Photoelectron spectroscopy and secondary ion mass spectrometry characterization of diamond-like carbon films

Photoelectron spectroscopy at different photon energies was used to optimize the photoexcitation cross section for valence band study of diamond-like hydrogenated carbon films. The electronic states of diamond-like carbon (DLC) were studied by synchrotron radiation photoelectron spectroscopy and ultraviolet photoelectron spectroscopy. The valence band spectra measured at different excitation energies show the gradual emergence of the p-π band in relation to the sample annealing and ion bombardment amorphization. The p-π band of the annealed DLC was characterized by localized p_z states whilst the formation of the amorphous carbon surface was accompanied by appearance of the delocalized p_z states in the gap. Secondary ion mass spectrometry and thermal desorption spectroscopy showed that sample annealing was accompanied by hydrogen content decrease.     

Effect of silver doping on optical property of diamond like carbon films

Optical properties of silver doped diamond like carbon films (Ag:DLC) deposited by the RF reactive sputtering technique were studied in detail. The chemical binding energy and the composition of the films were investigated by using an X-ray photoelectron spectroscopy. Optical transparency and optical band gap decreased with the silver incorporation to the DLC film. Optical band gap calculated from transmittance spectra decreased from 2.55 to 1.95 eV with a variation of Ag concentration from 0 to 12.5 at.%. Urbach parameter determined from the band tail of the transmittance spectra showed to increase with the doping concentration.     

The influence of fluorine doping on the optical properties of diamond-like carbon thin films

Optical properties of fluorine doped diamond-like carbon (F:DLC) films deposited by the direct current plasma enhanced chemical vapor deposition (PECVD) technique were studied in detail. Surface morphologies of the F:DLC films were studied by an atomic force microscope, which indicated surface roughness increased with increase in at.% of F in the films. The chemical binding was investigated by X-ray photoelectron spectroscopic studies. Fourier transformed infrared spectroscopic studies depicted the presence of CF_x (x = 1,2,3) and CH_n (n = 1,2) bonding within the F:DLC films. Optical transparency and the optical band gap decreased with the fluorine incorporation in the DLC film. Optical band gap calculated from the transmittance spectra decreased from 2.60 to 1.95 eV with a variation of 0-14.8 at.% of F concentration in the diamond-like carbon films. Urbach parameter determined from the band tail of the transmittance spectra showed that it increased with the doping concentration.     

Preparation of diamond-like carbon films by cathodic micro-arc discharge in aqueous solutions

Diamond-like carbon films (DLC) and silicon doped diamond-like carbon films were deposited on Ni substrate by cathodic micro-arc discharge at room temperature in aqueous solutions. The deposit potential was 130 V. The structure of the films was characterized by a scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Raman spectra and XPS analysis demonstrated that the films were diamond-like carbon clearly. SEM observation showed that the DLC films were uniform and the thickness was about 200 nm. Potentiodynamic polarization curve indicated the corrosion resistance of the Ni substrate was markedly improved by DLC films.     

电化学沉积DLC膜及其表征

采用电化学沉积方法，甲醇有机溶剂作碳源，在直流电源作用下在单晶硅表面沉积得到碳薄膜。薄膜不溶于苯、丙酮等有机溶剂，具有较高的硬度(16GPa左右)，用AFM、Raman和FTIR分析手段对该薄膜表面形貌和结构进行表征，Raman和FTIR结果表明电化学沉积得到的是含氢的类金刚石碳薄膜。通过研究样品薄膜的XPS和XAES谱图特征，进一步证实薄膜是DLC薄膜，并用线性插入法估算出样品薄膜中SP^3的相对含量为60％，同时推测了电化学沉积DLC薄膜的生长机理。     

Evaluation of microstructures and mechanical properties of diamond like carbon films deposited by filtered cathodic arc plasma

Diamond-like carbon (DLC) films were deposited by a cathodic arc plasma evaporation (CAPD) process, using a mechanical shield filter combined with a magnetic filter with enhanced arc structure at substrate-bias voltage ranging from − 50 to − 300 V. The film characteristics were investigated using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and high-resolution transmission electron microscopy (HRTEM). The mechanical properties were investigated by using a nanoindentation tester, scratch test and ball on disc wear test. The Raman spectra of the films showed that the wavenumber ranging from 900 to 1800 cm^− 1 could be deconvoluted into 1140 cm^− 1, D band and G band. The bias caused a significant effect on the sp³ content which was increased with the decreasing of I_D/I_G ratio. The XPS spectra data of the films which were etched by H⁺ plasma indicated the sp³ content are higher than those of the as-deposited DLC films. This implied that there is a sp²-rich layer present on the surface of the as-deposited DLC films. The nanoindentation hardness increased as the maximum load increased. A 380 nm thick and well adhered DLC film was successfully deposited on WC-Co substrate above a Ti interlayer. The adhesion critical load of the DLC films was about 33 N. The results of the wear tests demonstrated that the friction coefficient of the DLC films was between 0.12 and 0.2.     

Photoelectron spectroscopy of ion-irradiated B-doped CVD diamond surfaces

Chemical vapour deposition (CVD) diamond films were irradiated by 1 keV argon ions at room temperature with doses ranging from 3.6 × 10¹² to 1.1 × 10¹⁶ Ar⁺ cm². The influence of sputtering on the valence band density of states of a boron-doped CVD diamond film was investigated by ultraviolet photoelectron spectroscopy and the changes in the plasmon features were observed by X-ray photoelectron spectroscopy of the carbon Is core level and its loss region. A gradual change from typical diamond features to amorphous carbon was observed after prolonged bombardment times. Above a critical dose D_crit of 5.8 × 10¹⁴ Ar⁺ cm² the damaged surface layer is characterized by a splitting of the C Is bulk peak into two components: a bulk-like diamond peak at 285.3 eV binding energy and a defect peak with 1 eV lower binding energy, which is attributed to the production of an amorphous sp²-rich carbon matrix. Moreover additional occupied states in the range of 0–4 eV binding energy, completely different to those observed on reconstructed diamond surfaces, were observed in the valence band spectra of the ion-irradiated diamond surface. These filled states can also be attributed to the amorphous carbon matrix which is formed at high doses. At very low doses (< 3 × 10¹⁴ ions cm²) only a band bending of the C Is diamond core level peak, along with the formation of some occupied states in the band structure at around 3.8 eV binding energy was observed. A comparison with annealed hydrogen-free CVD diamond surfaces shows some similarities concerning these filled states. The obtained spectra are compared with other crystalline and amorphous forms of carbon and the results are discussed in terms of an irradiation-induced change in the atomic structure of the surface. A comparison of ion bombarded and annealed diamond samples clearly shows that no graphitization takes place in the latter case.     

Doping of rf plasma deposited diamond-like carbon films

Rf plasma deposited diamond-like carbon (DLC) films have been doped n-type with the addition of nitrogen as a feed gas to a magnetically confined rf plasma. Controlled amounts of nitrogen are added to the CH₄/He plasma and the films are characterised. The electronic properties together with the microstructure of the deposited films are examined. Activation energy studies show the Fermi level can be moved from 0.5 eV away from the valence band for the undoped DLC films, through a maximum activation energy of 0.9 eV corresponding to the midgap and to 0.45 eV away from the conduction band with maximum N incorporation. The optical band gap first increases, indicative of a reduction in the band-edge tail states, and then tends to a steady value of ˜2 eV. Activation energy studies together with the optical band gap data are used to analyse the density of states for the deposited films. The preferential doping configuration of the atomic nitrogen and the importance of the π-π* states for electronic conduction for DLC:N films is discussed in the light of the findings.     

High resolution X-ray photoelectron spectroscopy of beta gallium oxide films deposited by ultra high vacuum radio frequency magnetron sputtering

The gallium oxide thin films with amorphous, crystalline, and nanostructure morphologies were deposited by a radio frequency magnetron sputtering system in ultra high vacuum conditions. High resolution X-ray photoelectron spectroscopy spectra of films were analyzed relating on the preparation conditions. On the amorphous films, the density of states at valence band region is dependent on the sputtering gas compositions. Beta gallium oxide (100) films are epitaxially deposited on magnesium oxide (100) crystalline substrate. The high resolution X-ray photoelectron spectra suggest the presence of the density of states valence band region with oxygen deficiency out of the stoichiometry on the epitaxial crystalline beta gallium oxide films.     

Luminescent Properties of Porous Si Passivated by Diamond Film and DLC Film

Surface passivation methods for porous Si (PS) surfaces, i.e., depositing diamond film or diamond-like carbon (DLC) film on PS surfaces, were attempted. Two emission bands, weak blue band and strong red band existed in the PL spectrum of diamond film coated on PS, were discovered by the photoluminescence measurements. The luminescent mechanism and stability were discussed. The results indicated that diamond film may stabilize the PL wavelength and intensity of PS, and therefore could become a promising passivation film of porous Si. The PL properties of PS coated by DLC films, including hydrogenated diamond like carbon (DLC:H) film and nitrogen doped DLC film (DLC:N) were also studied in this paper. The DLC films may stabilize the PL of PS, but the photoluminescent intensity was obviously weaker than that of diamond film coated PS.     

Thermal stability of Cr-doped diamond-like carbon films synthesized by cathodic arc evaporation

Cr-doped diamond-like carbon (DLC) films were synthesized using a cathodic arc evaporation (CAE) process. The thermal oxidation behavior of Cr-doped DLC films was investigated using thermal gravimetric analysis (TGA) and differential thermal analysis (DTA). The phase identification and microstructural examinations were conducted by X-ray diffraction, scanning electron spectroscopy (SEM), transmission electron spectroscopy (TEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) in order to understand the characteristics of Cr-doped DLC films. The as-deposited Cr-doped DLC film exhibits a lamellar structure observed by TEM. A significant weight loss of film results from the thermal oxidation of carbon occurred at 290 to 342 °C. At the temperature higher than 342 °C, slight weight gain of specimen was observed due to the thermal oxidation of the underlying CrC_xN_y and CrN interlayer. By heat-treated specimens from 200 to 400 °C, Raman spectra reveal the increase of I_D/I_G value conforming to the graphitiation process of the Cr-doped DLC films. Finally, surface reactions of the annealed films using XPS analysis were discussed.     

XPS and TEM study of W-DLC/DLC double-layered film

A double-layered film of tungsten-containing diamond-like carbon (W-DLC) and DLC, (W-DLC)/DLC, was investigated. A film of 1.6 µm in thickness was deposited onto silicon substrate. The investigate double-layered coating was deposited by using the combination of PECVD and co-sputtering of tungsten metal target. Structure, interface and chemical bonding state of the investigated film were analyzed by Transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS). From the results of the analyses, the structure of double-layered film is that amorphous phase of carbon is continued from DLC to W-DLC and tungsten metal clusters are dispersed in W-DLC layer.     

Influence of PECVD parameters on the properties of diamond-like carbon films

The properties of diamond-like carbon (DLC) are strongly affected by the amount of carbon atoms bonded in sp² and sp³ electronic hybridizations. Also the amount of incorporated hydrogen and oxygen plays an important role in the final properties of DLC films. Usually, the structure and chemical composition of thin DLC films can be changed by varying the deposition parameters. Therefore, the influence of PECVD process parameters on the properties of DLC films, grown on Si substrates, was investigated in this work.Thin DLC films were deposited in a CH₄/H₂ plasma by using Ar as a gas carrier. Different ratios of gas flows were used as a variable parameter of the PECVD process. The effect of cathodic ion bombardment was also investigated.The chemical composition of DLC specimens was studied by X-ray photoelectron spectroscopy (XPS). The ratio of carbon in sp² and sp³ hybridizations was determined by analyzing the first derivative of Auger C KLL spectra. These results were also confirmed by the measurements of electrical resistivity. The changes of surface morphology and microadhesion were analyzed by Atomic Force Microscopy (AFM).     

Thickness of diamond-like carbon coatings quantified with Raman spectroscopy

A model is developed for quantifying the thickness of thin coatings and wear scars using Raman spectroscopy. The model, which assumes that both incident and Raman light obey Beer's law, was applied to Raman spectra from a diamond-like carbon (DLC) coating containing Si and O, known as DLN (diamond-like nanocomposite). The coatings ranged in thickness from 10 nm to 2 μm, according to stylus profilometry. Systematic variations in the Raman carbon (G band) and Si (1st order) peak intensities vs. thickness were found. Fits to the model gave an optical mean free path of λ250 nm for DLN. This value is in good agreement with optical absorption coefficient values of other DLC films. Thickness profiles of wear tracks in the coatings determined by the model compared well with depths determined by profilometry.     

Coating of diamond-like carbon nanofilm on alumina by microwave plasma enhanced chemical vapor deposition process

Diamond-like carbon (DLC) nanofilms with thickness varied from under one hundred to a few hundred nanometers have been successfully deposited on alumina substrates by microwave plasma enhanced chemical vapor deposition (MW-PECVD) process. To obtain dense continuous DLC nanofilm coating over the entire sample surface, alumina substrates were pre-treated to enhance the nucleation density. Raman spectra of DLC films on samples showed distinct diamond peak at around 1332 cm(-1), and the broad band of amorphous carbon phase at around 1550 cm(-1). Full width at half maximum height (FWHM) values indicated good formation of diamond phase in all films. The result of nano-indentation test show that the hardness of alumina samples increase from 7.3 +/- 2.0 GPa in uncoated samples to 15.8 +/- 4.5-52.2 +/- 2.1 GPa in samples coated with DLC depending on the process conditions. It is observed that the hardness values are still in good range although the thickness of the films is less than a hundred nanometer.     

Effects of molybdenum dithiocarbamate and zinc dialkyl dithiophosphate additives on tribological behaviors of hydrogenated diamond-like carbon coatings

The tribological behaviors of hydrogenated diamond-like carbon (DLC) coatings under varied load conditions lubricated with polyalpha olefin (PAO), molybdenum dithiocarbamate (MoDTC) and zinc dialkyl dithiophosphate (ZDDP) additives were investigated in this paper. Hydrogenated DLC coatings were synthesized through the decomposition of acetylene by the ion source. The tribological performances were measured on a SRV tribometer. The morphologies and chemical structures of the DLC coatings were investigated by the scanning electron microscope (SEM), Raman spectrometer (Raman) and X-ray photoelectron spectroscope (XPS). It was shown that the low friction and high wear were achieved on the hydrogenated DLC coating under MoDTC lubrication, while low wear was found on the hydrogenated DLC coating lubricated by ZDDP. The primary reason was attributed to different tribofilms formed on the contact area and the formation of graphitic layer. Both factors working together leaded to quite different tribological behaviors.     

Ab-initio valence band spectra of Al, In doped ZnO

We present the structural and electronic characterization of n-doped (Aluminium or Indium) ZnO and the effect of the doping on the calculated photoelectron spectroscopy (PES) spectra. The fully-relaxed calculations have been made using the density functional theory, including a Hubbard correlation term that increases the Zn-3d states binding energy, and which matches the experimental values. The effect of Oxygen vacancies is also included in our study. Our results show that the new Al or In-donor levels appearing in the conduction band hybridize with the Oxygen-2p states and help decrease the resistivity of these doped systems as was found experimentally. The calculated PES spectra show a small enhancement in the intensity close to the chemical potential as a result of these new Al or In levels.     

Room temperature photoluminescence spectrum modeling of hydrogenated amorphous silicon carbide thin films by a joint density of tail states approach and its application to plasma deposited hydrogenated amorphous silicon carbide thin films

Room temperature photoluminescence (PL) spectrum of hydrogenated amorphous silicon carbide (a-SiC_x:H) thin films was modeled by a joint density of tail states approach. In the frame of these analyses, the density of tail states was defined in terms of empirical Gaussian functions for conduction and valance bands. The PL spectrum was represented in terms of an integral of joint density of states functions and Fermi distribution function. The analyses were performed for various values of energy band gap, Fermi energy and disorder parameter, which is a parameter that represents the width of the energy band tails. Finally, the model was applied to the measured room temperature PL spectra of a-SiC_x:H thin films deposited by plasma enhanced chemical vapor deposition system, with various carbon contents, which were determined by X-ray photoelectron spectroscopy measurements. The energy band gap and disorder parameters of the conduction and valance band tails were determined and compared with the optical energies and Urbach energies, obtained by UV-Visible transmittance measurements. As a result of the analyses, it was observed that the proposed model sufficiently represents the room temperature PL spectra of a-SiC_x:H thin films.     

Visible light induced electron transfer process over nitrogen doped TiO(2) nanocrystals prepared by oxidation of titanium nitride

Nitrogen doped TiO(2) nanocrystals with anatase and rutile mixed phases were prepared by incomplete oxidation of titanium nitride at different temperatures. The as-prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), core level X-ray photoelectron spectroscopy (CL XPS), valence band X-ray photoelectron spectroscopy (VB XPS), UV-vis diffuse reflectance spectra (UV-vis DRS), and visible light excited photoluminescence (PL). The photocatalytic activity was evaluated for photocatalytic degradation of toluene in gas phase under visible light irradiation. The visible light absorption and photoactivities of these nitrogen doped TiO(2) nanocrystals can be clearly attributed to the change of the additional electronic (N(-)) states above the valence band of TiO(2) modified by N dopant as revealed by the VB XPS and visible light induced PL. A band gap structure model was established to explain the electron transfer process over nitrogen doped TiO(2) nanocrystals under visible light irradiation, which was consistent with the previous theoretical and experimental results. This model can also be applied to understand visible light induced photocatalysis over other nonmetal doped TiO(2).     

Electron structure of thin fullerene films deposited by various methods

The valence-band photoelectron spectra and the photoelectron energy loss spectra behind the C1s peak in the X-ray photoelectron spectra were studied in thin fullerene films deposited by various methods. The fine structure in the density of states near the valence band bottom observed for the fullerene films deposited by the method of pulsed supersonic molecular beam (SMB) with a helium carrier may be indicative of the presence of a long-range order. The spectra of π-plasmon losses in the films obtained by methods of thermal and SMB deposition exhibit a significant difference that can be related to a closer packing of C₆₀ molecules in the latter case.