Preparation and study of the optical properties of porous graphite

Optical properties of porous graphite samples prepared by electrochemical etching were investigated. It is found that electrochemical etching modifies their Raman spectra and gives rise to photoluminescence. The evolution of Raman spectra at the initial etching stages is studied in detail. A model is proposed explaining the salient features of the observed Raman spectra. It assumes the appearance of graphite nanoparticles and the formation of sp ³ bonds between the graphite planes at the nanocrystal boundaries.     

纳米级光滑石墨表面的拉曼光谱表征

石墨微结构的表面一般为原子级光滑或纳米级光滑,是研究表面、界面物理性质的重要基础,对结构超润滑、微机电器件的研究和应用非常重要。为了解石墨微结构表面的状态和性质,其无损表征具有重要意义。通过微加工方法制备出石墨微结构,使用微纳机械手上的针尖推动石墨微结构上部可以得到原子级光滑或纳米级光滑的石墨表面。使用拉曼光谱对获得的石墨表面进行表征。通过与原子力显微镜和电子显微镜的表征结果进行对比发现,拉曼光谱能够准确反映石墨表面的缺陷程度,同时具有非接触、无损和快速的优点。这表明拉曼光谱在纳米级光滑石墨表面的表征中能够提供可靠表征信息,并且检测快速、不破坏样品,为石墨结构超润滑和MEMS器件的后续研究和应用奠定了基础。     

Anisotropy of the Raman spectra of nanographite ribbons

A polarized Raman study of nanographite ribbons on a highly oriented pyrolytic graphite substrate is reported. The Raman peak of the nanographite ribbons exhibits an intensity dependence on the light polarization direction relative to the nanographite ribbon axis. This result is due to the quantum confinement of the electrons in the 1D band structure of the nanographite ribbons, combined with the anisotropy of the light absorption in 2D graphite, in agreement with theoretical predictions.     

湖南砂矿金刚石中石墨包裹体拉曼光谱原位测定：形成条件及成因指示

石墨是天然金刚石中最常见的包裹体之一,按其形成顺序可分为原生、同生、次生,原生/同生与次生石墨包裹体的存在指示了金刚石形成的环境及形成后可能经历的变化。对湖南沅水流域产出的13粒宝石级-半宝石级砂矿金刚石中的原生/同生石墨包裹体及次生石墨包裹体进行显微激光拉曼光谱的原位测试。测试显示,湖南沅水流域金刚石中原生/同生石墨包裹体与次生石墨包裹体的G带与D带拉曼位移均存在漂移,其中原生/同生石墨包裹体G带的漂移范围为1 591～1 600 cm-1,次生石墨的漂移范围为1 575～1 588 cm-1,显示其形成压力较低,结晶压力变化范围大。原生/同生石墨漂移程度估算出该区域压力范围为4.01～5.88 GPa,估算结果与利用橄榄石包裹体拉曼位移估算的源区压力范围基本一致。该区域内金刚石中原生/同生石墨包裹体的D带拉曼位移在1 350～1 368 cm-1之间,D带与G带的强度比(I_D/I_G值)值位于0.36～0.82之间,具有较低有序度结构/结晶程度与橄榄岩型金刚石的高结晶度石墨明显不同指示该区域部分砂矿来源的金刚石的形成深度较浅,成因与榴辉岩关系更为密切,形成过程极可能曾位于石墨-金刚石稳定域附近。研究结果表明,金刚石石墨包裹体拉曼位移的漂移程度可成为探索金刚石原生源区形成环境的有效方法之一。     

碳纳米管和高取向热解石墨的拉曼光谱对比研究

同时测量了碳纳米管（Ｄ－ＣＮＴ）和高取向热解石墨（ＨＯＰＧ）的拉曼光谱，第一次分别在ＨＯＰＧ和Ｄ－ＣＮＴ中观察到了位于４２６５ｃｍ－１和４２４８ｃｍ－１的（Ｇ＋Ｄ＊）三级模的拉曼散射；拉曼谱的研究显示，Ｄ－ＣＮＴ的结构比ＨＯＰＧ的无序，同时也进一步表明此无序程度主要来源于结构的缺陷，而非石墨层卷曲成筒状之故     

Double resonant Raman scattering in nanographite films

Experimental results are presented on Raman scattering in graphite films produced by DC plasmaenhanced chemical vapor deposition from a methane-hydrogen gas mixture. Scanning electron and probe microscopy data show that, depending on substrate material and deposition time, the deposited film is either a mesoporous material consisting of graphite nanocrystallites with basal planes oriented perpendicular to the substrate surface or an atomically flat, nanometer-thick stack of graphene layers parallel to the substrate. A comparative Raman spectroscopy analysis is performed for film samples deposited on nickel and silicon substrates for 5 and 60 min, as well as for highly ordered graphite samples. The Raman spectra of the examined samples correspond to the double resonant scattering mechanism. The behavior of Raman peak position and intensity as functions of excitation wavelength suggests a high degree of structural order in the graphite films deposited on nickel for 5 min. The results obtained are used to show that the thickness of these films is 1.5 ± 0.5 nm.     

热丝CVD生长金刚石薄膜喇曼散射研究

本文报道热丝化学气相沉积法（ＨＦＣＶＤ）生长金钢石薄膜的喇曼散射结果。选取多种峰型，对金钢石薄膜喇曼谱（１１０－１８００ｃｍ－１）采用最小二乘法进行非线性拟合，得到最佳拟合模型，其计算得到的拟合曲线怀实验谱图符合得较好。该模型揭示，石墨Ｄ峰（１３５５ｃｍ－１）是金刚石薄膜喇曼谱中不可缺少的一个组份，并且结合石墨Ｄ峰和金刚石喇曼的空间相关线型，可以解释金刚石喇曼区特殊峰形的物理机制，拟合参量的进一步     

PAN基碳纤维在表面处理中的拉曼光谱研究

采用激光拉曼光谱研究了PAN基碳纤维在表面处理中的微结构变化,分析了表面处理前后碳纤维的一级拉曼光谱特性。结果表明：拉曼光谱中主要的D峰和G峰的拉曼频移、半高宽以及各个不同拉曼频移位置对应肩峰的积分面积比是表征碳纤维物相结构变化的重要参数。经过不同的表面处理,PAN基碳纤维的一级拉曼光谱参数发生了一定程度变化,D峰和G峰的拉曼峰位向高波数偏移,表征石墨微晶尺寸的R值有所提高,这说明在表面处理后碳纤维的石墨微结构受到刻蚀,微晶尺寸有所减小,石墨微晶的边界活性增大;此外,表征碳纤维结构有序程度和缺陷多少的D峰和G峰的半高宽均有减小,表征无定型碳结构或某种有机官能团的A峰和D″峰的相对积分面积减小,这说明与乱层石墨结构相比,碳纤维中存在的无定型碳结构更容易被刻蚀,经过表面处理之后无定型碳的物相比例减小,这与碳纤维XRD图谱中表观结晶度提高的规律相一致。因此,利用激光拉曼光谱可研究碳纤维物相结构的变化规律。     

Raman scattering in graphite intercalation compounds

Raman scattering results are reported on graphite intercalated with Br₂, ICℓ and IBr. In all of these acceptor compounds, the single E_2g2 Raman peak for pure graphite is replaced by a doublet structure identified with in-plane carbon atom vibrations. In addition, Raman peaks specific to the intercalate species are found at frequencies down-shifted from the stretching modes of the free intercalate molecules.     

Double resonance Raman scattering of second-order Raman modes from an individual graphite whisker

Resonant Raman scattering of second-order Raman modes from an individual graphite whisker synthesized by a high-temperature heat-treatment method at a special pressure was discussed here. The dependence of phonon frequencies on the incoming laser light and the frequency difference between Stokes and anti-Stokes scattering show their origin from double resonance Raman scattering. Our results show that all the experimental results of second-order Raman modes in graphite whiskers, such as the excitation-energy dependence on the mode frequency, the frequency shift between a second-order Raman mode and its fundamentals, and the frequency discrepancy between Stokes and anti-Stokes components of a second-order Raman mode can be well understood by double resonance Raman scattering.     

Raman scattering and luminescence in coal and graphite

Raman scattering and luminescence have been observed in coal. The similarity of our results to those of disordered graphite is striking. The disorder-induced line in graphite is shown to be due to the high phonon density of states at 0 and K points of the Brillouin zone for graphite. The luminescence shows spectra having anti-stoke parts indicating the presence of multi-step processes. The Raman spectra are not affected significantly by the mineral matter contents in coal, thus our observations offer a new approach for the study of the microstructure of coal.     

膨胀石墨的Raman光谱研究

以波长为514.5nm的激光对550-920℃制备的膨胀石墨进行了Raman光谱研究,结果表明:膨胀石墨的Raman光谱与高取向热解石墨基本相同,分别在~1350、~1580、~2445、~2725、~3248和~4300cm-1处出现了相应的Raman位移;其中位于~1350、~2445和~4300cm-1的Raman峰位随着制备温度的不同会发生较大的移动,而不同温度制备的膨胀石墨位于~1580、~2725、~3248cm-1处的三个Ra-man峰位基本接近;~2725 cm-1处的二阶模包含两个分别位于2707和2730cm-1处的Raman峰。膨胀石墨的D模与G模强度比ID/IG随着温度升高下降,而D线的二阶模D*峰强ID*与IG的比值ID*/IG的大体变化趋势是随着温度升高而增大。     

Quantitative structure–property relationships of polyacrylonitrile-based graphite fibers revealed by laser confocal Raman spectroscopy

A series of polyacrylonitrile-based graphite fibers with different tensile modulus and electrical resistivity were characterized by laser confocal Raman spectroscopy. The Raman spectra of the graphite fibers were deconvolved into five constituent bands using Lorentzian peak fitting function. The Raman spectra parameters, including band position, full width at half maximum, and integrated band area, were extracted and correlated with the tensile modulus and electrical resistivity. Most of the Raman parameters changed monotonically with the tensile modulus and electrical resistivity. A good linear relationship between the electrical resistivity and the structural order was found.     

不同惰性气氛及压强下的碳纳米管的拉曼光谱

本文比较了央弧法中在两种不同气氛和不同压强下制备出的碳纳米管的一级和二级拉曼光谱。我们用直流碳弧法分别在He气氛下和Ar气氛下，压强从11kPa到92kPa制备出碳纳米管，对它们的拉曼光谱进行了分析和比较，发现谱线的峰位置和峰宽度取决于所制备的惰性气氛种类和气体压强。在Ar气氛下制备的碳纳米管的拉曼光谱更接近于石墨的拉曼光谱，而He气氛下制备的碳纳米管，其拉曼光谱与石墨比较，差别较大。并且拉曼位移的峰位置和宽度随着压强的变化而改变，在较高压强下产生的碳纳米管的拉曼光谱更类似于石墨的拉曼光谱。     

THE RAMAN SCATTERING OF CARBON NANOTUBES PRODUCED IN DIFFERENT INERT GASES AND THEIR PRESSURES BY ARC DISCHARGE

First- and second-order Raman spectra of carbon nanotubes produced in helium and argon atmospheres at a pressure ranging from 11 to 92 kPa by arc discharge have been measured and compared with each other. The position and bandwidth of the spectral lines depend on the kind of inert gases and their pressure. The Raman spectra of the nanotubes produced in argon gas atmosphere are much more similar to that of polycrystalline graphite than those of the nanotubes produced in helium gas atmosphere. The position and bandwidth of nanotube Raman peaks change with gas pressure in arc discharge because different diameter distribution of nanotubes is produced at different inert gas pressure. The Raman spectra of nanotubes produced at high pressure is much more like that of graphite than those produced in lower pressure     

Tip-Enhanced Raman Spectroscopy and Mapping of Graphene Sheets

Abstract: Single graphene sheets, a few graphene layers, and bulk graphite, obtained via both micromechanical cleavage of highly oriented pyrolytic graphite and carbon vapor deposition methods, were deposited on a thin glass substrate without the use of any chemical treatment. Micro-Raman spectroscopy, tip-enhanced Raman spectroscopy (TERS), and tip-enhanced Raman spectroscopy mapping (TERM) were used for characterization of the graphene layers. In particular, TERM allows for the investigation of individual graphene sheets with high Raman signal enhancement factors and allows for imaging of local defects with nanometer resolution. Enhancement up to 560% of the graphene Raman band intensity was obtained using TERS. TERM (with resolution better than 100 nm) showed an increase in the number of structural defects (D band) on the edges of both graphene and graphite regions.     

石墨Raman活性模E2g的压缩行为及C—C键力常数的压力效应

 本文在0~13 GPa压力范围内测量了石墨Raman活性模E_2g的频率随压力的变化，结果表明在4 GPa附近dν/dp出现了不连续点，该点前的dν/dp大于该点后的dν/dp，这是由于在压力的作用下石墨六角网格发生畸变所致。本工作还导出了高压状态下C—C键力常数的表达式，对E. Fitzer在常压下用Raman频率计算C—C键长的计算公式进行了修正。     

Melting of carbon heated by focused laser radiation in air at atmospheric pressure and temperature below 4000 K

The melting of carbon at a pressure of about 1 atm is observed. The escape of liquid carbon from the heating region and its spread over the sample surface are observed in the experiments. The structural changes in graphite occurring in the melting region are determined from scanning tunneling microscope (STM) images obtained by means of an atomic force microscope and from Raman spectra. The STM images exhibit significant rearrangement of the structure of the graphite surface in the region of the escape of liquid carbon. The Raman spectra show that the graphite ordering degree increases significantly.     

Graphite at high pressures: Pseudomelting at 44 GPa

Abstract

The Raman spectra comparative study of graphite-like modifications of carbon: monocrystalline graphite, pyrolytic graphite and amorphous (glassy) carbon was performed at high pressures and room temperature. At P = 44 GPa an abrupt broadening of Raman bands of pyrolytic graphite and glassy carbon was observed. The same process in monocrystalline graphite occures continuously from 23 to 44 GPa and for higher pressures the Raman spectra of all three substances under study become practically indistinguishable from one another and from that of amorphous carbon (a-C) at the same pressure. This result is ascribed to the formation at these pressures of the dence amorphous carbon modification.     

Crystal structure of cold compressed graphite

Through a systematic structural search we found an allotrope of carbon with Cmmm symmetry which we predict to be more stable than graphite for pressures above 10 GPa. This material, which we refer to as Z-carbon, is formed by pure sp(3) bonds and it provides an explanation to several features in experimental x-ray diffraction and Raman spectra of graphite under pressure. The transition from graphite to Z-carbon can occur through simple sliding and buckling of graphene sheets. Our calculations predict that Z-carbon is a transparent wide band-gap semiconductor with a hardness comparable to diamond.