Crystal Structures

Lecture Outline
How do atoms arrange themselves to form solids?
Fundamental concepts and language Unit cells Crystal structures Close packed crystal structures Density computations Types of solids

Types of Solids
Crystalline material: atoms self-organize in a periodic array Single crystal :atoms are in a repeating or periodic array over the entire extent of the material Polycrystalline material: comprised of many small crystals or grains

Crystal structure
To discuss crystalline structures it is useful to consider atoms as being hard spheres with well-defined radii. In this hard-sphere model, the shortest distance between two like atoms is one diameter. We can also consider crystalline structure as a lattice of points at atom/sphere centers.

Lattices
A Lattice is defined as an array of equivalent points in one, two or three dimensions (normally three for inorganic materials). The environment of an atom placed on any one of these lattice points would be identical to that placed on any other lattice point. Therefore the lattice locates equivalent positions and shows the translational symmetry. The actual positions of atoms or molecules, however, is not provided.

Unit Cell
The unit cell is the smallest structural unit or building block that can describe the crystal structure. Repetition of the unit cell generates the entire crystal.

This image shows a line of equally spaced points as a one dimensional lattice

Unit Cell
Example:2D honeycomb net can be represented by translation of two adjacent atoms that form a unit cell for this 2D crystalline structure

Metallic Crystal Structures

Metals are usually polycrystalline; although formation of amorphous metals is possible by rapid cooling. Amorphous: lacks a systematic atomic arrangement.

Metallic Crystal Structures

Two Dimensional Lattice
Is it real? Is it right? The atomic bonding in metals is non-directional no restriction on numbers or positions of nearest-neighbor atoms large number of nearest neighbors and dense atomic packing.

The Two Dimensional Lattice

12 balls inside

12 balls inside

6R

6R

Ways to Pack Close-Packed Peaks Layers in 3D

A
A B C A B C A B C A B C A A C A A B C A A B C A B C A C A B C A A B C A B
Valleys Valleys

A B

A C

B
B

C
A B C A B C A A A

Layer I - A Layer II - B Layer III A or C ?!

Close Package
Layer I - A
A B C A B C A B C A B C A A C A A B C A A B C A B C A C A B C A A B C A B A B C A B C A A B C A A B A

Layer II - B Layer III - A !!! Layer III = Layer I !!!

ABABABABABAB

Close Package
Layer I - A
A B C A B C A B C A B C A A C A A B C A A B C A B C A C A B C A A B C A B A B C A B C A A B C A A B A

Layer II - B Layer III - C !!! Layer III = Layer I !!!

ABCABCABCABC

Holes
TWO different types of HOLES (INTERSTITIAL sites) are left OCTAHEDRAL (O) holes with 6 nearest sphere neighbours TETRAHEDRAL (T ) holes with 4 nearest sphere neighbours

Bravais Lattices

BCC Crystal Structure

Examples: Alkali metals (Li, Na, K, Rb), Cr, Mo, W, Mn, -Fe (< C), -Ti (> C). Body centered cubic (BCC) crystal structure. (a) A BCC unit cell with closely packed hard spheres representing the Fe atoms. (b) A reduced-sphere unit cell.

FCC Crystal Structure

a a a (b) a (c)

(a) The crystal structure of copper is Face Centered Cubic (FCC). The atoms are positioned at well defined sites arranged periodically and there is a long range order in the crystal. (b) An FCC unit cell with closed packed spheres. (c) Reduced sphere representation of the FCC unit cell. Examples: Ag, Al, Au, Ca, Cu, -Fe (> C), Ni, Pd, Pt, Rh

HCP Crystal Structure

Layer B Layer A Layer B Layer A Layer A Lay er A

(a)

(b)

(c)

(d)

The Hexagonal Close Packed (HCP) Crystal Structure. (a) The Hexagonal Close Packed (HCP) Structure. A collection of many Zn atoms. Color difference distinguishes layers (stacks). (b) The stacking sequence of closely packed layers is ABAB (c) A unit cell with reduced spheres (d) The smallest unit cell with reduced spheres.

Examples: Be, Mg, -Ti ( < 882 C ), Cr, Co, Zn, Zr, Cd

The Diamond Structure

C

a a

The diamond unit cell is cubic. The cell has eight atoms. Grey Sn (-Sn) and the elemental semiconductors Ge and Si have this crystal structure.

The Zinc Blende Cubic Crystal Structure

a
Zn

a a

The Zinc blende (ZnS) cubic crystal structure. Many important compound crystals have the zinc blende structure. Examples: AlAs, GaAs, GaP, GaSb, InAs, InP, InSb, ZnS, ZnTe.

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Unit Cell Characterization

Face-Centered Cubic Crystal Structure

The hard spheres or ion cores touch one another across a face diagonal the cube edge length, a=2R 2

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Unit Cell Characterization

FCC Crystal Structure
The coordination number, CN =the number of closest neighbors to which an atom is bonded =number of touching atoms, CN =12 Number of atoms per u nit cell, n =4 .(For an atom that is shared with m adjacent unit cells, we only count a fraction of the atom, 1/m). In FCC unit cell we have: 6 face atoms shared by two cells:6 x 1/2 =3 8 corner atoms shared by eight cells: 8 x 1/8 =1 Atomic packing factor, APF = fraction of volume occupied by hard spheres =(Sum of atomic volumes)/(Volume of cell)=0.74 (maximum possible)

Unit Cell Characterization

FCC Crystal Structure
Corner and face atoms in the unit cell are equivalent FCC crystal has APF of 0.74,the maximum packing for a system equal-sized spheres FCC is a close-packed structure FCC can be represented by a stack of close-packed planes (planes with highest density of atoms)

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Unit Cell Characterization

Body-Centered Cubic Crystal Structure
The hard spheres touch one another along cube diagonal the cube edge length, a=4R/ 3 The coordination number, CN =8 Number of atoms per unit cell, n =2 Center atom (1) shared by no other cells:1 x 1 =1 8 corner atoms shared by eight cells: 8 x 1/8 =1 Atomic packing factor, APF =0.68 Corner and center atoms are equivalent

Unit Cell Characterization

Hexagonal Close-Packed Crystal Structure
Two lattice parameters a and c. Ideal ratio c/a =1.633 The coordination number, CN =12 (same as in FCC) Number of atoms per unit cell, n =6. 3 mid-plane atoms shared by no other cells:3 x 1 =3 12 hexagonal corner atoms shared by 6 cells:12 x 1/6 =2 2 top/bottom plane center atoms shared by 2 cells:2 x 1/2 =1 Atomic packing factor, APF =0.74 (same as in FCC) All atoms are equivalent

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Unit Cell Characterization

Close-packed Structures (FCC and HCP)
Both FCC and HCP crystal structures have atomic packing factors of 0.74 (maximum possible value) Both FCC and HCP crystal structures may be generated by the stacking of close-packed planes The difference between t he two structures is in the stacking sequence HCP: ABABAB... FCC: ABCABCABC

Density Computations
= the density of the unit cell, n = atoms in the unit cell, Vc = the volume of the unit cell, Mass of an atom A/NA = M = Atomic weight, A, in amu (or g/mol) is given in the periodic table. Thus, the formula for the density is:

Atoms in the unit cell, n = 2 (BCC); 4 (FCC); 6 (HCP) NA =6.023 10 23 atoms/mol The volume of the cell, Vc =a3 (FCC and BCC) a =2R 2 (FCC); a =4R/ 3 (BCC) where R is the atomic radius

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Polymorphism and Allotropy

Some materials may exist in more than one crystal structure, this is called polymorphism. If the material is an elemental solid, it is called allotropy. An example of allotropy is carbon, which can exist as diamond, graphite, and amorphous carbon.

Polymorphism

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Fullerenes
Two kinds of fullerenes are shown here:

buckminsterfullerene (buckyball)

carbon nanotube

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