We attempted to deposit carbon nitride films on flat Si (111) substrates and on sharp <111>-oriented silicon needles in a radio frequency (rf) inductively coupled plasma system utilizing a graphite source and a nitrogen plasma. The resultant polycrystalline films were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Auger electron spectroscopy (AES), and electron energy loss spectroscopy (EELS). Both selected area electron diffraction (SAED) and lattice imaging were used to identify and characterize the particles, which grew as faceted crystals up to 1 Rm in size. From SAED, high resolution TEM, and EELS, it was found that the particles on the Si needles were α-Si3N4 and that those on the Si wafer were mostly β-Si3N4 and β-C3N4, with some β-C3N4 possible. Auger quantitative analysis suggests that β-C3N4 could be stabilized by the presence of silicon, resulting in a material with compositions CxSiyNz.
The microstructure of highly sp2 bonded amorphous carbon and partially tetrahedrally bonded amorphous carbon deposited on needle-shaped molybdenum field emitters by pulsed laser ablation and cathodic arc deposition techniques was studied using transmission electron microscopy and electron energy loss spectroscopy. Undoped and nitrogen-doped films were included in this study. The undoped laser ablation films were approximately 50% sp2 at the emitter tip and 65% sp2 along the shank, while the N-doped laser ablation films were highly sp2 bonded both at the tip and along the shank. These laser ablation films were continuous and relatively uniform, exhibiting an isotropie microstructure at the emitter tip and a columnar microstructure along the shank. The cathodic arc deposited films were predominantly sp2 bonded both at the tip and along the shank; these films were non-uniform, with an isotropie microstructure at the tip and regions of isotropie, columnar, and mixed microstructure appearing along the shank.
Hard carbon films can be prepared by the condensation of energetic carbon species at or below room temperature. These amorphous films are primarily tetrahedrally coordinated and contain high fractions of sp3 bonds leading to the terminology amorphous diamond. These films have been successfully doped with phosphorus up to 1 at.%, by other researchers by using a phosphorus doped graphite target. We have also investigated evaporated phosphorus in conjuction with a filtered cathodic arc to incorporate phosphorus into the films and have successfully incorporated phosphorus up to 40 at.% into our films using this technique. XPS showed that some of the phosphorus was clustered. PEELS revealed that with an incorporation of 40 at.% of phosphorus, the sp3 content was approximately 20%.
Hard carbon films can be prepared by the condensation of energetic carbon species at and below room temperature. These hydrogen-free films are primarily tetrahedrally coordinated and contain high fractions of sp3 bonding. Field emission from these and other forms of carbon has been considered previously, but it was generally unstable or based on surface treatments that limit their operating conditions. We report electron emission from amorphous carbon-cesium (a-C:Cs) thin films at applied fields as low as 7 V/μm. This emission characteristic is relatively insensitive to surface treatment; films left under ambient laboratory environment for more than six months show these favorable characteristics with no pretreatment. We describe the fabrication process and emission properties of these films.
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