Synthesis of carbon planar structures with specified properties

A new method is proposed that allows an integrated technology to be used for the synthesis of carbon planar structures with predetermined properties. The method is based on the avalanche annealing of amorphous short-period superlattices. The synthesized samples are investigated by Raman spectroscopy and photoluminescence. The possibility of synthesizing carbon layers with diamond-like, graphite-like, graphene, or other structures is demonstrated experimentally using the example of a C/SiC superlattice.     

Evidence of structural strain in epitaxial graphene layers on 6H-SiC(0001)

The early stages of epitaxial graphene layer growth on the Si-terminated 6H-SiC (0001) are investigated by Auger electron spectroscopy (AES) and depolarized Raman spectroscopy. The selection of the depolarized component of the scattered light results in a significant increase in the C-C bond signal over the second order SiC Raman signal, which allows us to resolve submonolayer growth, including individual, localized C=C dimers in a diamondlike carbon matrix for AES C/Si ratio of approximately 3, and a strained graphene layer with delocalized electrons and Dirac single-band dispersion for AES C/Si ratio >6. The linear strain, measured at room temperature, is found to be compressive, which can be attributed to the large difference between the coefficients of thermal expansion of graphene and SiC. The magnitude of the compressive strain can be varied by adjusting the growth time at fixed annealing temperature.     

Angular dependence of Raman scattering selection rules for long-wavelength optical phonons in short-period GaAs/AlAs superlattices

The angular dependence of Raman scattering selection rules for optical phonons in short-period (001) GaAs/AlAs superlattices is calculated and experimentally studied. Experiments are performed using a micro-Raman setup, in the scattering geometry with the wavevectors of the incident and scattered light lying in the plane of superlattices (so-called in-plane geometry). Phonon frequencies are calculated using the Born model taking the Coulomb interaction into account in the rigid-ion approximation. Raman scattering spectra are calculated in the framework of the deformation potential and electro-optical mechanisms. Calculations show an angular dependence of the selection rules for optical phonons with different directions of the wavevectors. Drastic differences in the selection rules are found for experimental and calculated spectra. Presumably, these differences are due to the Fröhlich mechanism in Raman scattering for short-period superlattices.     

SiC过渡层制备温度对碳化硅/氟化类金刚石复合薄膜血液相容性的影响

以316L不锈钢为基底,SiC晶体为靶材,Ar为源气体,采用磁控溅射法在不同温度下制备出系列SiC过渡层.然后以高纯石墨作靶,Ar和CHF_3为源气体,在同一工艺条件下再续镀一层氟化类金刚石(F-DLC)薄膜,形成SiC/F-DLC复合薄膜.研究表明,相比于F-DLC薄膜,复合薄膜的附着力显著增加,血液相容性明显改善.通过样品的拉曼和红外光谱分析了不同温度下制备的SiC过渡层以及复合薄膜结构的演变.结果表明,控制SiC过渡层制备温度可以有效调制过渡层中C=C键的比例以及—C—C—不饱和键的密度,复合薄膜中保留较高比例的芳香环式结构以及合适的F/C比是薄膜的血液相容性得以进一步改善的原因,SiC过渡层制备温度控制在500℃左右效果尤为明显.SiC薄膜和F-DLC两种薄膜的界面处形成一定比例的Si—C键和C=C键是导致复合薄膜附着力显著上升的直接原因.适当条件下在316L不锈钢和F-DLC薄膜之间增加SiC过渡层对于增强薄膜的附着力、改善其血液相容性是可行、有效的.     

RF溅射的SiO_2和SiO_2/Al/SiO_2薄膜的喇曼散射光谱研究

用射频溅射(RF Sputtering)法制成了SiO_2和SiO_2/Al/SiO_2薄膜。应用喇曼光谱研究了薄膜结构。结果表明:RF溅射制成的SiO_2薄膜是含有大量环结构缺陷的玻璃态;SiO_2/Al/SiO_2层状薄膜的喇曼光谱中观察到Al_2O_3的特征峰,证实了Al/SiO_2薄膜界面确有氧化还原反应发生;从喇曼光谱中Al_2O_3的特性峰的位置和相对强度可推断出,SiO_2/Al/SiO_2薄膜界面处的Al_2O_3是非晶γ-Al_2O_3。     

反应磁控溅射法制备的氟化类金刚石薄膜的XPS结构研究

采用射频反应磁控溅射法用高纯石墨作靶、三氟甲烷(CHF₃)和氩气(Ar)作源气体制 备了氟化类金刚石（FDLC）薄膜，通过XPS光谱结合拉曼光谱、红外透射光谱和紫外 可见光光谱研究了源气体流量比等工艺条件对薄膜中键结构、sp2/sp3杂化比以及光学带隙等性能的影响.结果表明在低功率(60W)、高气压(2.0Pa)和适当的流量比(Ar/CHF₃=2∶ 1)下利用射频反应磁控溅射法可制备出氟含量高且具有较宽光学带隙和超低介电常数的FDLC薄膜. 关键词： 反应磁控溅射 氟化类金刚石薄膜 红外透射光谱 XPS光谱     

Diamond-like and graphite-like carbon states in short-period superlattices

The Raman and luminescence spectra are studied in superlattices consisting of carbon layers separated by thin SiC barrier layers. It is shown experimentally that, upon the avalanche annealing of an initially amorphous superlattice, the carbon layers can crystallize into either a diamond-like or graphite-like structure, depending on the geometrical parameters of the superlattice. A method is proposed for obtaining carbon films with a specified crystal modification within a unified technology.     

一维石墨烯超晶格上的氢吸附

通过化学气相沉积法在一种典型的高指数面铜(410)-氧上制备出了一维石墨烯超晶格,并利用拉曼光谱(Raman)、低能电子衍射(LEED)、扫描隧道显微术(STM)等方法研究了氢原子在该超晶格上的吸附.实验结果揭示了由于超晶格的调制作用所引起的无缺陷石墨烯区域的选择性吸附,氢原子优先吸附在石墨烯超晶格一维周期中的相同部位.这一发现为进一步通过一维超晶格调控石墨烯的性质提供了更多可能.在石墨烯上的吸附氢原子除了单个或成对存在之外,实验还首次观察到一种新的三氢原子位型.     

Comparative study of high temperature anti-oxidation property of sputtering deposited stoichiometric and Si-rich SiC films

Stoichiometric and silicon-rich (Si-rich) SiC films were deposited by microwave electron cyclotron resonance (MW-ECR) plasma enhanced RF magnetron sputtering method. As-deposited films were oxidized at 800 ℃, 900 ℃, and 1000 ℃ in air for 60 min. The chemical composition and structure of the films were analyzed by x-ray photoelectron spectroscopy (XPS), Raman spectroscopy and Fourier transform infrared spectroscopy (FT-IR). The surface morphology of the films before and after the high temperature oxidation was measured by atomic force microscopy. The mechanical property of the films was measured by a nano-indenter. The anti-oxidation temperature of the Si-rich SiC film is 100 ℃ higher than that of the stoichiometric SiC film. The oxidation layer thickness of the Si-rich SiC film is thinner than that of the stoichiometric SiC film in depth direction. The large amount of extra silicon in the Si-rich SiC film plays an important role in the improvement of its high temperature anti-oxidation property.     

SiC过渡层对氟化类金刚石薄膜附着特性的影响

采用射频反应磁控溅射法在316L不锈钢基片上分别沉积了两种薄膜:一种是氟化类金刚石薄膜(F-DLC),另一种是先镀上一定厚度的SiC过渡层再沉积F-DLC.着重研究了薄膜的附着力随过渡层制备条件的变化规律.结果显示,增加SiC过渡层后薄膜的附着力明显增加,且附着力随SiC过渡层的制备条件有所变化,在射频输入功率为200 W,沉积时间5min制备出的SiC过渡层上再沉积F-DLC时,附着力可达8.7 N,远高于未加过渡层时F-DLC膜的附着力(4 N).通过研究SiC的沉积速率曲线、表面形貌和红外光谱,探讨了SiC过渡层及其制备条件影响薄膜附着力的相关机制.     

Forward Raman scattering in GaAs/AlAs superlattices: Study of optical phonon anisotropy

We present the forward Raman scattering study of zone-centre optical phonon anisotropy in short-period GaAs/AlAs superlattices. Experiments were performed on specially prepared superlattice structures having anti-reflection dielectric coatings and removed substrates. The experimental data are compared with the angular dispersion of superlattice optical phonons calculated within the dielectric susceptibility model. We have found a good agreement between the experimental data and the calculations taking into account interface disorder. Received 9 September 1998 and Received in final form 22 October 1998     

Raman scattering study of ion bombardment induced amorphization of SiC

Abstract

Lattice disorder induced by ion bombardment of SiC surfaces has been studied using Raman spectroscopy. After bombardment with 15 keV H⁺, D⁺ or He⁺ to fluences of 10¹⁹ cm^?2 the SiC surface was found to amorphize as indicated by changes in the Raman spectra. Raman studies of the annealing behavior of the damaged surface showed that no recrystallization of the amorphous layer occurred after 12 hours at 1000°C. By using different wavelengths of the exciting radiation the spatial distribution of the ion induced damage was investigated. Evidence for the preferential sputtering of Si resulting in a carbon rich surface layer is discussed.

Based on work performed under the auspices of the US Energy Research and Development Administration.

By acceptance of this article, the publisher and/or recipient acknowledges the US Government's right to retain a nonexclusive, royalty-free license in and to any copyright covering this paper.     

Formation of graphene on amorphous SiC film by surface-confined heating with electron beam irradiation

It is demonstrated experimentally that graphene can form on the surface of an amorphous SiC film by irradiating electron beam (e-beam) at low acceleration voltage. As the electron irradiation fluency increases, the crystallinity and uniformity of graphene improve, which is confirmed by the changes of the measured Raman spectra and secondary electron microscopy images. Due to the shallow penetration depth of e-beam with low acceleration voltage, only the region near the surface of SiC film will be heated by the thermalization of irradiated electrons with multiple scattering processes. The thermalized electrons are expected to weaken the bond strength between Si and C atoms so that the thermal agitation required for triggering the sublimation of Si atoms decreases. With these assistances of irradiated electrons, it is considered that graphene can grow on the surface of SiC film at temperature reduced substantially in comparison with the conventional vacuum annealing process.     

Room temperature deposition of amorphous SiC thin films using low energy ion bombardment

Silicon carbide (SiC) films are prepared by single- and dual-ion beam sputtering deposition at room temperature, respectively. An assisting argon ion beam (ion energy Ei=150 eV) bombards directly the substrate surface to modify the SiC film surface. The thin films are characterized by the Fourier transform infrared spectroscopy (FTIR) and the Raman spectra. With assisting ion beam bombardment, the density of the Si–C bond in the film increases. Meanwhile, the excess carbon or the size of the sp² bonded clusters and the amorphous Si (a-Si) phase decrease. These results indicate that the composition of the films is mainly Si–C bond. UV-vis transmission shows that the E_opt increases steadily from 1.85 eV for the amorphous SiC (a-SiC) films without bombardment to about 2.29 eV for those with assisting ion beam bombardment.     

Preparation of graphene on Cu foils by ion implantation with negative carbon clusters

We report on few-layer graphene synthesized on Cu foils by ion implantation using negative carbon cluster ions,followed by annealing at 950?C in vacuum.Raman spectroscopy reveals IG/I2Dvalues varying from 1.55 to 2.38 depending on energy and dose of the cluster ions,indicating formation of multilayer graphene.The measurements show that the samples with more graphene layers have fewer defects.This is interpreted by graphene growth seeded by the first layers formed via outward diffusion of C from the Cu foil,though nonlinear damage and smoothing effects also play a role.Cluster ion implantation overcomes the solubility limit of carbon in Cu,providing a technique for multilayer graphene synthesis.     

Annealing temperature dependence of Raman scattering in Si/SiO2 superlattice prepared by magnetron sputtering

Si/SiO₂ superlattices were prepared by magnetron sputtering, and the deposition temperature and annealing temperature had a great influence on the superlattice structure. In terms of SEM images, the mean size of Si nanocrystals annealed at 1100 °C is larger than that of nanocrystals annealed at 850 °C. It was found that the films deposited at room temperature are amorphous. With increasing deposition temperature, the amorphous and crystalline phases coexist. With increasing annealing temperature, the Raman intensity of the peak near 470 cm⁻¹ decreases, and the intensity of that at 520 cm⁻¹ increases. Also, on increasing the annealing temperature, the Raman peak near 520 cm⁻¹ shifts and narrows, and asymmetry emerges. A spherical cluster is used to model the nanocrystals in Si/SiO₂ superlattices, and the observed Raman spectra are analyzed by combining the effects of confinement on the phonon frequencies. Raman spectra from a variety of nanocrystalline silicon structures were successfully explained in terms of the phonon confinement effect. The fitted results agreed well with the experimental observations from SEM images.     

Graphene films grown on sapphire substrates via solid source molecular beam epitaxy

A method for growing graphene on a sapphire substrate by depositing an SiC buffer layer and then annealing at high temperature in solid source molecular beam epitaxy (SSMBE) equipment was presented. The structural and electronic properties of the samples were characterized by reflection high energy diffraction (RHEED), X-ray diffraction Φ scans, Raman spectroscopy, and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The results of the RHEED and Φ scan, as well as the Raman spectra, showed that an epitaxial hexagonal α-SiC layer was grown on the sapphire substrate. The results of the Raman and NEXAFS spectra revealed that the graphene films with the AB Bernal stacking structure were formed on the sapphire substrate after annealing. The layer number of the graphene was between four and five, and the thickness of the unreacted SiC layer was about 1--1.5 nm.     

pH-Dependent shape changes of water-soluble CdS nanoparticles

Annealing of silicon-carbon nanoparticles was performed in argon at atmospheric pressure to enable formation of silicon carbide nanomaterials and/or carbon structures. Three precursor powders with increasing crystallinity and annealing temperatures from 1,900 to 2,600 °C were used to gain information about the effect of precursor properties (e.g. amorphous vs. nanocrystalline, carbon content) and annealing temperature on the produced materials. Three structures were found after annealing, i.e. silicon carbide crystals, carbon sheets and spherical carbon particles. The produced SiC crystals consisted of several polytypes. Low annealing temperature and increasing crystallinity of the precursor promoted the formation of the 3C-SiC polytype. Raman analysis indicated the presence of single-layer, undoped graphene in the sheets. The spherical carbon particles consisted of curved carbon layers growing from the amorphous Si–C core and forming a ‘nanoflower’ with a diameter below 60 nm. To our knowledge, the formation of this kind of structures has not been reported previously. The core was visible in transmission electron microscopy analysis at the annealing temperature of 1,900 °C, decreased in size with increasing temperature and disappeared above an annealing temperature of 2,200 °C. With increasing crystallinity of the precursor material, fewer layers (~5 with the most crystalline precursor) were detected in the carbon nanoflowers. The method presented opens up the possibility to produce new carbon nanostructures whose properties can be controlled by changing the properties of the precursor material or by adjusting an annealing temperature.     

Buffer layer free large area bi-layer graphene on SiC(0 0 0 1)

The influence of hydrogen exposures on monolayer graphene grown on the silicon terminated SiC(0 0 0 1) surface is investigated using photoelectron spectroscopy (PES), low-energy electron microscopy (LEEM) and micro low-energy electron diffraction (μ-LEED). Exposures to ionized hydrogen are shown to have a pronounced effect on the carbon buffer (interface) layer. Exposures to atomic hydrogen are shown to actually convert/transform the monolayer graphene plus carbon buffer layer to bi-layer graphene, i.e. to produce carbon buffer layer free bi-layer graphene on SiC(0 0 0 1). This process is shown to be reversible, so the initial monolayer graphene plus carbon buffer layer situation is recreated after heating to a temperature of about 950 °C. A tentative model of hydrogen intercalation is suggested to explain this single to bi-layer graphene transformation mechanism. Our findings are of relevance and importance for various potential applications based on graphene-SiC structures and hydrogen storage.     

Structural Characterization of RF‐Sputtered a‐C:N Thin Films by Raman,IR, and X‐ray Reflectometry Spectroscopies

Abstract

Amorphous carbon nitride thin films (a‐C:N) were deposited from a carbon target, at room temperature onto silicon substrates, by reactive RF sputtering in a gas mixture of argon and nitrogen. The structural properties of these films have been studied by Raman, infrared (IR), and X‐ray reflectometry spectroscopies. Both the IR and Raman spectra of the a‐C:N films reveal the presence of C–C, C?C, C?N, and C≡N bonding types. The Raman spectra analysis shows, an increase of the C≡N triple bonds content when the concentration of nitrogen C(N₂) in the gas mixture is increased. The Raman intensities ratio between the disorder (D) and graphitic (G) bands increases with C(N₂) suggesting an increased disorder with the incorporation of nitrogen in the carbon matrix. The effect of C(N₂) on the density of a‐C:N films was also investigated by X‐ray reflectometry measurement. The increase of the nitrogen concentration C(N₂) was found to have a significant effect on the density of the films: as C(N₂) increases from 0 to 100%, the density of the a‐C:N films decreases slightly from 1.81 to 1.62 g/cm³. The low values of density of the a‐C:N films were related (i) to the absence of C–N single bonds, (ii) to the increase of disorder introduced by the incorporation of nitrogen in the carbon matrix, and (iii) to the presence of the bands around 2350 cm^?1 and 3400 cm^?1 associated with the C–O bond stretching modes and the O–H vibration, respectively, suggesting a high atmospheric contamination by oxygen and water. The presence of these bands suggests the porous character of the studied samples.