Part 2:

Surface Characterization Methods

Dr. T. Dobbins
MSE 505 Surface and Surface Analysis Lecture Series
March 31, 2004
Reference Materials:
1. Metals Handbook Volume 10: Materials Characterization ASM Intl.
Publishing Group (1986).
2. Sibilia J.P., Materials Characterization and Chemical Analysis VCH
Publishers (1996).
3. Venables J., Introduction to Surface and Thin Film Processes
Cambridge University Press (UK) 2000.
4. Website sponsored by the UK Surface Analysis Forum (USAF)
http://www.siu.edu/~cafs/surface (written by D.T. Marx at Southern
Illinois University)

Assumed understanding of Quantum Mechanics and Crystallography.

Lecture Topics (Part 2)---
What is characterized using Surface Characterization?
Surfaces may be characterized with respect to their topography (i.e. roughness),
chemistry, surface orientation, and thickness of chemically homogeneous regions
at the surface. Typically, mean free path of probe into sample is low or sample is
comprised only of surface atoms.
What are the major categories of Surface Measurement Techniques?
• Contact Methods vs. Non-contact Methods
Which Surface Characterization Techniques will we learn about in this
lecture?
• X-ray and Neutron Reflectivity (XR or NR)
• X-ray Photoelectron Spectroscopy (XPS) also called Electron Spectroscopy
for Chemical Analysis (ESCA)
• TOF-Secondary Ion Mass Spectrometry (TOF-SIMS)
• Auger Electron Microscopy (AES)
• Low Energy Electron Diffraction (LEED)
What are some other Surface Characterization Techniques of practical
importance in research? ( Some of these techniques will be covered later
in the quarter, in part, by Drs. Kuila and Sit*)
• Near-IR Spectroscopy* • Rutherford Backscattering Spectroscopy
• Scanning Tunneling Microscopy* • Low Energy Ion Scattering Spectroscopy
• Atomic Force Spectroscopy*
• Surface Enhanced Raman Spectroscopy
Classification of Characterization Techniques
based upon ‘Probe’ used on sample
Approach

Elementary Particle Scanning ‘Direct’ Probe

Ions Electric/
Electrons Stylus Tip
Magnetic Field

AFM
SIMS
AES MFM Profilometry
Photons

Neutrons STM
LEED
Surface Enhanced
Raman XPS Neutron
Spectroscopy Reflectivity
Classification of Characterization Techniques
based upon ‘Probe’ used on sample
Approach

Elementary Particle ‘Direct’ Probe

Ions Electric/
Electrons Stylus Tip
Magnetic Field

AFM
SIMS
AES MFM Profilometry
Photons

Neutrons STM
LEED
Surface Enhanced
Raman XPS Neutron
Spectroscopy Reflectivity
Classification of Characterization
Techniques based upon Information Sought
Chemical Analysis
AES TOF-SIMS
LEED
Surface Enhanced
Raman XPS
Spectroscopy

Surface Topography
AFM Neutron
Reflectivity

Magnetic Domain Profilometry STM

MFM
 Elementary Particles are Good Probes at the
Nanoscale?
• Neutrons - an uncharged elementary particle that has a mass nearly equal to
that of the proton and is present in all known atomic nuclei except the
hydrogen nucleus

• X-rays - any of the electromagnetic radiations of the same nature as visible

radiation but having an extremely short wavelength of less than 100 angstroms
(or 10 nm). X-rays are produced by bombarding a metallic target with fast
electrons in vacuum or by transition of atoms to lower energy states and that
has the properties of ionizing a gas upon passage through it, of penetrating
various thicknesses of all solids, of producing secondary radiations by
impinging on material bodies, of acting on photographic films and plates as
light does, and of causing fluorescent screens to emit light

• Electrons - A charged elementary particle that has a mass much less than that
of the proton and is present in all known elements

• Ions – A charged particle that has a mass much greater than that of protons,
electrons, and neutrons.
Particle-Wave Duality of Matter (de Broglie, 1924)
Waves having  = 0.1 to 2nm are associated with electrons, neutrons and x-rays.

Wav e le ngth v s. Particle Ene rgy

100
Neutron (0.01 eV)
Electron (100 eV)
X-ray Photon (1000 eV)

10
Wavelength (Angstroms)

X-ray Photon

Neutron

1
1 Electron 10 100

0.1
Energy (eV)

for photons: for electrons and neutrons:

hc h
E E
 2 m
Overview of ‘Particle Probe’ Methods
---Differences when Probing Surfaces using Electrons,
Neutrons, Ions, and Photons

Particle Mass: Listed in order of increasing mass, we have:

Photons Electrons Neutrons Ions

Rule of Thumb:
Heavier Elementary Particles Scatter from Lighter Elements
Overview of ‘Particle Probe’ Methods
---Commonalities in Probing Surfaces using Electrons,
Neutrons, Ions, and Photons

Probe Response
Incident Particle Outgoing Particle
• Electron (generated by process between
• Neutron Incident particle and sample surface)
• Ion • Same type as Incident Particle
• Photon (light, x-rays) • Different type from Incident Particle

SAMPLE

Common to ALL particle probe methods is the fundamental concept that

energetic particles are incident onto the sample and energetic particles exit
from the sample. The type of incident and exit particle may vary among the
different techniques.
Interaction of Elementary Particles with matter.
Incident Probe Particle leads to…
• Emission of a different Response Particle
Examples,
1. XPS – absorption of x-rays and photoemission of electrons
2. SIMS – absorption of ions and emission of secondary ions
3. Flourescence signal –emission of x-ray characteristic of sample ---
x-rays are due to transition of electrons from excited energy level to
lower energy level
4. AES – absorption of electrons and emission of secondary electrons
• Emission of Probe Particle with lowered Intensity, I (called Attenuation
of Probe beam)
• Diffraction of Probe beam – change in trajectory by an angle 2 (Bragg’s
Law) due to internal periodic planes with spacing, d
• Scattering of Probe Particle– change in trajectory by an arbitrary angle
due to internal boundaries (typically, scattering angle is much smaller than
2of Bragg’s Law).
Example,
1. Neutron Reflectivity –neutrons are reflected by internal boundaries
 Electron Probe Technique
--- Auger Electron Spectroscopy (AES)
Information Gained: Chemical Analysis Auger Signal has Strong
dependence on Z.
Principle:
Primary electrons incident onto the
surface causes electron excitations
from core levels (K shell electrons)
within the solid.

De-excitation occurs to release the

excess energy by either emission of a
photon (flourescence) or emission of
an Auger electron.
KE = EK-2EL2,3-Work Function
Energy = EK-EL2,3
L2,3 or 2p shell L2,3 or 2p shell
L1 or 2s shell L1 or 2s shell

K or 1s shell K or 1s shell
Flourescence Signal Auger Electron Signal
(KLL Transition)
 Electron Probe Technique
--- Auger Electron Spectroscopy (AES)
Points to Note:
• Surface Depth Probed: 0-3nm
region
• Limitations: Insensitive to Z=1-2
Elements.
• Quantitative detection sensitive to
0.1 atomic percent.
Example:

Animated Image Courtesy of http://www.almaden.ibm.com/st/scientific_services/materials_analysis/auger/

Photographic Image Courtesy of http://www.matcoinc.com/auger.php
Electron Probe Technique
--- Low Energy Electron Diffraction (LEED)
Information Gained:
Chemical Analysis
Principle:
Primary electrons incident onto
the sample (inside of TEM)
 
diffract (i.e. undergo  
constructive interference) dhkl
according to Bragg’s Law 
d sin 
hkl


n=2dsin
when the probe has an integral
number (n) of wavelengths to Path Difference of incoming wave is d sin 
Path Difference of outgoing wave is d sin 
the path difference.
Tota Path Difference is 2d sin 

Measurement of electron
intensity vs. angle (2) gives
us the atom plane spacing (d).
 Electron Probe Technique
--- Low Energy Electron Diffraction (LEED)
Points to Note:
• Limitations: Samples must be conductive; Ultrahigh vacuum is
required
• Determination of surface atom positions to 0.1Angstroms.
• Used in combination with TEM--- so image of region of interest is
obtained.
Example: Si Crystal
Homoepitaxial growth of Si Structure (111) Plane
onto (111) Plane of Si

(Why 3-fold symmetry?)

LEED Image used for class lecture demonstration from
http://www.omicron.de/index2.html?/results/application_example_in_situ_adsorption_of_ag/~Omicron
Photon Probe Technique
--- X-ray Photoelectron Spectroscopy (XPS)
Information Gained: Chemical Analysis

Principle:
Primary x-rays incident onto the sample cause a core level
electron to leave the atom. The core level electron binding
energy (BE) is characteristic of the material.

KE = hphoton-BEK-Work Function
KE = EK-2EL2,3-Work Function

L2,3 or 2p shell L2,3 or 2p shell

L1 or 2s shell L1 or 2s shell

K or 1s shell K or 1s shell
XPS Signal Auger Electron Signal
(KLL Transition) (KLL Transition)
 Photon Probe Technique
--- X-ray Photoelectron Spectroscopy
Points to Note:
• Surface Depth Probed: less than 10 nm region (higher than Auger)
• Limitations: Insensitive to Z=1 element (Hydrogen). Poor lateral
resolution.
• Determines binding energy (and therefore oxidation states).
• Quantitative detection sensitive to 0.1 atomic percent.
Example:
Environmental Research Sample:

Notice Peak Shift from Pt-Si (green) to Pt bound to 2

O’s (black).

XPS data used for class lecture demonstration taken from http://www-cms.llnl.gov/s-
t/surface.html
 Ion Probe Technique
--- Secondary Ion Spectroscopy (SIMS)
Points to Note:
• Surface Depth Probed: 5-10 nm region (higher than Auger, similar to XPS)
• Sensitive to Z=1 element (Hydrogen).
• Parts-per-billion analysis possible
• Quantitative detection sensitive to parts per billion (ppb).
• Secondary Electron Images of Sample possible
Example:

SIMS data used for class demonstration taken from

http://www.siu.edu/~cafs/surface/file6.html
Ion Probe Technique
--- Secondary Ion Spectroscopy (SIMS)
Information Gained: Chemical Analysis
Principle:
Primary ion beam (10eV) incident upon the sample cause
chain reaction resulting in secondary ions (energy 5-50eV) to
be ejected from the sample. Secondary beam comprised of
molecule fragments, anions, cations, and neutral atoms. The
secondary beam species are introduced to a quadropole mass
spectrum (QMS) to give mass-to-charge information (4 poles –
+’ve and -’ve signals separated). Chemical information
reconstructed from here.

Time-of-Flight (TOF) SIMS includes a

pulsed (<1ns) incident beam and TOF
detector (rather than QMS alone). The
conversion is mass-to-time for each
primary pulse.
Neutron Probe Technique
--- Neutron Reflectivity (NR)
Information Gained: Layer Thickness and Surface Topography
Principle:
Primary neutron beam incident upon the sample having
monolayer or multilayer surface structure. Specularly reflection
(i.e. incident angle = outgoing angle) of beam is analyzed as a
function of angle (). From angles at which constructive
interference occurs for a given beam energy (i.e. wavelength),
reconstruction of layer thickness is possible.

 
 Neutron Probe Technique
--- Neutron Reflectivity (NR)
Points to Note:
• Sensitive to Layers between several Angstrom up to 5 micrometers
• Use of neutrons makes the technique sensitive to Z=1 element
(Hydrogen). X-ray reflectivity is not sensitive to low Z elements.
• Compatible with may in-situ growth experiments (e.g. molecular beam
epitaxial growth).
Overview of Direct Probe Methods
---Commonalities and Differences among Direct Probe
Methods (i.e. Stylus Tip, Electric Field or Magnetic Field)

SAMPLE

• Common to ALL direct probe methods is the fundamental concept that a

sharp cantilever tip is used to trace the sample surface. The tip is
deflected by the sample surface. This deflection is measured as an
electrical signal.
• The two major differences between the direct probe methods are (1) the
tip sharpness (lateral resolution) and (2) the force causing tip deflection
(magnetic field – as in MFM; electric field – as in AFM; or gravitational
force– as in Profilometry).
 Direct Probe Technique
--- Magnetic Force Microscopy (MFM)
Information Gained: Magnetic Domains at Sample Surface
Principle:
Constant distance (up to 100nm) is maintained between the
sample surface and the magnetic cantilever probe. The
cantilever undergoes a change in its resonance frequency due
to the sample’s magnetic domains. This shift in resonance
frequency is mapped spatially across the sample.

Animation used for Class Demo Courtesy of

http://www.almaden.ibm.com/vis/models/models.html
 Direct Probe Technique
--- Magnetic Force Microscopy (MFM)
Points to Note:
• Can detect magnetic fields that only extend forces within 100nm of
surface.

Example:

MFM image of a magnetic recording head.

Image used for Instructional Materials is published by the following authors:

(1) Y. Martin and H.K. Wickramasinghe, Appl. Phys. Lett. 50, 1455 (1987).
(2) - H.J. Mamin, D. Rugar, J.E. Stern, R.E. Fontana, Jr., and P. Kasiraj, Appl.
Phys. Lett. 55, 318 (1989).