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

yando@ccmfs.meijo-u.ac.jp 1

○ Moscow ○ Krasnoyarsk

○ Beijing○ Nagoya

2

◎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

4

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

7

Chirarity of Carbon Nanotubes

Chiral map

SWNT modelChirarity of tube

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 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

12

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

35

SWNTs Web Like Lace Curtain

1 cm

36

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

40

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

42

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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