碳材料的拉曼光譜

1、常見碳材料及其拉曼光譜陳翠紅2008.12.02常見的碳材料有:三維的石墨，金剛石 二維的石墨烯，碳納米帶維的碳納米管，碳納米線零維的富勒烯（C6。）鉆石的結(jié)構(gòu)昵系子范德華力石冬的錯(cuò)構(gòu)建筑學(xué)家理査德巴克明斯特富勒 (Richard Buckminster Fuller)設(shè)計(jì)的美國萬國博覽館球形圓頂薄殼建筑。石墨的拉曼光譜:自然界中并不存在宏觀尺寸的石墨單晶，而是含有許許 多多任意取向的微小晶粒（lOOum）。高定向熱解石墨（HOPG）是人工生長(zhǎng)的一種石墨，其碳平面幾乎完美地沿其垂直方向堆疊，然而沿著石墨平內(nèi)，晶粒仍然存在任意取向但非常小。DiamondGraphite(1)結(jié)構(gòu)不同，拉曼光譜不

2、同(2) Gband(1580cnri)是由碳環(huán)或長(zhǎng)鏈中 的所有必2原子對(duì)的拉伸運(yùn)動(dòng)產(chǎn)生的。a)b)c)(3) 缺陷和無序誘導(dǎo)D-band (-1360cm1)的產(chǎn)生。(4) 一般我們用D峰與G峰的強(qiáng)度比來衡量碳材料 的無序度。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峰的出現(xiàn)歸結(jié)于微晶尺寸效應(yīng)使得沒 有拉曼活性的某些聲子在選擇定則改變后變

4、得有了拉曼活性。發(fā)現(xiàn)D模對(duì)于拉曼活性G模的相對(duì)強(qiáng)度與樣品中石墨微晶尺寸的大小相關(guān)。D-band的發(fā)現(xiàn)及其研究1970年最先報(bào)道了無序誘導(dǎo)的D模。1981年，一些人利用不同的激發(fā)光能量研究了石墨的拉曼光譜，得出D 模頻率隨激發(fā)光能量的線性移動(dòng)。斜率在4050cml/ev之間。1990年，一些人通過實(shí)驗(yàn)總結(jié)了D模強(qiáng)度和樣品中各種無序或缺陷的相 互關(guān)系，證明無論石墨存在任何形式的無序，D模都會(huì)出現(xiàn)。無序誘導(dǎo)的D-band的產(chǎn)生-一雙共振拉曼散射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-伴隨著層數(shù)的增加強(qiáng)度提高2D-Band層數(shù)依賴性1 e excitation2 e-phonon scattering3. Phonon with opposite momentum(nn)-&-v?ue4u-激發(fā)光能量依賴性4. E-hole recombination石墨的拉曼光譜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(計(jì)(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)不同點(diǎn)不同偏振方向的拉曼光譜(a) 完美石墨晶體有缺陷的石墨()30Y2 2()x中10向高能方向移動(dòng)。激發(fā)光波長(zhǎng)在近紅外到近紫外是 線性的，斜率4050cnfi/ev2D的大概是D的兩倍(a) D模的相對(duì)強(qiáng)度與石墨微晶尺寸La的 相互關(guān)系。(b)石墨一階和二階拉曼模的激發(fā)光能依賴性。().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呂 gI al. (1090), Pocsik et al. (1998) nn<l Klnttliews et al. (1999).小結(jié)對(duì)完美石墨，1580cmT的E2g光學(xué)膜的拉曼峰強(qiáng)不依賴于拉曼實(shí)驗(yàn)中激發(fā)光偏振 方向?！毙Q鱷叡竄倉線在垂直和平行偏振配置下的強(qiáng)度不同，說明石墨微晶的尺 ：G*的頻率比G的兩倍大，可能是縱向光學(xué)聲子支的過度彎曲導(dǎo)致。：一般來說，非拉曼活性振動(dòng)倍頻模的二階拉曼散射在石墨中是允許的。：聲子頻率的激發(fā)光能量依賴性及其他效應(yīng)都起源于與石墨和其他sp2鍵碳材料特 殊的電子能帶結(jié)構(gòu)相關(guān)的雙共振拉曼散射效應(yīng)。Graphene的結(jié)構(gòu)及其拉曼光譜:A

10、RMCHAIR; ZIGZAG |II II石墨烯的手性石墨烯是一種其禁帶寬度幾乎為零的半金屬/半導(dǎo)體材料在2006 - 2008年間，石墨烯已被制成彈道輸運(yùn)晶體管(ballistic transistor), 平面場(chǎng)效應(yīng)管(Field-Effect Transistors),并且吸引了大批科學(xué)家的興趣week ending3 NOVEMBER 2<M>6石墨烯的拉曼光譜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 心無缺陷存在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峰的產(chǎn)生及峰位的不同(e) 2layer 2D峰由四個(gè)組成(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單層及雙層graphene2D峰的雙共振過程聲子支的分裂1-5cm1所以歸因?yàn)殡娮幽芗?jí)的分裂電子能帶的分裂， 使bilayer分裂為四個(gè)帶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當(dāng)兩相鄰邊緣的夾角是30。, 90°時(shí)， 兩邊緣有不同的手性，一個(gè)是armchair, 一個(gè)是 zigzag o當(dāng)夾角是60。時(shí)，有相同的手性。無序誘導(dǎo)的D峰的拉曼強(qiáng)度與邊緣 手性有關(guān)：玉armchair edge的邊緣D峰強(qiáng)度較強(qiáng)， 在zigzag邊緣較弱。小結(jié): Graphene般出現(xiàn)三個(gè)峰D，G,2D； D和2D峰具有激發(fā)光能量依賴性，SLG的2D峰是尖銳的單峰，BLG的2D峰有四個(gè)組成，其他的都是兩個(gè)組 成，可用來區(qū)分石墨烯單層與多層。 2D峰起源于動(dòng)量相反的兩個(gè)聲子

21、參與的雙共振拉曼過程。在所有sp2 碳材料中均有發(fā)現(xiàn)。石墨烯根據(jù)邊緣的不同，具有不同的手性，用拉曼光譜，根據(jù)Dband 的拉曼強(qiáng)度可以識(shí)別graphene edge的手性。對(duì)數(shù)百M(fèi)CG的研究表明，MCG邊緣夾角是30 °的倍數(shù)。兩相鄰邊緣的夾角是30° , 90°和150。時(shí)，兩邊緣有不同的手性，一 個(gè)是armchair,個(gè)是zigzago當(dāng)夾角是60°和120。時(shí)，有相同的手性。一維碳材料一碳納米管碳納米管(Carbon nanotube)是1991年才被發(fā)現(xiàn)的一種碳結(jié)構(gòu)。ire11理想納米碳管是由碳原子形成的石墨烯片層卷成的無縫、中空的管體SWNT的

22、直徑一般為1 一6nm,最小直徑大約為0.5 nm,直徑大于6nm 以后特別不穩(wěn)定，會(huì)發(fā)生SWNT管的塌陷，長(zhǎng)度則可達(dá)幾百納米到幾個(gè)微米MWNT的層間距約為034納米，直徑在幾個(gè)納米到幾十納米，長(zhǎng)度一般在微 米量級(jí)，最長(zhǎng)者可達(dá)數(shù)毫米碳納米管中的碳原子以sp2雜化，但是由于存在一定曲率 所以其中也有一小部分碳屬sp3雜化Hundreds of species depend on how it is folded.奇妙的碳納米管“太空電梯”的繩 索li4A】細(xì)的碳納米管（0.4 nm）2000年，香港科技大學(xué)的湯子康博士即宣布具有極好的可彎折性密度小，硬度強(qiáng)，鋼的100倍發(fā)現(xiàn)了世界上最細(xì)的純碳納米

23、碳管0.4nm, 這一結(jié)果已達(dá)到碳納米管的理論極限值。(b)317241037875xarmchair"(1Q4：92437億53i億4 丫電4<112156IQzigzag204X80(a)(b)(C):metal:semiconductorarmchairchiral二維石墨片的卷曲，沿不同點(diǎn)陣方向卷曲可形成不同類型的碳納米管碳納米管的性質(zhì)鱉的蠶鍔鬆牒手性'直徑越小'電子的T美國C.T.White教授計(jì)算得出n-m=3q （q為整數(shù)），碳管為金屬性。其 他情況表現(xiàn)半導(dǎo)體性，并且禁帶寬度正比于碳管直徑的倒數(shù)。讐納米管為金屬性，鋸齒形、手性碳管部分為金屬，部分為

24、半導(dǎo)體呈現(xiàn)金屬性質(zhì)。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從 w, I828585 Japan6Department of Chemistry. Harvard University. Ccunbridge, Massachusetts 02138r/JnmCVD方法制備的單臂碳納米管0.5 pmo123SW

27、NTs的平均直徑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普通的單個(gè)SWNTs的拉曼光譜有三個(gè)峰，RBMs D GRBM的頻率=A/dt實(shí)驗(yàn)測(cè)壓A=248cnrinm, Si/SiO2± 生長(zhǎng)的離散SWNTs比較準(zhǔn)確。D峰的頻率依賴于激發(fā)光能量和直

28、徑。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.碳納米管的拉曼光譜G-band1450155()1650frequency (cnT1)Ausuoa二 UHUCHGraphite:<| G峰單一，尖銳Nanotubes:兩個(gè)峰G+和G-起漏于 graphit

30、e E2gMetallic 工 semiconducting、對(duì)應(yīng)q=r=0, mode E2gG峰的振動(dòng)模式及其性質(zhì)160015801560154015201500.'1'1"I'1tiiiv+/*、 d Qc. °>Gjf L J . 1 旳匚*J f1 j=:bn. : I!°、- : : 、 ； 、 : : :、I:龍、 :*、； %、: :：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無序誘導(dǎo)的D-band在Si/SiO2襯底上CVD法生長(zhǎng)的離散單臂碳納米管的大量拉曼光譜中，有 一般有強(qiáng)度很弱的D-band信號(hào)與

32、缺陷石墨D-band相比：較小的線寬740,反應(yīng)電子和聲子的量子限 制效應(yīng)。存在非對(duì)稱展寬。D譜帶頻率與直徑有關(guān)，滿足wD=wD°+C/dtnr1 = 1C對(duì)于雙共振相關(guān)的過程是正的，強(qiáng)化了D普帶頻率。在彈性常數(shù)效應(yīng)情況 下，wD。就是二維石墨中觀察到的頻率數(shù)值。在實(shí)驗(yàn)中還發(fā)現(xiàn)扶手椅型與鋸齒形的單臂碳納米管的D普帶有24cnri 的頻率差。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濟(jì)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峰半高寬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-激發(fā)光能量降低最強(qiáng) RBM的頻率提高。 原因：管管相互作用， 內(nèi)外管相互作用WRBM=224/d+1 一般外管d>1.5nm W>160cm-1的峰只要 來源于內(nèi)管直徑(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的頻率隨激發(fā)光 能量的降低而減小相同激發(fā)光能量下，DWNTs的D 峰頻率最低。內(nèi)外層作用力的影響。Fig. 4. The dependence of lhe frequency of Dband of the CNTs on the £昨線性關(guān)系斜率 265cm-1/evCNTs:WD=W0+26.5ElaserMWNTs W0=1285DWNTs1260SWNTs1270結(jié)論由于內(nèi)外層相互作用，SWNTs與DWNTs的拉曼光譜不同。直徑越小，彎曲度越大，兀電子云形狀變化越大，相反，直徑越大，彎曲度越小，兀電子云接近石墨的情形，性質(zhì)接近 石墨。二維碳材一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,