Uhlíkové nanostruktury-materiály ypro budoucnost? Martin Kalbáč IFW Dresden Ústav fyzikální chemie J. Heyrovského, Praha Massachusetts Institute of Technology (MIT), Cambridge,USA
Forms of carbon Nanotubes Fullerenes Diamond Graphite Graphene
Content: 1) Grafen 2) Fullereny 3) Nanotuby 4) Peapody 5) DWCNTs 6) Spektroelektrochemie
Graphite Forms of carbon
Graphene Forms of carbon
Graphene applications Ultrathin conductive films Graphene Used To Create World's Smallest ttransistor 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 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 Graphene 0.70 per μm 2 700 000 per mm 2
Graphene Forms of carbon
Graphene Forms of carbon
Chemical vapor deposition (CVD) Cu or Ni Quartz substrate boat Quartz tube Electric furnace Ar H2/CH4 or Ar/H 2 Ethanol tank Hot 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 60 acc. to IUPAC: Hentriacontacyclo[29.29.0.0. 2,14.0 3,12.0 4,59.0 5,10.0 6,58.0 7,55.0 8,53.0 9,21.0 11,20.0 13,18.0 15,30.0 16,28.0 17,25.0 19,24.0 22,52.0 2 3.50.0 26,49.0 27,47.0 29,45.0 32,44.0 33,60.0 34,57.0 35,43.0 36,56.0 37,41. 0 38,54.0 39,51.0 40,48.0 42,46 ]hexaconta- 1,3,5(10),6,8,11,13(18),14,16,19,21,23,25,27,29(45), 11 13(18) 14 16 19 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 gallery C 60 C 70 C 76 C 78 C 82 La@C 84 Sc 3 N@C 84 Endohedral Fullerene M@C 84
Carbon nanotubes
Rolling of SWCNT -zag zigarm-chair
Carbon nanotubes (CNT) SWCNT MWCNT DW CNT
SWCNT Bundles
SWCNT Bundles
Single wall carbon nanotubes (SWCNT) Size: Nanostructures with dimensions of ~1 nm diameter (~10 atoms around the cylinder) Physics: 1D density of electronic states. Single molecule Raman spectroscopy, luminescence, and transport properties. Electronic Properties: Can be either metallic or semiconducting depending on diameter and orientation of the hexagons Mechanical Properties: Very high strength. Good properties on both compression and extension.
Carbon nanotubes (CNT) mechanical properties Fiber material Specific E Strength Strain at break density (TPa) (GPa) (%) CNT 1.3-2 1 10-60 10 HS Steel 78 7.8 02 0.2 41 4.1 <10 CF-PAN 1.7-2 0.2-0.6 1.7-5 0.3-2.4 Kevlar 49 1.4 0.13 3.6-4.1 2.8
Carbon nanotubes (CNT) mechanical properties
Single nanotube transistor Distinctive metallic and semiconducting transport properties IBM Ballistic transport Extremely high current carrying capacity
Chemical vapor deposition (CVD) Quartz boat Quartz tube Electric furnace Ar or Ar/H 2 Ethanol tank Hot bath
Quality vs. price
Commercial 90% carbon purity 500 $ /g Purity of carbon nanotubes
SWCNT from graphene A a 1 6 a 1 a 2 5a 2 C h B Chiral vector: C h = na 6a 1 + ma 5a 2 a 1, a 2. Unit vectors of 2D-hexagonal lattice (6,5)
SWCNT from graphene 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 semicond.
Density of states (DOS) in SWCNT Van Hove singularities 2.5 2.5 2.0 1.5 1.0 0.5 (5,5) Armchair tubes (5,5) 5) 2.0 1.5 1.0 0.5 Zig-zag tubes (5,0) om/ev) (states/c-at DOS 0.0 2.5 2.0 1.5 1.0 0.5 2.5-3 -2-1 0 1 2 3 (10,10) -3-2 -1 0 1 2 3 0.0-3 -2-1 0 1 2 3 2.5 20 2.0 (10,0) 1.5 1.0 0.5 0.0-3 -2-1 0 1 2 3 2.5 DOS (states/c-at tom/ev) 2.0 2.0 1.5 10 1.0 (20,20) 1.5 10 1.0 (20,0) 0.5 0.5 0.0 0.0-3 -2-1 0 1 2 3 Energy, ev -3-2 -1 0 1 2 3 Energy, ev
ΔE of singularities vs. diameter of SWCNT ( Kataura graph ) 2χ0 ac C ΔE = SWCNT d d 1.1-1.4 nm (10,10) Ene ergy, ev 1.5 1.0 0.5 0.0-0.5 Energy Sepa aration (ev) 1.8 1.2 0.7 v 2 m c m 2 v s3 c 3 s v m1 c 1 m Energy, ev -1.0-1.5 1.5 1.0 DOS v s2 c s 2 v s1 c s 1 (11,9) 0.5 0.0-0.5 Nanotube diameter (nm) -1.0 (n, m) to (40,40) -1.5 DOS
Vis/NIR spectrum of SWCNT/ITO 0.5 hv Absorbance 0.4 0.3 0.2 v s1 c s 1 v s2 c s 2 v m1 1 c m 0.1 SWCNT ITO 0.0 0.5 1.0 1.5 Energy, ev 2.0 2.5 3.0
SWCNT Bundles
Sorting SWCNT
What is the Raman spectroscopy py about C. V. Raman
Resonance enhanced Raman spectroscopy Approximately 1 in 10 7 photons is inelastically scattered The signal is usally very weak 1) Use of lasers - intensive light 2) Resonance enhancement
Resonance enhanced Raman spectroscopy Virtual state E 1 V 0 Optical transition? E 0 V 1 E 0 V 0 Resonance enhanced spectra 10 2-10 4
Resonance Raman spectroscopy of SWCNT I = c ( E E iγ )( E + E E iγ ) L ii L ph ii 2 E L - laser photon energy E ii - optical transition energy E ph - phonon energy γ - damping constant Typical values for RBM E ph 0.02 ev γ 0.05 ev
Raman spectrum of SWCNT 1.83 ev 2.41 ev TG Raman int tensity, a. u. x 5 x 25 RBM D G 100 150 200 250 300 1300 1400 1500 Raman shift, cm -1 1600 2500 2600 2700 2800 Diameter = 234/ω RBM
Growth of CNT
Raman spectra of SWCNT, hv exc = 1.83 ev x 1.5 y, a.u. man intensity Bundle Ra 150 200 250 300 350 400 Raman shift, cm -1 1520 1560 1600 1640
Creation of defects in SWCNT RF Ar plasma Individual SWCNT Mask Substrate
Defective SWCNT x 30 Raman inte ensity, a.u. x10 3 D mode Pristine part Defective part 140 160 180 200 220 1300 1400 1500 Raman shift, cm -1 1600 2660 2680 2700 2720 Diameter = 234/ω RBM
Formation of fullerene peapod (C 60 @SWCNT) C 60 (g) FULLERENE PEAPOD Nanotube, optimum 1.36 nm
Dy 3 N@C 80 @SWCNT Dy 3 N@C 80 @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 Dy 3 N@C 80 @SWCNT hv exc = 1.91 ev y, a. u. intensity Raman Dy 3 N@C 80 @SWCNT SWCNT Dy 3 N@C 80 x 5 200 400 600 800 1000 1200 Raman shift, cm -1 1400 1600 1800
Double walled nanotubes RT C 60 @SWCNT 800 o C 1200 o C DWCNT 1000 o C 1200 o C S. Bandow et al., Chem. Phys. Lett. 337 (2001) 48
Raman spectra of dry DWCNT, hv exc = 1.83 ev Raman intens sity, a. u. OUTER TUBES INNER TUBES 100 150 200 250 300 Raman shift, cm -1 350 400
Double walled nanotubes from different peapod sources (The spectra are excited by 1.83 ev) C 60 -DWCNT C 70 -DWCNT C 78 -DWCNT Raman intensity, a. u. Raman intensity, a. u. Raman intensity, a. u. 240 260 280 300 320 Raman shift, cm -1 340 360 240 260 280 Raman 300 shift, cm 320-1 340 360 240 260 280 300 320 Raman shift, cm -1 340 360 C 84 -DWCNT La@C 82 -DWCNT Dy 3 N@C 80 -DWCNT Raman in ntensity, a. u. Raman in ntensity, a. u. Raman in ntensity, a. u. 240 260 280 300 320 Raman shift, cm -1 340 360 240 260 280 300 320 340 Raman shift, cm -1 360 240 260 280 300 320 Raman shift, cm -1 340 360
In-situ spectroelectrochemistry The change of potential The change of electronic state The change of spectra Methods EPR UV-Vis-NIR Vis Raman FTIR Materials conducting polymers monomers, oligomers fullerenes CNT peapods
Cat2 An1 OCP Cat1 An2 In-situ electrochemical doping of SWCNT anodic/cathodic= extraction/insertion of e - Fermi level Fermi level Fermi level Fermi level Fermi level Fermi level Electrode
Vis-NIR spectra on ITO electrode of SWCNT (0.22 M LiClO 4 + acetonitrile) RE 0.50 Energy, ev 1.5 1.0 CE WE 0.45 0.5 0.0 0.40-0.5 hv bsorbance (A) 0.35-1.0-1.5 DOS A 0.30 Energy, ev 1.5 1.0 0.25 sample ITO 0.0 0.20 0.5 1.0 1.5 2.0 2.5 Energy, ev 3.0 3.5 4.0 0.5-0.5-1.0-1.5 E = 0.0V 0.2V 0.4V 0.6V 0.8V 1.0V 1.2V 1.4V 1.6V DOS
Raman spectra of SWCNT, hv exc = 2.54 ev (0.2 M LiClO 4 + acetonitrile) I = c ( E E iγ )( E + E E iγ ) L ii L ph ii 2 + 1.25 V Spectroelectrochemical cell x40 RE (Ag/AgCl) Pyrex window N -outlet 2 N 2 -inlet CE (Pt) Electrolyte solution -1.75 V an intens ity, a. u. Ram y, a. u. Raman intensity (vs. Fc/Fc + ) WE 140 160 180 200 220 240 1520 1560 1600 1640 Raman shift, cm -1
Raman spectra of DWCNT, hv exc = 1.83 ev (0.2 M LiClO 4 + acetonitrile) 1.5 V 1.2 V 0.9 V Raman inten nsity, a. u. 0.6 V 0.3 V 0V -0.3 V -0.6 V -0.9 V -1.2 V -1.5 V 100 150 200 250 Raman shift, cm -1 300 350 M. Kalbáč, L. Kavan, M. Zukalová and L. Dunsch: Adv. Funct. Mater., 15, 418-426, (2005).
THANK YOU!!! Financial support: GACR-DFG GA AV MSMT-USA Kontakt: martin.kalbac@jh-inst.cas.cz 1) M. Kalbac, L. Kavan, L. Dunsch and M.S. Dresselhaus. Nanoletters, 8, 1257-12641264 (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). 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).