2024-10-28

Crystal Structure
and X-ray Diffraction

2024/10/29
Prof. Don-Hyung Ha
[Link]

School of Integrative Engineering

Chung-Ang University
Nanomaterials and
1 Electrochemical
NEED Lab Energy
Design Laboratory

Bragg’s diffraction

• Interference
Path Diffevence
Path difference between wave I and II

Sw
  o / 2
Wave I + Wave I
 constructive
Constructive interference
interference

  0,
≈
  no (n  integer) A=2A0
no patu difference

Wave I + Wave II
☆
 Destructive
Destructive interference
Interference

1
  (n  )o (n  integer) A =
O
2
Wave I and Wave II (   o / 2 )
 Intensity a
α A2

Nanomaterials and
2 Electrochemical
NEED Lab Energy
Design Laboratory

1
 2024-10-28

Bragg’s diffraction
• 3 waves with δ=0 and λ=constant incoming to the plane

1 , 2, 3 same path
ino path lif )
.

8 =
0

Paths of wave 1,2,3 are the same from WN1-WN1 to WN2-WN2 after
scattering at A,B,C independent of an angle

Nanomaterials and
3 Electrochemical
NEED Lab Energy
Design Laboratory

Bragg’s diffraction
• Path difference from wave 1,2,3 hitting the crystal plane with angle θ

1 ,2 3 path dif
. .

Path difference of 1 and 2

hkl sin 
ABC  22ddnkesin θ

Path difference of 1 and 3

hkl sin  θ
DEF  44ddnkesim

⑲ √
For constructive interference
ABC   , DEF  2
a
[ √
andition tonave coms .
interference

nnλ=
 2d2hklssin 
d no

[Link]
[Link]
(
.
ppaggseq .

Nanomaterials and
4 Electrochemical
NEED Lab Energy
Design Laboratory

2
 2024-10-28

Bragg’s diffraction
William Henry Bragg William Lawrence Bragg

X-Ray diffraction proposed in 1913

Nobel Prize in Physics (1915)
Nanomaterials and
5 Electrochemical
NEED Lab Energy
Design Laboratory

Bragg Interference

• Diffraction pattern of Fe powder by monochromatic X-ray

m
atroom temp : BEE

Constructive interference at
anst
  52.3, 2  77.2, 2  99.6
2~
.

constmutive interferenme

Destructive interference at other angle θ

 Diffraation
Diffraction phenomenon
phenomenom (constructive
and destructive interference)

52 30
.

7 26
.
99 ‰.

Nanomaterials and
6 Electrochemical
NEED Lab Energy
Design Laboratory

3
 2024-10-28

Diffraction and Reflection

• Diffraction
– Only occurs at the crystalline plane
plane of
of crystal that has periodic atomic array
– Only occurs at specific
specific angles
angies (that follows Bragg’s equation) by interference
of monochromatic x-ray
– Efficiency of diffraction is only a few percent when using x-ray
• If each plane were perfectly reflection, only first plane will see the radiation, and
any wavelength would be reflected.

broad peaksnardto analuyze eta)

cangla 1
• Reflection
. ,

– Can occur at any surface plane

– Occurs by light and for any angle
_

– Possible up to 100%

Nanomaterials and
7 Electrochemical
NEED Lab Energy
Design Laboratory

Bragg’s diffraction
Incident X-ray

Diffracted 2θ
θ  2θ = diffraction angle

Specimen
Crystal plane
=

sin 0 0
, in 9 o =
• r
5

Bragg’s law

 sin   1,
2d
 22dd ; condition for diffractio n at any angles 2 .
K
• Interplanar spacing ~0.3 nm
– What’s the maximum wavelength? 0.6
λKnm(2)
( 0 3)
.
=
0 onm
.

Nanomaterials and
8 Electrochemical
NEED Lab Energy
Design Laboratory

4
 2024-10-28

Bragg’s diffraction

- e.g. 1. Uitraviolet
ultraviolet ( = 500 Ǻ, sample =Cu, a = 3.6 Ǻ)
d(111) = 3.6/(3)1/2 = 2.0 Ǻ
2d sin θ = λ,
sin θ = 500/4.0 >> 1; No θ can meet the diffraction condition! cannot seediffraEtion

- e.g. 2. Gamma
gamma-ray
ray ( = 0.0002 Ǻ, sample =Cu, a = 3.6 Ǻ)
-

2d sin θ = λ = 0.0002 Ǻ
sin θ = 0.0002/4.0, θ << 1o ; too small to be conveniently measured.

- e.g. 3. X
X-ray
ray ( = 1.54 Ǻ for Cu Kα, sample =Cu, a = 3.6 Ǻ)
-

2d sin θ = λ = 1.54 Ǻ

Δ
sin θ = 1.54/4.0, θ= 22.6o ; Angle is conveniently measured.

resonableang le
thatcaem be
easily
measured

Nanomaterials and
9 Electrochemical
NEED Lab Energy
Design Laboratory

Bragg diffraction
d (100)
• (100) and (200) plane  d ( 200)
2

√
/ patht 'it .
LPEF )
200 δ

xisfixed .
2d100 sin θ100 = λ, 2d200 sin θ200 =O
λ,  θ100 ≠ θ200
Smaller interplanar spacing, larger diffraction angle
i.e. d100>d200>d300 , θ300>θ200>θ100 , d 41 D α
Nanomaterials and
10 Electrochemical
NEED Lab Energy
Design Laboratory

5
 2024-10-28

Vector product

A1  3iˆ  0 ˆj  0kˆ A1  A2  A3

A  2iˆ  2 ˆj  0kˆ A3  5iˆ  2 ˆj  0kˆ

2

A  A1  A2
A  A1  A2  D
.
③
A1 A2 cos 
A  A1 A2 sin 

Nanomaterials and
11 Electrochemical
NEED Lab Energy
Design Laboratory

Reciprocal lattice

• Basis vector bib15

, b2:, b3
, ,
~

,
a , f
a real laffice
,

vector

V =Volume
V  a1  (a2  a3 )  a2  (a3  a1 )  a3  (a1  a2 )

 1    1    1  
b1  i(aaxas
2  a3 
a3 l
b2  iia ; a 
1 Dilaxas
b3  a1  a2 
V V V
Gi &
G
Nanomaterials and
12 Electrochemical
NEED Lab Energy
Design Laboratory

6
 2024-10-28

Reciprocal lattice
lattice vector
reciprocase
• The magnitude and orientation Nimaginarrs

I
a1  a2 1
b3 
V

dioon
d(001)
doo
the direction of b3 is normal to the
plane (001) which is defined by
a1 and a2

<Unit cell>

D
b3 normal to (001) crystal plane 1 / d ( 001)

I
 
b1 normal to (100 ) crystal plane Magnitude : 1 / d (100) "m

b2 normal to (010 ) crystal plane 1 / d ( 010)
( b1 , b2 , b3 = fundamental reciprocal lattice vector)
Nanomaterials and
13 Electrochemical
NEED Lab Energy
Design Laboratory

Reciprocal lattice

• Real space is described by translation vector T

• Reciprocal lattice is mapped by the basis vectors b1 , b2 , b3

crystal space  crystal plane  plane Fd


reciprocal lattice space  crystal plane  point
Point
Gkil)
Rhk  hb1 kbrt
 kb2 lbz
lb3
bit
hGe
• The amplitude of the reciprocal vector is inverse of dhkl and unit is 1/m
cmy

1
Rhkl  Ance IR t α
1

&φ

d hkl
Nanomaterials and
14 Electrochemical
NEED Lab Energy
Design Laboratory

7
 2024-10-28

Reciprocal lattice
• Reciprocal lattice at (001) plane of simple cubic
∅
(
O )
d00

I
,
XC
00 |) apoas
⑦
-

\
t
s

Real daro
☆

(001) ·mnp = 0
∅ → mno
mn0sattice
latticepoints
pointssbown
shown

∅
Reciprocal I D
O
= . .

g 0
W

t
~
I%
..

Pwint
plame ‰

. .=
Nanomaterials and
1 b, >
15 Electrochemical
=. NEED Lab Energy
Design Laboratory

Reciprocal lattice

• Reciprocal lattice plane on simple cubic with different lattice parameter

<
a  0.1 nm a  0.2 nm
d 1 {

{
=
0 1 nm =
lomm 1

.

Rhkl =
but reciprocl
d hkl =
5 nm .

( de t Ra ?
Nanomaterials and
16 Electrochemical
NEED Lab Energy
Design Laboratory

8
 2024-10-28

Reciprocal lattice
X
• Crystalline planes that shows the diffraction
h2+k2+l2 P-lattice F-lattice I-lattice Diamond
Δ 1 100
2 110 110
3 111 111 111
d - spavin
a 200 200 200
4
5 210
α
6 211 211
7
8 220 220 220 220
9 300, 221
10 310 310
11 311 311 311
12 222 222 222

Nanomaterials and
17 Electrochemical
NEED Lab Energy
Design Laboratory

Reciprocal lattice

• (100) reciprocal plane on simple cubic, fcc, and bcc with l.p.=0.2nm
~
io 0
reaiprocal battice

simple cubic

: (
-
fcupeak
fcc
{111} {200} {220}..

D
-

bcc
{110} {200} {211}..
_

bcc a  0.2 nm
fcc
18
4N 003 NEED Lab
Nanomaterials and
Electrochemical
Energy
Design Laboratory

B[
reaiprocal[atfile F

9
 2024-10-28

22
②
③ I2 2 BEE reciprocal lattice rFcC
=

FCC 1. BCC

① ih
e ABCC
reaiprocal

Nanomaterials and
19 Electrochemical
NEED Lab Energy
Design Laboratory

Reciprocal lattice

• (010) reciprocal plane on simple orthorhombic p lattice

10 a1  2 nm
a2  3 nm
| freal hafficeoelR,

6
a3  4 nm
'
D 25

25" y
.

o5
I × reciprocal
nm

Nanomaterials and
20 Electrochemical
NEED Lab Energy
Design Laboratory

10
 2024-10-28

Reciprocal lattice

• (011) reciprocal plane on simple cubic

All lattice points are (011)·(hkl)

[o ( ) . ( hkl ]=ω= 0

R100  R100  1.0 nm 1

.. .
=

R01 1  R0 11  1.414 nm 1
* =

R11 1  R1 11  1.732 nm 1
*
u=

a1  1.0 nm
Nanomaterials and
21 Electrochemical
NEED Lab Energy
Design Laboratory

Wave function

• 5 waves

Path difference from( ) wave1

Constructive
 
Jasna
Interference
Constructive
  2 Interference

Destructive
  1 / 2
]
_

~
Interference
18 *+ λ
Destructive
  3 / 2
≈
~

Interference

Nanomaterials and
22 Electrochemical
NEED Lab Energy
Design Laboratory

11
 2024-10-28

Wave function

• Superposition of waves with phase difference


  2 
differance

r path phasedifference
  0,  , 2 , 3 ⑦  0, 2 , 4 , 6
  1 / 2 , 3 / 2 , 5 / 2     , 3 , 5

  0, 2 , 4 , 6 Same phase : constructive

constructive interference

   , 3 , 5 Opposite phase : destructive

destructive interference

Nanomaterials and
23 Electrochemical
NEED Lab Energy
Design Laboratory

Wave function

• Wave is expressed with phase, wavelength and amplitude

– Can be expressed as sin
sinefunction
funcfion(A ) Ae
sin ϕ) or Ae
(Asinp
ϕi:

– A : amplitude
– Φ : phase

3 3 3
sin(0  )  sin(2  )  sin(4  )  e i  e3 i  e5 i  1.0
2 2 2
1 1 1
sin(0  )  sin(2  )  sin(4  )  e 2 i  e 4 i  e6 i  1.0
2 2 2

Nanomaterials and
24 Electrochemical
NEED Lab Energy
Design Laboratory

12
 2024-10-28

Diffraction and reciprocal lattice

• X ray diffraction from the atoms at two (hkl) planes

incident
groutcome D
-
S ,S
o 

• A  A atom’s vector
• Incoming X ray and outgoing X ray with the angle θ have vectors of So , S
• So , S : unit vector with the amplitude of 1
Nanomaterials and
25 Electrochemical
NEED Lab Energy
Design Laboratory

Diffraction and reciprocal lattice

• X ray diffraction from the atoms at two (hkl) planes

≈
≈
I
patendif .

  Ac  Ab  Oa  Od S
Oatod  So  AG
=
A ]
( S )- (A-
.   A  ( S  S o )
5 =

~
δ( ) =

2π
φ=

  2*π .
-

S
(

( S%  So ) 

)  A

Nanomaterials and
26 Electrochemical
NEED Lab Energy
Design Laboratory

13
 2024-10-28

Diffraction and reciprocal lattice

• X ray diffraction from the atoms at two (hkl) planes

• If ( S  So ) /  happens to be the same as reciprocal vector Rhkl  hb1  kb2  lb3

then, ϕ will be a multiple of 2π

☆
 ( S  So ) 
  2    A
  
 2 (hb1  kb2  lb3 )  (ma1  na2  pa3 )
=  2 (hm  kn  lp)  2 (integer)
~
Zπ
meltiple of

• This indicates that the diffraction condition (constructive interference)

  So.)l// =hbit
occurs when ((So-
s
a hb1  k
kb2 +l
lb3
: ,

~
^

Rnicl

Nanomaterials and
27 Electrochemical
NEED Lab Energy
Design Laboratory

b
Ewald sphere
…

• Ewald
Ewaldsphere
sphereininreciprocal
reciprocalspake
space
1. Reciprocal lattice
unit : [nm-1]

× 2. The distance from 000 to the

center of Ewald sphere : 111/λ

3. The position of the center of

Ewald sphere depends on the
direction of incident beam So
radius

P
L ,
(: λ ]

4. The end of the vector

S /   So / 
.

(: ] is always located on the Ewald

sphere

( S  So ) /   hb1  kb2  lb3

Nanomaterials and
28 Electrochemical
NEED Lab Energy
Design Laboratory

14
 2024-10-28

Ewald sphere

• Diffraction condition in Ewald sphere

Oreciprocal
point

Nanomaterials and
29 Electrochemical
NEED Lab Energy
Design Laboratory

Ewald sphere

• Diffraction condition in Ewald sphere

S  So
 Rhkl  hb1  kb2  lb3

I S /   So /  is the same as hkl  constructive interference, or, diffraction

All the planes having reciprocal lattice of {hkl} plane that is on Ewald sphere
will show constructive interference

Nanomaterials and
30 Electrochemical
NEED Lab Energy
Design Laboratory

15
 2024-10-28

Ewald sphere

• Bragg’s law

S  So
 sin 
2
S  So

→
2sin 
2sin   S  So , 
  sin θ

S  So
 Rhkl  hb1  kb2  lb3 θ
 ~
Λ
pee

2sin  S  So 1
  Rhkl 
  d hkl
 2d hkl sin    Bragqslaw
∴
Ldnkesino =
λ
^

Bragg seq
'

Nanomaterials and
31 Electrochemical
NEED Lab Energy
Design Laboratory

The angle on Ewald sphere

• Two incident waves from the opposite directions

– Ewald sphere on (001)
…
reciprocal plane

Drdiffraction

p 00 C
100
Q 10

Q ~
:| 10
diftraltion

a  1.0 nm same λ different λ

  0.25 nm
Nanomaterials and
32 Electrochemical
NEED Lab Energy
Design Laboratory

16
 2024-10-28

Incident waves and directions on Ewald sphere

Aquiz pafficeparameter =
= 1 m
( , p
0 . nm ,
5

• Ewald sphere with two incident waves EWaldsphere

– Same wavelength and different direction

– Case 1 : incident wave : [-100]

 -440, -4-40 : diffraction condition
– Case 2 : incident wave : [100]
 440, 4-40 : diffraction condition
h (Too
s ←
(1 D 0]
2D =9D
0

{
I
P
diffraction

a  1.0 nm
In the case of simple cubic with 1nm of lattice parameter   0.25 nm
Interplanar spacing of d440 {440} is 0.17677nm, angle θ will be 45o from the Bragg eqs.
_

(
As 2θ is 90o, {440} satisfy the diffraction condition, as shown in the picture.

Nanomaterials and
33
λ= 2dsin θ
Electrochemical
NEED Lab Energy
Design Laboratory

d44o =+ sin θ
. θ= 45
= .
=

I6 d 176 77

Incident waves and directions on Ewald sphere

• Ewald sphere with two incident waves

– Different wavelength and direction
– Case I : wavelength =0.2nm
Ewald sphere with 5nm-1 in radius
case II : wavelength=0.4nm λ 4 b 3 smaelker radiws
) *

Ewald sphere with 2.5nm-1 in radius

– [110] and [-1-10] has opposite

directions,
0
O10003
– But both S/λ are toward (000) TI %
]

θ
(000]

1Jaif raction
a  1.0 nm
1  0.4 nm, 2  0.2 nm
Nanomaterials and
34 Electrochemical
NEED Lab Energy
Design Laboratory

17
μ
 2024-10-28

Incident waves and directions on Ewald sphere

• Simple cubic lattice with lattice parameter of 1nm

• Reciprocal lattice points on (001) reciprocal lattice plane
– Direction : [100]
– Wavelength : 00.01 nm
O 1 mm o o1

(
diffraction
. .

–  Ewald sphere : 100 100 nm -1

mm in radius
⑦
– It seems to be straight, rather than curves

λ EM ( λ< O . O( )
m

<
[ ) To

– In TEM, wavelength of the beam is less than ~→0.003nm λ radins 49

– Therefore, the diffraction are obtained with large Ewald sphere.

m m

– ~
Diffraction patterns on (uvw) plane normal to [uvw]
d:fFracfion patfern Nanomaterials and
35 Electrochemical
NEED Lab Energy
Design Laboratory

TEM image

• Diffraction patterns obtained from TEM

COOD

∅
←

internssityte <

"

* plane

(hkl)∙(001) = 0
Diffraction patterns on (001) reciprocal plane
Nanomaterials and
36 Electrochemical
NEED Lab Energy
Design Laboratory

18
 .

Bragg' sEq :2 dcesin θ= nλ

-
Diffraction :
~ edestructive
construct

Reciprocal Vector
.

⑥
Wave function

a Ewald sphere
 2024-11-04

Crystal Structure
and X-ray Diffraction

2024/11/05
Prof. Don-Hyung Ha
[Link]

School of Integrative Engineering

Chung-Ang University
Nanomaterials and
1 Electrochemical
NEED Lab Energy
Design Laboratory

X-ray

• X-ray : Rontgenstrahl (1895) y ray

Aquiz
)
-

:
whitex- ray
Jans : aray( contipnousx -ray/

*
-
ay

1845 – 1923 First medical X-ray by

Wilhelm Röntgen Wilhelm Röntgen of his wife
Nobel Prize in Physics (1901) Anna Bertha Ludwig's hand
Nanomaterials and
2 Electrochemical
NEED Lab Energy
Design Laboratory

1
 2024-11-04

X-ray

• X-ray : Rontgenstrahl (1895)

– X ray is an electromagnetic wave. Not visible to human eyes. Can… penetrate
the black sheet
~

– When shine the fluorescent sheet with X-ray, visible light emits from
fluorescencing materials
– High penetration efficiency
Name of Frequency Wavelength Photon Energy
radiation [hertz] [nm] [eV]

Gamma ray  1019  0.05  100000

X-ray 30 1016 ~ 1019 0.05 ~ 0.5 100 ~ 100000

0.5 ~ 4 102 3 ~ 124

Ultraviolet 790 1012 ~ 30 1016
freqts
4
Visible light 430 1012 ~ 790 1012 4 102 ~ 7 102 1.7 ~ 3.3

Infrared 300 109 ~ 430 1012 7 102 ~ 1106 1.24 103 ~ 1.7

FM wave 300 106 ~ 300 1012 ∅ ~ 109 β

1.24 106 ~ 1.24 103 β

Nanomaterials and
3 Electrochemical
NEED Lab Energy
Design Laboratory

X-ray

• Wavelength, energy and frequency

λ v

c
g
const .

 , E  hv
electromagnetic

x-ray
wave
( Eav )
λα )
(Planck's constant) h  6.626 1034 joule  sec
c  2.998 108 m  sec1

x x
E  A s i n 2 ( ), H  A s i n 2 ( )
 
Shorter wavelength : larger frequency, higher energy
X-ray : high energy of 20000eV
Could be dangerous. Should be careful.
Nanomaterials and
4 Electrochemical
NEED Lab Energy
Design Laboratory

2
 2024-11-04

Production of x-rays

• Acceleration voltage
– Ions or electrons could be transferred
by potential of accelerating voltage
– Examples of accelerating device
with cathode and anode
– 30kV of voltage is applied
(w)

electrons come

ouut from filaument

^ and nitanode
very high vostage
6
depending on the Vol fage ,
huelpeltit
Less than 1% 99%
xray
ifferent
paattermis Energy for X-ray ①
heat Eas heat
temitted
shown

Nanomaterials and
5 Electrochemical
NEED Lab Energy
Design Laboratory

Production of x-rays (continuous)

biagnerintensity
,

shorterlead
Isuift
to
tonigmerE

N continuous
Vvotagessxsurs
raly

‰
Qrange : λ SWL N

• short
Short wavelength
Wavelength limit : the shortest wavelength that can produce the x-ray
Limitesuwy

Liotas
• When the potential energy eV is 100% transferred to x-ray energy, the short
wavelength could be calculated by eV=hvmax = hc/λshort wave length
4 tsmallerswr

Nanomaterials and
6 Electrochemical
NEED Lab Energy
Design Laboratory

3
 2024-11-04

Production of x-rays (continuous)

• General properties of x-ray

-
Eof puoton

eV  h max
c hc 12. 4 102
SWL    [nm]
 max eV V
Qev
π
– υ is inversely proportional to λ
– When electrons accelerated by V
collides with the specimen,
continuous x-rays larger than λSWL are produced
– These are called as continuous
Confinuoans X-x-ray
ray ③ xray
(or white x-ray, heterochromatic x-ray)
~

broad
manydifferant
can
warelangth
Be Skem

• Intensity of X ray
– Proportional to current
current hisI and atomic number
atomic number (z )Z

Iα i , E
Nanomaterials and
7 Electrochemical
NEED Lab Energy
Design Laboratory

Production of Characteristic x-rays

• Distribution of wavelength of x-ray upon acceleration voltage shanga

nrateriacd
,

when
change
peak also

'
continuous xray discomtinyoust Eharacteristic -
ray
Lused for medicoal ) • Characteristic X-rays are observed at specific wavelength when V>9kV_
(monocnromatic , used fordiffraations

– λ =0.154nm (Cu kα-line), λ=0.139nm(Cu kβ-line) b dlscontinuoms

≈ …
use
trary
• Discontimuous

(
Discontinuous-X-ray
ray or characteristic
characteristicx-ray
4
ray
-

– Characteristic x-ray is determined by the materials and their properties

• Source to determine the specimen
λ= 0 154mm
.

,
0 13aamarlay peak n (fargefica)

Nanomaterials and
8 Electrochemical
NEED Lab Energy
Design Laboratory

8 qai Xray discontinuous/ charateristic xray

nay

ele
x -

-
diffranatioon

4
 2024-11-04

Production of characteristic x-ray

• Critical acceleration voltage Vkcri

– When V> Vkcri, characteristic X-rays are shown
– Vkcri for Cu : 8.98V ≈ aV
– Vkcri depends on the target materials
– The intensity of each peak above qu
we sce peak
graphh
continnouns
is proportional to (V- Vkcri) shigher vshigher intensity but if not
w' ill
be seen

– Intensity of characteristic x-ray peak is VO

actually higher than that of continuous x-ray
by a factor of ~100

if w 9 tintensitye

OV

Nanomaterials and
9 Electrochemical
NEED Lab Energy
Design Laboratory

Production of characteristic x-ray

• Moseley’s relation

logscanle  =A / ( Z
Z  B)
2

Lit '
srelatedtoz

HigherEshorter tofka

Higher Z shorter λ of Kα higher E

T
einear

highert shorter xof ka s higherE

cneavy
meterls)

logscale 10
Nanomaterials and
Electrochemical
NEED Lab Energy
Design Laboratory

5
 2024-11-04

Production of characteristic x-ray

• Characteristic X-ray wavelength and the energy of Kαline

Element K [n m] K  1 [nm] L 1 [nm] E(Kα) [keV]

24 Cr 0.228970 0.208487 2.164 5.41

27 Co 0.1788965 0.162079 1.5972 6.93

4
cheavier
metal?

⑦
29 Cu 0.1540562 Ah 0.1392218 1.2336 8.04

42 Mo 0.0709300 ∞ 0.0632288 0.540655 17.44

– Higher Z, shorter wavelength of X-ray snigher E

– It depends on atomic structure, and the energy level of electrons of the materials
Nanomaterials and
11 Electrochemical
NEED Lab Energy
Design Laboratory

Production of characteristic x-ray

• Energy difference
m

>
DnsnaverErereased
→

bloelkenowt
ome

highert
bottom block tauken ouf
:

3m higherEcomingont

receased
Lmore Ewheen
blocksfall hown

Nanomaterials and
12 Electrochemical
NEED Lab Energy
Design Laboratory

6
 2024-11-04

Production of characteristic x-ray

• Electrons in K- L- M- shell of Cu atom

stable
dsmallE

∠
largert

It requires more energy to remove the electrons that are more closed to nucleus.

Nanomaterials and
13 Electrochemical
NEED Lab Energy
Design Laboratory

Production of characteristic x-ray

high voltage e accelerated
-

• Ionization of atoms by the electron vacancy Eneeded tokiuc oute

high
-

Energy required to remove

the electrons at K-shell
.
1 2
mv  EK s energy needed
2 to kiak out er

Electrons at k-shell is removed

 Formation of vacancy
in k smen
 Ionization of atom
-

Tossote
(excitation)

Nanomaterials and
14 Electrochemical
NEED Lab Energy
Design Laboratory

7
 2024-11-04

Production of characteristic x-ray

• Characteristic X-ray by filling the empty states (electron vacancy)

asvel s -snen

T noretkelythan
s

• Ionized (excited) atoms becomes normal state by filling the K-shell

• Electrons in L-shell fills the K-shell  kα-line (~90%)
• Electrons in M-shell fills the K-shell  kβ-line 34
kopka

• Characteristic x-ray depends on where electrons comes from

Nanomaterials and
15 Electrochemical
NEED Lab Energy
Design Laboratory

Production of characteristic x-ray

• Energy states of atom with the electron vacancy at K, L, M, or N- shell

largerDE
D
-

Electrons falls from L to K-shell Eliskel 3 EM snell

Ea-shalk s

ΔE=Ek-shell – EL-shell ^

harder toremoveer
Electrons falls from M to K-shell losertomnciensd

ΔE=Ek-shell – EM-shell

The wavelength and energy determined by the energy difference of each shell

Nanomaterials and
16 Electrochemical
NEED Lab Energy
Design Laboratory

8
 2024-11-04

Production of characteristic x-ray

• Sub-shell LI, LII, LIII

M
Three sub-L shell exists (L1,L2,L3)
L for the elements of Z>13
(aMs L shelly
-

LIII EE4

LII Energy difference: K   K1  K 2

LI
①
K 1
K E= hv = h(c/)
xx
v enysimiran K2
- Imsk-shell ? ☆

Ψ
usually
D

K Wavelength:  K    K   K
Qlevels Lonelevall
1 2
usejustarerage
siifted shifted
O . 154 mm
• Kα1 and Kα2 are almost the same in terms of energy (154.0 pm, 154.4 pm)
?
•
3
( 1 pm 10 1o
-

Experimentally we simply use the average of them mm

-
=
= m

Nanomaterials and
17 Electrochemical
NEED Lab Energy
Design Laboratory

Production of characteristic x-ray

• Acceleration voltage and energy to remove electrons from K and L III shell
Uaxk
^ ~
⑦
eNaie
Element V [KeV]
K EK shell [erg] VL III [KeV] EL III-shell [erg]
9
24 Cr 5.99 9.59 10 0.5990 0.96 109
27 Co
29 Cu
42 Mo
I 4
7.71
8.98
20.01
1 V4
12.35 109
14.29 109
32.06 109
1
9
0.7791
0.9331
2.5239
1.25 109
0.49 109
4.04 109

• The minimum acceleration voltage VK to remove the electron in K-shell

• eVK = EK-shell is required to remove electrons in K-shell
• Elements have different VK

Nanomaterials and
18 Electrochemical
NEED Lab Energy
Design Laboratory

9
μ
 2024-11-04

X-ray absorption

• The intensity of I on penetration depth x

dI
   dx,   linear absorption coeff.
I
m ≈
uniform
Integration gives I x  I 0 e    x
  const   , constant  (  /  )
menims
Dng D
I I abs 0  Ix
labsorpfion coefficient

Massabsomption
Mass absorption coefficient
coefficient (u !0 ) (μ/ρ)
μ :linear absorption coefficient
ρ : density of material
x
μ/ρ depends on the element type, wavelength of x-ray
Unit : cm2/gm
Constant regardless of phase (gas, liquid or solid)
Nanomaterials and
19 Electrochemical
NEED Lab Energy
Design Laboratory

X-ray absorption

• Mass absorption coefficient Element

Density Mo K
 Cu K
 K
Co K K
Cr K
[gm/cm3] 0.0711 [nm] 0.1542 [nm] 0.1790 [nm] 0.2291 [nm]
– Longer wavelength 11 Na 0.966 0.2939 0.3030 4.734 9.848
and higher
nigher ρ 12 Mg 1.74 0.3979 4.088 6.354 13.08
 more absorption 13 Al 2.70 0.5043 5.023 7.754 15.80
14 Si 2.33 0.6533 6.532 10.04 20.27

I x  I 0  exp[  (  /  )    x] 15 P 1.82(yellow) 0.7870 7.728 11.80 23.55

16 S 2.09 0.9625 9.253 14.12 28.19
17 Cl 3.214 103 1.164 10.92 16.47 32.15

higher E absorblessbuttransmiission φ 18 A 1.663 103 1.262 11.95 18.09 35.55

coner * t can absorbmora 19 K 0.862 1.620 14.84 22.20 42.68
20 Ca 1.53 1.900 17.14 25.74 49.96
density . s
φ
absorptiong 21 Sc 2.99 2.104 18.60 27.55 52.09
Chigher Et biagherdemsity) 22 Ti 4.51 2.325 20.24 30.05 57.14
23 V 6.09 2.524 22.26 33.27 7.506
24 Cr 7.19 2.925 25.23 37.50 8.571
25 Mn 7.47 3.186 27.25 40.51 9.608
26 Fe 7.87 3.774 30.44 5.625 11.31
27 Co 8.8 4.102 33.86 6.296 12.46
28 Ni 8.91 4.724 4.883 7.375 14.57
29 Cu 8.93 4.934 5.154 7.811 15.52
30 Zn 7.13 5.546 5.951 8.871 17.17

Nanomaterials and
20 Electrochemical
NEED Lab Energy
Design Laboratory

10
 2024-11-04

X-ray absorption

• Absorption of the materials with more than one element

 1    2    3   
( ) MIX  X wt    X wt    X wt  
 mixture   1   2   3
i
X wt : weight fraction of element i
For chemical compound, solid solution, or intermetallic compound
Mass absorption coefficient depends on weight fraction

Nanomaterials and
21 Electrochemical
NEED Lab Energy
Design Laboratory

X-ray absorption

• Absorption and Absorption edge

– Without any interaction between x-ray and specimen,
shorter wavelength penetrates deeper, and higher intensity of x-ray is
obtained tt s x rary energy 4
-

– Considering the interaction of x-ray and electrons in material,

the intensity of absorbed x-ray increase, while that of transmitted x-ray
~

decrease ~ ≈
– Shorter wavelength : smaller mass absorption coefficient
– Drastic increase of mass absorption coefficient at 0.1744nm and 1.7525nm
~ _

– (K absorption edge, L absorption edge)

at specific
Fe wavelemagth
fheve ismbre
absorption
rayyre -
* interaect
o

∞
xs E ×
x b . 3 b
1 1
☆ IF 44
,
1 75a5
.

Nanomaterials and
22 Electrochemical
NEED Lab Energy
Design Laboratory

11
 2024-11-04

X-ray absorption

• Mass absorption coefficient and atomic number Z


 k λ 3ZZ 3
" 3

x ray
-

• Proportional to Z3 and λ3 before absorption edge

• Drastic, abrupt change of mass absorption coefficient results from the
interaction between x-ray and the electrons
• When x-ray remove the electrons of k-shell or L-shell, the materials absorb
the x-ray K shels / c -shell
- e
-
e removed, ray - x -

Nanomaterials and
23 Electrochemical
NEED Lab Energy
Design Laboratory

X-ray absorption
Fe LAbs Edge  1.7525 nm,
• Mass absorption coefficient and energy III

KAbs Edge  0.1744 nm

OEforks
h  h K 1
Ab s Ed g e
K  h LIII
Ab s Ed g e

1 1 1
 
K 1
 Ab s Ed g e
K 
Ab s Ed g e
LIII

h KAb s Ed g e  EK -s h ell
_

absorptionedge
for lkshell

• Absorption edge at 0.1744nm, 1.7525nm for Fe

• X-ray generation is not always observed when empty states are filled with
_

outer electrons.  Auger electron generation

Nanomaterials and
24 Electrochemical
NEED Lab Energy
Design Laboratory

12
 2024-11-04

X-ray absorption

• Mass absorption coefficient

Element K [nm] L III [nm] Element K [nm] L III [nm]

11 Na 1.1569 40.5 21 Sc 0.2762
12 Mg 0.95122 25.07 22 Ti 0.249734 2.729
13 Al 0.794813 17.04 23 V 0.22691
14 Si 0.6738 12.3 24 Cr 0.201020 2.07
15 P 0.5784 9.4 25 Mn 0.189643
16 S 0.50185 26 Fe 0.174346 1.7525
17 Cl 0.43971 27 Co 0.160815 1.5915
18 A 0.387090 28 Ni 0.148807 1.4525
19 K 0.34365 4.21 29 Cu 0.138059 1.3288
20 Ca 0.30703 3.549 30 Zn 0.12834 1.2131

Nanomaterials and
25 Electrochemical
NEED Lab Energy
Design Laboratory

X-ray absorption

• Auger electron
– Electron emission from A-shell when electron falls off from B-shell to C-shell
– Ex) Electron emission from LII state when electron falls off from LIII shell to K-
shell
ka
nduce
outere fo
-

be released

EAuger  ( EK  EL II )  EL III

– Auger electron has specific energy (<1/1000 of characteristic x-ray)

– And very low energy (longer wavelength, and do not move much)
– It could generated within ~um,
1 but it would be absorbed in ~1nm.s hot easy todetect
Nanomaterials and
26 Electrochemical
NEED Lab Energy
Design Laboratory

13
 2024-11-04

X-ray absorption

• Probability of characteristic x-ray generation

n o . o f at o ms emi t K-rad i at i o n
PK 
n o . o f at o ms wi t h a K-s h ell vacan cy

– Depends on Element
(higher Z : higher PK) Onotprefferedfortray
generation

– 0.77 for Mo(Z=42)

~
k radintion 7 %
- : s

– 0.03 for Mg(Z=12) 35

~
5
Auger 17% – Smaller P  larger P
:

K Auger

k .
radiation
releuse 4
Auger e φ
-

Nanomaterials and
27 Electrochemical
NEED Lab Energy
Design Laboratory

X-ray tube

• Structure of X-ray tube

⑦
∅

□ ∞
I e

≈
target

Nanomaterials and
28 Electrochemical
NEED Lab Energy
Design Laboratory

14
 2024-11-04

X-ray filter

• X-ray intensity generated by Co X-ray tube

The intensity of X-ray

The intensity of X-ray after Fe foil filter of 0.017mm thickness
" Without filter
I K 7.5
 75 .

I K 1.0
With filter

☆
500

C
1 I K 500

I K 1.0
500

rabsorptiongraph

P
sron

filfer
Beak
less hoise , monwchromatic Kβ .

X-ray filter that block the Kβ and only allow the Kα transmission
Fe : λKAbsEdge = 0.0174nm : absorb Kβ
After Fe filter, the intensity of Kα becomes half, and that of Kβ will be very low
Nanomaterials and
29 Electrochemical
NEED Lab Energy
Design Laboratory

X-ray filter

• Filters and target

Target Target Filter Filter Thickness

Thickness[mm]
[mm] / /gm] 2of/gm]
[cm2[cm Filterof Filter
24 Cr Target
24 Cr 23 V Filter
23 V Thickness
0.015[mm]
0.015 (by2/gm]
[cm
75.06
75.06 ) K
Cr(byofCr
Filter  )

27 Co Target
24
27 Cr
Co Filter
23
26 Fe 26 V
Fe Thickness
0.015 [mm]
0.017
0.017 75.06 (by2Co
[cm
56.25
56.25 (by /gm]
(byofCo
Cr ) K
Filter  )

29 Cu 27 Co
24Cu
Cr
Target
29 2623FeV
Filter
28 Ni 28 Ni 0.017
0.015 [mm]
Thickness
0.020
0.020 56.25
75.06 (by2Cu
[cm
48.83
48.83 (by Co
Cr
/gm] )) KK )
(by ofCuFilter
42 Mo 27
29
42 Co
Cu
24MoCr 26
28
40 Zr 40 Fe
Ni
23Zr
V 0.017
0.020
0.116
0.116
0.015 56.25
48.83
16.10 (by
(by
(by
16.10
75.06 Co
Cu
(byMo
(by K )
Cr Mo)) K
4229 Cu
27Mo
Co 28
40 Ni
26Zr
Fe 0.020
0.116
0.017 48.83
16.10 (by
56.25(by Cu
(byMo
Co )))
42
29Mo
Cu 40
28 Zr
Ni 0.116
0.020 16.10
48.83(by
(byMo
Cu )
42 Mo 40 Zr 0.116 16.10 (by Mo )

Nanomaterials and
30 Electrochemical
NEED Lab Energy
Design Laboratory

15
 2024-11-04

Monochromator

• Monochromator
τ
n  2d
↑ ①
hkl sin  λ 1 θ 200

}
,

λ 1 θ 200 F
monocuromater
diffraction ()

Ci ffrac5ion

λ =
IdsinD

asually use si
monochvomater ldnke
0 2%
.
λ

• Even after X-ray filter, wavelength other than λKα is included ~0.2%.
• For single crystalline or thin film materials, exact X-ray is required
• Monochromator is made by single crystalline material β
_
mve ,

• Only wavelength of x-ray that satisfy λ=2dsinθ will be generated

• Ex ) NaCl, SiO2(quartz), LiF, InSb, graphite, Al, Si, Ge, etc 3 duce

Nanomaterials and
31 Electrochemical
NEED Lab Energy
Design Laboratory

Limitation of tube x-ray

Need filter to use only λKα Need a monochromator

Still small amount of other wavelength But low intensity
is included  need more time for the experiment
 Not perfect monochromatic x-ray We need higher intensity x-ray

Nanomaterials and
32 Electrochemical
NEED Lab Energy
Design Laboratory

16
 2024-11-04

Synchrotron X-ray
~

le
[Link]

x tuabe
- ray

x
→
ray t
- -

[Link]

Nanomaterials and
33 Electrochemical
NEED Lab Energy
Design Laboratory

Characteristics of Synchrotron X-ray

• High intensity (high brightness)

– High spatial resolution : high focusability. A lot of photons are focused at very
small spot, usually less than 20nm in diameter
– High spectral resolution : from high intensity, high resolution could be
achieved with monochromator
• Tunability of the wavelength
• High coherence
• Pulsed wave
• High flux

Nanomaterials and
34 Electrochemical
NEED Lab Energy
Design Laboratory

17
 2024-11-11

Crystal Structure
and X-ray Diffraction

2024/11/12
Prof. Don-Hyung Ha
[Link]

School of Integrative Engineering

Chung-Ang University
Nanomaterials and
1 Electrochemical
NEED Lab Energy
Design Laboratory

X-ray diffraction experiment

• The Laue diffraction pattern

– 1912, Maxwell von Laue report the diffraction pattern of
single crystalline copper sulfate using x-ray

Maxwell von Laue

Nobel Prize for Physics (1914)
The Laue diffraction pattern

The diffraction pattern of copper sulfate, published in 1912

Nanomaterials and
2 Electrochemical
NEED Lab Energy
Design Laboratory

1
 2024-11-11

X-ray diffraction experiment

• Laue camera

thinsample ?
needel (aO lum
.

"

Xray
Oaiffraction
points

<Transmission Laue camera> <back reflection Laue camera>

≈

doespitreaviire thin sample sadwantage

– Measure the orientation and crystallinity of crystalline materials

– Use continuous x-ray for the experiment. Cannot obtain the 2θ information directly
– Not widely used recently
not
very usefal becausecannotmeasure suuth .

Nanomaterials and
3 Electrochemical
NEED Lab Energy
Design Laboratory

X-ray diffraction experiment

• Debye-Scherrer camera

( ε l ) ) )

↑ krag
<
diffract x-

ray Peter Debye

Nobel Prize in Chemistry (1936)
purdar
X
ray
-

)
monocnromatiu

– Use black and white film for powder specimen Paul Scherrer

– Use monochromatic x-ray beam

Nanomaterials and
4 Electrochemical
NEED Lab Energy
Design Laboratory

2
 2024-11-11

X-ray diffraction experiment

• Debye-Scherrer camera
come

L
film
s
∞ ☆
ZO}
_
r
, ∞
2D ,
measure
angle
X ray diffraction pattern
1 : {hkl} with the largest interplanar
spacing smallest θ=s largest d
xraly 2 : {hkl} with the second largest
L L CD
=

brametoDdiffractionangle
=CD× x22θ
sBeEimen
interplanar spacing
…
– Monochromatic X-ray is incident on the specimen, and diffraction cones are
shown for the {hkl} satisfying the λ=2dsinθ
– In powder, they do have equal probability to have {hkl} satisfying the
diffraction condition
Nanomaterials and
5 Electrochemical
NEED Lab Energy
Design Laboratory

X-ray diffraction experiment

• Debye Scherrer camera

– Advantage
• Simple and low cost equipment
• Reliable data for the powder ☆

– Disadvantage
• The results will be shown at the film, and difficult to quantify the intensity at
~

×
specific angle
• One-time used film, and limited surrounding

Nanomaterials and
6 Electrochemical
NEED Lab Energy
Design Laboratory

3
 2024-11-11

X-ray Diffractometer

• Structure of X-ray diffractometer (XRD)

X-ray source
– Bragg-Brentano XRD

araysone ①

I x
-

ray

9 O - coanter

Detector
~

deteat x
-

ray

– X-ray detector measure the diffraction pattern quantitatively

– Detector is rotating with respect to the specimen O in a way that the angle
between incident x-ray and detector is 2θ. Therefore, the specimen is rotated
by θ and the detector is rotated by 2θ with respect to the specimen O.
– Called as θ-2θ diffraction experiment, most basic XRD experiment.
– Measure the intensity I2θ by the detector at 2θ
Nanomaterials and
7 Electrochemical
NEED Lab Energy
Design Laboratory

X-ray Diffractometer

• Structure of X-ray diffractometer (XRD)

– Bragg-Brentano XRD

" ↑
.
.
.

– The angle between specimen and incident beam should be maintained as θ

the angle between the detector and x-ray should be kept as 2θ
– Therefore, the x-ray source (tube) and x-ray detector rotates in counter
clockwise by θ for Bragg-Brentano θ-2θ diffraction experiment
– Can measure the liquid sample or powder, as the samples are located
horizontally
Nanomaterials and
8 Electrochemical
NEED Lab Energy
Design Laboratory

4
 2024-11-11

X-ray Diffractometer

• X-ray diffraction pattern of Cu powder using Cu Kα line

Qconatmectire

o
powdery only some are oriented
propeaply

Iitfatioromewenitwenimes
08080
④
  0.154 nm

– For bulk specimen, the diffractometer will show same 2θ but different intensity
– For powder specimen with less than 10um in size, they will show same intensity
~ ~
diffraatiom peak
and angle on average.
• For every set of planes, there would be a small percentage of crystallites that are
properly oriented to diffract (the plane perpendicular bisects the incident and
diffracted beams)
• basic assumptions of powder diffraction are that for every set of planes there is an
equal number of crystallites that will diffract and that there is a statistically relevant
number of crystallites, not just one or two.

Nanomaterials and
9 Electrochemical
NEED Lab Energy
Design Laboratory

Diffraction

• XRD pattern of Fe Iron measured by Co Kα X-ray beam

– Bragg’s law will provide possible angles that satisfy the condition for diffraction,
– However, not all planes corresponding to these angles show the XRD peak
– Also it cannot offer the information of intensity of diffraction peak.
(011) - BCC

nktl = event

(112)
(0023

– 2dsinθ=nλ
– X ray source : 0.179nm of Co Kα X-ray beam
– 10113 , 10021
XRD peak is observed at 2θ = 52.3o, 77.2o, 99.6o corresponding to {011}, {002}, {112} .
– Not all planes shows XRD peaks amnot 1001 , ( 117 ? 4 Bluintktl -
(
(
even

Nanomaterials and
10 Electrochemical
NEED Lab Energy
Design Laboratory

5
 2024-11-11

Diffraction

• XRD peak and atomic position

< C-base centered orthorhombic > < Body centered orthorhombic >

– In both cases, two

two atoms exist in a unit cell. In C-base centered orthorhombic
and body centered orthorhombic, interplanar spacing of {001}, d{001} is 0.3nm.
– According to Bragg’s law of 2dsinθ=nλ, θ=17.4o
( θ= 17 40
(
d=
.
sin θ= .

0. )3

Nanomaterials and
11 Electrochemical
NEED Lab Energy
Design Laboratory

Diffraction

• The path difference

– In c-base centered orthorhombic
• At θ=17.4o, the path difference, ABC,
is 0.179nm, same as the wavelength
• Constructive interference t
– In body centered orthorhombic, Patu alifterence : ABXBC

• At θ=17.4, the path difference, DEF, < C-base centered orthorhombic >
is 0.0895nm, same as λ/2
PO
• Destructive interference
Opathdifference blw ① &③ ← BEF
– Not all angles that satisfy the Bragg’s Ocdoesnit omatch?
scestrucfive
equation shows peaks or intense imterference
peak no peak for oo 1
θ

– The intensity of diffraction peak

@
depends on the atomic array in a unit
cell

< Body centered orthorhombic >

Nanomaterials and
12 Electrochemical
NEED Lab Energy
Design Laboratory

6
 2024-11-11

Scattering

• X-ray scattering results from the interaction between x-ray and outer
electrons, not nuclei.
– ElasticScattering
Elastic scattering : wavelength and energy are conserved
• After x-ray of λ1 interacts with electrons, scattered x-ray still has wavelength of λ1.
– inelasticscattering
Inelastic scattering : wavelength and energy are not conserved
• After x-ray of λ1 interacts with electrons, scattered x-ray has different wavelength of
λ2 where λ1 <<
< λ .
2

– Generally in heavier atoms, the attraction between nuclei and electron is

stronger, so elastic scattering occurs
– In lighter atoms, the attraction between nuclei and electron is weak, and
inelastic scattering occurs
• Inelastic scattering does not contribute to the diffraction
• Inelastic scattering always occurs, resulting in the background of the experiments

Nanomaterials and
13 Electrochemical
NEED Lab Energy
Design Laboratory

Scattering
• Scattering at one atom

2
I  A2  Aei  Aei  Aei
distance blav & defector
-

detector

velectron

– Incident beam intensity Io, after scattering with 2θ, The scattering beam
intensity, Ip, will be

I P  I0
r2 (


①①
K  1  cos 2 2 
2



– K is constant. (K=7.94 x 10-30 m2, when x-ray is propagating under air)

– Takes time.
– Ex) 2θ=0, 180, r=10cm → Ip/Io=7.94 x 10-28
ery
lowefer
14 ssattering
Nanomaterials and
Electrochemical
NEED Lab Energy
Design Laboratory

7
 2024-11-11

Scattering by an atom

• Path difference, δ, upon the scattering angle 2θ

Dumimetei ⑤
i

.
patrdiffaren IO AB & CG
interferenue B -

(a) 2θ=0o, x-ray 1 and 2 have path difference of 0 no patu dif

s .

the amplitude will be 2A and the intensity will be 4A2.

(b) 2θ>0o, x-ray 1 and 2 have path difference of CD- AB
therefore, the amplitude will be lower than 2A
Any angle other than 2θ=0o, there will be a path difference lose
s

scattering

Nanomaterials and
15 Electrochemical
NEED Lab Energy
Design Laboratory

Scattering by an atom

• Atomic scattering factor f

– The amplitude of scattered light depends on the path difference
• Any angle other than 2θ=0o, there will be a path difference
– Atomic scattering factor is defined as the ratio of amplitude of the wave
scattered by an atom to amplitude of the wave scattered by one electron
Oamplit
AAtom
• Also called as atomic form factor scatteredfrom afom
end

f 
lifference AElectron
Damplitude scattered from eletron
nopatn
– When 2θ=0o,
m
Aatom = Z Aelectron, and therefore f is Z
– f decreases as sinθ increases or λ decreases θ ∞ ☆ 13
⑥
=

θ
• f <=> sinθ/ λ
5 sA Al =☆
– Example of Al
• f=13 when θ=0o

Nanomaterials and
16 Electrochemical
NEED Lab Energy
Design Laboratory

8
 2024-11-11

Scattering by a unit cell

• Diffraction intensity depends on the crystal structure

• In the case of orthorhombic
– (a) : C-based orthorhombic
– (b) : body centered orthorhombic

Fractional coordinates: uvw=000 and ½ ½ 0 000 and ½ ½ ½

Nanomaterials and
17 Electrochemical
NEED Lab Energy
Design Laboratory

Scattering by a unit cell

• Phase difference ϕ
– Diffraction condition in (hkl) plane depends on uvw
– Diffraction condition is determined by hkl, and uvw, not the lattice parameter
– Phase difference is defined as

  22 ((nutkutlw
hu  kv ) lw)
π

uVW sfractional coord .

Nanomaterials and
18 Electrochemical
NEED Lab Energy
Design Laboratory

9
 2024-11-11

Scattering by a unit cell

hke
• Phase difference ϕ in C-based orthorhombic of (001) plane
UVW
– At atom (uvw=000)
  2 (0m  0  0  0  1  0)  0
he k V ew

)
– At atom (uvw= ½ ½ 0 )
same
1 1
  2 (0n   0   e1 0)  0
2 K 2 u
aV

– Constructive lnterference
Constructive interference
s
diffraction for C basedcenter
-

orthornombic occur

  2 (hu  kv  lw)
Nanomaterials and
19 Electrochemical
NEED Lab Energy
Design Laboratory

Scattering by a unit cell

• Phase difference ϕ in body centered orthorhombic

– At (001) plane
• At atom (uvw=000)
  2 (0  0  0  0  1  0)  0
• At atom (uvw= ½ ½ ½ ) |

1 1 1
  2 (0   0   1 )  
2 2 2
Odifferent
• Destructive
Destructive interference
 no
No diffraction
diffraction
– At (002) plane
• At atom (uvw=000)

Q
  2 (0  0  0  0  1  0)  0

• At atom (uvw= ½ ½ ½ )
difference
= ZT)
1 1 1
  2 (0   0   2  )  2
2 2 2
• constractive
Constructive interference
 diffraction
diffraction
  2 (hu  kv  lw)
Nanomaterials and
20 Electrochemical
NEED Lab Energy
Design Laboratory

10
 2024-11-11

Scattering by a unit cell

• Structural factor Fhkl

– Any scattered wave can be expressed in the complex exponential form
(from one atom where diffracts at (hkl))

Aei  fez
fe2( butkutlowl
( hu  kv lw)
π

– The structure factor, F, is obtained by simply adding together all the waves
scattered by the individual atoms.
– If a unit cell contains atoms 1,2,3,…,N, with fractional coordinates, u1v1w1,
u2v2w2,…, then the structure factor for the hkl reflection is given by

Fhkl  f1e2 ( hu1 kv1 lw1 )  f1e2 ( hu2 kv2 lw2 )  f1e2 ( hu3  kv3 lw3 )  ...
N
Fhkl  fFrez
f n e2chutkuntlwas
( hun  kvn lwn )
π

Nanomaterials and
21 Electrochemical
NEED Lab Energy
Design Laboratory

Scattering by a unit cell

• Structural factor Fhkl

– F is, in general, a complex number, and it expresses both the amplitude and
phase of the wave.
– Its absolute value F gives the amplitude of the resultant wave in terms of the
amplitude of the wave scattered by a single electron
– ІFІ is defined as a ratio of amplitudes of the wave scattered by all the atoms of
a unit cell to amplitude of the wave scattered by one electron

AAupit
Fhkl  Unit Cell
call

AAelectron
Electron

2
– The diffraction intensity of a unit cell is proportional to IFnkek
Fhkl

Nanomaterials and
22 Electrochemical
NEED Lab Energy
Design Laboratory

11
 2024-11-11

Structure factor

• Structural factor Fhkl in p-lattice primitive

– In p-lattice, there is only one atom
in a unit cell at 000.

N
Fhkl   f n e 2 i ( hun  kvn lwn )
1
1
  f e 2 i ( h0 k 0l 0)  f e 2 i (0)  f UVW OOO
+

2
– Diffraction intensity, I, is proportional to Fhkl  f 2

Nanomaterials and
23 Electrochemical
NEED Lab Energy
Design Laboratory

Structure factor

• Structural factor Fhkl in I-lattice Bodycentered

– In I-lattice, there are one atom
at 000 and the other at ½ ½ ½

1 1 1
2 i ( h   k   l  )
Fhkl  f e 2 i ( h0 k 0l 0)  f e 2 2 2

 f 1  e i ( h  k l ) 
Lelther | F = 2f
{
4

O
F can be 0Oor
or 22ff - 1
F =

– Diffraction intensity, I, is proportional to lFl2

rt
Ctlceven number = BCC

– Therefore it depends on hkl

2
Fhkl  4 f 2
h  k  l )= even
when (cniktl number  e n i  e1 i  e3 i  1
eveean numember,
= )

 n i 2 i 4 i
 e  e  e  1
2
Fhkl  0  k bll )=
when ((hutk ) odd
0 number =

Nanomaterials and
24 Electrochemical
NEED Lab Energy
Design Laboratory

12
 2024-11-11

Structure factor
Face centered -

• Structural factor Fhkl in F-lattice

– In F-lattice, there are four atoms
– at 000, ½½0, ½0½, 0½½

1 1 1 1 1 1
2 i ( h  k   l 0) 2  i ( h   k 0  l  ) 2  i ( h 0  k   l  )
Fhkl  f e 2 i ( h0 k 0l 0)  f e 2 2
 fe 2 2
 fe 2 2

 f 1  e i ( h  k )  e i ( h l )  e i ( k l )  F can be OOr 4f

0 or 4f

– Diffraction intensity, I, is proportional to lFl2

– Therefore it depends on hkl
(odd + odd) or (even + even) = even
(odd + even) = odd
2
Fhkl  16 f 2 when indices of ((hhikillare
, k , l ) areunmixed
unmixed number  en i  e1 i  e3 i  1
number

2  n i 2 i 4 i
Fhkl  0 when indices of ((hh, kil
k , )l )are
aremixed
mixed number
namber
,  e  e  e  1
Nanomaterials and
25 Electrochemical
NEED Lab Energy
Design Laboratory
e +ea
ex .
unmixed # ( 1 β
= f ( ItH π i
+ez
π : τ :
] =F ( l + + + 13 = 4f F
'=
16f

mixed # # 110 F
>
= f
( iHez πi + :← e ") =
f +-1 - 1) ω =
:2 =
O
e π ( π
[ =

Structure factor
( -
based center
• Structural factor Fhkl in C-based-lattice
– In F-lattice, there are two atoms
– at 000 and ½½0

1 1
2 i ( h  k   l 0)
Fhkl  f e 2 i ( h0 k 0l 0)  f e 2 2

 f 1  e i ( h  k ) 

F can be 0Ooraf
or 2f

– Diffraction intensity, I, is proportional to lFl2

– Therefore it depends on hkl

2
Fhkl  4 f 2 h  k) )are
when (Catk areeven
even number
number  en i  e1 i  e3 i  1
 n i 2 i 4 i
Fhkl  0
2
h  k) )are
when (cutk areodd
odd number
namber  e  e  e  1
Nanomaterials and
26 Electrochemical
NEED Lab Energy
Design Laboratory

13
 2024-11-11

Structure factor

• (hkl) planes of each lattice for diffraction

h2+k2+l2 P-lattice F-lattice I-lattice Diamond
1 100 X X

2 110 X 110
3 111 111 X 111
4 200 200 200
5 210
6 211 211
7
8 220 220 220 220
9 300, 221
10 310 310
11 311 311 311
12 222 222 222
Nanomaterials and
27 Electrochemical
NEED Lab Energy
Design Laboratory

14
 2024-11-18

Crystal Structure
and X-ray Diffraction

2024/11/19
Prof. Don-Hyung Ha
[Link]

School of Integrative Engineering

Chung-Ang University
Nanomaterials and
1 Electrochemical
NEED Lab Energy
Design Laboratory

X-ray Diffractometer

• X-ray diffraction pattern of SiO2 with different phase

amorpnous arystalline

– XRD Bragg-Brentano θ-2θ experiment can differentiate the structure, as seen

in the case of amorphous SiO2 and crystalline SiO2 diffraction pattern.

Nanomaterials and
2 Electrochemical
NEED Lab Energy
Design Laboratory

1
 2024-11-18

Path of x-ray and diffraction in XRD

• Φ slit and soller slit

ray

0
x ray
-

[ *]

I
Xray

• To reduce the divergence, use soller slits

• Soller slit : 10 pieces of metallic plates that can absorb the x ray having
angle

Nanomaterials and
3 Electrochemical
NEED Lab Energy
Design Laboratory

Path of x-ray and diffraction in XRD

• Diffraction cone from Cu powder

• Generally, a point detector is used by moving the circle
• However, it takes a long time to scan the diffraction
pattern as it detects each point at 2θ
– Assuming that only 1/1000 can contribute to diffraction
~

point collect 1/100,

[
– Assuming that point detector window can
diffrat:
on

"100 n
di ffract
– At specific angle of 2θ, only 1/100 powder
can contribute to the signal
efficieny
∴

• Bragg-Brentano θ-2θ powder experiment

– Small fraction of diffraction cone can @

contribute to the signal D

– Small fraction of powder can contribute

to the signal
– Therefore, the efficiency is low
Nanomaterials and
4 Electrochemical
NEED Lab Energy
Design Laboratory

2
 2024-11-18

Path of x-ray and diffraction in XRD

diffract anystallife

– For every set of planes, there would be a small percentage of crystallites that

[
are properly oriented to diffract (the plane perpendicular bisects the incident
assumption and diffracted beams)
– basic assumptions of powder diffraction are that for every set of planes there
is an equal number of crystallites that will diffract and that there is a

I
statistically relevant number of crystallites, not just one or two.
Nanomaterials and

* 5 Electrochemical
aiffrac cystalite NEED Lab Energy
Design Laboratory

Powder specimen for XRD …

• Sample preparation
– When powders have size less than 10um, the same diffraction pattern will be
shown no matter what kind of instruments are used
size 10 µ m β

[Link]
watch?v=1IWuOUF1_LU&a
b_channel=IAMMDiffractio
nFacility
• Grind or abrade the sample into powder
• Anneal at T>T(recrystallization) to remove the dislocation and residual strain
• Use sieve, collect the powder with the size <10um
*

• Fill the powder in the sample holder

• Add adhesive to enhance the cohesive force of the powder
– ZBH (zero background holder)
– Using the condition that does not satisfy the Bragg’s law, and subtract the
background to cancel the noise and make the background zero
Nanomaterials and
6 Electrochemical
NEED Lab Energy
Design Laboratory

3
 2024-11-18

XRD applications

• 1. Phase Identification of a Sample

• 2. Unit cell lattice parameters and Bravais lattice symmetry [ex FCCIBCC)
.

• 3. Residual Strain (macrostrain)

• 4. Crystal Structure
• 5. Texture/Orientation
• 6. Crystallite Size and Microstrain

Nanomaterials and
7 Electrochemical
NEED Lab Energy
Design Laboratory

Qualitative analysis
~

Can ko . = 0 th4 mm

• Mixture of Al powder and Cu powder

D
D
-

-Beakintamssity
aifferent
Q Cu stronger since cu (x5] 3 Ae (253

]
(

– As the XRD diffraction data for each elements are known (find the reference),
conduct Bragg-Brentano XRD experiment, and measure the 2θ and intensity
I2θ. Based on the result, we can tell which phase (crystalline structure) the
specimen have
Nanomaterials and
8 Electrochemical
NEED Lab Energy
Design Laboratory

4
 2024-11-18

Quantitative analysis
~

• Mixture of Al powder and Cu powder

• Reference sample : specimen with the weight ratio of A to B

•
•
Reference diffraction : diffraction data of A and B
From reference diffraction, we can extract the ratio of A and B } s toknow the exactamount
Cquantitative analysis)

Nanomaterials and
9 Electrochemical
NEED Lab Energy
Design Laboratory

Quantitative analysis

• Quantitative analysis by XRD

ideal

creference)

• We could determine how much of each phase is present

• In the sample (mixture of A and B), assume the intensity I σ and Iβ are the
intensity of each phase a
• Iσ and Iβ are the intensity peak area. The ratio of Iσ/(Iσ + Iβ) and I β /(Iσ + Iβ)
~
depends on the weight fraction  linear relative: Mensity
• In reality, however, there could be more factors (such as mass absorption
coefficient of mixture) that can contribute to the diffraction intensity 
not linear
Nanomaterials and
10 Electrochemical
NEED Lab Energy
Design Laboratory

5
 2024-11-18

Lattice parameter analysis

• The relationship between θ and sinθ

– At small θ, the deviation from θ results in large deviation of sin θ
– At large θ, the deviation from θ results in small deviation of sinθ
– It’s better to use large
sargenθ to extract the lattice parameter a from d(hkl)
D :-

θ :
×
] ∞ θ better

00
,
DsinD

1 1
D
θ (90
Nanomaterials and
11 Electrochemical
NEED Lab Energy
Design Laboratory

Lattice parameter analysis

• Au-Pt equilibrium phase and atomic fraction of Pt for the lattice parameter of
solid solution Au 100%
( affise parameter : 6 4 Dt
4 0t O
,

3 az
(pt : 50% An : 58%
.

) t+
O - Pt 108 % e

Solid solation lattise parameter : v zazmm

.

)
(Am& βE lnkficaparkmetev

FECmetal
Au &Pt -
– Au Pt can have solid solution through all fraction, and the crystal structure is FCC
FCC
. on average pt
– At room temperature the lattice parameter of Au and Pt are 0.407 and 0.392nm, ~

respectively. The l.p. of solid state has linear relationship of atomic fraction of Pt

(
cattale parumeter
– From Bragg Brentano XRD experiment, calculate 2θ and then extract the lattice
parameter, and achieve the atomic fraction XPt
Nanomaterials and
12 Electrochemical
NEED Lab Energy
Design Laboratory

(affice parameter
Beak shift ( θ)
hha
An pt
n Pe

Lole tee µ
L Auptu
6
 2024-11-18

Crystalline size analysis

• Diffraction pattern in single crystalline and powder

– (a) : {111} crystalline plane of single
singleanystalline
crystalline
– (B) : {111} plane of powder
powder single coystaline powder
– In single crystalline materials (a),
there is only one angle of 2θB that
satisfies the Bragg’s law
– In powder form,
the destructive interference occurs
when 2θ< 2θ1 or 2θ2< 2θ
Thus, the constructive interference
occurs when 2θ1 <2θ< 2θ2

~ Powroad

Ea ∞

13

!
NEED Lab
Nanomaterials and
Electrochemical
Energy
Design Laboratory

diffration .

Crystalline size analysis

• Size extraction
– In powder, the diffraction peak has intensity I and width FWHM (full width at
half maximum)

1
B (2 2  21 )   2  1
FWHM
2 smatlersize
grange
φ esbroader peak

– At smaller size, the x-ray diffraction range of 2θ1 and 2θ2 increases.
– Scherrer’s equation : the size, t, is determined by FWHM, B _

!
o g)

rconstantlusually
.

k 
tgos
?cos
K=0.9, θB = 49°, λ = 0.15 nm
B Q
B=0.00001°
0 000010 for t= 1.0 mm B

fbroader
.

size [ ]
B=0.23°
8 230
. for t= 50 nm
B=2.3°
2 0 for t= 5 nm
.

IC 1 λ B &② ε
, graph
Nanomaterials and
14 Electrochemical
NEED Lab Energy
Design Laboratory

7
 2024-11-18

Residual stress

• X-ray analysis of Residual stress

– Lattice parameter or interplanar spacing dhkl change induces 2θ(hkl)

de

← →
suomaller θ
laraer D

,
broaaer
peak

– (a) The sample under no strain

– (b) compressional strain  snorter
shorter interplanar spacing  nigher
higher 2θ
– (c) tensional strain  longer interplanar spacing smaller
smaller 2θ

– (d) Bending does not change 2θ, but induces the increase of FWHM B
Nanomaterials and
15 Electrochemical
NEED Lab Energy
Design Laboratory

Residual stress

CFOOH 14 )

Nanomaterials and
16 Electrochemical
NEED Lab Energy
Design Laboratory

8
 2024-11-18

X-ray analysis of residual stress

• The change of lattice parameter a upon residual stress

utfile pararmeter
samne

O ⑨
latfile oura meter

• After deformation, the metal or materials can have residual stress

• The sample having residual stress can have different lattice parameter
– Under compressional stress, a<ao when ψ=0o and a>ao when ψ=90o
– Residual stress depends on the angle, and ao/a is residual strain

laffice ×
paramefer
stress Iaffice parameter
Nanomaterials and
17 Electrochemical
NEED Lab Energy
Design Laboratory

Specimen

• For same materials

– Powder
• Random orientation f : sotropic)
• Statistics show the similar results on average
– Bulk canisotropic)
• Peak position, 2θ, will be the same regardless of sample
• Intensity will vary depending on the sample
• texture

Nanomaterials and
18 Electrochemical
NEED Lab Energy
Design Laboratory

9
 2024-11-18

X-ray Detector

• X-ray detector (Counter)

ccoanter)

– Detect the intensity of X-ray (amount) from the specimen

(1) Gas detector
Gasdetector
- Geiger detector
- Proportional detector
(2) Solid detector
soliddetector
- Scintillation detector
- Semiconductor detector

Nanomaterials and
19 Electrochemical
NEED Lab Energy
Design Laboratory

X-ray Detector

• Gas detector
– Ar, Xr and Kr gas in the chamber
tae
imert ogas
– Several hundreds volts of potential exists
≈

nigbusbetween anode and cathode

(Ar s Arite > -

– X-ray ionized gas and produces electrons

– Electrons are collected at the electrodes
generating current
Bionizedgectron
.

current

Iinertgas
Ipotential

Nanomaterials and
20 Electrochemical
NEED Lab Energy
Design Laboratory

10
 2024-11-18

X-ray Detector

• Scintillation detector

h
wisible ligut ~~

– Sodium iodide (NaI) crystal doped with thallium produces visible light when x-
ray comes
– Visible light produces creates electrons in photocathode
– A electron create 4-5 electrons in dynode
– After photomultiplier, number of electrons are amplified by a factor of 107.
– Intensity of x-ray is measured indirectly by the current (electrons)

4
ray
-

amplified high urrent

Nanomaterials and
21 Electrochemical
NEED Lab Energy
Design Laboratory

X-ray Detector

• Scintillation detector

– X-ray (λ<0.03nm) : energy is too high to be absorbed by the detector

– X-ray (λ>0.05nm) : high absorption efficiency
~

l
– Most of XRD use scintillation detector

. otamo 22
Nanomaterials and
Electrochemical
efficienary gooad NEED Lab Energy
Design Laboratory

11
 2024-11-18

X-ray Detector

• holepain
Nelectron
semiconductor detector -

e current s
intensity

– Use Li doped Si or Ge crystals

– X-ray incident to p-type semiconductor
– Electron hole pair created by x-ray. Built in potential prevent the
recombination the excitons and separate electrons and holes
– Detector collects electron and holes, and the current tells the intensity of x-ray

Nanomaterials and
23 Electrochemical
NEED Lab Energy
Design Laboratory

Detector

• 0D 1D and 2D detector
– Point detector or line detector or plane detector
…
better better

,
,

O Dalefector
-
1 Ddetector
-
2-
Ddetector

Nanomaterials and
24 Electrochemical
NEED Lab Energy
Design Laboratory

12
 2024-11-18

0D Detector

• Point detector

– Diffraction cone has angle of 2θ

– 0-D detector rotates the detector circle, and take long time to collect the data
– 1-D detector can reduce the time, because window can cover ~10o at once.

Nanomaterials and
25 Electrochemical
NEED Lab Energy
Design Laboratory

2D Detector

• 2D detector

– Can observe the diffraction cone, and investigate the intensity

– By 2-D detector rotation, 3d information can be obtained
– Specimen with strain induce the ellipsoid instead of circle
– Can reduce the time by investigating the large area of 2θ at once and
measuring the intensity simultaneously

Nanomaterials and
26 Electrochemical
NEED Lab Energy
Design Laboratory

13
 2024-11-18

exture
-
O

2D
…
detector integration
Gtexture

Nanomaterials and
27 Electrochemical
NEED Lab Energy
Design Laboratory

14
 2024-11-25

Crystal Structure
and X-ray Diffraction

2024/11/26
Prof. Don-Hyung Ha
[Link]

School of Integrative Engineering

Chung-Ang University
Nanomaterials and
1 Electrochemical
NEED Lab Energy
Design Laboratory

※ Interplanar spacing

• Interplanar spacings 1 2 3
– Determined by crystal system, lattice parameters, plane (hkl)
In cubic system
1 h2  k 2  l 2 1 02  12  02 1 02  22  02
 ,  , 
d2 a2 d 010 2 a2 d 020 2 a2
a a
d 010  , d 020 
1 2

1 h2  k 2  l 2
Cubic 
d2 a2
1 h2  k 2 l 2
Tetragonal   2
d2 a2 c
1 4  h 2  hk  k 2  l 2
    c 2
Hexagonal d 2 3  a2 
1

  
h 2  k 2  l 2 sin 2   2hk  kl  hl  cos 2   cos  
Rhombohedral
d2 
a 2 1  3 cos 2   2 cos 3  
1 h2 k 2 l 2
Orthorhombic   
d 2 a 2 b2 c2
1 1  h 2 k 2 sin 2  l 2 2hl cos  
    2  
Monoclinic d 2 sin 2   a 2 b2 c ac 
Nanomaterials and
2 Electrochemical
NEED Lab Energy
Design Laboratory

1
 2024-11-25

Structure factor

• Lattice parameter of Cu = 3.61 Å, (fcc) diffraction with λ = 1.54 Å

diffraction θ = 25.2°for {002}
→ sin θ / λ = 0.277 Å-1, f = 18.75 fromgraph
Fhkl = 4f = 4×18.75 = 75.00,
Therefore, the diffraction intensity of {002} in Cu unit cell
IUnit Cell  F0022 = (75.00)2

• Lattice parameter of Fe = 2.86 Å, (bcc)

diffraction with λ = 1.79 Å for {002}
θ = 38.6°and sin θ / λ = 0.349 Å-1, f = 14.47 from graph
Fhkl = 2f = 2×14.47 = 28.94, Fe
Therefore, the diffraction intensity of {002} in Cu
← unit cell

IUnit Cell  F0022 = (28.94)2

Nanomaterials and
3 Electrochemical
NEED Lab Energy
Design Laboratory

Structure factor
• Actual example 3
2 different nement
– CsCl : Simple cubic (P)

11 1 1 11
• Cs+ 000, 0, 0 , 0
22 2 2 22

• Cl- : 1 1 1 , 00 1 , 0 1 0, 1 00
222 2 2 2

1 1 1
2 i ( h   k   l  )
 i ( h0  k 0  l 0)
Fhkl  f C s e 2o  fC le 2 2 2

 f C s  f C l e i ( h  k  l )
≈

Lintensig differ
mikil
depenaring on

2
FF
hkl
hkl
= f h  k ) leven
+ ffcl2 when ((Gxctl
cs 4 )= even
#
number
=

FF
hkl
hkl
=2 f - fcl
cs 0  ktl) l )=odd
when ([hntk odd
# number
=

Nanomaterials and
4 Electrochemical
NEED Lab Energy
Design Laboratory

2
 2024-11-25

BStructure factor
m

• Actual example
– CsCl : Simple cubic (P)

– L.P of CsCl: 5.45 Å,

λ = 1.54 Å X-ray for diffraction
θ = 16.4°for {002} → sin θ / λ = 0.183 Å-1
fromgrapnt
f = 44.37, f = 11.57
Cs Cl

h+k+l is even for {002}

Fhkl = fCs + fCl, Fhkl = 55.94 s case of even

and Fhkl = fCs - fCl, Fhkl = 32.8 f case ofodd

2
Fhkl  ( f Cs  f Cl )2 when (h  k  l ) are even number
2
Fhkl  ( f Cs  f Cl ) 2
when (h  k  l ) are odd number

Nanomaterials and
5 Electrochemical
NEED Lab Energy
Design Laboratory

revan
brighminteansity

ad
loaw intensity

* Stucture fator but ,

fa r

Nanomaterials and
6 Electrochemical
NEED Lab Energy
Design Laboratory

3
 2024-11-25

Structure factor
• Actual example
– NaCl : FCC
11 1 1 11
• Na+ 000, 0, 0 , 0
22 2 2 22

• Cl- : 1 1 1 , 00 1 , 0 1 0, 1 00
222 2 2 2
1 1 1 1 1 1
2 i ( h   k  ) 2 i ( h   l  ) 2 i ( k   l  )
2 i (0)
Fhkl  f Na  e  f Na  e 2 2
 f Na  e 2 2
 f Na  e 2 2

1 1 1 1 1 1
2 i ( h   k   l  ) 2 i ( l  ) 2 i ( k  ) 2 i ( h  )
 f Cl e 2 2 2
 f Cl e 2
 f Cl e 2
 f Cl e 2

정리하면
Fhkl  1  e i ( h  k )  e i ( h l )  e i ( k l )   f Na   f C l e i ( h  k l ) 

For indices h, k , l are mixed,

2
Fhkl  0O = s
nopeak

For indices h, k , l are unmixed, Fnke = llt ItIt ( JIfmattfor -eπ ichtatus !
2
Fhkl  16( f Na   f Cl ) 2
 k  l )are
when (hIntkteJ are even
even number
number

2
Fhkl  16( f Na   f Cl ) 2
 k  l )) are
when ((hntkte are odd
odd number
nurmner
Nanomaterials and
7 Electrochemical
NEED Lab Energy
Design Laboratory

Structure factor

Dsrighintensuty

For indices h, k , l are mixed,

2 No diffraction in {100}, {110}, {120}, {112} mixed 4 no peak
Fhkl  0 ≈

Diffraction with high intensity in {002}, {220}, {222} jeven

For indices h, k , l are unmixed,
2
ummixeds Diffraction with low intensity in {111}, {311}m

sodd
Fhkl  16( f Na   f Cl ) 2 when (h  k  l ) are even number
m

2
Fhkl  16( f Na   f Cl ) 2 when (h  k  l ) are odd number
Nanomaterials and
8 Electrochemical
NEED Lab Energy
Design Laboratory

4
 2024-11-25

Diffraction intensity

• Structure factor

}
• Polarization factor
• Lorentz factor factors influencong diffraction intensity
• Multiplicity factor
• Temperature factor

Nanomaterials and
9 Electrochemical
NEED Lab Energy
Design Laboratory

Polarization factor

• Polarization factor

K  1  cos 2 2 
I P  I0 2  
r  2 
PF

– Scattering by an electron
– Intensity depends on r and 2θ

Nanomaterials and
10 Electrochemical
NEED Lab Energy
Design Laboratory

5
 2024-11-25

Lorentz factor
• Lorentz factor I

– In a powder form, diffraction occurs between 2θ1 and 2θ2. Integrated intensity
is proportional to the area.
1 1
  in , B2  1   2  io
I 2max
sin  cos θ
– Therefore, the total intensity is
1 1 1
I 2Integral
  I 2max
  B2  oso
sin inB  2
 B cos .
sin 2 B
Nanomaterials and
11 Electrochemical
NEED Lab Energy
Design Laboratory

Lorentz factor

• Lorentz factor II
– Over the surface area of sphere, 4πr2,
– The diffraction cone occurs only at 2θ
that satisfies the Bragg’s law
– The radius of circumference is
r sin (90o-θB)
– Therefore the circumference is
2π r sin (90o-θB)
Single crystal

i
⑥ m

Powder

Nanomaterials and
12 Electrochemical
NEED Lab Energy
Design Laboratory

6
 2024-11-25

Lorentz factor

• Lorentz factor II
– For powder, a slight deviation from the 2θ can contribute to the diffraction
– The intensity can be integrated from band with a width of rΔθ
– Therefore, a fraction of powders contributing to the diffraction intensity to all
powders is described as

rr22r sin( 90o BB)) r   2 r cos  B

sin(90
I 2Integral
 I 
44r 4 r 2
2

I 2Integral
  cos  B  두 번째 Lorentz 인자
I  cos( OB ))
cos (
(3
~

( oSO

Nanomaterials and
13 Electrochemical
NEED Lab Energy
Design Laboratory

Lorentz factor

• Lorentz factor III

– For powder, scattered wave having angle of 2θ make diffraction cone.
– The circumference of the diffraction cone is r sin2θ
– The detecting area is constant, and therefore the effective intensity that
detector measures is inversely proportional to the cone size

OO
≈

conesize φ
intensity →
infensitq
("
11 .

I
2 B
sinzDB
100m
sin 100

D α
s
ontensityp

Nanomaterials and
14 Electrochemical
NEED Lab Energy
Design Laboratory

7
 2024-11-25

Lorentz Polarization factor

• Lorentz Polarization factor

– Total Lorentz factor is defined as
1 2 3
 1   1  1
LF =     cos  B   
 sin 2 B   sin 2 B  4sin  B cos 
2

– Lorentz-Polarization (L-PF) factor is defined as

1  cos 2 2
L  PF = 60
1H

 B cos 
sin 2DBCoso

– L-PF is a function of θB.

b
• Max L-PF is achieved at 2θB=0o or 180o intensiy
LorentEfactor
• Min L-PF is achieved as 2.7 at 2θB=100o explain 3

Nanomaterials and
15 Electrochemical
NEED Lab Energy
Design Laboratory

Multiplicity factor

• Multiplicity factor
– The relative proportion of hkl planes contributing to the same reflection
enters the intensity equation as the quantity p, the multiplicity factor, that
may be defined as the number of permutations of position and sign of ±h, ±k,
±l for planes having the same d and F2.
Multiplicity
 uvw  Equivalent indices
factor
 001  [100],[100],[010],[0 10],[001],[00 1] 6

111  [111],[1 1 1],[111],[1 1 1],[1 11],[11 1],[11 1],[1 11] 8

[011],[0 1 1],[0 11],[01 1]
 011  [101],[10 1],[101],[10 1] 12
[110],[1 10],[110],[1 10]
[112],[1 1 2],[112],[1 1 2],[1 12],[11 2],[11 2],[1 12] ← for cubic
×
112  [121],[1 2 1],[121],[1 2 1],[1 21],[12 1],[12 1],[1 21] 24
[211],[2 1 1],[211],[2 1 1],[2 11],[21 1],[21 1],[2 11]
[123],[1 2 3],[123],[1 2 3],[1 23],[12 3],[12 3],[1 23]
[132],[1 3 2],[132],[1 3 2],[1 32],[13 2],[13 2],[1 32]
[213],[2 1 3],[213],[2 1 3],[2 13],[21 3],[21 3],[2 13]
123 
[231],[2 3 1],[231],[2 3 1],[2 31],[23 1],[23 1],[2 31] Os
48
multiplicity4
[312],[3 1 2],[312],[3 1 2],[3 12],[31 2],[31 2],[3 12] ainten sitys
[321],[3 2 1],[321],[3 2 1],[3 21],[32 1],[32 1],[3 21]
Nanomaterials and
16 Electrochemical
NEED Lab Energy
Design Laboratory

8
 2024-11-25

Multiplicity factor

• Multiplicity factors on {hkl} and crystal structures

– Generally, the diffraction intensity is proportional to the multiplicity
– Higher multiplicity shows higher intensity as more powders can contribute to
the diffraction statistically.

hkl hhl 0kl 0kk hhh 00l

cubic
48 24 24 12 8 6

I
Hexagonal hkl hh·l 0k·l hk·0 0k·0 00·l
Rhombohedral 24 12 12 12 6 2
hkl hhl 0kl hk0 0k0 00l
Tetragonal
16 8 8 4 4 2
hkl h0l 0kl hk0 h00 00l
Orthorhombic
8 4 4 4 2 2
hkl h0l 0k0
Monoclinic
4 2 2
hkl
Triclinic
2
Nanomaterials and
17 Electrochemical
NEED Lab Energy
Design Laboratory

Temperature factor

• Temperature factor
– At 0K, atoms are fixed, but at higher temperature, atoms are vibrating.
– Atomic scattering factor at 0K is defined as fo, and atomic scattering factor at
temperature T is defined as fT, and they show the relationship of

fT  f 0 e  M
– M is proportional to (u/d)2, where u is displacement and d is the interplanar
spacing (d=λ/2sinθ)
– Diffraction intensity is proportional to fT2, and therefore e-2M, which is called as
temperature factor TF.

Nanomaterials and
18 Electrochemical
NEED Lab Energy
Design Laboratory

9
 2024-11-25

Temperature factor

• TF and sinθ/λ
– As sinθ/λ increases f decreases

Nanomaterials and
19 Electrochemical
NEED Lab Energy
Design Laboratory

Temperature factor

• TF effect
– (a) : simulation of 4 peaks with same intensity
– (b) : simulation of same situation with consideration of atomic vibration
• Background increases with 2θ

Nanomaterials and
20 Electrochemical
NEED Lab Energy
Design Laboratory

10
 2024-11-25

Temperature factor

• Total intensity calculation

– Structure factor (Fhkl )
– Lorentz-polarization factor (L-PF)
– Multiplicity factor (PFhkl)
– Temperature factor (TF)

2 1  cos 2 2
I Integral
2 = Fhkl  2  PFhkl  TF
sin  B cos 

Nanomaterials and
21 Electrochemical
NEED Lab Energy
Design Laboratory

11