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.     

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.     

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.     

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.     

Effect of metal nanoparticle doping concentration on surface morphology and field emission properties of nano-diamond films

Nano-diamond particles are co-deposited on Ti substrates with metal (Ti/Ni) nanoparticles (NPs) by the electrophoretic deposition (EPD) method combined with a furnace annealing at 800℃ under N₂ atmosphere. Modifications of structural and electron field emission (EFE) properties of the metal-doped films are investigated with different metal NPs concentrations. Our results show that the surface characteristics and EFE performances of the samples are first enhanced and then reduced with metal NPs concentration increasing. Both the Ti-doped and Ni-doped nano-diamond composite films exhibit optimal EFE and microstructural performances when the doping quantity is 5 mg. Remarkably enhanced EFE properties with a low turn-on field of 1.38 V/μm and a high current density of 1.32 mA/cm² at an applied field of 2.94 V/μm are achieved for Ni-doped nano-diamond films, and are superior to those for Ti-doped ones. The enhancement of the EFE properties for the Ti-doped films results from the formation of the TiC-network after annealing. However, the doping of electron-rich Ni NPs and formation of high conductive graphitic phase are considered to be the factor, which results in marvelous EFE properties for these Ni-doped nano-diamond 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.     

The structure of copper-doped amorphous hydrogenated carbon films

A study of the nanostructure of a-C:H:Cu films by x-ray small-angle scattering, x-ray diffraction, TEM, and visible and UV spectroscopy is reported. It has been established that introduction of 9–16 at.% Cu not only decorates the original carbon fragments but produces extended (up to 4 μm in length) formations of copper-decorated strongly elongated ellipses as well. At 14–16 at.% Cu, these linear clusters represent copper nanotubes with a core made up of the original ellipses drawn in a line. It is these conducting copper formations that account primarily for the strong increase in conductivity at 12–16 at.% Cu contents in a-C:H films. Fiz. Tverd. Tela (St. Petersburg) 41, 2088–2096 (November 1999)     

硼掺杂对四面体非晶碳膜电导性能的影响

以单质硼和高纯石墨的混合粉末压制成型的靶材作为靶源,采用过滤阴极真空电弧技术制备不同硼含量的掺硼四面体非晶碳膜.分别采用四探针法、阻抗分析仪和电化学界面对薄膜的变温电导率、I-V特性和C-V特性进行了测试和研究.实验结果表明,当B含量由0增加至6.04 at%时,薄膜的室温电导率先逐渐增大而后逐渐减小,相应薄膜的电导激活能先逐渐减小而后逐渐增大,并在2.13 at%时分别出现最大和最小值1.42×10^-7S/cm和0.1eV.此外,掺硼四面体非晶碳/n型硅异质结的I-V曲线表现出典型的整流特性,表明p-n结二极管已经形成,且结两端的掺杂能级在空间上连续统一. 关键词： 四面体非晶碳 电导率 I-V曲线')" href="#">I-V曲线 C-V曲线')" href="#">C-V曲线     

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.     

退火对含氮氟非晶碳膜结构及光学带隙的影响

采用射频等离子体增强化学气相沉积法,在不同条件下制备了含氮氟非晶碳膜,着重考察了退火温度对膜结构和光学带隙的影响. 研究发现：在350℃时,膜仍很稳定,当退火温度达到400℃时,其内各化学键的相对含量发生很大的改变. 膜的光学带隙随着退火温度的升高而增大,红外和拉曼光谱分析显示其原因是：退火使得膜内F的相对浓度降低,sp²相对含量升高,导致σ-σ^*带边态密度降低. 关键词： 含氮氟非晶碳膜 退火 光学带隙     

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。     

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     

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.     

First principles calculation of field emission from carbon nanotubes with nitrogen and boron doping

We investigate the field emission properties of nitrogenated and boronated carbon nanotubes using time-dependent density functional theory, where the wave function propagation is performed using the Crank–Nicholson algorithm. We extract the current–voltage characteristics of the emitted electrons from nanotubes with different doping configurations. We found that boron doping alone either impedes, or slightly enhances, field emission. Nitrogen generally enhances the emission current, and the current is sensitive to the location of the nitrogen dopant in the nanotube. Doping with both nitrogen and boron will generally enhance emission, and the closer the nitrogen dopant is to the tip, the higher is the emitted current. The emitted charge cloud from nitrogen-doped carbon nanotubes, however, diffuse more than that from pristine ones, our simulations show the emergence of a branching structure from the charge cloud, which suggests that nitrogenated carbon nanotubes are less convenient for use in precision beam applications.     

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.     

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     

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.     

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.