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Superconducting thin films of vanadium nitride have been grown by low temperature (250–300 °C) chemical vapor deposition from tetrakis(dimethylamido)vanadium (TDMAV) and ammonia. For example, films grown from TDMAV (1 sccm Ar as carrier gas) and 7 mTorr ammonia at 300 °C are nanocrystalline (cubic δ-phase) with an average crystal size of 20 nm, have relatively low room temperature resistivities of 250 μΩ cm, and are superconducting with critical temperatures as high as 7.6 K (versus a bulk value of 9 K). The films have a V:N ratio of 1:1, with a carbon content of <5 at. % and an oxygen content of <3 at. % (as determined by high resolution XPS). The V 2p3/2 and N 1 s XPS binding energies of 513.5 and 397.3 eV, respectively, are consistent with the presence of a nitride phase. In contrast, films grown at lower temperatures <200 °C show carbon incorporation, have a much higher resistivity of ∼3000 μΩ cm, and are not superconducting. The results suggest that, at low temperatures, the thermally activated transamination reaction with ammonia becomes too slow to remove dimethylamido groups from the surface, resulting in carbon-rich films (10–15 at. % carbon). The conformal step coverage of the VN films depends on the growth conditions. For thermal growth of nonsuperconducting films at 150 °C, the step coverage is >95% in trenches of an aspect ratio of 4:1; for superconducting films grown at 250 °C, the step coverage is 65% for an aspect ratio of 3:1. At 150 °C, near-stoichiometric films with <2 at. % carbon and <3 at. % oxygen can be deposited if the gaseous ammonia is precracked by a remote plasma source; the resulting films have low resistivities of 320 μΩ cm but are not superconducting down to 4 K. [ABSTRACT FROM AUTHOR]

Thin films of molybdenum carbonitride, MoCxNy, are deposited by low temperature chemical vapor deposition from Mo(CO)6 and NH3 in the temperature range 150–300 °C. At a substrate temperature of 200 °C and Mo(CO)6 pressure of 0.01 mTorr, the composition varies from MoC0.48N0.20 to MoC0.36N0.33 (i.e., greater nitrogen and less carbon content) upon increasing the ammonia pressure from 0.3 to 3.3 mTorr. At a constant Mo(CO)6 pressure of 0.01 mTorr and an NH3 pressure of 2 mTorr, the composition varies from MoC0.50N0.30 to MoC0.12N0.40 with increasing substrate temperature from 150 to 300 °C. Selected films grown at substrate temperatures of 150, 200, and 250 °C are superconducting with critical temperatures of 4.7, 4.5, and 5.2 K, respectively. Grazing incidence x-ray diffraction data indicate that the films are crystalline and isomorphous with the cubic phases of Mo2N and Mo2C. With a forward-directed flux of precursors toward the surface, film growth is highly conformal in microtrenches of aspect ratio 6, with step coverages of ∼0.85 and 0.80 at growth temperatures of 150 and 200 °C, respectively. [ABSTRACT FROM AUTHOR]

The authors demonstrate that the addition of an ammonia coflow during the chemical vapor deposition of MoCxNy, Fe, or Ru thin films at ≤200 °C from the metal carbonyl precursors Mo(CO)6, Fe(CO)5, or Ru3(CO)12 affords area-selective growth: film grows readily on titanium metal or vanadium nitride substrate surfaces, but no nucleation occurs on air-exposed SiO2, TiO2, Al2O3, or MgO within the investigated times of 1–2 h. By contrast, in the absence of ammonia, nucleation and deposition on these oxide surfaces can either be slow or rapid, depending strongly on the oxide surface preparation. NH3 is also the source of N in MoCxNy, which has a resistivity of 200 μΩ cm and becomes superconducting at a critical temperature of 4 K. The authors hypothesize that the passivating effect of NH3 on oxide surfaces involves site blocking to prevent precursor adsorption, or an acid–base interaction to stabilize surface-bound metal subcarbonyl intermediates, or a combination of these mechanisms. A key finding is that surface selective growth is often crucially dependent on the sample history of the substrate, which must be specified in detail if reproducible results are to be obtained. [ABSTRACT FROM AUTHOR]