Hard nitrogenated carbon (C:N) films with C/N ratios that were as low
as 4 were deposited on r.f.-biased substrates by the excimer laser abl
ation of graphite in a nitrogen plasma ambient. This technique couples
the energy of the laser-ablated plasma plume with that of an r.f. pla
sma discharge. The characteristics of the films deposited by this tech
nique were a strong function of the substrate r.f. bias. The C/N ratio
could be varied from about 7 to 4 with a bias variation from 100 to 1
000 V. The properties of amorphous carbon (a-C) films deposited in an
argon plasma ambient were also investigated. All the a-C and C:N films
were devoid of hydrogen, hard and extremely scratch resistant and tho
se deposited at higher bias voltages were totally unaffected by oxygen
plasmas, making them potential candidates for low earth orbit coating
applications. The optical bandgap and electrical resistivity dropped
steadily with an increase in the substrate bias. A C/N ratio of 8.5 wa
s obtained for films deposited by laser ablation in a flowing nitrogen
ambient at 50 mTorr, in the absence of an r.f. discharge. The nitroge
n concentration could be increased further by increasing the nitrogen
partial pressure but was accompanied by softening of the films due to
a large increase in the hydrogen content as indicated by strong CH and
NH absorption in the IR. In contrast, the extent of incorporation of
nitrogen into the plasma-deposited films was substantially lower and g
rew exponentially with the amount of nitrogen in the feed gas mixture.
A C/N ratio of only 15:1 was obtained for films deposited From a feed
gas mixture with as much as 75% NH3. Moreover, extensive dilution of
the hydrocarbon gas, butadiene (C4H6), with nitrogen or ammonia result
ed in significant softening of the deposited films.