X-ray photoemission spectroscopy of nitrogen-doped UNCD/a-C:H films prepared by pulsed laser deposition

Nitrogen-doped ultrananocrystalline diamond (UNCD)/hydrogenated amorphous carbon (a-C:H) films were deposited by pulsed laser deposition (PLD). Nitrogen contents in the films were controlled by varying a ratio in the inflow amount between nitrogen and hydrogen gases. The film doped with a nitrogen content of 7.9 at.% possessed n-type conduction with an electrical conductivity of 18 Ω^? 1 cm^? 1 at 300 K. X-ray photoemission spectra, which were measured using synchrotron radiation, were decomposed into four component spectra due to sp², sp³ hybridized carbons, C=N and C–N. A full-width at half-maximum of the sp³ peak was 0.91 eV. This small value is specific to UNCD/a-C:H films. The sp²/(sp³ + sp²) value was enhanced from 32 to 40% with an increase in the nitrogen content from 0 to 7.9 at.%. This increment probably originates from the nitrogen incorporation into an a-C:H matrix and grain boundaries of UNCD crystallites. Since an electrical conductivity of a-C:H does not dramatically enhance for this doping amount according to previous reports, we believe that the electrical conductivity enhancement is predominantly due to the nitrogen incorporation into grain boundaries.     

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

Hydrogenated amorphous carbon nitride (a-C:N:H) has been synthesised 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 ∼65 to 40%, respectively. The transition is due to the formation of polymeric CN, CN and NH groups, not an increase in CH bonds. 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.     

Friction and wear property of a-CNx coatings sliding against ceramic and steel balls in water

The amorphous carbon nitride coatings (a-CN_x) were deposited on Si₃N₄ disks using ion beam assisted deposition (IBAD), and their composition and chemical bonding were determined by X-ray photoelectron spectroscopy (XPS). The a-CN_x coatings' hardness was measured by nano-indentation and the friction and wear property of the a-CN_x coatings sliding against Si₃N₄, SiC, Al₂O_3, SUS440C and SUJ2 balls in water were investigated by using ball-on-disk tribo-meter. The worn surfaces were observed using optical microscopy and analyzed by XPS. The results of XPS analysis showed that the a-CN_x coatings contained 12 at.% nitrogen and the major chemical bonding was sp² C = N and sp³C–N. The nano-hardness of the a-CN_x coatings was 29 GPa, higher than those of balls. Among five kinds of tribo-systems, the lowest friction coefficient was obtained in the range of 0.01 to 0.02 for the tribo-systems with SiC and Si₃N₄ balls, the largest wear rate of the a-CN_x coating of 1.77 × 10^− 7 mm³/Nm was obtained as sliding against Al₂O₃ ball, while the smallest wear rate of a-CN_x coating of 1.44 × 10^− 8 mm³/Nm was gotten as sliding against Si₃N₄ ball. However, SUJ2 ball showed the highest wear rate of 7.0 × 10^− 7 mm³/Nm, whereas Al₂O₃ ball exhibited the lowest wear rate of ball of 3.55 × 10^− 9 mm³/Nm. The XPS analysis on the worn surface for the a-CN_x coatings displayed that the nitrogen concentration decreased and the sp²-bonding-rich structure was formed after sliding tests in water.     

Microstructure and optical band gap control of DLC film deposited by pulsed discharge plasma CVD

DLC films were deposited on silicon and quartz glass substrates by pulsed discharge plasma chemical vapor deposition (CVD), where the plasma was generated by pulsed DC discharge in H₂–CH₄ gas mixture at about 90 Torr in pressure, and the substrates were located near the plasma. The repetition frequency and duty ratio of the pulse were 800 Hz and 20%, respectively. When CH₄ / (CH₄ + H₂) ratio, i.e. methane concentration (Cm), increased from 3 to 40%, C₂ species in the plasma was increased, and corresponding to the increase of C₂, deposition rate of the film was increased from about 0.2 to 2.4 μm/h. The absorption peaks of sp³C–H and sp²C–H structures were observed in the FT-IR spectra, and the peak of sp²C–H structure was increased with increasing Cm, showing that sp² to sp³ bonding ratio was increased when Cm was increased. Corresponding to these structural changes due to the increase of Cm, optical band gap (Eg) was decreased from 3 to 0.5 eV continuously when Cm was increased from 3 to 40%.     

Tribological study of amorphous BC4N coatings

Amorphous BC₄N thin films with a thickness of ∼ 2 μm have been deposited by Ion Beam Assisted Deposition (IBAD) on hard steels substrates, in order to study the wear behavior under high loads and the applicability as protective coatings. The bonding structure of the a-BC₄N film was assessed by X-ray Absorption Near Edge Spectroscopy (XANES) and Infrared Spectroscopy, indicating atomic mixing of B–C–N atoms, with a proportion of ∼ 70% sp² hybrids and ∼ 30% sp³ hybrids. Nanoindentation shows a hardness of ∼ 18 GPa and an elastic modulus of ∼ 170 GPa. A detailed tribological study is performed by pin-on-disk tests, combined with spectromicroscopy of the wear track at the coating and wear scar at pin. The tests were performed at ambient conditions, against WC/Co counterface balls under loads up to 30 N, with the sample rotating at 375 rpm. The coatings suffer a continuous wear, at a constant rate of 2 × 10^− 7 mm³/Nm, without catastrophic failure due to film spallation, and show a coefficient of friction of ∼ 0.2.     

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.     

Electrical contacts to nitrogen incorporated nanocrystalline diamond films

The effect of surface plasma treatment on the nature of the electrical contact to the nitrogen incorporated nanocrystalline diamond (n-NCD) films is reported. Nitrogen incorporated NCD films were grown in a microwave plasma enhanced chemical vapor deposition (MPECVD) reactor using CH₄ (1%)/N₂ (20%)/Ar (79%) gas chemistry. Raman spectra of the films showed features at ∼ 1140 cm^− 1, 1350 cm^− 1(D-band) and 1560 cm^− 1(G-band) respectively with changes in the bonding configuration of G-band after the plasma treatment. Electrical contacts to both untreated and surface plasma treated films are formed by sputtering and patterning Ti/Au metal electrodes. Ohmic nature of these contacts on the untreated films has changed to non-ohmic type after the hydrogen plasma treatment. The linear current–voltage characteristics could not be obtained even after annealing the contacts. The nature of the electrical contacts to these films depends on the surface conditions and the presence of defects and sp² carbon.     

Etching process of hydrogenated amorphous carbon (a-C:H) thin films in a dual ECR–r.f. nitrogen plasma

Hydrogenated amorphous carbon (a-C:H) films deposited from CH₄ in a dual electron cyclotron resonance (ECR)–r.f. plasma were treated in N₂ plasma at different r.f. substrate bias voltages after deposition. The etching process of a-C:H films in N₂ plasma was observed by in situ kinetic ellipsometry, mass spectroscopy (MS), and optical emission spectroscopy (OES). Ex situ atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) were used to characterize the etched film surface. XPS analysis proves that the nitrogen treatment on the a-C:H film, induced by r.f. substrate bias, causes a direct nitrogen incorporation in the film surface up to 15–17 at.% to a depth of about 20–40 Å depending on the r.f. bias. Various bonding states between carbon and nitrogen, such as tetrahedral sp³ C–N, and trigonal sp² C–N were confirmed by the deconvolution analysis of C 1s and N 1s core level spectra. The evolution of etching rate and the surface roughness in the film measured by AFM exhibit a clear dependence on the applied r.f. bias. MS and OES show the various neutral species in the N₂ plasma such as HCN, CN, and C₂N₂, which may be considered as the chemical etching products during the N₂ plasma treatment of a-C:H film.     

Electrical Properties of B-doped homoepitaxial diamond films grown from UHP gas sources

It is confirmed that a small amount of nitrogen incorporated into chemical vapor deposited diamond films dramatically affects their electrical properties. Nitrogen can be incorporated into diamond films through the leak of vacuum system and/or from the impurity in source gases. Because a nitrogen atom can be a deep donor in diamond crystal, the p-type semiconducting properties of boron doped diamond films can be degraded even by the small amount of nitrogen. The small amount of nitrogen in chemical vapor deposited diamond films was measured by cathodoluminescence spectroscopy. For the detection of nitrogen, the N–V center was intentionally induced by defect formation through ion beam irradiation and subsequent annealing. The luminescence intensity of the N–V center was decreased by reducing the leak of the vacuum system and by upgrading the purity of the source gases. Both the carrier density and the Hall mobility of the boron doped diamond films were successfully improved by the control of nitrogen contamination. Using extremely high pure CH₄, H₂ and B₂H₆ in a tightly sealed vacuum system, the total amount of nitrogen impurity in the source gas was controlled to <80 ppm in the N/C atomic ratio resulting in a Hall mobility of 1600 cm²/Vs with a hole concentration of >10¹⁴ cm⁻³ at the room temperature in a 10-ppm-boron doped homoepitaxial diamond film.     

Microstructure and tribological properties of ternary BCN thin films with different carbon contents

Boron carbon nitrogen (BCN) thin films with different carbon contents are deposited on high-speed steel substrates by reactive magnetron sputtering (RMS) and their microstructure and tribological properties are studied. The BCN films with carbon contents from 26.9 wt.% to 61.3 wt.% have an amorphous structure with variable amounts of carbon bonds (sp²C–C, sp²C–N and sp³C–N bonds). A higher carbon content enhances the film hardness but reduces the friction coefficient against GCr15 steel balls in air. BCN films with higher hardness, lower friction coefficient, and better wear resistance can be obtained by increasing the carbon content.     

Nitrogen implantation of suspended graphene flakes: Annealing effects and selectivity of sp2 nitrogen species

Nitrogen inclusion in both chemical vapour deposition and exfoliated few-layer graphene flakes was performed by nitrogen ion implantation in ultra-high vacuum. Inclusion of up to ∼20 at.% nitrogen can be reached through this clean technique with absence of oxygen species in the final product, while maintaining a largely sp²-carbon network. The nitrogen inclusion was observed by scanning X-ray photoelectron microscopy (SPEM) with energy resolution of 0.2 eV and spatial resolution of 10 nm. SPEM can be used to follow the evolution of nitrogen species: pyridinic, graphitic, and pyrrolic, at different doping stages and annealing temperatures. Variations in the ratio between sp² nitrogen species was observed for increasing treatment time; annealing results in quenching of the sp³ component, suggesting the graphitic nitrogen as the most thermal stable species. The occurrence of graphitic species together with the absence of pyrrolic is indicative of N-incorporation into a hexagonal graphene-based lattice. Ion irradiation followed by annealing performed in a controlled way is a promising strategy to fine control the nature of the nitrogen species grafted to the graphene while focusing on selected applications.     

Dependence of the composition and bonding structure of carbon nitride films deposited by direct current plasma assisted pulsed laser ablation on the deposition temperature

Carbon nitride films were deposited by direct current plasma assisted pulsed laser ablation of a graphite target under nitrogen atmosphere. Atomic force microscopy (AFM), Fourier transform infrared (FTIR), Raman, and X-ray photoelectron spectroscopy (XPS) were used to characterize the surface morphology, bonding structure, and composition of the deposited films. The influence of deposition temperature in the range 25–400 °C on the composition and bonding structure of carbon nitride films was systematically studied. AFM images show that surface roughness and cluster size increase monotonically with deposition temperature. XPS, FTIR, and Raman spectra indicate directly the existence of CN, CN, and CN bonds in the deposited films. The increase of deposition temperature results in a drastic decrease in the N/C ratio, the content of CN bond and N atoms bonded to sp³ C atoms, in addition to the increase in the content of disorder sp² C atoms and N atoms bonded to sp² C atoms in the deposited films. Raman spectra show that the intensity ratio of D peak over G peak increases with increasing deposition temperature to 200 °C, then decreases with the further increase of deposition temperature, which results from the continuous growth of sp² cluster in the films.     

Simultaneous reduction,exfoliation, and nitrogen doping of graphene oxide via a hydrothermal reaction for energy storage electrode materials

Nitrogen (N)-doped graphene (NG) sheets were prepared using (NH₄)₂CO₃ and an aqueous dispersion of graphene oxide (GO) by an eco-friendly hydrothermal reaction. The in situ produced ammonia played an important role in the simultaneous nitrogen doping, the reduction and exfoliation of GO. The (NH₄)₂CO₃/GO mass ratio and reaction temperature were varied to investigate the effects on the N doping level. The elemental analysis determined from the X-ray photoelectron spectroscopy showed that the nitrogen content of the NG was about 10.1 at.% and the oxygen content decreased significantly due to the hydrothermal reduction of GO. The electrochemical performances of the NG sheets increased with increasing doped N content. The highest specific capacitance of 295 F g⁻¹ at a current density of 5 A g⁻¹ and the highest specific surface area of 412 m² g⁻¹ were observed with the sample processed at 130 °C. The retention of the specific capacitance was maintained at ∼89.8% after 5000 charge–discharge cycles. These results imply that NG sheets obtained by this simple eco-friendly approach are suitable for use in high performance energy storage electrode materials.     

Enhancing the sintering ability of TiNx by introduction of nitrogen vacancy defects

Highly nitrogen-deficient non-stoichiometric TiN_x powders within nitrogen vacancy defects (0.3<x<0.5) were prepared by mechanical alloying and consolidated by high pressure sintering. The effects of nitrogen vacancy defects, sintering temperature and pressure on densification and grain growth of TiN_x were investigated for improving sintering ability and mechanical properties. Increasing nitrogen vacancy defects promoted densification and grain growth of TiN_x. Nitrogen vacancies accelerated material transport and diffusion during sintering and altered strong covalent bonding nature was believed to result in enhanced sintering ability. Densification of TiN_x was enhanced by increasing temperature and elevating pressure, grain growth was promoted by increasing temperature, whereas restrained by elevating pressure. TiN_x (x=0.32) ceramic with relative density of 99.4% and average grain size of 21 nm was obtained at 1200 °C, 5 GPa and 10 min. Vickers hardness of 22.6 GPa and fracture toughness of 5.0 MPa m^1/2 were achieved.     

Improvement of field-emission-lamp characteristics using nitrogen-doped carbon nanocoils

Carbon nanocoils (CNCs) synthesized using thermal pyrolysis chemical vapor deposition on 304 stainless steel wire substrates were used as the cathodes of field emission lamps (FELs). The effects of the growth temperature on the FE performances were studied, and we observed that uniform and dense CNCs that are suitable for use as FE cathodes can be synthesized at 600 °C. We also found that a nitrogen doping post-treatment can significantly improve the FE efficiency of the CNCs. When doped at 200 °C with a nitrogen flow rate of 500 sccm for 30 min, the nitrogen content of the CNC surface could reach 4.9 wt.%. ESCA analysis indicates that the doped nitrogen atoms formed CN_x bonding and increased the sp² clusters in the CNCs. The turn-on voltage was reduced from 2.1 V/μm to 1.4 V/μm, and the β value increased considerably from 2465 to 3241 after N-doping post-treatment. The bulb-type FELs using our N-doped CNC cathodes showed a good luminous efficiency as high as 75 lm/W at 8 kV.     

Formation and characteristics of undoped and doped tetrahedral amorphous carbon films

Synthesis of undoped and doped tetrahedral amorphous carbon (ta-C) films has been achieved using magnetic field filtered plasma stream system in an ambient gas of pure Ar and Ar with N₂, respectively. The optical and electrical properties of these films as a function of the substrate bias voltages (V_b) or nitrogen partial pressures (P_N) have been studied using UV-visible optical absorption spectroscopy, Fourier-transform infra-red spectroscopy (FTIR) and measurements of electrical conductivity. The results show that ta-C films with a high sp³ fraction were formed when the V_b was in the range of −10 to −50 V. The optical band gap of such ta-C films was found to be larger than 3 eV. The incorporation of nitrogen into the ta-C films deposited at low P_N (P_N<25%), results in a slight drop in activation energy, which indicates that there is evidently some doping effect of nitrogen. The configurations of N atoms in ta-C network are identified and discussed.     

Structural and mechanical properties of facing-target sputtered amorphous CNx films

Structural and mechanical properties of carbon nitride films, deposited using a DC facing-target reactive sputtering system at various N₂ fractions (P_N) in the gas mixture, were studied systematically. XPS analyses indicate that N concentration is not directly proportional to P_N, and it rises quickly to a saturation value of ∼ 33 at.% at a P_N of 20%. The ratio of N–C(sp²)/N–C(sp³) increases with the rise of P_N from 0% to 20%, and then decreases with further rising P_N. However, the number and size of disordered sp²-hybridized C clusters continue to increase over the whole range of P_N, which is consistent with the Raman and high-resolution transmission electron microscopy measurements. Nanoindenter measurements show that the hardness of the films continuously decreases from ∼ 17.5 to ∼ 5.6 GPa with the increasing P_N from 0% to 100%, due to the conversion from sp³ C to sp² C and the clustering of sp² C structure.     

Nitrogen-containing apatite

Two commercial hydroxyapatites were treated in dry ammonia at temperatures between 800 and 1300°C for different times up to 30 h. Nitrogen was incorporated with a maximum content of 3·7 wt% in presence of graphite. X-ray diffraction studies show no important phase transformation by the incorporation of nitrogen up to 1200°C. Treatments at temperatures above 1200°C resulted in the formation of CaO or Ca(OH)₂. ³¹P NMR studies indicate no direct bonding of nitrogen and phosphorous. Infrared spectra show increasing intensities of four new bands at 3250, 2016, 1966 and 700 cm⁻¹ with increasing nitrogen contents, while the OH-bands at 3570 and 630 cm⁻¹ vanish. Taking into account results of the carbon content, XRD, NMR and IR spectra it is suggested that nitrogen enters into the structure as [CN₂]²⁻ ion, substituting [OH]⁻ groups, and forming cyanamidapatite Ca₁₀(PO₄)₆(CN₂). ©     

Substrate temperature effects on the electron field emission properties of nitrogen doped ultra-nanocrystalline diamond

For the purpose of improving the electron field emission properties of ultra-nanocrystalline diamond (UNCD) films, nitrogen species were doped into UNCD films by microwave plasma chemical vapor deposition (MPCVD) process at high substrate temperature ranging from 600° to 830 °C, using 10% N₂ in Ar/CH₄ plasma. Secondary ion mass spectrometer (SIMS) analysis indicates that the specimens contain almost the same amount of nitrogen, regardless of the substrate temperature. But the electrical conductivity increased nearly 2 orders of magnitude, from 1 to 90 cm^− 1 Ω^− 1, when the substrate temperature increased from 600° to 830 °C. The electron field emission properties of the films were also pronouncedly improved, that is, the turn-on field decreased from 20 V/μm to 10 V/μm and the electron field emission current density increased from less than 0.05 mA/cm² to 15 mA/cm². The possible mechanism is presumed to be that the nitrogen incorporated in UNCD films are residing at grain boundary regions, converting sp³-bonded carbons into sp²-bonded ones. The nitrogen ions inject electrons into the grain boundary carbons, increasing the electrical conductivity of the grain boundary regions, which improves the efficiency for electron transport from the substrate to the emission sites, the diamond grains.     

Stability of carbon nitride films prepared from volatile CN species via atomic transport reactions

Thin CN_x films were deposited by inductively coupled plasma chemical vapour deposition (ICP-CVD) at different substrate temperatures. Instead of the conventional gaseous carbon precursors, a pure carbon mesh was used as carbon source with nitrogen as a carrier/reaction gas. The CN_x films are formed from volatile CN species produced via atomic transport reactions. The deposition rate decreases from 3.2 nm/min at room temperature to almost zero at 150°C. The nitrogen fraction N/(N+C) is at about 0.5, as revealed by various analytical techniques; the composition remains unchanged when varying the substrate temperature. The films are composed mainly of sp² carbon atoms bonded to nitrogen atoms. The CN_x layers are stable upon annealing at temperatures up to 300°C; the surface contamination is removed, while no changes in the nitrogen atomic fraction and in the bonding structure are observed.