First, the surface electronic state configuration was examined with regards to the polarization bound 1013 charges/cm2 that increases with aluminum content. This large bound charge requires compensation either externally by surface states or internally by the space charge regions as relates to band bending. In this work, band bending was measured after different surface treatments of GaN and AlGaN to determine the effects of specific surface states on the electronic state configuration. Results showed oxygen-terminated N-face GaN, Ga-face GaN, and Ga-face Al0.25Ga0.75N surface were characterized by similar band bending regardless of the polarization bound charge, suggesting a Fermi level pinning state ~0.4-0.8 eV below the conduction band minimum. On oxygen-free Ga-face GaN, Al0.15Ga0.85N, Al0.25Ga0.75N, and Al0.35Ga0.65N, band bending increased slightly with aluminum content and thus did not exhibit the same pinning behavior; however, there was still significant compensating charge on these surfaces (~1013 charges/cm2). This charge is likely related to nitrogen vacancies and/or gallium dangling bonds.
In addition, this wozrk investigated the interface electronic state configuration of dielectric/GaN and AlGaN interfaces with regards to deposition conditions and aluminum content. Specifically, oxygen plasma-enhanced atomic layer deposited (PEALD) was used to deposit SiO2. Growth temperature was shown to influence the film quality, where room temperature deposition produced the highest quality films in terms of electrical breakdown. In addition, the valence band offsets (VBOs) appeared to decrease with the deposition temperature, which likely related to an electric field across the Ga2O3 interfacial layer. VBOs were also determined with respect to aluminum content at the PEALD-SiO2/AlxGa1-xN interface, giving 3.0, 2.9, 2.9, and 2.8 eV for 0%, 15%, 25%, and 35% aluminum content, respectively—with corresponding conduction band offsets of 2.5, 2.2, 1.9, and 1.8 eV. This suggests the largest difference manifests in the conduction band, which is in agreement with the charge neutrality level model.
Alloyed Ti/Al/Ni/Au contact and non-alloyed Al/Au contact were developed to form low-resistivity contacts to n-GaN and their stability at high temperature were studied. The alloyed Ti/Al/Ni/Au contact offered a specific contact resistivity (ρc) of 6×10-6 Ω·cm2 at room temperature measured the same as the temperature increased to 400°C. No significant change in ρc was observed after the contacts being subjected to 400°C, 450°C, 500°C, 550°C, and 600°C, respectively, for at least 4 hours in air. Since several device technology prefer non-alloyed contacts Al/Au metal stack was applied to form the contacts to n-type GaN. An initial ρc of 3×10-4 Ω·cm2, measured after deposition, was observed to continuously reduce under thermal stress at 400°C, 450°C, 500°C, 550°C, and 600°C, respectively, finally stabilizing at 5×10-6 Ω·cm2. Both the alloyed and non-alloyed metal contacts showed exceptional capability of stable operation at temperature as high as 600°C in air with low resistivity ~10-6 Ω·cm2, with ρc lowering for the non-alloyed contacts with high temperatures.
The p-GaN contacts showed remarkably superior ohmic behavior at elevated temperatures. Both ρc and sheet resistance (Rsh) of p-GaN decreased by a factor of 10 as the ambient temperature increased from room temperature to 390°C. The annealed Ni/Au contact showed ρc of 2×10-3 Ω·cm2 at room temperature, reduced to 1.6×10-4 Ω·cm2 at 390°C. No degradation was observed after the contacts being subjected to 450°C in air for 48 hours. Indium Tin Oxide (ITO) contacts, which has been widely used as current spreading layer in GaN-base optoelectronic devices, measured an initial ρc [the resistivity of the ITO/p-GaN interface, since the metal/ITO ρc is negligible] of 1×10-2 Ω·cm2 at room temperature. No degradation was observed after the contact being subjected to 450°C in air for 8 hours.
Accelerated life testing (ALT) was performed to further evaluate the contacts stability at high temperatures quantitatively. The ALT results showed that the annealed Ni/Au to p-GaN contacts is more stable in nitrogen ambient, with a lifetime of 2,628 hours at 450°C which is approximately 12 times longer than that at 450°C in air.
Mg0.13Cd0.87Te (1.7 eV), also with high material quality, has been proposed as a current matching cell to Si (1.1 eV) solar cells, which could potentially enable a tandem solar cell with high efficiency and thus lower the electricity cost. The properties of Mg0.13Cd0.87Te/Mg0.5Cd0.5Te DHs and solar cells have been investigated. Carrier lifetime as long as 0.56 μs is observed and a solar cell with 11.2% efficiency and open circuit voltage of 1.176 V is demonstrated.
The CdTe/MgxCd1-xTe DHs could also be potentially applied to luminescence refrigeration, which could be used in vibration-free space applications. Both external luminescence quantum efficiency and excitation-dependent PL measurement show that the best quality samples are almost 100% dominated by radiative recombination, and calculation shows that the internal quantum efficiency can be as high as 99.7% at the optimal injection level (1017 cm-3). External luminescence quantum efficiency of over 98% can be realized for luminescence refrigeration with the proper design of optical structures.
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. Single-crystal 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[superscript 11] cm[superscript −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.