Enhanced adhesion of epoxy-bonded steel surfaces using O2/Ar microwave plasma treatment

Steel surfaces have been modified using low pressure microwave plasma to enhance its adhesion with an epoxy adhesive. Optimization of the wettability of the surface was done using contact angle measurements for varying plasma parameters. Maximum wettability (19.9°) was obtained at 1000 W microwave power with 20 min of treatment time, −50 V sample bias and 1.67% O₂/Ar gas flow rate ratio. Enhanced wettability of the steel surface was attributed to increased surface roughness and oxide deposition. Using atomic force microscopy, surface roughness was observed to increase from 64.4 nm for the untreated surface to 76.7 nm for the O₂/Ar plasma treated surface. Deposition of oxides on the steel surface was also confirmed by the energy dispersive x-ray spectroscopy. Moreover, the increase in the total surface energy to 53.2 mN/m for the O₂ plasma treated steel surface supported the enhancement of its wettability, and hence, the adhesion with epoxy. Based on tensile test results, the adhesion strength of epoxy-bonded O₂/Ar plasma treated surfaces at optimum settings was increased to 3816.0 N, which is significantly higher compared to 3038.3 N for the epoxy-bonded untreated surfaces.     

Development of a superhydrophobic polyurethane-based coating from a two-step plasma-fluoroalkyl silane treatment

A method of achieving a superhydrophobic surface based upon a highly filled polyurethane (PU) paint coating has been demonstrated through the use of a combined oxygen/argon plasma pretreatment and a fluoroalkyl silane (FAS) final treatment.The combined plasma-FAS treated PU surface has been investigated and characterised using: field emission gun secondary electron microscope (FEG-SEM); X-ray photoelectron spectroscopy (XPS); energy-dispersive X-ray spectroscopy (EDX); water contact angle analysis (WCA); atomic force microscopy (AFM), and; Fourier transform infrared spectroscopy (FTIR).It was found that the oxygen/argon plasma treatment increased both the surface roughness (R_a) and surface free energy (SFE) of the PU paint coating from approximately 60–320 nm, and, from ~52 to ~80 mN/m respectively. It was also found that the plasma process created a multiscale roughened texture through the process of differential ablation between the PU polymer and the barium sulphate solid content, which is present in the paint as an extender, and other additives. In addition, the process also imparted favourable polar groups into the PU surface from the ionised and radical oxygen species in the plasma.When the FAS coating was subsequently applied to the PU without prior plasma treatment, there was a significant increases in water contact angles. This parameter increased from approximately 60° on untreated PU to around 130° with FAS applied. In this case, the SFE decreased to ~7.5 mN/m and showed 42.0 at% fluorine present as indicated by XPS.However, subsequently applying the FAS polymer after plasma pretreatment takes advantage of the known synergistic relationship that exists between surface roughness and low surface free energy coatings. The two processes combined to create superhydrophobicity with a surface that exhibited water contact angles up to 153.1°. With this optimised process, the apparent SFE was 0.84 mN/m with a more highly fluorinated surface present. In this case 47.2 at% surface fluorine was observed by XPS.In addition to changes in SFE, plasma treatment was also observed to alter levels of surface gloss and colour. After exposure to 600 s of plasma gloss levels are shown to reduce from values of from ~50 to ~21 (GU), with small but significant corresponding increases in the lightness and yellowness of the surface.     

Influence of different etching protocols on the reliability of resin bonding to CAD/CAM feldspathic porcelain

ObjectivesTo evaluate the effects of different acid etching times on the mechanical strength of dental porcelain as well as the influence on the reliability of resin bonded CAD/CAM porcelain veneer.Material and MethodsRectangular CAM/CAM feldspathic porcelain (Mark II, Vita Zahnfabrik) specimens (12 mm×10 mm×4 mm) were prepared and polished with silicon carbide abrasive paper under running water. All the samples were randomly divided into four groups according to the corresponding etching protocols: control group (without any treatment), group A (etched with a gel etchant containing 5% hydrofluoric acid for 30 s and rinsed with de-ionized water), group B (etched for 1 min and rinsed), group C (etched for 2 min and rinsed). After silanization, resin stubs were adhered on porcelain surface. There are 25 resin–porcelain samples prepared in each group and subjected to the shear bond strength testing. Weibull analysis was conducted to evaluate of the reliability of resin–porcelain bonding. For each of the etching method, eight additional porcelain samples (3 mm×2 mm×10 mm) were prepared and etched. Then, surface roughness (R_a), microhardness (Vickers Hardness) and biaxial flexural strengths were measured on these porcelain specimens. Energy dispersive X-ray spectrometry technique was used to assess the changes in surface chemical composition after etching and the surface topography was recorded under atomic force microscope (AFM) and scanning electron microscopy (SEM).ResultsThe reliability of resin to CAD/CAM porcelain bonding was decreased with the increase in HF etching time. The application of HF etching for 30 s decreased the Vickers hardness number (HV) significantly from 651.6 (control group) to 488.7 (group A). With the extension of etching time, the Vickers hardness number was further reduced to 430.1 (group B) and 305.7 (group C). However, the biaxial flexural strengths of these four groups were not statistically significant different (p>0.05). AFM revealed the porous structures on the porcelain surface at microscopic level.ConclusionsThe application of HF to etch the CAD/CAM feldspathic porcelain surface reduced the microhardness number. Etching with 5% hydrofluoric acid on dental porcelain for more than 1 min might impair the reliability of resin bonded porcelain veneer.     

Effect of grain growth on the thermal conductivity of liquid-phase sintered silicon carbide ceramics

The effect of grain growth on the thermal conductivity of SiC ceramics sintered with 3 vol% equimolar Gd₂O₃-Y₂O₃ was investigated. During prolonged sintering at 2000 °C in an argon or nitrogen atmosphere, the β → α phase transformation, grain growth, and reduction in lattice oxygen content occurs in the ceramics. The effects of these parameters on the thermal conductivity of liquid-phase sintered SiC ceramics were investigated. The results suggest that (1) grain growth achieved by prolonged sintering at 2000 °C accompanies the decrease of lattice oxygen content and the occurrence of the β → α phase transformation; (2) the reduction of lattice oxygen content plays the most important role in enhancing the thermal conductivity; and (3) the thermal conductivity of the SiC ceramic was insensitive to the occurrence of the β → α phase transformation. The highest thermal conductivity obtained was 225 W(m K)⁻¹ after 12 h sintering at 2000 °C under an applied pressure of 40 MPa in argon.     

Hard silicon carbonitride films obtained by RF-plasma-enhanced chemical vapour deposition using the single-source precursor bis(trimethylsilyl)carbodiimide

Amorphous silicon carbon nitride (Si/C/N) coatings were prepared on steel substrates by RF plasma-enhanced chemical vapour deposition (RF-PECVD) from the single-source precursor bis(trimethylsilyl)carbodiimide (BTSC). The films were characterised by X-ray diffraction (XRD), ellipsometry, FTIR, glow discharge optical emission spectroscopy (GDOES), optical microscopy, AFM, hardness measurements, scratch-, tribological- and corrosion-tests. The results of these studies show that the coatings obtained on the RF-powered electrode (cathode) were black, thick (>20 μm) and hard (21–29 GPa), while those grown on the grounded electrode (anode) were yellow, thin (<4 μm) and soft (∼5 GPa). Coatings on the anode contained around 19 at.% oxygen and exhibited silicon predominantly bonded to oxygen. In contrast, the oxygen content of the films deposited on the cathode was below 2 at.%. Silicon atoms in these coatings are co-ordinated predominantly to nitrogen and carbon. The surface of all coatings was very smooth with a maximum rms roughness between 2 nm and 5 nm for an area of 5 μm × 5 μm. Scratch and tribological tests reveal a brittle nature of the cathode-coatings and rather weak adhesion to the metal substrates. Salt-spray tests indicate an excellent corrosion resistance of the material.     

Boron carbide films deposited by a magnetron sputter–ion plating process: film composition and tribological properties

Amorphous boron carbide films were deposited onto silicon substrates by a magnetron sputter–ion plating process in an argon plasma atmosphere (0.25 Pa) using a B₄C target. The substrates were polarized with a d.c. bias voltage in the range from 0 to −100 V. The film composition and the presence of contaminants were determined by ion beam analysis (IBA). The nanoscale tribological properties were investigated by atomic force microscopy (AFM). IBA revealed that the boron/carbon atomic ratio is around 4 and that oxygen contamination does not exceed 10 at.%. The hydrogen content is below 2 at.%. The film density is nearly the bulk value for all biases applied to the substrate. AFM measurements show that the surface roughness decreases with increase of bias from 0.85 to 0.15 nm. The friction coefficient obtained by lateral force measurements follows the same trend, decreasing with increasing bias from 0.25 to 0.1. Wear measurements were performed and the wear depth decreased for films with lower friction coefficients. A mechanism based on the removal of a modified B₄C surface layer is proposed to explain the wear results.     

Novel method for the synthesis of a β-tricalcium phosphate coating on a zirconia implant

A novel method for the synthesis of a thin β-tricalcium phosphate (β-TCP) coating on zirconia implants has been developed. The synthesis procedure involves two steps: (i) rapid wet-chemical deposition of a biomimetic CaP coating and (ii) subsequent post-deposition processing of the biomimetic CaP coating, which includes a heat treatment at 900 °C followed by a short sonication in a water bath. The obtained β-TCP coating showed a uniform and dense morphology with a thickness of ≈500 nm and displayed a roughness in the nanometre range (R_a = 28 nm). The β-TCP coating demonstrated an apatite-mineralization ability in a simulated body fluid and enhanced the adsorption of serum proteins on the zirconia. Moreover, the β-TCP coating adhered firmly to the zirconia substrate, developing a notable scratch resistance (L_c = 97 N) and tensile strength (52 MPa) and showed strong resistance towards mechanical forces present during implantation of the coated zirconia implant into the artificial bone.     

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.     

Characterization of physical and biomedical properties of nitrogenated diamond-like carbon films coated on polytetrafluoroethylene substrates

A technique to coat hydrogen-free diamond-like carbon (DLC) films on polytetrafluoroethylene (PTFE) substrates has been developed by sputtering of a negatively biased graphite target in a mixture of argon and nitrogen plasma. The coated films were characterized by various methods to investigate their chemical, electronic features, and particularly their biomedical properties. DLC films produced by this method have up to 20% sp³ carbon bonds depending on the nitrogen concentration in the plasma. Raman spectroscopy revealed that, bond-disorder increases with nitrogen doping. The average grain size of DLC decreases in the nitrogen doped samples by almost 30%. The roughness of the uncoated PTFE substrate surfaces decreased dramatically from 660 nm to 170 nm after DLC coating. However, the nitrogen contents in the plasma have little effects on the roughness, the cluster size, and shapes. Electronic band gap of the samples decreases with adding nitrogen from ~ 2 eV in nitrogen-free samples to ~ 1 eV in nitrogenated samples. Lower adhesion and aggregation of platelets on PTFE surfaces coated with DLC-10% nitrogen and DLC-20% nitrogen have been observed while there is greater adhesion of platelets on DLC-30% nitrogen and DLC-40% nitrogen.     

Surface modification of graphene and graphite by nitrogen plasma: Determination of chemical state alterations and assignments by quantitative X-ray photoelectron spectroscopy

Multilayer graphene (MLGR) and its bulk analog, highly oriented pyrolytic graphite (HOPG), were treated by radio frequency activated low pressure N₂ gas plasma (at negative bias 0–200 V, for 5–20 min). Surface composition and chemical-state alterations were delineated by X-ray photoelectron spectroscopy (XPS). Covalently bonded nitrogen of 5–15 at% incorporated into the surface. The higher N concentration in MLGR below 100 V is attributed to the larger number of defects. The equal N content at 200 V indicates intensive formation of reactive sites. In-depth distribution of N is restricted to 2–4 monolayers. Model calculation resulted in 23 at% N (at 100 V) in the top graphene layers of HOPG. Three different chemical states of nitrogen (pyridine-type at 398.3 eV, pyrrole- and triazine-type at 399.7 eV and N substituting C in graphite-like network at 400.9 eV) were determined from high-resolution N1s spectral region for all samples. Pyridine and pyrrole–triazine components increase preferentially with increasing bias. Alterations of the C1s and O1s spectra are discussed in a critical approach. The amount of reacted carbon was consistent with that required for the three different nitrogen and oxygen states, thus validating the proposed assignments.     

Effect of O2 plasma pretreatment on structural and optical properties of ZnO films on PES substrate by atomic layer deposition

ZnO films were deposited on the O₂ plasma treated polyethersulfone (PES) substrates by atomic layer deposition. X-ray diffraction (XRD) measurements reveals that the grains in ZnO films show strongly (0 0 2) preferential orientation, when the duration of plasma pretreatment increases. The decreased grain size and improved crystallinity results in the decreased surface roughness of ZnO films. In contrast, when the duration of plasma pretreatment increases to 60 min, the surface roughness increases again due to the increased grain size and worse crystallinity. In photoluminescence measurement, slight blue shift of near-band-edge emission occurs with increasing duration of plasma pretreatment up to 30 min.     

Cellulose nanocrystals (CNCs) reinforced acrylic pressure- sensitive adhesives (PSAs) prepared via miniemulsion polymerization

In this study, poly (n-butyl acrylate-co-2-ethyl hexyl acrylate) (P(nBA-co-2EHA)) pressure sensitive adhesives (PSAs) were successfully synthesized in the presence of cellulose nanocrystals (CNCs) via in-situ miniemulsion polymerization. First, the CNCs were prepared via acid hydrolysis of cellulose microcrystals (CMCs) at various temperatures, 42–54 °C, and characterized using atomic force microscopy (AFM), field emission scanning electron microscopy (FESEM), Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) apparatus. The results showed that hydrolysis of MCCs at 45 °C resulted in CNCs with a well-defined aspect ratio, average length of 206 nm and thickness of 3.9 nm, and the highest crystallinity. Adding further CNC to the copolymer adhesive enhanced the mean particle size of the composite latex and decreased the glass-rubber transition temperature (T_g) of the copolymer matrix. Molecular weights and viscoelastic properties of the resultant PSAs were determined using gel permeation chromatography (GPC) and dynamic mechanical thermal analysis (DMTA), respectively. Adhesion performance of the neat and reinforced PSAs containing 1–5 wt% CNCs was evaluated at room temperature. The results showed that the incorporation of CNCs up to 4 wt% in the copolymer adhesive increased the shear resistance by 518%, peel strength by 176% and probe tack by 13%, while further addition, 5 wt%, lowered the adhesion performance due to a lack of surface wettability.     

In situ doping of diamond coatings with silicon,aluminum and titanium through a modified laser-based CVD process

The aim of this study was to demonstrate the feasibility of in situ doping of chemical vapor deposition (CVD) fabricated diamond coatings through simultaneous evaporation of solids in a CVD plasma-based process. In order to achieve maximum flexibility and energy density, a laser-based plasma-jet CVD process was chosen, and expanded with the introduction of dopant rods. The rods, with diameters varying from 0.5 mm to 3.0 mm, were fed at rates from 0.25 mm/min to > 100 mm/min, and positioned 3 mm below the optical breakthrough which generates the plasma. Gas flows of 20.0 slm (standard liters per min) argon, 2.0 slm hydrogen and 0.02 slm methane were used for diamond coating deposition. At a surface temperature of about 1100 °C, an average linear diamond growth rate of 20 μm/h was achieved. The materials selected as solid precursors for the rods were SiO₂, Al₂O₃, and Ti due to their differing electrical characteristics, as they are an insulator, semiconductor, and conductor, respectively. The evaporation rate of these rods varied by more than six orders of magnitude, from < 1 × 10^− 8 g/min (Ti) to > 7 × 10^− 2 g/min (SiO₂). The doped diamond coatings were produced by simultaneous evaporation and CVD. To prove that the precursors were vaporized and the atomic bonds were broken by the plasma, the optical emission spectra are compared with published and calculated spectral lines. Analyses of the layers were performed using EDX (energy-dispersive X-ray) spectroscopy and WDS (wavelength dispersive X-ray spectroscopy). As a result, the maximum doping densities in the diamond coating were determined, and were 3.460 wt.% for silicon, 0.957 wt.% for aluminum, and 0.03 wt.% for titanium. To prove the diamond-like characteristics of these coatings, Raman measurements were performed.     

Effect of oxygen plasma treatment on non-thrombogenicity of diamond-like carbon films

The non-thrombogenicity of oxygen-plasma-treated DLC films was investigated as surface coatings for medical devices. DLC films were deposited on polycarbonate substrates by a radio frequency plasma enhanced chemical vapor deposition method using acetylene gas. The deposited DLC films were then treated with plasma of oxygen gas at powers of 15 W, 50 W, and 200 W. Wettability was evaluated by water contact angle measurements and the changes in surface chemistry and roughness were examined by X-ray photoelectron spectroscopy and atomic force microscope analysis, respectively. Each oxygen-plasma-treated DLC film exhibited a hydrophilic nature with water contact angles of 11.1°, 17.7° and 36.8°. The non-thrombogenicity of the samples was evaluated through the incubation with platelet-rich plasma isolated from human whole blood. Non-thrombogenic properties dramatically improved for both 15 W- and 50 W-oxygen-plasma-treated DLC films. These results demonstrate that the oxygen plasma treatment at lower powers promotes the non-thrombogenicity of DLC films with highly hydrophilic surfaces.     

Bond strength evaluation of composite resin bonded to glass ionomer cements after different periods of setting

This study investigated the time elapsed after setting of glass ionomer cements on the bond strength to composite resin restorations. Bovine incisors received cavity preparations on the buccal surface (6 mm×6 mm×2 mm) and the specimens were tested according to cement type (conventional and resin-modified) and time elapsed before performing the restorations: GC10m: conventional glass ionomer cement and 10 min time elapsed after setting; GC24h: conventional cement and 24 h after setting; GC7d: conventional cement and 7 days after setting; GRM10m: resin-modified glass ionomer cement and 10 min after setting; GRM24h: resin-modified cement and 24 h after setting; and GRM7d: resin-modified cement and 7 days after setting. Specimens were subjected to micro-shear testing and the data were analyzed by Analysis of Variance and Tukey′s test (p=0.05). Bond strength of restorations performed on conventional cement after 10 min of time elapsed presented the lowest mean values and differed statistically from values at 24 h and 7 days. Resin-modified cement after 24 h presented the highest mean values and differed statistically from values at 10 min and 7 days. The time elapsed after setting of glass ionomer cement may interfere in the bond strength to composite restorations.     

Spark plasma assisted carbothermal reduction-nitridation synthesis of (Ti,W, Mo)(C,N)-(Ni,Co) powders

Ultrafine (Ti, W, Mo)(C, N)-(Ni, Co) cermet powders were rapidly synthesized from various metal oxides, mainly anatase-TiO₂, by spark plasma assisted carbothermal reduction-nitridation (SPCRN) at low temperature. The phase evolution of the SPCRN reaction was investigated using X-ray diffraction (XRD) and the microstructure of the product powders was observed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). NiO, Co₃O₄ and MoO₃ were converted to Ni, Co and Mo₂C by CR reaction at temperatures below 900 °C. WO₃ was successively transformed from W₂C to WC by CR reaction up to 1100 °C. Finally, at up to 1350 °C, (Ti, W, Mo)(C, N) formed into the sequence of TiO₂, Ti₄O₇, Ti₃O₅, Ti(O, N), Ti(C, N), (Ti, W)(C, N) and (Ti, W, Mo)(C, N). The crystal structure of (Ti, W, Mo)(C, N)-(Ni, Co) cermet powders was analyzed by the Rietveld method and transmission electron microscopy (TEM). The findings demonstrated that the pure (Ti, W, Mo)(C, N)-(Ni, Co) cermet powders with grain size of below 0.5 µm were synthesized from metal oxides by SPCRN reaction at 1400 °C for 10 min.     

Optimization of wire electrical discharge machining parameters for cutting electrically conductive boron carbide

In this work, Pure boron carbide (B₄C) was consolidated using spark plasma sintering (SPS) at 2050 °C with a dwell of 10 min under 50 MPa uniaxial pressure in Argon atmosphere. The sintered specimen was >99% dense and offered characteristic Vickers hardness and fracture toughness of 31.4 GPa and 4.21 MPa-m^0.5, respectively, at 4.9 N indentation load. The specimen showed satisfactory wire electrical discharge machining (WEDM) performance because of its good electrical conductivity. The design of experiment (DOE) was arranged by L32 orthogonal array (OA) between the machining input parameters namely pulse on-time, pulse off-time, pulse peak current, dielectric fluid pressure and servo feed rate and the output responses like machining speed and surface roughness (R_a). Regression models were employed to establish the numerical correlation between the machining parameters and output responses. Experimental observations were utilized to formulate the first-order regression models to predict responses of WEDM. The optimized input parameters were 27 μs pulse on time, 48 μs pulse off time, 180 A pulse peak current, 7 kg/cm² water pressure and 2200 mm/min servo feed rate for the WEDM performance to produce an optimum machining speed and R_a.     

Trimethylamine sensing properties of nano-SnO2 prepared using microwave heating method

The precursor was obtained through the reaction between SnCl₄·5H₂O and NaOH in the presence of PEG400 (polyethylene glycol, M = 400). Tin oxide (SnO₂) nano-powders were prepared by heating the precursor with microwave method. SnO₂ thick film sensors were fabricated using SnO₂ nano-materials as sensing materials. The phase composition and morphology of the material particles were characterized through X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. The average particle sizes of the samples obtained with 616 W microwave heating and 800 W microwave heating (20 min) are about 5 and 15 nm, respectively. The influence of the heating duration and heating power on the gas-sensing properties of sensors based on SnO₂ nano-materials were investigated. The sensitivities of the sensors based on SnO₂ nano-materials heated with 616 and 800 W for 20 min were higher than those of the sensors based on SnO₂ nano-materials heated with 136, 264 and 440 W for 20 min. When operating at 200–310 °C, the sensor based on SnO₂ heated with 616 W for 20 min exhibits highest sensitivities in all sensors based on SnO₂ heated with 616 W for different duration. The sensitivity to a few kinds of organic gases, such as (CH₃)₃N and (CH₃)₂CO were studied. It was found that the sensor based on SnO₂ nano-materials (with 616 W microwave heating for 20 min) exhibited good performance characterized by high sensitivity and short response time to dilute trimethylamine when operated at 255 °C. The sensitivity to 0.001 ppm (CH₃)₃N at 255 °C was 3. The response time and recovery time were about 30 and 100 s, respectively.     

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.