Krasnoyarsk: 24th 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
○ Moscow ○ Krasnoyarsk
○ Beijing○ Nagoya
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◎Tokyo○Nagoya
名城Meijo:
Nagoya Castle
Meijo University 3
What’s Carbon? Carbon Element C [Atomic number 6,mass number12,13]
One of high existent in the earthCrystal made of Carbon Amorphous CarbonDiamond Graphite Carbon Nanotube Fullerene Charcoal3D crystal 2D crystal 1D crystal 0D crystal Amorphous
2 nm
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Carbon NanotubesCarbon Nanotubes (CNTs):
Tubes made by CarbonDiameter is the order of nm
Co-axial tubes are projected Side wall is projected as parallel linesHRTEM micrograph of
CNTsS. Iijima: Nature, 354 (1991), 56. 5
The Original Paper of Carbon NanotubesSumio Iijima: “Helical microtubles of graphitic carbon”, Nature, 354 (1991), 56.
Meijo Univ. is the birth place of carbon nanotubes!6
T. W. EbbesenPhysics Today 49(1996), 26. Review of Cabon Nanotubes
“Sumio Iijima of NEC had been using transmission electron microscopy to analyze a sample of carbonsoot received fromYoshinori Ando of MeijoUniversity.
Iijima observed that the sample contained tubules.”
History of Carbon of Carbon NanotubesNanotubes
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Chirarity of Carbon Nanotubes
Chiral map
SWNT modelChirarity of tube
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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.
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Fullerenes Carbon Nanotubes1970 Prediction of C60 Osawa
1985 Discover of C60 Kroto, Smalley
1990 Mass production of fullerenes
Krätschmer et al.
1996 Nobel prize in Chemistry
Kroto, Curl, Smalley
1991 Discover of MWNTs Iijima
1993 Discover of SWNTs Iijima & Ichihashi
Bethune et al.
1997 Mass producction of SWNTs by arc method Journet et
al.
1999 Discover of carbon nanohorn Iijima et al.
2000 Thinnnest 4Å 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 Thermal CVD1991~present(COE ’02 ~’07)
2000~present
(COE ’02 ~’07)
MWNTs: First specimen of CNTs discovery 1991
Yield of CNTs CH4 >> He > Ar 1994
Predominance of H2 ambient gas 1997
4Åinnermost tube in H2–arc MWNT 2000
Characteristic Raman spectra 2002
Carbon chain in H2–arc MWNT 2003
3Åinnermost tube in H2–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 MWNTson 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℃ 200411
Production ofMulti-walled CarbonNanotubes (MWNTs)
by Arc Discharge
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Production of CNTs by DC Arc Discharge
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.
AC resistive heating apparatus producing fullerenes
W. Krätschmer et al., Nature, 347 (1990), 354.
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Cathode deposit obtained by DC arc
Optical photo of a section of cathode depositY. Ando & S. Iijima: Jpn. J. Appl. Phys., 32(1993), L107. SEM micrograph of cathode
deposit: CNTs and nanoparticles14
Model of Multiwalled Carbon Nanotubes (MWNTs)
Double wall carbon nanotube
(DWNT) by S. IijimaFour walls carbon nanotube
an example of MWNTs15
Production of MWNTs in various kinds of gas
He: 100Torr Ar: 100Torr CH4: 100TorrAmong these three gasses, CH4 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-atomMass spectroscopy of CH4 gas after arc discharge
Thermal decomposition of CH4 ambient gas
2 CH4 C2H2 + 3H2Gas pressure ratio after and before evaporation:
Eva. in He gas ---1.05 times
Eva. in CH4 gas --- 2.0 timesSimilar results were obtained in C2H2 and CH4 ambient gases
What is the result of pure H2 gas as ambience?M. Wang et al.: Fuller. Sci. & Tech., 4 (1996), 1027. 17
Arc evaporation of pure graphite in pure H2 ambience
MWNTs
Carbon Roses
Optical photo of the top of cathode
Y.Ando, X.Zhao & M.Ohkohchi, Carbon, 35 (1997), 153. X. Zhao et al.: Carbon, 35 (1997), 775. 18
Purification of H2-arc MWNTs by Infrared Radiation
(a) As grown (b) Purified
Purification by infrared radiation
Y. Ando, X. Zhao & M. Ohkohchi,Jpn. J. Appl. Phys., 37 (1998), L61.
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HR-SEM before and after purification
Before purification After purificationArrows: nanoparticles 20
SEM micrograph of MWNTs purified by infra-red radiation
Low magnification SEM of purified MWNTs sponge
Y. Ando, X. Zhao & M. Ohkohchi,Jpn. J. Appl. Phys., 37 (1998), L61.SEM micrograph of a section
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HR-TEM micrograph of H2-arc MWNT
Regular spacing of 3.4 Å
Thin innermost tube, 11ÅOxidation starts from tip of MWNT
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The smallest carbon nanotube (0.4 nm diameter)(0.4 nm diameter)
L.-C.Qin, X. Zhao, K. Hirahara, Y. Miyamoto, Y. Ando & S. Iijima: Nature, 408 (2000), 50.
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3Å 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 (b) High frequency regionMWNTs :Multi-walled carbon nanotubes HOPG: Highly oriented pyrolytic graphiteSWNTs: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 H2-arc and D2-arc MWNTs
D-band
G-band
new Raman peak
Inte
nsity
(arb
. uni
t)
514.5 nm
Raman Shift (cm-1)M. Jinno, S. Bandow, Y. Ando; Chem. Phys. Lett., 398 (2004), 256.
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Carbon Carbon NanowireNanowire : Carbon Chain in MWNT: Carbon Chain in MWNT
X. Zhao, Y. Ando, Y. Liu, M. Jinno, T. Suzuki: Phys. Rev. Lett. 90 (2003), 187401.
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CNW and 3Åtube exist in the same MWNT
CNWMWNT
Inne
rmos
t tub
e
C-c
hain
(a)
(c)(b)
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Electric Resistance of Single MWNT
Using micro-manipulator
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Production ofSingle Wall Carbon Nanotube
by Arc Discharge Method In our Laboratory
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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, H2-Ar 200Torr mixed gas
macroscopic SWNTs web longer than 30cm
◎ AC-arc discharge method (Ohkohchi)
two electrodes including different metal catalysts31
SWNTs Produced by Arc Plasma Jet (APJ) Method
Production rates of SWNT soot (a) APJ (b) Normal arc
Apparatus of APJ methodY. 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
Excitation wavelength532nm
RBMG-band
D-band2D-band
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FHFH--arcarc MethodMethod
Usual DC Arc Evaporation:
Atmospheric Gas;
H2-Ar mixture gas
[Total Pressure 200 Torr]
Anode; 1.0 at% Fe-Graphite rod
Evaporation time; 5 min
Huge web of Huge web of SWNTsSWNTs
H2-Ar mixture gas
Macroscopic SWNT web produced by Macroscopic SWNT web produced by FHFH--arcarc
Photo of macroscopic SWNT web ~30cm
SWNTsbottled in one liter bottle
Mass is only 1g
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SWNTs Web Like Lace Curtain
1 cm
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Optical Photograph of Huge Optical Photograph of Huge SWNT WebWeb
Mass of this huge SWNT web is ~20 mg 37
Electron micrographs of macroscopic SWNTs web
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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.
Heat Treatment
HCl Treatment
Ultrasonic Cleaning
Centrifuge
Drying
Characterization
Purification of SWNTs
Heat Treatment
HCl Treatment39
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Raman Spectra of Raman Spectra of SWNTsSWNTs Made in HMade in H22--inert Gasinert Gas
50%H2 + 50%Ne50%H2 + 50%N2
50%H2 + 50%Kr 50%H2 + 50%Xe 41
Thermal Analysis
Temperature /Temperature /℃℃0 200 400 600 800 1000
TGTG((
%%))
120
100
80
60
40
20
0
as-grownpaper
Purified paperPurified web
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The first stage of double walled carbon nanotubes (DWNT) production
Arc evaporation of (Fe, Ni, Co)-including carbon rod added in H2S gas
Y. Ando, et al., Nanonetwork Materials, edited by S. Saito et al.,2001 AIP, CP590, pp. 7-10 (2001).
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Growth conditions and structure propertiesof CNTs produced by arc discharge method
in Ando laboratory
Kind of CNT Method Catalyst Ambient gas Producedposition ItemNumberof layers
Diameterof tube
(nm)
Length oftube(μ m)
APJ Ni4%+Y1% He: 500torr wholechamber mass productionof SWCNTs 1 1.2- 1.5 ~2- 10
FH- arc Fe1% H2+Ar: 200torr wholechamber macroscopic webof SWCNTs 1 0.8- 1.5 ~2- 10
DWCNT normal DC arc Fe0.25%+Ni0.9%+Co0.9%H2+H2S1%:
500torr wholechamberthick SWCNTsand DWCNTs 2 1.4- 4 ~2- 10
none H2: 30- 100torr cathode deposit thin inner tube &carbon nanowire 3- 30 10- 30 > 10
Y or Sc or La He: 500torr cathode deposit mass productionof MWCNTs 10- 40 20- 40 > 10
SWCNT
MWCNT normal DC arc
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