Problem: Fairly small number electrons in an atom but how
can one deal with electrons in a solid ( 1023 atoms)?
Solution: instead of number of electrons consider
the density of electronic states.
Definitions:
Density of states g(E) gives the number of energy states per
energy interval.
Probability that state of energy E is occupied is f(E)
Number of particles per energy interval nE = D(E) f(E,T)
Chemical potential
1.5
Probability of occupancy f(E,T)
The density of electronic states in a solid
Bose
(E-)/K T
-1)
1/(e
B
1.0
Fermi
(E-)/KBT
1/(e
+1)
Boltzmann
0.5
0.0
-10
(E-)/KBT
1/(e
E- >> KBT))
-5
(E-)/KBT
10
The schematic absorption for various excitation processes
Very different physical phenomena are responsible for excitations in different energy
ranges!
Low energy excitations
High energy excitations
Energy and momentum conservation
All transitions require the conservation of energy and momentum.
For photons in the visible (and below)
2
klight =
105 cm 1
the wave vector is very small:
This value of the photon wave vector k is
8
1
q
=
10
cm
electron
very small compared to typical wave vectors
a
q in the first Brillouin zone:
klight << qelectron
Different mechanisms for transitions involving free electrons
Inter-band transitions (direct and indirect): few eV
VBCB : Transitions between all states are possible but:
- direct transitions are much more likely
- Obey selection rules for symmetry of involved bands.
If there is no bandgap (metal) the absorption is continuous
and no absorption edge in this energy range occurs.
Single electron oscillations: below IR 0.5 meV
Described by dielectric function (,k).
Collective electron oscillations (Plasmons): 2 17 eV
In metals the free electrons collectively oscillate (longitudinal).
The quant of this excitation is the Plasmon.
indirect
direct
The quasi particles in condensed matter physics: Excitons
Excitons: some amount of coulomb interaction between electron and hole is retained
in a solid. Types of excitons are defined by how far apart electron and hole are:
Wannier-Mott type: weakly bonded excitons, separated by many lattice constants
(EBind few meV), in most classic semiconductors due to strong dielectric constant
shields Coulomb interaction.
Frenkel-type: highly localized excitons (EBind up to 1 eV) as in wide-band (ionic)
semiconductors, molecular crystals and noble-gas crystals.
Wannier-Mott excitons
CB
Frenkel-type exciton
VB
Phillips, Solid State Phys. 1966
Baumeister, PRB 1961
Overview: putting the fundamental processes together for Al
Question: At which energy range does which physical process lead to absorption?
Experimental absorption spectrum for Al
Fink, Adv. Electronics & Electron Phys. 1989
excitation of core electron (1s)
excitation of valence band electrons (2s, 2p)
Plasmons: Surface plasmons (SP), volume plasmons P, 2P, 3P, 4P
Intra-band transitions (IB)
Fundamental excitations and energy scales in solids
Due to free (VB) electrons:
- Intra-band transitions:
- Single electron oscillations (Plasmaoptic):
- Collective electron oscillations (Plasmons):
Due to bound electrons:
- Inner (core & valence) electron shells
- Inner-shell excitations (d-d, f-f):
- Inter-band transitions (VBCB):
- Absorption from localized states
- Excitons:
- Defects (Impurities, vacancies or interstitials):
- Spin-orbit splitting:
- Spin waves (Magnons):
- Charge transfer excitations:
- Correlation effects:
Eband width (few eV)
0.5 meV
2 17 eV
4 eV 98.5 keV
100 meV 2 eV
10 meV 11 eV
EBind few meV up to few eV
10 300 meV
few eV (for d and f electr.)
10 40 meV
up to several eV
order of eV
Due to coupling of photons to Phonons (lattice vibrations):
- Photons acoustic phonons (Brillouin scatt.)
10-6 0.1 meV
- Photons optical phonons (Polariton scatt.)
40 70 meV
An example of what you can do with XAS
D.L. Sparks et al
Absorption (XAS) Excitation
Binding Energy [eV]
hin
CB
284 eV
VB
XAS probes local unoccupied
partial density of states (pDOS)
or CB states.
C 1s
The selection rules for XAS and XES (l = 1) only allow for transitions
C, N, O : 2p 1s. (Photons carry angular momentum (spin) of . It is preserved
when photons interact. This gives rise to the selection rule l=1.)
Soft X-ray Emission Spectroscopy (XES)
What do X-ray Absorption & X-ray Emission Spectroscopy probe?
Excitation
Relaxation
Absorption (XAS)
Emission (XES)
Band structure of Si N
3
Binding Energy [eV]
Unoccupied states or CB
hin
Occupied states or VB
hout
XAS probes
unoccupied
pDOS (CB)
410 eV
N 1s
XES probes
occupied
pDOS (VB)
Note: (Dipole) selection rules for XAS and XES (l = 1)
only allow for (dipole) transitions C, N, O : 2p 1s
The principle of photon-in photon-out experiments
Sample
Monochromator
Obtain information on
electronic structure
and bonding
of materials
Intensity [Counts]
Spectrometer
265
270
275
280
285
Emission Energy [eV]
Counts
Soft X-ray Emission Spectroscopy (XES)
265
270
275
280
Energy [eV]
285
n = d (sin sin )
Resolving power and resolution for XAS & XES
Resolving power for emission experiments is in the order of E/E 1,000
This is worse than the best XAS experiments: E/E 10.000
Meridional Axis (um)
20 um
Sagittal Axis (um)
20um
XES is extremely photon hungry!
N0 photons on sample but loss factors
cannot be avoided.
Fluorescence Yield: Number of
fluorescence photons per core hole.
Loss mechanism
Sample (Fluorescence yield)
XES
10-3
XAS
0.9
Acceptance spectrometer
610-4
Detector & spectrometer
0.02
0.1
Total
1.210-8 0.09
XES needs 8106 more photons than XAS!
Could be avoided by
Slitless spectrometer.
Careful design can
improve this factor
by 10!
XES requires lots of photons in a small spot on the sample high brilliance!
XES is characteristic for each site
Si L2,3 XES: VB (3d3s) 2p
C K emission : VB (2p) 1s
Carbon compounds
Si L2,3 XES for different compounds
15000
Intensity [arbitrary anits]
SiO2
SiC
5000
CNx
10000
a-C
HOPG
5000
c-Si3N4
Diamond
C3N4
nanowire
0
80
85
90
95
Emission Energy [eV]
1.
Counts
Si
Counts
31-7-1
31-7-2
31-7-3
31-7-4
23-3-2
23-3-3
23-3-4
diamond paste
C K XES
15000
10000
Diamond films
100
105
260
265
270
275
280
Emission Energy [eV]
285
0
265
270
275
280
285
Emission Energy [eV]
XES & XAS spectra are specific to the chemical environment.
2. XES & XAS spectra are element specific.
3. XES spectra are site specific.
4. Plasma produced Diamond films turned out to be diamond.
290
Ion irradiated polymers
Si L2,3 emission :
3s3d (Valence Band) 2p
Si L2,3 XES
Intensity [arb. units]
Polymer C6H5Si(OC2H5)3
Phenyltriethoxysilene or PTES
PTES
unirrad.
15
A new method to modify polymers!
-2
-2
2.5x10 Au cm
Result:
PTES converts under ion irradiation
to Si:O:C (ceramic!).
85
90
95
100
15
-2
2.5x10 Au cm
Intensity [arb. units]
Application:
ceramic has different mechanical, electrical
and thermodynamic properties than PTES:
Scratch resistant,
Electrical conductivity,
Thermal conductivity.
14
5x10 Au cm
PTES
SiC
SiO2
c-Si
85
90
95
Emission Energy [eV]
100
Kurmaev, Moewes et al., Phys. Rev. B 60, 15100 (1999)
