cvd growth mechanism of single-walled carbon nanotubes...
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CVD Growth Mechanism of Single-Walled Carbon Nanotubes from Alcohol
Shigeo Maruyama, Yuhei Miyauchi, Yoichi Murakami,Shohei Chiashi, Erik Einarsson
Department of Mechanical Engineering The University of Tokyohttp://www.photon.t.u-tokyo.ac.jp
NT06 @ Nagano on June 19, 2006
Alcohol CCVD on Catalysts Supported with Zeolite Alcohol CCVD on Catalysts Supported with Zeolite
2.5/2.5 : Fe/Co (wt%) on USY Zeolite 30mg
AlcoholEthanolMethanol
vacuum
Electric FurnaceSimple, High-PurityLow-Temperature
(550-900°C)
S. Maruyama et al., Chem. Phys. Lett. 360 (2002) 229.
As-Grown
500 1000 1500
Inte
nsity
(arb
.uni
ts)
Raman shift (cm–1)
(a) 600°C
(b) 700°C
(c) 800°C
(d) 900°C
(e) Laser–oven
RBM
G band
D band
BWF
7.4[Å]Shinohara& Nagy
Most Used Carbon Source in NT06 synthesis session A
ACCVD Experimental ApparatusACCVD Experimental Apparatus
Ethanol tank
Hot bath
Pressure gauge
Mai
n dr
ain
tube
Sub
drai
n tu
be
Quartz tube
Electric furnace
Pressure gaug
Vacuum pump
Quartz boat
Ar/H2
Aror Ethanol tank
Hot bath
Ethanol tank
Hot bath
Pressure gauge
Mai
n dr
ain
tube
Sub
drai
n tu
be
Quartz tube
Electric furnace
Pressure gaugPressure gaug
Vacuum pumpVacuum pump
Quartz boat
Ar/H2
Aror
ACCVD is Simple!!ACCVD is Simple!!High School Students Presented
at Fullerene-Nanotubes General Symposium @ Univ. of Tokyo, July 28, 2004Synthesis of Single-walled Carbon Nanotubes
from Alcohol by CCVD Method○Miki Kanao, Kieko Sawaguchi and Masaru Moriyasu
東京工業大学工学部附属工業高等学校
0 500 1000 1500
100 200 300 400
2 1 0.9 0.8 0.7
Raman Shift (cm –1 )
Inte
nsity
(arb
. uni
ts)
Diameter (nm)
Large Scale ACCVD Production by TorayLarge Scale ACCVD Production by Toray
TEM Image
High purity SWNTs from Ethanol on Zeolite
Toray Industries, Inc. [東レ株式会社]Chemicals Research Laboratories [化成品研究所ケミカル研究室]9-1, Oe-cho, Minato-ku, Nagoya 455-8502 JAPAN
URL:http://www.toray.co.jpContact: Yuji Ozeki (Senior Research Chemist)[尾関雄治] TEL +81 (52)-613-5276, FAX +81 (52)-613-5347e-mail: [email protected]
Purified 10 g sample
Toray Lot # S050808-3
(7,6)(7,5)
(8.,4)
(8,6)(9,4)
(6,5)
Toray Lot # S050808-3
(7,6)(7,5)
(8.,4)
(8,6)(9,4)
(6,5)
NarrowChirality
isolator
lenscollimator collimator
SAINT sampleisolator
isolator 980/ 1550coupler
40cmF:EDFA
10 mspot size
μ
980nmpump LD
70%
30% output
coupler
Saturable Absorbers:Application to Mode-Locked Fiber Lasers
Saturable Absorbers:Application to Mode-Locked Fiber Lasers
S. Yamashita, S. Maruyama, Y. Murakami, Y. Inoue, H. Yaguchi, M. Jablonski, S. Y. Set, Optics Letters, 29 (2004) 1581.
Photoluminescence of SWNTs suspended in airPhotoluminescence of SWNTs suspended in air
S. Iwasaki, Y. Ohno, Y. Murakami, S. Kishimoto, S. Maruyama, T. Mizutani (2005)
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
0 500 1000 1500
100 200 300 400
2 1 0.9 0.8 0.7
Raman Shift (cm–1)
Inte
nsity
(arb
. uni
ts)
Diameter (nm)
10 μm
Narrow Chirality GrowthNarrow Chirality Growth
Catalysts and Alcohol Catalytic CVD MethodCatalysts and Alcohol Catalytic CVD Method
O
Molecular Dynamics Simulation for MechanismMolecular Dynamics Simulation for Mechanism500 Carbon & Ni108 : 2500K
1.2
nm
Y. Shibuta & S. Maruyama, Chem. Phys. Lett. 382 (2003) 381.
ACCVD Directly on Flat Surfaces (Dip-Coat)ACCVD Directly on Flat Surfaces (Dip-Coat)
Mo/Co 0.01wt % (each)Ethanol Solution
10 min soak& 4 cm/min
400 °C in Air, 5 min
Heat up to 800 °C in Ar/H2 (3 % H2)
(CH3COO)2Mo (CH3COO)2Co-4H2O
ACCVD
5 nm
Si or Quartz Substrate
1.5 nm MetalParticles
Y. Shibuta et al., CPL 382(2003)381.
bundle.pv
TEM images of Co-Mo catalysts on SiO2/Si after reductionTEM images of Co-Mo catalysts on SiO2/Si after reduction
M. Hu, Y. Murakami, M. Ogura, S. Maruyama, T. Okubo, J. Catalysis, 225 (2004) 230.
CoMoCoMoOx
Plan TEM [Quartz/catalyst/SiO2(10 nm)]
XTEM[Quartz/catalyst/glue
/catalyst/Quartz]
Slicing & PunchingMech. GrindingAr Ion Milling
Combinatorial Method to Prepare CatalystsNi Grows SWNTs
Combinatorial Method to Prepare CatalystsNi Grows SWNTs
S. Noda, Y. Tsuji, Y. Murakami, S. Maruyama, Appl. Phys. Lett., 86 (2005) 173106.
Ni: tNi = 0.22 nm
Co: tCo=0.081 nm
K. Kakehi, S. Noda, S. Chiashi, S. Maruyama (2006)
Best Condition
Combinatorial Method for (Co-Mo) CatalystsCombinatorial Method for (Co-Mo) Catalysts
S. Noda, H. Sugime, T. Osawa, Y. Tsuji, S. Chiashi, Y. Murakami, and S. Maruyama, Carbon 44 (2006) 1414.
Vertically Aligned
Combinatorial Method for (Co-Mo) Catalysts (2)Combinatorial Method for (Co-Mo) Catalysts (2)
10μm
100nm100nm
(III)(I) (II)
(I)
(II) (III)
H. Sugime, S. Noda, S. Maruyama, Y. Yamaguchi (2006).
Reduction temperature: 800℃Reaction temperature: 800℃Pressure of ethanol: 30TorrReaction time: 10min
Co/Mo [nm](I) 0.33/0.049(II) 0.19/0.13(III) 0.13/0.34
thin ← Mo → thick
thick↑Co↓
thin
Initial Reaction on CatalystInitial Reaction on Catalyst
Pulsed Valve
Target Disk
Waiting Room
Focused Laser Beam
He 10 atm
Expansion Cone
Cluster Beam
Cluster Source Nozzle for FT-ICRCluster Source Nozzle for FT-ICR
Turbopump
Gate Valve
Cluster Source
6 Tesla Superconducting Magnet
DecelerationTube
Front Door
Screen Door
Rear Door
Excite & DetectionCylinder
Electrical FeedthroughGas Addition
100 cm
Ionization Laser
Probe Laser
FT-ICR (Fourier Transform Ion Cyclotron Resonance)Mass Spectrometer
FT-ICR (Fourier Transform Ion Cyclotron Resonance)Mass Spectrometer
FT-ICR Study of Initial ReactionFT-ICR Study of Initial Reaction
800 1200
12 16 20 24
Mass (amu)
Inte
nsity
(arb
itrar
y)
(a)as injected
(b)0.2s
(c)0.5s
(d)1.0s
Number of Cobalt Atoms
C2H5OH (46amu)
C2HOH (42amu)
10 20 30
0.2
0.4
0.6
0.8
Number of Cobalt Atoms
reactive num. / total num.
this workSmalley et al.
10 20
0
2
4
6
Number of Cobalt Atoms
Inte
nsity
(–H
2 or –
2H2 /
che
mis
orpt
ion)
–2H2–H2
FT-ICR Chemical reaction of cobalt clusters (cation) with ethanol
FT-ICR Chemical reaction of cobalt clusters (cation) with ethanol
**
*
*820 840 860 880
14 15
Mass (amu)
Inte
nsity
(arb
itrar
y)
(a)C2H5OH
(b)C2H5OD
(c)CD3CH2OH
(d)C2D5OD
18
Number of Cobalt Atoms42
4amu
5amu
6amu
9amu
FT-ICR Study of Initial ReactionFT-ICR Study of Initial Reaction
5 10 15 20Number of Atoms
Rel
ativ
e R
eact
ion
Rat
e (a
rb. u
nit)
CobaltNickel
Iron
•Iron
Simple chemisorption
•Cobalt
Simple chemisorption
Dehydrogenation
•Nickel
Dehydrogenation
Single-Walled Carbon-13 Nanotubes (SW13CNTs)Single-Walled Carbon-13 Nanotubes (SW13CNTs)
Vacuum
Quartz test tube
Electric furnace
Quartz boat Dispersed metal particles embedded in Y-type zeolite
Isotopically-modifiedethanol (carbon-13) Coupler
Quartz tube
Flow channel
ACCVD technique optimized for the efficient production of SWNTs from very small amount of ethanol
1200 1400 1600
Inte
nsity
(arb
.uni
ts)
Raman Shift (cm–1)
(a) 12CH3 –12CH2 – OH
(b) 12CH3 –13CH2 – OH
(c) 13CH3 –12CH2 – OH
(d) 13CH3 –13CH2 – OH
0.988
0.974
0.9608
Comparison of Raman SpectraComparison of Raman Spectra
(a)
(b)
(c)
(d)
ααννα 1312)1(12 +−×= C
ααν131)1(
121
+−∝vib
Assuming…
Scaling factor
α: Ratio of 13C in a SWNT
α= 0.67
α= 0.31
α= 0
α= 1
Two carbon atoms in an ethanol molecule are not equally used for the SWNT formation in ACCVD process
200 300
Inte
nsity
(arb
.uni
ts)
Raman Shift (cm–1)
(a) 12CH3 –12CH2 – OH
(b) 12CH3 – 13CH2 – OH
(c) 13CH3 – 12CH2 – OH
(d) 13CH3 – 13CH2 – OH
0.970
0.986
13CH3- 13CH2- OH12CH3- 13CH2- OH13CH3- 12CH2- OH12CH3- 12CH2- OH
SWNTs with various amount of 13C abundance were synthesized from 3 types of isotope-modified ethanol
①②
Normal ethanol
Determination of ChiralityDetermination of Chirality
(6,5) SWNT with unique cap structure satisfying Isolated Pentagon Rule (IPR)
CVD Temperature DependenceCVD Temperature Dependence
(7,5) (7,6)
(6,5)
Emission wavelength (nm)
Exci
tatio
n w
avel
engt
h (n
m)
(7,5) (7,6)
(6,5)
Emission wavelength (nm)
Exci
tatio
n w
avel
engt
h (n
m)
(7,5) (7,6)
(6,5)
Emission wavelength (nm)
Exc
itatio
n w
avel
engt
h (n
m)
(7,5) (7,6)
(6,5)
Emission wavelength (nm)
Exc
itatio
n w
avel
engt
h (n
m)
Emission wavelength (nm)
Exc
itatio
n w
avel
engt
h (n
m)
(7,5) (7,6)
(8,6)
(8,4)
Emission wavelength (nm)
Exc
itatio
n w
avel
engt
h (n
m)
(7,5) (7,6)
(8,6)
(8,4)
850℃750℃650℃0.8 1
0
10
20
30
Tube diameter (nm)
Chi
ral a
ngle
(deg
.)
9,19,1
8,38,3
6,56,57,57,5
7,67,68,68,6
8,78,7
8,48,49,49,4
9,59,5
7,37,310,510,5
9,29,2 10,210,2
10,310,3 11,311,3
11,411,4
11,111,1
10,010,0 11,011,0
12,112,1
12,212,2
13,013,0
9,19,1
8,38,3
6,56,57,57,5
7,67,68,68,6
8,78,7
8,48,49,49,4
9,59,5
7,37,310,510,5
9,29,2 10,210,2
10,310,3 11,311,3
11,411,4
11,111,1
10,010,0 11,011,0
12,112,1
12,212,2
13,013,00.7 0.8 0.9 1
0
10
20
30
Tube diameter (nm)C
hira
l ang
le (d
eg.)
9,19,1
8,38,3
6,56,57,57,5
7,67,68,68,6
8,78,7
8,48,49,49,4
9,59,5
7,37,310,510,5
9,29,2 10,210,2
10,310,3 11,311,3
11,411,4
11,111,1
10,010,0 11,011,0
12,112,1
12,212,2
13,013,0
9,19,1
8,38,3
6,56,57,57,5
7,67,68,68,6
8,78,7
8,48,49,49,4
9,59,5
7,37,310,510,5
9,29,2 10,210,2
10,310,3 11,311,3
11,411,4
11,111,1
10,010,0 11,011,0
12,112,1
12,212,2
13,013,00.7 0.8 0.9 1
0
10
20
30
Tube diameter (nm)
Chi
ral a
ngle
(deg
.)
9,19,1
8,38,3
6,56,57,57,5
7,67,68,68,6
8,78,7
8,48,49,49,4
9,59,5
7,37,310,510,5
9,29,2 10,210,2
10,310,3 11,311,3
11,411,4
11,111,1
10,010,0 11,011,0
12,112,1
12,212,2
13,013,0
9,19,1
8,38,3
6,56,57,57,5
7,67,68,68,6
8,78,7
8,48,49,49,4
9,59,5
7,37,310,510,5
9,29,2 10,210,2
10,310,3 11,311,3
11,411,4
11,111,1
10,010,0 11,011,0
12,112,1
12,212,2
13,013,0
Carbon source : Ethanol, CVD time : 10min
Resasco’sCoMoCAT
S. M. Bachilo et al., JACS,
125 (2003) 11186.
Chirality dependent quantum yieldChirality dependent quantum yield
Y. Oyama, R. Saito, K. Sato, J. Jiang, Ge.G. Samsonidze, A. Gruneis, Y. Miyauchi, S. Maruyama, A. Jorio, G. Dresselhaus, M.S. Dresselhaus, Carbon in press.
(10,2)(8,3)
(6,4)
(12,1)
0.6 0.8 1 1.2 1.4
100
102
104
Nanotube diameter (nm)
Num
ber o
f IPR
Sat
isfy
ing
Cap
Stru
ctur
es
(10,10)
(5,5)
(6,5)&(9,1)
(9,9)
(8,8)
(7,7)
(6,6)
IPR (Isolated Pentagon Rule)-Satisfying Cap StructureIPR (Isolated Pentagon Rule)-Satisfying Cap Structure
armchair
zigzag
(6,5)(9,1)
T. Yu et al., Fullerene Sci. Tech., 7, 769 (1999).
7 7.5–7.4
–7.2
–7
Pot
entia
l ene
rgy
(eV
/ato
m)
(5,5)
(9,0)
(6,5)
(9,1)
(6,5)
(9,1)
(5,5)
(9,0)
Diameter(Å)
Energy of Nanotube Cap StructureEnergy of Nanotube Cap Structure
Brenner potential
(6,5) d = 7.64Å
(9,1) d = 7.64Å
(9,0) d = 7.20Å
(5,5) d = 6.93ÅWith Cap
Tube Only
PL peaks other than Eii ~ Phonon SidebandPL peaks other than Eii ~ Phonon Sideband
12C
(10,2)
I
II
13C
12C
(6, 5)
(7, 5)(8, 3)
1.5
2
2.5
Emission intensity (arb. units)
Exc
itatio
n en
ergy
(eV
)
(7, 5) E 22
(6, 5) E 22
x 5
(10, 2) E 22
(8, 3) E22
Y. Miyauchi and S. Maruyama, Phys.Rev. B, in press.
Phonon sideband
Phonon sideband
Phonon sideband and Raman
Ph
Ph
Ph
?
?
?
?
V. Perebeinos, J. Tersoff, P. Avouris, PRL 94, 027402 (2005).
PL peaks other than EiiPL peaks other than Eii
G-band (Raman)
Rayleigh
(7,5)(7,6)
(6,5)
(8,3)
(10,2)
E11emission
E11
E11 + phonon
E22 + phonon
E22
E12, E 21
Background for perpendicular excitation
⊥
//
//
//
//
⊥
Emission energy
Exci
tatio
n en
ergy
G-band
Rayleigh
G’-band
PL map of SWNTs (ACCVD SWNTs) Schematic of PL peak positions in a PL map
Y. Miyauchi, PhD thesis (2006)
Vertically Aligned SWNTs and Growth Process
10 µm
0 5 10 150
2
4
0
10
20
30
CVD time [min]
Abso
rban
ce [
– ]
VA–S
WN
T fil
m th
ickn
ess
[ μm
]
Stop herefor 25
μm
Stop herefor
10 μm
In-situ Measurement of Film ThicknessIn-situ Measurement of Film Thickness
Mai
n dr
ain
tube
Sub
drai
n tu
be
Quartz tubeElectric furnace
Pirani gauge
Vacuum pump
Substrate
Ethanol tank
Hot bath
Pressure manometer
Ar-H2
mixed gas
LaserPrism
or Mirror
Quartz tube
Electric furnace
SubstrateLaser light detector
PCUSB cable
Gas flow
S. Maruyama et al., CPL 403 (2005) 320.
0 10 20 300
0.5
1
0
2
4
6
8
CVD time (min)
Abs
orba
nce
VA
SW
NT
film
thic
knes
s (μ
m)
0 10 20 300
0.5
1
0
2
4
6
8
CVD time (min)
Abs
orba
nce
VA
SW
NT
film
thic
knes
s (μ
m)
η0 = 1.9x10–4 m2 mol–1
τ = 204 s
ε∞ = 28.0 m2 mol–1
Fitting Lines
η0 = 1.1x10–4 m2 mol–1
τ = 300 s
Catalyst-Consumption Growth ModelCatalyst-Consumption Growth Model
τηη−=
dtd
⎟⎠⎞⎜
⎝⎛ −=
−ττη
tetC 1)( 0
Growth Model
Catalyst Activity η
Carbon Mass C(t)
Additional Burning of SWNTsAdditional Burning of SWNTs
0 30 600
0.1
0.2
0.3
0
1
2
CVD time (min)
Abs
orba
nce
VAS
WN
T fil
m th
ickn
ess
(μm
)
η0 = 3.4x10–5 m2 mol–1
τ = 250 s
Ethanol Stopped
Detachment of VA-SWNT films with hot waterDetachment of VA-SWNT films with hot water
Y. Murakami and S. Maruyama, Chem. Phys. Lett. 422(2006) 575.
(a) As-grown on quartz
(b) Re-attached on Si
0.5 mm
a
0.5 mm
Hidetsugu Shiozawa & Thomas Pichler (IFW-Dresden e.V.),Erik Einarsson, Shigeo Maruyama
TEM Image from Top of CarpetTEM Image from Top of Carpet
Laser ACCVD and in situ Raman MeasurementsLaser ACCVD and in situ Raman Measurements
S. Chiashi, M. Kohno, Y. Takata, S. Maruyama, (2005)
0 2 4 6 8 100
200
400
600
800
1000
Time (min)
Inte
nsity
(arb
. uni
ts)
Tem
pera
ture
(°C
)
τ=100 (s)Δt=42 (s)
ethanol gas supply
(c) temperature
(b) silicon
(a) the G–band
⎥⎦
⎤⎢⎣
⎡⎟⎠⎞
⎜⎝⎛ Δ−
−=τ
ttAy exp1 τ =100 ∼ 200 (s)Δt=30∼40 (s)
Ar laser objective lens
collective lens
ethanolgas
Raman excitation laser(488, 514, 633 nm)
Laser ACCVD and in situ Raman MeasurementsLaser ACCVD and in situ Raman Measurements
S. Chiashi, M. Kohno, Y. Takata, S. Maruyama, (2005)
0 2 4 6 8 100
200
400
600
800
1000
Time (min)
Inte
nsity
(arb
. uni
ts)
Tem
pera
ture
(°C
)
τ=100 (s)Δt=42 (s)
ethanol gas supply
(c) temperature
(b) silicon
(a) the G–band
⎥⎦
⎤⎢⎣
⎡⎟⎠⎞
⎜⎝⎛ Δ−
−=τ
ttAy exp1 τ =100 ∼ 200 (s)Δt=30∼40 (s)
Ar laser objective lens
collective lens
ethanolgas
Raman excitation laser(488, 514, 633 nm)
10–2 10–1 100101
102
103
Ethanol Gas Pressure (Torr)
Incu
batio
n Ti
me,
Δt (
s)Δt=P–1.6
AcknowledgementsAcknowledgementsDr. Y. Murakami, Mr. Y. Miyauchi, Dr. S. Chiashi, Mr. Erik Einarsson, Mr. T. Nishii, Dr. T.
Shimada (Nagoya Univ.), Prof. M. Kohno (Kyushu Univ.) , Prof. S. Inoue (Hiroshima Univ.), Prof. Y. Shibuta, Dr. J. Shiomi, Dr. H. Yamaguchi (Nagoya Univ.)
Mr. K. Ishikawa, Mr. M. Oba, Mr. D. Yoshimatsu, Mr. K. Koizumi, Mr. S. Hirama, Mr. M. Kadowaki, Dr. M. Hu, Prof. T. Okubo, Prof. S. Noda @ Chem. Synthesis
Prof. R. E. Smalley, Prof. B. Weisman, Prof. J. Kono @ Rice Univ.Prof. H. Shinohara, Prof. Y. Ohno, Prof. T. Mizutani @ Nagoya Univ.,
Prof. K. Matsuda @ Kyoto University, Prof. R.Saito @ Tohoku Univ., Prof. S.Okada @ Tsukuba Univ., Prof. T. Miyake @ AISTProf. M. Endo @ Sinshu University, Dr. M. Yudasaka @ NEC, Prof. M. Dresselhaus @
MIT, Prof. A. Jorio @ UFMG, Prof. S. Suzuki, Prof. Y. Achiba @ Tokyo Metropolitan Univ., Prof. H. Kataura @ AIST, , Dr. H. Shiozawa & T. Pichler @ IFW-Dresden e.V.
Mr. H. Tsunakawa @ University of Tokyo, Mr. T. Sugawara @ University of TokyoMr. M. Sunose @ Seki-Tech.
Mr. N. Masuyama@ J-Power Co. Ltd., Mr. Y. Kondo@ Konica-Minolta, Mr. S. Watanabe, Ms. M. Nakagawa, Mr. R. Tamochi @ Hitachi Science Systems
JSPS, MEXT, Toray, XNRI, J-Power, DENSO, Konica-Minolta, Tokyo-Gas, SEL, Toso
Professor Richard E. Smalley at Rice University (1943-2005)Professor Richard E. Smalley at Rice University (1943-2005)
1943: Born in Akron, Ohio on June 61976: PhD from Princeton,
Assistant Professor at RiceLaser Vaporization Cluster Beam
1984: Discovery of C601996: Nobel Prize in Chemistry with Kroto and Curl1996: Bulk Production of SWNTs
Then HiPco Process2000: Testified for National Nanotechnology Initiative2000: Found Carbon Nanotechnology Inc.
Application of Nanotechnology to Energy Problem2005: Died at 62 on October 28, 2005
1990
20012001
20052005
Catalytic CVD Synthesis of SWNTs from FullereneCatalytic CVD Synthesis of SWNTs from Fullerene
vacuumvacuumvacuum
Quartz plate
Quartz tubeFurnace A
Furnace B
Dispersed metal particles (Fe/Co 2.5wt%) embedded in Y-type zeolite
Thermocouple
Inorganic adhesive
Quartz woolQuartz test tube
FullereneC60 or C70
0 200 400 600
200
400
600
deg
C [℃
][s]
Temperature up curve of TC
(CH3CO2)2Fe(CH3CO2)2Co-4H2O etc.
Catalysts
Supports
Zeolite USYHSZ-390HUA
Temperature: Furnace B 825℃Time: 10min
CCVD Generation of SWNTs from FullereneCCVD Generation of SWNTs from Fullerene
Fullerene
Up-StandingBundle
Up-StandingBundle
200 300
1.8
2
2.2
2.4
2.6
1 0.9 0.8Nanotube Diameter (nm)
Ene
rgy
Sep
arat
ion
(eV
)
488 nm
514.5 nm
633 nm
Inte
nsity
(arb
.uni
ts)
Raman Shift (cm–1)
(a) C70, 488
(b) C70, 514.5(c) C70, 633
(d) EtOH, 488
(e) EtOH, 514.5
(f) EtOH, 633* *
S. Maruyama et al, Chem. Phys. Lett., 375 (2003) 553.
Water Assisted Super-Growth
Iijima Group (K. Hata et al., Science, 2004)
2.5 mm height Catalysts: Al2O3 (10 nm)/Fe(1 nm) Buffer: Ar (99.9999%) or He (99.9999%) with 40% H2 (99.99999%) Water:175 ppmSource: 100 sccm ethylene (99.999%) CVD Temp.: 750°C x 10 min
Super Growth by Kawarada GroupSuper Growth by Kawarada Group
G. Zhong, JJAP 44 (2005) 1558.
Point arc Microwave Plasma CVD0.7nmAl2O3/0.5nmFe/5-70nmAl2O3 Catalysts
66kg/m3
270 micron/h
isolator
lenscollimator collimator
SAINT sampleisolator
isolator 980/ 1550coupler
40cmF:EDFA
10 mspot size
μ
980nmpump LD
70%
30% output
coupler
Saturable Absorbers:Application to Mode-Locked Fiber Lasers
Saturable Absorbers:Application to Mode-Locked Fiber Lasers
S. Yamashita, S. Maruyama, Y. Murakami, Y. Inoue, H. Yaguchi, M. Jablonski, S. Y. Set, Optics Letters, 29 (2004) 1581.
Polarized Optical Absorption of VA-SWNTs (2) Polarized Optical Absorption of VA-SWNTs (2)
Y. Murakami, E. Einarsson, T. Edamura, S. Maruyama: Phys. Rev. Lett., 94, 087402(2005)
0 2 4 60
1
2
Energy (eV)
Abs
orba
nce
0 2 4 60
1
2
Energy (eV)
Abs
orba
nce
0 2 4 60
1
2
Energy (eV)
Abs
orba
nce
0 2 4 60
10
20
30
σ (m
2 /mol
e C
)
Energy (eV)
σ||
σ_|_
(b)
0 30 60 900
1
2
Abs
orba
nce
θ (deg)
4.5 eV
5.3 eV2.8 eV4.0 eV
(a)
0 2 4 60
10
20
30
σ (m
2 /mol
e C
)
Energy (eV)
σ||
σ_|_
(b)
0 30 60 900
1
2
Abs
orba
nce
θ (deg)
4.5 eV
5.3 eV2.8 eV4.0 eV
(a)
( )⎭⎬⎫
⎩⎨⎧ −
++= ⊥⊥ S
ηηηησ ||
||||
22
31
⎟⎟⎠
⎞⎜⎜⎝
⎛ −−+= ⊥
⊥⊥ Sηη
ηησ ||||2
31
θ2sin
le //le ⊥
100 200 300
2 1 0.9 0.8
Inte
nsity
(arb
.uni
ts)
Raman Shift (cm–1)
Diameter (nm)
488 nm
Anomalous Raman Scattering Anomalous Raman Scattering
0
2
4
Nor
mal
ized
pea
k in
tens
ity [–
]
160 cm–1
203 cm–1
145 cm–1
257 cm–1
242 cm–1
180 cm–1
From top 45° Parallel488 nma
le //
le ⊥
Y. Murakami, S. Chiashi, E. Einarsson, S. Maruyama: Phys. Rev. B, 7, 085403(2005)
InGaAs Detector
Photoluminescence Spectroscopy of SWNTsPhotoluminescence Spectroscopy of SWNTs
M. J. O’Connell et al., Science 297 (2002) 593
S. M. Bachilo et al., Science 298 (2002) 2361
(7,5)
11νh22νh D2O 1.1g /cm3
1.0g / cm3
SDS
Strong sonicationSuper centrifuge 380,000g x 1h
E22
E11
(E11)
(E22)
–1
0
1
Ene
rgy
(eV
)
11νh
v1 v2
c1 c2
h
e
22νh