Dr.

Bencan Tang PMB436

[email protected]

H82INC: Interfacial Chemistry

Lecture 2B – Surface Science Studies
Studying Solid Surfaces

How do we study surfaces?

Reality is made of surfaces. We see, touch, taste, smell and hear via
surfaces.
Studying Solid Surfaces
Why do we need to study surfaces?
A full undersanding of the behaviour of the surface/interface at the
molecular level, which will allow us to explain, and then predict its
behaviour.
•What type of atoms are present and at what concentration?
•Where are they located and what are the bond lengths and angles?
•How strong is the surface bond and does it affect reactivity?

Surfaces at atomic/molecular level

Gas Collisions with a Surface
Under normal conditions, a surface exposed to a gas is constantly bombarded
with molecules and a freshly prepared surface is covered very quickly. Just how
quickly can be estimated using the kinetic model of gases and the expression
for the collision flux:

(Atkins & dePaula p. 911)

Ultra High Vacuum
• Ultra high vacuum is required for most surface science
experiments

• To enable atomically clean surfaces to be prepared for study,

and such surfaces to be maintained in a contamination-free
state for the duration of the experiment

• To permit the use of low energy electron and ion-

based experimental techniques without interferences
from gas phase scattering
Studying Solid Surfaces
Surface experiments almost always have three steps

1. Cleaning methods
1) Heat the sample to a sufficiently high temperature that all
the contaminants on the surface desorb off it. e.g. Used for Tungsten,
heat it to 2500 K
Problem: sample bonding needs to be stronger than sample-contaminant
bonding, to avoid the sample just evaporating.
Not a general method.
Studying Solid Surfaces
1. Cleaning methods
2) Argon ion bombardment.
Bombard surface with argon ions with a kinetic energy of 200-10,000 eV.
Surface chemical bonds are about 5 eV, so each argon ion can “sputter”
(knock off into the vacuum) dozens of surface atoms (contaminant and
sample atoms). The surface is then clean, but very disordered and
damaged, so you have to heat the sample to about half its melting point
so that the surface atoms re-arrange themselves back to a regular
crystalline structure.
Good general methods.
3) There are various specific methods which are used for particular
surfaces. For example, you can chemically clean some semiconductor
surfaces by exploring them to a beam of oxygen atoms, which oxides
surface carbonaceous contaminants to carbon monoxide and carbon
dioxide, which then leave the surface.
Studying Solid Surfaces
2. Preparing the Surfaces
Gas Adsorption
Expose the clean surface to a few Langmuirs of a particular gas (e.g. chlorine, ammonia,
ethene etc.). The gas sticks to the surface and then you study it.
Evaporation
Evaporate elemental species or molecules from small heated ovens. e.g. with a clean Si(100)
surface one can grow an artificial layer of GaAs on it by adsorbing a layer of Ga then a layer
of As by opening/ closing shutters in front of the Ga and As sources using a computer. The
epitaxial layer of GaAs formed can have very different properties to bulk GaAs. Or evaporate
glycine (at 100˚C) to deposit a layer of amino acid on a solid surface.
Self assembly from solution
For surfaces that stay clean in air (e.g. gold), drop the clean surface into a beaker of solvent
containing dissolved adsorbate (e.g. a thiol, R-SH). The thiol reacts with the gold surface to
form a monolayer of gold thiolate species, Au-S-R. The sample is removed from solution,
rinsed and then inserted into a UHV chamber for analysis.
There are also other methods of forming surfaces
Studying Solid Surfaces
3. Studying the Surface using Surface Techniques
i) Measure a big property on a small surface, e.g.
Either surface tension
ii) (ii) Measure a small property on a big surface,
e.g. powders

Probe a small area (1

Or cm2) on a single
surface using
something which is v.
surface sensitive, e.g.
atoms, molecules,
ions, electrons,
photons
Studying Solid Surfaces
Diffraction methods
•Low energy electron diffraction (LEED) (Atkins & dePaula p. 915)
Spectroscopic methods
•X-ray photoelectron spectroscopy (XPS) (Atkins & dePaula p. 912)
•Auger electron spectroscopy (AES) (Atkins & dePaula p. 914)
Scanning probe microscopy (SPM) methods
•Scanning tunneling microscopy (STM)
•Atomic force microscopy (AFM)

There are many other methods available for surface analyses but they
will not be covered here
Diffraction Methods - LEED
Low-Energy Electron Diffraction (LEED)

Is the sample surface regular?

Is anything adsorbed onto the surface? (overlayers)
Diffraction Methods - LEED
Useful for determining
ordered structures.
Electrons are backscattered
elastically from the sample
and analysed as a function of
angle.

Electrons are backscattered from an ordered array of atoms in

the solid, and emerge as discrete beams at certain angles.
The crystal structure of the surface layers, unit cell size and
symmetry is obtained from the position of the diffracted beams.
Diffraction Methods - LEED
As electrons in the energy range of 20-1000eV have very
short mean free path (0.5-1.5 nm) in solids, scattered
electrons reveal only the top few layers of solid.

Clean platinum surface After exposure to propyne

Spectroscopic Methods
Photoelectron spectroscopy
High energy X-ray or UV-visible radiation is fired at the sample
which causes electrons to be ejected from the sample and the
sample becomes ionized e−

XPS – Xray photoelectron spectroscopy (200-2000 eV)

Electrons are ejected from core molecular orbitals- Allows for the
elemental composition to be examined

UPS – UV photoelectron spectroscopy (10-45 eV)

Electrons are ejected from valence orbitals – Allows for bonding
to be studied. E = hv
Principle of XPS
X-ray photoelectron spectroscopy (XPS)
Principle of XPS
Spectroscopic Methods - XPS
Orbital Energy

• Overcomes the binding energy of the electron with its nucleus.

• Causes ejection of electrons from core levels in the atoms due
to photoelectric effect.
• To study the elemental composition, empirical formula, chemical
state and electronic state of the surface region of a sample.
Spectroscopic Methods - XPS

EK  hv  ( Eb   )
The kinetic energy of the ejected electron;
hν is the energy of the incidence photon,
Eb is the binding energy of the core level from
which the electron is ejected,
φ is the spectrometer work function.
The work function (φ eV) is the energy necessary to remove the least
tightly bound electron from the metal and place it at rest just outside the
metal.

XPS lines are identified by the shell from which the electron was ejected
(1s, 2s, 2p, etc)

The ejected photoelectron has kinetic energy which can be detected

The work function (φ eV) is the energy necessary to remove the least tightly
bound electron from the metal and place it at rest just outside the metal.
Example
Spectroscopic Methods - XPS

Each element has a characteristic binding

energy (Eb) associated with each core atomic
orbital
The exact binding energy of an electron
depends not only upon the level from which
photoemission is occurring, but also upon:
•Formal oxidation state of the atom

•The local chemical and physical environment

(see later slides)
Spectroscopic Methods - XPS

As energy levels for different atoms are unique, emission of

electrons from different atoms with different energy levels
measured
Peaks in an XPS spectrum are labeled according to the shell from
which the electron is removed in the ionisation process. Each
element has a unique set of binding energies.
Spectroscopic Methods - XPS

• Core orbitals of different energy can also be observed in

the spectrum
• Direct evidence for molecular orbitals!
Spectroscopic Methods - XPS
Ethyl trifluroacetate
4 separate chemical environments of
carbon can be distinguished!

Atoms of higher positive charge exhibit a

higher binding energy due to the extra
attraction between the electron at the
atom core
i.e. The carbon atom in the CF3 group has a
higher positive charge than the others due
to the electron withdrawing F atoms.
As a result the ejected electron has a
greater attraction to the nucleus and
therefore higher binding energy.
Spectroscopic Methods - AES
Auger Electron Spectroscopy (AES)

1923 – Pierre Auger

discovers a new process
Spectroscopic Methods - AES
Auger Electron Spectroscopy (AES)
1) Incident photon or electron can
eject a primary photoelectron at the 3) 3)
core level. (see XPS)
2) The resulting ion is excited and 1) 1)
relaxes as another electron in the
outer shells falls down
3) Energy released in step 2 can be
ejected in two ways
• Release of X-ray radiation 2) 2)
• Release of an electron
This is the Auger process.
Spectroscopic Methods - AES
Kinetic energy of the Auger electron is independent of the
energy of the incident photon/electron. Useful for identifying
Auger peaks in XPS spectra

EK  hv  Eb  
For XPS peaks

All elements other than H and He give Auger spectra.

Scanning Probe Microscopy
Scanning Probe Microscopy (SPM)

Binning and Roher. Nobel prize 1986

Scanning Probe Microscopy
Scanning Probe Microscopy (SPM)
• Involves scanning a tip along the surface and monitoring the
interaction.
• The tip is VERY sharp, ideally
ending in a single atom!
• The tip needs to be very accurately
controlled to 0.1 Å, this can be
done using piezoelectric devises
STM- is the tunnelling current between a metallic tip and a
conducting substrate which are very close proximity but not actually
in physical contact.
AFM- is the van der Waals force between the tip and the surface;
this may be either short range repulsive force (in contact-mode) or
the longer range attractive force (in non-contact mode).
Scanning Probe Microscopy
Scanning Probe Microscopy
Scanning Tunnelling Microscopy (STM)
• Electrons can tunnel between the
surface and the tip when a
potential is applied
• The probability of tunneling is
exponentially proportional to the
e−
distance and so very sensitive to
probe-surface separation
• 2 Modes,
Constant height
Constant current
• Surface needs to be conducting
STM Modes
Imaging of the surface topology may then be carried out in one of
two ways:
1) Constant height mode- a plot of tunneling current v’s tip
position therefore shows a periodic variation which matches that
of the surface structure.
2) Constant current mode- Normal way of imaging the surfaces is
to maintain the current constant whilst the tip is scanned across
the surface by adjusting the tip’s height above the surface so that
the tunneling current does not vary with the lateral tip position.

Constant height mode Constant current mode

STM Images
IBM STM Image Gallery.
The STM probe tip can also be used to move atoms around on a surface!

Iron on Copper (111)

Xenon on Nickel (110) Carbon Monoxide on Iron on Copper (111)

Platinum (111)
http://researcher.ibm.com/researcher/view_project_subpage.php?id=4251
Scanning Probe Microscopy
Atomic Force Microscopy (AFM)
An atomically sharp tip is scanned over a surface with feedback
mechanisms to maintain the tip at a constant force (to obtain height
information), or height (to obtain force information) above the sample.

This deflection is measures using a

diode laser
3 Modes,
• Contact mode – Can lead to surface
destruction
• Non contact mode – low resolution
Surface does not need to • Tapping mode – best of both
be conducting
AFM Images

Bacterial DNA plasmid

CD DVD
Studying Solid Surfaces
What do we want from Surface and Interface Studies?
A full understanding of the behavior of the surface/interface at the molecular
level, which will allow us to explain, and then predict its behavior.
Surface composition:
Diffraction methods
Chemical Species at Surfaces •Low energy electron diffraction (LEED)
Spectroscopic methods
•X-ray photoelectron spectroscopy (XPS)
Surface Structure •Auger electron spectroscopy (AES)
Scanning probe microscopy (SPM) methods
•Scanning tunneling microscopy (STM)
•Atomic force microscopy (AFM)
Surface Reactions
•Temperature programmed desportion
•Eley-Rideal & Langmuir-Hinshelwood mechanisms
Studying Solid Surfaces
What do we want from Surface and Interface Studies?
A full understanding of the behavior of the surface/interface at the molecular
level, which will allow us to explain, and then predict its behavior.
Surface composition:
Auger electron spectroscopy (AES)
Photoelectron Spectroscopy
Chemical Species at Surfaces
•Ultraviolet photoelectron spectroscopy Or
•Surface Vibrational Spectroscopy
Surface Structure
•Surface crystallography
•Scanning Tunnelling Microscopy
Surface Reactions
•Temperature programmed desportion
•Eley-Rideal & Langmuir-Hinshelwood mechanisms