Surface Engineering of Semiconductor

Materials

Electric and Microsystems Engineering

(Master)

Prof. Corinna Kaulen

S. 1
 Time Schedule

Week Topic
1 Introduction – Properties of surfaces – principles of surface engineering
2 Silicon as semiconducting material, standard cleaning processes
3 Top Down Processing: Wet etching of silicon, isotropic and anisotropic etching
4 Top Down Processing: Etching of metals and dry etching (reactive ion etching)
5 Bottom Up Processes: Chemical vapor Deposition, Sputtering,
6 Chemical Mechanical Polishing
7 Surface modifications of noble metals: Self assembled monolayers
8 Self assembled monolayers on oxidic materials and semiconductor materials
9 Surface patterning: conventional, non-conventional, and dip-pen-nanolithography
10 Microcontact printing, Microtransfer molding, nanosphere lithography,
11 Ink jet printing on the microscale
12 Surface characterization 1: Electron Microscopy, AFM, Ellipsometry, contact angle
13 Surface characterization 2: IRRAS, XPS, STM
14 Questions and Discussion (Preparation for the final exam) S. 2
 Outline: Surface Characterization Techniques

1. Electron Microscopy
2. Atomic Force Microscopy
3. Contact angle measurements
4. Ellipsometry
5. Infrared reflection absorption spectroscopy
6. X-Ray photoelectron spectroscopy
7. (Scanning tunneling microscopy)

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 InfraRed Reflection Absorption Spectroscopy:
IRRAS - The Instrument

• Molecules absorb infrared

radiation due to excitation
of molecular vibrations
• Very sensitive method:
detection of sub-
monomolecular layers
possible
• Requirement: Sample has
to reflect the IR beam (Au,
Pt, Pd, but not Si)
• Sample size: 2 x 1 cm

S. 4
 InfraRed Reflection Absorption Spectroscopy:
IRRAS - general working principle
By means of IRRAS the IR beam is directed at the sample´s surface at
grazing incidence:

a) Fotograph of the
IRRAS unit
b) Reflection of the
IR beam at the
sample
• a: Angle of incidence
• P: p-polarized light
• S: s-polarized light

S. 5
S. Bourone, PhD-Thesis, RWTH Aachen 2017
IRRAS: Molecular Vibrations of a Methylene Group

Different molecular vibrations of

a methylene group (-CH2-)
detectable by IR: On metal
surfaces, the process is subject
to an overriding selection rule
which states that only those
vibrational modes that have a
component of their dipole
change perpendicular to the
surface can be detected:
application of this metal surface
selection rule (MSSR) often yields
important information about
adsorption geometry

S. 6
 Typical methyl and methylene IR stretching
region for decanethiolate adsorbed on Au(111)

(a) d+: νs(CH2); d-: νas(CH2);

(b) The position of d- as a function of the
number of carbon atoms for: squares:
alkanethiolates on Au(111); triangles:
alkanedithiols on Au(111) prepared from
hexane solutions; circles: alkanedithiols on
Au(111) prepared from ethanolic solutions.
Dashed lines correspond to the position of
the d- band measured for a liquid and for a
crystalline solid alkanethiol.

Vericat et al. Chem. Soc. Rev., 2010, 39, 1805–1834 S. 7

 Comparison of bulk IR spectra with IRRAS allows to
conclude on the molecular orientation of the SAM

Surface selection rules lead to either enhanced or attenuated signals in the IRRA compared to
the bulk IR spectrum => orientation of the molecules was determined
S. 8
Peter et al. J. Phys. Chem. C 2019, 123, 6537.
 IRRAS at thiol-capped AuNP

Bourone et al. Langmuir 2016, 32, 954. S. 9

 IRRAS: Summary

• Characterization of molecules adsorbed to reflecting surfaces

• high sensitivity (<10−4 monolayers in favorable instances)
• operation under ambient pressure and temperature
• results can be correlated with those from other vibrational
spectroscopies
• One disadvantage is the difficulty in studying low‐wavenumber
vibrations, but this is being overcome by the development of more
intense far‐infrared sources.

S. 10
 Outline: Surface Characterization Techniques

1. Electron Microscopy
2. Atomic Force Microscopy
3. Contact angle measurements
4. Ellipsometry
5. Infrared reflection absorption spectroscopy
6. X-Ray photoelectron spectroscopy
7. (Scanning tunneling microscopy)

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 X-Ray Photoelectron Spectroscopy (XPS)

Image: https://en.wikipedia.org/wiki/X-ray_photoelectron_spectroscopy#/media/File:System2.gif S. 12
 X-Ray Photoelectron Spectroscopy (XPS)

• Method for the semiquantitative analysis of surface composition

• Also denoted as Electron Spectroscopy for Chemical Analysis (ESCA)
• It is based on the photoelectric effect, i.e., emission of electrons following
excitation of core level electrons by photons
• It is surface sensitive because of the low inelastic mean free path of electrons
• An XPS setup consists of a X-ray source, a sample chamber and an electron analyzer
• XPS requires a monochromatic source of X-rays, i.e., either from a lab based anode
or from a synchrotron, with a X-ray monochromator in both cases
• Ultrahigh vacuum required because of scattering of electrons in gases

More information: M. Ammann, Paul Scherrer Institut, Switzerland S. 13

XPS: Lab Instrument

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 XPS: The Photoemission Process

• X-Rays hit core electrons in the

electron shell of an atom
• Transferred energy leads to
emission of the electron, leaving
an e- hole in the electron shell
• Emitted electron is detected at the
detector
• detected kinetic energy allows
computation of binding energy of
the respective atom

J. Vac. Sci. Technol. A 38(6) Nov/Dec 2020; doi: 10.1116/6.0000412 S. 15

XPS provides surface sensitivity due to
emission depth

• Only electrons emitted close to surface can escape

without energy loss
• Inelastic mean free path is a strong function of
kinetic energy.
• Exponentially decreasing contribution from atoms
below the surface to the photoelectron peaks
(without loss)
• At close to normal detection angles 95% of the
signal comes from atoms within 3λ of the surface
• Probing depth varies with kinetic energy.
• Depth profiles can be obtained by varying the
incident photon energy with a tunable X-ray source
or by varying the detection angle

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 XPS: inelastic background

• Electrons from deeper below the

surface loose energy and emerge
with reduced KE (increased
apparent BE)
• Electrons very deep in surface
loose all energy and cannot escape
• XPS spectra show characteristic
"stepped" background (intensity of
background towards higher BE of
photoemission peak is always
greater than towards lower BE)

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 Detection of Photoelectrons

• Electrons are collected

by a lense and guided
into the hemispherical
analyzer
• At the outer
hemisphere a constant
negative voltage is
applied (Pass Energy)
• The voltage on the
inner hemisphere is
adjusted to allow
electrons of different
energies to pass
through the analyzer.

https://www.youtube.com/watch?v=RiaiacbOAQk S. 18
 XPS: Spin-orbit Splitting

• For l = 0, s levels are singlets, no splitting

• For l > 0, p,d,f levels are doublets, because
the unpaired electron left in an orbital can
have its spin and orbital angular
momentum either parallel or anti-parallel
• BE of lower j value in doublet is higher (BE
2p1/2 > BE 2p3/2)
• Magnitude of spin-orbit splitting increases
with Z
• Magnitude of spin-orbit splitting decreases
with distance from nucleus (increased
nuclear shielding)

n: principal quantum number (qn), l: orbital angular momentum qn

s: spin angular momentum qn, j =|l ± s|: total angular momentum qn
S. 19
XPS: Binding Energies (BE) as a function of
atomic number Z

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 XPS: Core Level Shifts

• Position of orbitals in an atom is sensitive to

its chemical environment
• Chemical shift correlates with overall charge
on atom
− number of substituents
− substituent electronegativity
− formal oxidation state (unreliable,
depending upon ionicity/covalency of
bonding)
• Chemical shift analysis is a powerful tool for
chemical composition, functional group and
oxidation state analysis

S. 21
 Oxygen Plasma treatment of Gold-Palladium and
Platinum Surfaces leads to partially oxidized surfaces

• Full line: 4f7/2 and 4f5/2 peaks for Au 4f5/2 Au 4f7/2

the oxygen plasma cleaned
substrate with oxidic peaks or
shoulder at higher energy values
• Dashed line: 4f7/2 and 4f5/2 peaks
for substrates without oxygen
plasma treatment for (a) AuPd and
(b) Pt. Pt 4f5/2 Pt 4f7/2

S. 22
XPS: Investigation of a self-assembled MPTP
monolayer on a gold surface

• XPS measurements were performed using the

PHI5000 VersaProbe II ULVAC-Phi Inc., USA
with monochromatic Al Ka radiation in large
area mode (200 µm², 50 W, 15 kV).
• Survey spectra were recorded at 187.5 eV
pass energy and a step size of 0.8 eV at 100
ms/step.
• Core level spectra were recorded at 23.5 eV
pass energy and a step size of 0.1 eV at 100
ms/step.
• Binding energies were scaled to 84.0 eV for
Au4f7/2.

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 XPS: full spectrum and C 1s core level spectrum

The survey spectrum of the first growth step (TP chemisorbed on Au) shows
in addition to the corresponding Au peaks only signals for C, N, O and in
magnification also S is visible. The respective binding energies of C, N and S
portend that TP is bound covalently to the Au surface.

S. 24
 XPS: Investigation of a self-assembled MPTP
monolayer on a Au surface after reaction with Ru

Full spectrum,
showing
additional
traces of Ag, I,
F and Na

S. 25
 XPS: Investigation of a self-assembled MPTP
monolayer on a Au surface after reaction with Ru

C1s core level spectrum with underlying peaks showing the presence of Ru

S. 26
 Outline: Surface Characterization Techniques

1. Electron Microscopy
2. Atomic Force Microscopy
3. Contact angle measurements
4. Ellipsometry
5. Infrared reflection absorption spectroscopy
6. X-Ray photoelectron spectroscopy
7. (Scanning tunneling microscopy)

S. 27
 Scanning Tunneling Microscopy (STM)

• Developed in 1981 by Gerd

Binnig and Heinrich Rohrer (IBM
Rüschlikon)
• Applicable with conducting and
semi-conducting substrates
• Based on quantum tunneling
effect of electrons
• Rectangular potential barrier
model (right)

S. 28
 Scanning Tunneling Microscopy (STM)

Samples:
• Surface properties: inorganic, organic surfaces, soft and hard, smooth and rough
• Adsorbate properties: organic molecules, inorganic layers, nanoparticle layers,
biomolecules
Measurement results:
• Topography of the surface is imaged very accurately: 0.1 nm – 100 nm
• Local physical properties are investigated: electrical, optical and magnetical properties
• Local spectroscopy (inelastic tunneling spectroscopy) by measuring the local I/U
characteristics of a individual molecule

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 Scanning Tunneling Microscopy (STM)

• Contact-less scanning of the surface with a metal tip (Pt/Ir, W)

• Upon applied voltage U the tunneling current I is detected
• Feedback-controller controls distance from tip to surface (constant-
height)
Piezoscanner
tip

Feedback-Controller
U tunneling
current I

sample sample

S. 30
 Scanning Tunneling Microscopy (STM)

Tunneling current I decreases as a function of

• increasing tunneling distance d
• Increasing energy difference of the electrons to the barrier DE
• High variations in tunneling current represent low changes in distance
=> high sensitivity
• Resolution: lateral 0.3 nm and vertical: 0.02 nm

d 2 m∆E
−
I ≈e h

S. 31
STM-Image of highly oriented pyrolytic
Graphite (HOPG)

High electron desity

due to orbital overlap

S. 32
 STM: Images from the IBM gallery

Iron on Copper (111)

http://researcher.watson.ibm.com/researcher/view_group.php?id=4245 S. 33
 STM: Biphenyl-molecules embedded in a
dodecanethiol monolayer

Au

B. Lüssem et al. Langmuir 2006 , 22 (7), 3021-3027 S. 34

 Summary: Surface Characterization methods

Method Measurement result Costs Data

interpretation
SEM/TEM Topography, chemical composition High Easy

AFM Topography Medium Easy

Contact angle Hydrophobicity/ Hydrophilicity Low Easy

Ellipsometry Layer thickness Medium Not easy, but

automatized
IRRAS functional groups present in the Medium Advanced
monolayer, orientation of the molecules

XPS Chemical composition of the surface Very expensive Advanced

STM Arrangement of atom or molecules on Very expensive Advanced

the surface
S. 35