Semiconducting boron carbide thin films: Structure, processing, and diode applications

The high energy density and long lifetime of betavoltaic devices make them very useful to provide the power for applications ranging from implantable cardiac pacemakers to deep space satellites and remote sensors. However, when made with conventional semiconductors, betavoltaic devices tend to suffer rapid degradation as a result of radiation damage. It has been suggested that the degradation problem could potentially be alleviated by replacing conventional semiconductors with a radiation hard semiconducting material like icosahedral boron carbide.;The goal of my dissertation was to better understand the fundamental properties and structure of boron carbide thin films and to explore the processes to fabricate boron carbide based devices for voltaic applications. A pulsed laser deposition system and a radio frequency (RF) magnetron sputtering deposition system were designed and built to achieve the goals. After comparing the experimental results obtained using these two techniques, it was concluded that RF magnetron sputtering deposition technique is a good method to make B4C boron carbide thin films to fabricate repeatable and reproducible voltaic devices. The B4C thin films deposited by RF magnetron sputtering require in situ dry pre-cleaning to make ohmic contacts for B4C thin films to fabricate the devices. By adding another RF sputtering to pre-clean the substrate and thin films, a process to fabricate B4C / n-Si heterojunctions has been established. In addition, a low energy electron accelerator (LEEA) was built to mimic beta particles emitted from Pm147 and used to characterize the betavoltaic performance of betavoltaic devices as a function of beta energy and beta flux as well as do accelerated lifetime testing for betavoltaic devices. The energy range of LEEA is 20 - 250 keV with the current from several nA to 50 muA. High efficiency Si solar cells were used to demonstrate the powerful capabilities of LEEA, i.e., the characterization of betavoltaic performance and the accelerated lifetime test of betavoltaic devices.;Structural analysis by X-ray diffraction and high resolution transmission electron microscopy showed that the prepared B4C thin films are amorphous. The presence of icosahedrons, which account for the radiation hardness of icosahedral boron rich solids, in the amorphous B4C thin films was supported by Fourier transform infrared spectroscopy. The pair distribution functions derived from selected area diffraction pattern of amorphous B 4C thin films showed that the short range order structure of amorphous B4C thin films is similar to beta-rhombohedral boron but with a shorter distance. The investigation of electrical properties of B4 C thin films showed that the resistivity of B4C thin films ranges from 695 O-cm to 9650 O-cm depending on the deposition temperature; the direct and indirect bandgaps for B4C thin films are 2.776 - 2.898 eV and 1.148 - 1.327 eV, respectively; the effective lifetime of excess charge carrier is close to 0.1 ms for B4C thin film deposited at room temperature and approximates to 1 ms for those deposited at 175 °C to 500 °C. Based on structural characterization and electrical properties of B4C thin films, a structural model of B4C thin films was proposed and supported by nanoindenter experiments, i.e., the hardness of thin films deposited at temperature in the range of 275 °C to 350 °C is lower than that of the films deposited at RT and 650 °C.;Heterojunctions of B4C / n-Si (100) possessing photovoltaic response have been fabricated. The suitable deposition temperature for B 4C thin film to fabricate photovoltaic device is from 175 °C to 350 °C. When the Si substrate surface was not pre-cleaned before depositing B4C thin film, the B4C / n-Si (100) heterojunction has better photovoltaic responses, presumably because there were no sputter-produced defects on the surface of Si (100) substrate. Until now, the best achievable photovoltaic performance is B4C / n-Si (100) heterojunction with 200 nm thick B4C thin film when the Si (100) substrate surface was not pre-cleaned by RF sputtering. When this heterojunction was characterized using solar simulator with air mass 1.5 spectra, the short circuit current density is 1.484 mA/cm2, the open circuit voltage is about 0.389 V, and the power conversion efficiency is about 0.214 %. In addition, B5C thin films deposited by plasma enhanced chemical vapor deposition were used to make some of the devices studied in this dissertation. It was found that the Si-doped BC / n-Si (111) heterojunctions also demonstrates their photovoltaic and betavoltaic responses. Even after irradiated by a 120 keV electron beam to a fluence of 4.38x1017 electrons/cm 2, the heterojunctions still posses betavoltaic behavior and their responses to the incident irradiance density are similar to that before irradiation.