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.

Deposition of diamond-like carbon films by photon-enhanced chemical vapour deposition of methane using a windowless hydrogen lamp

Thin films of diamond-like carbon (DLC) have been deposited using a novel photon-enhanced chemical vapour deposition (photo-CVD) method. This low energy method may be a way to produce better interfaces in electronic devices by reducing damage due to ion bombardment. Methane requires high energy photons for photolysis to take place and these are not transmitted in most photo-CVD methods owing to the presence of a window between the lamp and the deposition environment. In our photo-CVD system there is no window and all the high energy photons are transmitted into the reaction gas. Initial work has proved promising and this paper presents recent results. Films have been characterized by measuring electron energy loss spectra, by ellipsometry and by fabricating and testing diode structures. Results indicate that the films are of a largely amorphous nature and are semiconducting. Diode structures have on/off current ratios of up to 106.

Plasma enhancement of current from carbon cathodes for field emission displays

This paper examines the possibility of using a background gas medium to enhance the current available from low threshold carbon cathodes. The field emission current is used to initiate a plasma in the gas medium, and thereby achieve a current multiplication effect. Results on the variation of anode current as a function of electric field and gas pressure are presented. These are compared with model calculations to verify the principles of operation. The influence of ion bombardment on the long term performance thin film carbon cathodes is examined for He and Ar multiplication plasmas. A measure of the influence of current multiplication on display quality is presented by examining light output from two standard low voltage phosphors. Also studied are the influence of doping the carbon with N to lower the threshold voltage for emission as well as the consequent impact on anode current from the plasma.

High-density remote plasma sputtering of high-dielectric-constant amorphous hafnium oxide films

Hafnium oxide (HfOx) is a high dielectric constant (k) oxide which has been identified as being suitable for use as the gate dielectric in thin film transistors (TFTs). Amorphous materials are preferred for a gate dielectric, but it has been an ongoing challenge to produce amorphous HfOx while maintaining a high dielectric constant. A technique called high target utilization sputtering (HiTUS) is demonstrated to be capable of depositing high-k amorphous HfOx thin films at room temperature. The plasma is generated in a remote chamber, allowing higher rate deposition of films with minimal ion damage. Compared to a conventional sputtering system, the HiTUS technique allows finer control of the thin film microstructure. Using a conventional reactive rf magnetron sputtering technique, monoclinic nanocrystalline HfOx thin films have been deposited at a rate of ∼1.6nmmin-1 at room temperature, with a resistivity of 1013Ωcm, a breakdown strength of 3.5MVcm-1 and a dielectric constant of ∼18.2. By comparison, using the HiTUS process, amorphous HfOx (x=2.1) thin films which appear to have a cubic-like short-range order have been deposited at a high deposition rate of ∼25nmmin-1 with a high resistivity of 1014Ωcm, a breakdown strength of 3MVcm-1 and a high dielectric constant of ∼30. Two key conditions must be satisfied in the HiTUS system for high-k HfOx to be produced. Firstly, the correct oxygen flow rate is required for a given sputtering rate from the metallic target. Secondly, there must be an absence of energetic oxygen ion bombardment to maintain an amorphous microstructure and a high flux of medium energy species emitted from the metallic sputtering target to induce a cubic-like short range order. This HfOx is very attractive as a dielectric material for large-area electronic applications on flexible substrates. A remote plasma sputtering process (high target utilization sputtering, HiTUS) has been used to deposit amorphous hafnium oxide with a very high dielectric constant (∼30). X-ray diffraction shows that this material has a microstructure in which the atoms have a cubic-like short-range order, whereas radio frequency (rf) magnetron sputtering produced a monoclinic polycrystalline microstructure. This is correlated to the difference in the energetics of remote plasma and rf magnetron sputtering processes. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of ion energy and substrate temperature on the optical and electronic properties of tetrahedral amorphous carbon (ta-C) films

The properties of amorphous carbon (a-C) deposited using a filtered cathodic vacuum arc as a function of the ion energy and substrate temperature are reported. The sp3 fraction was found to strongly depend on the ion energy, giving a highly sp3 bonded a-C denoted as tetrahedral amorphous carbon (ta-C) at ion energies around 100 eV. The optical band gap was found to follow similar trends to other diamondlike carbon films, varying almost linearly with sp2 fraction. The dependence of the electronic properties are discussed in terms of models of the electronic structure of a-C. The structure of ta-C was also strongly dependent on the deposition temperature, changing sharply to sp2 above a transition temperature, T1, of ≈200°C. Furthermore, T1 was found to decrease with increasing ion energy. Most film properties, such as compressive stress and plasmon energy, were correlated to the sp3 fraction. However, the optical and electrical properties were found to undergo a more gradual transition with the deposition temperature which we attribute to the medium range order of sp2 sites. We attribute the variation in film properties with the deposition temperature to diffusion of interstitials to the surface above T1 due to thermal activation, leading to the relaxation of density in context of a growth model. © 1997 American Institute of Physics.

Material properties and tribological performance of rf-PECVD deposited DLC coatings

Diamond-like carbon (DLC) coatings were deposited on to silicon, glass and metal substrates, using an rf-plasma enhanced chemical vapour deposition (rf-PECVD) process. The resultant film properties were evaluated in respect of material and interfacial property control, based on bias voltage variation and the introduction of inert (He and Ar) and reactive (N2) diluting gases in a CH4 plasma. The analysis techniques used to assess the material properties of the films included AFM, EELS, RBS/ERDA, spectroscopic, electrical, stress, microhardness, and adhesion. These were correlated to the tribological performance of the coatings using wear measurements. The most important observation is that He dilution (>90%) promotes enhanced adhesion with respect to all substrate material studies. Coatings typically exhibit a microhardness of the order of 10-20 GPa in films 0.1ion surface bombardment, interfacial reactivity and changes in plasma gas breakdown processes. | Diamond-like carbon (DLC) coatings were deposited on to silicon, glass and metal substrates, using an rf-plasma enhanced chemical vapour deposition (rf-PECVD) process. The resultant film properties were evaluated in respect of material and interfacial property control, based on bias voltage variation and the introduction of inert (He and Ar) and reactive (N2) diluting gases in a CH4 plasma. The analysis techniques used to assess the material properties of the films included AFM, EELS, RBS/ERDA, spectroscopic, electrical, stress, microhardness, and adhesion. These were correlated to the tribological performance of the coatings using wear measurements. The most important observation is that He dilution (>90%) promotes enhanced adhesion with respect to all substrate materials studied. Coatings typically exhibit a microhardness of the order of 10-20 GPa in films 0.1 < d < 2 μm thick, with associated electrical resistivity in the range 108 < ρ < 1012 Ω·cm, coefficient of friction <0.1 and surface RMS roughness as low as 2 A. The results are discussed with respect to surface pre-treatment, ion surface bombardment, interfacial reactivity and changes in plasma gas breakdown processes.