Chapter 7

Introduction to Crystallography

7.1 Periodicity and lattices of crystal structure

7.2 Symmetry in crystal structures

7.3 X-ray diffraction of crystals

7.4 Quasi-crystal, liquid crystal and amorphous

Crystalline Substances: e.g., Diamond and Table Salt

Diamonds
7.1 periodicity and lattices of crystal structure
7.1.1 The characteristics of crystal structure
1. A few definitions:
• Solids can be divided into two primary categories,
crystalline solids and amorphous solids.
• Crystalline Solids are built from atoms or molecules
arranged in a periodic manner in space, e.g., rock salt and
diamond.
• Amorphous Solids possess short-range order only. They
are not related through symmetry, e.g. glass, rosin, amber
glass.

 Short-Range Order: Fixed bond lengths and angles

 Long-Range Order: Associated with a lattice point
 Crystals are solids that are built from atoms or
molecules arranged in a periodic manner in space.

C.N.:
Si = 4
O=2

Short range order: fixed bond lengths and angles

due to the bonding nature of constituent atoms.
2. Fundamental characteristics of crystal
a) Spontaneous formation of polyhedral shapes
F+V=E+2

No 5-fold axis
is allowed in a
single crystal!

b) Uniformity: periodic distribution of atoms/molecules

Single crystal gold bead with
naturally formed facets
HRTEM images of hollow beads
 •Anisotropy
Different periodicity and density for different direction.

2150 g/mm2

Conductivity

1150 g/mm2
Graphite
570 g/mm2
NaCl
 •Definite sharp melting points
T

t
• Symmetry: crystal shape (macroscopic)
lattice arrangement (microscopic)

•X-ray diffraction by crystals:

atomic distances match the wavelength of x-ray.
Sodium Chloride: Solid and Crystal structure
 7.1.2 The lattice and unit cell
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.
a. 1D lattice and its unit:
 Each motif in this
1D periodic pattern
can be represented
by a point.
 A lattice of
repeating points is
thus obtained to
represent the
above 1D system.

• The translation vectors connecting any two lattice points

constitute a translation group. i.e.,
Tm = ma (m = 0, 1,  2，, ) a: basic vector.
 Examples of 1D lattice

a)
b)

c)

Structural motif
d)

a is a 1D lattice itself;
b-d are not lattices, but can be represented by a lattice.

A pattern with periodicity = a lattice + structural motif!

b. Lattice and its unit in 2D:
Tmn = ma + nb（m, n = 0,1,  2， )
a & b: independent basic vectors
{Tmn } – a translation group

a
b

•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.

This 2D pattern itself 2D lattice. 2D lattice.

is not a lattice, but
can be represented
by a 2D Lattice.
2D Primitive Cell

Choice of Unit Cell

 There is always more than one

possible choice of unit cell.
 By convention, the chosen unit
cell should be as small as
possible while reflecting the
full symmetry of the lattice.

1) The highest symmetry

2) The smallest area (or volume)

 Five types of 2D lattices
There are literally thousands of crystalline materials,
there are only 5 distinct planar lattices.
-angle
between
two basic
vectors.
ab,   90 i a=b, =90
&   120 i,C4 ab, =90
i,C2
i) Primitive
a=b,
ii) Centered =120
i,C6
ab, =90
Centred cell: i + C2 // Primiative cell: i
Question:

Both the centred rectangular and simple hexagonal 2D

lattices have a rhombic primitive unit cell. What is the
key difference between them?

a=b,
=120
ab, =90
 Example: 2D-lattice of Graphene

or

• What’s the smallest structure motif of a graphene sheet?

• What type of lattice does a planar graphene sheet

belong to?
 stacking
graphite

3-D lattice can be used!

c. Lattices and its unit in 3D:

T = ma + nb + pc (m, n, p = 0, 1,  2, …)
c. Lattices and its unit in 3D:

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




b
a
c

a b

The Choice of a Unit Cell:

Having the highest symmetry and minimal size
The Choice of a Primitive Cell
1) The axial system consisting of the basis
vectors should be right handed.
2) The basis vectors should coincide as much as possible with
directions of the highest symmetry.
3) Should be the smallest volume that satisfies condition 2.
4) Of all lattice vectors none is shorter than a.
5) Of those not directed along a none is shorter than b.
6) Of those not lying in the a, b plane none is shorter than c.
7) The three angles between the basis vectors a,b,c are either
all acute or obtuse.
  
Conditions 4-6 define a b c
Crystal structure = lattice + structural motif
(basis)

Structural
motif
 Atomic Coordinates: Fractional coordinates

Fractional coordinates:

• The positions of atoms inside a

unit cell are specified using
0.5
fractional coordinates (x,y,z). i

• These coordinates specify the

0.6
position as fractions of the unit cell
edge lengths. i: (1.0, 0.6, 0.5)
Example:
Cubic unit cell of CsCl,
a=b=c
===90
Cs:(0,0,0)
Cl: (1/2,1/2,1/2)

In this case, the lattice point can be put at the position of either
Cs or Cl atom. Each unit cell contains both a Cs and Cl atom.

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

Polycrystalline matter: Clusters of multiple crystals.
7.1.3 Crystal systems and Bravais Lattices
a. Crystal systems
There are a total of seven types of
crystal systems differing in symmetry.
Crystal systems Characteristic Unit cell Choice of axis Lattic
symmetry parameters Point
elements Group
Triclinic Nil abc Ci

Monoclinic C2, h abc b // C2 C2h
==90
Orthorhombic 3C2, 2 h abc a, b, c // 3C2 D2h
===90
Unit cell is chosen in such a way that it contains as many symmetry
elements of the lattice as possible and has the smallest volume.
Trigonal C3 Rhombohedral D3d
a=b=c,
==<12090
Hexagonal D6h
a=bc, ==90
=120
Tetragonal C4 a=bc, c // C4 D4h
===90
Hexagonal C6 a=bc c // C6 D6h
==90, =120
Cubic 4C3 a=b=c Four C3 axes Oh
===90 are parallel to
the body
diagonals of
the cube
b. Bravais Lattices: (14) [developed by Bravais in 1850 !]
Primitive cell: minimal size，one lattice point only!
Unit Cell of Bravais Lattice: having the highest symmetry &
minimal size, may contain more than one lattice point.

Symmetry of Lattice Crystal Systems (7)

Unit Cell of Lattice

Bravais Lattices (14)
(Primitive or Centered)
Triclinic Monoclinic Orthor- Tetragonal Cubic Trigonal Hexagonal
hombic
aP mP, mC oP, oC tP, tI cP, cI, hR, hP hP
oF, oI cF
Lowercase letter (crystal system) + Capital letter (Type of cell)
e.g., hR-- R-centred hexagonal, mC-- C-centred monoclinic
* Triclinic
abc


aP (Primitive)
• Triclinic crystal system has the lowest symmetry.
• It can be simply represented by a primitive cell.
• Symmetry element: i
 A primitive cell contains one lattice point and a
* Monoclinic C-centered unit cell contains two lattice points.
abc Sym. Elements: 90
=  =90º i, C2(//b), h, 90

a'
c'
 a 

90° c b'  c
90° 90°
90°
b b
mP (Primitive) mC (C-centered or A-centered)

The primitive cell of a C-or A-centered monoclinic is triclinic!

Does I- or F-centered monoclinic lattice exist?
b
b

o
a
o a
c
a c
c

mI ? = mC mF ? = mC
Both I- and F-centered monoclinic are unnecessary and can be
represented by a mC!
 • The primitive cell of a C-centred orthor-
* Orthorhombic
hombic lattice is actually monoclinic!
abc
=  = =90º

c c b

90°90° O b
O b
a 90° c a
a
oP (Primitive) C-centered or A-centered or B-centered
* Orthorhombic
abc Sym. Elements:
=  = =90º 3C2 (//a,b,c), i, 3h (//A,B,C)

oP oC oI oF
or oA or oB (In-centered) (Face-centered)
* Orthorhombic
Face-centered cell (oF) and its primitive cell

• A Face-centered unit cell

contains four lattice points!!

• Its primitive cell is triclinic,

and does not contain such
symmetry elements as C2 and
h of the lattice.

Question: For a body-centered orthorhombic lattice, is its primitive

cell triclinic or monoclinic?
* Tetragonal
a=bc Sym. Elements:
=  = =90º C4(//c), 2C2 (//a,b), i, 3h (a,b,c)

90° 90°
O
a 90°
b
tP tI
Does a C- or F-centered tetragonal lattice exist?
 • Neither C-centered
tetragonal nor F-centered
tetragonal exists.

Please prove it!

tC = tP

a
* Trigonal ---- Rhombohedral
a=b=c
C3
=  =  90º

Sym. Elements: C3, i,

hR

c
b a A rhombohedral lattice can
be represented by a R-
O centered hexagonal lattice!
 hP unit cell
* Hexagonal c
a=bc Sym. Elements:
=  =90º, C6(//c), i,
 =120º h (c, //C) 90°
90°O b
a 120°

Hexagonal 2D lattice
c

O b
a
a. Primitive rhomohedral = b. primitive hexagonal
r-centered hexagonal r-centered rhombohedral

(1/3, 2/3, 2/3)

(2/3, 1/3, 1/3)
 Sym. Elements:
a=b=c
* Cubic 3C4(//a,b,c), 4C3, i,
=  =  =90º
3h (a,b,c, //A,B,C)

90° 90°
90° b
a
cP cI cF
Is there a c-centered cubic lattice?
• Introducing a C-center eliminates all C3-axes and results in
only one C4 axis. The lattice should be actually tetragonal.
• The primitive cell of a fcc or bcc lattice is rhombohedral,
which does not include the C4–axes of the lattice!
Bravais Lattices: (14)
Unit Cell: the highest symmetry + minimal size
Centered unit cell is thus introduced to contain the
highest symmetry of the lattice.
Crystal P C I F
systems
Triclinic

Monoclinic
Orthorhombic

Trigonal

Tetragonal

Hexagonal

Cubic
 Augusta Bravais
Lattices

Simple cubic Body-centered cubic Face-centered cubic

Simple C-centered Body-centered Face-centered

orthorhombic orthorhombic orthohombic orthohombic

Died on 30 Mar 1863

(born 23 Aug 1811)
Simple triclinic Rhombohedral Hexagonal French physicist best
remembered for his work
on the lattice theory of
crystals; Bravais lattices
Simple C-centered Simple Body-centered
are named for him.
monoclinic Monoclinic tetragonal tetragonal
 7.1.4 Crystal Planes and Miller Indices
a. Lattice planes
(010)
A 2D lattice plane, i.e.
(110)
(001), of an oP lattice.

Those lines are the

projections of crystal ( 2 10)
planes (//c-axis) onto (210)
this plane. b ( 1 20)
a

 It is possible to describe certain directions and planes

with respect to the crystal lattice using a set of three
integers referred to as Miller Indices.
 Miller indices describe the orientation and spacing of a
family of planes.
 tc
b. Miller indices (hkl)
 Introduced in 1939 by the British sb
mineralogist W. H. Miller. ra
 Miller indices are the reciprocal
intercepts of the lattice plane on the 1 1 1
unit cell axes. : :  h:k :l
r s t
For this special case: r = 3, s = 2, t = 1
h:k:l = (1/3):(1/2):(1/1) = 2:3:6
 The Miller index of this lattice plane is (236)!
Question: why do we not use r:s:t directly to represent a
lattice plane?
Example: Miller indices in a cubic lattice
(110) (1 1 0)

b (111)
O
a c
(100)
(010) b
(001)c
c O a

b For a cubic lattice, the (100), (010),

and (001) planes are symmetry-
O a
equivalent with respect to C3 axes.
Hexagonal , using four axes (a1,a2,a3,c)
(0001) c
(hkil), i = -(h+k)
c
( 1 2 1 0) a3 90° 90°
A third axis:
120° a2
(1 1 00) a3 = -(a1 + a2)
120°
b
a1
a
(10 1 1)
1 00
The use of only two 0 1 0 1 10
basis vectors a & b
does not reflect the
010
C6- symmetry 110
among such planes 010
-
as (100), (110) …！
C. Directions in lattice
• The direction of a lattice
Miller Indices [uvw]
vector, ua + vb +wc, is
[122] represented by three
indices [uvw], which are
[001] E prime to each other.
e.g. a axis: [100]. (OA)
c C [100] b axis: [010]. (OB)
c axis: [001]. (OC)
D [110] OD = a + b  [110].
bB
F
[210] OE = 0.5a + b + c  [122]
O [100]
G aA OF = a + 0.5b  [210]
[1 2 0]
BG = 0.5a - b  [210]
[1 2 0]
 Example: Directions on the (111) plane of a cubic lattice.
[ 1 1 2] [ 1 01] • Various lattice vectors
[ 1 10] can be defined by the
c lattice points within the
[0 1 1] B D (111) plane.
• e.g., the vector from
C points A to B, i.e., -0.5a
- 0.5b + c, defines the
direction [ 1 1 2] .
[ 1 1 0] O b
• The vector from points
A to C, -b+c, is defines
a A the direction [0 1 1] .
(111) • The vector CD, i.e., -
A (1.0, 1.0, 0.0); B(0.5, 0.5, 1.0); a+b, defines the
C(1.0, 0.0, 1.0); D(0.0, 1.0, 1.0) direction [ 1 10] .
Miller indices (hkl) are used to specify the orientation and
spacing of a family of planes.
{hkl} are used to specify all symmetry-
equivalent sets of planes
(100)
(010) e.g., For a cubic lattice system, the lattice
c planes (100), (010), (001) are symmetry-
equivalent upon C3 or C4 rotations, and can
b
be represented by {100}.
O a

[uvw] zone axis Direction Vector = ua + vb + wc

Miller indices: [hkl] are used to specify a direction in space

with respect of the unit cell axes.
<hkl> are used to specify a set of symmetry-
equivalent directions.
d. d-spacing dhkl
The spacing between adjacent planes in a family is
referred to as a “d-spacing”.
 oP:

(010) Projections
a of crystals
b d010 planes (//c-
(110)
axis) on the
a
b d110 a (001) plane.
b

a d210 ( 2 10)
a b
b (210)
( 1 20)
The spacing between adjacent planes in a family is
referred to as a “d-spacing”

 Cubic : 1/d2 = (h2+k2+l2)/a2 or d2 = a2/(h2+k2+l2)

 Tetragonal: 1/d2 = (h2+k2)/a2 + l2/c2

 Orthorhombic: 1/d2 = h2/a2+k2/b2 + l2/c2

 Hexagonal: 1/d2 = (4/3)(h2+hk+k2)/a2 + l2/c2

 Monoclinic: 1/d2 = [(h/a )2 + (k/b )2sin2 + (l/c )2-

(2hl/ac)cos]/sin2

 Triclinic:
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
 7.2 Symmetry in crystal structures.
7.2.1 Symmetry elements and symmetry operations
 Crystallographers make use of all the symmetry
elements available in a crystal to minimize the number of
independent coordinates.
 Three types of symmetry elements in a crystal lattice:
• Lattice symmetry (translational symmetry)
• Point symmetry (rotation, inversion & reflection etc.)
• Other translational symmetry elements: screw axes and
glide planes
 a. Lattice symmetry
--- translation operation

Tmnp= ma + nb + pc or

m 0 0  a  a, b, c: basic vectors!
   
Tmnp   0 n 0  b 
0 0  
 p  c 

All unique translation operations available in a crystal

lattice constitute a translation group {Tmnp} (order = ).
b. Point symmetry elements compatible with 3D translations
• A point-symmetry operation does not alter at least one point
that it operates on, e.g., rotation, reflection, inversion, and
rotation-inversion.
• Point symmetry elements available in a lattice must be
compatible with the 3D translations, including

Operation Point symmetry elements

Reflection Mirror Plane m
Rotation operation Rotation axis n = 1, 2, 3, 4, 6
Inversion Center of symmetry 1
Rotatory inversion Inversion axis 3, 4, 6

It is provable that translational symmetry of a lattice excludes

the presence of 5-fold axis!
Rotation axis: 1,2,3,4,6 only!! Why ???
Limitation induced by
ma Translation symmetry!
B1  B2


 
a a a
A1 A2 A3 A4
Four lattice points: A1, A2, A3, A4
 (m-1)/2 1  m-1 2
Upon an n-fold rotation,
 m = 3, 2, 1, 0, -1
A1  B1
 cos = 1, 1/2, 0, -1/2, -1
A4  B2
with A1A4 // B1B2.   = 2/n = 0º, 60º, 90º, 120º, 180º

B1B2 ＝a + 2acos = ma  n= 1, 6, 4, 3, 2

cos = (m-1)/2 rotation axes: 1,2,3,4,6 only!!

Example: The symmetry elements
in a primitive cell of a cubic lattice.

Twofold axis
Threefold axis 2 3 4 6
Fourfold axis
Rotation axis

Hexagonal lattice

Sixfold axis
General equivalent positions:
i) 2-fold axis (e.g., b axis in monoclinic lattice)
(x, y, z)  (-x, y, -z) (Note: in fractional coordinates)
Equivalent upon rotation around a 2-fold axis.

1 0 0 b
 
R(2)  0 1 0
0 0 1  (-x,y,-z) -z
 
-x x a
z
(x,y,z)

Note:  is not essentially 90.

General equivalent positions:
ii) 3-fold axis //c axis in a hexagonal lattice
(x,y,z), (-y, x-y, z), (-x+y, -x, z)
0 1 0 
 
R(3)  1 1 0
b 0 0 1 
|y| x  
x-y
(-y,x-y,z) (x,y,z)
y

-y x a
 0 1 0  4 fold axis // c axis (cubic lattice)
 
R(4)  1 0 0 general equivalent positions:
0 0 1  (x,y,z), (-y, x, z), (-x,-y,z), (y,-x,z)
 

6 fold axis // c axis (hexagonal lattice)

1 1 0
  general equivalent positions:
R(6)  1 1 0
(x,y,z), (x-y, x, z), (-y, x-y, z),
0 0 1 
  (-x,-y,z), (y-x, -x, z), (y, y-x,z)
c. Screw axes nm (m<n) and glide planes:
A screw axis symmetry is combination of rotation about an axis and
a translation parallel to that axis leaves a crystal unchanged.

Screw operation n  T ( ma )  C1 (C // a，m  1,2 ,..., n  1 )
m n n
n
An n-fold screw axis can be n1, n2, …, or nn-1.

Example: 21// a axis

(x, y, z) C2(//a)
(x, –y, –z) T(a/2)
(x+1/2, –y, –z)

A helical structure is
related to a screw axis!
A 31 screw axis in the crystal of tellurium
31
Screw axes: 31 and 32

Screw 31 Screw 32

= T(a/3) C31 = T(2a/3) C31

 Helical structures along screw axes
View perpendicular to axis View down axis

31
31
31

32

32
32

61-5
21 31 32 41 42 43
Glide operations: a, b, c, n and d glides
Glide operation: G = T(t)·M Mirror: M (reflection)
t = a/2, b/2, c/2, (a+b)/2, (b+c)/2, (a+c)/2, (a+b+c)/4 etc.
GG = [T(t)M]2 = T(2t), t = 2t (maybe a basis vector of lattice)

a glide
Zig-zag structure

a,b,c glide: t = a/2 , b/2, c/2

n glide: t =(a+b)/2, (b+c)/2, (a+c)/2
d glide: t= (a+b+c)/4, (a+b)/4, (b+c)/4,
or (a+c)/4 .
e glide (double glide plane).
 Graphical representations
of glide and mirror planes
Type Projection () Parallel (//)
 Summary of symmetry elements and
symmetry operations in crystal structure
Symm. operation Symm. Elements
• Rotation operation rotation axis Cn
• Reflection operation mirror plane m
• Inversion operation inversion center
• Rotation inversion operation inversion axis
• Translation operation lattice
• Screw operation screw axis nm
• Glide operation glide plane
(n=1, 2, 3, 4, 6)
Combinations of the 8 point symm. elements (5 n-axis, i,
m, S4) result in 32 crystallographic point groups.
 Combining symmetry elements
• When a crystal possesses more than one of the above
point symmetry elements, these macroscopic symmetry
elements must all pass through a common point.

• There are 32 possible combinations of the above symmetry

elements that pass through a point.

• There are the 32 crystallographic point groups.

• So far we have

7 Crystal systems  14 Bravais lattices (Translation) +

32 crystallographic point groups (Point symmetry)

 230 space groups

7.2.2 Crystallographic point group and space group
1. Crystallographic point group
Combinations of the 8 point symm. elements (5 n-axis, i, m,
S4) result in 32 crystallographic point groups.
e.g., Monoclinic system: point symmetry elements -- 2, m,
2 – {E, C2} -- C2 point group; m - {E,} -- Cs point group.
2,m -- {E, C2, , i} -- C2h point group.
Two notations of crystallographic point group
Schonflies notation vs. International notation
C2 2
CS m
C2h 2/m
 • Each crystal system includes a set of distinctive
crystallographic point groups.

• A total of 32 crystallographic point groups.

Crystal Schonflies International Symmetry Examples

system notation notation elements
monoclinic C2 2 C2 BiPO4
CS m  KNO2
C2h 2/m C2, h, i KAlSi3O8
orthorhombic D2 222 3C2 HIO3
C2v mm2 C2, 2 NaNO2
D2h mmm 3C2, 3, i MgSO4

a b c
2. Crystallographic space group
Point groups (32) + translational symmetries = Space groups (230)
Schonflies notation vs. International notation
e.g, D2h16 - P21/n 21/m 21/a C2h5 – P21/c

System directions
1 2 3
Cubic a a+b+c a+b
Hexagonal c a 2a+b
Tetragonal c a a+b
Trigonal (hR) a+b+c a-b -
Trigonal* (hP) c a
Orthorhombic a b c
Monoclinic b - -
 How to understand/use Space Group?
Symmetry elements & equivalent positions
1. Each space group can be schematically represented by
using two types of diagrams, i.e., diagrams of symmetry
elements and diagram of general equivalent positions.
2. The physical meaning of general equivalent positions: if
there is an X atom at position (x,y,z), there should a same X
atom at each equivalent position within a unit cell.
Diagram of Symmetry Diagram of general
elements equivalent position
Example: monoclinic point group C2h-2/m
Six space groups belong to C2h point group, denoted:
C2h1-P2/m, C2h2-P21/m, C2h3-C2/m,
C2h4-P2/c, C2h5-P21/c, C2h6-C2/c,
e.g., C2h5 – P21/c (i is always available!)

c glide
at b/4.

A set of equivalent positions located within a unit cell!

General equivalent positions :
4 e 1 (x, y, z), (-x, y  0.5, 0.5  z), (-x,  y,  z), (x, 0.5  y, 0.5  z)
Multiplicity, Wyckoff letter, site symmetry
e.g., C2h5 – P21/c

Special equivalent positions : Inversion center

2 d 1 ( 12 ,0, 12 ), ( 12 , 12 ,0); 2 c 1 (0,0, 12 ), ( 12 ,0,0);

2 b 1 ( 12 ,0,0), ( 12 , 12 , 12 ); 2 a 1 (0,0,0), (0, 12 , 12 )
• Equivalent positions are correlated by symmetry
elements and can be produced from a given position
upon available symmetry operations.

• Thus it is unnecessary to list all atoms, but unique type of

atoms within a unit cell.
 Diamond: face-centred cubic Oh7- Fd3m

41

d glide
plane at
1/8,3/8,
5/8,8/7
• Fcc Sideview topview
• Lattice points: (0,0,0)+, (1/2,1/2,0)+, (0,1/2,1/2)+, (1/2,0,1/2)+
• Structure motif – 2C 0,0,0; 1/4,1/4,1/4
• Totally 8 C atoms within a unit cell.
Note：In this case, the presence of same-type atoms in
structure motif introduces more symmetry elements!
7.2.3 The description and application of crystal structure
Example 1. Crystal of iodine
Crystal System orthorhombic
Space group D2h18-Cmca (or C 2/m 2/c 21/a)
Cell parameters a=713.6 pm b= 468.6 pm c = 987.4 pm
Number of molecules per unit cell Z = 4
Atomic coordinate for I x y z
0 0.15434 0.11741
Lattice points within a unit cell: (0,0,0)+, (1/2, 1/2, 0)+ (C-centered).
General equivalent positions: C 2/m 2/c 21/a
(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, .65434, .11741)

(0, -.15434, -.11741) (1/2, .34566, -.11741)
(0, .34566, .61741) (1/2, .84566, .61741)
(0, .65434, 38259) (1/2, .15434, 38259)
a) Bond length (Bond distance)
r1-2= [(x1-x2)2a2+(y1-y2)2b2+(z1-z2)2c2]1/2 = 2.715 Å
b) Density of crystal
V = a x b x c = 3.27 x 108 pm3
D = 8 x 127.0 /(6.02 x 1023 x 327.0 x 10–24 ) g cm-3 = 5.16 g cm-3
 7.3 X-ray diffraction of crystals

The wavelengths (0.05-2.5 Å) of x-rays match the d-

spacing of crystal planes, resulting in diffraction!
 7.3.1 The source and property of X-ray

X-ray tube
The wavelengths of X-ray are in the range
of 100-0.01Å

• 1-0.01Å: hard x-ray

• 100～1Å：soft x-ray
• 2.5-0.5Å: used in crystal structure analysis
• 1-0.05Å: used in medical perspective, detection of materials wound
 X-rays produced by electronic transition
between atomic energy levels A part of the
High energy electrons are
electron beam blocked; their
kinetic energies
M giving rise to
L L “white” x-ray.
radiation
As for Cu:
K Cu+ 1s12s22p6…
2S  1s22s22p5…
1/2
e
2P
3/2
K1= 1.540594 Å
2P K2= 1.544422 Å
1/2
e
IK1  2IK2
 154.056 pm
Weighted average of
K1 wavelength ~ 154.18pm.

154.439 pm
K2

Note: K2 can not be striped by the monochromator.

Synchrotron Radiation X-ray Source
Benefits of Synchrotron radiation X-ray :
• Narrow range of x-ray wave-lengths, i.e., high
monochromicity
• High intensity of x-ray.
• High intensity and high quality of diffraction data
• High resolution – characterization microcrystals
Toooooooo Expensive facility!
SPring-8, at Osaka, Japan. [Link]
ESRF - European Synchrotron Radiation Facility , Polygone
Scientifique Louis Néel - 6, rue Jules Horowitz - 38000 Grenoble
- France , [Link]
The Advanced Photon Source (APS) at Argonne National
Laboratory, [Link]
7.3.2 Laue equation and Bragg’s Law
1. Laue equations
Laue first mathematically described
diffraction from crystals.
• consider X-rays scattered from every atom
in every unit cell in the crystal. and how
they interfere with each other
• to get a diffraction spot you must have
Max Von Laue
constructive interference.
Nobel Prize in
Lead film Physics 1914
shield
crystal
X-ray
Laue diffraction
pattern of ruby

Laue Diffraction (1912)

Laue equations (Based on diffraction by 1D atomic lattice)
a — lattice parameter
0— angle between a and S0
 — angle between a and S
Interference condition:
The difference in path lengths of
adjacent lattice points must be a
multiple integral of the wavelength.
For each h value, the
diffraction rays from a 1D i .e ., Δ  AD-CB  hλ , h  0 ,1,2 ,...
lattice make a cone!
AD  a  S  a cos
CB  a  S0  a cos 0
Δ  a  (S - S0 )
 a(cos   cos0 )  hλ
 Expanded to 3D lattice case:
a·(S-S0) = a(cos-cos0) = h
b·(S-S0) = b(cos-cos0) = k Laue Equations!
c·(S-S0) = c(cos-cos0) = l
a,b,c—lattice parameter
0,0,0—angle between basis vectors a,b,c and S0
,, —angle between basis vectors a,b,c and S
h,k,l — indices of diffraction, integers
which may not be prime to each other and are different from
Miller indices for crystal plane!
• Each equation defines a cone of diffraction.
• Only when the three cones of diffraction intersect can
the diffraction beam be observable!
2. The Bragg’s Law
Bragg considered the diffraction arising from reflection
by lattice planes.

s0 s
 O P 
dhkl

Conditions to obtain constructive inferences,

a. The scattered x-ray must be coplanar with the incident
x-ray and the normal of the lattice plane.
b. S = S0
The difference in path lengths,
 = AD + DB = 2d(hkl)sin s0 s
Condition for diffraction:
 O 
 = n = 2d(hkl)sinn (n=1,2,3, … )
A
dhkl
B
n: the angle of reflection D
n: the order of the reflection

Define dnhnknl = d(hkl)/n  2dnhnknlsinnh,nk,nl = 

miller indices

Note: n is not measurable! Let dnhnknl = dhkl

Bragg’s Law: 2dhkl sin = 
reflection indices
What is the physical meaning of dhkl?
The Braggs, father and son, shared the 1915 Nobel Prize in Physics
for their work in crystallography.
 n=2
Virtual reflection plane

2d(hkl) sinn = n (n=1, 2, 3, … )

Lattice plane 2dhkl sin =  (dnhnknl = dhkl/n)
indices

Diffraction indices or virtual reflection plane indices.

The Bragg’s law defines the direction of diffraction
beams from a given set of lattice planes!
 (100)
diffraction crystal
planes -
(100), (200), … (100) (200) (300)
(200)
Families of planes
Lattice planes-(100)

The Bragg’s Law vs. Laue equation:

• Both equations define the relationship between the direction of

diffraction beams, the x-ray wavelength and the parameters of
a crystal lattice.

• The Bragg’s law: simple, easier to derive lattice parameters

from the direction of diffraction beams. 2dhklsin = 
3. Reciprocal lattice
      
 * b  c b *  c  a c *  a  b Basis vectors of a
a  reciprocal lattice
V V V
* * * * *
r  ha  kb  lc r  1 / d hkl
102 112 A reciprocal lattice
101 point corresponds to
111
100 110 a diffraction (lattice)
a* 001 plane of its original
c* lattice!!!!!!!!!!!!
b*
000 010 A reciprocal vector r*
r*
is perpendicular to a
1 22
1 11 lattice plane with the
1 01
1 00 1 10 same indices (hkl).
4. Ewald sphere (reflection sphere)
Radius = 1/ G: a diffraction point
G /a reciprocal lattice
r* point
S
1/dhkl
 2 Only when the reciprocal
A S0  O1 1/ O lattice point is located on
(hkl) the Ewald sphere can
constructive interference
occur !

OG  2 O1O * sin  ( 2 ) sin  1/d hkl  2d hkl sin θ  λ


• Monochromic x-ray  fixed radius of the Ewald sphere!
• Fixed single crystal  Very few diffraction data!
 How to get more diffraction data?
a) Fixed : Rotate the crystal to enable more
reciprocal points (diffractions) dynamically located
on the Ewald sphere.
b) Fixed crystal: use x-rays with varying wavelengths
(e.g., white x-ray). By doing so, the Ewald sphere
becomes filled.

• The first technique is preferred and has been widely

used in practice!

• The second method can be used to determine the

orientation of a single crystal.
7.3.3. The intensity of diffraction beam
1. The principle of X-ray scattering
To save your time,
Let’s neglect part 1 and
QR move directly to part 2!
r If you are interested in
s-s0 P s this part, just go
s0 O through it by yourself.

For elastic scattering, each electron scatters the plane wave

causing a spherical wave (exp[2i(kr)]).
The phase difference is: =(r•s - r•so)/λ
The scattered x-ray: exp{2i[r(s-s0)/]} or exp{2i[rq/]}
 The contribution of the scattering of all electrons of a given atom:

     3
( r ) exp( 2 iq r / ) d r
Rn
For the crystal structure ：
 (r )    cell (r  Rn )
b
n
c

A     cell (r  Rn ) exp( 2iq  r /  )d 3 r a

n

A   cell ( r ) exp( 2iq  r /  ) d3

r  exp( 2iq  Rn /  )
n

 F ( q) exp( 2iq  Rn /  )

n

F(q) --- structure factor

F ( q)    cell ( r ) exp( 2iq  r /  )d 3 r

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
scattering factor of atoms.
N1 1 N 2 1N 3 1
Amnp  f  e 2i /  ( n1a n2b n3c )q

n1 0 n2 0 n3 0

For the case of 1D and f=1,

2iNaq / 
N 1
1 e
AN   e 2inaq / 
 2iaq / 
n 0 1 e
 The intensity:

 N 
sin  2
a q
I  AN
2
 AN AN 
*    
sin 2
 Nh 
  
sin  a  q 
2 sin 2
h 
 
30 2
|A|(N=5) 250 |A|2(N=15)
200
20
150
100
10
50
0 h 0 h
-1.0 -0.6 -0.2 0.2 0.6 1.0 -1.0 -0.6 -0.2 0.2 0.6 1.0
In the case of 3-D:
 N1  2  N 2  2  N 3 
sin 
2
a  q  sin  b  q  sin  c q
I  Amnp 
2
 f
2         
2   2   2  
sin  a  q  sin  b  q  sin  c  q 
     
Therefore,
aq/=h，bq/=k，cq/=l (h，k，l should be integer)
or aq=h，bq=k，cq=l
----- Laue conditions for X-ray diffraction

I f N N N
2
I  Fhkl N N N
2 2 2 2 2 2 2
1 2 3 1 2 3

Only those scatterings fulfilling these conditions give

rise to measurable diffraction beams.
2. The intensity of diffraction beam

• The directions of the diffraction beams

Bragg’s Law
2dhkl  sin = 

The directions of the diffraction beams are determined

by the cell parameters.
• The intensity of diffraction beam
Systematic absence:
I hkl  K Fhkl
2
Structure factor Fhkl = 0  Ihkl = 0

Fhkl      ( x , y , z )e 2i ( hx  ky  lz )
dxdydz
n Electron density distribution in a unit cell.
  f je
2i ( hx j  ky j  lz j )
Phase difference between
the scattered and incident
j 1
x-ray over atom j.
Sum over all atoms fj: atomic scattering factor defined by
within a unit cell. atomic electron density distribution.

• The intensities of the diffraction beams are determined by

types of atoms and the arrangement of atoms in the cell!
• By measuring the cell parameters and the intensities of
diffraction points, the atomic arrangement can be derived.
3. systematic absence
Calculation of structure factor
Example A, Body-centered crystal
Simple case: Each lattice point is a metal atom.
(e.g., Na)
N
Fhkl   f j e
2i ( hx j  ky j  lz j ) N=2
j 1 (0,0,0)
1 1 1 (1/2,1/2,1/2)
2i ( h  k  l )
2i ( h 0  k 0  l 0 )
 f1e  f2 e 2 2 2

i ( h  k  l )
 f Na ( 1  e ) (f1 = f2 = fNa)
i ( h  k  l ) ( 2 n 1 )i
i) While h+k+l = 2n+1, e e  1
 Fhkl = 0, Systematic absence !
ii) While h+k+l = 2n, ei ( h  k  l )  1  Fhkl  2 f Na Strongest!
Body-centered crystal –Two lattice point in a unit cell!
General case: each lattice point contains m different atoms.
• The total number of atoms within a unit cell is 2m;
• For jth atom in a structural motif (a lattice point): (xj,yj,zj)
• Its body-centered equivalent: (0.5+xj, 0.5+yj, 0.5+zj)
2m
Fhkl   f i e2i ( hxi  kyi lzi )
i 1
m 1 1 1
2i [ h (  x j ) k (  y j ) l (  z j )]
 { f je
2i ( hx j  ky j  lz j )
 fj e 2 2 2
}
j 1
m
] f je
i ( h  k  l ) 2i ( hx j  ky j  lz j )
 [1  e
j 1

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

Systematic
πi ( hk l ) ( 2 n1 )πi
e e  1  Fhkl  0 absence
Face-centered cubic crystal – general case
• Lattice points (LPs): (0,0,0), (1/2,1/2,0)+, (0,1/2,1/2)+, (1/2,0,1/2)+
• Each lattice point contains m atoms, {(xj,yj,zj)} (j=1,…,m)
• Each unit cell contains N=4m atoms, e.g., an atom A(xi,yi,zi) in one
LP has other three equivalent A atoms within the same unit cell!
N 4m
Fhkl  i
f e
i 1
2i ( hxi  kyi  lzi ) Sum up over all atoms
within a unit cell!
h k h l k l m
2i (  ) 2i (  ) 2i (  )
]   f je
2i ( hx j  ky j  lz j )
Fhkl  [ 1  e 2 2
e 2 2
e 2 2

j 1
From translation symmetry of fcc! sum up over all
atoms within a LP!
When h,k,l are neither all even nor all odd, Fhkl = 0, systematic absence!

n
Fhkl  4 f j e
When h,k,l are all even or all odd, 2 πi ( hx j  ky j  lz j )

diffraction observable! j 1
Example. Unit cell has a 21 screw axis along the c axis.
 Equivalent positions: (x, y, z), (-x , -y , z+1/2)
N Each molecule has
Fhkl   f j {exp[i 2 ( hx j  ky j  lz j )] N atoms.
j 1
(x,y,z)
1
 exp[ i 2 ( hx j  ky j  l ( z j  ))]}
2
N
F00l  [( 1  exp( il )]  f j exp( i 2lz j )
j 1

( x , y , z  0.5）
l = 2n+1 F00l  0 Sum over all
atoms of a
systematic absence molecule. Herein two molecules
within a unit cell are
correlated by 21 axis.
 How about systematic absence arising from such
screw axes as 31, 41 and 61 ?
2li 4li N/3
• 31||c-axis F00l  [ 1  exp( )  exp( )]   exp( i 2lzi )
3 3 i 1

l N/3
 [ 1  2 cos( l ) cos( )]  exp( i 2lzi )
3 i 1

 Systematic absence when l  3m (m=1,2,…)!

• n1 //c-axis
n
2 ( j  1)li N / n
F00l   exp( )   exp( i 2lzi )
j 1 n i 1

 Systematic absence when l  m·

n (m=1,2,…)!
Systematic Absence
• Crystals of the same lattice type behave similarly in
systematic absence!

• Crystal structures which contain centering, glide plane

and screw axis will have systematic absences.

• Namely, some reflections/diffractions will be

systematically absent in such a crystal lattice that has
centering, glide plane or screw axis.
 Systematic Absence and Symmetry (p214-215)
Types of Conditions for extinction Cause of extinction Centering and
reflection (systematic absence) symmetry
elements
hkl h+k+l = odd I-centred I
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
odd
-h+k+l not multiples of 3 R-centred R(hexagonal)
0kl k =odd Translation in (100) b/2 b-glide a (b,c)
(or h0l, l =odd c/2 c-glidea (b,c)
hk0) k+l =odd (100) glide (b+c)/2 n-glidea (b,c)
k+l not multiples of 4 planes (b+c)/4 d-glidea (b,c)
00l l =odd Translation c/2 21, 42, 63
(or h00, l not multiples of 3 Along c/3 31, 32, 62, 64
or 0k0 l not multiples of 4 (001) c/4 41, 43
l not multiples of 6 Screw axis c/6 61, 65
7.3.4 Applications of X-ray diffraction
1. Methods
* Single crystal diffraction

Monochromatic camera method -- Monochromatic X-ray

Rotation, Oscillation, Weissenberg …
Laue photography --- white X-ray
Diffractometer -- Monochromatic X-ray

Crystal Diffraction beam

2
Incident beam
* Powder diffraction
Monochromatic X-ray
Film or trajectory of detector

Diffraction beam
Powder
sample 2
Incident beam 2 Powder Diffractometer

• In a powder sample, the microcrystalls orient differently,

so does a given lattice plane in the sample.

• Thus a given lattice plane gives a cone of diffraction

beam with an specific angle 2. (Why?)
Radiation sources
X-ray tubes Monochromator – [Link]
Synchrotron radiation Filter – e.g. Ni for Cu K

Detectors
• Film
- poor sensitivity, high background, low dynamic range
• Scintillation counters
- good sensitivity, low background, high dynamic range
• Imaging plates
- good sensitivity, low background, good dynamic range, very
efficient data collection
• CCDs and Multiwire detectors (widely used nowadays)
- fast readout, good sensitivity, low background, good dynamic range,
very efficient data collection
Automated diffractometer method

(2)
2. Applications of X-ray diffraction
a. crystal structure determination
Direction & intensity data collection

Indexing Crystal system and

Cell parameters
I hkl  K Fhkl
2

Phase problem

F (hkl)      ( x, y, z )e 2i ( hxky lz) dxdydz

Inverse
 ( x, y , z )  V 1
 F (hkl)e
h k l
2i ( hx ky lz )
Fourier
Transform

 A ( x, y , z )
i
 Example: Indexing of a cubic system

d hkl  a/ h 2  k 2  l 2 2dhkl sin =  Bragg’s law

sin 2   ( / 2a) 2 (h 2  k 2  l 2 )

sin   h  k  l
2 2 2 2 sin 2 1 : sin 2 2 : sin 2 3 : sin 2 4 : ...

General steps of indexing:

1. Get the directions of the diffraction beams, {i}

2. Get sin 2 1 : sin 2 2 : sin 2 3 : sin 2 4 : ...

3. Get ( h2  k 2  l 2 )1 : ( h2  k 2  l 2 )2 : ( h2  k 2  l 2 )3 ....

4. Get the lattice type and cell parameters.

 Indexing of a cubic system
sin 2   ( / 2a) 2 (h 2  k 2  l 2 ) sin   h  k  l
2 2 2 2

sin 2 1 : sin 2 2 : sin 2 3 : sin 2 4 : ...

 ( h2  k 2  l 2 )1 : ( h2  k 2  l 2 )2 : ( h2  k 2  l 2 )3 ....
Characteristic line sequences of cubic systems:
P: (hkl) 100, 110, 111, 200, 210, 211, 220, 221, 222, 300, ….
（h2＋k2＋l2) 1, 2, 3, 4, 5, 6, 8, 9, 10, 11, 12, 13, … Systematic absence

I: (hkl) 100, 110, 111, 200, 210, 211, 220, 221, 222, 300, …
（h2＋k2＋l2) 2, 4, 6, 8, 10, 12, 14, 16 … (1: 2: 3: 4: 5: 6: 7: 8:…)

F: (hkl) 100, 110, 111, 200, 210, 211, 220, 221, 300, 311, 222, ….
（h2＋k2＋l2) 3, 4, 8, 11, 12, 16, 19, 20 …
Example for the indexing of cubic system and its applications

Sample: NaCl Condition: Cu K, =1.5418 Å, R = 50 mm

(1) Measure sample and relative intensity
(2) Calculate the position of diffraction lines (usually 2 in Ewald
sphere)
(3) Calculate 
(4) Calculate sin2
(5) Calculate sin21: sin22 : sin23 : sin24 :…= 3:4:8:11:12:…
(6) Identify Bravais lattice → face-centered cubic
(7) Indexing and calculate h2+k2+l2, calculate dhkl and a.

FCC: (hkl) 100, 110, 111, 200, 210, 211, 220, 221, 300, 311,222, ….
（h2＋k2＋l2 ) 3, 4, 8, 11, 12, 16, 19, 20 …
(7) Index and calculate h2+k2+l2

No. I 2  sin2 h2+k2+l2 hkl

1 W 27.46 13.73 0.05631 3 111
2 S 31.80 15.90 0.07508 4 200
3 S 45.60 22.80 0.15016 8 220
4 W 54.06 27.03 0.20647 11 311
5 S 57.50 28.75 0.22524 12 222
6 S 66.44 33.22 0.30032 16 400
7 W 73.30 36.65 0.35663 19 331
8 S 77.56 38.78 0.37540 20 420
9 S 84.30 42.15 0.45045 24 422

Measured in Ewald sphere

FCC Indexing
by x-ray diffraction
 (8) Calculate lattice parameter
2
Why do we use high
1.5418
sin 2 θ  2
 ( h 2
 k 2
 l 2
) angle values?
4a
1.5418
a   h2  k 2  l 2
2 sin θ

Least-square method, plot

method, or high angle values,…
a=5.628 Å 0° 90° 
(9) = 2.165 g/cm3 for NaCl dhkl = /(2sin)

V 2.165  (5.628  108 )3

n  4
M / N 0 [( 23  35.5) / 6.022  10 ]
23

One unit cell contains 4 NaCl

(i.e., each lattice point contains a NaCl.)
 Example B. (x-ray =1.5418 Å)
Line 2  sin2 sin2i h2+k2+l2 hkl
/sin21
1 40.26 20.13 0.1184 1 2 110
2 58.26 29.13 0.2370 2 4 200
3 73.20 36.60 0.3555 3 6 211
4 87.02 43.51 0.4740 4 8 220
5 100.64 50.32 0.5923 5 10 310
6 114.92 57.46 0.7109 6 12 222
7 131.16 65.58 0.8290 7 14 321
8 153.58 76.79 0.9470 8 16 400

As =1.5418 Å, BCC indexing

 1.5418
a  h k l 
2 2 2
 42  02  02  3.16 A
2 sin 2 sin 76 .79
b. Applications of powder diffractions

Peak Positions Peak Intensities Peak Shapes and Widths

b. Applications of powder diffractions

Information contained in a Diffraction Pattern

Peak Positions
Crystal system, cell parameters, qualitative phase identification

Peak Intensities
Unit cell contents, quantitative phase fractions

Peak Shapes and Widths

Crystallite size, Non-uniform microstrain
 (i) Peak Positions and Intensities
• Qualitative Analysis:
a) One crystal phase
correspond to a set of
diffraction peaks. ( being
different from the
spectroscopic analysis)
b) Phase analysis

• Quantitative Analysis:
The peak intensities are proportional to the weight percentage of
the corresponding phase.
(ii) Changes of lattice parameters―Solid solution, doping
Using high-angle diffraction data or applying least square method.

2dhklsin = 
Why use high angle values?

Maximal 
 minimal d/

0° 90° 
(ii) Changes of lattice spacing along specific
directions―residue stress
stress 2dhklsin =  
d sin = /(2dhkl)

d d d

d

• The residue stress in a specific direction increases the

corresponding d-spacing of a crystal.

• d is proportional to the strength of crystal strain in the

direction.
(iii) The width of diffraction peaks ―― Crystallite size
30 2
|A|(N=5) 250 |A|2(N=15)
200
20
150
100
10
50
0 h 0 h
-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  Fhkl N N N  Fhkl A
2 2 2 2 2 2
1 2 3

N1, N2, N3 periods along the lattice axes within a microcrystal

• The smaller N in a specific direction [hkl], the broader
of the (hkl) diffraction peak.
 [100]

[001]
XRD pattern of ZnO nanowires

The diffraction peaks arising from (100)-like planes are

much more broad than those from (001)-like planes.
(iii) The width of diffraction peaks ―― Crystallite
size Widely exploited in the
research of nanoparticles!
Scherrer formula: (size ~1nm to 100nm)
K  K  (K =0.9 or 1.0)
Dhkl  
  cos ( B  B0 )  cos use small angle values!
Small-angle scattering – particle size
Dhkl average size along the direction perpendicular to (hkl) plane.
B measured peak width
B0 Instrumental width, using standard sample (e.g. -SiO2 with
crystallite size of 25－44m）

Instrumental width（B0）  B0 （B）

(iii) The width of diffraction peaks ― Lattice Distortion

晶格的畸变（不均匀应变、微观应变、内应力）

d1
＝d /d
d4 d5
2(d+d)sin(+)=
d2 d3
or 2d(1+)sin(+)=
 and  are very small,
d
d1 d2 and hence ,
2＝－2tg or
＝ 2tg
Separation of the effects of Crystallite size and Lattice
Distortion

K 
  i    '
 2tg
D  cos 
i

 cos  sin  K
 2 
  D

Measuring two or more diffraction peaks.

(iv) The profile of diffraction peaks ―― Crystallite size
distribution
 N 
sin  2
a  S  Derived from
   Bragg equation
I  AN  AN AN 
2 *

2 
sin  a  S 
 
m
sin 2 ns 
f p ( s )  K  P ( n)
n 1 sin (s )
2

fp(s) is the line profile of diffraction peak

P(n) is Crystallite size distribution function
Instrumental（B0） Convolution

 B0 （B）


h( s )   g (t ) f (s  t )dt

or h( s)  g ( s)  f ( s)

F (h( s))  F ( g ( s))  F ( f ( s))

(vi) Texture
30.0k (002)

25.0k

20.0k

Intensity a.u.
15.0k

10.0k

5.0k

(103) (004)
0.0
30 40 50 60 70 80 90
2-Theta degree

ZnO nano-arrays
140.0k (201)

120.0k

100.0k

Intensity
80.0k

60.0k

40.0k
(002)
20.0k

0.0
30 40 50 60 70 80
2-Theta degree
b. Applications of powder diffractions
Applications
Qualitative Analysis
Quantitative Analysis
Lattice Parameter Determination
Crystallite size / size distribution & Lattice Distortion
Analysis (Non-uniform microstrain)
Crystallinity Analysis
Residue Stress Analysis
Texture analysis
Structure Solution and Refinement
Radical distribution function (for amorphous materials)
7.3.5 Electron Diffraction and Neutron Diffraction
1. Electron Diffraction
de Brogli wave length
of electron in a field V:
h
＝
2meeV

100 kV ----  ~ 0.00370 nm

Atom-level resolution!
a) TEM image of the tip part of one TeO2 nanorod. (b)
Enlarged TEM image. (c) The corresponding electron
2. Neutron Diffraction diffraction pattern.

----- Scatterring of atomic nuclear

~ higher atomic resolution
 7.4 Quasicrystal, liquid crystal and
amorphous
Quasicrystal:
• quasiperiodic crystal
• 5-fold axis occurs in solid state,
seemingly challenging the
crystallographic theory.
• In 1984, Dan Shechtman et al. reported
their finding that the Al-Mn(14 at.%) alloy
adopts an icosahedral phase with 5-fold
axis. (first observed in 1982.4.8, see Phys.
Rev. Lett. 1984, 53, 1951).
• He won the Nobel Prize in Chemistry in 2011.
 Angew. Chem. Int. Ed. 2011, 50,

Even his cooperator, J. W Cahn, thought that the

pheonomenon was resulted from twinning of single crystals!
An icosahedral Yb-Cd
quasicrystal is composed
of an aperiodic ordered
arrangement of YbCd
clusters (yellow and blue
spheres at the vertices of
the polyhedra
 Quasi-crystal 3D quasicrystal:
Crystal
Icosahedral phase in
Al-Mn, Ti2Ni, Al-Li-
Cu, Mg-Al-Zn alloys.
2D quasicrystal:
With 1D translation
symmetry and 2D
quasiperiodicity.
8-fold, 10-fold
Translation symmetry, quasicrystals in some
Long-range order, alloys.
Directional.
No translation symmetry;
Long-range order, directional.
 History of quasicrystal concept
(extracted from wikipedia) Wang Tiles
1. Quasicrystal-like structures had been known
well before the 20th-century, e.g., tiles in a
medieval islamic mosque in Iran.

2. In 1961, Hao Wang proposed a mathematic

problem related to the planar tiling.

3. In 1966, Wang’s student, Robert Berger,

constructed a set of some 20,000 square tiles
(now called Wang tiles), which can tile the plane
aperiodically.

4. In particular, in 1976, Roger Penrose proposed

a set of just two tiles, up to rotation, (referred to
as Penrose tiles) that produced only non-periodic
tilings of the plane. Penrose Tiling
5. In 1982, Alan Mackay showed experimentally that the diffraction
pattern from the Penrose tiling had a two-dimensional Fourier
transform consisting of sharp 'delta' peaks arranged in a fivefold
symmetric pattern. (Physica A, 1982, 114, 609)

6. The history of quasicrystals begins with the 1984 paper "Metallic

Phase with Long-Range Orientational Order and No Translational
Symmetry" where Dan Shechtman et al. demonstrated a clear
diffraction pattern with a fivefold symmetry.

7. The term quasicrystal was first used in print shortly after the
announcement of Shechtman's discovery, in a paper by Steinhardt and
Levine. (Phys. Rev. Lett. 1984, 53,2477)

8. At the end of the 1980s, the idea of quasicrystal became widely

acceptable!
Liquid crystals
• Crystalline solid: anisotropic
• Liquid: isotropic
• Liquid crystal: anisotropic!
Liquids with well-ordered, crystal-like
structures.

More details of liquid crystals can be learnt in

material science!
 Chapter 7
Key points/concepts

1. Lattice of crystal structure: translation symmetry

a lattice point = a structure motif -- unit cell

2. Crystal systems (7), Bravais Lattice (14)

3. Symmetry operations (point & translation), Crystallographic

point groups(32), space groups (230), equivalent positions.

4. Miller index of crystal plane，d-spacing etc.

5. X-ray diffraction, Laue equation, Bragg’s Law, reciprocal

lattice, Ewald sphere, structural factor, system absence,
general process of x-ray crystal structure determination.
X-ray diffraction, Bragg’s Law, Ewald sphere
2d hkl sin    Bragg’s law Directions of
detected X-ray
Ewald sphere + reciprocal lattice
diffraction beams:
OG  2 O1O * sin   ( 2 ) sin   1 {2}
 d hkl
Radius = 1/
sin21:sin22:…:sin2n
G
indexing
S r* Crystal system,
1/dhkl Bravais lattice, cell
 2
parameters etc.
A S0  O1 1/ O
(hkl)
Fhkl & (x,y,z)
• Structure factor & systematic absence
I hkl  K Fhkl
2
Structure factor:

n Phase difference between

Fhkl   f j e
2i ( hx j  ky j  lz j )
the scattered and incident
x-ray over atom j.
j 1

Sum over all atoms fj: atomic scattering factor defined by

within a unit cell. atomic electron density distribution.

• some reflections/diffractions will be systematically

absent (Fhkl = 0  Ihkl = 0) in case a crystall lattice has
centering, glide plane and screw axis.
 Further applications of X-ray diffraction d d’
a) Change of
specific d-spacing
2d hkl sin   
b) Size effect of microcrystal—broadening of
dhkl vs. hkl
diffraction peaks

I  Fhkl N N N  Fhkl A
2 2 2 2 2 2
1 2 3

Scherrer formula K  K 
Dhkl  
(size: 1-100nm)   coshkl ( B  B0 )  coshkl
c) Deformation of lattice—broadening of diffraction peaks
d
d1 d4 d5 d1 d2
d2 d3
In the diffraction direction, the difference between the
incident and the diffracted beam through any two lattice
points must be an integral number of wavelengths.

The lattice vector from (000) to (mnp): Tmnp = ma + nb +pc

The differences in wavelengths for observed diffractions:
 =Tmnp·(S-S0)
=(ma + nb +pc) ·(S-S0)
= ma ·(S-S0) + nb ·(S-S0) + pc ·(S-S0)
=mh + nk + pl
=(mh+nk+pl)
Crystal Characteristic Unit cell Choice Lattic
systems symmetry parameters of axis Point
elements Group
Triclinic Nil abc Ci


2D lattices:
3 parellelograms

Inversion center:
(0,0,0); (1/2,1/2,1/2)
(0,0,1/2), (1/2,0,0),
(0,1/2,0);

(1/2,1/2,0),(0,1/2,1/2),
(1/2,0,1/2)
Crystal Characteristic Unit cell Choice of Lattic
systems symmetry parameters axis Point
elements Group
Monoclinic C2, i,h abc b // C2 C2h
==90 ac//h

2D lattices:
1 parellelogram
2 rectangles.
Crystal Characteristic Unit cell Choice of Lattic
systems symmetry parameters axis Point
elements Group
Orthorhombic 3C2,3h a≠b≠c a,b,c // 3C2 D2h
===90

2D lattices:
3 rectangles.
Tetragonal C4 a=bc c // C4 D4h
===90

2D lattices:
1 square
2 rectangles.
Cubic 4C3 a=b=c Four C3 axes are parallel Oh
===90 to the body diagonals
of the cube.

2D lattices:
3 squares
Hexagonal C6，h a=bc c // C6 D6h
==90
=120

C6

c b
a

aO b
2D lattices:
1 hexagon + 2 rectangles.
Trigonal C3 Rhombohedral D3d
a=b=c, ==<12090

Hexagonal D6h
a=bc, ==90, =120

C3

c
b a
O
Rhombohedral