Structural probes for

solid materials

Dr. Graeme Blake

Room 17:0015
Email [email protected]
 Structural probes for
solid materials
Learning objectives:

1. Analyse the symmetry of simple crystal structures

2. Describe the physical interaction of X-rays and neutrons with

solid materials

3. Explain how crystal structures can be investigated using X-ray

and neutron scattering techniques

4. Perform X-ray diffraction experiments to solve crystal

structures of simple inorganic materials
 Structural probes for
solid materials
1. Geometry of crystals

2. Physical interaction of X-rays with solid

materials

3. Using diffraction to probe crystal structures

4. Laboratory-based X-ray diffraction techniques

 Structural probes for
solid materials
5. Synchrotron and neutron diffraction

6. Other scattering techniques for probing the

structures of solids

7. Tutorials (usually one per week)

8. X-ray diffraction practical + data analysis

(compulsory for admission to exam)

9. Written examination (October 30)

 Structural Probes for Solid Materials 2019
Week Day Date Time Room Type Chapters
36 Mon 2-9-19 13:00-15:00 5173.0050 Lecture 1-5
Mon 2-9-19 15:00-17:00 5159.0114 Tutorial
Thu 5-9-19 17:00-19:00 5113.0201 Lecture 1-5
37 Mon 9-9-19 13:00-15:00 5173.0050 Lecture 7, 8.3, 9.8
Mon 9-9-19 15:00-17:00 5159.0114 Tutorial
Thu 12-9-19 17:00-19:00 5113.0201 Lecture 6, 8.4, 9.1-9.2
38 Mon 16-9-19 13:00-15:00 No class
Mon 16-9-19 15:00-17:00 5159.0114 Lecture 9.4, 9.5, 13
Thu 19-9-19 17:00-19:00 5113.0201 Lecture 9.3, 10
39 Mon 23-9-19 13:00-15:00 5173.0050 Lecture 10
Mon 23-9-19 15:00-17:00 5159.0114 Tutorial
Thu 26-9-19 17:00-19:00 5113.0201 Lecture Other topics
40 Mon 30-9-19 13:00-15:00 5173.0050 Lecture Other topics
Mon 30-9-19 15:00-17:00 5159.0114 Tutorial
41 Mon 7-10-19 13:00-15:00 5173.0050 Lecture Other topics
Mon 7-10-19 15:00-17:00 5159.0114 Tutorial
Tu-Fri 8-11 Oct Afternoons 5118.-166 Practical
42 Mon 14-10-19 13:00-15:00 5173.0050 Lecture 11
Mon 14-10-19 15:00-17:00 5159.0114 Tutorial
43 Mon 21-10-19 15:00-17:00 5159:0114 Tutorial
Tu 22-10-19 13:00-15:00 5116:0310 Computer lab
44 Mon 28-10-19 09:00-10:30 5113:0201 Q+A
Wed 30-10-19 15:00-18:00 5161:0165 Exam
 Structural probes for
solid materials

1. Geometry of crystals
 Geometry of Crystals
1. Basic crystallographic concepts

2. Symmetry in crystals

3. Common inorganic structural types

Reading:

1. “The Basics of Crystallography and Diffraction” (C. Hammond), Chapter 1-5

2. “Elements of X-ray Diffraction” (B.D. Cullity and S.R. Stock), Chapter 2
3. “Fundamentals of Powder Diffraction and Structural Characterization of
Materials” (V.K. Pecharsky and P.Y. Zavalij), Chapter 1
4. “Fundamentals of Crystallography” (C. Giacovazzo), Chapter 1
5. “X-ray Structure Determination” (G.H. Stout and L.H. Jensen), Chapter 3

Some of the lecture material in this part has been taken from:
“Fundamentals of Powder Diffraction and Structural Characterization of Materials” (V.K. Pecharsky and P.Y.
Zavalij)
http://www.chem.ox.ac.uk/icl/heyes/structure_of_solids/Strucsol.html
http://www.quartzpage.de

.wrl files obtained from

http://www.jcrystal.com/steffenweber/gallery/StructureTypes/st1.html
Basic crystallographic
concepts
 Crystals- basic properties

•In crystals there are symmetry relationships

involved in the arrangement of the
atoms/ions/molecules.

Quartz crystal (SiO2) www.quartzpage.de

X-ray Diffraction
 Basic definitions
LATTICE: An infinite array of points (of inifinitesimal size) in space, in which each point
has identical surroundings to all others. Lattice points are not necessarily atoms!

UNIT CELL: The smallest unit of the crystal that when repeated with pure translational
repetition reproduces the whole crystal. Can be “primitive” (P) containing only one
lattice point or non-primitive (NP) containing more than one lattice point.
 Basic definitions

CRYSTAL STRUCTURE: The ordered, periodic arrangement of atoms in a crystal. The

crystal structure can be described by associating a group of atoms known as the
MOTIF or BASIS with each lattice point.
 2D unit cell

M.C. Escher 1898 - 1972

•One lattice point (primitive)

•Motif consists of one white and one black bird
 Unit cell notation

(x,y,z)
c

βα b
a γ

An atom position is described by fractional coordinates (x,y,z)

where x, y and z are fractions of the unit cell dimensions a, b and c
 2D unit cell

•Graphene: primitive 2D unit cell with 2 atoms in motif

 2D unit cell

•Graphene: primitive 2D unit cell with 2 atoms in motif

 2D unit cell

www.quartzpage.de • Quartz motif consists of three

SiO4 tetrahedra.

• Can choose either group a or

group b as the motif.
 2D unit cell

2 2 3
3
1 1 2 2
2 3 3 2 2
3 1 1 3 3
1 1 1
2
3 2
1 3
1

unit cell based on motif a unit cell based on motif b other possible unit cells...
 3D unit cell

To count the number of atoms in a unit cell:

-Atom at cell corner: shared by 8 cells, contributes ⅛ of an atom
-Atom on cell edge: shared by 4 cells, contributes ¼ of an atom
-Atom on cell face: shared by 2 cells, contributes ½ of an atom
-Atom within unit cell: contributes 1 atom
-Graphite has (8×⅛) + (4×¼) + (2×½) + 1 = 4 atoms per unit cell.
 Unit cell with large motif

Unit cell of protein crystal AtHal3

(http://www.xtal.iqfr.csic.es/Cristalografia/parte_01-en.html)
 Close packing of spheres

•Many simple crystal structures are constructed from “close-packed” layers of

atoms / ions.

•A single layer of spheres is closest packed with a hexagonal coordination.

 Close packing of spheres

•A second layer of spheres can be placed on the indentations of the first layer.
•Tetrahedral holes (2 per sphere, r = 0.225) and octahedral holes (1 per
sphere, r = 0.414) are formed.
 Close packing of spheres

A third layer of spheres can be placed either in the indentations directly above
the atoms of the first layer, or in a third set of indentations.

C
Close packing of spheres
 Close packing of spheres

Many more complex close-packed structures are known with different

stacking sequences eg. four-layer ABCB...
 Close packing of spheres

Both HCP and CCP-packed spheres occupy 74% of the volume.

This is the most efficient way to fill space with spheres.

Johannes Kepler 1571 - 1630

In 1611 Kepler conjectured that cubic close

packing gives the greatest possible density
for equally sized spheres.
 Body-centred cubic structure

This is common but is not a close-packed structure; only 68% of the volume is filled.

Metal structures
 Crystallographic planes

1 1

1 1

0 1 0 ½ 1
(100) plane (200) plane

•Miller indices (hkl) describe an infinite set of lattice planes.

•(hkl) are the reciprocals of the fractional intercepts that the plane makes
with the crystallographic axes.
•h, k and l are integers.
•If the plane is parallel to an axis then that indice is zero.
 Crystallographic planes

1 h2 k 2 l 2
2
 2  2  2 for a unit cell with edge lengths a, b and c, and all angles 90°
d a b c

1 1

d d

1 1

0 1 0 ½ 1
(100) plane (200) plane

1/d2 = 1/a2 1/d2 = 4/a2

d=a d = a/2
 Crystallographic planes

(110) plane
d

0 1

1/d2 = 1/a2 + 1/b2

 Crystallographic planes

⅓
d

0 ½ 1
(213) plane

1/d2 = 4/a2 + 1/b2 + 9/c2

Crystallographic planes

?
 Crystallographic planes

c
•Planes can have negative indices

__
(111) plane

-1 a
0

-1
 Crystallographic planes

c 1
•Here (hkl) and –(hkl) are equivalent

0 1
a

__
(111) plane
_ =
(111) plane -1

1/d2 = 1/a2 + 1/b2 + 1/c2

 Crystallographic directions
[012]
[111]

(0, ½, 1)

[110]
b

[100]
(0,0,0) a
__
[111]
The direction vector should be drawn from the origin. Look at the coordinates at which the
vector intercepts the unit cell. If not equal to 0 or 1, multiply the coordinates until all three are
integers to obtain the direction indices.
Symmetry in crystals
 Simple symmetry operations

rotation center of mirror translation

axis inversion plane vector

Simple symmetry operations can be combined to give

complex symmetry elements.
 Finite symmetry elements

•Do not contain translations and thus produce a finite number of objects.

•Used to describe the symmetry of finite objects such as molecules and

coordination polyhedra.

_
One-fold rotation axis 1 Center of inversion 1
 Finite symmetry elements

_
Two-fold rotation axis 2 Two-fold inversion axis 2

_
2 is equivalent to mirror plane m
perpendicular to the axis
 Finite symmetry elements

_
3-fold rotation axis 3 3-fold inversion axis 3

1
2

3
6

4
5
 Finite symmetry elements

_
4-fold rotation axis 4 4-fold inversion axis 4

1
2

3
4
 Finite symmetry elements

5-fold rotation axis?

No translational symmetry hence no finite unit cell

 Finite symmetry elements
_
6-fold rotation axis 6 6-fold inversion axis 6

(equivalent to 3-fold rotation axis

+ mirror plane)
 Interaction of finite symmetry elements

2-fold rotation axis + mirror plane intersecting at 45º…

…generate another mirror plane, 2-fold rotation axis and 4-fold inversion axis

2 m

B C

A H

D E

G F
 Finite symmetry elements - summary

There are 10 finite crystallographic symmetry elements (11 including one-

fold rotation or identity).

mirror m
 7 crystal classes and 14 Bravais lattices

primitive body-centered face-centered

Requirement for cubic symmetry: four 3-fold axes (along the four cube body diagonals)

Auguste Bravais 1811-1863

7 crystal classes and 14 Bravais lattices

One 4-fold axis (through opposite square faces)

 7 crystal classes and 14 Bravais lattices

Side-centered; C
indicates ab plane
Three perpendicular 2-fold axes (through opposite faces)
 7 crystal classes and 14 Bravais lattices

RHOMBOHEDRAL

One 6-fold axis (parallel to c-axis) One 3-fold axis (along body
diagonal in “stretched” cube
direction)
7 crystal classes and 14 Bravais lattices

One 2-fold axis (through front and back faces)

7 crystal classes and 14 Bravais lattices

RHOMBOHEDRAL
Stereographic projections of finite symmetry elements

Arbitrary projection of sphere

containing 2-fold axis perpendicular
to mirror plane (and consequent
inversion centre)
Stereographic projections of finite symmetry elements

Standard projection of sphere Alternative standard projection:

containing 2-fold axis, mirror same sphere rotated by 90º
plane and inversion centre
 Stereographic projections of finite symmetry elements

Example of tetragonal symmetry Most complex cubic symmetry

Point group representation of finite symmetry elements

•Across the 7 crystal systems there are 32 unique combinations of finite

symmetry elements that leave one point fixed, known as point groups.

•There can be up to 24 symmetry elements in a point group- it is

complicated to represent them all in a picture.

•It is simpler to use a projection of only the “basic” symmetry elements

that will generate all the derivative symmetry elements.

•Detailed information on all the point groups is

listed in The International Tables for Crystallography.
 Point group notation
Three symbols: symmetry elements in (primary) (secondary) (tertiary) directions

primary secondary tertiary

Cubic all 3 axes body diagonal [111] face diagonal [110]

Tetragonal c [001] a,b [100],[010] base diagonal [110]

Orthorhombic a [100] b [010] c-axis [001]

Hexagonal c [001] a,b [100],[010] long base diagonal

[1-10]

Monoclinic b [010]

• Rotation axes are parallel to the directions in the table and mirror planes are
perpendicular.
Point group representation of finite symmetry elements

Monoclinic point group 2/m

2-fold axis parallel to unit cell b-

axis and mirror plane
perpendicular to b-axis

Simplified representation:
 Point group representation of finite symmetry elements

_
Tetragonal point group 42m

_
4 axis parallel to c-axis

2-fold axes parallel to a- and b-axes

mirror planes perpendicular to unit cell base diagonal

Simplified representation:
32 point groups
 Infinite symmetry elements

•Contain translations and thus generate an infinite number of objects.

•The crystal lattice is infinite due to the presence of translations.

 Infinite symmetry elements – glide planes

•Glide planes a, b and c reflect an object in the plane and translate it by ½

of the a, b, and c basis vectors, respectively, i.e. mirror + translation.

c b

glide plane b (perpendicular to a) glide plane c

 Infinite symmetry elements – glide planes

•Horizontal glide plane n, (in the case below perpendicular to c), reflects an
object in the plane and translates by ½ (a + b).

c b

a
 Infinite symmetry elements – screw axes

•A screw axis Nk involves an N-fold rotation and a translation of k/N with

respect to the a, b or c basis vector.

•k is an integer between 1 and N-1.

c b

horizontal 21 screw axis vertical 21 screw axis

 Interaction of infinite symmetry elements

21

c b

a
b

b´

b glide plane and centre of inversion (+ consequent 21 screw axis)

Space group representation of all symmetry elements
•Across the 7 crystal systems there are 32 point groups.

•When combined with the allowed infinite symmetry elements (glide planes
and screw axes) there are 230 space groups.

•Detailed information on all the space groups is listed in

The International Tables for Crystallography.

Evgraf Fedorov 1853 - 1919 Arthur Schönflies 1853 - 1928

 Space groups

•Space group symbol consists of a capital letter to denote the lattice

centering (P, F, I, C) followed by the point group symbol.

•Point group symbol is modified to include infinite symmetry elements

(glide planes and screw axes) if they are present.

•Example:

Pbcn

Primitive lattice n glide plane

perpendicular to c
b glide plane
c glide plane
perpendicular to a
perpendicular to b

To obtain the point group from the space group symbol, replace glide planes
by m and replace screw axes by the corresponding rotation axis.
For Pbcn the point group is mmm (orthorhombic).
 Space groups

P63cm

Primitive lattice mirror plane perpendicular

to long base diagonal
63 screw axis
c glide planes
parallel to c
perpendicular to a and b

Point group 6mm (hexagonal)

 Point group notation
Three symbols: symmetry elements in (primary) (secondary) (tertiary) directions

primary secondary tertiary

Cubic all 3 axes body diagonal [111] face diagonal [110]

Tetragonal c [001] a,b [100],[010] base diagonal [110]

Orthorhombic a [100] b [010] c-axis [001]

Hexagonal c [001] a,b [100],[010] long base diagonal

[1-10]

Monoclinic b [010]

• Rotation axes are parallel to the directions in the table and mirror planes are
perpendicular.
 Space groups

I 4/mcm

Body-centred lattice mirror plane

perpendicular to
4-fold rotation axis base diagonal
parallel to c and c glide planes
mirror plane perpendicular
perpendicular to c to a and b

Point group 4/mmm (tetragonal)

Extract from
International Tables Space groups Crystal class
for Crystallography
Point group

diagram of
symmetry elements
in ab plane
coordinates of atoms
generated by
symmetry elements at
general and “special”
(high symmetry)
positions in unit cell
 _
Example of P42m

CuFeS2
 Space groups

_
Fm3m

Face-centred lattice mirror plane

perpendicular to
mirror plane
face diagonal
perpendicular to 3-fold inversion
a (and b and c) axis parallel to
body diagonal

_
Point group m3m (cubic)
 Point group notation
Three symbols: symmetry elements in (primary) (secondary) (tertiary) directions

primary secondary tertiary

Cubic all 3 axes body diagonal [111] face diagonal [110]

Tetragonal c [001] a,b [100],[010] base diagonal [110]

Orthorhombic a [100] b [010] c-axis [001]

Hexagonal c [001] a,b [100],[010] long base diagonal

[1-10]

Monoclinic b [010]

• Rotation axes are parallel to the directions in the table and mirror planes are
perpendicular.
 _
Example of Fm3m
 _
Example of Fm3m
Common inorganic
structural types
 Rock salt

_
Fm3m

•NaCl has a CCP lattice of Cl- ions with Na+ in all the octahedral holes.
•The motif contains Cl- at (0,0,0) and Na+ at (½,0,0).
•There are 4 × NaCl in the unit cell.
•The coordination number of both Cl- and Na+ is 6.
•NaCl has a network of edge-shared octahedra.
 Fluorite

CaF
_2
Fm3m

•CaF2 has a CCP lattice of Ca2+ ions with F- in all the tetrahedral holes.
•The motif contains Ca2+ at (0,0,0) and 2F- at (¼,¼,¼) and (¾,¾,¾).
•There are 4 CaF2 units in the unit cell.
•Coordination number of Ca2+ is 8 and F- is 4.
•CaF2 contains a network of edge-shared FCa4 tetrahedra or CaF8 cubes.
 Fluorite

Fluorite CaF2

Equivalent fluorite unit cell

 Zinc blende ZnS
_
F43m

•ZnS has a CCP lattice of S2- ions with Zn2+ in half the tetrahedral holes (T+ or T-).
•The motif contains S2- at (0,0,0) and Zn2+ at (¼,¼,¼).
•There are 4 ZnS units in a unit cell.
•Coordination number of both Zn2+ and S2- is 4.
•ZnS contains a network of corner-linked tetrahedra.
 Diamond

•Diamond adopts the zinc blende structure but with all of the sites occupied by
carbon.

•However, this is not a close-packed structure because it is determined by covalent

bonds of fixed length and geometry.
CCP variants
Complex CCP variants
 Complex CCP variants

www.spring8.or.jp

• Both have cubic F (face centered) Bravais lattices.

 Nickel arsenide NiAs

P63/mmc

•NiAs has a HCP lattice of As2- ions with Ni2+ in all the octahedral holes.
•The motif contains 2Ni2+ at (0,0,0) and (0,0,½) and 2As2- at (⅔,⅓,¼) and
(⅓,⅔,¾).
•There are 2 NiAs units in a unit cell.
•Coordination number of Ni2+ is 6 (octahedral) and of As2- is 6 (trigonal prismatic).
Nickel arsenide NiAs
 Wurtzite ZnS

P63mc

•Wurtzite ZnS has a HCP lattice of S2- ions with Zn2+ in half the tetrahedral holes.
•The motif contains 2S2- at (0,0,0) and (⅔,⅓,½) and 2Zn2+ at (⅔,⅓,⅛) and (0,0,⅝).
•There are 2 ZnS units in the unit cell.
•The coordination number of both Zn2+ and S2- is 4 (tetrahedral).
 Caesium chloride CsCl
(non-close packed)

_
Pm3m

•CsCl has a primitive cubic lattice.

•The motif contains Cl- at (0,0,0) and Cs+ at (½,½,½).
•There is 1 × CsCl in the unit cell.
•Adopted by halides of cations that are too large to fit into the interstitial sites of
close-packed structures. Packing factor is only 68% (74% for close packed).
 Cs3C60

What is the Bravais lattice? -Cubic P (primitive)

Perovskite structure ABO3
Perovskite-type intergrowth structures
Spinel structure AB2O4
Organic molecular packing

“herringbone” motif
Organic molecular packing