Crystallinity: Repeating or periodic array over large atomic distances.

3-D pattern in
which each atom is bonded to its nearest neighbors.

Crystal Structure: The manner in which atoms, ions, or molecules are spatially arranged.
Crystallography is the experimental/Theoretical science of the arrangement of atoms in solids.
The word crystallography derives from the Greek word crystallon=cold drop/frozen drop, with
its meaning extending to all solids with some degree of transparency, and graph=write,

HRTEM image of crystalline

Strontium Titanate, Bright TEM image of amorphous
atoms are Sr and darker are Ti. interlayer at the Ti/(001)Sr
interface in an as doped sample
 Unit cell
Unit cell: small repeating entity of the atomic structure.
The basic building block of the crystal structure. It defines
the entire crystal structure with the atom positions within.

❑ Unit cell is the smallest unit of volume that permits identical cells to be stacked
together or to fill all space.

❑ By repeating the pattern of the unit cell over and over in all directions, the entire
crystal lattice can be constructed.
 Crystal Systems
▪ Unit cells need to be able to “Stack” them to fill all space!!
▪ This puts restrictions on unit cell shapes.
▪ Cubes work, but pentagons don’t!!
▪ Different types (but not infinite !!!) of unit cell are possible,
and they are classified based on their level of symmetry.

Symmetry
Symmetry is a set of mathematical rules that describe the shape of an object

There is only one object in

the geometrical universe Infinite planes of symmetry pass through its center, infinite
with perfect symmetry and it rotational axes are present, and no matter how little or much you
a SPHERE rotate it on any of its infinite number of axes, it appears the same.
A sphere is the Holy Grail of symmetry!!
Crystal: Space Group
 Point Symmetries

It is a macroscopically visible symmetry operations: after it has been

applied to the crystal at least on point remains where it was before.

These Operations Are:

• Reflection in a point (inversion)-Center of Symmetry

• Reflection in a plane or Mirror Symmetry

• Rotation about an imaginary axis- Rotational Symmetry

• Rotation-and-after-it-inversion or Roto-inversion
 Mirror symmetry
Reflection in a point or inversion

Three-fold Four-fold
Two-fold symmetry Six-fold
symmetry
symmetry symmetry

Figure looks the same n-times in 360 degree rotation is called n-fold symmetry.
 Sets for basic symmetry elements in crystal

➢ Mirror plane, symbol: m

➢ Center of symmetry, symbol: p

The Crystal System

There are six crystal system
1. Cubic a, b, c, axis of crystal
2. Tetragonal
3. Hexagonal
4. Orthorhombic
5. Monoclinic
6. Triclinic
Cubic
The three crystallographic axes are all equal
in length and intersect at right angles to
each other. 𝑎 = 𝑏 = 𝑐 α = 𝛽 = 𝛾 = 90°
In general this system involves 6 classes of
symmetries and 15 crystal forms.
Cube-is one of the easiest to recognize and
many minerals display it with little
modification: pyrite, fluorite, perovskite, or
halite cubes
Tetragonal
The three axes, all at right angles, two of
which are equal in length and one (c) which
is different in length (shorter or longer). 𝑎 =
𝑏 ≠ 𝑐 α = 𝛽 = 𝛾 = 90°
In general this system involves 7 classes of
symmetries and 9 crystal forms.
Cube-is one of the easiest to recognize and
many minerals display it with little
modification: pyrite, fluorite, perovskite, or
halite cubes
 Hexagonal Orthorhombic
𝑎 ≠ 𝑏 ≠ 𝑐 α = 𝛽 = 𝛾 = 90°
Four axes, three of the axis fall in the same plane
and intersect at the axial cross at 120° . These three
axes are the same length, and the fourth, c, may be
longer or shorter. The c axis also passes through
the intersection of the other three axes.

If any axis of equal length to any

other, then we would be in the
tetragonal system
 Monoclinic Triclinic
𝑎 ≠ 𝑏 ≠ 𝑐 α ≠ 𝛾 ≠ 90° ≠ 𝛽
The three axes all are unequal, two of
them (a and c ) intersect at an oblique
angle, third axis (b) is perpendicular to
the other two axes.
𝑎 ≠ 𝑏 ≠ 𝑐 α = 𝛾 = 90° ≠ 𝛽

If a and c crossed at 90 degree, then we

would be in the orthorhombic system.
 Bravais Lattices
➢ By means of unit cells we managed to reduce all possible crystal
structures to a relatively small numbers of basic unit cell geometries.
➢ Now let us consider the issue how atoms (viewed as hard spheres )
can be stacked together within a given unit cell.
➢ There is a limited number of possibilities, referred to as Bravais
Lattice
Remember!!! Lattice points are theoretical points arranged
periodically in 3-D space, rather than actual atoms.
The 14 Bravais lattices give the ways of arrangement of atoms in the lattice points.

The French scientist August Bravais, demonstrated in 1850 that only these 14 types
of unit cells are compatible with the orderly arrangement of atoms found in
crystals.

Each point represents one or more atoms in the actual crystal, and if the points are
connected by lines, a crystal lattice is formed.
 Tetragonal Cell

Orthorhombic Cells
 FCC (face centered cubic)

Atoms are arranged at the corners and

center of each cube face of the cell.

Close packed Plane: On each face of the cube

Atoms are assumed to touch along face diagonals.
4 atoms in one unit cell. 𝑎 = 2𝑅 2
 BCC: Body Centered Cubic
Atoms are arranged at the corners of the cube
with another atom at the cube center.
4𝑅
𝑎=
3

➢ Close Packed Plane cuts the unit cube in half diagonally

➢ 2 atoms in one unit cell
𝑁𝑃2 = 𝑁𝑂2 + 𝑂𝑃2 = 𝑎2 + 𝑎2 = 2𝑎2

𝑁𝑄2 = 𝑁𝑃2 + 𝑃𝑄2 = 𝑎2 + 𝑎2 = 2𝑎2

But, NQ=4R, where R is the atomic radius. So,

(4𝑅)2 = 2𝑎2 + 𝑎2 = 3𝑎2

4𝑅
𝑎=
3
 Hexagonal Close Packed (HCP)
➢ Cell of an HCP lattice is visualized as a top and bottom plane of
7 atoms, forming a regular hexagon around a central atom. In
between these planes is a half-hexagon of 3 atoms.
➢ There are two lattice parameters in HCP, a and c, representing
the basal and height parameters respectively.

Coordination number – the number of nearest neighbor atoms or ions surrounding an atom or ion
 Atomic Packing Factor
The ratio of atomic sphere volume to unit cell volume, assuming a hard sphere model.

For FCC and HCP it is 74% and for BCC it is 68%.

4 3
For HCP, there are the equivalent of six spheres per unit cell, and thus 𝑉𝑠 = 6 𝜋𝑅
3

The area of ACDE is just the length of CD times the height BC . But CD is
2𝑅 3
just a or 2R, and 𝐵𝐶 = 2𝑅 cos 30° = , Thus the base area is =3 ×
2
2𝑅 3
𝐶𝐷 × 𝐵𝐶 = 3 × 2𝑅 × = 6𝑅2 3
2
Now c=2R(1.633), So the volume of the cell is 𝑉𝑐 = 6𝑅2 3 × 2𝑅(1.633)
𝑉
APF=𝑉𝑠 = 0.74
𝑐
Crystallographic Points, Direction, and Plane
Crystal Planes
Indexing Planes