You are on page 1of 88

Classical Texture

Analysis

D. Chateigner
CRISMAT-ENSICAEN; IUT-UCBN
6 bd. M. Juin 14050 Caen
Outline
Qualitative aspects of crystallographic textures
Grains, Crystallites and Crystallographic planes
Normal diffraction
Effects on diffraction diagrams, their limitations
-2 scans
Asymmetric scans
-scans (rocking curves)
Representations of texture: pole figures
Pole Sphere
Stereographic projection
Equal-area projection: Lambert/Schmidt projection
Pole figures
Localisation of crystallographic directions from pole figures
Direct and normalised pole figures
Normalisation
Incompleteness and corrections of pole figures
Single texture component
Multiple texture components
Pole figures and (hkl) multiplicity
A real example
Pole figure types
Random texture
Planar textures
Fibre textures
Three-dimensional texture
Pole Figures and Orientation spaces
Mathematical expression of diffraction pole figures and ODF
From pole figures to the ODF
Orientations g and pole figures
Euler angle conventions
From f(g) to pole figures
Deal with ODF in the G space
Plotting the ODF
Inverse pole figures
ODF refinement
Generalised spherical harmonics
WIMV
Entropy modified WIMV and Entropy maximisation
ADC, Vector and component methods
ODF coverage
Reliability and texture strength estimators
Magnetic QTA
Why needing QTA !!

- correcting texture effects


powder XRD
spectroscopic methods (P-EXAFS, ESR, Raman )
- mollusc phylogeny, fossils
- predicting texture effect on macroscopic anisotropic properties
average to get macroscopic tensors
simulating elasticity, electric polarisation
Bulk Acoustic Waves
anisotropic magnetisation
- correlation texture - macroscopic anisotropic properties
Thermoelectric Power Factor
Pyroelectric coefficients
Tauc gap
Jc in superconductors
Levitation forces and trapped flux

But why classical QTA vanishes

Why needing Combined analysis

Minimum experimental requirements .


Qualitative aspects of texture

Polycrystal: aggregate of grains, different phases, sizes,


shapes, orientations, stress state, crystallinity, faults

Diffraction:
probes lattice planes: crystallites, not grains
x-rays, neutrons or electrons

SEM:
grains, not crystallites (coherent, single crystal domains)
shape vs crystallographic texture (EBSD)
Grains, crystallites, crystallographic planes

Friedel's law: Ihkl = I-h-k-l using normal diffraction


+ or - directions not distinguished
[hkl]
I+

-[hkl] I-
Texture effects on diffraction diagrams

-2 scan: probes only parallel planes


Li0.12La0.88TiO3 random bulk

10000

Li0.12La0.88TiO3/(100)-MgO Oriented film

MgO
5000

003

0
001
15 20 25 30 35
002
40 45 50 55 60
asymmetric scan: probes only inclined planes
mixed scan: probes specific planes for
specific orientations

006

008
005
scan: probes orientation of only one
plane type (fixed ), only for small -

2000

1500

Intensity (a.u)
1000 0.1

500

17.5 18.0 18.5


!()
limitations: available (or other) range
diamond (Fd3m), 2.52 neutrons, up to 2 = 150

111
limitations: 2 texture components
same c-axes direction, but not same a-axes orientation
10000

p - p0
L hkl = ; p 0 : random

MgO
1 ! p0
5000 003
" I{00l}
i
i
p= =1= L 00 l
0
" I{hkl}
hkl

15 20 25
001 30 35 40 45 50 55 60
002
limitations: 2 texture components, one inclined
2000

1500

Intensity (a.u)
1000 0.1

500

17.5 18.0 18.5


!()

2000

1500

Intensity (a.u)
1000

500

17.5 18.0 18.5


!()
Representations of texture: pole figures

One crystallite oriented


in the Pole sphere:
- location of all
[hkl] unit sphere
- dS = sin d d
- (,): angles in the
diffractometer space S

Hard to visualise: needs


pole figures
Stereographic projections: equal angle

Poles: p(r',):

r = R tan(/2)
Lambert projections (equal area)

Poles: p(r',):

r = 2R sin(/2)
90
stereographic Lambert/Schmidt
90
1.0
1.0 120 60
120 60
0.8
0.8
0.6
0.6 150 30
150 30
0.4
0.4

0.2 0.2

0.0 180 00.0 180 0

0.2 0.2

0.4 0.4
210 330 0.6 210 330
0.6

0.8 0.8
240 300 240 300
1.0 1.0
270 270

5 x 5 grid: 1368 points


Pole figures
{hkl}-Pole figure: location of distribution densities, for the {hkl} diffracting plane,
defined in the crystallite frame KB, relative to the sample frame KA.

Pole figures space: Y, with y = (y,y) = [hkl]*

Direct Pole Figure: built on diffracted intensities Ih(y), h = <hkl>*


Normalised Pole Figure: built on distribution densities Ph(y)

Density unit: the "multiple of a random distribution", or "m.r.d."


Usual pole figure frames KA

Lineation
direction
RD G

. TD
. M
. nF
ND N

Foliation plane

metallurgy malacology geophysics

Thin films: substrate directions XA, YA, ZA


Normalisation
2" "/2
90
total
1.0

0.8
120 60 Ih = ! !I h (# y , $ y ) sin# y d# y d$ y
0.6
$ y =0 # y =0
150 30
0.4
2" "/2
0.2
random total
0.0 180 0 Ih = Ih / ! ! sin# y d# y d$ y
0.2 $ y =0 # y =0
0.4
210 330
0.6

0.8
240 300 Ih (y )
1.0
270
Ph (y ) = random
Ih
I h (" y , ! y )

- Only valid for complete pole figures:


neutrons in symmetric geometry
- Needs a refinement strategy to get Irandom for all h's
Incompleteness and corrections of pole figures

Missing Bragg peaks


Absorption + volume
Defocusing (x-rays)

Blind area

Localisation
-defocusing 2-defocusing
-defocusing
Defocusing corrections:

Intensity
- Calibration on a random powder
I rand
0 ," ,! Net intensities
I cor meas
# ," ,! = I # ," ,! (point detector)
I rand
# ," ,! 0 90

* meas bkg I bkg # ," ,! ' I rand bkg


0 ," ,! $ I 0 ," ,! Peak maximum (point detector)
= (I # ," ,! - I 0 ," ,! bkg % rand bkg
Integrated intensity (1D or 2D detector)
() I 0 ," ,! I
%& # ," ,! $ I 0 ," ,!

- Total integration of the peak (direct integration or fit)


Absorption/Volume corrections:

Specific to each instrumental geometry


Sample dependent (films, multilayers )
beam
Modifies the defocusing curves
Can be integrated in fitting procedures

Top film

Intensity
I(0) = I( ! )
(1 # exp(# 2T / sin " i ))
(1 # exp(# 2T / sin " i cos ! ))
0 90

$ 2# j T j
j
(1 $ exp($ 2T / sin " i ))exp( )
sin " i
Covered layer I(0) = I( ! )
$ 2# j T j
j
(1 $ exp($ 2T / sin " i cos ! ))exp( )
sin " i cos !
Single or multiple texture components, multiplicity

Double

Single

Cubic Tetragonal
Program convention !
orientations are oriented objects
A real example

Cypraea testudinaria

Outer aragonite layer


Pnma space group
Texture types

Random texture
3 degree of freedom
All Ph(y) homogeneous
1 m.r.d. density whatever y

100 001 Planar texture


2 degree of freedom
1 [hkl] at random in a plane
100 001 Fibre texture
1 degree of freedom
1 [hkl] along 1 y direction

Cyclic-Fibre texture

c // ZA

Cyclic-Planar texture

(a,b) // (XA,YA)
100 110 Single crystal-like texture
0 degree of freedom
2 [hkl]'s along 2 y directions

Single-crystal and perfect 3D orientation not distinguished


Pole figure and Orientation spaces

dV(y ) 1
Pole figure expression: = Ph (y ) dy
V 4!
dy = siny dy dy
2! !/2

$ $ P (# , "
" y =0 # y =0
h y y ) sin# y d# y d" y = 4!

Orientation Distribution Function f(g):

dV(g) 1 dg = sin()ddd
= 2 f (g) dg
V 8!
2! ! / 2 2!

% % % f (g) dg = 8! 2
$ =0 # =0 " =0
From Pole figures to the ODF

Pole figure: one direction fixed in KA Orientation: two directions fixed in KA

1
Fundamental Equation of QTA Ph (y ) = ! f (g) d"~
2# h // y

Needs several pole figures to construct f(g)


Pole figures from g
- Rotation of KA about the axis ZA through the angle :
[KA aK'A]; associated rotation g1 = {,0,0}
- Rotation of K'A about the axis Y'A through the angle :
[K'A aK"A]; associated rotation g2 = {0,,0}
- Rotation of K"A about the axis Z"A through the angle :
[K"A aK"'A//KB]; associated rotation g3 = {0,0,}
finally: g = g1 g2 g3 = {,0,0} {0,,0} {0,0,} = {,,}

Y'A Y'A
X'A

Z''A Z''A
Y'''A

g1 = {45,0,0} g2 = {45,45,0} g3 = {45,55,45}


Euler angles conventions
Matthies Roe Bunge Canova Kocks
! " #1 = ! + $/2 % = $/2 & ! "
' ( ) ( (
* ) #2 = * + 3$/2 + = 3$/2 & * )=$&*

Bunge's convention Roe/Matthies's convention


From f(g) to the pole figures
Deal with components in the ODF space

ODF -sections

Pole figures

Component:
(Hexagonal system)
g = {85,80,35}
Plotting f(g)

A 3D plotting program: ODF plot

= 40
10
20
30
0

ODF sections (, , or ) ODF 3D-isometric view


Cartesian or Polar f(g) view

Cartesian Polar

= 0: space deformation
Inverse pole figures

1 1 ~
Ph (y ) = ! f (g) d"~ R y (h) = ! f (g) d"~
2# h // y
2# y // h

Pole figures Inverse Pole figures

24 equivalent cubic sectors for the


Inverse pole figure of a cubic system
ODF refinement

1
One has to invert: Ph (y ) = ! f (g) d"~
2# h // y

from Generalized Spherical Harmonics (Bunge):


$ l
f (g) = # #C mn mn
lT (g)
l
l= 0 m,n="l

#
1 l n l
mn *m
Ph (!
y) = ! ! k l (y )! C l k n ($ h% h )
l = 0 2l + 1 n = " l m="l

Least-squares Refinement procedure ! ! [I h (y ) " N h Ph (y )] dy


2

h y

" $
But even orders are the only available parts: e
f (g) = ! !C mn mn
$T $ (g)
$ =0 ( 2 ) m ,n = # $
from the WIMV iterative process (Williams-Imhof-Matthies-Vinel):

n +1 f n (g) f 0 (g)
f (g) = Nn 1 I Mh
1
IM h
& #
& I Mh
# IM h and f 0 ( g ) = N 0 $$ ' ' Phexp (y ) !!
$$ ' ' Phn (y ) !! % h =1 m =1 "
% h =1 m =1 "

E-WIMV (Rietveld only): wh


Mh rn
' P (y ) $ Mh
with 0 < rn < 1, relaxation parameter, f n +1 ( g ) = f n ( g )! %% hn ""
Mh number of division points of the integral around k, P
m =1 & h ( y ) #
wh reflection weight

Entropy maximisation (Schaeben) and exponential harmonics (van


Houtte):
rn fs(g) = eh(g) 0
Mh
n +1 n ' Ph (y ) $ Mh
f ( g ) = f ( g )! %% n "" C smn (2 1) h ( g ) mn
m =1 & Ph ( y ) #
" = " + ! T" ( g )dg
e
arbitrarily defined cells (ADC, Pawlik):
Very similar to E-WIMV, with integrals along path tubes

Vector method (Ruer, Baro, Vadon):

I linear equations for J unknown quantities: Pi(h) = [ij(h)] fj

Component method (Helming):

f (g) = F + ! I c f c (g)
c

2 0 & & g~ # 2 #
Gaussian component: f ( g , g ) = f ( g~ ) =
c
exp$ ' $$ !! !
.( 2
& & / # #+( $ %/ " !
/ -1 ' exp ' $ ! *
$ ! % "
(, $ % 2 " !(
% ")
ln 2 1
S= N (S ) =
&( # I 0 ( S ) ! I1 ( S )
1 ' cos$ !
%2"
Evaluation of the OD coverage
2
Say 20 measured (5 x 5) complete pole figures:

= 20 x 1368 = 27360 experimental points


0
ODF (5 x 5 x 5, triclinic): 98496 points to refine

5
{100} pole figure, measured up to = 45:

{100} + {110}, measured up to = 45:


3

{100} + {110} + {111}, up to = 45:

3
Estimators of Refinement Quality
Visual assessment

Helix pomatia (Burgundy land snail:


Outer com. crossed lamellar layer) Bathymodiolus thermophilus (deep
ocean mussel: Outer Prismatic layer)
RP Factors:

Individual pole figures:


J
~o ~c $1 for t > x
" hi j Phi (y j )
P (y ) -
~ &( x , t ) = #
( ) "0 for t % x
j=1
RPx (h i ) = J
! x, Phoi (y j )
~o
" Phi (y j )
j=1
x = !, 1, 10 ...

Averaged on all pole figures:

1 I
RP x = ! RPx (h i )
I i =1
Bragg R-Factors: J
~o ~c
"[ ]
2
Ph i (y j ) - Ph i (y j )
~
RB x (h i ) =
j=1
J
~
(
! x, Phoi (y j ) )
o2
"P
j=1
hi (y j )

Weighted Rw-Factors: J

" [w I ]
o o 2
ij h i (y j ) - w ijc I ch i (y j )
~
w ij =
1 Rw x (h i ) =
j=1
J
2
(
! x, Phoi (y j ) )
o
I (y j )
hi
" w ijo I zhi (y j )
j=1

150
RP 140 gRw0
RP1 gRw1
125
120

100 100

80
75

60
50
40

25
20

0 0
0 100 200 300 400 500 600 700 800 0 200 400 600 800

F2 F2
Texture strength estimators

ODF Texture Index: F2 [1,[ > 1 m.r.d2


= 1: powder
= : single crystal

1
F 2 (m.r.d.2 ) = " f 2 ( g i )!g i Discrete OD
8# 2 i

L
2 ) 1 & ! !
mn 2
F = 1+ " ' $" " C ! Continuous ODF
! =2 ( 2 ! + 1 % m=#! n=#!

Pole figures Texture Index:

1 2
J h2 = [P (y )]
" h i !y i
4# i
Texture Entropy: S [0,-[ 0
= 0: powder
= -: single crystal
-1
S= 2 # f (g ) ln[f (g )]!g
i i i
8" i

S - F2 :
Fon + 0
0 50 100 150 200 250 300
Fon +
smooth -1 F2 Dirac-like
texture component(s) -2 texture component
-3

-4

-5

-6
Lower bound:
-7
Entropy
Fon = 0
Magnetic QTA

r n r m r r r n r m r
r
I hr (y,0) = I hr (y,0) + I hr (y,0) I hr (y, B) = I hr (y,0) + I hr (y, B)

r r
m r r r
!I (y, B) = I h (y, B) - I h (y,0)
r
h
r r
r r
+p
!I (y, B)
r
h

r r
-p
!I (y, B)
r
h

**** True iteration step #120 ****


ODF min max: 0.64 2.26
Texture Index (F) 1.0294
Entropy -0.0144
Average RP 0.2427
Average RP1 0.3041
Why needing QTA

- Correct for QTA effects in XRD: structure analysis


QTA and structure correlations: yes, but
f(g) and |Fh|2 are different !

Charonia lampas lampas


OD maximum (m.r.d.) 299 196 2816
OD minimum (m.r.d.) 0 0 0
Texture index (m.r.d.2) 42.6 47 721
Texture reliability Rw (%) 14.3 11.2 32.5
factors
RB (%) 15.6 12.7 47.8
Rietveld GoF (%) 1.72 1.72 3.05
reliability factors
Rw (%) 29.2 28.0 57.3
RB (%) 22.9 21.7 47.2
Rexp(%) 22.2 21.3 32.8
Geological Charonia Charonia Charonia Strombus
reference lampas lampas lampas decorus
OCL RCL ICCL
a () 4.9623(3) 4.98563(7) 4.97538(4) 4.9813(1) 4.9694(3)
b () 7.968(1) 8.0103(1) 7.98848(8) 7.9679(1) 7.9591(4)
c () 5.7439(3) 5.74626(3) 5.74961(2) 5.76261(5) 5.7528(1)
Ca y 0.41500 0.41418(5) 0.414071(4) 0.41276(9) 0.4135(7)
z 0.75970 0.75939(3) 0.76057(2) 0.75818(8) 0.7601(8)
C y 0.76220 0.7628(2) 0.76341(2) 0.7356(4) 0.7607(4)
z -0.08620 -0.0920(1) -0.08702(9) -0.0833(2) -0.0851(7)
O1 y 0.92250 0.9115(2) 0.9238(1) 0.8957(3) 0.9228(4)
z -0.09620 -0.09205(8) -0.09456(6) -0.1018(2) -0.0905(9)
O2 x 0.47360 0.4768(1) 0.4754(1) 0.4864(3) 0.4763(6)
y 0.68100 0.6826(1) 0.68332(9) 0.6834(2) 0.6833(3)
z -0.08620 -0.08368(6) -0.08473(5) -0.0926(1) -0.0863(7)
ZC-O1 () 0.05744 0.00029 0.04335 0.1066 0.031

Calcite: Z = 0 Biogenic intercrystalline effect


- Correct for QTA effects in XRD: QPA
QTA and QPA correlations: yes, but
f(g) and S are different !

f(g) is on the individuals

S is on the sum
- Correct for QTA effects in spectroscopies: P-EXAFS on clays

Beam direction
= 0 = 90

tet
Absorber
tet Mg, Al, Fe
c* Si, Al

Oct-Tet: min Oct-Tet: max


Oct-Oct: max Oct-Oct: 0
! 0
"=
0 Z
0 = isolated atom


h
ij
Rij
Y

Film surface

absorbing atom
X
backscattering atom

2$
2 1 2 2 cos 2 " sin 2 !
2
cos # ij = &0 cos # ij d% = cos ! sin " +
2$ 2
Fe K-edge High quality range up
to 14-15-1
k3

Powder spectra

Strong dependence
= strong texture
k (-1)

& 2 2 cos 2 ( sin 2 ' #


N obs = 3 N real $cos ' sin ( + !
% 2 "
For ideally textured films:

O
1
I#
1+
2
( )( )
3 sin 2 # ! 1 3 cos 2 " ! 1
Fe =
I0 1
(
1 ! 3 cos 2 " ! 1
2
)
Flattened
Regular
- Mollusc shells and fossils: phylogeny
Closely related species, close textural characters, but significant variations: textural parameters can
serve character analysis
Atrina maurea " ISN ! a,4420

Pinna nobilis " ISN !a,2595


Lampsilis alatus " ISN !a,2590
<110 >
Fragum fragum $, 15 ICCL # 50
<110 >
Glycymeris gigantea $, 15 ICCL # 50
<110 > , -15
Spondylus princeps %, 10 ICCL # 50
Bivalvia Paphia solanderi " ICCL O &, 20 OSiP O

a, 90
Neotrigonia sp. " ISN !12

Pinctada margaritifera " ISN !8a, 90


a, 90
Pinctada maxima " ISN !14
a, -30
Pteria penguin " ISN !15
Monoplacophora Neopilina galatheae ! IN O
Rokopella zografi ! IN O

Nautilus pompilius ! ICN " a,6175


Cephalopoda Nautilus macromphalus ! ICN " a, 80

Scutellaster tabularis $,25 IRCL #<50110> , -10

Conus leopardus ! ICCL # a,4760 ! ORCL O

Muricanthus nigritus ! ICCL # a,47-50

Cyclophorus woodianus ! IRCL Ia, 20

Cypraea mus ! IP " a, 45

Cypraea testudinaria $, 15 ICCL Ia, 10


a, 30
Oliva miniacea ! OCCL # 50

- Euglandina sp. ! ICCL Ia, -80

Helix aspera ! OCCL Ia, 90

Helix pomatia ! OCCL Ia, 90


Gastropoda
Gastropoda
Entemnotrochus adansonianus ! ICN O
Perotrochus quoyanus ! ICN O

Haliotis cracherodi ", 15 ICN O


Haliotis rufescens ! ICN O

Tectus niloticus ! ICN O


Tectus pyramis ",15 OSP O
Turbo petholatus ! OSP O

Phasianella australis ! OICP O


| |
<110 >
\ \\ Fissurella oriens #, 20 ICoCL * 55
a, 90
Scutus antipodes ! ICCL $17
\ \\
a
Nerita polita ",25 ICCL % 58
Nerita scabricota ! ICoCL O
Viana regina ! ICCL O ! OCCL O ",15 OHC O
Phylogenic interest: nacre = ancestral (Carter & Clarck, 1985)

19 evolutionary events, from cladistics character analysis


nacre not ancestral

9 events
Calcitic fossils: trichites

Layer ODF ODF min RP0 RP1 c-axis a-axis {001} Max F2 -S
type Max (mrd) (%) (%) (mrd) (mrd2)
(mrd)
Pinna nobilis OP 303 0 50 29 // N random 68 29 2.3
Pteria penguin OP 84 0 29 15 // N random 31 13 1.9
Amussium OP 330 0 53 33 // G <110> // 20 31 2.6
parpiraceum M
Bathymodiolus OP 63 0 25 18 // G // M 27 13 1.9
thermophilus
Mytilus edulis OP 207 0 41 25 75 <110> // 23 21 2.2
from N M
Trichites P 390 0 52 28 15 random 56 41 2.2
from N
Crassostrea gigas IF 908 0 45 31 35 // M >100 329 5.1
from N

No DNA is available on fossils like Trichites, but Trichite's textural parameters


are close to the ones of pinnoids or pterioids: interesting for the classification of
extinct species
Calcitic fossils: Belemnites

c c

Belemnita mucronatus

c-axes perp. to the shell: as in other cephalopods: nacre ancestral ?


Aragonitic fossils: Baculities sp.

Baculities

c-axes perp. to the shell: as in other cephalopods,


strong c-calcite to c-aragonite fossils interaction
- Predict macroscopic anisotropic properties: Elastic

Arithmetic average T = ! T(g) f(g) dg


g
!1
(T) -1
" T

Voigt average CijklM = <Cijkl> Upper bound


Homogeneous strain

Reuss average SijklM = <Sijkl> Lower bound


Homogeneous stress
N
Geometric average !b" = # b k
wk
= exp( lnb ) scalar
k =1

N
lnb = ! lnb k w k
k =1
Tij = exp(<lnT>i'j') tensor

I = 1/ 1/I = I-1-1 Eigenvalues of Tij

-1 !1
(Cijkl ) = Cijkl

- Predict macroscopic anisotropic properties: Electric polarisation

!! p
y
h Ph (y ) dy
ph =
!! P (y ) dy
y
h
- Predict macroscopic anisotropic properties: BAW

# 2u i ilmn # 2u n
Propagation equation $ 2 = !C " m l
#t #x #x

Propagation VP VS1 VS2


direction
[100] ccM1111 c M 44 c M 44
!! ! !

[110] c M 11 + 2c M 44 + c M 12 c M 11 " c M 12 c M 44
2! 2! !
[111] c M 11 + 4c M 44 + 2c M 12 c M 11 + c M 44 " c M 12 c M 11 + c M 44 " c M 12
3! 3! 3!

Cubic crystal system


c11 or c11M c12 or c12M c13 or c13M c14 or c14M c33 or c33M c44 or c44M

Single crystal 201 54.52 71.43 8.4 246.5 60.55


LiNbO3/Si 206.4 68.5 67.6 0.48 216.5 64
LiNbO3/Al2O3 204 65.7 69.7 1.1 219.9 63.2

Single crystal

LiNbO3/Si

LiNbO3/Al2O3
- Predict macroscopic anisotropic properties: Magnetisation
!
2
M%
= 2#$ (1 " !0 )PV( g ) sin g cos( g " ) d g + !0 M random
MS 0

M|| simulated
M|| exp.

max {001}: 3.9 mrd


min: 0.5 mrd Mperp exp.

ErMn3Fe9C:
ODF + micros. macros.
- Correlate macroscopic anisotropic properties: Thermoelectric PF

9.8 MPa for 2 h 19.6 MPa for 6 h 19.6 MPa for 20 h

2.7 0.9

Power FactorPFab (mW/mK)


!ab (10 S/m)

2
2.6

0.8
2.5
4
Electrical conductivity

2.4
0.7
2.3

2.2
0.6
2.1

2.0
0.5

1.9

1.8 0.4
2h 6h 20h
Uniaxial Pressing duration time (h)
- Correlate macroscopic anisotropic properties: Pyroelectric coefficient

Texture Pyroelectric
Index Coefficient
m.r.d.2 10-8C cm-2 K-1
23
PCT on
Pt/TiO2/(100)Si 2.1 0.3

1 mrd

PCT on 5.1 1.5


Pt/(100)MgO
0.01

7.9 1.1
PCT on
Pt/(100)SrTiO3

Enhancement of <001> texture


- Correlate macroscopic anisotropic properties: Tauc gap in nano-Si

2.5
2.6

Refractive index n 2.4 2.5


A B C

Tauc gapgE(eV)
2.4
2.3 Eg
D E F 2.3
2.2
2.2
G H
010

2.1 110
221
2.1
332
011 443
111
113
111

2.0
0001 101 100

2.0
min 0 max

1.9
3 4 5 6 7 8 9 10 11 12 13
inter-electrode d spacing (cm)
-Correlate macroscopic anisotropic properties: Bi-2223 / Bi-2212
superconducting Jcs

Orientation Distribution
Max
Sinter-forging RP0 RP1 Jc
(m.r.d.)
dwell time (h) (%) (%) (A/cm2)
Bi2212 Bi2223

20 21.8 20.7 17.74 10.56 12500

50 24.1 24.4 17.05 11.04 15000

100 31.5 25.2 13.54 9.31 19000

150 65.4 27.2 16.24 12.25 20000

Texture strength

Sinter-forging
% Bi2223 Jc
Time

Crystallite Size
-Correlate macroscopic anisotropic properties: Levitation force
and trapped flux in MTG-YBCO

Neutron pole figures (D1B-ILL)

8 Levitation force
7
and trapped flux
6
Fz (N/cm
2
)

3 Models ?
2

-7 -6 -5 -4 -3

Texture Entropy
Why needing combined analysis

- Solve the peak-overlap problems (intra- and inter-phases)

104 Belemnite rostrum


~ pure calcite
Resolved during
113 ODF refinement

012
006 024/108
116 211/122
1010

110
202
Polyphased Mylonite (Palm Canyon, CA)

Q101 + B003
7

6
Using 0D detector
hardly manageable

Q110
P201 + B111
Intensity (x 10)

Q102
56

4
B001

B110+020
3

P131
P111
P111
2

0
10 20 30 40 50 60 70
2Theta ()

PC 82 mylonite Biotite Quartz Albite Anorthite K-spar


Composition (weight %) 9.0 24.2 31.7 17.4 14.1
Space group C2/m R3 C-1
Quartz

Biotite

lineation

foliation

Albite
Plasma-treated polypropylene films

110+011

-131+041+"121"
-111+130+031
60

040

111
Intensity (a.u.)
40

131
150+060

-102
220
20

10 15 20 25 30 35 40 45
2!()

Large broadening + overlaps + amorphous phase


PCT ferroelectric films

Substrate influence:
30
Interphase overlaps 111
of reflections from the 111-Pt PCT thin film
25
film and the substrate

Intensity (a.u.)
20

15 001 Pt reflections

10 100
Intraphase overlaps
002, 200
200-Pt 102
5 101,110 201 112
210 211

0
20 25 30 35 40 45 50 55 60
2! ()
Minimum experimental 2
requirements

1D or 2D Detector + 4-circle diffractometer


(X-rays and neutrons)
CRISMAT, ILL

~1000 experiments (2 diagrams)


in as many sample orientations

Instrument calibration
(peaks widths and shapes,
misalignments, defocusing )
2D Curved Area Position Sensitive Detector

D19 - ILL

Belemnite sp.
Calibration
= 20
= 40
60 60

0
0

FWHM (, , 2 )
KCl, LaB6 2 shift
gaussianity
asymmetry
misalignments ...
Extracted Intensities Specular Reflectivity
Roughness,
WIMV, E-WIMV electron
Harmonics Density &
EDP,
Thickness Fresnel,
Orientation Distribution Function pole figures Matrix (Parrat),
inverse pole figures DWBA
Rietveld

Structural parameters
Structure atomic positions, substitutions, vibrations
+ cell parameters
Microstructure Le Bail
Geometric + Multiphased, layered samples:
mean phase % Thickness,
Popa-Balzar, Anisotropic Sizes
sin2 and strains (Popa),
Stacking faults (Warren),

Residual stresses Phase ratio (amorphous + crystalline)


Strain Distribution Function Le Bail Rietveld
- Don't want or can't powderise your sample:
. Rare: Ice from deep cores, meteorite rocks ...
. Expensive: high-tech materials
. Impossible: hard materials, polymers, thin structures ...

- Decreases instrument time:


. 5 x 5 grid = 1368 points / pole figure
. ODF: needs as much pole figures as possible

- Access to other parameters:


. crystal sizes, micro-strains, stacking faults + twins (QMA)
. residual strains and stresses (QSA)
. Structure determination
. Phase proportions (QPA)
. Thicknesses, roughnesses (XRR)
- Avoid false minima due to parameter correlation:
. phase and texture
. Structure and texture
. Structure and strains
. Thickness and phase

- Benefit of these correlation to access "true" values


Textured materials: between powder and single-crystal,
angular discrimination

- Easier to practice !