Vacuum Ultraviolet Region Research Articles

Excitation and fragmentation of the dielectric gas C4F7N: Electrons vs photons.

C4F7N is a promising candidate for the replacement of sulfur hexafluoride as an insulating medium, and it is important to understand the chemical changes initiated in the molecule by collision with free electrons, specifically the formation of neutral fragments. The first step of neutral fragmentation is electronic excitation, yet neither the absorption spectrum in the vacuum ultraviolet (VUV) region nor the electron energy loss spectrum have previously been reported. Here, we experimentally probed the excited states by VUV photoabsorption spectroscopy and electron energy loss spectroscopy (EELS). We found that the distribution of states populated upon electron impact with low-energy electrons is significantly different from that following photoabsorption. This difference was confirmed and interpreted with ab initio modeling of both VUV and EELS spectra. We propose here a new computational protocol for the simulation of EELS spectra combining the Born approximation with approximate forms of correlated wave functions, which allows us to calculate the (usually very expensive) scattering cross sections at a cost similar to the calculation of oscillator strengths. Finally, we perform semi-classical non-adiabatic dynamics simulations to investigate the possible neutral fragments of the molecule formed through electron-induced neutral dissociation. We show that the product distribution is highly non-statistical.

Synchrotron-Excited Luminescence and Converting of Defects and Quantum Dots in Modified Silica Films

Optically active defects in modified silicon oxide films on a silicon substrate have been studied by low-temperature photoluminescence (PL) spectroscopy using excitation by synchrotron radiation in the vacuum ultraviolet region. Films of dry thermal silicon oxide obtained by treatment of stoichiometric SiO2 in hydrogen plasma, films of wet thermal silicon oxide, and films with low dielectric constant (so called "low-k" dielectrics) have been studied. Investigations of various type SiO2 films detect the PL centers, which can be conditionally divided into two groups. The first group includes intrinsic point defects, the different variants of oxygen-deficient centers (ODCs). The second group contains centers like the spatially confined excitons in silicon quantum dots (SiQDs). It is shown that SiQDs differ in spectral characteristics, are formed in different ways, due to the transformation and clustering of point defects such as E'-centers, ODC(I) and ODC(II). In this case, the size and spectral properties of quantum dots depend on the mechanism of their formation. Schemes for the conversion of these defects are proposed.It was found that for wet films and nonstoichiometric SiOx films treated in hydrogen plasma, "metastable" centers ODC(I) and ODC(II) arise only under the action of synchrotron radiation in the region of interband or exciton absorption and then they decay because of radiative relaxation. The absence of stable ODC centers in these films is due to their clustering and the formation of SiQDs. In "low-k" mesoporous films, on the contrary, silicon quantum dots SiQDs are not formed, but ODC(I) and ODC(II) centers are clearly manifested. A scheme of electronic transitions upon indirect excitation of silicon quantum dots through exciton states of the SiO2 matrix is considered. The presented results demonstrate the possibility of controlling the optical properties of silicon thin-film structures by creating in them both oxygen-deficient point defects and quantum dots of various sizes.

The electronic spectra of 2- chlorothiophene and 3-chlorothiophene in the vacuum ultraviolet photoabsorption energy region (3.9–10.8 eV)

The absolute photoabsorption cross-sections for 2-chlorothiophene (2-Cl-Th) and 3-chlorothiophene (3-Cl-Th), in the 3.9–10.8 eV energy range, were recorded for the first-time using synchrotron radiation. New ab initio theoretical calculations performed at the time-dependent density functional theory (TD-DFT) level were used to help interpret the photoabsorption spectra. These have provided important information on the nature of the excited states which have been assigned to valence, mixed valence-Rydberg and Rydberg transitions. The combination of high-resolution vacuum ultra-violet synchrotron radiation with TD-DFT, represents the most comprehensive and self-consistent assignment of the chlorothiophenes electronic excitation to date. Photolysis lifetimes in the Earth^{\\prime}s upper atmosphere for both chemical compounds have been estimated from the absolute photoabsorption cross-sections. Potential energy curves have been obtained at the TD-DFT level of theory, showing that the dissociative character of the lowest-lying electronic states is more efficient in 3-Cl-Th.

Machine learning models for binary molecular classification using VUV absorption spectra

Machine learning methods were combined with differential absorption spectroscopy measurements in the vacuum-ultraviolet region (5.167 – 9.920 eV) in order to develop predictive capabilities for inferring molecular structure from the spectra. Several types of species were analyzed and, for modeling purposes, were defined using a single classification: (1) alkane, (2) conjugation with oxygen (e.g. diacetyl, ethyl vinyl ether), (3) non-conjugated alkene (e.g. 1-butene, 1,4-cyclohexadiene), (4) oxygen-containing (e.g. 1-butanol, tetrahydrofuran), or (5) cyclic (e.g. cyclopentane, cyclohexanone). The latter molecular classification excluded cyclic ethers. Several modeling methods were employed in the analysis of 102 absorption spectra, 24 of which were measured for the first time.The primary objective was to identify suitable methods that enable accurate predictions of molecular structure classifications with minimized statistical uncertainties. Rather than identifying a single, unifying method to reliably predict molecular structure contributions to VUV absorption spectra, coordination is required among a particular method, the type of molecular structure detail (e.g. conjugation), and absorption region of interest. The latter is accomplished using a binning approach, wherein absorption regions of ∼0.5 eV were utilized rather than the entire ∼4.8 eV range. Photon energy binning enabled analysis of region-specific predictions of accuracy, precision, and recall. The outcome from the binning approach is that, rather than utilizing the entire spectrum, optimal determination of molecular structure using machine learning methods depends on the absorption region. The present work provides separate machine learning models for each molecular classification, which enables the identification of multi-functional species relevant to atmospheric chemistry and combustion chemistry, where isomer-resolved speciation is critical to understanding complex reaction networks.

A New Band System of the Dicarbon Molecule in the Vacuum Ultraviolet Region.

As one of the most abundant molecules in the universe, the long history of spectroscopic studies of the dicarbon molecule, C2, reaches back two centuries. While many electronic band systems with upper states below the lowest dissociation threshold have been well characterized, much less is known about transitions to higher-lying states. Here, we report the observation of a new band system of C2 from the lowest triplet state a3Πu through a resonance-enhanced multiphoton ionization scheme. The upper state is identified as 13Σg+, which is determined to be 61539.0 cm-1 (7.630 eV) above ground state X1Σg+. The spectroscopic parameters determined for the 13Σg+ state are in excellent agreement with those predicted by the high-level ab initio calculations. This study paves the way for systematic investigations of the photoabsorption and photodissociation of C2 in the vacuum ultraviolet region, which has important applications in the field of astrochemistry.

Reinvestigation of the Herzberg-Lagerqvist-Malmberg transitions of C2 in vacuum ultraviolet region and the implications for astronomical observations.

The dicarbon radical, C2, is one of the most abundant molecules in the universe, and has been widely observed in various energetic environments. Even though numerous experimental and theoretical investigations on C2 have been done during the last two centuries, spectroscopic study of C2 in vacuum ultraviolet (VUV) region has been rare. The only three known absorption band systems in VUV region were identified by Herzberg and co-workers in 1969 by VUV spectrograph, namely the electronic transitions F1Πu(v')-X1Σg +(v″), f3Σg -(v')-a3Πu(v″) and g3Δg(v')-a3Πu(v″) (Herzberg-Lagerqvist-Malmberg transitions). In this study, we employ a two-photon resonance-enhanced four-wave mixing based VUV laser source and a time-of-flight mass spectrometer for reinvestigating the above three electronic transitions of C2 through a resonant (1VUV + 1'UV) photoionization scheme. Besides those vibronic transitions as identified by Herzberg and co-workers, many more absorption bands belonging to the electronic transitions f3Σg -(v')-a3Πu(v″) and g3Δg(v')-a3Πu(v″) are observed with their spectroscopic parameters determined. The rather astrophysically important F1Πu state is not observed here by the resonant (1VUV + 1'UV) photoionization scheme, which must be due to its fast predissociation process. Instead, our study shows that the vibronic band g3Δg(v' = 2)-a3Πu(v″ = 0) exactly overlaps with F1Πu(v' = 0)-X1Σg +(v″ = 0), which was not realized in previous studies. The potential implications of these findings to astronomical observations are discussed.

Near and vacuum UV polarization spectroscopy of 1,4-distyrylbenzene

The UV absorbance bands of 1,4-distyrylbenzene (1,4-Bis[(E)-2-phenylethenyl]benzene, DSB) are investigated by Synchrotron Radiation Linear Dichroism (SRLD) spectroscopy using stretched polyethylene as an anisotropic solvent. The observed polarization data provide information on the transition moment directions of the observed spectral features. The investigation covers the range 15,000–58,000 cm−1 (667–172 nm), thereby providing new information on the transitions of DSB in the vacuum UV region. The observed spectrum is characterized by four main band systems centered at 27,600, 41,000, 49,800, and 57,500 cm−1 (362, 244, 201, and 174 nm). In general, the observed bands and their polarization directions are well predicted by the results of quantum chemical calculations using Time-Dependent Density Functional Theory (TD–DFT) with the functional CAM-B3LYP, and with the semiempirical all-valence-electrons method LCOAO.

Gas Dynamics Processes above the Polymers Surface under Irradiation with Broadband High-Brightness Radiation in the Vacuum Ultraviolet Spectrum Region.

Obtaining new data on the gas-dynamic responses from the polymer samples (polytetrafluoroethylene, PTFE) irradiated by powerful VUV radiation from compressed plasma flows is in the focus of the present study. An erosion type magnetoplasma compressor (MPC), a type of plasma focus discharge, was used as a radiation source. The operating voltages of the MPC were between 15 and 25 kV, the maximum measured discharge current was 200 kA, and the radiation energy in the VUV range was ≈1–2 kJ. The VUV fluxes on the sample surface were high and equal to ≈1022–1024 photons cm−2·s−1. Double-exposure laser holographic interferometry and schlieren photography were used to diagnose and visualize the gas-dynamic structures. The spatial distribution of the parameters (temperature, pressure and concentrations of electrons and ions) was defined based on the assumption of local thermodynamic equilibrium. It has been demonstrated that the maximum temperature ranged from ≈ 10 to 15 kK in the plasma layer. The electron concentration was ≈ (0.7–1.6) × 1018 cm−3 in this region. The used techniques of optical diagnostics and procedures of result processing make it possible to obtain data on the dynamics of polymer ablation, which occurs when their surface is exposed to powerful energy fluxes (thermal, shock-wave, radiation, and other extreme loads).

Influence of high pressure on Ce3+ luminescence in LuAlO3 and YAlO3 single crystals and single crystalline layers

Results of spectroscopic studies at ambient and high pressures of a LuAlO3:Ce3+ (LuAP:Ce) single crystalline film (SCF) as well as LuAP:Ce and YAlO3:Ce (YAP:Ce) single crystals are reported. Room temperature absorption measurements of the single crystals in the vacuum UV region allowed establishing the bandgap energies of 7.63 eV for YAP and 7.86 eV for LuAP, with an assumption of the direct band-gaps. Luminescence of Ce3+ in LuAP and YAP bulk crystals was measured as a function of temperature from 6 K up to 873 K. Temperature quenching of the Ce3+ luminescence in YAP:Ce was observed above 650 K, which is related to the location of the lowest Ce3+5d level at 1.27 eV below the conduction band minimum. No temperature quenching occurred in LuAP:Ce up to 873 K, mostly due to the lower energy of the 4f levels with respect to the valence band maximum. The barycenter energies and splittings of Ce3+5d states in YAP and LuAP at room temperature were precisely established. Theoretical calculations of the Ce3+5d states energy structure under pressure revealed a discrepancy between the obtained experimental results and the prediction of Dorenbos' theoretical model. The discrepancy can be removed if instead of the 5d state of the free Ce3+ ion the bandgap of the compound is taken as reference energy for the red-shift of the 5d level. This hypothesis also allows us to take into account the pressure-induced increase of the bandgap energy, expected for the studied compounds. Pressure dependences of LuAP:Ce luminescence spectra suggest that a certain type of phase transition occurs above 15 GPa.

Energy levels, wavelengths and radiative rates for transitions in Hg-like Bismuth

The fourth spectrum of bismuth (Bi IV) has been investigated in the vacuum ultraviolet region. Recordings of bismuth spectra were made on a 3-m normal incidence vacuum spectrograph at Antigonish laboratory in Canada using a triggered spark light source. The theoretical interpretation for this spectrum was made with the pseudo-relativistic Hartree-Fock approach implemented in Cowan's code. The previous analysis of the energy level structure of Bi IV is confirmed and extended with the identifications of the 6p2 1S0 and 5d96s26p 3D2 levels, which were not reported earlier. Two new doubly excited configurations 6p6d and 6p7s were studied for the first time with the identification of 56 spectral lines. In total, 84 energy levels were located in the 5d10[6s2+ 6snp (n = 6, 7) + 6p2 + 6snd (n = 6, 7) + 6s5f], 6p6d, 6p7s, 5d96s2np (n = 6–10) and 5d96s2nf (n = 5–13) configurations, among which fifteen were newly established. A total of 552 spectral lines have now been classified in Bi IV in the region 193–5000 Å. We also present the optimized energy level values, transition rates and Ritz wavelengths along with their uncertainties evaluated using the least-squares fitting procedure.

Engineering the band gap and optical properties of a two-dimensional molybdenum carbon fluoride MXene

Using first-principles density functional theory, we investigated the electronic and optical properties of monolayer and multilayer nanosheets of molybdenum carbon fluoride (Mo2CF2), a two-dimensional (2D) transition-metal carbide MXene. The indirect band gap of the Mo2CF2 semiconductor can be engineered by controlling the number of layers where the band gap energy changes from 0.278 eV for the monolayer to 0.249 eV for the trilayer nanosheet. The decrease in band gap energy in the multilayer is due to interlayer coupling, which splits the bands according to the number of layers. Mo2CF2 behaves as a metal with an anomalous dispersion and high optical conductivity at incident photon energies of 0.68–2.19, 3.49–6.68 and 7.30–8.31 eV. It has a relatively low reflectivity and is absorbing over a broad range of photon energies from about 0.429 (2890), 0.387 (3204) and 0.345 eV (3594 nm) for the monolayer, bilayer and trilayer nanosheets, respectively, achieving peak absorption in the vacuum ultraviolet region at about 7.9 eV (157 nm). The optical properties of Mo2CF2 can likewise be tuned by varying the number of layers. The unique behavior of its optical properties along with the ability to control its electronic and optical properties enhances the potential of 2D Mo2CF2 for various applications in the fields of electronics and energy storage.

Photoreflectance system based on vacuum ultraviolet laser at 177.3 nm

Photoreflectance (PR) spectroscopy is a powerful and non-destructive experimental technique to explore interband transitions of semiconductors. In most PR systems, the photon energy of the pumping beam is usually chosen to be higher than the bandgap energy of the sample. To the best of our knowledge, the highest energy of pumping laser in reported PR systems is 5.08 eV (244 nm), not yet in the vacuum ultraviolet (VUV) region. In this work, we report the design and construction of a PR system pumped by VUV laser of 7.0 eV (177.3 nm). At the same time, dual-modulated technique is applied and a dual channel lock-in-amplifier is integrated into the system for efficient PR measurement. The system’s performance is verified by the PR spectroscopy measurement of well-studied semiconductors, which testifies its ability to probe critical-point energies of the electronic band in semiconductors from ultraviolet to near-infrared spectral region.

Engineering nonlinear optical phenomena by arbitrarily manipulating the phase relationships among the relevant optical fields

Nonlinear optical processes are intrinsically dominated by the phase relationships among the relevant electromagnetic fields, including the phase of nonlinear polarization produced in them. If one can arbitrarily manipulate these phase relationships at a variety of desired interaction lengths, direct and highly designable manipulations for the nonlinear optical phenomenon could be achieved. Here, we report a proof-of-principle experiment in which a high-order Raman-resonant four-wave-mixing process is used as a representative nonlinear optical process and is tailored to a variety of targets by implementing such arbitrary manipulations of the phase relationships in the nonlinear optical process. We show that the output energy is accumulated to a specific, intentionally selected Raman mode on demand; and at the opposite extreme, we can also distribute the output energy equally over broad high-order Raman modes in the form of a frequency comb. This concept in nonlinear optical processes enables an attractive optical technology: a single-frequency tunable laser broadly covering the vacuum ultraviolet region, which will pave the way to frontiers in atomic-molecular-optical physics in the vacuum ultraviolet region.

Vacuum ultraviolet photoluminescence of NaMgF3:Sm and NaMgF3:Sm,Ce: energy levels of the lanthanides in NaMgF3:Ln compounds

The luminescence properties of NaMgF3:Sm and NaMgF3:Ce,Sm were studied in the vacuum ultraviolet spectral region. Excitation bands corresponding to the charge transfer processes F− → Sm3+, O2− → Sm3+, and O2− → Ce3+, and the energy transfer processes Ce3+ → Sm3+ and O2− → Sm3+, were observed. The energies of the Sm3+ charge transfer transitions and the crystal field split Ce3+ 4f 05d 1 transitions were used to construct a complete host referred binding energy diagram for the series of lanthanide-doped NaMgF3:Ln compounds. We demonstrate that the optical and luminescence properties predicted by the binding energy diagram are in good agreement with those predicted by the binding energy diagram constructed via the alternative impurity-informed method, and all available experimental data regarding the NaMgF3:Ln compounds. We demonstrate that NaMgF3:Ln compounds are model systems for the study of charge trapping phenomena and divalent lanthanide luminescence. Ultimately, we validate that the impurity-informed method can be used to establish the energy levels of lanthanides in fluoride systems.

Spectroscopic study of the 4f n−15d transitions of LaPO4 doped with Pr3+ or co-doped with Pr3+ and Gd3+ in the vacuum ultra violet region

The energy of f-d transitions depends on the crystalline field in which the lanthanide ion is inserted. Depending on the experimental setup, these transitions could occur at high energy, so several studies regarding theoretical data have been conducted. Here, we present the experimental determination of the energy of interconfigurational 4f n → 4f n−15d (f-d) transitions from Pr3+ ions to the lanthanum orthophosphate LaPO4 matrix; we have also determined the bandgap value for this host. The experiments were carried out at the Synchrotron setup of the Brazilian LNLS laboratory. Specifically, we synthesized LaPO4:Pr3+ and LaPO4:Pr3+/Gd3+ by the hydrothermal method under different pH conditions or by spray pyrolysis. The particles resulting from hydrothermal synthesis had different morphologies and the influence of pH value was showed: the reaction medium was controlled along the process, which changed the surface potential. On the basis of Raman spectroscopy and x-ray diffraction analyses, we found that the crystalline phase was monoclinic monazite for all the samples. We studied the 4f5d level and bandgap transitions at high energy by absorption analysis in the VUV range. The experimental results were 7.5 eV (LaPO4 bandgap) and 5 eV (4f n → 4f n−15d transition of the Pr3+ ion), which were close to the theoretical values reported in the literature for this ion and this matrix.

Multiphoton Resonance in Attosecond Transient Absorption

We present the theory and simulation of attosecond transient absorption in helium atoms under the single-active-electron approximation. This study investigates the attosecond dynamics of intrinsic atomic states that interact with a field comprising vacuum ultraviolet (VUV) and extreme ultraviolet (XUV) fields. The absorption spectrum of the helium atom is obtained from the response function, which is constructed by numerically solving the three-dimensional time-dependent Schrödinger equation. We observe a fine structure near the intrinsic atomic level, which is modulated with a 0.2 fs period. Based on high-order time-dependent perturbation theory, the frequency-dependent phase of the dipole response induced by the VUV and XUV fields is analytically obtained, and the fine structure is well explained by the phase difference. In addition, the absorption fringes are dependent on the chirp of the VUV field. This study investigates the features of the attosecond transient absorption in the VUV region, which may have valuable applications in the study of ultrafast phenomena in atoms, molecules, and solids.

Effect of erbium concentration on the Verdet constant dispersion of LiY1.0-xErxF4 single crystal

The dispersion of the Verdet constant of LiY1.0-xErxF4 crystals was evaluated from 190 nm to 500 nm for different doping concentrations of Er ions. A 15% doping concentration yielded a high Verdet constant of 54.5 rad/(T·m) at 193 nm. This value can be explained by the contribution of the diamagnetic term associated with LiYF4 and the paramagnetic term of the Er ions. Although the LiYF4 crystal yielded a lower value of −36.6 rad/(T·m) at 193 nm from Er-doped LiYF4, it can be used in the vacuum–ultraviolet region because of its high transmittance at wavelengths longer than 120 nm.

A versatile vacuum ultraviolet ion source for reduced pressure bipolar chemical ionization mass spectrometry

Abstract. We present the development of a chemical ionization mass spectrometer ion source specifically designed for in situ measurements of trace gases in the upper troposphere and lower stratosphere. The ion source utilizes a commercially available photoionization krypton lamp, primarily emitting photons in the vacuum ultraviolet (VUV) region at wavelengths of 124 and 117 nm (corresponding to energies of 10 and 10.6 eV, respectively), coupled to a commercially available Vocus proton transfer reaction mass spectrometer. The VUV ion source can produce both negative and positive reagent ions; however, here we primarily focus on generating iodide anions (I−). The instrument's drift tube (also known as ion–molecule reactor) operates at pressures between 2 and 10 mbar, which facilitates ambient sampling at atmospheric pressures as low as 50 mbar. The low operating pressure reduces secondary ion chemistry that can occur in iodide chemical ionization mass spectrometry (CIMS). It also allows the addition of water vapor to the drift tube to exceed typical ambient humidity by more than 1 order of magnitude, significantly reducing ambient humidity dependence of sensitivities. An additional benefit of this ion source and drift tube is a 10- to 100-fold reduction in nitrogen consumed during operation relative to standard I− ion sources, resulting in significantly reduced instrument weight and operational costs. In iodide mode, sensitivities of 76 cps ppt−1 for nitric acid, 35 cps ppt−1 for Br2 and 8.9 cps ppt−1 for Cl2 were achieved. Lastly, we demonstrate that this ion source can generate benzene (C6H6+) and ammonium (NH4+) reagent ions to expand the number of detected atmospheric trace gases.

Optical characteristics of Tl+ centers in CsCaCl3, KCaCl3, and CsCl crystals

We have investigated the absorption, luminescence, and excitation spectra of the Tl+ centers in CsCaCl3:Tl+, KCaCl3:Tl+, and CsCl:Tl+ crystals in the energy region up to the vacuum ultraviolet region. The A, B, and C absorption bands attributed to the intra-ionic transitions were observed in the transparent energy region below their respective fundamental absorption edge. The parameters characterizing the Tl+ centers were estimated by the energy positions of the A, B, and C absorption bands and the absorption intensity ratio of the C to A bands. These values are consistent with those of the Tl+ centers in other ionic chloride crystals. The luminescence bands attributed to the radiative transitions from several relaxed excited states were observed even under excitation of the A absorption band. Although the intensities of the luminescence bands change with an increase in temperature from low temperature, the total integrated luminescence intensity remained almost constant. The temperature dependence of the luminescence intensity can be explained by the thermally activated non-radiative transitions among the relaxed excited states and the radiative transitions from them. By including the Tl+ centers in alkali and ammonium chloride crystals, the features of the Tl+ centers in the resulting chloride compound crystals have been comprehensively discussed regardless of the different chloride-ionic configurations around the Tl+ ions.

Vacuum ultraviolet photoconductive detector based on anatase TiO2 thin film deposited on SiO2 substrate

We report on titanium dioxide (TiO2) thin film deposited on a quartz (SiO2) substrate as an improved photoconductive detector for radiation below 200 nm wavelength (vacuum ultraviolet region, VUV). The crystalline film has an anatase phase and an average crystallite size of 10.6 nm. It has a transmission edge at 322 nm and an optical band gap of 3.18 ± 0.02 eV. Under VUV illumination, the TiO2 photoconductive detector exhibited a photocurrent of 5.3 mA at an applied bias voltage of 100 V. The dark current measured without VUV illumination and at the same bias voltage is 8.8 × 10−6 mA, which is 6 orders of magnitude smaller compared to the photocurrent. The photoconductive VUV detector based on TiO2 thin film provides a means of directly measuring VUV radiation compared to detection via the photoluminescence of a scintillator.