Metastable Density Research Articles

Impact of front contact layers on performance of Cu(In,Ga)Se2 solar cells in relaxed and metastable states

AbstractWe studied the impacts of front contact layers composed of transparent conducting oxide (TCO) and transparent oxide semiconductor (TOS) layers on the performance of Cu(In,Ga)Se2 (CIGS) solar cells with glass/Mo/CIGS/CdS/TOS/TCO in relaxed and metastable states. After annealing under illumination, the CIGS solar cells with KF and NaF postdeposition treatments exhibited metastable increases in open‐circuit voltage, fill factor, and the resulting conversion efficiency with a metastable decrease in short‐circuit current density. These are partly attributed to an increase in metastable acceptor density in the CIGS layers, being stable for a day even at room temperature, with a reduced space charge width. We found that the net acceptor density evaluated by capacitance‐voltage measurements largely varied depending on the TOS/TCO layers, whereas the open‐circuit voltage was identical. On the other hand, no significant differences in both the net acceptor density and open‐circuit voltage were observed regardless of the TOS/TCO layers in the relaxed state produced by annealing in the dark. The results suggest that the CdS/CIGS heterojunction can no longer be treated as an n+/p junction in the metastable state and that the evaluated acceptor density was apparent values with large difference originating from different potential distribution in the CdS layer, which is related to the TOS/CdS and TCO/CdS junctions. In addition, the TOS/TCO layers largely affected the short‐circuit current density owing to their optical constants and film thicknesses. The presented results highlight the importance of the design of CdS/TOS/TCO layers in solar cells operated in metastable states.

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.

Photo-detachment of negative ions in Ar-CO2 dc discharge employing Langmuir probe

The electronegativity of the Ar−CO2 gas mixture was investigated, and the total relative negative oxygen ion density O2− + O− in the bulk of a dc discharge has been determined employing Langmuir probe assisted laser photo-detachment. The relative electron density and absolute temperature were obtained for the mixture at discharge powers between 200 and 3000 mW and pressures between 0.2 and 0.6 mbar, employing the collisional radiative model for several Ar gas mixtures. The absolute metastable number density for 1s3 and 1s5 levels was measured, and both showed an increasing trend as a function of pressure and power. The absolute number density of the 1s5 level was found to be higher than that of the 1s3 level. Electronegativity was found to decrease as a function of power and as a function of the increasing Ar percentage in the gas mixture.

Measurements of fireball onset

Laser-based measurements of the characteristic features of fireball onset and stabilization in response to a stepped voltage applied to an anode immersed in a low pressure (100 mTorr) helium afterglow are reported. These include spatial and temporal evolution of metastable species, electron density, and electric field magnitude as measured by planar laser induced fluorescence, laser-collision induced fluorescence, and laser-induced fluorescence-dip spectroscopy, respectively. These measurements are found to be in qualitative agreement with recent particle-in-cell simulations and theoretical models [Scheiner et al., Phys. Plasmas 24, 113520 (2017)]. The measurements validate the simulations and models in which fireball onset was predicted to follow from the trapping of electrons born from electron impact ionization within a potential well created by a buildup of ions in the sheath. The experimental measurements also demonstrate transient features following the onset that were not present in previous simulations. New simulation results are presented which demonstrate that these features are associated with the abruptness of the voltage step used to initiate fireball onset. An abrupt step in the anode bias causes rapid displacement of ions and an associated plasma potential response following the sheath and fireball expansion.

Metastable Ar(1s5) density dependence on pressure and argon-helium mixture in a high pressure radio frequency dielectric barrier discharge

Simulations of an α-mode radio frequency dielectric barrier discharge are performed for varying mixtures of argon and helium at pressures ranging from 200 to 500 Torr using both zero and one-dimensional models. Metastable densities are analyzed as a function of argon-helium mixture and pressure to determine the optimal conditions, maximizing metastable density for use in an optically pumped rare gas laser. Argon fractions corresponding to the peak metastable densities are found to be pressure dependent, shifting from approximately 15% Ar in He at 200 Torr to 10% at 500 Torr. A decrease in metastable density is observed as pressure is increased due to a diminution in the reduced electric field and a quadratic increase in metastable loss rates through Ar2* formation. A zero-dimensional effective direct current model of the dielectric barrier discharge is implemented, showing agreement with the trends predicted by the one-dimensional fluid model in the bulk plasma.

Inactivation of B. subtilis spores by low pressure plasma—influence of optical filters and photon/particle fluxes on the inactivation efficiency

Inactivation experiments were performed with Bacillus subtilis spores in a low pressure double inductively coupled plasma (DICP) system. Argon, nitrogen and oxygen at 5 Pa were used as feed gas to change the emission spectrum in the range of 100 nm to 400 nm, as well as between radical and metastable densities. Optical filters were applied, to block particles and selected wavelengths from the spores. By determining absolute photon fluxes, the sporicidal efficiency of various wavelength ranges was evaluated. The results showed good agreement with other plasma experiments, as well as with monochromatic light inactivation experiments from a synchrotron. The findings indicated that the inactivation rate constants of broadband plasma emission and monochromatic light were identical, and that no synergistic effect exists. Furthermore, the influence of radicals, ions and metastables on the inactivation efficiency was of minor importance in the set-up used, and radiation was the main reason for spore inactivation.

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.

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.

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.

Production of Ar and Xe metastables in rare gas mixtures in a dielectric barrier discharge

Optically pumped all-rare-gas lasers (OPRGL) utilize metastable atoms of the heavier rare gases as lasing species. The required number density of metastables for efficient laser operation is 1012–1013 cm−3 in He buffer gas at pressures in the 400–1000 Torr range. Such metastable densities are easily produced in a nanosecond pulsed discharge, even at pressures larger than atmospheric, but problems appear when one is trying to achieve continuous production. The reason for low production efficiency in many types of continuous discharge at atmospheric pressure is the low value of the E/N parameter (<5–6 Td). In the present work, we have examined the possibility of using a dielectric barrier discharge (DBD) to provide near continuous, high densities of Ar and Xe metastables. Experiments were performed using a 20 kHz DBD in binary Ar and Xe mixtures with He, and in ternary Ar:Xe:He mixtures at pressures up to 1 atmosphere. Concentrations were measured by means of tunable diode laser absorption spectroscopy. Time-averaged [Ar(1s5)] and [Xe(1s5)] number densities on the order of 1012 cm−3 were readily achieved. The temporal behavior of [Xe(1s5)] throughout the DBD cycle was observed. The results demonstrate the feasibility of using DBDs for OPRGL development. Spectral scans over the absorption lines were also used to examine the pressure broadening coefficients for the 912.3 nm Ar line in He and the Xe 904.5 nm line in Ne and He.

An advanced time-dependent collisional-radiative model of helium plasma discharges

A new spatially averaged time-dependent collisional-radiative model for helium plasmas, coupled to the electron Boltzmann equation (EBE), has been developed. Its main novelties are: (1) full time dependence for both the multi-species kinetics and the EBE. It is shown that this is necessary to correctly simulate discharges where the parameters vary on nanoseconds-microsecond timescales. (2) All electron processes are accounted for accurately. In particular, for the various ionization and recombination processes, free electrons are added or removed at the appropriate energy, with the appropriate interpolation on the energy grid. (3) The energy dependence of the electron loss by ambipolar diffusion is taken into account approximately. (4) All of the processes which are known to be important in helium discharges for pressure Torr are included, and 42 energy levels up to n = 6, where n is the main quantum number, are taken into account. Atomic and molecular ions, as well as excimers, are also included. (5) The gas temperature is calculated self-consistently. The model is validated through comparisons with known numerical steady-state results of Santos et al (2014 J. Phys. D. 47 265201) which they compared to their experimental results, and good agreement is obtained for their measured quantities. It is then applied to post-discharge decay cases with very short power decay times. The time evolution of the population densities and reaction rates are analyzed in detail with emphasis on the observed large increase of the metastable density.

Measurement of Ar resonance and metastable level number densities in argon containing plasmas

The resonance and metastable level number densities of argon are determined by means of the branching fraction method in an inductively coupled plasma at 5 Pa and 10 Pa in argon with admixture of hydrogen, nitrogen and oxygen. The densities are compared to laser absorption spectroscopy measurements to evaluate the reliability of the branching fraction method and its limitations. The results are in good agreement and the use of a compact, low cost, low resolution spectrometer ( = 1.3 nm) is sufficient to reliably determine the first four excited states of argon in argon-hydrogen and argon-oxygen mixtures. The addition of nitrogen results in unreliable densities, as the observed argon lines overlap with emission of the N transition.

Fluid modeling of plasma dynamics in pulsed RF capacitive glow discharges in low pressure argon

Based on the drift-diffusive approximation, one-dimensional fluid modeling is carried out for the pulsed RF capacitive glow discharges in low pressure argon. Investigated are the effects of various discharge parameters, such as the duty cycle ratio and frequency of the pulsed modulation, and the material properties of the electrode, on the plasma characteristics such as the electron recombination rate, during both the initial and the steady state phases of the discharge. The modeling results show that, after switching off the applied voltage during the pulsed modulation of the RF discharge, the electron density increases first and then decreases. This phenomenon is particularly pronounced before the discharge reaches steady state. Meanwhile, independent of whether the discharge has reached steady state or not, right after the applied voltage is switched on during each modulation period, the electron and ion densities and the metastable argon atom density, as well as their generation rate, experience a time delay (phase lag) with respect to the applied voltage. The results also show that, at the initial phase of the pulsed modulation, during the steady state discharge, the electron temperature in the center of the bulk plasma is almost not affected by the applied voltage, or by the material properties of the electrode such as the secondary electron emission rate. The electron density, however, does increase with these parameters, resulting in increased power density dissipation of the plasma. On the other hand, at fixed applied voltage, the central electron temperature of the bulk plasma is reduced by increasing several parameters, including the modulation duty ratio, the distance between two electrodes, and the modulation frequency, as well as the electron recombination rate due to different choices of the electrode material. This eventually leads to a reduction of the dissipated power density in the plasma. In particular, with the increase of the modulation duty ratio, the distance between electrodes, or the RF modulation frequency, the electron temperature decays slower after switching off the applied voltage within the modulation period. All the above studies are also accompanied by a systematic investigation of the temporal and spatial distributions of the electron energy conversion during the pulsed RF discharge.

Modeling of a DC glow discharge in a neon–xenon gas mixture at low pressure and with metastable atom densities

The physical properties of Ne–Xe DC glow discharges at low pressure are reported for a gap length of 1 cm for the first time in the literature. The model deals specifically with the first three moments of Boltzmann’s equation and includes the radiation processes and metastable atom densities. The spatio-temporal distributions of the electron and neon and xenon ion densities, the neon and xenon metastable atom densities, the electric potential and the electric field as well as the mean electron energy are presented at 1.5 Torr and 250 V. The current–voltage characteristic is shown at 3 Torr, and it is compared with previous work for pure neon gas. The model is validated theoretically and experimentally in the case of pure gas.

Role of Ag additives on light-induced metastable defects in a Se–In glassy system

The paper reports the role of Ag additives on light induced metastable defects in Se–In glassy alloys using a well-known thermally stimulated current (TSC) technique. Amorphous thin films of Se90In10−xAgx (x=0, 2, 4, 8) were prepared by thermal evaporation. Measurements were made in the given thin films prior to and after exposing amorphous thin films to white light for different exposure times (0–1.5hrs). The density of light induced metastable defects increases with exposure time, and the fractional increase in light induced metastable defect density decreases as Ag concentration increases.

Influence of nanoparticle formation on the time and the space resolved metastable density in argon-acetylene plasmas

Different diagnostic techniques are used to monitor the dynamics of electrons and Ar*(1s5) metastable atoms in the active plasma phase and in the afterglow of a capacitively coupled radio-frequency (RF) discharge operated in different gas mixtures and at different input powers. Diode laser absorption at 772.38 nm is used to measure the time resolved density of Ar*(1s5) atoms in either continuous-wave mode or pulsed RF discharges with 100 Hz pulsing frequency. Simultaneously, microwave interferometry recorded the time dependence of the electron density. Different plasma conditions, namely: (1) pure argon, (2) argon +5.9% acetylene before nanoparticle formation, (3) argon +5.9% acetylene after dust particles have been formed and (4) argon with dust particles remaining in the plasma volume but without acetylene are studied. The measured steady-state Ar*(1s5) density in the middle of the reactor is several times larger in the dusty argon plasma than in the pure argon discharge for the same discharge powers. At the same time, the electron density is several times less in the dusty plasma. These changes are caused by dust formation: the electric field in the bulk plasma is enhanced and thus consequently the electron temperature increases. Laser induced fluorescence (LIF) is used to measure the time and space resolved Ar*(1s5) axial distribution. In the pure argon discharge, the axial Ar*(1s5) metastable distribution has a characteristic saddle-like shape with maxima in the region of the sheaths. With dust particles inside, the axial distribution changes dramatically with the maximum at the discharge mid-plane, revealing an α–γ′ transition. The spatial distribution and absolute density of metastable atoms are influenced by the formation of a void in the cloud of nanoparticles. Depending on the size of the void, the Ar*(1s5) density reduction inside the void is between 30% and 50%. The high Ar*(1s5) metastable density in the dusty plasma afterglow strongly influences the time variation of the electron density in the afterglow. The observed increase of the electron density in the afterglow of the Ar/acetylene/dust plasmas is explained by the Penning ionization of acetylene by Ar*(1s5) metastable atoms. The time evolution of the electron density in the Ar/dust plasmas reveals that the nowadays assumed rate coefficient for generation of electrons by pooling reaction of Ar* metastable atoms is highly overestimated.

Spatially resolved modeling and measurements of metastable argon atoms in argon-helium microplasmas

Microwave-driven plasmas operating near atmospheric pressure have been shown to be a promising technique for producing the high density of argon metastable atoms required for optically pumped rare gas laser systems. Stable microwave-driven plasmas can be generated at high pressures using microstrip-based resonator circuits. We present results from computational modeling and laser absorption measurements of argon metastable densities in such plasmas operating in argon-helium gas mixtures at pressures up to 300 Torr. The model and measurements resolve the plasma characteristics both perpendicular to the substrate surface and along the resonator length. The measurements qualitatively and in many aspects quantitatively confirm the accuracy of the model. The plasmas exhibit distinct behaviors depending on whether the operating gas is mostly argon or mostly helium. In high-argon plasmas, the metastable density has a large peak value but is confined very closely to the electrode surfaces as well as being reduced near the discharge gap itself. In contrast, metastable densities in high helium-fraction mixtures extend through most of the plasma. In all systems, increasing the power extends the region of metastable along the resonator length, while the extent away from the substrate surface remains approximately constant.

Low-pressure low-frequency inductive discharge with ferrite cores for large-scale plasma processing

Electrophysical characteristics of a low–frequency (100 kHz) low–pressure (10–100 Pa) argon inductive discharge with ferrite cores have been investigated for discharge currents of 1–50 A, discharge chamber diameter of 230 mm. The dependencies of electric field strength on the argon pressure and discharge current were measured. Radial profiles of electron density and temperature were determined with double electric probes. Experimental results were compared with numerical results obtained by a self-consistent kinetic model of the low-frequency ICP, based on the simultaneous solution of a non-local Boltzmann equation for electron energy distribution function and balance equations for the metastable argon atoms density and gas temperature. Comparison of numerical and experimental results is presented.

On the E-H transition in inductively coupled radio frequency oxygen plasmas: I. Density and temperature of electrons, ground state and singlet metastable molecular oxygen

In this series of two papers, the E-H transition in a planar inductively coupled radio frequency discharge (13.56 MHz) in pure oxygen is studied using comprehensive plasma diagnostic methods. The electron density serves as the main plasma parameter to distinguish between the operation modes. The (effective) electron temperature, which is calculated from the electron energy distribution function and the difference between the floating and plasma potential, halves during the E-H transition. Furthermore, the pressure dependency of the RF sheath extension in the E-mode implies a collisional RF sheath for the considered total gas pressures. The gas temperature increases with the electron density during the E-H transition and doubles in the H-mode compared to the E-mode, whereas the molecular ground state density halves at the given total gas pressure. Moreover, the singlet molecular metastable density reaches 2% in the E-mode and 4% in the H-mode of the molecular ground state density. These measured plasma parameters can be used as input parameters for global rate equation calculations to analyze several elementary processes. Here, the ionization rate for the molecular oxygen ions is exemplarily determined and reveals, together with the optical excitation rate patterns, a change in electronegativity during the mode transition.

Bullet-to-streamer transition on the liquid surface of a plasma jet in atmospheric pressure

This study investigated the transition of the plasma shape from a ring-shaped bullet to a pin-like streamer adjacent to the electrolyte surface in a kHz-driven helium atmospheric pressure plasma jet. The transition was observed by synchronized fast images, plasma propagation speed, time-resolved emission profile of Hβ, and spatially and temporally resolved helium metastable density. The transition height increased when electrolyte evaporation was enhanced. The plasma continued to discharge on the electrolyte surface even in the absence of metastable species, i.e., the discharge mechanism changed from Penning ionization between helium metastable and ambient nitrogen to electron collision on evaporated water.