Intro.

to Electro-physics
Crystal vibration (1st)

Jaesang Lee
Dept. of Electrical and Computer Engineering
Seoul National University
(email: jsanglee@snu.ac.kr)
Introduction
• Major reasons for the failure of Drude’s and Sommerfeld’s models
- Free-electron approx.: the ignorance of the e ects of ions on electrons
- Lack of understanding of microstructure of crystalline solids

• Main theme of the part IV = The e ects of the periodic lattice & crystal vibrations

Monatomic

Diatomic

Quantized crystal vibrations = phonons Simple 1D atomic model

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General properties of 1D atomic model (1/3)
• Covalent bonding in 1D V (x)
V (x) : The potential between two neighboring atoms
x : The distance between atoms
x
- Taylor expansion around its minimum at x = xeq:

κ κ 3 V (xeq)
V (x) ≈ V (xeq) + (x − xeq) −
3! ( )
2 3
x − x + ⋯ x
eq xeq
2

- When the deviation of x from xeq (δxeq ≜ x − xeq) is small: κ

κ
V (x) ≈ V (xeq) + (x − xeq)
2

2
Quadratic potential based on Hooke’s law
 κ
V (x) ≈ V (xeq) + (x − xeq)
2

General properties of 1D atomic model (2/3) 2

• A force to compress the system (i.e., a pressure to 1D system)

F = − ∂V/∂x = − κ (x − xeq) = − κ (δxeq) Positive pressure reduces the distance between atoms!

- (Isothermal) compressibility

1 ∂V 1 ∂L 1 1 Compressibility:
β=− β=− = = A measure of the instantaneous relative volume change
V ∂P 1D L ∂F κxeq κa of a uid or solid in response to a pressure

- Speed of sound
Bulk modulus (sti ness):
ρ : mass density of a matter
ρβ {B ≜
B 1 - A measure of how resistant to compression that the matter is
υ= = , 1 ∂P
ρ β
=−V ∂V
: Bulk modulus - The ratio of the in nitesimal pressure increase to the resulting
relative decrease of the volume

m 1 κ
In a 1D solid, ρ = . ∴υ= =a
a m
⋅ 1 m
a κa
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General properties of 1D atomic model (3/3)
• Thermal expansion at T > 0 (K) V (x)

- The atoms oscillate around xeq between [xmin, xmax]

Since xmax − xeq > xmin − xeq ,

kBT
∴ ⟨x⟩ > xeq Thermal expansion! V (xeq)
x
xmin xeq xmax
Vibrations of a 1D monatomic chain (1/2)
• 1D monatomic chain

A chain of identical atoms of mass m, where the equilibrium spacing between atoms is a (i.e., lattice constant)

- The position of the n− th atom : xn a

κ
eq
- The equilibrium position of the n− th atom : xn ≜ na ··· m ···
eq
- The deviation from the equilibrium position : δxn ≜ xn − xn Spring with an equilibrium length a

• Total potential energy of the chain (i.e., stored energy in springs)

At low T, the interatomic potential holding atoms together is “quadratic”:

∑ 2 [( i )]
2
κ κ
∑2[ ] i+1) (
2
V (xi+1 − xi) = ( )
eq eq
∑
Vtot = xi+1 − xi − a = xi+1 − x − xi − x
i i i

κ
(δxi+1 − δxi)
2
∑2
=
i
 κ
(δi+1 − δi)
2
∑2
Vtot =
Vibrations of a 1D monatomic chain (2/2) i

• The force on the n− th atom of the chain

[ ]
∂Vtot ∂ κ
( ( ) ( ) )
2 2
Fn = − =− ⋯ + δxn − δxn−1 + δxn+1 − δxn + ⋯
∂xn ∂xn 2

= κ (δxn+1 − δxn) + κ (δxn−1 − δxn) = κ (δxn+1 − 2δxn + δxn−1)

• Newton’s equation of motion

mδxn = Fn = κ (δxn+1 − 2δxn + δxn−1)

··

- Educated solution

A : Amplitude of oscillation
j(ωt − kxneq) j(ωt − kna)
δxn = Ae = Ae ω : frequency
k : wave number

For any coupled system, a normal mode is de ned as

a collective oscillation where all particles move at the same frequency ω

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 The equation of motion
Dispersion relation mδx··n = κ (δxn+1 − 2δxn + δxn−1)
- Educated solution (ω ≥ 0) j(ωt − kna)
δxn = Ae

[e ]
2 i(ωt − kna) iωt −ik(n + 1)a −ik(n − 1)a −ikna
−mω Ae = κAe +e − 2e

(2)
ka
−mω = κ [e
2 −jka
+ e − 2] ⟶ mω = 2κ (1 − cos ka) = 4κ sin
jka 2 2

(2)
κ ka
∴ω=2 sin
m

Dispersion (ω vs. k) relation ω

A relationship between a frequency (ω) (energy)

and a wavevector (k) (momentum)

π π k
− 0
a a
Reciprocal lattice and Brillouin zone
• Reciprocal lattice

- A periodic system in real space with a periodicity a (i.e., x → x + a)

= A periodic k− space (or “reciprocal space”) with a periodicity 2π/a (i.e., k → k + 2π/a)

(2)
κ ka
ω=2 sin (Dispersion relation repeated in k → k + 2π/a)
m
ω
• Important terminologies

- Brillouin zone : The periodic unit cell in k− space

- The rst Brillouin zone : A unit cell centered around k =0

- Brillouin zone boundaries : k = ± π/a
π π k
− 0
a a
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Real vs. reciprocal lattices
• Meaning of the periodic dispersion relation (k → k + 2π/a)

( a )na)
j ωt − (k + 2π
j(ωt − kna) j(ωt − kna) −j2πn j(ωt − kna)
δxn = Ae = Ae = Ae ⋅e = Ae

∴ k and k + 2π/a represent physically equivalent oscillation modes!

−2πnp
∴ k and k + 2πp/a represent physically equivalent oscillation modes! (For any integer p, since e = 1)
• Direct (real-space) lattice: the periodic set of points in real space with a periodicity a, (xn = na)

• Reciprocal lattice: the periodic set of points in k− space that are physically equivalent to the point k = 0 (Gm)

Gm is a member of reciprocal lattice x

⋯ −2a −a 0 a 2a ⋯
if and only if exp (iGm xn) = 1 is true
2π k
for all xn → ∴ Gm = m 4π 2π 2π 4π
a ⋯ − − 0 ⋯
a a a a
Intro. to Electro-physics
Crystal vibration (2nd)

Jaesang Lee
Dept. of Electrical and Computer Engineering
Seoul National University
(email: jsanglee@snu.ac.kr)
Review of last lecture
• 1D monatomic chain a
κ
- A chain of identical atoms of mass m, where the equilibrium ··· m ···

spacing between atoms is a (i.e., lattice constant)

- Each atom vibrates with respect to the equilibrium position
1st Brillouin zone
- A collective vibration of atoms at the same frequency
ω
= “Normal mode”

• Dispersion relation for a vibrational wave (ω vs. k relation)

(2)
κ ka
ω=2 sin
m k
π 0 π
−
- Periodic in k− space with a periodicity 2π/a a a

[ a a]
π π * Brillouin zone : The periodic unit cell in k− space

- The dispersion in 1st Brillouin zone − , only matters! * 1st Brillouin zone : The unit cell around k =0
Number of normal modes
• Number of normal modes (= allowed k values)
xn+1
- Assumption: a 1D system consists of N atoms in a row with xn = xn+N
xn+N−1
a periodic boundary condition such that xn+N = xn
j(ωt − kna) j(ωt − k(n + N)a) −jkNa
δxn = Ae = Ae ⟶ e =1
- k is quantized as being:
2π
2π a
kNa = 2πp, where p : integer. ∴k= p
Na
- The number of modes in the First Brillouin zone

Range of k 2π/a 2π
= =N
Spacing between neighboring k's 2π/Na Na
k
π π
∴ One normal mode per particle in the system − 0
a a
= One normal mode per “degree of freedom” in the whole system
Phonon
• Vibrational wave of crystals in terms of quantum mechanics

- The vibrational wave with a given k− value ≜ ψk (x)

- The wave satis es Schrödinger’s equation: Interatomic
harmonic potential

( 2m )
2
ℏ 2 1 2
− ∇ + V (x) ψk (x) = Ekψk (x), where V (x) = κx
2

- The eigenstate (ψk (x)) yields the corresponding energy :

( 2)
Eigenstates and eigenvalues
1
Ek = ℏωk n + (n = 0, 1, 2,⋯) for quantum harmonic system

‣ At a given ωk, there are many possible quantized energy levels

‣ ωk determined by k : Dispersion relation

‣ [Quantum] Higher Ek (or higher n) = [Classic] Oscillations of increasing amplitude

‣ The discrete quantum of vibrational energy at a given ωk = Phonon

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Vibrations of a 1D diatomic chain
• 1D diatomic chain

A chain of two alternating atoms of masses m1 and m2 (e.g. NaCl, GaAs, ···)

• Important terminologies
- Unit cell : The smallest repeated unit in the structure (* De nition of the unit cell is non-unique)
- Lattice constant : The length of the unit cell
- Lattice : A periodic set of reference points inside each unit cell
- Basis : All of the atoms in the unit cell located with respect to the lattice point

Lattice point a Unit cell - Basis

‣ : at 3/10a left to the reference

m m ‣ : at 3/10a right to the reference

- The reference lattice point in n− th unit cell (rn = an)

3/10a 3/10a
eq
‣ : xn = rn − 3/10a
rn−1 rn
eq
‣ : yn = rn + 3/10a
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Normal modes of the 1D diatomic chain κ1 κ2
• Simplifying assumption m m

m1 = m2, κ1 ≠ κ2 (a.k.a. alternating chains) yn−1 xn yn xn+1

• Newton’s equation of motion for the deviations of the n− th atoms w.r.t. the n− th lattice point :
··
mδxn = κ2 (δyn − δxn) + κ1 (δyn−1 − δxn) eq

{mδyn = κ1 (δxn+1 − δyn) + κ2 (δxn − δyn) {δyn ≜ yn −

δxn ≜ xn − xn
·· , where
eq
yn

j(ωt − kna)
δxn = Axe
Educated solution:
j(ωt − kna)
δyn = Aye

→ mω = (κ1 + κ2)
2 ± jka
κ1 + κ2e . Here, κ1 + κ2e jka
= (κ1 + κ2e ) (κ1 + κ2e
jka
).
−jka

(κ1 + κ2) − 4κ1κ2 sin ( )

κ1 + κ2 1 2 ka
∴ ω± = ± 2
m m 2
 The Dispersion relation

Dispersion relation of 1D diatomic chain

(κ1 + κ2) − 4κ1κ2 sin ( )
κ1 + κ2 1 2 ka
ω± = ± 2
m ω m 2
• General characteristics

- The periodic system with a in real space yields

2π
the periodic dispersion relation with in reciprocal space ω
a

( a a)
π π
- Only the 1 st Brillouin zone − ≤ k < matters ω+

ω−
- The system has N unit cells with a periodic B.C. (xn+N = xn)

Na ( Na )
2π 2π ⋯ ⋯
‣ k : quantized in units of k = p
k
π 0 π
‣ The number of allowed k values within the 1st B.Z. : N −
a a
‣ Two atoms per unit cell (i.e., total 2N atoms)
Total N di erent k− values
= Two degrees of freedom per unit cell
Total 2N di erent modes
= Two possible normal modes per each k value
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 The low-energy branch
Acoustic phonon
(κ1 + κ2) − 4κ1κ2 sin ( )
κ1 + κ2 1 ka
ω− = ω− 2 2
m m 2
• Low-energy branch (ω−): Acoustic phonon

• High-energy branch (ω+): Optical phonon

• Characteristics of the acoustic phonon (ω−)

ω
- As k → 0 : linear dispersion like a sound wave (i.e., ω = υk)
ω+
2
dω− a κ1κ2
υ= = (HW!) ω−
dk 2m (κ1 + κ2)

- Why sound wave? ⋯ ⋯

‣ The density of the chain : 2m/a
κ1κ2 k
π 0 π
‣ The e ective spring constant : κ̃ = −
κ1 + κ2 a a

‣ Compressibility of the chain : β = 1/ κ̃a

B 1 a 2κ1κ2
The speed of sound : υ = = =
‣ ρ ρβ 2m (κ1 + κ2)
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 The high-energy branch
Optical phonon
(κ1 + κ2) − 4κ1κ2 sin ( )
κ1 + κ2 1 2 ka
ω+ =
m
ω +
m
2
2
• Characteristics of the optical phonon (ω+)

- At k =0
dω
‣ Momentum : υg = = 0 ⟶ p = mυg = 0 ω
dk

2 (κ1 + κ2) ω+
Energy : ω = ≠ 0 ⟶ ε = ℏω ≠ 0 ω−
‣ m

- Photons at k =0 ⋯ ⋯
‣ Momentum : p = ℏk = 0
k
‣ Energy : ε = ℏω ≠ 0 π 0 π
−
a a
- Such oscillation modes only possible via absorption of photon
→ Fluctuations in displacement between atoms
= Fluctuation of electrical polarization that couples to EM wave
= “Optical phonon”
Acoustic vs. optical phonons
• In the derivation of dispersion relation (as k → 0),

m (−1 1 ) (Ay)
A jka A A A
(Ay) (−κ2 − κ1e −jka κ1 + κ2 ) (Ay) (Ay)
2 x κ 1 + κ2 −κ2 − κ1 e x 2 x κ1 + κ2 1 −1 x
mω = ω =
k→0

(k→0 ) (k→0 m )
κ1 + κ2
Acoustic mode lim ω → 0 Optical mode lim ω →

(Ay) (1) (Ay) (−1)

Ax 1 Ax 1
Eigenvector: = Eigenvector: =

*Two masses move in same direction *Two masses move in opposite directions

δx, δy
δx, δy

k k
Phonons in 3D
• Number of modes

- M atoms per unit cell in 1D → M distinct modes per each k value

‣ The number of acoustic mode : 1 (ω = 0 at k = 0)

‣ The number of optical modes : M − 1 (ω ≠ 0 at k = 0)

- M atoms per unit cell in 3D → 3M distinct modes per each k value

(∵ 3 degrees of freedom per atom)

‣ The number of acoustic mode : 3 (ω = 0 at k = 0 along x, y, z)

‣ The number of optical modes : 3 (M − 1) (ω ≠ 0 at k = 0)

Energy gap 2nd B.Z. 1st Brillouin zone 2nd B.Z.

ω ω

2κ2
m 2κ1
m

κ1 ≠ κ2
κ1 = κ2
k
π π 2π π π 2π
− 0 − − 0
a a a a a a
Reduced zone scheme “Extended” zone scheme
Two modes per k value One mode per k value

• Above is when κ1 ≠ κ2 and κ1 < κ2 • When the two atoms are only slightly di erent
- A small perturbation applied to a situation where all atoms
• The case of κ1 = κ2
are identical
- A simple monatomic chain with a lattice constant a/2
- Due to the perturbation, a small energy gap opens up at

[ a a ]
2π 2π
- The 1st Brillouin zone : − , the zone boundary, but the rest of the dispersion mostly
looks alike that of the monatomic chain!
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