J. Ain. Ceramin.
Soc., 86 [1] 149-51 (2003)
journal
Two-Layer Crystallization of Amorphous YMnO 3 Thin Films on
Si (100) Substrates
Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology,
Semiconductor Materials Laboratory, Korea Institute of Science and Technology, Seoul 136-791. Korea
During a rapid thermal annealing process at 850°C in a N2
ambient, an as-deposited amorphous YMInO3 thin film on Si
(100) substrates was crystallized with two distinct layers.
High-resolution transmission electron microscopy showed a
top layer of c-axis-oriented YMnO3 and a bottom layer of
polycrystalline YMnO_ in the 100-nm-thick YMnO3 thin film.
The abrupt change of the crystalline orientation from the
c-axis-preferred orientation to the random orientation is
caused primarily by high stress induced by the c-axis-oriented
YMnOQ, layer. High-resolution X-ray diffraction showed that
the c-axis-oriented YMnO 3 /polycrystaliine YMnO3 structure
effectively relieved the stress.
I. Introduction
R EcENTLY, ferroelectric thin films have attracted much attention
Rfor use in nondestructive read out (NDRO) ferroelectric
random access memories (FRAM).1- 4 In metal-ferroelectric-
semiconductor field effect transistor (MFSFET) for FRAM, a high
dielectric constant in ferroelectric materials decreases an applied
voltage in ferroelectric materials, whereas an applied voltage in a
low dielectric interfacial layer is increased. This causes device
degradations such as charge injection and a high leakage current.
To resolve these problems, ferroelectric materials with a low
dielectric constant and new buffer layers at the ferroelectric/Si
interface have been extensively investigated. 5 6
Among the ferroelectric thin films, YMnO 3 has been proposed
as a promising ferroelectric material for metal-ferroelectric-
semiconductor (MFS) structures.7'-' 0 The YMnO3 has a hexagonal
structure and a unipolarization direction along [0001]. The YMnO3
thin film has low dielectric permittivity (e = 30 at RT), which is
a great advantage for a device directly on silicon.' So far,
considerable effort has been focused on the electrical properties,
such as memory window and leakage current.'-" However,
although the crystallization behavior and the crystallized atomic
structure of the YMnO 3 thin films are important to evaluate and to
improve the electrical properties of, they have not been sufficiently
studied. Moreover, there are no studies concerning a relationship
between stress and crystallization in the YMnO_ thin films. In this
study, the atomic structure of the YMnO_ thin films has been
characterized with high-resolution transmission electron micros-
copy (HRTEM), and the stress in the YMnO3 thin films has been
H. U. Anderson-contributing editor
Manuscript No. 187305. Received November26, 2001; approved August 23,2002.
This study was supported by the Ministry of Science and Technology through a
Project for National Research Laboratory in Korea and a Collaborative Project for
Excellence in Basic System IC Technology (SYSTEM IC 2010).
149
Dong Chul Yoo and Jeong Yong Lee
Daejeon 305-701, Korea
Ik Soo Kim and Yong Tae Kim
evaluated using high-resolution X-ray diffraction (HRXRD). The
relationship between stress and crystallization in the YMnO 3 thin
films is discussed.
H. Experimental Procedures
YMnO 3 thin films were deposited on p-Si (100) substrates with
radio frequency (rf) sputtering at room temperature using a
YMnO_ single target (purity 99.9%) made by mixing Y2 03 and
Mn2 03 powders at a ratio of 1:1. During the deposition in Ar + 02
ambient, the rf-power density and chamber pressure were fixed at
1.85 W/cm2 and 5 X l0-3 torr, respectively. The as-deposited
100-nm-thick YMnO_ films were crystallized by rapid thermal
processing (RTP) in N2 atmosphere at 850°C for 3 min. The
microstructure of the YMnO 3 thin films was characterized by
HRTEM (Model JEM-2000EX, JEOL, Tokyo, Japan) operating at
200 kV. To examine a stress in the YMnO3 /Si, Si (004) rocking
curves were measured using HRXRD (Model RINT2000, Rigaku
Co., Tokyo, Japan).
mH. Results and Discussion
Figure I shows a cross-sectional dark-field (DF) TEM micro-
graph of the YMnO 3 /Si, which was observed using a YMnO3
(0004) diffracted spot. This figure shows that the 100-nm-thick
YMnO3 thin film is composed of two distinct layers: a top layer of
a c-axis-oriented YMnO 3 -40 nm thick, which looks bright in the
(0004) DF image, and a bottom polycrystalline YMnO3 layer -60
nm thick. Figure 1 demonstrates that the YMnO3 thin film has
been crystallized with the two layers, which have different
crystallographic orientations.
Figure 2 shows an HRTEM micrograph of an interface between
the c-axis-oriented YMnO3 layer and the polycrystalline YMnO 3
layer. In Fig. 2, the top region shows YMnO, {0002} lattice
images with a distance of 0.57 nm. However, the bottom region
does not show YMnO 3 {000h} lattice images. The YMnO3 {12121
plane in the polycrystalline layer is parallel to a {00021 plane in
the c-axis-oriented layer. This abrupt change of the crystalline
orientation in the YMnO 3 thin film during an RTP annealing is
expected to relate to a composition difference or a stress effect
between the two layers in the YMnO 3 thin film. To examine the
composition difference between the two layers, energy-dispersive
spectroscopy and auger electron spectroscopy have been used.
However, no composition difference between the two layers was
detected. Accordingly, it is expected that this two-layer crystalli-
zation in the YMnO 3 thin film is caused primarily by the stress
effect.
To investigate the stress effect on crystallization of the YMnO 3
thin films on silicon, we prepared three YMnO 3 thin films on a Si
substrate, i.e., as-deposited amorphous YMnO3 , c-axis/amorphous
YMnO3 , and c-axis/polycrystalline YMnO 3 thin films. The c-axis/
150 Journalof the American Ceramic Sociery-Yoo and Lee
Fig. 1. Dark-field TEM micrograph observed using the YMnO3 (0004)
diffracted spot showing the two distinct layers in the YMnO 3 thin film on
Si substrate.
Fig. 2. High-resolution TEM micrograph showing the interfacial micro-
structure between the c-axis-oriented YMnO 3 layer and the polycrystalline
YMnO3 layer.
amorphous YMnO 3 thin film is made by a rapid annealing process
at 850°C for -30 s. The stress of polycrystalline thin films on a
single-crystal substrate can be evaluated by HRXRD using a
rocking curve of the substrate.' 2 Therefore, Si (004) rocking
curves were measured using HRXRD to investigate the stress of
the three YMnO 3 thin films. Figure 3 shows Si (004) rocking
curves taken from the as-deposited amorphous YMnO3 sample. the
c-axis/amorphous YMnO 3 sample, and the c-axis/polycrystalline
YMnO 3 sample. The full width at half maximums (FWHMs) of the
rocking curve from the as-deposited amorphous YMnO3 sample,
the c-axis/amorphous YMnO 3 sample, and the c-axis/polycrystal-
line YMnO3 sample were 17.24, 38.64, and 17.33 arcsec, respec-
tively. The FWHM of the c-axis/amorphous YMnO 3 sample was
considerably broader; however, the FWHM of the c-axis/polycrys-
talline YMnO3 sample was nearly the same as that of the
as-deposited sample. This result implies that the c-axis-oriented
YMnO 3 layer induces a high stress, and the c-axis/polycrystalline
YMnO 3 structure effectively reduces the stress. In our previous
work,' 3 stress was more effectively relieved in polycrystalline
YMnO 3 thin films than c-axis-oriented YMnO 3 thin films. Ac-
cordingly, to relieve the high stress of the c-axis-oriented YMnO 3
layer, the polycrystalline YMnO 3 layer was crystallized under the
c-axis-oriented YMnO 3 layer.
Figure 4 shows a schematic diagram of the crystallization
mechanism in the YMnO3 /Si structure. The as-deposited amor-
phous YMnO3 (a-YMnO 3 ) thin film has started to be crystallized
from the surface with a (0001) orientation. Because YMnO 3 has a
hexagonal structure, a (0001) plane of YMnO 3 is a closest packing
Vol. 86, No. I
I 0 200
Steps, arcsec
Fig. 3. High-resolution XRD showing the Si (004) rocking curves of
as-deposited, c-axis/amorphous and c-axis/polycrystalline YMnO 3 thin
films on Si (100) substrates.
plane and has low energy. Therefore, at free surface of the film, a
(0001) plane has been preferably crystallized.
Our previous report' 3 demonstrated that purely c-axis-oriented
YMnO3 thin films on silicon substrate were cracked. For a crack
formation, thin film has to have a tensile stress. The thermal
expansion coefficients along the a-axis and c-axis of YMnO3 thin
film and silicon are-18.5 X 10- 6 /SC,3.5 x 10-6/0C,and2.33 X
10-6/IC, respectively.14 Because the thermal expansion coeffi-
cient along the a-axis of YMnO 3 thin film has a negative value,
when the temperature is increased, the c-axis-oriented YMnO 3
layer has high-tensile stress. Therefore, to relieve high-tensile
stress, the crystallization with a c-axis-preferred orientation is
suppressed. and the crystallization with a random orientation is
favorable in the YMnO3 film. Accordingly, the polycrystalline
YMnO3 layer is formed under the c-axis-oriented YMnO3 layer, as
shown in Fig. 4. With falling temperature, the c-axis-oriented
YMnO3 layer has compressive stress, but it is relieved by the
polycrystalline YMnO 3 layer.
IV. Conclusion
During the crystallization of an as-deposited amorphous
YMnO3 thin film on Si (100) substrate at 850°C in N2 ambient, the
YMnO3 thin film crystallized with two distinct layers. Transmis-
sion electron microscopy revealed that the two layers were a
c-axis-oriented YMnO3 layer and a polycrystalline YMnO 3 layer.
Moreover, this c-axis/poly-YMnO 3 structure effectively relieved
the stress, which was confirmed by high-resolution X-ray diffrac-
tion. In this two-layer YMnO 3 structure, the improvement of a
ferroelectric property, because of the c-axis-oriented layer and the
Fig. 4. Schematic diagram showing the crystallization mechanism of the
YMnO 3 thin films on silicon substrates.
January 2003 Two-Layer Crystallization of Amorphous YMnO_ Thin Films on Si (100) Suibstrates 151

relief of high stress, is expected. Accordingly, the YMInO 3 thin
films could be differently crystallized by the control of the stress
in YMnO_ thin films.
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TITLE: Two-Layer Crystallization of Amorphous YMnO3 Thin

Films on Si (100) Substrates
SOURCE: Journal of the American Ceramic Society 86 no1 Ja
2003
PAGE(S): 149-51
WN: 0300102109024

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