3.

Spectroscopic methods
Typical questions asked : what are the suitable probes ?
What are the elements present in the sample?
The probe should be able to ''fingerprint'' the atoms
irrespective of the valence state they are in.

So the ''core levels'' should be identified (~100 ev – 1keV) Relatively high

High energy probes needed. These are typically energy probes.
XPS (X-ray photoelectron spectroscopy) also called : Periodicity of lattice
ESCA (Electron spectroscopy for Chemical Analysis) plays almost no role.
UPS (Ultra violet Photoelectron Spectroscopy)

What kind of bonds are there ?

Bonds are usually identified by their spring constants.
Usually Raman spectrum.

What is the electronic band structure? Band gaps?

Optical absorption, Photoluminescense, Angle resolved
Photo-emission (ARPES)
Relatively low
What is the phonon band structure? energy probes
Raman & Brillouin scattering
Thermal neutron scattering

Similar questions for molecules.....functional groups, excited states,

type of bond...
Scattering from molecules and solids
Molecules:
Raman scattering is a weak
process: 1 in 106 – 107 incident
photons

Most of the incident radiation will

be ''Rayleigh scattered'' (no
change in energy)

( )
2 2
8 π N α 1+cos θ
I =I 0 4 2
λ R
α : polarizability

Selection rule for HCl

(IR spectra)
vibrational levels
Δ ν = ±1 : why?
vibration & rotation ?
Scattering from molecules and solids
Molecules:
Raman scattering is a weak
process: 1 in 106 – 107 incident
photons

Most of the incident radiation will

be ''Rayleigh scattered'' (no
change in energy)

( )
2 2
8 π N α 1+cos θ
I =I 0 4 2
λ R
α : polarizability

Selection rule for HCl

(IR spectra)
vibrational levels
Δ ν = ±1 : why?
vibration & rotation ?
How stiff are the molecular springs (bonds)?
Suppose spectra of a diatomic molecule A-B is given

ω = μ √k

Calculate the reduced mass μ

−1
Then calculate k =480 Nm for HCl
So ∼0.5 kg will stretch this by 1 cm
5
(1 N =10 dyne)

Data: R.S Drago : Physical Methods for Chemists

Which energy levels do the transitions correspond to ?

Q branch : DJ=0
P branch : DJ=-1
R branch : DJ =+1

As the ''dumb-bell“ rotates,

the spring stretches out a
little changing the
rotational intertia

( )
E (ν , J ) = ℏ ω ν+
1
2
2 2 1
( )
+B e J (J +1) − D e J ( J +1) −α ν+ J ( J +1)
2
Uncoupled rotation & vibration Interaction between rotation & vibration
Rotation of the molecules (typically matches microwave energies)
Ĵ2 ⃗
P is the pre-existing
H = + ⃗p . E electric dipole moment
2I
2 J ( J +1)
EJ = ℏ
2I
⃗ | JM 〉
W = 〈 J ' M ' | ⃗p . E

selection rule (moment parallel to rotor axis)

Δ J =±1 Δ M =0 if M =0
Δ J =0,±1, Δ M =0 if M ≠0
Spherical rotor:
. E J +1 − E J ℏ All moments of inertia are
. .ν = = (J +1)
h 2π I equal.

The matrix elements are to be calculated between spherical Symmetric rotor :

harmonics. P is fixed, E is the electric field of incident Two moments are equal
radiation. Selection rules tell you which integrals will NOT
vanish. Linear rotor:
One moment is zero.
The typical values of the absorption are in the microwave to IR
Asymmetric rotor:
Note that the rotational intertia is a measure of the size of the All moments are unequal.
molecule.
A traditional example : IR spectra of HCl molecule

https://franklycaroline.com/writing/infrared-spectrometric-rotational-and-vibrational-analysis-of-hcl-and-dcl/
What changes if H is replaced with D ?

Notice the change in the x values, but the overall pattern is still same

https://franklycaroline.com/writing/infrared-spectrometric-rotational-and-vibrational-analysis-of-hcl-and-dcl/
IR spectra in gas liquid & solid phase would be different

WATER VAPOUR
IR spectra in gas liquid & solid phase would be different

Hydrogen bonding and hindered

rotations due to presence of other
molecules can change the
spectrum very significantly

Data ffrom : http://www1.lsbu.ac.uk/water/water_vibrational_spectrum.html

(A collection of lot of data about the spectrum of water and its molecular dynamics)
Vibrations of the H 2 O molecule : matches IR frequencies

http://www1.lsbu.ac.uk/water/water_vibrational_spectrum.html
What is the Terahertz gap ?
Vibration-Rotation spectra : the overall picture
Consider a AB type molecule.

Write the problem in terms of reduced mass and

relative distance.

Quantize this harmonic oscillator about equilibrium

''bond length''.

The eignestates are Hermite polynomials as usual.

The dipole moment may fluctuate as the bond stretches.

For symmetric diatomic molecules (N2,H2,O2) this
does not happen. That is why they are ''IR-inactive''.
Vibration +
Rotation
p.E type matrix element would give zero if p is fixed, between states
n and n+1 or n-1, due to the nature of the hermite polynomials.

But if p changes proportional to the change in normal co-ordinate

then the matrix element would be non-zero between n and n + 1.

So the first order derivative of the dipole moment w.r.t the

relevant normal co-ordinate must be non-zero

This is the selection rule.

Raman spectra : identifying the vibrations & characteristic lines

Where does
the 1330 line
in diamond
come from?

Which stretch
should give
higher freq?
C=C Why?
C-C

C-C or C-H

C-H
Data:
Renishaw
instruments

Classical normal mode problem for molecules:

N atoms → 3N normal co-ordinates : masses known, find eigenfrequencies
Subtract : 3 + 3 degrees of freedom for rotation + translation
2 +3 degrees of freedom for rotation + translation (linear molecule)
Enumerate degeneracies, symmetries
Raman spectra : identifying the vibrations & characteristic lines

Molecules with similar/nearly similar sections give signatures at close wavenumbers.

From known spectral lines → identify functional groups/ bond stretches.

What are the selection rules of Raman lines?

Handwaving argument....
Two transitions are involved : So J should change by 0 or 2.
More rigorous analysis : See I.M. Millis, Molecular Physics, 7, 549 (1964)
Molecular Physics, 8, 363 (1963)
Raman spectra : identifying the vibrations & characteristic lines

Rotation spectra of
molecular hydrogen
Rotational Raman
spectrum of H-H

Graphene/
HOPG

Data:
A Ferrari
Solid State Comm.
143, 37 (2007)
Raman & Brillouin scattering
Both involve emission/absorption of a phonon :
Raman : OPTIC branches :
so higher in energy (~ THz typically)
Brillouin : ACCOUSTIC branches :
so lower in energy (~Ghz typically)

Since the shifts are much smaller, scattering by

accoustic phonon gives energy shifts that require
Fabry-Perot type arrangement to analyse.

Raman shifts can usually be distinguished by

grating.

Phonon spectrum
of diamond:
Where does the
1332 cm-1 line
come from?

Diamond Graphene
Brillouin scattering detection is more complex than Raman....
Fairly simple, very little
sample preparation
required.

Even some protable

versions are avaialable now.

Raman Spectroscopy. R.L. McCreery

Requires the
resolution of a Fabry-
Perot interferometer,
since the energy shifts
are far smaller.

Serc.carleton.edu/NAGTW
orkshops/mineralogy/miner
al_physics/brillouin.html
Connecting elastic and inelastic scattering : dynamic structure factor
Consider a slow enough particle ( ⃗k ) scattering off a sample (Φ)
with a periodic structure
⃗n
∣k⃗i , Φi 〉 →∣k⃗f , Φ f 〉 V ( ⃗r )=∑ v ( ⃗r − R⃗n ) V ⃗q =v ⃗q ∑e i ⃗q . R

n lattice

2π 2
Pi→ f =
ℏ ∣ ∣
〈 k⃗f , Φ f ∣V (⃗r ) ∣k⃗i , Φ i 〉 δ( E f +ϵ f −E i−ϵi )
L3 3 ⃗ L3 M
δ N i→ f = Pi→ f × 3
d k f = P i→ f × 3
k f 2 dϵf d Ω
(2 π) (2 π) ℏ
Compare this with the incident particle current
ℏ ki ℏki
⃗j = ρ ⃗v = | ψi | 2
M
=
MV ( assume : ψi =
1 i k⃗ . ⃗r
√V
e i

)
| j |d2σ = δN i → f Definition of the scattering cross-section

(MV ) k f
( )
2 2
d σ 2π
d ϵf d Ω
= 3
ki
×
ℏ
∑ 〈 Φf ∣ V q ∣Φ i 〉 * 〈 Φ f ∣ V q ∣Φ i 〉 δ( E f +ϵ f −E i−ϵi )
h f

We only measure the state of the outgoing particle. So all the possible states of
the sample must be summed over. That is the origin of the sum over f
Connecting elastic and inelastic scattering : dynamic structure factor
2π
∑ Pi→ f =
ℏ q ∑
|v |2
〈
Φi | ∑ e
q . R⃗
−i ⃗
|Φ f m
〉〈 Φ | ∑ e
f
q . R⃗n
i⃗
〉
| Φi δ(E f −E i +ℏ ω)
f f

1 dt i(( E − E )/ ℏ+ω)t Notice how the index f has been switched and
δ(E f −E i +ℏ ω) =
ℏ ∫2π e f i
the complex conjugation removed

H |Φf 〉 = E f |Φ f 〉 Heisenberg
representation
2π dt i ω t
. . ∑ Pi → f
.

Φf
=
ℏ
2
| v q ∑∫
|
2
2π
e Φ i | 〈
e
q . R⃗
−i ⃗
|Φfm
〉〈 Φ f |e
iHt/ ℏ i ⃗
e
⃗ −iHt / ℏ
q. R
en
| Φi 〉
fmn

2π dt i ωt
=
ℏ
2
| v q |2
× ∑ ∫ 2 π e Φi | e
mn
〈
q . R ⃗(0 ) i ⃗
−i ⃗
e
q . R ⃗(t )
m
| Φi n
〉
The time dependence has come in because the lattice
points creating the potential are not stationary – this is how
the phonons enter into the picture.
R⃗m (t ) = R⃗0m +u⃗m (t)
Second we need to do a THERMAL average over the
initial states, beacuse the sample sits at some finite ⃗0
R : equilibrium position
m
temperature.

Follow the standard notation for thermal average of an

expectation value.
Connecting elastic and inelastic scattering : dynamic structure factor

dt i ωt ∑ 〈 Φi | A |Φ i 〉 e−β E
〈
q . R ⃗(0) i ⃗
q . R ⃗(t )
〉
i

∑ ∫ 2 π e Φi | e−i ⃗
e m
| Φi n

i
mn 〈 A〉 =
=∑ e
i ⃗q( R⃗m − R
0 ⃗0 )
n
dt i ω t −i ⃗q . u⃗ (0 ) i ⃗q . u⃗ (t)
∫ 2 π e 〈e m
e 〉
n ∑ e−β E i

i
mn Called the
thermal average

1 q ( R⃗ − R
⃗) dt i ω t −i ⃗q . u⃗ (0 ) i ⃗q . u⃗ (t)
0 0

∑ ∫ e 〈e 〉
i⃗
S ( ⃗q , ω) = e m n
e m n

N mn 2π
d2σ (ML 3 )2 k f 2 π 2
= 3 2
N | v |
q ×S (⃗
⃗ q , ω)
d ϵdΩ h ki ℏ

The dynamic structure factor is a characteristic of the lattice only, irrespective

of what (light, electron, neutron) is being scattered by the crystal.
Evaluating the dynamic structure factor

For harmonic vibrations a remarkable result holds for thermal averaging

Given two matrices or operators A and B which are both linear in ⃗r and ⃗p
〈 A +B +2 A B 〉 /2
2 2

〈e A
e
B
〉 = e
in general [ A , B]≠0

− 〈(⃗
q . u⃗m (0 )) 〉/ 2 −〈 (⃗
q . u⃗n(t)) 〉/ 2
2 2

〈e i⃗
q . u⃗m (0) i ⃗
e
q . u⃗n(t )
〉 = e ×e ×e
q . u⃗m (0))(⃗
−〈 (⃗ q . u⃗n(t )) 〉
All sites m,n are
q . u⃗ (0))(⃗
q . u⃗ (t )) 〉
= e−q u / 2×e−q u / 2×e 〈
2 2 2 2
− (⃗ m n equivalent so their
r.m.s amplitude
would be same
×e 〈
2
−q 〈u 〉
2
q . u⃗ (t ))〉
− (⃗q . u⃗ (0))(⃗
= e m n

Debye-Waller
factor 2 2
q . R⃗n
0
dt i ω t 〈(⃗q . u⃗ (0 ))(⃗q . u⃗ (t))〉
S ( ⃗q , ω) = e
−q 〈u 〉
∑e i⃗
∫ 2π e e 0 n

n
The exponential can
The 1/N factor cancels after one of the now be simple expanded
indices (in this case m) is summed over. and evaluated term by
term!
Evaluating the dynamic structure factor : expand term by term

−q 2 〈u2 〉 q . R⃗n
0
dt i ω t
S ( ⃗q , ω) = e ∑e i⃗
∫ 2 π e [ 1+〈(⃗q . u⃗0 (0))(q⃗ . u⃗n (t ))〉 + .... ]
n

The first term is just 1 : The integral reproduces the static structure factor which gives the
correct intensity for elastic scattering including the Debye-Waller factor for temperature.

The second term can be evaluated by writing un(t) in terms of the creation annihilation
operators as applicable to a harmonic oscillator.
The operator is written in
1
√ ℏ terms of the fourier
[ ]
i (⃗ ⃗ −ω t )0 ⃗ −ω t)
+ −i (⃗k . R
0

u n (t) = ∑ 2 m ωk
ak e k .R n
+ ak e k n k
transform of the
√N ⃗
k raising/lowering operators.

( )
2 2
ℏ q 1
[ −i( ⃗ −i( ⃗
]
2 2
q ). R⃗n q). R⃗n
S 1 (⃗
q , ω) = e
−q 〈u 〉
2m
∑ ℏω e
k −⃗
n k δ(ω−ω k )+e
k +⃗
(n k +1)δ (ω+ωk )
⃗
k ,n k

Here the phonon ω( ⃗k ) is created , n k is the boson occupation probability

The wave vector of the incident particle changes by ⃗q Notice how temperature
enteres in two ways in
Notice how the exponential sum forces the requirement inelastic process
⃗
k −q
⃗ =G⃗ (a reciprocal lattice vector)
Evaluating the dynamic structure factor : expand term by term

−q 2 〈u2 〉 q . R⃗n
0
dt i ω t
S ( ⃗q , ω) = e ∑e i⃗
∫ 2 π e [ 1+〈(⃗q . u⃗0 (0))(q⃗ . u⃗n (t ))〉 + .... ]
n

The first term is just 1 : The integral reproduces the static structure factor which gives the
correct intensity for elastic scattering including the Debye-Waller factor for temperature.

The second term can be evaluated by writing un(t) in terms of the creation annihilation
operators as applicable to a harmonic oscillator.
The operator is written in
1
√ ℏ terms of the fourier
[ ]
i (⃗ ⃗ −ω t )0 ⃗ −ω t)
+ −i (⃗k . R
0

u n (t) = ∑ 2 m ωk
ak e k .R n
+ ak e k n k
transform of the
√N ⃗
k raising/lowering operators.

( )
2 2
ℏ q 1
[ −i( ⃗ −i( ⃗
]
2 2
q ). R⃗n q). R⃗n
S 1 (⃗
q , ω) = e
−q 〈u 〉
2m
∑ ℏω e
k −⃗
n k δ(ω−ω k )+e
k +⃗
(n k +1)δ (ω+ωk )
⃗
k ,n k

Here the phonon ω( ⃗k ) is created , n k is the boson occupation probability

The wave vector of the incident particle changes by ⃗q Notice how temperature
enteres in two ways in
Notice how the exponential sum forces the requirement inelastic process
⃗
k −q
⃗ =G⃗ (a reciprocal lattice vector)
Two generic conservation laws for scattering from a crystal

The wave-vector conservation looks

E f −E i = ±ℏ ω(⃗q ) like momentum conservation.
But it is not momentum.
k⃗f −k⃗i = q + G
⃗ ⃗
Notice the presence of an arbitrary
reciprocal lattice vector.

Incident particle → i
Outgoing particle → f : w(q) is the excitation created or destroyed

When will the additional factor of G come into play?

In a situation where the incident particle has a wave vector comparable

in size with the Brillouin zone.

In case where the G comes into play and brings back the resultant vector
into the first Brillouin zone – the process is called UMKLAPP (flip over)

It is possible with neutrons, X-rays. (estimate the wave-vector ratio)

Very improbable with visible light.

Wavecector ~ /a
Visible light ~ 10-3 of the zone vector
X-ray, thermal neutron ~ comparable in size to Brillouin zone
Some examples of phonon dispersion : Silicon

In a 3D crystal there would always be 3 accoustic modes (this can be proved)

If the unit cell has p atoms, then there should be 3p-3 optical modes.

Many degeneracies are possible. (Calculations : Lattice Dynamics + refinements)

Plotting the dispersion is done following exactly the same convention as electronic
band structure...from zone centere towards various special points.

Direct : FCC
Reciprocal : BCC

J. Phys. : Condensed Matter 20 (2008) 145213 Direct : Hexagonal

Reciprocal: Hexagonal
Some examples of phonon dispersion : FCC - Cu

Methods used to map

out phonon w(q)

Inelastic neutron
scattering

High Resolution Electron

Energy Loss scattering
(HREELS)

Inelastic Helium atom

scattering (HAS)

A. Dal Corso, J. Phys.: Condens. Matter, 25, 145401 (2013)

Model calculation results & inelastic neutron diffraction data
Some examples of phonon dispersion : GaAs

GaAs...notice that frequencies are lower than Si.

For diamond it was much higher.
Some examples of phonon dispersion : Graphene

Al Taleb et al
J Phys. Condensed
matter: 28, 103005
(2016)
Excitation spectrum of a liquid by neutron scattering : Superfluid Helium

The principles are the same.

But here momentum is real.

Unlike phonons in solid, that do
not carry real momentum.

There is NO additional reciprocal

lattice vector.

The minima at a finite Q is a

special feature of a superfluid.

C. Kittel, Quantum theory of solids.

X-ray photoelectron spectroscopy : XPS (ESCA)

An atom is identified by its energy levels.

The outer levels overlap forming bands (Valence & Conduction bands)

The core levels are virtually unaffected by the ionisation state, chemical
bonding state of the outer electrons.

These core levels thus act as a fingerprint of the atom, irrespective of what
solid it is in.

KE = h ν−( E B +ϕ) The sample is

grounded means
Fermi level is at
f

zero potential.
e-

Depending on
X-r

whether the
ay

material is metallic,
EB

semiconducting or
insulating, the fermi
level position will
Basic idea : very simple! differ w.r.t the
bands.
Like photoelectric effect.
https://wiki.utep.edu/display/~dmarrufo/X-ray+Photoelectron+Spectroscopy
 XPS: Experimental aspects
What kind of X-ray to use?
We are not looking for diffracted spots....

Want a sharply defined energy

About 1 keV needed to probe core levels

Ultra high vacuum needed. Why?

The detector sees the electrons
and analyses their energies.

Without very high vacuum, the

electrons are going to scatter off
gas molecules.

P ∼ 1×10−9 mbar
XPS: Experimental aspects
What elements can be detected?
Hydrogen, Helium are too light. Otherwise all elements from Lithium
upwards.

However only the top ~ 5-10 nm of the sample actually responds.

Electrons emitted from deeper layers will not be able to come out.

So surface contamination must be avoided.

This is also another reason why very high vacuum (1e-9 mbar) is needed.

The electric field is radial and of

known value set by the user.

If the entry and the exit points

are fixed, then electrons with a
specific energy only will pass.

The spectrum is a plot of the

intensity vs KE.

Resolution ~ 0.5 eV

Detection limit ~ 0.1 – 1 %

XPS: Experimental aspects : How does an ESCA/XPS look ?

@IITB

@princeton

Resolution ~ 0.5 eV

Detection limit ~ 0.1 – 1 %

XPS and its relation to the three electron Auger process

Consider an atom with a vacancy in a core state (say K shell)

The FIRST electron left the atom in an unstable state with one vacancy.

It does not matter how this first vacancy was created (hit with an electron or a photon...)

An outer SECOND electron can now drop into the vacant state, realeasing another photon in
the process. (e.g. L → K)

This photon may be emitted as a characteristic line. (atom left with 1 vacancy)

But the photon may be reabsorbed by a THIRD electron in the atom and if the energy is in
excess of the binding energy of this THIRD electron , that will be emitted.

Finally The atom will be left with 2 vacancies.

This THREE electron process is called the Auger process. (The mechanism was discovered
by Meitner and Auger)

Since three electrons are needed, only atoms with Z > 2 can show Auger emission.

The electrons detected in the XPS spectra can also be Auger electrons.

Historically derivative of the intensity used to be plotted to suppress the background slope.
XPS and its relation to the three electron Auger process

KE = ( E K −E L1 )−E L2
= E K −( E L1 +E L2 )
Vacuum
level

L2

L1

Many combinations will be possible in a real atom.

These would be labelled with three indices...e.g. KL1L2
Sample XPS spectra : finding surface contamination/impurity

http://biointerface.org/surface/xps/

Identify the lines from known

values – use standard spectral
line libraries....

Quantitative analysis:
Peak area...
But absorption cross section of
every level is not necessarily
same.

https://commons.wikimedia.org/wiki/File:Monochromatic_XPS_survey_scan.jpg
Sample XPS spectra :Auger and XPS both will be present together

335
937

561
673

534

BE+Φ = h ν−KE

Example taken from: http://www.chem.qmul.ac.uk/surfaces/scc/scat5_3.htm

Sample XPS spectra :Binding energy data for Palladium

Identify the transitions in the

previous spectra and Auger electron

https://www.webelements.com/palladium/atoms.html
The scope of various photoemission processes : overview

https://xpssimiplified.com/UPS/php
Thermo-scientific.
Where does one find
10-100 eV photons?

Ne I 16.6eV
Ne II 26.8eV

He I 21.2eV
He II 40.8eV

Synchrotron
radiation
UPS applied to a gas : Electronic levels of molecular N 2

Electronic energy
levels of molecules
can be predicted :

Linear Molecular
Combination of Nitrogen (gas)
Atomic Orbitals/
Molecular orbitals

(similarity to tight
binding in solids)

UPS gives the

simplest test/proof
of this approach.

Turner & May, Jl of Chem Physics 45, 471 (1966)

Band alignment at interfaces using photoemission

We need to understand how the energy levels of two materials in contact evolve/behave.
Interfaces are essential in almost any device!

There is a generic class of problems.....

Molecule with metal (Q: How does vacuum level, HOMO-LUMO/Fermi levels align....)
Molecular electronics, organic semiconductor solar cell/devices...

Metal with Semiconductor (The Schottky barrier problem)

Free surface of a semiconductor (Band bending and location of surface states)

Semiconductor-Semiconductor (The heterointerface, conduction and valence band offsets)

We need to understand the behaviour of the energy levels in the ~1-10 nm region near the
surface and within ~1-10 eV typically.

No single technique is sufficient to answer all the questions....

But Photoemission (UPS) is one of the useful probes.

This is NOT a fingerprinting type spectroscopy problem....

cannot match features to known spectral lines etc..
Determining the work function Φ
` Vacuum level
Photons with E= hn incident on the surface
F
Work function
` Fermi level A typical E = 21.2 eV

Electrons coming from here should have

CB VB

KE = hn - F
Electrons coming from here should have
Energy

hn KE = 0
How would something with KE → 0
reach the detector? Ans: Small bias

The total spread of the KE is F less than the energy of

the photon.
From this determine the work function.

Cross sections for typical s,p,d bands are not same, so

intensity depends on incident photon energy, band
structure details of the material.
levels
Core

The measured work function is sensitive to surface

conditions, which crystal facet the electron is coming out
UPS will only see from, etc.
occupied states ~ 1-2 eV spread is possible due to these.
 Determining the work function Φ : An example

Indium Tin Oxide: commonly used transparent electrode.

Y Park et al. Applied Physics Letters 68, 2699 (1996)

Emission edge.
The deepest electrons Fermi level
Least sensitive to More sensitive to
temperature etc. temperature.

If plotted against Binding Energy, the plot will be reversed.

Larger KE → Smaller BE
Band alignment at an interface : An example

VB Maxima of SiO2

0.5 nm SiO2 Bulk Fermi level of Si

n - Silicon

Data: C. G. Fulton et al, Journal of Applied Physics, 99, 063708 (2006)

BiFeO3 : UPS data
Wei Ji, Applied Physics Letters, 103, 062901 (2013)
UPS at different incident photon energies: An example
UPS spectra of MoS2 measured with
different incident photon energies.

Notice the large qualitative difference.

http://www.wsu.edu/~scuderio
Semiconductor analogy of molecules

In molecules : Valence band maxima → HOMO (Highest Occupied Molecular Orbital)

Conduction band minima → LUMO (Lowest Unoccupied Molecular Orbital)

Work function → HOMO to Vacuum level

Yu-Z wang, J. Appl. Phys. 112, 033704 (2012)

The typical energy values indicate that UPS can be useful.....

What would one expect to see ?
Angle Resolved Photoelectron Emission Spectroscopy (ARPES)

It is a probe of the band structure.

Experimentally one measures:

Energy of the emitted electron &

Angle of emission of the electron.

The problem is to infer the E(k) relation

from this data.

The UV-photon energy is ~20-100 eV.

So the k-vector of the photon is still
much smaller compared to the Brillouin
zone dimensions. So transitions are
almost vertical.

Modelling this process is not as simple as photoelectric effect. Why?

To be quantitatively correct one needs to model the Bloch eigenstate wavefunction,

propagation of the generated electron to the surface, the emission process including
the effect of short lived gap states + surface states.
Angle Resolved Photoelectron Emission Spectroscopy (ARPES)

3 step model of photoemission

Photon of 100 eV will

have a wavevector of
~1% of the Brillouin
zone size.

The three step model is

intuitive, but has certain
oversimplifications.

Interpretation of ARPES data is

Huffner, Photolectron Spectroscopy (1994) more complex......
ARPES : Using the nearly free electron model for the transitions
sample

vacuum

EK Vacuum level

Figure : Andřej Šipr Notice the use of the repeated zone scheme to draw
the NEARLY FREE ELECTRON parabolas...

E f −E 0 = E K + Φ + ( E i−E 0 ) Parallel and perpendicular w.r.t. sample surface.

ℏ2
E f −E 0 =
2 m*
[( k || +G|| )2 +( k ⊥ +G ⊥ )2 ] Transition matrix elements between Bloch states
will have the additional G vector. Why ?
ARPES : Using the nearly free electron model for the transitions

}
1
Kx =
ℏ √2 m E K sin θ cos ϕ
K ||
1 E K , K || , K ⊥
Ky =
ℏ √2 m E K sin θ sin ϕ
are measured
Kz =
1
ℏ √2m E K cos θ } K⊥

As the electron emerges from the solid the K|| is conserved as in a barrier penetration problem.

EK = h ν−Φ−(E F −Ei )
K || = k || +G||
. 1
. . k || =
ℏ √ 2 m E K sin θ − G||
1
k⊥ =
ℏ √ 2 m [ E K cos θ+(E V −E 0) ] − G ⊥
2

Need to
model / guess
ARPES : What does one see ? Copper
ARPES : What does one see ? Graphene

Graphene supported on Cobalt (0001)

D. Usachov et al, Nano Lett. 15, 2396 (2015)
BESSY synchrotron facility, using 40 eV photon
ARPES : What does one see ? Black Phosphorous

Semimetal state of Black Phosphorous:: T = 15K

Jimim Kim et al.
Science 14 Aug 2015:
Vol. 349, Issue 6249, pp. 723-726

Semimetal : Small overlap between Valence and Conduction band

E_D denotes the ''Dirac Point''
ARPES : What does one see ? Sr2RuO4 (Superconductor)

A. Damascelli et al., Physical Review Letters, 85, 5194 (2000).

ARPES : What does one see ? An Iron containing superconductor

ARPES
Data
T~1K
(A-C)

Model
Calculation
(D-F)

Sahar Rinott et al: Science Advances 21 Apr 2017: Vol. 3, no. 4, e1602372
Note: The data can only show the states below the Fermi level.
ARPES : What we have not discussed.....

What is the correct final state of the electron?

A free aprticle outside, rapidly decaying inside....

The emitted electron crosses a few atomic layers → diffraction?

It does happen and can be detected as oscillations over the background.

The wavefunction of the N-1 electrons must relax. Single particle energy levels
cannot be the full story.

Correct, only for non-interacting electrons. What ARPES measures is the ''spectral
function'' of an interacting N-particle system.
Inverse Photoemission spectroscopy : probe the unfilled states

Basic idea: Hit a material with an electron beam. Detect photons which come out.

These are very low energy electrons : less than ~ 20 eV. (Unlike electron microscopes!)

EITHER :

Vary the energy of the electron beam & keep detector at fixed frequency.
Called Brehmastralung Isochromat Spectroscopy (BIS)
UV detector with a bandpass ~ 10 + 0.5 eV is common.

OR

Keep electron beam energy fixed. Detect emitted photons at all frequencies.
Inverse Photoemission Spectroscopy. (IPES)

Photoemission is not the only energy loss process for the electrons. The process has a
small probability. Photon counts in IPES is low (~100 cts/sec/Sr).

The angle-resolved version is called K-resolved IPES (KRIPES)

Inverse Photoemission spectroscopy :What is it useful for
Incident electron

EK

EV
E K +Φ=ℏ ω+E B
Φ
EB
E F =0

Antibonding states of molecules. (The unfilled Molecular Orbitals)

Surface states of semicondcutors (Usually they are in the bandgap region)

Conduction band states of materials, that are unfilled

Inverse Photoemission spectroscopy :Surface states of Silicon

http://www.fhi-berlin.mpg.de/~hermann/Balsac/pictures.html
Hill and McLean, Rev Sci Inst, 69, 261, (1998).