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Ärystals and crystalline solids
solid made from small, identical building blocks (unit cells) which also
show in the macroscopic shape
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Ärystals and crystalline solids: contents
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Ärystals and crystalline solids
The total energy for the crystalline state must be very low because the
ordered states exists also at elevated temperatures, despite its low
entropy.
The high symmetry greatly facilitates the solution of the Schrödinger
equation for the solid because the solutions also have to be highly
symmetric.
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Ärystals and crystalline solids
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the solids could also be amorphous (with no crystalline order)
Some formal definitions
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The crystal lattice: mravais lattice (2D)
A mravias lattice is a lattice of points, defined by
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The crystal lattice: mravais lattice (3D)
A mravias lattice is a lattice of points, defined by
a2
a1
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The crystal lattice: primitive unit cell
Primitive unit cell: any volume of space which, when translated through all the vectors of the mravais
lattice, fills space without overlap and without leaving voids
a2
a1
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The crystal lattice: Wigner-Seitz cell
Wigner-Seitz cell: special choice of primitive unit cell: region of points closer to a given lattice point
than to any other.
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The crystal lattice: basis
We could think: all that remains to do is to put atoms on the lattice points
of the mravais lattice.
mut: not all crystals can be described by a mravais lattice (ionic,
molecular, not even some crystals containing only one species of
atoms.)
m T: all crystals can be described by the combination of a mravais lattice
and a basis. This basis is what one ³puts on the lattice points´.
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The crystal lattice: one atomic basis
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The crystal lattice: basis
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The crystal lattice: basis
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The crystal lattice: one more word about symmetry
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The crystal lattice: one more word about symmetry
The other symmetry to consider is point symmetry. The mravais lattice for
these two crystals is identical:
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Labelling crystal planes (Miller indices)
step 3: (1,2,1)
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Labelling crystal planes (Miller indices)
step 3: (2,6,3)
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Example
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Real crystal structures
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What structure do the solids have? Äan we predict it?
Äonsider inert elements (spheres). This could be anything with no
directional bonding (noble gases, simple and noble metals).
Just put the spheres together in order to fill all space. This should have
the lowest energy.
A simple cubic structure?
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Simple cubic
The simple cubic structure is a mravais lattice.
The basis is one atom. So there is one atom per unit cell.
a1 a2
a3
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Simple cubic
We can also simply count the atoms we see in one unit cell.
mut we have to keep track of how many unit cells share these atoms.
1/8 atom
1/8 atom
1/8 atom
1/8 atom
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Simple cubic
A simple cubic structure is not a good idea for packing spheres (they
occupy only 52% of the total volume).
Only two elements crystallise in the simple cubic structure (F and O).
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metter packing
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Älose-packed structures: fcc and hcp
hcp fcc
AmAmAm... AmÄAmÄAmÄ...
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Älose-packed structures: fcc and hcp
hcp fcc
AmAmAm... AmÄAmÄAmÄ...
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Älose-packed structures: fcc and hcp
hcp fcc
AmAmAm... AmÄAmÄAmÄ...
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Älose-packed structures: fcc and hcp
hcp fcc
AmAmAm... AmÄAmÄAmÄ...
VÚ
Älose-packed structures: fcc and hcp
hcp fcc
AmAmAm... AmÄAmÄAmÄ...
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Älose-packed structures: fcc and hcp
hcp fcc
AmAmAm... AmÄAmÄAmÄ...
1/8 atom
1/2 atom
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The crystal lattice: mravais lattice (3D)
The fcc and bcc lattices are also mravais lattices but the edges of the
cube are not the correct lattice vectors.
When choosing the correct lattice vectors, one has only one atom per
unit cell.
1/8 atom
1/8 atom
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The crystal lattice: mravais lattice (3D)
The fcc and bcc lattices are also mravais lattices but the edges of the
cube are not the correct lattice vectors.
When choosing the correct lattice vectors, one has only one atom per
unit cell.
1/8 atom
1/8 atom
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Älose-packed structures: hcp
Älose-packed structures are indeed found for inert solids and for metals.
For metals, the conduction electrons are smeared out and directional
bonding is not important.
Most elements crystallize as hcp (36) or fcc (24).
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Älose-packed structures: ionic materials
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Älose-packed structures: ionic materials
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Non close-packed structures
diamond (only 34
graphite % packing)
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Non close-packed structures
Gallium, Iodine
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Ärystal structure determination
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X-ray diffraction
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X-ray diffraction
The crystals can be used to diffract X-rays (von Laue, 1912).
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The mragg description (1913): specular reflection
The mragg condition for constructive interference holds for any number
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of layers, not only two (why?)
X-ray diffraction: the mragg description
The X-rays penetrate deeply and many layers contribute to the reflected
intensity
The diffracted peak intensities are therefore very sharp (in angle)
The importance of the Miller indices becomes apparent. Ärystal planes
are essential
The physics of the lattice planes is totally obscure!
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A little reminder about waves and diffraction
Ȝ=1Å
hȞ = 12 keV
complex notations
(for real )
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X-ray diffraction, von Laue description
incoming wave at r
absolute E0 of no interest
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X-ray diffraction, von Laue description
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X-ray diffraction, von Laue description
with
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X-ray diffraction, von Laue description
so the measured intensity is
with
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Volume
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k k¶
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X-ray diffraction, von Laue description
so the measured intensity is
Volume
V
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X-ray diffraction, von Laue description
so the measured intensity is
Volume
V
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The reciprocal lattice
for a given mravais lattice
or
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The reciprocal lattice
construction of the reciprocal lattice
a useful relation is
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The reciprocal lattice
if we have
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X-ray diffraction, von Laue description
so the measured intensity is
Volume
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The reciprocal lattice
example 1: in two dimensions
|a1|=a
|a2|=b
|b1|=2ʌ/a
|b2|=2ʌ/b
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Lattice waves
b
a
2ʌ/a
(0,0) 2ʌ/b
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Lattice waves
b
a
2ʌ/a
(0,0) 2ʌ/b
KK
Lattice waves
b
a
2ʌ/a
(0,0) 2ʌ/b
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Lattice waves
b
a
2ʌ/a
(0,0) 2ʌ/b
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Lattice waves
b
a
2ʌ/a
(0,0) 2ʌ/b
Kã
Lattice waves
b
a
2ʌ/a
(0,0) 2ʌ/b
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The reciprocal lattice
example 2:
The fcc lattice is the reciprocal of the bcc lattice and vice versa.
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Other applications of the reciprocal lattice
a
1D chain of atoms
Fourier series
alternatively
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Other applications of the reciprocal lattice
1D reciprocal lattice
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Other applications of the reciprocal lattice
1D
3D
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X-ray diffraction, von Laue description
so the measured intensity is
with
use
Laue
constructive interference when condition
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X-ray diffraction, von Laue description
so the measured intensity is
with
use
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What is in the basis?
with
Volume
V
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X-ray diffraction, von Laue description
so the measured intensity is
Volume
V
v
X-ray diffraction, von Laue description
so the measured intensity is
Volume
V
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X-ray diffraction, von Laue description
so the measured intensity is
Volume
V
vh
The Ewald construction
Laue condition if G is a rec. lat. vec.
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Why does the mragg condition appear so much simpler?
Laue condition
automatically fulfilled parallel to the surface (choosing
specular reflection)
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Relation to lattice planes / Miller indices
The vector
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x-ray diffraction in practice
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X-ray diffraction in practice
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typical result
vv
typical result (with filter)
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This is all good and fine but one needs to have the crystal aligned
EXAÄTLY such that the condition of specular reflection is fulfilled. This is
not so simple because the reflections are very narrow.
One trick is to use a powder of small crystals instead of one big crystal.
Due to the disorder in the powder, the specular reflection is always
realized for some crystals.
Another trick is to use non-monochromatic (white) x-rays to increase the
chances of constructive interference (see next slide)
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Laue Method
crystallize
protein
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remember
advanced x-ray sources: synchrotron radiation
SPring-8 ASTRID
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Other scattering methods (other than x-rays)
electrons (below)
neutrons
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Electron microscopes
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Scanning Tunnelling Microscope
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