1

X-ray Scattering from Thin Films

Experimental methods for thin films analysis using X-ray
scattering
Conventional XRD diffraction
Glancing angle X-ray diffraction
X-ray reflectivity measurement
Grazing incidence X-ray diffraction
X-ray diffraction study of real structure of thin films
Phase analysis
Residual stress analysis
Crystallite size and strain determination
Study of the preferred orientation
Study of the crystal anisotropy
2

Conventional X-ray diffraction
+ Reliable information on
the preferred orientation of crystallites
the crystallite size and lattice strain (in one direction)
No information on the residual stress (constant direction
of the diffraction vector)
Low scattering from the layer (large penetration depth)
Diffracting crystallites
3

Glancing angle X-ray diffraction
GAXRD
0 20 40 60 80 100 120 140
10
-2
10
-1
10
0
o=2O/2
o=20
o
o=10
o
o=5
o
o=2
o
o=1
o


P
e
n
e
t
r
a
t
i
o
n

d
e
p
t
h

(

m
)
Diffraction angle (
o
2O)
Gold, CuKo,
~ 4000 cm
-1
( )
o i
o i
e
x
e
I
dz
dI
t
u u
u u
sin sin
sin sin
;
1
:
0
+

= =
Symmetrical mode
GAXRD
4

Other diffraction techniques used in
the thin film analysis
Conventional diffraction
with O-scanning
q
y
=0
Grazing incidence X-ray
diffraction (GIXRD)
q
z
~0
Conventional diffraction
with X-scanning
q
x
=0
5

Penetration depth of X-rays
L.G. Parratt, Surface Studies of Solids by Total Reflection of X-rays, Physical Review
95 (1954) 359-369.
Example: Gold (CuKo)
o = 4.2558 10
-5

| = 4.5875 10
-6

( )
1 1
2
1
2
1
2
1 1
0
2
2
s + ~
' ' ' + ~
= + ~ + =
| o

t
_
_
i n
f i f f
r
n
r
n
e
e
e
0.0 0.5 1.0 1.5 2.0 2.5 3.0
10
-3
10
-2
10
-1
10
0
R
e
f
l
e
c
t
i
v
i
t
y
0.0 0.5 1.0 1.5 2.0 2.5 3.0
10
-4
10
-3
10
-2
10
-1
TER

P
e
n
e
t
r
a
t
i
o
n

d
e
p
t
h

(

m
)
Glancing angle (
o
2O)
t

u
u

u u u
2 2 2
;
2
1
2
1
cos ; cos cos
e
c
c e
c j j j V
r r
n n n
~ ~
= =
6

X-ray reflectivity measurement
0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0
10
0
10
1
10
2
10
3
10
4
10
5
10
6
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Diffraction angle (
o
2u)
Si
Mo
Mo
Mo
t [] o []
0.68 19.6 5.8


0.93 236.5 34.0

1.09 14.1 2.7
1.00 5.0 2.7
1.00 2.8
Calculation of the electron density, thickness and interface roughness for
each particular layer
W
The surface must be smooth
(mirror-like)
Edge of TER
Kiessig oscillations (fringes)
7

Experimental set-up
Scintillation
detector
Flat monochromator
Sample
Goebel mirror
X-ray source
Sample
rotation, |
Normal direction
Diffraction vector
Diffraction
angle, 2u
Angle of
incidence,
Sample
inclination,
Used for XRR,
SAXS, GAXRD and
symmetrical XRD
Information on the
microstructure of thin films
Phase analysis
Residual stress analysis
Crystallite size and
strain determination
Study of the preferred
orientation
Study of the anisotropy
in the lattice deformation
Investigation of the
depth gradients of
microstructure
parameters
9

Uranium nitride phase analysis
20 40 60 80 100 120 140
0
200
400
600
800 GAXRD with = 3
o
Radiation: Cu Ko


I
n
t
e
n
s
i
t
y

(
c
p
s
)
Diffraction angle (
o
2u)
20 30 40 50 60 70
10
1
10
2
10
3
2
2
2
,

U
N 3
1
1
,

U
N
6
2
2
,

U
2
N
3
2
2
0
,

U
N
4
4
0
,

U
2
N
3
S
u
b
s
t
r
a
t
e
2
0
0
,

U
N
1
1
1
,

U
N
4
0
0
,

U
2
N
3
2
2
2
,

U
2
N
3


I
n
t
e
n
s
i
t
y

(
c
p
s
)
Diffraction angle (
o
2u)
Phase composition
1. UN, 80-90 mol.%
Fm3m, a = 4.8897
2. U
2
N
3
, 10-20% mol.%
Ia3, a = 10.64 10.68
Sample deposition
PVD in reactive atmosphere N
2

Heated quartz substrate (300C)
0 Atomic Percent Nitrogen 50 60 67
800

T(C)

400
U UN
U
2
N
3

U
N
2

Schematic phase diagram
10

U
2
N
3
versus UN
2
U
N
U
2
N
3
(Ia3), a = 10.66
U: 8b (, , )
U: 24d (-0.018, 0, )
N: 48e (0.38, 1/6, 0.398)
UN
2
(Fm3m)
a = 5.31
U: 4a (0, 0, 0)
N: 8c (, , )
Cannot be
distinguished
in thin films
11

Uranium nitride residual stress
analysis
0.0 0.2 0.4 0.6 0.8
4.91
4.92
4.93
4.94
4.95
1
1
1
2
0
0
2
2
0
3
1
1
2
2
2
4
0
0
3
3
1
4
2
0
4
2
2
5
1
1
4
4
0
5
3
1
4
4
2


L
a
t
t
i
c
e

p
a
t
a
m
e
t
e
r

(

)
sin
2

UN
a
0
= (4.926 0.015)
Compressive residual stress
o = (1.8 0.8) GPa
Strong anisotropy of lattice
deformation
U
2
N
3
a
0
= (10.636 0.002)
Compressive residual stress
o = (6.2 0.1) GPa
No anisotropy of lattice
deformation
GAXRD
at =3
0.00 0.04 0.08 0.12 0.16 0.20
10.74
10.76
10.78
10.80
10.82
2
2
2
4
0
0
4
4
0
6
2
2


L
a
t
t
i
c
e

p
a
r
a
m
e
t
e
r

(
1
0
-
1
0
m
)
sin
2
+
12

Uranium nitride anisotropic lattice
deformation
(111)
( )
}
+
A
= A
t
| | |
| |
t
2
0
2
) cos cos sin sin (sin 1
) (
2
) ( d g p
hk

0.0 0.2 0.4 0.6 0.8

4.91
4.92
4.93
4.94
4.95
1
1
1
2
0
0
2
2
0
3
1
1
2
2
2
4
0
0
3
3
1
4
2
0
4
2
2
5
1
1
4
4
0
5
3
1
4
4
2


L
a
t
t
i
c
e

p
a
t
a
m
e
t
e
r

(

)
sin
2

0.00 0.05 0.10 0.15 0.20

10.74
10.76
10.78
10.80
10.82


easy
hard
0.0 0.2 0.4 0.6 0.8
4.91
4.92
4.93
4.94
4.95
1
1
1
2
0
0
2
2
0
3
1
1
2
2
2
4
0
0
3
3
1
4
2
0
4
2
2
5
1
1
4
4
0
5
3
1
4
4
2
Measured
Calculated


L
a
t
t
i
c
e

p
a
t
a
m
e
t
e
r

(

)
sin
2

UN
a
0
= (4.9270 0.0015)
o = (1.0 0.1) GPa
directions
13

UN anisotropic lattice deformation
0.0 0.1 0.2 0.3 0.4 0.5
-1
0
1
2
3
4
5
422
511


R
e
l
a
t
i
v
e

d
e
f
o
r
m
a
t
i
o
n

(
1
0
-
3
)
sin
2
+
0.0 0.2 0.4 0.6 0.8 1.0
0.84
0.88
0.92
0.96
1.00
1.04
1.08
1
1
1
,

2
2
2
,

3
3
3
2
0
0
,

4
0
0
,

6
0
0
2
2
0
,

4
4
0
,

4
2
2
3
1
1
,

4
2
0
3
3
1
4
4
2
5
3
1
5
1
1

2
c
3
/
c
1

=

2
v
/
(
v

1
)
3I = 3(h
2
k
2
+k
2
l
2
+l
2
h
2
) / (h
2
+k
2
+l
2
)
2
0.0 0.2 0.4 0.6 0.8
-4
-2
0
2
4
6
440
531
442


R
e
l
a
t
i
v
e

d
e
f
o
r
m
a
t
i
o
n

(
1
0
-
3
)
sin
2
+
Dependence of the lattice
deformation on the
crystallographic direction
R.W. Vook and F. Witt, J.
Appl. Phys., 36 (1965) 2169.
Related to the anisotropy of the
elastic constants
14

UN versus U
2
N
3
U
N
UN (Fm3m)
a = 4.93
U: 4a (0, 0, 0)
N: 4b (, , )
Anisotropy of the
mechanical properties is
related to the crystal
structure
U
2
N
3
(Ia3), a = 10.66
U: 8b (, , )
U: 24d (-0.018, 0, )
N: 48e (0.38, 1/6, 0.398)
15

Methods for the size-strain
analysis using XRD
Crystallite size
Fourier transformation of finite
objects (with limited size)
Constant line broadening (with
increasing diffraction vector)
Lattice strain
Local changes in the d-spacing
Line broadening increases with
increasing q (a result of the Bragg
equation in the differential form)
Scherrer Williamson-Hall Warren-Averbach Krivoglaz
P. Klimanek (Freiberg) R. Kuzel (Prague) P. Scardi (Trento) T. Ungar (Budapest)
(000) (100)
(001)
(011)
(111)
(110)
(000) (100)
(001)
(011)
(111)
(110)
16

UN anisotropic line broadening
0.0 0.2 0.4 0.6 0.8 1.0
0
10
20
30
40
1
1
1
2
0
0
2
2
0







3
1
1
2
2
2
4
0
0
3
3
1






4
2
0
4
2
2
5
1
1
/
3
3
3
4
4
0
5
3
1






6
0
0
/
4
4
2
(D) = 40 nm
(e) = 11x10
-3


L
i
n
e

b
r
o
a
d
e
n
i
n
g

(
1
0
-
3

-
1
)
sin O
The Williamson-Hall plot
It recognises the anisotropy of the
line broadening
It is robust (weak intensity, overlap
of diffraction lines)
It is convenient if the higher-order
lines are not available
(nanocrystalline thin films, very
thin films, GAXRD)
(100)
(111)
17

UN texture measurement
Preferred orientation {110}
-3 -2 -1 0 1
q (1/)
2
3
4
5
q



(
1
/

)
z
x
111
200
220
311
222
400
111 200
220 311 222
-30 -20 -10 0 10 20 30
0
10
20
30
40
50


(220)
(311)
I
n
t
e
g
r
a
l

i
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Sample inclination (deg)
( ) ( )
0
sin sin
2
; cos cos
2
=
+ = =
y
i o z i o x
q
q q u u

t
u u

t
Reciprocal space mapping
18

Reciprocal space mapping
Measured using
CuKo radiation
-8 -7 -6 -5 -4 -3 -2 -1 0 1
0
1
2
3
4
5
6
7
8
9
1 1 1
-1 1 1
2 0 0
2 2 0
-2 2 0
3 1 1
3 -1 1
3 -1 -1
2 2 2
-2 2 2
4 0 0
3 3 1
-3 3 1
3 3 -1
4 2 0
4 -2 0
4 2 2
4 -2 2
4 -2 -2
3 3 3
5 1 1
5 -1 1
5 -1 -1
q
x
[1/A]
q
z

[
1
/
A
]

{111}
-7 -6 -5 -4 -3 -2 -1 0 1
q(x), 1/A
2
3
4
5
6
7
8
q
(
z
)
,

1
/
A
111
222
220
311
4-22
33-1
420
331
422
A highly textured gold layer
19

Epitaxial growth of SrTiO
3
on Al
2
O
3
O in SrTiO
3
a
b
c
PowderCel l 1. 0
a
b c
PowderCel l 1. 0
Sr
Al
Ti
O in Al
2
O
3
q(x)
q
(
y
)
100
200
300
400
500
600
700
800
900
211
211
112
112
121
121
018
_
118
_
108
Reciprocal space map Atomic ordering in direct
space
SrTiO
3
: Fm3m (111) axis -3 (001) Al
2
O
3
: R-3c
20

SrTiO
3
on Al
2
O
3
Atomic Force Microscopy
Pyramidal crystallites with two
different in-plane orientations
AFM micrograph courtesy of Dr. J. Lindner,
Aixtron AG, Aachen.
(111) (111)
_
(110)
_
(110)
21

TiCN
Depth resolved X-ray diffraction
122 123 124 125 126 127 128 129
30
45
60
75
90
= 10
o
= 8
o
= 6
o
= 4
o
= 2
o
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Diffraction angle (
o
2O)
TiN
TiC
TiN
WC
( )
}
}
|
|
.
|

\
|

|
|
.
|

\
|

=
t
t
dz z
dz z z p
p
0
0
sin sin
sin sin
exp
sin sin
sin sin
exp
| o
| o

| o
| o

Absorption of radiation
TiC TiN
22

Surface modification of thin films
1 10
-4
-3
-2
-1
0
250 nm
CVD TiN, Mo-implanted
35keV, 10
17
cm
-1
R
e
s
i
d
u
a
l

s
t
r
e
s
s

(
G
P
a
)
Angle of incidence (deg)
1 10
-4
-3
-2
-1
0
270 nm
CVD TiN, W-implanted
35keV, 10
17
cm
-1
R
e
s
i
d
u
a
l

s
t
r
e
s
s

(
G
P
a
)
Angle of incidence (deg)
1 10
-4
-3
-2
-1
0
1000 nm
CVD TiN, Al-implanted
70keV, 10
17
cm
-1
R
e
s
i
d
u
a
l

s
t
r
e
s
s

(
G
P
a
)
Angle of incidence (deg)
1 10
-4
-3
-2
-1
0
265 nm
CVD TiN, Y-implanted
35keV, 10
17
cm
-1
R
e
s
i
d
u
a
l

s
t
r
e
s
s

(
G
P
a
)
Angle of incidence (deg)
1 10
-4
-3
-2
-1
0
1170 nm
CVD TiN, Cr-implanted
70keV, 10
17
cm
-1
R
e
s
i
d
u
a
l

s
t
r
e
s
s

(
G
P
a
)
Angle of incidence (deg)
Gradient of the residual
stress in thin TiN coatings
(CVD) implanted by metal
ions: Y, Mo, W, Al and Cr
23

Functionally graded materials
W. Lengauer and K. Dreyer, J. Alloys Comp. 338 (2002) 194
SEM micrograph courtesy of C. Kral, Vienna University of Technology, Austria
Nitrogen in-diffusion
from N
2

N-rich zone of (Ti,W)(C,N)
Ti(C,N)

N-poor zone of (Ti,W)(C,N)
(Ti,W)C
24

Study of concentration profiles
26.0 26.5 27.0 27.5 28.0
0
10
20
30


Diffraction angle (
o
2u)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
0 2 4 6 8
4.30
4.28
4.26
4.24
~TiC
0.75
N
0.25
TiN
Depth (m)


a

(

)
122 124 126 128 130
0
5
10
15
20


I
n
t
e
n
s
i
t
y

(
c
p
s
)
Diffraction angle
o
2u
0.0 0.5 1.0 1.5
4.27
4.26
4.25
4.24
~TiC
0.3
N
0.7
TiN


Depth (m)
a

(

)
Copper radiation
Penetration depth: 1.8 m
Molybdenum radiation
Penetration depth: 12.5 m
The lattice parameter must depend on concentration
25

Summary
Benefits of X-ray scattering
... for investigation of the real structure of thin films
Length scale between 10
-2
and 10
3
is accessible
(from atomic resolution to the layer thickness)
Small and variable penetration depth of X-ray into
the solids (surface diffraction, study of the depth
gradients)
Easy preparation of samples, non-destructive testing
Integral measurement (over the whole irradiated
area)