THE FASCINATING WORLD OF

QUASICRYSTALS

Anandh Subramaniam
Materials Science and Engineering
INDIAN INSTITUTE OF TECHNOLOGY KANPUR
Kanpur- 208016
Email: anandh@iitk.ac.in
http://home.iitk.ac.in/~anandh

Oct 2011
Daniel Shechtman
7 April 1982 SOLIDS
Based on Structure

GLASS CRYSTALS
(AMORPHOUS)

8 April 1982 SOLIDS

Based on Structure

GLASS CRYSTALS
(AMORPHOUS)
QUASI CRYSTALS
A leaf from a diary…

Daniel Shechtman
Born: January 24, 1941

Enter the Decagon!


7 April 1982

8 April 1982

12 Nov 1984
Painting by Dr. Alok Singh, 1993
“If
“If you
you are
are aa scientist
scientist and
and believe
believe in
inyour
yourresults,
results,then
thenfight
fightfor
for the
the
truth”.
truth”.“Listen
“Listento toothers,
others,but
butfight
fightfor
forwhat
whatyou
youbelieve
believein…”
in…”
--DAN
DANSHECHTMAN
SHECHTMAN

"I must have shared with you my first ever meeting with him in July this year.
I was invited to Ames Lab by Mat Kramer and I was sitting in his office and
told him "I have been waiting to meet Prof. Shechtman from my PhD days".
That was the time one person entered his office and was asking Mat, "Mat, I
have been searching for the glue for ion milling my sample and could not find
it in the lab. Can you please let me know". Mat tuned towards me and told me
"the man you are looking forward to meet is here". He was about to celebrate
his 70th birthday in a few days from then. That speaks volumes about the
commitment to research from this great scientist."
– B.S. MURTHY
Why did it take so long?
 Are QC only made of rare- “hard to find” elements?
No! Most of them contain common elements like Al, Mn, Mg, Cu, Fe…

 Do we require ‘difficult conditions for synthesis’- High temperature, High

pressure,…?
They even
No! Many of them can be produced by simple casting (e.g. AlCuFe, MgZnY…)
occur naturally

Element 117 (with 177 neutrons) has a half life of 78 ms

 Having produced them- are they ‘unstable’ with small lifetimes?

No! Some of them are so stable (at RT) that they would survive for millennia (but for
corrosion!)

 Do we need extremely sensitive experimentation (like neutron diffraction…) to

detect their presence/identify them?

No! All you need is a Transmission Electron Microscope (TEM) (that too without EELS,
EDXS… however, HREM would help!)
QUASICRYSTALS: THE PRESAGES!
 Darb-I Imam shrine, Isfaha, Iran, 1453 AD

Gunbad-i Kabud tomb in Maragha, Iran, 1197 AD 1453 AD

 PENROSE TILING

The tiling has only one

point of global 5-fold
symmetry (the centre of
the pattern)

However if we
obtain a diffraction
pattern (FFT) of
any ‘broad’ region
in the tiling, we will
get a 10-fold
pattern!
(we get a 10-fold instead of a The tiling has regions of
5-fold because the SAD pattern local 5-fold symmetry
has inversion symmetry)

R. Penrose, “Pentaplexity”, Eureka, 39, 16, 1978

M. Gardner, Sci. Am. 236 (1977) 110
A brief history of aperiodic tilings
 Berger, 1966  20,000 tiles (then to 104 tiles)
 Robinson, 1971  6 tiles
 Penrose1 , 1974  4 (6) tiles
 Penrose2 , 1978  2 tiles

R. Berger, Mem. Am. Math. Soc., No.66, 1966.

R.W. Robinson, Invent. Math., 12, 177, 1971.
[1] R. Penrose, Bull. Inst. Math. Appl., 10, 266, 1974.
[2] R. Penrose, “Pentaplexity”, Eureka, 39, 16, 1978.
Penrose versus Kepler (Harmonice Mundi, 1619)
Kepler concluded that the pattern would never repeat- there would always be “surprises”
 Kepler had anticipated the concept of aperiodic tiling by 350 years!

Penrose’s Pattern Kepler’s Pattern

 A Circle has been placed on each quasi-lattice point
of the 2D pattern to model a possible atomic structure

Wonders of Numbers:
Adventures in Mathematics,
Mind and Meaning
Clifford A Pickover
WHAT IS A CRYSTAL?
 Crystal =
Space group (how to repeat)
+
Asymmetric unit (Motif’: what to repeat)
+
Wyckoff positions

a
=
Glide reflection
A L? a operator
YST
R Symbol g may also be used

IS AC
W HA
T + Positions entities
with respect to
symmetry operators

+Wyckoff label ‘a’

Usually asymmetric units are regions of space- which contain the entities (e.g. atoms, molecules)
Crystals have certain symmetries
Symmetry operators

t  Translation    
t
    

R  Rotation R  Inversion R  Mirror

m

R  Roto-inversion

G  Glide reflection

S  Screw axis

 Takes object to the same form

 Takes object to the enantiomorphic form
 Plato wrote about these solids in the dialogue Timaeus c.360 B.C.

3 out of the 5 Platonic solids have the symmetries seen in the

crystalline world
i.e. the symmetries of the Icosahedron and its dual the Dodecahedron are
not found in crystals

Fluorite
These symmetries (rotation, Octahedron
mirror, inversion) are also
expressed w.r.t. the external
shape of the crystal

Pyrite
Cube
Rüdiger Appel, http://www.3quarks.com/GIF-Animations/PlatonicSolids/ http://en.wikipedia.org/wiki/Crystal_habit http://www.galleries.com/minerals/property/crystal.htm
HOW IS A QUASICRYSTAL DIFFERENT
FROM A CRYSTAL?
 FOUND!
THE MISSING PLATONIC SOLID

[2]

Dodecahedral
single
quasicrystal
m35 [1] Mg-Zn-Ho

Octahedron and icosahedron were discovered by Theaetetus, a contemporary of Plato

[1] I.R. Fisher et al., Phil Mag B 77 (1998) 1601
[2] Rüdiger Appel,
Appel http://www.3quarks.com/GIF-Animations/PlatonicSolids/
 QUASICRYSTALS (QC)

ORDERED PERIODIC QC ARE

ORDERED
CRYSTALS   STRUCTURES
WHICH ARE
QC   NOT
AMORPHOUS   PERIODIC
 SYMMETRY

CRYSTAL QUASICRYSTAL
t  
RC  RCQ

t  translation
  inflation QC are characterized by Inflationary
Symmetry and can have disallowed
RC  rotation2,crystallographic
3, 4, 6 crystallographic symmetries*
RCQ  RC + 5,
other
8, 10, 12

* Quasicrystals can have allowed and disallowed crystallographic symmetries

 DIMENSION OF QUASIPERIODICITY (QP)

QC can have quasiperiodicity along 1,2 or 3

dimensions
(at least one dimension should be
quasiperiodic)

QC as a crystal?

QC can be thought of as crystals in higher

QP XAL
dimensions
1  4
(which are projected on to lower
dimensions → lose their periodicity*) 2  5
3  6

* At least in one dimension

QUASIPERIODICITY & INFLATIONARY SYMMETRY
The Fibonacci sequence has a curious connection with quasicrystals* via the GOLDEN MEAN ()

THE FIBONACCI SEQUENCE

Fibonacci  1 1 2 3 5 8 13 21 34 ... 

Ratio  1/1 2/1 3/2 5/3 8/5 13/8 21/13 34/21 ...  = ( 1+5)/2

Where  is the root of the quadratic equation: x2 – x – 1 = 0

Convergence of Fibonacci Ratios

The ratio of
successive terms of
2.2
the Fibonacci
sequence converges to
2
the Golden Mean
1.8
1.618… x 1 x

Ratio

1.6
1 x
In 1202 Fibonacci 1.4
discussed the
number sequence in
1.2 x2  x 1  0
connection with the 1
proliferation of 1 2 3 4 5 6 7 8 9 10
rabbits n

* There are many phases of quasicrystals and some are associated with other sequences and other irrational numbers
 Deflated
A
sequence

B
B A a
B A B b
Rational
Approximants B A B B A ba

Each one of these units

B A B B A B A B bab
(before we obtain the 1D
quasilattice in the limit)
can be used to get a
B A B B A B A B B A B B A babba
crystal (by repetition:
e.g. AB AB AB…or
BAB BAB BAB…)
Note: the deflated sequence is
identical to the original sequence

1-D QC
In the limit we obtain the
1D Quasilattice

Schematic diagram showing the structural analogue of the Fibonacci sequence

leading to a 1-D QC
Where is the Golden Mean?
1
 In the ratio of lengths
  1
1
1
 In the ratio of numbers 1
1
1
1
1 
nB LA
 
nA LB
Inflationary symmetry in the Penrose tiling The inflated tiles
can be used to
create an inflated
replica of the
original tiling

 Inflated tiling
HOW IS A DIFFRACTION PATTERN FROM A CRYSTAL
DIFFERENT FROM THAT OF A QUASICRYSTAL?
 Let us look at the Selected Area Diffraction Pattern (SAD) from a crystal → the spots/peaks are arranged periodically

The spots are

periodically
arranged

[112]
Superlattice spots [111] [011]

SAD patterns from a BCC phase (a = 10.7 Å) in as-cast Mg4Zn94Y2 alloy showing important zones
Now let us look at the SAD pattern from a quasicrystal from the same alloy system (Mg-Zn-Y)

The spots
show
inflationary
symmetry
Explained in
the next slide
[1 1 1]
[1  0]

[0 0 1] [ 1 3+ ]

SAD patterns from as-cast Mg23Zn68Y9 showing the formation of Face Centred Icosahedral QC
DIFFRACTION PATTERN
5-fold SAD pattern
from as-cast
Mg23Zn68Y9 alloy

Note the 10-fold pattern

1  2 3 4

Successive spots are at a distance inflated by 

Inflationary symmetry
 STRUCTURE OF QUASICRYSTALS

 QUASILATTICE APPROACH
(Construction of a quasilattice followed by the decoration of the lattice by atoms)

 PROJECTION FORMALISM
 TILINGS AND COVERINGS

 CLUSTER BASED CONSTRUCTION

(local symmetry and stage-wise construction are given importance)

 TRIACONTAHEDRON (45 Atoms)

 MACKAY ICOSAHEDRON (55 Atoms)
 BERGMAN CLUSTER (105 Atoms)
 HIGHER DIMENSIONS ARE NEAT

E2

GAPS

S2  E3

REGULAR
PENTAGONS

Regular pentagons cannot tile E2 space but can tile SPACE FILLING
S2 space (which is embedded in E3 space)
 For crystals  We require two basis vectors to index the diffraction pattern in 2D

For quasicrystals 
We require more than two basis vectors to index the diffraction pattern in 2D

For this SAD pattern

we require 5 basis vectors
(4 independent)
to index the diffraction pattern in 2D
 PROJECTION METHOD
QC considered a crystal in higher dimension → projection to lower dimension can
give a crystal or a quasicrystal

2D  1D

ow
E ind E||
W E||  

e2 To get RA 
approximations are made
 e1 in E (i.e to )

Irrational  QC
Slope = Tan ()  x '   Cos Sin   x 
R   
Rational  RA (XAL)  y '    Sin Cos   y 
1D 1-D QC

 B A B B A B A B B A B B A

2D

Penrose Tiling
Octogonal Tiling
 2 1 1 
   
  1 1 
1 0
 0  3 3  3 - 3  2 2
  
0 1 1 1 
R 2  1 1    2 2
    R  
1 1

 1 0 
 0 3 - 3  3  3   2 2 
   1 1 0 1 
 2 2 2 2 2   2 2 
3D ICOSAHEDRAL QUASILATTICE
 The icosahedral quasilattice is the 3D analogue of the Penrose tiling.
 It is quasiperiodic in all three dimensions.
 The quasilattice can be generated by projection from 6D.
 It has got a characteristic 5-fold symmetry.

1 0  1  0
 1 0  0 1

0  1 0 1  
R 
  1 0  1 0 
5-fold [1  0]  1 0  1

0  

 0  1 0  1

Note the occurrence of

irrational Miller indices
3-fold [2+1  0]

2-fold [+1  1]
Cluster Based Construction

(a) (b)

Rhombic Triacontahedron

Bergman cluster Mackay double icosahedron

Kreiner, G., and Franzen, H. F., J. Alloys and Compounds, 221 (1995) 15

(a) Bergman, G., Waugh, J. L. T., and Pauling, L., Acta Cryst., 10 (1957) 2454 Hiraga, K et al, S., Phil. Mag. B67 (1993) 193
(b) Ranganathan, S., and Chattopadhyay, K., Annu. Rev. Mater. Sci., 21 (1991) 437
Comparison of a crystal with a quasicrystal

CRYSTAL QUASICRYSTAL
Translational symmetry Inflationary symmetry

Crystallographic rotational symmetries Allowed + some disallowed rotational

symmetries
Single unit cell to generate the structure Two prototiles are required to generate the
structure (covering possible with one tile!)
3D periodic Periodic in higher dimensions

Sharp peaks in reciprocal space with Sharp peaks in reciprocal space with
translational symmetry inflationary symmetry
Underlying metric is a rational number Irrational metric

Usually made of ‘small’ clusters Large clusters

SYSTEMS FORMING QUASICRYSTALS
&
TYPES OF QUASICRYSTALS
List of quasicrystals with diverse kinds of symmetries
Type QP+ Rank Metric Symmetry System Reference

Icosahedral 3D 6  (5) m35

__
AlMn Shechtman et al., 1984

Cubic 3D 6 3 _
43m
VNiSi Feng et al., 1989

Tetrahedral 3D 6 3 m3
_
AlLiCu Donnadieu, 1994

Decagonal 2D 5  (5) 10/mmm AlMn Chattopadhyay et al., 1985

and Bendersky, 1985

Dodecagonal 2D 5 3 12/mmm NiCr Ishimasa et al., 1985

Octagonal 2D 5 2 8/mmm VNiSi, Wang et al., 1987

CrNiSi

Pentagonal 2D 5  (5) _
5m
AlCuFe Bancel, 1993

Hexagonal 2D 5 3 6/mmm AlCr Selke et al., 1994

Trigonal 1D 4 3 _
3m
AlCuNi Chattopadhyay et al., 1987

Digonal 1D 4 2 222 AlCuCo He et al., 1988

Naturally Occurring QC

 First naturally occurring QC was reported associated with the mineral Khatyrkite.
Indian Contributions
http://www.iucr.org/news/newsletter/volume-15/number-4/crystallography-in-india
“However, India missed some opportunities in this area. Early work of
T.R. Anantharaman on Mn-Ga alloys and G.V.S. Sastry and C. Suryanarayana
(BHU) on Al-Pd alloys came tantalizingly close to the discovery of quasicrystals”.

Conference in Honour of Prof. T.R. Anantharaman

IITK

S. Lele

C. Suryanarayana
G.V.S SASTRY

S. Ranganathan

http://www.iitk.ac.in/infocell/announce/metallo/collection.htm
Allowed crystallographic symmetry- tiled aperiodically

Discovery of the decagonal phase

Basis for synthesis of QC

1-D quasiperiodicity
 =1
=2 Icosahedral Quasicrystal =3
Decagonal Hexagonal
Quasicrystal Quasicrystal
=1
Digonal Pentagonal Cubic R.A.S. Trigonal Hexagonal
Quasicrystal Quasicrystal Mackay Bergman Quasicrystal R.A.S.

Orthorhombic Orthorhombic Trigonal Orthorhombic

R.A.S. R.A.S R.A.S. R.A.S.
Taylor Little
Robinson Monoclinic
R.A.S. Monoclinic R.A.S.
Monoclinic R.A.S.   120o Unified view of quasicrystals,
R.A.S.  = 90o rational approximants and
 = 108o related structures

Trigonal and Pentagonal

quasilattices
Fundamental
work on
Vacancy
Ordered Phases

x3  x 2  2 x  1  0
First observation of a
relation between five-fold
and hexagonal symmetry

Approximant to 7-
Uniform deformation along the arrow of the [0 0 1] 2-fold pattern
fold quasilattice from IQC giving rise to a pattern similar to the [ 1 3+ ] pattern