http://support.spring8.or.jp/Report_JSR/PDF_JSR_31A/2019A1812.pdf

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2019A1812

BL19B2/D6U0Q2)[ ᒙ≧࣌ࣟࣈࢫ࢝࢖ࢺ໬ྜ≀ࡢ⤖ᬗᵓ㐀࡜ ) ⃰ᗘ࡟క࠺ᵓ㐀ኚ໬
6WUXFWXUDO,QYHVWLJDWLRQRI5XGGOHVGHQí3RSSHU&RPSRXQGV/D6U0Q2)[ᯇỌ ฼அ,᭪☒ࠊ⋤ᙪᫀࠊᒣᮏ೺ኴ㑻ࠊෆᮏ ႐ᬕ Toshiyuki Matsunaga, Shuo Cao, Yanchang Wang, Kenotaro Yamamoto, Yoshiharu Uchimotoி㒔኱Ꮫ
Kyoto Universityᮏㄢ㢟࡛ࡣࠊࣇࢵ໬࢖࢜ࣥ஧ḟ㟁ụ⏝ṇᴟᮦᩱ La1.2Sr1.8Mn2O7F[ ࡢ⤖ᬗᵓ㐀࡟㛵ࡋࠊᨺᑕග⢊ᮎᅇᢡἲ࡟ࡼࡾࠊヲ⣽࡟ゎ᫂ࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋLa1.2Sr1.8Mn2O7FࠊLa1.2Sr1.8Mn2O7F2 ⤖ᬗࡣࠊ᪤ሗ࿌㏻ࡾࡢᵓ㐀㸦ཎᏊ㓄ิ㸧ࢆྲྀࡗ࡚࠸ࡓࡀࠊF ࡜ O ࡀࠊሗ࿌ࡢࡶࡢ㸦つ๎㓄ิ㸧࡜ࡣ␗࡞ࡾࠊ୙つ๎ⓗ࡟ኵࠎࡢ࢔ࢽ࢜ࣥࢧ࢖ࢺࢆ༨᭷ࡋ࡚࠸ࡓࠋ୍᪉ La1.2Sr1.8Mn2O7F[㸦[2㸧࡟ࡘ࠸࡚ࡣࠊཎᏊ㓄ิࡣ La1.2Sr1.8Mn2O7F2 ࡢࡲࡲࠊ࢔ࢽ࢜ࣥࢧ࢖ࢺ࡟࠾ࡅࡿ F/O ࡢ๭ྜࡀࠊ⤌ᡂ [ ࡟ᛂࡌ࡚ኚ໬ࡋ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ࣮࣮࢟࣡ࢻ㸸 ࣇࢵ⣲࢖࢜ࣥ஧ḟ㟁ụࠊ⢊ᮎ X ⥺ᅇᢡࠊᒙ≧࣌ࣟࣈࢫ࢝࢖ࢺᆺ໬ྜ≀ࠊ࣮ࣜࢺ࣋ࣝࢺゎᯒ⫼ᬒ࡜◊✲┠ⓗ㸸 㠉᪂ᆺḟୡ௦㧗ᛶ⬟஧ḟ㟁ụࡢ᪩ᮇ㛤Ⓨ㸪ᐇ⏝໬ࡀᡃࡀᅜ⏘ᴗࡢ⏕࿨⥺ࢆᢸࡗ࡚࠸ࡿ࡜࠸ࡗ࡚ࡶ㐣ゝ࡛ࡣ࡞࠸ࠋLi ஧ḟ㟁ụ㸦LIB㸧࡟௦ࢃࡿ㠉᪂ⓗ஧ḟ㟁ụೃ⿵ࡢࡦ࡜ࡘࡀࣇࢵ⣲໬ྜ≀࡛࠶ࡾࠊࡇࢀࡽࡢೃ⿵ࡢ௦⾲ⓗ໬ྜ≀ࡢ୍ࡘࡀ La1.2Sr1.8Mn2O7 ᒙ≧࣌ࣟࣈࢫ࢝࢖ࢺᆺ໬ྜ≀࡛࠶ࡿ[1]ࠋ
LIB ࡟࠾࠸࡚ࡣ㸪౛࠼ࡤ LiCoO2 ᒙ≧ᒾሷᆺ໬ྜ≀ࢆṇᴟ࡟⏝࠸࡚ࠊLi ࢖࢜ࣥࢆ CoO2 ࡢᙧᡂࡍࡿᒙ㛫࡟྾཰/⬺㞳ࡉࡏࠊᨺ㟁/඘㟁ືసࢆ⾜࠺ࡀࠊLa1.2Sr1.8Mn2O7 ࡟࠾࠸࡚ࡶ㸪 F ࢖࢜ࣥࡀࡇࡢᒙ≧໬ྜ≀ࡢᒙ㛫࡟ฟධࡾࡍࡿࡇ࡜࡟ࡼࡾࠊྠᵝ࡟඘ᨺ㟁ືసࢆ⧞ࡾ㏉ࡍࠋ༶ࡕ඘㟁᫬࡟ࡣࡇࡢ໬ྜ≀ࡢᒙ㛫࡟ F ࢆᤄධࡋࢆᙧᡂࡋ࡚࠾ࡁࠊᨺ㟁᫬࡟ࡣṇᴟ࡜ࡋ࡚స⏝ࡉࡏ㸪F-ࡣ࢖࢜ࣥఏᑟయࢆ௓ࡋ࡚㈇ᴟ࡟㸪୍᪉ṇ㟁Ⲵࡢ᪉ࡣᅇ㊰ࢆὶࢀ࡚௙஦ࢆࡍࡿࡢ࡛࠶ࡿࠋࡓࡔ࢔ࢽ࢜ࣥ⛣ືᆺ஧ḟ㟁ụ࡟㛵ࡋ࡚ࡣ㸪◊✲㛤ⓎࡢṔྐࡀὸ࠸ࡇ࡜ࡶ࠶ࡗ࡚㸪ࣇࢵ⣲྾⬺╔㐣⛬࡟࠾ࡅࡿ⤖ᬗᵓ㐀ཬࡧࡑࡢኚ໬ࠊࡑࡋ࡚ᵓ㐀Ꮫⓗ཯ᛂ࣓࢝ࢽࢬ࣒ࡶṤ࡝ゎ᫂ࡉࢀ࡚࠸࡞࠸ࡢࡀ⌧≧࡛࠶ࡿ㸬౛࠼ࡤ
La1.2Sr1.8Mn2O7 ࡟࠾ࡅࡿࣇࢵ໬໬ྜ≀ࡣࠊLa1.2Sr1.8Mn2O7F [2]ࠊLa1.2Sr1.8Mn2O7Fʹ [3]ࡀ▱ࡽࢀ࡚࠸ࡿ
ࡀ ࠊ La1.2Sr1.8Mn2O7 ཬ ࡧ La1.2Sr1.8Mn2O7Fʹ ࡣ ✵ 㛫 ⩌ 㸸 I4/mmm ࡜ ゎ ᯒ ࡉ ࢀ ࡚ ࠸ ࡿ ୍ ᪉ ࡛ ࠊ
La1.2Sr1.8Mn2O7F ࡣ✵㛫⩌㸸P4/nmm ࡜ࡉࢀ࡚࠸ࡿࠋࡲࡓࠊLa1.2Sr1.8Mn2O7 ࡣࠊ㟁Ẽ໬Ꮫⓗ࡟ࠊF ࡀ୍ศᏊᘧᙜࡓࡾࠊ2 ཎᏊ࡟␃ࡲࡽࡎࠊ4 ཎᏊࠊ5 ཎᏊࡲ࡛໬ྜࡉࡏᚓࡿࡇ࡜ࡀุ᫂ࡋ࡚࠸ࡿࠋࡇࢀ
࡟ࡼࡾ⌧⾜ Li ஧ḟ㟁ụࢆ㐶࠿࡟෽㥙ࡍࡿࠊ᱁ẁ࡟ඃࢀࡓయ✚࢚ࢿࣝࢠ࣮ᐦᗘࡀᚓࡽࢀࡿࠋࡓࡔࡑࢀࡽ㔜ࣇࢵ໬໬ྜ≀ᵓ㐀ࡢᵓ㐀࡟ࡘ࠸࡚ࡶ඲ࡃゎ᫂ࡉࢀ࡚࠸࡞࠸ࠋࡇࡢㄢ㢟࡛ࡣ㸪La1.2Sr1.8Mn2O7ࣇࢵ໬໬ྜ≀ࡢࣇࢵ໬࡟క࠺⤖ᬗᵓ㐀㸭⤖ᬗᵓ㐀ኚ໬ࢆヲ⣽࡞ゎ᫂࡟ྲྀࡾ⤌ࢇࡔࠋᐇ㦂㸸
La1.2Sr1.8Mn2O7Fx ໬ྜ≀ࡣࠊLa1.2Sr1.8Mn2O7 ࡜ PVDF㸦࣏ࣜࣇࢵ໬ࣅࢽࣜࢹࣥࠊPolyVinylidene
DiFluoride㸧ࢆ⢊○㸭ΰྜࡋࠊຍᅽ࣌ࣞࢵࢺ໬ࡋࡓᚋࠊ↝ᡂࡋస〇ࡋࡓࠋᨺᑕග⢊ᮎᅇᢡ ᐃヨᩱࡣࠊ↝ᡂヨᩱࢆ⢊○ࠊ࣓ࢵࢩࣗࢆ⏝࠸⢏ᚄㄪᩚࡋࡓࡶࡢࢆࠊෆᚄ㸸0.6 mmĳ ࡢ࢞ࣛࢫ〇࢟ࣕࣆࣛࣜ
࣮࡟඘ሸࡋస〇ࡋࡓࠋᅇᢡ ᐃࡣࠊBL19B2 ࣅ࣮࣒ࣛ࢖ࣥࡢ➨ 1 ࣁࢵࢳ࡟タ⨨ࡉࢀࡓከ┠ⓗࣁ࢖ࢫ࣮ࣝࣉࢵࢺᅇᢡィࢆ⏝࠸ࠊධᑕගࡢ࢚ࢿࣝࢠ࣮ࢆࠊ35keV ࡟タᐃࡋ⾜ࡗࡓࠋ⤖ᬗᵓ㐀ゎᯒࡣࠊRietveld
ἲ㸦JANA2006 [4]㸧࡟ࡼࡾ⾜ࡗࡓࠋ䠉㻝㻠㻟䠉⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸 La1.2Sr1.8Mn2O7 ࡟ࡘ࠸࡚ࡣ᪤࡟ᵓ㐀ゎᯒࡀ࡞ࡉࢀ࡚࠾ࡾ[1]ࠊᡃࠎࡀࣇࢵ໬໬ྜ≀స〇࡟⏝࠸ࡓࡶࡢࡶࠊࡑࡢሗ࿌㏻ࡾࡢᵓ㐀࡛࠶ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓ㸦✵㛫⩌㸸I4/mmm㸧ࠋ᭦࡟ La1.2Sr1.8Mn2O7 ࢆࣇࢵ໬ྜᡂࡋస〇ࡋࡓ La1.2Sr1.8Mn2O7F [2]ࠊLa1.2Sr1.8Mn2O7F2 [3]࡟ࡘ࠸࡚ࡶࠊࡣࡰࠊ᪤ሗ࿌㏻ࡾࡢᵓ㐀࡛࠶ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓ㸦✵㛫⩌㸸I4/mmm ཬࡧ P4/nmm㸧ࠋࡓࡔࠊᡃࠎࡀస〇ࡋࡓࡇࢀࡽࣇࢵ໬≀࡟࠾࠸࡚ࡣࠊFࠊO ࡀࠊࡑࢀࡽࡢᅛ᭷ࡢࢧ࢖ࢺࢆࠊኵࠎࡀ 100%༨᭷ࡋ࡚࠸ࡿࡢ࡛ࡣ࡞ࡃࠊ
ఱࢀࡢ FࠊO ࢧ࢖ࢺࡶࠊ୧᪉ࡢඖ⣲࡟ࡼࡗ࡚ࠊࣛࣥࢲ࣒࡟༨᭷ࡉࢀ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ
༶ࡕ᪤ሗ࿌ࡢᵓ㐀࡟࠾࠸࡚ FࠊO ࡀつ๎㓄ิࡋ࡚࠸ࡿࡢ࡟ᑐࡋࠊᡃࠎࡢస〇ࡋࡓࣇࢵ໬≀ࡣࠊ୙つ๎㓄ิࡋࡓᵓ㐀࡜࡞ࡗ࡚࠸ࡓ㸦ᅗ 1㸧ࠋLa1.2Sr1.8Mn2O7 ཬࡧ La1.2Sr1.8Mn2O7F ࡢ㛫ࠊLa1.2Sr1.8Mn2O7F
ཬࡧ La1.2Sr1.8Mn2O7F2 ࡢ㛫ࡣࠊኵࠎࡢ໬ྜ≀ࡢ஧┦ඹᏑ࡜࡞ࡗ࡚࠸ࡓࠋLa1.2Sr1.8Mn2O7F2 ࠿ࡽ᭦࡟ࣇࢵ໬ࢆ㐍ࡵࡓヨᩱࠊLa1.2Sr1.8Mn2O7F[㸦[=3, 4, 5, 6㸧࡟㛵ࡍࡿᵓ㐀ゎᯒ⤖ᯝࢆᅗ㸯࡟♧ࡍࠋࡇࢀࡽ
ࡢᵓ㐀࡟ࡘ࠸࡚ࡣࡇࢀࡲ࡛඲ࡃ୙࡛᫂࠶ࡗࡓࡀࠊ௒ᅇࠊLa1.2Sr1.8Mn2O7F2 ࡢ୙つ๎ᵓ㐀࡟࠾࠸࡚ࠊ
F/O ࢧ࢖ࢺ࡟࠾ࡅࡿ F ࡢ⨨᥮๭ྜࡀ⤌ᡂ [ ࡟ᛂࡌ࡚኱ࡁࡃ࡞ࡗ࡚⾜ࡃࡇ࡜ࡀศ࠿ࡗࡓࠋ
La1.2Sr1.8Mn2O7F[㸦[2㸧ࡢ✵㛫⩌ࡣ඲࡚ I4/mmm ࡛࠶ࡿࠋ/D6U0Q)
2[       [       [        [         [       [       [ I4/mmm
P4/nmm
I4/mmm
I4/mmm
I4/mmm
I4/mmm
I4/Fig. 1 Crystal structures of La1.2Sr1.8Mn2O7, La1.2Sr1.8Mn2O7F, and La1.2Sr1.8Mn2O9-[F[䠄[>2䠅determinedthrough Rietveld analysis. The red circled layers show the ones newly generated inLa1.2Sr1.8Mn2O7 by fluoridation.
௒ᚋࡢㄢ㢟㸸La1.2Sr1.8Mn2O9-[ F[ ࡣࠊLaࠊSrࠊMnࠊOࠊF ࡀࠊ໬ྜ≀୰࡛ࠊኵࠎࠊ+3 ౯ࠊ+2 ౯ࠊ+2 ౯ࠊ-2 ౯ࠊ-1 ౯࡛࠶ࡿ࡜ࡍࡿ࡜ࠊLa1.2Sr1.8Mn2O7 ࡣ La1.2Sr1.8Mn2O2.2F6.8 ㎾ࠊࣇࢵ໬ࡉࡏࡿࡇ࡜ࡀྍ⬟࡛࠶ࡿࠋ௒ᚋࠊࡇࢀࡽ La1.2Sr1.8Mn2O7 ᒙ≧࣌ࣟࣈࢫ࢝࢖ࢺᆺ໬ྜ≀ࡢ඘ᨺ㟁≉ᛶ࡜⤖ᬗᵓ㐀㸭⤖ᬗᵓ㐀ኚ໬࡜ࡢ㛵ಀࢆヲ⣽࡟ゎ᫂ࡋ࡚࠸ࡃᡤᏑ࡛࠶ࡿ㸬ཧ⪃ᩥ⊩㸸[1] R. Seshadri, M. Hervieu, C. Martin, A. Maignan, B. Domenges, B. Raveau, &KHP0DWHU䠄1997䠅1778[2] L. D. Aikens, L. J. Gillie, R. K. Li and C. Greaves, -0DWHU&KHP., 䠄2002䠅264[3] C. Greaves, J. L. Kissick, M. G. Francesconi, L. D. Aikens, L. J. Gillie, -0DWHU&KHP., 䠄1999䠅111[4] PetĜíþek. V.; Dušek, M.; Palatinus,L. Crystallographic Computing System JANA2006: General features.
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