Transport and optical properties of amorphous carbon and hydrogenated amorphous carbon films

In this paper we report on the electrical and optical properties of amorphous carbon (a-C) and hydrogenated amorphous carbon (a-C:H) films. Resistivity of both types of films decreases with increase in temperature. At lower temperatures (60-250 K) the electron transport is due to variable range hopping for the a-C films. At higher temperatures (300-430 K) it is thermally activated for both types of films. Analysis of the heterojunction between diamond-like carbon (DLC) and bulk silicon (Si) leads to the conclusion that our a-C films are of n-type and our a-C:H films are of p-type. The optical measurements with DLC revealed a Tauc bandgap of 0.6 eV for the a-C films and 1-1.2 eV for the a-C:H films. An Urbach energy around 170 meV could be determined for the a-C:H films. Strain versus resistance plots were measured resulting in piezoresistive gauge factors around 50 for the a-C films and in between 100 and 1200 for the a-C:H films.     

Thermopower of doped semiconducting hydrogenated amorphous carbon films

The thermopower S(T) and electrical conductivity have been measured from 25 to 250C for semiconducting a-C:H films doped with boron or phosphorus. S has the expected sign (positive for B-doping and negative for P-doping), is low for all films (10–50 μ V/K), and increases nearly linearly with T. This behavior, along with that observed for the electrical conductivity, is consistent with conduction via hopping at or near the Fermi level which has been shifted via doping from near mid-gap into broad bands of tail states at the appropriate band edges.     

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.     

Formation of hydrogenated amorphous carbon films from polymer pyrolysis

Free-standing and supported hydrogenated amorphous carbon films (a:C–H) were prepared upon pyrolysis of the polymer formed by ethanolamine (EA) and citric acid (CA), under an ambient atmosphere at 300 °C. EA facilitates the formation of the macroscopic films, while CA is essential for obtaining the a:C–H microstructure, which comprises a mixture of sp² and sp³ carbon. Received: 29 May 2001 / Accepted: 17 August 2001 / Published online: 20 December 2001     

Ripple surface generated on hydrogenated amorphous carbon nitride films

It is reported for the first time that the periodical ripple surface feature at micrometer-scale was observed on hydrogenated amorphous carbon nitride films deposited by pulse plasma chemical vapor deposition (CVD) technique. Nitrogen incorporation to hydrogenated amorphous carbon films and the different growing environments of pulse dc plasma discharge perhaps played crucial role in the surface morphology transformation of hydrogenated amorphous carbon nitride films.     

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。     

Solid state NMR study of carbon bonding in amorphous hydrogenated carbon films

Carbon bonding environments in hydrogenated amorphous carbon films (a-C:H) deposited from an rf-biased methane plasma onto various substrates have been quantified by application of solid state¹³C NMR. A family of films were prepared by systematically varying the substrate bias voltage. Quantitative data on carbon chemistry in these films is required for modeling the impact of structure on mechanical and optical properties. A variety of NMR acquisition pulse sequences have been investigated to determine the conditions under which quantitative¹³C NMR data can be acquired in this system. The results indicate that data acquisition from this material requires different protocols than for the study of polymeric hydrocarbon films. With proper experimental design, NMR is an excellent technique for structural studies of these materials.     

Substrate effects on the microstructure of hydrogenated amorphous carbon films

In this work, plasma enhanced chemical vapour deposition was used to prepare hydrogenated amorphous carbon films (a-C:H) on different substrates over a wide range of thickness. In order to observe clear substrate effect the films were produced under identical growth conditions. Raman and near edge X-ray absorption fine structure (NEXAFS) spectroscopies were employed to probe the chemical bonding of the films. For the films deposited on silicon substrates, the Raman I_D/I_G ratio and G-peak positions were constant for most thickness. For metallic and polymeric substrates, these parameters increased with film thickness, suggesting a change from a sp³-bonded hydrogenated structure to a more sp² network, NEXAFS results also indicate a higher sp² content of a-C:H films grown on metals than silicon. The metals, which are poor carbide precursors, gave carbon films with low adhesion, easily delaminated from the substrate. The delamination can be decreased/eliminated by deposition of a thin (∼10 nm) silicon layer on stainless steel substrates prior to a-C:H coatings. Additionally we noted the electrical resistivity decreased with thickness and higher dielectric breakdown strength for a-C:H on silicon substrate.     

Chemical modification of the electrical properties of hydrogenated amorphous carbon films

Semiconducting films of hydrogenated amorphous carbon (a-C:H), prepared via the dc glow discharge decomposition of C₂H₂, have been successfully doped via incorporation of B and P during growth. The doping efficiency achieved was comparable to that achieved in a-Si:H produced in a like manner. For a-C:H films deposited at T_d=250C,

(RT) increased from 10^-12 to 10^-7 ohm^-1 cm^-1 when either 1% PH₃ or 10% B₂H₆ were added to the C₂H₂. A shift of the Fermi level E_F of about 0.7 eV is inferred from changes in the “activation” energy of conduction.     

The effect of hydrogen dilution on the field emission from hydrogenated amorphous carbon films

The microstructures and field emission characteristics of hydrogenated amorphous carbon films prepared by using different hydrogen dilution ratio were investigated. It was found that a very low threshold electric field emission could be achieved for samples with moderated hydrogen dilution ratio. However, the field emission characteristics became worse for samples with high hydrogen dilution ratio. The change of field emission can be attributed to the change of electronic structures due to the hydrogen dilution in addition to the increase of the hydrogen surface termination.     

Influence of film thickness on laser ablation of hydrogenated amorphous carbon films

Single-pulse damage thresholds of hydrogenated amorphous carbon (a-C:H) films were measured for 8-ns laser pulses at 532-nm wavelength. Layer thicknesses from below the optical penetration depth to above the thermal diffusion length (60 nm–13 μm) were examined. After correction of the damage-threshold values for the fraction of energy effectively absorbed by the material, the damage threshold was found to increase linearly with the layer thickness, also for film thicknesses below the optical penetration depth of a-C:H. The threshold fluence reached the bulk value for a layer thickness equal to the thermal diffusion length. The thermal diffusion coefficient was obtained from fitting the experimental data. Several phenomena like graphitization, blistering, exfoliation, and ablation were observed for different fluence regimes and film thicknesses. PACS 79.20.Ds; 06.60.Jn; 78.66.Jg     

Laser annealing study of PECVD deposited hydrogenated amorphous silicon carbon alloy films

The influence of carbon content on the crystallization process has been investigated for the excimer laser annealed hydrogenated amorphous silicon carbon alloy films deposited by Plasma Enhanced Chemical Vapour Deposition (PECVD) technique, using silane methane gas mixture diluted in helium, as well as for the hydrogenated microcrystalline silicon carbon alloy films prepared by PECVD from silane methane gas mixture highly diluted in hydrogen, for comparison. The study demonstrates clearly that the increase in the carbon content prevents the crystallization process in the hydrogen diluted samples while the crystallization process is enhanced in the laser annealing of amorphous samples because of the increase in the absorbed laser energy density that occurs for the amorphous films with the higher carbon content. This, in turn, facilitates the crystallization for the laser annealed samples with higher carbon content, resulting in the formation of SiC crystallites along with Si crystallites.     

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.     

脉冲激光气相沉积法制备的非晶CH薄膜特性分析

采用脉冲激光气相沉积(PLD)法,研究了氢气压强对非晶CH薄膜性能的影响。原子力显微镜图和白光干涉图显示,薄膜表面平整致密,随着氢气压强增大,粗糙度变大。拉曼光谱分析表明,氢气压强增加,G峰和D峰位置都在向高波数方向移动。傅里叶变换红外光谱分析显示,薄膜中存在sp3—CH2和sp2—CH等基团。最后,采用PLD漂浮法在最优参数氢气压强为0.3 Pa下,成功制备了不同厚度(100~300 nm)、满足一定力学强度、无明显宏观缺陷的自支撑CH薄膜。     

Characterization of hydrogenated amorphous carbon thin films by end-Hall ion beam deposition

Pure hydrogenated amorphous carbon (α-C:H) and nitrogen doped hydrogenated amorphous carbon (α-C:H:N) thin films were prepared using end-Hall (EH) ion beam deposition with a beam energy ranging from 24 eV to 48 eV. The composition, microstructure and mechanical properties of the films were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, scanning probe microscopy (SPM), and nano-scratch tests. The films are uniform and smooth with root mean square roughness values of 0.5-0.8 nm for α-C:H and 0.35 nm for α-C:H:N films. When the ion energy was increased from 24 eV to 48 eV, the fraction of sp³ bonding in the α-C:H films increased from 36% to 55%, the hardness increased from 8 GPa to 12.5 GPa, and the Young's modulus increased from 100 GPa to 130 GPa. In the α-C:H:N films, N/C atomic ratio, the hardness and Young's modulus of the α-C:H:N films are, 0.087, 15 and 145 GPa, respectively. The results indicate that both higher ion energy and a small amount of N doping improve the mechanical properties of the films. The results have demonstrated that smooth and uniform α-C:H and α-C:H:N films with large area and reasonably high hardness and Young's modulus can be synthesized by EH ion source.     

脉冲激光气相沉积法制备的非晶CH薄膜特性分析

采用脉冲激光气相沉积(PLD)法,研究了氢气压强对非晶CH薄膜性能的影响。原子力显微镜图和白光干涉图显示,薄膜表面平整致密,随着氢气压强增大,粗糙度变大。拉曼光谱分析表明,氢气压强增加,G峰和D峰位置都在向高波数方向移动。傅里叶变换红外光谱分析显示,薄膜中存在sp3—CH2和sp2—CH等基团。最后,采用PLD漂浮法在最优参数氢气压强为0.3 Pa下,成功制备了不同厚度（100~300 nm）、满足一定力学强度、无明显宏观缺陷的自支撑CH薄膜。     

Crystallization of hydrogenated amorphous silicon carbon films with laser and thermal annealing

The crystallization of silicon rich hydrogenated amorphous silicon carbon films prepared by Plasma Enhanced Chemical Vapor Deposition technique has been induced by excimer laser annealing as well as thermal annealing. The excimer laser energy density (E_d) and the annealing temperature were varied from 123 to 242 mJ/cm² and from 250 to 1200 °C respectively. The effects of the two crystallization processes on the structural properties and bonding configurations of the films have been studied. The main results are that for the laser annealed samples, cubic SiC crystallites are formed for E_d ≥ 188 mJ/cm², while for the thermal annealed samples, micro-crystallites SiC and polycrystalline hexagonal SiC are observed for the annealing temperature of 800 and 1200 °C respectively. The crystallinity degree has been found to improve with the increase in the laser energy density as well as with the increase in the annealing temperature.     

Copper nanoclusters in amorphous hydrogenated carbon

A study of the geometric characteristics of copper nanoclusters incorporated in an amorphous hydrogenated carbon matrix is reported. It makes use of small-angle x-ray scattering and transmission electron microscopy (100 keV). The fractal dimension and nanocluster diameter have been determined from the x-ray scattering indicatrix for different copper concentrations. TEM images of copper nanoclusters have been analyzed, and a cluster distribution function in size constructed. The shape of the distribution function is discussed in terms of the theory of nucleation of a new phase. Fiz. Tverd. Tela (St. Petersburg) 40, 568–572 (March 1998)