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Duncan Alexander: Structure factors and crystal stacking LSME, EPFL
Structure factors and crystal stacking
1
Duncan AlexanderEPFL-CIME
Duncan Alexander: Structure factors and crystal stacking LSME, EPFL
Contents
• Atomic scattering theory
• Crystal structure factors
• Close packed structures
• Systematic absences
• Twinning and stacking faults in diffraction
• Ring diffraction patterns (nanocrystalline and amorphous)
• Measuring epitaxial relationships
2
Duncan Alexander: Structure factors and crystal stacking LSME, EPFL
Repetition of translated structure to infinity
Crystals: translational periodicity & symmetry
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Duncan Alexander: Structure factors and crystal stacking LSME, EPFL
Repetition of translated structure to infinity
Crystals: translational periodicity & symmetry
3
Duncan Alexander: Structure factors and crystal stacking LSME, EPFL
Elastic scattering theory
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Duncan Alexander: Structure factors and crystal stacking LSME, EPFL
Consider coherent elastic scattering of electrons from isolated atom
Differential elastic scatteringcross section:
Atomic scattering factor
Scattering theory - Atomic scattering factor
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Duncan Alexander: Structure factors and crystal stacking LSME, EPFL
Amplitude of a diffracted beam from a unit cell:
ri: position of each atom => ri: = xi a + yi b + zi c
K = g: K = h a* + k b* + l c*
Define structure factor:
Intensity of reflection:
Structure factor
6
Note fi is a function of s and (h k l)
Duncan Alexander: Structure factors and crystal stacking LSME, EPFL
Stacking of close packed structures
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● For monoatomic compounds face centred cubic (FCC) and hexagonal close packed (HCP) are the most dense arrangements of atoms possible
● Both consist of hexagonal rafts of atoms called close packed planes
● These rafts stack together in sequences:
Hexagonal close packed:A - B - A - B - A -B
Cubic close packed/face centred cubic:
A - B - C - A - B - C - A - B - C
Animations from: http://departments.kings.edu/chemlab/animation/clospack.html
Duncan Alexander: Structure factors and crystal stacking LSME, EPFL
Stacking of close packed structures
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● FCC has a crystal structure of:
Cubic lattice(a = b = c, α = β = γ = 90º)
Lattice points:0,0,0; ½,½,0; ½,0,½; 0,½,½
● HCP has a crystal structure of:
Hexagonal lattice(a = b ≠ c, α = β = 90º, γ = 120º)
Lattice points:0,0,0; 2⁄3,1⁄3,½
● Both can have > 1 atom in the motif that combines with the lattice point, e.g.:– zinc blende structure (AaBbCc) packing based on FCC– wurtzite structure (AaBbAaBb) packing based on HCP
Duncan Alexander: Structure factors and crystal stacking LSME, EPFL
Consider FCC lattice with lattice point coordinates:0,0,0; ½,½,0; ½,0,½; 0,½,½
x
z
y
Calculate structure factor for plane (h k l) (assume single atom motif):
x
z
y
x
z
y
x
z
y
Structure factor and forbidden reflections
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where:
For atomic structure factor f find:
Since:
For h k l all even or all odd:
For h k l mixed even and odd:
Duncan Alexander: Structure factors and crystal stacking LSME, EPFL
Systematic absences
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● Face-centred cubic: reflections with mixed odd, even h, k, l absent:
● Body-centred cubic: reflections with h + k + l = odd absent:
● Reciprocal lattice of FCC is BCC and vice-versa
● What do such systematic absences mean for diffraction?
When we have them we only see diffraction spots forthe non-absent planes (h k l).
Duncan Alexander: Structure factors and crystal stacking LSME, EPFL
Twinning in diffraction
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Example: FCC twinsStacking of close-packed {1 1 1} planes reversed at twin boundary:
A B C A B C A B C A B C➔ A B C A B C B A C B A C
Example: FCC twinsStacking of close-packed {1 1 1} planes reversed at twin boundary:
A B C A B C A B C A B C
View on [1 1 0] zone axis:
{1 1 1} planes:
1 -1 1
0 0 2
1 -1 -1
Duncan Alexander: Structure factors and crystal stacking LSME, EPFL
Twinning in diffraction
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Example: FCC twinsStacking of close-packed {1 1 1} planes reversed at twin boundary:
A B C A B C A B C A B C➔ A B C A B C B A C B A C
Example: FCC twinsStacking of close-packed {1 1 1} planes reversed at twin boundary:
A B C A B C A B C A B C
View on [1 1 0] zone axis:
{1 1 1} planes:
1 -1 1
0 0 2
1 -1 -1
{1 1 1} planes:{1 1 1} planes:
1 -1 1A
1 -1 -1B
A B
Duncan Alexander: Structure factors and crystal stacking LSME, EPFL 12
Example: Co-Ni-Al shape memory FCC twins observed on [1 1 0] zone axis
Images provided by Barbora Bartová, CIME
(1 1 1) close-packed twin planes overlap in SADP
Twinning in diffraction
Duncan Alexander: Structure factors and crystal stacking LSME, EPFL
With scattering from the cubic crystal we can note that the diffracted beam for plane (1 0 0)is parallel to the lattice vector [1 0 0]; makes life easy
However, not true in non-orthogonal systems - e.g. hexagonal:
x
yz
120
a
a
(1 0 0) planes
yz
120
a
a
[1 0 0]
(1 0 0) planes
yz
120
a
a
[1 0 0] g1 0 0
(1 0 0) planes
=> care must be taken in reciprocal space!
Scattering from non-orthogonal crystals
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Duncan Alexander: Structure factors and crystal stacking LSME, EPFL
Stacking faults in diffraction
SADP on [1 1 00] zone axis Bright-field g = 1 -1 0 0 Dark-field g = 1 -1 0 0
g g
● Stacking fault: error in stacking sequence
● Example: intrinsic stacking fault in wurtzite ZnO:– one unit cell of zinc blende structure in sequence: …AaBbAaBbAaBbCcAaBbAaBb…
● Creates thin slice of material; the convolution of its Fourier transform with diffraction spots creates streaking in wurtzite diffraction pattern
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Duncan Alexander: TEM Imaging and diffraction examples LSME, EPFL
Ring diffraction patterns
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If selected area aperture selects numerous, randomly-oriented nanocrystals,SADP consists of rings sampling all possible diffracting planes
- like powder X-ray diffraction
Example: “needles” of contaminant cubic MnZnO3 - which XRD failed to observe!Note: if scattering sufficiently kinematical, can compare intensities with those of X-ray PDF files
Duncan Alexander: TEM Imaging and diffraction examples LSME, EPFL
Nanocrystalline sample image/diffraction
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Image modeDiffraction mode
Bright field image setup - select direct beam with objective aperture
Duncan Alexander: TEM Imaging and diffraction examples LSME, EPFL
Nanocrystalline sample image/diffraction
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Image modeDiffraction mode
Bright field image setup - select direct beam with objective aperture
Contrast from different crystals according to diffraction condition
Duncan Alexander: TEM Imaging and diffraction examples LSME, EPFL
Nanocrystalline sample image/diffraction
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Image mode
Dark field image setup - select some transmitted beams with objective aperture
Diffraction mode
Only crystals diffracting strongly into objective aperture give bright contrast in image
Duncan Alexander: TEM Imaging and diffraction examples LSME, EPFL
Nanocrystalline sample image/diffraction
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Image mode
Dark field image setup - select some transmitted beams with objective aperture
Diffraction mode
Only crystals diffracting strongly into objective aperture give bright contrast in image
Duncan Alexander: TEM Imaging and diffraction examples LSME, EPFL
Amorphous diffraction pattern
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Crystals: short-range order and long-range order
Vitrified germanium (M. H. Bhat et al. Nature 448 787 (2007)
Example:
Amorphous materials: no long-range order, but do have short-range order(roughly uniform interatomic distances as atoms pack around each other)
Short-range order produces diffuse rings in diffraction pattern
Figure from Williams & Carter“Transmission Electron Microscopy”
Duncan Alexander: TEM Imaging and diffraction examples LSME, EPFL
Measuring epitaxial relationships
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SADP excellent tool for studying orientation relationships across interfaces
Example: Mn-doped ZnO on sapphire
Sapphire substrate Sapphire + film
Zone axes:[1 -1 0]ZnO // [0 -1 0]sapphire
Planes:c-planeZnO // c-planesapphire
Duncan Alexander: Structure factors and crystal stacking LSME, EPFL 21
• The sequence of stacking of atoms in a crystal structure determines which crystal planes diffract or are systematic absences
• Specific changes in stacking sequence such as twinning and stacking faults can be identified and localised by a combination of electron diffraction and diffraction contrast imaging
• Sampling of many randomly oriented nanocrystals by selected area aperture gives ring pattern, with one ring for each family of diffracting planes
• Zone axis diffraction patterns can be used to characterise orientation relationships between neighbouring crystals
Summary on Structure Factors and Crystal Stacking