Vacuum Ultraviolet Radiation Research Articles

Giant enhancement of second harmonic generation via merging bound states in the continuum for vacuum ultraviolet radiation

Vacuum ultraviolet (VUV) light plays a crucial role in various scientific and technological fields, such as nanolithography and biomedical treatments. However, the inherent nonlinear optical coefficient of nonlinear optical crystals is typically very low, and increasing the action length is often necessary to improve the nonlinear conversion efficiency. This makes it challenging for these materials to achieve high-density optoelectronic integration at the micro-/nano-scale. In this study, we propose a design for generating coherent VUV radiation close to 175 nm using second harmonic generation (SHG) with an absolute efficiency exceeding 1.2‰ mW−1. This is achieved by merging multiple bound state in the continuum modes in a free-standing photonic crystal slab. Even with fabrication imperfections at a level lower than 10% disorder, the SHG efficiency of the samples remains robust, maintaining an efficiency of at least 2‰. This research provides a beneficial platform for generating efficient VUV light in the nanoscale.

High-Quality TiO2 Electron Transport Film Prepared via Vacuum Ultraviolet Illumination for MAPbI3 Perovskite Solar Cells.

The electron transport layer (ETL) plays an important role in determining the conversion efficiency and stability of perovskite solar cells (PSCs). Here, TiO2 thin film was prepared by irradiating diisopropoxy diacetylacetone titanium precursor thin film with 172 nm vacuum ultraviolet (VUV) at a low temperature. The prepared TiO2 thin film has higher electron mobility and conductivity. As it is used as an ETL for MAPbI3 PSCs, its band structure is better matched with the perovskite, and at the same time, due to the good interface contact, more uniform perovskite crystals are formed. Most importantly, a large number of hydroxyl radicals were formed during VUV irradiation of the precursor film, which made up for the oxygen defect present on the surface of the TiO2 thin film, and were adsorbed to the film surface. These hydroxyl groups form hydrogen bonds with methylammonium (MA) components on the MAPbI3 buried surface, thus promoting the transfer of photogenerated electrons at the MAPbI3/ETL interface. The power conversion efficiency of PSCs fabricated in air with the ETL prepared by VUV irradiation is 20.46%, which is higher than that of the contrast solar cell based on the sintered ETL (17.96%).

Vacuum Ultraviolet Single Photon Ionization and Decomposition of 2-Aminopropionitrile in Astrophysical Objects

The molecule 2-aminopropionitrile (2-APN; H3CCH(NH2)CN) is a chiral precursor of the amino acid alanine and could play an important role in the emergence of the homochirality of life. To date, 2-APN has not yet been detected in the interstellar medium. To address the question of its absence, possibly through destruction by vacuum ultraviolet radiation in astrophysical media, we studied its photoionization and dissociative photoionization in the 9–14 eV (89–137 nm) energy range using photoelectron–photoion coincidence spectroscopy with velocity map imaging. Density functional theory calculations were performed at the PBE0/aug-cc-pVTZ level to determine structures for the various cationic fragments identified experimentally. Their appearance energies were calculated. The adiabatic ionization energy (AIE) of 2-APN is AIE = (9.85±0.01) eV and the appearance energy (AE) of the major fragment ion N≡CC(H)NH2 + is AE = (10.57±0.01) eV. Both ions, 2-APN+ and N≡CC(H)NH2 +, make up more than 90% of the formed ions. N≡CC(H)NH2 +, an isomer of the protonated HCN dimer, is also formed with high yield in the dissociative photoionization of aminoacetonitrile (NH2CH2CN), another α-aminonitrile observed in Sgr B2(N). Photoion yield spectra have been calibrated to absolute ionization cross sections. From these, we derive photoionization rates in several typical radiation fields relevant to different astrophysical objects. The rates show that, under almost all explored radiation fields, dissociative ionization is the dominant pathway for photoionization, leading to the loss of a methyl group (CH3) to form the planar thermodynamically stable amino cyano methylidynium ion N≡CC(H)NH2 +. The observed absence of 2-APN in Sgr B2 could thus be due to dominant dissociative photoionization.

Conformer-Specific Photoelectron Spectroscopy of Carbonic Acid: H2CO3.

Carbonic acid (H2CO3) is a fundamental species in biological, ecological, and astronomical systems. However, its spectroscopic characterization is incomplete because of its reactive nature. The photoionization (PI) and the photoion mass-selected threshold photoelectron (ms-TPE) spectra of H2CO3 were obtained by utilizing vacuum ultraviolet (VUV) synchrotron radiation and double imaging photoelectron photoion coincidence spectroscopy. Two carbonic acid conformers, namely, cis-cis and cis-trans, were identified. Experimental adiabatic ionization energies (AIEs) of cis-cis and cis-trans H2CO3 were determined to be 11.27 ± 0.02 and 11.18 ± 0.03 eV, and the cation enthalpies of formation could be derived as ΔfH°0K = 485 ± 2 and 482 ± 3 kJ mol-1, respectively. The cis-cis conformer shows intense peaks in the ms-TPES that are assigned to the C=O/C-OH stretching mode, while the cis-trans conformer exhibits a long progression to which two C=O/C-OH stretching modes contribute. The TPE spectra allow for the sensitive and conformer-selective detection of carbonic acid in terrestrial experiments to better understand astrochemical reactions.

A Comparative Analysis of the Solar Ultraviolet Spectral Irradiance Measured from Earth and Mars: Toward a General Empirical Model for the Study of Planetary Aeronomy

Accurate estimation of the solar vacuum ultraviolet irradiance between 0.1 and 200 nm is critical for the study of planetary aeronomy. Previous empirical models have relied on a limited number of reference spectra, or on multiple data sets with various degrees of uncertainty, and on an empirical selection of solar proxies. Here we propose a novel method for the development of empirical models based on Fourier transform and least-squares fitting of the long-term measurements from the Solar EUV Experiment on the Thermosphere Ionosphere Mesosphere Energetics and Dynamics mission. A Fourier transform analysis is performed to examine a large number of solar proxies, which reveals that the solar radio flux at 10.7 cm and the solar Lyα flux at 121.6 nm are better proxies for solar irradiance below and above ∼120 nm, respectively. Using these two proxies, a nonlinear empirical model is developed through Fourier transform and least-squares fitting of solar irradiance measurements, which can reproduce the solar irradiance with uncertainties of only ∼1%–2% above ∼120 nm, ∼2%–4% within ∼45–120 nm, and ∼4%–8% below ∼45 nm. Comparison with measurements from the Extreme Ultraviolet Monitor on the Mars Atmosphere and Volatile Evolution mission indicates that the solar irradiance at Mars can be predicted with uncertainties of less than ∼8% by geometric extrapolation of the solar irradiance measured from Earth, provided that the measurements from Earth can be calibrated accurately. Our study provides a general method for the development of empirical models using long-term observations in planetary aeronomy.

Insights into the efficient mineralization of antibiotic trimethoprim in aqueous media by Fe2+ catalytically enhanced vacuum-UV irradiation: Kinetics, mechanisms, and toxicity evaluation

The widespread existence of antibiotics in the environment has attracted growing concerns regarding the potential adverse effects on aquatic organisms, ecosystems, and human health even at low concentrations. Extensive efforts have been devoted to developing new methods for effective elimination of antibiotics from wastewater. Herein, a novel process of Fe2+ catalytically enhanced vacuum ultraviolet (VUV) irradiation was proposed as a promising approach for the removal of antibiotic trimethoprim (TMP) in water. Compared with UVC photolysis, VUV photolysis, and UVC/Fe2+, VUV/Fe2+ could increase the pseudo-first-order reaction rate constant of TMP removal by 6.6–38.4 times and the mineralization rate by 36.5%–59.9%. The excellent performance might originate from the synergistic effect of VUV and Fe2+, i.e., VUV irradiation could effectively split water and largely accelerate the Fe3+/Fe2+ cycle to generate more reactive oxygen species (ROS). EPR results indicated that •OH and O2•- were identified as the main ROS in the UVC/Fe2+ and VUV/Fe2+ processes, while •OH, O2•-, and 1O2 were involved in the VUV process. The operating parameters, such as Fe2+ dosage and initial TMP contents, were evaluated and optimized. Up to 8 aromatic intermediates derived from hydroxylation, demethylation, carbonylation, and methylene group cleavage were identified by UPLC-QTOF-MS/MS technique, the possible pathways of TMP degradation were proposed. Finally, the acute and chronic toxicity of intermediates formed during TMP degradation in the VUV/Fe2+ process were also evaluated.

Improved Adhesion of Direct Copper Seed Layer by Medium-Vacuum Sputtering Using Vacuum Ultraviolet Light

A sputtering method is used to form the seed layer for copper electric plating. In general, copper sputtering has weak adhesion to resin, so titanium sputter is combined to increase the adhesion strength. However, etching in the lithography process requires two types of processes, titanium and copper metal. Adhesion strength was improved by performing vacuum ultraviolet (VUV) treatment as a pretreatment for medium-vacuum sputtering. We discovered the relationship between the hydroxyl groups on the resin surface and the adhesion strength by the chemical modification XPS method. Furthermore, by XPS analysis of the peeled copper interface, the adhesion mechanism between the resin and copper due to VUV irradiation was estimated. We evaluated the absorption properties in the vacuum ultraviolet region of a thinly polished glass epoxy resin. We investigated the behavior of functional groups at the interface and considered the effect of vacuum ultraviolet light in the depth direction.

Challenges in scaling of IPVD deposited Ta barriers on OSG low‐k films: Carbonization of Ta by CHx radicals generated through VUV‐induced decomposition of carbon‐containing groups

AbstractThe effect of vacuum ultraviolet (VUV) radiation during ionized physical vapor deposition (IPVD) of tantalum barriers on various porous organosilicate glass low‐k SiCOH films is studied using advanced diagnostics and quantum chemical calculations. VUV photons break the Si–C bonds, releasing hydrocarbon radicals from the pore surfaces. These radicals, trapped in pores that are partially sealed by tantalum deposition, can either react with tantalum to form carbide‐like compounds, TaCx, or be redeposited in the pores as CHx polymers. This is evidenced by a decrease in CH3 groups that correlates with an increase in TaCx. The formation of TaCx poses a significant challenge in the back end of line (BEOL) technology when reducing the barrier thickness.

Vacuum-ultraviolet irradiation of pyridine:acetylene ices relevant to Titan astrochemistry.

Nitrogen-containing polycyclic aromatic hydrocarbons (NPAHs) are important molecules for astrochemistry and prebiotic chemistry, as their occurrence spans from interstellar molecular clouds to planetary systems. Their formation has been previously explored in gas phase experiments, but the role of solid-state chemical reactions in their formation under cryogenic conditions remains elusive. Here, we explore the formation of NPAHs through vacuum ultraviolet (VUV) irradiation of pyridine:acetylene ices in amorphous and co-crystalline phases, with the aim to simulate conditions relevant to the interstellar medium and Titan's atmosphere. Our results show that the synthesis of ethynylpyridines from VUV-irradiated pyridine:acetylene amorphous ices is achievable at 18 K. In the co-crystal phase, photolysis at 110 K leads to the formation of NPAHs such as quinolizinium+ and precursors, reflecting a dynamical system under our conditions. In contrast, irradiation at 90 K under stable conditions did not produce volatile photoproducts. These results suggest that such chemical processes can occur in Titan's atmosphere and potentially in its stratosphere, where the co-condensation of these molecules can form composite ices. Concurrently, the formation of stable co-crystals can influence the depletion rates of pyridine, which suggests that these structures can be preserved and potentially delivered to Titan's surface. Our findings provide insights into the molecular diversity and chemical evolution of organic matter on Titan, crucial for future space exploration missions, such as the Dragonfly mission, which may uncover higher-order organics derived from pyridine precursors on Titan's surface.

Tracking the reaction networks of acetaldehyde oxide and glyoxal oxide Criegee intermediates in the ozone-assisted oxidation reaction of crotonaldehyde.

The reaction of unsaturated compounds with ozone (O3) is recognized to lead to the formation of Criegee intermediates (CIs), which play a key role in controlling the atmospheric budget of hydroxyl radicals and secondary organic aerosols. The reaction network of two CIs with different functionality, i.e. acetaldehyde oxide (CH3CHOO) and glyoxal oxide (CHOCHOO) formed in the ozone-assisted oxidation reaction of crotanaldehyde (CA), is investigated over a temperature range between 390 K and 840 K in an atmospheric pressure jet-stirred reactor (JSR) at a residence time of 1.3 s, stoichiometry of 0.5 with a mixture of 1% crotonaldehyde, 10% O2, at an fixed ozone concentration of 1000 ppm and 89% Ar dilution. Molecular-beam mass spectrometry in conjunction with single photon tunable synchrotron vacuum-ultraviolet (VUV) radiation is used to identify elusive intermediates by means of experimental photoionization energy scans and ab initio threshold energy calculations for isomer identification. Addition of ozone (1000 ppm) is observed to trigger the oxidation of CA already at 390 K, which is below the temperature where the oxidation reaction of CA was observed in the absence of ozone. The observed CA + O3 product, C4H6O4, is found to be linked to a ketohydroperoxide (2-hydroperoxy-3-oxobutanal) resulting from the isomerization of the primary ozonide. Products corresponding to the CIs uni- and bi-molecular reactions were observed and identified. A network of CI reactions is identified in the temperature region below 600 K, characterized by CIs bimolecular reactions with species like aldehydes, i.e., formaldehyde, acetaldehyde, and crotonaldehyde and alkenes, i.e., ethene and propene. The region below 600 K is also characterized by the formation of important amounts of typical low-temperature oxidation products, such as hydrogen peroxide (H2O2), methyl hydroperoxide (CH3OOH), and ethyl hydroperoxide (C2H5OOH). Detection of additional oxygenated species such as alcohols, ketene, and aldehydes are indicative of multiple active oxidation routes. This study provides important information about the initial step involved in the CIs assisted oligomerization reactions in complex reactive environments where CIs with different functionalities are reacting simultaneously. It provides new mechanistic insights into ozone-assisted oxidation reactions of unsaturated aldehydes, which is critical for the development of improved atmospheric and combustion kinetics models.

Exploring the oxidation chemistry of diethyl carbonate in lithium-ion battery thermal runaway using SVUV-PIMS

With the extensive applications of lithium-ion batteries and widespread concerns about their security, it is necessary to deeply understand the reaction mechanism of thermal runaway process of Li-ion batteries. Oxygen released from cathode and anode materials could react with electrolyte solvents with increased temperatures. However, the chemical mechanism remains elusive due to the complexity of the battery system. In this work, we developed a method to study the oxidation chemistry of electrolyte solvents and oxygen in lithium-ion battery thermal runaway process. The liquid phase oxidation of diethyl carbonate (DEC) with oxygen was studied in a closed autoclave with diverse oxygen concentrations, temperatures and reaction times. The samples were measured by synchrotron vacuum ultraviolet radiation photoionization mass spectrometry (SVUV-PIMS) to quantitatively analyze the oxidation products. It was found that the onset reaction temperature is less than 120 °C, which indicates that it maybe occurs in the early stage of Li-ion battery thermal runaway. Besides, the feasible reaction scheme is discussed to rationalize the formation of the primary products.

Time-resolved quantification of key species and mechanistic insights in low-temperature tetrahydrofuran oxidation.

We investigate the kinetics and report the time-resolved concentrations of key chemical species in the oxidation of tetrahydrofuran (THF) at 7500 torr and 450-675 K. Experiments are carried out using high-pressure multiplexed photoionization mass spectrometry (MPIMS) combined with tunable vacuum ultraviolet radiation from the Berkely Lab Advanced Light Source. Intermediates and products are quantified using reference photoionization (PI) cross sections, when available, and constrained by a global carbon balance tracking approach at all experimental temperatures simultaneously for the species without reference cross sections. From carbon balancing, we determine time-resolved concentrations for the ROO˙ and ˙OOQOOH radical intermediates, butanedial, and the combined concentration of ketohydroperoxide (KHP) and unsaturated hydroperoxide (UHP) products stemming from the ˙QOOH + O2 reaction. Furthermore, we quantify a product that we tentatively assign as fumaraldehyde, which arises from UHP decomposition via H2O or ˙OH + H loss. The experimentally derived species concentrations are compared with model predictions using the most recent literature THF oxidation mechanism of Fenard et al., (Combust. Flame, 2018, 191, 252-269). Our results indicate that the literature mechanism significantly overestimates THF consumption and the UHP + KHP concentration at our conditions. The model predictions are sensitive to the rate coefficient for the ROO˙ isomerization to ˙QOOH, which is the gateway for radical chain propagating and branching pathways. Comparisons with our recent results for cyclopentane (Demireva et al., Combust. Flame, 2023, 257, 112506) provide insights into the effect of the ether group on reactivity and highlight the need to determine accurate rate coefficients of ROO˙ isomerization and subsequent reactions.

Uniform broad-area deposition and patterning of SiO2 nanofilms by 172 nm photochemical conversion of liquid tetraethoxysilane layers at 300 K

Oxide films of the quality required for the fabrication of electronic and photonic devices are typically deposited at elevated temperatures and thermal equilibrium, thereby adversely impacting thermal budgets. We report the deposition and patterning of silicon dioxide (SiO2) films of high electrical and optical quality on Si(100) or polymer substrates in a N2 atmosphere and at 300 K by the photochemical conversion of thin liquid tetraethoxysilane (TEOS) layers with narrowband vacuum ultraviolet radiation [vacuum ultraviolet (VUV), 172 nm] provided by efficient microplasma lamps. Irradiating liquid TEOS layers, produced by spin-coating the precursor onto a substrate, with a VUV intensity of 13 mW cm−2, yields 40 nm-thick SiO2 films having a dielectric breakdown strength (Eb) of 5 MV cm−1, for which no precedent exists in the deposition of oxide films at 300 K. If room temperature-deposited films are post-annealed at 200 °C, Eb rises to 7.5 MV cm−1, which is <12% below the measured value (8.5 MV cm−1) for 40 nm SiO2 films grown by thermal oxidation. The deposition of 1 µm thick, stoichiometric SiO2 films requires only 20 min of VUV illumination at low optical fluences, and films with thicknesses of ∼35–60 nm exhibit a refractive index of 1.45 (633 nm). X-ray photoelectron spectrometry and Rutherford backscattering analysis indicate that, despite the deposition temperature, hydrocarbon impurity levels are near or below the detection limit. The capability for depositing 960 nm-thick SiO2 films uniformly (to within 0.6%) by liquid → solid photochemical conversion over a 5 cm diameter Si substrate and patterning films onto flexible polymer substrates has also been demonstrated.

Revealing the low to moderate temperature oxidation kinetics of 1,2,4-trimethylbenzene sensitized by dimethyl ether

Low to moderate temperature oxidation has been a vital topic in the combustion chemistry due to its critical role in controlling the combustion characteristics such as autoignition and pollutant emissions. Low temperature oxidation kinetics of alkanes and oxygenated biofuels have been widely explored, while that of branched aromatics is poorly understood. This work aims to investigate the low to moderate temperature oxidation kinetics of 1,2,4-trimethylbenzene (TMB, C9H12), which is a multi-branched alkylbenzene with weak low temperature oxidation reactivity. To enhance the low temperature oxidation reactivity of TMB, dimethyl ether (DME) was added to efficiently provide chain initiators. The oxidation experiment of TMB/DME mixture was performed with an atmospheric jet stirred reactor coupled with synchrotron vacuum ultraviolet radiation photoionization mass spectrometry. The negative temperature coefficient (NTC) behavior, as well as featured aromatic intermediates, especially phenyl hydroperoxides and unexpected highly oxygenated molecules (HOMs), were observed in the experiment. The detection of these fingerprint aromatic intermediates provide crucial evidence for revealing the low to moderate oxidation kinetics of TMB. In addition, a kinetic model was developed to provide in-depth kinetic analysis. The results demonstrate that the active chain initiators produced from DME oxidation trigger the low temperature chain-branching reactions of TMB. The chain recycling process is further sustained due to the regeneration of active intermediates such as phenyl hydroperoxides and •OH radicals. Aromatic intermediates with chemical compositions of C9H12Ox and C9H10Ox were measured and identified to be key indicators for the low temperature chemistry of TMB. In particular, the aromatic HOMs (C9H12O6 and C9H10O5) are fingerprint intermediates produced from the third O2 addition and subsequent reactions of TMB. Besides, the sensitivity analysis indicates that the interaction kinetics between TMB and DME by sharing the highly sensitive reactions of hydroperoxides and •OH radicals. The present work extends the conceptual reaction schemes proposed in alkanes towards branched aromatics, especially sequential O2 addition reactions that contributing to the formation of phenyl hydroperoxides and HOMs.

Numerical study on the non-equilibrium characteristics of high-speed atmospheric re-entry flow and radiation of aircraft based on fully coupled model

The strong coupling interactions of non-equilibrium flow, microscopic particle collisions and radiative transitions within the shock layer of hypersonic atmospheric re-entry vehicles makes accurate prediction of the aerothermodynamics challenging. Therefore, in this study a self-consistent non-equilibrium flow, collisional–radiative reactions and radiative transfer fully coupled model are established to study the non-equilibrium characteristics of the flow field and radiation of vehicle atmospheric re-entry. The comparison of the present calculation results with flight data of FIRE II and previous results in the literature shows a reasonable agreement. The thermal, chemical and excited energy level non-equilibrium phenomena are obtained and analysed for the different FIRE II trajectory points, which form the critical basis for studying the heat transfer and radiation. The non-equilibrium distribution of excited energy levels significantly exists in the post-shock and near-wall regions due to the rapid vibrational dissociation and electronic under-excitation, as well as the wall catalytic reactions. The analysis of stagnation-point heating of FIRE II illustrates that the translational–rotational convection and the dissociation component diffusion play key roles in the aerodynamic heating of the wall region. The spectrally resolved radiative intensity in the entire flow field indicates that the vacuum ultraviolet radiation caused by the high-energy nitrogen atomic spectral lines makes the main contribution to the radiative transfer. Finally, it is found that the non-equilibrium flow–radiation coupling effect can exacerbate the excited energy level non-equilibrium, and further affect the gas radiative properties and radiative transfer. This fully coupled study provides an effective method for reasonable prediction of atmospheric re-entry flow and radiation fields.

Preparation of Low-Defect Aluminum-Doped Zinc Oxide Nanostructure-Based Compact Layer by Vacuum Ultraviolet Irradiation for Quantum Dot-Sensitized Solar Cells

Preparation of Low-Defect Aluminum-Doped Zinc Oxide Nanostructure-Based Compact Layer by Vacuum Ultraviolet Irradiation for Quantum Dot-Sensitized Solar Cells

Chemical-free vacuum ultraviolet irradiation as ultrafiltration membrane pretreatment technique: Performance, mechanisms and DBPs formation

Membrane fouling induced by natural organic matter (NOM) has seriously affected the further extensive application of ultrafiltration (UF). Herein, a simple, green and robust vacuum ultraviolet (VUV) technology was adopted as pretreatment before UF and ultraviolet (UV) technology was used for comparison. The results showed that control effect of VUV pretreatment on membrane fouling was better than that of UV pretreatment, as evidenced by the increase of normalized flux from 0.27 to 0.38 and 0.73 after 30 min UV or VUV pretreatment, respectively. This is related to the fact that VUV pretreatment exhibited stronger NOM degradation ability than UV pretreatment owing to the formation of HO•. The steady-state concentration of HO• was calculated as 3.04 × 10−13 M and the cumulative exposure of HO• reached 5.52 × 10−10 M s after 30 min of VUV irradiation. And the second-order rate constant between NOM and HO• was determined as 1.36 × 104 L mg−1 s−1. Furthermore, fluorescence EEM could be applied to predict membrane fouling induced by humic-enriched water. Standard blocking and cake filtration were major fouling mechanisms. Moreover, extension of UV pretreatment time increased the disinfection by-products (DBPs) formation, the DBPs concentration was enhanced from 322.36 to 1187.80 μg/L after 210 min pretreatment. However, VUV pretreatment for 150 min reduced DBPs content to 282.57 μg/L, and DBPs content continued to decrease with the extension of pretreatment time, revealing that VUV pretreatment achieved effective control of DBPs. The variation trend of cytotoxicity and health risk of DBPs was similar to that of DBPs concentration. In summary, VUV pretreatment exhibited excellent effect on membrane fouling alleviation, NOM degradation and DBPs control under a certain pretreatment time.

Influence of Annealing on Thin Film/Substrate Interface and Vacuum Ultraviolet Photoconductivity of Neodymium Fluoride Thin Films

AbstractHigh photon energy vacuum ultraviolet radiation (VUV, 100−200 nm wavelength) is challenging to detect. It easily degrades conventional silicon and semiconductor photodetectors. Fluoride photodetectors can be the answer, but the correlation between fabrication parameters and photodetector performance is not known. Here, the effect of annealing is investigated on the characteristics of neodymium trifluoride thin film/quartz substrate interface and NdF3 photoconductivity within the VUV. Thin films are deposited on unheated and heated (600 °C) substrates with post‐deposition annealing. Dark current of films on unheated substrates decreases by as much as 1/10 as resistance increases from 1 −12 TΩ after annealing. Dark current of films on heated substrates increases even after annealing, resulting in similar photo and dark currents of ≈303.7 nA and poor detectors. Fluorine diffuses from the film to the substrate during deposition, exacerbated by substrate heating but not by annealing. Fluorine diffusion degrades crystallinity near the interface, increasing the dark current. Fluorine diffusion is absent when MgF2 is used as the heated substrate. Unannealed NdF3/MgF2 detector on 600 °C‐heated substrate and 600 °C‐annealed NdF3/SiO2 detector on unheated substrate exhibit similar resistances of ≈14 TΩ. Considering the film/substrate interface and annealing is crucial when developing VUV photodetectors.

Enlightening salt: enthalpy of formation of gaseous sodium chloride by photoelectron photoion coincidence spectroscopy

An in-vacuum flash pyrolysis microreactor was used to seed a molecular beam with gaseous sodium chloride. The vapour was ionised with tuneable synchrotron vacuum ultraviolet radiation to determine the 0 K appearance energy of the sodium cation from sodium chloride using photoelectron photoion coincidence spectroscopy. In addition to the Na+ and NaCl+ peaks, Na2Cl+ was also observed in the mass spectrum, as a tracer for gaseous (NaCl)2. Larger clusters were not observed. The breakdown diagram showed that the monomer underwent significant collisional cooling in the molecular beam, tentatively because of the increased stagnation pressure in the reactor. It also yielded an Na+ appearance energy of E 0 = 9.351 ± 0.007 eV. By the ion cycle, this leads to D 0(NaCl) = 406.4 ± 0.7 kJ mol−1 and Δf H o⦵ 0K(NaCl(g)) = −179.0 ± 1.0 kJ mol−1, which agree with but are better defined than the previous values. This enthalpy of formation is independent of the crystalline phase, and therefore confirms the literature sublimation enthalpy, as well.

Low temperature chemistry of 1,2,4-trimethylbenzene in a blend with n-heptane

As a representative aromatic component of practical fuels, understanding the low temperature chemistry of 1,2,4-trimethylbenzene under the reaction environment of fuel mixtures is necessary to improve the ignition and combustion process. In this work, low temperature oxidation of 1,2,4-trimethylbenzene was examined in a jet stirred reactor with reactants of n-heptane and 1,2,4-trimethybenzene in a fuel mixture (1:1 in mole, 500–800 K, ϕ = 0.5, τ = 2.0 s, p = 1 bar). Chemical species and their mole fraction evolution with reaction temperatures were recorded by the time of flight molecular beam mass spectrometer using synchrotron vacuum ultraviolet radiation as photon ionization source. Molecular structures of 56 species were identified by comparing the species ionization energies and the photonionization efficiency curves. 25 chemical formula of monocyclic oxygenated aromatics and oxygenated polycyclic aromatic hydrocarbons (OPAH) are detected, and 12 of them are identified. Some of the OPAHs are more toxic than the polycyclic aromatic hydrocarbons, indicating the importance of revealing their formation pathways in low temperature oxidation of aromatics. Numerical simulations using the latest kinetic model from Lawrence Livermore National Laboratory well predict the mole fractions of the reactants and most intermediates, but many monocyclic oxygenated aromatics and OPAHs are missing. The detection and identification of key monocyclic oxygenated aromatics (e.g., peroxides, aldehydes, dialdehydes, and ketohydroperoxides of 1,2,4-trimethylbenzene) provide important clues to unravel the low temperature oxidation pathways of alkylated aromatics like 1,2,4-trimethylbenzene. For monocyclic oxygenated aromatics and OPAHs that are missing in the kinetic model, potential formation pathways were proposed based on the molecular structure information, which might be useful for future kinetic model development.