Crystal Structure Analysis

X-ray Diffraction

Electron Diffraction

Neutron Diffraction

Essence of diffraction: Bragg Diffraction

Reading: West 5
A/M 5-6
G/S 3
217
REFERENCES

Elements of Modern X-ray Physics, 2nd Ed. by Jens Als-Nielsen and Des McMorrow,
John Wiley & Sons, Ltd., 2011 (Modern x-ray physics & new developments)

X-ray Diffraction, by B.E. Warren, General Publishing Company, 1969, 1990

(Classic X-ray physics book)

Elements of X-ray Diffraction, 3rd Ed., by B.D. Cullity, Addison-Wesley, 2001

(Covers most techniques used in traditional materials characterization)

High Resolution X-ray Diffractometry and Topography, by D. Keith Bowen and Brian
K. Tanner, Taylor & Francis, Ltd., 1998 (Semiconductors and thin film analysis)

Modern Aspects of Small-Angle Scattering, by H. Brumberger, Editor, Kluwer

Academic Publishers, 1993 (SAXS techniques)

Principles of Protein X-ray Crystallography, 3rd Ed. by Jan Drenth, Springer, 2007
(Crystallography)

218
SCATTERING
Scattering is the process in which waves or particles are forced to deviate from a
straight trajectory because of scattering centers in the propagation medium.

X-rays scatter by interaction with the electron density of a material.

Neutrons are scattered by nuclei and by any magnetic moments in a sample.
Electrons are scattered by electric/magnetic fields.

Momentum transfer: p'  p  q Energy change: E'  E  h

Elastic (E’ = E) For X-rays: E  pc
• Rayleigh (λ >> dobject) Elastic scattering geometry
• Mie (λ ≈ dobject)
• Geometric (λ << dobject)
• Thompson (X-rays)

Inelastic (E’ ≠ E)
• Compton (photons + electrons)
p 
• Brillouin (photons + quasiparticles) q  2 sin
• Raman (photons + molecular vib./rot.)  2
X-RAY SCATTERING
X-rays: λ (in Å) = 12400/E (in eV)
• 100 eV (“soft”) – 100 keV (“hard”) photons
• 12,400 eV X-rays have wavelengths of 1 Å,
somewhat smaller than interatomic distances in solids
Diffraction from crystals!
Roentgen
1901 Nobel
elastic (Thompson, ΔE = 0)
• wide-angle diffraction (θ > 5°)
• small-angle diffraction (θ close to 0°)
• X-ray reflectivity (films)

inelastic (ΔE ≠ 0)
• Compton X-ray scattering
• resonant inelastic X-ray scattering (RIXS)
First X-ray: 1895
• X-ray Raman scattering
225
DIFFRACTION
Diffraction refers to the apparent bending of waves around small objects and the
spreading out of waves past small apertures.

In our context, diffraction is the scattering of a coherent wave by the atoms in a

crystal. A diffraction pattern results from interference of the scattered waves.
Refraction is the change in the direction of a wave due to a change in its speed.

Crystal diffraction
I. Real space description (Bragg)
II. Momentum (k) space description
(von Laue)

diffraction of plane waves

W. H. Bragg W. L. Bragg von Laue 226

OPTICAL INTERFERENCE

perfectly in phase:
δ = nλ, n = 0, 1, 2, …
δ: phase difference
n: order

perfectly out of phase:

δ = nλ, n = 1/2, 3/2, …
 BRAGG’S LAW OF DIFFRACTION
When a collimated beam of X-rays strikes pair of parallel lattice planes in a crystal,
each atom acts as a scattering center and emits a secondary wave.
 All of the secondary waves interfere with each other to produce the diffracted beam

Bragg provided a simple, intuitive approach to diffraction:

• Regard crystal as parallel planes of atoms separated by distance d
• Assume specular reflection of X-rays from any given plane
→ Peaks in the intensity of scattered radiation will occur when rays
from successive planes interfere constructively

2Θ 228
BRAGG’S LAW OF DIFFRACTION
No peak is observed unless the condition for constructive interference
(δ = nλ, with n an integer) is precisely met:

AC  d sin 

ACB  2d sin 

n  ACB

Bragg’s Law: n  2d sin 

When Bragg’s Law is satisfied, “reflected” beams are in phase
and interfere constructively. Specular “reflections” can
occur only at these angles. 229
 DIFFRACTION ORDERS

1st order:
  2d sin 1

2nd order:
2  2d sin  2

By convention, we set the diffraction order = 1 for XRD.

For instance, when n=2 (as above), we just halve the d-spacing to make n=1.

2  2d sin  2   2(d / 2) sin  2

e.g. the 2nd order reflection of d100 occurs at same θ as 1st order reflection of d200
XRD TECHNIQUES AND APPLICATIONS

• powder diffraction
• single-crystal diffraction
• thin film techniques
• small-angle diffraction

Uses:

• phase identification • crystal size

• crystal structure determination • residual stress/strain
• radial distribution functions • defect studies
• thin film quality • in situ analysis (phase transitions,
• crystallographic texture thermal expansion coefficients, etc)
• percent crystalline/amorphous • superlattice structure
POWDER X-RAY DIFFRACTION
• uses monochromatic radiation, scans angle
• sample is powder → all orientations simultaneously presented to beam
• some crystals will always be oriented at the various Bragg angles
• this results in cones of diffracted radiation
• cones will be spotty in coarse samples (those w/ few crystallites)

no restriction
on rotational orientation
relative to beam

crystallite

  2d hkl sin  hkl

232
Transmission
geometry
233
DEBYE-SCHERRER METHOD

  2d hkl sin  hkl

…or we can use a diffractometer to intercept sections of the cones

234
BASIC DIFFRACTOMETER SETUP

235
THETA-2THETA GEOMETRY

• X-ray tube stationary

• sample moves by angle theta, detector by 2theta
238
POWDER DIFFRACTOGRAMS
In powder XRD, a finely powdered sample is probed with monochromatic X-rays of a
known wavelength in order to evaluate the d-spacings according to Bragg’s Law.

Cu Kα radiation: λ = 1.54 Å

peak positions depend on:

• d-spacings of {hkl}
• “systematic absences”

Minimum d?
increasing θ, decreasing d d min   / 2 240
 ACTUAL EXAMPLE: PYRITE THIN FILM
FeS2 – cubic (a = 5.43 Å)
Random crystal orientations Cu Kα = 1.54 Å

“powder pattern”
Intensity

200
210
111 211 311
220

2 Theta
2θ = 28.3° → d = 1.54/[2sin(14.15)] reference pattern from ICDD
= 3.13 Å = d111 (384,000+ datasets)

On casual inspection, peaks give us d-spacings, unit cell size, crystal

symmetry, preferred orientation, crystal size, and impurity phases (none!)
d-SPACING FORMULAS

242
POWDER DIFFRACTION

Peak positions determined by size and shape of unit cell

Peak intensities determined by the atomic number and

position of the various atoms within the unit cell

Peak widths determined by instrument parameters,

temperature, and crystal size, strain, and imperfections

we will return to this later…

244
GENERATION OF X-RAYS
X-rays beams are usually generated by colliding high-energy electrons with metals.

X-ray emission
spectrum
2p3/2 → 1s

+ HEAT

Siegbahn notation
Generating Bremsstrahlung

Generating Characteristic X-rays

246
 GENERATION OF X-RAYS
Side-window Coolidge X-ray tube

X-ray energy is determined by anode material, accelerating voltage,

and monochromators:
E  h  hc / 
Co Kα1 : 1.79 Å
Cu Kα1 : 1.54 Å (~8 keV)
Moseley’s Law:  1/ 2
 C (Z   ) Mo Kα1 : 0.71 Å
247
SYNCHROTRON LIGHT SOURCES
GeV electron accelerators

• brightest X-ray sources

• high collimation
• tunable energy
• pulsed operation

SOLEIL
Bremsstrahlung (“braking radiation”)

249
MONOCHROMATIC X-RAYS
Filters (old way)

A foil of the next lightest element

(Ni in the case of Cu anode) can
often be used to absorb the
unwanted higher-energy radiation to
give a clean Kα beam

Crystal Monochromators
Use diffraction from a curved
crystal (or multilayer) to select
X-rays of a specific wavelength

250
DETECTION OF X-RAYS

Detection principles
• gas ionization
• scintillation
• creation of e-h pairs

• Point detectors

• Strip detectors

• Area detectors

251
DETECTION OF X-RAYS
Point detectors

Scintillation counters

Gas proportional counters

252
X-RAY DETECTORS
Area detectors
• film
• imaging plate
• CCD
• multiwire
Charge-coupled devices

253
X-RAY DETECTORS
Imaging plates
photostimulated luminescence
from BaFBr0.85I0.15:Eu2+

254
X-RAY DETECTORS
Imaging plates
photostimulated luminescence
from BaFBr0.85I0.15:Eu2+

tetragonal Matlockite structure

9-coordinate Ba!
255
The Reciprocal Lattice and the
Laue Description of Diffraction

Reading: A/M 5-6

G/S 3

256
PLANE WAVES
A wave whose surfaces of constant phase are infinite parallel planes of
equal spacing normal to the direction of propagation.

|k|=2π/λ

ψ: wave amplitude at point r

A: max amplitude of wave k
k: wave vector
r: space vector from arbitrary origin

Amplitude is constant in any plane normal to k because k•r is a constant

for such planes:
k k
wavefront k•r1 = kr1
r1 45° r2 k•r2 = kr1√2(cos45) = kr1
origin k•r is indeed constant on wavefronts
THE RECIPROCAL LATTICE
The reciprocal lattice of a Bravais lattice is the set of all vectors K such that

e iK R
1
for all real lattice position vectors R.

Reciprocal lattice: The set of all wave vectors K that yield plane waves
with the periodicity of a given Bravais lattice.

Direct lattice position vectors: R = n1a1 + n2a2 + n3a3

Reciprocal lattice vectors: K = hb1 + kb2 + lb3
where the primitive vectors a2  a3
b1  2
of the reciprocal lattice are: a1   a 2  a 3 
a 3  a1
b 2  2
a1   a 2  a 3  and {ni} and {h,k,l}
are integers
a1  a 2
b 3  2
a1   a 2  a 3  258
 is satisfied when K•R = 2πn, with n an integer

To verify that the {bi} are primitive vectors of the reciprocal

lattice, let’s first show that bi•aj = 2πδij

a2  a3 a1   a 2  a 3 
b1  a1  2  a1  2  2
a1   a 2  a 3  a1   a 2  a 3 

a 3  a1
b 2  a1  2  a1  0 (since cross product of two
a1   a 2  a 3  vectors is perpendicular to both)

a1  a 2
b 3  a1  2  a1  0 Indeed, bi•aj = 2πδij
a1   a 2  a 3 

so, K•R = (hb1 + kb2 + lb3)•(n1a1 + n2a2 + n3a3)

= 2π(hn1 + kn2 + ln3) = 2π × integer
K is indeed a reciprocal lattice vector
 WHAT IS A RECIPROCAL LATTICE VECTOR?
The reciprocal lattice is defined at the lattice generated from the set of all
vectors K that satisfy

e iK R
1
for all direct lattice position vectors R.

What is K?
a wave vector of a plane wave that has the periodicity of the direct lattice

The direct lattice is periodic (invariant under translation by R)

Reciprocal lattice vectors = wave vectors of plane waves that are unity
at all direct lattice sites 260
THE RECIPROCAL LATTICE
• the reciprocal lattice is defined in terms of a Bravais lattice

• the reciprocal lattice is itself one of the 14 Bravais lattices

• the reciprocal of the reciprocal lattice is the original direct lattice

e.g., simple cubic direct lattice

a1  axˆ a 2  ayˆ a 3  azˆ

a2  a3 a2 2
b1  2  2 3 xˆ  xˆ
a1   a 2  a 3  a a
2 2
b2  yˆ b3  zˆ → simple cubic reciprocal lattice
a a with lattice constant 2π/a
→ b1 parallel to a1, etc. 261
Crystals with orthogonal axes (cubic, tetragonal, orthorhombic)
b1, b2, b3 are parallel to a1, a2, a3, respectively.

a1  axˆ a 2  byˆ a 3  czˆ

b3 reciprocal lattice 2
b1  xˆ
a
a3 2
b2 b2  yˆ
direct lattice b
a2
2
b1 a1 b3  zˆ
c
262
RECIPROCAL LATTICE OF FCC IS BCC
FCC primitive vectors:

Note: not orthogonal

a2
(yˆ  zˆ - xˆ )
a2  a3 4 1
b1  2  2 4 3  (yˆ  zˆ - xˆ )
a1   a 2  a 3  a a 2
(2)
8
4 1 4 1
b2  (zˆ + xˆ - yˆ ) b3  (xˆ + yˆ - zˆ )
a 2 a 2
→ BCC reciprocal lattice with lattice constant 4π/a 263
RECIPROCAL LATTICE OF BCC IS FCC
BCC primitive vectors (not orthogonal):

a2
(2yˆ  2zˆ )
a2  a3 4 1
b1  2  2 4 3  (yˆ  zˆ )
a1   a 2  a 3  a a 2
(4)
8
4 1 4 1
b2  ˆ ˆ
( z + x) b3  (xˆ + yˆ )
a 2 a 2

→ FCC reciprocal lattice with lattice constant 4π/a 264

RECIPROCAL LATTICES

• simple orthorhombic → simple orthorhombic

• FCC → BCC

• BCC → FCC

• simple hexagonal → simple hexagonal (rotated)

265
FIRST BRILLOUIN ZONES
The Wigner-Seitz cell of the reciprocal lattice is called the first Brillouin zone
(FBZ).

Wigner-Seitz cell: primitive cell with lattice point at its center

d.l. FCC d.l. BCC

r.l. BCC r.l. FCC
1st Brillouin zone: 1st Brillouin zone:

enclosed region is W-S cell

for 2D hexagonal lattice

rhombic dodecahedron
truncated octahedron
269
K and LATTICE PLANES
Theorem:
For any family of lattice planes separated by distance d, there are
reciprocal lattice vectors perpendicular to the planes, the shortest of
which has a length of 2π/d.

Conversely, any reciprocal lattice vector K has a family of real-space

planes normal to it, separated by d.

here, g = K

hk in 2D
hkl in 3D

275
MILLER INDICES OF LATTICE PLANES
Orientation of a plane is determined by its normal vector

It is natural to pick the shortest perpendicular reciprocal

lattice vector to represent the normal

Miller indices: coordinates of this reciprocal lattice vector

i.e., A plane with Miller indices hkl is normal to

the reciprocal lattice vector K = hb1 + kb2 + lb3

→ Definition #2: directions in k-space

(Definition #1 was inverse intercepts in the real lattice)

276
 Proof that K = hb1 + kb2 + lb3 is normal to (hkl)

a2 If K = hb1 + kb2 + lb3 is normal to the plane at left,

its dot product with any in-plane vector is zero.
k
Consider vector AB that lies in the plane.

a3
a1
(hkl)
By vector addition,   AB
h l
a1 The dot product,

a3
a1
a

b1

b2

b3
AB h  
3

AB K =    (h k l )
l  h l 
= 2  2  0 etc.
So the reciprocal vector formed by using the Miller indices of a plane as its
components forms a vector in space that is normal to the Miller plane.

Furthermore, the length of the shortest vector K is equal to 2π/dhkl.

a1
K
In the figure above, the spacing between the planes is the projection of on :
a

h K
1

K h 2 2 2
d hkl    → K   K0
h K h K K d hkl 277
POWDER (DEBYE-SCHERRER) METHOD
• single wavelength
• fixed powder sample
• equivalent to rotating the reciprocal lattice through all possible
angles about the origin

every point in Each shell with radius K < 2k

reciprocal space intersects the Ewald sphere to
traces out a shell form a circle.
of radius K
All the diffracted beams from a
powder lie on the surface of cones
291
PEAK INTENSITIES

Peak intensities depend on (in large part):

1) intensity scattered by individual atoms (form factors)
2) the resultant wave from atoms in unit cell (structure factor)

In many cases, the intensity from certain planes (hkl) is zero.

Possible reasons: • symmetry of crystal causes complete cancellation of beam

“systematic absences”
• happenstance

Other factors that affect intensity: • scattering angle

• multiplicities
• temperature factor
• absorption factor
• preferred orientation
292
MONOATOMIC BASES
up to now we have considered diffraction only from Bravais lattices
with single atom bases (i.e., atoms only at the lattice points R).

We found the diffraction condition: ei (k' -k ) R = ei 2 n  1

iK R
which is the same as: e =1
The scattering amplitude FK is the sum over the lattice sites:

FK   f R (K )eiK R
R
where fR(K) is the “atomic form factor” for a given atom (disc. later).

The scattered intensity is proportional to the absolute square of the

amplitude: 2
I K  I 0 FK
…this is what is actually measured in an experiment.
n-ATOM BASES
Crystals with n atoms in each primitive cell must be further analyzed
into a set of scatterers at positions d1, d2 … dn within each primitive
cell.

The positions of the atoms are: A j (R )  R  d j

FK   f j (K )e
iK ( R+d j )
making the scattering amplitude:
R j

  e iK  R  f j ( K ) e
iK d j

L   e iK  R R j

R
“Lattice sum”
 K   f j (K )e
iK d j

j
“Structure factor” of the basis
*If the structure factor = 0, there is no diffraction peak.
STRUCTURE FACTOR
The structure factor gives the amplitude of a scattered wave arising
from the atoms with a single primitive cell.

 K   f j (K )e
iK d j

For crystals composed of only one type of atom, it’s common to split
the structure factor into two parts:

 K  f j (K ) S K

“atomic form factor”

SK   e
iK d j

j
“geometric structure factor”

S = 0 gives a systematic absence (i.e., absence of expected diff. peak).

295
STRUCTURE FACTORS
The amplitude of the rays scattered at positions d1, …, dn
are in the ratios:
iK d1 iK d n
e … e
The net ray scattered by the entire cell is the sum of
the individual rays:
n
Geometric
SK   e
iK d j
-Adds up scattered
structure
waves from unit cell
factor j 1

2
I ( hkl )  SK -In particular, no
peak when SK = 0
296
SIMPLE CUBIC

For simple cubic: one atom basis (0,0,0)

d1 = 0a1 + 0a2 + 0a3

iK 0
SK  e 1
Same result as simple monatomic basis

297
MONATOMIC BCC
For monoatomic BCC:
we can think of this as SC with two point basis (0,0,0), (½,½,½)
2 a   
iK  ( x  y  z )
SK   e
iK d j
 eiK 0  e 2

j 1
2
For SC, K (hxˆ  kyˆ  lzˆ )
a

 1  ei ( h  k l )
h  k l
 1  (1)
S = 2, when h + k + l even
S = 0, when h + k + l odd (systematic absences)
298
 e.g. consider the powder pattern of BCC molybdenum

Powder card shows only even hkl sums b/c Mo is BCC

Why?
- Diffraction from other (hkl) results in destructive interference:

(100) (200)

d100
d200

Beam cancels b/c body center atoms Strong reflection b/c all atoms lie on
scatter exactly 180° out of phase 200 planes and scatter in phase
MONATOMIC FCC

For monoatomic FCC:

SC with four point basis (0,0,0), (½,½,0), (0,½,½), (½,0,½)

4 a  a  a 
iK ( x  y ) iK ( y  z ) iK ( x  z )
SK  e
iKd j
 eiK0  e 2
e 2
e 2

j1

2
For SC, K (hxˆ  kyˆ  lzˆ )
a

SK  1  ei ( h  k )  ei ( k l )  ei ( h l )

S = 4 when h + k, k + l, h + l all even (h, k, l all even or all odd)

S = 0 otherwise. 300
Once again, there are more systematic absences for
isoelectronic ions (e.g., K and Cl)
(110) always absent in RS
(hkl) NaCl KCl
(100)
(110)
(111) 
(200)  
(210)
(211)
(220)   (111) sometimes absent

(221)
(300)
(310)
(311)  306
 DIAMOND STRUCTURE
Diamond: FCC lattice with two-atom basis (0,0,0,), (¼,¼,¼)

a  
iK ( x  y  z )
iK0
SK,diamond  [e e 4
][SK,FCC ]
i( /2)(hk l )
 [1 e ][SK,FCC ]

Only for all even or all odd hkl is S ≠ 0. For these unmixed values,
Additional condition: S = 8 h + k + l twice an even number
S = 4(1 ± i) h + k + l odd
S = 0 h + k + l twice an odd number

IFCC : all nonvanishing spots have equal intensity.

Idiamond : spots allowed by FCC have relative intensities

of 64, 32, or 0. 308
 FCC diamond
(hkl) Al Si
(100)
(110)
(111)  
(200) 
(210)
(211)
(220)  
(221)
(300)
(310) What about
zinc blende?
(311)  
309
SUMMARY OF SYSTEMATIC ABSENCES
crystal structure condition for peak to occur
SC any h,k,l
BCC h + k + l = even
FCC h,k,l all even or all odd
NaCl h,k,l all even,
or allsumodd if f ≠ fB
=h+k+l=4n A

diamond h,k,l all even and twice an even #,

and Silicon
or all odd
HCP any h,k,l except when h + 2k = 3n
and l is odd

 K   f j (K )e
iK d j

j 310
SIMPLE ANALYSIS OF SIMPLE PATTERNS
What will we see in XRD patterns of SC, BCC, FCC?

h k l
2 2 2

SC: 1,2,3,4,5,6,8,9,10,11,12,…

BCC: 2,4,6,8,10,12,...

FCC: 3,4,8,11,12,16,24,…

Observable diffraction
peaks for monoatomic
SC FCC BCC
crystals

We can take ratios of (h2 + k2 + l2) to determine structure.

SIMPLE ANALYSIS OF SIMPLE PATTERNS

1
2d sin   n sin   2
2

d hkl
a
For cubic crystals: d hkl 
h2  k 2  l 2

sin   (h  k  l )
2 2 2 2

sin  nth peak

2
(h  k  l ) nth peak
2 2 2


sin 1st peak
2
(h  k  l )1st peak
2 2 2

312
SIMPLE ANALYSIS OF SIMPLE PATTERNS
α-Fe is cubic. Is it FCC or BCC?
BCC!
110
sin 2  2 sin 2 33
 2
sin 1 sin 22
2 2  211

200

What about Al?

111 FCC!
sin 2  2 sin 2 22.5
  1.33
sin 1
2 2
sin 19 

200 311
220 331 420
222
400
313
Ex: An element, BCC or FCC, shows diffraction
peaks at 2: 40, 58, 73, 86.8,100.4 and 114.7.
Determine:(a) Crystal structure?(b) Lattice constant?
(c) What is the element?
2theta theta normalized (hkl)
sin 
2
h k l
2 2 2

40 20 0.117 1 (110)
58 29 0.235 2 (200)
73 36.5 0.3538 3 (211)
86.8 43.4 0.4721 4 (220)
100.4 50.2 0.5903 5 (310)
114.7 57.35 0.7090 6 (222)

BCC, a =3.18 Å  W
314
ELASTIC X-RAY SCATTERING BY ATOMS
Atoms scatter X-rays because the oscillating electric field of an X-ray sets
each electron in an atom into vibration. Each vibrating electron acts as a
secondary point source of coherent X-rays (in elastic scattering).
The X-ray scattered from an atom is the resultant wave from all its electrons

Particle picture:

• zero phase difference for forward/backward scattering

→ scattering factor (form factor, f ) proportional to atomic number, Z
• increasingly destructive interference with larger scattering angle (to 90°)
• for a given angle, intensity decreases with decreasing X-ray wavelength

1
Thomson relation: I  (1  cos 2 2 )
2
• max scattering intensity at 2θ = 0 & 180°
• gradual decrease to 50% as 2θ approaches 90°
SCATTERING OF X-RAYS BY ATOMS
scattering angle probabilities for a free electron:

Klein–Nishina formula

Low energy: Thomson

High energy: Compton

1
Thomson relation: I  (1  cos 2 2 )
2
ATOMIC FORM FACTORS
Form factor f = scattering amplitude of a wave by an isolated atom

For X-rays, f depends on: • Z (# electrons)

• scattering angle
scattering vector q
• X-ray wavelength
General elastic formula:

3 Cl-
f j (q)    j (r )e  iq r
dr Cl
0 K+
4 sin 
with, q

For θ = 0 (forward scattering),
 O
3
f j (0)    (r )dr = # electrons
0
θ = 37°

consequences: • powder patterns show weak lines at large 2θ.

• light atoms scatter weakly and are difficult to see.
PEAK WIDTHS
Peak shape is a Voigt function (mixture of Gaussian and Lorentzian)
• Gaussian component arises from natural linewidth and strain
• Lorentzian component arises from coherent domain size

Pure
Gaussian

Pure
Lorentzian

Peak width (broadening) is determined by several factors:

• natural linewidth of X-ray emission
• instrumental effects (polychromatic λ, focusing, detector)
• specimen effects
1) crystallite size
2) crystallite strain 319
FULL WIDTH AT HALF MAXIMUM (FWHM)

320
 Instrument and Sample Contributions to the Peak Profile
must be Deconvoluted

• In order to analyze crystallite size, we must deconvolute:

– Instrumental Broadening FW(I)
• also referred to as the Instrumental Profile, Instrumental
FWHM Curve, Instrumental Peak Profile
– Specimen Broadening FW(S)
• also referred to as the Sample Profile, Specimen Profile

• We must then separate the different contributions to specimen

broadening
– Crystallite size and microstrain broadening of diffraction peaks

321
SIZE BROADENING
Small crystallites (< 200 nm) show broadened diffraction lines

Nanocrystal X-ray
Diffraction

322
323
 Which of these diffraction patterns comes from a
nanocrystalline material?

Intensity (a.u.)

66 67 68 69 70 71 72 73 74

2 (deg.)
These diffraction patterns were produced from the same sample!
• Two different diffractometers, with different optical configurations, were used
• The apparent peak broadening is due solely to the instrumentation in
this case
324
The finite size of real crystals results
in incomplete destructive interference
at Bragg angle,  B
over some range of angles

 B1 phase lag between two planes =

perfectly in phase, constructive

2
At some angle 1   B
1
2
Phase lag between two planes:   
3
4 At (j+1)th plane:
Phase lag: 
   j    2
j-1
j
j+1

T = (2j-1)d • Rays from planes 1 and j+1 cancel

2j-1
2j
• Ditto for 2 & j+2, … j & 2j
• Net diffraction over 2j planes = 0
Crystal with 2j planes
Total thickness T The angular range θB to θ1 is the range where
diffracted intensity falls from a maximum to
zero (half of Bragg peak profile).
 Same arguments apply to 2  B
So we see diffracted X-rays over all scattering angles between 2θ1
and 2θ2.

– If we assume a triangular shape for the peak, the full width at

half maximum of the peak will be B = (2θ1 – 2θ2)/2 = θ1 – θ2

326
If we have more than 2j planes: If we have fewer than 2j planes:

 B1  B1
2 2

1 1
2 2
3 3
4 4

j-1 j-1
j j
j+1 j+1

2j+1 2j-3
2j+2 2j-2

Rays from new planes are canceled Rays from planes j-1 & j not canceled
still zero intensity at θ1 nonzero intensity at θ1
Peak sharpens! Peak broadens!
Thinner crystals result in broader peaks! 327
Let’s derive the relation between crystal thickness T and peak width B:

2d sin   
Considering the path length differences between X-rays scattered from the front
and back planes of a crystal with 2j+1 planes and total thickness T:
2T sin 1  (2 j  1)
Here, T = 2jd
2T sin  2  (2 j  1)
1   2 1   2
sin 1  sin  2  2 cos sin
If we subtract them: T (sin 1  sin  2 )   2 2

1   2 1   2
Using trig identity: 2T (cos( ) sin( ))  
2 2
1   2 1   2 1   2
Since  B and sin( ) ,
2 2 2
1   2 1   2 
2T (cos  B )( ))  . But, B  2( ) , so T
2 2 B cos  B
SCHERRER FORMULA
A more rigorous treatment includes a unitless shape factor:

K T = crystallite thickness
Scherrer Formula (1918) T λ (X-ray wavelength, Å)
B cos  B K (shape factor) ~ 0.9
B, θB in radians

Accurate size analysis requires correction for instrument broadening:

B  B B
2 2
M
2
R

BM: Measured FWHM (in radians)

BR: Corresponding FWHM of bulk reference (large grain size, > 200 nm)

Readily applied for crystal size of 2-100 nm.

Up to 500 nm if synchrotron is used.
329
SCHERRER CONSTANT
K 0.94
T T
B cos  B B cos  B
• The constant of proportionality, K (the Scherrer constant)
depends on the how the width is determined, the shape of the
crystal, and the size distribution
– the most common values for K are:
• 0.94 for FWHM of spherical crystals with cubic symmetry
• 0.89 for integral breadth of spherical crystals w/ cubic symmetry
• 1, because 0.94 and 0.89 both round up to 1
– K actually varies from 0.62 to 2.08
• For an excellent discussion of K, refer to JI Langford and AJC
Wilson, “Scherrer after sixty years: A survey and some new
results in the determination of crystallite size,” J. Appl. Cryst. 11
(1978) 102-113.

330
Suppose =1.5 Å, d=1.0 Å, and =49˚. Then for a crystal 1
mm in diameter, the width B, due to the small crystal
effect alone, would be about 2x10-7 radian (10-5 degree),
too small to be observable. Such a crystal would contain
some 107 parallel lattice planes of the spacing assumed
above.

However, if the crystal were only 50 Å thick, it would

contain only 51 planes, and the diffraction curve would be
very broad, namely about 43x10-2 radian (2.46˚), which is
easily measurable.

“Incomplete destructive interference

at angles slightly off the Bragg angles”
331
DIFFRACTION FROM DISORDERED SOLIDS

amorphous solids

367