School of Physics & Astronomy
Tel Aviv University
Quasicrystals - Introduction
by Ron Lifshitz
What are quasicrystals? Why was their discovery by Dan
Shechtman in April of 1982 met by so much disbelief that it took it
more than two and a half years to find its way into the scientific literature?
Why was there so much fuss about having 5-fold symmetry in the first place?
What do we actually mean when we say that a crystal has such a symmetry?
Before we answer these questions let us first review some of
the background. For centuries crystals were merely thought of as solids
which have flat surfaces (facets) that intersect at characteristic angles.
This is what we often see at mineral exhibitions in
museums of natural history. It is also what we see
when we look at certain quasicrystals like the ones shown in the figure
below.
Single grains of quasicrystals Figure
1. Scanning electron micrographs of single grains of quasicrystals:
(a) an Aluminum - Copper - Iron alloy which crystallizes in the shape of
a dodecahedron. This is one of the five Platonic
solids, containing 12 faces of regular pentagons. Its symmetry is the
same as that of the icosahedron, one of the other platonic solid with 20
faces of equilateral triangles. (b) An Aluminum - Nickel - Cobalt alloy
which crystallizes in the shape of a decagonal (10-sided) prism.
Photographs courtesy of An
Pang Tsai, NRIM, Tsukuba, Japan.
During the 17th century, initial ideas regarding the microscopic
structure of crystals began to emerge in the works of scientists such as
Johannes Kepler and Robert Hooke (for a brief historical sketch see the
book
by Marjorie Senechal [4]). These ideas were formalized into a theory
of crystallography by René-Just Haüy in the early 19th century.
The basic notion of this theory is that crystals are
solids which
are ordered at a microscopic level. It was assumed that the only
way to achieve order is by having periodicity, that is, some basic structural
unit which repeats itself infinitely in all directions, filling up all
of space. This is very much like the way in which identical square tiles
can be used to tile a bathroom floor; like the way in which bees arrange
their honeycombs in periodic hexagonal arrays; and like lizards, fish,
angels, and devils fill the plane in the popular periodic drawings of the
artist M. C. Escher.
[
画像:Escher's angels and devils]
Figure
2. One of the many periodic drawings of the Dutch artist M. C. Escher.
© Copyright Cordon Art B.V.
The idea that crystals are periodically ordered was amazingly
successful. Crystallographers were able to predict all the characteristic
angles that could appear between the facets of crystals of any given type.
With the discovery of x-ray diffraction in crystals by Max von Laue in
1912 and the subsequent development of x-ray crystallography by William
H. and William L. Bragg the theory of crystallography received an unequivocal
stamp of approval. During the seventy (!!) years that followed, all observed
diffraction diagrams were in complete agreement with the predictions of
this theory and with the notion that all crystals achieve their order through
periodicity. It is no surprise then that periodicity, though never proven
to be a requirement for order, was incorporated into the definition of
crystal. Thus, on the eve of the discovery of quasicrystals, everybody
"knew" that crystals were solids composed of a periodic arrangement
of identical unit cells.
Diffraction diagram
Among the the most well known
consequences of periodicity is the fact that the only rotational symmetries
that are possible are 2-, 3-, 4-, and 6-fold rotations. Five-fold rotations
(and any
n-fold rotation for
n>6) are incompatible with periodicity.
We shall say more about what we mean by symmetry in the
next
section, but for the meantime let us think of the set of rotations
that leave the directions of the facets (Figure 1) unchanged, or the set
of rotations that leave the diffraction diagram (Figure 3) unchanged. Thus,
on the eve of the discovery of quasicrystals, everybody "knew" that crystals
and their diffraction diagrams cannot have 5-fold symmetry. One can only
imagine what Shechtman felt when on April 8, 1982, while performing an
electron diffraction experiment on an alloy of Aluminum and Manganese he
observed a diffraction diagram similar to the one in Figure 3. By
orienting the alloy in different directions he found that it had the symmetry
of an icosahedron, containing six axes of 5-fold symmetry, along with ten
axes of 3-fold symmetry and 15 axes of 2-fold symmetry.
Figure
3. Typical diffraction diagram of a quasicrystal, exhibiting 5-fold
or 10-fold rotational symmetry. Source unknown.
The crystal that Shechtman discovered, as well as scores of
other crystals that have been discovered since 1982, have been named
"
quasicrystals," which is short for "
quasiperiodic
crystals," by Levine and Steinhardt in 1984, in a first of a series
of papers from the University of Pennsylvania that set up much of the
initial theoretical foundations of the field . Quasicrystals share many
of the characteristics of their periodic siblings: they can exhibit
facets (Figure 1); they produce diffraction diagrams with sharp peaks
(Figure 3,
see more detail below); and
those which are thermodynamically stable, like the AlPdMn quasicrystal
in Figure 4, can be grown to very large dimensions and have a degree
of microscopic order which surpasses even that of the most perfect
periodic crystals. Quasicrystals are also very different from periodic
crystals. They may
possess rotational
symmetry which is incompatible with periodicity. To this date,
quasicrystals have been found that have the symmetry of a tetrahedron,
a cube, an icosahedron [Figure 1(a)], and that of 5-sided, 8-sided,
10-sided [Figure 1(b)], and 12-sided prisms. They also possess unique
physical properties that are currently under vigorous study, most
notably the fact that even though they are all alloys of two or three
metals they are very poor conductors of electricity and of heat.
Figure 4. A single Aluminum
- Palladium - Manganese quasicrystal with icosahedral symmetry. This single
crystal, grown at the IFF
Forschungszentrum J ülich,
is more than 6 cm long. Photograph courtesy of M. Feuerbacher, M.
Beyss, and B. Grushko, Jülich,
Germany.
[
画像:Al-Pd-Mn single crystal]
On
diffraction and the new definition of "crystal"
Before we end this introduction we should say a few words about diffraction
experiments and the current definition of "crystal." A diffraction experiment
directly probes the degree of order in a solid by measuring density correlations,
namely, what are the chances of finding an atom at a certain location if
we know that there is another atom at some other given location. [In more
technical terms: The diffraction experiment displays the Fourier transform
of the two-point density correlation function of the solid, also known
as the "Patterson function."] If there is order the diffraction diagram
shows a set of spots, called "
Bragg peaks," in an otherwise essentially
dark background. The longer the range of the correlations in the solid
the sharper these peaks are.
In 1991, the International
Union of Crystallography decided to redefine the term "crystal"
to mean any solid having an essentially discrete diffraction diagram.
Within the family of crystals we distinguishes between "periodic crystals,"
which are periodic on the atomic scale, and "aperiodic crystals" which
are not. This broader definition reflects our current understanding that
microscopic periodicity is not necessary for achieving order, yet it is
sufficiently vague to reflect our uncertainty as to what are the necessary
requirements for order. The new definition is based on the outcome of an
experiment rather than a set of microscopic rules.
One can also use the diffraction diagram to distinguish between
periodic crystals and quasicrystals as follows: Each Bragg peak in the
discrete diffraction diagram defines a vector which points from the center
of the diagram to that peak. In a diffraction diagram of a periodic
crystal (in three dimensions) one can always find three peaks, corresponding
to three vectors b1,
b2, and b3,
which can be used to index all the other peaks. This means that any other
peak can be generated as a vector sum with three integer coefficients (h,k,l)
as hb1+
kb2+
lb3.
In the case of a quasicrystal one needs more than three wave vectors
to generate all the peaks and therefore more than three integers to index
each peak.
Upcoming Conference in
Israel
October 14-19, 2007, Tel Aviv, Israel.
Suggested
Further Reading
-
Somewhat technical but this is the paper that
started it all:
D. Shechtman, I. Blech, D. Gratias, and J.W.
Cahn, "Metalic phase with with long-range orientational order and no translational
symmetry," Phys. Rev. Lett. 53 (1984) 1951-1953.
-
The paper where the term "quasicrystal" was first defined:
D. Levine and P.J. Steinhardt, "Quasicrystals: A New Class of Ordered
Structures," Phys. Rev. Lett. 53 (1984) 2477 - 2480.
-
Personal recollections on the discovery of quasicrystals:
D. Shechtman and C. Lang, "Quasiperiodic materials: Discovery and recent
developments," MRS
Bulletin Vol. 22 No. 11 (1997) 40-42.
-
On the discovery of quasicrystals as a Kuhnian Scientific Revolution:
J. W. Cahn, "Epilogue," Proceedings of the 5th International Conference
on Quasicrystals, Ed. C. Janot and R. Mosseri (World Scientific, Singapore
1995) 807-810.
-
A good informal introduction to crystallography:
M. Senechal, "Crystalline symmetries: An informal mathematical introduction"
(Adam Hilger, Bristol, 1990).
-
One of the first general textbooks on quasicrystals:
C. Janot, "Quasicrystals: A primer," 2nd edition (Clarendon Press,
Oxford, 1994).
[Click
here for a book review by Walter Steurer.]
-
A textbook on the mathematics of quasicrystals:
M. Senechal, "Quasicrystals and geometry" (Cambridge University Press,
Cambridge, 1995).
Some
of My Related Publications
Other
Quasicrystal Sites
-
Ames Lab, Iowa State University.
[Surface properties, magnetism, and applications.]
-
Aperiodic
Solids Research Team, National Research Institute for Metals, Japan.
[Metallurgy.]
-
Laboratory of Crystallography,
ETH Zürich. [Crystallography.]
-
Special Interest Group
on Aperiodic Crystals of the European Crystallographic Association.
-
Structure of
Matter group, Universidad Nacional Autónoma de México.
[Structure and electronic properties.]
-
Pat
Thiel, Iowa State University. [Surface properties.]
-
Steffen Weber, NIRIM,
Tsukuba, Japan. [Introduction, mainly structure and geometry.]
-
Mike
Widom, Carnegie Mellon University. [Tiling, structure, and thermodynamics.]