Crystal Structures of Interest

Elemental solids:
Face-centered cubic (fcc)
Hexagonal close-packed (hcp)
Body-centered cubic (bcc)
Diamond cubic (dc)

Binary compounds
Fcc-based (Cu3Au,NaCl, -ZnS)
Hcp-based (-ZnS)
Bcc-based (CsCl, Nb3Sn)

MSE 200A
Fall, 2008

J.W. Morris, Jr.

University of California, Berkeley

The Common Crystal Structures:

Body-Centered Cubic (BCC)

Atoms at the corners of a cube plus one atom in the center

Common in

MSE 200A
Fall, 2008

Is a Bravais lattice, but drawn with 2 atoms/cell to show

symmetry
Bcc is not ideally close-packed
Closest-packed direction: <111>
Closest-packed plane: {110}
Alkali metals (K, Na, Cs)
Transition metals (Fe, Cr, V, Mo, Nb, Ta)

J.W. Morris, Jr.

University of California, Berkeley

The Face-Centered Cubic (fcc) and

Hexagonal Close-Packed (hcp) Structures

Fcc: atoms at the corners of the cube and in the center of each face

Hcp: close-packed hexagonal planes stacked to fit one another

Is a Bravais lattice, but drawn with 4 atoms/cell to show symmetry

Found in natural and noble metals: Al, Cu, Ag, Au, Pt, Pb
Transition metals: Ni, Co, Pd, Ir

Does not have a primitive cell (two atoms in primitive lattice of hexagon)
Divalent solids: Be, Mg, Zn, Cd
Transition metals and rare earths: Ti, Zr, Co, Gd, Hf, Rh, Os
MSE 200A
Fall, 2008

J.W. Morris, Jr.

University of California, Berkeley

fcc and hcp from Stacking

Close-Packed Planes
A

A
B

A
B

B
C

B
C
A
A
BB
C
A
A

C
A
B
A

AB

ABA = hcp

A
B
C
C
A
A

A
B
B
C
A
A
A

There are two ways to stack spheres

The sequence ABA creates hcp
The sequence ABC creates fcc
MSE 200A
Fall, 2008

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ABC = fcc
J.W. Morris, Jr.
University of California, Berkeley

Hexagonal Close-Packed

MSE 200A
Fall, 2008

HCP does not have a primitive cell

Common in

Anisotropy limits engineering use of these elements

2 atoms in primitive cell of hexagonal lattice

6 atoms in cell drawn to show hexagonal symmetry
Divalent elements: Be, Mg, Zn, Cd
Transition metals and rare earths: Ti, Zr, Co, Gd, Hf, Rh, Os

J.W. Morris, Jr.

University of California, Berkeley

Face-Centered Cubic Structure

ABC stacking

Fcc cell

View along diagonal (<111>)

FCC is cubic stacking of close-packed planes ({111})

Common in

1 atom in primitive cell; 4 in cell with cubic symmetry

<110> is close-packed direction
Natural and noble metals: Cu, Ag, Au, Pt, Al, Pb
Transition metals: Ni, Co, Pd, Ir

MSE 200A
Fall, 2008

J.W. Morris, Jr.

University of California, Berkeley

Interstitial Sites:
Octahedral Voids in fcc

MSE 200A
Fall, 2008

Octahedral interstitial site is equidistant from six atoms

There are 4 octahedral voids per fcc cell

Octahedral void
Located at {1/2,1/2,1/2} and {1/2,0,0}
One per atom

J.W. Morris, Jr.

University of California, Berkeley

Interstitial Sites:
Tetrahedral Voids in FCC

Tetrahedral site is equidistant from four atoms

tetrahedral void
Located at {1/4,1/4,1/4} - center of cell octet

There are 8 tetrahedral voids per fcc cell

Two per atom
MSE 200A
Fall, 2008

J.W. Morris, Jr.

University of California, Berkeley

Interstitial Sites:
Voids between Close-packed Planes
A

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

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

In both FCC and HCP packing:

Stacking including voids:

Tetrahedral void above and below each atom (2 per atom)

Octahedral void in third site between planes
Fcc: ...(aAa)c(bBb)a(cCc)b(aAa)
Hcp: ...(aAa)c(bBb)c(aAa) (octahedral voids all on c-sites)
Size and shape of voids are the same in fcc and hcp

MSE 200A
Fall, 2008

J.W. Morris, Jr.

University of California, Berkeley

The Diamond Cubic Structure

Fcc plus atoms in 1/2 of tetrahedral voids

DC is the structure of the Group IV elements

Close-packed plane stacking is ...AaBbCc or ... aAbBcC...

- Each atom has four neighbors in tetrahedral coordination
- Natural configuration for covalent bonding
C, Si, Ge, Sn (grey)
Are all semiconductors or insulators

MSE 200A
Fall, 2008

J.W. Morris, Jr.

University of California, Berkeley

Solid Solutions and Compounds

Solid solution
Solute distributed through solid
- Substitutional: solutes on atom sites
- Interstitial: solutes in interstitial sites

- Ordinarily small solutes (C, N, O, )

Ordered solution (compound)

Two or more atoms in regular pattern
(AxBy)
Atoms may be substitutional or interstitial
on parent lattice
Compound does not imply
distinguishable molecules
MSE 200A
Fall, 2008

J.W. Morris, Jr.

University of California, Berkeley

Atomic Resolution Image of Gum Metal

Gum metal: Ti-23Nb-0.7Ta-2Zr-1.2O

MSE 200A
Fall, 2008

J.W. Morris, Jr.

University of California, Berkeley

Binary Compounds: Examples

Substitutional:
Bcc: CsCl
Fcc: Cu3Au

Interstitial:

MSE 200A
Fall, 2008

Fcc octahedral: NaCl

Fcc tetrahedral: -ZnS
Hcp tetrahedral: -ZnS
Bcc tetrahedral: Nb3Sn (A15)

J.W. Morris, Jr.

University of California, Berkeley

BCC Substitutional: CsCl

BCC parent

Stoichiometric formula AB
A-atoms on edges
B-atoms in centers
Either specie may be A

Found in:

Ionic solids (CsCl)

Small size difference
RB/RA > 0.732 to avoid like-ion
impingement

Intermetallic compounds
CuZn (-brass)
MSE 200A
Fall, 2008

J.W. Morris, Jr.

University of California, Berkeley

FCC Substitutional: Cu3Au

FCC parent
Stoichiometric formula A3B
B-atoms on edges
A-atoms on faces

Found in:
Intermetallic compounds (Cu3Au)
As sublattice in complex ionics
E.g., perovskites
BaTiO3 (ferroelectric)
YBa2Cu3O7 (superconductor)
Lattices of + and - ions must
interpenetrate since like ions cannot
be neighbors

MSE 200A
Fall, 2008

J.W. Morris, Jr.

University of California, Berkeley

FCC Octahedral Interstitial: NaCl

FCC parent

Stoichiometric formula AB
A-atoms on fcc sites
B-atoms in octahedral voids
Either can be A

Found in:

Ionic compounds:
NaCl, MgO (RB/RA ~ 0.5)
Perovskites (substitutional
ordering on both sites)

Metallic compounds
Carbonitrides (TiC, TiN, HfC)
MSE 200A
Fall, 2008

J.W. Morris, Jr.

University of California, Berkeley

FCC Tetrahedral Interstitial: -ZnS

Binary analogue of DC
Stoichiometric formula AB
A-atoms on fcc sites
B-atoms in 1/2 of tetrahedral voids
AaBbCc

Either element can be A

Found in:
Covalent compounds:
GaAs, InSb, -ZnS, BN

Ionic compounds:
AgCl
Large size difference (RB/RA < .414)
MSE 200A
Fall, 2008

J.W. Morris, Jr.

University of California, Berkeley

Hcp Tetrahedral Interstitial: -ZnS

Hexagonal analogue of -ZnS
Stoichiometric formula AB
A-atoms on hcp sites
B-atoms in 1/2 of tetrahedral voids
AaBbAaBb

Either element can be A

Found in:
Covalent compounds:
ZnO, CdS, -ZnS, Lonsdalite C

Ionic compounds:
Silver halides
Large size difference (RB/RA < .414)
MSE 200A
Fall, 2008

J.W. Morris, Jr.

University of California, Berkeley

Interstitial Sites:
Octahedral Voids in Bcc Crystals

Octahedral voids in face center and edge center

Octahedral voids in bcc are asymmetric

MSE 200A
Fall, 2008

Located at {1/2,1/2,0} and {1/2,0,0}

Each has a short axis parallel to cube edge (Ox, Oy, Oz)
Total of six octahedral voids, three of each orientation

J.W. Morris, Jr.

University of California, Berkeley

Interstitial Sites:
Tetrahedral Voids in Bcc Crystals

Tetrahedral voids in each quadrant of each face

Located at {1/2,1/4,0}
12/cell => 6/atom

MSE 200A
Fall, 2008

Tetrahedral voids in bcc are asymmetric

J.W. Morris, Jr.

University of California, Berkeley

Bcc Tetrahedral Interstitial: 15

Complex BCC derivative
Stoichiometric formula A3B
B-atoms on bcc sites
A-atoms in 1/2 of tetrahedral voids
Form chains in x, y, and z

Found in:
A15 compounds:
Nb3Sn, Nb3Al, Nb3Ge, V3Ga

These are the type-II

superconductors used for wire in
high-field magnets, etc.
MSE 200A
Fall, 2008

J.W. Morris, Jr.

University of California, Berkeley

Description of
Complex Crystal Structures
Most crystals can be referred to a close-packed frame
Fcc or hcp network
Possibly plus small distortions along symmetry axes
Cubic tetragonal (edge unique),
Cubic rhombohedral (diagonal unique)

Atoms in ordered configurations in

Substitutional sites
Interstital sites: octahedral or tetrahedral
Vacancies are useful as atoms to complete the configuration

MSE 200A
Fall, 2008

J.W. Morris, Jr.

University of California, Berkeley

Hierarchical Description of
Complex Crystal Structures

Construct planar layers

Identify ordered pattern

Order layers

Network (fcc or hcp)

Interstitial planes that contain atoms
Primary and interstitial planes
Pattern is the same on all planes
Including vacancies, if necessary, as species
Physical pattern (fcc or hcp)
Chemical pattern

composition may change from layer to layer (differentiation)

Stacking pattern is the same for network and interstitial layers

MSE 200A
Fall, 2008

J.W. Morris, Jr.

University of California, Berkeley

Substitutional X-Compounds
Undifferentiated

All atoms are the same: fcc, hcp, polytypes (e.g., ABCBABCBA)

Differentiated

Planes of atoms alternate: CuPt, WC

Note that cubic symmetry is broken in CuPt: rhombohedral
^
^

^
^

MSE 200A
Fall, 2008

= Cu

=W

= Pt

=C

J.W. Morris, Jr.

University of California, Berkeley

Octahedral Interstital X-Compounds

Undifferentiated

Differentiated

= Na

= As

= Cl

= Ni

Fcc or hcp planes alternate with filled octahedral planes: NaCl, NiAs
Note that o-sites in NiAs are ccc, can tell which atom is in octahedral hole
Alternate lattice or interstitial planes differ
CdI2: like NiAs but octahedral Cd planes alternate with vacant planes

MSE 200A
Fall, 2008

J.W. Morris, Jr.

University of California, Berkeley

Tetrahedral(I) X-compounds

= Zn

= Zn

=S

=S

Lattice planes plus alternate planes of tetrahedral voids

Examples:
Unary: diamond cubic, hexagonal diamond (Lonsdaleite)
Binary: -ZnS, -ZnS
MSE 200A
Fall, 2008

J.W. Morris, Jr.

University of California, Berkeley

Tetrahedral(II) X-Compounds

= Ca
=F

Lattice planes plus planes on both tetrahedral sites

Fcc-based: CaF2 (flourite) and Li2O
Hcp-based: none known
MSE 200A
Fall, 2008

J.W. Morris, Jr.

University of California, Berkeley