Materials Chemistry III 2

July 17, 2018 Schedule

Materials Chemistry III
(Nano‐Photonics Materials)

Research Institute for Electronic Science

Hideo Kaiju

3 4
Contents Magnetic moment of one atom
1. Materials and Devices for Optical Communication B m
B( z )  Let’s calculate the magnitude of 
2z 3 magnetic moment m of one atom!!
2. Nature of Optical Wave
N S v
3. Diffraction and Optical Thin Film I  e S  a 2
z 2a
4. Optical Intensity and Surface Plasmon v
-e m  ( e )(a 2 )
2a
5. Fundamentals of Magnetism m
Today a e e
 ( )aM e v  ( )L
6. Electron Spin and Paramagnetism Fe 2M e 2M e
I
Spin Angular momentum
7. Exchange Interaction and Ferromagnetism 
According to quantum theory,
8. Spintronics and Its Application
Spin “up”
m  IS an angular momentum L is an 
(E-B)  ( h / 2 )
integer multiple of                       .
L
Then we put            , 
Spin “down ”
Quantum well
 5 6
Angular momentum Origin of magnetism
   Conservation of angular momentum 
Lrp in central force field Revolution Rotation
    
p( M e v ) dL dr   dp
  pr B B
 -e dt dt dt B B
r    
  v  M ev  r  F -e
+e F  
0 ( r  F ) N N
+e ＝ m -e ＝ m
Angular momentum is conserved!! S S

F : Central force Spin
Quantum number!!

cf. | L |  l (l  1) Lz  ml 
l : Azimuthal quantum number ml : Magnetic quantum number

7 8
Angular momentum Spin
Schrödinger equation Schrödinger equation
 2 2   2 2 
   V (r )   (r )    (r )    V (r )   (r )    (r )
 2M e   2M e 
 n ,l ,m (r , ,  )  Rn ,l (r )Yl m ( ,  )  n ,l ,m (r , ,  )  Rn ,l (r )Yl m ( ,  )


Spherical function Yl m Lz  i LzYl m  ml Yl m Spin function  SmS
S z SmS  mS  SmS ①

s l 0 L2Yl m   2l (l  1)Yl m 1 S 2 SmS   2 S ( S  1) SmS ②
p l 1 S
[ Lx , Ly ]  iLz 2 [ S x , S y ]  i S z
d l2
[ S y , S z ]  i S x ③
f l 3 [ Ly , Lz ]  iLx 1 1
mS   mS   [ S z , S x ]  iS y
m  3,  2,  1, 0, 1, 2, 3 [ Lz , Lx ]  iLy 2 2
m  l , l  1, , 0, , l  1, l 2l  1 mS   S ,  S  1, , 0, , S  1, S 2S  1
 9 10
Spin Commutation relation
Notice !!
 
① S z mS
 mS  mS
Sz  ,  [ px , x]  px x  xpx  i
S S
2 2 [ A, B]  AB  BA
3 px x   / 2
② S 2 SmS   2 S ( S  1) SmS | S |  S ( S  1)  
2 A: To measure the height AB
[ px , x]  px x  xpx
We cannot determine Sx and Sy
③ [ S x , S y ]  i S z B: To measure the weight
at the same time.  
 (i ) x  x(i )
z We can only determine one  x x
3 Spin precession
 parameter, for example Sz.
2 [ px , x] f  ( px x  xpx ) f
 173 cm
2 Notice !!  
 (i ) xf  x(i ) f 63 kg
y [ px , x]  px x  xpx  i x x
px x   / 2 f f Commutable
2  i( f  x )  ix  if [ A, B]  0
x  x x
2

11 12
Commutation relation Quiz 1
Notice !!
Prove the following commutation relation. 
[ px , x]  px x  xpx  i
[ A, B]  AB  BA
px x   / 2 [ S x , S y ]  iS z
A: To study for exam.
Here Sx, Sy, and Sz are given as follows:
[ px , x]  px x  xpx B: To take the exam.

   1   i   1 
 (i ) x  x(i )  0   0 2   0
x x 2   
Sx    Sy    Sz   2 
[ px , x] f  ( px x  xpx ) f  1 0   i 0   0 1 
    
BA ( A  B) High score  2   2   2 
 
 (i ) xf  x(i ) f AB ( B  A) Low score
x x
f f Not Commutable
 i( f  x )  ix  if [ A, B]  0
x x
 13 14
Magnetic ordering Magnetic ordering
N
N ① Paramagnetism ② Ferromagnetism
m
Electron -e S
Spin Magnetic moment Simplified 
S version

Interaction  M = 0 Na, Pd, Al M ≠ 0 Fe, Co, Ni

No between spins Yes
③ Diamagnetism ④ Antiferromagnetism

H
Random Magnetic ordering
M = 0 M≠0 M < 0 C, Cu, Pb M = 0 Cr, CoO, Fe2O3
N
(   0)
Magnetization (Wb/m2) M  m
i
i
M  H : Susceptibility

15 16
Magnetic ordering Diamagnetism
Compound, 
oxide materials Faraday's law
H
d d ( BS )
④ ② V  
AFM FM I dt dt
① ③ r
DM
S   BS
PM
-e

dH B
2 rEs   r 0 2

dt I
http://www.jst.go.jp/sicp/ 0 dH ＋ －
ws2011_eu/presentation/p Es   r
resentation_02.pdf H2O, superconductor
2 dt V
 17 18
Diamagnetism Diamagnetism
v
H Ms
t
 eEs H m
02 e 2
4m
r2H  
4m
x
02 e 2 2
 y2 H
e 02 e 2 2 N 02 e 2 Z 2
I v   Es t I  a H   a
6m 6m
r Ms r M  ZNm
-e -e M  H
e 0
 r H z
2M s H
dH x2  y 2  z 2  a2
2 rEs   r 2 0
dt  ev  r
m  0   ( r )
2 x2  y 2  z 2
0 dH  2 r  x
y
y
Es   r 2 2
2 dt 02 e 2 2 x2  y 2  a
 r H x 3
4m a: Radius

19 20
Quiz 2 Diamagnetism

Calculate the relative diamagnetic susceptibility  for copper, 
in which atomic number is 29, atomic mass is 63.54, density 
is 8.94 g/cc, and average orbital radius is 0.5A. Here, 
Avogadro’s number NA is 6.02 x 1023 mol‐1, electric charge of 
electron e is 1.6 x 10‐19 C, and electron mass is 9.11 x 10‐31 kg. 

A.  = 3.6 x 10‐5
N 02 e 2
  Z a2
6m
0  4 107 H / m Naphthalene Graphite
 21 22
Susceptibility of Fe-based superconductors Magnetic ordering
Meissner effect
Pauli paramagnetism ① Paramagnetism ② Ferromagnetism
 
0 = 4 x 10‐7 H/m Si S j

   / 0  = 3.8 x 10‐9 H/m
Tc
0.0040
M = 0 Na, Pd, Al
0.0
Jij > 0
SmFeAsO1‐xFx
0.0035 i) Pauli exclusion principle M ≠ 0 Fe, Co, Ni
-0.5 0.00
-0.05
-0.10
57.4 K ii) Many‐body effect
4

4
-1.0
4 

-0.15
0.0030
-0.20
-0.25 ④ Antiferromagnetism
-1.5 -0.30
48 50 52 54 56 58
0.0025
Temperature (K)
Exchange interaction
-2.0
 
0 10 20 30
Temperature (K)
40 50 60 70
0.0020
0 10 20 30 40 50 60 70 wij  2 J ij Si  S j
Temperature (K) Jij < 0
Perfect diamagnetism
Jij: Exchange integral  M = 0 Cr, CoO, Fe2O3
M  H : Susceptibility Courtesy of Prof. M. Fujioka

23 24
Paramagnetism Torque and potential energy
  
Langevin theory For a spin which makes an  Torque T  r  F qm
angle  with H, the potential     l qm H
energy is given by  | T || r || F | sin  
d  qm H
U  mH cos  ,

H
so that the probability for a   qm H
m 
spin to take this direction is
| T | lqm H sin 
U  mH sin 
P  exp( )
Angular distribution of  k BT
paramagnetic spins in a  mH cos  U   mH sin  d
magnetic field H P  A exp( )
k BT  mH cos 
 25 26
Paramagnetism Paramagnetism
Langevin theory For a spin which makes an  Langevin theory The probability for a spin to 
angle  with H, the potential  make an angle between 
energy is given by  and d is given by
d d
mH cos 
U  mH cos  , p ( )d  A exp( ) 2 sin  d
  k BT
H H d
m so that the probability for a  m sin 
spin to take this direction is
U
P  exp( )
Angular distribution of  k BT Angular distribution of   mH cos 
 A exp( ) 2 sin  d  1
mH cos  k BT
0
paramagnetic spins in a  paramagnetic spins in a 
magnetic field H P  A exp( ) magnetic field H A
1
k BT  mH cos 
0
A exp(
k BT
) 2 sin  d

27 28
Paramagnetism Paramagnetism
mH cos  1
) 2 sin  d
 e xdx
exp( x
Langevin theory k BT Langevin theory M  Nm 1
p ( )d 
mH cos  1
 e dx
  x
0 exp( k BT ) 2 sin  d 1

d d 1 1
e
x 
M  Nmcos  dx   e  )
(eQ3(2)
1 
 
H  Nm  cos  p( )d H
m  0
m
1
e
x
xdx 
1
(e  e Q3(3)
1
)  2 (e  e  )
 mH cos 
1  
0
exp(
k BT
) cos  sin  d
 Nm  e  e  1 
 mH cos  M  Nm   
0 exp( k BT ) sin  d  e  e 

Angular distribution of  Angular distribution of 
1 mH  1
paramagnetic spins in a  
 Nm 11
e x xdx  
k BT
paramagnetic spins in a   Nm coth
Q3(4)    NmL( )

magnetic field H Q3(1) magnetic field H 
1e dx
x
cos   x Langevin function
 29 30
Paramagnetism Paramagnetism
mH
Langevin theory M  NmL( )  Langevin theory Nm 2
M: Large k BT 
1 Curie law 3k BT
0.8
d d
0.6 CuSO4K2SO46H2O Paramagnetic salts

L()
 e  e  1 
H 0.4
L( )  
m 0.2 e  e   m Nm 2
3k B
0
0 2 4 6 8 10

  1 H: Large 1
Angular distribution of   Angular distribution of  
L( ) ~ T: Low T
paramagnetic spins in a  3 paramagnetic spins in a 
magnetic field H Nm Nm 2 magnetic field H Henry, PR 88, 559 (1952)
M  H  H
3 3k BT Susceptibility Magnetic moment

31 32
Paramagnetism Paramagnetism
In the previous calculation, we assumed that the spin can  Curie law
take all possible orientation. In reality, a spin can have only  Nm 2
discrete orientations because of spatial quantization. Classical theory 
3k BT
M  NmL( ) (Classical picture)
Paramagnetic salts Ng 2 J ( J  1)  B2 Paramagnetic salts
Quantum theory  
3k BT
M  NgJ B BJ ( ) (Quantum theory)
Brillouin function
2J 1 2J 1 1  m  g J ( J  1)  B2 Nm 2
BJ ( )  coth   coth 3k B
2J 2J 2J 2J

gJ B H   1 J: Total angular momentum
 J 1 L: Orbital angular momentum 
1
k BT BJ ( ) ~  Ng 2 J ( J  1)  B2 T
3J  Henry, PR 88, 559 (1952) S: Spin angular momentum Henry, PR 88, 559 (1952)
3k BT
Russell-Saunders interaction: J=L+S
 33
Quiz 4
Calculate the paramagnetic susceptibility  for an ideal gas, 
in which each molecule has a magnetic moment with J = 1, g
= 2, at 1 atmosphere pressure and 0oC. The 1 mol ideal gas 
takes a volume of 22.4 l at the above‐mentioned 
temperature and pressure. Avogadro’s number NA is 6.02 x 
1023 mol‐1. Boltzmann constant kB is 1.38 x 10‐23 J/K. Bohr 
magneton B is 1.17x 10‐29 Wb・m.

A.  = 2.6 x 10‐12 H/m