Solid State Physics (I)

Kuo Kan LIANG [email protected] 312 27823212#887 Yia-Chung CHANG and Chao-Cheng KAUN (in the order of lectures)

Textbooks
Main text: Fundamentals of Solid State Physics by J. Richard Christman (John Wiley & Sons, NY, 1988). Main reference: Introduction to Solid State Physics 8th ed. by Charles Kittel (Wiley, NY, 2004)

Grading
Presence: 10% Homework: 30% Three exams: 20% each
The range of the three exams will not overlap

Part 1 (Lectures by K.K.Liang)

Introduction Crystal lattices Crystal structures and reciprocal lattices X ray diffraction Crystal binding Elastic properties

Solid State Physics

Understanding the properties of solid materials in terms of their constituent particles: electrons and nuclei Developing tailored-made materials and devices for particular applications

Solid State Theory

Atoms molecules solids
Maxwells equation for EM fields Schrdinger equation for particles

Schrdinger equation particle wavefunctions (eigenvector) + other dynamical quantities (such as energy, the eigenvalue) various material properties External forces (perturbations) may be added into the SE to study the responses

Solid State Theory Takes Care of:

The structure of solids
Atomic equilibrium positions fixed structure of a solid Distinction from liquids and gases Classes of solids:
Crystalline Amorphous Polycrystalline

High symmetry makes crystals simpler to handle theoretically, as the SE need be solved only for points within a single pattern rather than throughout the crystal.

Solid State Theory Takes Care of:

Electrons
The electrons are usually separated into core electrons and outer electrons Outer electrons contribute the most to material properties:
Produce forces of attractions that hold atoms of the solid together In conjunction with ion cores, they produce restoring forces that are responsible for the vibratory motion of the atoms

Core electrons are responsible for short-range forces of repulsion between atoms and so prevent the collapse of solids. Transition elements with d and f subshells partially filled have to be considered on a case-by-case basis.

Solid State Theory Takes Care of:

Atomic vibrations
Collective oscillations normal modes Fixed allowed frequencies, determined by the equilibrium structure and strength of interactions between atoms (thus differ from solid to solid) Quantized normal mode energies phonons Number of phonons does not conserve Any deviations from regularity in pattern of atomic positions, or impurity, in a crystal Impurity in amorphous materials Defects influence nearly all properties of materials

Defects anomalies in the atomic structure

Properties of Solids
Mechanical
Mass density Cohesive energy Elastic properties (bulk modulus)

Thermal
Heat capacity (Cv, Cp) Thermal conductivity Contributions from phonons and electrons

Electrical
(electrical) conductivity Dielectric constant

Properties of Solids
Magnetic
Magnetic susceptibility (para, dia, ferro)

Optical
Reflectance Index of refraction absorption

Solid State Experiments

Scattering
X ray Electrons Neutrons

Hall effect Optical

Absorption Reflection

Magnetic resonance De Haas van Alphen effect

Crystal Lattice
Idealized description of the geometry of crystals Mathematical techniques for precise definition of the meaning of crystalline periodicity The description and use of crystalline symmetry Notation for specifying directions and planes in crystals

Crystalline Periodicity
In a crystalline material, the equilibrium positions of all the atoms form crystal Crystal = lattice + basis Lattice = 3D periodic array of points, unbounded in all directions

Bravais Lattice
Definition 1: Periodic structure form by infinite number of points in the space. The distribution of other points in space, observed from any of the points, is exactly the same. Definition 2: In a 3-D lattice, the position vector of one of the points can be written as the linear combination of three fundamental vectors with integral coefficients.

Lattice and Fundamental Vectors

The fundamental vectors are chosen nonuniquely to describe the lattice The fundamental vectors form the unit cell (*) If both the volume of the unit cell and the basis are chosen to be the smallest, they are primitive

Unit Cells
Unit cell: A volume which, through translation by all of the lattice vectors, can fill the space without overlapping between the replica. Primitive unit cell: unit cell with the smallest volume Unit cell can form from fundamental vectors, but it can also be constructed by other methods (e. g. Wigner-Seitz primitive cell). As long as the fundamental vectors are fixed, all the unit cells have the same volume (why?)

Crystal Symmetry Operations

Symmetry operations: Operations under which there is no change in the spatial distances and angles, and there is no distortion, compression or extension, and yet after application of the operation, there is still a lattice point where there were a lattice point and there is not a lattice point where there were no lattice point.
Translation Rotation Reflection Inversion

Crystal Symmetry
Any symmetry operation of a Bravais lattice = a translation + point group operators A collection of these operations forms a symmetry group of the Bravais lattice.

Frequently used symmetry op notations (Schnflies notations)

E : Identity i : Inversion Cn : n-fold axis (rotation over 2 / n) (h and v): reflection (horizontal or vertical w.r.t. Cn axis) Dn, Dnh, Dnd : Cn C2, Cnh C2, Sn C2 (C2 axis is perpendicular to the Cn axis) Sn = hCn

Classification of the Crystal Systems

c a b

Point group (only rotation or reflection) 7 crystal systems

Cubic (a = b = c, = = = 90) Tetragonal (a = b c, = = = 90) Orthorhombic (a b c, = = = 90) Monoclinic (a b c, = = 90 ) Triclinic (a b c, = 90) Trigonal (a = b = c, = = < 120 90) Hexagonal (a = b c, = = 90, = 120)

Bravais Lattices
Space group (point group + translation)
Considering the addition of lattice points by certain centering conditions Check if it is still a lattice Check if it is a new lattice

14 Bravais lattices:
P (primitive) (6) : 7 lattice systems, but primitive trigonal = primitive hexagonal I (3) : Body-centered, cubic, tetragonal, orthorhombic F (2) : Face-centered, cubic, orthorhombic A, B, or C (2) : One-side-centered, monoclinic-B, orthorhombic-C R (1) : Special-centering, trigonal-R

Alternative grouping
Cubic (3) : simple cubic, body-centered cubic, face-centered cubic Tetragonal (2) : simple, body-centered Orthorhombic (4) : simple, base-centered, face-centered, body-centered Monoclinic (2) : simple, base-centered One for triclinic, trigonal and hexagonal each. (simple)

14 Bravais Cells

Crystal
Lattice + Basis
32 point groups 230 space groups

Lattice Planes
Lattice plane: a plane passing three non-colinear points Description of lattice plane
Choose the lattice origin (not on the plane considered) and lattice vectors a1, a2 and a3 (primitive if possible, otherwise conventional) The plane intersects the crystal axes at 3 points: x1a1, x2a2, x3a3. x1, x2, and x3 are integers if the lattice vectors are primitive. Take the inverse of x1, x2 and x3 (H=1/x1, K=1/x2, L=1/x3) and multiply by the LCM of x1, x2 and x3 ( h, k, l ) ( h, k, l ) = Miller indices of the plane

Properties of Miller Indices

( h, k, l ) may denote not only one but a set of parallel planes { h, k, l } = the set of planes equivalent to ( h, k, l ). For example, { 1 0 0 } in cubic system = ( 1 0 0 ) + ( 0 1 0 ) + ( 0 0 1 ) + ( -1 0 0 ) + ( 0 -1 0 ) + ( 0 0 -1 ) (200)=(100)? [ h k l ] denotes a direction ( ha1 + ka2 + la3 ). In cubic system [ h k l ] ( h k l )

Inter-Planar Distance
The distance d between adjacent planes with the same Miller indices ( h k l ) is given by

d=

where t is the volume of the primitive unit cell and

g = hb c + kc a + la b

Some more terms

Coordination number: number of nearest neighboring lattice points
sc : 6 bcc : 8 fcc : 12

Conventional unit cell

Cubic systems : sc, bcc, fcc The length of the sides of the underlying sc is chosen as the lattice constant. The fundamental vectors of the underlying sc are chosen as the fundamental vectors

Examples of Crystal Structures

Body-centered cubic (bcc)
Conventional lattice fundamental vectors: a1 = a ( 1, 0, 0 ); a2 = a ( 0, 1, 0 ); a3 = a ( 0, 0, 1 ) 2 atoms per unit cell (bases at ( 0, 0, 0 ) and a ( 1, 1, 1 ) / 2) Bravais lattice vectors (primitive, coord# = 8): a1 = a ( -1, 1, 0 ) / 2; a2 = a ( 1, -1, 1 ) / 2; a3 = a ( 1, 1, -1 ) / 2 The usually seen bcc crystals are all metals:
Ba, Cr, Cs, Fe, K, Li, Mo,

Examples of Crystal Structures

Face-centered cubic (fcc)
Conventional lattice fundamental vectors: 4 atoms per unit cell (bases at ( 0, 0, 0 ), a ( 0, 1, 1 ) / 2, a ( 1, 0, 1 ) / 2 and a ( 1, 1, 0 ) / 2) Bravais lattice vectors (primitive, coord# = 12): a1 = a ( 0, 1, 1 ) / 2; a2 = a ( 1, 0, 1 ) / 2; a3 = a ( 1, 1, 0)/2 All kinds of materials including noble gases may form fcc crystal because the larger the coord# the more stable the structure:
Ca, Ce, Ag, Al, Au, Cu, Ni, Pb, Pt, and Ar, Ne, Xe, Kr at low temperature,

Examples of Crystal Structures

Diamond structure (not a Barvais lattice)
fcc lattice with a 2-point basis at ( 0, 0, 0 ) and a ( 1, 1, 1)/4 Primitive: 2 atoms / unit cell Conventional: 8 atoms / unit cell Coordination # = 4 Next-nearest neighbors (nnn) = 12 Few neighbors, but since it is suitable for covalent bonding, it is stiff. Usually semiconductors (valence 4 materials):
C (diamond), Si, Ge, -Sn,

Diamond structure

2-D Closest-Packed Structures

FCC Closest-Packed Structure

Plane stacking order: ABCABC stacking

FCC Closest-Packed Structure

Plane stacking order: ABAB stacking

Ideally a

c 8 = a 3

Points of Symmetry in BZ (SC)

Most commonly used: M: center of an edge R: corner point X: center of a face

SC

Points of Symmetry in BZ (FCC)

Most commonly used: K: middle of an edge joining two hexagonal faces L: center of a hexagonal face U: middle of an edge joining a hexagonal and a square face W: corner point X: center of a square face

FCC

Points of Symmetry in BZ (BCC)

Most commonly used: H: corner point joining four edges N: center of a face P: corner point joining three edges

BCC

Points of Symmetry in BZ (HCP)

Most commonly used: A: center of a hexagonal face H: corner point K: middle of an edge joining two rectangular faces L: middle of an edge joining a hexagonal and a rectangular face M: center of a rectangular face

HEX

Braggs formulation

Assumptions: Static ions (atoms) Elastic scattering ( = ) Specular reflection from a crystal plane ( = )

Laues formulation
r k r k r k

r R

r k

r R

r k

r R

r k

Assumptions: Static ions (atoms) Elastic scattering Each ion reflects the incident wave into all directions

Ewald Construction
r Draw the incident wave vector k , it starts from
a reciprocal lattice point O. r Draw a sphere with radius k and centered at r the other end of k . If there is a reciprocal lattice point on the sphere, then the vector connecting this point to the center of the sphere ris the allowed diffraction wave vector k .

Ewald Construction (Fig.)

Experiment: Laue Method

Single crystal Fixed direction of k but with continuous values of k (from k0 to k1) Used for determination of the orientation of a single crystal with known structure

Experiment: Rotating-Crystal Method

Monochromic wave (fixed magnitude of k) A single crystal rotating about a fixed axis Used for crystal structure determination

Experiment: Powder (DebyeScherrer) Method

Fixed magnitude of k Powdered sample (or a polycrystalline sample) continuous crystal orientation; otherwise the same as the rotatingcrystal method With different diffraction rings, DSM measures all the size of K which are shorter than 2k