Monday, 4 January 2010

3-D Crystal Lattice

Simple lattices and their unit cells

Simple Cubic (SC) - There is one host atom ("lattice point") at each corner of a cubic unit cell. The unit cell is described by three edge lengths a = b = c = 2r (r is the host atom radius), and the angles between the edges, alpha = beta = gamma = 90 degrees. There is one atom wholly inside the cube (Z = 1). Unit cells in which there are host atoms (or lattice points) only at the eight corners are called primitive.

Body Centered Cubic (BCC) - There is one host atom at each corner of the cubic unit cell and one atom in the cell center. Each atom touches eight other host atoms along the body diagonal of the cube (a = 2.3094r, Z = 2).

Face Centered Cubic (FCC) - There is one host atom at each corner, one host atom in each face, and the host atoms touch along the face diagonal (a = 2.8284r, Z = 4). This lattice is "closest packed", because spheres of equal size occupy the maximum amount of space in this arrangment (74.05%); since this closest packing is based on a cubic array, it is called "cubic closest packing": CCP = FCC.

FCC Primitive - It is also possible to choose a primitive unit cell to describe the FCC lattice. The cell is a rhombohedron, with a = b = c = 2r, and alpha = beta = gamma = 60 degrees. [A cube is a rhombohedron with alpha = beta = gamma = 90 degrees!]

Simple Hexagonal (SH) - Spheres of equal size are most densely packed (with the least amount of empty space) in a plane when each sphere touches six other spheres arranged in the form of a regular hexagon. When these hexagonally closest packed planes (the plane through the centers of all spheres) are stacked directly on top of one another, a simple hexagonal array results; this is not, however, a three-dimensional closest packed arrangement. The unit cell, outlined in black, is composed of one atom at each corner of a primitive unit cell (Z = 1), the edges of which are: a = b = c = 2r, where cell edges a and b lie in the hexagonal plane with angle a-b = gamma = 120 degrees, and edge c is the vertical stacking distance.

Closest Packing

Hexagonal Closest Packing (HCP) - To form a three-dimensional closest packed structure, the hexagonal closest packed planes must be stacked such that atoms in successive planes nestle in the triangular "grooves" of the preceeding plane. Note that there are six of these "grooves" surrounding each atom in the hexagonal plane, but only three of them can be covered by atoms in the adjacent plane. The first plane is labeled "A" and the second plane is labeled "B", and the perpendicular interplanar spacing between plane A and plane B is 1.633r (compared to 2.000r for simple hexagonal). If the third plane is again in the "A" orientation and succeeding planes are stacked in the repeating pattern ABABA... = (AB), the resulting closest packed structure is HCP.

HCP Coordination - Each host atom in an HCP lattice is surrounded by and touches 12 nearest neighbors, each at a distance of 2r: six are in the planar hexagonal array (B layer), and six (three in the A layer above and three in the A layer below) form a trigonal prism around the central atom.

Cubic Closest Packing (CCP) - If the atoms in the third layer lie over the three grooves in the A layer which were not covered by the atoms in the B layer, then the third layer is different from either A or B and is labeled "C". If a fourth layer then repeats the A layer orientation, and succeeding layers repeat the pattern ABCABCA... = (ABC), the resulting closest packed structure is CCP = FCC. Again, the perpendicular spacing between any two successive layers is 1.633r.

CCP Coordination - Each host atom in a CCP lattice is surrounded by and touches 12 nearest neighbors, each at a distance of 2r: six are in the planar hexagonal (B) plane, and six (three in the C layer above and three in the A layer below) form a trigonal anti-prism (also known as a distorted octahedron) around the central atom.

Rhombohedral (R) lattice - If, in the (ABC) layered lattice, the interplanar spacing is not the closest packed value (1.633r), then the primitive (Z = 1) unit cell is a rhombohedron with a = b = c <> 2r and alpha = beta = gamma <> 60 degrees. The non-primitive hexagonal unit cell (Z = 3).may also be chosen.

2- & 3-layer repeats - There is only one way to produce a repeat pattern (crystal lattice) in two layers of hexagonally closest packed planes: (AB) = HCP. Likewise, there is only one way to produce a repeat pattern in three layers of hexagonally closest packed planes: (ABC) = CCP.

4-layer repeats - However, there are two ways to produce a closest packed lattice in four layers: (ABAC) and (ABCB). By extension, there are increasing numbers of ways to produce closest packed lattices in five layers, six layers, etc., up to and including non-repeating random stacking. Thus, there are many closest (and pseudo-closest) packings in natural and artificial materials.

Holes ("Interstices") in Closest Packed Arrays

Tetrahedral Hole - Consider any two successive planes in a closest packed lattice. One atom in the A layer nestles in the triangular groove formed by three adjacent atoms in the B layer, and the four atoms touch along the edges (of length 2r) of a regular tetrahedron; the center of the tetrahedron is a cavity called the Tetrahedral (or Td) hole; a guest sphere will just fill this cavity (and touch the four host spheres) if its radius is 0.2247r.

Octahedral Hole - Adjacent to the Td hole, three atoms in the B layer touch three atoms in the A layer such that a trigonal antiprismatic polyhedron (a regular octahedron) is formed; the center of the octahedron is a cavity called the Octahedral (or Oh) hole. A guest sphere will just fill this cavity (and touch the six host spheres) if its radius is 0.4142r. It can be shown that there are twice as many Td as Oh holes in any closest packed bilayer.

Simple Crystal Structures

CsCl Structure - Each ion resides on a separate, interpenetrating SC lattice such that the cation is in the center of the anion unit cell and visa versa. The two lattices have the same unit cell dimension.

NaCl Structure - Each ion resides on a separate, interpenetrating FCC lattice. The two lattices have the same unit cell dimension.

Halite Structure - The sodium chloride structure may also be viewed as a CCP lattice of anions (Z = 4), with smaller cations occupying all Oh cavities (Z = 4).

Fluorite Structure - The structure of the mineral fluorite (calcium fluoride) may be viewed as a CCP lattice of cations (Z = 4), with the smaller anion occupying all of the Td holes (Z = 8). The Td cavities reside on a SC lattice which is half the dimension of the CCP lattice.

Zinc Blende Structure - The structure of cubic ZnS (mineral name "zinc blende") may be viewed as a CCP lattice of anions (Z = 4), with the smaller cations occupying every other Td hole (Z = 4). [Note: the other ZnS mineral, wurtzite, can be described as a HCP lattice of anions with cations in every other Td hole.]

Zinc Blende lattices - The lattice of cations in zinc blende is a FCC lattice of the same dimension as the anion lattice, so the structure can be described as interpenetrating FCC lattices of the same unit cell dimension. Note that the only difference between the halite and zinc blende structures is a simple shift in relative position of the two FCC lattices.

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