graphene and graphenoids from molecules: engineering ...solid state physics hard excellent...
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Graphene and Graphenoids from Molecules: Engineering Carbon Nanomembranes
Armin Gölzhäuser
Universität Bielefeld
„Natural“ Carbon Nanomembranes
Graphene Solid state physics
Hard Excellent electronic properties
Top and bottom look alike ! Difficult to functionalize
Cell membrane Supramolecular Chemistry Soft Basic constituent of life Inside differs from Outside ! Functional by nature
Membrane Applications:
•Barrier (gases / liquids) •Filter (gases / liquids) •Separation of ions (batteries) •Medicine (dialysis) •Sensors / Actuator •Electronics (conductors, dielectrics) •Microscopy (transparent TEM support) •…….
Objective: Creating a molecular platform for the fabrication of tailored carbon nano membranes
A modular construction system for functional carbon nano membranes
A modular construction system for functional carbon nano membranes
physical & chemical
Molecules Solid substrates
Self-Assembled Monolayer (SAM)
Carbon Nanomembrane (CNM)
self-assembly
cross-linking by electron-beam
chemical processing
Electronics,Sensors, Medical, Filtration, Biotechnology, …
physical processing
Head group
Spacer
Terminal group
Amphiphilic organic molecules Head group : -SH, -OH, -SiCl3 ... Spacer : Aliphatic, Aromatic, ... Terminal group : -H, -COOH, -NO2, -NH2, -OH ... Coupling to substrates : Au, Ag, Si, SiO2, Fe, Ti, ITO, Cr, ...
S
NO2
H
S
H
Self-assembled monolayers (SAM)
SAM: •Molecularly ordered •Uniform thickness •Functional surface
Molecular precursors
S
NO2
H
S
NO2
H
with K. Müllen group, MPI Mainz, unpublished
Electron and Photon induced Chemical Control in SAMs
e-
e-
DEA
EUV
A. Turchanin, M. Schnietz, M. El-Desawy, H.H. Solak, Ch. David, A. Gölzhäuser, Small 3, 2114 (2007) A. Turchanin, D. Käfer, M. El-Desawy, Ch. Wöll, G. Witte, A. Gölzhäuser, Langmuir 25, 7372 (2009)
Cross-linking by electrons or EUV
~1 nm
Preparation of carbon nanomembrane (CNM)
dissolve substrate
dissolve substrate
Comparison of Membranes
•Molecularly thin (~1nm) •Homogeneous thickness •Large areas •Arbitrary size •Large area
Handling of Carbon nanomembrane
solid substrate holey substrate
1 nm thick Membrane on SiO/Si: Interference Contrast
1 nm membrane 300 nm SiO2 Si
200 µm
photograph optical micrograph
ChemPhysChem 11, 2331 (2010)
Large area multilayers by stacking of CNMs
C. T. Nottbohm, A. Turchanin, A. Beyer, R. Stosch,
A. Gölzhäuser, Small 7, 847 (2011)
100 µm
Large area Free-standing CNMs
Free-standing CNM on TEM grids, imaged by SEM and HIM ChemPhysChem 11, 2331 (2010)
Carbon Nanomembrane supports for TEM: Imaging of - Co nanoparticles (ca. 4 nm)
10 nm 10 nm 10 nm
1 nm CNM 10 nm carbon
Ultramicroscopy 108, 885 (2008)
Tool
s fo
r ele
ctro
n m
icro
scop
y
Carbon Nanomembrane supports for TEM: Imaging of - gold clusters (1-2 nm)
Tool
s fo
r ele
ctro
n m
icro
scop
y
Ultramicroscopy 108, 885 (2008) (Joachim Mayer, RWTH Aachen)
1 nm CNM 10 nm carbon
(D. Gerthsen, KIT) Tool
s fo
r ele
ctro
n m
icro
scop
y Carbon Nanomembrane supports for TEM:
Imaging of single Pt atoms and clusters
Membrane mechanics: Bulge Tests
μm20
p=0
μm20
p=750Pa
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
0
1
2
3
4
5
Pres
sure
(KPa
)
Deflection (um)
Test cycle 1 (0-->780Pa)Test cycle 2 (0-->1350Pa)Test cycle 3 (0-->2262Pa)Test cycle 4 (0-->5050Pa)
ha
tha
EtPPP 203
421 )1(σ
ν+
−=+=
E = 10.0 GPa σ0 = 40.0 MPa
J.J.Vlassak and W.D. Nix, J. Mater. Res. 7 (1992) 3242
t=1.5nm: thickness v=0.35: Poisson’s ratio E=Young’s modulus σ0 = residual stress a: half-width b/a: aspect ratio
Thermal Properties of Carbon Nanomembranes Heating of cross-linked biphenylthiol
CNM on SiO2-Si in UHV up to 1200K
Appl. Phys. Lett. 90, 053102 (2007) Langmuir 25, 7372 (2009)
SAM desorbs at ~450K CNM stable above ~1200K
Electrical conductivity of nanomembrane:
⇒Nanomembrane conductive after annealing ⇒Tunable electrical resistance !!
Adv. Mater. 21, 1233 (2009)
1 layer graphene mechanical exfoliation Novoselov et al. Nature 438, 197 (2005)
1 layer chemically reduced graphene Gómez-Navarro et al. Nano. Lett . 7, 3499 (2007)
annealing temperature (K)
shee
t res
istiv
ity (
kΩ/s
q. a
t RT)
Transition to graphene
annealed at 1200 K
2 nm
non-annealed
A. Turchanin, D. Weber, M. Büenfeld, C. Kisielowski, M. Fistul, K. B. Efetov, T. Weimann, R. Stosch, J. Mayer, A. Gölzhäuser ACS Nano 5, 3896 (2011)
TEAM 0.5, 80 keV
Raman HR-TEM
Perf
orat
ing
and
func
tiona
lizin
g
carb
on n
anom
embr
anes
Transfer of Nanoribbons
10 µm line pattern
1 nm membrane 300 nm SiO2 Si
C. T. Nottbohm, A. Turchanin, A. Beyer, R. Stosch, A. Gölzhäuser, Small 7, 847 (2011)
Transfer of Nanoribbons
10 µm line pattern Two layers (≈90°)
2 nm membrane 1 nm membrane 300 nm SiO2 Si
C. T. Nottbohm, A. Turchanin, A. Beyer, R. Stosch, A. Gölzhäuser, Small 7, 847 (2011)
Transfer of Nanoribbons
10 µm line pattern Two layers (≈90°)
Three layers (≈60°)
C. T. Nottbohm, A. Turchanin, A. Beyer, R. Stosch, A. Gölzhäuser, Small 7, 847 (2011)
Small 23, 2651 (2009)
Perforated Nanolayers via EUV-Interference
Lithography
Chemically functionalized CNM
Helium Ion Micrograph
Adv. Mater. 12, 805 (2000); Small 3, 2114(2007) Chemical Lithography: electron induced cross-linking with NO2 to NH2 conversion
Polymer Carpets
I. Amin, M. Steenackers, N. Zhang, A. Beyer, X. Zhang, T. Pirzer, Th. Hugel, R. Jordan, A. Gölzhäuser, Small 6, 1623 (2010)
Patterned Polymer Carpets
I. Amin, M. Steenackers, N. Zhang, R. Schubel, A. Beyer, A. Gölzhäuser, R. Jordan, Small 7, 683 (2011)
Patterned Polymer Carpets
I. Amin et al, Small 7, 683 (2011)
Bifunctional Nanomembranes: „Janus Membranes“
Use the directionality of the cross-linked SAM to create bifunctional “Janus” CNMs
SAMs have 2 functional groups!
accesible for chemistry
buried S
NO2
H
accesible for chemistry
Tetramethylrhodamine isothiocyanate (TMR)
ATTO647N
Bifunctional Nanolayers: Fluorescent dye molecules on top and bottom of „Janus Membrane“
Angew. Chem. Intl. Ed. 49, 8493 (2010)
FRET
e-beam/EUV
lithography
o
=
tris-NTA functional immobilization of His6-taged 20S-Proteasome
Adv. Mater. 20, 471 (2008)
EG3
o o
o oH HS
o
Functional Immobilization of Proteins
e-
A modular construction system for functional carbon nano membranes
A modular construction system for functional carbon nano membranes
Carbon Nanomembranes • Made from molecules (SAMs) • 1 nm thick (freestanding or supported) • Tunable resistance • Tunable mechanical properties • Transition to graphene • Surface functionalization • Polymer carpets • Proteins • Nanosieves • Janus Membranes • Mod
Bielefeld group: Andrey Turchanin André Beyer Berthold Völkel Polina Angelova Xianghui Zhang Min Ai Nils Mellech Heiko Muzik Matthias Büenfeld Henning Vieker Nils Weber Alumni: Christoph Nottbohm Ishan Amin Mohamed El-Desawy Mark Schnietz Dirk Weber Zinkun Zheng
Acknowledgements: Graphenoid consortium: Klaus Müllen, Markus Klapper (MPI Mainz) Jürgen Rabe (HU Berlin) Collaborations: Harun H. Solak (Paul-Scherrer-Institut) Mike Heilemann, Markus Sauer (U Würzburg) Thomas Weimann (Physikalisch Technische Bundesanstalt) Wolfgang Eck, Michael Grunze (U Heidelberg) Robert Tampé (U Frankfurt) Christof Wöll (KIT) Dagmar Gerthsen, Holger Blank (KIT) Daniel Rhinow (MPI Frankfurt) Joachim Mayer (RWTH Aachen) Rainer Jordan, Ishan Amin (TU Dresden) Christian Kisielowski (NCEM Berkeley) www.physik.uni-bielefeld.de/pss