C N R

Powder Diffraction Pattern: Origin of Line Broadening & Peak Shape Functions
Antonella Guagliardi
antonella.guagliardi@ic.cnr.it

Istituto I tit t di Cristallografia

B a r i Italy

Summer School on Structure Determination from Powder Diffraction Data Paul Scherrer Institute, June 18th - 22nd, 2008

Experimental diffraction pattern of a polycrystalline material

Sample Profile

h=fg
Instrumental profile

Paul Scherrer Institute, June 18th-22nd, 2008

Experimental diffraction pattern of a polycrystalline material

Y (2) = f g = f (2) g(2 2)d 2

crystal structure and volume of the illuminated sample size and shape of coherent domains lattice distorsions and defects size, divergence, energy dispersion of the beam optics (mirrors, monochromators, analyzers, slits, collimators) axial divergence geometrical aberrations (flat sample, transparency,...)

f = f1 f 2 f 3 K f n

g = g1 g 2 g 3 K g n
Paul Scherrer Institute, June 18th-22nd, 2008

Experimental diffraction pattern of a polycrystalline material

h profile dominated by The sample profile f LaB6 - SRM 660
ESRF - European Synchrotron Radiation Facility - Grenoble - FRANCE

(30.93 KeV, 0.4008 )

h profile Au NPs D~4nm

LNLS -Laboratorio Nacional de Luz Sincrotron - Campinas, BRASIL

dominated by The Instrumental profile g

Paul Scherrer Institute, June 18th-22nd, 2008

(8.040 KeV, =1.542 )

Powder diffraction pattern modeling:

Convolution-based Approach vs Analytical Peak Function
Convolution-based Approach
Physically based instrument aberration functions + sample broadenings Traditionally related to microstructural analysis, for extracting the sample contribution from the experimental pattern Empirically based functions, to describe shape and width of diffraction peaks. Traditionally related to structural analysis

Analytical Peak Shape Function

Klug & Alexander, 1954

(H.P. Klug, L.E. Alexander, X-ray Diffraction Procedures, 2nd ed., 1974, New York, John Wiley)

describe the diffraction pattern as the convolution of functions able to model various contributions of the instrumental and sample profiles

Multiple convolution integrals are highly time consuming operations!

Conventional convolution approach determines the g profile from a standard material (LaB6, Na2Ca3Al2F4)
Paul Scherrer Institute, June 18th - 22nd, 2008

90 : Convolution-based Profile Fitting

Advantages

In principle can be used for any experimental set-up Allows to control the diffractometer Instrument parameters directly refinable
Ability to construct a wide variety of profile shapes

Limits the number of (and the correlations among) parameters

Main limitations

Many different experimental set-ups (geometries & optics) Mirrors and monochromators difficult to be dealt with (depending on thermal stability)

Most methods restricted to functions that can be convoluted analytically (Lorentzians, Gaussians, impulse & exponential functions) R.W. Cheary & A. Coehlo (J. Appl. Cryst.,1987, 20, 173) described a number of tricks" for fast calculation of multiple convolution integrals (numerical integrations, integrations based on semianalitycal procedures) Fundamental Parameters Approach, implemented in TOPAS
Paul Scherrer Institute, June 18th - 22nd, 2008

Fundamental Parameters Approach

Instrumental profile

Sample profile

Final profile

K1 and K2 (99% of intensity) + group of satellite lines in the high energy tail K1 e K2 made of doublets (1,a 1,b 2,a 2,b) 5 Lorentzian profiles Cu-K Emission profile
Info & Figs. from: A. Kern, A.A. Coelho and R.W. Cheary, in Diffraction Analysis of the Microstructure of Materials, 2004, Springer, ISBN 3-540-40519-4
Paul Scherrer Institute, June 18th - 22nd, 2008

Emission Profile
What can modify it:
Parabolic mirror (different separation of K1 and K2 ) Ni filter for K (tails attenuation) monochromators curve of graphite riduces , can modify Int(K1)/ Int(K2) Ge asymmetric produces a very narrow , eliminates satellites and K2 peaks Different Targets (Cr, Mn, Fe, Co and Ni, up to 7 lorentzians! ) All instrumental contributions vary with 2, except the aberration related to the receiving optic and the finite Lab-source width

Geometric instrumental aberrations tend to determine the peak profile at low to medium angles Emission profile tends to become dominant at higher angle W(2) dominates at 2 > 100 Gi(2) dominate up to 2 40-60
Paul Scherrer Institute, June 18th - 22nd, 2008

Cu-target

Synthesis of (100)-LaB6 (SRM 660) line profile Lab-Diffractometer

Sample Size & microstrain

fg
WCuK W GEq
Equatorial plane Target width Divergence slit angle Receiving slit angle Sample thickness

W Geq GAx
Axial plane Target length Soller slits Receiving slit length Sample length

Paul Scherrer Institute, June 18th - 22nd, 2008

Rietveld Method
Rietveld, 1969
(H.Rietveld, J. Appl. Cryst, 1969, 2,65)

introduces a phenomenologic approach, aiming at refining a structural model from neutron powder diffraction data. The method describes the powder diffraction peaks through analytical functions

Y c (i ) = S IhLp hP (i , h) A(i, h) + Y b (i )
h

Lecture focused on

WPPD
S = scale factor Ih = reflection intensity (peaks area) Lph = Lorenz and polarization factors P(i,h) = analytical peak shape function (symmetric & normalized) A(i,h) = peak asymmetry function Yb(i) = background
Paul Scherrer Institute, June 18th - 22nd, 2008

Analytical Peak Shape Functions

Y c (i ) = S IhLp hP (i , h ) A (i , h ) + Y b (i )
h

Rietveld Neutrons Gaussian Peaks

Gaussiana Lorentziana

G (i,h) =
C = 4 ln 2

( )
C0

1 2

2 C0 2 i 2 h exp 2 Hh Hh 1

2 = scan angle 2 = Braggs angle of reflection h Hh = Full Width at Half Maximum (FWHM)
h
i

X-Ray Voigtian Peaks

L(i, h ) =

V=GL

2 1+ 4 ( 2 i 2 h )2 2 H h Hh

Paul Scherrer Institute, June 18th-22nd, 2008

Analytical Peak Shape Functions

Pseudo-Voigt
h =01 h =1 h =0

PV (i , h ) = h L (i , h ) + (1 h )G (i , h )
mixing parameter (fraction of L)

completely Lorentzian peak shape completely Gaussian peak shape

Pearson VII
mh = 1 mh =1 mh = mixing parameter

PVII(i,h) =

C0 1 + C1 (2 i 2 h) Hh Hh

mh

completely Lorentzian peak shape completely Gaussian peak shape

2(m) 21 m 1 2 C0 = 1 (m 0.5)( ) 2
1

C1 = 4 21 m 1

Hh, h, mh variables dependent on h

Paul Scherrer Institute, June 18th-22nd, 2008

Peak shape/width angular dependence

Pearson VII
2 2 H h = U tan h+V tan h+W h

Cagliotis equation

mh = m0 + m1 /2h + m2 /2h2
U, V, W, m0 , m1, m2 Parameters to be refined Voigt Pseudo-Voigt (TCH) Pseudo-Voigt
Allow to combine the G and L components so that they can be related to instrumental and sample broadenings

(P. Thompson, D.E. Cox, J.B. Hastings, J. Appl. Cryst., 1987, 20, 79)

2 2 2 H G = U tan h+V tan h+W + P cos h

Hh = F(HG, HL)

Cagliotis equation

(R.A. Young & P. Desai, Arch. Nauk Mater., 1989, 20, 79)

h = F(Hh, HL)

H L = X cos h + Y tan h
U, V, W, P, X, Y Parameters to be refined
Paul Scherrer Institute, June 18th-22nd, 2008

Cagliotis equation
HG dependence on through W,V,U

Caglioti et al., 1958, proposed to model the instrumental function of neutron diffraction patterns with gaussian peaks. The Cagliotis model relies on the hypothesis that, for each optical elements of the diffractometer (crystal and/or collimator) the probability of a neutron to reach the detector is described by a gaussian distribution. (G. Caglioti, A. Paoletti, F.P. Ricci, Nuclear Instrum., 1958, 3, 23).

Sabine, 1987, generalised the Cagliotis approach to any system of alternating crystals and collimators, to deal with the more complex intrumental configuration of synchrotrons and high resolution lab diffractometers, still within a gaussian approximation.
(T.M. Sabine, J. Appl. Cryst.,1987, 20, 173)

Gozzo et al., 2006, extended the Caglioti/Sabines approach by including the effect of collimating and refocusing mirrors, still within a gaussian approximation.
(F. Gozzo, L. De Caro, C. Giannini, A. Guagliardi, B. Schimtt, A. Prodi, J. Appl. Cryst.,2006, 39, 347)
Paul Scherrer Institute, June 18th-22nd, 2008

Sabines generalization of Cagliotis equation

The probability of a foton to reach the detector Is the product of the gaussian probability of each optical element Product of esponential terms
2 exp ' m

Double crystal monochromator, sample, crystal analyzer - Setting (+,-,+,-) Total reflection probability
2 2 b + 2 I ( ) = dd exp ' + 2 ' + ' a m m

finite detector acceptance

divergence of the initial beam

= - m = difference between the monochromator Bragg

angles of an individual () and the central (m) ray

b=

tan a tan 2 tan m tan m

Monochromator crystal

m = Bragg angle of

a = Bragg angle of
Analyzer crystal

m = width of the beam

divergence probability distribution function

m = width of the monochromator

crystal mosaic block probability distribution function (Darwin width )

a =

width of the analyzer crystal

mosaic block probability distribution function (Darwin width )

Paul Scherrer Institute, June 18th-22nd, 2008

Instrumental Resolution Function

tan tan a tan 1 2 tan a 2 2 1 + + m + 2a H G (2 ) = m 2 2 tan m 2 tan m tan m tan m
m = FWHM of the divergence initial beam distribution function i = FWHM of the mosaic-block distribution function ( Darwin width) of the monochromator / analyzer crystal
2 2

IRF

2 2 4 m 8 m 22m 22m 2 1 2 2 tan tan + 4 m + 2m + 2a HG = + + tan 2 tan tan m 2 tan m m m

Paul Scherrer Institute, June 18th-22nd, 2008

IRF at SLS-MS

2 m 2 tan a tan 2 + 2a + 2f ,eff 2 H G (2 ) = p + tan 2 tan m m

2

2 2 4 p p 22m 2 22m 2 tan tan + p + 1 2m + 2a + 2 ,eff + + H = f tan 2 tan tan 2 m tan m 2 m m 2 G

W
Paul Scherrer Institute, June 18th-22nd, 2008

Sample Profile: Scattering from a crystal

sin Ma r * sin Nb r * sin Pc r * G (r *) = f i ( S ) exp 2i (hxi + kyi + lzi ) sin a r * sin b r * sin c r * i =1
q

Structure Factor Reciprocal vector

Interference Function

r * = ha * + kb * +lc* =

s s0

Laue equations

s s0

=h

s s0

sin 2 [N a a (s - s0 )] sin 2 [N b b (s - s0 )] sin 2 [N c c (s - s0 )] I = GG* = F sin 2 [a (s - s0 )] sin 2 [b (s - s0 )] sin 2 [c (s - s0 )]

2

b c Ncc

sin 2 (Nh ) I ( h) F sin 2 (h )

2

Column of unit cells

Paul Scherrer Institute, June 18th-22nd, 2008

Naa

=k

s s0

=l

Sample Profile: Scattering from a powder sample

For the periodicity of the Interference Function
sin 2 (Nh ) sin 2 (Nh ) = 2 2 sin (h ) h = h h '

sin 2 (Nh ) (h )2
Translated in h=h h = -1 h = +1

Reciprocal Lattice plane of a single crystal cubic in shape

Fig Diffraction along r* = d* = (100)

-3

-2

-1

+1

+2

+3

Powder diffraction sphere

Powder sample
Diffraction over a sphere of radius |r*| = |d*| Interference Function should be integrated over the sphere to obtain the powder diffraction profile
Tangent plane

Integration depends on shape of crystallites and on point crossing direction (Miller indices of the reflection) Good approximation simplifying calculations: integration over the tangent plane
(domains not too small / shape not strongly anisotropic!).

(Fig. 2a from: P. Scardi, in Analisi di Materiali Policristallini, 2006, Insubria University Press, ISBN 978-88-95362-04-5)
Paul Scherrer Institute, June 18th-22nd, 2008

Sample Profile: size broadening

Cubic unit cell (lattice parameter = a) Crystallites cubic in shape, all with same size D=Na Diffraction profile along h00 constant section of tangent plane & diffraction sphere intersection

sin 2 (Nas ) I h 00 ( s) (as )2

Integral Breadth

s = r * rh*00

sin 2 (Nas ) ds Peak Area Na 1 I (s)ds = (as )2 h 00 ( s ) = = = = sin 2 (Ns ) ( Na ) 2 D Peak Maximum I (0) Lim s 0 (s )2

Integral Breadth inversely proportional to the domain size General relationship, independent of domain shape, lattice symmetry and hkl

( r*) =

K D

(2 ) =

K
D cos

Scherrer formula
(P. Scherrer, Gott. Nachr., 1918, 2, 98)

It holds also for crystallites polydisperse in size!

Paul Scherrer Institute, June 18th-22nd, 2008

Sample Profile: lattice distorsion effects

Real materials often include defects limiting the coherence of their crystal lattice non-homeneous strain field effetcs on position, size and shape of reciprocal space points/ powder peak profile complex problem

Heuristic approach to obtain a useful relationship between peak broadening & lattice distorsions

d d =
strain

macrostrain (macroscopic homogeneous strain) microstrain (non-homeneous strain field - on the length scale of crystallite size or smaller)
microstructure

zero strain (no macro/microstrain)

macrostrain

Peak shift

microstrain

Peak broadening

macrostrain & microstrain

(Fig. 13.4 from: P. Scardi, in Powder Diffraction Theory and Practice, 2008, Royal Society of Chemistry, ISBN 9780-85404-231-9)

Peak shift & broadening

Paul Scherrer Institute, June 18th-22nd, 2008

Sample Profile: strain broadening

Differentiating Braggs law at constant wavelength

0 = 2d sin +2d cos microstrain

2 = -2 tan d d = -2 tan (2) -2 < 2 >1/2 tan

macrostrain

A.R. Stokes, A.J.C. Wilson, Proc. Phys. Soc., London, 1944, 56, 174

peak profile (width & shape) depending on the strain field distribution within the sample

FWHM

1 2 = H G 2 ln 2

L
HL

(2 )
r.m.s. strain Root mean square deformation

K
D cos

+2 2

12

tan

Combined size-strain

< 2 >1/2

P/cos X/cos

(HG) (HL)

U tan Y tan

(HG) (HL)

(r*) =cos (2) (r*) < 2 >1/2 r*

strain broadening affects the peak in a r*-dependent way

Paul Scherrer Institute, June 18th-22nd, 2008

Sample Profile: size broadening vs

Size broadening (D = 2 m)

IRF

Paul Scherrer Institute, June 18th-22nd, 2008

Sample Profile: size & strain broadening

IRF Size broadening (D = 2 m)

Strain broadening ( = 510-5)

Paul Scherrer Institute, June 18th-22nd, 2008

2 2 2 H G = U tan h+V tan h+W + P cos h

H L = X cos h + Y tan h
Instrumental contributions Sample contributions

G
Optics
Caglioti, Sabine (1958, 1987)

G, L
size

G, L
strain

tan
(Klug & Alexander ,1954)

1/cos
(Scherrer, 1918)

tan
(Stokes & Wilson, 1944)

W,V,U

P, X

U, Y

Same parameters include effects from different sources Difficult separation of different contributions Correlation problems & instability during refinement
Paul Scherrer Institute, June 18th-22nd, 2008

Asymmetry Correction

Y c (i ) = S IhLp hP (i, h) A(i, h) + Y b (i )

h

Intensity (a.u.)

FWHM=0.8, m=2

FWHM=0.4, m=2

13

14

15

16

17

18

19

20

21

22

Axial Divergence (up to ~ 50 in 2 ) Flat Sample Transparency Beam divergence in the axial plane (soller slits)

2 (deg)

Semi-empirical analytical functions (1-2 parameters to be refined) Split-Functions (PV, PVII)

Paul Scherrer Institute, June 18th-22nd, 2008

Axial Divergence

Detector aperture

Detector 2 scan across successive D-S cones

Incoming beam Perpendicular to the slide plane

Perfectly monochromatic and horizontally & vertically collimated incident beam Diffracted beam exhibits an axial divergence simply because it describes a Debye-Scherrer cone

0 < 2 < 90

At low angle the detector intercepts first the corners A and B, then goes across the arc AB At high angles, AB tends to a straight line and the detector intercepts the arc AB all at once
Paul Scherrer Institute, June 18th-22nd, 2008

Correction of axial divergence asymmetry

Convolution-based model
(FPA R.W. Cheary, A. Coelho, J. Appl. Cryst., 1998, 31, 862)

(L.W. Finger, D.E. Cox and A.P. Jephcoat, J. Appl. Cryst., 1994, 27, 892)

Rietveld analytical PSF

Inte ntensity (a.u.)

H = 10 mm H = 5 mm H = 3 mm

L = sample-to-RS distance S = illuminated sample length H = RS aperture S/L & H/L parameters to be refined

Si (111)

FWHM=0.04 =0.2 =0.40

L=800 mm
S =2.75 mm

7.44

7.52

7.60

2 (deg)

AD effects reduced by controlling the aperture of the receiving slit

Paul Scherrer Institute, June 18th-22nd, 2008