Vacuum Ultraviolet Light Research Articles

A Revealing Insight into Gold Cluster Photocatalysts: Visible versus (Vacuum) Ultraviolet Light.

[Au25(PPh3)10(SC2H4Ph)5Cl2]2+ (Au25) supported on TiO2 (P25) exhibited distinct photocatalytic behaviors in the oxidation of amines using visible or ultraviolet light. The activity under visible light (455 nm) was superior to that under ultraviolet light. To gain insight into the origin of this difference, we investigated the photoreaction pathways of Au25 isolated in the gas phase upon irradiation with a pulsed laser with wavelengths of 455, 193, and 154 nm. High-resolution mass spectrometry revealed photon energy-dependent pathways for Au25: dissociation of the PPh3 ligands and PPh3AuCl units at 455 nm, dissociation into small [AunSm]+ ions (n = 3-20; m = 0-4) at 193 nm, and ionization affording the triply charged state at 154 nm. These results were substantiated by density functional theory simulations. On the basis of these results, we proposed that the inferior photocatalytic activity of Au25/P25 under ultraviolet light is mainly due to the poor photostability of Au25.

Vacuum UV photoabsorption spectroscopic and photoionization mass spectrometric study of geminal dibromoethylene (1,1-Br2C2H2) in the 5–15eV range. Experiment and theory

The vacuum UV photoabsorption spectrum (PAS) of 1,1-C2H2Br2 has been examined between 5 eV and 15 eV using the vacuum UV light of synchrotron radiation. For the first time the photoionization mass spectroscopy and efficiency of 1,1-C2H2Br2+ has been measured in the same energy range. A quantum chemical calculation is proposed for the investigation of the neutral and ionized states. The photoionization efficiency curve (PIEC) of 1,1-C2H2Br2+ provided the IEad(X˜2B1)= 9.617±0.005 eV. A vibrational structure gave ω3+=1336 cm−1 and most likely ω4+=483 cm−1. The PIEC of C2H2Br+ shows the lowest appearance energy to be at 11.14±0.02 eV. The onset at 11.56±0.01 eV likely corresponds to the excitation of Br in the 2P1/2 spin-orbit state. In the vacuum UV-PAS the broad band observed at 6.231 eV includes nσ→Rs, 2b1(π)→π* valence transitions and the 2b1→3 s Rydberg transition in agreement with the present calculations. An isolated weak continuum at 7.15 eV is assigned to the nπ→π* transition. The 2b1→3 s Rydberg transition is characterized by a short progression starting at 6.583 eV. A series of long progressions observed between 7.364 eV and 9.666 eV has been analyzed in terms of vibrational transitions to np- (δ= 0.544) and nd-type (δ= -0.04) Rydberg states all converging to the X˜2B1 ionic ground state. An analysis has been attempted providing average values of the vibrational wavenumbers ω3≈1300 cm−1 (or 162 meV), ω4≈480 cm−1 (or 60 meV) and ω5≈145 cm−1 (or 18 meV). By the same way several other Rydberg states were analyzed. For the first time the vacuum UV spectrum of 1,1-C2H2Br2 has been recorded above 10 eV and up to 15 eV. Several broad bands are tentatively assigned to transitions to Rydberg states converging to excited ionic states of 1,1-C2H2Br2+. For one of these a vibrational structure is observed and a tentative assignment is proposed.

Reflectance and fluorescence characteristics of PTFE coated with TPB at visible, UV, and VUV as a function of thickness

Polytetrafluoroethylene (PTFE) is an excellent diffuse reflector widely used in light collection systems for particle physics experiments. In noble element systems, it is often coated with tetraphenyl butadiene (TPB) to allow detection of vacuum ultraviolet scintillation light. In this work this dependence is investigated for PTFE coated with TPB in air for light of wavelengths of 200 nm, 260 nm, and 450 nm. The results show that TPB-coated PTFE has a reflectance of approximately 92% for thicknesses ranging from 5 mm to 10 mm at 450 nm, with negligible variation as a function of thickness within this range. A cross-check of these results using an argon chamber supports the conclusion that the change in thickness from 5 mm to 10 mm does not affect significantly the light response at 128 nm. Our results indicate that pieces of TPB-coated PTFE thinner than the typical 10 mm can be used in particle physics detectors without compromising the light signal.

Rapid characterization of silicon photomultipliers for noble liquid experiments

Silicon photomultipliers (SiPMs) are emerging as the photodetector technology to be used in upcoming noble liquid experiments. Newly developed SiPMs sensitive to vacuum ultraviolet (VUV) light will be directly used for the readout of scintillation photons (λ = 175 nm) from liquid xenon in future tonne-scale experiments, such as nEXO, searching for neutrinoless double beta decay in 136Xe. In this research project, VUV-SiPMs from two different vendors are characterized using current–voltage (IV) and pulse-level measurements performed at TRIUMF, from room temperature to liquid xenon temperature. These data are analysed to extract the SiPM’s features such as breakdown voltage, gain, crosstalk, afterpulsing and dark noise rates. The IV and pulse-level results are compared. A method is proposed for rapid quality control of large numbers of SiPM using IV measurements.

Intense Lyman-alpha light source for ultra-slow muon generation

A small-momentum-width muon beam, so-called ultra-slow muon beam, can be generated by laser ionization of muonium. To realize efficient ultra-slow muon generation, the Lyman-alpha and below 360 nm coherent light are required to resonantly excite the muonium from the ground state to 2p and sequentially ionizes excited muonium to the unbound state. At the J-PARC MLF Ultra-Slow Muon beamline, we have successfully generated Lyman-alpha coherent light exceeding 10 μJ using an all-solid-state laser and high-efficiency vacuum ultraviolet light generation technologies. In this paper, we will describe the intense Lyman-alpha light source.

Reconstruction of Low Dimensional Electronic States by Altering the Chemical Arrangement at the SrTiO3 Surface

AbstractDeveloping reliable methods for modulating the electronic structure of the 2D electron gas (2DEG) in SrTiO3 is crucial for utilizing its full potential and inducing novel properties. Herein, it is shown that relatively simple surface preparation reconstructs the 2DEG at the SrTiO3 (STO) surface, leading to a Lifshitz‐like transition. Combining experimental methods, such as angle‐resolved photoemission spectroscopy (ARPES) and X‐ray photoemission spectroscopy with ab initio calculations, that the modulation of the surface band structures can be effectively achieved via transforming the chemical composition at the atomic scale is found. In addition, ARPES experiments demonstrate that vacuum ultraviolet light can be efficiently employed to alter the band renormalization of the 2DEG system and control the electron‐phonon interaction . This study provides a robust and straightforward route to stabilize and tune the low‐dimensional electronic structure via the chemical degeneracy of the STO surface.

Photo-oxidative degradation of fluorinated chemisorbed monolayers studied by contact angle measurements and time-of-flight secondary ion mass spectrometry

This study investigates photo-degradation of tridecafluoro-1,1,2,2-tetrahydrooctyltrimethoxysilane (FAS13) used for antisticking surface modifiers in nanoimprint lithography by exposure to vacuum UV light (VUV; λ = 172 nm) or UV/ozone (λ = 185 and 254 nm). The degradation of FAS13 molecules chemisorbed on silicon surfaces was monitored sensitively in the contact angle measurements using diiodomethane rather than water. Photo-oxidation made the contact angles of FAS13-modified surfaces after water wash lower than those of unwashed FAS13-modified surfaces. This suggested that photo-decomposition products were left on exposed FAS13-modified surfaces and removed with water. Time-of-flight secondary ion mass spectrometry defined that the FAS13 chemisorbed monolayer was detected as a characteristic parent anion of C8F13 −, whereas the decomposition products were detected as C6F13 − and C3F7 −. Further exposure made the decomposition products photo-degraded to low-molecular-weight species and finally disappear from the surface. With the photo-degradation mechanism, UV/ozone exposure in an ambient condition was essentially the same as VUV exposure.

A Novel High-Energy Vacuum Ultraviolet Light Photofunctionalization Approach for Decomposing Organic Molecules around Titanium.

Titanium undergoes biological aging, represented by increased hydrophobicity and surface accumulation of organic molecules over time, which compromises the osseointegration of dental and orthopedic implants. Here, we evaluated the efficacy of a novel UV light source, 172 nm wavelength vacuum UV (VUV), in decomposing organic molecules around titanium. Methylene blue solution used as a model organic molecule placed in a quartz ampoule with and without titanium specimens was treated with four different UV light sources: (i) ultraviolet C (UVC), (ii) high-energy UVC (HUVC), (iii) proprietary UV (PUV), and (iv) VUV. After one minute of treatment, VUV decomposed over 90% of methylene blue, while there was 3-, 3-, and 8-fold more methylene blue after the HUVC, PUV, and UVC treatments, respectively. In dose-dependency experiments, maximal methylene blue decomposition occurred after one minute of VUV treatment and after 20-30 min of UVC treatment. Rapid and effective VUV-mediated organic decomposition was not influenced by the surface topography of titanium or its alloy and even occurred in the absence of titanium, indicating only a minimal photocatalytic contribution of titanium dioxide to organic decomposition. VUV-mediated but not other light source-mediated methylene blue decomposition was proportional to its concentration. Plastic tubes significantly reduced methylene blue decomposition for all light sources. These results suggest that VUV, in synergy with quartz ampoules, mediates rapid and effective organic decomposition compared with other UV sources. This proof-of-concept study paves the way for rapid and effective VUV-powered photofunctionalization of titanium to overcome biological aging.

Study of Color Change Characteristics of Plasma Indicators by Vacuum Ultraviolet Light from Excimer Lamps

We examined the color change characteristics of two types of "Plasma Indicators" (referred to as Indicators hereinafter) irradiated by vacuum ultraviolet (VUV) light from excimer lamps. We found that the colors of both Indicators change in accordance with the sensitivity of the VUV irradiation dose when the oxygen concentration is constant. We concluded that an appropriate Indicator must be selected according to the required VUV irradiation dose of each excimer lamp application. Moreover, we demonstrated that both Indicators were useful, and the reproducibility of VUV irradiation was confirmed only under the same VUV irradiation conditions.

Room-temperature processed TiO2 to construct composite electron transport layers for efficient planar perovskite solar cells

High-quality amorphous TiO2 films were prepared using vacuum ultraviolet light at room temperature and combined with SnO2 to form a composite ETL. The composite ETL-based PSC device achieved a champion PCE of 24.59% and showed improved stability.

Development of a novel, windowless, amorphous selenium based photodetector for use in liquid noble detectors

Detection of the vacuum ultraviolet (VUV) scintillation light produced by liquid noble elements is a central challenge in order to fully exploit the available timing, topological, and calorimetric information in detectors leveraging these media. In this paper, we characterize a novel, windowless amorphous selenium based photodetector with direct sensitivity to VUV light. We present here the manufacturing and experimental setup used to operate this detector at low transport electric fields (2.7–5.2 V/μm) and across a wide range of temperatures (77 K–290 K). This work shows that the first proof-of-principle windowless amorphous selenium device is robust under cryogenic conditions, responsive to VUV light at cryogenic temperatures, and preserves argon purity. These findings motivate a continued exploration of amorphous selenium devices for simultaneous detection of scintillation light and ionization charge in noble element detectors.

A unified reaction network on the formation of five-membered ringed polycyclic aromatic hydrocarbons (PAHs) and their role in ring expansion processes through radical-radical reactions.

Exploiting a chemical microreactor in combination with an isomer-selective product identification through fragment-free photoionization utilizing tunable vacuum ultraviolet (VUV) light in tandem with the detection of the ionized molecules by a high resolution reflection time-of-flight mass spectrometer (Re-TOF-MS), the present investigation reveals molecular mass growth processes to four distinct polycyclic aromatic hydrocarbons carrying two six- and one five-membered ring (C13H10): 3H-cyclopenta[a]naphthalene, 1H-cyclopenta[b]naphthalene, 1H-cyclopenta[a]naphthalene, and fluorene in the gas phase. Temperatures of 973 and 1023 K simulating conditions in combustion settings along with circumstellar envelopes of carbon-rich stars and planetary nebulae. These reactions highlight the importance of methyl-substituted aromatic reactants (biphenyl, naphthalene) which can be converted to the methylene (-CH2˙) motive by hydrogen abstraction or photolysis. Upon reaction with acetylene, methylene-substituted aromatics carrying a hydrogen atom at the ortho position of the ring can be then converted to cyclopentadiene-annulated aromatics thus providing a versatile pathway to five-membered ring aromatics at elevated temperatures.

Decomposing Organic Molecules on Titanium with Vacuum Ultraviolet Light for Effective and Rapid Photofunctionalization.

Ultraviolet (UV) photofunctionalization counteracts the biological aging of titanium to increase the bioactivity and osseointegration of titanium implants. However, UV photofunctionalization currently requires long treatment times of between 12 min and 48 h, precluding routine clinical use. Here, we tested the ability of a novel, xenon excimer lamp emitting 172 nm vacuum UV (VUV) to decompose organic molecules coated on titanium as a surrogate of photofunctionalization. Methylene blue as a model organic molecule was coated on grade 4 commercially pure titanium and treated with four UV light sources: (i) ultraviolet C (UVC), (ii) high-energy UVC (HUVC), (iii) proprietary UV (PUV), and (iv) VUV. After one minute of treatment, VUV decomposed 57% of methylene blue compared with 2%, 36%, and 42% for UVC, HUVC, and PUV, respectively. UV dose-dependency testing revealed maximal methylene blue decomposition with VUV within one minute. Equivalent decomposition was observed on grade 5 titanium alloy specimens, and placing titanium specimens in quartz ampoules did not compromise efficacy. Methylene blue was decomposed even on polymethyl methacrylate acrylic specimens at 20-25% lower efficiency than on titanium specimens, indicating a relatively small contribution of titanium dioxide-mediated photocatalytic decomposition to the total decomposition. Load-testing revealed that VUV maintained high efficacy of methylene blue decomposition regardless of the coating density, whereas other UV light sources showed low efficacy with thin coatings and plateauing efficacy with thicker coatings. This study provides foundational data on rapid and efficient VUV-mediated organic decomposition on titanium. In synergy with quartz ampoules used as containers, VUV has the potential to overcome current technical challenges hampering the clinical application of UV photofunctionalization.

Soliton dynamics in a piecewise gas-filled hollow-core fiber for efficient dispersive wave emission in the vacuum-ultraviolet range

Table-top coherent vacuum-ultraviolet (VUV) sources are important in many researches. Dispersive wave (DW) emission in a gas-filled hollow-core fiber (HCF) is an efficient way to obtain tunable VUV source with microjoule-level pulse energy. However, the shortest VUV wavelength is limited above 110 nm. This work investigated a method using a piecewise HCF in order to push the shortest VUV DW emission below 110 nm efficiently. The rich and complex spatiotemporal soliton dynamics in the HCF is revealed through rigorous numerical simulations and quantitative analysis. It is found that both the generation of VUV light below 110 nm and the overall conversion efficiencies below 150 nm can be significantly improved if the piecewise gas-filled HCF system is properly designed. As a result, the whole VUV spectrum (200--100 nm) can now be accessed efficiently, with single pulse energy of microjoule level. Different from other widely used intense VUV sources, this source has broad spectrum along with femtosecond time width. These unique characteristics in the VUV spectrum can lead to new research opportunities in various areas.

Crystallinity improvement of room-temperature PLD-deposited ZnO thin films on cyclo-olefin polymer substrates subject to surface-pretreatment with vacuum-UV-light irradiation

The effect of the surface-pretreatment of cyclo-olefin polymer (COP) substrates with vacuum-ultraviolet (VUV) light irradiation on the crystal growth of ZnO thin films deposited by room-temperature pulsed laser deposition (PLD) was investigated for development of flexible optical devices. 172-nm-excimer light irradiation with durations of 60 to 600 s in air was found to make the COP surface more hydrophilic and smooth. It was verified from measurements of X-ray diffraction, atomic force microscope and high-resolution transmission electron microscope that the ZnO thin films grown on the VUV-light-pretreated COP substrates exhibited enhanced (0001) orientation growth and increased crystallinity compared with the samples grown on substrates not subject to the pretreatment; the samples on the pretreated substrates also showed a smooth surface and atomically sharp interface between the thin film and the substrate. The electrical resistivity of the ZnO thin film grown on the VUV-light-pretreated COP substrate was estimated to be 2.3 × 10−3 Ωcm, which was 40% lower than that of the film grown on the untreated substrate.

Formation of Para-H2O by Vacuum-UV Photolysis of O2 in Solid Hydrogen: Implication for Astrochemistry.

The observation that the ortho to para ratio (OPR) of interstellar H2O is smaller than 3 is an important yet unresolved subject in astronomy. We irradiated O2 embedded in solid H2 at 3 K with vacuum-ultraviolet (VUV) light and observed IR lines associated with para-H2O (denoted as pH2O) and nonrotating H2O-(oH2)n (where oH2 denotes ortho-H2) but no lines associated with ortho-H2O (denoted as oH2O). After maintaining the matrix in darkness for ∼30 h, the amount of pH2O decreased, accompanied by an increase in H2O-(oH2)n via diffusion of oH2. After that, the continuous nuclear-spin conversion from oH2 to para-H2 (denoted as pH2) in solid H2 over time resulted in the conversion of nonrotating H2O-(oH2)n to rotating pH2O in solid pH2. The observation of the formation and conversion of pH2O in our experiment suggests a plausible route in which VUV irradiation of O2 and H2 adsorbed on grain surfaces might be responsible for the smaller OPR of interstellar H2O.

Hydrogen-polarized vacuum ultraviolet photolysis system for enhanced destruction of perfluoroalkyl substances

Reductive water treatment using hydrated electrons (eaq−) is a promising technology to destruct perfluoroalkyl substances; however, it faces challenges of slow reaction kinetics, undesirable chemical addition, and high energy consumption. Herein, we developed a hydrogen (H2)-polarized water photolysis system using vacuum UV (VUV) light at 185 nm for reductive destruction of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). The 185-nm photons directly photolyzed H2O and OH- into HO·, H·, and eaq−. H2 elevated the quasi steady-state concentration of eaq− 18 times in untuned VUV systems through eliminating the scavenging effect of dissolved oxygen and converting hydroxyl radicals (HO·/O·-) into eaq−. The polarization effect of H2 increased the degradation of PFOA from 10 % to 95 % and the defluorination from 17 % to 94 % and led to 87 % of defluorination for PFOS. The pH impacted VUV photon adsorption between H2O and OH- and shifted the equilibrium between H· and eaq−, which led to an optimal pH of 10.3 for PFOA destruction. The presence of chloride and sulfate enhanced the production of eaq− and promoted PFOA destruction. H2-polarized VUV water photolysis systems produced high levels of eaq− from clean water constituents and significantly reduced energy consumption for PFAS treatment under mild alkaline conditions.

Improved Adhesion of Copper Seed Layer Using Vacuum Ultraviolet Light for Direct High-Speed Sputtering

The dry process is progressing in the manufacturing process of semiconductor packages. The semi-additive process for forming the rewiring layer is required to be finer and more reliable than ever. The interface between the insulating resin and the copper wiring is being smoothed in order to reduce transmission loss during high-frequency communication. The conventional electroless plating method using the anchor effect is disadvantageous for smoothing. Therefore, a sputtering method is used to form the seed layer. In general, copper spatter has weak adhesion to resin, so titanium spatter is combined to increase the adhesion strength. However, etching in the lithography process requires two types of processes, titanium and copper.We investigated the improvement of copper sputtering adhesion to glass epoxy resin by a high-speed sputtering device. Adhesion strength was improved by performing plasma treatment and vacuum ultraviolet treatment as pretreatment for high-speed sputtering. Surface modification was analyzed and evaluated by XPS. We report on the process and evaluation method that contribute to the dryness of the packaging process.

Characterization of vacuum ultraviolet-irradiated surface modification of CoO(111) crystal by low-energy atom scattering spectroscopy

The surface of a CoO(111) single crystal was treated with vacuum ultraviolet (VUV) light at a wavelength of 172 nm without heat treatment. We studied the surface structural analysis of CoO(111) before and after VUV light irradiation in air using low-energy atom scattering spectroscopy. The primary beam was 3 keV-4He0, and backscattered 4He particles from Co atoms were detected using a microchannel plate detector. We compared the experimental spectra to simulation results, and the results demonstrated that the rock-salt CoO(111) surface was transformed to a spinel Co3O4(111) surface after VUV light irradiation. We also identified details about the chemical properties and topmost layers of CoO(111) surfaces before and after VUV light irradiation.

Boron Nitride Nanoribbons Grown by Chemical Vapor Deposition for VUV Applications.

The fabrication process of vacuum ultraviolet (VUV) detectors based on traditional semiconductor materials is complex and costly. The new generation of wide-bandgap semiconductor materials greatly reduce the fabrication cost of the entire VUV detector. We use the chemical vapor deposition (CVD) method to grow boron nitride nanoribbons (BNNRs) for VUV detectors. Morphological and compositional characterization of the BNNRs was tested. VUV detector based on BNNRs exhibits strong response to VUV light with wavelengths as short as 185 nm. The photo–dark current ratio (PDCR) of this detector is 272.43, the responsivity is 0.47 nA/W, and the rise time and fall time are 0.3 s and 0.6 s. The response speed is faster than the same type of BN-based VUV detectors. This paper offers more opportunities for high-performance and low-cost VUV detectors made of wide-bandgap semiconductor materials in the future.