Among transition metal nitrides, molybdenum nitrides have been much less studied even though their mechanical properties as well as their electrical and catalytic properties make them very attractive for many applications. The δ-MoN phase of hexagonal structure is a potential candidate for an ultra-incompressible and hard material and can be compared with c-BN and diamond. The predicted superconducting temperature of the metastable MoN phase of NaCl-B1-type cubic structure is the highest of all refractory carbides and nitrides. The composition of molybdenum nitride films as well as the structures and properties depend on the parameters of the process used to deposit the films. They are also strongly correlated to the electronic structure and chemical bonding. An unusual mixture of metallic, covalent and ionic bonding is found in the stoichiometric compounds.
NH3 and NHx<3 radicals
are produced downstream a microwave discharge containing
Ar-N2-H2 gas mixture. The chemical mechanism under investigation
consists of heterogenous reactions between adsorbed species NH or
NH2 (denoted NHs and NH2s) and H or
H2 flowing downstream the discharge. NHs is adsorbed on the
stainless steel reactor wall and reacts with H or H2 producing
NH2s or .
Then, part of NH2s produced reacts with H atoms producing ; another
part is desorbed from the tube wall: .
We assume that NH3 is spontaneously and totally desorbed. From the balance equations, we determine analytical
relations for NH2s, NH2 and NH3
concentrations. We then measure values of reaction rate constants and
compare the numerical results to measurements performed in the afterglow by
means of mass spectrometer versus the %H2 injected in the
discharge. We measure values in two different initial gas mixtures,
98.7% Ar-1.3% N2 and 66.6% Ar-33.3% N2. In the first gas
mixture, k1, k2(NHs), k3(NHs) and
ksg range between 1×10-17 and
2×10-17 m3 s-1, 0.035 and 0.045 m s-1,
9 and 11 m s-1,
and 0.30 and 0.35 m-1 s-1, respectively.
In the second gas mixture, as expected, similar
values are found for k1 and ksg but the
other two values increase by a factor of 5. Such an increase for
k2(NHs) and k3(NHs) is probably
due to the increase of the (NHs) concentration on the reactor
wall. The recombination coefficient γ is deduced from the previous
rate constant values. We find γ1 = 4.12×10-4,
γ2 = 4.91×10-6 and γ3 = 7.93×10-4, using the
mean values of reaction rate constants determined for k1, k2 and k3,
respectively, in the first gas mixture. To our knowledge, these results have
never been published before. They are in good agreement with values given in
the literature for other similar mechanisms. Finally, we conclude that
the loss of H atoms on the reactor wall mainly results in producing
NH2s and NH3.
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