On the thermionic emission from nitrogen-doped diamond films with respect to energy conversion

Thermionic energy converters utilize thermal energy and efficiently transform it into more useful electrical energy. A key aspect in thermionic energy conversion is the emission of electrons at elevated temperatures, where the electron emitter is separated from the collector by a vacuum gap and a voltage is generated due to the temperature difference between the emitter and collector. In this study, nitrogen-doped diamond films with a negative electron affinity surface have been synthesized with plasma-assisted chemical vapor deposition, and the electron emission has been imaged using high-resolution electron emission microscopy. This study reports the measurement of a thermovoltage and current, i.e. energy conversion, at temperatures considerably less than 1000 °C.     

Field penetration and its contribution to field enhanced thermionic electron emission from nanocrystalline diamond films

Field emission from sulfur doped nanocrystalline diamond films is characterized by intense emission sites with nm scale diameters. Field emission measurements were obtained at room temperature and analyzed in terms of the Fowler–Nordheim expression where electron emission is due to tunneling through a diminished barrier. The electron emission versus temperature was also recorded at a series of applied fields from 0.5 to 0.8 V/μm. These results were analyzed in terms of a modified Richardson–Dushman relation which describes field dependent thermionic emission. It was found that both sets of data could be fit with a work function of 2.0 eV and a field enhancement factor of  1750. The large field enhancement could not be correlated with specific structures on the relatively flat surfaces. The field and thermionic-field emission from the sulfur doped nanocrystalline diamond films is evaluated by a model which includes barrier lowering as a result of field penetration effects.     

Enhanced thermionic energy conversion and thermionic emission from doped diamond films through methane exposure

Thermionic electron emitters are a crucial component in applications ranging from high power telecommunication, electron guns, space thrusters and direct thermal to electrical energy converters. One key characteristic of diamond based electron sources is the negative electron affinity (NEA) properties of hydrogen terminated surfaces which can significantly reduce the emission barrier. Nitrogen and phosphorus doped diamond films have been prepared by plasma assisted chemical vapor deposition on metallic substrates for thermionic emitter application. Electron emission current versus temperature was measured and analyzed with respect to the Richardson-Dushman relation, with work function and Richardson constant deduced from the results. Initial emission measurements up to 500 °C in vacuum were followed by emitter characterization while the sample was exposed to methane. Vacuum measurements indicated a work function of 1.18 eV and 1.44 eV for phosphorus and nitrogen doped diamond films, respectively. Introduction of methane resulted in a significant increase of the emission current which was ascribed to contribution from ionization processes which increase charge transfer from the emitter surface. This phenomenon was utilized in a thermionic energy conversion structure by introduction of methane in the inter electrode gap where a two-fold increase in output power was observed upon introduction of the gaseous species.     

Low-temperature thermionic emission from nitrogen-doped nanocrystalline diamond films on n-type Si grown by MPCVD

Temperature-dependent emission current–voltage measurements were carried out for nitrogen (N)-doped nanocrystalline diamond (NCD) films grown on n-type Si substrates by microwave plasma-assisted chemical vapor deposition (MP-CVD). Low threshold temperature (~ 260 °C) and low threshold electric field (~ 5 × 10^− 5 V/µm) were observed. Both the temperature dependence and the electric field dependence have shown that the obtained emission current was based on electron thermionic emission from N-doped NCD films. We have also studied the relation between nitrogen concentration and the saturation emission current. The saturation current obtained was as high as 1.4 mA at 5.6 × 10^− 3 V/µm at 670 °C when the nitrogen concentration was 2.4 × 10²⁰ cm^− 3. Low value of effective work function (1.99 eV) and relatively high value of Richardson constant (~ 70) were estimated by well fitting to Richardson–Dushman equation. The results of smaller φ and larger A′ suggest that N-doped NCD has great possibility of being a highly efficient thermionic emitter material.     

Using negative electron affinity diamond emitters to mitigate space charge in vacuum thermionic energy conversion devices

A negative electron affinity (NEA) diamond surface is employed as an emitter electrode in a vacuum thermionic energy conversion device in order to mitigate the negative space charge effect. The motive diagram of an NEA device operating at the virtual saturation point is compared to a similar device with a conventional emitter material operating in the space charge limited regime in order to understand how NEA mitigates space charge. Output current characteristics are calculated for various NEA values, and the results are compared to an ideal (no space charge) model. Increasing the value of the NEA causes the output current characteristic to approach that of the ideal model. Motive diagrams for various values of NEA are calculated and used to explain this phenomenon. It is shown that an NEA device can achieve a maximum output power density equal to the maximum output power density of a similar ideal device.     

Breakdown field enhancement and energy storage performance in four-layered Aurivillius films

In dielectric capacitors, ferroelectric thin films with slim polarisation electric (P-E) hysteresis loops, which are mainly characterised by small residual polarisation (P_r) and large saturation polarisation (P_s) are expected to obtain high recoverable energy density (U_r) and efficiency (η). However, a lower breakdown in ferroelectric thin films usually impedes this result. Here, through the co-doping of La³⁺ and Pr³⁺ ions, a larger U_r of 54.27 J/cm³ and high η of 85.6% were obtained in four-layered Aurivillius phase ferroelectric thin films capacitors due to the enhanced breakdown electric field. The doped films annealed at relatively low temperatures showed similar energy storage properties compared with those of the prototype and higher energy storage efficiency compared with that of higher annealing films. In addition, the obtained thin film shows excellent energy storage properties in a wide frequency range, fatigue durability and good thermal stability. These results indicated that four-layered Aurivillius films are promising candidate materials for dielectric energy storage capacitors. The co-doping of double ions was an effective way to improve energy storage performance.