Crystalline Solid States: Geometry of Crystal Lattice

A crystal is formed by adding atoms in a constant environment, usually in a solution.

Natural quartz crystal grown in a slow geological process from a silicate solution in hot water under pressure

The original experimental evidence for the periodicity of the structure rests on the discovery by mineralogists that the index numbers that define the orientations of the faces of a crystal are exact integers. This evidence was supported by the discovery in 1912 of Xray diffraction by crystals. Crystalline materials have very different properties. Happy families are all alike; every unhappy family is unhappy in its own way.
Leo Tolstoy, Anna Karenina

Q: Why properties of crystalline materials are so different? A: Because they are mostly determined by the crystal symmetry.

We will start with description of crystal symmetry, and after that we will try to understand what is the reason behind this periodicity

An ideal crystal is constructed by the in finite repetition of identical groups of atoms . A group is called the basis. The set of mathematical points to which the basis is attached is called the lattice. Translational invariance: All the properties are invariant with respect to the translation

- translation vectors - integers

Lattice is defined by the minimal translation vectors, , called the primitive vectors

Bravais Lattices
The Bravais lattice is the basic building block from which all crystals can be constructed. The concept originated as a mathematical problem of finding the number of different ways to arrange points in space where each point would have an identical atmosphere.

All blue atoms are equivalent

All brown atoms are also equivalent. However, blue and brown sites are nor equivalent to each other.
In a Bravais lattice all lattice points are equivalent. Combining a blue and a brown atoms into a basis we come back to a Bravais lattice. Therefore the crystal structure is defined by the Bravais lattice and the basis: crystal structure = lattice + basis

Lattice: Main definitions

The unit cell is the smallest group of atoms, ions or molecules that, when repeated at regular intervals in three dimensions, will produce the lattice of a crystal system
A primitive unit cell is the unit cell with the smallest area which produces this coverage. In the two dimensional case the area of the unit cell is given by Primitive cell contains 1 lattice point

The choice of the primitive cell is not unique

Special choice: Wigner-Seits unit cell

Primitive versus non-primitive (conventional) unit cells

Non-primitive (conventional)

Primitive

Sometimes conventional cells better reflect symmetry.

In the second case the cell contains 2 atoms (basis)

Symmetry properties of the lattice

Inversion: A cell has an inversion center if there is a point at which the cell remains invariant under transformation r -> -r. All the Bravais lattices are inversion symmetric. Non-Bravais lattices may or may not have an inversion center depending on the symmetry of the basis. Reflection plane: A cell has a reflection plane if it remains invariant when a mirror reflection in this plane is performed.

Rotation axis: This is an axis such that, if the cell is rotated around the axis through some angle, the cell remains invariant. Improper rotation: the combination of a rotation and an inversion in a point on the axis 4-fold rotational axis

2D Bravais lattices

1D Bravais lattice: 1D Non- Bravais lattice:

2D Bravais lattices (5)

Only 2-fold rotational symmetry

- arbitrary
Oblique Square

Rectangular

Centered rectangular

Hexagonal

Five Bravais lattices in 2D and their symmetry elements

For non-Bravais lattices we have to take into account the symmetry of the basis which is referred as point-group symmetry. The point group symmetry includes all possible rotations, reflections and inversion, which leave the basis invariant.

Symmetry properties

Q: Can 5-fold symmetry axis exist?

Since b is the lattice vector,

5-fold symmetry cannot exist in a periodic manner

When Dan Shechtman entered the discovery awarded with the Nobel Prize in Chemistry 2011 into his notebook, he jotted down three question marks next to it.

The atoms in the crystal in front of him yielded a forbidden symmetry. It was just as impossible as a football a sphere made of only sixcornered polygons. Since then, mosaics with intriguing patterns and the golden ratio in mathematics and art have helped scientists to explain Shechtmans bewildering observation.
Dan Shechtmans diffraction pattern was tenfold: turning the picture a tenth of a full circle (36 degrees) results in the same pattern.

In this way Dan Shechtman has discovered Quasicrystals, which are quasi-periodic.

3D Bravais lattices
14 different Bravais crystal lattices which belong to 7 crystal systems Reflection:
The triclinic structure has no reflection plane, the monoclinic has one plane midway between and parallel to the basis plane, and so forth. The cubic cell has nine reflection planes: three parallel to the faces, and six other, each of which passes through two opposite edges.

Rotation: The triclinic structure has no axis of rotation (do not take into account 1-fold axis), The monoclinic has a 2-fold axis normal to the base. The cubic cell has three 4-fold axis normal to the faces and four 3-fold axis, each passing through two opposite corners.

Summary (from Kittels book)

Common crystal structures

Cubic lattices SC BCC BCC

(a) A plane of symmetry parallel to the faces of a cube. (b) A diagonal plane of symmetry in a cube. (c) The three tetrad axes of a cube. (d) The four triad axes of a cube. (e) The six diad axes of a cube.

Cubic lattices are most symmetric

Body-centered cubic (bcc) lattice

The packing ratio is 0.68, defined as the maximum volume which can be filled by touching hard spheres in atomic positions. Each atom has 8 nearest neighbors; the primitive cell is rhombohedron . The conventional unit cell is a cube based on vectors

It is twice big compared to the primitive unit cell and has two atoms in it with coordinates

The bcc lattice have alkali metals such as Na, Li, K, Rb, Cs, magnetic metals such as Cr and Fe, and refractory metals such as Nb, W, Mo ,Ta.

Face-centered cubic (fcc) lattice

The packing ratio is 0.74, the primitive cell is rhombohedron Each atom has 12 nearest neighbors.

The conventional unit cell is a cube based on vectors

It is 4 times bigger than the primitive unit cell and has 4 atoms in it with coordinates

The fcc lattice have noble metals such as Cu, Ag, Au, common metals such as Al, Pb, Ni and inert gas solids such as Ne, Ar, Kr, Xe.

Sodium chloride structure

We may construct the sodium chloride crystal structure by arranging Na+ and CI- ions alternately at the lattice points of a simple cubic lattice. In the crystal each ion is surrounded by six nearest neighbors of the opposite charge. The space lattice is fcc, and the basis has one CI- ion at 000 and one Na+ ion at 111. The figure shows one conventional cubic cell . The ionic diameters here are reduced in relation to the cell in order to clarify the spatial arrangement. The image on the right is closer to the realistic scale. There are four units of NaCI in each unit cube with atoms in the positions Cl Na 000 0 00 0 00 0 00

Representative crystals

Cesium chloride structure

There is one molecule per primitive cell, with atoms at the corners 000 and body-centered positions of the simple cubic space lattice. Each atom may be viewed as at the center of a cube of atoms of the opposite kind, so that the number of nearest neighbors or coordination number is eight. Comparison of CsCl with NaCl Representative crystals Crystal BeCu a, 2.70 Crystal LiHg a, 3.29

AlNi
CuZn (-brass) CuPd AgMg

2.88
2.94 2.99 3.28

NH4Cl
TlBr CsCl TlI

3.87
3.97 4.11 4.20

Hexagonal close packed (hcp) lattice

In the hexagonal system the primitive cell is a right prism based on a rhombus with an included angle of 120.

How to make a close-packed structure? A closed-packed structure is created by placing a layer of spheres B on top of identical close-packed layer of spheres A.

Column II: Be, Mg, Zn, and Cd. Several transition elements, such as Ti and Co

hcp

Maximal packing ratio 0.74

fcc

The number of nearest-neighbor atoms is 12 for both hcp and fcc structures. If the binding energy (or free energy) depended only on the number of nearest-neighbor bonds per atom, there would be no difference in energy between the fcc and hcp structures.

An ideal hcp structure has a3/a=1.633. One atom of the basis is at the origin, while the second one occupies the position (2/3,1/3,1/2)
Representative crystals Crystal He Be Mg Ti a3/a 1.633 1.581 1.623 1.586 Crystal Zn Cd Co Y a3/a 1.861 1.886 1.622 1.570 Crystal Zr Cd Lu a3/a 1.594 1.592 1.586

Diamond structure

Because the conventional unit cube of the fcc lattice contains 4 lattice points, it follows that the conventional unit cube of the diamond structure contains 2 X 4 = 8 atoms. There is no way to choose a primitive cell such that the basis of diamond contains only one atom. Diamond structure is adopted by solids with four symmetrically placed covalent bonds. This is the situation in silicon, germanium, and grey tin, as well as in diamond. Diamond has the translational symmetry of fcc lattice with a basis of two atoms, one at 000 and the other at . Diamond structure represents two inter-penetrating fcc sublattices displaced from each other by one quarter of the cube diagonal distance.

Cubic Zinc Sulfide structure

The diamond structure may be viewed as two fcc structures displaced from each other by one-quarter of a body diagonal. The cubic zinc sulfide (zinc blende) structure results when Zn atoms are placed on one fcc lattice and S atoms 011 the other fcc lattice, The conventional cell is a cube. The coordinates of the Zn atoms are 000; 0 ; 0 ; 0 ; the coordinates of the S atoms are ; ; ; . There are 4 molecules of ZnS per conventional cell. About each atom there are four equally distant atoms of the opposite kind arranged at the comers of a regular tetrahedron. The diamond structure allows a center-of-inversion symmetry operation at the midpoint of every line between nearest-neighbor atoms. The inversion operation carries an atom at r into an atom at r . The cubic ZnS structure does not have inversion symmetry. Crystal SiC ZnS AlP GaP a, 4.35 5.41 5.45 5.45 Crystal ZnSe GaAs AlAs InSb a, 5.65 5.65 5.66 6.46 The close equality of the lattice constants of several pairs, notably (AI, Ga)P and (AI, Ga)As, makes possible the construction of semiconductor heterojunctions

Index system for crystal directions

The direction is then specified by the three integers . If the numbers have a common factor, this factor is removed. For example, [111] is used rather than [222], or [100], rather than [400].

Opposite orientation is denoted by the negative sign over a number

When we speak about directions, we mean a whole set of parallel lines, which are equivalent due to transnational symmetry.

Index system for crystal planes

The orientation of a plane in a lattice is specified by Miller indices. We find intercept of the plane with the axes along the primitive translation vectors a1, a2 and a3. Lets these intercepts be x, y, and z. We can measure x, y, and z in units a1, a2 and a3.

Then we invert it (1/x 1/y 1/z) and reduce this set to a similar one having the smallest integers by multiplying by a common factor.
This set is called Miller indices of the plane (hkl).

Example:

The Miller indices specify not just one plane but an infinite set of equivalent planes.

Index system for crystal planes (2)

For cubic crystals the direction [hkl] is perpendicular to a plane (hkl) having the same indices, but this is not generally true for other crystal systems.

Please read Kittels book about Simple Crystal Structures and solve the problems.

Direct imaging of atomic structures

Scanning tunneling microscope

Quantum corrals
Gerd Binnig and Heinrich Rohrer (at IBM Zrich), the Nobel Prize in Physics in 1986. Donald M. Eigler (the Kavli Prize in Nonoscience 2010)

Non-ideal crystal structures

The ideal crystal of classical crystallographers is formed by the periodic repetition of identical units in space. But no general proof has been given that the ideal crystal is the state of minimum energy of identical atoms at the temperature of absolute zero. At finite temperatures this is likely not to be true. We will give several examples. Random Stacking The fcc and hcp structures are made up of close-packed planes of atoms. The structures differ in the stacking sequence of the planes, fcc having the sequence ABCABC ... and hcp having the sequence ABABAB ... . Structures are known in which the stacking sequence of close-packed planes is random . This is known as random stacking and may be thought of as crystalline in two dimensions and non-crystalline or glass-like in the third.

Polytypism is characterized by a stacking sequence with a long repeat unit along the stacking axis. The best known example is zinc sulfide, ZnS, in which more than 150 polytypes have been identified, with the longest periodicity being 360 layers.

Another example is silicon carbide, SiC, which occurs with more than 45 stacking sequences of the close-packed layers. The polytype of SiC known as 393R has a primitive cell with a = 3.079 and c = 989.6 . The longest primitive cell observed for SiC has a repeat distance of 594 layers. A given sequence is repeated many times with in a single crystal. The mechanism that induces such long-range crystallographic order is not a long-range force, but arises from spiral steps due to dislocations in the growth nucleus. Dislocations will be discussed later. Silicon carbide (SiC), also known as carborundum, is a compound of silicon and carbon with chemical formula SiC. It occurs in nature as the extremely rare mineral moissanite.

Silicon carbide powder has been mass-produced since 1893 for use as an abrasive. Grains of silicon carbide can be bonded together by sintering to form very hard ceramics which are widely used in applications requiring high endurance, such as car brakes, car clutches and ceramic plates in bulletproof vests. Electronic applications of silicon carbide as light emitting diodes (LEDs) and detectors in early radios were first demonstrated around 1907, and today SiC is widely used in hightemperature/high-voltage semiconductor electronics.

Reference material from Kittels book

Reference material from Kittels book

To take home

A lattice is an array of points related by the lattice translation operator where ui are integers and ai are the lattice vectors To form a crystal we attach to every lattice point an identical basis composed of s atoms at the positions

The vectors ai are primitive for the minimum cell volume for which the crystal can be constructed from a lattice translation operator T and a basis at every lattice point.