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64  úËõ March 2013 Vol.26 No.2
(C) 2013 The Japanese Society for Synchrotron Radiation Researchðà ¡ VK@\«_»¨Þ¿Ì\¢¨«]¿FúËõðgÁ½ A TCg^yuXJCg\¢_»¨Ì¤©ç

Fig. 1(Color online) Crystal structure of A­site­ordered perov­
skite­structure oxide AA
3B4O12. A­site ions (yellow spheres)and A
­site ions (square­coordinated blue spheres) are or­dered at the ratio of 1:3, and B­site ions form BO6 octahedra.

¤Lµ½ BO6 ªÊÌÍå«­X¢Ä¢éB±Ì\¢ð

Fig. 2 (Color online) Synchrotron X­ray diraction pattern (dots)
at room temperature and the calculated (solid line) prole of
Rietveld renement for LaCu3Fe4O12. Tick marks cor­
respond to the Bragg peak positions of LaCu3Fe4O12 (top),and small amount of impurity phases of a­Fe2O3 (middle)
and LaFeO3 (bottom).

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Ì BVS Í2.90Æ3.05ÆÈèCeXÌCIóÔª Cu3{®ÆÌMc£Á«7_9)¨æÑ Fe3{ ÆÈÁÄCV¨¿ªCI»fÅÍCV¨¿Ì]¿ÌæêÍ¨¿Ì¯èÆ»Ì»\¢ðÍÅ

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Cu3{ Æ¢¤Ùí´q¿óÔÍÉßÄ¿µ¢BÁÙÈ_ÆÈéBêûCFe_O £ÍZ­ÈÁÄCFe ÌCIf½Ê 4 zÊ\¢ÅC±Ìæ¤È¿µ¢CI¿ªÀ¿ÍêÊIÈ{3 æèà¢Ùí´q¿óÔÖÆÏ

è»µ½àÌÆl¦çêéB»µÄ¢é±Æª¦³êéB¥»âXoEA[øÊÈ±Ì LaCu3Fe4O12 É¨¢ÄC\¢Ì·xÏ»ðÏ@·ÇC»Ì¼ÌªèÊàí¹Äl¦éÆC±Ì]ÚÅÍ

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æ¤ÉiqÌÏªå«­¸­·éB·xã¸Éº¢¨¿ÌÌd×Ú®i3Cu3{{3e|¨3Cu2{, 4Fe3{|3e|¨4Fe3.75{jÌÏª¸­·éÌÅC±ÌÏ»ÍuÌMc£vÆÝé±ªN±ÁÄ¢é±Æª¾ç©ÆÈÁ½B±Ìæ¤È·xÏÆªÅ«éB±ÌC»iqÌÏ»Éº¢CCu_O ¨æ»ÉæéTCgÔd×Ú®Æ»êÉº¤ÌMc£ªN±

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BiCu3Mn4O12 ÅÌ¥«ðÍFA_B tF¥«Æå¥CïRÁ«14,15)

A TCg^yuXJCg\¢_»¨ BiCu3Mn4
O12 ÅÍCATCgÌ Cu Æ B TCgÌ Mn ÌÔÌ½­¥«ÝìpÉæétF¥«ª»êéÆ¯ÉCå«È¥CïRª­»·éB»\¢ðÍÌÊÍC±ÌV¨¿ÌC I  ª z ª C LaCu3Fe4O12 Ì  ·  Æ ¯ l Å C Bi3{
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Fig. 3(Color online) Temperature dependence of unit cell volume,Cu_
O and Fe_O bond lengths, and bond valence sums
(BVS) value for LaCu3Fe4O12.

66  úËõ March 2013 Vol.26 No.2

Fig. 4

é9KÅ

(Color online) Magnetoresistance ratios of BiCu3Mn4O12 at
various temperatures.

ðà ¡ VK@\«_»¨Þ¿Ì\¢¨«]¿FúËõðgÁ½ A TCg^yuXJCg\¢_»¨Ì¤©ç

Fig. 6(Color online) Calculated density of states (DOSs) (states/eV cell spin) and band structure for ferrimagnetic BiCu3Mn4
O12. Total DOSs (shaded region) and partial DOSs of Cu(blue), Mn (red), and Bi (green) are also shown.

ûüÌXsðàÁ½dq¾¯ªdC`±Á«Éñ^µÄ¢é±Æªí©éBtF~ÊÅÌóÔ§xÍåÆµÄ
Mn Ì 3d O¹ÉRµÄ¢éBÂÜèC±ÌnÅÍCB
TCgÌ¬´q¿óÔÉé Mn CIªdC`±Á«ðS¢CXsª®SÉÎÉµ½`±dqÉæéUªå«È¥CïRðø«N±µÄ¢éÌÅéBBiCu3Mn4

O12 ÅÌtF¥«]Ú·xÍº·æèà­C¥CïR
Fig. 5(Color online) Cu­L2,3 and Mn L2,3 edges X­ray absorption
spectra (XAS) for BiCu3Mn4O12 taken at 9 K. I{ (red) andI| (blue) spectra were measured with external eld (1.9 T)
applied parallel and antiparallel to the light propagation
axis. Magnetic circular dichroism (MCD) intensities wereobtained by I{_I|.

øÊÍº·ÅàÏª³êé½ßC±Ì¨¿ÍVµ¢Xs
gjNXÞ¿ÆµÄàdvÅ

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CaCu3B4O12 iBGe, Ti, Sn) ÌdqóÔðÍF
A TCg¥«16_20)

A TCg^yuXJCg\¢_»¨É¨¢ÄCBsÁ½BFig. 5 ÍüËÎõ X üÉÎ·é Cu_L2,3 [Æ Mn_

TCgÉñ¥«CIªüéÆCyuXJCg\¢ÅÍL2,3 [ÌzûXyNgÆ»Ì·ª©ç¾½ MCD XyN¿ µ ¢ A T C g¥ « ª »ê é B CaCu3Ge4O12, CaCu3Ti4gð¦·B±±ÅCI{ Í¿ÌD¨È¥C[gO12, CaCu3Sn4O12 ÅÍ CeX B TCg Éñ¥ «Ì Ge4{,

Æ~ÎõXsª½sÅézuÌzû­xiI| Í½½

Ti4{, Sn4{ ª ü Á Ä ¢ é ª C CaCu3Ge4O12 Æ CaCu3Sn4sÈzuÌzû­xjÅèC¥«ÌÉÆËµ½ X üÌ

O12 Í]Ú·xª13 K Æ10 K Ì­¥«CêûCCaCu3Ti4zûXyNgÍ~ÎõÉæèÙÈéÌÅC»ê¼êÌz

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OiÌÍ Cu Æ Mn ÅtÆÈÁÄ¢éB±êÍC«iCaCu3Ti4O12)|­¥«iCaCu3Sn4O12jÆA±IÉÏATCgÌ Cu Ì¥C[gÆ B TCgÌ Mn Ì¥»µÄ¢é±Æª¾ç©ÆÈÁÄ¢éB¯¶§ûiqãÉ

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B ÔÅÌ½­¥ÝìpªtF¥«ðø«N±µÄ¢é·Éæè­¥«©ç½­¥«ÖÆÏ»·éáÍ¼ÉÍÈ¢Bæê´vZÉæédqóÔðÍÌÊÍC_fª½Ê

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XAS_MCD ©ç¾çê½tF¥«Xszuð¼èµµÄ¢é½ßCæêßÚÌ Cu2{ XsÔÉÍC½­ÌJÄæê´vZðsÁÄ¾½oh\¢ð Fig. 6 É¦·BÚà®_»¨É©çêéæ¤È_fðîµ½´ð·Ýì_EXsÌohÅÍtF~ÊÅMbvªó¢ÄpªÍ½ç©¸C¼Úð·ÝìpÉæé­¥«ªxzI¢éªCAbvXsÌohÍtF~Êð¡ØèCêÅ

é±Æð¦·iFig. 8jB±Ìæ¤È¼Úð·ÝìpúËõ March 2013 Vol.26 No.2  67

Fig. 7

(Color online) Magnetization of CaCu3B4O12 (BGe, Ti,
Sn) at 5 K.

Fig. 9(Color online) Oxygen K­edge X­ray absorption spectra(XAS) of CaCu3B4O12 (BGe, Ti, Sn).

Þ¿ÆµÄÌÀpÍïµ¢ªC±êçÌÀ±ÊÍCñ¥«CIðã¦é±ÆÅ¥CóÔðXCb`OÅ«é¨¿ÌÝvwjð^¦éàÌÅ

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Cu_
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3 Cr4 O12 ÌCIªzðÂ±ÆªùÉª¬ª½­¥«ÝìpÉèIÈððÊ½µÄ¢é±Æ©ÁÄ¨èCMn_L2,3 [ÌzûXyNgÍ Mn3{ ÌCIð¾mÉ¦·BCaCu3Ti4O12 ÅÍ B TCgÌ Ti Í{4 ¿óÔð½fµ½àÌÅé21) B±Ì¼ÒÌXyNg

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éBµ©µC±Ì Ti_3d O¹ª Cu_3d Æ O_2pÍ¾ç©É LaMn3Cr4O12 ÌàÌÆÍÙÈÁÄ¨èC»Æ­­¬¬·é±ÆÅCFig. 8 É¦·æ¤ÈæOßÚÌ

3{ÌCIªzÍ La3{Mn3{
3 Ti4 O12 ÅÍÈ¢±Æª­­¦Cu2{ XsÔÉ Cu_O_Ti_O_Cu Æ¢¤¥CIÈpXÉæ

´ ³ ê é B ³ ç É C Ti _L2,3 [ Å Ì z û X y N g  ðè½­¥«´ð·ÝìpªUN³êÄ¢éBcOÈª

CaCu3Ti4O12 Å¾çê½àÌÆär·éÆC¡xÍ»Ì¼çCêAÌ¨¿Ì¥C]Ú·xÍá¢ÌÅC·®É@\«ÒÌXyNgÍñíÉæ­êvµÄ¨èCTi ÌCIÅÍóÅ

68  úËõ March 2013 Vol.26 No.2

ðà ¡ VK@\«_»¨Þ¿Ì\¢¨«]¿FúËõðgÁ½ A TCg^yuXJCg\¢_»¨Ì¤©ç

Fig. 11
Fig. 10(Color online) X­ray absorption spectra (XAS) of Mn­L2,3
and Ti­L2,3 edges of LaMn3Ti4O12 (red). Mn­L2,3 edge spec­3{
trum of LaMn3{
3 Cr4 O12 (blue) and Ti­L2,3 edge spectrum
4{of CaCu2{
3 Ti4 O12 (red) are also shown.

4{4{ ÅóÔÍ Ca2{Cu2{
3 Ti4 O12 Æ¯lÉ Ti(Color online) Energy dependence of anomalous dispersioncoecients, fand f
, in X­ray scattering factors for Ti and
Mn. The beam energies used in the experiments, 6.53 keV
for resonant diraction and 14.99 keV for nonresonantdiraction, are indicated with dashed lines.

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3{Æl¦êÎCLa3{Mn2{
3 (Ti0.75Mn0.25 )O12 Æ¢¤CIª

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ç¼ÒÌÝu·ððÍ·é±ÆÍ¢ïÅg^yuXJCg\¢_»¨à½©Â©ÁÄ¢äXÍCúËõ X üÌüËGlM[ð Mn Ì¤ÂðèCñÜf[^©
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ÄCiLa/Bi)Cu3Mn4O12 ÅÍ B TCgÍ Mn3.75{ Ì¬´ß­É·é±ÆÅCñÜÉ¨¯éÙíªUÉæéU\Ìè14,23) C±Ì\¢Ì B TCgÉÍ Mn3{ àá¢ðgÁÄCeTCgÌèL¦ð³mÉßé±Æðq¿óÔÅ

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¢ÄC¼É B TCgÌ Ti4{ Ì25÷ª Mn3{ Åu·³ê½

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ñæèã°½ A TCg^yuXJCg\¢_»¨ÉÀç¸C3d JÚà®_»¨ÅÍCJÚà®CIÆ»ÌzÊ_fÌªdqóÔðå«­Ï»³¹C½­Ì»¡[¢Á«ðø«oµÄ¢éB»Ì@\Á«ÌîÆÈéC
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Fig. 12 (Color online) Nonresonant (l0.82716 Å) and resonant(l1.898161 Å) synchrotron X­ray diraction (SXRD)
patterns and the Rietveld renement results for LaMn3Ti4
O12. Small amounts of impurity phases, TiO2 and LaMnO3
were included in the renements.

TCg^yuXJCg\¢_»¨ÍåÉC´L¶CcapCØGCRÍÌeª³¬Éæèì¬µ½àÌÅ·B¨¿¬C¨«]¿ÉÖµÄ½­ÌÊ©ç²¦Í¢½¾¢½såwÉ»w¤Ìijì¤ºiì²v³öj¨æÑì¤ºÌw¶CX^btÌ
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DIAMOND ÅÌúËõÀ±ÅÍCer[CSÌTi Æ Mn ÌU\Í\ªÈRgXgðàÁÄñÜÉ

ûXÉÀ±©çðÍÜÅ½­Ì²¦Íð¢½¾«Üµ½B

ñ^·é±ÆÉÈéÌÅC»\¢ðÍÉ¨¯éèL¦ÅÁÉCSPring­8 ÆÌAgÉÖµÄÍCØºiPxàC\ªÉM«Ì¢ÊðúÒÅ«éBÀ±ÍpúõÈw¤Z^[jCDIAMOND ÅÌÀ±ðÜß½Û

ËõÀ±{Ý DIAMOND Ì I11Ås¢CãLÌ¤ÂÉß¤¯¤ÅÍCJ. Paul Atteld ³öiGWoåwj¢ði6.53 keVCg·1.898161 ÅjÅÌñÜf[^ÆÉ ¨ ¢ b É È è Ü µ ½ B Ü ½ C ¤  Ì ê  Í JST _X üÌzûÈÇÌâèª­È­ªð\ð¾çêéÊí

CREST ¤©çÌxðó¯Ä¢Ü·BÌñ¤Âði14.99 keVCg·0.82716 ÅjÅÌñÜf[Ql¶£^ð¯ðÍ·é±ÆÅC»\¢Ì¸§»ðsÁ½B
Fig. 12 É¼ðÅÌñÜp^[ÆCTopas vO25)Éæé[gxgðÍÌÊð¦·BB TCgÌèL¦ð¸§»µ½ÊÍCg(Ti/Mn)0.949(3)/0.051(3)Æ
ÈèCMn CIÌ B TCgÖÌ¬üð¼èµÄà A
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CgÌ Mn CIª{2 ¿ÆÈéÙÇÌu·ÍN±ÁÄ¢È¢±Æª»¾µ½BÂÜèC½­ÌÀ±ÊÍ·×ÄC
LaMn3Ti4O12 ÅÍÙíá´q¿Ì Mn{ ªÀ»µÄ¢éÂ\«ð­­¦µÄ¢éÌÅ

éB±Ìæ¤ÈÉßÄ¿µ¢´q¿óÔªVïÈ¨«ðø«N±·Â\«Í\ªÉèCÙíá´q¿ Mn CIðÜñ¾V¨¿ª¡ãVµ

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@\«_»¨Þ¿ÆµÄäXªÚµÄ¢é A TCg

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såwÉ»w¤É³ö
E­mail: shimakscl.kyoto­u.ac.jpêåFÅÌ»wCÞ¿Èwmªðn
1987NCsåwåw@w¤ÈCm
ÛöI¹Cmiw)B1987N_2003NC
 åC ¤ õB » ÌÔ 1993N _ú {d Cò
1994NCÄASk§¤qõ¤õB2003Næè»EBqmêN(öà)PxõÈw¤Z^[ÉSPr­
ing­8Éå²¤õE­mail: mizumakispring8.or.jpêåFX üªõwCÅÌ¨
mªðn
1997NCåwHwn¤ÈmÛö
C¹CmiHw)B1997NCPxõÈw¤Z^[¦Í¤õB1998NC¯¤õB2003Næè»EB¡usåwÉ»w¤É³
E­mail: saitoscl.kyoto­u.ac.jpêåFÅÌ»wmªðn
2002NCsåwåw@w¤ÈmãúÛöC¹Cmiw)Bú{wpU»ïÁÊ¤õðoÄC2004Næè»EB

Crystal structures and physical properties of
new functional­oxide materials:
Recent studies with synchrotron radiation onA­site­ordered perovskite­structure oxides
Yuichi SHIMAKAWA

Institute for Chemical Research, Kyoto University
Gokasho, Uji, Kyoto 611_0011, Japan

Takashi SAITO

Institute for Chemical Research, Kyoto University
Gokasho, Uji, Kyoto 611_0011, Japan

Masaichiro MIZUMAKI

Japan Synchrotron Radiation Research Institute, SPring­8
1_1_1 Kouto, Sayo­cho, Sayo­gun, Hyogo 678_5148, Japan

AbstractA­site­ordered perovskite­structure oxides attract lots of attention recently because the com­pounds show interesting and potentially useful properties. We will report recent studies on crys­tal, electronic, and magnetic structures of the compounds by synchrotron X­ray radiation tech­niques such as high­resolution powder X­ray diraction and X­ray absorption spectroscopy.

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