Modern thermodynamics in CVD of hard materials

Abstract The diamond growth together with the graphite etching under low pressure had often been regarded as a “thermodynamic paradox” maybe “violating the second law of thermodynamics”, since the success of the activated chemical vapor deposited (CVD) diamond processes in 1970. After quantitative verification of reaction coupling, a series of nonequilibrium phase diagrams for the activated diamond processes have been quantitatively calculated. These nonequilibrium phase diagrams agree excellently with experiments. However, there is no room for the nonequilibrium phase diagram in both classical equilibrium thermodynamics and traditional nonequilibrium thermodynamics. Therefore, the systematization of modern thermodynamics has been drastically changed and a new field for nonequilibrium phase diagrams emerges. Nonequilibrium phase diagrams for activated CVD cubic boron nitride processes have also been calculated in this paper.