Microstructural evolution as a function of substrate temperature (T
S) for conducting ultrananocrystalline diamond (UNCD) films is systematically studied. Variation of the sp2 graphitic and sp3 diamond content with T
S in the films is analysed from the Raman and near-edge x-ray absorption fine structure spectra. Morphological and microstructural studies confirm that at T
S = 700 °C well-defined acicular structures evolve. These nanowire structures comprise sp3 phased diamond, encased in a sheath of sp2 bonded graphitic phase. T
S causes a change in morphology and thereby the various properties of the films. For T
S = 800 °C the acicular grain growth ceases, while that for T
S = 700 °C ceases only upon termination of the deposition process. The grain-growth process for the unique needle-like granular structure is proposed such that the CN species invariably occupy the tip of the nanowire, promoting an anisotropic grain-growth process and the formation of acicular structure of the grains. The electron field emission studies substantiate that the films grown at T
S = 700 °C are the most conducting, with conduction mediated through the graphitic phase present in the films.
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