Crystallite size broadening
Structure Analysis
Materials Science & Engineering, Seoul National University
CHAN PARK
Degree of being “out-of-phase” that can be tolerated vs.
crystallite size
Cullity Chapter 5, 14-3, 14-4 & 14-6
Hammond p180
Krawitz p343
Jenkins & Snyder p89
1 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses
Peak broadening
bulk ceria
nanocrystalline ceria
same sample run on two
different instruments
Peak broadening may indicate:
Smaller crystallite size
More stacking faults, microstrain, and other defects in the crystal structure
An inhomogeneous composition in a solid solution or alloy
Different instrument configurations can change the peak width, too
2 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses Scott A. Speakman
Geometrical factor – 1 of Lorenz Factor
θ1 = θB + ∆θ
θ2 = θB - ∆θ
3 4
5 6
Total length
of the plane
Path difference b/w rays scattered by atoms
at either end of the plane (3 & 4)
Diffracted intensity = zero when
Size & strain
broadening
Imax ∝ 1/sin θB B ∝ 1/cos θB
∆θ Imax B ∝ (1/sin θB) (1/cos θB) ∝
Max angular range of crystal rotation over which
appreciable energy can be diffracted in the direction 2θB
3 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses Cullity page 145~147
Crystallite size broadening
θ1 = θB + ∆θ (B, B’) θ2 = θB - ∆θ (C, C’) m + 1 planes
δ(A’D’) = 1λ, δ(A’M’) = mλ
@ θ1 or θ2 ≠ θB, incomplete destructive
interference
If δ(B’L’) = (m+1)λ, intensity zero
If δ(C’N’) = (m-1)λ, intensity zero
@ 2θ2 < 2θ < 2θ1, intensity is not zero
0 X Imax
1 X
2 Top
X
3 half
4 X Β
X
X Bottom
X half
m-1 2θ2 2θΒ 2θ1
t = thickness ~ size
m X
4 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses MUST READ Cullity Chap 5-2
Crystallite size broadening
θ1 = θB + ∆θ (B, B’) θ2 = θB - ∆θ (C, C’) Ray B; θ1 = θΒ + ∆θ, δ(B’L’) = (m+1)λ
Compare when m = 10 and m = 10,000
m = 10 @ θ1, δ(B’L’) = δ(0m) = 11λ, δ(01) = 1.1λ
m = 10,000 @ θ1, δ(B’L’) = δ(0m) = 10,001λ,
δ(01) = 1.0001λ
θ1(m = 10) >>> θ1(m = 10,000)
θ1 ↑ as m ↓ θ2 ↓ as m ↓
(2θ1-2θ2) ↑ as m ↓
B ↑ as thickness ↓
t = md
Peak width ↑ as size ↓
Β
t(sinθ1-sinθ2) = λ
2θ2 2θΒ 2θ1
5 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses Cullity page 168
Crystallite size broadening
Assume diffraction line is triangular in shape
Imax
Β
B; an angular width, in terms
of 2θ (not a linear width)
2θ2 2θΒ 2θ1
Shape factor; depends on the
shape of the crystallites
Scherrer equation
6 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses Cullity p169
Crystallite size broadening 1 1’
@ θB; ABC = λ, DEF = 2λ diffraction peak 2 2’
θB O θB
ABC = 0.5λ, DEF = 1λ no diffraction peak 1st plane
3 A C 3’
ABC = 1.1λ, DEF = 2.2λ
2nd plane
PD (path diff.) in 6th plane = 5.5λ B
D F
1’ & 6’ out of phase no net diffraction 3rd plane
E
ABC = 1.001λ 1’ & 501’ out of phase; ABC = 1.00001λ 1’ & 50001’ out of phase
Sharp diffraction peak @ θB
When crystal is only 100nm in size, 5000’ or 50000’ are not present
Peak begins to show intensity at a lower θ and ends at a higher θ than θB particle
size broadening
Crystallites smaller than 1um can cause broadening size can be determined using
the peak width incomplete destructive interference
100um 0.1um
7 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses Jenkins & Snyder page 89
Crystallite size broadening
In case λ = 1.5 Å, d= 1.0 Å, θ = 49 ° ,
1mm(millimeter) diameter crystal 107 parallel lattice planes,
~10-7 radian*, ~10-5 degree too small to observe
500 Å diameter crystal 500 parallel lattice planes, ~10-3 radian,
~0.2 degree measurable
Non-parallel incident beam, non-monochromatic incident beam
diffraction @ angles not exactly satisfying Bragg’s law line
broadening
* B = (0.9 X 1.5 X 10-10)/(10-3 X cos 49°) ~ 2 X 10-7 rad
8 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses Cullity, p170
@ θB @ θ + ∆θ Crystallite size broadening
between planes 0 & (m/2)
Constructive interference at angle θ
Destructive interference at angle θ + δθ
δ(1, (m/2)+1) = 0.5λ
B=
Scherrer equation
9 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses Hammond, Chapter 9.3, p180 ~ 181
Crystallite size broadening
Scherrer equation
Particle size
Crystallite
size
Waseda etal. page 123
Jenkins & Snyder page 90
Waseda & Matsubara, X-ray diffraction
10 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses Crystallography, Springer, 2011
Particle size vs. Crystallite size
Particles can be Particles may be
individual crystallites imperfect single crystals
Particle size = crystallite size Particle size > crystallite size
Individual crystallites are perfect
Boundaries
Dislocations
Twin walls
Anti-phase walls Particle size
Stacking faults Crystallite
size
From presentation of Dr. Mark Rodriguez Waseda et al. page 123
@ DXC 2017 “What usually causes trouble?“
11 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses
Crystallite size broadening
platinum nano-particle in a
matrix of amorphous carbon
rolled platinum sheet
12 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses
Strain broadening
13 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses
Strain/Stress
Macrostrain/Macrostress shift in peak
position
stress is uniformly compressive or tensile over
large distances lattice parameter measurement
shift in
Macro strain peak
Microstrain/Microstress peak broadening position
Distribution of both tensile & compressive stress
distribution of d-values
Micro strain peak
Can come from dislocations, vacancies, defects, broadening
shear planes, thermal expansion/contraction, etc.
peak profile analysis
Cullity page 176
14 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses Jenkins & Snyder, page 91~93
Peak shift macrostrain
Diffraction from AgBr
in a photographic film
Differential expansion between the film substrate & AgBr causes
macrostrain changes lattice parameter peak shift
15 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses Jenkins & Snyder, page 92
Strain broadening, Size & Strain broadening
λ = 2d sinθ Strain broadening
0 = 2d cosθ δθ + 2 sinθ δd
∆(2θ) = -2(δd/d)tanθ = B ; extra broadening produced by microstrain B
βε = 4ε tanθ (Jenkins & Snyder p93)
2θ2 2θΒ 2θ1
β = -2ε tanθ (Hammond p214)
Size & Strain broadening
βsize = λ/(tcosθ), βstrain = 4ε tanθ, βinstrument
βcosθ
β(total) = λ/(tcosθ) + 4ε tanθ + βinstrument
β = λ/(tcosθ) + 4ε (sinθ/cosθ) ε
βcosθ = λ/t + 4ε sinθ
λ/t
βcosθ/λ = 1/t + (4ε sinθ)/λ
4sinθ
plot βcosθ/λ vs sinθ/λ (Williamson-Hall plot) can separate size & strain
contributions to line broadening --- semi-quantitative
16 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses Cullity page 401
Broadening
Darwin width
Incident photon is confined to certain volume
Result of uncertainty principle (∆p∆x = h) --- Location of the photon in a xtal is
restricted to a certain volume
∆p must be finite ∆λ must be finite finite width of diffraction peak
Specimen contribution (S)
Spectral distribution (radiation source contribution) (W)
Instrumental contribution (G)
(W * G) X-ray source image, flat specimen, axial divergence of incident
beam, specimen transparency, receiving slit, etc.
(W * G) ; fixed for a particular instrument/target system instrumental
profile g(x)
Overall line profile h(x) = (W * G) * S + background = g(x) * S + BKG
LaB6 SRM
17 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses
S W * G h h(x) = (W * G) * S
Crystallite Line shape convolution of a profile
size
representing instrument (W*G) and
286 nm
specimen (S) contributions
Intergrated line intensity of the
143 nm convolution product remains the same
while the peak broadens and the peak
intensity decreases
Lorentzian
Bobs = Bsize / strain + Binst profile
70 nm
2
Bobs = Bsize
2
/ strain + Binst
2 Gaussian
profile
18 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses Bish & Post
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Intensity
ZnO, TiO2 (rutile), Cr2O3, CeO2 (SRM 674b); $916/10g
Quantitative phase analysis
Al2O3 (SRM 676a ); “notify me“/20g, Silicon Nitride (SRM 656); $492/20g
Instrument Response Std
Alumina plate (SRM 1976b); $700/1 disc
Gold
$41.46 / gram
(2017-12-28)
Prices; 2017-12-28
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goldprice.org
19 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses
Conventional Williamson-Hall Plot
Size + Strain A; Ball mill 2 hrs
B; Ball mill 2 hrs + 1350C 2hrs
B cos θ 0.9 ∆d sin θ
= −2
λ d d λ MgO
A
B(cosθ)/λ
Al2O3
y = a + bx
Size >> strain
Horizontal line
Size << strain B
Linear function
sinθ/λ
20 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses Cullity
Modified Williamson-Hall Plot
explained strain broadening by dislocations
B cos θ 0.9
= + ∆K D y = a+ X
λ d
∆d sin θ
Classical X = −2
d λ
Modified X = A( ρ *)1 2 + A' (Q*)1 2
21 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses
Modified Williamson-Hall Plot
B cos θ 0.9
= + A( ρ*)1 2 + A' (Q*)1 2
λ d
ρ * : (formal) dislocation density
Q * : (formal) two-particle correlations in the dislocation ensemble
A, A' : parameter determined by dislocations
True values of dislocation density, correlation factor
ρ * = ρ (πg 2b 2 C ) 2 Q* = Q (πg 2 b 2 C ) 2 4
C :average contrast factor of dislocation
b :Burgers vector of dislocation
2 sin θ
g=
Particular reflection
λ
22 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses Appl. Phys. Lett. 69 (21),3173 (1996)
Conventional vs. Modified W-H Plot
y =a+ X
Modified
Conventional
sin θ
K =2
λ
23 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses Appl. Phys. Lett. 69 (21),3173 (1996)
Conventional vs. Modified W-H Plot
Conventional
W-H Plot
Modified
W-H Plot
Appl. Phys. Lett. 69 (21),3173 (1996)
24 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses
Mosaic structure
Angle of disorientation between the tiny blocks is ε diffraction occur at all
angles between θB and θB + ε
Increases the integrated intensity relative to that obtained (or calculated)
for an ideally perfect crystal strains & strain gradients associated with
the groups of dislocations
25 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses Cullity page 174
Mosaic Spread
Mosaicity is created by slight misorientations of different crystals as they
nucleate and grow on the substrate. When the crystals join, they form low
energy grain boundaries.
In an ideal case, each nuclei (red) is per If the nuclei (red) are slightly misa
fectly oriented. ligned, then low angle
When the crystals grow and meet, grain boundaries will be formed.
there is perfect bounding between
the crystallites no grain boundary.
26 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses Scott A Speakman
Mosaic Spread - reciprocal space
Mosaic Spread can be quantified by measuring the broadening of the lattice
point in reciprocal space
The amount of broadening of the reciprocal lattice point that is
perpendicular to the reflecting plane normal can be attributed to mosaic
spread
The peak broadening parallel to the interface can be attributed to lateral
correlation length
Lateral correlation
27 CHAN PARK, MSE, SNU Spring-2019 Crystal Structure Analyses Scott A Speakman
