HERCULES Vol.

II

CHAPTERIX

QUASICRYSTALS
C.JANOT

IX.1. Introduction
The discovery of new solids exhibiting symmetries forbidden for ordinary
crystals was first reported by Shechtman, Blech, Gratias and Cahn (1984) in Al-Mn
and AI-Mn-Si alloys. In the intervening eight years, hundreds of other compounds
have been observed with quasicrystalline phases. Classically forbidden symmetries,
namely 5-fold, 8-fold, 10-fold and 12-fold, have been reported. Most of the
quasicrystalline materials which are known now are Al-based binary or ternary
metallic alloys, or analogous alloys with Ga or Ti playing the role of Al.
During the early years of the field, there were some speculations that
quasicrystals might be inherently disordered and unstable. The speculations proved
wrong, though. There are now at least a dozen known compounds which are
thought to be thermodynamically stable. In a few cases, the phase diagram has been
worked out to some extent (Faudot 1991, Bancel 1991). Also, many of the newer,
thermodynamically stable quasicrystals have translational correlation lengths and
faceting morphology (with icosahedral symmetry) which riyal the best conventional
metallic crystals.
At the time of the experimental discovery of icosahedral alloys, Levine and
Steinhardt (1984) were independently formulating their hypo thesis of a new class of
solids which they dubbed "quasiperiodic crystals", or "quasicrystals". They proposed
that the new alloys might be laboratory examples of quasicrystals and they outlined
some basic mathematical and structural principles.
Quasicrystallography has not yet achieve the level of structure refinement
which is currently reported in regular crystallography. Also, the description of the
structure, though very easy in its high-dimensional periodic image, is not that
straightforward when one deals with the 3-dimensional physical atomic arrange-
ments. This has stimulated many attempts toward atomic modelling, directly in the
real space, by approaching the quasiperiodic structures with periodic approximants
crystals. So-called "random tiling" models where also introduced in order to give an
easy ans wer to quasicrystal growth problems and also to support the idea that
quasicrystals phases may be favoured for entropic reasons (Henley 1991).
In the present paper, the basic principles of quasiperiodicity will be introduced
and illustrated with an example of structure determination. (For a complete over-
view of the subject, see Janot 1992).

IX.2.. Quasicrystallography: the basic principles

Quasicrystals are new types of solids wh ich defy previous standard
classifications. They are neither periodically ordered like ordinary crystals, nor are
they disordered or amorphous solids. They have a weIl defined, discrete group
symmetry, like crystals, but one which is explicitly incompatible with 3-dimensional

J. Baruchel et al. (eds.), Neutron and Synchrotron Radiation for Condensed Matter Studies
© Springer-Verlag Berlin Heidelberg 1994
198 C.JANOT

periodic translational order (e.g., exhibiting five-, eight-, ten- or twelve-fold

symmetry axes). Instead, quasicrystals possess a novel kind of translational order
known as quasiperiodicity.
Atomic order is best defined in terms of the Fourier transform of the mass
density of the solid. In an ordinary crystal, this transforrn can be written as a Fourier
series:
p(r) = l L p(G) exp(iG· r)
V G (IX.I)

The set of wavevectors G define a discrete reciprocal lattice in which each wave-
vector in the sum can be written as an integer linear cornbination of three "basis"
vectors a~ :
(IX.2)

The a~'s are said to span the reciprocallattice. In a quasicrystal, the Fourier transform
of the mass density in also a Fourier series and the wavevectors in the Fourier surn

Figure DU. - Vertex reciprocal lattice vectors a~ for a regular icosahedron. Cubic axes are also
shown on which the a~ vectors have components of the form (± 1, ± ~,O).

also form a discrete reciprocal lattice. However, the nurnber of integer linearly
independent basis vectors required to "span" the reciprocal space exceeds the spatial
dimension and the point symrnetry is incornpatible with periodic translational order.
For example, six basis vectors are required to span the reciprocal space for three-
dimensional quasicrystals with icosahedral symrnetry: