautomers, which appear to have different excited state dynamics. These decay to a dark state, possibly a triplet state, with rates depending on tautomer form and on excitation wavelength, with the fastest rate on the order of 10¹⁰ s^–1. We also compare 6-TG with 9-enolguanine, for which we observed decay to a dark state with a 2 orders of magnitude smaller rate. At increased excitation energy (∼+500 cm^–1) an additional pathway appears for the predominant thiol tautomer. Moreover, the excited state dynamics for 6-TG thiols is different from that recently predicted for thiones.

We present resonant two-photon ionization (R2PI) spectra of isocytosine (isoC) and pump–probe results on two of its tautomers. IsoC is one of a handful of alternative bases that have been proposed in scenarios of prebiotic chemistry. It is structurally similar to both cytosine (C) and guanine (G). We compare the excited-state dynamics with the Watson–Crick (WC) C and G tautomeric forms. These results suggest that the excited-state dynamics of WC form of G may primarily depend on the heterocyclic substructure of the pyrimidine moiety, which is chemically identical to isoC. For WC isoC we find a single excited-state decay with a rate of ∼10¹⁰ s^–1, while the enol form has multiple decay rates, the fastest of which is 7 times slower than for WC isoC. The excited-state dynamics of isoC exhibits striking similarities with that of G, more so than with the photodynamics of C.

The laser oxidation of thin metallic films followed by its selective chemical etching is a promising method for the formation of binary metal structures on the glass substrates. It is important to confirm that even a single ultrashort laser pulse irradiation is able to create the protective oxide layer that makes possible to imprint the thermochemical image.

Results of the thermo-chemical treatment of thin chromium films irradiated by picosecond laser pulse utilizing two and four beam interference combined with the chemical etching are presented. The spatial resolution of this method can be high enough due to thermo-chemical sharpening and can be close to the diffraction limit. Micro-Raman spectroscopy was applied for characterization of the chemical composition of the protective oxide layers formed under atmospheric conditions on the surface of thin chromium films.

Quantitative concentrations measurements using time-resolved laser-induced fluorescence have been demonstrated for nitric oxide (NO) in flame. Fluorescence lifetimes measured using a picosecond Nd:YAG laser and optical parametric amplifier system have been used to directly compensate the measured signal for collisional quenching and evaluate NO concentration. The full evaluation also includes the spectral overlap between the ∼15 cm⁻¹ broad laser pulse and multiple NO absorption lines as well as the populations of the probed energy levels. Effective fluorescence lifetimes of 1.2 and 1.5 ns were measured in prepared NO/N₂/O₂ mixtures at ambient pressure and temperature and in a premixed NH₃-seeded CH₄/N₂/O₂ flame, respectively. Concentrations evaluated from measurements in NO/N₂/O₂ mixtures with NO concentrations of 100–600 ppm were in agreement with set values within 3% at higher concentrations. An accuracy of 13% was estimated by analysis of experimental uncertainties. An NO profile measured in the flame showed concentrations of ∼1000 ppm in the post-flame region and is in good agreement with NO concentrations predicted by a chemical mechanism for NH₃ combustion. An accuracy of 16% was estimated for the flame measurements. The direct concentration evaluation from time-resolved fluorescence allows for quantitative measurements in flames where the composition of major species and their collisional quenching on the probed species is unknown. In particular, this is valid for non-stationary turbulent combustion and implementation of the presented approach for measurements under such conditions is discussed.