Chapter 3 - Introduction To Crystallography

9/28/2017
Basic
crystallography
Dr. Luis César R. Aliaga

Department o f Materials
Polytechnic Institute of Rio de Janeiro
Overview
• Crystalline and non-crystalline materials

• Crystals
• Crystal lattices
• Some relevant crystal structures
• Crystal planes
• Reciprocal lattice
• X-rays
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What is crystallography?
Crystallography is the experimental science of the arrangement of

atoms in solids. The word "crystallography" derives from the Greek
words crystallon = cold drop / frozen drop, with its meaning extending
to all solids with some degree of transparency, and grapho = write.
A crystalline solid: HRTEM image of strontium

titanate. Brighter atoms are Sr and darker are Ti.
A TEM image of amorphous interlayer
at the Ti/(001)Si interface in an
as-deposited sample.
 The structure o f
materials
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Crystalline and non-crystalline materials
Crystalline solids Non-crystalline systems
Quasicrystals
Amorphous
- Long-range order
- Translate symetry - No long-range order
- Rotational symetry - No translate symetry
- No convectional rotational symetry
Crystals
Simulated structure
Monocrystal polycrystalline
Translate symetry
´ 1 1 2 2 3 3 Polycrystal is composed for many

crystals usually known as grains
- Rotational symetry which have diferente orientations and
n = 1, 2, 3, 4 and 6 limited by grain boundaries.
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Symmetry
Symmetry is a the set of mathematical rules
that describe the shape of an object
Do you know that there is only ONE

object in the geometrical universe
with perfect symmetry?
Infinite planes of symmetry pass through its center, infinite

rotational axes are present, and no matter how little or much you
rotate it on any of its infinite number of axes, it appears the same!
A sphere is the HOLY GRAIL of symmetry!!

Matter presenten just limited symetry
Ideal Crystals → Real Crystals → Microstructures → Material → Component

Geometrical entity
Ideal Crystal Ideal Mathematical Crystal

Physical Property
Consider only the Geometrical Entity Part of the infinite crystal

or
only the Physical Property
Crystal*
Part of the infinite crystal Consider only the Orientational
or
Positional Order
Crystal**
Part of the infinite crystal
Put in Crystalline defects

& Free Surface
& Thermal Vibration
Vacancy shown as an example of a defect
‘Real Crystal’
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Crystalline and non-crystalline materials
Quasicrystals Amorphous
Simulated structure
Rotational symmetry: n = 5, 7, 10, 12..
Most quasicrystals are icosahedral
and decagonal.
Cooling rate
Slow cooling Fast cooling
High T:
liquid
Low T:
solid
Thermodynamic No thermodynamic
equilibrium equilibrium
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Radial Distribution Function

Paolo
Fornasini
Univ. Trento
average density
RDF = 4 πr 2 ρ(r ) = 4 πr 2 ρ 0 g(r )
PDF = Pair Distribution Function
g(r)
0
Short-range order r
 Crystals
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Crystals
Macroscopic regularities
(e.g. constancy o f angles)
Classification of crystals
Quartz crystal (SiO2 )
Regular packing
of microscopic structural units
R.J. Haüy (1743-1822)
Atoms and crystals
HYPOTHESIS: Structural units = atoms
Example: NaCl Atomic masses: Na 38.12 x 1 0 -24 g

Cl 58.85 x 1 0 -24 g
Cubic structure
1 cm 3 m = 2.165 g
N = 44.6 x 1 0 21 atoms
0.28 nm = 2.8 Å
Inter-atomic distances
CONCLUSION: ≈X-ray wavelengths
Atomic dimensions
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X-ray diffraction from crystals
Munich, 1912:
• Max von Laue
• W. Friedrich & P.Knipping
Crystallography
Cambridge, 1 9 1 2 / 1 3
William Lawrence Bragg

William Henry Bragg (1890-1971)
(1862-1942)
Bragg spectrometer
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Crystal structure
Bravais lattice + Basis = C.S.
1- D Atom
Molecule
2- D
333-D
- -DD Protein
Bravais lattice + basis
1-D
2-D
3-D
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 Crystal lattices
Translation vectors (2D)
2-D
→
R
For every lattice point
→ →
→ R = n1a→+ n2b
b
a→
integers primitive
Arbitrary origin vectors
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Primitive vectors (2D)
→ →→ 2-D
R = n1a + n2b
→ →
→ R
R R
→
b
→
a
→ →
Different choices of primitive vectors a,b
Non-primitive vectors (2D)
2-D
→→
Not all a,b pairs are primitive
→ →
R → R
R
→
b
→
a
→ →
R ≠ n1a→+ n2b
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Primitive vectors (3D)
→ → →
R = n1a→+ n2b + n3c 3-D
→ →
c b
→
a
→→ →
Different choices of primitive vectors a,b,c
Primitive unit cells (2D)
2-D
→
b
→
a
Different choices of primitive unit cells
Primitive cell = 1 lattice point
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Conventional unit cells (2D)
2-D
→
b
→
a
More than 1 lattice point per unit cell
Non-Bravais lattices
Atoms 2-D
→ → →
R ≠ n1a + n2b
Un-equivalent
sites
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Bravais lattices
Bravais
lattice
Basis
Classification o f cells
2-D 3-D
→
b c→

→
a α →
b

β →
a
a b c latin
α β  greek
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Surface Bravais lattice
2-D
Non-primitive unit cell
3-D Bravais lattices
3-D
4 unit cells
7 14
crystal P = primitive = Bravais
+
I = body centered
systems lattices
F = face centered
C = side centered
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Coordinates
2 (3,2)
Lattice points:
integer
coordinates
→ →
R = n1→
a + n2b
1
1
2
1
4
0 1
4
3
4 1 2 3
Inside cell: fractional coordinates
1 1  3 1
 ,   , 
4 4 4 2
Lattices
Packing of objects displaying 5- and 8-

fold symmetry. Note that they do not
fill completely space and therefore
they are not compatible with crystals
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 Some relevant crystal

structures
Simple cubic lattice
84-Po a=3.35 Å
Bravais lattice
a
lattice parameter
Primitive unit cell

(1 lattice point per cell)
Coordination number = 6
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Body centered cubic lattice (bcc)
24-Cr a=2.88 Å
26-Fe a=2.87 Å
42-Mo a=3.15 Å
Bravais lattice
a
lattice parameter
conventional unit cell

(2 lattice points per cell)
Face centered cubic lattice (fcc)
29-Cu a=3.61 Å
47-Ag a=4.09 Å
79-Au a=4.08 Å
Bravais lattice
a
lattice parameter

(4 lattice points per cell)
Coordination number = 1 2
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Diamond structure
6-C a=3.57 Å
14-Si a=5.43 Å
32-Ge a=5.66 Å
Non-Bravais lattice
fcc Bravais lattice + 2-atom basis
1 1 1
 , ,
4 4 4
a (0, 0,0) 

(8 atoms per cell)
Zincblende (sphalerite) structure
ZnS a=5.41 Å
GaAs a=5.65 Å
SiC a=4.35 Å
Non-Bravais lattice
1 1 1
 , ,
4 4 4
(0, 0,0) 
a

(8 atoms per cell)
Cordination number = 4
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Rock-salt (NaCl) structure
NaCl a=5.64 Å
KBr a=6.60 Å
CaO a=4.81 Å
Non-Bravais lattice
1 1 1
 , ,
2 2 2 
(0, 0,0) 
a

(8 atoms per cell)
Cordination number = 6
Simple hexagonal structure
Top view
a Hexagonal symmetry Primitive cell

2 lattice parameters
a→2
Primitive unit cell
(1 lattice point per cell) a1 = a2
→
a1
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Hexagonal close packed structure
4-Be a=2.29 Å
12-Mg a=3.21 Å
48-Cd a=2.98 Å
Non-Bravais lattice
primitive cell + 2-atom basis

c
1 1 1
 , ,
2 2 2
(0, 0,0) 
a
8
c= a
3
Conventional unit cell

(2 atoms per cell)
Cordination number = 1 2
Coordination number
diamond cubic bcc
N=4 N=6 N=8
fcc hcp
Close packing
N=12
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Close-packing o f spheres
A A A A A
B B B B
A A A A
B B B
1st 2nd
A A A A A layer
layer B B B B
A A A A
B B B
A A A A A
A A A A A
A A A A C C C
A A A A A C C
3rd
layer A A A A C C C
A A A A A
A BA ABC
hcp versus fcc
hcp fcc
A A A A A
A A A A C C C
A A A A A C C
A A A A C C C
A A A A A
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 Crystal planes
Crystal planes
2-D
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Miller indices, 2-D (a)
2-D
→
b
a→
(hk) = ( 2 1 ) (hk) = ( 11 )
Miller indices, 2-D (b)
(hk) = (01) (hk) = (1 1)
(hk) = (10) (hk) = (21)
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Miller indices, 3-D

→ (hkl) = (100) →
c c (hkl) = (111)
→ →
b b
→ →
a a
3-D
→ (hkl) = (114) → (hkl) = (210)
c cc
→
b →
b
→ →
a a
Miller indices, cubic lattices
sc
(100) (110) (111)
bcc
(200) (110) (222)
fcc
(200) (220) (111)
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Interplanar distance
dhkl Cubic lattices
2 a2
dhkl =
h2 + k 2 + l 2
Copper, fcc, a=3.61 Å
a a a
d200 = =1.805 Å d220 = =1.276 Å d111 = = 2.084 Å
2 2 2 3
Planes and directions
Perpendicular direction
[hkl]
Family of planes
(hkl)
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Equivalent planes and directions
Equivalent directions <100 >
[010] [001]
[100]
(100) (010) (001)
Equivalent planes {100}
 Reciprocal lattice
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Reciprocal quantities
Periodic behaviour
T ω = 2 π /T
time frequency
λ k = 2π / λ
position wave-vector
Harmonics
Periodic behaviour
T ω0 fundamental
2ω0 2nd harmonic
3ω0 3rd harmonic
time
frequency
Periodic behaviour
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1-D
Direct space Reciprocal space
2
a* = a
→ →*
a a
→ →
a a*
2-D, rectangular lattice (a)
2 π 2 π.b
a* = a =
ab
→ 2 π 2 π.a
R b* = b = →
ab *
→
R
→
b a ⊥b
→*
→ →*
a →* → b
b ⊥a
→*
a
→ → → →* →*
R = n1a + n2b R = m1a→* + m2b
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2-D, rectangular lattice (b)
2-D, rectangular lattice (c)
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2-D, rectangular lattice (d)
2-D, oblique lattice (a)
2π 2 πb
a* = =
a sin θ ab sin θ
b = 2 π = 2 πa
*
→ b sin θ ab sin θ
→ R
b → →
→ a ⊥b
→* b*
a →* →
b ⊥a
a→*
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2-D, oblique lattice (b)
Cubic lattices (a):SC
(111)
→ →*
c c
→ →
b b*
(110)
a→ a→ * (100)
(100) (110) (111)
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Cubic lattices (b): BCC
c→ r
c→*
→
→
b b*
→
(200)
a a→*
(200) (110) (222)
Cubic lattices (c): FCC
c→ c→*
→
→
b b*
→ (200)
a a→*
(200) (220) (111)
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Primitive vectors: general rule
c→ → c→*
b ×c
→
a = 2 π→ → →
→*
a · (b ×c ) →
→
→
→
c ×a
→ a→* b*
→ b b * = 2 π→ → →
a a · (b ×c )
c*
→
c→ →
a ×b
→
c = 2π → → →
→*
a · (b ×c )
→
→
a→ b →*
a b*
( )
→
a· b ×c
→ →
Reciprocal lattice and lattice planes
For any family of lattice planes separated by a

distance d there are reciprocal lattice vectors
perpendicular to the planes, the shortest of which
have a length 2π/d.
For any reciprocal lattice vector R*,

there is a family of lattice planes
normal to R* and separated
by a distance d,
where 2π/d is the length of the shortest
reciprocal lattice vector
parallel to R*.
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 X-rays and electrons

Difraction
X-ray diffraction pattern
Direct space
3-dimensional lattice
Reciprocal space
2-dimensional projection
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Basic idea
A ) Family of planes → wave-vector
→
K hkl dh'k'l' →
2π
K h'k'l'
K hkl =
dhkl
dhkl
B) Wave-vectors → set of points
C) Set of points → lattice
1 8 9 5 - Discovery o f X-rays
Wilhelm Konrad Röntgen

(1845-1923)
Würzburg (Germany)
November 8,1895
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Electromagnetic waves
Speed (in vacuum):
c ≈ 3×108 m/s
λ
Electric field
Magnetic field
c
1 Å = 1 0 -10 m
Wavelength λ 1 nm = 1 0 -9 m
Frequency ν = c/λ ω = 2 πν
Photon energy E = hν = hω
Wave-vector
r
k
2π
k=
λ
λ
Plane wave
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Plane wave
r
k 2π
k=
λ
r
→ →→
E(r) = Eo.exp(2i[k.r – v.t])
{ }
→ →
Complex
ik ·r
Re e notation
Electromagnetic spectrum
E (eV) ν (Hz) λ (m)

Photon 102 ELF
Wavelength 1 0 -12 106
energy
Radio
waves
E = hν = hc / λ 1 0 -8
106
102
Micro
Frequency 1 0 10
1 0 -4 waves 1 0 -2
IR
X-rays 1 0 14
1 1 0 -6
λ ≈ 0.01÷10 Å
UV
ν ≈ 1017 ÷10 20 Hz 104

1 0 18
1 0 -10
X
E ≈ 0.4 ÷ 400 keV
γ
1 0 22
108 1 0 -14
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Interaction o f x-rays with matter
Auger
electrons
Photo-electrons Fluorescence
EA Photo-electric
E hν F absorption
hν
Beam attenuation
Incoming beam
(monochromatic)
Scattering
hν ' hν
Inelastic Elastic
scattering scattering
X-RAYS and X-ray techniques
X-rays U.V. I.R.

12.4
λ (m) E[keV] =
10-12 10-10 10-8 10-6 10-4 10-2 λ [Å]
1Å 1 µm
Imaging Scattering Spectroscopy
λ =2dsinθ
Absorption
Intensity
Bragg angle Energy
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Let us consider in‐plane scattering
A B
X Y
Atomic Planes
Extra path traveled by incoming waves  AY
These can be in phase if
Extra path traveled by scattered waves  XB  incident = scattered
But this is still reinforced scattering
A B
and NOT reflection
X Y
BRAGG’s EQUATION Let us consider scattering across planes
Click here to visualize
constructive and
destructive
interference
See Note Ӂ later
 A portion of the crystal is shown for clarity- actually, for destructive interference to occur
many planes are required (and the interaction volume of x-rays is large as compared to that shown in the schematic).
 The scattering planes have a spacing ‘d’.
 Ray-2 travels an extra path as compared to Ray-1 (= ABC). The path difference between Ray-
1 and Ray-2 = ABC = (d Sin + d Sin) = (2d.Sin).
 For constructive interference, this path difference should be an integral multiple of :
n = 2d Sin  the Bragg’s equation. (More about this sooner).
 The path difference between Ray-1 and Ray-3 is = 2(2d.Sin) = 2n = 2n. This implies that if Ray-1
and Ray-2 constructively interfere Ray-1 and Ray-3 will also constructively interfere. (And so forth).
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 The previous page explained how constructive interference occurs. How about the rays just of
Bragg angle? Obviously the path difference would be just off  as in the figure below. How
come these rays ‘go missing’?
Click here to understand how
destructive interference of
just ‘of‐Bragg rays’ occur
Interference of Ray‐1 with Ray‐2
Which remains same
Note that they ‘almost’ constructively interfere! thereafter (like in the
BB’ plane)
How to ‘see’ that path difference increases with angle?
Clearly A’BC’ > ABC
Laue versus Bragg
 In Laue’s picture constructive and destructive interference at various points in space is
computed using path differences (and hence phase differences) given a crystalline array of
scatterers.
 Bragg simplified this picture by considering this process as ‘reflections from atomic planes’.
Reflection versus Diffraction
 Though diffraction (according to Bragg’s picture) has been visualized as a reflection from a
set of planes with interplanar spacing ‘d’  diffraction should not be confused with reflection
(specular reflection).
Reflection Diffraction
Occurs throughout the bulk
Occurs from surface (though often the penetration of x-rays in only of the
order of 10s of microns in a material)
Takes place at any angle Takes place only at Bragg angles
~100 % of the intensity may be reflected Small fraction of intensity is diffracted

Planes are imaginary constructs
Note: X‐rays can ALSO be reflected at very small angles of incidence
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Understanding the Bragg’s equation
 n = 2d Sin
The equation is written better with some descriptive subscripts:
n Cu K  2 d hkl Sin hkl If this equation is satisfied, then  is Bragg
 n is an integer and is the order of the reflection

(i.e. how many wavelengths of the X-ray go on to make the path difference between planes). Note: Ӂ
Note: if hkl reflection (corresponding to n=1) occurs at hkl then 2h 2k 2l reflection (n=2) will occur at a higher angle 2h 2k 2l.
 Bragg’s equation is a negative statement

 If Bragg’s eq. is NOT satisfied  NO ‘reflection’ can occur
 If Bragg’s eq. is satisfied  ‘reflection’ MAY occur
(How?- we shall see this a little later).
 The interplanar spacing appears in the Bragg’s equation, but not the interatomic
spacing ‘a’ along the plane (which had forced incident = scattered); but we are not
free to move the atoms along the plane ‘randomly’  click here to know more.
  For large interplanar spacing the angle of reflection tends towards zero → as d increases,
Sin decreases (and so does ).
 The smallest interplanar spacing from which Bragg diffraction can be obtained is /2 →
maximum value of  is 90, Sin is 1  from Bragg equation d = /2.
Order of the reflection (n)
 For Cu K radiation ( = 1.54 Å) and d110= 2.22 Å
n Sin = n/2d 
1 0.34 20.7º • First order reflection from (110)  110
43.92 • Second order reflection from (110) planes  110

2 0.69
º • Also considered as first order reflection from (220) planes  220
Relation between dnh nk nl and dhkl
a e.g.
Cubic crystal
d hkl 
h k l
2 2 2
a
d 220  d 220 1
d nh nk nl 
a
8 
(nh) 2  (nk ) 2  (nl ) 2 d110 2
a
a d hkl
d110 
d nh nk nl   2
n h2  k 2  l 2 n
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X-rays spectra from materials: Crystals
Powder diffraction pattern from Al Note:
 This is a schematic pattern
Radiation:  In real patterns peaks or not
idealized  peaks 
Cu K,  = 1.54 Å broadened
 Increasing splitting of peaks
These are Miller indices in reciprocal with g 
space (these are not planes they (1 & 2 peaks get resolved in the high
correspond to panes in real space) angle peaks)
 Peaks are all not of same
intensity
 No brackets are used around
the indexed numbers
(the peaks correspond to planes in the
real space)
X-rays spectra from materials: Quasicrystals

The First Natural QC (Icosahedrite)
Al63Cu24Fe13,the first natural quasicrystal Dicovered in 2009

Natural Quasicrystals, Luca Bindi, Paul J. Steinhardt, Nan Yao, Peter J. Lu, SCIENCE,324, 2009.
quasiperiodic crystals possessing symmetries that are forbidden for periodic crystals
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X-rays spectra from materials: Amorphous
X‐rays of CuZrTi alloy
Due to lack atomic order there is

no peaks just a long halo !!
Electrons Diffraction: Crystals
Visualising the reciprocal lattice

Weiss Zone Law
Instead of drawing vectors, show lattice of
points or “nodes” If the lattice vector [U V W]
Each node represents plane (hkl) in
reciprocal space lies in the plane (h k l) then:
Illustrative example: section of reciprocal
lattice for BCC metal: hU + kV + lW = 0
Electron diffraction
Electron beam oriented parallel to
lattice vector called the “zone axis”
Diffracting planes must be parallel to
electron beam
therefore they obey the Weiss Zone
law*
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Fe‐ Standard 001 projection of a cubic crystal
[110]
[001]
‐ ‐
[111]
‐
SAED pattern of the Ni21–C79 film
The diffraction pattern from poly-

crystalline regions contain multiple
rings around the bright spot. The The diffraction pattern shows the
multiple rings are due to the polycrystal structure of the nickel to be
crystalline nature of sample face centred cubic, as marked. The
(different grains in different ring pattern indicates that the
orientation nickel crystals are randomly
orientated.
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Electrons Diffraction: quasicrystals

The First Natural QC (Icosahedrite)
The 5-fold
Diffraction Pattern
The 3-fold
Diffraction Pattern
SEM image of
Khatyrka
meteorite, The
White part contains
Natural QCs
The 2-fold
Diffraction Pattern
Icosahedrite, Al63Cu24Fe13, the first natural quasicrystal,L. Bindi,PJ. Steinhardt, N. Yao,PJ. Lu,
American Mineralogist, Volume 96, pages 928–931, 2011
Electrons diffraction: Amorphous
Selected Area Electron Selected Area Electron Diffraction

Diffraction of Ti95Si5 thin film. of Ti70Si30 tin film.
sample showed
polycrystalline diffraction
pattern.
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XRD TECHNIQUES AND APPLICATIONS
• powder diffraction
• single‐crystal diffraction
• thin film techniques
• small‐angle diffraction
• phase identification • crystal size

• crystal structure determination • residual stress/strain
• radial distribution functions • defect studies
• thin film quality • in situ analysis (phase
• crystallographic texture transitions, thermal expansion
• percent crystalline/amorphous coefficients, etc)
• superlattice structure
THE POWDER METHOD
 In the powder method the specimen has crystallites (or grains) in many orientations
(usually random).
 Monochromatic* X-rays are irradiated on the specimen and the intensity of the
diffracted beams is measured as a function of the diffracted angle.
 In this elementary text we shall consider cubic crystals.
d hkl Cubic  a
  2 d Sin (1) Cubic crystal (2)
h  k2  l2
2
(2) in (1)
4a 2 sin 2  4a 2
  2 2 2
2
 (h 2  k 2  l 2 )  sin 2 
h k l  2
2
a2  (h 2  k 2  l 2 )  (h 2  k 2  l 2 )  sin 2 
4 sin  2
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The ratio of (h2 + k2 + l2) derived from extinction rules

As we shall see soon the ratios of (h2 + k2 + l2) is proportional to Sin2
 which can be used in the determination of the lattice type
SC 1 2 3 4 5 6 8 …
BCC 1 2 3 4 5 6 7 …
FCC 3 4 8 11 12 …
DC 3 8 11 16 …
 Note that we have to consider the ratio of only two lines to distinguish FCC
and DC. I.e. if the ratios are 3:4 then the lattice is FCC.
 But, to distinguish between SC and BCC we have to go to 7 lines!
Determination of Crystal Structure (lattice type) from 2 versus Intensity Data Solved example 1

Let us assume that we have the 2 versus intensity plot from a diffractometer
 To know the lattice type we need only the position of the peaks (as tabulated below)
# 2  Sin Sin2  ratio Index d
1 38.52 19.26 0.33 0.11 3 111 2.34
2 44.76 22.38 0.38 0.14 4 200 2.03
3 65.14 32.57 0.54 0.29 8 220 1.43
4 78.26 39.13 0.63 0.40 11 311 1.22
5 82.47 41.235 0.66 0.43 12 222 1.17
6 99.11 49.555 0.76 0.58 16 400 1.01
7 112.03 56.015 0.83 0.69 19 331 0.93
8 116.60 58.3 0.85 0.72 20 420 0.91
9 137.47 68.735 0.93 0.87 24 422 0.83
10 163.78 81.89 0.99 0.98 27 333 0.78
Note that Sin cannot be > 1

From the ratios in column 6 we conclude that FCC Note
(h 2  k 2  l 2 )  sin 2 
a
Using   2 d Sin 1.54  2 d111 Sin111  2 0.33
3
o
a  4.04 A  Al We can get the lattice parameter  which correspond to that for Al
Note: Error in d spacing decreases with  → so we should use high angle lines for la ce parameter calcula on
48
9/28/2017
Solved example 2
Another example:
Given the positions of the Bragg peaks we find the lattice type
Dividing Sin2 by Whole

Ratios
2→  Sin Sin2  number
of Sin2 0.134/3 = 0.044667 ratios
1 21.5 0.366 0.134 1 3
2 25 0.422 0.178 1.33 3.99 4
3 37 0.60 0.362 2.70 8.10 8
4 45 0.707 0.500 3.73 11.19 11
5 47 0.731 0.535 4 11.98 12
6 58 0.848 0.719 5.37 16.10 16
7 68 0.927 0.859 6.41 19.23 19
FCC
What happens when we increase or decrease ?
We had pointed out that  ~ a is preferred for diffraction. Let us see what happens if we ‘drastically’
increase or decrease . (This is only a thought experiment!!)
Aluminium = 1.54 Å = 3 Å = 0.1 Å

hkl d Sin()  2 Sin()  2 Sin()  2
111 2.34 0.33 19.26 38.52 0.64 39.87 79.74 0.02 1.22 2.45
200 2.03 0.38 22.38 44.76 0.74 47.64 95.28 0.02 1.41 2.82
220 1.43 0.54 32.57 65.14 1.05 - - 0.03 2.00 4.01
311 1.22 0.63 39.13 78.26 1.23 - - 0.04 2.35 4.70
222 1.17 0.66 41.24 82.47 1.28 - - 0.04 2.45 4.90
400 1.01 0.76 49.56 99.11 1.49 - - 0.05 2.84 5.68
331 0.93 0.83 56.02 112.03 1.61 - - 0.05 3.08 6.16
420 0.91 0.85 58.30 116.60 1.65 - - 0.05 3.15 6.30
422 0.83 0.93 68.74 137.47 1.81 - - 0.06 3.45 6.91
333 0.78 0.99 81.89 163.78 1.92 - - 0.06 3.68 7.35
If we ~double  → we get too If we make  small→

With CuK  = 1.54 Å few peaks all the peaks get
crowded to small
angles
And the detector may not be able to
resolve these peaks if they come too close!
49

Chapter 3 - Introduction To Crystallography

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Chapter 3 - Introduction To Crystallography

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Dr. Luis César R. Aliaga

• Crystalline and non-crystalline materials

Crystallography is the experimental science of the arrangement of

A crystalline solid: HRTEM image of strontium

Crystalline and non-crystalline materials

Crystalline solids Non-crystalline systems

´ 1 1 2 2 3 3 Polycrystal is composed for many

Do you know that there is only ONE

Infinite planes of symmetry pass through its center, infinite

A sphere is the HOLY GRAIL of symmetry!!

Ideal Crystals → Real Crystals → Microstructures → Material → Component

Ideal Crystal Ideal Mathematical Crystal

Consider only the Geometrical Entity Part of the infinite crystal

Put in Crystalline defects

Vacancy shown as an example of a defect

Crystalline and non-crystalline materials

Slow cooling Fast cooling

Radial Distribution Function

RDF = 4 πr 2 ρ(r ) = 4 πr 2 ρ 0 g(r )

PDF = Pair Distribution Function

Quartz crystal (SiO2 )

Atoms and crystals

HYPOTHESIS: Structural units = atoms

Example: NaCl Atomic masses: Na 38.12 x 1 0 -24 g

X-ray diffraction from crystals

William Lawrence Bragg

Bravais lattice + Basis = C.S.

Bravais lattice + basis

Translation vectors (2D)

Primitive vectors (2D)

Non-primitive vectors (2D)

Primitive vectors (3D)

Primitive unit cells (2D)

Primitive cell = 1 lattice point

Conventional unit cells (2D)

More than 1 lattice point per unit cell

Surface Bravais lattice

Non-primitive unit cell

3-D Bravais lattices

Packing of objects displaying 5- and 8-

 Some relevant crystal

Simple cubic lattice

Primitive unit cell

Body centered cubic lattice (bcc)

conventional unit cell

Face centered cubic lattice (fcc)

conventional unit cell

fcc Bravais lattice + 2-atom basis

conventional unit cell

Zincblende (sphalerite) structure

fcc Bravais lattice + 2-atom basis

conventional unit cell

Rock-salt (NaCl) structure

fcc Bravais lattice + 2-atom basis

conventional unit cell

Simple hexagonal structure

a Hexagonal symmetry Primitive cell

Hexagonal close packed structure

primitive cell + 2-atom basis

Conventional unit cell

diamond cubic bcc

N=4 N=6 N=8