APPLIED PHYSICS LETTERS 96, 191906 共2010兲

Kinetic roughening of a ZnO grain boundary

Sung Bo Lee,1,a兲 Young-Min Kim,2 Dong-Su Ko,1 Tae-Young Ahn,1 Young-Woon Kim,1
and Jucheol Park1
1
Department of Materials Science and Engineering, Seoul National University, Seoul 151-744,
Republic of Korea
2
Korea Basic Science Institute, Daejeon 305-333, Republic of Korea
共Received 15 February 2010; accepted 16 April 2010; published online 12 May 2010兲
Using a model ZnO bicrystal, we examine grain boundary kinetics by high-resolution transmission
electron microscopy. The grain boundary undergoes a transition from atomically stepped to
undulating appearances with increasing driving force for migration at a given temperature,
producing clear evidence that grain boundaries undergo kinetic roughening. © 2010 American
Institute of Physics. 关doi:10.1063/1.3428369兴

Crystalline interfaces are observed to undergo kinetic
roughening at sufficiently high driving forces for
migration.1–6 Kinetic roughening is understood in relation to
thermal roughening transition.7–9 Below the thermal rough-
ening transition temperature, TR, at small driving forces in-
terfaces are smooth, and because of the existence of the free
energy required to form a step on a crystalline terrace surface
关step free energy, or two-dimensional 共2D兲 nucleation bar-
rier兴, migration is mediated by 2D nucleation or by growth
spirals supplied by screw dislocations 共stepwise mechanism兲,
exhibiting a nonlinear, exponential relationship between mi-
gration rate, and driving force. With increasing driving force,
an interface which migrates by a stepwise mechanism is cov-
ered by many 2D clusters, steps becoming heavily kinked
and thus having a large width.1,2 At a critical driving force
for migration, the width of a step exceeds the radius of the
2D nucleus1 and the step formed by the 2D nucleus loses its
“identity” in the background of the interface, as discussed by
Peteves and Abbaschian.2 Thus it is proposed that, under
such nonequilibrium conditions, the step free energy goes to
zero and the interface becomes rough.1,2,4 A rough interface
advances by local migration of the interface normal 共continu-
ous mechanism兲, its migration rate showing a linear relation-
ship with driving force. The transition from stepwise to
continuous migration regimes at a critical driving force is
called kinetic roughening.1–4 Above TR, a crystalline inter-
face is already rough in equilibrium. Kinetic roughening of
crystal-melt2,5 and crystal-vapor interfaces6 has been inten-
sively studied but that of grain boundaries 共GBs兲 has re-
mained unexplored.
Lee and Kim10 observed that a ⌺5 GB in SrTiO3 under-
goes a transition from lateral motion of atomic steps to a
continuous mechanism with increasing temperature from 700
to 900 ° C. They interpreted the observation as being an in-
dication of kinetic roughening because the thermal roughen-
ing transition temperature of the SrTiO3 GB 共approximately
1600 ° C兲 is much higher than the annealing temperatures.11
However, in the previous work,10 the experimental criterion
for kinetic roughening,1–4 such as the transition from flat to
curved GB shapes with increasing driving force for migra-
tion, was not explored, which must have been addressed to
characterize kinetic roughening of the GB.
a兲
Electronic mail: bolee@snu.ac.kr.
Here we report clear evidence of kinetic roughening of a
GB in a model ZnO bicrystal examined by high-resolution
transmission electron microscopy 共HRTEM兲. The GB in the
bicrystal was subject to driving forces for migration provided
by the difference in surface energy between the two grains.
At a given temperature, with increasing driving force for
migration, the GB changed from atomically stepped to undu-
lating, suggesting a transition from stepwise to continuous
migration mechanisms and thus satisfying the criterion for
kinetic roughening.1–4
In the present study, we used as a model system a pure
ZnO bicrystal with a GB with a misorientation relationship
of 关0001兴/30° bounded by 共101̄0兲 and 共112̄0兲 planes, whose
dimensions were 10共w兲 ⫻ 5共h兲 ⫻ 0.5共t兲 mm3 关Fig. 1共a兲兴.
Cross-section TEM specimens were prepared from the bic-
rystal on a focused Ga-ion beam 共FIB兲 workstation to, as a
result, be composed of two grains with surface normal direc-
tions of 关112̄0兴 and 关101̄0兴 关Fig. 1共b兲兴. All FIB-prepared
specimens were cleaned in a laboratory-built plasma etcher
at a negative specimen bias of 150 V using Ar-25 vol % O2
mixed gas to remove surface damage and Ga contamination
induced by Ga ions during FIB.12 Their removal was con-
firmed by energy dispersive x-ray spectroscopy equipped at a
TEM operating at 400 keV 共JEM-4010, JEOL, Co., Ltd.,
Japan兲. The prepared specimens were annealed at 626 ° C
共0.4 Tm兲 for 1 h, where Tm is the melting temperature of
ZnO in absolute scale 共2248 K兲, in a high-voltage TEM op-
erating at 1.25 MeV 共JEOL JEM-ARM1300S, JEOL, Co.,
Ltd., Japan兲 and after cooling to room temperature the GB
structure was examined. 共With increasing temperature during
in situ observation, knock-on damage by high-energy elec-
trons would not be negligible.13 Actually, in the present
study, specimens were observed to be severely damaged un-
der the illumination of the electron beam, even at the tem-
perature of 200 ° C or above. This is the reason why we
heated up and annealed specimens without beam and ob-
served them ex situ at room temperature.兲
Thickness of the specimens was determined by electron
energy loss spectroscopy 共EELS兲 log-ratio method14 using
the GATAN® DigitalMicrograph® software in a field-emission
TEM operating at 200 keV 共Tecnai F20, Eindhoven, The
Netherlands兲.
Figure 1共c兲 shows the initial microstructure of the
boundary between the 关112̄0兴 and 关101̄0兴 grains before an-

0003-6951/2010/96共19兲/191906/3/$30.00 96, 191906-1 © 2010 American Institute of Physics

Author complimentary copy. Redistribution subject to AIP license or copyright, see http://apl.aip.org/apl/copyright.jsp
191906-2 Lee et al.
FIG. 1. Crystallographic geometry of the bicrystal used and initial micro-
structures of the grain boundary in the specimen. 共a兲 Schematic diagram of
the top view 共10⫻ 5 mm2兲 of the bicrystal with a grain boundary with a
misorientation relationship of 30°/关0001兴 bounded by 共101̄0兲 and 共112̄0兲
planes. 共b兲 Scanning electron microscopy image taken during preparation of
a cross-section FIB TEM specimen prepared from the bicrystal shown in 共a兲.
The resulting FIB specimen had a thickness gradient, assuming a wedge
shape. 共c兲 HRTEM image of the grain boundary in the specimen before
annealing.
nealing. The GB was atomically flat. A calculated HRTEM
image based on the multislice method, which is implemented
in the MacTempas software package,15 proves the image to
be the structure of 关112̄0兴 oriented ZnO 关inset in Fig. 1共c兲兴.
Figure 2 shows a HRTEM image of the GB of a specimen
annealed at 626 ° C 共0.4 Tm兲 with specimen thicknesses
ranging from 24 to 50 nm. For the region whose thickness
approximated to 50 nm 关Fig. 2共a兲兴, the GB demonstrated
highly populated, atomic steps 共indicated by arrows兲 with a
height of 0.28 nm corresponding to the interplanar spacing of
the 共101̄0兲 plane of the 关112̄0兴 grain 共marked in the figure兲.
The steps was not observed before annealing 关Fig. 1共c兲兴, sug-
gesting a stepwise migration mechanism during annealing.
In a thinner region of the specimen, of which thickness was
determined to be about 24 nm, however, the 关112̄0兴 grain
locally grew into the 关101̄0兴 one without the requirement of
atomic steps, exhibiting a curved GB shape and a moiré
fringe 关Figs. 2共b兲 and 2共c兲兴. The observed moiré fringe was
well matched with a translational moiré pattern 关Fig. 2共d兲兴
formed by superposing the experimentally obtained 关112̄0兴
and 关101̄0兴 grain lattices and thus had no rotational and
Author complimentary copy. Redistribution subject to AIP license or copyright, see http://apl.aip.org/apl/copyright.jsp
Appl. Phys. Lett. 96, 191906 共2010兲
FIG. 2. HRTEM images of the grain boundary in the specimen annealed at
626 ° C. 共a兲 In the region at a specimen thickness of ⬃50 nm, the grain
boundary shows atomic steps. 共b兲 The grain boundary at a thinner specimen
thickness of ⬃24 nm migrates from the 关112̄0兴 into the 关101̄0兴 grain, ex-
hibiting a curved shape. A moiré pattern is observed. Inset of 共b兲: Fourier
transform of 共b兲. 共c兲 Enlarged image of the moiré pattern shown in 共b兲. 共d兲 A
translational moiré fringe obtained by superposing the two experimentally
obtained 关112̄0兴 and 关101̄0兴 grain lattices. 共e兲 Morphology of the grain
boundary near the region shown in 共b兲. Inset of 共e兲: Fourier transform of 共e兲.
stress contrasts. Double diffraction reflections produced by
the superposed 关112̄0兴 and 关101̄0兴 grains are shown in the
Fourier transform 共inset兲 of Fig. 2共b兲. Such migration behav-
ior was also observed in a neighboring area, as shown in Fig.
2共e兲, whose moiré fringe and double diffraction spots were
analogous to that shown in Fig. 2共b兲.
Since the specimens were observed at room temperature
after annealing at the high temperature without beam and
effects of local beam heating was calculated to be negligible
共⌬T = ⬃ 0.04 K兲 due to the high thermal conductivity of
ZnO 共100 W m−1 K−1兲, the observed GB migration shown
in Fig. 2 was not affected by any beam irradiation effects. In
addition to the annealing at 626 ° C, we annealed some
specimens at 200 and 400 ° C 共whose microstructures are not
shown here兲. As for the specimen annealed at 626 ° C, their
GB structures were examined after cooling them down to
room temperature, but boundary migration could not be ob-
served. This indicates that those temperatures 共200 and
400 ° C兲 are not high enough for thermal activation for GB
migration and provides evidence that the migration behavior
shown in Fig. 2 corresponds to the structures annealed at
626 ° C.
In the present study, the driving force for GB migration
is provided by the difference in surface energy between the
191906-3 Lee et al.
two grains, ⌬␥, because the 共112̄0兲 plane is calculated to
have a lower surface energy than the 共101̄0兲 plane 共2.0 J / m2
and 3.4 J / m2, respectively兲,16 which explains the direction
of GB migration from the 关112̄0兴 grain to the 关101̄0兴 one.
The driving force is given by 2⌬␥ / d, where d is the speci-
men thickness. For example, the specimen thickness of about
24 nm, where the GB in the specimen annealed at 626 ° C
was observed to become undulating, corresponds to a driving
force of ⬃108 Pa.
For a crystalline surface, where a 2D nucleus on the
terrace surface is a circular disk with an atomic height of h,
with a step free energy, ␧, the 2D nucleation rate is given by
冉 冊
␲␧2
v ⬀ exp − , undergo kinetic roughening like other crystalline interfaces,
kTh⌬g
where k is the Boltzmann constant, T temperature, and ⌬g
the driving force for nucleation.17 Below TR, as mentioned
above, with increasing driving force, ⌬g, to a critical value,
⌬gⴱ, the step free energy, ␧, decreases to zero. At and above
the critical driving force, ⌬gⴱ, eventually, the surface be-
comes kinetically roughened and the variation in migration
rate, v, with ⌬g turns from exponential 共stepwise mecha-
nism兲 to linear 共continuous mechanism兲.1–4 The above equa-
tion holds the following for GBs:1 h is an atomic step height
on the GB plane, ␧ the step free energy of the GB, and ⌬g
the driving force for GB migration. For the specimen an-
nealed at 626 ° C 共Fig. 2兲, with decreasing specimen thick-
ness 共in other words, increasing driving force for migration兲,
the GB shape turned from atomically stepped to undulating,
implying the transition between stepwise and continuous mi-
gration regimes. Although taking into account that the accu-
racy in determination of specimen thickness by EELS log-
ratio method is within 20%,14 such a tendency is obvious,
corroborating the idea of kinetic roughening of GBs.
Our present observations did not show the transition
from stepwise to continuous mechanisms explicitly because
the observations were made at room temperature. Olmsted
et al.18 showed using molecular dynamics simulations of
face-centered cubic Ni that bicrystalline GBs undergo rough-
ening transition, and that above the roughening transition
temperatures the GBs migrate by a continuous mechanism
with high mobility and below the temperatures by a stepwise
mechanism with low mobility. This simulation result18 and
our present observations well complement each other.
It is worth addressing what significance kinetic roughen-
ing observed in a single GB has for GB structure in poly-
crystals. The driving force for GB migration has several
forms according to systems.19 For a thin bicrystal TEM
specimen with a flat GB as in the present study, the driving
force is expressed as a function of specimen thickness, and
for bulk polycrystals, the driving force is provided by GB
curvature, which is expressed as 2␥gb / r, where r is the radius
of curvature.19 Setting the equation for the driving force aris-
ing from the surface-energy difference 共2⌬␥ / d兲 equivalent to
2␥gb / r and assuming that ␥gb is 1 – 2 J / m2 for ZnO 共Ref.
20兲, r approximates to d; the specimen thicknesses of tens of
nanometers in the present study are equivalent to radii of
Author complimentary copy. Redistribution subject to AIP license or copyright, see http://apl.aip.org/apl/copyright.jsp
Appl. Phys. Lett. 96, 191906 共2010兲
curvature of the same order of magnitude and, taking into
account that the radius of curvature is an order of magnitude
larger than the mean radius of an individual grain,19 to finer
nanometer-scale grain radii. The HRTEM of kinetic rough-
ening of bicrystalline GBs is envisaged to help us explore
GB structure in nanocrystalline 共NC兲 materials. Kinetic
roughening, which is likely to be accelerated at finer grain
sizes, might produce a clue to the origin of larger grain
boundary diffusivities21 and thus higher creep and
superplasticity22 in NC materials than in ordinary polycrys-
tals, because roughened GBs are expected to show higher
GB diffusivities than unroughened ones. This idea stimulates
further study.
The results presented here produce evidence that GBs
which was identified in HRTEM investigations of a model
ZnO bicrystalline GB. Our present observations seem to in-
dicate the possible correlation between GB kinetic roughen-
ing and structures of GBs in NC materials. By extension, the
concept of GB kinetic roughening can be applied to a wide
range of practical applications, such as heat treatments of
metal and ceramic polycrystalline materials, where under-
standing of GB structure and migration is crucial.
This research was supported by the National Research
Foundation of Korea 共NRF兲 funded by the Ministry of Edu-
cation, Science, and Technology 共Grant No. 2009-0085412兲
共RIAM兲.
1
J. W. Cahn, Acta Metall. 8, 554 共1960兲.
2
S. D. Peteves and R. Abbaschian, Metall. Trans. A 22, 1271 共1991兲.
3
E. van Veenendaal, P. J. C. M. van Hoof, J. van Suchtelen, W. J. P. van
Enckevort, and P. Bennema, Surf. Sci. 417, 121 共1998兲.
4
H. M. Cuppen, H. Meekes, W. J. P. van Enckevort, E. Vlieg, and H. J. F.
Knops, Phys. Rev. B 69, 245404 共2004兲.
5
D. Li and D. M. Herlach, Phys. Rev. Lett. 77, 1801 共1996兲.
6
J. Krug, Adv. Phys. 46, 139 共1997兲.
7
W. K. Burton, N. Cabrera, and F. C. Frank, Philos. Trans. R. Soc. London,
Ser. A 243, 299 共1951兲.
8
S. T. Chui and J. D. Weeks, Phys. Rev. B 14, 4978 共1976兲.
9
P. E. Wolf, F. Gallet, S. Balibar, E. Rolley, and P. Nozières, J. Phys. 共Paris兲
46, 1987 共1985兲.
10
S. B. Lee and Y.-M. Kim, Acta Mater. 57, 5264 共2009兲.
11
S. B. Lee, W. Sigle, W. Kurtz, and M. Rühle, Acta Mater. 51, 975 共2003兲.
12
D.-S. Ko, Y. M. Park, S. D. Kim, and Y.-W. Kim, Ultramicroscopy 107,
368 共2007兲.
13
R. F. Egerton, P. Li, and M. Malac, Micron 35, 399 共2004兲.
14
T. Malis, S. C. Cheng, and R. F. Egerton, J. Electron Microsc. Tech. 8,
193 共1988兲.
15
R. Kilaas, Proceedings of the 45th Annual Meeting of EMSA, edited by G.
W. Bailey 共San Francisco Press, San Francisco, 1987兲, pp. 66⫺69.
16
N. Fujimura, T. Nishihara, S. Goto, J. Xu, and T. Ito, J. Cryst. Growth
130, 269 共1993兲.
17
J. P. Hirth and G. M. Pound, Condensation and Evaporation: Nucleation
and Growth Kinetics 共Pergamon, Oxford, 1963兲, pp. 77–148.
18
D. L. Olmsted, S. M. Foiles, and E. A. Holm, Scr. Mater. 57, 1161 共2007兲.
19
G. Gottstein and L. S. Shvindlerman, Grain Boundary Migration in Metals
20
共CRC, Boca Raton, 1999兲.
P. Ruterana, M. Abouzaid, A. Bére, and J. Chen, J. Appl. Phys. 103,
033501 共2008兲.
21
J. Horváth, R. Birringer, and H. Gleiter, Solid State Commun. 62, 319
共1987兲.
22
L. Lu, M. L. Sui, and K. Lu, Science 287, 1463 共2000兲.