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 0.1EELS, 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.

Analysis of the ellipsometric spectra of amorphous carbon thin films for evaluation of the sp3-bonded carbon content

Using spcctroscopic ellipsometry (SE), we have measured the optical properties and optical gaps of a series of amorphous carbon (a-C) films ∼ 100-300 Å thick, prepared using a filtered beam of C+ ions from a cathodic arc. Such films exhibit a wide range of sp3-bonded carbon contents from 20 to 76 at.%, as measured by electron energy loss spectroscopy (EELS). The Taue optical gaps of the a-C films increase monotonically from 0.65 eV for 20 at.% sp3 C to 2.25 eV for 76 at.% sp3 C. Spectra in the ellipsometric angles (1.5-5 eV) have been analyzed using different effective medium theories (EMTs) applying a simplified optical model for the dielectric function of a-C, assuming a composite material with sp2 C and sp3 C components. The most widely used EMT, namely that of Bruggeman (with three-dimensionally isotropic screening), yields atomic fractions of sp3 C that correlate monotonically with those obtained from EELS. The results of the SE analysis, however, range from 10 to 25 at.% higher than those from EELS. In fact, we have found that the volume percent sp3 C from SE using the Bruggeman EMT shows good numerical agreement with the atomic percent sp3 C from EELS. The SE-EELS discrepancy has been reduced by using an optical model in which the dielectric function of the a-C is determined as a volume-fraction-weighted average of the dielectric functions of the sp2 C and sp3 C components. © 1998 Elsevier Science S.A.

Analysis of amorphous carbon thin films by spectroscopic ellipsometry

Using spectroscopic ellipsometry (SE), we have measured the optical properties of amorphous carbon (a-C) films ∼ 10-30 nm thick prepared using a filtered beam of C+ ions from a cathodic arc. Such films exhibit a wide range of sp3-bonded carbon contents from 20 to 76 at.% as measured by electron energy loss spectroscopy (EELS), and a range of optical gaps from 0.65 eV (20 at.% sp3 C) to 2.25 eV (76 at.% sp3 C) as measured by SE. SE data from 1.5 to 5 eV have been analyzed by applying the most widely used effective medium theory (EMT) namely that of Bruggeman with isotropic screening, assuming a model of the material as a composite with sp2 C and sp3 C components. Although the atomic fractions of sp3 C deduced by SE with the Bruggeman EMT correlate monotonically with those obtained by EELS, the SE results range from 10 to 25 at.% higher. The possible origins of this discrepancy are discussed within the framework of an optical composite. Improved agreement between SE and EELS is obtained by employing a simple form for the EMT, in which the effective dielectric function is determined as a volume-fraction-weighted average of the dielectric functions of the two components. © 1998 Elsevier Science B.V. All rights reserved.

Calculation of the electronic structure of carbon films using electron energy loss spectroscopy.

The detailed understanding of the electronic properties of carbon-based materials requires the determination of their electronic structure and more precisely the calculation of their joint density of states (JDOS) and dielectric constant. Low electron energy loss spectroscopy (EELS) provides a continuous spectrum which represents all the excitations of the electrons within the material with energies ranging between zero and about 100 eV. Therefore, EELS is potentially more powerful than conventional optical spectroscopy which has an intrinsic upper information limit of about 6 eV due to absorption of light from the optical components of the system or the ambient. However, when analysing EELS data, the extraction of the single scattered data needed for Kramers Kronig calculations is subject to the deconvolution of the zero loss peak from the raw data. This procedure is particularly critical when attempting to study the near-bandgap region of materials with a bandgap below 1.5 eV. In this paper, we have calculated the electronic properties of three widely studied carbon materials; namely amorphous carbon (a-C), tetrahedral amorphous carbon (ta-C) and C60 fullerite crystal. The JDOS curve starts from zero for energy values below the bandgap and then starts to rise with a rate depending on whether the material has a direct or an indirect bandgap. Extrapolating a fit to the data immediately above the bandgap in the stronger energy loss region was used to get an accurate value for the bandgap energy and to determine whether the bandgap is direct or indirect in character. Particular problems relating to the extraction of the single scattered data for these materials are also addressed. The ta-C and C60 fullerite materials are found to be direct bandgap-like semiconductors having a bandgaps of 2.63 and 1.59eV, respectively. On the other hand, the electronic structure of a-C was unobtainable because it had such a small bandgap that most of the information is contained in the first 1.2 eV of the spectrum, which is a region removed during the zero loss deconvolution.

Optical and electronic properties of amorphous diamond

The optical and electronic properties of highly tetrahedral amorphous diamond-like carbon (amorphous diamond, a-D) films were investigated. The structure of the films grown on silicon and glass substrates, under similar deposition conditions using a compact filtered cathodic vacuum arc system, are compared using electron energy loss spectroscopy (EELS). Results from hydrogenation of the films are also reported. The hydrogenated films show two prominent IR absorption peaks centered at 2920 and 2840 cm-1, which are assigned to the stretch mode of the C-H bond in the sp3 configuration on the C-H3 and C-H sites respectively. The high loss EELS spectra show no reduction in the high sp3 content in the hydrogenated films. UV and visible transmission spectra of a-D thin films are also presented. The optical band gap of 2.0-2.2 eV for the a-D films is found to be consistent with the electronic bandgap. The relationship between the intrinsic compressive stress in the films and the refractive index is also presented. The space charge limited current flow is analyzed and coupled with the optical absorption data to give an estimate of 1018 cm-3 eV-1 for the valence band edge density of states.

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.

Density, sp3 content and internal layering of DLC films by X-ray reflectivity and electron energy loss spectroscopy

A variety of hydrogenated and non-hydrogenated amorphous carbon thin films have been characterized by means of grazing-incidence X-ray reflectivity (XRR) to give information about their density, thickness, surface roughness and layering. We used XRR to validate the density of ta-C, ta-C:H and a-C:H films derived from the valence plasmon in electron energy loss spectroscopy measurements, up to 3.26 and 2.39 g/cm3 for ta-C and ta-C:H, respectively. By comparing XRR and electron energy loss spectroscopy (EELS) data, we have been able for the first time to fit a common electron effective mass of m*/me = 0.87 for all amorphous carbons and diamond, validating the `quasi-free' electron approach to density from valence plasmon energy. While hydrogenated films are found to be substantially uniform in density across the film, ta-C films grown by the filtered cathodic vacuum arc (FCVA) show a multilayer structure. However, ta-C films grown with an S-bend filter show a high uniformity and only a slight dependence on the substrate bias of both sp3 and layering.

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.

High-efficiency InGaN/GaN quantum well structures on large area silicon substrates

The growth techniques which have enabled the realization of InGaN-based multi-quantum-well (MQW) structures with high internal quantum efficiencies (IQE) on 150mm (6-in.) silicon substrates are reviewed. InGaN/GaN MQWs are deposited onto GaN templates on large-area (111) silicon substrates, using AlGaN strain-mediating interlayers to inhibit thermal-induced cracking and wafer-bowing, and using a SiN x interlayer to reduce threading dislocation densities in the active region of the MQW structure. MQWs with high IQE approaching 60% have been demonstrated. Atomic resolution electron microscopy and EELS analysis have been used to study the nature of the important interface between the Si(111) substrate and the AlN nucleation layer. We demonstrate an amorphous SiN x interlayer at the interface about 2nm wide, which does not, however, prevent good epitaxy of the AlN on the Si(111) substrate. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.