Crystal Structure

Ref. Book: Solid State Physics By S.O. Pillai

Chapter 4
OR Solid state physics, Kittel (Wiley)

Prof. Navendu Goswami

 ELEMENTARY CRYSTALLOGRAPHY
SOLID MATERIALS

AMORPHOUS
CRYSTALLINE
(Non-crystalline)

Single Crystal Polycrystallıne

Short range order

Long range order

More than one crystal

❖Distinguished by size of ordered region.
❖ Structure of materials decides mechanical, thermal , electrical and magnetic
properties.
❖Crystal is a solid composed of atoms or other microscopic particles
arranged in an orderly repetitive array 2
Crystal Lattice
■ An infinite periodic array of points in space
with identical surroundings →Lattice points
■ 3-D (or 2-D) picture of lattice points in
space → Space Lattice.
■ If points are identical →Bravais Lattice

Crystal Structure
■ Crystal structure can be obtained by attaching atoms, groups of
atoms or molecules which are called basis (motif) to the lattice sides
of the lattice point.
Crystal Structure = Crystal Lattice + Basis

Ex : 1. Cu and Na (basis is a single atom)

2. NaCl, CsCl (basis is diatomic)
3. CaF2 (basis is triatomic)

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 Crystal Lattice
Bravais Lattice (BL)
▪ All atoms are of the same
kind
▪ All lattice points are
equivalent
Bravais lattice is an infinite array of
discrete points with an arrangement and
orientation that appears exactly the
same, from whichever of the points the
array is viewed. Lattice is invariant
under a translation.
Nb
film
Non-Bravais Lattice (non-BL)
▪ Atoms can be of different kind
▪ Some lattice points are not
equivalent
▪A combination of two or more BL
Non-Bravais Lattice: Not only the
arrangement but also the orientation
must appear exactly the same from every
point in a bravais lattice
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Honey
 Translational Lattice Vectors – 2D
A space lattice is a set of points such that a
translation from any point in the lattice by a vector;

In 2-D
P
In 3-D

locates an exactly equivalent point, i.e. a point with

the same environment as P . This is translational
symmetry. The vectors a, b are known as lattice
vectors and (n1, n2, n3,) is a pair of integers whose
values depend on the lattice point.

■ The two vectors a and b form a set of

Point D(n1, n2) = (0,2) lattice vectors for the lattice.
Point F (n1, n2) = (0,-1)
■ The choice of lattice vectors is not
What is T for point P in terms of unique. Thus one could equally well
a,b and a, b’? take the vectors a and b’ as a lattice
vectors.
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Unit Cell in 2D ( Building block)
■ The smallest component of the crystal (group of atoms, ions or
molecules), which when stacked together with pure translational
repetition reproduces the whole crystal.

S
S S
S S S
b S S S S S
a

■ The smallest component of the crystal (group of atoms, ions or

molecules), which when stacked together with pure translational
repetition reproduces the whole crystal.
S
The choice S
of
unit cell
is not S S
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unique. b
2D Unit Cell example -(NaCl)
We define lattice points ; these are points with
identical environments
Choice
This isisof origin
also a ISis arbitrary
unit cell - cell - lattice points
This
In 2D, NOT
this a a
unit
unitcell even though they
need
itare not matter
doesn’t be atomsif you- start
but unit
from cell
Nais size
or Cl
In all itthe
3D, same
is NOT - empty space not
should always be the same.
allowed!
- or if you don’t start from an atom

Which one is not a unit cell.

Why can't the blue triangle be a unit cell?

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8
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 Primitive Unit Cell and vectors
■ A primitive unit cell is made of primitive
translation vectors a1 ,a2, and a3 such
that there is no cell of smaller volume
that can be used as a building block for
crystal structures.

■ A primitive unit cell will fill space by

repetition of suitable crystal translation
vectors. This defined by the parallelpiped
a1, a2 and a3. The volume of a primitive
unit cell can be found by

■ V = a1.(a2 x a3) (vector products) Cubic cell volume = a3

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 TYPICAL CRYSTAL STRUCTURES

3D – 14 BRAVAIS LATTICES AND THE SEVEN CRYSTAL SYSTEM

■ There are only seven different shapes of unit cell which

can be stacked together to completely fill all space (in 3
dimensions) without overlapping. This gives the seven
crystal systems, in which all crystal structures can be
classified.

■ Cubic Crystal System (SC, BCC,FCC)

■ Hexagonal Crystal System (S)
■ Triclinic Crystal System (S)
■ Monoclinic Crystal System (S, Base-C)
■ Orthorhombic Crystal System (S, Base-C, BC, FC)
■ Tetragonal Crystal System (S, BC)
■ Trigonal (Rhombohedral) Crystal System (S)
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Im
po
rta
nt

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Crystal Structures of Interest

• Elemental Solids
– Face-centered cubic (fcc)
– Hexagonal close-packed (hcp)
– Body-centered cubic (bcc)
– Diamond cubic (dc)

• Binary compounds
– Fcc-based (Cu3Au,NaCl, ß-ZnS)
– Hcp-based (α-ZnS)
– Bcc-based (CsCl, Nb3Sn)

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14
Here: a2 =(r+r)2

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Loosely packed
 b-Body Centered Cubic (BCC)
■ BCC has two lattice points so BCC is a non-primitive cell.

■ BCC has eight nearest neighbors. Each atom is in contact

with its neighbors only along the body-diagonal directions.

■ Many metals (Fe,Li,Na..etc), including the alkalis and

several transition elements choose the BCC structure.
b c
Atomic Packing Factor of BCC
a

Here: a2 +a2 +a2=(r+2r+r)2 2 (0.433a)

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Closely packed
 c- Face Centered Cubic (FCC)
■ There are atoms at the corners of the unit cell and at the
center of each face.

■ Face centered cubic has 4 atoms so its non primitive

cell.

■ Many of common metals (Cu,Ni,Pb..etc) crystallize in

FCC structure.
Here: a2 +a2=(r+2r+r)2
Atomic Packing Factor of FCC

Closely packed

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 Unit cell contents
Counting the number of atoms within the unit cell

Atoms Shared Between:Each atom counts:

Corner (P) 8 cells 1/8
body centre(I) 1 cell 1
face centre(F) 2 cells 1/2
side centre(C) 2 cells 1/2

lattice type cell contents

P 1 [=8 x 1/8]
I 2 [=(8 x 1/8) + (1 x 1)]
F 4 [=(8 x 1/8) + (6 x 1/2)]
C 2 [=(8 x 1/8) + (2 x 1/2)]
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Example; Atomic Packing Factor
(already done)

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 Hexagonal Close-packed Structure
Bravais Lattice : Hexagonal Lattice
He, Be, Mg, Hf, Re (Group II elements) A A A
ABABAB Type of Stacking B B
A A A
B B
A A A

2 6

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The top layer contains seven atoms. Each corner shared by 6
surrounding hexagon cells and the centre atom is shared by 2
surrounding cells. The three atoms within the body of the cell fully
contributing to the cell.

Thus the total number of atoms in a unit cell is

2×(1/2+6×1/6)+3=6

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Calculation of c/a Ratio for an Ideal Hexagonal Close Packed Structure

In the right angle ΔABY,

Cos YAB =

In the right angle ΔAXZ

Y Since AZ=BZ=AB=a; XZ=c/2

X
B A

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Bottom layer of hcp structure

Volume of unit cell

Area of the base=six times area of
the ΔAOB
Area of ΔAOB = 1/2(BO)(AY)
= 1/2a×a√3/2
Thus area of the base is 3√3a2/2
VOLUME of the cell, V = 3√3a2c/2
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Calculation of packing factor of hcp:

Coordination number (for bottom center atom), N = 12

Lattice constant , a = 2r
Nearest neighbor distance, 2r = a
Number of atoms per unit cell, n = 6

Volume of all the atoms in a unit cell,

Volume of the unit cell

Therefore , APF=v/V=0.74

Hence closely packed structure. Same as fcc!

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DENSITY OF ATOMS IN
CRYSTALS

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Example: Calculation of theoretical density of NaCl.
For NaCl: The Unit Cell of NaCl is shown below:

Formula Unit in this case: NaCl, hence

Now, No. of formula units per unit cell: n’ = 4

Since No. of atoms of Na & Cl are 4 each in the unit cell, as
shown above (1 corner + 3 face centered = 4).

Thus,

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Numerical:
1. Zinc has hcp structure. The height of the unit cell is 0.494nm. The nearest
neighbor’s distance is 0.27nm. The atomic weight of the Zinc is 65.37. Calculate the
volume of the unit cell and density of Zn. Ans: V = 9.35×10-29m3
ρ = 6968 kg/m3

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 Crystal Planes:
■ Within a crystal lattice it is possible to identify sets of equally
spaced parallel planes. These are called lattice planes.

The set of
planes in b b
2D lattice.
a a

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Directions
In a Crystal there exist directions and planes which contain a large concentration of
atoms. It is necessary to locate these directions and planes for crystal analysis

The directions are described by the coordinates of the first whole numbered point
(x, y, z) . Generally , square brackets are used to indicate a direction.

OA[110]
OB[010]
OC[111]
OD[102]
OE[112]

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Planes and Miller Indices

Lattice planes→ How to designate these

planes in the crystals?

→ Miller evolved a method to designate a

set of parallel planes in a crystal by three
numbers (h k l) known as Miller indices

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 Miller Indices (h k l)
Miller Indices are a symbolic vector representation for the orientation of
an atomic plane in a crystal lattice and are defined as the reciprocals of
the fractional intercepts which the plane makes with the crystallographic
axes.

To determine Miller indices of a plane, take the following steps;

1) Determine the intercepts of the plane along each of the three

crystallographic directions

2) Take the reciprocals of the intercepts

3) If fractions result, multiply each by the denominator of the smallest

fraction

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 features of Miller Indices of crystals planes
(i) the parallel equidistant planes have same Miller indices ⇒
defines a set of parallel planes

(ii) A plane parallel to one of the coordinate axes has an intercept

of infinity.

(iii) If the Miller indices of two planes have the same ratio , i.e., (8
4 4) and (4 2 2) or (2 1 1), then the planes are parallel to each
other.

(iv) If (h k l ) are the miller indices of a plane, then the plane cuts
the axes into h, k and l equal segments respectively.

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Example

Axis X Y Z
Intercept
points 1/2 1 ∞
Reciprocals 1/(½) 1/ 1 1/ ∞
Smallest
(0,1,0 Ratio 2 1 0
(1/2, 0, )
0) Miller İndices (210)

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 Miller Indices
[2,3,3] Plane intercepts axes at
2
Reciprocal numbers are:

Indices of the plane (Miller): (2,3,3)

2
Indices of the direction: [2,3,3]
3

(200)
(111)
(110) (100)

(100) 35
Example-7

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 Indices of a Family or Form

■ Sometimes when the unit cell has rotational symmetry,

several nonparallel planes may be equivalent by virtue of this
symmetry, in which case it is convenient to lump all these
planes in the same Miller Indices, but with curly brackets.

Thus indices {h,k,l} represent all the planes equivalent to the

plane (hkl) through rotational symmetry.

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 Distribution Of Atoms In The Atomic Planes Of A
Simple Cubic Crystal
(i) (0 1 0 ) plane
Let ‘a’ be the lattice constant in millimeter and r be the
radius of the atom in millimeter. a2 sq. mm contains 1
atom
hence, 1sq. mm contains = 1/a2=1/4r2 atoms
(ii) (1 1 0 ) plane
Area of the plane = a*√2a = √2a2
the number of atom in this plane = 1
Atoms per sq. mm is 1/ √2a2= (1/ √2)(1/4r2)

(iii) ( 1 1 1) plane
Area of the plane = (a√2)*(a√(3/2)) = √3a2/2
and the number of atoms = (1/6)×3 =1/2
Atoms per sq. mm is

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 Separation between lattice planes in a cubic crystal
The cube edge is ‘a’. Let ( h k l ) be the Miller Indices of the plane A B
C.
Let ON=d1 be the ⊥ distance of the plane ABC from the origin.
Let α’, β’ and γ’ ( different from the interfacial angles) be the
angles between coordinates axes X, Y and Z respectively and ON.
The intercepts of the plane on the three axes are

From the figure we have

Using directional cosine relation

Substituting the values

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 Numerical
In a cubic crystal structure lattice constant ‘a’

1. Determine Interplanar spacing for planes (0 1 1), ( 0 0 1) ( 1 1 1)

2. Determine ‘d’ for (2 3 1) plane in terms of ‘a’

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 Interplanar spacing in SC, BCC and FCC
(i) Simple cubic

(ii) Body-centered cubic

(iii) Face centered cubic

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BCC

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FCC

d100 is a/2 on the assumption that d100 for cubic lattice is a

(d110)

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FCC

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 X-Ray Diffraction
X-rays→E.M.Waves→Interference and diffraction
X-rays→
λ ≈ 0.1nm, so that ordinary devices such as ruled diffraction gratings can not
produce observable effects with X-rays ( atomic spacing 2-4 Ao)
In 1912 , German Physicist “Laue” suggested that a crystal which consisted of 3D
array of regularly spaced atoms could serve the purpose of a grating .
Later on , Bragg (1913) gave the idea of Bragg’s planes and Law for diffraction
through crystal structure.
Bragg's Law
Glancing angle When x-rays are scattered from a crystal lattice, peaks of
scattered intensity are observed which correspond to the
following conditions:

1. The angle of incidence = angle of scattering.

2. The path length difference is equal to an integer
number of wavelengths.
The condition for maximum intensity contained in Bragg's law above allow us to calculate
details about the crystal structure, or if the crystal structure is known, to determine the
wavelength of the x-rays incident upon the crystal.

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 Bragg’s X-Ray Spectrometer

Where θ1, θ2, θ3 are

glancing angles for
n=1, 2, 3 respt.

Sin θ1 :Sin θ2 : Sin θ3 =1:2:3 Hence by measuring

the glancing angles at which reflection occur, we
can determine the interplanar spacing.
For NaCl Crystal
Make a plot between ionization current and incident angles.
• To study particular plane→keep position of crystal fix
• To compare d100, d110, d111→measure the values of θ1 ( first order
diffraction for different planes)
⇒ d ∝ 1/sin θ
Hence

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 For NaCl Crystal:

❑Powder crystal method:→ Crystal having powder form

❑Rotating crystal method:→ Single crystal having rotating holder

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