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DOI: 10.1002/adma.200602153
High-Temperature Resistance Anomaly at a Strontium TitanateGrain Boundary and Its Correlation with the Grain-BoundaryFaceting–Defaceting Transition**
By
 Sung Bo Lee
,*
 Jong-Heun Lee
,
 Pyeong-Seok Cho
,
 Doh-Yeon Kim
,
 Wilfried Sigle
, and
 Fritz Phillipp
With the development of nanotechnology, more attentionand care should be paid to grain-boundary structure and itsstructural transition in order to understand the behavior of polycrystalline materials with grain sizes down to nanometerlevels. Here, we report direct evidence suggesting a correla-tion between a grain-boundary structural transition and achange in the electrical property, using a strontium titanate(SrTiO
3
) bicrystalline grain boundary as a model system. Theelectrical properties of grain boundaries in SrTiO
3
 play a criti-cal role in barrier-layer devices, such as capacitors and varis-tors.
[1]
It is believed that the electrical behavior depends onthe double Schottky barrier established by the interfacecharge and the associated space charge across the grainboundary.
[2–4]
The interface charge arises from the segregationof point defects, which form because the energies to move an-ions and cations to the grain boundary are different.
[5]
Theconsequent electrostatic potential obstructs the transport of charge carriers across the grain boundary. For pure, undopedSrTiO
3
, Kim et al.,
[6]
using electron energy loss spectrometry(EELS), showed that the ratio of Ti to O concentration in var-ious boundaries is higher than in the bulk, indicating that thegrain boundaries are enriched in Ti or deficient in O. Brown-ing et al.
[7]
reported that a
 ∑
5 grain boundary (
 denotes thereciprocal of the fraction of common lattice points of the ad- joining grains) is segregated by oxygen vacancies. Klie andBrowning
[8]
reported the segregation of oxygen vacancies at agrain boundary (nominally undoped with a 58°/[001] tilt) inSrTiO
3
, which was compensated by a decrease in the Ti va-lence. The oxygen vacancies segregated at grain boundariesinduced a positive grain-boundary charge along with a nega-tive space-charge region, which formed a double Schottkyelectrical barrier.
[9]
In relation to barrier-layer formation, un-derstanding the relation between electrical and structural be-havior of individual grain boundaries is important. However,studies about the influence of high-angle grain-boundarystructure and its structural transition on electrical propertiesare rare.Cahn
[10]
suggested that most grain-boundary structural tran-sitions belong to faceting–defaceting transitions where an ini-tially flat grain boundary is transformed into a faceted struc-ture with a hill-and-valley shape and vice versa, based on theassumption that the thermodynamics for the surface faceting–defaceting transition
[11–13]
also hold for the grain-boundarycounterpart. The defaceting transition of faceted grain bound-aries has been observed with temperature increase
[14–16]
orcomposition change.
[15,17]
Lee et al.
[18]
showed that a SrTiO
3
grain boundary with a
 
5 [001] misorientation relationshipalso underwent a faceting–defaceting transition. Grain bound-aries annealed in air below 1600°C showed faceting, whereasthey became defaceted after annealing at 1600°C. In this re-port, we show the grain-boundary faceting–defaceting transi-tion in the SrTiO
3
 
5 bicrystalline grain boundary causes asudden change in the charge-carrier transport across the grainboundary.Details of the experimental procedure are given in the Ex-perimental section. The dimensions of the bicrystal examinedand the position and size of electrodes for impedance mea-surements are illustrated in Figure 1. Figure 2 shows theimpedance spectra of the bicrystals examined. As shown inFigures 2a–d, only one semicircle, corresponding to theimpedance response of the bulk, appeared in the as-receivedbicrystal and in those annealed below 1600°C: the grain-boundary impedance was negligible. Only in the bicrystalannealed at 1600°C (Fig. 2e) did a semicircle for the imped-ance response of the grain boundary appear in the lower fre-quency range. The ratio of grain-boundary and bulk resis-tances,
 R
GB
/
R
B
, was 0.281 (Fig. 2e). To check if the change ingrain-boundary impedance was reversible, additionally, abicrystal was
 step-annealed
 and its impedance was measured:The bicrystal was annealed at 1600°C for 1 day, then cooled
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 Adv. Mater.
 2007
,
 19 
, 391395 © 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 391
[*] Prof. S. B. Lee
[+]
Department of Ceramic Engineering, Hanyang UniversitySeoul 133-791 (South Korea)E-mail: bolee@snu.ac.krProf. J.-H. Lee, P.-S. ChoDepartment of Materials Science and Engineering, Korea UniversitySeoul 136-713 (South Korea)Prof. D.-Y. KimSchool of Materials Science and EngineeringSeoul National UniversitySeoul 151-744 (South Korea)Dr. W. Sigle, Dr. F. PhillippMax-Planck-Institut für MetallforschungHeisenbergstrasse 3, 70569 Stuttgart (Germany)[+] Present Address: School of Materials Science and Engineering,Seoul National University, Seoul 151-744 (South Korea)[**] The Alexander von Humboldt Foundation is acknowledged for thefinancial support.
 
directly to 1100°C at a rate of 17 Kmin
–1
, and was maintainedat this temperature for 3 h. Then it was cooled in the furnaceto room temperature. Like the other bicrystals annealedbelow 1600°C, the step-annealed bicrystal exhibited no grain-boundary impedance, as shown in Figure 2f. (Hereafter, eachbicrystal examined in this study will be designated by itsannealing temperature. For example, the bicrystal annealed at1100°C is designated as 1100.)The as-received bicrystal grain boundary and the annealedones were imaged by using high-resolution transmission elec-tron microscopy (HRTEM) in the [001] projection. Figure 3ashows that the as-received bicrystal grain boundary was facet-ed into the symmetric (310) and short asymmetric (100)//(430)plane components. The grain boundary remained faceted if annealed below 1600°C. Figure 3b shows the faceting of the1500 bicrystal. (Images from the 1100 and 1300 bicrystals arenot shown here). At 1600°C, the grain boundary became de-faceted and appeared wavy (Fig. 3c). The step-annealing pro-duced faceting into the symmetric (310) and asymmetric(100)//(430) planes (Fig. 3d), as in the other grain boundariesannealed below 1600°C. No second phase was observed inany of the grain boundaries investigated.Edges accessible for EELS analysis in the present studywere Ti L
2,3
 and O K, where the symbols, such as K, L, M,and so forth, are customarily used to denote the groups of electrons with principal quantum numbers n=1, 2, 3, and soforth. To know how the grain-boundary defaceting transitionaffects the grain boundary’s chemical and electronic structure,the Ti:O intensity ratio, Ti-L
3
:L
2
 intensity ratio, crystal-fieldsplitting, and Ti-L edge-onset shift were measured from thegrain boundary and from the bulk in 1100, 1500, and 1600 bi-crystals. Whereas the 1100 and 1500 bicrystals did not showany discernible increase in Ti:O intensity ratio at the grainboundary with respect to the bulk, in the 1600 bicrystal theTi:O ratio at the grain boundary was increased by about 9%with respect to the bulk (Fig. 4a). The Ti-L
3
: L
2
 intensityratios at the grain boundary were higher than in the bulk atall temperatures measured and, with increasing temperature,the Ti-L
3
:L
2
 ratio increased both in the bulk and at the grainboundary (Fig. 4b). Both the Ti-L
3
 and -L
2
 edges are split intotwo peaks, designated as e
g
 and t
2g
, by the crystal-field ef-fect.
[19]
Whereas the separation between the e
g
 and t
2g
 peaksin the Ti-L edge did not show any change at the grain bound-ary with respect to the bulk in the 1100 bicrystal, the 1500 and1600 bicrystals showed lower crystal-field splitting at the grainboundary with respect to the bulk by (0.2
±
0.1) eV and0.1 eV, respectively. The t
2g
:e
g
 ratio increased with increasingannealing temperature. Only in the 1600 bicrystal was there adrop of the edge onset (both for Ti and O) by about 0.15 eVfor the grain boundary, whereas the 1100 and 1500 bicrystalsdid not clearly show any edge-onset shift.Typically there are trivalent cation impurities, such as Fe
3+
and Al
3+
, in undoped SrTiO
3
, although these are not reportedin the impurity data from the company, and so the nominallyundoped bicrystal used in the present study is assumed to beacceptor-doped.
[20]
As the bicrystal was pure and the anneal-ing was carried out at high temperatures in air (high oxygenpartial pressure), the oxygen-vacancy concentration was low,pinned at a constant level by background acceptors, and the
    C    O    M    M    U    N    I    C    A    T    I    O    N
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 Adv. Mater.
 2007
,
 19 
, 391–395
10 mm
  5 m  m
 I 
in
 I 
out 
0.5 mm5
×
3 mm
2
Figure 1.
 A schematic diagram showing the dimensions of the bicrystaland the position of the electrodes. The thickness of the bicrystal is exag-gerated, compared with its width and length. Note that the two elec-trodes were placed in a diagonal direction with the grain boundary inbetween to prevent surface conduction and to force conduction to bethrough the grain boundary.
Figure 2.
 Impedance spectra measured at 450°C. a) The spectrum fromthe as-received bicrystal. b–e) Spectra from the bicrystals annealed at1100°C for 3 days, at 1300°C for 3 days, at 1500°C for 1 day, and at1600°C for 1 day, respectively. f) The spectrum from the bicrystal under-going the step-annealing.
 
major charge carrier under the oxidizing or mildly reducingatmosphere is believed to be holes.
[20,21]
To support the sug-gestion, we briefly measured the electrical conductivity withincreasing oxygen partial pressure (
O
2
) from 10
–2
to 10
0
at600°C. In the log conductivity versus log
 P 
O
2
plot, the electri-cal conductivity increased with increasing
 P 
O
2
, the slope beingca. 0.24. This value is close to the theoretical value of 1/4,
[21]
which indicates that the bicrystal is p-type.The as-received bicrystal and those annealed in the temper-ature range from 1100 to 1500°C underwent faceting into thesymmetric (310) and asymmetric (100)//(430) components, asshown in Figure 3a and 3b, and defaceting of the initially fac-eted grain boundary occurred at 1600°C (Fig. 3c), showingthat the defaceting transition occurred between 1500 and1600°C. Such tendencies are also found in the previous studyof Lee et al.
[18]
where, as in the present study, a nominallyundoped
 ∑
5 bicrystal was used. The observed grain-boundaryfaceting denotes that the average grain-boundary-plane orien-tation of the faceted grain boundaries deviates from the exactsymmetric (310) plane, a deviation that originates from the in-trinsic surface miscut of the mating single crystals. These twokinds of facets are regarded as singular planes correspondingto cusp orientations in the polar plot of the grain-boundaryenergy versus the grain-boundary-plane normal. The initiallyfaceted boundary shown in the as-received bicrystal (Fig. 3a)became defaceted at 1600°C (Fig. 3c) and, as shown in Fig-ure 3d, a faceted boundary was recovered at 1100°C by thestep-annealing, indicating that the faceting–defaceting transi-tion is reversible, as observed by Hsieh and Balluffi.
[14]
As grain-boundary impedance distinctly appeared abovethe defaceting transition temperature (Fig. 2e) and disap-peared again below that temperature because of the step-annealing (Fig. 2f), the change in grain-boundary impedance was shown to be reversible,further suggesting that the change in grain-bound-ary impedance was determined by the grain-boundary faceting–defaceting transition.The higher Ti:O intensity ratio at the grainboundary at 1600°C (Fig. 4a) evidences the pres-ence of oxygen vacancies at the grain boundary.The increase in the Ti-L
3
:L
2
 intensity ratio both atthe grain boundary and in the bulk with tempera-ture is caused by the reduction of the system at ele-vated temperatures.
[8,19]
The higher Ti-L
3
:L
2
 ratioat the grain boundary at all the observed tempera-tures (Fig. 4b) indicates an additional reduction of the Ti valence state at the grain boundary to com-pensate for oxygen-vacancy segregation at thegrain-boundary core indicated in Figure 4a.
[8,19]
The observed loss of oxygen at the grain boundaryis consistent with the small reduction of the crys-tal-field splitting: missing oxygen atoms lead to adistortion in the symmetry of the Ti–O environ-ment and a reduction of the electrostatic fieldimposed by the oxygen on the Ti atom. For the1600 bicrystal, as mentioned above, the shifts inthe Ti-L and O-K edges at the grain boundary were very simi-lar in magnitude, resulting in no significant change in theseparation between the Ti-L and O-K edges. The separationwas always close to 72.5 eV, which is, according to Sankarara-man and Perry,
[22]
typical for TiO
2
. Those for Ti
2
O
3
 and TiOare reported to be 74.5 and 75.5 eV, respectively.
[22]
Althoughthe unchanged separation seems to indicate that there is nochange in the Ti valence at the grain boundary, the down-wards shift of the Ti-L edge, the increase in the Ti-L
3
:L
2
 inten-sity ratio, and the reduced crystal field are enough evidencefor a reduction of the Ti valence state at the grain bound-ary.
[8,19]
Klie and Browning
[8]
compared Ti:O and Ti-L
3
:L
2
 intensityratios at room temperature and 724 K. The Ti:O ratio at thegrain boundary is higher than in the bulk, both values beingincreased at higher temperature. The Ti-L
3
:L
2
 intensity ratioexhibits similar tendencies. The loss of oxygen is driven by en-tropy and thus increases with temperature.
[8]
However, thesudden increase in oxygen-vacancy concentration at the grainboundary between 1500 and 1600°C, as shown in the presentstudy (Fig. 4a), cannot be explained simply by the tempera-ture increase. We attribute this effect to the defaceting of thegrain boundary structure at 1600°C (Fig. 3c). The faceting–defaceting transition is a first-order phase transition,
[10–13]
andthus explains the discontinuous change in the oxygen-vacancyconcentration at the grain boundary. For the Ti-L
3
:L
2
 ratio atthe grain boundary no indication of an abrupt change between1500 and 1600°C was found (Fig. 4b). However, because boththe increase in the Ti-L
3
:L
2
 ratio and in the Ti:O ratio at thegrain boundary were evidence for a reduction or a loss of oxygen at the grain boundary,
[8,19]
it appears that the Ti-L
3
:L
2
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 Adv. Mater.
 2007
,
 19 
, 391395 © 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 www.advmat.de 393
Figure 3.
 An HRTEM image of the grain boundary in a) the as-received bicrystal.b,c) Grain-boundary shapes of the bicrystals annealed at 1500°C for 1 day and1600°C for 1 day, respectively, and d) the step-annealed sample. The faceted structureis composed of symmetric (310) and asymmetric (100)//(430) plane components,regardless of the types of heat treatments.

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