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ÁÄ«½B1. Í¶ßÉX}[gtHâ^ubg[ÈÇÌîñ@íÍC¬^åeÊÌÏwZ~bNRfT[iMLCCjÉx¦çêÄ¢éBMLCC ÌÁ«ÍàÉ[U·éUdÌZ~bNªßèÅéB]CUdÞ¿ÉÍyuXJCg\¢ðàÂ`^_âWR_ÈÇÌÜL¨¿ªp¢çêÄ«½ªCÂ«K§Ì­»©çC»ÌgpªÀãÖ~ÉÇ¢ÜêÄ¢é1)B»ÌãÖ¨¿ÆµÄC¯¶»\¢ðàÂ`^_oEiBaTiO3 jÉH
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Unit cell of Barium titanates. An arrow indicates displace­ment of a Ti ion from the body­center position, i.e. an elec­tric dipole moment in the unit cell.

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B»ÌÛC|d 0 rÆ­­¬¬·éÎÌ^Ìg®ÖðàÂd×Ú®óÔ |d 1{LrÆC¬¬Ìã¢½ÎÌ^Ìd×Ú®óÔ |d 1| LrÌñÂÌd×Ú®óÔðl¦é±ÆªÅ«éiL ÍzÊq³Eð\·jB¼ÒÆÌ¬¬ÌÊC½O¹IÈd×Ú®óÔ |CT1rÆñO¹IÈd×Ú®óÔ |CT2rª`¬³êéBîêóÔ |GSrÆÌGlM[·id×Ú®GlM[jðC»ê¼ê D1 ¨æÑ D2 ÆFig. 2

Two intrinsically dierent X­ray emission processes. (a)Fluorescence X­ray or (also known as) characteristic X­ray:the incident X­ray excites a core electron followed by the de­excitation of a shallower core electron. (b) Raman Scatter­
ing: the incident X­ray excites a core electron followed by thecoherent de­excitation of the electron via charge­transfer(CT) excitations or crystal eld (dd) excitations.

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úËõ Jan. 2015 Vol.28 No.1  13

Fig. 4

Fig. 3

Schematic transition diagram of the X­ray Raman scatteringin the X­ray emission process. Taking pd hybridization intoaccount, the |d 0rground state is hybridized with the |d 1{Lrstates with dierent symmetry through a conguration inter­action to form a ground state |GSrand two charge­transferstates, |CT1rand |CT2ras an initial state |ir. Black (Blue)arrows correspond to the elastic (Raman) processes.

Ti Kb resonant X­ray emission spectrum of BaTiO3. The ex­
citation energy of the incident X­ray, which is equal to theelastic peak energy, is tuned to the white­line peak of the ab­sorption spectrum shown in the inset. Besides the four, Kb, Kb2,5), two faint Ra­uorescence peaks (Kb1,3, Kb
man peaks (CT1 and CT2) are observed.

¶E³êéBFig. 4 ÌÊÍ²¿ÌàÌÅé½ßCärIã­ÈÁÄ¢éBêûCTi 4p Êæè[¢ 3p àkÊ©çÌEãNÅZÉæêÎC§ûÎÌêÌàÆÅÍ CT2 ãNÍÙÆñÇ, Kb,éuõ¬ªiKb1,3, Kb

Kb2,5 jÍCÊîñðZbg·éÉaßöðî·é½N±ç¸CCT1 ãNÌÝª}s[NÆµÄ­õXyßCÎõÛ¶zu¨æÑñÛ¶zuÌÇ¿çÅàÏª³êNgÉÏª³êéBµ©µCÎÌ«ªáºµÄ³û»É

éBÜ½C»Ì­xà­¢B¿©çÍC³çÉ­xÌ­ÈÁ½r[ÉCCT2 ãNÉæé}s[NiCT2 s[¢ Ti Ka XyNgi`4500 eVjàúo³êÄ¢éªCNjª»êéBÁÉC`^CIÌÌSÊu©çÌÏÊoíÅêxÉoÅ«éGlM[ÍÍÌ§ñ©çC{éB±Ì±ÆÍC­õX¤ÅÍªèµÄ¢È¢BKa â Kb ÈÇÌuõ X üiÁyNgÉ»êé CT2 s[NªCPÊiqàÉ¶¶éU« X üjÍC¨¿Ì\¬³fð¯è·é½ßÉp¢çÊiItZ^[ÊjÉq´ÅdªÉC·Èí¿dCoÉqÌÇIÈv[uÆÈé±êÄ¢éBµ©µCêçzÊqi_fjÆÌÉÍ¼ÚÆðÓ¡·éBÖ^µÈ¢àkO¹ª­õßöÉ^é½ßC¨¿Ì­Ud«ÈÇð½f·édqóÔÏ»Íuõ X üÉÍ»êÈ¢B4. ­UdÌ BaTiO3 Ì}s[NÆÇUdªÉ}UÍe«UÆ¯lÉÎõÛ¶zuÅÌÝÏª³êéB½¾µCFig. 4 ð©Äª©éÊèC»Ì­xÍuõ¬ªÉä×Ä¹¢º¢ 1/100öxÆÉßÄã¢i}ÌBaTiO3 Å¾çê½ CT s[NÆUdªÉÌÀ±Êð

CT1, CT2jB³çÉC¤Âð©çOêéÆ}¬É¸Ðî·éBÀ±ÍCPhoton Factory (BL7C, BL15B1j¨µÄÏª³êÈ­ÈéBê©©Æ³ê»¤Ès[NÅÍæ Ñ SPring­8 ( BL39XU j Å s Á ½ B  u Ì Ú × Í ¶éªCtÉ±Ì¤ÂðÌµµ³Æ¾mÈÎõË¶«±£12,13) ðQlÉ³ê½¢BFig. 4 É BaTiO3 Ì Ti Kb ¤Â»ªC±Ìs[Nª­õ´qÌÇIÈdqóÔð½fµ­ õ X y N g  i RXES j ð ¦ · B e « U  s [ N½dvÈXyNg\¢ÅiElasticjÌGlM[ÍC}ü}É¦µ½ Ti K zûX5 É}s[NÌÌæðgåµÄ¦·B(a)²¿Ì

y N g  i 1s ¨ 4p j Ì white line s [ N Ì G l  M [·xË¶«14) C(b)im±qÌ±aË¶«12) ¨æÑ(c)Pi4985.3 eVjÉÎ·éBe«Us[NªÏª³êé½»ÌdêË¶«14) Ì»ê¼êðCx[XCÉItßÉÍC±ÌõwßöªüË X üÅU®³¹çê½¨¿ZbgðÁ¦Ä¦µÄÌd×ÉæéoÉqúËÉæÁÄø«N±³êé½ßC»Ð¸Ýic/a äjª¦éæ¤ÉÀ×ÄüË X üÆU X üÌÎõûüðÛÁ½ÜÜªèzuðgÞKvªéiÎõÛ¶zu)8) BÜ½Ce«Us[NÌ­xÍåÉ¿\ÊÌ½R³ÈÇÌô½wIÈvöÉ

14  úËõ Jan. 2015 Vol.28 No.1

é±Æð¦´µÄ¢éBFig.

éBÇÌêàCº©çãÉ³ûBaTiO3 ÍCº·ÅÍ­UdÉ»ÅéBè c/a1.01Ì³ûCð´¦éÆ§û»É\¢]ÚµéªCTc120ÄíUdÌÉÈé15) B±ÌÏ»ÉÄµÄCCT2 s[NgsbNX ¡ ¤Â X ü­õªõÉæéT^­UdÌ`^_oEÌÇªÉóÔÌ¤

Fig. 5

Enlarged graphs of Ti Kb resonant X­ray emission spectra of BaTiO3 around the CT peaks. (a) Temperature de­pendence of the powder sample. (b) Particle­size dependence of the nanopowder samples. (c) Electronic eld de­pendence of a crystalline sample. For each graph, tetragonal distortion of the sample is increased from bottom totop with an oset for each spectrum.

gªo»µnßéÆñ¥³êÄ¢é16) BÅßÅÍCîX ü[U[ðp¢½XybNÏ@©çCTc æèà4.5C·¤Å[gÌå«³Æzüäç¬ÌÉaÔªÅåÉÈé±Æªñ³êÄ¢é17)B

5. BaTiO3 im±qÌUdÙíX üñÜp^[©ç_³êé]Ú_Æ X ü­õªõ©ç_³êé]Ú_Ìá¢ÍCim±qÌêÉ³ç
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Temperature variation (a) and particle­size dependence (b)of X­ray diraction pattern around {200} peaks of BaTiO3.

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Ocal Journal of the European Union L 174, 88 (2011).
ºP¾YC­UdÌÆ\¢]ÚCÖØ[i1998).
S.­H. Yoon, C. A. Randall and K.­H. Hur: J. Appl. Phys. 108,064101 (2010).
S. Wada, H. Yasuno, T. Hoshina, S.­M. Nam, H. Kakemoto
and T. Tsurumi: Jpn. J. Appl. Phys. 42, 6188 (2003).
h ûFúËõ 8, 470 (1995).
½ª ]F³ÍÌÈwÆZp 23, 252 (2013).
cû@FFÅÌ¨ 48, 379 (2013).
Y. Harada, T. Kinugasa, R. Eguchi, M. Matsubara, A. Kota­
ni, M. Watanabe, A. Yagishita and S. Shin: Phys. Rev. B 6112854 (2000).
A. Kotani and S. Shin: Rev. Mod. Phys. 73, 203 (2001).
R. E. Cohen: Nature 358, 136 (1992).
Y. Kuroiwa, S. Aoyagi, A. Sawada, J. Harada, E. Nishibori,
M. Takata and M. Sakata: Phys. Rev. Lett. 87, 217601(2001).
N. Nakajima, M, Oki, Y. Isohama, H. Maruyama, Y. Tezu­ka, K. Ishiji, T. Iwazumi and K. Okada: Phys. Rev. B 86,224114 (2012).
Y. Isohama, N. Nakajima, G. Watanabe, M. Mizumaki, N.
Kawamura and H. Maruyama: Jpn. J. Appl. Phys. 50,09NE04 (2011).
Y. Isohama, N. Nakajima, H. Maruyama, Y. Tezuka and T.
Iwazumi: J. Electron Spectrosc. Relat. Phenom. 184, 207

gsbNX ¡ ¤Â X ü­õªõÉæéT^­UdÌ`^_oEÌÇªÉóÔÌ¤

(2011).
W. J. Merz: Phys. Rev. 75, 687 (1949).
G. Burns: Phys. Lett 43A, 271 (1973).
K. Namikawa, M. Kishimoto, K. Nasu, E. Matsushita, R. Z.
Tai, K. Sukegawa, H. Yamatani, H. Hasegawa, M. Nishiki­no, M. Tanaka and K. Nagashima: Phys. Rev. Lett. 103,197401 (2009).
18) H. Moriwake, C. A. J. Fisher, A. Kuwabara and T. Hashi­
moto: Jpn. J. Appl. Phys. 50, 09NE02 (2011).

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E­mail: nobuohiroshima­u.ac.jpêåFÅÌ¨«CúËõÈwmªðn
1997N 3 HÆåwåw@Hw¤ÈmÛöC¹BmiwjB1997N4 GlM[Á¬í¤@\ COE ¤õB1998N 4 OOåwHwèB
2004N 6 æè»ELocal electric polarization of a typical ferroelectricbarium titanate probed by resonant X­ray emis­
sion spectroscopy
Nobuo NAKAJIMA
Abstract

Graduate School of Science, Hiroshima UniversityHigashi­Hiroshima 739_8526, Japan

With the rapid improvement of nanofabrication techniques of electronic devices, an atomic­scalecharacterization is required to understand the electric eld response of dielectric materials inmultilayer ceramic capacitors. We have intensively studied the dielectric property of a typical fer­roelectric material, BaTiO3, using resonant X­ray emission spectroscopy, with a focus on thecovalency between Ti4{ cations and O2| anions. Especially, Raman scatterings mediated by char­ge­transfer excitations contain local information around the emitting atoms, since the scattering is
a rapid­response and coherent second­order optical process. This enables one to observe appliedeld response of a single electric polarization in dielectric domains. In BaTiO3, it is found that theelectric dipole moment remains above the Curie temperature with sucient intensity, and that thedisplacive­type mechanism of ferroelectric phase transition becomes conspicuous in nanoparti­cles, leading to novel properties such as gigantic enhancement of dielectric constant.

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