Deposition of carbon nitride films using an electron cyclotron wave resonance plasma source

Hydrogenated amorphous carbon nitride (a-C:N:H) has been synthesized using a high plasma density electron cyclotron wave resonance (ECWR) technique using N2 and C2H2 as source gases, at different ratios and a fixed ion energy (80 eV). The composition, structure and bonding state of the films were investigated and related to their optical and electrical properties. The nitrogen content in the film rises rapidly until the N2/C2H2 gas ratio reaches 2 and then increases more gradually, while the deposition rate decreases steeply, placing an upper limit for the nitrogen incorporation at 30 at%. For nitrogen contents above 20 at%, the band gap and sp3-bonded carbon fraction decrease from 1.7 to 1.1 eV and approximately 65 to 40%, respectively. Films with higher nitrogen content are less dense than the original hydrogenated tetrahedral amorphous carbon (ta-C:H) film but, because they have a relatively high band gap (1.1 eV), high resistivity (109 Ω cm) and moderate sp3-bonded carbon fraction (40%), they should be classed as polymeric in nature.

Chemical sputtering of ta-C: Implications for the deposition of carbon nitride

The majority of attempts to synthesize the theoretically predicted superhard phase β-C3N4 have been driven towards the use of techniques which maximize both the carbon sp3 levels and the amount of nitrogen incorporated within the film. However, as yet no attempt has been made to understand the mechanism behind the resultant chemical sputter process and its obvious effect upon film growth. In this work, however, the chemical sputtering process has been investigated through the use of an as-deposited tetrahedrally bonded amorphous carbon film with a high density nitrogen plasma produced using an rf-based electron cyclotron wave resonance source. The results obtained suggested the presence of two distinct ion energy dependent regimes. The first, below 100 eV, involves the chemical sputtering of carbon from the surface, whereas the second at ion energies in excess of 100 eV exhibits a drop in sputter rate associated with the subplantation of nitrogen within the carbon matrix. Furthermore, as the sample temperature is increased there is a concomitant decrease in sputter rate suggesting that the rate is controlled by the adsorption and desorption of additional precursor species rather than the thermal desorption of CN. A simple empirical model has been developed in order to elucidate some of the primary reactions involved in the sputter process. Through the incorporation of various previously determined experimental parameters including electron temperature, ion current density, and nitrogen partial pressure the results indicated that molecular nitrogen physisorbed at the ta-C surface was the dominant precursor involved in the chemical sputter process. However, as the physisorption enthalpy of molecular nitrogen is low this suggests that activation of this molecular species takes place only through ion impact at the surface. The obtained results therefore provide important information for the modeling and growth of high density carbon nitride. © 2001 American Institute of Physics.

Nitrogen incorporation into tetrahedral hydrogenated amorphous carbon

Structural changes induced by the incorporation of nitrogen into ta-C : H films have been studied by Electron Energy Loss Spectroscopy, X-Ray Photoelectron Spectroscopy, Fourier Transformed Infrared Spectroscopy and Ultraviolet-Visible Spectroscopy. ta-C:H films have been synthesised using a low pressure Electron Cyclotron Wave Resonance (ECWR) source which provides a plasma beam with a high degree of ionisation and dissociation. Nitrogen was incorporated by adding N2 to the C2H2 plasma used for the deposition of ta-C : H films. The N/C atomic ratio in the films rises rapidly until the N2/C2H2 gas ratio reaches three, and then increases more gradually, while the deposition rate decreases steeply. Chemical sputtering of the forming films and the formation of molecular nitrogen within the films limit the maximum nitrogen content to about N/C = 0.6. For low nitrogen content the films retain their diamond-like properties, however as N/C atomic ratio increases, a polymeric-like material is formed, with >C=N- structures and terminating C=N and NH groups that decrease the connectivity of the network.

Effect of deposition conditions on the chemical bonding in sputtered carbon nitride films

A balanced planar r.f. powered magnetron sputter source has been used to deposit carbon nitride films from a graphite target under various conditions. Sample temperature, bias voltage and nitrogen content in the gas mixture were varied. The effects of oxygen, methane and ammonia on the film growth were also studied. Special attention was paid to the effects of the deposition parameters on the structure of the films, in particular the hybridisation of the carbon and nitrogen bonding. The chemical bonding of the carbon and nitrogen atoms was studied by electron energy loss spectroscopy (EELS). The chemical composition was evaluated by Rutherford back-scattering. The intensity of transitions to π antibonding orbitals, as revealed by EELS, was found to increase with the nitrogen content in the films. Ion bombardment of the films during growth and the addition of oxygen or hydrogen-rich gases further increased the proportion of π bonds of both the carbon and nitrogen atoms. It is suggested that the increase in the transitions to μ antibond orbitals is to be explained by increased sp2 or possibly sp hybridisation of the carbon and nitrogen. Also, the effect of annealing on the bonding of nitrogen rich films after deposition was tested. The changes caused by nitrogen and deposition conditions are consistent with previous reports on the formation of paracyanogen structures.

Bonding regimes of nitrogen in amorphous carbon

Nitrogen can have numerous effects on diamond-like carbon: it can dope, it can form the hypothetical superhard compound C3N4, or it can create fullerene-like bonding structures. We studied amorphous carbon nitrogen films deposited by a filtered cathodic vacuum arc as a function of nitrogen content, ion energy and deposition temperature. The incorporation of nitrogen from 10-2 to 10 at% was measured by secondary ion mass spectrometry and elastic recoil detection analysis and was found to vary slightly sublinearly with N2 partial pressure during deposition. In the doping regime from 0 to about 0.4% N, the conductivity changes while the sp3 content and optical gap remain constant. From 0.4 to approximately 10% N, existing sp2 sites condense into clusters and reduce the band gap. Nitrogen contents over 10% change the bonding from mainly sp3 to mainly sp2. Ion energies between 20 and 250 eV do not greatly modify this behaviour. Deposition at higher temperatures causes a sudden loss of sp3 bonding above about 150 °C. Raman spectroscopy and optical gap data show that existing sp2 sites begin to cluster below this temperature, and the clustering continues above this temperature. This transition is found to vary only weakly with nitrogen addition, for N contents below 10%.

Preparation of tetrahedral amorphous carbon films by filtered cathodic vacuum arc deposition

Tetrahedrally bonded amorphous carbon (ta-C) and nitrogen doped (ta-C:N) films were obtained at room temperature in a filtered cathodic vacuum arc (FCVA) system incorporating an off-plane double bend (S-bend) magnetic filter. The influence of the negative bias voltage applied to substrates (from -20 to -350 V) and the nitrogen background pressure (up to 10-3 Torr) on film properties was studied by scanning electron microscopy (SEM), electron energy loss spectroscopy (EELS), Raman spectroscopy, X-ray photoemission spectroscopy (XPS), secondary ion mass spectroscopy (SIMS) and X-ray reflectivity (XRR). The ta-C films showed sp3 fractions between 84% and 88%, and mass densities around 3.2 g/cm3 in the wide range of bias voltage studied. In contrast, the compressive stress showed a maximum value of 11 GPa for bias voltages around -90 V, whereas for lower and higher bias voltages the stress decreased to 6 GPa. As for the ta-C:N films grown at bias voltages below -200 V and with N contents up to 7%, it has been found that the N atoms were preferentially sp3 bonded to the carbon network with a reduction in stress below 8 GPa. Further increase in bias voltage or N content increased the sp2 fraction, leading to a reduction in film density to 2.7 g/cm3.