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Active semiconductor devices including heterojunction diodes and thin film transistors are formed by PECVD deposition of a boron carbide thin film on an N-type substrate. The boron to carbon ratio of the deposited material is controlled so that the film has a suitable band gap energy. Boron carbides such as B4.7C, B7.2C and B19C have suitable band gap energies between 0.8 and 1.7 eV. The stoichiometry of the film can be selected by varying the partial pressure of precursor gases, such as nido pentaborane and methane. The precursor gas or gases are energized. e.g., in a plasma reactor. The heterojunction diodes retain good rectifying properties at elevated temperature, e.g., up to 400° C.