2010B1820                       

BL19B2Lu2SiO5 ༢⤖ᬗࡢ᪉఩ ᐃ
Measurement of orientation of Lu2SiO5 single crystalඵᮌ ᗣὒ, ᑠᯘ ᰤྖ
Yasuhiro Yagi, Eiji Kobayashi᪥❧໬ᡂᕤᴗ㻔ᰴ㻕 Hitachi Chemical Co., Ltd.
་⒪⏝ࢩࣥࢳ࣮ࣞࢱᮦᩱ࡛࠶ࡿ Lu2SiO5 ༢⤖ᬗࡢ᪉఩ ᐃࢆ⾜ࡗࡓࠋSPring–8 ࡢᣦྥᛶࡀ㧗࠸ X⥺ࢆ⏝࠸ࡿ஦࡟ࡼࡾࣛ࣎⣔ᐇ㦂࡛ࡣᚓࡿ஦ࡢ࡛ࡁ࡞࠸㧗⢭ᗘࡢ ᐃࢹ࣮ࢱࢆྲྀᚓࡍࡿ஦ࡀ࡛ࡁࡓࠋ
SPring–8 ࡢᐇ㦂⤖ᯝࢆࣛ࣎⣔ࡢ ᐃ࡟⏕࠿ࡋࠊ⌧ᅾࠊࣛ࣎ෆࡢᐇ㦂ࡢࡳ࡛ Lu2SiO5 ༢⤖ᬗࡢ᪉఩☜ㄆࢆ⾜࠺ᙜ♫⊂⮬ࡢ᪉ἲㄽࢆ☜❧ࡋࡼ࠺࡜ヨࡳ࡚࠸ࡿࠋ࣮࣮࢟࣡ࢻ㸸 ༢⤖ᬗࠊ᪉఩ᐃࠊȭࢫ࢟ࣕࣥࠊȰࢫ࢟ࣕࣥ⫼ᬒ࡜◊✲┠ⓗ㸸 ⤖ᬗᵓ㐀ࡢ␗᪉ᛶ࡟㉳ᅉࡋ࡚ᶵᲔⓗ㸪ගᏛⓗ㸪㟁Ẽⓗ࡞ᛶ㉁ࡀ␗࡞ࡿ஦ࢆ✚ᴟⓗ࡟฼⏝ࡋࡓ౛ࡣỈᬗ᣺ືᏊ➼࡟ぢࡽࢀࡿࠋࡇࡢࡼ࠺࡞༢⤖ᬗᮦᩱࡢရ㉁Ᏻᐃࡢࡓࡵ࡟ࡣࠊ⤖ᬗࢆ୍ᐃ᪉ྥ࡛ษࡾฟࡍᚲせࡀ࠶ࡾࠊ༢⤖ᬗࡢ᪉఩ࢆṇ☜࡟▱ࡿ஦ࡣ㔜せ࡛࠶ࡿࠋᙜ♫࡛ࡣ་⒪⏝ࢩࣥࢳ࣮ࣞࢱᮦᩱ࡜ࡋ࡚ Ln2SiO5㸦Ln ࡣᕼᅵ㢮㸧༢⤖ᬗࢆ〇㐀ࡋ࡚࠾ࡾࠊᏳᐃࡋࡓṌ␃ࢆ☜ಖࡍࡿࡓࡵ࡟⤖ᬗᘬࡁୖࡆࡢ᪉఩ࢆ☜ㄆࡍࡿ᪉ἲㄽࢆ☜❧ࡍࡿ஦ࡀᚲせ࡛࠶ࡿࠋLn2SiO5 ࡣ Ln ࡢ࢖༙࢜ࣥᚄ࡟ᛂࡌ࡚2 ✀㢮ࡢ⤖ᬗᵓ㐀ࢆྲྀࡾࠊ࠸ࡎࢀࡶ༢ᩳᬗ࡟ᒓࡍࡿ[1,2]ࠋ༢⤖ᬗࡢ᪉఩ࢆ☜ㄆࡍࡿᡭẁ࡜ࡋ࡚࢚ࣛ࢘ἲࡀ୍⯡ⓗ࡛࠶ࡿࡀ[3]ࠊLn2SiO5 ࡢࡼ࠺࡟ゎᯒࡀ」㞧࡟࡞ࡿᮦᩱ࡟ࡣ୙ྥࡁ࡛࠶ࡿࠋᡃࠎࡣከ㍈ᅇᢡィࢆ⏝࠸ࠊ3 ᮏࡢࣆ࣮ࢡ࠿ࡽ⤖ᬗ᪉఩ࢆồࡵࡿ᪉ἲ[4]ࢆ᥇⏝ࡋࡓࠋ ᙜ♫ࡣከ㍈ᅇᢡィ࡜ࡋ࡚㻔ᰴ㻕ࣜ࢞ࢡ〇ࡢⷧ⭷⏝ X ⥺ᅇᢡ⿦⨨ ATX–G ࢆಖ᭷ࡋ࡚࠸ࡿࠋᮏ⿦⨨ࡣேᕤከᒙ⭷ࢆ⏝࠸࡚ᖹ⾜ࣅ࣮࣒ࢆసࡾฟࡍᶵᵓࢆഛ࠼࡚࠾ࡾࠊ2T᪉ྥ㸪Z᪉ྥ࡟ࡣᖹ⾜ᛶࡢ㧗࠸ࣅ࣮࣒ࢆ฼⏝ࡍࡿ஦ࡀ࡛ࡁࡿࠋࡑࡢ୍᪉࡛I᪉ྥ࡟ࡣⓎᩓࡋࡓࣅ࣮࣒ࢆ᳨ฟࡍࡿ஦࡟࡞ࡾࠊࣛ࣎⣔ࡢ⿦⨨࡛ 2T㸪Z㸪Iࡢ඲࡚ࡢ㉮ᰝ࡟࠾࠸࡚⢭ᗘࡢ㧗࠸ࢹ࣮ࢱࢆᚓࡿ஦ࡣᅔ㞴࡛࠶ࡿࠋࡑࡇ࡛ࠊࣔ
ࢹࣝヨᩱ࡜ࡋ࡚ Lu2SiO5 ༢⤖ᬗࢆస〇ࡋࠊᣦྥᛶࡢ㧗࠸ SPring–8 ࡢᨺᑕගࢆ฼⏝ࡋ࡚ࡑࡢ㧗⢭ᗘࡢ᪉఩ ᐃࡢࢹ࣮ࢱࢆྲྀᚓࠊࣛ࣎⣔ࡢ ᐃ࡟ࣇ࢕࣮ࢻࣂࢵࢡࡍࡿ஦࡛ࠊᙜ♫⊂⮬ࡢ Lu2SiO5 ༢⤖ᬗ᪉఩☜ㄆࡢ᪉ἲㄽࢆ☜❧ࡍࡿ஦ࢆ┠ⓗ࡜ࡋࡓࠋᐇ㦂㸸ࢳࣙࢡࣛࣝࢫ࢟ἲ࡟ࡼࡾ⫱ᡂࡋࡓ Lu2SiO5 ༢⤖ᬗࢆ㻔11 1㻕㠃ࡀฟࡿࡼ࠺࡟ 30 u 30 u 5 mm3 ࡢᯈ≧࡟ษ᩿ࡋࠊࣔࢹࣝヨᩱ࡜ࡋࡓࠋヨᩱࡢ୍㒊ࢆ⢊○ࡋࠊI0.1 mm ࡢ࢞ࣛࢫ࢟ࣕࣆࣛࣜ࡟ワࡵ࡚ࣅ࣮࣒ࣛ࢖ࣥ BL19B2 ࡟࡚⢊ᮎᅇᢡ ᐃࢆ⾜ࡗࡓࠋ⢊ᮎᅇᢡ ᐃ࡟⏝࠸ࡓ X ⥺ࡢἼ㛗ࡣ 0.5 Å ࡛࠶ࡿࠋḟ࠸࡛ X ⥺ࡢἼ㛗ࢆ 1.24 Å ࡟タᐃࡋࠊྠࡌࣅ࣮࣒ࣛ࢖ࣥ࡟࠶ࡿ Huber 〇ከ㍈ᅇᢡィࢆ⏝࠸࡚ᯈ≧ヨᩱࡢ᪉఩ ᐃࢆ⾜ࡗࡓࠋ ྠࡌヨᩱࡢ ᐃࢆࣛ࣎⣔ⷧ⭷⏝ X ⥺ᅇᢡ⿦⨨ ATX–G ࡛ࡶ⾜࠸ࠊSPring–8 ࡢ⤖ᯝ࡜ẚ㍑ࡋࡓࠋ
ࣛ࣎⣔ࡢᐇ㦂࡛ࡣ X ⥺࡜ࡋ࡚ Cu KD1 ⥺ࢆ฼⏝ࡋࡓࠋ⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸⢊ᮎᅇᢡ ᐃࡢ⤖ᯝࢆᅗ 1 ࡟♧ࡍࠋLe Bail ἲ࡟ࡼࡾ᱁Ꮚᐃᩘࢆィ⟬ࡋࡓ࡜ࡇࢁࠊa = 14.27 Å, b =6.65 Å, c = 12.73 Å, E = 135.4°࡛࠶ࡗࡓࠋᩥ⊩[2]࡛ࡣ Y2SiO5㸦Lu2SiO5 ࡶྠࡌ⤖ᬗᵓ㐀࡟࡞ࡿ㸧ࡢ✵㛫⩌ࡀ B2/b㸦B2/n ࡢㄗࡾ࡛࠶ࢁ࠺㸧࡛࠶ࡿ࡜ࡋ࡚ࡑࡢ⤖ᬗᵓ㐀ࢆሗ࿌ࡋ࡚࠸ࡿࡀࠊᮏሗ࿌࡛ࡣྠࡌ
International Tables[5]ࡢ No. 15 ࡟ᒓࡍࡿ C2/c ࡛⤖ᬗᵓ㐀ࢆ⾲グࡋ࡚࠸ࡿࠋ᪉఩ ᐃ࡟࠾࠸࡚ࡣ㻔22 2㻕
㠃㸪㻔75 6㻕㠃㸪㻔57 4㻕㠃ࡢ 2T㸪Z㸪I ᐃࢆ⾜࠸ࠊ᱁Ꮚᐃᩘࡢ್ࢆ⏝࠸࡚᪉఩ࡢィ⟬ࢆࡋࡓࠋ⤖ᯝࢆ⾲
1 ࡟♧ࡍࠋ
ᅗ 2 ࡜ᅗ 3 ࡟ࡑࢀࡒࢀࢩࣥࢡࣟࢺࣟࣥᨺᑕගࢆ⏝࠸ࡓ㻔22 2㻕㠃ࡢIࢫ࢟ࣕࣥࡢ⤖ᯝ࡜ ATX–G࡟࠾ࡅࡿྠ㠃㸪ྠࢫ࢟ࣕࣥࡢ⤖ᯝࢆ♧ࡍࠋࣆ࣮ࢡࡢᗈࡀࡾࢆẚ㍑ࡍࡿ࡜ᅗ 2 ࡛ࡣ್༙ᖜࡀ 1.97°࡛࠶ࡿࡢ࡟ᑐࡋࠊᅗ 3 ࡛ࡣ 23.3°࡛࠶ࡿࠋࡍ࡞ࢃࡕᨺᑕගࢆ⏝࠸ࡓ᫬ࡢ᪉ࡀࣆ࣮ࢡࡢᖜࡀ⊃ࡃ࡞ࡗ࡚࠾ࡾࠊࣛ࣎⣔ࡢⓎᩓගࡢ᳨ฟ࡟ẚ࡭࡚ࠊᣦྥᛶࡢ㧗࠸ࢩࣥࢡࣟࢺࣟࣥᨺᑕගࢆ฼⏝ࡋࡓሙྜࡢඃ
఩ᛶࢆ☜ㄆࡍࡿ஦ࡀ࡛ࡁࡿࠋྠࡌ஦ࡀ㻔75 6㻕㠃㸪㻔57 4㻕㠃ࡢIࢫ࡛࢟ࣕࣥࡶ☜ㄆࡉࢀࠊᮏㄢ㢟ᐇ㦂࡟࠾࠸࡚ࣛ࣎⣔ࡢᐇ㦂࡛ࡣᚓࡽࢀ࡞࠸⢭ᗘࡢ㧗࠸ࢹ࣮ࢱࢆྲྀᚓࡍࡿ஦ࡀ࡛ࡁࡓࠋ

ᅗ 1㸬Lu2SiO5 ༢⤖ᬗࡢ⢊ᮎᅇᢡ ᐃࡢ⤖ᯝ㸦ᨺᑕග㸧㍈abc

⾲ 1㸬᪉఩ィ⟬ࡢ⤖ᯝ
᪉఩ゅ
௮ゅ
20.9°
65.1°
–126.4°28.9°–109.1°117.8°

ᅗ 2㸬Lu2SiO5 ༢⤖ᬗࡢIࢫ࢟ࣕࣥ㸦ᨺᑕග㸧 ࣛ࣎⣔ࡢᐇ㦂࡛ࡣᨺᑕග࡜ྠ⛬ᗘࡢ⢭ᗘࢆせồࡍࡿ஦ࡀ࡛ࡁ࡞࠸ࡀࠊ᪉఩☜ㄆࡢ┠ⓗ࡟㝈ࢀࡤྠ➼ࡢ⢭ᗘࢆฟࡍ஦ࡶྍ⬟࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋᅗ 4 ࡟ྠࡌᯈ≧ࣔࢹࣝヨᩱࡢ ATX–G ࡟ࡼࡿ㻔22 2㻕
㠃ࡢZࢫ࢟ࣕࣥࡢ⤖ᯝࢆ♧ࡍࠋATX–G ࡣZ᪉ྥ࡛ᖹ⾜ᛶࡢ㧗࠸ࣅ࣮࣒ࢆ฼⏝ࡍࡿ஦ࡀ࡛ࡁࡿࡓࡵࠊ
Iࢆ 0°, 180°, 90°, –90°࡛Zࢫ࢟ࣕࣥࢆ⾜࠸ࠊࡑࢀࡽࡢࣆ࣮ࢡ఩⨨࠿ࡽ㻔22 2㻕㠃ࡢ᪉఩ࢆ㧗⢭ᗘ࡟ồࡵࡿ஦ࡀ࡛ࡁࡿࠋᅗ 4 ࡢZࢫ࢟ࣕࣥ࡟࠾࠸࡚ᨺᑕගࡢ ᐃ᫬࡜࡯ࡰྠࡌ᪉఩ࡢ್ࡀฟࡿ஦ࡀศ࠿ࡗࡓࠋᮏᐇ㦂࡟ࡼࡾࠊSPring–8 ࢆά⏝ࡋ࡚㧗⢭ᗘࡢ Lu2SiO5 ༢⤖ᬗࡢ᪉఩ ᐃ⤖ᯝࢆฟࡋ࡚࠾ࡅࡤࠊࡑࢀࢆ฼⏝ࡋ࡚ࣛ࣎⣔࡛ࡶྠ➼ࡢ⢭ᗘࡢ᪉఩☜ㄆࢆ⾜࠺஦ࡀྍ⬟࡛࠶ࡿ஦ࢆᐇドࡍࡿ஦ࡀ࡛ࡁࡓࠋ⌧ᅾࠊ≉ᚩⓗ࡞㻔hkl㻕㠃࠿ࡽࡎࡽࡋࡓ᫬࡟ࣛ࣎⣔࡛࡝ࡢࡼ࠺࡞ Lu2SiO5 ༢⤖ᬗࡢ᪉఩☜ㄆࡀྍ⬟࡟࡞ࡿࡢ࠿ࠊᐇ㦂ࢆ㔜ࡡ࡚࠸ࡿ࡜ࡇࢁ࡛࠶ࡿࠋࡇࢀࡀ☜❧ࡉࢀࢀࡤࠊ௵ពࡢᘬࡁୖࡆ᪉ྥ࡛⤖ᬗࡢ᪉఩ࡎࢀࢆ᳨
ᰝࡍࡿ஦ࡀ࡛ࡁࡿࡼ࠺࡟࡞ࡾࠊLu2SiO5 ༢⤖ᬗࡢ♫ෆ࡛ࡢ᪉఩☜ㄆᡭἲࡀ☜❧ࡉࢀࡿࠋᅗ 3㸬Lu2SiO5 ༢⤖ᬗࡢIࢫ࢟ࣕࣥ㻔ATX–G㻕㻌㻌㻌㻌㻌㻌ᅗ 4㸬Lu2SiO5 ༢⤖ᬗࡢZࢫ࢟ࣕࣥ㻔ATX–G㻕௒ᚋࡢㄢ㢟㸸 ⌧ᅾࠊࣛ࣎⣔ࡢᐇ㦂࡟࠾࠸࡚≉ᚩⓗ࡞㻔hkl㻕㠃࠿ࡽࡎࢀࡓษ᩿㠃࡛࡝ࡢࡼ࠺࡟ Ln2SiO5 ༢⤖ᬗࡢ㧗⢭ᗘ࡞᪉఩☜ㄆࢆࡋࡓࡽⰋ࠸ࡢ࠿ࠊ᪉ἲㄽࢆ᥈ࡗ࡚࠸ࡿ࡜ࡇࢁ࡛࠶ࡿࠋ࠶ࡿ⛬ᗘࡢᐇ㦂ᡂᯝࡀฟࡓẁ㝵࡛෌ᗘ SPring–8 ࡛ࡢᐇ㦂ࢆㄢ㢟⏦ㄳࡍࡿணᐃ࡛࠶ࡿࠋཧ⪃ᩥ⊩㸸[1] C. Michel, G. Buisson, E. F. Bertaut, C. R. Seances Acad. Sci. Ser. B 246, 397 㻔1967㻕.
[2] Y. Smolin, S. P. Tkachev, Kristallografiya 14, 22 㻔1969㻕.
[3] ⳥ụဴኵࠊ⌮Ꮫ㟁ᶵࢪ࣮ࣕࢼࣝࠊ19, 24 㻔1988㻕.
[4] W. R. Busing, H. A. Levy, Acta Crystallogr. 22, 457 㻔1967㻕.
[5] “International Tables for Crystallography,” Vol. A, 3rd Revised Edition, Ed. by D. Hahn, Kluwer
Academic Publishers, Dordrecht 㻔1992㻕.