STM and Applications

MERVE AYVAZ
Boazii University
ChE 592

What is STM?
STM is a device that is used to produce atomic
resolution images.
The theory behind the STM is electron
tunneling between the tip and the sample.
Sample has to be conductor or semiconductor.
Tip does not touch to the sample, it is
ordinarily kept between 5 and 15 A away from
the sample.
The tip is attached to piezoelectric crystals
which, moves the tip on the sample with some
electronic feed back control.

Quantum Mechanical Tunneling

The electrons, that have particle and wave nature, are
free to move around the metal but cannot leave it.
When the cloud of electrons collides with the barrier,
part of the cloud may penetrate the barriers and appear
on the other side.
This process is called tunneling because the electron
does not have enough kinetic energy to travel over the
barrier, but is able to exist on the other side
It is as if the electron found a way to dig a tunnel
through the barrier.
A very small current will flow between a sharp metal
probe tip and the surface of an electrically conductive
material.

Bardeens Tunneling Theory

The tip and sample are sufficiently far apart
The bias (potential difference between the tip and the sample) is low enough.

Topography and Spectroscopy

STM characterization of size-selected V1, V2, VO, and

VO2 clusters on a TiO2
(110)-(11) surface at room temperature

Scott P. Price, Xiao Tong, Claron Ridge, Vladimir Shapovalov, Zhenpeng Hu, Paul
Kemper, Horia Metiu, Michael T. Bowers, Steven K. Buratto

Department of Chemistry and Biochemistry, University of California, Santa

Barbara, CA 93106-9510, USA

Surface Science 605 (2011)

Summary of Work

Ultra-high vacuum scanning tunneling microscopy (UHVSTM) is used to

investigate structure of V1, V2, VO and VO2 clusters deposited on rutile TiO2 (110)
by ion soft landing.
Investigated factors
Interaction of species with the TiO2 surface

Ultimate binding site

Balance configuration
Results
1. Vanadium atoms prefer to bind in the upper threefold hollow sites on the surface and
have a slight tendency to pair
2. Vanadium dimers bind to the surface oriented along the [001] direction exclusively
3. VO and VO2 clusters bind with the vanadium atom in the upper threefold hollow site
and with the oxygen atom bound to an adjacent fivefold coordinated Ti atom (5c-Ti)

Experiments
TiO2 Preparation

TiO2(110) samples were cleaned in UHV with several cycles of argon ion
bombardment (1 kV) and annealing (~1200 K for 10 s).
Sample cleanliness was verified by STM.
Samples were flashed to ~1000 K for several seconds to ensure that surface hydroxyls
were removed.
Cluster Preparation
Laser is focused onto a rotating, translating
vanadium rod, which generates a plasma of
ablated vanadium atoms.
A pulse of argon is introduced into the source,
resulting in plasma reactions that cause
vanadium and vanadium oxide cluster growth.
Seeding the argon expansion gas with 20%
oxygen yields an ion beam composed of VxOy+
ions, as shown in the mass spectrum.

Experiments

Deposition on the sample

Clusters are deposited on the TiO2(110) substrate focusing the ion beam and towards
the sample, which is housed in the UHV deposition chamber.
During deposition, the TiO2 sample is positively biased at a voltage equal to the
average ion kinetic energy that was measured on the detector.
This allows the clusters to be soft-landed with incident kinetic energy between 0
and 3 eV/atom.
STM Analysis
The actual cluster coverage is determined from analysis of the STM data at room
temperature.
Sample bias of +1.3 to +2.1 V and a constant tunneling current of 0.2 nA.
Most STM images were recorded within 20min to several hours following
deposition.
Samples were also imaged for several days after deposition with no significant
changes in the density or appearance of the clusters.

Results and Discussion

STM images recorded after depositing V1

Clean TiO2(110)-(11) surface shows an

array of alternating bright and dark stripes,
which correspond to rows of fivefold
coordinated Ti atoms (5c-Ti) and bridging
oxygen atoms, respectively.
The bright spots that appear on the rows are
vanadium atoms.
The V1 atoms bind to the TiO2 surface with
no preference.
They do not form large three-dimensional
clusters.
The low mobility and monodisperse size of
these clusters indicates that the monomers
do not sinter.
That was attributed to the high reactivity of
vanadium with the titania surface.

Results and Discussion

STM images recorded after depositing V1

The vanadium monomers appear slightly

elongated (~9 ) in the [001] direction and
are 1.7 in height, indicating that the
features are one atomic layer tall.
V1 atoms are positioned between the 5c-Ti
and bridging oxygen rows.
Both vanadium atoms are located in upper
threefold hollow sites and are separated by a
bridging oxygen.
The bonding of the vanadium to these three
oxygen atoms, coupled with DFT
calculations showing that the vanadium atom
transfers electrons to its neighboring oxygen
atoms, suggests that this electronic effect is
responsible for the observed elongation of
the vanadium clusters.

Results and Discussion

STM images recorded after depositing V1

Upon deposition of size-selected vanadium

monomer, a statistical analysis of 21 images
similar to that shown in Fig. exhibits a
distribution
where 45% of the features are isolated
monomers
55% of the features are pairs of atoms along

The vanadium monomers have a greater

tendency to pair along.
This is attributed to the mobility of the V
atoms due to their excess kinetic energy
(between 0 and 3 eV) upon impact with the
surface.

Results and Discussion

STM images recorded after depositing V2

Clusters are distributed evenly across the titania, with no preference

for a specific type of adsorption site.
The V2 clusters appear as ovals of length ~13 along and height of
1.7 .
The high-resolution image indicates that the V2 clusters are
symmetrically oriented along a bridging oxygen rows.
The deposited V2 cluster is completely different than the two atom
clusters that form after deposition of size-selected V1.
V1 and V2 species bind differently to the surface.

Results and Discussion

STM images recorded after depositing VO

VO binds to the TiO2 surface without any

preference for step edge sites.
A higher resolution image indicates that
these clusters are positioned between the
titanium and bridging oxygen rows.
The asymmetric positioning of the cluster
suggests that the vanadium atom in the
VO cluster is bound to a threefold hollow
site, similar to the binding site for
vanadium atoms, and the oxygen atom
binds to a 5c-Ti atom making the cluster
planar.

Results and Discussion

STM images recorded after depositing VO

It is interesting to note that model is identical

to the lowest-energy DFT structure for VO on
TiO2.

The VO clusters have a length of 10 in the

[001] direction and are 1.7 tall.
Although the height of the VO cluster is the
same as that of a V monomer, the VO cluster is
slightly longer along [001].
The elongation of the VO cluster is attributed
to the binding of the oxygen atom to a 5c-Ti,
as shown in the model.

Results and Discussion

STM images recorded after depositing VO2

VO2 clusters deposited on titania are shown

as white spots.
The high-resolution image indicates that the
VO2 clusters are asymmetrically positioned
over the 5c-Ti rows.
The vanadium atom (green) is positioned in
the upper threefold hollow site and both
oxygen atoms (dark blue) are bound to
neighboring 5c-Ti atoms.
The VO2 cluster is 1.7 tall and 14 long
in the [001] direction.
The degree of elongation along [001] of VO2
clusters on TiO2(110) is much greater than
the VO clusters.
This structure is only 0.25 eV lower in
energy than that presented in the DFT
model.

Conclusion

Preferred adsorption sites of V1, V2, VO, and VO2 clusters are determined by using
STM.
V1, VO, and VO2 clusters are centered asymmetrically over the 5c-Ti rows and have
varying lengths along the [001] direction.
V2 clusters appear symmetrically positioned over the bridging oxygen row.
Comparison of the STM results to DFT calculations determined an atomistic model for
these structures.

Direct interactions between metal nanoparticles

and support: STM studies of Pd on TiO2
(1 1 0)

Michael Bowker *, Elodie Fourre

Wolfson Nanoscience Laboratory, School of Chemistry, Cardiff University, Wales, UK

Applied Surface Science 254 (2008)

Summary of Work

Ultra-nanoparticulate model catalysts of Pd had fabricated on TiO 2 (1 1 0) using metal

vapour deposition (MVD) to form particles in the size range 150 nm.
That was imaged at very high spatial resolution (and in some cases at atomic resolution)
using scanning tunnelling microscopy (STM).
Investigated Parameters
The atomic level mechanism responsible for certain phenomena in catalysis.
Spillover and the so-called strong metalsupport interaction (SMSI) effect.
Results
Oxygen spillover from Pd particles to the titania support occurs due to the fast adsorption
of oxygen on Pd compared with titania.
Ti layers are partially oxidised and form very well defined structures of two main types
a rectangular lattice and hexagonal unit cells of large dimension.
These layers passivate the surface for the adsorption of CO.

Parameters Affecting Catalytic Efficiency

Fabrication of Model Catalysts

Single crystals of titania are used and metal nanoparticles are fabricated onto them by
either evaporation (metal vapour deposition, MVD) or by chemical deposition (metalorganic chemical vapour deposition, MOCVD).

The support must be conductive and vacuum-annealed titania has reasonably good
conductivity.

The other approach is theinverse catalyst methodology, that is, the deposition of thin
layers of support onto a metal substrate; metal nanoparticles may be deposited onto this
layer in the same ways as described above.

Fabrication of Model Catalysts

Pd nanoparticles deposited onto TiO2(1 1 0).

4 nm in diameter particles, have fairly well defined dispersion and
the particle size distribution is rather narrow.
The particle size can be controlled to some degree by varying the
anneal temperature of the layer.
Sintering of the particles (reduction in number, density, increase of
average size) begins to occur at >600 K.
Atomic resolution on such small particles is not possible because the
curvature is similar to that of the tip itself and the response of the two
is convoluted together.
In order to carry out atomic resolution studies films or flat
nanoparticles are needed. Then, by annealing thicker layers of
deposited metal can be formed.

Spillover observed directly

The spillover of oxygen from Pd nanoparticles is seen

as a region around the nanoparticles.

The extent and nature of this spillover is strongly

dependent on the temperature of the experiment.

The spillover results in the creation of new layers of

titania around the particle, which eventually bury the
particle.

This occurs because Ti3+ is present in the sample.

Before
Oxygen
treatment

During
exposure
to oxygen

After further
The new layers of titania at the surface are formed by oxygen with
diffusion of these interstitials to the surface, which are near complete
then oxidised when impacted by gas phase oxygen
Encapsulation
molecules.
of the particle.

Atomic resolution of the SMSI structures

Clean TiO2(1 1 0), showing mainly the (1x1) structure with some (1x2), 66 eV beam
energy.

Low temperature annealing after Pd deposition, LEED shows that such structures are
mainly single crystals of Pd in nanoparticle form, with the (1 1 1) plane parallel to the
titania surface.

Much more complex LEED patterns are seen after high-temperature annealing

LEED Pattern

pure titania

600 K

800 K

Atomic resolution of the SMSI structures

STM images of two different regions of a Pd film on TiO2

(1 1 0) at >800 K.
centrosymmetric hexagonal wagon wheel structure
rectangular unit cell, zig-zag structure

When this layer is analysed by XPS, Ti at the surface of the

Pd appears in the +2 state and associated with some
oxygen.

The surface layer is some kind of intermetallic/alloy metal

-Ti structure, or whether it is simply a titanium oxide
surface layer covering the metal.

Atomic resolution of the SMSI structures

Treatment in oxygen at these and higher temperatures leads to the net spillover of
oxygen to the adjacent oxide lattice.
Models to explain this behavior:
It is simply oxygen which spills off the Pd. This spillover oxygen then traps Ti3+
species at the periphery of the metal nanoparticle and grows new layers of TiO 2
adjacent to it.
The Ti3+ diffuses through the metal particle first, decorates the surface of the particle,
probably initially as metal atoms at low temperature, but is quickly oxidised through
low oxidation states to finally spill off the particle onto the adjacent support as TiO 2.

Conclusion

The resulting surface has been shown to be a complex function of thermal treatment and
redox potential in the gas phase.

Vacuum is effectively a reducing environment because loss of oxygen can occur by

desorption from the surface during annealing.

Under such conditions new layers of titanium oxide can form at the surface of the metal
nanoparticles.

In oxidising environments spillover of oxygen can occur from the reactive Pd centres to the
surrounding oxide, providing the oxide is already in a reduced state.

Catalytic oxidation of graphite by mass-selected

ruthenium nanoparticles

S. Murphy, R.M. Nielsen, C. Strebel, M. Johansson, J.H. Nielsen *

Center for Individual Nanoparticle Functionality (CINF), Department of Physics,

Technical University of Denmark, 2800 Kongens Lyngby, Denmark

CA R B O N 4 9 ( 2 0 1 1 )

Summary of Work

The catalytic oxidation of graphite by mass-selected Ru nanoparticles was studied by

using the scanning tunneling microscopy and temperature programmed oxidation
methods.
Channeling by the nanoparticles was observed on the highly-oriented pyrolytic graphite
(HOPG) basal surface at temperatures above 750 C.
Ar+ ion bombardment was used to create layers of disordered carbon of various depths
on the HOPG surface.
Investigated Parameters
Depths of carbon layers
Channeling propagation rate
Results
Larger nanoparticles creates higher channel propagation rate in the carbon layer.
The depth of the interface determined whether the nanoparticles etched paths parallel or
perpendicular to the surface.
Sputtered surfaces undergoing gasification at much lower temperatures than the
unsputtered surface.

Experiments

The experiments were performed in a multichamber ultrahigh vacuum (UHV) system

with a base pressure in the low 10-11 mbar region.
HOPG substrates (SPI-1, 7 mm7mm 0.5 mm) were cleaved in air and put in radiative
heater about 700 C.
The influence of the degree of graphitisation of the support on the oxidation behaviour
was investigated by pre-sputtering the HOPG surfaces with 500 eV Ar+ ions.
Pre-formed mass-selected Ru particles were soft-landed onto the HOPG substrates at
room temperature using an inert gas-aggregation source.
The particles are formed by gas-phase condensation from a flux of Ru atoms that are
sputtered from a 99.99% pure Ru target using a magnetron sputter source (B).
The cooled argon gas thermalises the sputtered Ru atoms so that they condense into
clusters, which further coalesce to form nanoparticles.

Experiments

Ruthenium nanoparticles are applied as a beam to the substrate.

The substrate is placed at a small positive bias (36 V) so that negatively charged
nanoparticles are soft-landed onto the surface.
Ion scattering spectroscopy (ISS) measurements were used to confirm the surface
cleanliness of the deposited particles.
TPO experiments were performed by backfilling the UHV chamber with high purity O 2.
The sample temperature was ramped at a rate of 1 C/s in the oxygen atmosphere.
The local gas composition evolved at the surface during the temperature ramp was
monitored using a mass spectrometer.
STM was performed at room temperature in constant current mode.
SEM and TEM analysis of the nanoparticles.

Results

Mass-selected Ru nanoparticles

Approximately 10% of the surface is

covered by nanoparticles after deposition
of 8.4 nm Ru nanoparticles onto a HOPG
surface that had been sputtered for 30 s.

The ISS shows a ruthenium peak at 865

eV and a broad carbon peak at around
300 eV.

Degree of cleanliness of the as-deposited

nanoparticles is high beacouse only
carbon and Ru picks are observed.

Results

Mass-selected Ru nanoparticles

A STM image of Ru nanoparticles deposited onto a

HOPG surface.
1040% of the surface was covered by nanoparticles.
The nanoparticles generally appear round in the STM
that are larger than around 8 nm.
The mean nanoparticle diameter measured by STM is
overestimated due to tip convolution effects.
Several of these particle height distributions are shown
in graph.

the diameter
2 nm to 16 nm.

Results

Mass-selected Ru nanoparticles

TEM images shows that the nanoparticles are not homogeneous.

They display a range of different polymorphs especially for larger nanoparticles.

Good agreement was obtained between the particle diameter distributions measured by
TEM and height distribution in STM.
6 nm

12 nm

16 nm

Results

Temperature programmed oxidation

When TPO measurements were performed on

HOPG surfaces without nanoparticles the CO
background did not rise, indicating that the
oxidation process is catalysed by the Ru
nanoparticles.

TPO measurements were performed to

investigate the support oxidation
process.
These were performed by heating
linearly to 770 C in 106 mbar O2.
CO, CO2 and O2 signals measured
above the sample surface during
oxidation of a sputtered HOPG surface
15% covered by 2.3 nm Ru
nanoparticles.
The CO signal continues to rise for
some temperature interval above Ti
(ignition temp.), before reaching a peak
value at Tp.

Results

Influence of support graphitisation

STM images of these surfaces show significant

modification after catalysed oxidation.
Figure shows the nanoparticles deposited on an
unsputtered HOPG surface after oxidation.
The nanoparticles have sintered into large hexagonal
islands.
The mean height of these nanoparticles is of the order of
8.0 nm.
These channels are generally initiated from substrate step
edges.
The depth of the channels is uniformly 0.3 nm, their
lateral width depends on the lateral dimensions of the
particle at which the channel terminates.

Results

Influence of support graphitisation

Figures show the effect of catalysed oxidation on a HOPG

surface with 500 eV Ar+ ions.

First one has been sputtered for 2 min.

The surface is decorated with well-oriented etch channels.
Channels are oriented by 60o with respect to one another
and they are 0.32.4 nm deep.
Second one sputtered for 15 min.
The surface is randomly etched with around ten layers of
the surface exposed.
The deepest channels are around 3 nm deep.

Results

Influence of support graphitisation

Final one has been sputtered for 60 min

It is difficult to discern any Ru particles on the

surface.

The density of etch channels is much lower

than that observed in one sputtered for 15 min.

The depth of the largest channels is in the range

of 45 nm.

Conclusion

Ar+ ion bombardment can be used to create a layer of disordered carbon with
controlled thickness on the HOPG surface.

The etch channels are highly directional when the nanoparticles are in contact with the
graphite basal plane.

The gasification temperature depends on the degree of graphitisation of the support.

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