碳材料的拉曼光谱

1、常见碳材料及其拉曼光谱陈翠红2008.12.02常见的碳材料有:三维的石墨，金刚石 二维的石墨烯，碳纳米带维的碳纳米管，碳纳米线零维的富勒烯（C6。）钻石的结构昵系子范德华力石冬的錯构建筑学家理査德巴克明斯特富勒 (Richard Buckminster Fuller)设计的美国万国博览馆球形圆顶薄壳建筑。石墨的拉曼光谱:自然界中并不存在宏观尺寸的石墨单晶，而是含有许许 多多任意取向的微小晶粒（lOOum）。高定向热解石墨（HOPG）是人工生长的一种石墨，其碳平面几乎完美地沿其垂直方向堆叠，然而沿着石墨平内，晶粒仍然存在任意取向但非常小。DiamondGraphite(1)结构不同，拉曼光谱不

2、同(2) Gband(1580cnri)是由碳环或长链中 的所有必2原子对的拉伸运动产生的。a)b)c)(3) 缺陷和无序诱导D-band (-1360cm1)的产生。(4) 一般我们用D峰与G峰的强度比来衡量碳材料 的无序度。Highly oriented pyrolytic graphite (No D-band) at 1582 cm1Activated Charcoal (D and G bands at 1360,1580cm1)Amorphous Carbon (a very broad peak)Raman Spectrum of GraphiteF- Xmikstra* azq

3、 J. L. K-okwioDivision oj u>croniolccular Science9 Case W extern Reserve University Glevclatvd, Ohio 44106(Received 丄3 November 1969)lOOOcrrr1G«APH：T£ SINGLE CRYSTAL1000 =500RgAN 5HirT in (*Fic I Raman wcdrum of a jungle crystal of gnhilc.商用石墨1355cm-l峰的出现归结于微晶尺寸效应使得没 有拉曼活性的某些声子在选择定则改变后变

4、得有了拉曼活性。发现D模对于拉曼活性G模的相对强度与样品中石墨微晶尺寸的大小相关。D-band的发现及其研究1970年最先报道了无序诱导的D模。1981年，一些人利用不同的激发光能量研究了石墨的拉曼光谱，得出D 模频率随激发光能量的线性移动。斜率在4050cml/ev之间。1990年，一些人通过实验总结了D模强度和样品中各种无序或缺陷的相 互关系，证明无论石墨存在任何形式的无序，D模都会出现。无序诱导的D-band的产生-一双共振拉曼散射D?2D-Band-Double ResonanceD-Band1 e excitation2. e-phonon scattering3 defect sc

5、attering4. E-hole recombinationG-BandS3GCO 400CO 肚(XX) 20OCO 13GCO=>SAUSUSU-伴随着层数的增加强度提高2D-Band层数依赖性1 e excitation2 e-phonon scattering3. Phonon with opposite momentum(nn)-&-v?ue4u-激发光能量依赖性4. E-hole recombination石墨的拉曼光谱Roiineiii spectroscopy of graplaite13 v S rEL> ii/ n i 口 FC e I c： 111

6、azq On丄 Vi io rvis 口 rsPIDt of Eiz/z7a-/va/, t/?zz7?7sz/?/ </f C7<j/trt.hzv</rJV/.7/7?z7A/Zor/, StructUwlwUy, C；B比 1PN, CJJk (:si：379©ou莒沁iu nx： ul<)2 IiLttut f fh FadSrporz Wk, Tn：hzi.z:haDwliu,H(计(lmbm勺卅Tm. ：3&, I ()623 Z?Q7Z“7?yG"7/"77,"jPuZe.sh.ed cTr.lirbG /-

7、/ Sejrtember 2()04Raman spectivscopy of graphiteRaman shift (cm-1)不同点不同偏振方向的拉曼光谱(a) 完美石墨晶体有缺陷的石墨()30Y2 2()x中10向高能方向移动。激发光波长在近红外到近紫外是 线性的，斜率4050cnfi/ev2D的大概是D的两倍(a) D模的相对强度与石墨微晶尺寸La的 相互关系。(b)石墨一阶和二阶拉曼模的激发光能依赖性。().1 1.(),1355/,1575140013501300130014(H)15001.52.()2.53.()3.5Raman shift (cm-1)excitation

8、energy (eV)Figure 7. (a) Citlcukited Riunaii spectral for the D mode in grciphite for three diflerent kuser enetGies. (6) Calculated (full squares) and measured (open symbols) frequencies of the D mode a. function of oxcitation energy From l?homsoii & Rx?ich (2000); tlie ineaKiiroinants were tke

9、n from Wun吕 gI al. (1090), Pocsik et al. (1998) nn<l Klnttliews et al. (1999).小结对完美石墨，1580cmT的E2g光学膜的拉曼峰强不依赖于拉曼实验中激发光偏振 方向。”蠶鱷叡竄倉线在垂直和平行偏振配置下的强度不同，说明石墨微晶的尺 ：G*的频率比G的两倍大，可能是纵向光学声子支的过度弯曲导致。：一般来说，非拉曼活性振动倍频模的二阶拉曼散射在石墨中是允许的。：声子频率的激发光能量依赖性及其他效应都起源于与石墨和其他sp2键碳材料特 殊的电子能带结构相关的双共振拉曼散射效应。Graphene的结构及其拉曼光谱:A

10、RMCHAIR; ZIGZAG |II II石墨烯的手性石墨烯是一种其禁带宽度几乎为零的半金属/半导体材料在2006 - 2008年间，石墨烯已被制成弹道输运晶体管(ballistic transistor), 平面场效应管(Field-Effect Transistors),并且吸引了大批科学家的兴趣week ending3 NOVEMBER 2<M>6石墨烯的拉曼光谱week ending3 NOVEMBER 2<M>6week ending3 NOVEMBER 2<M>6PRL I 87401 ( 2CXXS)PHYSICAL REVIEW LETTE

11、RSRaman Spectrum of Graphene and Graphene LayersA. C FerrarisJC Meyer,2 V. Scarclacu1 C Casi rag hi J M. Lazzeri,5 F. Mauri»3 S. Piscancc,1 ). Jiang,K S. Novoselov,4 S. Roth»2 and A K. Gei1Utnversiry. Enghwering Deprfmetm J J ThontpsanCatfibridc UB3 OFA United Kingdom2Max Planck hisiiime J

12、(w Snlid Stare Researclh STunan 7O5C9. Gcr/nanyyiMPMC. Universites Paris 6 et 7. CNRS, I PGP, 140 rue de 14 nt rme L 750/5 Paris. FranceDcpurfmcnt af Physics <utd Astranoniy. University of Xtmichester, Manchester. jW /.? yPL, United Kinda/n(Received 9 June 2<M)>； published50000(a)' 1 1

13、1 b 1 514 nm40000-Graphite130000. L .J-L.,v20000-10000-Graphe ne-nI 1定ill1500200025003000Graphene 中 心无缺陷存在Raman shift (cm'1)(a) Comparison of Raman spectra at 514 nm for bulk graphite and graphene. They are scaled to have similar height of the 2D peak at 2700 cm-1.(b) Evolution of the spectra at

14、 514 nm with the number of layers.(c) Evolution of the Raman spectra at 633 nm with the number of layers.2500(n .<ausuom(n<(d) D峰的产生及峰位的不同(e) 2layer 2D峰由四个组成(d) Comparison of the D band at 514 nm at the edge of bulk graphite and single layer graphene. The fit of the D1 and D2 components of the

15、 D band of bulk graphite is shown.The four components of the 2D band in 2 layer graphene at 514 and 633 nm.FIG. 3. DR for the 2D peak in (a) single layer and (b) bi layer.Bilayer graphene单层及双层graphene2D峰的双共振过程声子支的分裂1-5cm1所以归因为电子能级的分裂电子能带的分裂， 使bilayer分裂为四个带APPLIED PHYSICS LETTERS 93, 163112 (2008)n&l

16、t;) AuuanbtAngle between edges(C)Edge chirality determination of graphene by Raman spectroscopyYu Meng You, ZhenHua Ni, Ting Yu, and ZeXiang Shena,Division of Physics and Applied Physics, School of Physical and Mathematical Sciences, Nanyang Technological University Singapore 637371, Singapore(Recei

17、ved 21 July 2008: accepted 30 September 2008; published online 22 October 2008)FIG. 1. Color onlinea Optical image of a typical MCG sheet and the angles between edges.b The statistical results of the angle measurements>The standard deviation is 5.4° c Illustration of the relationship between

18、 angles and the chiralities of the adjacent edges.(b) 603 ZigzagD band intensity0 band intensityG band intensityFIG 3. (Color online) Raman imaging results from edges with angles (a) 30°, (b) 60° (xigz:唱h (c) 90°, and (d) 60° (armchair). The images coi> tructed by the G hand i

19、ntensity show the positions and ahnpw of the SLG sheets. The laser polarization is indicated by the green anows. The supcr- imposed frameworks are guides for the eye indicating lhe edge chirality. Note that the chirality of (b) and (d) were determined by the other pair of edges (not hown) wi【h 30

20、76;/Q0c on (be same piece of SLG. The scale har 2 1 /xm当两相邻边缘的夹角是30。, 90°时， 两边缘有不同的手性，一个是armchair, 一个是 zigzag o当夹角是60。时，有相同的手性。无序诱导的D峰的拉曼强度与边缘 手性有关：玉armchair edge的边缘D峰强度较强， 在zigzag边缘较弱。小结: Graphene般出现三个峰D，G,2D； D和2D峰具有激发光能量依赖性，SLG的2D峰是尖锐的单峰，BLG的2D峰有四个组成，其他的都是两个组 成，可用来区分石墨烯单层与多层。 2D峰起源于动量相反的两个声子

21、参与的双共振拉曼过程。在所有sp2 碳材料中均有发现。石墨烯根据边缘的不同，具有不同的手性，用拉曼光谱，根据Dband 的拉曼强度可以识别graphene edge的手性。对数百MCG的研究表明，MCG边缘夹角是30 °的倍数。两相邻边缘的夹角是30° , 90°和150。时，两边缘有不同的手性，一 个是armchair,个是zigzago当夹角是60°和120。时，有相同的手性。一维碳材料一碳纳米管碳纳米管(Carbon nanotube)是1991年才被发现的一种碳结构。ire11理想纳米碳管是由碳原子形成的石墨烯片层卷成的无缝、中空的管体SWNT的

22、直径一般为1 一6nm,最小直径大约为0.5 nm,直径大于6nm 以后特别不稳定，会发生SWNT管的塌陷，长度则可达几百纳米到几个微米MWNT的层间距约为034纳米，直径在几个纳米到几十纳米，长度一般在微 米量级，最长者可达数毫米碳纳米管中的碳原子以sp2杂化，但是由于存在一定曲率 所以其中也有一小部分碳属sp3杂化Hundreds of species depend on how it is folded.奇妙的碳纳米管“太空电梯”的绳 索li4A】细的碳纳米管（0.4 nm）2000年，香港科技大学的汤子康博士即宣布具有极好的可弯折性密度小，硬度强，钢的100倍发现了世界上最细的纯碳纳米

23、碳管0.4nm, 这一结果已达到碳纳米管的理论极限值。(b)317241037875xarmchair"(1Q4：92437亿53i亿4 丫电4<112156IQzigzag204X80(a)(b)(C):metal:semiconductorarmchairchiral二维石墨片的卷曲，沿不同点阵方向卷曲可形成不同类型的碳纳米管碳纳米管的性质鳖的蠶鍔鬆牒手性'直径越小'电子的T美国C.T.White教授计算得出n-m=3q （q为整数），碳管为金属性。其 他情况表现半导体性，并且禁带宽度正比于碳管直径的倒数。讐纳米管为金属性，锯齿形、手性碳管部分为金属，部分为

24、半导体呈现金属性质。Volume 86, Number 6PHYSICAL REVIEW LETTERS5 February 2001Structural (ii.m) Determination of Isolatecl Single-Wall Carbon Nanotubesby Resonant Raman ScatteringA. Jorio? R. Saito? J. H. Hafner? C. M. Lieber,6 M. Hunter,2 T. McClure,3 G. Dressci ha us? and M.S. Dresselhaus1*1 Deparimenl of Ph

25、ysics, Massachusetts Instilule of Technology, Cambridge. Massa( Cutset Is 02/392Department of Earilh Atmospheric and Planetary S( ien( est Massa(uisefls hxstilule of Technology.Cambridge. Massachusetts 02139Cen ter for Materials Science, Massachusetts Institute of Technology, Cambridge. Massachusett

26、s 021394 Franc is Hitter Magnet Laboratory. Massachusetts institute of Technology, Cambridge. Massachusetts 02139Deparlmeaf of Eledronic-Enineenng. University of Electg(川x 77从 w, I828585 Japan6Department of Chemistry. Harvard University. Ccunbridge, Massachusetts 02138r/JnmCVD方法制备的单臂碳纳米管0.5 pmo123SW

27、NTs的平均直径1.85nmFIG. 1. AFM images of the sample. The small particles are iron catalysts. The inset shows rhe diameter distribution of the sample taken from 40 observed SWNTs100150200250300350A 二 SU3UI普通的单个SWNTs的拉曼光谱有三个峰，RBMs D GRBM的频率=A/dt实验测压A=248cnrinm, Si/SiO2± 生长的离散SWNTs比较准确。D峰的频率依赖于激发光能量和直

28、径。Frequency (enfFIG 2 Raman spectra from three different spots on the Si substrate, showing only one resonant nanotube and on已 RBM liequency for each of 3 spots. Tlie RBM frequencies (vvidtlis) and (n, nt) assignment for each resonant SWNT are displayed. The 303 cm 1 feature comes from the Si substr

29、ate Inset (a) shows Raman spectra from one spot on the sample, including 303, 521, and 963 cm 1 Raman features from the Si substrate. Inset (b) shows a zoom of the corresponding G-band region.碳纳米管的拉曼光谱G-band1450155()1650frequency (cnT1)Ausuoa二 UHUCHGraphite:<| G峰单一，尖锐Nanotubes:两个峰G+和G-起漏于 graphit

30、e E2gMetallic 工 semiconducting、对应q=r=0, mode E2gG峰的振动模式及其性质160015801560154015201500.'1'1"I'1tiiiv+/*、 d Qc. °>Gjf L J . 1 旳匚*J f1 j=:bn. : I!°、- : : 、 ； 、 : : :、I:龙、 :*、； %、: :：1/metallic、/ 7、 /X: : : : :/ : semiconducting 亍ii1ifiKG+: no diameter dependenee9 LO axial00.

31、20.40.60.81G- diameter dependence T TO circumferential15601550154015301.01.21.41.61.8 2.0 2.2 2.4Diameter (nm)o o8 76 5 5 5o o o o6 5 4 35 5 5 5o o8 76 5 5 50.81520Metallic tubes: GTL 0&G+TTOSemiconducting tubes:G- TTO & G+ TLO无序诱导的D-band在Si/SiO2衬底上CVD法生长的离散单臂碳纳米管的大量拉曼光谱中，有 一般有强度很弱的D-band信号与

32、缺陷石墨D-band相比：较小的线宽740,反应电子和声子的量子限 制效应。存在非对称展宽。D谱带频率与直径有关，满足wD=wD°+C/dtnr1 = 1C对于双共振相关的过程是正的，强化了D普带频率。在弹性常数效应情况 下，wD。就是二维石墨中观察到的频率数值。在实验中还发现扶手椅型与锯齿形的单臂碳纳米管的D普带有24cnri 的频率差。Raman srudy on doubow巴led carbon nanotubesJinQUZS WeiBs-JiangXEnfcng zhangv Hongwei zhF Dchai WuDw 二三代三 0一 Mechu 二 E二 Esplmi

33、二g- Tsi二xh=u UHiLeJify-童=二兀 10(584. PR ChinuReceived 13 April 2003二n hi邑 form 1 June 2003Published onhne二 2 July 2003CVD即 c翁：-ffl济Lengthoum 叫取“ +2nmFig- Micrograph ofEc purinaDWNTS (a) > SEM image of Lbc purified DWNTS(b二 IRTEM image of a cross.sccuonvicw of a DWNTs bundleD峰半高宽20cm-1LLZO 工(a)(n e

34、) A=su5u-200Raman Shift (cm ')300400500100015002000Raman Shift (cm')Fig. 2. (a) Raman spectra of the DWNTs at diflcrent Er excitationWSU2U-激发光能量降低最强 RBM的频率提高。 原因：管管相互作用， 内外管相互作用WRBM=224/d+1 一般外管d>1.5nm W>160cm-1的峰只要 来源于内管直径(b) A close-up view of the RBM of the DWNTs at different Eiaser

35、 excitation1301.612C01250130013501403Raman Shift (cm* j120012501X»13501400Raman Shift (cm1)(ns2>-su2u-Fig. 3. D-band of the CNTs at different ex ci led Q 昨：(a) flaser = 1.58 eV, (b) £bwr = 1.96 eV and (c) £bwr = 2.41 eV.(n e) AJ-SUSU 一12001250130013501400Raman Shift (cm ")CNTs

36、的Dband的频率随激发光 能量的降低而减小相同激发光能量下，DWNTs的D 峰频率最低。内外层作用力的影响。Fig. 4. The dependence of lhe frequency of Dband of the CNTs on the £昨线性关系斜率 265cm-1/evCNTs:WD=W0+26.5ElaserMWNTs W0=1285DWNTs1260SWNTs1270结论由于内外层相互作用，SWNTs与DWNTs的拉曼光谱不同。直径越小，弯曲度越大，兀电子云形状变化越大，相反，直径越大，弯曲度越小，兀电子云接近石墨的情形，性质接近 石墨。二维碳材一carbon nanowallsTHE JOURNAL OP CHEMICAL PHYSICS 124, 2047()3 (2006)Raman spectroscopic investigation of carbon nanowalls乙 H. Ni, H. M. Fan, and Y. P. FengDe part men I of Physics, National University of Singapore,