Crystallite sizes and microstrains

from x-ray diffraction line profile analysis

P. Lamparter

Introduction
Williamson-Hall Method
Warren-Averbach Method
Application to ball-milled Mo
 Diffraction Line Broadening due to Lattice Imperfections

5000
110 Mo powder
annealed
intensity

211

310 sharp Bragg peaks

200 220
222 no imperfections
0
500
Mo powder
ball milled, 120 hr
intensity

broad Bragg peaks

nanocrystalline
microstrains
0
40 60 80 100 120
diffraction angle 2
 Diffraction Vector and Braggs Law

Diffraction vector
Q = K K0 Braggs law
Q
= 2d sinP
Q = 2K sin
K
|K|=1/ K0 Q = 2/ sin

QP = 1/d

crystallite
column

Diffraction experiment probes structure along direction L

parallel to the diffraction vector Q
 Peakfitting by Analytical Function

Pseudo-Voigt function (+ background)

Peak parameters
AL - position QP
I (Q ) = AG exp( (Q QP ) / w ) + 2 2

1 + (Q QP ) 2 / wL2
G
- amplitude A
- width w
I(Q) = Gau + Lorentz

400 . measured
fit
integral width
= area / amplitude
intensity

200

background

0
6,2 6,4 6,6
-1
momentum transfer Q [ ]
 Broadening by Instrument and by Imperfections

integral width
3 measured convolution
m
m I(2)m = I(2)i * I(2)s

2
I(2)

instrumental
i i instrumental resolution
1
structural
s s structural imperfections
0 2 2 2
40 45 50 Gau: s =m -i
diffraction angle 2
Lorentz: s=m-i
 Fourier Transformation and Convolution

I (Q ) = A( L) exp( 2iQL ) dQ A( L) = I (Q ) exp( 2iQL ) dQ

symmetric: exp(2 iQL) => cos(2 QL)

I 1(Q) A1( L)

I 2(Q) A2 ( L )

I (Q) A(L)

reciprocal space Q real space L

I(Q) = I1(Q)*I2(Q) A(L) = A1(L)A2(L)

convolution product
 Broadening by Crystallite Size (Coherence Length)

Stokes equation S = 1/D not dependent on QP

lattice planes d Bragg peak

infinite sharp

QP = 1/d
size width
window D

broad peak
finite crystal

Real space L reciprocal space Q

product convolution
Broadening by Microstrain (Varying Lattice Parameter)

Microstrain <> =<d>/d d = 2<>Q increase with Q

2+
2- 20

d0 - d
d0
d0(1-)
d0 + d
Q
d0(1+)
Q = 1/d Braggs law
d
|Q| = d/d2 = Q

4 d = 2 |Q| = 2Q
Q = 2 sin

 Williamson-Hall Analysis, ball milled Mo

0,3 310 222 = 1/D + 2Q

211 220
200
[nm ]

0,2
-1

110
) linear fit
0,1
D
0,0 intercept:
0 2 4 6 8 10 12
-1
Q [nm ] size D = 15 nm

Mo powder slope:
ball milled 50 hrs
strain = 0.006
intensity

nanocrystalline
large microstrains
0 2 4 6 8 10 12 (dislocations)
-1
Q [nm ]
 Nanocrystalline CeO2 Powder, WH-Plot

0,04
no strain
[nm ]
-1

only size effect

0,02
D = 1/ = 28 nm
0,00
0 2 4 6 8 10 12
-1
Q [nm ]
intensity

0 2 4 6 8 10 12
-1
Q [nm ]
 a
Nb Film, WH-Plot

b
columnar
500 nm
grains
size = 500 nm Si substrate
c

strong 110 texture

110 planes || surface 0.1
4 110 220
10 no size effect
[nm ]
log I(2)

220 -1

2
110
10
= 0.4%
0
10 0.0
0 20 40 60 80 100 120 0 2 4 6 8
-1
2 Q [nm ]
 Ball-milled Mo Powder, W-H Plot
milling time, hrs
222
310 180
0.3 211 90
220
200 50
110 10
0.2
[nm ]
-1

4
0.1 increase
2
of
1.5
0.0
decrease 0 2 4 6 8 10 12
of D -1
Q [nm ]
 Ball Milled Mo Powder: Size and Strain
size: decrease strain: increase
1
3

[%]
10
Size D [nm]

2 1/2
Dmax = 150 nm

Strain < >

2
10

1
10 0.1

0 40 80 120 160 200 0 40 80 120 160 200

Milling time [h] Milling time [h]

instrumental broadening
= d/d
i[] 0.05
average
i[nm-1] = i[]cos/ 0.006[nm-1]
Structural broadening < 2>1/2

s = 1/D > i
detectable sizes D < 150 nm
 Correction for Instrumental Broadening, Stokes

structural

instrumental

measured

Rreciprocal space Q real space L

Im(Q) = Ii(Q)*Is(Q) Am(L) = Ai(L)As(L)

convolution Fourier product
transformation
Ii(Q) Ai(L)

correction As(L) = Am(L)/Ai(L)

 Fourier-Coefficient of Diffraction-Line

A( L) = I (Q ) exp( 2iQL ) dQ

I(Q) 1.0 A(L)

0.5

0.0
0 0 5 10 15
Q L [nm ]

decay of A(L):
correlation between lattice planes gets lost
at large distances L

finite size D microstrain

A(L) = AD(L)A(L) L
 a
Warren-Averbach Analysis, ball milled Mo Powder

110 1.0 Fourier coefficient

100
b 220
log I

A(L)
10 0.5 110
220
1
40 60 80 100 120
diffraction angle 2 0.0
c
0 5 10 15
L [nm]
A(L,QP) = AD(L)A(L,QP) L fixed
W-A plot
theoretical expression for A(L,QP)
A(L,QP) = AD(L) exp[-2L2<2(L)>QP2] lnA(L,QP)

lnA(L,QP) = lnAD(L) - 2L2<2(L)>QP2

intercept
AD(L)
slope
<2(L)>, A(L,QP) Q P2

 Warren-Averbach Analysis
Mo milled, 90 hrs
1.0 size coefficient AD(L)
AD(L)
0.5

0.0
1.0 strain coefficient
110 A(L,QP) = exp[-22L2<2(L)>QP2]
A(L)
0.5
X X
220
0.0
L1
0.4 Strain depends on length
L2
<2(L)>1/2
[%] 0.2
L1
L2 =0
0.0
0 10 20 30 40 50 2 = (L/L)2: (L1) > (L2)
L (nm)
 Column Length Distribution P(D)

column length D
grain size D0
thin film
columnar grains spherical grain

D0 D

P(D) different D0
different shapes

D D D
D0 D0
 Column Length Distribution P(D) and Size Coefficient AD(L)

A D ( L) = 1

<D>L
( D L )P ( D ) dD

Size coefficient log-normal distribution

1 .0 ... experiment 0 .1 0
2 parameters
AD(L) fit =0.6 P(D) width
0 .5 <D>=8nm 0 .0 5
average <D>

<D> <D>
0 .0 0 .0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
real space coordinate L column length D
calculate, easy
at small L:
AD(L) 1 L/<D> fit
<D> from tangent
Nanocrystalline
a
Powder: Different Length Parameters

particle
b particle
grain size

c
column
d
length length
lattice grain
spacing L D
size
 Williamson-Hall and Warren-Averbach, ball milled Mo

size strain
3
1

[%]
10 Williamson-Hall
Size D [nm]

2 1/2
Warren-Averbach

Strain <0 >

2
10

1
10
0.1
0
10
0 40 80 120 160 200 0 40 80 120 160 200
Milling time [h] Milling time [h]

Both methods size a few nm

strain 1%

<D>(W-H) larger than <D>(W-A)

volume-weighted area-weighted
 Conclusions

Williamson-Hall Method
- Easy to be done
- Only width of peaks needed

Warren-Averbach Method
- More mathematics
- Precise peak shapes needed
- Distributions of size and microstrain
- Relation to other properties
(dislocations)
 Some Literature

B.E. Warren, X-ray Diffraction. Reading, MA. Addison-Wesley (1969)

Mittemeijer, E.J. and P. Scardi (Eds.), Diffraction Analysis of the Microstructure of Materials. Springer Series
in Materials Science Vol. 68, Springer-Verlag, Berlin Heidelberg New York, 2004.

R. Delhez, Th. De Keijser, E.J. Mittemeijer, Determination of Crystallite Size and Lattice Distortions through
X-Ray Diffraction Line Profile Analysis, Fresenius Z. Anal. Chem. 312 (1982) 1.

P. Scardi, M. Leoni, Diffraction Line Profiles from Polydisperse Crystalline Systems, Acta Cryst. A57 (2001) 604.

C. Krill, R. Birringer, Estimating Grain-Size Distributions in Nanocrystalline Materials from X-Ray Diffraction
Profile Analysis, Philos. Mag. A77 (1998) 621.

T. Ungar, J. Gubicza, G. Ribarik, A. Borbely, Crystallite Size Distribution and Dislocation Structure Determined
by Diffraction Profile Analysis: Principles and Practical Application to Cubic and Hexagonal Crystals,
J. Appl. Cryst. 34 (2001) 298.

I. Lucks, P. Lamparter, E.J. Mittemeijer, An evaluation of Methods of Diffraction-Line Broadening Analysis

Applied to Ball-Milled Molybdenum, J. Appl. Cryst. 37 (2004) 300.

Lucks, I., P. Lamparter, J. Xu and E.J. Mittemeijer, XRD Line Broadening Analysis with Ball Milled Palladium,
Materials Science Forum 443-444 (2004) 119.