Krasnoyarsk: 24 th August, 2009 Carbon Nanotube: The Inside Story Review written for Journal of Nanoscience and Nanotechnology Yoshinori ANDO Dean of Faculty of Science and Technology, Meijo University Department of Materials Science and Engineering, Meijo University Shiogamaguchi 1-501,Tempaku-ku, Nagoya 468-8502, Japan yando@ccmfs.meijo-u.ac.jp 1
Moscow Krasnoyarsk Beijing Nagoya 2
名城 Meijo: Nagoya Castle Tokyo Nagoya Meijo University 3
4 What s Carbon? Carbon Element C [Atomic number 6,mass number12, 13] One of high existent in the earth Crystal made of Carbon Amorphous Carbon Diamond Graphite Carbon Nanotube Fullerene Charcoal 3D crystal 2D crystal 1D crystal 0D crystal Amorphous 2 nm
Carbon Nanotubes (CNTs): Tubes made by Carbon Diameter is the order of nm Carbon Nanotubes HRTEM micrograph of CNTs Co-axial tubes are projected Side wall is projected as parallel lines 5
The Original Paper of Carbon Nanotubes Sumio Iijima: Helical microtubles of graphitic carbon, Nature, 354 (1991), 56. Meijo Univ. is the birth place of carbon nanotubes! 6
History of Carbon Nanotubes T. W. Ebbesen Physics Today 49(1996), 26. Review of Cabon Nanotubes Sumio Iijima of NEC had been using transmission electron microscopy to analyze a sample of carbon soot received from Yoshinori Ando of Meijo University. Iijima observed that the sample contained tubules. 7
Chirarity of Carbon Nanotubes Chiral map Chirarity of tube SWNT model 8
Tip of tube and bamboo basket model Six pentagons close hemi-sphere Heptagon at corner B S. Iijima, T. Ichihashi & Y.Ando: Nature, 356 (1992), 776. 9
Fullerenes 1970 Prediction of C 60 Osawa Carbon Nanotubes 1985 Discover of C 60 Kroto, Smalley 1990 Mass production of fullerenes Krätschmer et al. 1991 Discover of MWNTs Iijima 1993 Discover of SWNTs Iijima & Ichihashi Bethune et al. 1996 Nobel prize in Chemistry Kroto, Curl, Smalley 1997 Mass producction of SWNTs by arc method Journet et al. 1999 Discover of carbon nanohorn Iijima et al. 2000 Thinnnest 4A MWNTs Qin et al. 2003 Macroscopic net of SWNTs Zhao et al. 2004 Super growth of SWNTs Hata et al. 2005 DIPS growth of SWNTs Saito et al. Green terms are related with Y. Ando 10
Production of CNTs in Ando Lab Arc Discharge 1991~present (COE 02 ~ 07) Thermal CVD 2000~present (COE 02 ~ 07) MWNTs: First specimen of CNTs discovery 1991 Yield of CNTs CH 4 >> He > Ar 1994 Predominance of H 2 ambient gas 1997 4A innermost tube in H 2 arc MWNT 2000 Characteristic Raman spectra 2002 Carbon chain in H 2 arc MWNT 2003 3A innermost tube in H 2 arc MWNT 2004 SWNTs: ac arc to produce SWNTs 1999 Mass production of SWNTs, APJ 2000 Macroscopic web (~30cm) of SWNTs 2003 Precursor: camphor 1. Catalyst: ferrocene (floating catalyst) Substrate: quartz plate 2001 High yield of vertically aligned MWNTs 40mg per run (20 min reaction) 2002 Patterned growth of aligned MWNTs on Co/Si & Ni/Si substrates 2003 2. Catalyst: Fe-Co (supported catalyst) Support: zeolite powder 2003 High yield of MWNTs with narrow diameter distribution at 650 2004 11
12 Production of Multi-walled Carbon Nanotubes (MWNTs) by Arc Discharge
Production of CNTs by DC Arc Discharge AC resistive heating apparatus producing fullerenes W. Krätschmer et al., Nature, 347 (1990), 354. The original apparatus for producing CNTs Y. Ando & S. Iijima: Jpn. J. Appl. Phys., 32(1993), L107. DC arc apparatus producing ultrafine particles of SiC Y. Ando & M. Ohkohchi, J. Cryst. Growth, 60(1982), 147. 13
Cathode deposit obtained by DC arc Optical photo of a section of cathode deposit Y. Ando & S. Iijima: Jpn. J. Appl. Phys., 32(1993), L107. SEM micrograph of cathode 14 deposit: CNTs and nanoparticles
Model of Multiwalled Carbon Nanotubes (MWNTs) Double wall carbon nanotube (DWNT) by S. Iijima Four walls carbon nanotube an example of MWNTs 15
Production of MWNTs in various kinds of gas He: 100Torr Ar: 100Torr CH 4 : 100Torr Among these three gasses, CH 4 gas (including H-atom) is the best. This is the essential difference between CNT and fullerene synthesis. Fullerene can t be formed in gas including H-atom. Y. Ando: Fuller. Sci. & Tech., 2 (1994), 173. 16
Predominance of ambient gas including H-atom Mass spectroscopy of CH 4 gas after arc discharge Thermal decomposition of CH 4 ambient gas H 2 2 CH 4 C 2 H 2 + 3 Gas pressure ratio after and before evaporation: Eva. in He gas ---1.05 times Eva. in CH 4 gas --- 2.0 times Similar results were obtained in C 2 H 2 and CH 4 ambient gases What is the result of pure H 2 gas as ambience? M. Wang et al.: Fuller. Sci. & Tech., 4 (1996), 1027. 17
Arc evaporation of pure graphite in pure H 2 ambience Optical photo of the top of cathode MWNTs Carbon Roses Y.Ando, X.Zhao & M.Ohkohchi, Carbon, 35 (1997), 153. X. Zhao et al.: Carbon, 35 (1997), 775. 18
Purification of H 2 -arc MWNTs by Infrared Radiation (a) As grown (b) Purified Y. Ando, X. Zhao & M. Ohkohchi, Jpn. J. Appl. Phys., 37 (1998), L61. Purification by infrared radiation 19
HR-SEM before and after purification Before purification After purification Arrows: nanoparticles 20
SEM micrograph of MWNTs purified by infra-red radiation Low magnification SEM of purified MWNTs sponge SEM micrograph of a section Y. Ando, X. Zhao & M. Ohkohchi, Jpn. J. Appl. Phys., 37 (1998), L61. 21
HR-TEM micrograph of H 2 -arc MWNT Regular spacing of 3.4 A Oxidation starts from tip of MWNT Thin innermost tube, 11A 22
The smallest carbon nanotube (0.4 nm diameter) L.-C.Qin, X. Zhao, K. Hirahara, Y. Miyamoto, Y. Ando & S. Iijima: Nature, 408 (2000), 50. 23
3A diameter innermost tube X. Zhao, Y. Ando et al., Phys. Rev. Lett., 92 (2004), 125502. 24
1D Quantum Confinement Effect Observed in Raman Spectra (a) Low frequency region MWNTs :Multi-walled carbon nanotubes (b) High frequency region HOPG: Highly oriented pyrolytic graphite SWNTs:Singlewall carbon nanotubes prepared by APJ method X. Zhao, Y. Ando, L-C. Qin, H. Kataura, Y. Maniwa, R. Saito: Physica B 323 (2002), 265. Chem. Phys. Lett. 361(2002), 169. Appl. Phys. Lett. 81 (2002), 2550. 25
New Raman peak for H 2 -arc and D 2 -arc MWNTs Intensity (arb. unit) 514.5 nm new Raman peak G-band D-band Raman Shift (cm -1 ) M. Jinno, S. Bandow, Y. Ando; Chem. Phys. Lett., 398 (2004), 256. 26
Carbon Nanowire : Carbon Chain in MWNT X. Zhao, Y. Ando, Y. Liu, M. Jinno, T. Suzuki: Phys. Rev. Lett. 90 (2003), 187401. 27
Innermost tube CNW and 3A tube exist in the same MWNT (a) MWNT CNW C-chain (b) (c) 28
29 Electric Resistance of Single MWNT Using micromanipulator
Production of Single Wall Carbon Nanotube by Arc Discharge Method In our Laboratory 30
Production of SWNTs by arc discharge method Arc discharge of graphite rod including metal catalysts Arc Plasma Jet (APJ) method 4%Ni-1%Y catalyst, He 500Torr ambient gas Inclined electrodes, 30 ; Yield: 1g / min conventional DC-arc discharge method (FH-arc method) single Fe catalyst, H 2 -Ar 200Torr mixed gas macroscopic SWNTs web longer than 30cm AC-arc discharge method (Ohkohchi) two electrodes including different metal catalysts 31
SWNTs Produced by Arc Plasma Jet (APJ) Method Production rates of SWNT soot (a) APJ (b) Normal arc Apparatus of APJ method Y. Ando et al.:chem.phys. Lett., 323 (2000), 580. SEM & TEM images of SWNTs prepared by APJ method 32
Raman and TG measurement of APJ-SWNT 33 RBM D-band G-band Excitation wavelength 532nm 2D-band
FH-arc Method Usual DC Arc Evaporation: Atmospheric Gas; H 2 -Ar mixture gas H 2 -Ar mixture gas [Total Pressure 200 Torr] Anode; 1.0 at% Fe-Graphite rod Evaporation time; 5 min Huge web of SWNTs
Macroscopic SWNT web produced by FH-arc Photo of macroscopic SWNT web ~30cm 35 SWNTs bottled in one liter bottle Mass is only 1g
SWNTs Web Like Lace Curtain 1 cm 36
Optical Photograph of Huge SWNT Web Mass of this huge SWNT web is ~20 mg 37
Electron micrographs of macroscopic SWNTs web As grown: (a) SEM, (b) HR-TEM Purified: (c) SEM, (d) TEM X. Zhao, S. Inoue, M. Jinno, T. Suzuki, Y. Ando: Chem. Phys. Lett. 373 (2003), 266. 38
Purification of SWNTs Heat Treatment Heat Treatment HCl Treatment Ultrasonic Cleaning Centrifuge Drying HCl Treatment Characterization 39
40
Raman Spectra of SWNTs Made in H 2 -inert Gas 50%H 2 + 50%N 2 50%H 2 + 50%Ne 50%H 2 + 50%Kr 50%H 2 + 50%Xe 41
0 200 400 600 800 1000 Temperature / / 42 Thermal Analysis 120 100 as-grown paper TG (%) 80 60 40 20 0 Purified paper Purified web
The first stage of double walled carbon nanotubes (DWNT) production Arc evaporation of (Fe, Ni, Co)-including carbon rod added in H 2 S gas Y. Ando, et al., Nanonetwork Materials, edited by S. Saito et al., 2001 AIP, CP590, pp. 7-10 (2001). 43
Growth conditions and structure properties of CNTs produced by arc discharge method in Ando laboratory Kind of CNT Method Catalyst Ambient gas SWCNT DWCNT MWCNT Produced position APJ Ni4%+Y1% He: 500torr wholechamber FH- arc Fe1% H 2 +Ar: 200torr wholechamber normal DC arc Fe0.25%+Ni0.9% +Co0.9% normal DC arc none H 2 +H 2 S1%: 500torr wholechamber H 2 : 30-100torr cathode deposit Y or Sc or La He: 500torr cathode deposit Item mass production of SWCNTs macroscopic web of SWCNTs thick SWCNTs and DWCNTs thin inner tube & carbon nanowire mass production of MWCNTs Number of layers Diameter of tube (nm) Length of tube (μ m) 1 1.2-1.5 ~2-10 1 0.8-1.5 ~2-10 2 1.4-4 ~2-10 3-30 10-30 > 10 10-40 20-40 > 10 44