Thermionic electron emitters are a key component in applications ranging from travelling wave tubes for communications, space propulsion and direct energy conversion. As the conventional approach based on metallic emitters requires high operating temperatures the negative electron affinity (NEA) characteristic of diamond surfaces in conjunction with suitable donors would allow an electronic structure corresponding to a low effective work function. We have thus prepared phosphorus-doped polycrystalline diamond films on metallic substrates by plasma assisted chemical vapor deposition where an NEA surface characteristics was induced by exposure of the film surface to a hydrogen plasma. Thermionic electron emission measurements in an UHV environment were conducted with respect to the Richardson-Dushman relation observing an emission current at temperatures < 375 ºC. Measurements were terminated at 765 ºC without significant reduction in the electron emission current indicating a stable hydrogen passivation of the diamond surface. A fit of the emission data to the Richardson equation allowed for the extraction of emission parameters where the value of the materials work function was
We compare experimental fluctuation electron microscopy (FEM) speckle data with electron diffraction simulations for thin amorphous carbon and silicon samples. We find that the experimental speckle intensity variance is generally more than an order of magnitude lower than kinematical scattering theory predicts for spatially coherent illumination. We hypothesize that decoherence, which randomizes the phase relationship between scattered waves, is responsible for the anomaly. Specifically, displacement decoherence can contribute strongly to speckle suppression, particularly at higher beam energies. Displacement decoherence arises when the local structure is rearranged significantly by interactions with the beam during the exposure. Such motions cause diffraction speckle to twinkle, some of it at observable time scales. We also find that the continuous random network model of amorphous silicon can explain the experimental variance data if displacement decoherence and multiple scattering is included in the modeling. This may resolve the longstanding discrepancy between X-ray and electron diffraction studies of radial distribution functions, and conclusions reached from previous FEM studies. Decoherence likely affects all quantitative electron imaging and diffraction studies. It likely contributes to the so-called Stobbs factor, where high-resolution atomic-column image intensities are anomalously lower than predicted by a similar factor to that observed here.
This study reports a photoemission threshold of ∼1.5 eV from nitrogen-doped nanocrystalline diamond, which ranks among the lowest photo-threshold of any non-cesiated material. Diamond films on molybdenum substrates have been illuminated with light from 340 to 550 nm, and the electron emission spectrum has been recorded from ambient to ∼320 °C. The results display combined thermionic and photo-electron emission limited by the same low work function and indicate that the two emission processes are spatially separated. These results indicate the potential for a solar energy conversion structure that takes advantage of both photoemission and thermionic emission.
Thermionic electron emission from low work function doped diamond films can be related to materials' properties, which include donor states, surface electron affinity, and substrate-diamond interface properties. The focus of this study is on how the properties of the substrate material affect the emission. Two aspects are considered, the substrate electrical resistance and the substrate Richardson constant, and the effects of tungsten, molybdenum and rhenium substrates are explored. Low work function diamond films were deposited on the substrates, and the thermionic emission was measured to $530 C and described in terms of a fit to the Richardson-Dushman formalism. The results establish that all surfaces exhibit a similar work function but the Richardson constant and maximum emission current vary considerably. The rhenium based emitter displayed a low work function of 1.34 eV, a significant Richardson constant of 53.1 A/cm 2 K 2 , and an emission current density of $44 mA/cm 2 at a temperature of 530 C. The results indicated that interface carbide formation could limit the emission presumably because of increased electrical resistance. For non-carbide forming substrates, an increased substrate Richardson constant corresponded to enhanced emission from the diamond based emitter. V C 2012 American Institute of Physics.
Thermionic energy conversion, a process that allows direct transformation of thermal to electrical energy, presents a means of efficient electrical power generation as the hot and cold side of the corresponding heat engine are separated by a vacuum gap. Conversion efficiencies approaching those of the Carnot cycle are possible if material parameters of the active elements at the converter, i.e., electron emitter or cathode and collector or anode, are optimized for operation in the desired temperature range. These parameters can be defined through the law of Richardson-Dushman that quantifies the ability of a material to release an electron current at a certain temperature as a function of the emission barrier or work function and the emission or Richardson constant. Engineering materials to defined parameter values presents the key challenge in constructing practical thermionic converters. The elevated temperature regime of operation presents a constraint that eliminates most semiconductors and identifies diamond, a wide band-gap semiconductor, as a suitable thermionic material through its unique material properties. For its surface, a configuration can be established, the negative electron affinity, that shifts the vacuum level below the conduction band minimum eliminating the surface barrier for electron emission. In addition, its ability to accept impurities as donor states allows materials engineering to control the work function and the emission constant. Singlecrystal diamond electrodes with nitrogen levels at 1.7 eV and phosphorus levels at 0.6 eV were prepared by plasma-enhanced chemical vapor deposition where the work function was controlled from 2.88 to 0.67 eV, one of the lowest thermionic work functions reported. This work function range was achieved through control of the doping concentration where a relation to the amount of band bending emerged. Upward band bending that contributed to the work function was attributed to surface states where lower doped homoepitaxial films exhibited a surface state density of ∼3 × 10 11 cm −2 . With these optimized doped diamond electrodes, highly efficient thermionic converters are feasible with a Schottky barrier at the diamond collector contact mitigated through operation at elevated temperatures.
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