Condensed Matter II

Interfaces & Nanostructures

Motto: "God made solids,

but surfaces were the work of the devil.“
Wolfgang Pauli (1900‐1958)
 Application Examples of Surface Science

• understanding and design of catalysts

(e.g., car exhaust)
• understanding and inhibition of corrosion (ships, cars, buildings)
• modification of surface properties like:
‐ friction (tires, bearings)
‐ wear (polymer lenses of glasses → ormocers)
‐ stickiness (frying pan, adhesive tape)
‐ wetting, condensation
(outdoor gear, inkjet printing)
‐ anti‐reflection (picture frames, displays)
‐ color (paint)
• chip manufacturing / microelectronics
• biological surfaces (biocompatibility, patterned cell growth)
• sensors (chemical, biological)
• microfluidics ...
 Probing surfaces
electrons

particles

ions
neutral

Surface

photons
 Surface Science Acronyms http://www.cem.msu.edu/~cem924sg/Acronyms.html
AEPAPS Auger electron appearance potential spectroscopy LFM Lateral force microscopy
AES Auger electron spectroscopy MBE Molecular beam epitaxy
AFM Atomic force microscopy MEED Medium energy electron diffraction
APS Appearance potential spectroscopy MEIS Medium energy ion scattering
AREAS Angle‐resolved Auger electron spectroscopy MOCVD Metal‐organic chemical vapor deposition
ARXPD Angle‐resolved x‐ray photoemission/photoelectron diffraction NEXAFS Near‐edge x‐ray absorption fine structure (same as XANES)
ARXPS Angle‐resolved x‐ray photoelectron spectroscopy PEEM Photoemission electron microscopy
ARUPS Angle‐resolved ultraviolet spectroscopy PES Photoemission spectroscopy
BIS Bremmstrahlung isochromat spectroscopy (same as IPES) PSD Photon stimulated desorption/position sensitive detector
CHA Concentric hemispherical analyzer QMS Quadrupole mass spectrometer
CITS Current imaging tunneling spectroscopy RAIRS Reflection‐absorption infrared spectroscopy (same as IRAS)
CMA Cylindrical mirror analyzer RBS Rutherford backscattering spectroscopy
CPD Contact potential difference RFA Retarding field analyzer
CVD Chemical vapor deposition RGA Residual gas analyzer
DAPS Disappearance potential spectroscopy RHEED Reflection high energy electron diffraction
DSIMS Dynamic secondary ion mass spectrometry SAM Scanning Auger microprobe
EAPFS Extended appearance potential spectroscopy SEM Scanning electron microscopy
EELS Electron energy loss spectroscopy (same as ELS) SERS Surface‐enhanced Raman spectroscopy
ELS Energy loss spectroscopy (same as EELS) SEXAFS Surface extended x‐ray absorption fine structure
ESCA Electron spectroscopy for chemical analysis (same as XPS) SFG Sum frequency generation
ESD Electron stimulated desorption SHG Second harmonic generation
ESDIAD Electron stimulated desorption ion angular distributions SIMS Secondary ion mass spectrometry
ESFD Electron stimulated field desorption SPALEED Spot‐profile analysis low energy electron diffraction
EXAFS Extended x‐ray absorption fine structure SPLEED Spin‐polarized low energy electron diffraction
EXELFS Extended energy loss fine structure SPIES Surface Penning ionization electron spectroscopy
FEM Field emission microscopy SPM Scanning probe microscopy
FIM Field ionization microscopy SSIMS Static secondary ion mass spectrometry
FTRAIS Fourier transform reflection‐absorption infrared spectroscopy STM Scanning tunneling microscopy
HAD Helium atom diffraction STS Scanning tunneling spectroscopy
HAS Helium atom scattering SXAPS Soft x‐ray appearance potential spectroscopy
HEIS High energy ion scattering SXRD Standing x‐ray diffraction
HREELS High resolution electron energy loss spectroscopy SXW Standing x‐ray wavefield absorption (same as XSW)
HV High vacuum/high voltage TDS Thermal desorption spectroscopy (same as TPD and TPR)
IMBS Inelastic molecular beam scattering TEAS Thermal energy atom scattering
INS Inelastic neutralization spectroscopy TEM Transmission electron microscopy
IPES Inverse photoemission spectroscopy (same as BIS) TPD Temperature programmed desorption (same as TPR and TDS)
IRAS Infrared reflection‐absorption spectroscopy (same as RAIRS) TPR Temperature programmed reaction (same as TPD and TDS)
ISS Ion scattering spectroscopy UHV Ultrahigh vacuum
KRIPES k‐resolved inverse photoemission spectroscopy UPS Ultraviolet photoelectron/photoemission spectroscopy
LEED Low energy electron diffraction XANES X‐ray absorption near‐edge structure (same as NEXAFS)
LEIS Low energy ion scattering XPS X‐ray photoelectron spectroscopy (same as ESCA)
LEPD Low energy positron diffraction XRD X‐ray diffraction
LITD Laser‐induced thermal desorption XSW X‐ray standing wavefield absorption (same as SXW)
Measuring Properties of Surfaces:
Examples
 Physical processes on surfaces

Adsorption and
catalysis

Recontruction Layer growth

Physical processes controlling growth on surfaces
 Surface Defects and Structures

→ Surface defects are important for crystal growth:

• Traps for newly adsorbed atoms / molecules
• Restructuring of surfaces happens at defects first
Kink−, step−, and terrace−atoms have large equilibrium concentra ons on real
surfaces (hard to get perfect surface...)

Isolated adatoms and vacancies are important for atomistic transport (restructuring),
but equilibrium concentration is low (< 1% of monolayer even at Tmelt)
 What is Ultra High Vacuum (UHV) ?
Vacuum technology has advanced considerably over the last 50 years
and very low pressures are now routinely obtainable
Rough (low) vacuum : 103 ‐ 1 mbar
Medium vacuum : 1 ‐ 10‐3 mbar
High vacuum (HV) : 10‐3 ‐ 10‐7 mbar
Ultra‐high vacuum (UHV) : < 10‐7 mbar
 Creating an Ultra‐High Vacuum
A typical UHV apparatus

Pre‐vacuum pump
UHV pumps
Bake‐out
Pressure measurement device
 How long does it take to cover a surface?

Assumption: Sticking coefficient =1

Pressure = 105 Pa, Temperature = 300K
 1% of surface covered in ca. 10‐11 sec

Pressure = 10‐4 Pa, Temperature = 300K

 1% of surface covered in ca. 10‐2 sec

Pressure = 10‐8 Pa, Temperature = 300K

 1% of surface covered in ca. 100 sec
Experiments on surfaces require excellent vacuum
Only under UHV conditions, a surface can be kept clean for sufficiently long times
 Relation between
pressure and
number of particles
and mean free path
Vapor pressure of some materials
Measuring low pressures
Some questions for a discussion:

Creating a good vacuum: How?

Characterizing Surfaces:
Which molecules are on a surface?
Liquid versus solid surface

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Interfaces

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An example: the Lotus leaf effect

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Walking on water

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http://www.hu.gatech.edu/Striderweb/striderweb.html
Some Examples

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 Surface Energy
The work W11 to bring two identical ideal surfaces in vacuum
together is related to the surface energy 1 of the material:

W11 = −2 1
W11 corresponds to the work of cohesion in an ideal case
and is normalized to the area of the surfaces.
This work should be identical to separating a body into two halves.

In reality the separation process is irreversible (due to energy dissipation),

thus the separation / cohesion work is larger than the surface energy.
⇒ high surface energy ↔ strong cohesion → high boiling point ...

⇒ High energy surfaces tend to reduce energy

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by adsorption of contaminants from environment !
 Cohesion
Cohesion forces act within a condensed material (liquid, solid) to keep it together.

Work of cohesion W11: free energy change, or reversible work done,

to cleave / separate a material from contact to infinity in vacuum

Cohesion in amorphous solids and liquids is

isotropic: → random fracture plane (e.g. glass)

Cohesion in crystalline solids is anisotropic:

→ fracture along crystal planes
(e.g. Si single crystal wafer) 22
 Adhesion
The adhesion forces act between the surfaces of two different condensed bodies in contact.

2x A

Dupré equation: total free energy change

corresponds to interfacial energy 12

→ this process can be split into two hypothetical steps:

a) generate new surface for materials 1 and 2 in vacuum:

W = 1 + 2 (normalized to unit area! )

b) bring two new surfaces into contact (work of adhesion): W12

⇒ since all media attract each other (assuming neutral total charge) in vacuum:
work of cohesion (W11) and work of adhesion (W12) are always positive
(work is required to separate material ! ) 23
 Surface Tension
Surface tension  is defined by the infinitesimal work dw required
to increase the surface by an infinitesimal area δσ :
of the material:
dw = γ δσ
→ work has to be applied to increase
surface, since liquids tend to minimize
their surface (spherical droplet)
→ force balance

→ surface tension of liquids corresponds to surface energy of solids

→ surface tension / surface energy correlates to evapora on enthalpy ΔHvap (approximation)

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 Surface Tension – a microscopic view
Why is surface tension a force parallel to the interface?
Antonin Marchand, Joost H. Weijs, Jacco H. Snoeijer, and Bruno Andreotti
Am. J. Phys. 79, 999 (2011); doi: 10.1119/1.3619866

POTENTIAL
FORCE

Sketch showing repulsive (dashed black

arrows) and attractive (gray arrows)
forces in the bulk and at the surface.

Lennard‐Jones intermolecular potential:

The interaction is strongly repulsive for intermolecular distances r<r0.
At large distances, the molecules are attracted to one another.
The gray arrow points to the presence of thermal fluctuations,
which, in a liquid, lead to substantial variations of the intermolecular distance. 25
 Surface Tension – a microscopic view

The liquid‐vapor interface. The vertical axis is in units of r.

(a) Snapshot of a molecular dynamics simulation of a liquid‐vapor interface using the

Lennard‐Jones potential.
(b) Time‐averaged normalized density profile *(z) across the interface.
(c) Tangential force per unit area exerted by the left part on the right part of the system.
The plot shows the difference Π =pNN – pTT
between the normal and tangential components of the stress tensor. 26
A characteristic measurement

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 Measuring Surface Tension
The Young−Laplace equa on describes the pressure difference Δp between the inside
and the outside of a curved object (bubble, droplet, cavity) with radius ra and rb
(ra rb, for a symmetric geometry r = ra = rb) with respect to the surface tension  :

maximum bubble pressure method: a gas is pressed through a capillary

with radius rK till the cavity reaches
2l
rB = rK → · Δ /2
with Δp = pbubble − h ρ g
(hydrostatic pressure, ρ: density of liquid,
rB g: gravitational constant)
l

Wilhelmi plate method:

drop weight method:
force (in addition to
maximum drop size before release:
gravitational force)
· 2 · ·
on a plate with width l partially
with weight of drop
immersed into a liquid
⇒ · · 2 · · 2· · 28
Some examples

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Experiments in the Kitchen

Variation of the surface area

by moving a barrier

1898‐1979

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Volume 43

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 Langmuir−Blodge (LB) Technique: Troughs
Trough made of hydrophobic material (→ Teflon) is filled with a sub‐phase
(water, salt solution,...)
Barrier of hydrophobic material confines surface region
→ total area of air−water interface can be controlled by barrier posi on
Device to measure surface tension of subphase (→ Wilhelmi plate, Langmuir pressure
pickup / floating barrier)
Dipping device to pass a substrate through a floa ng film (→ LB transfer);
Computer control to set barrier position / movement (direction and speed), to measure
surface tension with respect to barrier posi on (→ film compression and expansion), to
control dipper speed / direction with respect to surface pressure and barrier movement
(→ LB transfer)

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