Nitrogen-doped Ultrananocrystalline Diamond Research Articles

Bonding structure in nitrogen doped ultrananocrystalline diamond

The transport properties of diamond thin films are well known to be sensitive to the sp2/sp3-bonded carbon ratio, the presence of the grain boundaries and other defects, and to the presence of various impurities. In order to clarify the roles these factors play in the conduction mechanisms of nitrogen-doped ultrananocrystalline diamond (UNCD), Raman scattering, near edge x-ray absorption fine structure (NEXAFS), soft x-ray fluorescence (SXF), and secondary ion mass spectroscopy (SIMS) measurements were performed. Transmission electron microscopy analysis of nitrogen doped UNCD has previously indicated that the films are composed of crystalline diamond nano-grains with boundaries of amorphous carbon, and NEXAFS measurements reveal that the global amount of sp2-bonded carbon in these films increases slightly with nitrogen doping. The nitrogen content is quantified with high-resolution SIMS analysis, while NEXAFS and SXF indicates that the nitrogen exists primarily in tetrahedrally coordinated sites. These measurements indicate that the overall grain boundary volume of nitrogen-doped ultrananocrystalline diamond is increasing, while the grains themselves remain pure diamond. This supports our previously reported hypothesis that grain boundary conduction is the mechanism for the observed increase in conductivity in ultrananocrystalline diamond with nitrogen doping.

Morphology and electronic structure in nitrogen-doped ultrananocrystalline diamond

Ultrananocrystalline diamond (UNCD) thin films consist of 2–5 nm grains of pure sp3-bonded carbon and ∼0.5-nm-wide grain boundaries with a disordered mixture of sp2- and sp3-bonded carbon. UNCD exhibits many interesting materials properties that are a direct consequence of its nanoscale morphology. In this work, we report the changes in morphology induced in UNCD by the addition of nitrogen gas to the Ar/CH4 microwave plasma, as studied using high-resolution transmission electron microscopy and nanoprobe-based electron energy-loss spectroscopy. Both the grain size and grain-boundary widths increase with the addition of N2, but the overall bonding structure in both regions remains mostly unchanged. These results are used to explain the variation of materials properties of nitrogen-incorporated UNCD films.

Synthesis and characterization of highly-conducting nitrogen-doped ultrananocrystalline diamond films

Ultrananocrystalline diamond (UNCD) films with up to 0.2% total nitrogen content were synthesized by a microwave plasma-enhanced chemical-vapor-deposition method using a CH4(1%)/Ar gas mixture and 1%–20% nitrogen gas added. The electrical conductivity of the nitrogen-doped UNCD films increases by five orders of magnitude (up to 143 Ω−1 cm−1) with increasing nitrogen content. Conductivity and Hall measurements made as a function of film temperature down to 4.2 K indicate that these films have the highest n-type conductivity and carrier concentration demonstrated for phase-pure diamond thin films. Grain-boundary conduction is proposed to explain the remarkable transport properties of these films.