Shechtman et al

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What are Quasicrystals?

Prologue

Crystals can only exhibit certain symmetries

In crystals, atoms or atomic clusters repeat periodically, analogous to a tesselation in 2D constructed from a single type of tile.

Try tiling the plane with identical units

… only certain symmetries are possible

YES

YES

YES

YES

YES

So far so good … but what about five-fold, seven-fold or other symmetries??

?

No!

?

No!

According to the well-known theorems of crystallography, only certain symmetries are allowed: the symmetry of a square, rectangle, parallelogram triangle or hexagon, but not others, such as pentagons.

Crystals can only exhibit certain symmetries

Crystals can only exhibit these same rotational symmetries *

..and the symmetries determine many of their physical properties and applications

*in 3D, there can be different rotational symmetries

Along different axes, but they are restricted to the same set (2-, 3, 4-, and 6- fold)

Which leads us to…

Quasicrystals (Impossible Crystals) were first discoveredin the laboratory by

Daniel Shechtman, Ilan Blech, Denis Gratias and John Cahn in a beautiful study of an alloy of Al and Mn

D. Shechtman, I. Blech, D. Gratias, J.W. Cahn (1984)

1 m m

Al

6

Mn

Their surprising claim:

“Diffracts electrons like a crystal . . .

But with a symmetry strictly forbidden for crystals”

Al

6

Mn

By rotating the sample, they found the new alloy has icosahedral symmetry the symmetry of a soccer ball

– the most forbidden symmetry for crystals!

Their symmetry axes of an icosahedron three-fold symmetry axis five-fold symmetry axis two-fold symmetry axis

As it turned out, a theoretical explanation was waiting in the wings…

QUASICRYSTALS

Similar to crystals

• Orderly arrangement

• Rotational Symmetry

• Structure can be reduced to repeating units

D. Levine and P.J. Steinhardt (1984)

Similar to crystals,

BUT…

• Orderly arrangment . . .

But QUASIPERIODIC instead of PERIODIC

• Rotational Symmetry

• Structure can be reduced to repeating units

D. Levine and P.J. Steinhardt (1984)

QUASICRYSTALS

Similar to crystals,

BUT…

• Orderly arrangment . . .

But QUASIPERIODIC instead of PERIODIC

• Rotational Symmetry . . .

But with FORBIDDEN symmetry

• Structure can be reduced to repeating units

D. Levine and P.J. Steinhardt (1984)

QUASICRYSTALS

Similar to crystals,

BUT…

• Orderly arrangmenet . . .

But QUASIPERIODIC instead of PERIODIC

• Rotational Symmetry . . .

But with FORBIDDEN symmetry

• Structure can be reduced to a finite number of repeating units

D. Levine and P.J. Steinhardt (1984)

QUASICRYSTALS

Inspired by Penrose Tiles

Invented by Sir Roger Penrose in 1974

Penrose’s goal:

Can you find a set of shapes that can only tile the plane non-periodically?

With these two shapes,

Peirod or non-periodic is possible

But these rules

Force non-periodicity:

Must match edges & lines

And these “Ammann lines” reveal the hidden symmetry of the

“non-periodic” pattern

They are not simply

“non-periodic”:

They are quasiperiodic!

(in this case, the lines form a

Fibonacci lattice of long and short intervals

Fibonacci = example of quasiperiodic pattern

Surprise: with quasiperiodicity , a whole new class of solids is possible!

Not just 5-fold symmetry

– any symmetry in any # of dimensions !

New family of solids dubbed

Quasicrystals = Quasiperiodic Crystals

D. Levine and PJS (1984)

J. Socolar, D. Levine, and PJS (1985)

Surprise: with quasiperiodicity , a whole new class of solids is possible!

Not just 5-fold symmetry

– any symmetry in any # of dimensions !

Including Quasicrystals

With Icosahedral Symmetry in 3D:

D. Levine and PJS (1984)

J. Socolar, D. Levine, and PJS (1985)

First comparison of diffraction patterns (1984) between experiment (right) and theoretical prediction (left)

D. Levine and P.J. Steinhardt (1984)

Shechtman et al. (1984) evidence for icosahedral symmetry

Reasons to be skeptical:

Requires non-local interactions in order to grow?

Two or more repeating units with complex rules for how to join:

Too complicated?

Reasons to be skeptical:

Requires non-local interactions in order to grow?

Non-local Growth Rules ?

...

L S LL S L S LL S LL S L S LL S L S L ...

Suppose you are given a bunch of L and S links (top).

?

YOUR ASSIGNMENT: make a Fibonacci chain of L and S links (bottom) using a set of LOCAL rules

(only allowed to check the chain a finite way back from the end to decide what to add next)

N.B. You can consult a perfect pattern (middle) to develop your rules

For example, you learn from this that S is always followed by L

Non-local Growth Rules ?

...

L S LL S L S LL S LL S L S LL S L S L ...

L S L S LL S L S LL S L

?

L

S L

So, what should be added next, L or SL?

Comparing to an ideal pattern. it seems like you can choose either…

Non-local Growth Rules ?

...

L S LL S L S LL S LL S L S LL S L S L ...

?

L

L S L S LL S L S LL S L

S L

Unless you go all the way back to the front of the chain –

Then you notice that choosing S+L produces LSLSL repeating 3 times in a row

Non-local Growth Rules ?

...

L S LL S L S LL S LL S L S LL S L S L ...

L S L S LL S L S LL S L

L

S L

That never occurs in a real Fibonacci pattern, so it is ruled out…

But you could only discover the problem by studying the ENTIRE chain (not LOCAL) !

Non-local Growth Rules ?

...

L S LL S L S LL S LL S L S LL S L S L ...

L

L S L S LL S L S LL S L

S L

L

L S LL S LL S L S LL S LL S L S LL S LL S

L S

The same occurs for ever-longer chains – LOCAL rules are impossible in 1D

Penrose Rules Don’t Guarantee a Perfect Tiling

In fact, it appears at first that the problem is 5x worse in 5D because there are 5 Fibonacci sequences of Ammann lines to be constructed

Question:

Can we find local rules for adding tiles that make perfect QCs?

Onoda et al (1988):

Surprising answer: Yes!

But not Penrose’s rule; instead

Only add at forced sites

Penrose tiling has 8 types of vertices

Forced = only one way to add consistent w/8 types

G. Onoda, P.J. Steinhardt, D. DiVincenzo, J. Socolar (1988)

UNFORCED

FORCED

In 1988, Onoda et al. provided the first mathematical proof that a perfect quasicrystal of arbitrarily large size

Ccn be constructed with just local ( short-range ) interactions

Since then, highly perfect quasicrystals with many different symmetries have been discovered in the laboratory …

Al

70

Ni

15

Co

15

Al

60

Li

30

Cu

10

Zn

56.8

Mg

34.6

Ho

8.7

AlMnPd

Faceting was predicted: Example of prediction of facets

Reasons to be skeptical:

Requires non-local interactions in order to grow?

Two or more repeating units with complex rules for how to join:

Too complicated?

Not so! A single repeating unit suffices!

The Quasi-unit Cell Picture

P.J. Steinhardt, H.-C. Jeong (1996)

Gummelt Tile

(discovered by Petra Gummelt)

Quasi-unit Cell Picture:

A single repeating unit with overlap rules (A and B) produces a structure isomorphic to a Penrose tiling!

Gummelt Tile

For simple proof, see P.J. Steinhardt, H.-C. Jeong (1996)

Quasi-unit Cell Picture

Can interpret overlap rules as atomic clusters sharing atoms

Gummelt Tile

The Tiling (or Covering) obtained using a single Quasi-unit Cell + overlap rules

Another Surprise:

Overlap Rules  Maximizing Cluster Density

Clusters energetically favored 

Quasicrystal has minimum energy

P.J. Steinhardt, H.-C. Jeong (1998)

High Angle Annular Dark Field Imaging shows a real decagonal quasicrystal = overlapping decagons

Al

72

Ni

20

Co

8

P.J. Steinhardt, H.-C. Jeong, K. Saitoh, M. Tanaka, E. Abe, A.P. Tsai

Nature 396, 55-57 (1998)

Example of decagon

Fully overlapping decagons (try toggling back and forth with previous image)

Focus on single decagonal cluster – note that center is not 10-fold symmetric (similar to Quasi-unit Cell)

Focus on single decagonal cluster – note that center is not 10-fold symmetric (similar to Quasi-unit Cell)

Quasi-unit cell picture constrains possible atomic decorations

– leads to simpler solution of atomic structure (below) that matches well with all measurements (next slide) and total energy calculations

Blue = Al

Red = Ni

Purple = Co

Prediction agrees with Later Higher Resolution Imaging

Yan & Pennycook (2001)

Mihalkovic et al (2002)

New Physical Properties  New Applications

• Diffraction

• Faceting

• Elastic Properties

• Electronic Properties

A commercial application:

Cookware with Quasicrystal Coating

(nearly as slippery as Teflon)

Epilogue 1:

A new application -- synthetic quasicrystals

Experimental measurement of the photonic properties of icosahedral quasicrystals

W. Man, M. Megans, P.M. Chaikin, and P. Steinhardt, Nature (2003)

Weining Man , M. Megans, P. Chaikin, & PJS, Nature (2005)

Photonic Quasicrystal for Microwaves

Y. Roichman, et al. (2005): photonic quasicrystal synthesized from colloids

Epilogue 2:

The first “natural quasicrystal”

Discovery of a Natural Quasicrystal

L Bindi, P. Steinhardt, N. Yao and P. Lu

Science 324, 1306 (2009)

LEFT: Fig. 1 (A) The original khatyrkite-bearing sample used in the study. The lighter-colored material on the exterior contains a mixture of spinel, augite, and olivine. The dark material consists predominantly of khatyrkite (CuAl

2

) and cupalite

(CuAl) but also includes granules, like the one in (B), with composition Al

63

Cu

24

Fe

13

. The diffraction patterns in Fig. 4 were obtained from the thin region of this granule indicated by the red dashed circle, an area 0.1 µm across. (C) The inverted

Fourier transform of the HRTEM image taken from a subregion about 15 nm across displays a homogeneous, quasiperiodically ordered, fivefold symmetric, real space pattern characteristic of quasicrystals.

RIGHT: Diffraction patterns obtained from natural quasicrystal grain

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