Uhlíkové nanostruktury-materiály pro budoucnost?
Martin Kalbáč
y y p
Martin Kalbáč
Ústav fyzikální chemie J. Heyrovského, Praha
IFW Dresden Massachusetts Institute of Technology (MIT), Cambridge,USA
Forms of carbon
NanotubesNanotubes
Fullerenes
Graphene
Diamond Graphite
Graphene
Content:1) Grafen
2) Fullereny
3) Nanotuby
4) Peapody
5) DWCNTs
6) Spektroelektrochemie
Forms of carbon
GraphiteGraphite
Forms of carbon
GrapheneGraphene
Graphene –applications
Ultrathin conductive films Graphene Used To Create W ld' S ll t T i tWorld's Smallest Transistor
Liquid Crystal Device with electrodes made of graphene with different voltages applied. The overall width of the insert image is 30 microns. (Image: Mesoscopic Physics Group, University of Manchester)
Dr Ponomarenko, who carried out this work, shows his research sample: graphene quantum dots on a chip.
Graphene –applications
Single molecule gas detectionSingle molecule gas detection
Ultracapacitors
Spin transport
Schematic of the resonator. The graphene is in contact with a gold electrode that can be used to electrostatically actuate the resonator. A red laser is used to detect the motion of the resonator by laser interferometry.
Forms of carbon
GrapheneGraphene
≈ £ 0.70 per μm2
≈ £ 700 000 per mm2p
Forms of carbon
GrapheneGraphene
Forms of carbon
GrapheneGraphene
Chemical vapor deposition (CVD)
Quartz boatQuartz boatCu or Ni substrate
Quartz tube
Electric furnace
Quartz tube
Electric furnace
Ethanol tank
Ar/H2
Aror Ethanol tankEthanol tankArorH2/CH4
Hot bathHot bathHot bath
Chemical vapor deposition (CVD)
Transfer of graphene
Transfer of graphene
Chemical vapor deposition (CVD)
Expo '67 American Pavillion by R. Buckminster Fuller, on Ile Sainte-Hélène, Montreal
C acc to IUPAC:C60 acc. to IUPAC:
Hentriacontacyclo[29.29.0.0.2,14.03,12.04,59.05,10.06,58.07,55 08,53 09,21 011,20 013,18 015,30 016,28 017,25 019,24 022,52 02.0 .0 .0 .0 .0 .0 .0 .0 .0 .03.50.026,49.027,47.029,45.032,44.033,60.034,57.035,43.036,56.037,41.038,54.039,51.040,48.042,46]hexaconta-1 3 5(10) 6 8 11 13(18) 14 16 19 21 23 25 27 29(45)1,3,5(10),6,8,11,13(18),14,16,19,21,23,25,27,29(45), 30,32(44),33,35(43),36,38(54),39(51),40(48),41,46,49,52,55,57, 59-triaconten
Kroto, Allaf, Balm, Chem. Rev. 91, 1991, 1213
Fullerene galleryFullerene gallery
C60 C70 C78 C82C76
La@C84
Sc3N@C84
Endohedral Fullerene M@C84
Carbon nanotubes
Rolling of SWCNTRolling of SWCNT
-zag
zig-
arm-chair
Carbon nanotubes (CNT)
MWCNTSWCNT
DWDWCNT
SWCNT BundlesSWCNT Bundles
SWCNT BundlesSWCNT Bundles
Single wall carbon nanotubes (SWCNT)
• Size: Nanostructures with dimensionsof ~1 nm diameter (~10 atoms around
• Electronic Properties: Can be eithermetallic or semiconducting depending on
the cylinder)
• Physics: 1D density of electronic states. Single molecule Raman spectroscopy,
diameter and orientation of the hexagons
•Mechanical Properties: Very high strength. Good properties on both compression and
luminescence, and transport properties. extension.
Carbon nanotubes (CNT) mechanical propertiesCarbon nanotubes (CNT) mechanical properties
Fiber material
Specific density
E (TPa)
Strength (GPa)
Strain at break (%) y ( ) ( ) ( )
CNT 1.3 - 2 1 10-60 10
HS St l 7 8 0 2 4 1 10HS Steel 7.8 0.2 4.1 <10
CF-PAN 1.7 - 2 0.2 -0.6
1.7 - 5 0.3 - 2.4 0.6
Kevlar 49 1.4 0.13 3.6-4.1 2.8
Carbon nanotubes (CNT) mechanical propertiesCarbon nanotubes (CNT) mechanical properties
Single nanotube transistor
• Distinctive metallic and semiconducting
iIBM
transport properties
• Ballistic transport• Ballistic transport
• Extremely high y gcurrent carrying capacity
Chemical vapor deposition (CVD)
Quartz boatQuartz boat
Quartz tube
Electric furnace
Quartz tube
Electric furnace
Ethanol tank
Ar/H2
Aror Ethanol tankEthanol tank
Ar/H2
Aror
Hot bathHot bathHot bath
Quality vs. price
Purity of carbon nanotubes
Commercial „90% carbon purity“500 $ /gg
SWCNT from graphene
a1 6 a1Aa2
5 a5 a2Ch
BB
Chiral vector: Ch = na1 + ma2a1 , a2 …. Unit vectors of 2D-hexagonal lattice Chiral vector: Ch = 6a1 + 5a2a1 , a2 …. Unit vectors of 2D-hexagonal lattice
(6,5)1 , 2 g1 , 2 g
SWCNT from grapheneg p
Armchair nT(n=m) metal
Zig-zag nT(n-m) = 3i metal(n-m) ≠ 3i semicond.
Chiral nT(n m) = 3i metal(n-m) = 3i metal(n-m) ≠ 3i semicond.
Density of states (DOS) in SWCNT→Van Hove singularities
2.5
2.0
1.5
1.0(5 0)
Zig-zag tubes
2.5
2.0
1.5
1.0
(5,5)
(5 5)
Armchair tubes
2.5
2 0
0.5
0.0
-3 -2 -1 0 1 2 3
tom
/eV
)
(5,0)
2.5
0.5
0.0
-3 -2 -1 0 1 2 3
(5,5)
om/e
V)
2.0
1.5
1.0
0.5
0.0
S (s
tate
s/C
-at
(10,0)2.0
1.5
1.0
0.5
(10,10)(10,10)
(sta
tes/
C-a
t
-3 -2 -1 0 1 2 3
2.5
2.0
1.5
1 0
DO
S
(20,0)
2.5
2.0
1.5
1 0
-3 -2 -1 0 1 2 3
(20,20)(20,20)
DO
S
1.0
0.5
0.0
-3 -2 -1 0 1 2 3
Energy, eV
( , )1.0
0.5
0.0
-3 -2 -1 0 1 2 3
Energy, eV
ΔE of singularities vs. diameter of SWCNT (“Kataura graph”)
a2χ1.5
ergy
, eV
daE CC−=Δ 02χ
SWCNT d ≈ 1.1-1.4 nm
0.0
0.5
1.0Ene
(10,10)
arat
ion
(eV)
v 2→c
1.8-1.5
-1.0
-0.5
Ener
gy S
epa
vm1→cm
1
vm →cm2
vs3→cs3
0.7
1.2DOS
1.0
1.5
Ene
rgy,
eV
vs1→cs1
vs2→cs
2
-0.5
0.0
0.5
(11,9)
Nanotube diameter (nm)
(n, m) to (40,40) -1.5
-1.0
DOS
Vis/NIR spectrum of SWCNT/ITO
0.5
0.4vss
11→→ ccss11
vss22→→ ccss
22
vmm11→→ ccmm
110.3
0.2Abso
rban
ce vmm →→ ccmmhv
0.1
0.0ITOSWCNT
3.02.52.01.51.00.5Energy, eV
SWCNT Bundles
Sorting SWCNT
What is the Raman spectroscopy aboutp py
C. V. Raman
Resonance enhanced Raman spectroscopy
Approximately 1 in 107 photons is inelastically scattered
The signal is usally very weak
Approximately 1 in 107 photons is inelastically scattered
1) Use of lasers - intensive light2) Resonance enhancement2) Resonance enhancement
R h d R tResonance enhanced Raman spectroscopy
E1 V0
Virtual state
E0 V1Optical transition ?E0 V0
Optical transition ?
Resonance enhanced spectra102-104
Resonance Raman spectroscopy of SWCNT
2))(( γγ iEEEiEE
cIiiphLiiL −−+−−
=
EL - laser photon energyEii - optical transition energyEph - phonon energyγ damping constantγ - damping constant
Typical values for RBMEph ≈ 0.02 eVγ ≈ 0.05 eV
Raman spectrum of SWCNT
2.41 eV
1.83 eV
2.41 eV
TG
tens
ity, a
. u.
tens
ity, a
. u.
TG
Ram
an in
t
x 25x 5Ram
an in
t
G’RBM D
G’
28002700260025001600150014001300300250200150100
Raman shift, cm-128002700260025001600150014001300300250200150100
Raman shift, cm-1
Diameter = 234/ωRBM
Growth of CNT
Raman spectra of SWCNT, hvexc= 1.83 eV
x 1.5
y, a
.u.
man
inte
nsity Bundle
Ra
1640160015601520400350300250200150
Raman shift, cm-1
Creation of defects in SWCNT
RF Ar plasma
Individual SWCNT
Mask
SubstrateMask
Defective SWCNT
x 30
x103
ensi
ty, a
.u. D mode
x
Ram
an in
te
Pristine part
27202700268026601600150014001300220200180160140
Raman shift cm-1
Defective part
Diameter = 234/ωRBM
Raman shift, cm
Formation of fullerene peapod (C60@SWCNT)
C60 (g) Nanotube, optimum ∅ ≈1.36 nmFULLERENE PEAPODNanotube, optimum ∅ 1.36 nm
Dy3N@C80@SWCNT
Dy3N@C80@SWCNTDy3N@C80@SWCNT
Dysprosium (at approx. 154 eV) from EELS spectra
J.Cech, M. Kalbáč, S.A. Curran, D. Zhang, U. Dettlaff-Weglikowska, L. Dunsch, S. Yang and S. Roth: Physica E: Low-dimensional Systems and Nanostructures, in press (2006)
Distance (nm)
Raman spectra of Dy3N@C80@SWCNT hvexc= 1.91 eVy,
a. u
. in
tens
ity
Dy3N@C80@SWCNT
Ram
an
5Dy3N@C80
SWCNT
18001600140012001000800600400200Raman shift, cm -1
x 5
Double walled nanotubesRT
C60@SWCNT800 oC
1200 oC
DWCNT1000 oC
1200 oC
S. Bandow et al., Chem. Phys. Lett. 337 (2001) 48
Raman spectra of dry DWCNT, hvexc= 1.83 eV
sity
, a. u
. INNER TUBESOUTER TUBES
Ram
an in
tens
400350300250200150100Raman shift, cm -1
Double walled nanotubes from different peapod sources(The spectra are excited by 1.83 eV)
C78-DWCNT
a. u
.
C70-DWCNT
a. u
.
C60-DWCNT
a. u
.
Ram
an in
tens
ity, a
Ram
an in
tens
ity, a
Ram
an in
tens
ity, a
360340320300280260240Raman shift, cm -1360340320300280260240
Raman shift, cm -1360340320300280260240Raman shift, cm -1
Dy3N@C80-DWCNTLa@C82-DWCNTC84-DWCNT
nten
sity
, a. u
.
nten
sity
, a. u
.
nten
sity
, a. u
.
Ram
an in
360340320300280260240Raman shift, cm -1
Ram
an in
360340320300280260240Raman shift, cm -1
Ram
an in
360340320300280260240Raman shift, cm -1
In-situ spectroelectrochemistry
The change of potential
The change of potential
The change of electronic stateThe change of electronic state
The change of spectra
The change of spectra
Methods Materials
EPR UV-Vis-NIR
conducting polymersmonomers, oligomersUV Vis NIR
RamanFTIR
fullerenesCNT peapodspeapods
In-situ electrochemical doping of SWCNTanodic/cathodic= extraction/insertion of e-
OCPAn1An2OCPCat1Cat2
Fermi level
Fermi levelFermi level
Fermi level
Fermi level
Fermi level
Electrode
Vis-NIR spectra on ITO electrode of SWCNT(0 2 M LiClO + acetonitrile)(0.2 M LiClO4 + acetonitrile)
0.50
0.45
0.50
0.45
0.50
0.45
0.50
0.45
0.50
0.45
0.50
0.45
0.50
0.45
0.50
0.45
0.50
0.45CE WE
RE
0.0
0.5
1.0
1.5
Ener
gy, e
V
0.40
0.35
bsor
banc
e (A
) 0.40
0.35
bsor
banc
e (A
) 0.40
0.35
bsor
banc
e (A
) 0.40
0.35
bsor
banc
e (A
) 0.40
0.35
bsor
banc
e (A
) 0.40
0.35
bsor
banc
e (A
) 0.40
0.35
bsor
banc
e (A
) 0.40
0.35
bsor
banc
e (A
) 0.40
0.35
bsor
banc
e (A
)
hv -1.5
-1.0
-0.5
DOS
0.30
0.25
A
0.30
0.25
A
0.30
0.25
A
0.30
0.25
A
0.30
0.25
A
0.30
0.25
A
0.30
0.25
A
0.30
0.25
A
0.30
0.25
A
ITOsample 0.0
0.5
1.0
1.5
Ene
rgy,
eV
0.20
4.03.53.02.52.01.51.00.5Energy, eV
0.20
4.03.53.02.52.01.51.00.5Energy, eV
0.20
4.03.53.02.52.01.51.00.5Energy, eV
0.20
4.03.53.02.52.01.51.00.5Energy, eV
0.20
4.03.53.02.52.01.51.00.5Energy, eV
0.20
4.03.53.02.52.01.51.00.5Energy, eV
0.20
4.03.53.02.52.01.51.00.5Energy, eV
0.20
4.03.53.02.52.01.51.00.5Energy, eV
0.20
4.03.53.02.52.01.51.00.5Energy, eV
-1.5
-1.0
-0.5
DOS
E = 0.0VE = 0.2VE = 0.4VE = 0.6VE = 0.8VE = 1.0VE = 1.2VE = 1.4VE = 1.6V
Raman spectra of SWCNT hv = 2 54 eVRaman spectra of SWCNT, hvexc= 2.54 eV(0.2 M LiClO4 + acetonitrile)
cI
Spectroelectrochemical cell
x40+ 1.25 V
2))(( γγ iEEEiEE
IiiphLiiL −−+−−
=
RE (A /A Cl) N -inlet2
N -outlet2
y, a
. u.
sity
, a. u
.
RE (Ag/AgCl)CE (Pt)
Electrolyte solution
N inlet2
Ram
an in
tens
ity
an in
tens
Electrolyte solutionPyrex window
WE 1640160015601520
Ram
240220200180160140
-1.75 V
(vs. Fc/Fc+)WE 1640160015601520240220200180160140
Raman shift, cm -1
Raman spectra of DWCNT, hvexc= 1.83 eV(0.2 M LiClO4 + acetonitrile)
0.9 V
1.2 V
1.5 V
nsity
, a. u
.
0 V
0.3 V
0.6 V
0.9 VR
aman
inte
n 0 V
-0.3 V
-0.6 V
-0.9 V
-1.2 V
-1.5 V
350300250200150100Raman shift, cm -1
M. Kalbáč, L. Kavan, M. Zukalová and L. Dunsch: Adv. Funct. Mater., 15, 418-426, (2005).
THANK YOU !!!
• GACR-DFG
Financial support:
• GA AV• MSMT-USA
K k
1) M Kalbac L Kavan L Dunsch and M S Dresselhaus Nanoletters 8 1257 1264 (2008)
1) M. Kalbac, L. Kavan, L. Dunsch and M.S. Dresselhaus. Nanoletters, 8, 1257-1264 (2008).2) M. Kalbac, L. Kavan, M. Zukalová and L. Dunsch. Chemistry - A Eur. J., 14, 6231-6236 (2008).3) M. Kalbac, L. Kavan, L. Dunsch. J. Phys. Chem C. 112(43), 16759-16763 (2008).4) M. Kalbac, H. Farhat, L. Kavan, J. Kong, M.S. Dresselhaus. Nanoletters, 8 (10), 3532-3537 (2008).5) M. Kalbac, L. Kavan, L. Dunsch. J. Phys. Chem C. 113(4), 1340-1345 (2009).6) M. Kalbac, L. Kavan, H. Farhat, J. Kong, M.S. Dresselhaus. J. Phys. Chem C. 113(5), 1751-1757 (2009).) , , , g, y ( ), ( )7) M. Kalbac, L. Kavan, L. Dunsch: J. Am. Chem. Soc. 131(12) 4529-4534, (2009).8) M. Kalbac, H. Farhat, L. Kavan, J. Kong, K. Sasaki, R.Saito and M. S. Dresselhaus. ACS Nano, 3 (8), 2320-2328 (2009).9) M. Kalbac, A. A. Green, M. C. Hersam, and L. Kavan. ACS Nano, 4 (1), 459-469 (2010). 10) M. Kalbac, V. Zólyomi, Á. Rusznyák, J. Koltai, J. Kürti and L. Kavan. J. Phys. Chem C. 114, 25015-2511 (2010).