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Diffraction Physics PDF
Diffraction Physics PDF
PERSONAL LIBRARY
DIFFRACTION PHYSICS
JOHN M. COWLEY
Regents'Professor emeritus
Arizona State University
1995
ELSEVIER
Amsterdam - Lausanne - New York- Oxford - Shannon - Tokyo
ELSEVIER SCIENCE B.V.
Sara Burgerhartstraat 25
EO. Box 211,1000 AE Amsterdam, The Netherlands
Library oF C o n g r e s s C a t a l o g i n g - i n - P u b l i c a t i o n Data
C o w l e y , J. M. (John M a x w e l l ) , 1923-
Diffraction p h # s i c s / John M. C o w l e # . - - 3 r d r e v . ed.
p. cm. - - ( N o r t h - H o l l a n d personal library)
Includes bibliographical references and i n d e x .
ISBN 0 - 4 4 4 - 8 2 2 1 8 - 6 ( a l k . paper)
1. D i f f r a c t i o n . I. Title.
QC415.C75 1995
535'.4--dc20 95-38709
CIP
ISBN: 0-444-82218-6
No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or
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No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a
matter of products liability, negligence or otherwise, or from any use or operation of any methods,
products, instructions or ideas contained in the material herein.
In this t h i r d e d i t i o n an a t t e m p t has b e e n m a d e to m a k e
this book more consistent with the present status of
d i f f r a c t i o n a c t i v i t y w h i c h has u n d e r g o n e i m p o r t a n t d e v e l o p -
ments in the last f i f t e e n years. It is not f e a s i b l e to
a t t e m p t an a d e q u a t e d e s c r i p t i o n of current t e c h n i q u e s or the
most recent theoretical developments, but it is h o p e d that
s u f f i c i e n t r e f e r e n c e has b e e n m a d e to t h e s e things to a l l o w
t h e m to be p l a c e d in the c o n t e x t of the e l e m e n t a r y t h e o r e t -
ical ideas w h i c h f o r m the b a s i s for this book. In p r e p a r i n g
this E d i t i o n , I have b e n e f i t t e d greatly from interactions
with, and a s s i s t a n c e from, the faculty, r e s e a r c h a s s o c i a t e s ,
staff and students associated w i t h the C e n t e r for H i g h
R e s o l u t i o n E l e c t r o n M i c r o s c o p y at A r i z o n a State U n i v e r s i t y .
In p a r t i c u l a r , I w o u l d like to e x p r e s s my g r a t i t u d e to K a y e
F r i x for her p a i n s t a k i n g w o r k on p r e p a r i n g the c a m e r a - r e a d y
copy.
CONTENTS
2.1. Preliminaries 25
2.1.i. Delta-functions and discontinuities 25
2.1.2. Convolutions 26
2.1.3. Examples of convolutions 27
2.2. Fourier transforms- general 30
2.2.1. Definitions 30
viii CONTENTS
Section II - KINEMATICAL D I F F R A C T I O N
4.1. X-rays 77
4.1.i. X-ray sources 77
4.1.2. Scattering by electrons 78
CONTENTS ix
References 457
Index 477
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Section I
PHYSICAL OPTICS
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CHAPTER 1
1 .I. Introduction
h2 ~U
-2-~ V2U + e~(r)u-- -ih-~, (4)
k 2 = ( 2 m e / h 2) {E + ~p(r) } .
8 F R E S N E L AND F R A U N H O F E R D I F F R A C T I O N CH. 1
~t = ~t o e x p { 2 g i ( v t - k-r) }. (8)
1.3.1. Superposition
where the phase factor ~(l) has been added to suggest that the
phase of ~2 relative to xVI varies in a r a n d o m m a n n e r with
time as separate, i n d e p e n d e n t quanta of r a d i a t i o n are
g e n e r a t e d at the two points. The a m p l i t u d e s AI, A2 are
a s s u m e d real. The i n t e n s i t y at P at any one time is
l(t) = I ~ l P + W2P 12
i. 4. i. Kirchhoff's formulation
where n^r and n^rq are the angles between the surface normal n
and the vectors r and ~ to the points P and Q, as in Fig.
i.I the usual convention in this case being that all
distances are measured from the surface.
Making the approximation that all the dimensions
involved are much greater than the wavelength, r-I and rq-I can
be neglected in comparison with k and we obtain
r.
i ~ exp{-2rcikrq}
--- "q
r-r'
exp { - ~ ik0. r}
+ Ix [ e x p { - 2 r d k l r - r'l}
(19)
4rc J Ir-r'l ~(g) exp{-2~ik~
Under the usual conditions of a scattering experiment we may
assume that the point of observation is at r = R where R is
very large compared with the dimensions of the scattering
field. Then, w r i t i n g q = k-ko, we obtain the asymptotic form,
I. 6. Reciprocity
I. 7. Fresnel diffraction
i ~ exp{-2rdkr}
~t1(x,y) = ~-~ q(X,Y) r (1 + cosZ^r)dX dY (23)
where r2 = (x - X) 2 + (y _ y) 2 + R 2.
If, as was a s s u m e d earlier, the w a v e l e n g t h is small
c o m p a r e d w i t h the d i m e n s i o n s of the object the angles of
d e f l e c t i o n of the r a d i a t i o n will be small a n d we m a y m a k e a
small a n g l e a p p r o x i m a t i o n , p u t t i n g cos Z ^ r - i, r = R in the
d e n o m i n a t o r and, in the exponent,
r = {R 2 + (x - X) 2 + (y _ y) 2}1/2
(x - X) 2 + (y _ y) 2
-- R + , (24)
2R
so that
V(x,y) =
i exp{-2rfik. R)
R~
{-2rci[(x- X) 2 + ( y _ y) 2]
X [[.q(X,Y) exp ~dX dY. (25)
RI
oo
exp,
so that
1 if Ixl<a/2
q (x) = {
0 if Ixl >a/2
a2 {ex,
-a/2
- n i ( x - X)
R ~,
21
,:IX.
There are very few functions q(X) for which the integral
(26) can be e v a l u a t e d analytically, but the few favorable
cases include the important one of p e r i o d i c functions which
we c o n s i d e r in some detail here b e c a u s e of its i n t e r e s t i n g
i m p l i c a t i o n s for the e l e c t r o n o p t i c a l imaging of crystals.
C o n s i d e r a p l a n a r object with t r a n s m i s s i o n function q(X)
= cos(2~X/a). This w o u l d be d i f f i c u l t to achieve in practice,
but not i m p o s s i b l e since the n e g a t i v e sign r e q u i r e d could be
o b t a i n e d by use of a "half-wave plate" which changes the
phase of the incident r a d i a t i o n by ~. The integral (26)
becomes
-xi(x-X) 2 }
~/(x) = exp { -2~ik2 } cos exp. RX , dX, (27)
moo
or, p u t t i n g X = x - W,
we obtain
q(X) = ~ Fh exp{2Kihxla}.
h
x}
Then (26) becomes
e x a m i n e d in d e t a i l for p o s s i b l e a p p l i c a t i o n s to e l e c t r o n
d i f f r a c t i o n and e l e c t r o n m i c r o s c o p y by C o w l e y and M o o d i e
[1957a, b, c; 1960] who n a m e d these s e l f - i m a g e s of a p e r i o d i c
object " F o u r i e r Images". A n u m b e r of d i f f e r e n t aspects of the
p h e n o m e n o n will be e x p l o r e d in various c o n t e x t s in later
pages. Here we m e n t i o n only the case that the incident
r a d i a t i o n comes from a point source at a finite distance, say
RI, from the p e r i o d i c object. Then (26) is r e p l a c e d by
I. 8. Fraunhofer diffraction
"~--R~ ~ ~ -"~.
Fig. 1.3. Positions of the Fourier images of a periodic object, n = 0,
illuminated by a point source. The Fourier image, n = 5, is at infinity.
22 FRESNEL AND F R A U N H O F E R DIFFRACTION CH. 1
~ (x, y) = -~
(1+co)ss
2 q (X, Y)
exo r ,- dX d Y . (36)
= ro - ~Xx - ---YY.
ro ro
Putting
x/ro = l= sin~x,
y/ro = m = sin~y,
and
C = (I + cos~) iexp{-2gKr~
2rok
i. 8 FRAUNHOFER DIFFRACTION 23
k0 i
Fig. 1.5. Definition of scattering vectors.
]q[ = 2k sin(~/2),
Problems
2. I. Preliminaries
In t h i s c h a p t e r we p r o v i d e the m a t h e m a t i c a l b a c k g r o u n d for
m u c h of w h a t f o l l o w s . M o s t c o n s i d e r a t i o n s of k i n e m a t i c a l
d i f f r a c t i o n i n v o l v e the use of the F o u r i e r t r a n s f o r m in one
f o r m or a n o t h e r . One of the m o s t i m p o r t a n t p r o p e r t i e s of the
F o u r i e r t r a n s f o r m i n v o l v e s the c o n c e p t of a C o n v o l u t i o n , or
C o n v o l u t i o n i n t e g r a l , a n d for b o t h t h i s a n d the F o u r i e r
t r a n s f o r m it is c o n v e n i e n t to use d e l t a - f u n c t i o n s . H e n c e we
d e f i n e a n d d i s c u s s t h i s l a t t e r f u n c t i o n first so that we m a y
m a k e use of it later.
In this, as in all s u b s e q u e n t m a t h e m a t i c a l e x p o s i t i o n ,
we do not s t r i v e for m a t h e m a t i c a l rigor. We a s s u m e that all
f u n c t i o n s c o n s i d e r e d are s u f f i c i e n t l y w e l l - b e h a v e d in a
m a t h e m a t i c a l s e n s e to a l l o w us to u s e t h e m in a w a y w h i c h
m a k e s p h y s i c a l sense. W h e n we m a k e use of d e l t a - f u n c t i o n s a n d
o t h e r d i s c o n t i n u o u s f u n c t i o n s we do so as a m a t t e r of
c o n v e n i e n c e . W h e n we w i s h to r e p r e s e n t real s i t u a t i o n s , in
w h i c h t h e r e c a n be no d i s c o n t i n u i t i e s , we use the
d i s c o n t i n u o u s m a t h e m a t i c a l f u n c t i o n s as a s h o r t - h a n d n o t a t i o n
for t h e c o n t i n u o u s f u n c t i o n s of p h y s i c a l r e a l i t y to w h i c h
they approximate.
F o r e x a m p l e , a D i r a c d e l t a f u n c t i o n at x = a is d e f i n e d
by
0 for X ~ a
8(x- a) = {
for X = a
and
~ ~(x,y)dxdy = 1.
2.1.2. Convolutions
f (x) . 5 (x - a) = f (x - a) . (7)
2.1.3. Examples of c o n v o l u t i o n s
0 for IXl>__a/2,
+ixl : {
1 for IXl<a/2,
28 FOURIER TRANSFORMS AND C O N V O L U T I O N S CH. 2
g(x-X)
C{x) = ](x) 9 g ( x )
l(x).g{x-X)
. . . .
[iexp{-2~ikR}exp{-2~(x2+y2)}]
~(x.y) = q(x,y) . , , (10)
RX 2R
exp {-2~ikr}
V(r) exp{-2Kik0-r } , . (ii)
r
The first function here is the incident wave m o d i f i e d
by the potential field V(r). This is c o n v o l u t e d with the
amplitude due to a point source, namely the amplitude of a
spherical wave from the origin. Thus the equation (1.19) or
(ii) simply states that the observed amplitude is the sum of
the amplitudes of spherical waves from all points of the
scatterer, and the amplitude of scattering from each point is
proportional to the product of the incident wave amplitude
and the value of the potential function, V(r) at the point.
30 FOURIER TRANSFORMS AND C O N V O L U T I O N S CH. 2
2.2.1. Definitions
f(x) = 5-115{f(x)}]
and
we m a y w r i t e
7
A(u) = 2 | fe(X) cos(2~ux) dx,
0
32 FOURIER TRANSFORMS AND CONVOLUTIONS CH. 2
and
7
B (u) = 2 | f0 (x) sin (2~ux)dx. (20)
0
f f(ax) exp{2Kiux}dx
= 1F(u/a) .
a
2.2 FOURIER TRANSFORMS" GENERAL 33
For (26)-
S
--oo
f(x - a) exp { 2Kiux} dx
= ~ f(x) e x p { 2 K i ( u X + u a ) }dX
= F(u) exp{2Kiua}.
For (27) :
d
f -~ f(x) exp { 2gi~r }dx
= f f(X)exp{2KiuX}dX}f g(y)exp{2xiuy}dy
= F(u).G(u).
and
oo
m ~
2 .3 FOURIER TRANSFORMS : GENERAL 35
5 8 (x) = I,
(33)
8(x - a) = exp{2Kiua}.
i 8(X - a) exp{2Kiux}clr.
The a m p l i t u d e of a d i f f r a c t i o n p a t t e r n is p r o p o r t i o n a l to
F(u) = ~ 8(x - a) where u = I/l. The i n t e n s i t y o b s e r v e d is then
p r o p o r t i o n a l to IF (u) 12 = I.
Thus, as is well known, the F r a u n h o f e r d i f f r a c t i o n
p a t t e r n f r o m a point source has u n i f o r m intensity, apart f r o m
the f a c t o r I / R 2 and the o b l i q u i t y factor (if applicable)
w h i c h have b e e n omitted.
0 if Ix[>a/2,
g(X) = {
1 if Ixl<_a/2.
The F o u r i e r t r a n s f o r m of this is
a/2
F(u) = ] exp{2~iux}dx = sin(~au)/(~u). (38)
-a/2
I(1) = a 2 s i n 2 ( ~ l a / l ) / ( ~ l a / l ) 2, (40)
w h i c h h a s a c e n t r a l m a x i m u m v a l u e a 2 f o r I = 0, a n d has
decreasing subsidiary maxima with increasing Ill w i t h z e r o
v a l u e s f o r I = nl/a for , ~ 0 (see Fig. 2.2).
it f o l l o w s that, as in e q u a t i o n (38),
q(x)
[F(u)l
I !
d q(x)
g(x) = (-~
Fig. 2.2. Derivation of the Fourier transform of a slit function by
consideration of its differential.
38 FOURIER TRANSFORMS AND C O N V O L U T I O N S CH. 2
0 if X<0,
f(x) = {
1 if x_>0.
Then
G(u) = 1
and
F(u) = (2~iu)-i
i r189 = o.
Then
al2 bl2
E(u,v) = f exp{2Eiux}dx I exp{2~ivy}dy
-al2 -bl2
q(x,y) 0 0
F(u,v)
Fig. 2.3. Diagram suggesting the form of the Fourier transform of a
rectangular aperture, equation (2.43) .
and
F (u) = exp { -IriAu } + exp { rriAu }
f(x) = 2 cos(ru4x)sB(x),
I ~- - A-------I
_I! I ! il
I~- a - q I-- a ~I
q(x)
IF'<u)l 2
Fig. 2.4. Diagram suggesting the diffraction pattern from two parallel
slits, equation (2.47).
A
k/ M/
o "-tl~C
F{u)
Fig. 2.5. A wave train cut off by multiplying by a slit function and its
Fourier transform, equation (2.48).
42 FOURIER TRANSFORMS AND C O N V O L U T I O N S CH. 2
We a s s u m e a p e r i o d i c a r r a y of slits h a v i n g zero w i d t h
and r e p e a t e d at r e g u l a r intervals, a i n d e f i n i t e l y . T h e n
oo
F(u) = Z exp{2~iuna}.
This s u m m a t i o n of a F o u r i e r s e r i e s w i t h all c o e f f i c i e n t s
unity gives a well-known result w h i c h we can d e r i v e by
e l e m e n t a r y m e t h o d s as follows.
Since
oo
Z xn = (i - x) -I,
0
we m a y write
= [i - e x p { 2 K i u a } ] - I + [i - e x p { - 2 K i u a } ] - i _ 1
= 0,
except that
Then
r,u, Z rh f exp
{ C hx
----+ ux dx.
F (u) = Z Fh 8 (u - h / a ) . (51)
--oo
(N-I)/2
f (x) = Z ~ (x - h a ) . (52)
-(N-l)/2
Then
F(u) = exp{2~iuna}
-(N-I)/2
so that
I. . . . . Na "1
l[ll[lll[{I
Na
Fig. 2.6. The amplitude distribution for diffraction from a large number
of parallel very fine slits, as given by equation (2.53) or (2.55).
2.3 FOURIER TRANSFORMS AND D I F F R A C T I O N : EXAMPLES 45
or
where we h a v e u s e d 5 ( x - ha, 2) to i n d i c a t e a d e l t a f u n c t i o n at
x = ha, y = 0, a n d O(x,y) is the t r a n s m i s s i o n f u n c t i o n for a
c i r c u l a r a p e r t u r e as d e f i n e d in 2.3.8, above. See Fig. 2.7.
The F o u r i e r t r a n s f o r m a t i o n of the set of d e l t a
f u n c t i o n s w i t h r e s p e c t to x is
8(u - h/a)
h
, i i I,
\
\
00000
1.22
A
/
/
l
' I I ' "
I/a
Fig. 2.7. The diffraction pattern from a row of circular holes equally
spaced in an opaque screen. The widths of the lines are made to suggest
their intensities.
2.3 F O U R I E R TRANSFORMS AND DIFFRACTION: EXAMPLES 47
ql (x,y) + q2 ( x , y ) - 1. (64)
q2(x,Y) = 1 - ql(x,Y).
In a d i f f r a c t i o n experiment, c o n s e r v a t i o n of e n e r g y
implies that the total i n t e n s i t y in the d i f f r a c t i o n p a t t e r n
is equal to the total i n t e n s i t y at the exit surface of the
object, i.e.
(65)
--oo --oo
Problems
F(u) F'~u')
s=uR=u'R"
r(x.y) = [ f ( ( - R / R 1 ) x , ( - R / R 1 ) y ) . J l (rcuor) / ( r c r ) * s [ e x p { i ~ ( u ) }] [ 2.
It(x,y) 12 = J2(rcu~
(rl:r)2
~'(xy)
f(xy)
F E)
Fig. 3.2. Geometric optics ray diagram used to suggest the plausibility of
the wave-optics description of the imaging process in the Abbe theory.
56 IMAGING AND DIFFRACTION CH. 3
[~(x.y),exp.-hi(x2f~,+y2)}]exp, ~:i(xz +
fz
y2)~= 1.
J
(10)
In this a p p r o x i m a t i o n the amplitude given on a plane of
o b s e r v a t i o n when a plane wave passes through an object of
t r a n s m i s s i o n function q(x,y) and then an ideal thin lens, as
s u g g e s t e d in Fig. 3.3, is, in one d i m e n s i o n and o m i t t i n g
constant multipliers,
(11)
_ [-rl:iY2}
~(x) - IIq(Y)expl~,R~ .. exp{.~ (--.~
1+ .--~-~)X
1 2}
x ex-l'-gix2p' [ni('Y+-~')X}
R't ['} expi--f [,~- dxdy"
Then if (l/R) + (I/R') = I// the integral over X is seen to be
(Y+R x/R') and the integral over Y then gives ~ (x) = Cq (-Rx/R'),
q( i~,,s ~(x,y)
Fig. 3.3. Diagram defining the imaging system described by equation (3.11).
58 IMAGING AND DIFFRACTION CH. 3
X expI~ix21[
f),. J ]*exP{ -~:ix2R'~}"
, (12)
Q(u) e x p { - ~ i ~ u 2} .
exp{i~A~u 2} = 1 + i ~ u 2,
3.4 PHASE CONTRAST 61
dx 2 [exp{ i~(x) } ] =
j" (-4K2u2)~(u) exp{-2Kiax}d,;
d2
dx 2 [exp{i~(x) }] = -exp{i~} [{~'(x) }2 + i~"(x)],
(x) = 1 + i~(x)
3.5. Holography
Hologram
II Specimen
II
Fig.3.4(a)
Hologram
Conjugate Image
Fig. 3.4(b).
mirrors
~ 8 (u+u0)
8(u-uo)
~ reconstruction
Fig. 3.5. Diagrams suggesting the formation of an off-axis hologram
with light when a plane reference wave interferes with the wave scatter
by an object and the reconstruction of the object wave in the direction
8(u-uo) when the hologram is illuminated by a plane wave.
WN+I (x)=qN (x) [... ~q2 (x) ~ql (x) [qo (x) *Po (x) ]*Pl (x) ] *P2 (x) 1... ] *PN (x)
N I 2 3 N
(34)
where the brackets have been numbered for clarity. The
contents of the N bracket represent the amplitude of the wave
68 IMAGING AND D I F F R A C T I O N CH. 3
R2
I. Ro ~i= R!
.po(X)
~N+I (u) = Q N (u) *...[Q2 (u) *[QI (u) *Qo (u)P (u) ]PI (u) ]P2 (u)... ]PN (u),
2 1 1 2 N
(35)
where again, the m u l t i p l i c a t i o n takes place before the
convolution. This represents the F r a u n h o f e r d i f f r a c t i o n
p a t t e r n given by the radiation e m e r g i n g from the N objects.
In the case of the small angle a p p r o x i m a t i o n using (32)
and (33), the e x p r e s s i o n for either the amplitude, (34), or
the d i f f r a c t i o n pattern, (35), may be written in terms of any
c o m b i n a t i o n of the functions in real space, q,(x), p,(x), or
the functions of Fourier t r a n s f o r m space, an(u), Pn(u). This
follows from the special p r o p e r t i e s of the complex e x p o n e n -
tials with respect to Fourier t r a n s f o r m and convolution.
Thus we have
Similarly
Similarly,
or
]Jl(v) e x p (2~l.v/c) dv ] . / ~ I (v) d v .
Problems
KINEMATICAL DIFFRACTION
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CHAPTER 4
Radiations and
their scattering by matter
4.1. X-rays
4.1.i. X - r a y sources
The s c a t t e r i n g of X-rays by m a t t e r is u s u a l l y c o n s i d e r e d
in terms of the s c a t t e r i n g by a single electron, l o c a l i z e d at
the origin of c o o r d i n a t e s by some sort of r e s t o r i n g force and
so h a v i n g some resonant frequency, v0, a s s o c i a t e d with it.
For incident r a d i a t i o n
E = Eo e x p { 2 ~ i (vt - k . r) }
IEI = Eo ( e 2 / m c 2 ) R -1 c o s ~ .
IEI -- Eo (e21mc 2) I R .
4.1 X-RAY SOURCES 79
,# x
AAAA
z
or, putting q = g,
p(r) = ~ pn(r),
n
so that
f(u) = ~/.(u)
n
= Z - ~ If.l2, (7)
n
-5
Fig. 4.2. The variation of the magnitude of the real and imaginary
"anomalous scattering" components f' and f" of the atom scattering factor
for X-rays as a function of wavelength. The K absorption edge of the
atoms is at l K.
4.2. Electrons
The e l e c t r o n s to be c o n s i d e r e d for e l e c t r o n d i f f r a c t i o n
and m i c r o s c o p y have energies m o s t l y in the range I00 to 400
keV a l t h o u g h with the advent of high v o l t a g e e l e c t r o n
m i c r o s c o p e s this range needs to be e x t e n d e d to 1 M e V or more.
For e l e c t r o n s in the range 10-200 eV used in Low E n e r g y
82 RADIATIONS AND THEIR SCATTERING BY M A T T E R CH. 4
V2[Ife(u) exp{-2~iu.r}du]
4.3. Neutrons
X-rays X-rays
5 e:o " O)/~:o.sk j
f x I()-12 cn
Potential
scattering
1 . . . . . . . . . . . I _ _
O.
I t.wt.
Fig. 4.3. Variation of the atomic scattering factor for neutrons, b, and
the atomic scattering factor for X-rays (at particular values of (sinS)/~)
with atomic weight (after Bacon [1975]).
concepts to be d e v e l o p e d in C h a p t e r 7, the s c a t t e r i n g
c o n s i s t s of "coherent" s c a t t e r i n g from the average of the two
states with a c r o s s - s e c t i o n
(Yinc = (y - (Yc ~-
4~ (w+b+ 2 + w_b_ 2) - 4~ (w+b+ + w_b_) 2 g (30)
b = s wnb, (31)
n
Problems
If an e l e c t r o n d e n s i t y distribution, p(r), is c o n s i d e r e d
to be the sum of the distributions pi(r) a t t r i b u t e d to
individual atoms as in equation (i) and if
oo
then
F(u) = ~ ~
I
~_~ FhkI ~ ( u -
I
(h/a), v - (k/b), w- (l/c) ) ,
I
h k l
. ABC sin(rtAu) sin(rd3v) sin(~;Cw) (10)
xAu xBv ~Cw
= Jp(r) exp{-2xiu.r}dr
= F* (u), (11)
so that
IF(-u) 12 = I F ( u ) 12.
5 -1 { IF(u)12} - P(r)
= p (r) . p (-r)
Then
_ r~.r2 .
r l ~ r 2 ~ 2 r = r l - rz r~O r = r~- rl
(c) _ 3,4"~ ~ . . . . ~ 3
1 2
3,1. 4,1 3,2 4,2
P P P
Fig. 5.2. Representation of the Patterson function for three atoms, Fig.
5.1(b), as a superposition of images of the object or its inverse.
In reciprocal space,
0 if Ixl<_Al2,
s (x) = {
1 if IxI>A/2.
Then
x + A if -A < x < O,
s(x) ,s(x) - { A - x if O < x < A ,
0 elsewhere,
Fig. 5.3. Diagram of a shape function $(x) and its Patterson function
P(x), and the corresponding Fourier transforms.
S i m i l a r l y in t h r e e d i m e n s i o n s , if the s a m p l e is a
rectangular block limited by planes x = + A/2, y = + B/2, z =
+ C / 2 , w h e r e the d i m e n s i o n s A,B, C a r e m u c h g r e a t e r t h a n the
d i m e n s i o n s of the g r o u p s of atoms of interest, the P a t t e r s o n
per unit v o l u m e is m u l t i p l i e d by a f a c t o r A B C = V at the
o r i g i n a n d d e c r e a s e s l i n e a r l y to zero in a d i s t a n c e A in the
x d i r e c t i o n , B in the y d i r e c t i o n , C in the z d i r e c t i o n ,
c o r r e s p o n d i n g to the fact that no i n t e r a t o m i c v e c t o r can h a v e
x, y, z c o m p o n e n t s g r e a t e r t h a n A,B, C.
U s u a l l y , on the a s s u m p t i o n that A , B a n d C are v e r y m u c h
g r e a t e r t h a n any i n t e r a t o m i c v e c t o r s of interest, this
" s h a p e - c o n v o l u t i o n " f u n c t i o n is i g n o r e d or omitted.
AS a s i m p l e model, we c o n s i d e r a c r y s t a l h a v i n g one a t o m
in a r e c t a n g u l a r unit cell w h i c h has axes a,b,c. The c r y s t a l
has d i m e n s i o n s A - Nla, B = N2b, C = N3c a n d so can be
represented by
[Po (r) ~_j 8 (r - R n) ] s (r) , (20)
n
'!~ ., A=N~a . . ~!
l
p(r)
'~ A - N, a
P(r)
(21)
n m
5.5. I. F o u r - d i m e n s i o n a l Patterson
P ( r , t) - ~ p ( R , T) p ( r + R, t + T) dRdT
IF(u,v) 12 , (/I;M2)-1/2 e x p { - v 2 / M 2 } ,
P(r, t) exp{-2/I;2M2t 2 } .
JIF(u,V) 12 exp{-V2/M2}dV.
The Fourier t r a n s f o r m of this is
}'(r,()) /llV<u>l dv
Fig. 5.5. Instantaneous correlation function, P (r, 0), for an ideal
monatomic gas and the corresponding distribution in reciprocal space.
p ( r , t) = po(r) , g ( r , t)
where
G ( r , 0) = [ g ( r , t) 9 g(-r,-t)]t=o
- ~g(R, T) g ( r + R , T) dR d T
G ( r , t ) d t = ;; g ( R , T) g(r + R, t + T)dtdTdR
An i m p o r t a n t d i f f e r e n c e b e t w e e n (33) a n d (34) a p p e a r s
w h e n we i n t r o d u c e the r e s t r i c t i o n that atoms c a n n o t o v e r l a p
a p p r e c i a b l y , i.e. that at a p a r t i c u l a r time t the d i s t r i b u t i o n
P a t t e r s o n g (r, t) 9 g(-r, -t) a n d t h e r e f o r e in g e n e r a l G(r, 0)
c a n n o t c o n t a i n a n y p o i n t s b e t w e e n Irl = 0 a n d Irl = 2r0 w h e r e
r0 is the e f f e c t i v e r a d i u s of an atom. For Irl > 2r0 some
f l u c t u a t i o n s in G(r, 0) o c c u r b e c a u s e atoms u s u a l l y have an
a t t r a c t i v e i n t e r a c t i o n . T h e r e tends to be an e x c e s s of atoms
at the s m a l l e s t p o s s i b l e , " n e a r e s t n e i g h b o r " d i s t a n c e ; t h e n
e s p e c i a l l y for liquids, an a p p r e c i a b l e but less m a r k e d
t e n d e n c y for a t o m s to o c c u r also at a s e c o n d nearest, t h i r d
nearest, etc. n e i g h b o r d i s t a n c e , so that G(r, 0) has a f o r m as
suggested, in one d i m e n s i o n , in Fig. 5.6(a), w i t h a d e l t a -
f u n c t i o n at the origin. The f o r m of e(r, 0) is t h e n as
s u g g e s t e d in Fig. 5.6(b) a n d the d i s t r i b u t i o n of s c a t t e r i n g
p o w e r o s c i l l a t e s w i t h lul as s u g g e s t e d in Fig. 5.6(c).
On the o t h e r h a n d the p u r e l y e l a s t i c s c a t t e r i n g IF(u00)12
d e r i v e s f r o m the self c o n v o l u t i o n of the time a v e r a g e of the
d i s t r i b u t i o n function, <g(r, l)>t. But, since all atoms are
(a)
g(r)~g(-r) I r l -~
(b)
V(r) I r l -~
(C) ~_
. . . . . i u)i iu I
Fig. 5.6. Diagrams suggesting the form of, (a) the distribution Patterson,
(b) the actual Patterson function and (c) the scattering power distribution
for a real monatomic gas or liquid.
II0 SCATTERING FROM ASSEMBLIES OF ATOMS CH. 5
N N
I (s) = (K2Io/R 2) Z Z fi (s) ~* (s) (sinsri] /srij) (36)
i=1 /=1
7
D (r) = | s Im (s) sin (sr) ds (37)
el
i
P(r/ [r ]-~ II,'(u~l 2 [u] -~
Fig. 5.7. Diagrams suggesting the Patterson function for a molecular gas,
and the corresponding variation of scattering power in reciprocal space.
W h e n d e a l i n g with q u a n t u m p r o c e s s e s of e x c i t a t i o n of the
s c a t t e r i n g object, c o n s i d e r a b l e c a u t i o n is r e q u i r e d and it
cannot n e c e s s a r i l y be a s s u m e d that the simple c l a s s i c a l
c o n s i d e r a t i o n s we have used can be c a r r i e d over (van Hove
[1954]). H o w e v e r a direct a p p l i c a t i o n of the above t h e o r y
gives an a d e q u a t e t r e a t m e n t for one case; the s c a t t e r i n g of
X-rays by a h y d r o g e n atom, i.e. by the e l e c t r o n of a h y d r o g e n
atom. For this e l e c t r o n P(r, 0) is a delta f u n c t i o n at the
origin, since all i n s t a n t a n e o u s p i c t u r e s show a single point,
one electron. Then the total scattering, in e l e c t r o n units
squared, is given by
IF(u,v) 12dv = 1.
1 - f2 e (u), (39)
Fig. 5.9. Comparison of the scales of the Ewald spheres for X-rays,
neutrons and electrons, in relation to normal scattering power
distributions.
The d i f f r a c t i o n p a t t e r n m a y be r e c o r d e d on a flat p l a t e or
f i l m p l a c e d p e r p e n d i c u l a r to the i n c i d e n t b e a m at some
d i s t a n c e b e h i n d the s p e c i m e n and r e p r e s e n t s an a l m o s t p l a n a r
s e c t i o n of the d i s t r i b u t i o n of s c a t t e r i n g p o w e r in r e c i p r o c a l
space.
In this way it w o u l d s e e m that the i n t e n s i t i e s to be
o b s e r v e d for a g i v e n r a d i a t i o n and for a p a r t i c u l a r g e o m e t r y
of the e x p e r i m e n t m a y be d e d u c e d for s c a t t e r i n g f r o m any
s y s t e m for w h i c h the P a t t e r s o n f u n c t i o n can be d e r i v e d or
p o s t u l a t e d . H o w e v e r our d i s c u s s i o n so far has b e e n for the
i d e a l i z e d case of p e r f e c t l y p l a n e and m o n o c h r o m a t i c waves.
These c o n s i d e r a t i o n s m u s t be b r o a d e n e d in order to m a k e
c o n t a c t with e x p e r i m e n t a l s i t u a t i o n s .
In X - r a y d i f f r a c t i o n e x p e r i m e n t s , the finite s o u r c e
size results in an angle of c o n v e r g e n c e of the i n c i d e n t b e a m
at any p o i n t of the sample of s o m e t h i n g like 10 -4 to 10 -3
radians a l t h o u g h with s y n c h r o t r o n r a d i a t i o n m u c h s m a l l e r
c o n v e r g e n c e angles m a y be achieved. The i n t e n s i t y is not
n e c e s s a r i l y u n i f o r m over this range of angles. In n e u t r o n
d i f f r a c t i o n the angle of c o n v e r g e n c e is often made g r e a t e r
than this since the source i n t e n s i t y is low.
116 SCATTERING FROM ASSEMBLIES OF A T O M S CH. 5
P
k2
0
Fig. 5.10. The effect of a finite source size in spreading the Ewald
sphere into a spherical shell of varying thickness.
0
Fig. 5.11. The combined effects of finite source size and finite detector
aperture size to define "scattering volumes" in reciprocal space over
which the scattering power is integrated.
A f u r t h e r c o m p l i c a t i o n c o m e s f r o m the f i n i t e r a n g e of
w a v e l e n g t h s p r e s e n t for a n y real source. F o r X - r a y s the
n a t u r a l h a l f - w i d t h s of the c h a r a c t e r i s t i c e m i s s i o n lines are
of the o r d e r of 10 -4 ~ or more. F o r n e u t r o n d i f f r a c t i o n or
for s y n c h r o t r o n X-rays, s i n c e the r a d i a t i o n u s e d is s e l e c t e d
out of a c o n t i n u o u s " w h i t e r a d i a t i o n " d i s t r i b u t i o n , the r a n g e
of w a v e l e n g t h s u s e d m a y be m a d e g r e a t e r in o r d e r to i n c r e a s e
the t o t a l i n t e n s i t y of i n c i d e n t r a d i a t i o n . F o r e l e c t r o n s the
r a d i a t i o n is u s u a l l y m u c h m o r e n e a r l y m o n o c h r o m a t i c w i t h a
w i d t h of a b o u t 10 -6 I.
ko
0
Fig. 5.12. The effect of a spread of wavelength in producing a spread in
values of the Ewald sphere radius.
118 SCATTERING FROM ASSEMBLIES OF A T O M S CH. 5
l(u,v) = IF ( u , v ) 12 . S ( u , v ) . (42)
The Lorentz factor then derives solely from the way in which
intensities are integrated over time when a sample is rotated
or, more commonly, integrated over crystal orientation when
the sample contains a range of crystal orientations.
In neutron diffraction involving measurements of
intensity as a function of energy loss as well as diffraction
angles, the complications may be c o r r e s p o n d i n g l y greater than
for X-ray diffraction. We prefer not to deal with them here.
and
5.8 SECTIONS AND PROJECTIONS 121
Problems
or
a
, ~ ~
b Xc ~'-
b Xc
--,-.--~
a(b Xc) v
b* -- c Xa
V
, aXb
C = , (2)
V
a * -b = a * -c = b* .c = ... - o, (3)
abc
Fhkl = f~ p(x,y,z) e x p { 2 K i ( (hxla)+(ky/b)+(Izlc) ) } d x d y d z
ooo
or
I
FhM - V ; ~ ; p (X, Y, Z) exp { 2xi ( hX + kY + lZ) } dX dY dZ. (9)
o
so that
P (X, Y, Z)
(16)
s s IFhid 12 exp { -2~i ((lucia)+ (kylb) + (Izlc) ) } Is (r) ,s (-r) ],
h k I
P (r)
q- a = h, q- b = k, q- c = 1, (19)
Iql = lldhk.t,
or, since Ik01 = Ikl = I/~, and the angle between k and k0 is
20, we have
2dhkl sin0h~ = ~, (21)
t . . l:;wald
. . spllere ko I
I I I
~ phere
Fig. 6.2. Ewald sphere diagram for CuK~ X-rays and for 80 keV electrons
for a crystal of gold or aluminum when the Bragg condition is satisfied
for the 400 reflection. The crystal dimensions in the beam direction are
assumed to be I000 ~ for the X-rays and 50 A for the electrons.
Fig. 6.3. Electron diffraction pattern from a thin, slightly bent crystal
of Mo5014 with the incident beam nearly parallel to the c-axis.
Then IFh [2calc is compared with IFB[ 2obs derived from the
intensities.
As a measure of agreement for the often large number of
values involved it is usual to calculate the R-factor,
F h = fo.Ziexp(2Kih.ri) .
138 DIFFRACTION FROM CRYSTALS CH. 6
IEhl 2 = IFhl2/SZifi 2
p = (e2'y/2mc 2) g J r , (37)
where
IFn(u) 12 = [~ bi e x p { - M i } e x p { 2 = i h . r i } [2 (39)
l
IFmag (U) 1 2 = ~ ~ Pi q[ "Pj qj exp { - M i -Mj } exp { 2~ih. (ri -rj ) }, (40)
z j
= sin2~, (41)
IF2mag(U) 12= sin2~ (+) Pi Pj exp { -Mi -M] } exp { 2Kih. (ri -r] ) }
i j
(42)
where the plus and minus signs refer to pairs of atoms with
parallel and antiparallel spins. Correspondingly if the sin2~
factor is ignored, a Patterson function can be drawn with
positive peaks for parallel pairs of spins and negative peaks
for anti-parallel pairs.
For anti-ferromagnetic crystals the separation of like
atoms, in the simplest case, into two sets, spin up and spin
down, will almost inevitably lower the symmetry of the
crystal and in many cases produces a unit cell size which is
some multiple of that seen by X-rays. Then new, purely
magnetic, "superlattice" reflections appear in the
diffraction pattern. Gradually more and more complicated
magnetic superlattice structures are being found with large
repeat distances and spins inclined to each other at a
variety of angles. For these, the simple formulation of (42)
cannot be used.
6.6 ELECTRON DIFFRACTION STRUCTURE ANALYSIS 141
Problems
2. For a c e r t a i n p r o b l e m of s t r u c t u r e analysis it is
d e s i r a b l e to have a p r o j e c t i o n on the x - y plane of the
l i m i t e d region of the unit cell lying b e t w e e n z - 0.4 and
z - 0.6. What series should be s u m m e d to give this?
4. B e l o w a c e r t a i n c r i t i c a l t e m p e r a t u r e MnF 2 is anti-
f e r r o m a g n e t i c with the spin of the Mn a t o m at 0, 0, 0,
d i r e c t e d a l o n g the p o s i t i v e c-axis and the spin of the atom
at 1/2, 1/2, 1/2, d i r e c t e d along the n e g a t i v e c-axis (see
Bacon, p. 311).
(a) How will the s y m m e t r y and f o r b i d d e n reflections for
n e u t r o n d i f f r a c t i o n d i f f e r from those for X-ray d i f f r a c t i o n
(c.f. p r o b l e m 3)?
(b) Sketch the P a t t e r s o n function for the p r o j e c t i o n on to
the x - z plane d e r i v e d from n e u t r o n d i f f r a c t i o n i n t e n s i t i e s
i n c l u d i n g both n u c l e a r and m a g n e t i c scattering.
(c) How do the various r e f l e c t i o n i n t e n s i t i e s vary with
temperature?
6. Two crystal s t r u c t u r e s m a y be a s s u m e d to be i d e n t i c a l
except that one a t o m per unit cell (which may be a s s u m e d to
be at the origin) is d i f f e r e n t for the two cases. How will
the two c o r r e s p o n d i n g P a t t e r s o n f u n c t i o n s differ? How m a y the
d i f f e r e n c e s be u s e d to d e t e r m i n e the crystal s t r u c t u r e s
unambiguously?
CHAPTER 7
i j
= ~ ~ ~<exp2Ki,-(r i - r])>t 9 (6)
i j
where F and 2Uv are the Fourier transforms of <p(r)) and Ap.
7.2 PATTERSON FUNCT ION APPROACH 14 9
As a first simple e x a m p l e we c o n s i d e r a m o n a t o m i c
c r y s t a l of simple structure. There are N a t o m sites but a
n u m b e r n of them, d i s t r i b u t e d at random, are vacant. We
ignore any d i s p l a c e m e n t of the atoms a r o u n d the v a c a n c i e s
from t h e i r e q u i l i b r i u m lattice sites (relaxation).
Then the s c a t t e r i n g p o w e r J(u) can be e v a l u a t e d f r o m
e q u a t i o n (2) by c o n s i d e r i n g in turn the various p o s s i b l e
v e c t o r s ri - r].
For i = j and ri - r] = O, there are N - , vectors for
which fi = ~ = f and n vectors for which f/ = ~ = O, so that the
c o n t r i b u t i o n is ( N - n)f 2.
For any other vector length there is a p r o b a b i l i t y ( N -
n ) / N of h a v i n g an a t o m at i and (N - n ) / N of h a v i n g an a t o m at
j so that the c o n t r i b u t i o n to J(u) is
AA ,tA AAs
I~ a "~l
,,,:r,
Ap~Ap
---1/a----I
J(u)_ ~ ~
0
Fig. 7.1. One-dimensional diagrams representing the electron density
distribution, p(r) for a structure having random vacancies, the periodic
average structure <p(r)>, the deviations from the average structure Ap(r),
the Patterson function for this deviation function, and the scattering
power distribution in reciprocal space showing sharp peaks plus diffuse
scattering.
152 DIFFRACTION FROM IMPERFECT CRYSTALS CH. 7
oo, , rL \Iv .)
, \iv)
]j
n(N-n)
Po (r) , Po ( r ) . ( I 6)
N
as in equation (15) .
~p~p
~ad
0
Fig. 7.2. The deviation from the average structure, the corresponding
Patterson function and the scattering power distribution for a case such
as in Fig. 7.1 when the vacancies occur in pairs.
AAA
A A A A A A.
J(,,)
Fig. 7.3. The same set of functions as in Fig. 7.1 for the case of a one-
dimensional structure in which a light interstitial atom at X displaces
its nearest neighbors by a distance d/4.
7.3 DEVIATIONS FROM AN AVERAGE LATTICE 155
N-n +2 --
n cOS2K (au/4),
N N
1 + 2 N-n COS2~(all/4) .
By c o n s i d e r i n g the vectors between positive and negative
peaks of ~(r) it is seen that the defect Patterson has a
positive peak of relative weight 4 at the origin and negative
peaks of relative weight 2 at x = • Then there are the
same grouping of peaks, inverted, around x = • 5a/4. Thus the
diffuse scattering distribution is of the form
Then
F" = F 0 (u) ~,1 (~ (u - h/a) e x p { -~262u2 } .
h
and
IF'I 2 = IFo(u)12 exp{-2~;2b2u 2} '~ 8(u-hla). (20)
P(r,O) 0
/,J(u,v)dv
Fig. 7.4. One-dimensional diagrams illustrating the Patterson function and
corresponding scattering distributions for uncorrelated atomic vibrations
(Einstein model).
d(z)
d (z) * d (z)
L ,
t
4 -3 -2 -1 0 1 2 3 4
[D (w)2l
-4 -3 -2 41 0 1 2 3
W'---~
Fig. 7.5. The distribution function Patterson and its Fourier transform
for the case of parallel planes of atoms having random variations of the
inter-planar spacing.
1
d (z) . d ( - z ) = n=-** ~ (z - n c ) . (nlnl~12),,2 e x p { - z 2 / I n l ~ 2 } . (26)
We note t h e n e e d to i n s e r t Inl in o r d e r to m a k e t h e
distribution symmetrical. F o u r i e r t r a n s f o r m of t h i s g i v e s
•
11=--~
e x p { - (E2w2y2 u 2Eiwc) Inl }, (27)
ID (w) 12 = [1 - e x p { -/i;2w2'y 2 + 2 ~ i w c } ] - 1
+ [1 - e x p { - / I ; 2 W 2 y 2 - 2 ~ i w c } ] - I _ 1
1 - exp{-2~;2w272 }
(28)
1 + exp {-2/1;2w2~/2} - 2 exp{-/I;2W2)r 2} cos 2/l:WC
(b) .J(u)
......
i......
0 0
Fig. 7.6. (a) The Patterson function, and (b) the corresponding
distribution in reciprocal space for a turbo-stratic structure of
parallel, equally-spaced planes of atoms, having arbitrary relative
orientations of the axes within the planes. The diagram (c) suggests the
form of the powder pattern given by such a structure, consisting of sharp
rings corresponding to the (0 0 I) reflections and broad asymmetrical
peaks corresponding to the (hkl) reflections with intensity a continuous
function of the variable l, but with integral h,k values.
Problems
DYNAMICAL SCATI'ERING
This Page Intentionally Left Blank
CHAPTER 8
(k) = ~ ~ h 8 (k - kh) ,
kh = ko + h, (4)
or n = i + ~o/2E. (6)
,%,
~:e - k ~ Vo~ Vo,
Vho
9 . 9 ~Z-k~
" 9 " ~hg % - 0
9 o 9 .
9 o 9 .
(7)
9 o 9 o
9 . . K2-k~
vg o 9 . . Vg h
K0
///////// ///////////
[ ~L crystal
h.1 0 h1 h z
Fig. 8.1. Diagram illustrating the wave vectors for waves within a crystal
when an incident wave, K 0, strikes the surface. The excitation errors,
~h, for the lattice points h, and the anpassung ~i, Laue point Li and wave
vectors kih for one Bloch wave are shown.
(a) (b)
8. 4. Two-beam approximation
\o ~-k %
For a n o n - t r i v i a l solution the d e t e r m i n a n t of the m a t r i x
must be zero, giving, in general, four solutions for the wave
vectors. H o w e v e r two of these solutions c o r r e s p o n d to the
b a c k - s c a t t e r i n g of e l e c t r o n s and m a y u s u a l l y be i g n o r e d for
high v o l t a g e t r a n s m i s s i o n diffraction. An a l t e r n a t i v e
d e r i v a t i o n of the two b e a m approximation, s t a r t i n g from the
s c a t t e r i n g m a t r i x formulation, is given in S u b s e c t i o n 10.2.5.
176 DIFFRACTION BY P E R F E C T C R Y S T A L S CH. 8
, _
IT, Branch 1
anch 2
o
Fig. 8.3. The dispersion surface construction for the 2-beam case.
K - kih = • (11)
Ivhl
(12)
2~cosO h
- U-h
e'cUh (].3)
voh IIW~ = 0
I 2k%cosO o
vho 2k~c~ ~h '
(15)
The total wave in the crystal is given by the sum of the two
Bloch waves
51 + f~2 = 1
ul Cl + u2 C2 = O,
so that
180 DIFFRACTION BY PERFECT CRYSTALS CH. 8
A0 = 2tcos0h . (22)
~:sin20B
If we m a y m a k e the s m a l l - a n g l e a p p r o x i m a t i o n s c o m m o n in
t r a n s m i s s i o n e l e c t r o n d i f f r a c t i o n and put cos8 0 = cos8 h -- 1
and sin20 B = 2sin0B, we o b t a i n
K 1
w =
~0.~ =
~O-~h (25)
dh(vhv_h) ~1~ dh "
w = ~h'~h- (26)
(Xl = 89 2)1/2],
~2 = 89
[l-w~ (l+w 2) 1/2] ,
C1 = w - ( l + w 2)1/2,
= (l+w2)-i w2 + c~ ~h (28)
]h = IO~lC1 e x p { i k l h - r } + (x2C2 e x p { i k 2 h - r } 12
and
lh = exp[-~0H}2(1
+ w 2) cosh (|+ w2),/2 j-cos ~h . (31)
-h 0 h 2h 3h
Fig. 8.5. The excitation of a systematic set of reflections. When the
Bragg condition for one reflection is satisfied, the other reflections of
the systematic set always have the same excitation errors.
or
Wg : - (VsW?O+ Vs-hWh) , (32)
K2-kg2
where we i m p l y that the d e n o m i n a t o r must be large.
Then in r e d u c i n g the set of e q u a t i o n s (5) or (7) to give
the t w o - b e a m case we include the c o n t r i b u t i o n s (32) to the
s u m m a t i o n in (5) and i n s t e a d of (I0) we o b t a i n
(33)
U,,o ,=~-k~, +h
184 DIFFRACTION BY P E R F E C T C R Y S T A L S CH. 8
where
w,~ = K~+Uhh,
and
" VcV r
U00
_ = V0 - ~ 2 -
2,
8 ~ -k g
##
J
8~ .- Iv, 2
8
X- rays
O- electrons
Fig. 8.6. The intensity of reflection as a function of the deviation from
the Bragg angle for no absorption and with absorption (dotted line) for
the Bragg case of reflection from a large perfect crystal.
186 D I F F R A C T I O N BY PERFECT CRYSTALS CH. 8
ti1111111IIIIIi1III,
2
h
Fig. 8.7. The dispersion surface construction for the two beam Bragg case,
when the surface normal may pass through the gap between the two branches.
= 1 - X 0 = sin 2 { K H I ~ I / ~ } . (3)
9. i. 2. Real space p i c t u r e
0 0 0 0 0
W a]vo
0 0 0 0 0
W ~ V0
2
0 0 0 0 0
Fig. 9.1. Illustrating the relation of the two Bloch waves to the lattice
planes for a two-beam approximation.
9. i. 3. R o c k i n g curves
l 'h =
Ivhl2~2/_/2 sin2(~/-/~h) (5)
+c2 (r,+H~h)2
[o I0
Fig. 9.2. The bright-field and dark-field images of a bent crystal show
the variation of diffracted intensity as a function of angle of incidence.
9. I. 5. Convergent b e a m diffraction
// /,H~
1 ~ ,," ,
\\"-
./I l~ kk "x
,
/ ~ \t l 1~
5",~ , ",,..
/ I I I . x,\ \
t o I I II ~ xx xx\
o e 0 i
! ! o !
r e p r e s e n t e d in the c o n v e r g e n t b e a m the a p p r o p r i a t e E w a l d
sphere m a y be drawn and the d i f f r a c t i o n i n t e n s i t i e s found, as
s u g g e s t e d in the (kinematical) r e c i p r o c a l space diagram, Fig.
9.4 (b). The v a r i a t i o n of i n t e n s i t y across the central spot
and d i f f r a c t e d spot discs in the d i f f r a c t i o n p a t t e r n then
gives the v a r i a t i o n of i n t e n s i t i e s with angle of incidence.
Fig. 9.5 gives a t y p i c a l c o n v e r g e n t b e a m d i f f r a c t i o n p a t t e r n
from a thin p e r f e c t c r y s t a l of MgO.
For a t w o - b e a m case, the incident and d i f f r a c t e d b e a m
discs are c r o s s e d by p a r a l l e l fringes of i n t e n s i t y given by
e q u a t i o n (4) for Ih and I0 = 1 - Ih. On this basis M a c G i l l a v r y
[1940] i n t e r p r e t e d the c o n v e r g e n t b e a m p a t t e r n s o b t a i n e d by
K o s s e l and M o l l e n s t e d t from thin mica crystals and f r o m the
form of the i n t e n s i t y v a r i a t i o n s was able to deduce values of
]Dh[ for the v a r i o u s r e f l e c t i o n s by use of e q u a t i o n (4) or
the equivalent. The values she d e r i v e d were, fortuitously, in
e x c e l l e n t a g r e e m e n t with the values c a l c u l a t e d from the
s t r u c t u r e of mica as then known.
The c o n v e r g e n t b e a m d i f f r a c t i o n t e c h n i q u e has more
r e c e n t l y been refined by G o o d m a n and L e h m p f u h l [1964] and
C o c k a y n e et al. [1967]. As will be r e c o u n t e d later (Chapter
14), the t e c h n i q u e has been w i d e l y d e v e l o p e d as a means for
9.1 THICKNESS FRINGES AND ROCKING CURVES 195
Fig. 9.5. Convergent beam diffraction pattern for a thin perfect crystal
of MgO showing the variation of intensity with angle of incidence for the
2h, 0, 0 reflections, some perturbation of the fringes by non-systematic
interactions is visible.
m a k i n g a c c u r a t e m e a s u r e m e n t s of intensities, d e m o n s t r a t i n g
that the t w o - b e a m results form only a first a p p r o x i m a t i o n to
the n - b e a m d i f f r a c t i o n s i t u a t i o n and m a k i n g use of the n-beam
d y n a m i c a l d i f f r a c t i o n effects to derive h i g h l y accurate
values for the F o u r i e r c o e f f i c i e n t s vh or 9h.
I lW ,
,',
~I;
i !iA,.; _
,.
' I V V VV'.,A
i I i
U V V V V '.iv v v :;
0 1 2 3 4 5 6
H
a m p l i t u d e of the o s c i l l a t i n g part w h i c h is p r o p o r t i o n a l to
e x p { -~t0H } .
In principle then it is possible to deduce the values of
~0 a n d ~th f r o m t h e f o r m o f t h e t h i c k n e s s fringes. Attempts to
do t h i s by Uyeda et al. [1965] gave some results but showed
deviations from the two-beam formulas.
In terms of the picture of Bloch waves transmitted
t h r o u g h the crystal, Fig. 9.1, it can be seen that, if the
a b s o r p t i o n p r o c e s s takes place when e l e c t r o n s pass close to
the atoms, the two Bloch waves will be a b s o r b e d d i f f e r e n t l y .
Since the p r o b a b i l i t y of f i n d i n g an e l e c t r o n at a c e r t a i n
p o s i t i o n is p r o p o r t i o n a l to the square of the wave f u n c t i o n
modulus, the e l e c t r o n s of Bloch wave 1 are more likely to be
in the v i c i n i t y of atoms and so are m o r e s t r o n g l y absorbed,
with an a b s o r p t i o n c o e f f i c i e n t ~0 + ~h, while those of B l o c h
wave 2 s p e n d most of t h e i r time b e t w e e n the planes of atoms
and so are less absorbed, with an a b s o r p t i o n c o e f f i c i e n t ~ 0 -
~h. Then when they leave the c r y s t a l the c o n t r i b u t i o n s f r o m
the two Bloch waves to the d i f f r a c t e d b e a m do not have equal
a m p l i t u d e and so are not be able to p r o d u c e i n t e r f e r e n c e
fringes of m a x i m u m contrast.
We saw b e f o r e that the two Bloch waves have d i f f e r e n t
r e f r a c t i v e indices in the crystal and so give v a c u u m waves in
s l i g h t l y d i f f e r e n t d i r e c t i o n s from a wedge shaped crystal.
W i t h absorption, the d i f f r a c t i o n spot is split into two
c o m p o n e n t s of unequal intensity. The wave r e f r a c t e d most,
from Bloch wave i, is also a t t e n u a t e d most. This was first
o b s e r v e d and a n a l y s e d by Honjo and M i h a m a [1954].
9.1 THICKNESS FRINGES AND ROCKING CURVES 199
I x
beam
I
I
f
I
I I
Fig. 9.8. The method used to obtain X-ray "projection topographs". The
sample, S, in this case a wedge crystal, and the film F are rigidly
coupled and move backward and forward together.
Fig. 9.11. Energy flow and diffracted beam configurations for a narrow
X-ray beam incident on a thick perfect crystal.
la. = Bo I+P
21oJIEhl"h)
,, . (9)
E~+E~ ~o
The two values of P for the two polarizations imply that there
206 DYNAMICAL D I F F R A C T I O N EFFECTS CH. 9
Hence virtually all the t ransmitted energy comes from the one
branch with ~ polarization. The enhancement of transmission
relative to the n o n - d i f f r a c t i n g crystal is by a factor of
(1/4) exp{+36.1}.
Because of the smallness of the angular range over which
X-ray reflections take place for perfect crystals, the
Borrmann effect transmission gives X-ray beams which are very
well c o l l i m a t e d as well as being almost perfectly polarized.
This has p r o v i d e d the incentive and basis for a considerable
expansion of the possibilities for experiments involving
precision measurements on near-perfect crystals and a means
for a more complete study of the diffraction, absorption and
scattering processes of X-rays.
For electron diffraction the absorption comes mostly
from plasmon excitation, which contributes to ~0 only, and
thermal diffuse scattering which gives a ~h value falling off
m o d e r a t i n g rapidly with scattering angle (Hall and Hirsch
[1968]). The ratio of ~h to ~0 is usually small and the
Borrmann effect not very striking.
One interesting consequence of the variation of
absorption processes under Borrmann diffraction conditions
is that changes in absorption in turn affect the intensity
of any secondary radiation produced as a result of the
absorption. Thus when electrons are strongly diffracted in a
thick crystal there is a variation of the X-ray emission with
angle of incidence (Duncumb [1962]; Miyake et al. [1968]).
Likewise Knowles [1956] showed that for neutron diffraction
the establishment of standing wave fields which reduced the
density the neutrons in the vicinity of the nuclei of the
atoms have the effect of decreasing the inelastic interaction
of the neutrons with the nuclei which give rise to a y-
emission. For X-rays the corresponding observation made by
Batterman [1962, 1964] is that the intensity of secondary
9.3 BORRMANN EFFECT 207
Problems
)}12
would be i n f e r r e d from the n o n - r e l a t i v i s t i c relationship,
since the relativistic form is
(i)
2moc2
210 EXTENSION TO MANY BEAMS CH. I0
2 2nm~ I h2 ! 1/2
o' - 1~2)1/2 = h2 1 + ~2 C2~2
- (2)
EX 1+(1- mo
10.2.1. M a t r i x formulation
det
l("-x'
I ~
O-xl
= 0
212 EXTENSION TO M A N Y BEAMS CH. I0
kh = w, - ~h - ~, (3)
and
K2 - k2h = 2w,~ + 2K~h - ~2h = -x + Ph, (4)
where we have put
x = -2K~ (5)
Ph = 2W,~h - ~2 h, (6)
where
:" " " 100 " " " vOh " " " Vog " " "'~
9 9 9
9 9 o
n __
Vho " " " Ph " " " Vhg " " " (8)
9 o 9
VgO 9 .. Vg h 9 .. pg 9
9 . .
10.2 EXTENSION OF BETHE THEORY - TRANSMISSION 213
oo o
~h = aiWlih . (i0)
aj ~ ~J h"~J* h = 'FJ* o
h
or
(~] = ~ I o (13)
and
F o r a p a r a l l e l s i d e d p l a t e - s h a p e d crystal, all w a v e s in
the c r y s t a l c o r r e s p o n d i n g to the one r e c i p r o c a l l a t t i c e p o i n t
h are r e f r a c t e d i n t o the same d i r e c t i o n at the e x i t face to
f o r m the v a c u u m d i f f r a c t e d w a v e Kh. In the c r y s t a l the
a m p l i t u d e of t h i s w a v e are
R e f r a c t i o n at t h e e x i t face g i v e s a c h a n g e in l e n g t h of the
p r o j e c t i o n of the w a v e v e c t o r on the s u r f a c e normal, as
s u g g e s t e d in Fig. 10.2. In the s m a l l a n g l @ a p p r o x i m a t i o n , the
d i f f e r e n c e in p r o j e c t i o n of K a n d K h is %t = ~ / 2 K , a n d the
d i f f e r e n c e in p r o j e c t i o n of K 0 a n d ~ is Vo/2K. T h e n if the
s u r f a c e n o r m a l is u n i t v e c t o r Z a n d r.z = z, we h a v e
kih.z = ~: . z - ~i
0 h
Fig. 10.2. The relationship of wave vectors in a crystal and in space for
a two-beam case.
216 EXTENSION TO MANY BEAMS CH. I0
I! o. voh vo8il
I!
'" ~o ""~oh"'~os"" /
M = Vho Ph vh& + i ~ho ~o ~h& " (19)
V&o v&h Pg ~8o ~sh ~0
Then both of these matrices are Hermitian, but the sum of the
two is general, complex.
MWi = ~ wi . (20)
and, in general
Mnwi = (~ ) n w?i . (21)
i i g
g i
10.2 EXTENSION OF BETHE THEORY - T R A N S M I S S I O N 217
Zi ~i*o~z'ih -- 8ho.
= Z "?i*oVih Z n[ exp{2~iKh.r}
i n
-- Z ---nll~~z~ (Mn) hO exp{2=iKh " " (24)
n
1
exp {iM} = 1 + iM - --M 2 + ... (25)
2!
1
[exp { i M } ]hg = (I) hg + i (M) hg ----(M2)hg + (26)
2!
[ rciz
:uj(o)
% --o
(28)
lc
~(n) = sn~(O)
and
(29)
(31)
1
where we have subtracted out yPh which adds the same phase
factor to each beam.
10.2 EXTENSION OF B E T H E THEORY - TRANSMISSION 219
M = A + B = a(;1 + bG2
M 2 = A2 + B2 = (a 2 + b2 ) I - r2 1
M 3 = (A 2 + B 2) (A + B ) = M. (a 2 + b 2)
M 4 = (A 2 + B 2) 2 = r4 .I.
~~ = c~ - i P--!h2rsin~TJ(~zr'~
~llh = v h / r Ir,zr 1
sin[T
Vh/W,
sin{Rz(~2h + y2h/K2)l/2 } .
dW~ - i ~ O h Wh,
dz
d%
ffi - ~ ' 0 g 0 + a ( i ~ h - ~'h) gh,
where
d
[~h ffi --'- ( h - R ( z ) ) . (34)
dz
d
--g = 2~i(A + ~)g (35)
dz
O40
(b)
220 02Of--- --~20 420
9 /'~ ~ ' ~ ~ " ~ c ) 9 9
200 2 0
9 9 9 9
9 9 9 9 9
Fig. 10.3. Illustrating the interaction of the Ewald sphere with t h e hkO
plane of reflections for a F.C.C. crystal in three special cases where
beam-reduction techniques can be used.
10.4 SPECIAL CASES - BEAM REDUCTION 223
parallel to the c-axis, the four beams 200, 020, 200 and 0 2 0
are exactly equivalent having the same excitation error,
interacting between themselves through the Fourier
coefficients of the types 0220 and 0400, interacting with the
zero b e a m through coefficients 0200, interacting with the set
of 200 beams through 0200 and 0420 and so on. Thus the four
200-type beams may be combined to give an equivalent single
beam with definable interactions with the 000 beam, the
representative b e a m of the 220 set, and so on.
If a 5-beam calculation is to be made, including only
the 000 and the 200 set, this is immediately reduced to a 2-
beam calculation. Similarly the p r o b l e m is greatly reduced if
more beams are included. Fisher [1968] calculated the
intensities for this orientation (with no absorption) for a
49-beam case including reflections out to the 660. By
symmetry the number of effective beams to be considered is
reduced to i0. The result of the calculation shown in Fig.
10.4 indicates the interesting situation that there is
something resembling a two b e a m solution in that the zero
beam oscillates out of phase with all the d i f f r a c t e d beams,
varying together. This result may be influenced by the
special circumstance that the excitation errors for the hkO
reflections are proportional to the square of d-lhko and so to
h 2 + k2 . Hence the phase changes introduced, in (36) for
example, by the excitation errors are integral multiples of
2~ when that for the 200 reflections is 2~. An investigation
of such special cases by Fejes, Iijima and Cowley [1973]
suggests, however, that the situation is more c o m p l i c a t e d and
that the p e r i o d i c i t y of the intensity variation with
thickness depends on the presence of a particular relation-
ship between scattering amplitudes and excitation errors.
A second special case indicated by (b) in Fig. 10.3 is
for a tilt of the incident b e a m so that the Ewald sphere cuts
exactly the 000, 200, 220 and 020 reciprocal lattice points.
Then the four c o r r e s p o n d i n g beams are equivalent in that they
have the same excitation error and interact among themselves
and with successive concentric sets of beams, through the
same i n t e r a c t i o n potentials. By grouping these sets of
reflections together the effective number of beams is again
reduced. In this case the 000 beam is d i s t i n g u i s h e d from the
rest of the set when the boundary conditions for the entrance
surface are applied but the b e a m - r e d u c t i o n is effective in
simplifying the p r o b l e m up to that stage.
Similarly the case (c) of Fig. 10.3 with the Ewald sphere
224 EXTENSION TO M A N Y BEAMS CH. i0
1.0
Zh(,)
[ / \ 2oo / ~.\
1~::.......:................:,~,'=r.'. .......... :......:.~...~... ....... ":'.-..::~,,,r.,; ........... ~~....~ ....... ::.'.'..'...~,,,./....:: ...... --
0 thickness z J~ 500
940
%
920
k \
= 900
\
\
%%%.
880
860 I I I | i i i i i i
20 40 60 80 1 O0
N e t beams c o n s i d e r e d
!.o
L
~l~(~) 000
400
,"~
/ ,
i \ t
, \ i , l
i "\ l
I
020 I \
i
l ' / \
\ ,
/
%
.! : "..
200 ... 1"-.2 2 ,-) : '.
/--,/, --,,,
if-;,' \ .
5OO
o
thickness z
Fig. 10.6. Calculated intensities of ~ O reflections as a function of
thickness for the incident beam tilted slightly away from the c-axis of
the F.C.C. copper-gold alloy of Figs. 10.3 and 10.4 to give the Ewald
sphere intersection indicated by (c) in Fig. 10.3.
C a l c u l a t i o n b a s e d on the H o w i e - W h e l a n e q u a t i o n s (35)
i n v o l v e the p r o g r e s s i v e i n t e g r a t i o n of the a m p l i t u d e s t h r o u g h
the c r y s t a l .
P
Fig. 10.7. Diagram illustrating assumptions of the "column approximation".
exp~ikx2~ = exp{i~}
(2RJ
or
x = (R~) 1/2.
Problems
ll = 1 + q)(r) (I)
2E
X XE Az ~ (x, y, z . ) . (2)
or, in r e c i p r o c a l space we m u l t i p l y by
T r a n s m i s s i o n t h r o u g h a t h r e e - d i m e n s i o n a l object is given
by the l i m i t i n g case, for N going to infinity, of e q u a t i o n
(3.31) w r i t t e n in one d i m e n s i o n only;
which m u l t i p l i e s ql (x) .
It is c o n v e n i e n t when d e a l i n g with d i f f r a c t i o n by crys-
tals to work with the reciprocal space e x p r e s s i o n given, in one
dimension, by the limiting case of e q u a t i o n (3.32), namely,
~(u)=[QN(u),...[Q2(u),[QI(u),Qo(u)Po(u)]PI(u)]P2(u)...]PN(u) . (14)
N 2 1 1 2 N
and
F. (h, k) = c4~n (h, k) - iMn (h, k ) , (18)
where
(19)
l
(20)
!
hi h2
( 'i"2"'1
3 3
h 1 ha h3
(U) = (-iAz)N e x p { K i k H u 2}
X X
h,
~
h2
" " X F1 (hl)F2 (h2)...FN(hN)8
h~
u-
hi + h 2 +...+h N
a
-uo)
X exp 2~il x Zn- '+ + X " (24)
n=l a a2 m=n+l 2a2
236 THE "PHYSICAL OPTICS" APPROACH CH. ii
""' ""':ZI"
n ~ n
xZ Z Z Z Z Z ...Z Z 7. Z ,,,h,,~,,,,,,,,~,,~,,~,
h, ~ l, h2 k2 12 hN_, k~t_, l#_, l
h=~nN-11 hn, and so on. We note that while the structure ampli-
tudes F(hn, kn, In) refer to the nth s c a t t e r i n g process only, the
e x c i t a t i o n errors ~ are cumulative and d e p e n d on the history
of scatterings by all slices from 1 to n. This is the factor
which makes it very difficult to simplify (28) further.
(-iAT)F(0, 0, 0) = l - i ~ A z O ( 0 , 0 , 0 ) -AzM(0,0,0),
9 o(h,k) = lira { ( - i A z ) N F N ( o , o , o ) }
N.-~....
= hm [1-icAzO(0,0,0) -AzM(0,0,0) ]N
N-.~
=exp{-i~H~(0,0,0) - H M ( 0 , 0 , 0 ) }. (30)
238 THE "PHYSICAL OPTICS" APPROACH CH. Ii
{~ for n < m,
(31)
x- for n>_m.
•1 (h.k) = exp{-ioH~>(0, 0, 0) - H M ( O , O , O ) }
IW 1 (h,k) I 2
sin2 (~/-/~)
=exp{-2HM(0,0, 0) } [(;24~2 (h,k, 0) +M2(h,k, O) ] , (34)
(~)2
Then
exponent
f
for
for
for
in
m<n<p
p<n<r
r<n<N.
(28) b e c o m e s
(35)
N-I
H [~ - Az ' ~ [~. = z:~l+z2 ([~2-[~3.) +z3 (~-~2) 9 (36)
n=l
W3 (h,k) = e x p { - i o H ~ ( 0 , 0 , 0 ) -HM(O,O,O)}
x~ ~ ~ ~ ~ ~ ~ F(h 1, k 1, ll)F(h 2, k2, 12)F(h-hl-h 2, k-kl-k 2,
h: ka l, h2 k2 12 l
1-11-12)
+
(-2~iH)s (~2 +~21 +~22 + ~ 1 + ~ 2 +~1 ~2) +'" etc. (43)
5!
Then adding the appropriate operators En(h) we obtain a
t w o - d i m e n s i o n a l array of terms with n i n c r e a s i n g v e r t i c a l l y
and r horizontally. This t w o - d i m e n s i o n a l array can then be
summed in a number of ways. For example, we may sum the rows
horizontally. This gives for the first row
F I
l L~" r!
T1 (h) = ~ {-2~;iH}n
n=l (2~;)nnt
h k l a b
h k I a
is the Fourier t r a n s f o r m of
where ~(x,y) and It(x,y) are the values per unit thickness of
the p r o j e c t i o n s in the z d i r e c t i o n of the potential and
a b s o r p t i o n functions ~(r) and It(r) .
Thus the e x p r e s s i o n (44) given by summing the first
v e r t i c a l column from (43) gives the amplitudes of the
d i f f r a c t e d beams when all e x c i t a t i o n errors are a s s u m e d to be
zero, as if the Ewald sphere were planar or the w a v e l e n g t h
were zero. Thus it gives a h i g h - e n e r g y approximation.
It is also the "phase-grating" approximation, given by
a s s u m i n g that the total s c a t t e r i n g and a b s o r p t i o n power of
the crystal is c o n c e n t r a t e d on a single plane. More c o m m o n l y
the functions ~(x,y) and It(x,y) are taken to be the p r o j e c t i o n s
in the z d i r e c t i o n of the p o t e n t i a l d i s t r i b u t i o n ~(x,y,z) and
the a b s o r p t i o n function It(x,y,z). The crystal is then r e p l a c e d
by a t w o - d i m e n s i o n a l d i s t r i b u t i o n having t r a n s m i s s i o n
function
q(x, y) =exp{-i~(x, y)-~(x, y) }. (46)
Ii. 3 GENERAL D O U B L E - S U M M A T I O N SOLUTION 243
the p h a s e - g r a t i n g approximation as
ZZ lu--,v--:
H K~ (55)
H K A B
where the intervals I/A and I/B are made small enough to
allow a reasonable representation of the fluctuations of
interest in Qn(u.v). The equivalent operation in real space
is to consider that the region of interest in qn(x.y) is
reproduced at regular intervals A,B thus
m p
Thus the crystal defect, or other arrangement of atoms of
interest, is repeated regularly to form a superlattice having
the diffraction pattern (55). Then the intensities of the
diffraction pattern or image for this superlattice may be
calculated using the perfect-crystal slice-method computer
programs. The variation of scattering in the z direction is
included by varying the contents of the successive slices.
Such a calculation may involve a very large number of
diffracted beams corresponding to the very large unit cell
size for the superlattice which must normally be assumed.
The calculation may often be brought within reasonable bounds
by use of special assumptions such as the consideration of a
250 THE "PHYSICAL OPTICS" APPROACH CH. II
I )
neglected. Then (60) may be rearranged to give
az 4zkz kz 4zk z
or,
where 2 + 4 z ikx2Vxy
A = VaT
_ 02 02 a 4gikyOy
a~o(r) i
-------- = ~ V(r). tp(r)
Oz 4zk z
dq~g(Z) (63)
dz
~(xye) = 9(xyO) + 4 ~ kz
i ;oelA+ V(xyz)].r (64)
~(~)--[~+ '---10~A
4=k z
+ v(~z)~z
i
+ 4~k, Io'[A +v(~z)lI2[A +v(~z )]e~ ez+ .....]~(~0) (65)
Vp = ~:V(xyz)dz
= {(z(~))- ~ / 2} /(~ / 2)
(z(~)) = f~zV(~Zldz
~o Vp(xy)
Problem
APPLICATIONS TO SELECTED
TOPICS
This Page Intentionally Left Blank
CHAPTER 12
tPo(x,t) = po(X+A,t)
do A2(X, t) c)2po I
= Po (X) + A (X, t) --;-o + + .... (2)
dx x=X 2! Oxa'l==x
The c o r r e s p o n d i n g generalized Patterson function is then
or we can write
= p0 + 89 a p_ 0 + . . . .
gx 2
12.1 THERMAL DIFFUSE SCATTERING 259
, ~ ~(x+ma)Acos2~(lma-vlt),
in
i/
/
tI x=vt
fITh(Uv)dv
Fig. 12.1. (a) The Patterson function for the deviation from the time-
averaged structure as a function of one spatial coordinate, x, and time,
t, for the case of a longitudinal wave travelling in the x direction. (b)
The Fourier transform of the function (a) giving the variation of
scattering power with u and the change of frequency, V. (c) The intensity
distribution resulting from (b) when the measurement does not distinguish
differences of frequency.
F (,) = ~ ~ e x p { 2 K i , - (R i+Ai) }
i
and
oA {~ foran A onsite i,
i= fora B on site i,
mA A A +roB AB = O, (9)
and, by d e f i n i t i o n
(Ai) = 0, (~)
= ~ exp{2Kiu.R i } ( ~ e x p { 2 x i u - A i} ). (12)
X ~ (u-ABi0)2 c o s 2 x u - R i. (21)
(it)
(b)
(c)
((l)
(23)
k k Irki 16 '
12.2 STATIC ATOM DISPLACEMENTS 269
S ;P(r t ) ~
J = IF(u p O)12 ~ I/e(U) ! 2 ,
k
= Z + ZZ ,.s,
k j~k
O c = 0.74(EF/Eo)I/2.
(31)
2m m~n
where
Hn,, (r) = ~ a*n (rI ...rN) H (r, rl ...rN) am (rl ...rN) drl ...drN. (32)
Here an(rl.., rN) is the wave function for the electrons in the
crystal h a v i n g positions rI... rN and H (r, rI ... rN) is the
interaction energy of the incident electron (position r) with
the crystal electrons.
For electrons in a crystal the interaction energy must
show the p e r i o d i c i t y of the crystal lattice and it was shown
by Howie [1963] that
where qnm is the wave vector for the excitation in the crystal
and g is the reciprocal lattice vector.
A s s u m i n g a simple Coulomb interaction of the electrons
the interaction energy is of the form H(r) = ~ n e 2 / ( r - r n),
which allows the integration over r in (32) to be carried out
directly. Then, following Cundy et al. [1966] the kinematical
amplitude of the scattering involving a single electron
excitation from a state m to a state n is proportional to
e2
H~= ~ a*n(r)exp{2Ki( q - g).r}am(r)d~r (34)
~Ve(q- g,o~).lq - gl 2
7 I / !'"! / 1 7 1 ! / ! I ....
t I!1'!I
N
I 7I I / I/-7
III
L l l / l l l i l l l l l l ~ lli/_z
Bwald
6'q i 'q 2 q 5
Fig. 12.4. The intersection of the Ewald sphere with the regions of
scattering power corresponding to a pbonon having momentum q.
12.4 DYNAMICAL EFFECTS IN DIFFUSE SCATTERING 277
= - ~p (., v) I 2. (37)
m
n p=m-n/2
uf* u f_
U -
Fig. 12.5. Sketch suggesting the relation between the functions f (u), uf
(,) and the self-convolution of uf(u), where f (,) is an atomic scattering
factor.
Table 12.1
Calculated absorption coefficients due to plasmon scattering (P),
thermal diffuse scattering (TDS) and singje electron excitations (SE)
for iii systematic reflections of A1 at 40 keV (from Doyle [1970]).
Units: X 10 -3 A -I
1
~P0 . . . .
88 ~ x G-*(x)
dx, (42)
A ao Jo x 2+(0e/%)2
Specimen
Objective lens
S e l e c t e d area aperture
Intermediate lens
If\
I I \
i
I
I
P r o j e c t o r lens
\ \ \ ,.,'~"
_ Final image
Fig. 13.1. The ray paths in an electron microscope used (a) to produce a
high magnification image and (b) to produce a diffraction pattern of a
selected area of the specimen.
ADF BF
Detector Detector
. J I-I
sFEuGrce Lens Spec,rnen I I I
. . . .
L.t co C ] l
Fig. 13.2. Diagram suggesting the mode of operation of a scanning
transmission electron microscope.
d 2 = do 2 + dc 2 + di 2. (4)
I - ..... ----~.
9
I
|
%
I
I
t
I
I
e
l
I
I il I I I
I I I I '1
| I I I
II I I I
I ! I I
0 - ; ~ ; '
--•%
II I
' II '!1 '11,1
I r.l ill itllt
! |~. t I~! IPl,t
11"I Ill 'P.llt
' I; I .I;I 'I;I'~
lil,l!l,l;i,~
I I !
I : l, l 'lil'l,l i
I I i I
-1
0 0.1 0.2 0.3 0.4 0.5 0 . 6 U 0.7 0.8
', : r;l
0 ' 9 I ~ I '
9 9 I ,l'
.... '
l
Fig. 13.3. The functions s;nX(u) (continuous line) and co~(u) (dotted line)
for 300key electrons and C s = 1.0mm from equation (13.1). The defocus
values, A are (a) 0, (b) -160~ and (c) 510~ (the optimum defocus).
T h e f o r m of t h e sin Z(u) f u n c t i o n f o r a s i n g l e r a d i a l
variable u, (and a l s o t h e cosX(u)), is s h o w n in F i g . 1 3 . 3 f o r
v a r i o u s d e f o c u s v a l u e s a n d a t y p i c a l C s v a l u e . It is s e e n
t h a t f o r a l l t h e d e f o c u s v a l u e s , sin X is z e r o f o r u = 0 a n d
is s m a l l f o r s m a l l u v a l u e s . H e n c e t h e c o n t r i b u t i o n of a l l
Fourier coefficients in t h e i n n e r p a r t of t h e d i f f r a c t i o n
pattern, corresponding to l a r g e p e r i o d i c i t i e s in r e a l s p a c e ,
298 ELECTRON MICROSCOPE IMAGING CH. 13
Fig. 13.4. A thin crystal of Ti2Nb10029 viewed along the short b-axis with
a=28.SA, c=20.5A. (a) Diffraction pattern, (b) Diagram of the structure with
two layers of metal atoms (dark and light) surrounded by oxygen octahedra.
(c) Image at 100keV with resolution approx. 3~ (Iijima [1971]). (d) Image at
350keY with resolution less than 2A (after Smith [1989]).
13.4 THE IMAGING OF CRYSTALS 303
Fig. 13.6 High resolution 'profile' image of a (II0) surface on the edge of
a thin gold crystal showing a 2xl reconstruction of the surface. The insert
is the image calculated by use of the periodic-continuation multi-slice
method. (Marks and Smith [1983])
I (r) =! t/ro (r)* to (r)l 2 + Z. (I A ~., (r, t)* t,. (r)P) (19)
,
,u(x)= ~ -gZx) (20)
I (x) = e x p { - 2 ~ o H } [I +
{2w/ (i +w 2) }. sin 2 { 2 ~ h H (I +w 2) 1/2 }. cos (2~hx/a)
+ {i/(l+w2) I/2} . s i n { 4 ~ h H ( l + w 2 ) I/2} .sin (2~hx/a) ] (25)
where 2~ = tan -I ( ~ h / ~ h ) .
If we assume that ~ h < < ~ h , the phase angle 2 ~ is
a p p r o x i m a t e l y ~/2 so that the image shows sinusoidal fringes
with m a x i m u m intensity at one quarter of the distance between
the atomic planes. The contrast of the fringes varies sinu-
soidally with the thickness, H. When 4 ~ H becomes equal to
K, i.e. for the thickness equal to half the extinction dis-
tance, Ch, the fringe contrast goes to zero and then reverses.
The more general situations, involving deviations from
the exact Bragg condition, were explored in detail by
Hashimoto et al. [1961]. They showed that for varying Ch and
H, the fringes are no longer parallel to the lattice planes.
On occasion this can give the false impression that crystal
defects are present when, in fact, there is just a local
variation in crystal tilt, as in a strain field, or in
thickness. From (25) it is seen, for example, that for w
13.4 THE IMAGING OF CRYSTALS 311
term and its complex conjugate are of first order in p(X) and
are d e r i v e d from the coherent interference effect of the super-
imposed incident and scattered waves and so contribute to the
intensity only within the central b e a m spot defined by A (u).
F r o m these expressions, it is s t r a i g h t f o r w a r d to derive
the image intensities obtained for various forms of the
detector function, D(u). For example, for a very small
detector located on the axis, a good approximation is D(u) =
~(u). Then (33) reduces to
Mask , Hologram
Reconstruction
Mathematically, we m a y a s s u m e t h a t a t i l t e d p l a n e wave,
e x p { 2 ~ i u o x} is a d d e d to t h e i m a g e w a v e so t h a t t h e h o l o g r a m
i n t e n s i t y is
S e l e c t i n g out t h e t e r m c e n t e r e d on t h e d i r e c t i o n d e f i n e d
b y ~ ( u + u O) b y u s e of an a p e r t u r e , m u l t i p l y i n g b y T*(u) a n d
F o u r i e r t r a n s f o r m i n g t h e n g i v e s q(x) d i r e c t l y , w i t h no
a b e r r a t i o n s a n d no c o n j u g a t e image.
T h e e s s e n t i a l r e q u i r e m e n t for t h i s p r o c e s s is t h a t t h e
F o u r i e r t r a n s f o r m of t h e d e s i r e d image, c e n t e r e d on ~ ( u + u 0),
s h o u l d be w e l l s e p a r a t e d f r o m t h e d i f f r a c t i o n p a t t e r n of t h e
o b j e c t , r e p r e s e n t e d b y t h e s e c o n d t e r m of (42). T h i s i m p l i e s
13.6 ELECTRON HOLOGRAPHY 323
s t r u c t u r e s of m a g n e t i c d o m a i n s in t h i n f e r r o m a g n e t i c films,
a n d a c c u r a t e m e a s u r e m e n t s of m a g n e t i z a t i o n s in s m a l l r e g i o n s
c a n be o b t a i n e d w i t h e x c e l l e n t s p a t i a l r e s o l u t i o n s .
M a n y o t h e r f o r m s of e l e c t r o n h o l o g r a p h y m a y be e n v i s a g e d .
More than twenty possible forms have been described (Cowley
[1992]; Ru et al. [1992]). F o r e a c h f o r m i n v o l v i n g a C T E M
i n s t r u m e n t , t h e r e is a form, e q u i v a l e n t b y the r e c i p r o c i t y
relationship, involving a STEM instrument. For each on-line
f o r m t h e r e is an o f f - a x i s f o r m i n v o l v i n g the u s e of a b i -
prism, a n d t h e r e are b o t h b r i g h t - f i e l d a n d d a r k - f i e l d forms.
If an e l e c t r o s t a t i c b i p r i s m is i n s e r t e d c l o s e to t h e g u n
in a S T E M i n s t r u m e n t , the e f f e c t is to p r o d u c e two m u t u a l l y
c o h e r e n t v i r t u a l s o u r c e s so t h a t t w o c o h e r e n t p r o b e s are
f o r m e d at the s p e c i m e n l e v e l as s u g g e s t e d in Fig. 1 3 . 8 ( a ) .
I n t e r f e r e n c e b e t w e e n t h e s e p r o b e s p r o d u c e s a set of f r i n g e s
Source Biprism ~
Ii Spec.
ram
..=.
II
Hologram
Image
Conjugate
Problems
i. From the expressions (13.14) and (13.15), derive the
variation of the contrast and the position of the t w o - b e a m
lattice fringes as a function of crystal thickness and
excitation error for the case of no absorption. (c.f.
Hashimoto et al. [1961]).
2. Inelastic scattering effects tend to decrease the
contrast of thickness fringes. Phonon scattering gives little
contrast and the plasmon contribution, although showing
strong dynamical effects, is defocussed by the chromatic
aberration of the lens. Assuming an average energy loss of 20
eV, a chromatic aberration constant C c of 2 m m and a loss of
resolution given by AF = C c ~ / E , (E = I00 kV) find the loss
of contrast of thickness fringes of 200 ~ p e r i o d i c i t y given
by the 200 reflection from MgO. How does this affect the
d e r i v a t i o n of absorption coefficients from thickness fringe
intensity variations? What other factors cause errors in
absorption coefficients derived in this way?
3. A perfect crystal has flat faces and uniform thickness
except that there is a small rectangular protuberance 20
high on one face. Assuming i00 keY electrons, a mean inner
potential D 0 of 20 volts and that the amplitude for the h
reflection is i0 volts, find the contrast in the image due to
the protuberance, when
(a) no strong d iffracted beams occur and the m i c r o s c o p e is
suitably de-focussed;
(b) the Bragg angle for the reflection h is exactly
satisfied? (Use a column approximation and find the bright-
and d a r k - f i e l d images assuming that the lattice spacing is
not resolved.)
CHAPTER 14
Th Dh
Fig. 14.1. Diagram illustrating the formation of Kossel line patterns with
radiation produced at a point P in a crystal.
K2 ao~F'h~l"h
2(K2~F'2h + cz2 / 4 )
0
Fig. 14.2. The intensity distribution K~ across a Kossel line shown as the
sum of symmetric and antisymmetric parts.
(a) (b)
Fig. 14.4. Kossel line pattern from a crystal of germanium, thickness 0.23
mm, produced by placing a source of CuK~ radiation 3 cm from the crystal.
u m
A number of transmission lines and one reflection line, iii, are visible.
(From Borrmann [1964].)
14.1 KOSSEL LINES 335
Oh 0 +O h
I
- Oh +Oh
Fig. 14.7. Diagram suggesting the origin of a Kikuchi band with excess
intensity between the lines.
o
3,,,~" kz
\
14.5. Channelling
/////Z
200
Ph(Z)
~ A T
thickness z R
I00~
~ P~ s"% ,-,
! f,,
',% 1'1%
A \! 'l I
A 9 I
;,.
! // I I I ! I ! 1 I ~-
"i,oo./I:
Ivl ~,'i --'~' ' ' '" '"' '' ' " ' " '"
Ph(Z)
\, .... ii V \ I /\ ! ',/ \
v',,,
./-\,,.,x-,\.j t
Fig. 15.3. Plot similar to 15.2 but for a crystal of CdS in <120>
orientation with Bragg condition satisfied for (0002) reflection and
systematic interactions only. (Fisher [1969])
..-~- ".......
(a) ....
Relative1"0]
Intensity "51
(b) | ~ ~ ~ " ~ _
460 soo ~2oo ~6oo 20'00
[ 222(222) Thickness;k
Fig. 15.4. Variation of intensity with thickness for the (222) reflection
from a silicon crystal set at the (222) Bragg condition. (a) Measurement
of intensity of a dark-field electron microscope image of a crystal wedge.
(b) Calculated curve.
A f u r t h e r set of e x p e r i m e n t a l m e t h o d s for d e d u c i n g
s t r u c t u r e a m p l i t u d e s depends on the m e a s u r e m e n t of d i f f r a c t i o n
i n t e n s i t i e s as a function of the angle of i n c i d e n c e of the
incident beam. For X - r a y d i f f r a c t i o n the e x p e r i m e n t g i v i n g the
most direct and a c c u r a t e data on structure a m p l i t u d e s seems to
be that of m e a s u r i n g the width of the B r a g g - c a s e r e f l e c t i o n
from the surface of a large perfect crystal under strict two-
b e a m c o n d i t i o n s (Kikuta et al. [1970], Kikuta [1971]) . The
t h e o r e t i c a l curve (see C h a p t e r 9) has a width p r o p o r t i o n a l to
IFhl. This is b r o a d e n e d in p r a c t i c e by the a n g u l a r width of
the incident b e a m but if this incident b e a m is p r o v i d e d by a
d o u b l e - c r y s t a l s p e c t r o m e t e r using a s y m m e t r i c r e f l e c t i o n s from
perfect crystals (Kohra and Kikuta [1968]) the a n g u l a r width
may be as small as 0.10" and accurate c o r r e c t i o n s for this can
be made.
358 DYNAMICAL EFFECTS IN SINGLE CRYSTALS CH. 15
000 400
'6_:,,_2 4. -4-2 0 2 4
2O0 ~00
-6-4-2 0 2 4 -4-2 0 2 4
x 10-3 rad.
Fig, 15,5, Experimental(broken lines) and c a l c u l a t e d ( f u l l lines) intensity
distributions across spots in the convergent beam diffraction pattern from
a thin MgO crystal, set at the Bragg angle for the 400 reflection with
systematic interactions only (Goodman and Lehmpfuhl [1967]) .
Fig. 15.7 CBED patterns showing h00 spots from (a) thin and (b) thick
crystals of FeS 2. The black G-M lines are visible in odd-order reflections.
(After Tanaka and Terauchi [1985]).
366 DYNAMICAL EFFECTS IN SINGLE CRYSTALS CH. 15
16.1. General
dh
Fig. 16.1. The elongation and bending of the "shape-transform" spikes
around reciprocal lattice points for a thin crystal, bent to give an
angular spread of orientations, (Z.
372 MOSAIC CRYSTALS AND POLYCRYSTALLINE MATERIALS CH. 16
lh Io
(y21r exp {} lr'2c2d~w2
, , (2)
~'22 (C2a 2 + d ~)1/2 C2a 2 + d
lh (y210h12
= I o ~ ~ .
~*/2dhV (3)
~e .
1
at, = + Ge ,
(4)
PI / pO = ~I exp(-p.D)[1- exp(-2oD)]
The quantity G is determined from the assumptions
regarding the crystal imperfections, expressed in terms of
the intensity and angular distribution of the local
scattering. For X-ray or neutron scattering (but not for
electron scattering), it is a reasonable approximation to
express G in terms of the kinematical approximation for the
integrated intensity and angular distribution (preferrably in
Lorentzian form following Sabine [1988]) for the coherently-
scattering crystal region. Expressions can then be obtained
in terms of these variables which give either primary or
secondary extinction as limiting cases.
374 MOSAIC CRYSTALS AND P O L Y C R Y S T A L L I N E MATERIALS CH. 16
anar
ald
here
(a)
hk0
hk2
hkl
(b)
i',I t.I[i hkO
hkl
hk2
Fig. 16.2. The production of an "oblique texture" arc pattern when the
Ewald sphere intersects the set of rings generated in reciprocal space by
the reciprocal lattice points of crystals randomly oriented except that
their c-axes are all parallel.
16 .3 POLYCRYSTALLINE MATERIAL 377
(e l+m+2(,cos2201
powder as (Warren [1964])
(5)
P =Io m2c:~ 4~22 2sinO "
a21~ h 12 V R b n
Ih = I 0 ~ ~ (7)
f/2 2 7tr"sin t~
rh = lh/rtx. (8)
16.3.4. R i e t v e l d refinements
- sin2[A(l+w2)I/2 ] A
dw - lr'A ~ Jo ( 2x) dx" (11)
l+w 2
--~ 0
In t h i s case
A - Ah = ~}hkH/4rc = {;H4)h. (12)
,: !! !! ) j IL I
a5 ~-
0 I , , ~ , I 1 ~ I ,~ I ~ I ~ I ,, i, I,
0,05 0,10 0.2 0,~ ~ a,a 7,0 ~0 3,0
A~
Fig. 16.3. The Blackman curve (Blackman [1939]) for the ratio of dynamical
to kinematical intensities for a ring pattern as a function of A = (~H4)h.
The experimental points are those obtained by Horstmann and Meyer [1965],
from measurements on ring patterns from aluminum films at various
voltages. The short horizontal lanes indicate values calculated using the
Bethe potentials, equation (12). (After Horstmann and Meyer [1965] .)
382 MOSAIC CRYSTALS AND P O L Y C R Y S T A L L I N E MATERIALS CH. 16
Fig. 17.1. The disordered and ordered structures of (a) ~-brass, (b) Cu3Au
and (c) CuAu.
1 for an A at site i,
cAi = 0 for a B at site i,
(I)
1 for a B at site i,
(~Bi = 0 for an A at site i.
~ m B for an A at i
(2)
ci = [_mA f o r a B a t i ,
where the < > brackets are used to devote an average over all
sites.
The p r o b a b i l i t y pABi] is readily seen to be given by
Similarly
(oi )n = An + Bn oi,
where
An = { m A m"S + (-I)" m"B roB},
<Oi(3"/> = <O2i> = m A m B ,
and so on.
The t w o ' a t o m correlation parameters, or "Warren short-
range order-parameters", commonly used are (xi], given by
mAl lrrmB1
sites. For the case of Cu3Au structure (Cowley [1950])
(I0)
and
-~**} r{ <(mA
Sl = >lhn iyi~]]ms = --~mAmB $2 . (Ii)
i i
. ~ ( r - r i +rj ) . (13)
and (15) b e c o m e s
Ai = ~_~ ck Aik (17)
k
where
Aik = AAik / mB .
8 ( r - R i + Rj -~_~ ffk(Aik - A j k ) ) ,
k
and when the a v e r a g i n g process is performed, instead of (14)
we o b t a i n
392 O R D E R I N G OF ATOMS IN CRYSTALS CH. 17
k
>
+ < (mAPA+mBPB)*(PA-PB)(Ci+O0)*8 { r - R , - X ok (A~-A]k) } >
k
(18)
k
Thus for the Patterson of the average lattice, the first
term of (18), there is a spread of the peaks around the
average lattice vector positions, R i. For the c o n t r i b u t i o n s
from the deviations from the average lattice, the Patterson
peaks are likewise spread but the displacements given by
individual atom-pair vectors from the e i positions are
c o r r e l a t e d with the site occupancies so that there can be
d i s p l a c e m e n t s of the mean positions of the peaks as well as
an order-dependent b r o a d e n i n g of the peaks.
As indicated earlier, this simplified formulation of the
Patterson function rests on a number of assumptions which are
not n e c e s s a r i l y justified, but it can serve to illustrate the
type of diffraction effects to be observed.
is o r d e r d e p e n d e n t , g i v i n g rise to d i f f u s e s c a t t e r i n g a n d is
w r i t t e n s e p a r a t e l y as /d-
In the limiting, h i g h t e m p e r a t u r e case of c o m p l e t e
r a n d o m n e s s all < ~ 0 ~ i > v a l u e s are zero e x c e p t that, f r o m (8),
<(~0(;0> = m A m B a n d the s e c o n d t e r m of (19) b e c o m e s
w h i c h g i v e s rise to a u n i f o r m b a c k g r o u n d s c a t t e r i n g , f a l l i n g
off s m o o t h l y w i t h s c a t t e r i n g angle r o u g h l y in p r o p o r t i o n to f2
C o r r e l a t i o n of o c c u p a n c y of n e i g h b o r i n g sites g i v e s a
m o d u l a t i o n of this b a c k g r o u n d . For a t e n d e n c y for c l u s t e r i n g
of like atoms, all < ~ 0 ~ i > v a l u e s t e n d to be of the same sign
so that m a x i m a in Id a p p e a r a r o u n d the r e c i p r o c a l l a t t i c e
p o i n t s for the a v e r a g e s t r u c t u r e . If t h e r e is a t e n d e n c y for
o r d e r i n g into a s u p e r l a t t i c e , with an a l t e r n a t i o n of the two
Table 1
Measured values of i (for the ith neighbor shell)
given by Chen et al. [1979] for Cu3Au
i imn ~i(T=o)
1 ii0 -1/3 -0.176 -0.125 -0.130
2 200 1 +0.214 0.154 0.106
3 211 -1/3 +0.005 0.023 0.032
4 220 1 +0.062 0.049 0.019
5 310 -1/3 -0.079 -0.078 -0.066
6 222 1 +0.022 0.010 -0.009
7 321 -1/3 -0.010 -0.012 -0.002
8 400 1 +0.073 0.071 0.029
9 330 -1/3 -0.030 -0.022 -0.000
i0 411 -1/3 +0.026 0.018 0.007
Ii 420 1 +0.034 0.024 0.000
2~ 2 (27)
k 1
are c e n t r o s y m m e t r i c and d e c r e a s i n g m o r e - o r - l e s s u n i f o r m l y
with IRi I and so give rise to a diffuse s c a t t e r i n g a r o u n d the
f u n d a m e n t a l reciprocal lattice points, the Huang s c a t t e r i n g
(Huang [1947]) .
For the second t e r m of (23), the average is r e w r i t t e n
-2~2__E ~ { <Oi OkOl >+<O0 akOl > } { u" (Aik -Aok) } { u- (AU - Aol) } - i Iit
k 1
(28)
observable quantity.
From (32) V(k) and hence the interaction energies may be
obtained directly from the diffuse scattering measurements.
For reasons of practical convenience the determinations of
interaction energies to date have relied on the real-space
relations between ~ and V~, equivalent to (32).
One immediate consequence of (32) is that the maxima of
the diffuse scattering will occur at the points where V(k)
has minima. Hence for various assumptions of the nature of
the interatomic energy functions and so the relative values
for the Vii, the positions of the diffuse scattering maxima
may be predicted and hence the type of ordered structure
which will tend to form in the alloy may be deduced. This
aspect of the situation has been explored by Clapp and Moss
[1968] who found interesting correlations with the ordered
structures of real alloy systems.
Determinations of Vii values from observed diffraction
intensities have been used, in particular, to investigate the
contributions of conduction electrons to the configuration
energy of alloys. It has been shown that minima of V(k) and
hence maxima of ~(k) may occur for k values corresponding to
k vectors between flat areas of the Fermi surface for the
alloy. Hence the form of the Fermi surface may strongly
influence the form of the diffuse scattering and so the type
of superlattice which tends to be formed. The relationship
with Fermi surfaces is discussed by Cowley and Wilkins [1972]
and a more general discussion including an account of the
formation of long-period (i0 to 40 A) out-of phase domain
superlattices in relation to long-range oscillatory
potentials and speculations on the situation for non-metals
is given by Cowley [1971].
(o)
! ! i
(b)
I I I I
000 100 200 300 400
Fig. 17.3. Diffuse scattering intensity measured along the h00 line in
reciprocal space for a disordered crystal of CuAu3. (a) X-ray measurement
(Batterman [1957]) showing size-effect displacement of the 300 diffuse
scattering peaks. (b) Electron diffraction measurement (Watanabe and
Fisher [1965]) showing no displacement of the 300 peak.
o Au al;om
9 Ctl a t o m
~o/././././-.j~
(a) ~Ih/. I. I. ~. ~" ! ~ ! o! o! o ! o ~ ~/~
9
Don iain ] )oln a ill Doln ai n
I}ou n(I ary Bou lid ary I}ou ildary
(b)
i00i i T T T T Ill T T I I
Fig. 17.4. (a) Diagram of the periodic out-of-phase domain structure of the
Cu-Au-II superlattice. (b) The distribution function of one point per unit
cell used in the derivation of equation (17.35).
Problems
Extended defects
18 .i. Introduction
Probability of 1 fault = ~ n e x p { - ~ n } ,
(~),,,
Probability of m faults = ------exp{-0~} .
m!
The vectors between the origins of two layers separated by n
normal translations plus m faults will be na + ms. The
g e n e r a l i z e d Patterson function is then
+~ ~ 8(r+na+ms,~(~ ]. (1)
n=l m=O m!
+ (I - e x p { - 2 ~ i u - a - ~ + a exp(-2~iu-s)})-I _ I] = IF(u)12
X [ 1-exp{2a(cos2~u.s)-l} ]
1 + exp{2a(cos 2 r ~ u - s - 1)} - 2 exp{a(cos 2 n u . s - 1} cos(2nu- a + a sin 2rcu. s)
(3)
We c o n s i d e r the c r y s t a l to be made up of an a r b i t r a r y
n u m b e r of d i f f e r e n t types of layers. The ith type of layer
has an e l e c t r o n d e n s i t y d i s t r i b u t i o n Pi (r) and if such layers
were s t a c k e d r e g u l a r l y the t r a n s l a t i o n v e c t o r w o u l d be Ri. If
18.2 STACKING FAULTS-STATISTICAL KINEMATICAL THEORY 415
For vectors -Ri we obtain terms Ln = l*n. Then summing for all
interplanar vectors we obtain the general expression:
F* otexp{2niu.(R + S)}
I/N = IF +
1 - ( 1 - or) exp{2rciu 9R} 1 - ( 1 - or) e x p { 2 ~ u 9R}
ctexp{2niu.(R + S)}
-IF+ [F+...] ] ] + c.c.-IFl 2
1 - (1 - ~) exp{2rciu 9R}
I/N
IFI 2 ct(1- ~ ) ( 1 - c o s 2 n u . S)
(11)
1 - ot + ct z - (1 - or) cos 2rcu 9R - ot cos 2rcu .(R + S) + o r ( l - o0 cos 2rcu- S
+ (ReF, G) {l+cos2~,- (R + S ) - c o s 2 ~ , - R - c o s 2 ~ , - S }
- (ImF, G) { s i n 2 ~ u - R + (l-2~)sin2=u-S
- sin2~,- (R +S) }
+ IG 12 (I_cos2~..R) ], (12)
a ( 1 - o ~ ) n + c ( 1 - 7 ) n.
420 EXTENDED DEFECTS CH. 18
A A
/
A
/
j
Fig. 18.2. The stacking sequences of close-packed structures. (a) The
labelling of alternate stacking positions for two-dimensional close-packed
layers. (b) Stacking sequences illustrated by the atom positions in (ii0)
planes.
18.2 STACKING FAULTS-STATISTICAL KINEMATICAL THEORY 421
I(u) =~ exp{2giu-RN} IF 0 ( u ) 12
N
1 - [ 1 - 2 a ( 1 - cos 2rcu-s)] 2
- . (15)
/ / /
~ itl;III/
top
fault J
(a) bottom
//f/iN/ i il lillllllli
A I
Fig. 18.3. (a) Illustration of the relative contributions from various
Bloch waves to the contrast of the image of a stacking fault in a thick
absorbing crystal. (b) The dark-field and bright field intensity profiles
generated under the conditions of (a).
424 EXTENDED DEFECTS CH. 18
wave ~(2), giving ~21 and ~22 which interfere with almost
equal amplitude at the exit face to give strong fringes in
bright field and dark field, as for a thin wedge-shaped
crystal.
For the fault in the middle of the crystal, the Bloch
wave ~(2) is strongest at the fault and gives ~21 and ~22, but
in the second half of the crystal ~21 is more strongly atten-
uated. Then the image is given by the interference of ~22 with
a much weaker ~21 and the fringes have very low contrast.
For the fault at the top of the crystal all four waves
~II, ~12, ~21 and ~22 are generated at the fault but ~Ii and
~21 are more strongly attenuated so that the image is given
by interference of equally strong ~12 and ~22, giving strong
fringes. However, it can be seen from (16) that for this case
the phase of the diffracted wave component relative to the
incident wave component of the Bloch wave is opposite for ~12
and ~22 whereas the phases are the same for ~21 and ~22 which
were important for the fault at the b o t t o m of the crystal.
Hence for the dark field image, the fringes are out of phase
with the b r i g h t - f i e l d fringes for the fault at the b o t t o m but
in phase for the fault at the top, as suggested by Fig.
18.3(b). The top and b o t t o m of the foil may thereby be
distinguished.
For deviations from the Bragg angle the difference
between k (I) and k (2) increases and the initial amplitudes of
the Bloch waves cease to be equal. The fringes therefore
become weaker and more closely spaced.
Deviations from the ideal two beam conditions add more
Bloch waves and render the fringe pattern more complicated.
Interpretation then depends on complete n-beam calculations.
18.4. Dislocations
b[(i, sin2(I,]
R1 = ~ +4(1-v--"--"S
19 .i. Introduction
(700)
Zero
Laue
zone
-- _-__~,
Shadow
edge
(000)
Fig. 19.5. Reciprocal space diagram showing the intersection of the Ewald
sphere with lines perpendicular to a crystal surface through reciprocal
lattice points to produce the spots in a RHEED pattern.
Fig. 19.6. Reflection electron microscopy (REM) image of the Iii surface
of a Pt crystal showing steps on the surface, one atom high. The thin
horizontal ellipses are foreshortened images of circular, atom-high,
hollows or protrusions. A black-white pair of streaks (bottom left)
indicates a dislocation which travelled across the crystal leaving a
slip-trace step. (courtesy of T. Hsu).
10
Ii Slices
Masking
function
Fig. 19.7. Scheme for calculating RHEED and REM intensities using a
multi-slice formulation and the assumption of a large artificial
periodicity perpendicular to the crystal face.
h,k lines
,i II
',," I-. l I/
I-0
I I I
Fig. 19.8. Reciprocal space diagram for the production of LEED spots by
intersection of the Ewald sphere with h,k lines, shown for two different
wavelengths.
452 D I F F R A C T I O N FROM SURFACES CH. 19
Screen
9 I Go~niome~Tt
r e
Window
" ~ I Grids
Fig. 19.9. Diagram of a LEED system. The electron beam from the gun is
back-scattered by the crystal. Diffracted beams are energy-filtered and
accelerated by concentric screens to a fluorescent screen which is
photographed through a window.
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INDEX
Uncertainty Principle, 9