Nanomechanical characterization of amorphous hydrogenated carbon thin films

Amorphous hydrogenated carbon (a-C:H) thin films deposited on a silicon substrate under various mixtures of methane-hydrogen gas by electron cyclotron resonance microwave plasma chemical vapor deposition (ECR-MPCVD) was investigated. Microstructure, surface morphology and mechanical characterizations of the a-C:H films were analyzed using Raman spectroscopy, atomic force microscopy (AFM) and nanoindentation technique, respectively. The results indicated there was an increase of the hydrogen content, the ratio of the D-peak to the G-peak (I_D/I_G) increased but the surface roughness of the films was reduced. Both hardness and Young's modulus increased as the hydrogen content was increased. In addition, the contact stress-strain analysis is reported. The results confirmed that the mechanical properties of the amorphous hydrogenated carbon thin films improved using a higher H₂ content in the source gas.     

Preparation and characterization of Al doped ZnO thin films by PLD

This paper describes the effect of doping on the composition, surface morphology and optical, structural and electrical properties of Al doped ZnO thin films by pulsed laser deposition. SEM analysis shows that the crystalline nature of the deposited films decreases with an increase of Al doping concentration from 1% to 6%. In the AFM analysis, the surface roughness of the deposited films increases by increasing the doping concentration of Al. Al doping strongly influences the optical properties of the ZnO thin films. Optical transmittance spectra show a very good transmittance in the visible region (450–700 nm). The calculated optical band gap was found to be in the range from 3.405 to 3.464 eV. Structural analysis confirms that the increases of Al concentration decrease the crystallinity of the ZnO films and the particle size decreases from 45.7±0.09 to 28.0±0.02 nm. In the Raman analysis, the active mode of Al(=1%) doped ZnO films were observed at 434.81 cm⁻¹. The shifts of the active mode (_E2)$\left(E_2\right)$ show the presence of tensile stress in the deposited films. The electrical properties of the deposited films showed that the values of the Hall mobility was in the range between 2.51 and 10.64 cm²/V s and the carrier concentration between 15.7 and 0.78×10¹⁷ and the resistivity values between 1.59 and 10.97 Ωcm, depending on the doping concentration.     

Few-layer graphene growth from polystyrene as solid carbon source utilizing simple APCVD method

This research article presents development of an economical, simple, immune and environment friendly process to grow few-layer graphene by controlling evaporation rate of polystyrene on copper foil as catalyst and substrate utilizing atmospheric pressure chemical vapor deposition (APCVD) method. Evaporation rate of polystyrene depends on molecular structure, amount of used material and temperature. We have found controlling rate of evaporation of polystyrene by controlling the source temperature is easier than controlling the material weight. Atomic force microscopy (AFM) as well as Raman Spectroscopy has been used for characterization of the layers. The frequency of G′ to G band ratio intensity in some samples varied between 0.8 and 1.6 corresponding to few-layer graphene. Topography characterization by atomic force microscopy confirmed Raman results.     

Preparation and characterization of nano and microcrystalline ZnO thin films by PLD

Nano and microcrystalline ZnO thin films were prepared on glass substrates using pulsed laser deposition technique under a vacuum of 3 × 10⁻⁷ Torr at different laser power density. Composition analyses show that the films deposited at low laser power density have more structural defects than the film deposited at high laser power density. It confirms that the content of Zn in free-state decreased greatly at high laser power density. Atomic force microscopy analysis shows that the surface roughness of the deposited films increases with an increase in laser power density. X-ray diffraction analyses show that all the films are oriented along (0 0 2) direction independently on the laser power density applied. The structural quality increases with an increase in laser power density. It is due to the fact that the increase of laser power density leads to the enhancement of peak intensity. The increase of laser power density reduces the film transmission in the visible range of the spectra. The optical band gap value is found to be in the range from 3.42 to 3.39 eV. It shows that the optical band gap value decreases with an increase in laser power density. FTIR analysis shows that the hydrated oxide content in the deposited films decreases with an increase in laser power density.     

Fe掺杂氢化非晶碳薄膜制备及其热稳定性能

 以H₂、反式-2-丁烯（T₂B）和二茂铁混合气体为工作气体,用金属有机等离子体增强化学气相沉积法（PECVD）制备了Fe掺杂氢化非晶碳（a-C:H:Fe）薄膜。使用X射线光电子能谱（XPS）对a-C:H:Fe薄膜成分进行了分析。使用台阶仪、场发射扫描电镜（FESEM）、热重分析和紫外可见分光光度计（UV-VIS）,对比分析了a-C:H薄膜和a-C:H:Fe薄膜的沉积速率、表面形貌、热稳定性和光学带隙变化。研究表明：相同制备条件下,相比a-C:H薄膜,a-C:H:Fe薄膜的沉积速率高,表面颗粒小,容易碳化,光学带隙变窄。     

Fe掺杂氢化非晶碳薄膜制备及其热稳定性能

以H2、反式-2-丁烯（T2B）和二茂铁混合气体为工作气体,用金属有机等离子体增强化学气相沉积法（PECVD）制备了Fe掺杂氢化非晶碳（a-C:H:Fe）薄膜。使用X射线光电子能谱（XPS）对a-C:H:Fe薄膜成分进行了分析。使用台阶仪、场发射扫描电镜（FESEM）、热重分析和紫外可见分光光度计（UV-VIS）,对比分析了a-C:H薄膜和a-C:H:Fe薄膜的沉积速率、表面形貌、热稳定性和光学带隙变化。研究表明：相同制备条件下,相比a-C:H薄膜,a-C:H:Fe薄膜的沉积速率高,表面颗粒小,容易碳化,光学带隙变窄。     

Deposition of hydrogenated amorphous carbon nitride films by dielectric barrier discharge plasmas

Hydrogenated amorphous carbon nitride (a-C:N:H) films were synthesized from CH₄/N₂, C₂H₄/N₂ and C₂H₂/N₂ mixtures using dielectric barrier discharge (DBD) plasmas. Atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) were used to characterize the surface morphology, bonding structure, and composition of the a-C:N:H films. The influences of plasma parameters (discharge pressure in the range of 25-1000 Pa) and feed gases used on the composition and the structure of deposited films were systematically studied. The a-C:N:H films with the uniform surface structure were deposited by low-pressure DBD plasmas with various systems. Compared to the films deposited in C₂H₄/N₂ and C₂H₂/N₂ systems, the films deposited in the CH₄/N₂ system exhibit the relatively lower surface roughness and deposition rate. For all the films prepared in these three systems, increasing the discharge pressure leads to an increase in film surface roughness and deposition rate. Significant differences among the FTIR spectra of all deposited a-C:N:H films were also observed. Both FTIR and XPS spectra show that for all the films deposited in three different systems, increasing the N₂ fraction leads to a decrease in the H content of deposited a-C:N:H films and an increase in the N content. The properties of deposited films may change from those of polymerlike to diamond-like when the discharge pressure is increased. Correlations between the film properties and growth processes are discussed in this study.     

Preparation of boron carbon nitride thin films by radio frequency magnetron sputtering

Boron carbon nitride films were deposited by radio frequency magnetron sputtering using a composite target consisting of h-BN and graphite in an Ar-N₂ gas mixture. The samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The results suggest that the films are atomic-level hybrids composed of B, C and N atoms. The boron carbon nitride films prepared in the present experiment have a disordered structure. The sputtering power varied from 80 W to 130 W. This sputtering power was shown to have regular effect on the composition of boron carbon nitride films. The samples deposited at 80 W and 130 W are close to the stoichiometry of BC₃N. The sample deposited at 110 W is close to the stoichiometry of BCN. The samples deposited at 100 W and 120 W approach to BC₂N. It is very significant for us to synthesize boron carbon nitride compound with controllable composition by changing the sputtering power.     

Preparation and characterization of amorphous hydrogenated carbon films containing Au nanoparticles from heat-treatment of polymer precursors

Amorphous hydrogenated carbon (aC:H) films containing Au nanoparticles have been successfully prepared by heat-treatment of the precursors including poly(phenylcarbyne) polymer and HAuCl₄ at 600 °C in Ar atmosphere. The microstructure and morphology of the obtained films were investigated by means of Raman, XPS, XRD, TEM, and AFM. The sheet resistivity of the films was measured by a four-point probe method. Moreover, a ball-on-disc test was employed to obtain information about the frictional properties and sliding wear resistance of the films. The results show that heat-treatment of the precursors at 600 °C causes the change of the polymer into amorphous hydrogenated carbon phase, and the reduction of AuCl₄^- anions into zero-valence Au. All of the AuaC:H films exhibit smooth morphologies, with the RMS roughness smaller than 0.80 nm. Au nanoparticles are well dispersed in the amorphous carbon matrix, with size ranging from several to tens of nanometers, and the particle size increases with increasing gold content. The incorporation of Au in the carbon matrix can drastically decrease the resistivity and the resistivity of composite films gradually decreases with increasing Au concentration. AuaC:H films with the Au concentration of 2% and 4% show much better friction-reduction and wear-resistance than aC:H film. PACS 81.15.Np; 81.07.-b; 81.40.Pq     

Opto-electrical properties of amorphous carbon thin film deposited from natural precursor camphor

A simple thermal chemical vapor deposition technique is employed for the pyrolysis of a natural precursor “camphor” and deposition of carbon films on alumina substrate at higher temperatures (600-900 °C). X-ray diffraction measurement reveals the amorphous structure of these films. The carbon films properties are found to significantly vary with the deposition temperatures. At higher deposition temperature, films have shown predominately sp²-bonded carbon and therefore, higher conductivity and lower optical band gap (Tauc gap). These amorphous carbon (a-C) films are also characterized with Raman and X-ray photoelectron spectroscopy. In addition, electrical and optical properties are measured. The thermoelectric measurement shows these as-grown a-C films are p-type in nature.     

Microstructural analysis of hard amorphous carbon films deposited with high-energy ion beams

Hard amorphous carbon films produced using high-energy (ca. 30 keV) ion beam deposition of CH₃⁺ and CH₄⁺ on silicon wafers, have been investigated by Positron Annihilation Spectroscopy (PAS), the results are correlated with Raman Spectroscopy and Electrical Resistivity measurements. The microstructural modifications of the films as a function of the annealing temperature in the 300–600°C range have been studied. The evolution of the fractions of sp² and sp³ bonds is described and related to the changes of the open volume defect distribution and the graphitization process.     

Synthesis and structure of nitrogenated tetrahedral amorphous carbon films prepared by nitrogen ion bombardment

The tetrahedral amorphous carbon (ta-C) films with more than 80% sp³ fraction firstly were deposited by filtered cathode vacuum arc (FCVA) technique. Then the energetic nitrogen (N) ion was used to bombard the ta-C films to fabricate nitrogenated tetrahedral amorphous carbon (ta-C:N) films. The composition and structure of the films were analyzed by visible Raman spectrum and X-ray photoelectron spectroscopy (XPS). The result shows that the bombardment of energetic nitrogen ions can induce the formation of CN bonds, the conversion of C-C bonds to CC bonds, and the increase of size of sp² cluster. The CN bonds are made of CN bonds and C-N bonds. The content of CN bonds increases with the increment of N ion bombardment energy, but the content of C-N bonds is inversely proportional to the increment of nitrogen ion energy. In addition, C≡N bonds are not existed in the films. By the investigation of AFM (atom force microscopy), the RMS (root mean square) of surface roughness of the ta-C film is about 0.21 nm. When the bombarding energy of N ion is 1000 eV, the RMS of surface roughness of the ta-C:N film decreases from 0.21 to 0.18 nm. But along with the increment of the N ion energy ranging from 1400 to 2200 eV again, the RMS of surface roughness of the ta-C:N film increases from 0.19 to 0.33 nm.     

Polymeric like carbon films prepared from liquid gas and the effect of nitrogen

Polymeric like carbon (PLC) films are grown by a capacitance coupled RF-PECVD on the grounded electrode at room temperature from liquid gas (40% propane and 60% butane) in two regimes with nitrogen and without nitrogen gas. Films are characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), Fourier transform infrared (FTIR) absorption and Raman spectroscopy. The result of FTIR analyses indicates that more than 90% of hydrogen atoms are bonded to carbon with sp³ hybridization. The abundance of CH₃ is more than that of CH₂ and this one is more than that of CH for carbon with sp³ hybridization in these films. The C 1s line of the XPS spectra is deconvoluted to several peaks that are attributed to the CH₃, CH₂ and CH terminations. The result of this deconvolution is consistent with FTIR results. AFM images show that the mean nanoparticle size is reduced from about 100 nm for films without nitrogen to less than 80 nm for films with nitrogen. This is in agreement with our Raman results. By addition of nitrogen to the feed gas, no variation in the C-H stretching vibration mode is observed. The effect of N-H bonds is observable in both FTIR and XPS spectra and a very small trace of N-C bonds is present only in deconvolution of N 1s line of XPS spectra. These results indicate that by addition of nitrogen to feed gas, internal structure of a-C:H nanoparticles is not changed but particle size is decreased. We suggest that the internal stress reduction due to nitrogen addition in the feed gas for PLC films can be related to decreasing of the a-C:H particle size.     

Ti/Ti-类金刚石多层膜的制备与表征

采用电子回旋共振-化学气相沉积结合中频磁控溅射的真空镀膜技术, 以99.99%Ti为靶材, 乙炔为碳源制备了Ti/Ti-类金刚石(DLC)多层膜. 利用X射线衍射仪、扫描电子显微镜、X射线光电子能谱仪 对Ti/Ti-DLC多层膜进行了相结构、组织、成分及形态分析. 采用显微硬度仪、摩擦磨损仪、表面粗糙度仪对Ti/Ti-DLC多层膜进行了力学性能考察. 结果表明: Ti/Ti-DLC多层膜中主要含有TiC晶相; Ti层和Ti-DLC层中未出现柱状晶体生长模式, 分层中均以岛状模式生长; 当调制周期Λ≤ 50 nm时, 分层结构变模糊; 调制周期Λ对Ti/Ti-DLC多层膜的复合硬度、摩擦系数、表面形貌、表面粗糙度都有影响, 当调制周期Λ较小时表现出纳米增硬效应, 表面出现大颗粒, 表面粗糙度和摩擦系数均变大.     

Electrical and electronic properties of nitrogen doped amorphous carbon (a-CNx) thin films

Nitrogen-doped amorphous carbon thin films (a-CN_x) were prepared on silicon substrate by pulsed laser deposition process using methane (CH₄) and nitrogen (N₂) as source gas. The electrical properties of a-CN_x films changes with nitrogen concentration in the film structure. The intensity ratio of the D and G peak (I_D/I_G) increases with higher nitrogen concentration, which means that sp²-clusters were formed in these films and is responsible for the enhancement of conductivity of the a-CN_x films. We observed that the amorphous carbon (a-C) films becoming more graphitic in nature yielding higher conductivity/lower resistivity with increase of nitrogen concentration. Electron field emission result shows that the emission current density enhances with nitrogen doping that indicates the useful in electron field emission devices application.     

特定折射率材料及光学薄膜制备

根据太阳电池阵激光防护膜性能优化的需要,应用离子辅助电子束双源共蒸工艺方法制备了优化设计所需的特定折射率的薄膜材料并用于制备激光防护膜。测试结果显示:用该工艺方法制备的掺杂材料薄膜的折射率n=1.75,与优化设计所需数值相符;激光防护膜性能优良,太阳辐射能透过率提高6%以上,实现了对该激光防护膜性能的进一步优化。为了使该双源共蒸方法适于大面积薄膜的制备,应用均匀性挡板技术来提高该方法制备大面积薄膜的膜厚均匀性,使制备的掺杂材料薄膜在口径为400 mm时的不均匀性小于2.1%。该双源共蒸方法制备工艺简单、可靠,适于实际工程应用。薄膜性能测试结果与理论优化结果相符,达到预期优化目标。     

Evolution of amorphous carbon films into nano-crystalline graphite with increasing growth temperature in plasma-enhanced chemical vapor deposition

Amorphous carbon films (ACFs) have recently emerged as one of the best candidates for etching-resistant hardmask materials in advanced semiconductor manufacturing processes. Etching resistivity of ACFs is known to be improved by controlling the relative abundance between sp² and sp³ bonds. We have investigated the relative abundance between sp² and sp³ bonds in several ACFs, fabricated by plasma-enhanced chemical vapor deposition at different temperatures, which were analyzed by using X-ray photoemission spectroscopy, Raman spectroscopy, and transmission electron microscopy. We found that the relative abundance of sp² bond increased as the growth temperature was raised. Furthermore, the ACFs eventually evolved into nano-crystalline graphite with increasing growth temperature.     

Diamond-like phase formation in an amorphous carbon films prepared by periodic pulsed laser deposition and laser irradiation method

Diamond-like carbon (DLC) films were fabricated by pulsed laser ablation of a liquid target. During deposition process the growing films were exited by a laser beam irradiation. The films were deposited onto the fused silica using 248 nm KrF eximer laser at room temperature and 10⁻³ mbar pressure. Film irradiation was carried out by the same KrF laser operating periodically between the deposition and excitation regimes. Deposited DLC films were characterized by Raman scattering spectroscopy. The results obtained suggested that laser irradiation intensity has noticeable influence on the structure and hybridization of carbon atoms deposited. For materials deposited at moderate irradiation intensities a very high and sharp peak appeared at 1332 cm⁻¹, characteristic of diamond crystals. At higher irradiation intensities the graphitization of the amorphous films was observed. Thus, at optimal energy density the individual sp³-hybridized carbon phase was deposited inside the amorphous carbon structure. Surface morphology for DLC has been analyzed using atomic force microscopy (AFM) indicating that more regular diamond cluster formation at optimal additional laser illumination conditions (∼20 mJ per impulse) is possible.     

Effects of flow ratios on surface morphology and structure of hydrogenated amorphous carbon films prepared by microwave plasma chemical vapor deposition

A series of hydrogenated amorphous carbon (a-C:H) films were deposited on silicon substrates by microwave plasma chemical vapor deposition technique with a mixture of hydrogen and acetylene. The effects of flow ratio of hydrogen to acetylene on surface morphology and structure of a-C:H films were investigated using surface-enhanced Raman spectroscopy and scanning probe microscope (SPM) in the tapping AFM mode. Raman data imply a transition from graphite-like phase to diamond-like bonding configurations when the flow ratio increases. AFM measurements show that the increase in hydrogen content, to some extent, can smoothen the surface morphology and decrease the RMS roughness. Excessive hydrogen is found to cause the formation of polymeric hydrocarbon clusters in the films and reduce deposition rate.     

Synthesis of amorphous boron carbide by single and multiple charged boron ions bombardment of fullerene thin films

In this paper, results of structural modification of fullerene thin films by single and multiple charged boron ions (B⁺, B³⁺) are presented. The applied ion energies were in the range of 15-45 keV. The characterization of as-deposited and irradiated specimens has been performed by atomic force microscopy, Raman and Fourier transform infrared spectroscopy and UV/vis spectrophotometry. The results of Raman analysis have shown the formation of amorphous layer after irradiation of fullerene thin films. Fourier transform infrared spectroscopy has confirmed the formation of new B-C bonds in irradiated films at higher fluences (2 × 10¹⁶ cm⁻²). The morphology of bombarded films has been changed significantly. The optical band gap was found to be reduced from 1.7 to 1.06 eV for irradiated films by B³⁺ ions and 0.7 eV for irradiated films by B⁺ ions.