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Single phase, polycrystalline perovskite oxide SrVO3, with its intrinsic low effective work function and facile synthesis process, is a promising thermionic electron emitter cathode candidate, in which previous works have shown evidence of an effective work function as low as 2.3 eV. In this work, we study the vacuum activation process of SrVO3 and find that it has promising emission stability over 15 days of continuous high temperature operation. We find that SrVO3 shows surface Sr and O segregation during its operation, which we hypothesize is needed to create a positive surface dipole, leading to a low effective work function. Emission repeatability from cyclic heating and cooling suggests the promising stability of the low effective work function surface, and additional observations of drift-free emission during 1 h of continuous emission testing at high temperature further demonstrate its excellent performance stability. This assessment of the emission stability over time and the interplay of evolving surface chemistry with emission behavior are necessary for understanding how best to prepare, process, and operate SrVO3 cathodes. [ABSTRACT FROM AUTHOR]

Experimental observations have long-established that there exists a smooth roll-off or knee transition between the temperature-limited (TL) and full-space-charge-limited (FSCL) emission regions of the emission current density-temperature (J – T) (Miram) curve, or the emission current density-voltage (J – V) curve for a thermionic emission cathode. In this article, we demonstrate that this experimentally observed smooth transition does not require frequently used a priori assumptions of a continuous distribution of work functions on the cathode surface. Instead, we find that the smooth transition arises as a natural consequence of the physics of nonuniform thermionic emission from a spatially heterogeneous cathode surface. We obtain this smooth transition for both J – T and J – V curves using a predictive nonuniform thermionic emission model that includes 3-D space charge, patch fields (electrostatic potential nonuniformity on the cathode surface based on local work function values), and Schottky barrier lowering physics and illustrates that a smooth knee can arise from a thermionic cathode surface with as few as two discrete work function values. Importantly, we find that the inclusion of patch field effects is crucial for obtaining accurate J – T and J – V curves, and the further inclusion of Schottky barrier lowering is needed for accurate J – V curves. This finding and the emission model provided in this article have important implications for modeling electron emission from realistic, heterogeneous surfaces. Such modeling is important for an improved understanding of the interplay of emission physics, cathode materials engineering, and the design of numerous devices employing electron emission cathodes. [ABSTRACT FROM AUTHOR]

Analysis of temperature-limited flow, space-charge-limited flow, and the transition between them using a simple planar diode with a thermionic cathode, in which the cathode surface has spatially nonuniform emission properties, is presented. Our theoretical results, which are derived from a model based on solutions to the Vlasov and Poisson equations, compare well with the results of particle-in-cell simulations. We find that the location and the shape of the knee in the anode current versus temperature characteristic (Miram or “rollover” curve) are significantly affected by non-uniformities in the space-charge density in the A–K gap, but are relatively unaffected by the electron motion parallel to the electrode surfaces. In particular, emission from an actively emitting region is strongly affected by the forces (or lack thereof) exerted by the space-charge of the electrons emitted by their neighbors. Perhaps, most remarkably, we find that the limiting current reaching the anode is approximately given by the classical 1-D Child–Langmuir law, even if a significant fraction of the cathode surface is non-emitting. [ABSTRACT FROM AUTHOR]

The high electron emission resulting from low-work-function scandate-added dispenser cathodes has generated a great deal of interest and research since the late 1970s. Despite the reported high current density at low temperatures, scandate cathodes have not yet seen wide-scale industrial adoption due to poor emission uniformity, inadequate reproducibility, and short lifetimes. This lack of industrial adoption stemming from the above issues is likely due to insufficient fundamental understanding of the role that scandium plays in the emission process. Recent work by five research teams under the U.S. Defense Advanced Research Projects Agency Innovative Vacuum Electronics Science and Technology Program aims at advancing this fundamental understanding and the cathode manufacturing processing. Emission microscopy of model surfaces of adsorbed Ba–Sc–O on single crystal tungsten and detailed characterization techniques, such as Wulff shape analysis, are being used to understand the morphology, composition and phase of each of the species that comprise the cathode emitting surfaces. The structure of tungsten grains at the cathode surface of activated and unactivated scandate cathodes and the resulting emission performance are observed. 3-D printing is being investigated as an advanced manufacturing method to meet the demanding requirements of modern vacuum electron devices. Finally, density functional theory is being employed to study the work function of perovskite oxides as a novel class of alternative materials to tungsten dispenser cathodes. [ABSTRACT FROM AUTHOR]

Materials that exhibit a low work function and therefore easily emit electrons into vacuum form the basis of electronic devices used in applications ranging from satellite communications to thermionic energy conversion. W-Ba-O is the canonical materials system that functions as the thermionic electron emitter commercially used in a range of high-power electron devices. However, the work functions, surface stability, and kinetic characteristics of a polycrystalline W emitter surface are still not well understood or characterized. In this study, we examined the work function and surface stability of the eight lowest index surfaces of the W-Ba-O system using density functional theory methods. We found that under the typical thermionic cathode operating conditions of high temperature and low oxygen partial pressure, the most stable surface adsorbates are Ba-O species with compositions in the range of Ba0.125O-Ba0.25O per surface W atom, with O passivating all dangling W bonds and Ba creating work function-lowering surface dipoles. Wulff construction analysis reveals that the presence of O and Ba significantly alters the surface energetics and changes the proportions of surface facets present under equilibrium conditions. Analysis of previously published data on W sintering kinetics suggests that fine W particles in the size range of 100-500 nm may be at or near equilibrium during cathode synthesis and thus may exhibit surface orientation fractions well described by the calculatedWulff construction. [ABSTRACT FROM AUTHOR]

Atomic layer deposition (ALD) of conformal AlF3 coatings onto both flat silicon substrates and high-voltage LiNi0.5Mn0.3Co0.2O2 (NMC) Li-ion battery cathode powders was investigated using a Al(CH3)3/TaF5 precursor combination. This optimized approach employs easily handled ALD precursors, while also obviating the use of highly toxic HF(g). In studies conducted on planar Si wafers, the film's growth mode was dictated by a competition between the desorption and decomposition of Ta reaction byproducts. At T⩾200 °C, a rapid decomposition of the Ta reaction byproducts to TaC led to continuous deposition and high concentrations of TaC in the films. A self-limited ALD growth mode was found to occur when the deposition temperature was reduced to 125 °C, and the TaF5 exposures were followed by an extended purge. The lower temperature process subpressed conversion of TaFx(CH3)5-x to nonvolatile TaC, and the long purges enabled nearly complete TaFx(CH3)5-x desorption, leaving behind the AlF3 thin films. NMC cathode powders were coated using these optimized conditions, and coin cells employing these coated cathode particles exhibited significant improvements in charge capacity fade at high discharge rates. [ABSTRACT FROM AUTHOR]

Scandate cathodes (BaxScyOz on W) are important thermionic electron emission materials whose emission mechanism remains unclear. Ab initio modeling is used to investigate the surface properties of both scandate and traditional B-type (Ba–O on W) cathodes. We demonstrate that the Ba–O dipole surface structure believed to be present in active B-type cathodes is not thermodynamically stable, suggesting that a nonequilibrium steady state dominates the active cathode’s surface structure. We identify a stable, low work function BaxScyOz surface structure, which may be responsible for some scandate cathode properties and demonstrate that multicomponent surface coatings can lower cathode work functions. [ABSTRACT FROM AUTHOR]

Cesium-iodide (CsI)-coated graphite cathodes are promising electron sources for high power microwave generators, but the mechanism driving the improved emission is not well understood. Therefore, an ab initio modeling investigation on the effects of thin CsI coatings on graphite has been carried out. It is demonstrated that the CsI coatings reduce the work function of the system significantly through a mechanism of induced dipoles. The results suggest that work function modification is a major contribution to the improved emission seen when CsI coatings are applied to C. [ABSTRACT FROM AUTHOR]

Recent experimental observations indicate that bulk Sc²0³ (~200 nm thick), an insulator at room temperature and pressure, must act as a good electronic conductor during thermionic cathode operation, leading to the observed high emitted current densities and overall superior emission properties over conventional thermionic emitters which do not contain ²0³. Here, we employ ab initio methods using both semilocal and hybrid functionals to calculate the intrinsic defect energetics of Sc and O vacancies and interstitials and their effects on the electronic properties of ²0³ in an effort to explain the good conduction of ²0³ observed in experiment. The defect energetics were used in an equilibrium defect model to calculate the concentrations of defects and their compensating electron and hole concentrations at equilibrium. Overall, our results indicate that the conductivity of ²0³ solely due to the presence of intrinsic defects in the cathode operating environment is unlikely to be high enough to maintain the magnitude of emitted current densities obtained from experiment, and that the presence of impurities is necessary to raise the conductivity of ²0³ to a high enough value to explain the current densities observed in experiment. The necessary minimum impurity concentration to impart sufficient electronic conduction is very small (approximately 7.5 × 10-³ ppm) and is probably present in all experiments. [ABSTRACT FROM AUTHOR]