This article was downloaded by: [University of California Santa Cruz]

On: 02 April 2015, At: 19:38

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK

Ferroelectrics
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gfer20

Surface morphology of ferroelectric

Gd2(MoO4)3 observed by atomic
force microscope
a a
Masaaki Takashige , Sin-Ichi Hamazaki , Nobutaka Fukurai
a a b
, Fuminao Shimizu & Seiji Kojima
a
College of Science and Engineering, Iwaki Meisei
University , 5–5–1 Iino, Chuohdai, Iwaki-shi, Fukushima 970,
Japan
b
Institute of Applied Physics, University of Tsukuba ,
Tsukuba-shi, Ibaraki, Japan , 305
Published online: 07 Mar 2011.

To cite this article: Masaaki Takashige , Sin-Ichi Hamazaki , Nobutaka Fukurai , Fuminao
Shimizu & Seiji Kojima (1997) Surface morphology of ferroelectric Gd2(MoO4)3 observed by
atomic force microscope, Ferroelectrics, 203:1, 221-225, DOI: 10.1080/00150199708012848

To link to this article: http://dx.doi.org/10.1080/00150199708012848

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information
(the “Content”) contained in the publications on our platform. However, Taylor
& Francis, our agents, and our licensors make no representations or warranties
whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and
views of the authors, and are not the views of or endorsed by Taylor & Francis. The
accuracy of the Content should not be relied upon and should be independently
verified with primary sources of information. Taylor and Francis shall not be liable
for any losses, actions, claims, proceedings, demands, costs, expenses, damages,
and other liabilities whatsoever or howsoever caused arising directly or indirectly in
connection with, in relation to or arising out of the use of the Content.

This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden.
 Terms & Conditions of access and use can be found at http://www.tandfonline.com/
page/terms-and-conditions
Downloaded by [University of California Santa Cruz] at 19:38 02 April 2015
 Fern,rlectrm, 1997, Vol. 203, pp. 221-225
Reprints available directly from the publisher
Photocopying permitted by license only
Downloaded by [University of California Santa Cruz] at 19:38 02 April 2015
8 1997 OPA (Overseas Publishers Association)
Amsterdam B.V. Published under license
under the Gordon and Breach Science
Publishers imprint.
Printed tn India.

SURFACE MORPHOLOGY
OF FERROELECTRIC Gd,(MoO&
OBSERVED BY ATOMIC FORCE MICROSCOPE
MASAAKI TAKASHIGEa, SIN-ICHI HAMAZAKI",
NOBUTAKA FUKURAI", FUMINAO SHIMIZU"
and SEIJI KOJIMAb
"College of Science and Engineering, Iwaki Meisei University, 5 -5 - 1 Iino,
Chuohdai, Iwaki-shi, Fukushima 970, Japan; bInstitute of Applied Physics,
University of Tsukuba, Tsukuba-shi, Ibaraki 305, Japan

(Received 20 November 1996)

We applied the atomic force microscopy (AFM) for studying the surface morphology of
Gd,(MoO,), (Gadolinium Molybdate, GMO). At room temperature, an undulation of the
(100) surface was observed around the orthorhombic twin boundary, which is reasonably
explained by the lattice distortion due to 160°C phase transition of this material.

Kejjwords: AFM; atomic force microscopy; ferroelectric domain; ferroelastic domain,

Gd,(MoO,),,GMO

To celebrate Prof. Jinzo Kobayashi's special issue of "FERROELEC-

TRICS" for his 70th birthday, we would like to present the atomic force
microscopy (AFM) image of the (100) surface of P-Gd,(MoO,), (P-Gado-
linium Molybdate, denoted as GMO), that is one of the famous ferroelectric
crystals, to which Prof. Kobayashi also had ever concerned.
G M O has a ferroelectric phase transition at around 16OoC['].In the late
~O'S,this phase transition attracted much research interest, since below the
Curie point (Tc),the crystal state can be switched from one orientation to
the other, not only by applying an electric field (ferroelectricity) but also by
applying a mechanical stress (ferroelasticity) ['I. G M O is actually the first
crystal where these two phenomena were observed simultaneously.
22 1
 222 M. TAKASHIGE et al.

In this paper, we shall focus our attention on the AFM image of the
surface morphology due to the domain structure of GMO. AFM is one of
the useful techniques for visualization of the surface morphology due to the
ferroelectric or ferroelastic domain configurations, since the measurement
is possible without any modification or damage of the sample surface in
contrast to other methods such as surface etching, scanning electron micro-
scopy, etc.
Downloaded by [University of California Santa Cruz] at 19:38 02 April 2015

In the past few years, we have been engaged in AFM observations on

surfaces of several ferroelectrics such as BaTiO, (barium titanate, BT) I3],
NaKC4H406.4H,O (Rochelle salt, RS) [41. When such crystals are cooled
from above Tc the spontaneous polarization P, occurs along one of the
crystallographic axes but this is accompanied by the spontaneous lattice
strain due to the crystal system alternation, namely from cubic to tetragonal
in BT and from orthorhombic to monoclinic in RS. Thus, the surface of the
crystal is necessarily influenced by the lattice strain due to such alternations
of the cyrstal system. Actually the surface undulation of the crystal has been
observed around the 90" domain boundaries in BT and the monoclinic
domain boundaries in RS.
As well as in the above two ferroelectrics, the alternation of the crystal
system takes place around T, of GMO, from the high temperature tetra-
gonal phase with P42rn(D;,) to low temperature orthorhombic phase with
P ~ U ~ ( C ~ , , Below +
) [ ~ , ~T,,' . P, can develop along or - directions of the
c-axis, however, there is a bi-linear coupling between P, and strain compo-
nent x6 in this system. Thus, the orthorhombic crystal has adjacent do-
+
mains characterized with + x 6 and -x6, according to P, and -P,. Or
we should say inversely that the crystal has adjacent domains to be polariz-
+
ed with P, and - P,, according to the orthorhombic distortion characteri-
zed with + x6 and - x 6 if we prefer the view point of ferroelasticity.
The example of a domain configuration for a (100) plate is schematically
shown in Figure l(a), where one laminar domain with the a-axis parallel to
the upper surface transects through the crystal plate, having boundaries at
about 45" to the upper surface. Strictly speaking, the angle between a-axis
(b-axis) on both sides of the boundary differs slightly from 90" due to the
geometric condition of the lattice matching at the boundary, as depicted
schematically in Figure l(b) for a strain-free model. The a-and b-axis are
exchanged each other on both sides of the domain boundary, Evidently,
from the figure, the deviation angle 0 is given by 2tan-'b/a-90, where a and
b are lattice parameters. Note that there is a relationship between the lattice
+
parameters and the strain, like b/a = (1 x6)/(l - x6), or x 6 = (b/a - 1)/
(b/a + 1). The aim of the present work is the direct observation of this
 SURFACE MORPHOLOGY O F Gd,(MoO,), 223
Downloaded by [University of California Santa Cruz] at 19:38 02 April 2015

FIGURE 1 The domain arrangement of orthorhombic Gd,(MoO,),. (a) Schematic of do-

main arrangement of (100) plate. Arrows represent the crystallographic axis, in particular, the
direction of the c-axis is that of P,. (b) Schematic of condition for lattice matching at the
domain boundary. A rectangle represents one unit cell. The ratio of the lattice parameters of
a- and b-axis is greatly exaggerated.
deviation angle 0 in the real surface of a bulk crystal and to compare with
the results by crystallographic methods.
One more interesting point is the nature of the boundary on the side
surface (normal to Ps,(001) surface) in Figure l(a), however there is a
pioneer work by Saurenbach and Terrist7I, reporting the electro-static force
microscopy image of the (001) surface of GMO, which confirms a change of
electro-static force on both sides of the boundary. Thus, in the present
work, we focus on the image only for the (100) surface.
The AFM images were taken by a commercially available apparatus
(Digital Instruments, Inc., NanoScope 111), operating in the tapping mode,
which means that the AFM tip oscillates over the sample surface at high
frequency, touching the sample surface only at the bottom of the oscillation.
The AFM imaging were made with the scan range of 100 x 100pm2, rates
 224 M. TAKASHIGE et al.

-
ranged from 0.25 to 0.5 Hz (about 50 100 pm/s) and tapping frequencies
ranged from 360 to 370 kHz.
The top-view of the AFM image for an optically polished (100) plate with
thickness of about 0.24mm is shown in Figure 2(a), where a height change
is observed at the domain boundaries. The nature of the surface comes out
clearer by showing the three dimensional oblique perspective for the same
surface area in Figure 2(b). Figure 2(c) is the cross-sectional profile along
Downloaded by [University of California Santa Cruz] at 19:38 02 April 2015

the b-direction shown in Figure 2(b), indicating that the surface of the plate
makes an angle of 0.142' at one of the domain boundaries. As described
previously, this angle is given by a function of a and b-axis lattice para-
meters or the strain x6. Thus, we can estimate x6 from the angle observed
there. The value of x6 calculated is about 1.24 x
In Table I, several data of x6 and the corresponding angle 6 (calculated
by the strain-free model) determined by other researchers are listed, to-
gether with the present result. Among these data, the result with
x6 = 1.28 x l o p 3and 6 = 0.146" obtained by X-ray is conspicuously close to
the present result. The original lattice parameters to calculate the above

EE
00 25
0.142O
50 75 100
w
FIGURE 2 The observation of domains for a (100) surface Gd,(MoO,),. (a) top-view AFM
image. (b) three dimensional obligue perspective of the AFM image. The bottom bar is the gray
scale indicating the height. (c) cross-sectional profile along the line shown in the above figures.
 SURFACE MORPHOLOGY O F Gd,(MoO,), 225

TABLE1 Spontaneous strain x6 and bending angle of the

(100) surface 8, at room temperature

‘6 0 Experimental Reference
x 10-3 deg methods No.

1.83 0.209 X-ray 9.

0.82 0.094 X-ray 10.
1.58 0.181 X-ray 6.
1.49 0.170 X-ray 11.
Downloaded by [University of California Santa Cruz] at 19:38 02 April 2015

1.28 0.146 X-ray 8.

1.5 0.17 X-Eplot 9.
1.5 0.17 optical fringe 12.
1.6 0.183 optical fringe 12.
1.24 0.142 AFM present work

values are a= 10.39449A and b = 10.42052A (at 40°C), quoted from the
paper entitled “X-Ray Study on Thermal Expansion of Ferrolectric
Gd,(MoO,),” by J. Kobayashi, Y. Sat0 and T. Nakamura, published in
phys. stat. sol. (a), 14, 259 (1972).
It is our great pleasure to present this short article about the AFM image
of G M O related to the lattice parameters, which convincingly supports the
old data by Prof. J. Kobayashi’s group, to his celebration issue.

Acknowledgements
We gratefully acknowlege Prof. S. Katsumata, Iwaki Meisei University
(IMU), for support of experiments. Two of the authors (MT and SK) would
like to thank the late Prof. T. Nakamura for giving them Gd,(MoO,),
cyrstals used in the present study.

References
[l] Borchardt, H. J. and Biestedt, P. E. (1966). Appl. Phys. Letters, 8, 50.
123 Aizu, K. (1969). J . Phys. SOC.Jpn., 27, 387.
[3] Hamazaki, %-I., Shimizu, F., Kojima, S. and Takashige, M. (1995). J . Phys. SOC.Jpn., 64,
3660.
[4] Takashige, M., Hamazaki, S.-I., Fukurai, N., Shimizu, F. and Kojima, S. (1996). J p n .
J . Appl. Phys., 35, 5181.
[ 5 ] Preweitt, C. T. (1970). Solid State Commun., 8, 2037.
[6] Keve, E. T., Abraham, S. C. and Bernsein, J. L. (1971). J . Chem. Phys., 54, 3185.
[7] Saurenbach, F. and Terris, B. D. (1990). Appl. Phys. Lett., 56, 1703.
[8] Kobayashi, J., Sato, Y. and Nakamura, T. (1972). Phys. Stat. Sol. (a), 14, 259.
[9] Aizu, K., Kumada, A., Yumoto, H. and Ashida, S. (1969). J . Phys. SOC.Jpn., 27, 551.
[lo] Kvapil, J. and John, V . (1970). Phys. Stat. Soli., 39, K15.
[11] Jeitschko, W . (1972). Acta. Cryst., B28, 60.
[12] Kojima, S. and Nakamura, T. (1978). Jpn. J . Appl. Phys., 17, 947.