1.

5 Light absorption by solids

Bloch-Brilloin model
In a unidimensional approximation,
electrons in a solid experience a
E e– periodic potential due to the
positively charged atomic nuclei of
the crystal lattice. In Kronig-Penny’s
model, this situation is further
L
simplified by considering equidistant
+ + + + + potential wells of constant depth.
x
Solving the Schrödinger’s equation in
E this case yields:
allowed energy bands
!2
En = n2 ⋅
8m*e ⋅ L2
band gaps with n = ±1, ± 2, ...
me* is the electron effective mass, such
as it satisfies (within an allowed band)
de Broglie's relation :
p2 !2 ⋅ k 2
p E = =
2m*e 2m*e 47

Band theory
Energy bands can also be understood by
E considering mutual interactions of
N carbon atoms
4N states electronic wave functions of atoms
0 electron
constituting the solid. When a large
8N states
4N electrons number of atoms are brought together,
6N states (2p)
2N electrons
energy levels split, yielding many new
energy gap 2N states (2s) orbitals. The difference in energy between
2N electrons them becomes very small, so the levels may
cohesive energy
be considered as forming continuous bands
4N states
4N electron of energy. Some intervals of energy contain
C-C equilibrium distance (diamond) r no orbitals, no matter how many atoms are
aggregated, forming band gaps.

E cb conduction band
lowest empty or partially filled energy band
Ecb
Eg band gap
Evb band of forbidden energy
valence band
vb highest entirely occupied energy band
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Electric conduction in solids

E cb cb cb

Eg Eg

vb vb vb

insulator conductor conductor

empty cb, large band gap overlapping cb and vb partially filled cb

Insulators' conduction band is Conductors, or metals are characterized by

totally empty, while their valence a partially filled conduction band. Electrons,
band is entirely occupied. Electrons, when subjected to an electric field, may
then, may not contribute to the acquire some kinetic energy. The specific
electrical conductivity of the electrical conductivity s is given by the
material, because no energy level is product of the density n of charge carriers
available for them to acquire and their mobility µ:
kinetic energy and to move. s = q ⋅ n ⋅ µ ⎡⎣Ω−1 ⋅ m −1 ⎤⎦

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Semiconductors

E cb cb cb

Eg < 3kBT
Eg Eg

vb vb vb

semiconductor semiconductor semiconductor

small band gap donor impurities (n-doping) acceptor impurities (p-doping)

Semiconductors are insulators for which a Charge carriers can also be produced
conduction can however be obtained under by chemical doping of the solid.
some conditions. If Eg < 3 kBT, for instance, Donor impurities yield n-doping (ecb–
electrons can jump thermally across the band carriers). Acceptor impurities
gap and be promoted from the valence band produce holes in the valence band
to the conduction band. Both conduction (h vb + carriers) and p-doping. In
band electrons and valence band holes charge semiconductors, the density of charge
carriers contribute then to the conduction. carriers n is always rather small.
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Intrinsic light absorption

E The promotion of an electron from the fully occupied

cb
e– valence band to the conduction band can also be
achieved by intrinsic light absorption of photons of
energy hν ≥ Eg . The photo-conduction of the
hν ≥ Eg semiconductor under band-gap irradiation is due to
both ecb– and hvb+ charge carriers.
h+
vb Example:
Titanium dioxide TiO2 is a solid with a rather ionic
character. It can be seen as being constituted of Ti4+
and O2– ions.
α
Ti 3d2 4s2 Ti4+ 3d0 empty conduction band
O 2p4 O2– 2p6 entirely occupied
valence band.

hν Photons of energy hν ≥ Eg = 3.2 eV (λ ≤ 380 nm) are

absorbed, yielding a transition 2p(O) 3d(Ti).

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Band structure

Band structure in the reciprocal

space is a compact and elegant
way to represent all electronic
states in a periodic system. In
such a representation, bands
appear ideally as a series of de
Broglie's parabolas E = ƒ(k):

p2 !2 ⋅ k 2
E = =
2m*e 2m*e

where k is the wave vector of a

c h a r g e c a rr i e r a n d p i t s
momentum: k = 2π ⋅ p / h
However, because me* is not the
same in all directions of the 3D
space, a complex structure is Band structure of TiO2 rutile. Left: Energy vs. wave vector
observed rather than simple along symmetry lines in the Brillouin zone. Right:
parabolas. schematic of energy bands.
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Direct vs indirect transitions

cb Since photons do not carry any mechanical

momentum, k should remain unchanged
during an electronic transition if no
direct vibration is coupled to it. A transition
following the Frank-Condon principle
indirect (k constant) is called a direct transition.
vb
hν = E g Δk = 0

cb An indirect transition implies a

vibration of the solid lattice is coupled to
the electronic movement. The change of
the momentum is brought by absorption
of a phonon of energy Ep (Δk > 0) or
released during the emission of a phonon
in the solid (Δk > 0).
hν = E g ± E p Δk = ± k p
vb
53

Gärtner's relations
direct transition: α ∝ hν − Eg
α
( )
2
indirect transition: α ∝ hν − Eg
α ∝ hν
2

α ∝ hν

λ ∝ 1 / hν

indirect transition:
absorption threshold
hν = Eg − E p

hν

Eg – Ep Eg Eg + Ep
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Excitonic absorption
cb
An exciton is an electron-hole pair in
which charge carriers are bound Ex
together by Coulombic interaction. The
Eg
exciton is a neutral entity which can hν = Eg – Ex
move easily in an insulator and carry
excitation energy.
vb

exciton absorption
α2 GaAs
α Exciton bond energy Ex [meV]

free e–cb absorption Si 14.7 CdS 29 KCl 400

Ge 4 CdSe 15 KBr 400
Eg GaAs 4.2 BaO 56 AgCl 30
GaP 3.5 InP 4 AgBr 20

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Size and bond energy of an exciton

Bohr's planetary model (hydrogen atom)

n2 ⋅ !2 ⋅ ε 0 me*
rH = = n 2 ⋅ 0.56Å with 1 / µ = 1 / me + 1 / m p ! 1 / me
µ ⋅ e2 –
mh*
!2 ⋅ ε ⋅ ε 0 me*
rx = = ε ⋅ ⋅ rH with 1 / m = 1 / me + 1 / mh
* * * rx +
m * ⋅ e2 m*

m * ⋅ e2 m*
Ex = = ⋅ 13.6 [eV ]
2me ⋅ ε 2 ⋅ rH me ⋅ ε 2

for comparison: ε (H2O) = 87

Exciton radius rx and bond energy Ex [meV]

Eg / eV me*/me mh*/mh ε/- rx / Å Ex / meV

CdS 2.6 0.19 0.8 5.7 20.8 64

ZnO 3.2 0.24 0.45 3.7 13.2 155

TiO2 3.2 30 4 184 37.8 1.1

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Quantum size effect

Confinement of electrons in particles

whose size is comparable or smaller than
! 2 me e2 that of the exciton in the bulk material
ΔEg = ⋅ −
8r 2 m * ε ⋅ r leads to an increase of the excitation
energy Eg.
As a result, the bandgap increases and the
absorption threshold shifts to the blue
when particle size is decreased.
This quantum size effect, which is a
direct evidence of the "particle in a box"
concept, allows to adjust the color of
Absorbance

colloidal particles of wide bandgap

= 80 Å
semiconductors.
= 35 Å
Left: Absorption spectra of aqueous colloidal
suspensions of CdS particles. Particle
2r = 20 Å diameter is reduced from 80 Å to 20 Å,
causing an important hypsochromic shift.
300 400 500
λ / nm
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Quantum dots

Quantum dots (QDs) are

semiconducting nanoparticles in particle diameter
which excitons are confined in all
three spatial dimensions. 20 Å 74 Å
Quantum confinement affects the
absorption and emission of photons
from the dot. Thus, the absorption
edge of a material can be tuned by
control of the particle size.
Quantum dots are particularly
significant for optical applications
(bio-imaging, diode lasers, LEDs, solar
cells, ...) due to their high extinction
coefficients.
Solutions of monodisperse CdSe nanocrystals
Similar to a molecule, a quantum dot with increasing diameter (from left to right).
has both a quantized energy spectrum Photoemission (fluorescence) wavelengths are
and a quantized density of electronic indicative of the respective bandgap energies.
states near the edge of the band gap.

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