Diamond, because of its electrical and chemical properties, may be a suitable material for integrated sensing and signal processing. But methods to control chemical or biological modifications on diamond surfaces have not been established. Here, we show that nanocrystalline diamond thin-films covalently modified with DNA oligonucleotides provide an extremely stable, highly selective platform in subsequent surface hybridization processes. We used a photochemical modification scheme to chemically modify clean, H-terminated nanocrystalline diamond surfaces grown on silicon substrates, producing a homogeneous layer of amine groups that serve as sites for DNA attachment. After linking DNA to the amine groups, hybridization reactions with fluorescently tagged complementary and non-complementary oligonucleotides showed no detectable non-specific adsorption, with extremely good selectivity between matched and mismatched sequences. Comparison of DNA-modified ultra-nanocrystalline diamond films with other commonly used surfaces for biological modification, such as gold, silicon, glass and glassy carbon, showed that diamond is unique in its ability to achieve very high stability and sensitivity while also being compatible with microelectronics processing technologies. These results suggest that diamond thin-films may be a nearly ideal substrate for integration of microelectronics with biological modification and sensing.

Imagine you are in the last stages of typing your thesis, the year is 1980, and it's a hot, hazy summer afternoon, a thunderstorm brews on the horizon. Tense and tired, you have forgotten to save the document on your hard disk. Suddenly, lightning strikes! Your computer shuts down. Your final chapter is lost.

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.

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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.

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Ultrananocrystalline diamond (UNCD) films were prepared by microwave plasma chemical vapor deposition using argon-rich Ar∕CH4 plasmas at substrate temperatures from ∼400 to 800°C. Different seeding processes were employed to enhance the initial nucleation density for UNCD growth to about 1011sites∕cm2. High-resolution transmission electron microscopy, near-edge x-ray absorption fine structure, visible and ultraviolet Raman spectroscopy, and scanning electron microscopy were used to study the bonding structure as a function of growth temperature. The results showed that the growth of UNCD films is much less dependent on substrate temperature than for hydrogen-based CH4∕H2 plasmas. UNCD with nearly the same nanoscale structure as those characteristic of high-temperature deposition can be grown at temperatures as low as 400°C with growth rates of about 0.2μm∕hr. The average grain size increased to about 8nm from 3 to 5nm that is characteristic of high-temperature growth, but the relative amounts of sp3 and sp2 bonding remained unchanged. These results suggest that the activation energy for UNCD growth is about 2–3Kcal∕mole compared with ∼28kcal∕mole for traditional growth chemistries, and that hydrogen plays an important role in the growth of UNCD films using hydrogen-poor plasmas.

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