Vacuum Ultraviolet Radiation Research Articles

Emergence of Optical Activity and Surface Morphology Changes in Racemic Amino Acid Films Under Circularly Polarized Lyman-α Light Irradiation.

The homochirality of life remains one of the most enigmatic issues in the study of the origin of life. A proposed mechanism for symmetry breaking involves irradiation by circularly polarized light (CPL). To investigate the photoreaction of amino acids under CPL irradiation, a vacuum ultraviolet (VUV) CPL irradiation system was developed at the synchrotron light source UVSOR-III. Hydrogen Lyman-α CPL (121.6 nm) is considered a potential asymmetric source in space. Therefore, racemic alanine film samples were irradiated with Lyman-α CPL to explore the photoreaction of biomolecules. Circular dichroism (CD) spectra measurements revealed that irradiation with right- (left-) handed CPL induced a positive (negative) anisotropy factor g in the wavelength range of 180-240 nm. However, the spectra differed from those of enantiopure alanine, exhibiting broad wavelength ranges and no sign change. Liquid chromatography-mass spectrometry (LC-MS) measurements indicate formation of larger molecules, such as oligomeric alanine adducts or modified oligomers after the Lyman-α CPL irradiation. Additionally, CPL irradiation considerably changes the microstructure of the alanine film surface, leading to the formation of circular network aggregates on the scale of 100 nm. The morphology changes in the alanine film and/or the formation of the larger molecules could be possible causes of the modified anisotropy factor spectra compared to those of enantiopure alanine. These findings highlight the need for further research on the photoreaction of biomolecules in solid states under VUV CPL irradiation, particularly in the photoionization energy range, to validate the cosmic scenario of homochirality.

Near-Surfaces and Bulk Modification of Silicone Rubber under UV- and Vacuum UV-Irradiation Using Excimer and Hg Lamps

Near-Surfaces and Bulk Modification of Silicone Rubber under UV- and Vacuum UV-Irradiation Using Excimer and Hg Lamps

Study on Plasma Surface Modification of Hydrophobic Materials

The hydrophobic materials were treated by plasma continual treater to achieve its surface modification and improve its wettability. The influences of treating time, discharge power, working gases and gas pressure on the surface modification of the materials have been investigated. The chemical states and species on the surface of materials have been investigated by some technologies such as contact angles. After plasma surface treatment, the contact angles of PTFE sharply decrease, and the alkali liquid absorption of PE increased to three times of its weight. The contact angles of silicon rubber and polyester decreased remarkably after surface modification. PTFE films were grafted with crylic acid to evaluate the ageing. The effect of vacuum ultraviolet radiation to surface modification was initially described. The results of experiment demonstrate that the better wettability of hydrophobic material can be achieved. The technique and the equipment have the promotional value for industrial application.

Deposition of Thin Films From HMDSO Utilizing the Vacuum UV Radiation From an Atmospheric Plasma

ABSTRACTThis study presents a source for studying thin‐film deposition utilizing vacuum UV (VUV) radiation from a remote argon or helium atmospheric plasma to initiate photochemistry in the precursor gas. We aim to assess how this radiation affects the deposition process and film structure while avoiding deposition inside the plasma source or particle formation. Deposition occurs where radiation interacts with the precursor and the growing film, as well as further downstream. The measured film properties clearly show that photon interaction with the film has a significant effect. Using hexamethyldisiloxane (HMDSO) as a precursor, we achieved nearly carbon‐free silicon dioxide () film growth due to photodesorption of hydrocarbons from the growing film, as confirmed by infrared spectra and positive ion mass spectrometry.

Numerical investigation of vacuum ultra-violet emission in Ar/O2 inductively coupled plasmas

Abstract Controlling fluxes of vacuum ultraviolet (VUV) radiation is important in a number of industrial and biomedical applications of low pressure plasma sources because, depending on the process, VUV radiation may be desired, required to a certain degree, or unwanted. In this work, the emission of VUV radiation from O atoms is investigated in low-pressure Ar/O2 inductively coupled plasmas via numerical simulations. For this purpose, a self-consistent Ar/O2 plasma-chemical reaction scheme has been implemented in a zero dimensional plasma chemical kinetics model and is used to investigate VUV emission from excited O atoms (3s 5S 2 0 and 3s 3S 1 0 ) at 130 and 135 nm. The model is extensively compared with experimental measurements of absolute VUV emission intensities, electron densities and Ar excited state densities. In addition, oxygen VUV emission intensities are investigated as a function of pressure, Ar/O2 mixture, and power deposition and the dominant reaction pathways leading to oxygen VUV emission are identified and described. In general terms, absolute oxygen VUV emission intensities increase with power and oxygen fraction over the ranges investigated and peak emission intensities are found for pressures between 5–50 Pa. The emission is dominated by the 130 nm resonance line from the decay of the O(3s 3S 1 0 ) state to the ground state. Besides, at low pressure (0.3–1 Pa), the flux of oxygen VUV photons to surfaces is much lower than that of positive ions, whereas oxygen VUV fluxes dominate at higher pressure, ≳ 5–50 Pa depending on O2 fraction. Finally, oxygen atom fluxes to surfaces are, in general, larger than those of VUV photons for the parameter space investigated.

Abatement of algal extracellular organic matter by vacuum ultraviolet: Effect of dissolved oxygen and role of in-situ formed reactive oxygen species

Algal extracellular organic matter (EOM) in water produced during the outbreak of algal blooms is difficult to be effectively removed by conventional water treatment processes. Compared with ultraviolet (UV), vacuum ultraviolet (VUV) can additionally radiate 185 nm photons, and VUV can split water to produce reactive oxygen species (ROS) in-situ. Herein, abatement and characteristic variation of EOM under VUV irradiation and the mechanism were investigated. Results indicated that EOM abatement by VUV irradiation were significantly higher than that by UV irradiation. The mineralization rate constant of EOM under VUV was 2.25 times of that under UV. Besides, under VUV irradiation, the abatement efficiency of EOM was promoted with the increased dissolved oxygen (DO), and EOM with a lower initial concentration had a higher abatement efficiency. Intensities of characteristic fluorescence peaks of EOM decreased obviously after VUV irradiation, and removal rates of specific fluorescent organic components were ≥ 74.4%. Under VUV irradiation, organic matter in EOM with higher molecular weight was transformed into that with lower molecular weight. Moreover, hydroxyl radical (•OH) generated in-situ by VUV dissociating water with different DO was directly identified by fluorescence molecular probe technology, and the higher DO caused the higher production of •OH. Furthermore, the mechanism of EOM abatement by VUV was proposed. DO and the produced ROS enhanced the abatement efficiency of EOM, and they played important roles in EOM abatement. This study disclosed abatement characteristics of EOM under VUV irradiation and provided great value for expanding the utilization of VUV in water treatment.

Experimental and modeling investigation of the oxidation of n-hexylbenzene: Insight into the formation of low-temperature intermediates

As vital components in transportation fuels, an in-depth understanding of the oxidation mechanism of n-alkylbenzenes is pivotal for minimizing pollutant emissions during combustion processes. However, previous research was mostly focused on high-temperature oxidation, while investigations on low-temperature oxidation of long-chain n-alkylbenzenes remains scarce. In this work, n-hexylbenzene (C12H18) was selected to conduct low-temperature oxidation experiments in a jet-stirred reactor. A series of crucial intermediates and products were detected and then quantified by the synchrotron vacuum ultraviolet radiation photoionization mass spectrometry (SVUV-PIMS). In particular, characteristic aromatic oxygenated intermediates with compositions of C12H18Oy, C12H16Oy, C12H14Oy and C12H12Oy (0 ≤ y ≤ 3) were measured, which reveal the occurrence of first O2 addition, second O2 addition, and sequential oxidation reactions. To disclose the crucial reactions that control the fuel decomposition and formation of oxygenated intermediates, a detailed kinetic model of n-hexylbenzene was developed. This model was further utilized to explore the oxidation behaviors of C6 to C12n-alkylbenzenes. It was revealed that n-hexylbenzene exhibits the strongest low-temperature oxidation reactivity, while C6C10n-alkylbenzenes display little reactivity under present conditions. In conclusion, the reasonable performance of this model in predicting the oxidation behaviors of n-alkylbenzenes indicates its potential application in elucidating the low-temperature oxidation chemistry of heavier n-alkylbenzenes.

Room-temperature solution processed silicon nanocluster: Theory prediction and experiment achievement

We have presented in this work that silicon nanoclusters (Si NCs) embedded in silicon nitride (▪) can be synthesized by vacuum ultra-violet irradiation of perhydropolysilazane (PHPS) at room temperature. The formation of Si NCs is first predicted by reactive molecular dynamics (ReaxFF-MD) simulations based on a self-developed Si/N/H force field. Then the existence of Si NCs is further verified by photoluminescence (PL) spectroscopy and Raman spectroscopy characterization. Additionally, the photochemical conversion mechanism of PHPS is examined. Moreover, it has been found based on Fourier transform infrared (FT-IR) measurements that ▪ samples prepared with an intermediate irradiation time are the most readily to be oxidized, which can be attributed to the high concentration of the active group -▪, being consistent with the reaction mechanism. We have demonstrated that ReaxFF-MD simulation can be a powerful complement to experimental investigations in revealing the conversion mechanism of polymer precursor to ceramics at the atomic level.

The Unimolecular Decomposition Mechanism of Trimethyl Phosphate.

Trimethyl phosphate (TMP), an organophosphorus compound (OPC), is a promising fire-retardant candidate for lithium-ion battery (LIB) electrolytes to mitigate fire spread. This study aims to understand the mechanism of TMP unimolecular thermal decomposition to support the integration of a TMP chemical kinetic model into a LIB electrolyte surrogate model. Reactive intermediates and products of TMP thermal decomposition were experimentally detected using vacuum ultraviolet (VUV) synchrotron radiation and double imaging photoelectron photoion coincidence (i2PEPICO) spectroscopy. Phosphorus-containing intermediates such as PO, HPO and HPO2 were identified. Sampling effects could successfully be obviated thanks to photoion imaging, which also showed evidence for isomerization reactions upon wall collisions in the ionization chamber. Quantum chemical calculations performed for the unimolecular decomposition of TMP revealed for the first time that isomerization channels via hydrogen and methyl transfer (barrier heights of 65.9 and 72.6 kcal/mol, respectively) are the lowest-energy primary steps of TMP decomposition followed by CH3OH/CH3/CH2O or dimethyl ether (DME) production, respectively. We found an analogous DME production channel in the unimolecular decomposition of dimethyl methylphosphonate (DMMP), another important OPC fire-retardant additive with a similar molecular structure to TMP, which are not included in currently available chemical kinetic models.

Comprehensive Review on the Impact of Chemical Composition, Plasma Treatment, and Vacuum Ultraviolet (VUV) Irradiation on the Electrical Properties of Organosilicate Films.

Organosilicate glass (OSG) films are a critical component in modern electronic devices, with their electrical properties playing a crucial role in device performance. This comprehensive review systematically examines the influence of chemical composition, vacuum ultraviolet (VUV) irradiation, and plasma treatment on the electrical properties of these films. Through an extensive survey of literature and experimental findings, we elucidate the intricate interplay between these factors and the resulting alterations in electrical conductivity, dielectric constant, and breakdown strength of OSG films. Key focus areas include the impact of diverse organic moieties incorporated into the silica matrix, the effects of VUV irradiation on film properties, and the modifications induced by various plasma treatment techniques. Furthermore, the underlying mechanisms governing these phenomena are discussed, shedding light on the complex molecular interactions and structural rearrangements occurring within OSG films under different environmental conditions. It is shown that phonon-assisted electron tunneling between adjacent neutral traps provides a more accurate description of charge transport in OSG low-k materials compared to the previously reported Fowler-Nordheim mechanism. Additionally, the quality of low-k materials significantly influences the behavior of leakage currents. Materials retaining residual porogens or adsorbed water on pore walls show electrical conductivity directly correlated with pore surface area and porosity. Conversely, porogen-free materials, developed by Urbanowicz, exhibit leakage currents that are independent of porosity. This underscores the critical importance of considering internal defects such as oxygen-deficient centers (ODC) or similar entities in understanding the electrical properties of these materials.

Characterization of low-pressure gaseous plasma radiation and its usage for inactivation of waterborne viruses

Water disinfection is a critical treatment step for removing harmful organisms from contaminated water sources. Vacuum ultra-violet (V-UV) radiation, generated by a low-pressure gaseous plasma discharge, consists of photons with high enough energy to break molecular bonds. In this work, we constructed and characterized a low-pressure capacitively coupled gaseous plasma and used it as a V-UV radiation source to inactivate MS2 bacteriophage, a surrogate for human enteric viruses. The treatment system allows for variation of gas composition inside the sample chamber and the modulation of V-UV radiation intensity. Both were used to separate the actual germicidal contribution of V-UV radiation from producing germicidal species by using virus inactivation to determine efficiency. OH* radical production was determined through the terephthalic acid chemical probe, which showed that when air was present in the sample chamber, it resulted in the highest OH* production and the best inactivation of MS2. Furthermore, we showcase that the OH* production rate was wavelength dependent and that ozone, generated by plasma treatment in the gas phase, leads to hydroxy terephthalic acid degradation, allowing us to determine better the actual OH* production rate with different treatment regimes. Lastly, by adding an OH* scavenger to the liquid, we were able to elucidate it as the primary inactivation agent in this setup while also providing evidence of its production in the bulk liquid by the transport and subsequent decomposition of the longer-lasting ozone molecule. This study demonstrates, for the first time, the applicability of low-pressure plasma radiation as a water treatment method.

Physicochemical and structural properties of silica films prepared from perhydropolysilazane using vacuum ultraviolet irradiation

Developing techniques to form functional films at low temperatures is crucial for enabling their application on materials with limited heat resistance. In this study, silica films were prepared by irradiating a perhydropolysilazane (PHPS) precursor, which contains reactive Si–H and N–H groups and is free from organics, with vacuum ultraviolet (VUV) light under a controlled atmosphere. To investigate the quality of the resulting films and mechanisms behind photochemical conversion, infrared and electron spectroscopic measurements were performed. The results revealed that VUV irradiation converted the top surface of the film into silica, irrespective of the atmospheric conditions. However, differences in the oxygen concentration affected both the VUV light intensity penetrating the film and the oxygen diffusion into it, leading to the formation of silica or silicon oxynitride within the film. Under irradiation, PHPS was converted to silica not only from the surface but also from the interface with the substrate. In addition, silica was formed even at long irradiation distances, in which case VUV light barely reached the PHPS surface owing to absorption by atmospheric oxygen. These findings demonstrate that the silica-film formation involved two processes: breaking of chemical bonds induced by VUV photons and oxidation due to oxygen diffusion from the surface. The spectroscopic measurements and X-ray reflectivity results indicated that the composition, chemical state, Auger parameter, and density of the prepared silica film were comparable to those of a silica film prepared through heat treatment at 500°C. Further, the prepared silica film using VUV irradiation had a smoother surface than that of the heat-treated film. The thickness of the prepared film remained unchanged before and after VUV irradiation, indicating that the formation process using VUV irradiation suppressed the shrinkage of the film during the conversion of PHPS to silica.

Effect of vacuum-ultraviolet irradiation on structure and resistivity of epitaxial copper oxide thin films

Effect of vacuum-ultraviolet irradiation on structure and resistivity of epitaxial copper oxide thin films

Degradation of sodium dodecylbenzene sulfonate (SDBS) and high efficiency treatment of real grey water by TiO2-loaded stainless steel mesh under VUV irradiation

Reusing treated greywater indoors in buildings is an advanced strategy to increase the utilization of limited water resources, but currently there is a lack of feasible technologies for efficiently purifying greywater indoors. In this study, we construct the heterogeneous TiO2-stainless steel mesh (SSM) interface with photocatalytic degradation of sodium dodecylbenzene sulfonate (SDBS) by under vacuum ultraviolet (VUV) irradiation. At the initial SDBS of 10 mg/L, the degradation rates of SDBS with UV/TiO2-SSM and VUV/TiO2-SSM process were 53 % and 74 % respectively within 50 min. The results of specific scavengers experiments and EPR analysis revealed that the ·OH, h+ and direct photolysis contributed to SDBS degradation and mineralization. The degradation rate of SDBS in VUV/TiO2-SSM process was higher at weak acid or weak alkali conditions, while the performance of UV/TiO2-SSM process was better at alkaline conditions. Both Cl− and HCO3− could inhibit SDBS degradation, while SO42− slightly promoted the degradation. Active oxygen species mainly degrade SDBS in two ways: by attacking the α carbon, β carbon, or branched chain carbon on the alkane chain; or by attacking the adjacent carbon on the alkane chain, resulting in the formation of three branch forms of products. The toxicity of the intermediate products shows a decreasing or stable trend. The experiment shows that UV or VUV photocatalytic TiO2-SSM has a good prospect of removing anionic surfactant in the real greywater. This study provides strategies for the development and design of indoor water reuse technologies and devices in buildings.

Insights into enhanced degradation of antibiotic trimethoprim in water using a novel K doped g-C3N4 photocatalyst under vacuum-UV irradiation: Performance and mechanisms

In this work, an innovative strategy combining vacuum ultraviolet (VUV) and K doping graphite carbon nitride (K-g-C3N4) was proposed for antibiotic removal in aqueous. The properties of K-g-C3N4 were systematically characterized by XRD, FT-IR, BET, SEM, UV-vis DRS, and XPS, showing that K-g-C3N4 possessed a larger specific surface and richer functional groups than g-C3N4. The catalytic efficiency of K-g-C3N4 was investigated for the trimethoprim (TMP) removal under VUV irradiation. Compared with UVC photolysis, VUV photolysis, UVC/g-C3N4, VUV/g-C3N4, and UVC/K-g-C3N4 processes, VUV/K-g-C3N4 enhanced the pseudo-first-order reaction rate constant of TMP removal by 2.0–19.7 times and the mineralization rate by 9.0%-38.2%. Electron paramagnetic resonance results and quenching experiments validated that O2•-, •OH, 1O2, h+, and e- were engaged in the VUV/K-g-C3N4 process. The fluorescent spectra of O2•--substituted and •OH-substituted products revealed that the K-g-C3N4 greatly enhanced the quantity of O2•- and •OH during VUV irradiation. The VUV/K-g-C3N4 system produced marginally more H2O2 and •OH than the UVC/K-g-C3N4 system, confirming that K-g-C3N4 predominantly utilized the UVC and other ultraviolet–visible light emitted by the VUV lamp, with VUV having a minor effect. Furthermore, K-g-C3N4 had exceptional stability and reusability, efficiently degrading various contaminants under VUV irradiation. This work offered a comprehensive insight into VUV/K-g-C3N4 process as a novel approach for antibiotic removal from water.

Partitioning photochemically formed CO2 into clathrate hydrate under interstellar conditions.

Clathrate hydrates (CHs), host-guest compounds of water forming hydrogen-bonded cages around guest molecules, are now known to exist under interstellar conditions. Experimental evidence demonstrated that prolonged thermal treatment of a solid mixture of water and CO2/CH4 produces CHs at 10-30 K under simulated interstellar conditions. However, in the current study, we show that CO2 produced photochemically by vacuum ultraviolet irradiation of H2O-CO mixtures at 10 K and ∼10-10 mbar, gets partitioned into its CH phase and a matrix phase embedded in amorphous ice. The process occurring under simulated interstellar conditions was studied at different temperatures and H2O-CO compositions. The formation of CO2 CH and other photoproducts was confirmed using reflection absorption infrared spectroscopy. The UV-induced photodesorption event of CO2 may provide the mobility required for the formation of CHs, while photoproducts like methanol can stabilize such CH structures. Our study suggests that new species originating during such energetic processing in ice matrices may form CH, potentially altering the chemical composition of astrophysical environments.

Comparison of vacuum ultraviolet irradiation and oxygen plasma treatment as pretreatment for copper seed layer on cycloolefin polymer

This study explores the factors governing the peel strength characteristics between a cycloolefin polymer (COP) film and a copper plating layer with a copper seed layer, for applying to antenna circuits in 6 G communications. The peel strength depended on the surface modification methods as pretreatment for copper seed layer formation: vacuum ultraviolet (VUV) irradiation and oxygen plasma treatment. VUV irradiation induced a modified layer with brittleness on the COP surface, leading to substrate failure. Conversely, oxygen plasma treatment formed a quite thin modified layer and facilitated Cu2O formation by bonding functional groups on the topmost COP surface with copper in the seed layer at the interface between the COP film and the copper plating layer, resulting in interface failure rather than substrate failure. Therefore, enhancing peel strength involves preventing the formation of a modified layer on the surface and generating a significant quantity of functional groups on the topmost surface.

Polyethylene, whose surface has been modified by UV irradiation, induces cytotoxicity: A comparison with microplastics found in beaches

Microplastics, plastic particles 5 mm or less in size, are abundant in the environment; hence, the exposure of humans to microplastics is a great concern. Usually, the surface of microplastics found in the environment has undergone degradation by external factors such as ultraviolet rays and water waves. One of the characteristics of changes caused by surface degradation of microplastics is the introduction of oxygen-containing functional groups. Surface degradation alters the physicochemical properties of plastics, suggesting that the biological effects of environmentally degraded plastics may differ from those of pure plastics. However, the biological effects of plastics introduced with oxygen-containing functional groups through degradation are poorly elucidated owing to the lack of a plastic sample that imitates the degradation state of plastics found in the environment. In this study, we investigated the degradation state of microplastics collected from a beach. Next, we degraded a commercially available polyethylene (PE) particles via vacuum ultraviolet (VUV) irradiation and showed that chemical surface state of PE imitates that of microplastics in the environment. We evaluated the cytotoxic effects of degraded PE samples on immune and epithelial cell lines. We found that VUV irradiation was effective in degrading PE within a short period, and concentration-dependent cytotoxicity was induced by degraded PE in all cell lines. Our results indicate that the cytotoxic effect of PE on different cell types depends on the degree of microplastic degradation, which contributes to our understanding of the effects of PE microplastics on humans.

Plasma confinement by an optoelectronic system

Plasma confinement was succeeded by an optoelectronic system with the aid of a vacuum ultraviolet (VUV) light source, called the photoemission-assisted plasma system. The photoemission-assisted plasma was generated by utilizing photoelectrons from the substrate cathode. The photoelectrons were emitted from the substrate by external VUV irradiation via the photoelectric effect and then worked as initial electrons triggering the plasma generation. The photoemission-assisted plasma was confined with bright luminescence in an argon atmosphere by controlling the flow rate and pressure. The plasma confinement survived at up to 6400 Pa, which was much higher than the pressure estimated from the current–voltage characteristics. These results suggested that the area exhibiting luminescence dominated by the γ regime becomes small as the argon flow rate increases; however, the area does not vanish because the VUV-excited photoelectrons are sufficiently supplied. The residual area is dominated by the α regime without luminescence. Thus, the photoemission-assisted plasma seems to be confined on the balance between α and γ regimes. Because the current in the α-regime area is one hundredth in magnitude compared with that in the γ-regime area, the actual current density results in over 40 times with strong luminescence. This confined plasma with certain voltage and current condition may be expected for developing a new plasma reaction system and for application in semiconductor engineering.

Photochemistry of micro-solvated benzonitrile complexes with water/ammonia bordering on the formation of icy grains

Polycyclic aromatic hydrocarbons (PAHs) act as condensation nuclei for water/ammonia molecules forming icy water clusters. In the context of small aromatic rings, we have theoretically examined complexes of benzonitrile with water/ammonia molecules in order to investigate the photochemical kinetics of the icy grain formation. First, we obtain the structure of energetically stable complexes containing different H-bonding patterns and analyze their effects in the infrared (IR) and vacuum ultraviolet (VUV) spectra, before and after ionization. Second, we evaluate the H-bonding reorientation kinetics of the complexes at low temperatures, which indicates that the process involving water occurs faster than the corresponding process involving ammonia. Finally, the thermal rate constants indicate which configurations are the most likely to be ionized under vacuum ultraviolet (VUV) irradiation. Our results are consistent with what has experimentally been observed for related complexes, and are useful as a starting point to investigate the process of the icy grains formation. This study provides insight into possible subsequent photochemical reactions occurring in the interstellar medium (ISM) or in jet-cooled molecular complexes.