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Abstract: The plasma treatment of rapid heating was introduced for increasing fracture strength of free-standing diamond films. The effects of plasma high temperature annealing treatment on surface morphology, internal stress, vacancy defects, impurities and fracture strength of free-standing diamond films were investigated by scanning electron microscopy (SEM), Raman, positron annihilation technique (PAT) and mechanical property testing. It showed that the fracture strength of the diamond films increases up to 70% for lower fracture diamond films with treating temperature (1500–1600°C). The graphitization in surface and interior of diamond films would be produced by high temperature treatment more than 1700°C. Fracture strengths of diamond films could be enhanced after high temperature treatment and the main factor of that was compressive stress state in diamond films induced by graphitization. The impurity of N was segregated and integrated with vacancy cluster to become [N–V]0 and [N–V]−. [Copyright &y& Elsevier]

Slightly graphitization might be incurred on CVD diamond films when suffering instantaneous high temperature thermal shock. In this paper, phase transitions of CVD free-standing diamond films have been studied experimentally at the temperature range of 1500–1800 °C through a plasma rapid heating process. Raman spectra and X-ray photoelectron spectra (XPS) are compared and discussed for the purpose of measuring the percentage of graphitic carbon component in CVD diamond films after heat treatment at different temperatures. An obvious optical degradation took place in both visible and infrared bands with the increased treating temperature. The result indicates that graphitization is dominated along grain boundaries rather than in internal grains. In addition, the nitrogen related absorption peaks were not covered by the enhanced optical absorption background, which was caused by the opaque graphitic carbon formed at high temperature. Nitrogen concentrations have also been evaluated for these graphitized diamond films and there is no evidence to show the movement or aggregation of nitrogen atoms. [ABSTRACT FROM AUTHOR]

Polycrystalline CVD free-standing diamond films have been heat treated through a rapid heating process using a direct current (DC) arc plasma jet system within the temperature range of 1500–2000 °C. The optical transmission of the diamond film decreases when the treatment temperature exceeds 1500 °C. When the diamond film was annealed to 1800 °C for just 1 min, the infrared (IR) transmittance at λ = 10.6 μm of the film was significantly decreased from 60.5% to 4.0%, due to the transformation from diamond to graphite. Further increase of the temperature to 2000 °C leads to complete loss of optical transmittance in only 30 s, due to the detrimental occurrence of graphitization. XRD patterns indicate that graphite ultimately grows preferentially along the (0002) plane by forming disordered or turbostratic graphite as intermediate product. Raman spectra and SEM images verify that at 1500–1850 °C graphitic carbon transforms from the diamond surface in the form of protruding submicron crystallites, which were still containing a number of sp 3 C C bonds. In addition to graphitization on the external surface, the diamond-graphite phase transition also occurs along the grain boundaries and the calculated activation energy of the grain boundary graphitization process is 276 kJ·mol − 1 for the CVD diamond. [ABSTRACT FROM AUTHOR]

A plasma arc generator was used to heat treat the free-standing CVD diamond films at 1450–1900 °C. An Arrhenius curve was fit according to trends in the measured Raman peak intensity ratio of diamond to graphite as a function of heat treatment temperature, and the curve was extrapolated linearly. It was found that the extrapolation lines intersected at the Debye temperature, Θ D = 2021 K. By comparing the activation energies of diamond graphitization in literature and from different measurement modes in our study, it was found that the graphitization mechanisms were different on both sides of Debye temperature due to differences in the excited lattice vibration modes. When the heat treatment temperature was just below the Debye temperature, the graphitization process was promoted by generating vacancies or the breaking of single C C bonds, and the apparent activation energy was 366 ± 60 kJ·mol−1. When the heat treatment temperature was above the Debye temperature, the graphitization process was promoted by the simultaneous breaking of multiple C C bonds, and the apparent activation energy was 887 ± 141 kJ·mol−1. In combination with the morphology changes on the surface of the CVD diamond film after high temperature heat treatment, the mechanism of the micro-cyclic phase transition on the surface of the diamond film at temperatures lower than Debye temperature was summarized as follows. First, C C bonds on the diamond surface were activated and broken at high temperatures, and some diamond carbon atoms dissociated from solid phase sites to the gas phase by forming hydrocarbon free radicals. Then, the carbon atoms from these hydrocarbons entered the graphite lattice step by step to complete the spontaneous deposition of sp2 clusters. [Display omitted] • The morphological changes of diamond surface dependent on temperature and hydrogen plasma environment were observed. • Taking the Debye temperature as a critical point, the graphitization activation energy exhibits a significant difference. • The graphitization mechanism of CVD diamond surface was proposed based on the kinetics analysis. [ABSTRACT FROM AUTHOR]

Polycrystalline CVD diamond films were subjected to transient heat treatment at the temperature range of 1500–1900 °C in the Ar/H 2 plasma arc environment. The structural changes of the diamond grain boundaries (GB) were indirectly investigated by employing IR optical absorption, Raman spectroscopy, X-ray diffraction (XRD), and fractographic scanning electron microscopy (SEM). The graphitization difference between near-nucleation side and near-growth side is mainly due to the difference in the GBs' content. It is proposed that the bonded‑hydrogen atoms, of which a large amount remained in the diamond GBs, play an active role in the process of graphitization. We recognized the intensity evolution of a peak in Raman spectra located at 1470 cm−1, which was attributed to the trans -polyacetylene at diamond GBs. This result suggests the likelihood that the long-chain hydrocarbon precursor is involved in a mechanism for the sp3-to-sp2 transformation. As the propagation of the graphitization from diamond GB to grain interior, sp2 carbon with compressed state forms in its place due to the limited space for expansion. The graphite along GBs affects the fracture mode of the diamond films, which causes partial GBs to tear, while transgranular fracture occurs instead of directly intergranular fracture. [Display omitted] • A transient heat treatment method was employed to effectively keep the GB graphitization at an early stage. • The Graphitization model demonstrated the long-chain hydrocarbon precursor was involved in the sp3-to-sp2 transformation. • The fracture of annealed diamond was completed between transgranular and intergranular crack propagation. [ABSTRACT FROM AUTHOR]