hydrogen interaction with aromatic carbon systems...
TRANSCRIPT
Hydrogen interaction with
aromatic carbon systems
-Experimental techniques
Liv Hornekær
Aromatic carbon systems
Interstellar Catalysis
Graphene electronics
H chemisorbed on graphite
Eva Rauls
Jeloica & Sidis, Chem. Phys. Lett. 300, 157 (1999)
Sha et al, Surface Science 496, 318 (2002)
V
Tip
Z S
erv
o
STM – 2
Surface
Tunnel current I
Tip
V
Z S
erv
o
Surface
STM – 3
Tunnel current
Tip
V
X Servo
I
Tip movement
Computer
Z S
erv
o
Surface
STM – 4
STM
STM
κ=
STM Princip
Prøve Tantal-holder
Invar-top
Kvartskugle Wolfram tip
Isolator
Skannerør
Invar hus
Fjeder
Aksel InchWorm
Holder
Al-hus
5 mm
Aarhus STM
Prøve Tantal-holder
Invar-top
Kvartskugle Wolfram tip
Isolator
Skannerør
Invar hus
Fjeder
Aksel InchWorm
Holder
Al-hus
5 mm
Aarhus STM
5 mm
Typiske data for ScannerRør
Afbøjning i X og Y: 5 nm/V
Afbøjning i Z: 1.3 nm/V
Resonansfrekvens: 10 kHz
Skannerør
Aarhus STM
5 mm
1 nm
Forstørrelse
5000000 gange!
Aarhus STM
Typiske data for InchWorm
Skridtlængde: 1 nm
Hastighed: 0.01 mm/sek
10000 skridt/sek!
5 mm
InchWorm
Aarhus STM
The Inchworm
Center Rod – ZrO2
Clamp 1 Clamp 2
Center
Electrode
The Inchworm
Center Rod – ZrO2
Clamp 1 Clamp 2
Center
Electrode
The Inchworm
Center Rod – ZrO2
Clamp 1 Clamp 2
Center
Electrode
The Inchworm
Center Rod – ZrO2
Clamp 1 Clamp 2
Center
Electrode
The Inchworm
Center Rod – ZrO2
Clamp 1 Clamp 2
Center
Electrode
The Inchworm
Center Rod – ZrO2
Clamp 1 Clamp 2
Center
Electrode
The Inchworm
Center Rod – ZrO2
Clamp 1 Clamp 2
Center
Electrode
The Inchworm
Center Rod – ZrO2
Clamp 1 Clamp 2
Center
Electrode
STM and vibrations
STM tip: ~ 3 cm
Tip-sample: 0.1 nm
Eiffeltower 320 m
Eiffeltower – ground: 0.1 mm
Tip-sample vibration < 0.01 nm
Eiffeltower – ground vib. < 1 μm !!
STM and Vacuum
STM on graphite
2.46 Å
Hydrogen on graphite –
Monomers
Zeljko Sljivancanin
Vt~ -710mV, I
t~ -0.16nA
155 x 171 Å2 , 180 K
H-Dimers on graphite
A: Ortho–dimer
B: Para-dimer
103 x 114 Å2
Vt = 884 mV, I
t = 0.16 nA
Dimers: Theory vs. Experiment
Vt = 884 mV, I
t = 0.16 nA
Vt=0.9 V, LDOS=1x10
-6 (eV)
-1 Å
-3
e. f.
Ortho dimer Para dimer Hornekær et al.
Phys. Rev. Lett.
96, 156104
(2006)
Similar results for
ortho dimer:
Ferro et al. Chem.
Phys. Lett. 368,
609 (2003).
Y. Miura et al. J.
Appl. Phys. 93,
3395 (2003).
Dimer formation
Hornekær et al. Phys. Rev. Lett. 97, 186102 (2006)
Zero barrier sticking into para-dimer also found by:
Rougeau et al. Chem. Phys. Lett. 431, 135 (2006)
Kinetic Monte Carlo Simulations
-Experimental benchmarks
Cuppen & Hornekær, J. Chem. Phys. 128, 174707 (2008)
All D abstracted
at long H exposure
Thomas et al,
Surf. Sci. 602, 2311 (2008)
Ortho/para ratio ~0.15
Abstraction Mechanisms
J. Chem. Phys. 128, 174707 (2008)
Diffusion
Barrier to diffusion for an isolated H atom: 1.15 eV
Barrier to desorption for an isolated H atom: 0.9 eV
H-Dimers on graphite
A: Ortho–dimer
B: Para-dimer
103 x 114 Å2
Vt = 884 mV, I
t = 0.16 nA
n=1 => First order
desorption
490 K => 1.4 eV
580 K => 1.6 eV
dQ
dt = -k0 e
- / T Qn kB EB
Zecho et al, J. Chem. Phys. 117, 8486 (2002)
H2 formation on graphite - TDS
Dimers after Anneal
103 x 114 Å2
Vt = 884 mV, I
t = 0.19 nA
Vt = 884 mV, I
t = 0.36 nA
80 x 72 Å2
Recombination pathways
Hornekær et al. Phys. Rev. Lett. 96, 156104 (2006)
Ortho Meta Para
Ortho-dimer - high barrier
E. Rauls
Para-dimer - low barrier
E. Rauls
Recombination pathways
Hornekær et al. Phys. Rev. Lett. 96, 156104 (2006)
Ortho Meta Para
Measuring the kinetic energy of
formed molecules
Laser Induced
Thermal Desorption
(LITD)
Alexandrite Laser
760 nm
150 mJ/cm2
/ 400 mJ/cm2
150 ns pulse
Time of Flight Measurement
D
QMS
Laser
D2
Kinetic energy distribution
Baouche et al., J. Chem. Phys. 125, 084712 (2006 )
Atom detection - REMPI
REMPI
detector
LAAD
Laser
REMPI
Laser
2+1 REMPI
Frequency tripled
Nd:YAG pumped Dye laser
~202-210 nm
~0.5 mJ, d=0.1 mm spot
5 ns pulse, 0.1-0.2 cm-1
Atom: 1S1/2
-> 1S1/2
Molecules: X1S
g
+ X-> E,F
1Sg
+
Dv=0, DJ=0
v=0, J=2 and v=1, J=2
Atom desorption
Baouche et al., J. Chem. Phys. 131, 244707 (2009)
Desorption flux
Baouche et al., J. Chem. Phys. 131, 244707 (2009)
Kerwin & Jackson, JCP 128, 084702 (2008)
H on HOPG
High Coverage
Medium Coverage
80 x 72 Å2
171 x 155 Å2
Low Coverage
103 x 114 Å2
Vt~800mV, I
t~0.15-0.2nA
Preferential sticking and clustering
Diffusion
Barrier to diffusion for an isolated H atom: 1.15 eV
Eley Rideal - Abstraction
Sha et al. (2002)
Zecho et al. (2002)
Matinazzo & Tantardini (2006)
Morisset et al. (2004)
Jeloaica & Sidis (2001)
Meijer et al. (2001)
Bachellerie et al. (2007)
Thomas et al. (2008)
Random adsorption and cluster formation
171 x 155 Å2
In accord with LEED and UPS measurements:
Neumann et al. Appl. Phys. A 55, 489 (1992)
Guttler et al. Chem. Phys. Lett. 395, 171 (2004)
Large cluster formation also found in HREELS and DFT studies:
Allouche et al, JCP 123, 124701 (2005)
Trimer Configurations
Sljivancanin et al.,
PRB 83, 205426 (2011)
Vt = -1051 mV, I
t = -0.53 nA
High coverage
171 x 155 Å2
High Coverage
Vt = -1.05 V, I
t = -0.55 nA
80 x 72 Å2
Vt = -1.05 V, I
t = -0.18 nA,
171 x 155 Å2
Ferro et al., Chem. Phys. Lett.
478, 42 (2009) Hornekær et al., Chem. Phys. Lett. 446, 237 (2007)
525K anneal
RT
Status:
Astrochemistry: H2 formation on
graphitic grains possible under
PDR conditions - Good
Energy partitioning dependent on
small scale surface structure – smooth
surface ~1/3 into translation
Graphene electronics: No ordered
structures - Bad
Hydrogen induced band gap
opening
STM desorption of H
70 x 70 Å2
Vt = -1.25 V, I
t = -0.37 nA,
Templated H adsorption by a
SAM of CyA on graphite
A
B • Red = Oxygen
• Blue = Nitrogen
• Black = Carbon
• White = Hydrogen
100 Å
Vt = -1.25 V, I
t = -0.39 nA,
Formation of linear H
adsorbate structures
100 Å
Vt = -1.25 V, I
t = -0.37 nA,
30 Å
Vt = -1.25 V, I
t = -0.37 nA,
Formation of linear H
adsorbate structures
Model structure
30 Å
Vt = -1.25 V, I
t = -0.37 nA,
Dark areas between lines – local
band gap opening?
Would this work on graphene?
Graphene on SiC
30x30Å,
V= -0.41V,
I= -0.39nA
Bi-layer graphene
showing
triangular pattern
100x100Å, V= -0.41V, I= -0.36nA
step edge height 3.1Å
30x30Å,
V= -0.41V,
I= -0.38nA
Mono-layer graphene
showing
honeycomb structure
Hydrogen dose at 1600K, F=3x1012
atoms/cm2 s, t=5s
200x200Å, V= -0.245V, I= -0.26nA
H on graphene/SiC
Balog et al. JACS 131, 8741 (2009)
H on graphene/SiC
200x200Å, V= -0.36V, I= -0.32nA
Hydrogenation: T=1600K,
F=3x1012
atoms/cm2 s, t=90s
De-hydrogenation: Anneal to 800°C
Balog et al. JACS 131, 8741 (2009)
Graphene/Ir
Wavevector kx (Å-1)
STM of H/Graphene/Ir
Balog et al., Nat. Mat. 9, 315 (2010)
XPS:
M. L. Ng, R. Balog, L. Hornekær,
B. Preobrajenski, K. Schulte, N. A.
Vinogradov, and N. Mårtensson.
Adsorbate structures
Balog et al., Nat. Mat. 9, 315 (2010)
Global bandgap opening
Pedersen et al. PRL 100, (2008)
ARUPS of H/Graphene/Ir
– bandgap opening
Balog et al., Nat. Mat. 9, 315 (2010)
XPS-doping
80 meV 20 meV 20 meV
450 meV
BG=940mV
Band gap opening by patterned H adsorption
Balog et al., Nat. Mat. 9, 315 (2010)
STM of H/Graphene/Ir
Global bandgap opening
Thermal stability - TDS
Challenges
Chemical stability
Substrate
Generality of method
What is important – confinement, order/disorder
Mobility – shape of dispersion
Hydrogenation of
Graphene/Pt(100) - STM
5s, 300x300Å2
25s, 500x500Å2
1 min, 200x200Å2
Pt(100) - TDS
Hydrogenation of
Graphene/Pt(100) - STM
5s, 300x300Å2
25s, 500x500Å2
1 min, 200x200Å2
Conclusions – graphite/graphene
•High diffusion barrier prevents formation of ordered H
adsorbate structures on graphite
•Pre-pairing of H atoms on the surface => unusual desorption kinetics
•H2 formation under PDR conditions
•Hydrogen induced substrate interactions =>
increased binding – and in some cases
nano-patterning
•H nano-patterns on graphite =>
~1 eV band gap opening.
How is interstellar H2 produced ?
Hgas
+Hgas
H2
H + H + H
2
H + H + H
2
H-PAH interaction
Density Functional Theory (DFT) calculations
reveal low barrier routes to
H-PAH formation and PAH catalyzed H2 formation
Rauls and Hornekær, Astrophys. J. 679, 531 (2008)
H-PAH interaction
Rauls and Hornekær, Astrophys. J. 679, 531 (2008)
Density Functional Theory (DFT) calculations
reveal low barrier routes to
H-PAH formation and PAH catalyzed H2 formation
Experimental procedure
HPAH TDS/TPD
H-PAH formation
C24
H22
Hydrogenation: STM images
70 x 70 Å
Coronene Coronene exposed to D
Substrate: Cu(100)
H – aromatic carbon
Very reactive defect/edge sites
Basal plane: Coverage effects
Curvature effects
Substrate can play an active role
Low mobility in chemisorbed state
Outlook
Frame 1
Frame 2
Frame 3
In situ Hydrogen dosing
HPAH-UV/IR interaction
Graphene – deeper understanding
other substrates
HPAH – H beam energy
People involved
Richard Balog
Bjarke Jørgensen
Louis Nilsson
Saoud Baouche
Emil Friis
John Thrower
Arnd Baurichter
Victor Petrunin
Marco Bianchi
Emil Rienks
Philip Hofmann
Mie Andersen
Bjørk Hammer
Thomas G. Pedersen
Eva Rauls
Zeljko Sljivancanin
Alan Luntz
Erik Lægsgaard
Ivan Steensgaard
Flemming Besenbacher
Silvano Lizzit
Mattia Fanetti
Allessandro Baraldi
Rosanna Laciprete
Dept. Phys. and Astron. and iNANO, University of Aarhus
Funding
StG HPAH