Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.

43 177

Characterization of Surfaces and Thin Films

Using a High Performance Grazing Incidence X-ray Diffractometer

Shin-Ya Matsuno, Masayuki Kuba, Yoshitaka Moriyasu, Takashi Morishita

Analytical and Computational Science Laboratories, Asahi Chemical Industry Co.,
LTD.,
2-1, Samejima, Fuji, Shizuoka, 416-8501, Japan
and
Kazuhiko Omote
X-ray Laboratories, RIGAKU Co., LTD.,
3-9-12, Matsubara-cho, Akishima, Tokyo, 196-8666, Japan

Abstract
A newly developed grazing-incidence X-ray diffractometer system was used for the
characterization of surfaces and thin films. The system uses a high-intensity rotating anode
X-ray generator, a parabolic graded multilayer mirror, and an asymmetric-cut Ge(220)
channel monochrometer to generate an intense, parallel and monochromatic incident Cu K
(;\! X-ray beam for grazing-incidence X-ray analysis. A reflectivity analysis of ultra thin
SiOa films on Si substrates and a grazing-incidence diffraction analysis of a polycrystalline
Ti film deposited on Si and epitaxial Si films grown on sapphire substrates have been
successfully obtained.

Introduction
Grazing-incidence X-ray techniques have been used extensively for the characterization
of surfaces and thin films (l)y (2). Grazing-incidence X-ray reflectivity technique is used for
determining the values of layer thickness, density and roughness of thin films, while grazing
incidence X-ray diffraction techniques are used for analysis of in-plane and out-of-plane
thin-film structures. Ultra thin-film experiments can best be done using a, high-intensity
synchrotron radiation source (3)1 (4). It is , however, inconvenient and difficult to use
synchrotron radiation in most development and manufacturing environments.
In this paper, we report the use of a newly developed grazing-incidence X-ray
diffractometer system with a high-intensity laboratory X-ray source for the analysis of
surfaces and thin films. Results on the characterization of Ultra thin Si02 films on Si
substrates, a polycrystalline Ti film deposited on Si and epitaxial Si films grown on
sapphire substrates are also given.

Grazing-Incidence X-Ray Diffraction System

A high-performance grazing-incidence X-ray diffractometer system has recently been
developed for characterization of thin films. As shown in Fig. 1, the system consists of an
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Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.43 178

18-kW rotating anode X-ray generator, a graded parabolic multilayer mirror a Ge(220)
asymmetric channel-cut monochrometer, a specially designed four-axis goniometer, etc.@‘.

Graded Parabolic Cu ved

Multi-layer Mirror
Goniometer : W, 2 8
4329 ,y
Fig. 1 Schematic illustration of the grazing-incidence X-ray diffractometer system

Divergent incidence Cu K X-rays from the rotating anode X-ray generator are first
collimated and monochromatized by the graded multilayer mirror to a broad Cu K (1: X-ray
beam with 0.045” divergence ( see Fig. 2a ). The Cu K a! X-ray beam is further collimated
to a narrow and parallel X-ray beam of 0.015” divergence by the asymmetric-cut Ge(220)
channel-cut monochrometer ( Fig. 2b ).

- Si(O04) eQa
-2 FWHM=O.O42deg Z’ 8, FWHM=O.O15deg
0
% 0 00
E 00 00
3 _ 0
E 8 00
i P - 0e”
A
*i
I * I. I. I. t. I. I. I. I, u. I. I. I
34.75 34.80 34.85 34.90 34.95 35.00 35.05 35.10 34.28 34.30 34.32 34.34 34.38 34.38 34.40

Omega(deg) Omega(deg)

(a) (b)

Fig. 2 X-ray rocking curves of Si(O04) obtained with : (a) a parabolic graded multilayers,
and (b) a parabolic multilayers and asymmetric-cut Ge(220) channel monochrometer

The four-axis goniometer has two conventional o /2 0 axes and two in-plane $ /2 8 x
axes. As shown in Fig. 3, the + /2 8 x axes are mounted horizontally ‘on the vertical co axis.
The o /2 0 axes are used for measurements of out-of-plane diffraction, and the $I /2 8 x
axes for in-plane diffraction. A switch between in-plane and out-of-plane measurements can
Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.43 179

be done rapidly.
The specimen stage has two rotation axes, Rx and Ry, for tilting the specimen surface so
that the surface normal is properly aligned parallel to the @ axis and centered at the
intersection of the rj and the o axes.

Fig. 3 Schematic illustration of four-axis goniometer

Results and Discussion

GIXR Analvsis of Ultra Thin SiO? Films on Si Wafers
Two SiOz films grown by the-thermal oxidation process on Si wafers were used in this
study. Specimen 1 was grown under pure 02, and Specimen 2 under N2/02 ( see Fig. 4 ).

Heating Formation of Si02

Isisubstrate/eSiLlbstratp/epi

Fig. 4 Preparation procedure for an ultra thin SiO2 film thermally grown on a Si substrate
I
lcp
10'
2 - SpecimenV flow)
-2
a:: d
:z I@ x-
.=
3 10’
5 iv f .
w 10' s _
lad
10'
IO' 0 5 10 15 20
2 4 6 6 IO
ZTheata(deg) Thickness (nm>

(4 @I

Fig. 5 (a) X-ray specular reflectivity curves for Specimen 1 and 2, and. 1 :
(b) Fourier transform of the reflectivity curves for Specimen 1
Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.43 180

The GIXR technique was used to determine the layer thickness, surface and interface
roughness of the films. The experimental reflectivity curves for Specimen 1 and 2 are
plotted in Fig. 5a. The interface fringes were weak because of a small difference between
the electron densities for SiO2 and Si. Reflectivity intensities, varied over eight orders of
magnitude, were collected so that a reliable analysis of the reflectivity data could be
obtained. A Fourier transform analysis of both reflectivity curves shows that each strong
peak at thickness of 6.5nm ( see Fig. 5b for Specimen 1 ).
The experimental reflectivity curves were also analyzed by fitting with calculated
reflectivity curves derived from Parratt’s recursive formula modified with the distorted
wave Born approximation (DWBA) (6),(7). The Marquardt method was used in this study to
match the calculated with the experimental reflectivity data. The fitting results for
Specimen 1 are shown in Fig. 6, and the analysis results on layer thickness and roughness
for both specimens for both specimens are given in Table 1.

I 6 I
2 4 6 a

PTheta(deg)

Fig. 6 Experimental reflectivity data ( open circles ) and fitted curves ( solid line ) for
Specimen 1

Table 1. Sample Preparation Conditions and Their Analyzed Results

Specimen 1 Specimen 2
Atmosphere N2/02-flow
Temperature(°C) 1000
Time(min) 8 10
Si02 thicknesdnm) 6.5 6.5
Sutface roughness(nm) 0.36
InterFace roughnesdnm) 0.1

As shown in Table 1, both Specimens 1 and 2 have the same SiOz layer thickness of
6.5nm, in good agreement with the results obtained by the Fourier transform method.
Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.43 181

Values of the SiO2 surface roughness for the both specimens were approximately the same
and within 0.04nm. The interface roughness between the SiO2 layers and the Si substrate for
the two specimens are, however, significantly different from each other with O.lnm for
specimen 1 and 0.25nm for specimen 2. The results indicate that the buried interface
between the SiO2 layer and its Si substrate were significantly smoother for the layer
thermally grown under NJ02 than under 02.

In-Plane XRD Measurements of TiSil Films on Si Wafer

The film used in this study was prepared by the procedure shown in Fig. 7. A thin film
was first deposited from a Ti target onto a Si substrate. The film was subsequently annealed
at 650°C for lminute under nitrogen atmosphere.
Reaction of Si and Ti
(Thickness: about 75nm)

Atmosphere: N2
65O”C, lmin
Si Substrate
rL -
Fig. 7 Preparation procedure for a Ti film deposited on a Si substrate

A conventional X-ray diffraction pattern for the film obtained by a o /2 8 (or 6 /2 8 )

scan is shown in Fig. 8a. A strong and sharp TiSi2( 150) diffraction peak together with two
relatively weaker and broad TiN(111) and TiN(200) peaks were observed. No Ti diffraction
peaks were detected. This indicates that the Ti film was reacted with the Si substrate during
high-temperature annealing process and transformed into TiSi2, and that the Ti film reacted
also with the nitrogen gas to form a thin TiN layer.
The in-plane diffraction technique was used to positively identify the surface and the
interface layers. In-plane diffraction patterns obtained with incident angles ( u ) fixed at
0.20, 0.25 and 0.30 are plotted in Fig. 8b. For the pattern obtained at o =0.20” s, only two
TiN peaks, TiN(111) and TiN(200), were detected. At co=0.20” , the l/e penetration depth
for a Cu K a! X-ray beam was calculated to be 4nm. At larger incident angles, the X-ray
beam penetrates deeper into the film. TiSi2 C49(060) and C49( 13 1) peaks began to appear
when o increased to 0.25 and 0.30” (see Fig. 8b).
It can be concluded from the X-ray diffraction results that the Ti film transformed into
two layers: a TiN layer with an estimated surface thickness of about 1Onm at the surface,
and a TiSi2 layer at the interface between the film and the Si substrate (see Fig. 9).

r
Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.43 182

I I_
C49(131

Ilyizd;;;e .A
d

r STheta(deg)
I: 35 40
1
45

2 e,y@g)
(a) XRD Pattern (b) In-plane XRD Patterns
Fig. 8 XRD patterns for Ti on Si: (a) Conventional o /2 8 scan, and (b) in-plane 4 /2 8 x
scan
TiN (About 1Onn-1)
J

TiSi2
Fig. 9 Schematic Illustration of the layer structure for TiN and TiSi2 on Si

In-Plane X-ray Rocking Curve Measurements of Si Films on Sannhire Substrates

The procedure for growing epitaxial Si films on Sapphire substrate (SOS) is shown in
Fig. 10. Two SOS films were used in this study: Film A was prepared with and Film B
without substrate cooling during Si ion implantation (see Fig. 10).

Si Ion Imnlantation
increasing cystallinity Solid Phase Epitaxy (SPE) by Heating

‘I Sapphire Sub. 1 1 Sapphire Sub. )

As-grown-SOS (a) Cooling Substrate, ( b) Not cooling SPE-SOS

Fig. 10 Preparation procedure for a Si film epitaxially grown on a sapphire substrate

In-plane X-ray rocking curve (XRC) measurements were done by rotating the specimen
about the $I axis, while keeping the detector at a fixed angle 2 8 x to record the Si(O40)
peak. The in-plane XRC obtained with an incident angle o =0.25” is plotted in Fig. 11. It
shows that the full width at half maximum (FWHM) for Film A is narrow thanthat for Film
B. This indicates that the epitaxial Si film obtained with substrate cooling had a smaller in-
plane Si(O40) axis dispersion and better crystallinity than the film without substrate cooling.
Similar results with smaller FWHMs for Film A and larger FWHMs for Film B were also
Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.43 183

obtained at co=0.15, 0.20, 0.25, 0.30 and 0.35” (see Fig. 12). Values of FWHM are found
to be more uniform for Film A than for Film B.
0.28 - n
n
n
= 0.27 -
;:
v w
(I) 0.26 -

i 0; 1 (b; Not cooling

024: (a) Cooli+ngSubstrate . l

0.23 - . a
I L t 11 " " "1
0.25 0 0.25 0.15 0.20 0.25 0.30 0.35
Incident Angie
A Phi(deg) 4nm 1Onm 1OOm *
X-ray Penetration Depth

Fig. 11 In-plane XRC of Si(O40) at o =0.25deg Fig. 12 FWHM of Si(O40) profiles

The penetration depth of the X-ray beam changes from a few nm to a few hundred nm as
one changes o. We therefore made clear the difference between the SOS samples. The
crystallinity of one Si thin film (Not cooled) changes from surface to substrate, and
crystallinity of the other Si thin film (Cooled substrate) is uniform from surface to substrate.
In this way, In-plane XRC using a changing incident angle can clarify the depth profiles of
crystallinity on a nm scale.

Conclusions
A high-intensity grazing-incidence X-ray diffractometer system was developed for the
characterization of surfaces and thin films. Reflectivity measurements were done on two
ultra thin films thermally grown on Si substrates with one under pure 02 and the other under
N2/02. Results showed that both films had essentially the same thickness and surface
roughness, but different SiO#i interface roughness. Diffraction patterns obtained with a
conventional co/
2 19scan and in-plane 4 /2 8 x scans for a polycrystalline Ti films deposited on a Si
substrate revealed the Ti film transformed into a TiN surface layer and a TiSi2 interface ’
layer after annealing at 650°C for lminute under nitrogen atmosphere. The grazing-
incidence in-plane rocking curve measurements were used to analyze two epitaxial Si films
grown on sapphire substrates. Results showed that the film prepared with substrate cooling
during the Si ion-implantation process had smaller in-plane Si(O40)-axis dispersions, better
crystallinity and was more uniform throughout the depth of the film than the film without
substrate cooling.

Acknowledgments .
The ,authors are grateful to Mr. S. Ibe, Dr. K. Neki, Mr. T. Konishi, Mr. T. Yamada, Mr. I’
A. Yasujima, and all members of Analytical and Computational Science..Laboratories for
Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.43 184

their fruitful discussions and continuous encouragement. One of the authors (S. -Y. M.)
would like to thank Dr. T. C. Huang for reading the manuscript.

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