Thin Solid Films, Vol.347, No.1-2, 31-38, 1999
Plasma substrate interaction effects on composition and chemical structure of reactively r.f. magnetron sputtered carbon nitride films
During variable unbalanced r.f. magnetron sputtering of graphite in a 70/30 N-2/He atmosphere the neutral and ionic particle fluxes on the substrate were analyzed for various discharge conditions using energy-resolved mass spectrometry and probe measurements. These data were related to the chemical composition, bonding structure and Young's modulus of the deposited CNx films. The magnetron discharge was found to produce an unexpectedly high concentration of N atoms being the predominant nitrogen precursors for the carbon nitride formation. Depending on r.f. power density and discharge pressure, the arriving fluxes of N and C atoms range from 3 x 10(16) to 6 x 10(18) cm(-2) s(-1) and from 1 x 10(15) to about 8 x 10(15) cm(-2) s(-1), respectively, while the ionic fluxes of nitrogen and carbon were measured to be two orders of magnitude lower. The energy flux density of the ion bombardment varies from 5 x 10(-4) to 2 x 10(-1) W/cm(2) over the range of discharge conditions. The overall chemical composition of the CNx films is primarily governed by the flux ratio of N to C atoms. For low Phi(N)/Phi(C) ratios, N atoms are incorporated up to 25 at.% as substitutions of C atoms in aromatic clusters of a sp(2)/sp(3) hybridized carbon matrix. With increasing arrival flux ratio the excess of N atoms is additionally bonded in linear CN structures terminated with H atoms when hydrogen is present in the discharge. An intensive for bombardment results in a reduced N concentration of the films due to an enhanced desorption of N atoms from the growing surface, mainly, however, in changing the film structure from graphite-like to amorphous. Caused by these structural changes, the Youngs modulus of the CNx films decreases from about 110 to 55 GPa.
Keywords:THIN-FILMS;MECHANICAL-PROPERTIES;ION-BOMBARDMENT;CNX FILMS;AMORPHOUS-CARBON;DEPOSITION;NITROGEN;MICROSTRUCTURE;SIMULATION