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The fabrication, initial structural characterization, and diode measurements are reported for a boron carbide/silicon carbide heterojunction diode. Current–voltage curves are obtained for operation at temperatures from 24 to 351 °C. Plasma-enhanced chemical-vapor deposition (PECVD) -deposited undoped boron carbide material is highly crystalline and consists of a variety of polytypes of boron carbide (BC) with crystal sizes as large as 110 nm. Crystal phases are similar to those for PECVD BC on Si but only partially match known boron and boron-rich BC phases.