LOW DIMENSIONAL SYSTEMS AND NANOSTRUCTURES

2. Electronic states and quantum confined systems

Nerea Zabala
Fall 2007

• From last lecture...

“Top-down” approach------update of solid state physics

• Not bad for many metals and doped semiconductors

• Shows qualitative features that hold true in detailed

treatments.

• Successive approximations:

- “Free particles” –no external potential

- Independent electron approximation
- Assumes many-particle system can be modeled by starting from single-
particle case.
Beyond these approximations...Density Functional Theory (DFT), Quantum
Montecarlo.....

First, find allowed single-particle states and energies....

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 LOW DIMENSIONAL SYSTEMS AND NANOSTRUCTURES

2.Electronic states and quantum confined systems

• Contents:
• Electrons in solids: approaches
• Independent electrons
• Electrons in a 1d box: confinement
• 3D electrons gas. Filling states. The density of states
• 2D electron gas
• Electrons in 1D
•Quantum dot
• DOS in 3, 2,1D
• Crystal structure and effective mass approximation. Semiconductors
•Quantum size effects
• Some useful confining potentials
• Summary
3

• Electrons in solids: approaches

Metal and conduction electrons
valence
electrons
free atoms a solid nuclei

core
electrons

Pseudopotentials,
jellium models

Pseudopotentials,
Jellium models

Ions smeared out into a positive

background

4
 • Independent electrons
Time-independent SchrÖdinger equation:

!2 2
− ∇ Ψ + V (!r)Ψ = "Ψ
2m
Solve, consistent with boundary conditions.

Free ! V= 0
!(k)
Solutions, electron wave functions:
! !
Ψ = Aeik·!r + Be−ik·!r
, traveling plane waves with wave vector !k
Time-independent Schroedinger equation (TISE):
2

k = 2π/λ
# and
" !λ+ is
V (rthe
)! =wave
E! length
2

2m
Must solve, consistent with boundary conditions. Free
particle means V = 0. Solutions are of the form k
! ~ Ae!ik2$rk+2 Be # ik $r
Energies : !(k)
These are traveling = with wavevector k.
waves No restriction for allowed values of k or E, continuous.
2m
|k| = 2%/&, where & is wavelength.
2
Energies are then k2
E (k ) = 5
E

2m
Dispersion relation
k

No restrictions here on allowed values of k or E.

• Electrons inparticle
Now try a 1d a 1din box: confinement
a box potential:

1d particle in a box potential: V

V
Infinite wall potential
0,0 < x < L
V=
), x ( 0; x ' L
Interior of box, V = 0, so solution must look
like superposition of plane waves, but ! must
Inside eht box,Interior
V= 0, so solution
vanish
of box, V at must
= 0,walls. look like0 look
Answer:
so solution must
L
superposition of
plane waves, but
like" must vanish
superposition Interior
waves, of
at walls.
of plane butbox, V = 0, so solutionVmust look
! must
vanish at walls. Answer: like superposition
2 " V of plane waves, but ! must
# n ( x) =vanish sinat walls.nxAnswer: 0 L
2 " L L V
# ( x) =
n sin nx
2 "
L L
n = 1,2#,3n ( x) = L
sin nx
L
n = 1,2,3
So,k allowed
So, allowed values are k values are n = 1,2,3 V
n" n"
Allowed k values:k = L , n =k1,=2,3 , nSo,= allowed
1,2,3 k values are 2
L n"
meaning allowed energy values kare= , n = 1,2,3
meaning
2 2
allowed energy
2 2 2
L values are
k " n meaning allowed
0 energy valuesLare
E (k ) = = 2 2 2 2 2
2m 2mL2 k " 2n 2 2 2 2 0 L
E (k ) =
Allowed energy values = k " n 0 L
2m E (k ) 2=mL2 =
2m 2mL2
0 L
6

Finite sample size drastically alters allowed energy levels!

100
100

80
/2mL2]

80
mL2]

Dispersion 60
Finite sample size drastically alters allowed energy levels!
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• Electrons in a 1d box: confinement
Finite sample size drastically alters allowed energy levels!
! Energy spectrum is now discrete rather than continuous.
!(k) !(k)

Dispersion relation plot

!(k)
k k

Energy level diagram Energy

Energy
(allowed energy values)

! Allowed wavevectors are uniformly spaced in k-space

with a separation of #/L.

k-space plot k[π/L] k[π/L]

(allowed k values)
! Sample size L determines spacing of allowed wavevectors and single-particle energies,
with a smaller box giving larger spacings. 7

• 3D electrons gas. Filling states. The density of states

Non-interacting many-electron systems

• Interested in ground state of many-electron system.

• No interactions $many-body eigenstates should be linear combinations of products of

single-particle eigenstates.

• They obey Pauli principle $correct total wavefunction should be antisymmetric under
exchange of any two particles.
Many-body eigenstates should be linear combinations of Slater determinants built out of
single- particle eigenstates.
Approximation (or shorthand):
start filling each single-particle state from the lowest energy, each with
one spin-up and one spin-down electron.

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• 3D electrons gas. Filling states. The density of states
! "
!2 ∂2 ∂2 ∂2
− + + Ψ!k ("r) = #!k ("r)Ψ!k ("r)
2m ∂x2 ∂y 2 ∂z 2

1 i!k·!r !2 k 2
Ψ!k (!r) = e traveling waves and energies !!k =
V 2m
•Boundary conditions:
Confined in a cube of size L ! Ψ!k = 0 at the boundaries

! allowed momentum values and standing waves

nx , ny , nz = 0, 1, 2, 3...
2πnx 2πny 2πnz
kx = ± , ky = ± , kz = ±
Lx Ly Lz

• 3D electrons gas. Filling states. The density of states

•Filling states:
1√
!2 kF2 kF = 2m!F
!F = Fermi energy !
2m Fermi momentum/velocity

•Counting states:
Fermi sphere
(2π)3
1 state → volume in "k space
V

! "
V
→ d"k
(2π)3
k

! kF
V V 3
N =2 4πk 2 dk = k
(2π)3 0 3π 2 F
For spin

N k3
•Electron density n= = F2
V 3π

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• 3D electrons gas. Filling states. The density of states

•Fermi energy and momentum increase with density of electrons!

!2
!F = (3π 2 )2/3 n2/3 pF = !kF = !(3π 2 n)1/3
2m

•All single-particle states with below the Fermi energy are occupied at
T=0. These states are called the Fermi Sea. The set of points in k-space
that divides empty and full states is the Fermi surface.

•Exactly how the Fermi energy depends on density depends

drastically on dimensionality.

•Usually dimensionless parameter , radius of sphere containing one

electron:

4π 1
(rs a0 )3 =
3 n
Bohr
11

• 3D electrons gas. Filling states. The density of states

•Some values (Kittel)

12
• 3D electrons gas. Filling states. The density of states

•Some numbers for Cu

•Hall measurements in macroscopic samples yield the electron density

of Cu (it can be also estimated from from interatomic distances) :

n = 8.47 × 1028 m−3

Calculate kF , λF , "F and vF

Note that the Fermi velocity is less than a percent of the velocity of light, so no relativistic
treatment is needed.

13

• 3D electrons gas. Filling states. The density of states

The density of states (DOS),
The number of allowed single-particle states with energies
between E and E+dE,in an element of length/area/volume.

! From our expressions for n(E), nd is the spatial electron density in d dimensions
! "3/2
1 2m
! 2
n(!) = !3/2
!F = (3π 2 )2/3 n2/3 3π 2 !2
2m ν(")
! "3/2
dn 1 2m
ν(") = ν(") = "1/2
d" 2π 2 !2
!
! Higher DOS means levels are more closely-spaced.

! From this definition, we can find the spacing of single particle levels in a piece of material!

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• 3D electrons gas. Filling states. The density of states
Some numbers...

! Estimate the energy level spacing in 1 cm3 of Na

Consider one valence electron per Na atom.

We use the density and fermi energy from the table
n ∼ 2.65 × 1022 cm−3
!F = 3.2eV = 5.2 × 10−19 J

−1
ν("F ) ∼ 8 × 1046 J m−3

Energy level spacing: ∆! = 1/ν(!F )V ∼ 10−41 J The particle energy levels are continuous

15

• 3D electrons gas. Filling states. The density of states

Some numbers...

!Now suppose we have 1nm3 of Na, instead

A similar calculation yields the energy level spacing:

∆! ∼ 3 meV

This is actually measurable!

At low temperatures, the individual electronic levels in a piece of metal can

dominate many properties, something that doesn´t happen at macroscopic sizes

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•3D electrons gas. Filling states. The density of states
The density of states of the free electron gas at finite temperature

! Fermi-Dirac distribution function (fermions)

T =0

1
f (!) =
e(!−µ)/kT + 1
T != 0

!
n= n(!)f (!, T )d!

T → 0 ⇒ f (!) → θ(!F − !) , step function

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2. Quantum Well States (QWS) and Quantum Size

• 2D electron gas Effects
Qualitative D
explanation…
∼ λF

kz •Confinement in z direction, free in x and y

!k! = (kx , ky ) Paraboloidal subbands

k !
Ψn,!k! (!r) = yΦn (z)eik! ·!r! D
kx
(!k! )2 !3
!nElectronic
("k) = !n + structure !F
2m
in parabolic subbands !2
•Strictly 2D if !1 < !F < !2
ik x x ik y y
!1
" ( x, y , z ) = ! n ( z )e e
•In infinite well confining potential (1D):
2 !
! nπ "22 2 k 2 + k 2
!n =E (n, k x , k y ) = ! n2 + x y
2m D 2 D 2 4

•Discrete continuous

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• 2D electron gas
•Filling states in 2D, occupation of subbands
2πnx 2πny
•Periodic boundary conditions!allowed kx = ± , ky = ±
Lx Ly
(2π)2
•Consider T=0 1 state → surface
L2
! " kF ! 1
L2
N2D = 2 2πkdk = L2 kF2
(2π)2 0 2π
nf illed nf illed

•Density (per surface) ! k2

n2D = F
2π
nf illed

•As a function of energy:

! m
n2D = (!F − !n )
π!2
nf illed

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• 2D electron gas
•Density of states in 2D: ! m
n2D (!) = (!n − !)
π!2
nf illed
dn
ν(") = m !
d" ν2D (") = θ(" − "n )
π!2 n
Infinitely deep square well
Subbands,
(GaAs, D=10 nm) step or Heaviside function
transverse kinetic energy
, energy levels

Steplike DOS of a quasi 2D system

Parabolid density of states for unconfined

3D electrons

m
π!2

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•Electrons in 1D
•Further confinement (in 2D), x and y : quantum wire
or electron wave guide Lx , Ly ∼ λF
Ψm,n,kz (!r) = Φm,n (x, y)eikz z
(!kz )2
!m,n (kz ) = !m,n +
2m z
•Parabolic subbands
! " kF !
L L
N1D = 2 2 dk = 2 kF
2π 0 π
m,nf illed m,nf illed

•Density (per unit length)

! kF
n1D = 2
π
m,nf illed

•As a function of energy:

(Use the dispersion relation for each subband)

"
! 2m(!F − !m,n )
n1D = 2
!π
m,nf illed
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•Electrons in 1D

•Density of states in 1D:

"
! 2m(! − !m,n )
n1D = 2
!π
m,nf illed

! (2m)1/2 (" − "m,n )−1/2

ν1D (") = θ(" − "m,n )
m,n
!π

DOS of a quasi 1D system,

GaAs, 9!11 nm infinitle deep well

Parabolid density of states for unconfined

3D electrons
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•Electrons in 0D
•Further confinement (in 3D): quantum dot or
artificial atom
Lx , Ly , Lz ∼ λF
•Discrete energy levels, as in atoms

•DOS is just asum of delta functions

!
ν0D (") = 2 δ(" − "j )
j

discrete eigenenergies of the system

ν(")

23

• DOS in 3, 2,1D

Quantum Confinement and Dimensionality

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•Crystal structure and effective mass approximation. Semiconductors
•Electrons in periodic potential (Nearly free electron model)

Electrons in a periodic potential !

V (!r) = V (!r + R)
Bloch's theorem:
Probability
density for standing
waves produced ψn!k ("r) = exp(i"k · "r)un!k ("r)
n: band index
ion Bloch wave functions
core
! = u ! (!r),
un!k (!r + R) nk
R
periodic Lattice vector
potential

! = ei!k·R! Ψ! (!r)
Ψ!k (!r + R) k

Standing waves

25

•Crystal structure and effective mass approximation. Semiconductors

Two wave vectors and the solutions of Schrödinger equation are related to each other. This leads to equal
eigenvalues

!n ("k) = !n ("k + K)
"

and equal wave functions

ψn!k ("r) = ψn!k+K
! ("
r).

Each energy branch has the same period as the reciprocal lattice. As the functions are
periodic, they have maxima and minima which determine the width of the bands.

The wave vector k can always be chosen in a way to belong to the first Brillouin zone because k!! = K
! + !k
! !
eiK·R = 1

Reciprocal lattice vector

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•Crystal structure and effective mass approximation. Semiconductors

•Exercise: Solve 1D periodic square-well potential model: Kronig-Penney

Kittel

27

•Crystal structure and effective mass approximation. Semiconductors

Gap opening

First Brillouin zone

Nearly quadratic
•The effective mass approximation: m*

(valid for low

electron momenta)

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•Crystal structure and effective mass approximation. Semiconductors
•Occupation of energy bands: type of materials

Metal or semimetal Metal

Insulator
(if band overlap small)

Sketch

29

•Crystal structure and effective mass approximation. Semiconductors

Effective Mass
from band dispersion

h̄2
m!e = 2
∂ "/∂k 2

30
•Crystal structure and effective mass approximation. Semiconductors

Band structure of some semiconductors

Ge Si GaAs

31

•Crystal structure and effective mass approximation. Semiconductors

•Positive and negative effective mass:

Negative m*, holes

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•Crystal structure and effective mass approximation. Semiconductors
•Insummary: we can consider also semiconductors including m* in the Schrodinger
equation.
Then, for the density of states in 0,1,2,3D one can extrapolate the results

!
ν0D = 2 δ(# − #j )
j

! (2m∗ )1/2 (" − "m,n )−1/2

ν1D = θ(" − "m,n )
m,n
!π

m∗ !
ν2D (") = θ(" − "n )
π!2 n
! "3/2
1 2m∗
ν(") = "1/2
2π 2 !2

• Signature of dimensionality
33

•Quantum size effects

•Confinement !Discrete Quantum Well States!Oscillations in the physical properties (as energy,
Fermi level....) as a function of size

34
•Quantum size effects

Condition of QWS existence

L = 2 D = !n n = 1,2,3,...

" 2n2
E= n = 1,2,3,...
2D 2

#F

Energy of system
(per electron)

35

•Quantum size effects

•An example: magic heights of Pb islands on Cu(111) studied with STS

Building island heights Number of islands Covered area

histograms

Courtesy: Rodolfo Miranda

R. Otero, A. L. Vázquez de Parga and R. Miranda PRB 66, 115401 (2002)

36
 The model seems to give reasonable res
(fortunately)

•Quantum size effects

1D potential model (self-consistent calculation)

Island stability (II)

• Very good agreement with the

experiments.

? • Shell and supershell structure like

for nanowires and clusters.
• It can now be observed indirectly
in the experiments.

Ogando, Zabala, Chulkov, Puska, Phys. Rev.B 69, 153410

(2004)

37

•Quantum size effects

•Find other examples of quantum size effects in the literature

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•Some useful confining potentials

•Square well of finite depth -quantum wells, thin slabs-

•Parabolic well -quantum dots-
•Triangular well -heterojunctions-
•Cylindrical well -quantum corral, metallic nanowire-
•Spherical well -clusters, quantum dots-

See for example J.H. Davies

Also in next lectures

39

•Some useful confining potentials

•Triangular well -heterojunctions-
•Confining potential
(z perpendicular to 2DEG)

Introduce dimensionless variable

equation:
solutions with boundary conditions (finite at infinity an zero at z=0)
40
•Some useful confining potentials
solutions
with

Airy functions

Subbands

m, effective mass
41

•Summary
• The effects of confinement have been studied qualitatively starting from non-
interacting electrons confined in potential wells.
•Confinement produces discreteness of allowed electron energies giving rise to
quantum size effects.
•The characteristic pattern of the density of states in one, two and three
dimensions has been obtained.
•The conclusions are valid for metals and semiconductors, when the effective
mass approximation is considered.

• Electron interactions in low D have not been considered but they may very
important in many problems, for example to explain superconductivity,
magnetism, quantum Hall effect... In low D screening, response etc... is
different

• In another course: phonons, plasmons, excitations in low dimensions

42