Structural and optical properties of Fe-doped hydrogenated amorphous carbon films prepared from trans-2-butene by plasma enhanced metal organic chemical vapor deposition

Fe-doped hydrogenated amorphous carbon (a-C:H:Fe) films were deposited from a gas mixture of trans-2-butene/ferrocene/H₂ by plasma enhanced metal organic chemical vapor deposition. X-ray photoelectron spectroscopy, Fourier transform infrared spectra and Raman spectra were used to characterize the composition and the bonding structure of the a-C:H:Fe and a-C:H films. Optical properties were investigated by the UV–visible spectroscopy and the photoluminescence (PL) spectra. The Fe-doped films contain more aromatic structures and C=C bonds than the undoped films. The sp ² carbon content and sp ² clustering of the films increase, and aromatic-like rings’ structures become richer after Fe-doping. The Tauc optical gap of the a-C:H:Fe films become narrower by 0.3 eV relative to the value of the a-C:H films. The PL peak shifts from 2.35 eV of the a-C:H films to 1.95 eV of the a-C:H:Fe films, and the PL intensity of the a-C:H:Fe films is greatly enhanced. A deep level emission peak around 2.04 eV of the a-C:H:Fe films is observed.     

The electronic structure of different forms of solid carbon studied by electron momentum spectroscopy

The purpose of this paper is to first give an overview of the information obtained by electron momentum spectroscopy (EMS) on the electronic structure of different forms of solid carbon (single crystal graphite, polycrystalline carbon, different forms of amorphous carbon, and fullerenes). We show for sp² bonded carbon that, with decreasing order, the structures observed change but certain basic features remain. sp³-bonded carbon films and fullerene films both have electronic structures different from these graphitic films. The results of EMS are compared with the results of other spectroscopic and scattering techniques. It is argued that the combination of energy and momentum resolution is crucial in order to get a clear picture of the changes in the electronic structure due to the changes in atomic arangements. Only EMS resolves both energy and momentum for all these solids.     

The sp2 and sp3 fractions of unknown carbon materials: electron energy-loss near-edge structure analysis of C-K spectra acquired under the magic-angle condition by the electron nanobeam technique

A method is described for the quantification of the sp², sp³ and intermediate hybridizations in several carbon (C) material samples. Electron energy-loss near-edge spectra were acquired using fast electrons (120 keV) in an electron microscope in nanobeam configuration under the so-called ”magic-angle” condition, and were analysed to extract the sp² and sp³ fractions, and identify the possible mixed sp^2+ε hybridizations. The method consists in projecting the unknown spectra on a basis made up of pure sp² and sp³ spectra, obtained under the same experimental conditions from graphite and diamond crystals, respectively. The residual spectra contain information about the intermediate hybridizations sp^2+ε occurring in the samples. The method was successfully tested on “ab initio” numerically generated spectra relative to amorphous C materials. Finally, it was applied to actual C amorphous and pyrolytic samples, and results were compared to those obtained by the most commonly used, conventional ”three-Gaussian” method. The combined application of electron diffraction and spectroscopy, in the nanobeam configuration, yielded useful information about the atomic and electronic structure from very small volumes of the unknown C material.     

非晶碳结构建模和电子结构的第一性原理研究

基于密度泛函理论,采用了一种更为精确的交换相关泛函OLYP(OPTX+LYP),对密度范围从2.0到3.2 g/cm³的非晶碳进行结构建模. 模拟得到的5个碳网络结构无论从径向分布函数还是sp³含量都与实验符合得很好. 对非晶碳电子结构的研究表明费米能级附近的电子态密度主要是sp²碳原子的贡献. 随着密度的增加,sp³碳原子增加,费米能级附近的态密度越来越小. 小环结构增加了费米能级附近的电子态密度,缺陷态在费米能级形 关键词： 非晶碳 密度泛函理论 电子结构     

非晶碳结构建模和电子结构的第一性原理研究

基于密度泛函理论，采用了一种更为精确的交换相关泛函OLYP(OPTX+LYP)，对密度范围从2.0到3.2 g/cm³的非晶碳进行结构建模. 模拟得到的5个碳网络结构无论从径向分布函数还是sp³含量都与实验符合得很好. 对非晶碳电子结构的研究表明费米能级附近的电子态密度主要是sp²碳原子的贡献. 随着密度的增加，sp³碳原子增加，费米能级附近的态密度越来越小. 小环结构增加了费米能级附近的电子态密度，缺陷态在费米能级形     

Carbon systems of polymerized nanotubes: Crystal and electronic structures

Molecular dynamic calculations are carried out for the (P, T) phase diagram of a covalent compound of cross-linked carbon single-wall nanotubes (SWNT) and for the structures and electronic spectra of the novel crystals of polymerized carbon nanotubes. It is shown that the transformation of covalently bonded nanotubes in a close-packed conducting structure cardinally modifies their electronic properties. The P-SWNT crystal becomes semiconducting and, upon complete transformation of sp ²-hybridized carbon atoms into sp ³-hybridized ones, it becomes an insulator.     

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.     

Wide wavelength-range optical studies of hydrogenated amorphous carbon films: from 700 nm to 10 μm

Hydrogenated amorphous carbon (a-C:H) films were deposited on double-side polished germanium substrates by RF plasma-assisted chemical vapour deposition method using benzene as a precursor, and their optical properties were investigated in the wavelength range from 700 nm to 10 μm. In particular, we used a dispersion-function-based non-linear regression to fit the reflectance in the range from 700 to 1800 nm and the baselines of the infrared transmittance in the range from 1000 to 5000 cm⁻¹, respectively. Optical constants determined in both ranges, together with their respective thickness values, showed overall consistency. As a function of self-bias, we found that the refractive index increased while the band gap decreased, which was indicative of film densification and increase of sp²-bonded carbons. Detailed information on the self-bias-dependent evolution of microscopic bonding structure in a-C:H films was revealed via the quantitative vibration-absorption spectra in the mid-infrared region, which was obtained after taking Urbach-tail-like electronic absorption into consideration. More specifically, it was found that as self-bias was increased hydrogen content decreased, olefinic sp²-bonding decreased while aromatic sp²-bonding increased, and more carbon bonding was distorted due to increased cross-linking. Maximum sp²-bonding was observed between −300 and −400 V of self-bias.     

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.     

Correlation of sp and sp fraction of carbon with electrical, optical and nano-mechanical properties of argon-diluted diamond-like carbon films

In the present work the correlation of electrical, optical and nano-mechanical properties of argon-diluted diamond-like carbon (Ar-DLC) thin films with sp³ and sp² fractions of carbon have been explored. These Ar-DLC thin films have been deposited, under varying C₂H₂ gas pressures from 25 to 75 mTorr, by radio frequency-plasma enhanced chemical vapor deposition technique. X-ray photoelectron spectroscopy studies are performed to estimate the sp³ and sp² fractions of carbon by deconvoluting C 1s core level spectra. Various electrical, optical and nano-mechanical parameters such as conductivity, I-V characteristics, optical band gap, stress, hardness, elastic modulus, plastic resistance parameter, elastic recovery and plastic deformation energy have been estimated and then correlated with calculated sp³ and sp² fractions of carbon and sp³/sp² ratios. Observed tremendous electrical, optical and nano-mechanical properties in Ar-DLC films deposited under high base pressure conditions made it a cost effective material for not only hard and protective coating applications but also for electronic and optoelectronic applications.     

Effect of nickel on the structure and bond type in amorphous diamond-like carbon films

Experimental data are presented from studies of the structure and bond type of carbon atoms in amorphous carbon-nickel films deposited from pulsed vacuum-arc discharge plasma sources. X-ray photoelectron spectroscopy was used. The characteristics of the plasmon loss spectra depend significantly on the deposition parameters. Carbon exists in a mixed sp²+sp³ hybridized state in the carbon–nickel films. The ratio of sp³/sp² carbon bonds increases when the nickel content is reduced (from 5.5 to 1.0 atomic %) and the deposition angle is increased. The structure closest to that of diamond was with a substrate bias voltage of –80 to –100 V and a deposition angle of 90°.     

New allotropic form of silicon

A new allotropic form of amorphous silicon with sp hybridization of the valence electrons is discovered. The new material consists of linear chains of atoms. A small fraction of the atoms are in the sp ² state. Acting as bridges, these atoms couple the linear chains into a single random network. This conclusion is based on an analysis of experimental data on the effect of annealing and ion implantation on the structure of the short-range order and the properties of amorphous-silicon films obtained by different methods. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 9, 646–649 (10 May 1998)     

Structure and gas-barrier properties of amorphous hydrogenated carbon films deposited on inner walls of cylindrical polyethylene terephthalate by plasma-enhanced chemical vapor deposition

The influence of radio-frequency (RF) power on the structure and gas permeation through amorphous hydrogenated carbon films deposited on cylindrical polyethylene terephthalate (PET) samples is investigated. The results show that a higher radio-frequency power leads to a smaller sp³/sp² value but produces fewer defects with smaller size. The permeability of PET samples decreases significantly after a-C:H deposition and the RF only exerts a small influence. However, the coating uniformity, color, and wettability of the surface are affected by the RF power. A higher RF power results in to better uniformity and it may be attributed to the combination of the high-density plasma and sample heating.     

X-ray photoelectron spectroscopic study of nitrogen incorporated amorphous carbon films embedded with nanoparticles

The effect of substrate bias on X-ray photoelectron spectroscopy (XPS) study of nitrogen incorporated amorphous carbon (a-C:N) films embedded with nanoparticles deposited by filtered cathodic jet carbon arc technique is discussed. High resolution transmission electron microscope exhibited initially the amorphous structure but on closer examination the film was constituted of amorphous phase with the nanoparticle embedded in the amorphous matrix. X-ray diffraction study reveals dominantly an amorphous nature of the film. A straight forward method of deconvolution of XPS spectra has been used to evaluate the sp³ and sp² contents present in these a-C:N films. The carbon (C 1s) peaks have been deconvoluted into four different peaks and nitrogen (N 1s) peaks have been deconvoluted into three different peaks which attribute to different bonding state between C, N and O. The full width at half maxima (FWHM) of C 1s peak, sp³ content and sp³/sp² ratio of a-C:N films increase up to −150 V substrate bias and beyond −150 V substrate bias these parameters are found to decrease. Thus, the parameters evaluated are found to be dependent on the substrate bias which peaks at −150 V substrate bias.     

Photoluminescence of amorphous carbon films fabricated by layer—by—layer hydrogen plasma chemical annealing method

A method in which nanometre-thick film deposition was alternated with hydrogen plasma annealing (layer-by-layer method) was applied to fabricate hydrogenated amorphous carbon films in a conventional plasma-enhanced chemical vapour deposition system.It was found that the hydrogen plasma treatment could decrease the hydrogen concentration in the films and change the sp^2/sp^3 ratio to some extent by chemical etching.Blue photoluminescence was observed at room temperature,as a result of the reduction of sp^2 clusters in the films.     

A new carbon allotrope with C28 cage: T-C64

A new tetragonal carbon allotrope (named T-C₆₄) is predicted by swarm structural searches combined with first principles calculation. It contains 64 carbon atoms in a Tetragonal unit cell with I4₁/amd symmetry and exhibits distinct topologies including C28 cages. This new carbon phase has an sp²-sp³ network with calculated hardness of 68.2 GPa. In order to examine the stability of T-C₆₄ under ambient pressure, we calculated the properties of elastic constant and phonon spectrum. In addition, by calculating the electronic properties of the crystal, it is concluded that T-C₆₄ is an indirect band gap semiconductor with a band gap of 2.23 eV.     

Electronic density of states of group-IV semiconductors: A cluster-Bethe lattice approach for realistic Hamiltonians

We have extended the cluster-Bethe lattice method to study realistic tight-binding Hamiltonians. The numerical solution of the transfer matrix in the Bethe lattice is very stable and requires about 50 steps of our iterative procedure to reach convergency. We apply this method to study the density of states of group-IV semiconductors (C, Si, Ge) using a five-parameter sp³ Hamiltonian, which takes into account all possible interactions between sp³ hybrids in nearest-neighbor atoms. Our results show clearly that the main features of the density of states are due to short-range order. Clusters of about 30 atoms reproduce very well the crystalline density of states. Based on our results we propose a model for the density of states in the gap region of an amorphous semiconductor.     

Effect of phosphorus content on structural properties of phosphorus incorporated tetrahedral amorphous carbon films

With phosphorus incorporated tetrahedral amorphous carbon (ta-C:P) films prepared using filtered cathodic vacuum arc technique with PH₃ as the dopant source, we investigate the effect of phosphorus content on the structural properties of the films by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. XPS analysis indicates that a function is established between the atomic fraction of phosphorus in the samples and the flow rate of PH₃ during deposition, and that phosphorus implantation increases the graphite-like trihedral sp² bonds deduced from fitted C 1s and P 2p core level spectra. Raman spectra of a broad range show that there are two notable features for all ta-C:P films: the first-order band centered at about 1560 cm^-1 and the second-order band between 2400 and 3400 cm^-1. The broad first-order band demonstrates that the amorphous structure of all samples does not remarkably change when a lower flow rate of PH₃ is implanted, while a higher concentration of phosphorus impurity enhances the clustering of sp² sites dispersed in sp³ skeleton and the evolution of structural ordering. Furthermore, the second-order Raman spectra confirm the formation of small graphitic crystallites in size due to a finite-crystal-size effect. PACS 81.05.Uw; 81.15.Ef; 63.50.+x     

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     

The structure of thin carbon films deposited at 13.5 nm EUV irradiation

In this work, the structure and chemistry of thin nm-thick carbon films deposited on a substrate using strong 13.5 nm EUV irradiation under a strong vacuum were studied. The film structure was studied by Raman spectroscopy in comparison with the Raman spectra of well-known carbon phases: diamond, single-wall nanotubes, nano- and micro-crystalline graphite and amorphous carbon. As well, FTIR spectroscopy was used to study possible IR-active chemical bonds, primarily, hydrogen bonds. It was shown that films deposited on a surface under EUV irradiation consists of amorphous sp ²-carbon. The mechanisms of deposition are discussed briefly. Knowledge about the structure and chemistry of such carbon films is very important for EUV lithography.