Metastable Atoms Research Articles

Helium atom line-intensity ratios as an integrated diagnostic tool for low-pressure and low-density plasmas

The intensity ratios between specific pairs of helium atom (HeI) emission lines are functions of the electron temperature (Te) and density (ne), and these functions have been used for the analysis of Te and ne in various types of discharge plasma. We applied this method to a low-density (ne < 1018 m−3) plasma, where the procedure of the analysis is markedly different from that of higher-density plasmas. The 21S and 23S metastable atom densities are affected by transport, making it practically necessary to set Te, ne, the metastable atom densities, and the optical escape factors, which represent the effect of photoexcitation, as unknown variables and determine them simultaneously. Conversely, the transport of metastable atoms can be evaluated from the analysis.

Two discharge modes of a repetitive nanosecond pulsed helium glow discharge under sub-atmospheric pressure in the repetition frequency range of 20 to 600 kHz

Two discharge modes, α and γ, of a repetitive nanosecond pulsed helium glow discharge at a gas pressure of 10 kPa in the repetition frequency range from 20 to 600 kHz are reported for the first time. The pulsed glow discharge is produced in a pair of parallel plate metal electrodes without insertion of dielectrics. The α mode discharge is volumetrically produced in the electrode gap at a low-repetition frequency, whereas the γ mode discharge is localized at the cathode surface at a high-repetition frequency. At high-repetition frequency, the time interval between voltage pulses is shorter than the lifetime of the afterglow produced by the preceding discharge. Then, the γ mode discharge is maintained by a large number of secondary electrons emitted from the cathode exposed to high-density ions and metastable helium atoms in the afterglow. In the α mode discharge with a low-repetition frequency operation, primary electrons due to gas ionization dominate the ionization process. Thus, a large discharge voltage is needed for the excitation of the α mode discharge. It is established that the bifurcation of α-γ discharge mode, accompanied by a decrease in the discharge voltage, occurs at the high-repetition frequency of ∼120 kHz.

Dirac Cone Spin Polarization of Graphene by Magnetic Insulator Proximity Effect Probed with Outermost Surface Spin Spectroscopy

AbstractThe effects of the proximity contact with magnetic insulator on the spin‐dependent electronic structure of graphene are explored for the heterostructure of single‐layer graphene (SLG) and yttrium iron garnet Y3Fe5O12 (YIG) by means of outermost surface spin spectroscopy using a spin‐polarized metastable He atom beam. In the SLG/YIG heterostructure, the Dirac cone electrons of graphene are found to be negatively spin polarized in parallel to the minority spins of YIG with a large polarization degree, without giving rise to significant changes in the π band structure. Theoretical calculations reveal the electrostatic interfacial interactions providing a strong physical adhesion and the indirect exchange interaction causing the spin polarization of SLG at the interface with YIG. The Hall device of the SLG/YIG heterostructure exhibits a nonlinear Hall resistance attributable to the anomalous Hall effect, implying the extrinsic spin–orbit interactions as another manifestation of the proximity effect.

Calculation of the Ionization Coefficient in the Townsend Discharge in the Mixture of Argon and Mercury Vapors with Temperature-Dependent Composition

For a hybrid model of the low-current discharge considering, along with direct ionization of the mixture components by electrons, the Penning ionization of mercury atoms by metastable argon atoms, the ionization coefficient in the argon–mercury mixture used in illuminating lamps is calculated. The analytical approximation formula describing the dependence of the ionization coefficient of the mixture on the reduced electric field strength and temperature is obtained for sufficiently wide ranges of their variations, and its accuracy is estimated. It is demonstrated that the discharge ignition voltage calculated using this formula is in agreement with the results of simulation and the available experimental data.

Low energy collisions of spin-polarized metastable argon atoms with ground state argon atoms

The collision between a spin-polarized metastable argon atom in Ar* (3p54s, 3P2, M = +2) state slightly decelerated by the Zeeman slower-laser technique and a co-propagating thermal ground state argon atom Ar (3p6, 1S0), both merged from the same supersonic beam, but coming through adjacent slots of a rotating disk, is investigated at the center of mass energies ranging from 1 to 10 meV. The duration of the laser pulse synchronised with the disk allows the tuning of the relative velocity and thus the collision energy. At these sub-thermal energies, the ‘resonant metastability transfer’ signal is too small to be evidenced. The explored energy range requires using indiscernibility amplitudes for identical isotopes to have a correct interpretation of the experimental results. Nevertheless, excitation transfers are expected to increase significantly at much lower energies as suggested by previous theoretical predictions of potentials 2g(3P2) and 2u(3P2). Limits at ultra-low collisional energies of the order of 1 mK (0.086 μeV) or less, where gigantic elastic cross sections are expected, will also be discussed. The experimental method is versatile and could be applied using different isotopes of Argon like 36Ar combined with 40Ar, as well as other rare gases among which Krypton should be of great interest thanks to the available numerous isotopes present in a natural gas mixture.

The influence of gas pressure on E↔H mode transition in argon inductively coupled plasmas

Considering the gas pressure and radio frequency power change, the mode transition of E↔H were investigated in inductively coupled plasmas. It can be found that the transition power has almost the same trend decreasing with gas pressure, whether it is in H mode or E mode. However, the transition density increases slowly with gas pressure from E to H mode. The transition points of E to H mode can be understood by the propagation of electromagnetic wave in the plasma, while the H to E should be illustrated by the electric field strength. Moreover, the electron density, increasing with the pressure and power, can be attributed to the multiple ionization, which changes the energy loss per electron-ion pair created. In addition, the optical emission characteristics in E and H mode is also shown. The line ratio of I750.4 and I811.5, taken as a proxy of the density of metastable state atoms, was used to illustrate the hysteresis. The 750.4 nm line intensity, which has almost the same trend with the 811.5 nm line intensity in H mode, both of them increases with power but decreases with gas pressure. The line ratio of 811.5/750.4 has a different change rule in E mode and H mode, and at the transition point of H to E, it can be one significant factor that results in the hysteresis as the gas pressure change. And compared with the 811.5 nm intensity, it seems like a similar change rule with RF power in E mode. Moreover, some emitted lines with lower rate constants don’t turn up in E mode, while can be seen in H mode because the excited state atom density increasing with the electron density.

Soft Argon-Propane Dielectric Barrier Discharge Ionization.

Dielectric barrier discharges (DBDs) have been used as soft ionization sources (DBDI) for organic mass spectrometry (DBDI-MS) for approximately ten years. Helium-based DBDI is often used because of its good ionization efficiency, low ignition voltage, and homogeneous plasma conditions. Argon needs much higher ignition voltages than helium when the same discharge geometry is used. A filamentary plasma, which is not suitable for soft ionization, may be produced instead of a homogeneous plasma. This difference results in N2, present in helium and argon as an impurity, being Penning-ionized by helium but not by metastable argon atoms. In this study, a mixture of argon and propane (C3H8) was used as an ignition aid to decrease the ignition and working voltages, because propane can be Penning-ionized by argon metastables. This approach leads to homogeneous argon-based DBDI. Furthermore, operating DBDI in an open environment assumes that many uncharged analyte molecules do not interact with the reactant ions. To overcome this disadvantage, we present a novel approach, where the analyte is introduced in an enclosed system through the discharge capillary itself. This nonambient DBDI-MS arrangement is presented and characterized and could advance the novel connection of DBDI with analytical separation techniques such as gas chromatography (GC) and high-pressure liquid chromatography (HPLC) in the near future.

Doppler-free spectroscopy of metastable Sr atoms using a hollow cathode lamp.

We report on the demonstration of Doppler-free spectroscopy of metastable Sr atoms using a hollow cathode lamp (HCL). We employed a custom Sr HCL, which is filled with a mixture of 0.5 Torr Ne and 0.5 Torr Xe as a buffer gas to suppress velocity changing collisions and increase the populations in all of the (5s5p)3PJ(J=0,1,2) metastable states. We performed frequency modulation spectroscopy for the (5s5p)3P0-(5s6s)3S1, (5s5p)3P1-(5s6s)3S1, (5s5p)3P2-(5s5d)3D2, and (5s5p)3P2-(5s5d)3D3 transitions with sufficient signal-to-noise ratios for laser frequency stabilization. We also observed the hyperfine transitions of (5s5p)3P2-(5s5d)3D3 of Sr87. This method would greatly facilitate laser cooling of Sr.

Ionization Mechanism of Positive-Ion Nitrogen Direct Analysis in Real Time.

Nitrogen can be an inexpensive alternative to helium used by direct analysis in real time (DART), especially in consideration of the looming helium shortage. Therefore, the ionization mechanism of positive-ion N2 DART has been systematically investigated. Our experiments suggest that a range of metastable nitrogen species with a variety of internal energies existed and all of them were less energetic than metastable helium atoms. However, compounds with ionization energies (IE) equal to or lower than 10.2 eV (all organic compounds except the extremely small ones) can be efficiently ionized. Because N2 DART was unable to efficiently ionize ambient moisture and common organic solvents such as methanol and acetonitrile, the most important ionization mechanism was direct Penning ionization followed by self-protonation of polar compounds generating [M+H]+ ions. On the other hand, N2 DART was able to efficiently ionize ammonia, which was beneficial in the ionization of hydrogen-bonding compounds with proton affinities (PA) weaker than ammonia generating [M+NH4]+ ions and large PAHs generating [M+H]+ ions through proton transfer. N2 DART was also able to efficiently ionize NO, which led to the ionization of nonpolar compounds such as alkanes and small aromatics generating [M-(2m+1)H]+ (m=0,1…) ions. Lastly, metastable nitrogen species was also able to produce oxygen atoms, which resulted in increased oxygen adducts as the polarity of organic compounds decreased. In comparison with He DART, N2 DART was approximately one order of magnitude less sensitive in generating [M+H]+ ions, but could be more sensitive in generating [M+NH4]+ ions. Graphical Abstract ᅟ.

Kinetic analysis of rare gas metastable production and optically pumped Xe lasers

Optically pumped all-rare-gas lasers use metastable rare gas atoms as the lasing species in mixtures with He or Ar buffer gas. The metastables are generated in a glow discharge, and we report model calculations for the optimal production of Ne*, Ar*, Kr* and Xe*. Discharge efficiency was estimated by solving the Boltzmann equation.Laser efficiency, gain and output power of the CW optically pumped Xe laser were assessed as functions of heavier rare gas content, pressure, optical pump intensity and the optical path length. It was found that, for efficient operation the heavier rare gas content has to be of the order of one percent or less, and the total pressure—in the range 0.3–1.5 atm. Output power and specific discharge power increase approximately linearly with pump intensity over the output range from 300–500 W cm−2. Ternary mixtures Xe:Ar:He were found to be the most promising. Total laser efficiency was found to be nearly the same for pumping the 2p8 or 2p9 state, reaching 61%–70% for a pump intensity of ~720 W cm−2 when the Xe fraction was in the range 0.001 ÷ 0.01 and Ar fraction—0.1 ÷ 0.5. However, when the 2p8 state was pumped, the maximum total efficiency occurred at larger pressures than for pumping of the 2p9 state. The discharge power density required to sustain a sufficient Xe* number density was in the range of tens of watts per cubic centimeter for 50% Ar in the mixture.

Emission spectral diagnosis of argon-helium plasma produced by radio frequency capacitive discharge

Optically pumped metastable rare-gas laser (OPRGL) have been proposed to overcome the shortcomings of diode-pumped alkali-vapor laser in the recent years. The OPRGL promises to realize high-scale output. But how to achieve enough particle density of metastable atoms is still an open problem. Usually, plasma produced by discharge serves as a gain medium of the OPRGL. Here in this paper, we are to reveal the effects of different discharge parameters on the plasma properties, such as particle density of metastable argon atoms. Gas discharge at a radio frequency of 13.56 MHz is adopted to excite argon atoms. Emission spectrum is employed to study argon and helium radio frequency discharge of optically pumped argon laser at high pressure, different powers of discharge and various content of argon. Gas temperature is obtained by analyzing rotational spectrum (A2∑+ → X2Π) of OH radical generated by residual water vapor and comparing simulated spectrum with the measured spectrum. The electronic excitation temperature relating to electron temperature is obtained by the method of Boltzmann's plot. Stark broadening of the spectrum is used to determine the electron density. The results show that gas temperature rises slightly with the increase of pressure and varies little with content and discharge power changing. The electronic excitation temperature increases with the decrease of pressure evidently and decreases slightly with the increase of content. The electron density is on the order of 1015 cm-3 under various conditions controlled by us. Long time discharge test reveals that residual water vapor can lead to the decrease of electron temperature, and thus reducing the yield of argon metastable state. In conclusion, considering that the higher gas temperature can improve the collision relaxation rate of helium and argon, and the higher electron temperature can improve the rate of production of argon metastable state. Thus a proposal is put forward that appropriately heating gas and reducing gas pressure can obtain higher particle density of metastable argon. Furthermore, It can be found from these results that heating and cleaning the gas during discharge may be candidate methods to obtain and sustain the higher particle density in the plasma.

Triple Differential Cross-Sections for Ionization of H(3d) by Incident Electron

Triple differential cross sections (TDCS) are estimated for the ionization of metastable 3d-state hydrogen atoms by electron at 250 eV for various kinematic conditions pursuing a multiple scattering theory. The present new results are compared with the theoretical results of hydrogenic different metastable states as well as the hydrogenic ground state experimental data. Obtained new finding results are in good qualitative agreement with those of compared theories. The present results give an immense opportunity for experimental trial in the field of ionization problems.

Time-resolved study of the electron temperature and number density of argon metastable atoms in argon-based dielectric barrier discharges

A combination of optical emission spectroscopy and collisional-radiative modelling is used to determine the time-resolved electron temperature (assuming Maxwellian electron energy distribution function) and number density of Ar 1s states in atmospheric pressure Ar-based dielectric barrier discharges in presence of either NH3 or ethyl lactate. In both cases, Te values were higher early in the discharge cycle (around 0.8 eV), decreased down to about 0.35 eV with the rise of the discharge current, and then remained fairly constant during discharge extinction. The opposite behaviour was observed for Ar 1s states, with cycle-averaged values in the 1017 m−3 range. Based on these findings, a link was established between the discharge ionization kinetics (and thus the electron temperature) and the number density of Ar 1s state.

Physical proprieties of DC glow discharges in a neon–argon gas mixture

This paper reports a detailed study of 90% Ne – 10% Ar gas mixture DC glow discharge at low pressure, wherein 15 chemical reactions are considered. The second-order fluid model is used. The parameters of particle transport and their rate coefficients strictly depend on mean electron energy. In the framework of the local electric field approximation, we have developed an analytical expression of the drift velocity of positive argon ions in a neon gas [Formula: see text], which is in good agreement with the experimental results, and serves to give best results than the results obtained using [Formula: see text] that exist in the literature. The results show that the argon ion density is more important than the neon ion density despite the presence of more constant background neon gas density in the mixture. The current density reaches 0.1729 mA/cm2 for 250 V applied potential under 2 Torr pressure in a gas mixture. The spatio-temporal evolution of both electric and energetic characteristics, as well as their spatial distribution in the steady state, are shown and discussed. The maximum value of the neon metastable atom density is 4.54957 × 108 cm−3, and for argon metastable atom density is 5.4689 × 108 cm−3. The model is verified experimentally and theoretically in the particular case.

Simple Closed-Form Expression for Penning Reaction Rate Coefficients for Cold Molecular Collisions by Non-Hermitian Time-Independent Adiabatic Scattering Theory.

We present a simple expression and its derivation for reaction rate coefficients for cold anisotropic collision experiments based on adiabatic variational theory and time-independent non-Hermitian scattering theory. We demonstrate that only the eigenenergies of the resulting one-dimensional Schrödinger equation for different complex adiabats are required. The expression is applied to calculate the Penning ionization rate coefficients of an excited metastable helium atom with molecular hydrogen in an energy range spanning from hundreds of kelvins down to the millikelvin regime. Except for trivial quantities like the masses of the nuclei and the bond length of the diatomic molecule participating in the collision, one needs as input data only the complex potential energy surface (CPES). In calculations, we used recently obtained ab initio CPES by D. Bhattacharya et al. ( J. Chem. Theory Comput. 2017 , 13 , 1682 - 1690 ) without fitting parameters. The results show good accord with current measurements ( Nat. Phys. 2017 , 13 , 35 - 38 ).

Study of Gaseous Sample Ionization by Excited Particles Formed in Glow Discharge Using High-Resolution Orthogonal Acceleration Time-of-Flight Mass Spectrometer

The experimental results of a mass spectral analysis of volatile organic compounds in a gaseous sample, obtained using an original design of an ion source based on the Penning ionization of a gas sample by excited metastable inert gas atoms, are presented. Using ANSYS software, a gas-dynamic simulation of reagent gas flow from discharge zone to ionization region was carried out to analyze the effect of gas flow profile on the transport of metastable atoms and ionization efficiency. The n-octane and toluene samples diluted with helium at 100 ppb mole concentrations were used for our experiments. The resulting mass spectra of n-octane and toluene samples containe far more intensive molecular ions in comparison to n-octane and toluene electron ionization mass spectra from the NIST database. The sensitivity of 5 ions per 1 pg and 130 ions per 1 pg was achieved for n-octane and toluene molecular ions using the developed ion source combined with our mass spectrometer. The corresponding detection limits are 2.3 pg s–1 for n-octane molecular ions and 0.08 pg s–1 for toluene molecular ions. The detection limit for the reported ion source was considered theoretically.

Measurements and kinetic modeling of atomic species in fuel-oxidizer mixtures excited by a repetitive nanosecond pulse discharge

This work presents the results of number density measurements of metastable Ar atoms and ground state H atoms in diluted mixtures of H2 and O2 with Ar, as well as ground state O atoms in diluted H2–O2–Ar, CH4–O2–Ar, C3H8–O2–Ar, and C2H4–O2–Ar mixtures excited by a repetitive nanosecond pulse discharge. The measurements have been made in a nanosecond pulse, double dielectric barrier discharge plasma sustained in a flow reactor between two plane electrodes encapsulated within dielectric material, at an initial temperature of 500 K and pressures ranging from 300 Torr to 700 Torr. Metastable Ar atom number density distribution in the afterglow is measured by tunable diode laser absorption spectroscopy, and used to characterize plasma uniformity. Temperature rise in the reacting flow is measured by Rayleigh scattering. H atom and O atom number densities are measured by two-photon absorption laser induced fluorescence. The results are compared with kinetic model predictions, showing good agreement, with the exception of extremely lean mixtures. O atoms and H atoms in the plasma are produced mainly during quenching of electronically excited Ar atoms generated by electron impact. In H2–Ar and O2–Ar mixtures, the atoms decay by three-body recombination. In H2–O2–Ar, CH4–O2–Ar, and C3H8–O2–Ar mixtures, O atoms decay in a reaction with OH, generated during H atom reaction with HO2, with the latter produced by three-body H atom recombination with O2. The net process of O atom decay is O + H → OH, such that the decay rate is controlled by the amount of H atoms produced in the discharge. In extra lean mixtures of propane and ethylene with O2–Ar the model underpredicts the O atom decay rate. At these conditions, when fuel is completely oxidized by the end of the discharge burst, the net process of O atom decay, O + O → O2, becomes nearly independent of H atom number density. Lack of agreement with the data at these conditions is likely due to diffusion of H atoms from the partially oxidized regions near the side walls of the reactor into the plasma. Although significant fractions of hydrogen and hydrocarbon fuels are oxidized by O atoms produced in the plasma, chain branching remains a minor effect at these relatively low temperature conditions.

Electron-ion recombination in low temperature hydrogen/deuterium plasma

The stationary afterglow with cavity ring down spectrometer (SA-CRDS) was used to study the recombination of H3 + , H2 D+ , HD2 + and D3 + ions with electrons in low temperature (77–300 K) plasmas in He/Ar/H2 /D2 gas mixtures. By measuring effective recombination rate coefficients (α eff ) in plasma with mixtures of ions and their dependences on temperature and partial densities of He, H2 and D2 , α eff (T , [He],[H2 ],[D2 ]), we determined binary (α binH3 , α binH2D , α binHD2 , α binD3 ) and ternary (K H3 , K H2D , K HD2 , K D3 ) recombination rate coefficients for H3 + , H2 D+ , HD2 + and D3 + ions. For all four ions we observed very efficient He assisted ternary recombination which is comparable with binary recombination already at [He] =1 × 1017 cm−3 . The removal of excited particles in afterglow plasma was monitored to obtain the plasma thermalisation rate at given experimental conditions. The inferred deexcitation rates for reaction of helium metastable atoms with D2 are k D2 (300 K)=(2.1 ± 0.3) × 10−10 cm3 s−1 and k D2 (140 K)=(1.3 ± 0.3) × 10−10 cm3 s−1 .

Long-Range Interactions for Hydrogen: 6P–1S and 6P–2S Systems

The collisional shift of a transition constitutes an important systematic effect in high-precision spectroscopy. Accurate values for van der Waals interaction coefficients are required in order to evaluate the distance-dependent frequency shift. We here consider the interaction of excited hydrogen 6 P atoms with metastable atoms (in the 2 S state), in order to explore the influence of quasi-degenerate 2 P and 6 S states on the dipole-dipole interaction. The motivation for the calculation is given by planned high-precision measurements of the transition. Due to the presence of quasi-degenerate levels, one can use the non-retarded approximation for the interaction terms over wide distance ranges.

Laser absorption spectroscopy for measurement of He metastable atoms of a microhollow cathode plasma

We generated a 0.3-mm-diameter DC, hollow-cathode helium discharge in a gas pressure range of 10–80 kPa. In discharge plasmas, we measured position-dependent laser absorption spectra for helium 23S1–23P0 transition with a spatial resolution of 55 µm. From the results of the analysis of the measured spectra using Voigt functions and including both the Doppler and collision broadening, we produced two-dimensional maps of the metastable 23S1 atomic densities and gas temperatures of the plasmas. We found that, at all pressures, the gas temperatures were approximately uniform in space with values in the range of 400–1500 K and the 23S1 atomic densities were ∼1019 m−3. We also found that the two-dimensional density distribution profiles became ring-shaped at high gas pressures, which is qualitatively consistent with the two-dimensional fluid simulation results.