1

単層カーボンナノチューブSingle-Walled Carbon Nanotubes

電子顕微鏡観察と分光Electron Microscopy & Spectroscopy

単層カーボンナノチューブSingle-Walled Carbon Nanotubes

電子顕微鏡観察と分光Electron Microscopy & Spectroscopy

Molecular Thermo-Fluid Engineering 2010

Electron Microscopy & Spectroscopy Electron Microscopy & Spectroscopy

2 1 0.9 0.8 0.7

units

)

Diameter (nm)

5 nm

http://www.photon.t.u-tokyo.ac.jp0 500 1000 1500

100 200 300 400

Raman Shift (cm–1)

Inte

nsity

(ar

b.

Raman Shift (cm–1) 丸山 茂夫Shigeo Maruyama東京大学大学院工学系研究科

機械工学専攻

Energy (J)

HeNe633nm

Ar488nm

ArF193nm

G1590cm–1

RBM200cm–1

YAG1064nm

Ar1.67x10

–21JSEM

1keV

Microw ave2.45GHz

Docomo800MHz

H2–H23.18meV

C–C2.4meV

BS12GHz

C1s284.5eV

Al–K1468.6eV

TEM120keV

NHK Radio594KHz

TV 1–12ch93–219MHz

UHF 13ch473MHz

Toky oFM80MHz

–15 –18 –21 –24

Length, Wavelength and Energy Scale

Raman

Frequency (Hz)THz GHz

Energy (eV)eV meVkeV

gy ( )

Temperature (K)

sun6000K

300K

SWNTabsorb.

(7,5)

103 100 10–3

106 103 100

1015

1018

1021

1024

Planck

Absorb.PLE

XPS

Length (m)nm m mm mÅ

Wavenumber (cm–1

)

Frequency (Hz)

10–9 10–6 10–3 100

106 103 100

1018

1015

1012

109

2

Energy (J)

HeNe633nm

Ar488nm

ArF193nm

G1590cm–1

RBM200cm–1

YAG1064nm

–18 –19 –20

Length, Wavelength and Energy Scale 2

Raman

Frequency (Hz)

Energy (eV)eV

gy ( )

Temperature (K)

sun6000K

300K

(7,5)

101 100 10–1

105 104 103

1018

1019

1020

Planck

Absorb.PLE

Length (m)m

Wavenumber (cm–1

)

q y ( )

10–7 10–6 10–5 10–4

105 104 103 102

1015

1014

1013

Energy (J)

HeNe633nm

Ar488nm

ArF193nm

G1590cm–1

YAG1064nm

10–18

10–19

Length, Wavelength and Energy Scale 3

Raman

Frequency (Hz)

Energy (eV)eV

Temperature (K)

sun6000K 300K

(7,5)

101 100

105 104

1018

1019

Planck

Absorb.

PLE

Length (m)m

Wavenumber (cm–1

)

q y ( )

10–7 10–6 10–5

105 104 103

1015

1014

3

Characterization of Carbon Nanotubes

Electron MicroscopyTransmission Electron Microscopy (TEM)Scanning Electron Microscopy (SEM)Scanning Electron Microscopy (SEM)Scanning Transmission Electron Microscopy (STEM)

Scanning Probe MicroscopyAtomic Force Microscopy (AFM)Scanning Tunneling Microscopy (STM)

Optical SpectroscopyyResonant Raman ScatteringAbsorption Spectroscopy (UV-Vis-NIR)Fluorescence Spectroscopy

X-rayX-ray diffractionX-ray photoelectron spectroscopy (XPS, ESCA)

Transmission Electron Spectroscopy

透過型電子顕微鏡(TEM)高分解能像(Phase contrast)電子線回折(Electron diffraction)電子線分光(EELS Electron energy loss spectroscopy)電子線分光(EELS, Electron energy loss spectroscopy)

末永和知，カーボンナノチューブの基礎と応用，培風館

4

Transmission Electron Spectroscopy

Phase Contrast

末永和知，カーボンナノチューブの基礎と応用，培風館

Diffraction

EELS

TEM Images of Carbon Nanotubes

S.Iijima, Nature, 354, pp.56-58 (1991).

5

TEM Pictures of SWNT Ropes

5 nm

By ACCVD

Individual tube diameter: 1.3 nmSpacing: 0.34 nmMisalignments and Terminations

TEM from Smalley et al. at Rice University

About 100 SWNTs

HRTEM images of DWNTs & TWNTsHRTEM images of DWNTs & TWNTsHRTEM images of DWNTs & TWNTsHRTEM images of DWNTs & TWNTs

バンドルのDWNTs（直径分布は1～2nm）

2nm Bundles of DWNTs

2nm

N. Shinohara’s Powerpoint

6

Peapods

Suenaga et al., PRL 2003

Peapod with Sc2@C84Shinohara, 培風館

Scanning Electron Spectroscopy

Hitachi S4800, 日立ハイテクＨＰより

http://www.remus.dti.ne.jp/~kkkkwing/

7

Images of As-Grown SampleImages of As-Grown Sample

Vertically Aligned SWNTs on Quartz Substrate

Y. Murakami, S. Chiashi, Y. Miyauchi, M. Hu, M. Ogura, T. Okubo, S. Maruyama, Chem. Phys. Lett. 385 (2004) 298

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STEM Image of Vertically Aligned SWNTs

Amorphous Carbon Support

Substrate 150 nm Slice by FIB

Scanning Probe Microscopy

中山喜萬，カーボンナノチューブの基礎と応用，培風館

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SWNTs Directly Generation on the AFM Stage

isolated SWNT(not bundle)

length : 100150 nmdiameter : 1.32.2 nmdensity : 10 m-2

0 100 200 3000

1

2

3

Position (nm)

He

igh

t (n

m)

AFM image of SWNTs directly grown on silicon.

STM Image of Individual Atoms

http://vortex.tn.tudelft.nl/~dekker/nanotubes.html

10

Absorption Spectra

(a) On quartzAs Grown

2

gy [e

V] c1

c2

2

]

EE

c1

c2

bso

rba

nce

(a

rb. u

nit)

(c) HiPco Isolated

(b) On zeolite Isolated

As–Grown

0–2

0

Ene

rg

v1

v2

0–2

0

DOS

E22E11

v1

v2

2

3

para

tion

(e

V)

500 1000 1500

Ab

Wavelength (nm)

(d) HiPco Bundle

0.5 1 1.5 20

1

Nanotube Diameter (nm)

En

erg

y S

e

Resonance Raman Spectra of SWNTsA.M. Rao et al, Science 275 (1997) 187

• RBM (Radial breathing Mode)– 100-400cm-1 dt

-1

• G Band (Graphite)

Diameter Selective

• G-Band, (Graphite)– 1550-1600cm-1, Splitting dt

-2

• BWF (Breit-Wigner-Fano) peaks dt-1

– 1520-1540cm-1, Metallic SWNT• D-band, (Disorder) depends on dt

– 1250-1350cm-1, depends on Elaser

BWF

Electronic density of states 500 1500 [cm-1]1000

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ラマン分光装置

AFM/STM

Micro and Macro Raman

2 1 0.9 0.8 0.7Diameter (nm)

Raman Scattering(Excitation 488nm)

248

G band(Tangential

Mode)

100 200 300 400

ens

ity (

arb.

uni

ts)

Raman Shift (cm–1)

)(

248)(

1cm

nmd

RadialB thi

0 500 1000 1500

Raman Shift (cm–1)

Inte

laser

CCVD 800

D band

BreathingMode(RBM)

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Kataura Plot

(5,5)

)

tcctM dadE /6)( 011 tcct

S dadE /2)( 011

2

3

ara

tion

(eV

)

2.54±0.1eV

EM

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ES22ES

11(10,10)

(10,0)

of S

tate

s (s

tate

s/1

C–

ato

m/e

V)

E11

E22

0 1 20

1

Nanotube Diameter (nm)

En

erg

y S

ep

a

0=2.9 eV, acc=0.144nm–2 0 2

0

1

(17,0)

Energy (eV)

De

nsi

ty

Raman Spectra

2.4

2.6

2 1 0.9 0.8 0.7Nanotube Diameter (nm)

ara

tion

(e

V)

488 nm

514.5 nm

488

1.8

2

2.2

En

erg

y S

ep

a

633 nm

b.u

nits

) (c) HiPco

(b) On zeolite

(a) On quartz

(d) On quartz

488 nm

nsi

ty (

arb

.un

its)

488 nm

(b) ACCVD on zeolite

(a) ACCVD on quartz

100 200 300 400

Inte

nsi

ty(a

rb

Raman Shift (cm –1)

(f) HiPco

(e) On zeolite

(i) HiPco

(h) On zeolite

(g) On quartz

514.5 nm

633 nm

* ** ** * 0 500 1000 1500

Inte

n

Raman Shift (cm–1)

(c) HiPco

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Kataura Plot

市田正夫，中村新男，カーボンナノチューブの基礎と応用，培風館

Observed RBM

RBM

Resonance Raman spectroscopy

(7,5)

(10 3)

(7,6)3

2

200 300

atio

n (e

V)

Calculated RBM

(10,3)

1

2

nerg

y S

epar

atio

n (e

V)

200 300

1

Raman shift (cm–1)

Ene

rgy

Sep

ara

0.5 1 1.5 20

1

Nanotube Diameter (nm)

En

Tight–BindingLDAempirical TB

)5.12/(5.223 d

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Optical absorption and Raman RBM

2 1 0.9 0.8 0.7Diameter (nm) by d = 248/

Diameter (nm) by d = 223.5/(–12.5)

0.60.70.80.912

s) (a) 850 °C

A

ensi

ty (

arb.

units

) (a) 850 °C

(b) 750 °C

(c) 650 °C

B

Abs

orba

nce

(arb

.uni

ts (a) 850 °C

(b) 750 °C

(c) 650 °C

Absorption of Isolated SWNTs

100 200 300 400

Inte

Raman Shift (cm–1)

(d) HiPco

(c) 650 C

500 1000 1500Wavelength (nm)

(d) HiPco

Raman RBM of ‘as grown’ samples

Band Gap Fluorescence

D2O 1.1g /cm3 SDS or NaDDBS

Strong Sonication 60min

1.0g / cm3

NaDDBS

0

2

Ene

rgy

[eV

]

absorptionfluorescence

v1

c1

c2

0

2

Ene

rgy

[eV

]

absorptionfluorescence

v1

c1

c2

DOS (10,5)

M. J. O’Connell et al., Science 297 (2002) 593

Centrifugation 20,627g x 24h

S. M. Bachilo et al., Science 298 (2002) 2361.InGaAs Detector

0–2Density of Electronic States　（arb. units）

v2

0–2Density of Electronic States　（arb. units）

v2

Centrifugation 180,000g x 1h

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Comparison of ACCVD and HiPco

(12,1) (10,5)

(7,5) (7,6)

(8,6)

(9,4)(10,2)

(8,4)

( , )

(11,3)

(7,5) (7,6)

(8,3)

(8,7)

(9,5)

(10,3)

(11,1)

(8,6)

(a) ACCVD 850℃ (b) HiPco

(8,4)(6,5)

Photoluminescence from Individual Nanotube0°

45°

1.0

rb. u

nits

)

expfit

90°

135°

180°

5m

0 45 90 135 1800

0.5

PL

Inte

nsity

(ar

Excitation Polarization (degrees) Strong polarized emission: ideal 1D electronic structure

IPL |p(θ) •µ|2

µ:dipole momentp:light polarizationθ :angle of light polarization and dipole

Collaboration with K. Matsuda (KAST, Saeki Group) (2004)

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XPS

日東分析センタHPより，http://www.natc.co.jp/index.html

Demonstration of Root Growth and Yield by XPS

Co: 0.05 at%, Mo: 0.03 at%C: 91.23 at%, O: 8.69 at% C/M=114,000

Root Side (10,10) x 5 m=813,005 atoms

C/M = 271000

Co: 0.04 at%, Mo: 0.01 at%C: 98.67 at%, O: 1.29 at%

Co: 0.41 at%, Mo: 0.15 at%C: 19.65 at%, O: 79.8 at%

C/M=197,300Removed & Left

Metal of 1.3 nm= 300 atoms

Acknowledgement to Shimazu for the use of KRATOS (AXIS-NOVA)

Tip Side

Hatas’s SuperGrowth0.013Fe

Supergrowth:50,000 wt%

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X-Ray Diffraction

触媒金属SWNTs

真庭 豊，カーボンナノチューブの基礎と応用，培風館