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with K. Müllen group, MPI Mainz, unpublished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