Introduction to Solids (PH2302/PAP232) Lecture 1

Cesare Soci () SPMS PAP 03-03 csoci@ntu.edu.sg http://www3.ntu.edu.sg/home/csoci/ August 14, 2013

Chapter 1. Crystal Structure

1.1 What is a crystal?
Motivations: importance of crystals Crystal external shape as key to structure Definitions: lattice, basis, translation vectors, primitive unit cells Bravais lattices in two-dimensions Lattice with a basis: the honeycomb net Non-ideal crystals: finite size and crystallographic defects

1.2 Fundamental Types of Lattices 1.3 Index Systems for Crystal Planes 1.4 Simple Crystal Structures

Crystalline vs. Amorphous Solids

Crystals (90% of solids!)
Long-range order and periodicity characteristic geometrical shape, sharp melting and boiling points Examples: minerals (quartz, calcite), sand, clay, metals, carbon (diamond, graphite), salts ( NaCl, KCl), sugar

Amorphous Solids
Atoms (molecules) are randomly arranged indefinite geometrical shape, isotropic physical properties, melt over a wide range of temperature Examples: glass, plastic, rubber

Crystalline SiO2 (quartz)

Amorphous SiO2 (glass)

Importance of Crystals: Enabling Science

The properties of the most important semiconductors depend on the crystalline structure of the host, essentially because electrons have short wavelength components that respond dramatically to the regular periodic atomic order of the specimen ---- Kittel Semiconductors (Si, Ge, GaAs) Materials for optics (Y3Al5O12)

Superconductors (YBa2Cu3O7)

2D

Low-dimensional materials (nanotechnology)

1D 0D
GaAs

PbSe

Crystalline Solids: Symmetry and Periodicity

Due to the large number of atoms involved, condensed matter systems are of enormous complexity, hence we need to rely on concepts like symmetry and periodicity to describe them quantitatively

Wiki: In ancient Greek, the word (krustallos), from (kruos), "icy cold, frost, originally referred to ice

http://www.its.caltech.edu/~atomic/snowcrystals/photos/photos.htm

A general definition: an ideal crystal is constructed by the infinite repetition (i.e. lattice) of identical structural units (i.e. basis)

Crystal External Shape: Faceting

In their macroscopic form, crystals display flat surfaces (faces or facets) intersecting at sharp angles; these facets develop spontaneously and naturally as the solid forms from a melt or from solution.

Naturally occurring crystals of iron pyrite

Small equilibrium crystals of gold at 1000 C, roughly 5 m in diameter

Equilibrium crystal of 4He at 0.8 K

Michael P. Marder, Condensed Matter Physics

Crystal External Shape: Cleavage Planes

When applying force in certain directions a crystal tends to break cleanly along cleavage planes. The new faces formed always correspond to the symmetry planes associated with a particular crystal type, and make constant angles with any other faces
Rocksalt crystal (Kittel)

Joseph Asscher cleaving the 3,107 carats (621.35 g) Cullinan diamond for King Edward VII of Britain in 1908

Crystal External Shape as Key to Structure

Ren Hay (17431822) is regarded as the father of the science of crystallography. He was the first to establish mathematical relationship between various forms of crystals

The first published picture of the structure of a crystal (Hay, "Trait De Minralogie" 1801)

Hauys Crystal Theory: Six Primary Forms and Three Integrant Molecules
By studying the cleavage of various crystals, Hay concluded that only six primary forms existed (in gray color).
Tetrahedron Parallelepiped Octahedron

Right Hexagonal Prism

Dodecahedron with isosceles triangular faces

Dodecahedron with rhombic faces

Through further mechanical or mathematical division, the six primary forms could be reduced to three basic geometries. They were called by Hay as integrant molecules (shown in blue color). The integrant molecules are the ultimate geometry units of a crystal, and reflect the particular system of symmetry to which the substance belongs. By adding layers of integrant molecules to primary forms, various secondary forms can be constructed following some rules he called the laws of decrements.

Tetrahedron

Triangular Prism

Parallelepiped

References J. G. Burke, Origins of the Science of Crystals, University of California Press, 1966 R. Jameson, A Treatise on the External, Chemical, and Physical Characters of Minerals, 1817

First Law of Decrement: Decrements on Edges (I)

Cube (primary form)

Dodecahedron with rhombic faces (secondary form)

By an orthogonal stacking of cube shaped integrant molecules one gets a crystal of cubic habit (its visible external shape), but by regularly omitting rows in the stacking process, other habits (like the octahedron, the dodecahedron, the pentagonal dodecahedron, etc.) emerge.

First Law of Decrement: Decrements on Edges (II)

A dodecahedron with pentagonal faces (pyritohedron) is constructed from a cubic nucleus by decrement of two rows of "integrant cubic molecules" for each newly added layer on two opposite edges combined with a decrement of only one row of molecules on every two successive layers on the other two edges. This combination occurs in three perpendicular directions.

Cube (primary form)

Dodecahedron with pentagonal faces (secondary form)

Wooden model illustrating Hay's laws of decrement on the edges. France, early 19th century (height 5.5 cm). www.mineralogy.eu

Second Law of Decrement: Decrements on Angles

The primary form in this example is a cube (red). By adding new layers (green) of integrant molecules on each face of the cube while subtracting integrant molecules from the angles of newly added layer, the secondary form, a regular octahedron, is constructed.

Cube (primary form) Octahedron (secondary form)

Wooden model illustrating Hay's laws of decrement on the edges and vertices. France, early 19th century (height 7 cm). www.mineralogy.eu

What is a Crystal?
a lattice with the structural unit or basis attached to each lattice point. Crystals can of course be three-dimensional (3D), but much can be conveyed in simple two-dimensional (2D) diagrams:

Space lattice

Basis

Crystal structure

The lattice points form a set of mathematical points such that the structure is the same as seen from each point. The basis is the structural unit that is repeated at every lattice point.

Basis of the Crystal Structure

Every basis in a given crystal is identical to every other in composition, arrangement, and orientation. A basis may comprise of single or multiple atoms:

Space lattice

Basis

Crystal structure

Examples: single atom for the simplest crystals like metals (copper - Cu, iron - Fe), or multiple atoms (or molecules) for crystals like sodium chloride (NaCl), gallium arsenide (GaAs), etc

Lattice Translation Vectors

For an ideal crystal (constructed by the infinite repetition of identical structural units, i.e. with no defects) we can describe a 3D lattice by 3 translation vectors a1, a2, a3 such that the arrangement of atoms in the crystal looks the same when viewed from the point R as when viewed from every point R:

R ' = R + n1a1 + n2a 2 + n3a3

Here n1, n2, and n3 are arbitrary integers (positive or negative, including zero)

a1
a2
'' a1

' 1

All pairs of vectors a1, a2 are translation vectors of the 2D lattice (net)

a'2
Notation: bold letter for vectors x x vector product of a and b: axb scalar product of a and b: a b=abcos

a''2

Primitive Translation Vectors

R ' = R + n1a1 + n2a2 + n3a3
n1, n2, and n3 are arbitrary integers The translation vectors a1 , a2 , a3 are said to be primitive if any two points of the lattice can be linked via the relation above (with a suitable choice of the integers ni). because we cannot form the lattice translation '' and a ''2 T from integral combinations of a 1 .
'' are not primitive translation vectors a1 and a'' 2

a1
a2
'' a1

' a1

a'2
Normally the primitive translation vectors are used to identify the crystal axes (although nonprimitive axes may also be chosen based on symmetry)

a''2

CQ1: Which pairs of vectors are primitive translation vectors for the oblique net?
(A)

(B) (C) (D)

(E) (F)

1. 2. 3. 4.

Only A and B A, B, C and D E and F All of them

Primitive Unit Cell

A primitive cell (or primitive unite cell) is a volume of space that, when translated through all the (primitive) vectors in a lattice, fills all the space without any overlapping.

Primitive cells are the building blocks of a crystal. There are many (infinite) possible ways to define the primitive translation vectors and the underlying primitive cell. A unit cell (or conventional unit cell) is a volume of space which fills all space without any overlapping when translated through some subset of the vectors of a lattice. It is generally bigger than the primitive cell and is chosen to reflect the symmetry of the crystal.

Some Properties of Primitive Cells

(i) a primitive cell is a minimum-volume cell with only one primitive lattice point per unit cell:

VC = a1 a 2 a3
(ii) a primitive cell contains precisely one lattice point; if n is the density of points in the lattice and v is the volume of the primitive cell, then nv=1. Therefore v=1/n is independent of the choice of the cell: Primitive cell (i.e. cell 1)

a1 1
a2
' a1

1.
I III II IV

Scell1 = a1 a2

2. Each lattice point shared by 4 cells: 4 X = 1 Non-primitive cell (i.e. cell 2)

1. 2.

' Scell2 = a1 a'2 = 2 Scell1

' 2

4X+2X=2

The basis associated with a primitive cell is called a primitive basis: (iii) no basis contains fewer atoms than a primitive basis

Wigner-Seitz Primitive Cell

The Wigner-Seitz cell about a lattice point is the region of space that is closer to that point than to any other lattice point. The Wigner-Seitz cell is a standard primitive cell with the full symmetry of the Bravais lattice. Construction procedure (valid also in 3D): 1. Draw lines to connect a given lattice point to all nearby lattice points (nearest neighbors) 2. At the midpoint and normal to these lines, draw new lines or planes. 3. The smallest volume enclosed in this way around the given lattice point is the Wigner-Seitz primitive cell.

The space is fully filled with adjacent Wigner-Seitz cell

Bravais Lattices
Definition 1 A (three dimensional) Bravais lattice (from Auguste Bravais ~1850) consists of all points with position vectors R of the form:

R ' = n1a1 + n2a 2 + n3a3

where ni are arbitrary integers and ai are primitive vectors (which are said to generate or span the lattice). Definition 2 A 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. Definitions 1 and 2 are equivalent: see Problem 8a, Chapter 4 of Ashcroft/Mermin Symmetry operations restrict the number of Bravais lattices to 5 in 2D and 14 in 3D

CQ2: Do the vertices of a two-dimensional honeycomb net form a Bravais lattice?

1. 2.

Yes No

CQ3: How many Bravais lattices there are in one-dimension?

1. 2. 3. 4. Zero One Two Infinite

Two-Dimensional Bravais Lattices

Oblique

Rectangular

Centered rectangular

Hexagonal

Square

Tiling of the Plane

Although everyone has seen and admired the huge variety of patterns on printed fabrics or wallpapers, few are aware that these are all based on one of five types of two-dimensional "unit cells" that form the basis for these infinitely-extendable patterns. One of the most remarkable uses of this principle is in the work of the Dutch artist M.Escher (1888-1972).

www.mcescher.com: picture gallery "Symmetry"

Lattice with a Basis

Most lattices occurring in nature are not Bravais lattices, but are lattices with a basis. They are constructing from Bravais lattices adding an identical assembly of particles at each lattice site, rather than a single rotationally invariant particle. An example is given by the honeycomb lattice, which is found for instance in graphene.

The honeycomb lattice of graphene Graphene flakes obtained by mechanical espholiation

The Honeycomb Net (1)

a1
a2

v1

v2

Hexagonal lattice Primitive vectors (in Cartesian coordinates):

3 a1 = a 2 3 a2 = a 2 1 2 1 2

Each lattice point decorated with basis particles at:

1 v1 = a 0 2 3 1 v2 = a 0 2 3

Because the upper and the lower particle in each cell do not have identical neighborhoods, the honeycomb lattice is a lattice with a basis, not a Bravais lattice

The Honeycomb Net (2)

Alternatively one could decorate an oblique Bravais lattice with two-point bases identically placed in the primitive cells

Non-ideal Crystals: Finite Size

diamond (C) crystal cut quartz (SiO2) crystal cluster

polycrystalline silicon (Si): domains/grain boundaries

graphite (C) powder

If the crystals are large enough, the vast majority of points are so far from the surface as to be unaffected by its existence, and the lattice structure still determines the physicochemical properties of the crystal

Crystallographic Defects
The world is largely constructed of solids whose crystalline order is defective, or absent altogether ---- Marder

Line defects Point defects

Edge dislocation Screw dislocation

Point defects are defects that occur only at or around a single lattice point. Example: doping in semiconductors

Dislocations are linear defects around which some of the atoms of the crystal lattice are misaligned

Planar defects
A stacking fault is a one or two layer interruption in the stacking sequence

Concept Map (Summary)

exhibits plane faces The external appearance of crystals reveals the symmetry properties of the mirror planes which can develop to varying extents to produce interfacial angles Miller indeces ordered lattice point described by one of the 14 Bravais lattices which belong to the one of the 7 crystal systems built up from repeated translations of the rotational axes

having reproducible described by

cleavage faces

such as

all having the same

various growth habits

unit cell

Stephen Lower: http://www.chem1.com/acad/webtext/states/crystals-ext.html