Chapter 7 Diamonds

Introduction to
Crystallography

7.1 periodicity and lattices of crystal Crystals:

Crystals are solids that are built from atoms or
structure
molecules arranged in a periodic manner in space.
7.1.1 The characteristics of crystal structure
1. A few definitions:
• Solids can be divided into to primary categories,
crystalline and amorphous.

• Crystalline Solids that are built from atoms or

molecules arranged in a periodic manner in space.
• Amorphous Solids posses short range order only.
They are not related through symmetry.

• Short Range Order: Fixed bond lengths and angles

• Long Range Order: Associated with a lattice point

1
2. Fundamental characteristics of crystal

•Spontaneous formation of polyhedral shapes

F+V=E+2

Single crystal gold bead with

naturally formed facets

•Anisotropy

2150 g/mm2

Conductivity

1150 g/mm2

HRTEM images of hollow beads 570 g/mm2

Graphite
NaCl

2
 •Definite sharp melting points 7.1.2 The lattice and unit cell

• Lattice:
T
• A periodic pattern of points in space, such
that each lattice point has identical
t surroundings.
• Can be reproduced by translational
• Symmetry motion along the vector between any two
points.
•X-ray diffraction by crystals

a. The lattice and its unit in 1D:

T = ma (m = 0, ±1, ± 2 …)

One dimensional lattice

3
b. Lattice and its unit in 2D:
T = ma + nb m, n = 0,±1, ± 2 …)

•Crystal structure = lattice + structural motif
(basis)
Lattice:
•A periodic pattern of points in space, such that
each lattice point has identical surroundings.
•Can be reproduced by translational motion
along the vector between any two points.

Crystal structure = lattice + structural motif

(basis)

b
a

4
 Unit Cell Choice

¾ There is always more than possible choice

of unit cell
¾ By convention the unit cell is chosen so
that it is as small as possible while
reflecting the full symmetry of the lattice

1) The highest symmetry

2) The smallest area (or volume)

There are literally thousands of crystalline materials,

there are only 5 distinct planar lattices

Five 2D lattices
c. Lattices and its unit in 3D:

T = ma + nb + pc (m, n, p = 0, ±1, ± 2, …)

a≠b γ ≠ 90°, a=b γ=90°

γ ≠ 120° a≠b γ=90°

Primitive unit cell

a≠b γ=90° a=b γ=120°

Conventional unit cell (centered unit)

Primitive
unit cell
Centered

5
Unit Cell: Have maximum symmetry and minimum size
1) The axial system should be right handed
2) The basis vectors should coincide as much as possible
c
with directions of highest symmetry
3) Should be the smallest volume that satisfies condition 2

α
4) Of all lattice vectors none is shorter than a
β

a
γ
b 5) Of those not directed along a none is shorter than b
c

6) Of those not lying in the a, b plane none is shorter than c

a b

7) The three angles between the basis vectors a,b,c are either
all acute or obtuse

Example:
Atomic Coordinates: Fractional coordinates
Cubic unit cell of CsCl,
Fractional coordinates: a=b=c
The positions of atoms inside a α=β=γ=90°
unit cell are specified using 0.5 Cs:(0,0,0)
fractional coordinates(x,y,z). i
These coordinates specify the Cl: (1/2,1/2,1/2)
position as fractions of the unit 0.6

cell edge lengths

i: (1.0, 0.6, 0.5)

Single Crystal: Composed of only one particular type of space lattice.

Polycrystalline matter: Clusters of multiple crystals.

6
7.1.3 crystal systems and Bravais Lattices Trigonal 3-fold rotation Rhombohedr D3d
axes al
a. crystal systems a=b=c
α=β=γ<120°
≠90°
Hexagonal D6h
a=b≠c
α=β=90°
γ=120°
Crystal Characteristic Unit cell Choice of axis Lattic Tetragonal 4-fold rotation a=b≠c c // 4-fold axis D4h
systems symmetry parameters Point axes α=β=γ=90°
elements Group Hexagonal 6-fold rotation a=b≠c c // 6-fold axis D6h
Triclinic Nil a≠b≠c Ci axes α=β=90°
α≠β≠γ γ=120°
Monoclinic b // 2-fold axis C2h Cubic Four 3-fold a=b=c Four 3-fold axes Oh
a≠b≠c
rotation axes α=β=γ=90° are parallel to
α=γ=90°≠β the four body
Orthorhombic a≠b≠c a, b, c // 2-fold D2h diagonals of the
α=β=γ=90° axes cube

Orthorhombic

b. Bravais Lattice: (14)

Trigonal
Unit Cell: have maximum symmetry and minimum size
Centred Unit cell:
Tetragonal
Crystal P C I F
systems
Triclinic

Hexagonal

Monoclinic
Cubic

7
Monoclinic Tetragonal
I =C C=P
Monoclinic F = C

3-D Lattice (11) – Trigonal system

a=b=c
α≠ β ≠ γ ≠ 0
P – Rhombohedral
R ( Primitive )

In plane: C6 and C3 belong to D6h

8
 a.Primitive rhomohedral- b.primitive hexagonal
r-centered hexagonal Bravais Lattices
r-centered rhombohedral

Body-centered cubic Face-centered cubic

Simple cubic

Simple orthorhombic C-centered orthorhombic Face-centered orthohombic

Body-centered orthohombic

Died 30 Mar 1863 (born 23 Simple triclinic Rhombohedral Hexagonal

Aug 1811)
French physicist best
remembered for his work
on the lattice theory of
crystals; Bravais lattices
are named for him.
Simple C-centered Simple Body-centered
monoclinic Monoclinic tetragonal tetragonal

7.1.4 Crystal Planes and Miller Indices b.Miller indices (hkl)

a.Lattice planes
Miller indices are the
It is possible to describe certain directions and planes reciprocal intercepts of
with respect to the crystal lattice using a set of three the plane on the unit cell
integers referred to as Miller Indices. Miller indices axes.
describe the orientation and spacing of a family of
planes. 1 1 1
: : = h:k :l
r s t
(010)
(110)

( 10)

( 20)

(210)

9
Examples of Miller indices hexagonal, four axis (a1,a2,a3,c) (hkil), i=-(h+k)
(110) (1 1 0) (0001) c

c
c a3 90 90
( 1 2 1 0)

b (1 1 00) 120 a2
(111) 120

a b a1
c
(100) a
(10 1 1)
(010) b

c
a

a origin
hexagonal, four axis (a1,a2,-(a1+a2),c)

C. Directions in lattice Example: Directions on the (111) plane.

[122]
[ 1 1 2]
[001] [ 1 10]
c
c [100] [0 1 1]

b [110]
[210]
a [100] b
[1 2 0]

[1 2 0]
a
(111)

10
Miller indices (hkl) are used specify the orientation and
d. d-spacing formulae
spacing of a family of planes.
{hkl} are used to specify all symmetry The spacing between adjacent planes in a family is
equivalent sets of planes referred to as a “d-spacing”

ƒCubic : 1/d2 = (h2+k2+l2)/a2

ƒOrthorhombic: 1/d2 = (h2+k2+)/a2 + l2/c2
Miller indices [hkl] are used to specify a direction in space ƒTetragonal: 1/d2 = h2/a2+k2/b2 + l2/c2
with respect of the unit cell axes.
ƒHexagonal: 1/d2 = (4/3)(h2+hk+k2)/a2 + l2/c2
<hkl> are used to specify a set of symmetry
equivalent directions. ƒMonoclinic: 1/d2 = [(h/a )2 + (k/b )2sin2β + (l/c )2-
(2hl/ac)cosβ]/sin2β
[hkl] zone axis
ƒTriclinic:

7.1.5 Real crystals and Crystal defects

Real crystals are only close approximations of space lattices

Edge dislocation
Screw Dislocation
• Formed by shear stress
• Also linear and along a
dislocation line

11
 ¾ Crystallographers make use of all the symmetry in a
crystal to minimize the number of independent
coordinates

7.2 Symmetry in crystal structures.

a. Lattice symmetry
b. Point symmetry
c. Other translational symmetry elements: screw axes
and glide planes
7.2.1 Symmetry elements and symmetry
operations a. Lattice symmetry --- translation operation
m 
Tmnp=ma+nb+pc  
Tmnp= n
 
 p 

b. Point symmetry elements compatible with 3D translations

Rotation axes, 1,2,3,4,6 only!! Why ???
ma
B1 α B2
Reflection Mirror Plane m α

Rotation operation Rotation axis n, 1, 2, 3, 4, 6

Inversion Center of symmetry 1 α α
a a a
Rotatory inversion Inversion axis 3, 4, 6 A1 A2 A3 A4
Lattice points A1, A2, A3, A4 (m-1)/2≤ 1
• Point symmetry operation does not alter at least one Through n-fold operation m-1≤ 2
point that it operates on: rotation axes, mirror planes,
A1 → B1 m= 3, 2, 1, 0, -1
rotation-inversion axes
A4 → B2 cos α=1, 1/2, 0, -1/2, -1
A1A4 // B1B2 α = 0º, 60º, 90º, 120º, 180º
B1 B2 a +2acosα = ma n= 1, 6, 4, 3, 2
cos α = (m-1)/2 rotation axes, 1,2,3,4,6 only!!

12
 The symmetry elements of a cube
Packing objects in 3D space
¾Certain point symmetry Twofold axis
elements are not possible if a Threefold axis
possible an object is to have Fourfold axis
translation symmetry as well
¾For 3D periodicity
--rotation axes, 1,2,3,4,6 only!! 2 3 4 6
--not 5,7,8 etc.. Rotation axis

¾There are only 32 point

groups consistent with
periodicity in 3D
1 2

 0 1 0 general equivalent positions: (x,y,z),

1 0 0  general equivalent positions:  
  (x,y,z); (-x, y, -z) R (4) =  1 0 0 (-y, -x, z), (-x,-y,z), (y,-x,z)
R ( 2) =  0 1 0   0 0 1
0 0 1  2 fold axis // b   4 fold axis // c
 

0 1 0  1 1 0  general equivalent positions: (x,y,z), (x-

    y, x, z), (-y, x-y,z), (-x,-y,z), (y-x, -x, z),
R(3) = 1 1 0 R ( 6) = 1 1 0 
0 0 1  0 0 1  (y, y-x,z)
   
6 fold axis // c
general equivalent positions:
(x,y,z), (-y, x-y, z) (-x+y, -x, z)
3 fold axis // c

13
 c.Screw axes and glide planes: Higher order screw axes
A two fold scew 21

(x,y,z)→(x, –y, -z)

→(x+1/2,-y, -z)

Helical
structure

Screw 32

The direction of such an axis is usually along a unit cell edge, and the Screw 31
translation must be a subintegral fraction of the unit translation in that direction.

Other glide operations

An a glide • a, b, c, n and d glides occur Summary of symmetry elements and symmetry
• a glide has translational operations in crystal structure
component of 1/2a
• n glide has trandlational • Rotation operation rotation axis
component 1/2a+1/b or • Reflection operation mirror plane
1/2b+1/2c or …
• Inversion operation center of symmetry
• Rotation inversion operation inversion axis
• d glide has translational
• Translation operation lattice
(xyz)→(-x y z) component of the type
• Screw operation screw axis
→(-x+1/2 y z) 1/4a+1/4b • Glide operation glide plane
n=1, 2, 3, 4, 6

Zig-zag structure

14
 Symbols for symmetry elements 1 Symbols for symmetry elements 2

7.2.2 Space group and point group

C2h5 – P21/c
Space group: 230
General equivalent positions:
Schonflies notation and International notation
4 1 e (1) x,y,z; (2) -x, 1/2+y, 1/2-z; (3)x, 1/2-y, 1/2+z; -x,-y,-z
D2h16 - P21/n 21/m 21/a C2h5 – P21/c
Special equivalent positions
system directions
2 d 1bar 1/2,0, 1/2; 1/2, 1/2, 0
1 2 3
2 c 1bar 0,0, 1/2; 0, 1/2, 0
Cubic a a+b+c a+b
hexagonal c a 2a+b 2 b 1bar 1/2,0,0; 1/2, 1/2, 1/2
Tetragonal c a a+b 2 a 1bar 0,0,0; 0, 1/2, 1/2
Trigonal a+b+c a-b - International tables for crystallography
Trigonal* c a
P21/c~20%
Orthorhombic a b c
monoclinic b - - efficiency packing

15
 Combining symmetry elements
When a crystal possesses more than one of the above 7.2.3 The description and application of crystal structure
symmetry elements, these macroscopic symmetry
Example 1. Crystal of iodine
elements must all pass through a common point. There
are 32 possible combinations of the above symmetry Crystal System orthorhombic
elements that pass through a point and these are the 32
Space group D182h-Cmca
crystallographic point groups.
Cell parameters a=713.6 pm b= 468.6 pm c = 987.4 pm
Number of molecules per unit cell Z = 4
32 point groups
Atomic coordinate for I x y z
14 Bravais lattices
0 0.15434 0.11741
7 Crystal systems
but only 230 space groups

Equivalent positions: (0,0,0)+, (1/2, 1/2, 0)+,

7.3 X-ray diffraction of crystals
x,y,z; -x, -y, -z; -x, -y+1/2, z+1/2; x, y+1/2, -z+1/2
(0, .15434, .11741) (1/2, 0.65434, .11741)
(0, .84566, .88259)
(0, .34566, .61741)
(0, .65434, 38259)
a) Bond length (Bond distance)
r1-2= [(x1-x2)2a2+(y1-y2)2b2+(z1-z2)2c2]1/2 = 2.715 A
c) Density of crystal
V = a x b x c = 3.27 x 10 8 pm 3
D = 8 x 127.0 /( 6.02 x 10 23 x 327.0 x 10 –24 ) g cm-3
=5.16 g cm-3

16
 X-rays produced by electronic transition between
7.3.1 The source and property of X-ray atomic energy levels
High energy
electron beam

M
L L
radiation
X-ray tube
the wavelengths of X-ray are in the range
K
As for Cu:
of 100-0.01Å
• 1-0.01Å: hard x-ray e Kα1=1.540594Å
• 100 1Å soft x-ray 1.54056Å
• 2.5-0.5Å: used in crystal structure
analysis Kα2=1.544422Å
e
• 1-0.05Å: used in medical perspective,
detection of materials wound IKα1 ≈ 2IKα2

Synchrotron Radiation X ray Source

Kα1

Kα2

Notice: Kα2 can not be striped by the monochromator.

17
SPring-8, at Osaka, Japan. www.spring8.or.jp

18
 ESRF - European Synchrotron Radiation Facility , Polygone The Advanced Photon Source (APS) at Argonne National
Scientifique Louis Néel - 6, rue Jules Horowitz - 38000 Grenoble Laboratory, http://www.aps.anl.gov/aps.php
- France , http://www.esrf.fr

The derivation of the Laue equation

7.3.2 Laue equation and Bragg’s Law Interference condition:
1. Laue equations the difference in path lengths of
Laue first mathematically adjacent lattice points must be a
multiple integral of the
described diffraction from wavelength.
crystals
• consider X-rays scattered AD-CB = a·s-a·s0 =
from every atom in every a·(s-s0) = hλ
unit cell in the crystal and Or,
how they interfere with each
other a(cosα- cosα0) = hλ
α
• to get a diffraction spot you Max Von Lane Where,
α0
must have constructive a— lattice parameter
interference
α0—angle which a makes with s0
α— angle which a makes with s

19
 2. The Bragg’s Law
Expanded to 3D lattice In the diffraction direction, the
difference between the incident Bragg discovered that you could consider the
a·(s-s0) = a(cosα-cosα0) = hλ and the diffracted beam through diffraction to have arisen from reflection from
any two lattice points must be lattice planes
b·(s-s0) = b(cosβ-cosβ0) = kλ an integral number of s0 s
wavelengths. ∆=AD+DB = 2d(hkl)sinθn
c·(s-s0) = c(cosγ-cosγ0) = lλ
The vector form (000) to (mnp): Condition for diffraction: θ O θ
Tmnp = ma + nb +pc dhkl
2d(hkl) sinθn = nλ (n=1, 2, 3, … ) A B
D
where,
The differences in wavelengths: θn: the angle of reflection
∆ =Tmnp · (s-s0) n: the order of the reflection
a,b,c—lattice parameter
=(ma + nb +pc) ·(s-s0) 2⋅dnhnknl⋅sinθnh,nk,nl=λ
α0,β0,γ0—angle which a makes with s0 (dnhnknl = dhkl/n)
α,β,γ —angle which a makes with s = ma ·(s-s0)+nb ·(s-s0)+pc ·(s-s0)
Reformulated Laue equations:
h,k,l — indices of diffraction, integers =mhλ+ nkλ+plλ
2dhkl ⋅sinθ = λ
=(mh+nk+pl)λ
hkl — reflection indices

3. Reciprocal lattice
diffraction v v v v
crystal planes - v* b × c v cv × av v* a × b
a = b* = c =
Vv V V
(100), (200), … v v v v
(100) (200) (300) r * = ha * + kb * + lc * r * = 1 / d hkl
Families of planes 102 112
101
Lattice plane 111
100 110
directions-(100) (100)
a* 001
c*
b*
000 010
r*
(200)
1 22
1 01 1 11
1 00 1 10

20
 7.3.3. The intensity of diffraction beam

4. Ewald sphere 1. The principle of X-ray scattering

G QR
r
S 1/dhkl s-s0 r P s
θ 2θ s0 O
A S0 O1 1/λ O
For elastic scattering, each electrons scatters the plane wave
causing a spherical wave (exp2πi(k⋅r)).
The phase difference is: ∆=(r•s - r•so)/
The scattered x-ray: exp2πi[r⋅(s-s0)/λ] or exp2πi[r⋅q/λ]

The contribution of the scattering of all electrons: Supposed that there are N1 N2 N3 periods along a
b c, and all the atoms locate on the position of lattice
points, F(q) can be replace with a constant ‘f’. f is
∫ ρ (r ) exp(2πiq ⋅ r / λ )d
3
r Rn scattering factor of atoms.
For the crystal structure N1 −1 N 2 −1 N 3 −1
ρ (r ) = ∑ ρ cell (r + Rn ) b Amnp = f ∑ ∑ ∑e 2 πi / λ ( n1a + n2 b + n3c )⋅q

n c
n1 = 0 n2 = 0 n3 = 0

A = ∑ ∫ ρ cell (r + Rn ) exp(2πiq ⋅ r / λ )d r 3 a
n
For the case of 1D and f=1,
A= (∫ ρ )
( r ) exp( 2πiq ⋅ r / λ )d r ∑ exp( 2πiq ⋅ Rn / λ )
3

1 − e 2πiNa ⋅q / λ
cell
N −1
AN = ∑ e
n
2πina ⋅q / λ
= F ( q)∑ exp( 2πiq ⋅ Rn / λ ) =
n
n =0 1 − e 2πia⋅q / λ
F(q) --- structure factor
F ( q) = ∫ ρ cell ( r ) exp(2πiq ⋅ r / λ )d 3 r

21
 The intensity: In the case of 3-D:
 πN 
sin 2  a ⋅q  πN   πN   πN 
λ  = sin (πNh )
2
2  sin 2  1 a ⋅ q  sin 2  2 b ⋅ q  sin 2  3 c ⋅ q 
I ∝ AN = AN AN* =  λ   λ   λ 
sin 2 (πh ) I ∝ Amnp  = f
2 2
π  ⋅ ⋅
sin 2  a ⋅ q  2 π  2 π  2 π 
λ  sin  a ⋅ q  sin  b ⋅ q  sin  c ⋅ q 
λ  λ  λ 
30 |A|2(N=5) 250 |A|2(N=15) Therefore,
200 a⋅S/λ=h b⋅S/λ=k c⋅S/λ=l (h k l should be integer)
20
150
or a⋅S=hλ b⋅S=kλ c⋅S=lλ
100
10
50 ----- Laue conditions
0 h 0 h
2 2
-1.0 -0.6 -0.2 0.2 0.6 1.0 -1.0 -0.6 -0.2 0.2 0.6 1.0
I ∝ f N 12 N 22 N 32 I ∝ Fhkl N12 N 22 N 32

2. The intensity of diffraction beam 3. systematic absence

2 Calculation for structure factor
I ∝ Fhkl N12 N 22 N 32
2 Example A, Body center crystal
I hkl = K Fhkl N /2
Fhkl= ∑ fj {exp(i 2π(hxj+kyj+lzj))+ exp(i 2π(h(xj+1/2)+k(yj+1/2)+l(zj+1/2)))}
F ( q) = ∫ ρ cell ( r ) exp(2πiq ⋅ r / λ )d r 3
N / 2j =1
= ∑ fj exp(i 2π(hxj+kyj+lzj)) (1+ exp(iπ(h+k+l))
Fhkl = ∫ ∫ ∫ ρ ( x, y , z )e 2πi ( hx + ky + lz ) dxdydz j =1

n While h+k+l =2n+1, Fhkl=0

Fhkl = ∑ f j e
2πi ( hx j + ky j + lz j )

j =1
The directions of the diffraction beams are determined
by the cell parameters systematic absence

The intensity of the diffraction beams are determined by

the arrangement of atoms in the cell.

22
 Example II. Unit cell has a 21 screw axis along the c axis at
x=y=0 systematic absence
Equivalent position (x,y,z) and ( -x , -y , z+1/2)
Crystal structure which contain centering, glide plane
and screw axis will have systematic absences.
N /2
fjexp2πi[(h x+k y +l(zj+1/2)]
N /2
Fhkl = ∑ fjexp[2πi(hxj+kyj+lzj)]+ ∑ Namely, some reflections will be systematically absent
j =1 j =1

N /2

∑
N /2
F00l= ∑j =1
fjexp2πi (lzj)]+
j =1
fjexp2πi l(zj+1/2)

N /2
= ∑j =1
fjexp2πI (lzj)](1+ exp2πi ·l/2) (x,y,z)
N /2
2 ∑ fjexp2πi (lzj)] (l=2n)
= j =1

0 (l=2n+1)

(x , y , z+1/2)
systematic absence

systematic absence and sysmmetry

Types Conditions for extinction Cause of extinction Centering and 7.2.4 Methods of X-ray diffraction—Power method
of symmetry
reflecti elements 1. Methods
on
hkl h+k+l=odd In-centred (bodycentred) I * Single crystal diffraction
h+k =odd C-centred C
h+l =odd B-centred B
k+l =odd A-centred A
h,k,l not all even and not all Face-centred F
Monochromatic camera method -- Monochromatic X-ray
odd
Rotation, Oscillation, Weissenberg …
-h+k+l not multiples of 3 R-centred R(hexagonal)
okl k =odd Translation in b/2 b Laue photography --- white X-ray
l =odd (100) c/2 c
Diffractometer -- Monochromatic X-ray
k+l =odd glid (b+c)/2 n
Crystal Diffraction beam
k+l not multiples of 4 Planes (b+c)/4 d
2θ
00l l =odd Translation c/2 21, 42, 63
Incident beam
l not multiples of 3 Along c/3 31, 32, 62, 64
l not multiples of 4 (oo1) c/4 41, 43
l not multiples of 6 Screw axis c/6 61, 65

23
 Radiation sources
* Powder diffraction Monochromator – e.g.HOPG
X-ray tubes
Monochromatic X-ray Diffraction beam Synchrotron radiation Filter – e.g. Ni for CuKα
poder
2θ Detectors
Incident beam 2θ •Film
- poor sensitivity, high background, low dynamic range
•Scintillation counters
- good sensitivity, low background, high dynamic range
P •Imaging plates
- good sensitivity, low background, good dynamic range, very
Diffraction beam
efficient data collection
Incident beam 2θ
θ
O •CCDs and Multiwire detectors
sample R - fast readout, good sensitivity, low background, good dynamic range,
very efficient data collection
Powder Diffractometer

2. The applications Indexing of the cubic system:

a0
d hkl =
a. crystal structure determination h + k2 + l2
2

sin 2 θ = (λ / 2a ) 2 (h 2 + k 2 + l 2 )
Intensity data
sin 2 θ ∝ h 2 + k 2 + l 2 sin 2 θ1 : sin 2 θ 2 : sin 2 θ 31 : sin 2 θ 41 :
collection
Characteristic line sequence in cubic system:
Indexing Crystal system
and Cell P: (hkl) 100, 110, 111, 200, 210, 211, 220, 221, 222, 300, ….
2 parameters
I hkl = K Fhkl h2 k2 l2 ) 1, 2, 3, 4, 5, 6, 8, 9, 10, 11, 12, 13, …
I: (hkl) 100, 110, 111, 200, 210, 211, 220, 221, 222, 300, ….
Phase problem
F ( hkl ) = ∫ ∫ ∫ ρ ( x, y , z )e 2πi ( hx +ky +lz ) dxdydz h2 k2 l2 ) 2, 4, 6, 8, 10, 12, 14, 16 … Æ(1: 2: 3: 4: 5: 6: 7: 8:…)
P: (hkl) 100, 110, 111, 200, 210, 211, 220, 221, 222, 300, ….
ρ ( x, y , z ) = V −1 ∑∑∑ F ( hkl )e −2πi ( hx +ky +lz ) h2 k2 l2 ) 3, 4, 8, 11, 12, 16, 19, 20 …
h k l

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 Automated diffractometer method Example for the indexing of cubic system and its applications

Sample: NaCl
Condition: Cu Kα, λ=1.5418Å, R=50mm

(1) Measure sample and relative intensity

(2) Calculate the position of diffraction lines (usually 2θ)
(3) Calculate θ in according to the formulae
(4) Calculate sin2θ
(5) Calculate sin2θ1: sin2θ2 : sin2θ3 : sin2θ4 :…=3:4:8:11:…
(6) Identify Bravais lattice face cubic
(7) Index and calculate h2+k2+l2

(8) Calculate lattice parameter

(7) Index and calculate h2+k2+l2 Why use high angle
1.54182
sin 2 θ = × (h 2 + k 2 + l 2 )
No. I 2θ θ sin2θ hkl h2+k2+l2 4a 2 values?
1 W 27.46 13.73 0.05631 111 3 Least-square method, plot
2 S 31.80 15.90 0.07508 200 4 method, high angle values,…
3 S 45.60 22.80 0.15016 220 8
4 W 54.06 27.03 0.20647 311 11 a=5.628 Å
5 S 57.50 28.75 0.22524 222 12
0° 90° θ
6 S 66.44 33.22 0.30032 400 16
7 W 73.30 36.65 0.35663 331 19 (9) ρ= 2.165g/cm3 for NaCl
8 S 77.56 38.78 0.37540 420 20
9 S 84.30 42.15 0.45045 422 24 ρV 2.165 × (5.628 × 10−8 )
n= = =4
M 23 + 35.5
N0 6.022 × 1023
One unit cell contains 4 NaCl

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 Index cubic pattern and calculation lattice parameter
Line 2θ θ sin2θ sin2θi h2+k2+l2 hkl
b. Applications of powder diffractions
/sin2θ1
1 40.26 20.13 0.1184 1 2 110
Information contained in a Diffraction Pattern
2 28.26 29.13 0.2370 2 4 200

3 73.20 36.60 0.3555 3 6 211 Peak Positions

4 87.02 43.51 0.4740 4 8 220 Crystal system, cell parameters, qualitative phase identification
5 100.64 50.32 0.5923 5 10 310

6 114.92 57.46 0.7109 6 12 222

Peak Intensities
7 131.16 65.58 0.8290 7 14 321 Unit cell contents, quantitative phase fractions
8 153.58 76.79 0.9470 8 16 400
Peak Shapes and Widths
If λ=1.5418 Å,
Crystallite size, Non-uniform microstrain
λ 1.5418
a= ⋅ h2 + k 2 + l 2 = × 4 2 + 0 2 + 0 2 = 3.16 Å
2 sin θ 2 sin 76.79

b. Applications of powder diffractions 7.2.5 Electron Diffraction and Neutron Diffraction

Applications 1. Electron Diffraction

Qualitative Analysis h
λ
2meV
Quantitative Analysis
Lattice Parameter Determination
100 kV ---- 0.00370 nm
Crystallite size / size distribution & Lattice Distortion
Analysis (Non-uniform microstrain)
Crystallinity Analysis a) TEM image of the tip part of one TeO2 nanorod.
(b)Enlarged TEM image. (c) The corresponding
2. Neutron Diffraction electron diffraction pattern.
Residue Stress Analysis
----- Scatterring of atomic nuclear
Structure Solution and Refinement

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