Real samples measurement

Deconvolution Instrumental profile - g

h=g*f
• Calculation - convolution g1*g2*...
experimental
• Standard measurement
physical
instrumental ideal real

Possibilities
Reciprocal space Direct space
reciprocal space direct space
Fitting of profiles with
analytical functions I ( s)  k  A( L) cos( 2sL )dL

Separation of influence Separation of Fourier coefficients on:

of defects from:

Size part Deformation part

Peak shifts Peak broadening
 Peak broadening
a) size effect b) strain effect
• a finite width of diffraction lines is caused by a finite size of coherently
scattering domains, lattice defects - static and dynamic (thermal vibrations),
samples inhomogeneities
• studied by an x-ray profile analysis

A

Transformation into the reciprocal space I (0)
FWHM I(0)

D an infinite crystal a crystal of a finite size A

and a given shape
k 2Q0
d - peak  hkl 
D
the integral breadth of a (hkl) reflexion
no changes in a peak position
 Peak broadening
Size effect

 
I  I 02 F M 12 M 22 M 32 exp  2  2 cos 2   D 2 ; D  M 12 a 2  M 22b 2  M 32c 2
2

1    
 exp  2 D12 2 cos 2    ln 2  2 D12 2 cos 2 
2    

12
 ln 2 
 2
 
   D cos
12

Deformation (strain) effect (stresses of

the 2nd type)
2d sin   
2d sin   2d cos   0
d d
  cot     tan 
d d
d FWHM
 4 tan 
d
 cos  4e sin  FWHM – Full width in half

  of maxima
 Peak broadening
Combination: size effect + change of the interplanar spacing

12
 ln 2   d
   4 tan 
   D cos  d
Williamson-Hall-plot
12
 cos   ln 2  1 4e sin 
  
    D 

General formula:

n n
 K   d 
 
n
  4 tan   ~e
 D cos    d 
n n n
  cos    K   4e sin  
     
   D    1/D

sin 
 Peak broadening
Size effect Strain effect

I0  x  x0 2 
y y  I 0 exp   
Cauchy
x  x0  2  w  Gauss
1  
w
 ad a) size effect Dhkl  K shkl V 1/ 3
Broadening does not depend
on diffraction vector length
“imaginary”crystallite size V … “true” size
 hkl 1 / d  
1
Scherrer constant
Dhkl
Example:
Cubic crystallites KS 
6h 3
6h 2
 2(k  l )h  kl 
h k l
2 2 2

D crystals have not

properly defined
broadening anisotropy lattice parameter, ...
0.04
(111)
(200)

(220)

(311)
(222)

(400)
(331)
(420)

1.20
size broadening
 [1/nm]

1.14
1/3

0.02 a resolution of a conventional

(s0)Vc

1.08 diffractometr (Bragg-Brentano)

cube
1.02
sphere synchrotrons
0
2 3 4 0 50 100 150
2 2 2 1/2 D [nm]
(h +k +l )
 ad b) deformation (strain) effect
Micro-deformation = small inhomogeneities lattice points distances in
grains, caused by deformation fields of large defects (dislocations)

Deformation broadening is
proportional to the diffraction sin 
 (1 / d )  f  (  hkl ) D f  (  )
vector length 
• lattice defects
(dislocations, dislocation loops, precipitates)

Function of
• second kind stress in polycrystalline
density of
materials defects
 Function of orientation
factor corresponding Function of ‘power’ of
222
to defects defects
220 400
111
311
200
slope ~ e

sin 
 Microdeformation - anisotropy
• caused by the anisotropic diffraction contrast of
dislocations which imply the strain broadening
• treatment: dislocation density
sin(  hkl )
 hkl 1 / d  
k hkl
 B0  C hkl
Dhkl 

averaged Contrast factors

0.04 0.04

0.03 0.03
 [1/nm]
 [1/nm]

0.02 0.02

0.01 0.01

0 4 6 8 10 12 0 0 10 20 30 40
G [1/nm] ChklG2[1/nm]
 The Williamson-Hall plot
• a different dependence on the

 hkl 1 / d  
length of the diffraction vector for k hkl 4e
each effect offer an universal  sin(  hkl )
method for their separation Dhkl 
 222
220 size effect microdeformation
400
111
311 • single-crystals • lattice defects
microtwins, stacking (dislocations, dislocation
200 slope ~ e faults loops, precipitates)
• polycrystalline • second kind stress
~ 1/<D> materials in polycrstalline
small crystallite size materials
sin  microtwins
stacking faults
sharp dislocation walls
• W-H plot is valid only for Cauchy
distribution of crystallite size and stress.
• It is not very “realistic”.
k hkl 4e
• This method can give us complex picture  hkl (2 )   tan 
and can show anisotropy. Dhkl cos  
• We have to hold in mind its restrictions.
 Cu prepared by SPD

400
Cu-Al as-prepared

420
Cu-Al as-prepared (calc)
0.006 Cu-Al annealed at 580 C

311
 (1010m-1)

Cu-Al ann. at 580 C (calc)

Cu as-prepared

220

331
Cu as-prepared (calc)

222
200
0.004

111

0.002

0.000
0.0 0.2 0.4 0.6 0.8 1.0
sin 
 Whole profile modeling,
Fourier coefficients approach
Fourier Coefficients

I ( s)  k  A( L) cos( 2sL )dL

reciprocal space direct space

physical FT whole
calculation diffraction
model in of Fourier powder
profile
real space coefficients pattern

Programs: PM2k, MWP-fit Separation of A(L) on

AS(L) AD(L)
 microdeformation
• theWilkens-Krivoglaz model gives an analytical formula
for the deformation Fourier coefficients AD(L)
 1 
D
Ahkl ( L)  exp  b 2 C hkl L2 d hkl
*2
f * ( L / Re )
 2 
Burgers vector dislocation cut-off radius

dislocation random
correlation, distribution
ordering

M  Re   1 M 1
M - Dislocation arrangement parameter