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Radiative recombination coefficients for all Fe ions are calculated by use of the Milne relation of detailed balance. Analytic fits are made to the dielectronic recombination rates computed by Jacobs (1977) and the Burgess general formula (1965). Higher level rates are treated hydrogenically by a quantum defect method based on the energies of the levels. Recombination coefficients for Fe I to Fe 26 are listed.
The ion-electron recombination coefficients for the lithium-like ions C IV, O VI, Ne VIII, Si XII and Ar XVI are computed by the bottleneck method of Byron et al. (1962). In this method, the minimum rate of transitions down the ladder of energy level is taken as the limiting recombination rate, and the particular energy level corresponding to the minimum transition rate is found. The partial collisional radiative recombination coefficient is obtained in terms of the equilibrium population, the rate of collisional de-excitation, the mean radiative transition probability from the bottleneck level and the total transition probability from a level above the bottleneck level to all levels below it. The full collisional-radiative recombination is then obtained by the addition of the values of the radiative recombination coefficient and the three-body recombination coefficient to the ground level. Results of the calculation are shown to be in good agreement with those of Drawin and Emard (1975) for the case of hydrogen. It is also noted that the process of dielectronic recombination, which is not accounted for here, may be significant at lower densities.
Anatase TiO2 is used extensively in a wide range of catalytic and photocatalytic processes and is a promising catalyst for hydrogen production. Here, we show that molecular hydrogen was produced from bridging hydroxyls, HOb, on the (101) surface of single crystal anatase (a-TiO2(101)). Electron bombardment at 30 K produced bridging oxygen vacancies in the surface. Deuterated bridging hydroxyls, DOb, were subsequently formed via dissociation of adsorbed D2O and confirmed by infrared reflection-absorption spectroscopy. During temperature programmed desorption (TPD) spectroscopy, D2 desorption was observed at 520 K. Density functional theory calculations show that both H2 and H2O production from HOb are endothermic at 0 K on a-TiO2(101), but H2 (H2O) desorption is entropically driven above 230 K (800 K). The calculated activation barrier for H2 desorption is 1.40 eV, which is similar to the desorption energy obtained from analysis of the D2 TPD spectra. The H2 desorption likely proceeds in two steps: H atom diffusion on the surface and then recombination. The calculations indicate that diffusion of the hydrogen atoms into the subsurface could also be an important process. We thank Drs. Z. Dohnalek and R. Rousseau for stimulating discussions. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, & Biosciences and performed in EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for DOE by Battelle. We also acknowledge the WPI computational facilities for providing resources to perform the DFT studies.
Temperature measurements in supersonic nozzles for hydrogen-air and methane-air combustion products at stagnation temperatures up to 5400 degrees rankine and pressures up to 4.5 atmospheres
Various factors affecting the frequency stability of hydrogen masers are described and related to maser design parameters. The long-term frequency stability of a hydrogen maser is limited by the mechanical stability of the cavity, and the magnitudes of the wall relaxation, spin exchange, and recombination rates which affect the Q of the line. Magnetic resonance studies of hydrogen atoms at temperatures below 1 K and in containers coated with liquid helium films demonstrated that cryogenic masers may allow substantial improvements in all of these parameters. In particular the thermal expansion coefficients of most materials are negligible at 1 K. Spin exchange broadening is three orders of magnitude smaller at 1 K than at room temperature, and the recombination and wall relaxation rates are negligible at 0.52 K where the frequency shift due to the 4 He-coated walls of the container has a broad minimum as a function of temperature. Other advantages of the helium-cooled maser result from the high purity, homogeneity, and resilence of helium-film-coated walls and the natural compatibility of the apparatus with helium-cooled amplifiers.
The thermoneutral potential of a nickel cadmium or nickel hydrogen cell is the potential at which the cell charge or discharge process puts out zero heat, and thus is the potential corresponding to the enthalpy change of the charge/discharge reaction, delta H. A relatively straightforward method for obtaining the thermoneutral potential E(sub tn), is based on the measured potential and temperature derivative of the cell reactions, which are related to the free energy change delta G, and entropy change delta S, respectively. Particularly in the nickel hydrogen cell, the pressure of hydrogen can often vary over an order of magnitude or more during the course of a charge or discharge. In a nickel cadmium cell, although significant changes in oxygen pressure can occur during charge or discharge, since oxygen does not enter into the charge/discharge reaction, these pressure changes are related to the heat generated from oxygen evolution and recombination. However, the entropy changes due to changes in hydrogen pressure relative to the 1 atm standard state must be included to apply this method to the nickel hydrogen cell.
During periods of low obliquity, previous work has shown that martian CO2 partial pressures decreased to 0.1 mbar; CO2 partial pressures decreased to 0.02 mbar prior to the formation of the Tharsis bulge. The permanent polar caps act as a cold trap and projected global average water vapor abundances drop to possibly as low as 0.00001 precipitable micron. As a result, the odd hydrogen catalytic cycle would not be effective at recombining CO and O back into CO2, and as much as 0.12 mbar of CO and 0.06 mbar of O2 could exist. These increased abundances would radically affect surface oxidation, change the lower atmospheric thermal structure, and completely alter the upper atmosphere.
The importance of odd hydrogen (or HO(x)) radicals in the catalytic recombination of carbon monoxide and oxygen in the Martian atmosphere is a well known fact. The inclusion of recent chemical kinetics data, specifically temperature-dependent CO2 absorption cross sections, into our one dimensional photochemical model shows that HO(x) is too efficient in this regard. The absorption cross sections of CO2 are smaller than previously assumed; this leads to a reduction in the photolysis rate of CO2 while the photolysis rate of H2O has increased. As a consequence the predicted mixing ratio of CO in our models is substantially less than the observed value of 6.5(10)(exp -4). Simultaneous measurements of water, ozone, and carbon monoxide were obtained in the Martian atmosphere in early Dec. 1990 (L(sub s) for Mars was 344 deg.).
We pursued two major projects. In the first, we studied the degradation of a-Si/c-Si Heterojunction cells. We substantially expanded our previously developed SolDeg platform, and incorporated hydrogen into it. We also expanded the capabilities of SolDeg by developing a three channel model for a very efficient way to determine long term junction dynamics. The first main result was that we identified hydrogen drifting away from the interface as a key degradation channel. The second was that we developed and proposed the concept of a “reverse silicon density gradient” in the a-Si layer that had the promise of reducing degradation by up to 80%. In the second project, we studied the degradation of TOPCon solar cells. We again identified a key degradation channel, which in these cells was the formation of pinholes across the oxide layer. We then again were able to develop and to propose a way to dramatically reduce degradation by discovering that tuning the hydrogen concentration forms a sharp and deep minimum of the recombination current.
Observation of solar Ly alpha radiation scattered by coronal neutral hydrogen atoms can be used to investigate the acceleration region of the solar wind. In this paper we focus on the use of these observations to study Alfven waves, which can accelerate the solar wind plasma to flow speeds observed in high-speed streams if their amplitude at the coronal base is 20 km/s or larger. The wave amplitude is then larger than the proton thermal speed in the outer corona, so that the mean proton speed (averaged over a wave period) is significantly larger than the proton thermal speed. For low-frequency wave the hydrogen atoms follow the proton motion in the waves, while for higher frequencies the protons move relative to the neutrals. Nevertheless, in the higher frequency case, the rates for charge exchange and recombination are high enough to broaden the velocity distribution function of neutral hydrogen. Both the wave motion of the hydrogen atoms in low-frequency Alfven waves and the 'heating' by higher frequency waves lead to a broadening of the scattered solar Ly alpha line. For coronal base amplitues of 20 km/s, the line broadening increases with heliocentric distance beyond 4-5 solar radii.
Ripples of graphene are known to manipulate electronic and hydrogenation properties of graphitic materials. More detailed work is needed to elucidate the structure–property relationship of these systems. In this work, the density functional theory is used to compute the energy and electronic structure of the graphene models with respect to variable curvatures and hydrogen adsorption sites. The magnitude of finite bandgap opening depends on the orientation of ripples, and the hydrogen adsorption energy depends on the local curvature of graphene. An adsorbed hydrogen alters the local curvature, resulting in relatively weakened adsorption on the neighboring three sites, which gives a rationale to experimentally observed dynamic equilibrium stoichiometry (H:C = 1:4) of hydrogenated graphene. The surface diffusion transition state energy of adsorbed hydrogen is computed, which indicates that the Eley–Rideal surface recombination mechanism may be important to establish the dynamic equilibrium, instead of the commonly assumed Langmuir–Hinshelwood mechanism.
Effective surface passivation of crystalline silicon (c-Si) surface by reducing the carrier recombination rate has led to modern c-Si solar cells with efficiencies > 25% in both laboratory and industrial settings. Typical mainstream surface passivation techniques include high-temperature silicon oxide (SiOx), amorphous silicon (a-Si:H), hydrogen-rich silicon nitride (SiNx), and aluminum oxide (Al2O3) [1]. They have demonstrated excellent surface recombination velocity of < 1 cm/s owing to both chemical passivation (via the hydrogen saturation of Si dangling bonds at the c-Si surface), and field-effect passivation (via the band bending from the fixed charge of the dielectric layers). Recently, several groups have studied solution-based organic materials for c-Si passivation, including bis(trifluoromethane)sulfonimide (TFSI), polystyrenesulfonate, and Nafion [2, 3] via spin or dip coating. All films were processed at ambient room temperature, and a high lifetime of 12 ms, as well as a low saturation current density (J0) of 16 fA/cm2, have been demonstrated using Nafion passivation [2]. However, despite the air instability, Nafion has several advantages when introduced to PV applications: (a) Wafer quality can be measured at high throughput after several process stages. (b) It is compatible with PL mapping, compared to HF liquid passivation which cannot be performed in room ambient. (c) Nafion process is fast and poses fewer constraints on process complexity, and cleanness, compared to Al2O3 and a-Si:H passivation. (d) Nafion is the ideal room temperature passivation, which can be applied onto a small fragment of a degraded module to investigate microscopic mechanisms when studying degradation mechanisms. Edge passivation is needed for advanced characterization tests such as Electron Paramagnetic Resonance (EPR), Electrically Detected Magnetic Resonance (EDMR), Deep Level Transient Spectroscopy (DLTS), local cell current-voltage (J-V), and Suns-Voc. In such cases, the laser-damaged minicell edges will obscure the true degradation mechanisms, and Nafion can effectively passivate them without causing further degradation through elevated-temperature processes. In this contribution, we show the passivation results of Nafion on bare nCz and compare it with a Al2O3 witness. We highlight the importance of edge pre-treatment before Nafion to achieve good passivation. We show that Nafion can reach decent passivation without undergoing high-temperature processes. We also explore the temperature dependency of Nafion through photoluminescence (PL) study and demonstrate the application of Nafion under cryogenic temperature (~6 K) through EPR. Our results reveal that Nafion can reduce surface and edge Si dangling bonds at low temperatures. Thus, it can be used as an effective room temperature passivation technique for advanced characterization methods.
Abstract Among silicon-based solar cells, heterojunction cells hold the world efficiency record. However, their market acceptance is hindered by an initial 0.5% per year degradation of their open circuit voltage which doubles the overall cell degradation rate. Here, we study the performance degradation of crystalline-Si/amorphous-Si:H heterojunction stacks. First, we experimentally measure the interface defect density over a year, the primary driver of the degradation. Second, we develop SolDeg, a multiscale, hierarchical simulator to analyze this degradation by combining Machine Learning, Molecular Dynamics, Density Functional Theory, and Nudged Elastic Band methods with analytical modeling. We discover that the chemical potential for mobile hydrogen develops a gradient, forcing the hydrogen to drift from the interface, leaving behind recombination-active defects. We find quantitative correspondence between the calculated and experimentally determined defect generation dynamics. Finally, we propose a reversed Si-density gradient architecture for the amorphous-Si:H layer that promises to reduce the initial open circuit voltage degradation from 0.5% per year to 0.1% per year.
Optimum nonequilibrium nozzle performance for hydrogen-fluorine propellant system, considering contour, engine/nozzle weights and recombination kinetics
A consistent theory for dealing with transport phenomena in stellar atmospheres starting with the kinetic equations and introducing three cases (LTE, partial LTE, and non-LTE) was developed. The consistent hydrodynamical equations were presented for partial-LTE, the transport coefficients defined, and a method shown to calculate them. The method is based on the numerical solution of kinetic equations considering Landau, Boltzmann, and Focker-Planck collision terms. Finally a set of results for the transport coefficients derived for a partially ionized hydrogen gas with radiation was shown, considering ionization and recombination as well as elastic collisions. The results obtained imply major changes is some types of theoretical model calculations and can resolve some important current problems concerning energy and mass balance in the solar atmosphere. It is shown that energy balance in the lower solar transition region can be fully explained by means of radiation losses and conductive flux.
H-He partially ionized plasma bremsstrahlung, radiative and dielectronic recombination, discrete levels excitation and collisional ionization
Si heterojunction (SHJ) solar cells have demonstrated record efficiency >27%, approaching the theoretical limit of ≈ 29%, primarily due to best surface/interface defect passivation provided by deposited thin layers of hydrogenated amorphous silicon (a-Si:H). Such excellent surface/interface passivation reduces recombination loss and result in >100 mV improvement of cell open circuit voltage (V OC ) to ≈ 750 mV, thus the cell efficiency. However, fielded SHJ modules exhibit loss of V OC and hence efficiency over time in years, presumably due to degradation related to a-Si:H layers. This adversely affects the technology’s market acceptance, and levelized cost of energy (LCOE). It is hypothesized that the origin of a-Si:H degradation is somehow related to the presence of weak Si–Si bonds and hydrogen in a-Si:H films. The objective of this project is to test this hypothesis by directly measuring chemical and structural changes occurring within SHJ component layers and solar cells. This is achieved by developing an innovative in-situ Fourier transform infrared (FTIR) spectrometry apparatus to monitor hydrogen microstructural changes occurring within amorphous silicon and decipher hydrogen evolution kinetics over time when samples are exposed to heat and/or light stress. These in-situ measured hydrogen microstructural changes are correlated to the changes in effective minority carrier lifetime (τ eff ), implied V OC (iV OC ), surface recombination velocity (S), and cell V OC . These mechanistic understandings will provide critical guidance to mitigate the V OC -driven degradation of SHJ solar cell performance. Passivation optimization and degradation analysis of individual SHJ component structures were achieved through systematic deposition of three symmetric structures and the completed SHJ solar cell structure. The three symmetric structures used were intrinsic a-Si:H [(i)a-Si:H] layers in a bilayer structure, intrinsic and p-type doped stacked layers [(i-p)a-Si:H] representing the front heterojunction in the SHJ cell, and intrinsic and n-typed doped stacked layers [(i-n)a-Si:H] representing the back-side back surface field (BSF) in the SHJ cell. State-of-the-art passivation qualities are demonstrated by a champion iV OC of 740 mV for the (i)a-Si:H layers, and the (i-n)a-Si:H symmetric structure. A 725 mV iV OC is observed for the (i-p)a-Si:H symmetric structure. These symmetric passivated SHJ component structures were subsequently subjected to different accelerated lifetime (ALT) stressors to identify which conditions contribute the most to iV OC degradation. Degradation of the thin (10 nm) (i)a-Si:H passivation layers without any additional overlying layers is minimal; complexity of this study arises due to unavoidable surface oxidation of (i)a-Si:H layer during most of the stress application, which is likely irrelevant for a full SHJ cell configuration with overlying protective layers. The iV OC degradation of symmetric structures is found to occur primarily at the (i-p)a-Si:H passivation stack under dark heat stress with associated hydrogen loss from the (p)a-Si:H layer. An activation energy for increase in S (defect creation) of 0.65 eV can be correlated to the activation energy of ≈ 0.4 eV for hydrogen loss from the (i-p)a-Si:H stack. This also suggests the presence of weakly bonded hydrogen in the (p)a-Si:H films, which effuses out of the film stack at such low activation energy. When light and heat stress are applied together, similar hydrogen loss from (i-p)a-Si:H stack is observed, however, does not appreciably degrade iV OC or increase S. This is an important result and departure from direct correlation between hydrogen loss and defect creation. This perhaps indicates additional defect chemistries or annealing that might be occurring in the presence of light requiring further detailed defect measurements. The full SHJ cell structure used for this project is depicted in Fig.1(d). SHJ cells with an initial V OC ≈ 700 mV were fabricated and subjected to similar ALT stress conditions. Cell V OC is found to degrade the most under dark heat stress and is confirmed by observed hydrogen migration out of the (i-p)a-Si:H stack. However, hydrogen cannot escape from the cell stack, it accumulates near the (p)a-Si:H/ITO contact interface, where ITO acts as a barrier preventing hydrogen loss. Furthermore, light-heat combined stress does not degrade V OC appreciably, confirming the occurrence of a defect annealing process.
In photoredox reactions, charge recombination (CR) limits quantum yields, hindering the efficient conversion of light energy into catalytic activity. To address this, we drew inspiration from redox relays in photosystem II (PSII) and developed a new series of iridium(III) complexes featuring covalently attached benzimidazole-phenol-pyridine (BIP-Py) groups to facilitate intramolecular multiproton-coupled electron transfer (MPCET). Herein, we evaluate the effects of MPCET through an extended and well-defined hydrogen-bond network to improve photocatalytic activity and mitigate rapid charge recombination. Infrared spectroelectrochemistry reveals pyridine protonation upon phenol oxidation, while visible spectroelectrochemistry and transient absorption spectroscopy confirm the electro- and photochemical formation of chargeseparated states (CSS) involving oxidized BIP, resulting from intramolecular proton-coupled electron transfer (PCET). The application of the BIP-Py platform in a photocatalytic Nhydroxyphthalimide ester reduction reaction resulted in a ∼106-fold reduction in CR rate and a quantum yield enhancement of up to 157%. Our findings suggest that incorporating MPCET-based redox relays into photocatalyst frameworks is an effective strategy to enhance the efficiency of photocatalytic systems.