SURFACE

ANALYTICAL
TECHNIQUES
(KIM4606)
DR HANIS MOHD YUSOFF
Annex Room N39

Chapter 1 1
Chapter 1 2
Chapter 1 3
Chapter 1 4
Chap 1: Introduction to Surface Analysis
Chap 2: Scanning Electron Microscopy
Chap 3: Transmission Electron Microscopy
Chap 4: Scanning Probe Microscopy
Chap 5: Auger Electron Spectroscopy
Chap 6: X-ray Diffraction

Chapter 1 5
 ASSESSMENTS

Test 1 15%
Test 2 15%
Quiz 1 5%
Quiz 2 5%
Assignment 20%
Final Exam 40%
Total 100%
LECTURE:
Tuesday (1 3 pm) BK4-02
Wednesday (1 2 pm) BK4-05

Chapter 1 6
 TEST 1 & 2

TEST 1 : 29th March 2016

TEST 2 : 24th May 2016

Any changes to these dates will be updated later

Chapter 1 7
 ASSIGNMENT

 You have to choose 2 or 3 journals (according to group

members) which discussed about the SURFACE ANALYSIS
TECHNIQUE on DIFFERENT SUBSTRATES.

 Then, make a report according the journals that you have

been reviewed and do the presentation.

 Submit the report during lecture in WEEK 12

 PRESENTATION will be held in WEEK 13 14 during

lecture.

Chapter 1 8
 ASSIGNMENT

 Find ONE surface analytical technique/ instrument

 Which describe or elaborate the characterization of different

materials (could be any material but should be more than 1
material)-----> BASED ON THE JOURNALS

 Basic principle of the technique/ instrumentation (NO COPY

AND PASTE FROM THE LECTURE NOTES)
PRESENTATION.

 Importance of the techniques/ instruments to the chosen

materials (referring to the review from the journals) in
particular applications.

Chapter 1 9
 TEM
LEED
Transmission electron microscopy

Low-energy ion scattering

SEM
Scanning electron microscopy

AED
Auger electron diffraction AFM
Atomic force microscopy

STM
NIS
Scanning tunneling microscopy
Chapter 1 Neutron inelastic scattering 10
 XPS
XRD
X-Ray photoelectron spectroscopy

X-Ray diffraction

AES
Auger electron spectroscopy

Chapter 1 11
Quiz 1 (Match those information)
What is/are the main information that you can
get from these instruments
SEM Defects
Elemental
TEM Phase
STM Structure
Image
XPS Electron emission spectroscopy
XRD Imaging techniques (microscopy)
Structure determination by diffraction and scattering

Chapter 1 12
Quiz 1 - answer
Imaging Structure Electron emission
techniques determination by spectroscopy
(microscopy) diffraction and
scattering

SEM XRD XPS

-Defects, image -Phase, defects, -elemental
TEM structure
-Phase, defects,
structure, image
STM
-Defects, image,
structure
Chapter 1 13
1)Basic principle of surface analysis

2)Importance of surface analysis

3)Instrumentation & techniques

4)Nanotechnology micro & nano structure

Chapter 1 14
1) Basic principle of surface analysis

What is surface?
The boundary layer between any two phases (solid,
liquid or gas/ vacuum)
Modern surface science:
- refers to the surface between solid in contact with
liquid or gas/ vacuum
- study of the nature of surfaces and their interaction
with the surrounding

Chapter 1 15
1) Basic principle of surface analysis (cont.)
Surface differs substantially from the interior of the
solid both in chemical composition & physical
properties
As such surface/ interface critical for many phenomena
and applications
Surface Chemistry: The study of physical & chemistry
phenomena that occur at the interface of the 2 phase
e.g. sol-liq interfaces, sol-gas interfaces, solid-vacuum
interfaces & liq-gas interfaces.
Chapter 1 16
1) Basic principle of surface analysis (cont.)

As dimension of solid becomes smaller (in

nanometer range), ratio of surface atoms
increases dramatically.
Example:
- Nanosized particle ~ most atoms are on the
surface.
- Bulk material ~ tiny fraction of the total solid
are on the surface.
Chapter 1 17
 As particles get smaller
their surface area to
volume ratio increases
dramatically more
surface is available for
interactions with other
substances around
them.
Chapter 1 18
1) Basic principle of surface analysis (cont.)

Surface structure
Rough consisting of high miller indexes planes

Chapter 1 19
1) Basic principle of surface analysis (cont.)

Surface sites & defects

Planar atoms
Edge atoms
Corner atoms
Adatoms
Kinks
Defect

Chapter 1 20
Good or bad?
Chapter 1 21
2) Importance of surface analysis

Why surface?
Electronic devices

Corrosion Catalysis
Surface
processes

Sensors

Energy conversion

Chapter 1 22
2) Importance of surface analysis (cont.)

Electronic Devices

Chapter 1 23
2) Importance of surface analysis (cont.)

Corrosion

Chapter 1 24
2) Importance of surface analysis (cont.)
Energy Conversion

Chapter 1 25
2) Importance of surface analysis (cont.)

Sensor

Catalyst

Chapter 1

26
2) Importance of surface analysis (cont.)

Why surface analysis so important?

Surface characterization is crucial for:

- Explaining many surface phenomena

- Improving the properties of solid materials

Chapter 1 27
3) Instrumentation & Techniques (cont.)

Surface Sensitivity & Specificity

Two major difficulties in surface studies are:

1. Absolute number of atoms in surface is small

(sensitivity problem)

2. Ratio of surface atoms to bulk atoms is small

(specificity problem)

Chapter 1 28
3) Instrumentation & Techniques (cont.)

1. Absolute number of atoms in surface is small

(sensitivity problem)
Typical single crystal surface of 1 cm2 area contains
~1015 atoms/ 10-9 moles
Therefore the probe should be:
 1 mm2
 Sensitivity 1% for monolayer (10-11 moles).
 Need analytical techniques with picomolar.
(10-12 moles) detection limits.
 OR to detect the presence of impurity atoms
present at the 1 % level, a technique must be
sensitive to ca. 1013 atoms.
Chapter 1 29
3) Instrumentation & Techniques (cont.)

2. Ratio of surface atoms to bulk atoms is small

(specificity problem)

Typical surface: bulk atom ratio in solid ~ 10-7 -

10-8 depending on surface structure.

Need to be able to separate surface signal from

bulk signal.

Chapter 1 30
3) Instrumentation & Techniques (cont.)

Surface signal is distinguishable from the

comparable bulk signal ~ detection system has
sufficient dynamic range to detect very small
signals in the presence of neighboring large
signals.

Bulk signal is small compared to the surface

signal ~ vast majority of detected signal comes
from the surface region of the sample.

Chapter 1 31
3) Instrumentation & Techniques (cont.)

Chemistry & physical properties of surface depend on

its electronic structure, which in turn a function of nature
of atoms comprising surface & their spatial distribution.

Surface consist of a mixture of flat regions (terraces)

and defects (steps, kinks, point defects), with different
distribution of atoms and hence electronic properties at
these surface sites.

Each surface site exhibits its own chemistry & physical

response ~ impossible to investigate real surface
reliably/ reproducibly at atomic level.

Chapter 1 32
3) Instrumentation & Techniques (cont.)

Surface Science Approach

Necessary to define precisely chemical & structural

state of surface under investigation in order to
extract atomic level information.

Most simplified systems: well defined single crystal

surfaces with high ratio of terrace to defect sites.

Chapter 1 33
3) Instrumentation & Techniques (cont.)

Greater complexity can be introduced into system by

adding controlled amounts of surface defects or
coverage of chemically distinguishable adsorbate
atoms & molecules.

Once model system has been established, a range

of experimental surface techniques can be used to
analyze the surface.

Chapter 1 34
3) Instrumentation & Techniques (cont.)

What information do we need?

Surface composition
- What elements are present?

Surface geometry
- arrangement of atoms
- adsorption sites
- bond lengths
- bond angles

Chapter 1 35
3) Instrumentation & Techniques (cont.)

Chemical bonds at surfaces

- bond making & breaking
- bond order
- vibrational properties

Chapter 1 36
3) Instrumentation & Techniques (cont.)
General aspects of surface analysis

Problem: surface sensitivity

~ 1015 atoms at surface

Solution: use particles

Probe particles Analyzed particles

Electrons 1 eV ~ 15 keV Electrons
Photons IR, X-Ray etc Photons
Ions 1 keV He+ Ions
Atoms supersonic He Atoms

surface

Chapter 1 37
3) Instrumentation & Techniques (cont.)

Surface analytical techniques

Modern surface analytical techniques are

characterized by a beam in/ beam out or probe
measure approach.

Incident beam (beam in) interacts with surface

layer.

Output beam (beam out) carrying the measured

surface information will be analyzed.

Chapter 1 38
3) Instrumentation & Techniques (cont.)

Beams may consist of electrons, photons,

ions, atoms or molecules

Chapter 1 39
3) Instrumentation & Techniques (cont.)

Two major instrumentation techniques for surface

analysis:
1. Surface spectroscopy
Identifying the surface chemical species &
determining the concentrations.
Providing both qualitative & quantitative
information about the composition of
surface layer.
E.g. X-ray photoelectron spectroscopy
(XPS) & Auger electron spectroscopy
(AES).
Chapter 1 40
3) Instrumentation & Techniques (cont.)

2. Surface microscopy
Imaging the surface & determining the
morphology, atomic crystalline structure, &
other physical properties & features at
different size scale (nano to micrometer).
3D surface structure with high resolution.
E.g. Scanning electron microscope (SEM)
and scanning tunneling microscope (STM)

Chapter 1 41
3) Instrumentation & Techniques (cont.)

Chapter 1 42
 Recall

What is the two major difficulties in surface

studies?
Sensitivity problem (absolute number in
surface is small)
Specificity problem (ratio of surface atoms to
bulk is small)

Chapter 1 43
4) Nanotechnology micro & nano structure

Where are we???

1.4 Gm (109m)

12756 km (107m)

Chapter 1 44
4) Nanotechnology micro & nano structure

Moon: 3476 km (106m)

? 8.8 km (103m)

Earth: 12756 km (107m)

Chapter 1 45
4) Nanotechnology micro & nano structure

?
1.47 hectometer (102m)
Mount Everest
8.8 km (103m)

Chapter 1 46
4) Nanotechnology micro & nano structure

?
1.7 m (100m)

Pyramid of Giza Blue whale

1.47 hectometer (102m) 3.3 decameter (101m)

Chapter 1 47
4) Nanotechnology micro & nano structure

?
5 mm (103m)

4.3 cm (102m)

Human
1.7 m (100m)
Chapter 1 48
4) Nanotechnology micro & nano structure

Human hair
150 m (106m)

Red ant
5 mm (103m)
Chapter 1 49
4) Nanotechnology micro & nano structure

Human hair
150 m (106m)
150,000 nm Red blood cells Virus Carbon
10 m (106m) 20 - 450 nanotube
10,000 nm nm (109m) 5-10 nm(109m)

Atom
0.1 nm (109m)

Chapter 1 50
4) Nanotechnology micro & nano structure
Microstructure
 The micro-scale (10-3m) exists between nano-scale
(10-9m) and macro-scale (100m)
 Typical micro-structures: individual grains in a
polycrystalline material, or "lamina" in a fiber-
reinforced composite laminate.

Chapter 1 51
4) Nanotechnology micro & nano structure

Why microstructure?
 Macroscopic mechanical behavior can be
influenced by structures at the microscopic scales
of 10-3m.

 Example:
~ Elastic properties of a polycrystalline material are
controlled by the orientation of individual grains
sizes of 10 -3m, i.e. random orientation leads to
isotropic macroscopic elastic properties.

Chapter 1 52
4) Nanotechnology micro & nano structure

 Example:
~ Macroscopic properties of laminated composites
are influenced by the elastic properties and fiber
orientation in each laminate layer ("lamina").

~ Cumulative damage events, i.e. ply cracks, at the

lamina-microscopic scale can also influence
mechanical behavior and failure at the macroscopic
laminate scale

Chapter 1 53
4) Nanotechnology micro & nano structure

What is nanostructure?

 Any structure with one or more dimensions

measuring in the nanometer (109m) range.

 Nanostructure should have a characteristic

dimension lying between 1 nm and 100 nm, putting
nanostructures as intermediate in size between a
molecule and a bacterium.

Chapter 1 54
4) Nanotechnology micro & nano structure
How small is 1 nm? 1 inch = 25,400,000 nm
1 human hair = 150,000 nm

Chapter 1 55
4) Nanotechnology micro & nano structure

Why nanostructure?
 Technology based on nanostructures promises to be
hugely important economically - makes up one of
the frontiers of modern science.
 Understanding how electrons behave over such tiny
distant scales importance to the electronics,
communication and computation industries (eg:
semiconductor industry)

Chapter 1 56
4) Nanotechnology micro & nano structure

Evolution of computer:
1st generation Vacuum tube (1942-1955)
2nd generation Transistors (1955-1964)
3rd generation Integrated circuits (1964-1975)
4th generation Microprocessors (1975-1989)
5th generation Artificial intelligence (1989
Present)

Chapter 1 IC 57
4) Nanotechnology micro & nano structure

Chapter 1 58
4) Nanotechnology micro & nano structure

 Nanostructures and nanomaterials are having real-

world impact elsewhere.
 E.g: Quantum dots, in many modern application
areas such as photovoltaic devices, QD lasers, and
as even as fluorescent tracers in biological and
medical settings.
 We have the role to play in understanding, an
learning how to control nanostructures.
 Atomic manipulation (e.g. Carbon)

Chapter 1 59
4) Nanotechnology micro & nano structure

Chapter 1 60
4) Nanotechnology micro & nano structure

Chapter 1 61
4) Nanotechnology micro & nano structure

Nano is everywhere..

Chapter 1 62
4) Nanotechnology micro & nano structure
Nano is everywhere..

Nanowriting

A single-molecule car was

developed by Kelly, Tour and
co-workers (Nano Lett, 2005,
5, 2330)

Nanoalignment
Nanocross
Chapter 1 63
4) Nanotechnology micro & nano structure
Where was nanotechnology originated?

Chapter 1 64
4) Nanotechnology micro & nano structure
What is nanotechnology?

Chapter 1 65
4) Nanotechnology micro & nano structure
Why at nanoscale?

Chapter 1 66
4) Nanotechnology micro & nano structure
Why at nanoscale?

Chapter 1 67