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Cubic and hexagonal boron nitride (cBN and hBN) heterojunctions to n-type Si are fabricated under low-energy ion bombardment by inductively coupled plasma-enhanced chemical vapor deposition using the chemistry of fluorine. The sp2-bonded BN/Si heterojunction shows no rectification, while the cBN/sp2BN/Si heterojunction has rectification properties analogue to typical p-n junction diodes despite a large thickness (∼130 nm) of the sp2BN interlayer. The current-voltage characteristics at temperatures up to 573 K are governed by thermal excitation of carriers, and mostly described with the ideal diode equation and the Frenkel-Poole emission model at low and high bias voltages, respectively. The rectification in the cBN/sp2BN/Si heterojunction is caused by a bias-dependent change in the barrier height for holes arising from stronger p-type conduction in the cBN layer and enhanced with the thick sp2BN interlayer for impeding the reverse current flow at defect levels mainly associated with grain boundaries.

Thick cubic boron nitride (cBN) films in micrometer-scale are deposited on tungsten carbide-cobalt (WC-Co) substrates without adhesion interlayers by inductively coupled plasma-enhanced chemical vapor deposition (ICP-CVD) using the chemistry of fluorine. The residual film stress is reduced because of very low ion-impact energies (a few eV to ∼25 eV) controlled by the plasma sheath potential. Two types of substrate pretreatment are used successively; the removal of surface Co binder using an acid solution suppresses the catalytic effect of Co and triggers cBN formation, and the surface roughening using mechanical scratching and hydrogen plasma etching increases both the in-depth cBN fraction and deposition rate. The substrate surface condition is evaluated by the wettability of the probe liquids with different polarities and quantified by the apparent surface free energy calculated from the contact angle. The surface roughening enhances the compatibility in energy between the cBN and substrate, which are bridged by the interfacial sp(2)-bonded hexagonal BN buffer layer, and then, the cBN overlayer is nucleated and evolved easier.