Crystal Structure Continued!

NOTE!!
Much of the discussion & many figures in what follows was constructed from lectures posted on the web by Prof. Be!ire GNL in Turkey. She has done an excellent job of covering many details of crystallography & she illustrates her topics with many very nice pictures of lattice structures. Her lectures on this are posted Here:
http://www1.gantep.edu.tr/~bgonul/dersnotlari/.

Her homepage is Here: http://www1.gantep.edu.tr/~bgonul/.

Crystal Lattices
Bravais Lattices
(BL)

Non-Bravais Lattices
(non-BL)

All atoms are the same kind

All lattice points are equivalent

Atoms are of different kinds. Some Some lattice points arent equivalent. lattice points are not equivalent. A combination of 2 or more BL

Atoms are of different kinds.

2 d examples

Lattice Translation Vectors In General

Mathematically, a lattice is defined by 3 vectors called

Primitive Lattice Vectors

a1, a2, a3 are 3d vectors which depend on the geometry. Once a1, a2, a3 are specified, the

Primitive Lattice Structure

is known. The infinite lattice is generated by translating through a

Direct Lattice Vector: T = n1a1 + n2a2 + n3a3

n1,n2,n3 are integers. T generates the lattice points. Each lattice point corresponds to a set of integers (n1,n2,n3).

2 Dimensional Lattice Translation Vectors

Consider a 2-dimensional lattice (figure). Let the

2 Dimensional Translation Vector be Rn = n1a + n2b

(Sorry for the notation change!!)

a & b are 2 d Primitive Lattice Vectors, n1, n2 are integers. Once a & b are specified by the lattice geometry & an origin is chosen, all symmetrically equivalent points in the lattice are determined by the translation vector Rn. That is, the lattice has translational symmetry. Note that the choice of Primitive Lattice vectors is not unique! So, one could equally well take vectors a & b' as primitive lattice vectors.

Point D(n1, n2) = (0,2) Point F(n1, n2) = (0,-1)

The Basis
(or basis set)

! The set of atoms which, when placed at each lattice point, generates the Crystal Structure.

Crystal Structure ! Primitive Lattice + Basis

Translate the basis through all possible lattice vectors

T = n1a1 + n2a2 + n3a3

to get the Crystal Structure or the

DIRECT LATTICE

 The periodic lattice symmetry is such that the

atomic arrangement looks the same from an arbitrary vector position r as when viewed from the point

r' = r + T

(1)

where T is the translation vector for the lattice:

T = n1a1 + n2a2 + n3a3

Mathematically, the lattice & the vectors a1,a2,a3 are

Primitive
if any 2 points r & r' always satisfy (1) with a suitable choice of integers n1,n2,n3.

 In 3 dimensions, no 2 of the 3 primitive lattice vectors a1,a2,a3 can be along the same line. But,

Dont think of a1,a2,a3 as a mutually orthogonal set!

Usually, they are neither mutually perpendicular nor all

the same length!

For examples, see Fig. 3a (2 dimensions):

The Primitive Lattice Vectors a1,a2,a3 arent necessarily a mutually orthogonal set!
Usually Usually, they are neither mutually perpendicular nor all

the same length!

Crystal Lattice Types

Bravais Lattice !
An infinite array of discrete points with an arrangement & orientation that appears exactly the same, from whichever of the points the array is viewed. A Bravais Lattice is invariant under a translation

T = n1a1 + n2a2 + n3a3

Nb film

Non-Bravais Lattices
In a Bravais Lattice, not only the atomic arrangement but also the orientations must appear exactly the same from every lattice point.
2 Dimensional Honeycomb Lattice
The red dots each have a neighbor to the immediate left. The blue dot has a neighbor to its right.

The red (& blue) sides are equivalent & have the same appearance. But, the red & blue dots are not equivalent.
If the blue side is rotated through 180 the lattice is invariant.

" The Honeycomb Lattice is NOT a Bravais Lattice!!

Honeycomb Lattice

It can be shown that, in 2 Dimensions, there are

Five

(5) & ONLY Five Bravais Lattices!

2-Dimensional Unit Cells Unit Cell !

The smallest component of the crystal (group of
atoms, ions or molecules), which, when stacked together with

pure translational repetition, reproduces the whole crystal.

b a
Unit Cell

S S S S S S S S S

2D-Crystal

S S S S S S

Unit Cell !
The smallest component of the crystal (group of atoms,
ions or molecules), which, when stacked together with pure

translational repetition, reproduces the whole crystal.

The choice of unit cell is not unique!

2D-Crystal

S S S

2-Dimensional Unit Cells

Artificial Example: NaCl

Lattice points are points with identical environments.

2-Dimensional Unit Cells: NaCl

The choice of origin is arbitrary - lattice points need not be atoms - but the unit cell size must always be the same.

2-Dimensional Unit Cells: NaCl

These are also unit cells it doesnt matter if the origin is at Na or Cl !

2-Dimensional Unit Cells: NaCl

These are also unit cells the origin does not have to be on an atom!

2-Dimensional Unit Cells: NaCl

These are NOT unit cells - empty space is not allowed!

2-Dimensional Unit Cells: NaCl

In 2 dimensions, these are unit cells in 3 dimensions, they would not be.

2-Dimensional Unit Cells

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

Example: 2 Dimensional, Periodic Art!

A Painting by Dutch Artist Maurits Cornelis Escher (1898-1972)

Escher was famous for his so called impossible structures, such as Ascending & Descending, Relativity, ..

Can you find the Unit Cell in this painting?

3-Dimensional Unit Cells

3-Dimensional Unit Cells

3 Common Unit Cells with Cubic Symmetry

Simple Cubic (SC)

Body Centered Cubic (BCC)

Face Centered Cubic (FCC)

Conventional & Primitive Unit Cells Unt Cell Types

Primitive
A single lattice point per cell
The smallest area in 2 dimensions, or The smallest volume in 3 dimensions

Conventional
(Non-primitive)
More than one lattice point per cell
Volume (area) = integer multiple of that for primitive cell

Simple Cubic (sc)

Conventional Cell = Primitive cell

Body Centered Cubic (bcc)

Conventional Cell " Primitive cell

Face Centered Cubic (FCC) Structure

Conventional Unit Cells

A Conventional Unit Cell just fills space when translated through a subset of Bravais lattice vectors. The conventional unit cell is larger than the primitive cell, but with the full symmetry of the Bravais lattice.
The size of the conventional cell is given by the lattice constant a.

FCC Bravais Lattice The full cube is the Conventional Unit Cell for the FCC Lattice

Conventional & Primitive Unit Cells Face Centered Cubic Lattice

Primitive Unit Cell
(Shaded)

Primitive Lattice Vectors

Lattice Constant

a1 = (!)a(0,1,0) a2 = (!)a(1,0,1) a3 = (!)a(1,1,0)

Note that the ais are

Conventional Unit Cell

(Full Cube)

NOT Mutually Orthogonal!

Elements That Form Solids with the FCC Structure

Body Centered Cubic (BCC) Structure

Conventional & Primitive Unit Cells Body Centered Cubic Lattice

Primitive Unit Cell

Primitive Lattice Vectors

a1 = (!)a(1,1,-1) a2 = (!)a(-1,1,1) a3 = (!)a(1,-1,1)

Note that the ais are
Lattice Constant Conventional Unit Cell
(Full Cube)

NOT mutually orthogonal!

Elements That Form Solids with the BCC Structure

Conventional & Primitive Unit Cells

Cubic Lattices Simple Cubic (SC)
Primitive Cell = Conventional Cell
Fractional coordinates of lattice points: 000, 100, 010, 001, 110,101, 011, 111

Body Centered Cubic (BCC)

Primitive Cell # Conventional Cell
Fractional coordinates of lattice points in conventional cell: 000,100, 010, 001, 110,101, 011 111, # # #

Primitive Cell = Rombohedron

Conventional & Primitive Unit Cells

Cubic Lattices

Face Centered Cubic (FCC)

Primitive Cell # Conventional Cell
Fractional coordinates of lattice points in conventional cell: 000,100, 010, 001, 110,101, 011,111, # # 0, # 0 #, 0 # # #1 # , 1 # # , # # 1

Simple Hexagonal Bravais Lattice

Conventional & Primitive Unit Cells

Points of Primitive Cell

Hexagonal Bravais Lattice

Primitive Cell = Conventional Cell Fractional coordinates of lattice points in conventional cell:

100, 010, 110, 101, 011 111, 000, 001

120 o

Hexagonal Close Packed (HCP) Structure:

(A Simple Hexagonal Bravais Lattice with a 2 Atom Basis)

The HCP lattice is not a Bravais lattice, because the orientation of the environment of a point varies from layer to layer along the c-axis.

General Unit Cell Discussion

For any lattice, the unit cell &, thus, the entire lattice, is UNIQUELY determined by 6 constants (figure):

a, b, c, $, % and &
which depend on lattice geometry. As well see, we sometimes want to calculate the number of atoms in a unit cell. To do this, imagine stacking

hard spheres centered at each lattice point & just touching each neighboring sphere. Then, for the cubic lattices, only 1/8 of each lattice point in a unit cell assigned to that cell. In the cubic lattice in the

figure, each unit cell is associated with (8) $ (1/8) = 1 lattice point.

Primitive Unit Cells & Primitive Lattice Vectors

In general, a Primitive Unit Cell is determined by the parallelepiped formed by the Primitive Vectors a1 ,a2, & a3 such that there is no cell of smaller volume that can be used as a building block for the crystal structure. As weve discussed, a Primitive Unit Cell can be repeated to fill space by periodic repetition of it through the translation vectors T = n1a1 + n2a2 + n3a3.

The Primitive Unit Cell volume can be found by vector manipulation:

V = a1(a2 $ a3)
For the cubic unit cell in the figure, V = a3

Primitive Unit Cells

Note that, by definition, the Primitive Unit Cell must

contain ONLY ONE lattice point.

of that choice.

There can be different choices for the Primitive Lattice Vectors, but the Primitive Cell volume must be independent

A 2 Dimensional Example!
P = Primitive Unit Cell NP = Non-Primitive Unit Cell