SPring-8/SACLA ฼⏝◊✲ᡂᯝ㞟
2018A1545                 Section
SectionB B        BL40XU࣐࢖ࢡࣟ ; ⥺ᅇᢡ࡟ࡼࡿᙉㄏ㟁ᮦᩱࡢ㟁ᴟ㸭ㄏ㟁య⏺㠃ᵓ㐀࡜ㄏ㟁≉ᛶࡢ㛵ಀゎ᫂
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ᮌᮧ ᏹஅ , ᆏ಴ ㍤ಇ , ᆤෆ ᫂ , Ᏻ⏣ ఙᗈ aabc
Hiroyuki Kimura , Terutoshi Sakakura , Akira Tsubouchi , Nobuhiro Yasudaabcᮾ໭኱Ꮫከඖ≀㉁⛉Ꮫ◊✲ᡤ, (ᰴ)ᮧ⏣〇సᡤ, (බ㈈)㧗㍤ᗘග⛉Ꮫ◊✲ࢭࣥࢱ࣮abc
 IMRAM, Tohoku Univ., Murata Manufacturing Co., Ltd., JASRI✚ᒙࢭ࣑ࣛࢵࢡ࢟ࣕࣃࢩࢱ㸦MLCC㸧ࡢᐇᮦᩱ࡟ࡘ࠸࡚ࠊࢧࣈ࣐࢖ࢡࣟ X ⥺ᅇᢡࢆ⏝࠸࡚㟁ᴟ㸭ㄏ㟁య⏺㠃࡜ㄏ㟁య⣲Ꮚ㒊ศࡢᵓ㐀ࢆㄪ࡭ࡓࠋࢧࣈ࣐࢖ࢡࣟ㡿ᇦࡢ⢊ᮎᅇᢡࣃࢱ࣮ࣥࡢ࣐ࢵࣆࣥࢢ࡟ᡂຌࡋࡓࠋࡑࡢ⤖ᯝࠊ⏺㠃㏆ഐ࡛ࠊ᱁Ꮚᐃᩘࡢኚ໬ࠊ࠶ࡿ࠸ࡣ BaTiO3 ṇ᪉ᬗࢻ࣓࢖ࣥศᕸ
࡟⣔⤫ⓗ࡞ኚ໬ࡀ࠶ࡿࡇ࡜ࢆⓎぢࡋࡓࠋNi 㟁ᴟ࠿ࡽࡢᛂຊࢆཷࡅ࡚ࠊㄏ㟁య⣲Ꮚࡀṍࢇ࡛࠸ࡿࡇ࡜ࢆ♧ࡍ⤖ᯝ࡛࠶ࡿࠋ࣮࣮࢟࣡ࢻ㸸 ✚ᒙࢭ࣑ࣛࢵࢡ࢟ࣕࣃࢩࢱ㸪࣐࢖ࢡࣟ㡿ᇦ X ⥺ᅇᢡ⫼ᬒ࡜◊✲┠ⓗ㸸  MLCC ࡣෆ㒊㟁ᴟ࡜ࡑࢀ࡟ᣳࡲࢀࡓㄏ㟁య⣲Ꮚࢆ 1 ࣘࢽࢵࢺ࡜ࡋ࡚ࠊከ✚ᒙ໬ࡉࢀࡓᮦᩱ࡛࠶ࡿࠋ⌧ᅾ㸪MLCC ෆࡢㄏ㟁యᒙཬࡧ㟁ᴟᒙࡢཌࡳࡣࡑࢀࡒࢀ 1 ȝmࠊ0.5 ȝm ௨ୗࡀᐇ⌧ࡉࢀ࡚࠾ࡾࠊ᭦࡞ࡿⷧ⭷໬ࢆ┠ᣦࡋ࡚࣓࣮࣮࢝ࡀࡋࡢࡂࢆ๐ࡗ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊࡇࡢⷧᒙ໬࡟ࡼࡿ㟁ᴟ㸭ㄏ㟁య⏺㠃ࡢᵓ㐀࣭㟁Ꮚ≧ែࡢᙳ㡪ࡀࠊㄏ㟁≉ᛶࡢྥୖࢆጉࡆࡿ኱ࡁ࡞せᅉ࡜࡞ࡾࠊ୍᪉࡛ㄏ㟁య⣲Ꮚࡢⷧ⭷໬ࡸㄏ㟁య⢏⮬㌟ࡢᚤᑠ໬࡟కࡗ࡚ㄏ㟁⋡ࡀపୗࡍࡿࡇ࡜ࡶྂࡃ࠿ࡽ▱ࡽࢀ࡚࠾ࡾ[1,2]ࠊMLCC ࢳࢵࣉࡢᑠᆺ኱ᐜ㔞໬ࡀ㢌ᡴࡕ࡟࡞ࡗ࡚࠸ࡿ⌧≧ࡀ࠶ࡿࠋࡇࡢ⌧≧ࢆᡴ◚ࡍࡿࡓࡵ࡟ࡣࠊ㸯㸬ㄏ㟁యཌ࡜ෆ㒊㟁ᴟཌࠊཬࡧ㸰㸬㟁ᴟ㸭ㄏ㟁య⏺㠃ࡢᵓ㐀࡜㟁Ꮚ≧ែࠊ࡟ࡘ࠸࡚ࠊ᝟ሗࢆᚓ࡚ࠊ≉ᛶຎ໬ࡢᚤどⓗᶵᵓࢆ᫂ࡽ࠿࡟ࡋࠊ᪂ࡓ࡞≀㉁㛤Ⓨ࣭タィ࡟⧅ࡆ࡚⾜ࡃᚲせࡀ࠶ࡿࠋࡋ࠿ࡋࠊᒙෆࡸᒙ㛫ࡢᒁᡤ㡿ᇦࡢᵓ㐀ࡸṍࡳࠊ㟁Ꮚ≧ែ࡟ࡘ࠸࡚ࡢ᝟ሗࡀ඲ࡃᚓࡽࢀ࡚࠸࡞࠸ࡓࡵࠊᐇᮦᩱࡢᵓ㐀࡟࠾࠸࡚ࠊࢼࣀࢫࢣ࣮࡛ࣝఱࡀ㉳ࡇࡗ࡚࠸ࡿࡢ࠿ࠊࡑࡢᒁᡤᵓ㐀࠶ࡿ࠸ࡣᒁᡤṍࡳࡀ࡝ࡢࡼ࠺࡟≀ᛶⓎ⌧࣭≉ᛶྥୖࠊ࠶ࡿ࠸ࡣ≉ᛶຎ໬࡟ࡘ࡞ࡀࡗ࡚࠸ࡿ࠿ࠊṤ࡝᫂ࡽ࠿࡟ࡉࢀ࡚࠸࡞࠸ࠋ⌧≧࡛ࡣࠊ௬ㄝ᳨࣭ドࢆ⧞ࡾ㏉ࡍヨ⾜㘒ㄗ࡜ࠊࡑࡢ⤖ᯝ࡜ࡋ࡚ᚓࡽࢀࡓ▱ぢࡢ✚ࡳ㔜ࡡ࡟ࡼࡾࠊࡇࢀࡽࡢࣃ࣓࣮ࣛࢱࡢ᭱㐺໬ࡀ⾜ࢃࢀ࡚࠸ࡿࠋᚑࡗ࡚ࠊMLCC ࡢ᭦࡞ࡿᑠᆺ໬࣭㧗ᛶ⬟໬ࢆᐇ⌧ࡍࡿࡓࡵ࡟ࡣࠊࡇࡢ⌧≧ࢆᡴ◚ࡋࠊᚤᑠ㡿ᇦࡢᵓ㐀࣭ṍࡳゎ᫂࡜ࠊࡑࢀࡽࢆ⏕࠿ࡋࡓᵓ㐀ไᚚࠊࡍ࡞ࢃࡕ“Materials by Design”ࡢ☜❧ࡀᴟࡵ࡚㔜せ࡞㘽ࢆᥱࡗ࡚࠸ࡿࠋ ᮏㄢ㢟ࡢ┠ⓗࡣࠊMLCC ᐇᮦᩱ࡟࠾ࡅࡿㄏ㟁యᒙࡢෆ㒊㸦ࢢࣞ࢖ࣥ㞟ྜయ㸧ࡢᵓ㐀࡜ࠊ㟁ᴟ/ㄏ㟁య⏺㠃௜㏆ࡢᵓ㐀࡟ࡘ࠸࡚ࠊࡑࢀࡽࡢ✵㛫ศᕸࢆ࣐ࢵࣆࣥࢢࡋࠊᵓ㐀ࡀᒁᡤⓗ࡟࡝ࡢࡼ࠺࡟ኚ໬ࡋࠊࡲࡓṍࡳࡀ࡝ࡢࡼ࠺࡟ධࡗ࡚࠸ࡿ࠿ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜࡛࠶ࡿࠋᐇ㦂㸸ᐇ㦂ࡣ SPring-8 ࡢ BL-40XU ࡟タ⨨ࡉࢀࡓ࣐࢖ࢡࣟ X ⥺ᅇᢡィࢆ⏝࠸࡚⾜ࢃࢀࡓࠋヨᩱᯫྎࡣXYZ ᪉ྥࡢࢧࣈ࣐࢖ࢡ࣮ࣟ࢜ࢲ࣮ࡢ఩⨨ไᚚࡀྍ⬟࡞ࣆ࢚ࢰ࣮ࣔࢱ࣮ࢫࢸ࣮ࢪࡀ࠶ࡾࠊȝm 㡿ᇦࢆ㧗࠸఩⨨෌⌧ᛶ࡛ไᚚྍ⬟࡛࠶ࡿࠋMLCC ᐇᮦᩱࡣᮧ⏣〇సᡤ࠿ࡽᥦ౪ࡉࢀࠊBaTiO3 ㄏ㟁య⣲Ꮚ㒊ศࡢཌࡳࡀ 9ࠊ4ࠊ3 ȝm ࡢ 3 ✀ࡢࡶࡢࡀ⏝࠸ࡽࢀࡓࠋNi 㟁ᴟࡢཌࡳࡣ඲࡚ 1 ȝm ࡛࠶ࡿࠋ
 X ⥺࢚ࢿࣝࢠ࣮ࡣ 8 keV ࡟ᅛᐃࡋࠊヨᩱ఩⨨࡛ࡢࣅ࣮࣒ࢧ࢖ࢬࢆ 1 ȝmࠊ0.7 ȝm ࡟㞟ගࡋࡓࠋᅗ䠉㻞㻣㻡䠉SPring-8/SACLA ฼⏝◊✲ᡂᯝ㞟

ᅗ 1. ᅇᢡᐇ㦂ࡢࣞ࢖࢔࢘ࢺᅗࠋ㯤Ⰽ㒊ศࡀࣅ࣮࣒ࡢࣇࢵࢺࣉࣜࣥࢺࠋ⦪᪉ྥ㸦Z ᪉ྥ㸧࡜ᶓ᪉ྥ㸦X ᪉ྥ㸧࡟ࣅ࣮࣒↷ᑕ఩⨨ࢆኚ࠼࡚ࠊᅇᢡࣃࢱ࣮ࣥࢆ࣐ࢵࣆࣥࢢࡍࡿࠋ

SectionSectionB B

ᅗ 2. 1 ↷ᑕⅬ࡟ࡘ࠸࡚ࡢ⢊ᮎᅇᢡࣃࢱ࣮
ࣥࠋࣅ࣮࣒ࢧ࢖ࢬ࡜ࢢࣞ࢖ࣥࢧ࢖ࢬࡀྠ⛬ᗘࡢࡓࡵࠊ㑅ᢥ㓄ྥࡀࡁࢃࡵ࡚ᙉࡃฟ࡚࠸ࡿࠋ

1 ࡟♧ࡍࡼ࠺࡟ࠊNi 㟁ᴟ࡜ BaTiO3 ㄏ㟁య⣲Ꮚ㒊ศ࡟ࣅ࣮࣒ࢆᙜ࡚࡚ࠊᅇᢡࣃࢱ࣮ࣥࢆ᣺ື෗┿࡛ྲྀᚓࡋࠊ⦪᪉ྥ㸦Z ᪉ྥ㸧࡜ᶓ᪉ྥ㸦X ᪉ྥ㸧࡟ࢫ࢟ࣕࣥࡋ࡚ࠊᅇᢡࣃࢱ࣮ࣥࡢ 2 ḟඖ࣐ࢵࣆࣥࢢ
ࢆྲྀᚓࡋࡓࠋBaTiO3 ࡢṇ᪉ᬗࢻ࣓࢖ࣥ࡟ࡼࡾࣆ࣮ࢡࡀศ⿣ࡍࡿ 111 ᅇᢡ࡜ࠊศ⿣ࡍࡿ 002/200ࠊ
102/201/210ࠊ112/211 ᅇᢡࡀほ ྍ⬟࡞㡿ᇦࢆ☜ಖࡍࡿࡓࡵࠊᩓ஘ゅ୰ᚰࢆ 45°࡟ᅛᐃࡋࡓࠋ2 ḟඖ㧗㏿᳨ฟჾࢆ⏝࠸ࡿࡇ࡜࡛ࠊ35°  2ș  55°ࡢ⠊ᅖࡢᅇᢡࣃࢱ࣮ࣥࢆྠ᫬࡟ほ ࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋ1 ↷ᑕⅬ࡟ࡘ࠸࡚ࡢ᣺ື෗┿ࢆᅗ 2 ࡟♧ࡍࠋపゅഃ࠿ࡽࡑࢀࡒࢀ 111ࠊ002/200ࠊ102/201/210ࠊ112/211ᅇᢡ࡟ᑐᛂࡋ࡚࠸ࡿࠋ⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸 ᅗ 2 ࡢᅇᢡࣃࢱ࣮ࣥࢆぢࡿ࡜ࠊࣅ࣮࣒ࢧ࢖ࢬ࡟ᑐࡋ࡚ BaTiO3 ࡢ⤖ᬗࢢࣞ࢖ࣥࢧ࢖ࢬࡀྠ⛬ᗘࡢࡓࡵࠊ㑅ᢥ㓄ྥࡀ࠿࡞ࡾᙉࡃฟ࡚࠸ࡿࠋࡑࡇ࡛ᅇᢡࣃࢱ࣮ࣥࡢ఩⨨౫Ꮡᛶࢆẚ㍑ࡍࡿࡓࡵࠊX ᪉ྥ࡟ࢫ࢟ࣕࣥࡋࡓࢹ࣮ࢱࢆ඲࡚㊊ࡋྜࢃࡏ࡚ᖹᆒ໬ࡋࠊࡉࡽ࡟ 4 ᮏᅇᢡ⥺࡟ᑐࡋ࡚ࠊZ ᪉ྥࡢ᭱኱ᙉᗘ࡛ᙉᗘࢆつ᱁໬ࡋ࡚ᅇᢡࣃࢱ࣮ࣥࡢ Z ᪉ྥ౫Ꮡᛶࢆ࣐ࢵ
ࣆࣥࢢࡋࡓࠋᅗ 3 ࡟ࠊ112/211 ᅇᢡࡢᙉᗘࡢ➼㧗⥺ᅗ࡟ࡘ࠸࡚ 9ࠊ4ࠊ3 ȝm ࡢ 3 ✀ࡢ⤖ᯝࢆ♧ࡍࠋ⦪㍈ࡀ Z᪉ྥࠊᶓ㍈ࡀ 2ș ᪉ྥ࡟ᑐᛂࡋ࡚࠸ࡿࠋ2ș ᪉ྥ࡟Ỉᖹ࡟㉮ࡗ࡚࠸ࡿᙉᗘࡣ㸪Ni 㟁ᴟ࠿ࡽࡢ⺯ග X ⥺࡛࠶ࡾࠊNi 㟁ᴟࡢ఩⨨࡟ࡑࡢࡲࡲᑐᛂࡋ࡚࠸ࡿ࡜⪃࠼࡚Ⰻ࠸ࠋ

ᅗ 3. 112/211 ᅇᢡࡢᙉᗘ࣐ࢵࣆࣥࢢࠋ

ᅗ 4. 112/211 ᅇᢡࡢ Peak Position ࡜HWHM ࡢ Z ᪉ྥ౫Ꮡᛶࠋ

䠉㻞㻣㻢䠉SPring-8/SACLA ฼⏝◊✲ᡂᯝ㞟

SectionSectionB Bᅇᢡ⥺ࡢࣆ࣮ࢡ఩⨨ࡣᐇ㦂⢭ᗘࡢ⠊ᅖෆ࡛࡯࡜ࢇ࡝ኚ໬ࡋ࡚࠸࡞࠸ࡼ࠺࡟ぢ࠼ࡿࡀࠊNi 㟁ᴟ௜㏆࡛⣔⤫ⓗ࡟ࢬ࡚ࣞ࠸ࡿࡢࡀぢࡽࢀࡿࠋ᭦࡟ BaTiO3 ⣲Ꮚཌࡀ 3 ȝm ࡟ῶᑡࡍࡿ࡜ࠊ⥺ᖜࡀቑ኱ࡋ࡚
࠸ࡿࡢࡶศ࠿ࡿࠋࡇࡢഴྥࡣࠊ௚ࡢ 111ࠊ002/200ࠊ102/201/210 ᅇᢡ࡟࠾࠸࡚ࡶほ ࡉࢀࡓࠋᅗ 4࡟⣲Ꮚཌ 3 ȝm ࡢሙྜࡢ 112/211 ᅇᢡࡢ Peak Position ࡜⥺ᖜ HWHM ࡢ Z ᪉ྥ౫Ꮡᛶࢆ♧ࡋࡓࠋⅬ⥺఩⨨ࡀ Ni 㟁ᴟࡢ఩⨨࡟ᑐᛂࡋ࡚࠸ࡿࡀࠊ㟁ᴟ௜㏆࡛ Peak Position ࡀῶᑡࡋ࡚᱁Ꮚᐃᩘࡀ㛗ࡃ࡞ࡗ࡚࠸ࡿ࡜ྠ᫬࡟ࠊ⥺ᖜࡀቑ኱ࡋ࡚࠸ࡿࠋࡇࢀࡣࠊ㟁ᴟ࠿ࡽࡢᛂຊ࡟ࡼࡾ BaTiO3 ࡢᵓ㐀ࡀṍࡳࢆཷࡅ࡚࠸ࡿࡇ࡜ࢆ♧၀ࡋ࡚࠸ࡿࠋᐃ㔞ゎᯒࡣࡇࢀ࠿ࡽ⾜࠺ணᐃ࡛࠶ࡿࡀࠊ㟁ᴟ௜㏆࡛⣲Ꮚࡢᵓ㐀ࡀኚ໬ࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ௒ᚋࡢㄢ㢟㸸 ௒ᚋࡣᐃ㔞ゎᯒࢆ㐍ࡵࡿ࡜࡜ࡶ࡟ࠊ᭦࡟㧗ゅ㡿ᇦࡢ཯ᑕࢹ࣮ࢱࢆྲྀᚓࡋ࡚ࠊᵓ㐀ኚ໬ࠊᡈ࠸ࡣṍࡳࡢ᝟ሗ࡟ࡘ࠸࡚ࠊࡼࡾ⢭ᗘࡢ㧗࠸᝟ሗࢆᘬࡁฟࡍࡇ࡜ࡀᚲせ࡛࠶ࡿࠋ᭦࡟ࡣ㟁ሙ༳ຍ᫬ࡸ ᗘኚ໬࡞࡝ࠊࡼࡾ࢜࣌ࣛࣥࢻ࡟㏆࠸≧ែ࡛ MLCC ᐇᮦᩱࡢᵓ㐀ࡀᚤどⓗ࡟࡝ࡢࡼ࠺࡟ኚ໬ࡋ࡚࠸ࡿ࠿ࠊࡑࡢኚ໬࡜ㄏ㟁≉ᛶࡢኚ໬ࡀ࡝ࡢࡼ࠺࡟ᑐᛂࡋ࡚࠸ࡿ࠿ࠊゎ᫂࡟ࡘ࡞ࡆ࡚⾜ࡃࡇ࡜ࡀᚲせ࡛࠶ࡿࠋཧ⪃ᩥ⊩㸸[1] G. Arit et al., Journal of Applied Physics , 1619 (1989).
[2] S. K. Streiffer et al., Journal of Applied Physics , 4565 (1999).

(Received: December 4, 2018; Early edition: February 26, 2019;
Accepted: July 16, 2019; Published: August 29, 2019)䠉㻞㻣㻣䠉