H. S. Leipner, R.

Krause-Rehberg

Structure of imperfect materials

hartmut.leipner@cmat.uni-halle.de reinhard.krause-rehberg@physik.uni-halle.de www.cmat.uni-halle.de/~hsl/Curriculum.html

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Summary

The presence of nanosize structures (lattice imperfections) as perturbations of the ideal lattice periodicity determines essential physical properties of crystals. A survey is given on zero to three dimensional crystal defects: Point defects, dislocations, stacking faults, grain boundaries, and precipitates. Basic features of these defects are treated in conjunction with phenomena like material transport in the lattice, growth of crystals, and plasticity.

hsl 2011 Structure of imperfect materials 1. Introduction

Literature

Bergmann Schfer Lehrbuch der Experimentalphysik. Band 6 Festkrper. Hrg. W. Raith. Berlin: De Gruyter 1992. J. Bohm: Realstruktur von Kristallen. Stuttgart: Schweizerbartsche Verlagsbuchhandlung 1995. D. B. Holt, B. G. Yacobi: Extended defects in semiconductors. Cambridge University Press 2007. D. Hull, D. J. Bacon: Introduction to dislocations. Oxford: Pergamon 31994. P. Haasen: Physikalische Metallkunde. Berlin: Akademieverlag 1985. J. P. Hirth, J. Lothe: Theory of dislocations. New York: Wiley 1982. Identication of defects in semiconductors. Ed. M. Stavola. San Diego: Academic Press 1998. Silicon devices. Ed. K. A Jackson. Weinheim: Wiley-VCH 1998. F. Vollertsen, S. Vogler: Werkstoffeigenschaften und Mikrostruktur. Mnchen: Hanser 1989. Electronic properties of semiconductors. Materials Science and technology, vol. 4. Ed. W. Schrter. Weinheim: VCH 1991.

hsl 2011 Structure of imperfect materials 1. Introduction

Syllabus
1. Introduc<on: Crystal structures 2. Structure of point defects * 3. Defect chemistry * 4. Diusion * 5. Basic proper<es of disloca<ons 6. Elas<c theory of disloca<ons 7. Core structure of disloca<ons 9. Disloca<on mo<on 10. Plas<c deforma<on 11. Two-dimensional defects 13. Three-dimensional defects *
(* given by Reinhard Krause-Rehberg)
hsl 2011 Structure of imperfect materials 1. Introduction

H. S. Leipner: Structure of imperfect materials

1. Introduction: Crystal structures

Atomic bonding Lattices Atom packing Interstitial sites Coordinate systems Real structure of crystals: Defect classication

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1.1 Bonding types

Classication of solids based on geometrical symmetry: Crystal structures (later) Here: less rigorous classication scheme based on the conguration of valence electrons Distinction based on electron distribution in k space

Insulators

Metals

Ne

Na
[Hartree, Hartree 1948/Ashcroft, Mermin 2001]

Radial wave functions calculated for neon and sodium

hsl 2011 Structure of imperfect materials 1. Introduction

Classication of solids

18+ 18

18+ 18

18+ 18

18+ 18

17+ 18

19+ 18

17+ 18

19+ 18

18+ 18

18+ 18

18+ 18

18+ 18

19+ 18

17+ 18

19+ 18

17+ 18

van der Waals

ionic

6+

6+

6+

6+

19+

19+

19+

19+

6+

6+

6+

6+

19+

19+

19+

19+

covalent
Scheme of the electronic charge distribution in the basic solid types
hsl 2011 Structure of imperfect materials 1. Introduction

metallic

Mixed bonding
Ge4+ Ge4+ Ga3+ As5+

Ge
Ge4+ Ge4+ As5+ Ga3+

GaAs

Ca2+

Se6+

K+

Cl7+

CaSe
Se6+ Ca2+ Cl7+ K+

KCl

Continuity from perfect covalent to perfect ionic crystals

hsl 2011 Structure of imperfect materials 1. Introduction

1.2 Structure of condensed matter

If we want to understand the properties of solids, we must have a basic understanding of

the forces keeping the solid together, the structural order.

Key element in the description of condensed matter are the crystals. Name crystal originating from crystallus, lat. quartz Crystallography as the science describing the structure, the properties, and the genesis of crystals
[Physik:00]

hsl 2010 Structure of imperfect materials I. Introduction

The geometry of the ideal crystal

Regular arrangement of atoms Mathema1cal descrip1on as a la#ce of equivalent points Descrip1on as transla1on opera1on in the 3-dimensional space, la#ce vector: T = n1a + n2b + n3c

a, b, c fundamental la=ce transla1on vectors, ni integer (i = 1, 2, 3), , , angles between them

hsl 2010 Structure of imperfect materials I. Introduction

Crystal lattices
Long-range order, innite periodic arrangement of atoms (ideal crystal) Translation symmetry: Physical property f(r) = f(r + T) Crystal structure: Lattice + atomic basis (motif) 7 crystal systems

Different choices of a primitive unit cell in the Bravais lattice

[Weimantel, Haman 1989]
hsl 2011 Structure of imperfect materials 1. Introduction

Honeycomb net as a Bravais lattice with a two-point basis

[Ashcroft, Mermin 2001]

Crystal systems

Crystal axes abc abc abc a=bc a=bc a=b=c a=b=c

Angle 90 = = 90, 90 = = = 90 = = = 90 = = 90, = 120 = = 90 = = = 90

Crystal system triclinic monoclinic orthorhombic tetragonal hexagonal rhombohedral (trigonal) cubic

hsl 2011 Structure of imperfect materials 1. Introduction

Bravais lattices

P triclinic

P monoclinic

C orthorhombic

P tetragonal

P hexagonal trigonal

14 (non-primitive) Bravais lattices (translation lattices)

P cubic I F

[Luger 1992]

hsl 2011 Structure of imperfect materials 1. Introduction

Symmetry elements

Combination of rotation axes

Coverage of a plane with heptagons

[Weimantel, Haman 1989]

hsl 2011 Structure of imperfect materials 1. Introduction

Symmetry Crystallographic point groups

Symmetry elements

Schoeniess notation

Reec<on m, 1/m Inversion Rota<on (a Bravais laVce can contain only 2-, 3-, 4-, or 6-fold axes) Rota<oninversion

Taking transla<on into account: Screw axis 21, 31, 32, 41, 42, 43, 61, 62, 63, 64, 65 Glide plane Combina<on of symmetry elements: Abelian group 32 crystallographic point groups 230 space groups
hsl 2011 Structure of imperfect materials 1. Introduction

Cn n-fold rota<on axis Cnv addi<onal ver<cal mirror plane (|| axis) Cnh addi<onal horizontal mirror ( axis) Sn n-fold rota<oninversion axis Dn n two-fold axes n-fold main axis Dnh addi<onal horizontal mirror ( n-fold axis) Dnd addi<onal mirrors containing the n-fold axis and bisec<ng the angles between the 2-fold axes T 4 3- and 3 2-fold axes as in the tetrahedron (Td, Th) O 4 3- and 3 4-fold axes as in the octahedron Ci inversion center Cs symmetry plane

Crystal classes examples

Crystal system
Short symbol
Cubic 23 m3 432 m3m Rhombohedral 32 6/mmm Tetragonal Orthorhombic Monoclinic 4/mmm mmm 2/m HM symbol
23 432 m3m 32 6/m2/m2/m 4/m2/m2/m 2/m2/m2/m 2/m S symbol
T Th O Td Oh D3 D3d D3h D4h D2h C2h Substances NaClO3 FeS2 (pyrite) Mn ZnS, GaAs Si, MgO, NaCl Se, Te, SiO2 As, Al2O3 Mg, Li, Ti TiO2 (rutile) P (black), Br CaSO4.H2O (gypsum)

hsl 2011 Structure of imperfect materials 1. Introduction

Ideal crystal
Ideal crystal: innite, can be described with the innite lattice; no perturbations of periodicity Perfect crystal: ideal perfection is only perturbed by thermal vibrations Real crystal: a number of defects is present in the crystal; nite dimensions crystals have a surface Due to the periodicity, there is a long-range order in crystals, in contrast to amorphous materials with a short-range order

Long-range order in a crystal vs. the short-range order in a liquid

hsl 2011 Structure of imperfect materials 1. Introduction
Long-range order [Weimantel:89]

Polycrystals

Color-etched gray pig iron

[Leica]

Arrangement of grains in a polycrystal. Within each grain the atoms are in the same order. [Turton:2000]

hsl 2011 Structure of imperfect materials 1. Introduction

Crystal structure
Crystal structure: lattice + atomic basis (motif) A set of j atoms (j 1) is attributed to each lattice point Position of atoms j given with respect to a lattice point rj = xja + yjb + zjc

hsl 2011 Structure of imperfect materials 1. Introduction

Unit cell

For a lattice, different basic sets of fundamental vectors can be chosen. The shortest vectors are the primitive lattice vectors, forming the primitive unit cell. Characteristic feature of the primitive cell: contains one lattice point Sometimes, the choice of a non-primitive, conventional unit cell reects better the symmetry of the lattice.

Different primitive unit cells and a conventional unit cell containing 2 lattice points

hsl 2011 Structure of imperfect materials 1. Introduction

1.3 Particular lattices and structures

The cubic lattice
simple cubic (sc), face-centered cubic (fcc), body-centered cubic (bcc)

sc

fcc

bcc

hsl 2011 Structure of imperfect materials 1. Introduction

Conventional fcc and primitive unit cell

z

c a a y x b

The primitive unit cell of the fcc lattice is a rhombohedron. The primitive lattice translation vectors enclose angles of 60 and are obtained as a a = (i + j) 2 a b = ( j + k) 2 a c = ( k + i) 2

hsl 2011 Structure of imperfect materials 1. Introduction

Closed-packed structures

Atoms with closed shells regarded as hard spheres Minimizing the energy means the effective arrangement of the spheres. Highest packing density achieved in the fcc structure (74 %) Two-dimensional dense arrangement of spheres

hsl 2011 Structure of imperfect materials 1. Introduction

Stacking of spheres

A B

A B C A B C A

A B C A B C A B B C A A

A B C A B C A B C A

A C A B C A C A

A B

A C A

Extension of hexagonal stacking of spheres in three dimensions. The stacking positions are labeled A, B, and C.

hsl 2011 Structure of imperfect materials 1. Introduction

Closed packing in the fcc structure

Closed packed atomic plane in the fcc structure

hsl 2011 Structure of imperfect materials 1. Introduction

Closed packing [Turton::00]

Cesium chloride structure

In the simple cubic lattice, each lattice point has a basis of one Cs atom at 000 and a Cl atom at 1/2a 1/2a 1/2a.

hsl 2011 Structure of imperfect materials 1. Introduction

NaCl structure
fcc Bravais lattice with a basis of 1 Na+ at 000, 1 Cl at 1/2a 1/2a 1/2a

Conventional unit cell of NaCl. The sodium ions are smaller than the chlorine ions. The ionic radii are made smaller in order to visualize the spatial arrangement of the ions. Every ion has 6 NN of the other kind.

hsl 2011 Structure of imperfect materials 1. Introduction

Diamond structure

fcc Bravais lattice Two identical atoms at 000 and 1/4a 1/4a 1/4a forming the basis Tetrahedral bonding structure Each atom with 4 NN Packing density 34 % C, Si, Ge, Sn

hsl 2011 Structure of imperfect materials 1. Introduction

Zinc blende structure

cf. diamond structure Two dierent atoms at 000 and 1/4a 1/4a 1/4a forming the basis

Tetrahedral bonding structure No inversion center exists. GaAs, CdTe, AgI

hsl 2010 Structure of imperfect materials I. Introduction

1.4 Interstitial sites

Tetrahedral interstices in the facecentered cubic structure

[Russ 1995]

hsl 2011 Structure of imperfect materials 1. Introduction

Octahedral interstices in the facecentered cubic structure

[Russ 1995]

hsl 2011 Structure of imperfect materials 1. Introduction

Ratio of radii for different interstitialcies

fcc

Octahedral interstices

Tetrahedral interstices

Trigonal interstices

Roct/R = 0.414 Rtetr/R = 0.225 Rtri/R = 0.155

sc

Hexagonal interstices

Quadratic interstices

Rhex/R = 0.732 Rquad/R = 0.414

bcc 6-fold coordinated interstices

R6/R = 0.154

4-fold coordinated interstices

R4/R = 0.291

hsl 2011 Structure of imperfect materials 1. Introduction

1.5 Crystallographic labeling

Description of positions, directions, faces in relation to the latticerelated coordinate system (in general a non-orthogonal system) Lattice vector R = n1a + n2b + n3c Lattice points: given as numbers n1, n2, n3 Directions in the lattice: given as the smallest integer numbers of the lattice vector as [uvw] Direction of the crystal axes: a [100] , b [010], c [001]

] , b [010 ] , c [001 ] Negative direction of the axes: a [100

The whole set of equivalent directions is labeled uvw, e. g. 100 .

hsl 2011 Structure of imperfect materials 1. Introduction

1.5 Crystallographic indexing

Labeling of crystallographic planes 1. Determine the intersections with the axes as fractions of the unit distances. 2. Take the reciprocals of these numbers. 3. Reduce to the smallest integers having the same ratio. 4. The result is given as the Miller indices as (hkl). Example 1. 0A/0A = 2, 0B/0B = 3, 0C/0C = 3 2. 1/2, 1/3, 1/3 3. 3, 2, 2 4. Plane (322)

[Hull, Bacon 1994]

hsl 2011 Structure of imperfect materials 1. Introduction

Planes in a cubic lattice

Different crystallographic planes in a cubic lattice with different distances

hsl 2011 Structure of imperfect materials 1. Introduction

hkl [Weimantel:89]

Crystallographic planes

(hkl) indicates a plane or a set of parallel planes. {hkl} signifies a form, i. e. those planes which are equivalent in the crystal. The faces of the cube are the {100} planes: ), (010 ), (100 ) (001), (010), (100), (001

(100)

(110)

(111)

hsl 2011 Structure of imperfect materials 1. Introduction

1.6 Classication of lattice defects

Ideal crystal Innite dimensions, atoms in rest, chemically pure Zero-dimensional defects Intrinsic/native point defects Impurity atoms

Perfect crystal The only perturbation of periodicity: thermal vibrations One-dimensional defects (Electronic excitations, quasi-particles, Dislocations such as excitons, plasmons, etc.) Disclinations (Internal elds and strain) Two-dimensional defects Imperfect crystal Stacking faults Surface Antiphase boundaries Contains zero- to three-dimensional defects Grain boundaries, twin boundaries Domain walls Three-dimensional defects Precipitates Agglomerates of point defects Inclusions
hsl 2011 Structure of imperfect materials 1. Introduction

References

N. W. Ashcro`, N. D. Mermin: Solid State Physics. Philadelphia: Saunders College 1988. C. Weimantel, C. Hamann: Grundlagen der Festkrperphysik. Berlin: Deutscher Verlag der Wissenscha`en 1989. J. C. Russ: Materials Science. Pacic Grove: PWS 1996. D. Hull, D. J. Bacon: Introduc<on to Disloca<ons. Oxford: Pergamon Press 1992.

hsl 2011 Structure of imperfect materials 1. Introduction