ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू
Status Report of Hyogo-Beamlines with Research Results
Vol. 5 (2016)ฌ‫ཱݝݿ‬େֶ์ࣹޫφϊςΫηϯλʔɹ໨ɹɹɹ࣍
೥ɹɹɹใ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Iฌ‫ݝݿ‬ϏʔϜϥΠϯ BL08B2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

IIIฌ‫ݝݿ‬ϏʔϜϥΠϯ BL24XUࢪઃӡ༻͓Αͼར༻ঢ়‫گ‬. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VII. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . XII੒ɹՌɹू . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1

DSC/USAXS-SAXS-WAXS ʹΑΔϙϦΞϛυφϊϑΝΠόʔͷߴ࣍ߏ଄ղੳ . . . . . . . . . . .

3

ʢ೔࢈ΞʔΫʣ௕୩઒རଇɼߴඌ௚थɼੴ઒େีɼࠓҪӳਓcos α ๏ʹΑΔ൒ಋମύοέʔδ෧ࢭ༻೤ߗԽੑथࢷ/ಔք໘ͷ೤࣌࢒ཹԠྗͦͷ৔ղੳ . . . . . . . .

7

ʢॅ༑ϕʔΫϥΠτʣՃʑྑ߶ࢤɼएྛΈͲΓɼதҪ‫ށ‬஦ɼ௕ౡେɼ࿨ઘಞ࢜

Li ΠΦϯి஑ਖ਼‫ࡐۃ‬அ໘ͷ X ઢϚΠΫϩϏʔϜʹΑΔ൓Ԡ෼෍ղੳ . . . . . . . . . . . . . . . . . .

12ʢϚπμʣࡾࠜੜ৾ɼॅా߂༞ɼ
ʢφϊςΫηϯλʔʣट౻େ‫ث‬ɼ஛ా৾‫ޗ‬ɼԣࢁ࿨࢘

In-situ XAFS/SAXS ಉ࣌ଌఆʹΑΔ Au φϊཻࢠੜ੒աఔղੳ . . . . . . . . . . . . . . . . . . . .
ʢѴԽ੒ʣ౦‫ޫޱ‬੖ɼࡔຊ௚‫ل‬

i

15

ɹ

ɹ

೥ɹɹɹใ

–I–ɹฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू

ฌ‫ݝݿ‬ϏʔϜϥΠϯ BL08B2
1. ͸͡Ίʹ

βʔͷར༻૬ஊ΍՝୊‫ݕ‬౼࣌ͷ૬ஊ͸ਵ࣌ड͚෇͚ͯ

SPring-8 ʹ͋Δฌ‫ݝݿ‬ઐ༻ϏʔϜϥΠϯ BL08B2
͸ɼฌ‫ཱݝݿ‬େֶ์ࣹޫφϊςΫηϯλʔ͕؅ཧӡӦ͍ͯ͠Δɽภ޲ి࣓ੴޫ‫ݯ‬Λ༗͢ΔϏʔϜϥΠϯ
Ͱ͋Δɽ࢈‫ۀ‬քʹ͓͚Δࡐྉ‫ڀݚ‬։ൃʹରͯ͠ɼελϯμʔτͳ෼ੳ๏Λ‫ج‬ຊͱ࣮ͨ͠‫ݧ‬εςʔγϣϯͷར༻‫ػ‬ձΛ࢈‫ۀ‬քʹରͯ͠ఏ‫͍ͯ͠ڙ‬Δɽখ̭֯ઢࢄཚʢSAXSʣɼ̭ઢ‫ٵ‬ऩඍࡉߏ଄ʢXAFSʣɼCTɼΠϝʔδϯάɼ୯৭̭ઢτϙάϥϑΟɼค຤̭ઢճંͷ֤࣮‫ݧ‬εςʔγϣϯͰ͸ɼϢʔβͷར༻ͱͱ΋ʹɼߴ‫ػ‬ೳ͍Δɽ·࣮ͨ‫ݧ‬લͷ૷ஔͷηοτΞοϓ΍࣮‫࣌ݧ‬ͷαϙʔτɼ͞Βʹ͸࣮‫͍͓ͯʹޙݧ‬΋σʔλղੳͷ૬ஊͳͲ෯޿͘ࢧԉ‫׆‬ಈʹऔΓ૊ΜͰ͍ΔɽϢʔβʔ͔Βͷཁ๬ʹԠͯ͡ɼ࣮‫ݧ‬εςʔγϣϯ΁ͷ‫ػ‬ೳ௥Ճ౳ͷ੔උ΋ߦ͍ͬͯΔɽ2015 ೥౓ʹ͓͍ͯ΋࢈‫ۀ‬ք͕ར༻͠қ͍࣮‫ڥ؀ݧ‬ͷҡ࣋ʹ౒Ί͖ͯͨɽ2015 ೥౓ʹ͓͚Δ֤࣮‫ݧ‬εςʔγϣϯͷঢ়‫گ‬ɼར༻ঢ়‫گ‬΍੔උ‫׆‬ಈʹ͍ͭͯҎԼʹ঺հ͢Δɽ

2. 1 খ֯ X ઢࢄཚʢSAXSʣԽͷ੔උʹ΋औΓ૊ΜͰ͍Δɽར༻෼໺ͱͯ͠͸ɼߴ෼ࢠࡐྉɼۚଐࡐྉɼ৮ഔࡐྉɼ஝ి஑ࡐྉ౳ͱ෯޿
͍ɽ֤෼໺͕‫ٻ‬ΊΔ৽‫ػ‬ೳͱͯ͠ɼ൓ԠੑΨεงғ‫ؾ‬தͰͷͦͷ৔‫࡯؍‬΍ɼখ̭֯ઢࢄཚͱߴ̭֯ઢࢄཚɼ
͞Βʹ͸ XAFS ‫ػ‬ೳ΋૊Έ߹Θͤͨෳ߹తͳଌఆ‫ػ‬ೳΛఏ‫͍ͯ͠ڙ‬Δɽ‫ݶ‬ΒΕͨϚγϯλΠϜͷதͰϢʔ
βʔ͕༷ʑͳ৘ใΛಘͳ͕Βࡐྉ‫ʹڀݚ‬औΓ૊ΉΑ͏ࢧԉ͍ͯ͠Δɽߴ෼ࢠࡐྉɼۚଐࡐྉɼφϊཻࢠίϯϙδοτࡐྉ౳ͷ௕प‫ߏظ‬଄ͷධՁΛ໨తͱͯ͠ɼ࢈‫ۀ‬քϢʔβʔΛத৺ʹ SAXS εςʔγϣϯ͕ར༻͞Ε͍ͯΔɽ

BL08B2 ͷ SAXS Χϝϥ௕͸ඪ४഑ஔͰ 0.5 ∼ 6 mɼ‫ۃ‬খ̭֯ઢࢄཚଌఆͷ௕ई഑ஔͰ 16 m ͕ՄೳͰ͋Δɽ෯޿͍ SAXS ෼ղೳͷબ୒ੑΛ༗͢Δɽར༻ՄೳͰ
͋ΔޫࢠΤωϧΪʔ͸ 7 ∼ 25.5 keV ͷൣғͰ͋Δɽ

SAXS/WAXS ಉ࣌ଌఆɼGI-SWAXSɼRheo-SAXSɼASAXSɼQuick-XAFS/SAXS/WAXS ಉ࣌ଌఆͷ֤

2. ࣮‫ݧ‬εςʔγϣϯͷ‫ݱ‬ঢ়छ෼ੳϞʔυΛఏ‫͠ڙ‬ɼ࢈‫ۀ‬քͷ༷ʑͳࡐྉߏ଄ͷ෼֤࣮‫ݧ‬εςʔγϣϯʹ͸ઐ೚ͷٕज़ελοϑ͕͓ΓɼੳධՁʹରԠ͍ͯ͠Δɽ૷ஔͷҡ࣋؅ཧ΍Ϣʔβʔར༻ʹରԠ͍ͯ͠ΔɽϢʔ

ਤ 1. BL08B2 ͷߏ੒ུ֓ɽ

– III –

Status Report of Hyogo-Beamlines with Research Results, Vol. 5 (2016)2015 ೥౓΋ߴ෼ࢠࡐྉΛத৺ͱͯ͠ɼ෯޿͍࢈‫ۀ‬ಛʹ৮ഔ։ൃʹ͓͍ͯ͸ XAFS ʹΑΔͦͷ৔‫࡯؍‬ͷ෼໺ͷ‫ڀݚ‬ςʔϚ͕࣮ߦ͞Εͨɽ૷ஔར༻ͷ‫Ͱ఺؍‬ར༻χʔζ͕ߴ͍ɽ‫ڥ؀‬໰୊΍ΤωϧΪʔʹ൐͍৮ഔ͸ɼैདྷͱಉ༷ɼՃ೤࿍΍Ҿு‫ػ‬౳Λ༻͍ͨͦͷ৔‫؍‬ͷߴ‫ػ‬ೳԽ͕‫ٻ‬ΊΒΕɼߴ‫׆‬ੑԽ΍બ୒తͳ൓ԠΛࣔ࡯ͷଌఆ΍ɼଟ‫ݕ‬ମ෼ੳΛ໨తͱͨ͠αϯϓϧνΣϯ

͢ࡐྉ։ൃ͕‫ٻ‬ΊΒΕ͍ͯΔഎ‫͕͋ܠ‬Δɽ͜ͷঢ়‫ʹگ‬δϟʔΛར༻͢Δ‫ڀݚ‬ςʔϚ͕େ൒Λ઎ΊͨɽಛʹՃରͯ͠ɼ൓Ԡ৚݅Λม͑ͳ͕Β‫ߏॴہ‬଄Λղੳ͠ɼ൓

೤࿍ར༻ͷϢʔβʔ͸ଟ͋͘Δ͕ɼ‫ݱ‬ঢ়ͷઃඋͰ͸ԠͷϝΧχζϜͱࡐྉಛੑͱͷ૬ؔੑΛղ໌͢Δ͜ͱϢʔβʔ͕ཁ‫͢ٻ‬ΔҰ෦ͷԹ౓৚݅ʹ͸ରԠͰ͖ͳ

͕ඞਢͱͳ͍ͬͯΔɽ஝ి஑ͷ‫ڀݚ‬։ൃʹ͓͍ͯ΋ɼ◦͍ঢ়‫ͳͱگ‬Γͭͭ͋Δɽ͜ͷͨΊԹ౓ൣғ –190 C ∼߹੒΍ߴԹম݁ͳͲͷ੡଄աఔͷঢ়‫گ‬೺Ѳ͕ඞཁͱ͞

600 Cɼߴ଎Թ౓ௐ੔͕ՄೳͰ͋Δখ‫ྫྷܕ‬٫ɾՃ೤࿍

Ε͓ͯΓɼXAFS ʹ͓͚Δͦͷ৔‫࡯؍‬ͷར༻χʔζ͸Λ৽ͨʹಋೖ͢Δ‫ܭ‬ըΛ‫ݕ‬౼͠ɼ2016 ೥౓ʹ੔උ͢ߴ͍ɽ◦Ҏ্ͷঢ়‫گ‬ͷதͰɼ2015 ೥౓͸൓ԠੑΨεงғ‫ؾ‬Δ͜ͱͱͨ͠ɽ

X ઢಁա཰͕খ͍͞ࢼྉʢߴີ౓ࢼྉʣ΍ۚଐࡐྉΛར༻ͨͦ͠ͷ৔‫ػ࡯؍‬ೳͷ੔උΛਐΊͨɽBL08B2

΁΋Ԡ༻͢ΔͨΊɼ20 ∼ 25 keV ͷޫࢠΤωϧΪʔΛͰ͸ɼ‫ݐ‬ઃ౰ॳʹ͓͍ͯΨε‫૷څڙ‬ஔͱഉΨεॲཧ૷ར༻ͨ͠ଌఆ΋૿͑ͭͭ͋Δɽ‫ج‬ຊతͳӡస৚݅Ͱ͋

ஔΛ੔උͨ͠ɽ൓ԠੑΨε‫څڙ‬ઃඋͰ͸Մ೩ੑ‫ܥ‬ɼࢧ

Δ 8 ∼ 15 keV ͷൣғ಺Ͱ͸ɼΤωϧΪʔมߋʹ൐͏೤ੑ‫ܥ‬ͷ̎ͭͷऔ෇ᝑମΛඋ͍͑ͯΔɽ࣮‫͠ͱ్༻ݧ‬૷ஔηοςΟϯάͷ੾Γସ͑͸ൺֱత୹࣌ؒͰ࣮ࢪͰ

ͯਃ੥ࡁΈͰ͋ΔΨεछ͸ɼՄ೩ੑΨεͱͯ͠ҰࢎԽ

͖ΔɽҰํͰ 15 keV Λ௒͑Δ৚݅΁มߋͷ৔߹ʹ͸ɼ୸ૉɼਫૉɼγΫϩϓϩύϯ͕ɼࢧ೩ੑΨεͱͯ͠ҰX ઢϛϥʔͷ൓ࣹ৚݅ʹ‫ى‬Ҽͯ͠ޫ࣠Ґஔ͕େ͖͘ม

ࢎԽ஠ૉɼࢎૉ͕͋Δɽ൓ԠੑΨεͷ‫څڙ‬ϥΠϯΛ̐Ґ͢ΔͨΊɼ૷ஔηοςΟϯάͷ੾Γସ͑ʹ௕࣌ؒΛ‫ܥ‬౷උ͍͑ͯΔɽ͜ͷঢ়‫ʹگ‬ରͯ͠ 2015 ೥౓͸Ψεཁͨ͠ɽࠓ೥౓͸͜ͷௐ੔࡞‫ۀ‬ͷޮ཰ԽΛਤΔͨΊʹɼਫ਼ີ੍‫૷߹ࠞޚ‬ஔɼͦͷ৔‫༻࡯؍‬൓ԠηϧͷಋೖΛ͸

SAXS ઐ༻Ͱ͋ΔϏʔϜ༌ૹ༻ਅۭύΠϓͷҐஔܾΊ͔ͬͨɽεςʔδΛશͯࣗಈૢ࡞Խͱ͢Δվ଄Λࢪͨ͠ɽ͜Ε৮ഔ΍஝ి஑ͷ࣮‫Ͱݧ‬ΨεΛ࢖༻͢Δ৔߹ɼ൓Ԡ

ʹΑΓ޿͍ΤωϧΪʔൣғͷؒͰͷɼ૷ஔηοςΟϯ

ηϧ΁ͷ‫ྔྲྀڅڙ‬ͷਫ਼ີίϯτϩʔϧ͕ॏཁͰ͋Δɽάͷ੾Γସ͑ʹ͍ͭͯௐ੔࣌ؒΛେ෯ʹ୹ॖ͢Δ͜ͱ࣮‫ݧ‬ϋον֎͔Βͷԕִૢ࡞‫ػ‬ೳ΋ඞཁͱͳΔɽ͜

͕Ͱ͖ͨɽX ઢϛϥʔ΍෼ޫ‫ث‬౳ͷ֤ίϯϙʔωϯτͷ‫ػ‬ೳΛ࣮‫͢ݱ‬ΔͨΊʹɼKOFLOC ੡Ψεࠞ߹૷ஔ΋‫ؚ‬Ίͨࣗಈૢ࡞Խͷվ଄΋Ҿ͖ଓ͖औΓ૊ΉɽҎ্

BRENDA γϦʔζͷΨεࠞ߹૷ஔΛ৽ͨʹಋೖͨ͠ɽ

ͷ੔උʹΑΓɼ7 ∼ 25.5 keV ͷશΤωϧΪʔൣғʹߴਫ਼౓σδλϧϚεϑϩʔίϯτϩʔϥʹΑͬͯߴ͍Ҏ্ͷΑ͏ʹൺֱతߴ͍ΤωϧΪʔར༻͕૿͍͑ͯ

ྔઃఆʹཁ͢Δൺ཰੍‫ޚ‬౳ΛՄೳͱͨ͠ɽ૷ஔ੍‫ޚ‬͸͓͍ͯ SAXS ௐ੔ͷ‫׬‬શࣗಈԽΛ໨ࢦ͢ɽਫ਼౓Ͱߴ଎Ԡ౴͕ՄೳͰ͋Δɽ‫څڙ‬ϥΠϯ͝ͱͷྲྀ

Δ͜ͱ͔Βɼ‫ࡏݱ‬ͷ 0.5 ∼ 6 mɼ16 m ͷ SAXS ΧϝωοτϫʔΫΛհͯ͠ԕִͰߦ͏ɽɹɹɹɹ

ϥ഑ஔʹՃ͑ͯɼ৽ͨʹ 10 m ͷΧϝϥ഑ஔΛ 2016ࢼྉ‫ͯ͠ͱڥ؀‬͸ɼಁա XAFS ๏ʹ࢖༻͢Δੴӳ੡೥౓ʹ৽ઃ͢Δ͜ͱͱͨ͠ɽ͜ΕʹΑΓߴΤωϧΪʔηϧΛ੔උͨ͠ɽ࠷ߴઃఆԹ౓͸ 800◦ C Ͱ͋Δɽਤ̎

ར༻࣌ͷ SAXS ෼ղೳͷબ୒ੑ֦ு͕‫ظ‬଴Ͱ͖Δɽ·ʹੴӳ੡ηϧΛར༻ͨͦ͠ͷ৔‫࡯؍‬ͷελσΟΛߦͬͨɼߴΤωϧΪʔଌఆͷߴޮ཰ԽΛ໨తͱ͠ɼ‫ݕ‬ग़ૉͨࡍͷ༷ࢠΛࣔ͢ɽࢠͰ͋ΔγϦίϯηϯαʔͷްΈ͕ 1 mm Λ༗͢Δ΋͏Ұͭͷࢼྉ‫ؒ࣌ͯ͠ͱڥ؀‬෼ղ XAFS ༻ϑϩʔPILATUS-300K ͷಋೖΛ‫ݕ‬౼͠ɼ2016 ೥౓Լ‫ʹظ‬੔ηϧΛ੔උͨ͠ɽ͜Ε͸Ψεϑϩʔ‫ڥ؀‬ԼͰࢼྉͱΨ

උ͢Δ͜ͱͱͨ͠ɽ

εΛ൓Ԡͤ͞ͳ͕Βɼಁա๏ͷ࣌෼ׂଌఆΛߦ͏༻్ͷ΋ͷͰ͋ΔɽΧʔτϦοδώʔλʔΛ༻͍ͯࣨԹ͔

2. 2 XAFSΒ 700◦ C ͷൣғͷԹ౓ઃఆ͕Ͱ͖Δɽಛ௃ͱͯ͠ɼηࡐྉͷߏ଄มԽΛଊ͑Δ্Ͱ஫໨͞Ε͍ͯΔͦͷ৔ϧ಺෦ͷࢼྉۭ͕ؒ‫ۃ‬Ίͯ‫͍ͨڱ‬ΊɼΨεϑϩʔ࣌ʹ‫Ͱ࡯؍‬͸ɼ์ࣹޫΛར༻͢Δ͜ͱͰɼΑΓਫ਼ີʹɼΑ଎΍͔ʹࢼྉද໘ʹ͓͚Δ൓ԠΛਐߦͤ͞Δ͜ͱ͕ͰΓਝ଎ʹ‫ܭ‬ଌΛߦ͏͜ͱ͕ՄೳͱͳΔɽSPring-8 ʹ͓͖Δɽ͜ΕʹΑΓ୹࣌ؒͷؒͰͷ൓ԠΛ‫࡯؍‬ର৅ͱ͍ͯ͠΋ɼ࢈‫ۀ‬ք͕੝Μʹར༻͍ͯ͠Δଌఆํ๏Ͱ͋Δɽ

͏Δɽ

– IV –

ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू
ߏ଄มԽͷ࣌෼ׂଌఆΛߦ͏ͨΊͷ੔උͱͯ͠ɼ

ྉ‫ʹํޙ‬͸ೋ࣍‫ݕݩ‬ग़‫ث‬Λ഑͠ɼ೾௕Λ૸ࠪͤ͞ͳ͕

Quick XAFS ‫ػ‬ೳͷվྑΛਐΊͨɽଌఆ࣌ؒͷ୹ॖΒࢼྉ͔ΒͷಁաϏʔϜͷೋ࣍‫౓ڧݩ‬෼෍Λ࿈ଓతʹԽΛ໨ࢦ͠ɼे਺ඵ͔Β਺෼ͷ࣌ؒʹ͓͍ͯे෼ʹղऩू͢Δɽ

ੳʹͰ͖Δ XAFS εϖΫτϧΛऔಘՄೳͱͨ͠ɽ

͜ͷख๏Ͱ͸ϏʔϜͷஅ໘‫౓ڧ‬෼෍͕‫ۉ‬ҰͰ͋Δ͜ࠓ‫ޙ‬΋࢈‫ۀ‬քϢʔβʔͷར༻ಈ޲Λଊ͑ͳ͕Βɼιͱ͕๬·͍͠ɽ͔͠͠ͳ͕ΒϏʔϜϥΠϯ্ʹ͋Δάϑτͱϋʔυͷ྆໘ʹ͓͍ͯߴ‫ػ‬ೳԽͷ੔උʹऔΓϥϑΝΠτϑΟϧλ΍෼ޫ݁থͷԚછʹ‫ى‬Ҽ͠ɼஅ໘૊ΉɽϓϩϑΝΠϧ্ʹ͸‫౓ڧ‬Ϝϥ͕ଘࡏ͍ͯͨ͠ɽ͜ͷͨΊσʔλͷղੳ͕ෳࡶʹͳΔ໰୊͕͋ͬͨɽ͜ͷ՝୊Λղܾ͢ΔͨΊʹɼ2015 ೥౓͸அ໘‫౓ڧ‬෼෍Λ‫ۉ‬Ұͱ͢Δ͜ͱΛ໨ඪͱͨ͠੔උΛߦͬͨɽσϑϡʔβʔΛར༻ͨ͠ϏʔϜͷ֦ࢄʹΑΔ‫ۉ‬ҰԽͷํ๏Λ࠾༻͠ɼσΟϑϡʔβʔγεςϜΛ࣮‫ݧ‬ϋονͷ࠷্ྲྀʹઃஔͨ͠ɽϏʔϜͷ֦ࢄޮՌ͕େ͖͘ಘΒΕΔΑ͏ɼ࣮‫ݧ‬ϋον಺ͷ૷ஔϨΠΞ΢τ΋มߋͨ͠ɽग़དྷΔ‫ݶ‬ΓσΟϑϡʔβʔ͔Β཭ͨ͠Ґஔʹ࣮‫ݧ‬εςʔγϣϯΛҠಈͤͨ͞ɽ੔උͷ݁Ռͱͯ͠ɼ‫ۉ‬Ұͳஅ໘‫౓ڧ‬Λ༗͢ΔϏʔϜΛ੔‫͢ܗ‬Δ͜ͱʹ੒ޭͨ͠ɽΠϝʔδϯάͷσʔλʹ͓͍ͯը࣭ͷ޲্Λ֬ೝͨ͠ɽCTɼϥϛϊάϥϑΟʹ͓͍ͯ΋ߴը࣭ԽͷޮՌΛಘΔ͜ͱ͕Ͱ͖ͨɽࠓ‫ޙ‬͸άϥϑΝΠτϑΟϧλͳͲΛϏʔϜϥΠϯ্͔Βআ͘ͳͲɼ͞ΒͳΔஅ໘‫౓ڧ‬෼෍ͷ‫ۉ‬ҰԽͷ޲্ͷରԠΛߦ͏ɽ࢈‫ۀ‬քϢʔβʔ͕ղੳΛߦ͍қ͍Α͏ɼΠϝʔδϯάσʔλͷߴ඼࣭ԽΛਐΊΔɽΠϝʔδϯ

ਤ 2. ಁա XAFS ༻ੴӳηϧͷ࣮‫ݧ‬഑ஔɽά XAFS ʹ͍ͭͯ΋ૢ࡞ੑΛߴΊͯ࢈‫ۀ‬քϢʔβʔʹར༻ఏ‫͢ڙ‬Δɽ

2. 4 ୯৭ X ઢτϙάϥϑΟ

2. 3 Πϝʔδϯά
CTɼΠϝʔδϯάͷख๏͸ɼࡐྉΛඇഁյͷ··γϦίϯΧʔόΠυʢSiCʣͷ݁থܽؕͷධՁ‫ڀݚ‬ʹͦͷ಺෦ͷ࣮ۭؒղੳΛߦ͏͜ͱΛ໨తͱͯ͠੔උ

͕औΓ૊·ΕͨɽSiC ͸޿όϯυΪϟοϓɼߴ೤఻ಋ

͖ͯͨ͠ɽฌ‫ݝݿ‬ϏʔϜϥΠϯͰ͸ΞϯδϡϨʔλޫ‫ݯ‬Λඋ͑Δ BL24XU ʹ͓͍ͯ͜ͷख๏Λఏ‫͍ͯ͠ڙ‬͕ͨɼภޫి࣓ੴޫ‫ݯ‬ͷ೾௕Մมੑ΍ϫΠυϏʔϜͷಛ௃Λ‫ ͔ͯ͠׆‬BL08B2 ʹ͓͍ͯ΋࢈‫ۀ‬քͷར༻Λࠓ‫ืޙ‬Δ༧ఆͰ͋Δɽಛʹ CTɼϥϛϊάϥϑΟ๏Ͱ͸ɼࡾ࣍‫ݩ‬తͳߏ଄৘ใΛࢹ֮తʹཧղ͠қ͍ը૾ͱͯ͠දࣔͰ͖ΔͨΊɼBL24XU ʹ͓͍ͯ΋ར༻χʔζ͕ߴ͍ɽ

BL08B2 Ͱ͸௨ৗͷΠϝʔδϯά‫·ཹʹ࡯؍‬Βͣɼೋ࣍‫ݩ‬໘಺ͷ XAFS ৘ใΛऔಘͰ͖ΔΠϝʔδϯά

XAFS ʹ΋஫໨͠ɼ੔උΛਐΊͨɽΠϝʔδϯά XAFSͷ࣮‫Ͱݧ‬͸ɼ୯৭ϏʔϜ͕༗͢Δ೾௕Λ෼ޫ‫ʹث‬ΑΓ૸ࠪͤ͞ͳ͕ΒɼϫΠυϏʔϜΛࢼྉʹরࣹ͢Δɽࢼ

ਤ 3. ࣮‫ݧ‬ϋον಺ͰͷϏʔϜ‫݁࡯؍‬Ռɹ aɿσΟϑϡʔβʔແ͠ͷ৔߹ɼbɿσΟϑϡʔβʔ༗Γͷ৔߹ɽ–V–

Status Report of Hyogo-Beamlines with Research Results, Vol. 5 (2016)཰ɼߴઈԑഁյిѹ‫Ͳͳ౓ڧ‬ͷ༏ΕͨಛੑΛ༗͢Δͱ

4. 2016 ೥౓ͷ‫ܭ‬ը‫ظ‬଴͞ΕΔ͕ɼΤϐλΩγϟϧບ΍‫ج‬൘ʹଘࡏ͢Δ݁
থ͕ܽؕૉࢠͷେ໘ੵԽͷࡍʹ໰୊ͱͳΔɽߴ඼࣭݁
থͷϓϩηε‫ݕ‬౼ʹ͓͍ͯɼBL08B2 ͷ୯৭̭ઢτϙάϥϑΟ͕‫͞༻׆‬ΕɼSiC ݁থதͷܽؕ‫ߦ͕࡯؍‬ΘΕ͍ͯΔɽSiC ݁থதʹ͓͍ͯɼΒͤΜసҐɼਕঢ়సҐɼ‫ج‬ఈ໘಺సҐͳͲΛৄ͘͠ௐ΂ΔͨΊʹ͸ɼ̭ઢτϙάϥϑΟ͕‫ۃ‬Ίͯ༗ޮͳखஈͱͳΔɽBL08B2 ͷ࣮‫ݧ‬εςʔγϣϯͰ͸ɼΰχΦϝʔλɼ̭ઢϑΟϧϜ΍̭ઢΧϝϥɼ‫૾ݱ‬खஈͳͲ͕ར༻ՄೳͰ͋Γɼ࣮‫ʹݧ‬ద͢Δ‫ڥ؀‬Λඋ͍͑ͯΔɽίϯτϥετ૾͕઱໌ʹಘΒΕΔΑ͏ɼΠϝʔδϯάͷ৔߹ͱಉ༷ʹɼϏʔϜͷΫΦϦςΟΛ‫͛ڍ‬ΔͨΊͷ޻෉΋ࢪ͍ͯ͘͠ɽ

2015 ೥౓͸࣮‫૷ݧ‬ஔͷ੾Γସ͑ૢ࡞ͷࣗಈ੍‫ޚ‬ԽͳͲͷ՝୊͕࢒ͬͨɽ͜Εʹ͍ͭͯҾ͖ଓ͖औΓ૊ΈɼϢʔβʔͷϚγϯλΠϜΛग़དྷΔ‫ݶ‬Γ֬อ͢ΔΑ͏ʹ౒Ί͍ͨɽ

XAFS ͷͦͷ৔‫ػ࡯؍‬ೳ͸ɼελσΟͰੑೳ‫ূݕ‬Λߦ͍ͳ͕Β࣮༻ԽΛਐΊ͍ͯ͘ɽ·ͨ SAXS ౳Ͱར༻͞ΕΔೋ࣍‫ݕݩ‬ग़‫ث‬Λ༻͍ͨଌఆγεςϜʹ͍ͭͯ΋ߴ౓Խʹ޲͚ͨ‫ܭ‬ըΛཱͯͯਐΊΔ༧ఆͰ͋Δɽ

CTɼΠϝʔδϯάʹ͍ͭͯ͸ը૾σʔλͷਫ਼౓Λ্͛ΔͳͲͷ੔උΛߦ͍ͳ͕ΒϢʔβʔར༻Λड͚ೖΕ͍ͯ͘ɽ࢈‫ۀ‬քʹ͓͚Δࡐྉ։ൃʹରͯ͠৽ͨͳऔΓ૊Έ΋‫ݕ‬౼͍ͨ͠ɽ͜Ε·Ͱ΋‫ࡐࢉܭ‬ྉՊֶͷར༻ʹ஫໨͠ɼ

3. ࢈‫ۀ‬ར༻ͷঢ়‫گ‬์ࣹޫར༻ʹ໾ཱͭΑ͏࣮श‫ػ‬ձΛઃ͚͖ͯͨɽ৽ͨ

BL08B2 ͷϢʔβʔʹ͓͍ͯ͸ɼͦͷ৔‫࡯؍‬ͷχʔʹ৘ใՊֶͷར༻ʹ஫໨͠ɼࡐྉߏ଄σʔλΛ༗ޮ‫׆‬ζ΍ෳ਺ͷ෼ੳख๏Λಉ࣌ʹར༻͍ͨ͠ͱ͢Δχʔζ༻͢ΔͨΊͷωοτϫʔΫγεςϜͷՄೳੑΛௐ͕ࠪ͠૿͍͑ͯΔɽ͜ͷঢ়‫ʹگ‬ରͯ͠ࠓ‫ޙ‬΋ར༻ࢧԉΛ‫ܧ‬͍ͨɽ͜Εʹ͍ͭͯ͸֎෦‫ؔػ‬ͷಈ͖ʹ஫ࢹ͠ͳ͕Βଓ͍ͯ͘͠ɽ

์ࣹޫ෼ੳͱͷ༥߹ར༻Λ‫ݕ‬౼͢Δɽ

2015 ೥౓ʹ͓͚ΔϢʔβʔ͸ɼ‫ ͕ۀا‬16 ࣾɼେֶ‫ۀ‬քʹ͓͚Δ੡඼։ൃ΁໾ཱͭϏʔϜϥΠϯͰ͋Δ

͕̍‫ͨͬ͋Ͱؔػ‬ɽϚγϯλΠϜͷ಺༁ʹ໨Λ޲͚Δ

͜ͱΛॏཁͳϛογϣϯͱͨ͠ӡӦΛଓ͚͖͕ͯͨɼ

ͱখ̭֯ઢࢄཚͷར༻͕ 52%ɼXAFS ͕ 28%ɼ୯৭

࢈‫ۀ‬քͱ࿈‫͢ܞ‬ΔΞΧσϛΞ΁ͷར༻‫ػ‬ձͷఏ‫ڙ‬΋‫ݕ‬̭ઢτϙάϥϑΟ͕ 15%ɼค຤̭ઢճં͕ 5%Ͱ͋ͬ౼͢ΔɽϢʔβʔར༻͕ൺֱతগͳ͍೥ॳʹ͓͍࣮ͯ

ͨɽCTɼΠϝʔδϯά͸ߴ‫ػ‬ೳԽͷ੔උΛਐΊ͓ͯ‫ݱ‬ͷՄೳੑ͕͋Δɽ͜ͷར༻γεςϜΛ‫ݕ‬౼͍ͨ͠ɽ

ΓɼϢʔβʔʹΑΔ‫ظ͕༻׆‬଴͞ΕΔɽค຤̭ઢճં

·ͨ੒Ռެ։ͷ࣮੷ͱͯ͠࿦จͷ‫ͱ͜͢࢒Ͱܗ‬Λࠓ‫ޙ‬ʹ͍ͭͯ͸ SAXS ͱ૊Έ߹Θͤͨར༻΍ BL24XU ͷ͸ҙࣝ͠ͳ͕Βར༻ͷࡏΓํΛ‫ݕ‬౼͢Δɽ

ϚΠΫϩϏʔϜͱ૊Έ߹Θͤͨར༻ͳΞυόϯεͳ࢖͍ํ͕૿͓͑ͯΓɼଞͷ࣮‫ݧ‬εςʔγϣϯ্Ͱར༻͞

ฌ‫ཱݝݿ‬େֶ ࢈ֶ࿈‫ܞ‬ɾ‫ڀݚ‬ਪਐ‫ޫࣹ์ ߏػ‬φϊς

ΕΔ܏޲ʹ͋Δɽར༻՝୊਺ͱͯ͠͸ଟ͕͘੒Ռඇઐ

Ϋηϯλʔ༗Ͱ࣮ߦ͞Εͨɽ૯՝୊਺ 18 ݅ͷ͏ͪ 14 ͕݅઎ΊΔɽԣࢁ࿨࢘ɼ‫܂‬ຊ࣎ੜɼ࣫‫ྑݪ‬ণɼཥ ཕɼ໺੉૜Ұɼ

BL08B2 ͷར༻Ϣʔβʔͷதʹ͸ BL24XU ͱͷซ༻௡ࡔՂ޾ɼদҪ७࣐ɼ࿜ౡ ༃ʹΑΓ‫ڀݚ‬ςʔϚʹऔΓ૊Ήέʔε͕͋ͬͨɽBL08B2
౰ॳʹఏҊ͍ͯͨ͠ BL24XU ͱͷ૬ิతར༻͕࣮‫ݱ‬
͍ͯ͠Δঢ়‫͋ʹگ‬Δɽ

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ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू

ฌ‫ݝݿ‬ϏʔϜϥΠϯ BL24XU
BL24XU ͸ɼ์ࣹޫͷ࢈‫ۀ‬ར༻ਪਐΛ໨తͱͯ͠

Bonse-Hart ‫ܕ‬௒খ̭֯ઢࢄཚ (USAXS) εςʔγϣฌ‫͕ݝݿ‬ઃஔͨ͠ɼSPring-8 ॳͷઐ༻ϏʔϜϥΠϯϯ, ࣮‫ݧ‬ϋον A2 Ͱ͸ࣼೖࣹ̭ઢճંεςʔγϣϯ

Ͱ͋Δɽฏ੒ 10 ೥ 6 ݄ͷ‫༻ڙ‬։࢝࣌ΑΓɼߴً౓Ξͷӡ༻Λߦ͍ͬͯΔ. Bonse-Hart ‫ ܕ‬USAXS Ͱ͸ਤ 2ϯδϡϨʔλʔޫ‫ݯ‬ͷಛੑΛ‫͘΂͔͢׆‬ϚΠΫϩϏʔʹࣔ͢Α͏ʹ, ୯݁থΛ༻͍ͨ֯౓෼ղޫֶ‫ܥ‬Λར༻Ϝޫֶ‫ܥ‬΍ϚΠΫϩΠϝʔδϯάޫֶ‫ʹܥ‬ಛԽͨ͠ଌ

͢ΔͨΊҰ࣍‫޲ํݩ‬ͷΈͷଌఆʹ‫ݶ‬ΒΕΔ͕, ௨ৗͷఆεςʔγϣϯΛ഑උ͠ɼ‫ܧ‬ଓతʹߴ౓ԽΛਐΊ͖ͯখ̭֯ઢࢄཚ (SAXS) ޫֶ‫Ͱܥ‬͸ଌఆ͕ࠔ೉ͳ਺ϛ

͍ͯΔɽಛʹϚΠΫϩϏʔϜར༻ʹؔͯ͠͸ɼฌ‫ݝݿ‬Ϋϩϯͷप‫ߏظ‬଄ͷ‫͕࡯؍‬ՄೳͰ͋Δ. ‫ࡏݱ‬ͷଌఆྖཱେֶେֶӃ෺࣭ཧֶ‫ڀݚ‬Պ X ઢޫֶ෼໺ʹΑΔઐҬ͸ q (nm−1 ) = 0.001∼0.4, ଌఆ࣌ؒ͸໿ 5 ෼Ͱ͋໳తͳӡ༻Λߦ͓ͬͯΓɼߴ౓ͳٕज़ΛϢʔβʔར༻Δ. ଌఆྖҬΛ‫ݶ‬ఆ͢Δ͜ͱͰ໿ 90 ඵִؒͷ࣌෼ׂޫֶ‫ͯ͠ͱܥ‬ఏ‫͍ͯ͠ڙ‬ΔɽଌఆΛ࣮‫͓ͯ͠ݱ‬Γ, ࢼྉͷ‫࣌ܦ‬มԽͷ௥੻΋ՄೳͰϏʔϜϥΠϯͷུ֓Λਤ 1 ʹࣔ͢ɽ̎ຊͷϒϥϯν
ʢϒϥϯν AɼBʣͰߏ੒͞Ε͓ͯΓɼμΠϠϞϯυ
ബ൘݁থΛར༻ͨ͠௕Φϑηοτ̎݁থ෼‫ذ‬෼ޫ‫ʹث‬ΑΓɼϞϊΫϩޫΛϒϥϯν AɼಁաޫΛϒϥϯν B΁ಉ࣌ʹ‫͢څڙ‬Δɽ֤ϒϥϯνʹ͸ͦΕͧΕ 2 ͭͷ࣮‫ݧ‬ϋονΛλϯσϜʹ഑ஔʢ࣮‫ݧ‬ϋον A1ɼA2ʀޫ
ֶϋον B2ɼ࣮‫ݧ‬ϋον B1ʣ͍ͯ͠Δɽޫ‫ʹݯ‬͸̔ͷࣈΞϯδϡϨʔλʔΛ࠾༻͓ͯ͠Γɼେ‫ͱ౓ڧ‬௿ෛՙΛཱ྆͢Δ͚ͩͰͳ͘ɼ൒੔਺࣍ͷߴௐ೾Λར༻͢
Δ͜ͱͰਨ௚ɼਫฏภޫͷબ୒ΛՄೳͱ͍ͯ͠Δɽ͋Δ.
ࣼೖࣹ̭ઢճંεςʔγϣϯͰ͸ 4 ࣠ද໘ճં‫ܭ‬Λઃஔ͓ͯ͠Γɼࣼೖࣹ৚݅ͰࢼྉͷճંଌఆΛߦͳͬ
͍ͯΔ. ද໘ɾք໘ͷ݁থߏ଄΍ബບߏ଄ͷධՁ, Χ΢ϯλ๏Λ༻͍ͨค຤ճંଌఆΛߦ͍ͬͯΔ. ͞Βʹ͸, ճં‫ʹܭ‬Ճ೤࿍Λ౥ࡌ͠ೋ࣍‫ݕݩ‬ग़‫ث‬Λར༻͢Δ
͜ͱͰ൒ಋମࢼྉ౳ͷ൓Ԡաఔͷͦͷ৔‫΁࡯؍‬ͷԠ༻΋ߦΘΕ͍ͯΔ.
্‫ʹه‬Ճ͑, ࣮‫ݧ‬ϋον A2 ʹͯϚΠΫϩϏʔϜ

SAXS (µ-SAXS) ͷ੔උΛ 2015A ‫ྃ͠׬ʹظ‬, 2015B‫ظ‬ΑΓϢʔβʔར༻Λ։࢝ͨ͠. ૷ஔߏ੒ͱ֓‫؍‬Λ

1. ֤࣮‫ݧ‬εςʔγϣϯͷঢ়‫گ‬

ਤ 3 ʹࣔ͢. µ-SAXS Ͱ͸, ूޫૉࢠʹ۶ંϨϯζΛ

1. 1 ϒϥϯν A

ར༻͠, ࢼྉҐஔʹͯ໿ 5 µm, ϑΥτϯ਺ 1∼3×109

ϒϥϯν A Ͱ͸, μΠϠϞϯυ݁থ෼ޫ‫ʹث‬ΑΔphotons/sec. ͷϚΠΫϩϏʔϜΛར༻ͨ͠‫ߏॴہ‬଄

10 keV ͷ୯৭ޫ͕ར༻Ͱ͖Δɽ࣮‫ݧ‬ϋον A1 Ͱ͸ධՁ͕ՄೳͰ͋Δ. SAXS Χϝϥ௕͸ 0.5∼1.5 m ͷൣ

ਤ 1. BL24XU ϋονߏ੒ུ֓ɽ

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Status Report of Hyogo-Beamlines with Research Results, Vol. 5 (2016)ਤ 2. Bonse-Hart ‫ۃܕ‬খ֯ࢄཚଌఆޫֶ‫ܥ‬ɽ

ਤ 3. µ-SAXS ૷ஔɽғΛબ୒Ͱ͖, WAXS ͱͷಉ࣌ଌఆ΋ՄೳͰ͋Δ. ‫ݱ‬ఆ΋Մೳͱͳ͍ͬͯΔɽຊޫֶ‫ܥ‬͸ɼओʹୈҰભҠۚࡏ͸ໟ൅΍ࡉણҡͷ 1 ຊଌఆ, ిઢࡐྉ౳΁Ԡ༻ͯ͠ଐͷԽֶঢ়ଶΛௐ΂ɼࢎૉͷ഑Ґߏ଄Λ୳ΔͨΊʹརΔ. ·ͨ 2016A ‫ʹظ‬ϏʔϜαΠζ 2 µm ͷελσΟΛ༻͞Ε͓ͯΓɼϦν΢ϜΠΦϯೋ࣍ి஑ɼ‫ݻ‬ମ೩ྉి༧ఆ͓ͯ͠Γ, 2016B ‫͔ظ‬Βར༻։࢝͢Δ༧ఆͰ͋Δ.

஑ɼಃ࣓‫ث‬ᬵༀͷߏ଄ධՁ౳ʹԠ༻͞Ε͍ͯΔɽ͞ΒʹɼಉҰεςʔγϣϯ্Ͱ‫ߏॴہ‬଄͓Αͼ݁থ

1. 2 ϒϥϯν Bߏ଄ͷ྆ධՁΛ࣮‫͢ݱ‬Δ໨తͰɼPilatus 100K Λར༻ϒϥϯν B ͸ਫฏΦϑηοτͷγϦίϯ̎݁থ෼ޫ

ͨ͠ೋ࣍‫ݩ‬ค຤ X ઢճં‫ػ‬ೳ΋௥Ճ౥ࡌ͢Δ༧ఆͰ‫ث‬Λ࠾༻͓ͯ͠Γɼ5 keV∼30 keV ͷ୯৭ޫΛར༻͢

͋Δɽࠓ‫ޙ‬ɼNewSUBARU ʹ͓͚Δೈ X ઢ‫ٵ‬ऩ෼ޫ

Δ͜ͱ͕Ͱ͖ΔɽλϯσϜϋονͷ্ྲྀଆʢޫֶϋο๏ɼεϖΫτϧͷཧ࿦‫ࢉܭ‬๏ͱซͤͯɼ౷߹ߏ଄ධՁ

ν B2ʣ͸ޫֶϋον࢓༷Ͱ͋Γɼ෼ޫ‫ ث‬B ͷୈҰ݁εςʔγϣϯͷͻͱͭͱͯ͠ͷ‫༻׆‬ͷՄೳੑΛ୳Δɽ

থΛୀආ͢Δ͜ͱʹΑΓΞϯδϡϨʔλʔന৭ޫͷར2) X ઢ‫ݦ‬ඍ‫ڸ‬εςʔγϣϯ༻͕ՄೳͰ͋Δɽޫֶϋον B2 ʹ͸ɼϚΠΫϩϏʔX ઢ‫ݦ‬ඍ‫ڸ‬εςʔγϣϯͰ͸ɼX ઢूޫϏʔϜɼX

Ϝ XAFS ʹಛԽͨ͠ XAFS εςʔγϣϯɼۭؒ෼ղ

ઢΠϝʔδϯάޫֶ‫ܥ‬Λར༻ͨ͠ɼαϒϛΫϩϯ ∼ೳʹಛԽͨ͠ϚΠΫϩϏʔϜར༻ޫֶ‫ܥ‬΍ߴ෼ղೳΠϛΫϩϯͷۭؒ෼ղೳͱߴ͍࣌ؒ෼ղೳΛ༗͢Δଌఆϝʔδϯάޫֶ‫ܥ‬Λར༻Ͱ͖Δ X ઢ‫ݦ‬ඍ‫ڸ‬εςʔγϣͷϢʔβʔར༻Λల։͍ͯ͠Δɽ·ͨɼฌ‫ཱݝݿ‬େֶϯΛઃஔ͓ͯ͠Γɼ֤छࡐྉධՁʹར༻͞Ε͍ͯΔɽ

X ઢޫֶ෼໺ͷֶज़‫ͯ͠ͱڀݚ‬ɼ࣍ੈ୅ X ઢूޫૉԼྲྀଆͷ࣮‫ݧ‬ϋον B1 Ͱ͸ߴฏߦ౓ϚΠΫϩϏʔϜ

ࢠͰ͋Δଟ૚ບκʔϯϓϨʔτɼશ൓ࣹκʔϯϓϨʔޫֶ‫ܥ‬Λ༻͍ͨਫ਼ີ X ઢճંεςʔγϣϯΛӡ༻͠τ౳ͷ։ൃධՁ΍ɼ৽‫ ن‬X ઢΠϝʔδϯά๏ͷ։ൃɼ͓ͯΓɼओʹ࣍ੈ୅൒ಋମ‫ج‬൘΍ిࢠσόΠεධՁʹߴ౓Խ΋ߦΘΕ͓ͯΓɼϢʔβʔར༻ޫֶ‫΁ܥ‬ϑΟʔԠ༻͞Ε͍ͯΔɽ

υόοΫ͞Ε͍ͯΔɽଌఆޫֶ‫ܥ‬΍ଌఆ৚݅͸ɼٕज़1) XAFS εςʔγϣϯ૬ஊ಺༰ʹΑΓΦʔμʔϝΠυతʹઃఆՄೳͰɼଌఆXAFS εςʔγϣϯ͸ਤ 4 ʹࣔ͢ޫֶ‫ߏܥ‬੒Λ͓ͯ͠Γɼશ൓ࣹूޫϛϥʔʹΑΓ 1∼2 ϛΫϩϯαΠ

ޫֶ‫ܥ‬ͷ४උௐ੔ɼ࣮‫ݧ‬αϙʔτɼղੳΞυόΠε·ͰҰ؏ͯ͠ߦ͍ͬͯΔɽζʹ੔‫ ͨ͠ܗ‬X ઢϏʔϜΛར༻ͨ͠ඍখྖҬʹ͓͚ूޫϏʔϜ͸ɼ‫ج‬ຊతʹϑϨωϧκʔϯϓϨʔτ

Δߏ଄ධՁ๏ͱͯ͠ఏ‫͍ͯ͠ڙ‬ΔɽνϟωϧΧοτ݁

ʢFZPʣΛ༻͍ͯ‫ܗ‬੒͢Δɽද 1 ʹ୅දతͳϚΠΫϩথΛूޫޫֶ‫͠༻࠾ʹܥ‬ɼߴΤωϧΪʔ෼ղԽͰͷଌϏʔϜͷੑೳ‫ͦͼٴ‬ͷԠ༻ଌఆ‫͍ࣔͯͭ͢ʹܥ‬ɽ‫ޫܬ‬– VIII –ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू

ਤ 4. ߴΤωϧΪʔ෼ղϚΠΫϩ XAFS ޫֶ‫ܥ‬ɽ
ද 1. ୅දతͳϚΠΫϩϏʔϜੑೳɽ

Energy(keV)য఺‫཭ڑ‬

ूޫαΠζ

ൃࢄ֯

‫౓ڧ‬

(mm)

(ޫࢠ/s)

72(ॎ × ԣ µm)(arecsec)

10

500

4×108

XRF, Imaging

915

0.15×0.3

Ԡ༻ଌఆ‫ܥ‬

286
800
2000

0.3×0.7
0.6×1.7
1.5×9

290
50
25

3×10
2×109
4×1010

XRF, WAXD
XRF, WAXD
WAXD

108
108

0.2×0.4
0.2×4

333
10

3×108
5×106

XRF, Imaging
ਫ਼ີճં

3000

2.5×8.513

5×109

WAXD, SAXSX ઢϚοϐϯάʢµ–XRFʣɼ̎࣍‫ݕݩ‬ग़‫ث‬Λ༻͍ͨ޿‫ݦ‬ඍ‫Ͱܥֶޫڸ‬͸ɼޫֶϋον B2 ಺Ͱల։͍ͯͨ͠

֯ճંʢµ–WAXDʣɼ౳ഒҐ૬ίϯτϥετΠϝʔ૷ஔΛ࣮‫ݧ‬ϋον B1 ·Ͱ֦ுͨ͠ɽਤ 5 ʹޫֶ‫ܥ‬ΛδϯάʢCT ΋ՄೳʣɼX ઢ݁૾ޫֶ‫ܥ‬Λར༻ͨ͠ߴ

ࣔ͢ɽର෺Ϩϯζͷ֦େഒ཰ʹ௚݁͢Δࢼྉʵ̭ઢը

ۭؒ෼ղೳ CT ͷར༻͕ՄೳͰ͋Δɽ૾‫ݕ‬ग़‫཭ڑؒث‬Λ࠷௕ 6 m ·Ͱʢैདྷ͸ 3 m ఔ౓ʣΠϝʔδϯάޫֶ‫Ͱܥ‬͸ɼϢʔβʔར༻ͷଟ͍ CT

֬อ͢Δ͜ͱ͕ՄೳͱͳΓɼ̭ઢը૾‫ݕ‬ग़‫ث‬໘্Ͱͷଌఆ‫ܥ‬ͷߴ౓ԽΛߦͬͨɽࢼྉΛճస૸ࠪ͢Δεςʔ

ࢹ໺͕֦େ͞Εɼۭؒ෼ղೳ͕޲্ͨ͠ɽਤ 6 ʹςδΛภ৺ਫ਼౓͕ 0.5 ϛΫϩϯ/360◦ ͷߴਫ਼౓ճసεςʔετνϟʔτͰ͋Δδʔϝϯεύλʔϯͷ‫ݦ‬ඍ‫૾ڸ‬Λδ΁ͱަ‫ͨ͠׵‬ɽ͞Βʹࢼྉͷճసத৺Ґஔௐ੔Λ༰ࣔ͢ɽࠨਤ͕޿͍ࢹ໺Ͱ͋Γɼന͍఺ઢ࿮಺ͷζʔϜқʹ͢ΔͨΊɼߴਫ਼౓ճసεςʔδ্ʹࣗಈฒਐ XYΞοϓ૾͕ӈਤͰ͋Δɽ200 nm ͷ lines-&-spaces ·εςʔδʹ౥ࡌͨ͠ɽ·ͨଌఆ࣌ؒͷ୹ॖʹ༗ޮͳͰղ૾Ͱ͖͍ͯΔ͜ͱ͕Θ͔Δɽ

On-the-fly εΩϟϯ‫ܕ‬ͷଌఆϓϩάϥϜΛ੔උͨ͠ɽ
ϢʔβʔΠϯλʔϑΣΠε΋ൈຊతͳվྑΛߦ͍ߴޮ཰͔ͭϢʔβʔϑϨϯυϦʔͳଌఆ‫ڥ؀‬Λ੔͑ͨɽϑϨωϧκʔϯϓϨʔτΛର෺Ϩϯζͱͯ͠༻͍ͨ݁૾

3) ਫ਼ີ X ઢճંεςʔγϣϯ
ࡢ೥౓·Ͱ͸ओʹ൒ಋମ݁থͷඍখྖҬߴ‫౓ײ‬࿪Έ‫ܭ‬ଌΛ໨తʹɼߴฏߦ౓ϚΠΫϩϏʔϜޫֶ‫ܥ‬Λ༻͍ͨඍখྖҬਫ਼ີճં࣮‫ݧ‬Λߦ͖͕ͬͯͨɼࠓ೥౓৽ͨ

ਤ 5. ݁૾‫ ܕ‬X ઢ‫ݦ‬ඍ‫ ڸ‬CT ͷޫֶ‫ܥ‬ɽ– IX –

Status Report of Hyogo-Beamlines with Research Results, Vol. 5 (2016)

ਤ 8. ಉ࣌ճંͷճંεϙοτࣸਅɽ(a) 6 ೾ۙࣅɼ(b)2 ೾ۙࣅɽ

ਤ 6. δʔϝϯεύλʔϯͷ‫ݦ‬ඍ‫૾ڸ‬ɽʹલํಁա‫ܕ‬ଟ೾ճંτϙάϥϑ๏Λ։ൃɾಋೖͨ͠ɽ

-2 0 ൓ࣹ (E) ΋ಉ࣌ʹ‫͍͖ͯى‬Δ༷ࢠΛ‫ޫܬ‬൘Ͱ‫ه‬࿥ͦͷޫֶ‫ܥ‬Λਤ 7 ʹࣔ͢ɽ͜Ε·Ͱτϙάϥϑͷࡱ૾ͨࣸ͠ਅͰ͋Δɽਤ 8(b) ͸ਤ 8(a) ͷঢ়ଶ͔Β݁থΛʹ͸ओʹ X ઢϑΟϧϜ΍‫ס֩ࢠݪ‬൘ͳͲ͕༻͍ΒΕͯOB ࣠·ΘΓʹ໿ 0.1 ౓ճసͨ͠ͱ͖ͷճંεϙοτ͖͕ͨɼ͜ΕΛ CMOS ηϯαʔʹஔ͖‫͑׵‬Δ͜ͱͰɼͰ͋ΓɼͦΕͧΕಈྗֶతճંཧ࿦ͷ 6 ೾ۙࣅͱ 2 ೾‫ݕ‬ग़‫ث‬ͷઢ‫ܗ‬ੑ͕ߴ͘ͳΓɼ݁Ռͱͯ͠Ґஔ෼ղೳΛۙࣅͷ৔߹ʹରԠ͍ͯ͠Δɽਤ 9(a)ɼ(b) ͸ɼਤ 8(a)ɼ

վળ͢Δ͜ͱ͕Ͱ͖Δɽ·ͨɼ௨ৗ͸ճંͨ͠ϏʔϜ(b) ʹରԠͯ͠ࡱΒΕͨτϙάϥϑɼਤ 9(c) ͸௨ৗͷͷΠϝʔδ͔Β֨ࢠܽؕ૾ΛಘΔ͕ɼલํʹಁաͨ͠ճંϏʔϜͷΠϝʔδΛ X ઢϑΟϧϜͰऔಘͨ͠΋ϏʔϜͷΠϝʔδΛࡱ૾͢Δ͜ͱͰɼม‫ܗ‬ͷͳ͍֨ࢠܽؕ૾͕ಘΒΕΔɽͨͩ͜͠ͷ৔߹ɼίϯτϥετ͸
௨ৗͷτϙάϥϑͷ൓స૾ͱͳΔɽ

ਤ 7. લํಁա‫ܕ‬τϙάϥϑͷޫֶ‫ܥ‬ɽલํಁա‫ܕ‬τϙάϥϑ࣮‫ݧ‬Λಉ࣌ճં৚݅ʢଟ೾ۙ
ࣅ৚݅ʣۙ๣Ͱߦ͑͹ɼճંϕΫτϧͷมߋΛ༰қʹߦ͏͜ͱ͕Ͱ͖Δɽਤ 8(a) ͸ද໘͕ c ໘ͷαϑΝΠ
Ξ݁থͰɼ4 -2 -2 0 ൓ࣹ (A) ͕‫͖ى‬Δͱ͖ʹɼ3 -3 0

0 ൓ࣹ (B), 3 0 -3 0 ൓ࣹ (C), 1 -2 1 0 ൓ࣹ (D), 1 1

ਤ 9. αϑΝΠΞ݁থͷτϙάϥϑ૾ɽ(a) 6 ೾ۙࣅ৚݅Ͱͷલํಁաτϙάϥϑ૾ɽ(b) 2 ೾ۙࣅ৚݅Ͱͷલํಁաτϙάϥϑ૾ɽ(c) ࣮‫ࣨݧ‬ͷϥϯάΧϝϥͰಘΒΕͨτϙάϥϑ૾ɽX ઢϑΟϧϜͰࡱӨɽ

–X–ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू
ͷͰ͋Γɼ(a)ɼ(b) ͷҐஔ෼ղೳ͕֨ஈʹ޲্͍ͯ͠

ฌ‫ཱݝݿ‬େֶ࢈ֶ࿈‫ܞ‬ɾ‫ڀݚ‬ਪਐ‫ޫࣹ์ߏػ‬φϊςΫΔ͜ͱ͕෼͔Δɽ·ͨɼਤ 9(b) Ͱ͸ [1 -1 0 0] ํ޲ͷηϯλʔసҐઢ͕ΈΒΕͳ͍͜ͱ͔Βɼಁա૾Ͱ΋ g · b = 0஛ా৾‫ޗ‬ɼԣࢁ࿨࢘ɼ࣫‫ྑݪ‬ণɼ‫܂‬ຊ࣎ੜɼߴ໺ल࿨*ɼʢg ͸ճંϕΫτϧɼb ͸όʔΨʔεϕΫτϧʣʹΑΔ

௡ࡔՂ޾ɼ࿜ౡɹ༃

సҐ૾ͷফࣦϧʔϧ͕੒ཱ͍ͯ͠Δ͜ͱ͕෼͔Δɽ͜

*‫ॴݱ‬ଐɿ౦๺େֶଟ‫ݩ‬෺࣭Պֶ‫ॴڀݚ‬ͷଟ೾ճંτϙάϥϑΟ͸ɼSi ݁থɼSiC ݁থɼGaN
݁থͳͲͷ݁থͰ΋ద༻ՄೳͰ͋Δɽ

– XI –

Status Report of Hyogo-Beamlines with Research Results, Vol. 5 (2016)ࢪઃӡ༻͓Αͼར༻ঢ়‫گ‬େ‫ࢪޫࣹ์ܕ‬ઃ SPring-8 Λ‫ࡐ৽ͨ͠༻׆‬ྉ։ൃ౳Ճ͑ɼখ̭֯ઢࢄཚʢSAXSʣɼ޿Ҭ̭ઢ‫ٵ‬ऩඍࡉߏΛଅਐ͢ΔͨΊɼฌ‫Ͱݝݿ‬͸̎ຊͷ‫ݝ‬ઐ༻ϏʔϜϥΠ

଄ղੳʢXAFSʣɼߴਫ਼౓ค຤̭ઢճંɼ୯৭̭ઢτϯΛ੔උ͠ɼ2013 ೥౓͔Β͸ެཱେֶ๏ਓฌ‫ཱݝݿ‬ϙάϥϑΟ౳ͷख๏ʹ͍ͭͯ΋ରԠ͍ͯ͠Δɽ

େֶ࢈ֶ࿈‫ܞ‬ɾ‫ڀݚ‬ਪਐ‫ޫࣹ์ߏػ‬φϊςΫηϯλʔ

2008 ೥ 1 ݄ʹ͸ɼ͜ͷ̎ຊͷฌ‫ݝݿ‬ϏʔϜϥΠϯʢҎԼɼʮ์ࣹޫφϊςΫηϯλʔʯͱ͍͏ʣ͕ฌ‫ݝݿ‬ͷ࢈‫ۀ‬ར༻ਪਐ‫ͯ͠ͱ఺ڌ‬ɼฌ‫ޫࣹ์ݝݿ‬φϊςΫ‫ݚ‬͔ΒҕୗΛड͚؅ཧɾӡӦΛߦ͍ͬͯΔɽ์ࣹޫφϊ‫ॴڀ‬ͷ‫༻ڙ‬Λ։࢝ͨ͠ɽ౰‫ॴڀݚ‬͸ɼଟ͘ͷ࢈‫ۀ‬քͰςΫηϯλʔͰ͸ɼฌ‫ݝݿ‬ϏʔϜϥΠϯͷઃஔ໨త࣮ࢪ͞Ε͍ͯΔ৽ࡐྉ։ൃ্ඞཁͳ෼ੳධՁʹ์ࣹޫ

Ͱ͋Δ์ࣹޫͷ࢈‫ۀ‬ར༻ਪਐΛਤΔͨΊɼ‫ۀا‬ͷ‫ڀݚ‬Λੵ‫ۃ‬తʹద༻͢Δ͜ͱΛ໨తʹઃஔ͞Εɼిք์ग़

։ൃ΁ར༻ఏ‫͢ڙ‬Δͱͱ΋ʹɼ‫ۀا‬ͷར༻ࢧԉ΍‫ڞ‬ಉ‫ݦࢠిࠪ૸ܕ‬ඍ‫ڸ‬ɼ૸ࠪϓϩʔϒ‫ݦ‬ඍ‫ڸ‬ɼ‫ڞ‬য఺Ϩʔ‫ڀݚ‬ɼडୗ‫ڀݚ‬Λ௨ͯ͠࢈‫ۀ‬քͷར༻ࢧԉΛ࣮ࢪͯ͠βʔϥϚϯ‫ݦ‬ඍ‫Ͳͳڸ‬ͷ෼ੳ૷ஔ΍ࢼྉ४උࣨΛඋ

͍Δɽ͑ɼར༻‫ۀا‬౳Λࢧԉ͍ͯ͠Δɽ

̎ຊ͋Δฌ‫ݝݿ‬ϏʔϜϥΠϯ͸ɼҟͳΔछྨͷޫ‫ݯ‬Λ࣋ͪɼͦͷಘҙͱ͢Δ෼ੳख๏΋ҧ͍ͬͯΔɽ

·ͨɼେֶ΍‫ͱۀا‬ͷ‫ڞ‬ಉ‫ڀݚ‬Λߦ͏ͨΊͷ‫ڞ‬ಉ‫ࣨڀݚ‬ɼձٞࣨͳͲ΋උ͑ͨଟ‫ػ‬ೳࢪઃͰ͋Γɼίʔ·ͣɼ̍ຊ໨ͷϏʔϜϥΠϯ͸ΞϯδϡϨʔλޫ‫ݯ‬σΟωʔλʔ΍‫ڀݚ‬һ͕഑ஔ͞Εɼར༻‫ۀا‬౳͔Βͷ BL24XU Ͱ͋ΔɽBL24XU ͸ SPring-8 ͷ‫༻ڙ‬։ͷ͞·͟·ͳ૬ஊɾཁ੥ʹରԠ͢Δͱͱ΋ʹɼฌ‫ݝݿ‬࢝ͱͱ΋ʹ੔උΛ࢝Ίɼ1998 ೥౓ʹ‫༻ڙ‬Λ։࢝ɼϚϏʔϜϥΠϯͷར༻‫ۀا‬౳ʹର͠ɼ֤छਃ੥ɼ࣮‫ݧ‬४ΠΫϩϏʔϜΛ࢖֤ͬͨछΠϝʔδϯάɼճં૷ஔ౳

උɼ෼ੳΞυόΠε౳Λߦ͓ͬͯΓɼ์ࣹޫར༻͕ະ

Λ‫ͯ͠༻׆‬ɼ൒ಋମࡐྉɼੜମࡐྉɼߴ෼ࢠࡐྉ౳෯

‫͋Ͱݧܦ‬Δ‫ʹۀا‬ରͯ͠΋ɼٕज़૬ஊɾτϥΠΞϧత޿͍ࡐྉ෼໺Ͱͷ‫ॴہ‬෼ੳʹରԠ͠ɼ۩ମతͳ‫ڀݚ‬੒ͳར༻‫ػ‬ձͷఏ‫ڙ‬Λ௨ٕͯ͡ज़తࢧԉΛߦ͍ͬͯΔɽՌΛ‫͖ͨͯ͛ڍ‬ɽ͞ΒʹɼSPring-8 αΠτ಺ʹ͸ಉେֶ͕อ༗͢Δ

̎ຊ໨ͷϏʔϜϥΠϯ͸ภ޲ి࣓ੴޫ‫ݯ‬ͷ BL08B2

ೈ̭ઢ์ࣹޫࢪઃͰ͋Δ NewSUBARU ͕͋Γɼ૊৫

Ͱ͋ΔɽBL08B2 ͸ 2005 ೥౓ΑΓ‫༻ڙ‬Λ։࢝ͨ͠ɽ࢈

తͳ࿈‫ܞ‬ΛਤΔ͜ͱʹΑΓɼ࢈ֶ‫ڞ‬ಉ‫ʹڀݚ‬ର͢Δମ‫ۀ‬քʹ͓͍ͯɼΑΓ੡඼Խʹ௚݁͢Δٕज़։ൃஈ֊Ͱ

੍Λ‫ڧ‬Խ͠ɼ࢈‫ۀ‬քʹ͓͚Δ์ࣹޫར༻ͷ੄໺ͷ֦େͷࡐྉ෼ੳχʔζ͕૿Ճɼ·ͨࡐྉར༻ٕज़ͷߴ౓Խʹ΋औΓ૊ΜͰ͍Δɽ

ʹ൐ͬͯɼ৽͍͠‫ػ‬ೳΛ༗͢Δࡐྉͷ։ൃ౳͕੝ΜʹҰํɼ࢈‫ۀ‬քʹ͓͚Δ์ࣹޫͷར༻͕ਐΈɼ·ͨͳ͖ͬͯͨ͜ͱͳͲ͔ΒɼBL24XU ͕༗͢Δख๏ʹੈքτοϓϨϕϧͷεʔύʔίϯϐϡʔλʮ‫ژ‬ʯ΍࢈

ਤ 1. ฌ‫ݝݿ‬ϏʔϜϥΠϯͷར༻ମ੍– XII –

ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू

ਤ 2. ฌ‫ݝݿ‬ϏʔϜϥΠϯͷӡӦମ੍‫ۀ‬ར༻ઐ༻ͷεʔύʔίϯϐϡʔλͰ͋ΔʮFOCUSʯ

‫͢ڙ‬Δͱͱ΋ʹɼ࢈‫ۀ‬քʹ͓͚Δજࡏతχʔζͷ։୓͕ฌ‫ʹ಺ݝݿ‬ઃஔ͞Εɼ์ࣹޫͷղੳͱεʔύʔίϯΛਐΊΔͨΊɼ2009 ೥౓ΑΓɼ‫ۀا‬౳͔ΒͷҕୗΛϐϡʔλʹΑΔγϛϡϨʔγϣϯٕज़Λ૊Έ߹Θͤͨड͚ͯ์ࣹޫφϊςΫηϯλʔͷ‫ڀݚ‬һ͕ɼࢼྉͷଌֵ৽తͳࡐྉ։ൃͷχʔζ͕ߴ·͖͍ͬͯͯΔɽ์ࣹ

ఆɾղੳΛߦ͏डୗ‫ڀݚ‬Λ࣮ࢪ͍ͯ͠Δɽ

ޫφϊςΫηϯλʔͰ͸ɼ์ࣹޫࢪઃ‫ͼٴ‬εʔύʔί෼ੳͷ಺༰ͱͯ͠͸ɼ౰ॳɼXAFS ͱখ֯ X ઢࢄϯϐϡʔλͷ૬‫ޓ‬ར༻Λଅਐ͢ΔͨΊɼ‫ۀا‬ͷٕज़ऀཚͷ྆ଌఆ๏Λର৅ͱͯ͠ελʔτ͕ͨ͠ɼ࢈‫ۀ‬քͷ౳ʹࡐྉγϛϡϨʔγϣϯٕज़ͷशಘࢧԉΛߦ͖ͬͯཁ๬Λ౿·͑ɼX ઢΠϝʔδϯάɼτϞάϥϑΟͳͲɼ

ͨͱ͜ΖͰ͋Γɼࠓ‫ޙ‬΋‫ܧ‬ଓͯ͠ࢧԉ͍͖͍ͯͨ͠ɽॱ࣍෼ੳαʔϏεͷଌఆ๏Λॆ࣮͍ͤͯ͞Δɽ͜Ε·ͰҎ্ʹɼར༻‫ۀا‬౳ʹͱͬͯ࢖͍΍͍͢‫؀‬‫ڥ‬Λ੔͑ɼ࢈‫ۀ‬෼໺ʹ͓͚Δ์ࣹޫͷར༻͕ԁ‫ʹ׈‬ਐҡ࣋؅ཧɾ‫ܦ‬අෛ୲ΉΑ͏౒ΊΔͱͱ΋ʹɼٕज़૬ஊɾडୗ‫ڀݚ‬౳ͷ࣮ࢪΛ௨ͯ͡ɼ‫ཱʹ಺ݝ‬஍͢Δଟ਺ͷத‫ݎ‬ɾதখ‫ۀا‬΍஍৔࢈‫΁ۀ‬ͷ์ࣹޫར༻͕ਐΉΑ͏ɼ์ࣹޫར༻ͷ੄໺ͷ֦େʹ΋औΓ૊ΜͰ͍͘ɽฌ‫ݝݿ‬ϏʔϜϥΠϯ͓Αͼฌ‫ޫࣹ์ݝݿ‬φϊςΫ‫ݚ‬‫ॴڀ‬ͷҡ࣋؅ཧɼ‫ثػ‬੔උɼϢʔβʔαϙʔτʹ͍ͭͯ͸ɼ์ࣹޫφϊςΫηϯλʔ͕Ұ‫ݩ‬తʹ؅ཧΛߦͬ·ͨɼؔ੢஍Ҭʹࢭ·Βͣɼશࠃͷઌ୺తٕज़։ൃ

͍ͯΔɽͳ͓ɼBL24XU ͷٕज़తͳ؅ཧɾӡӦ෦෼ΛਐΊΔ‫ʹۀا‬΋ฌ‫ݝݿ‬ϏʔϜϥΠϯΛੵ‫ۃ‬తʹఏ‫ڙ‬ʹؔͯ͠͸ɼಉେֶେֶӃ෺࣭ཧֶ‫ڀݚ‬Պ̭ઢޫֶߨ

͠ɼ৽ࡐྉͷධՁɾ։ൃ౳ʹଟ͘ͷ஌‫ݟ‬Λ஝ੵ͢Δ͜࠲ͷ‫ڭ‬һ͕ɼ์ࣹޫφϊςΫηϯλʔͱͱ΋ʹ୲ͬͯͱͰɼར༻‫ۀا‬౳ͷχʔζʹԠͨ͡ߴ౓ͳٕज़త՝୊

͍Δɽฌ‫ݝݿ‬ϏʔϜϥΠϯͷҡ࣋؅ཧʹ͔͔Δඅ༻ʹ͍ͭʹରԠͰ͖ΔΑ͏౒Ί͍ͯ͘ɽͯ͸ɼઃஔऀͰ͋Δฌ‫͕ݝݿ‬ෛ୲͍ͯ͠Δ͕ɼ࣮‫ʹݧ‬ར༻ମ੍ඞཁͳ‫ثػ‬౳ͷ੔උඅ΍‫ڀݚ‬අ౳ʹ͍ͭͯ͸ɼར༻‫ا‬ฌ‫ݝݿ‬ϏʔϜϥΠϯͷར༻ʹࢸΔաఔΛਤ 1 ʹࣔ͢.

‫ۀ‬౳ʹෛ୲͍͍͍ͨͩͯΔɽͳ͓ɼϏʔϜϥΠϯͷར༻ʹ͍ͭͯ͸ɼϢʔβʔλΠϜͷ഑෼ʹԠͨ͡ར༻ྉۚʢ59.4 ສԁ/೔ʣΛෛ୲ӡӦମ੍ฌ‫ݝݿ‬ϏʔϜϥΠϯͷར༻ʹؔΘΔӡӦମ੍Λਤ 2ʹࣔ͢.

͍͍͍ͨͩͯΔɽར༻ঢ়‫گ‬
ฌ‫ݝݿ‬ϏʔϜϥΠϯͷར༻ʹ౰ͨͬͯɼར༻ਃ੥͸डୗ‫ڀݚ‬ʢ෼ੳαʔϏεʣฌ‫ݝݿ‬ϏʔϜϥΠϯ͕උ͑Δ൚༻తͳ෼ੳπʔϧΛ‫͠༻׆‬ɼ࢈‫ۀ‬ք͕์ࣹޫΛར༻͠΍͍͢γεςϜΛఏਵ࣌ड෇͚͓ͯΓɼར༻࣌‫͍ͯͭʹظ‬΋ɼຖ݄࣮ࢪ͠
͍ͯΔεέδϡʔϧձٞʹ͓͍ͯɼฌ‫ݝݿ‬ϏʔϜϥΠ– XIII –Status Report of Hyogo-Beamlines with Research Results, Vol. 5 (2016)ϯͷޮ཰తͳӡ༻Λߟྀͭͭ͠ɼ‫ۀا‬ͷҙ޲ΛͳΔ΂͘ଚॏ͢Δ‫Ͱܗ‬೔ఔௐ੔Λߦ͓ͬͯΓɼSPring-8 ͷશϏʔϜλΠϜʹର͢Δฌ‫ݝݿ‬ϏʔϜϥΠϯͷՔಇ཰͸ɼ΄΅ 100 ˋͱͳ͍ͬͯΔɽฌ‫ݝݿ‬ϏʔϜϥΠϯʹ͓͚Δɼ࠷ۙ̏Χ೥ͷ૷ஔผར༻ׂ߹Λਤ̏ʹ͕ࣔ͢ɼϚΠΫϩϏʔϜΛ༻͍ͨ‫ہ‬ॴ෼ੳ΍খ֯ X ઢࢄཚʢSAXSʣɼX ઢ‫ٵ‬ऩඍࡉߏ଄
ʢXAFSʣͷར༻͕ߴׂ͍߹ͰਪҠ͍ͯ͠Δɽ
·ͨɼར༻෼໺ʹ͍ͭͯ͸ਤ̐ͷͱ͓ΓͰ͋Γɼฌ‫ݝݿ‬ͷओͨΔ࢈‫͋Ͱۀ‬Δమ߯΍ۚଐؔ܎ͷར༻ׂ߹͸͘͝‫Ͱ͔ۇ‬ɼʮؔ੢Πϊϕʔγϣϯࠃࡍઓུ૯߹ಛ۠ʯ
ʹ͓͍ͯɼ࣍ੈ୅লΤωϧΪʔؔ࿈ࡐྉͷ։ൃΛ࠷ॏ఺՝୊ͱͯ͠औΓ૊ΜͰ͍Δ͜ͱ΋ؔ܎͍ͯ͠ΔͱࢥΘΕΔ͕ɼ‫ؔͼٴ಺ݝ‬੢‫ۀا‬ͷχʔζ͕ߴ͍ి஑΍൒ಋମͱ͍ͬͨলΤωɼ࣍ੈ୅ΤωϧΪʔؔ࿈෼໺ͷར༻͕ଟ͍ɽ

ਤ 3. ฌ‫ݝݿ‬ϏʔϜϥΠϯͷ૷ஔผར༻ׂ߹

ฌ‫ཱݝݿ‬େֶ࢈ֶ࿈‫ܞ‬ɾ‫ڀݚ‬ਪਐ‫ߏػ‬์ࣹޫφϊςΫηϯλʔࣄ຿‫ہ‬෱Ӭහ޿
ਤ 4. ฌ‫ݝݿ‬ϏʔϜϥΠϯͷ෼໺ผར༻ׂ߹

– XIV –

ɹɹɹ੒ɹՌɹू
ຊ੒Ռू͸ɼSPring-8 ੒Ռ৹ࠪҕһձʹ͓͍ͯެ։ٕज़ใࠂॻͷೝఆΛड͚͓ͯΓ·͢ɽ

–1–

ɹ

ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू

BL08B2

2014B3381

DSC/USAXS-SAXS-WAXS ʹΑΔϙϦΞϛυφϊϑΝΠόʔͷߴ࣍ߏ଄ղੳ
Higher Order Structural Analysis of a Polyamide 66 Nanofiber by
DSC/USAXS-SAXS-WAXS௕୩઒ རଇɼߴඌ ௚थɼੴ઒ େีɼࠓҪ ӳਓ
Toshinori Hasegawa, Naoki Takao, Daisuke Ishikawa, Hideto Imai‫ࣜג‬ձࣾ೔࢈ΞʔΫNISSAN ARC, LID.

֓ཁɿߴ༥఺݁থΛ༗͢ΔϙϦΞϛυ 66 φϊϑΝΠόʔͷߏ଄มԽΛௐ΂ΔͨΊɼࣔࠩ૸ࠪ೤ྔଌఆʢDSCʣ
ͱখ֯ X ઢࢄཚଌఆʢSAXSʣ͓Αͼ޿֯ X ઢࢄཚଌఆʢWAXSʣͷಉ࣌ଌఆΛ࣮ࢪͨ͠ɽঢԹաఔʹ͓͍ͯ‫ط‬ଘͷϥϝϥߏ଄ͷ੒௕΍༥ղʹΑΔϐʔΫͷফࣦ͕ DSC ‫ۂ‬ઢͱͱ΋ʹ‫͞࡯؍‬Εͨɽ͞ΒʹɼφϊϑΝΠ
όʔͷ DSC ‫ۂ‬ઢͰ‫؍‬ଌ͞ΕͨߴԹͷ༥఺͸‫ط‬ଘͷϥϝϥߏ଄ΑΓେ͖ͳɼ৳ͼ͖Γ࠯݁থͷΑ͏ͳߏ଄ମͰ
͋Δ͜ͱ͕ࣔࠦ͞ΕͨɽΩʔϫʔυɿɹφϊϑΝΠόʔɼϙϦΞϛυɼDSCɼSAXSɼUSAXSɼWAXSɼin-situഎ‫ڀݚͱܠ‬໨తߴੑೳͳ LIB όοςϦ༻ηύϨʔλ΍ɼߴ‫ͳ౓ڧ‬ણҡ΁ͷԠ༻Λࢹ໺ʹɼ৽‫ن‬φϊϑΝΠόʔͷ։ൃ͕ਐΊΒΕ͍ͯΔɽߴ෼ࢠͷߴ࣍ߏ଄͸ྗֶಛੑ΍೤ಛੑ౳ʹେ͖ؔ͘༩͢ΔͨΊɼͦͷৄࡉͷ೺Ѳ͕͔ܽͤͳ͍ɽ
લใࠂʹͯɼCO2 Ϩʔβʔ௒Ի଎Ԇ৳ (CLSD) ๏Ͱ࡞੡ͨ͠ϙϦΞϛυ 66(PA66) φϊϑΝΠόʔʹ͍ͭͯࣔࠩ૸ࠪ೤ྔଌఆ (DSC) Λ࣮ࢪͨ͠ͱ͜ΖɼφϊϑΝΠόʔʹ͸‫ݪ‬ણҡʹଘࡏ͠ͳ͍ߴԹͷ༥఺ (279◦ C) ͕‫؍‬ଌ͞ΕͨʢFig. 1ʣɽPA66 ͷ Gibbs–Thomson ϓϩοτ͔ΒߴԹͷ༥఺͸਺ඦ nm αΠζͷߏ଄ମͰ͋
ΔՄೳੑ͕ࣔࠦ͞ΕͨʢFig. 2ʣ[1,2]ɽ·ͨɼTEM ‫؍‬࡯ͷ݁Ռ Fig. 3 ʹࣔ͢Α͏ʹް͞ 100∼200 nm ͷߏ଄ମ͕֬ೝ͞Εͨɽ͔͠͠ɼDSC ଌఆ࣌ͷࢼྉ͸೤తʹඇฏߧͳঢ়ଶʹ͋ΓɼߴԹͷ༥఺ʹ༝དྷ͢Δߏ଄ͷղੳ͸ঢԹதʹ࣮ࢪ͢Δඞཁ͕͋Δɽ·ͨɼTEM ʹͯ‫͞࡯؍‬Εͨߏ଄ମ͸݁থ༝དྷ͔Ͳ͏͸൑அͰ͖ͳ͍
ͨΊɼ݁থߏ଄ͱ೤త‫ڍ‬ಈΛಉ࣌ʹ‫͢࡯؍‬Δ͜ͱ͕ՄೳͳɼDSC-SAXS-WAXS ಉ࣌ଌఆ͕༗ޮͰ͋ΔɽҰ

Fig. 1. DSC curves of (a) original fiber and (b)ൠʹ SAXS ͸ 100 nm Ҏ্ͷߏ଄ମͷධՁ͸ଌఆൣғ

nanofiber1 .

֎ͱͳΔͨΊɼຊ‫͍͓ͯʹڀݚ‬͸ɼߴً౓ͳ์ࣹޫΛ༻͍ͨ DSC/USAXS-WAXS ಉ࣌ଌఆʹΑΓɼPA66–3–

Status Report of Hyogo-Beamlines with Research Results, Vol. 5 (2016)φϊϑΝΠόʔͷ݁থ༥ղ‫ڍ‬ಈͷ‫؍‬ଌͱ 100 nm Λ௒ੜମ΁ͷӨ‫ݒ͕ڹ‬೦͞ΕΔༀ඼ྨ͸Ұ੾࢖༻͠ͳ͍ɽ

͑Δߏ଄ମͷ݁থੑΛ‫ؚ‬Ίͨߴ࣍ߏ଄มԽͷղੳΛ࣮ద༻ࡐྉ͸೤Մ઼ੑथࢷશൠͰ͋Γɼϑοૉ‫ܥ‬थࢷʹࢪͨ͠ɽ΋ద༻ՄೳͰ͋Δɽ
ɾDSC/SAXS ଌఆ

DSC/SAXS ଌఆ͸ɼSPring-8 ͷ BL08B2 ʹ࣮ͯࢪͨ͠ɽX ઢೖࣹଆޫֶ‫ܥ‬͸ 3 εϦοτϐϯϗʔϧޫֶ‫ܥ‬Λ༻͍ͨɽࢼྉ෦ʹ DSC ૷ஔΛઃஔ͠ɼࢼྉΛ Alധʹ‫ڬ‬ΜͰอ࣋ͨ͠ɽ‫ݕ‬ग़‫ث‬͸ PILATUS-100K Λ༻͍ͨɽX ઢͷ೾௕͸ λ=0.1 nmɼࢼྉ͔Β‫ݕ‬ग़‫Ͱ·ث‬ͷΧϝϥ௕Λ໿ 2 m ͱ͠ɼq ϨϯδͰ 0.0664∼2.18

nm−1 ͷൣғΛଌఆͨ͠ɽ‫ݕ‬ग़‫ث‬ͷ֯౓ΩϟϦϒϨʔγϣϯʹ͸ίϥʔήϯΛ༻͍ͨɽϏʔϜετοϓ݉༻ͷ PIN-photodiode ‫ݕ‬ग़ʹͯࢼྉͷಁա཰Λଌఆ͠ɼಁա཰Λิਖ਼‫ ʹޙ‬Al ധͷΈͷࢄཚ‫ۂ‬ઢʹͯόοΫάϥϯΛআ‫ͨ͠ڈ‬ɽDSC ͷঢԹ଎౓͸ 10◦ C/minɼଌఆ͸ 6 ඵִؒʹ࣮ͯࢪͨͨ͠Ίɼ1◦ C ຖͷ SAXS ଌఆ͕ՄೳͰ͋ͬͨɽ·ͨɼDSC ͸ Sn ͓Αͼ In Λ༻͍

Fig. 2. Gibbs-Thomson plot1 .

ͯߍਖ਼Λ࣮ࢪͨ͠ɽ
ɾDSC/USAXS-WAXS ଌఆ

DSC/USAXS-WAXS ଌఆ͸ɼલड़ͷ BL08B2 ʹ࣮ͯࢪͨ͠ɽlow-q ଆ·Ͱଌఆ͢ΔͨΊɼX ઢͷ೾௕͸

λ=0.15 nmɼࢼྉ͔Β‫ݕ‬ग़‫Ͱ·ث‬ͷΧϝϥ௕Λ໿ 16
m ͱ͠ɼq ϨϯδͰ 0.006∼0.198 nm−1 ͷൣғΛଌఆͨ͠ɽ‫ݕ‬ग़‫ث‬ͷΩϟϦϒϨʔγϣϯ΍ DSC ͷঢԹ଎౓ͳͲ͸લड़ͷ DSC/SAXS ଌఆͱಉ͡ํ๏ʹ࣮ͯࢪͨ͠ɽWAXS ଌఆ͸ USAXS ଌఆͱಉ࣌ʹ࣮ࢪ͢Δ
ͨΊɼΧϝϥ௕໿ 15 cm ͷҐஔʹ PILATUS-100K ‫ݕ‬ग़‫ث‬Λઃஔ͠ɼ2θ=15∼36 deg ͷϨϯδʹ࣮ͯࢪͨ͠ɽ

Fig. 3. TEM observation image of nanofiber.

WAXS ଌఆͷࡍͷ PILATUS ‫ݕ‬ग़‫ث‬ͷ֯౓ΩϟϦϒϨʔγϣϯ͸ Si Λ༻͍࣮ͯࢪͨ͠ɽ
݁Ռ͓Αͼߟ࡯

࣮‫ݧ‬φϊϑΝΠόʔͷଌఆ݁ՌΛ Fig. 4 ʹɼ‫ݪ‬ઢҡͷɾφϊϑΝΠόʔͷ࡞੒ࢼྉʹ͸ɼCLSD ๏Ͱ࡞੡ͨ͠ PA66 φϊϑΝΠόʔ

DSC/SAXS ‫ۂ‬ઢΛ Fig. 5 ʹࣔ͢ɽFig. 5 ͷ‫ݪ‬ઢҡʢฏ‫ۉ‬ણҡ‫ ܘ‬0.6 µmɼ279◦ C×10 min ೤ॲཧʣͱԆʹ͸ϥϝϥߏ଄༝དྷͷࢄཚϐʔΫʢ2θ=0.6∼0.8 degʣ৳લͷ‫ݪ‬ણҡΛ༻͍ͨ [1]ɽCLSD ๏͸ɼਅۭνϟϯ͕֬ೝ͞ΕɼঢԹͱͱ΋ʹϐʔΫҐஔ͕௿֯ଆʹҠಈόʔʹઃஔͨ͠ΦϦϑΟε௚ԼͰൃੜ͢Δ௒Ի଎ͷۭ

͍ͯ͠Δɽ‫౓ڧ‬΋૿Ճ͍ͯ͠Δ͜ͱ͔Βɼϥϝϥ͕ް‫ؾ‬δΣοτͱ୸ࢎΨεϨʔβʔΛར༻ͯ͠ɼ‫ݪ‬ણҡΛ͘ͳΓɼϥϝϥͷྔ͕૿Ճ͍ͯ͠Δͱߟ͑ΒΕɼϥϝ਺ສ ∼ ਺ेສഒʹ௒Ԇ৳ͤ͞ɼφϊϑΝΠόʔΛ࡞੡ϥͷ੒௕͕֬ೝ͞Εͨɽ༥఺Ҏ্ʢ260◦ CʣͰ͸ϥϝ͢Δ৽‫ن‬ͷԆ৳๏Ͱ͋Δ [3]ɽφϊϑΝΠόʔͷ࡞੡ϥ༝དྷͷϐʔΫ͸ফࣦ͠ɼDSC ‫ۂ‬ઢͱ SAXS ‫ۂ‬ઢ‫ڞ‬ʹ͋ͨΓɼಛผʹࡐྉΛ४උ͢Δඞཁ͸ͳ͘ɼ‫ڥ؀‬΍ʹ݁থͷ༥ղ͕֬ೝ͞Εͨɽ–4–ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू

Fig. 4 DSC/SAXS measurements of nanofiber.

Fig. 5 DSC/SAXS measurements of original fiber.

Fig. 6 DSC/USAXS-WAXS measurements ofnanofiber.

Fig. 7 DSC/USAXS-WAXS measurements oforiginal fiber.

ҰํɼFig. 4 ͷφϊϑΝΠόʔଌఆ݁ՌΑΓɼϥϝΛ Fig. 8 ʹࣔ͢ɽࢄཚ‫౓ڧ‬͸ q −2 ʹͯ‫ݮ‬ਰ͕‫ݟ‬ΒΕϥߏ଄ʹ༝དྷ͢ΔࢄཚϐʔΫʢ2θ=0.6∼0.8 degʣͱɼdisk ঢ়ͷࢄཚମͰ͋Δͱߟ͑ΒΕΔɽdisk ঢ়ͷࢄཚ͞Βʹ௿֯ଆʢ2θ=0.2∼0.3 degʣʹࢄཚ͕֬ೝ͞Εମͷஅ໘ͷް͞ͷճస൒‫ ܘ‬R ͸ࣜ (1) ʹͯ‫ٻ‬ΊΔͨ͜ɽͦͷ௿֯౓ଆͷࢄཚ͸ϥϝϥ༥ղ‫ޙ‬΋ଘࡏ͍ͯ͠

ͱ͕Ͱ͖ɼճస൒‫ܘ‬ΑΓஅ໘ް͞Λࢉग़Ͱ͖Δ͜ͱ͕

ͨʢFig. 4 ͷ˞ʣɽϥϝϥ༥ղ‫ޙ‬΋ࢄཚମ͕ଘࡏ͠ɼ

஌ΒΕ͍ͯΔ [4]ɽFig. 9 ʹ ln(Iq 2 ) vs q 2 ϓϩοτ௿֯౓ଆʹࢄཚ͕͋Δ͜ͱ͔Βɼϥϝϥߏ଄ΑΓେ͖ʢthickness-plotʣͷ݁ՌΛࣔ͢ɽFig. 9 ͷ܏͖ΑΓ‫ٻ‬ͳࢄཚମͷଘࡏ͕ࣔࠦ͞ΕΔɽΊͨ disk ͷް͞͸໿ 150 nm ͱࢉग़͞Εͨɽલใࠂ

φϊϑΝΠόʔͷ DSC/SAXS ଌఆʹͯ֬ೝ͞Εͨɼେ͖ͳߏ଄ମͷ֬ೝͨΊ DSC/USAXS-WAXS ଌఆΛ࣮ࢪͨ͠ɽφϊϑΝΠόʔͷ݁ՌΛ Fig. 6 ʹɼ‫ݪ‬ઢҡͷ݁ՌΛ Fig. 7 ʹࣔ͢ɽ

Fig. 7 ͷ‫ݪ‬ઢҡͰ͸ɼ260◦ C ෇ۙͷϥϝϥ༥ղʹ
ΑΔ DSC ϐʔΫΑΓߴԹଆʹ͓͍ͯ͸ɼUSAXS ͷࢄཚ‫ʹ౓ڧ‬มԽ͕ͳ͔ͬͨɽFig. 6 ͷφϊϑΝΠόʔʹ͓͍ͯ͸ɼ260◦ C ෇ۙͷϥϝϥͷ༥ղϐʔΫΑΓߴԹଆͰ΋ࢄཚମ͕ଘࡏ͍ͯ͠Δ͜ͱ͕֬ೝ͞Εͨ
ʢFig. 6–IIʣɽ͜ͷ݁Ռ͸ SAXS ͷ݁ՌͱҰக͢Δɽத [1] ͷ TEM ‫ʹ࡯؍‬ΑΓ֬ೝ͞Εͨߏ଄ମʢFig. 3ʣͷେ͖͞ͱΑ͘Ұக͍ͯͨ͠ɽ
ߋʹɼಉ࣌ʹଌఆͨ͠ WAXS ͷ݁ՌΑΓɼϐʔΫ‫ڧ‬౓͸ऑ͍͕ɼ݁থੑͷϐʔΫ͕֬ೝ͞ΕʢFig. 6–Iʣɼ
લड़ͷ໿ 150 nm ްͷ disk ঢ়ࢄཚମ͸݁থΛ༗ͯ͠
͍Δ͜ͱ͕෼͔ͬͨɽҎ্ΑΓɼφϊϑΝΠόʔʹ֬ೝ͞ΕΔߴԹଆͷ DSC ϐʔΫ͸લड़ͷใࠂ [1] Λࢧ࣋͢Δ৳ͼ͖Γ࠯ͷΑ͏ͳେ͖ͳࢄཚମͰ͋ΔՄೳੑ
͕͋Δͱߟ͑ΒΕΔɽ

ͦͷࢄཚମͷධՁͷͨΊɼ280◦ C ͷࢄཚ‫ۂ‬ઢͱ 285◦ Cͷࢄཚ‫ۂ‬ઢʢFig. 6 ͷ A–BʣͷࠩΛͱͬͨࢄཚ‫ۂ‬ઢ–5–ln(I(q)q 2 ) = ln(I(0)q 2 ) − R2 q 2 , t =

√

12R

(1)

Status Report of Hyogo-Beamlines with Research Results, Vol. 5 (2016)

Fig. 9 Thickness-plot.

Fig. 8 Scattering curve difference of 280◦ C and285◦ C on USAXS measurements of nanofiber.

์ࣹޫͷߴً౓ͳ X ઢΛ༻͍ͨ DSC ଌఆதͷμΠँࣙφϛοΫͳߏ଄ղੳͱɼUSAXS ʹΑΔ 100 nm Λ௒͑Δࢄཚମͷଌఆ͓ΑͼɼWAXS ʹΑΔ݁থੑͷ‫؍‬࡯ʹΑΓɼφϊϑΝΠόʔͰ͸ϥϝϥͷ༥఺Ҏ্Ͱ΋

150 nm ఔ౓ͷσΟεΫঢ়ͷେ͖ͳࢄཚମ͕ଘࡏ͠ɼ
ͳ͓͔ͭͦͷࢄཚମ͸݁থΛ༗͢Δ͜ͱ͕൑໌ͨ͠ɽ
͜ͷࢄཚମ͸৳ͼ͖Γ࠯Ͱ͋ΔՄೳੑ͕ߴ͍͜ͱ͕ࣔࠦ͞Εͨɽࠓճͷ‫ڀݚ‬Λߦ͏ʹ౰ͨΓɼฌ‫ཱݝݿ‬େֶ࢈ֶ࿈‫ܞ‬ɾ‫ڀݚ‬ਪਐ‫ޫࣹ์ߏػ‬φϊςΫηϯλʔͷ‫܂‬ຊ࣎ੜࢯɼ
࣫‫ྑݪ‬ণࢯɼཥ ཕࢯΛ͸͡Ίଟ͘ͷํʑʹ͓ੈ࿩ʹͳΓ·ͨ͠ɽ͜ͷ৔ΛआΓ͓ͯྱΛਃ͋͛͠·͢ɽຊ੒Ռ͸ SPring-8 ՝୊൪߸ 2012B5090/BL16XUͰͷ݁ՌΛ‫ʹج‬ɼ2014B3381/BL08B2 ʹ࣮ͯࢪͨ͠΋ͷͰ͋Δɽ

ࠓ‫ޙ‬ͷ՝୊

ࢀߟจ‫ݙ‬

ࠓճͷ DSC/SAXS ಉ࣌ଌఆʹΑͬͯɼφϊϑΝΠ
όʔͷߴ࣍ߏ଄ͷҰ୺Λ໌Β͔ʹ͢Δ͜ͱ͕Ͱ͖ͨɽ
·ͨࠓճͷଌఆ݁Ռ͸ɼφϊϑΝΠόʔͷߴ࣍ߏ଄ͱ
೤ಛੑͷ૬ؔؔ܎Λཱ֬͢ΔҰॿʹͳΔͱ‫ظ‬଴Ͱ͖ɼࠓ‫ʹࡉৄޙ‬ղੳ͢Δ༧ఆͰ͋Δɽࣄ‫΁ۀ‬ͷߩ‫ݙ‬[1] T. Hasegawa and T. Mikuni: J. Appl. Polym.
Sci.131, 40361 (2014).
[2] B. Wunderlich: Macromolecular Physics vol.3,
161-162 (Academic Press, New York, 1980).
[3] A. Suzuki and K. Aoki: Eur. Polym. J., 44, 2499
(2008).
[4] O. Kratly and O. Glatter, Small-angle X-ray
Scattering, (Academic Press, New York, 1982).

ࠓճ࣮ࢪͨ͠์ࣹޫ SAXS ͳͲɼ์ࣹޫΛར༻ͨ͠෼ੳධՁ͸ͳͯ͘͸ͳΒͳ͍ख๏ͱͳ͖͍ͬͯͯΔɽ
ࠓ՝୊ͷ DSC/SAXS Ͱ͸ɼ࣮‫ܥࣨݧ‬ධՁख๏Ͱ͸ಘ
Δ͜ͱ͕ग़དྷͳ͍ධՁ݁ՌΛಘΔ͜ͱ͕ग़དྷͨɻࠓ‫ޙ‬
͸ DSC/SAXS Λ৽‫ࡐن‬ྉ։ൃͷχʔζʹԠ༻͍ͯ͠
͖͍ͨɽ

–6–

ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू

BL08B2

2015A3330, 2015B3330

cos α ๏ʹΑΔ൒ಋମύοέʔδ෧ࢭ༻೤ߗԽੑथࢷ/ಔք໘ͷ೤࣌࢒ཹԠྗ
ͦͷ৔ղੳIn-situ residual stress analysis at the interface between
semiconductor package encapsulation resins and copper during
heating process by using cos α methodՃʑྑ ߶ࢤɼएྛ ΈͲΓɼதҪ‫ ށ‬஦ɼ௕ౡ େɼ࿨ઘ ಞ࢜
Takeshi Kakara, Midori Wakabayashi, Hiroshi Nakaido, Dai Nagashima, Atsushi Izumi
ॅ༑ϕʔΫϥΠτ‫ࣜג‬ձࣾ

Sumitomo Bakelite Co., Ltd.
֓ཁɿX ઢճં๏Λ༻͍ͨ൒ಋମύοέʔδ༻෧ࢭथࢷ/Cu ք໘ͷ࢒ཹԠྗධՁٕज़ʹ͍ͭͯ‫ݕ‬౼ͨ͠ɽCuഩ/෧ࢭथࢷ/Cu ഩͷࡾ૚ߏ଄͔ΒͳΔࢼྉΛ൒ಋମύοέʔδͷϞσϧࡐͱͯ͠༻͍ɼΠϝʔδϯάϓϨʔτʹΑΓଌఆͨ͠ Cu(331) ໘ͷ 2 ࣍‫ݩ‬ճં‫؀‬ͷ࿪Λ cos α ๏ʹΑΓղੳ͢Δ͜ͱͰɼथࢷ/Cu ք໘ʹ͓͚Δ
਺े MPa Φʔμʔͷ࢒ཹԠྗධՁʹ੒ޭͨ͠ɽߋʹɼՃ೤εςʔδΛ༻͍ͨ೤࣌ͦͷ৔‫ʹ࡯؍‬ΑΓɼ೤ϓϩηεաఔʹ͓͚Δथࢷ/Cu ք໘ͷ࢒ཹԠྗมԽ͸ɼथࢷͷ೤๲ுɼߗԽऩॖɼथࢷͱ Cu ͷઢ๲ு܎਺ࠩͳͲ
ʹΑͬͯઆ໌ՄೳͰ͋ͬͨɽҎ্ΑΓɼ౰ख๏͸൒ಋମύοέʔδ༻෧ࢭथࢷ/Cu ք໘ͷ࢒ཹԠྗධՁٕज़ͱ
ͯ͠༗ޮͰ͋Δ͜ͱ͕֬ೝ͞ΕͨɽΩʔϫʔυɿresidual stress, semiconductor package, resin-copper-interfaceഎ‫ڀݚͱܠ‬໨త΍ϦʔυϑϨʔϜ͸ओʹ Cu Ͱ͋ΔͨΊɼथࢷ/Cu ք൒ಋମύοέʔδͷߴ৴པੑɾബ‫ܕ‬Խɾߴີ౓࣮૷
ԽΛ࣮‫͢ݱ‬Δ্Ͱɼ൒ಋମύοέʔδ෧ࢭ༻थࢷ͸ඞਢͷࡐྉͰ͋Δɽ൒ಋମͷߴੑೳԽʹ൐͍ɼͦͷ൒ಋମύοέʔδ෧ࢭ༻थࢷʹ΋ߋͳΔੇ๏҆ఆੑɼ௿೤
๲ு཰ɼ଱೤ੑɼి‫ؾ‬ઈԑੑɼ೤఻ಋੑɼ଱࣪ੑͳͲ
ͷಛੑ͕‫ٻ‬ΊΒΕɼ͜ΕΒ͸൒ಋମύοέʔδͷ௕‫ظ‬৴པੑʹ΋Ө‫͢ڹ‬ΔॏཁҼࢠͰ͋Δɽ
൒ಋମύοέʔδ͸ओʹɼγϦΧͳͲͷແ‫ػ‬ϑΟϥʔΛ‫ؚ‬༗ͨ͠೤ߗԽੑथࢷͱɼͦΕʹΑΓ෧ࢭ͞ΕΔ഑ઢ΍ϦʔυϑϨʔϜͱ͍ͬͨۚଐ͔ΒͳΔෳ߹෦ࡐͰ
͋Δɽ൒ಋମύοέʔδ͸ɼͦͷ੡଄޻ఔʹ͓͍ͯथࢷ੒‫ܗ‬ɾ೤ߗԽɾ൒ాϦϑϩʔͳͲͷෳ਺ͷՃ೤ྫྷ٫ϓϩηεΛ‫ܦ‬ΔͨΊɼथࢷͱۚଐͱ͍ͬͨ஄ੑ཰΍ઢ๲ு܎਺ (CTE) ͳͲͷ෺ੑ஋͕େ͖͘ҟͳΔࡐྉؒ

໘ʹ͓͚Δ࢒ཹԠྗͷධՁٕज़ͷཱ֬ɼ͓Αͼ࢒ཹԠྗൃੜϝΧχζϜͷղ໌͸ɼ൒ಋମύοέʔδͷෆྑൃੜΛ཈੍͠ɼߴ৴པੑ੡඼ͷ։ൃʹ͓͍ͯ‫ۃ‬Ίͯॏཁͳ՝୊ͱͳΔɽ
࢒ཹԠྗ͸ X ઢճં͔֯Β‫·ٻ‬Δ݁থ֨ࢠ࿪ͱࡐ
ྉͷ஄ੑ཰ΑΓࢉग़ՄೳͰ͋Δɽฏ໘Ԡྗঢ়ଶΛԾ
ఆͰ͖Δ৔߹ͷղੳख๏ͱͯ͠͸ɼࢼྉද໘ͱ Cu ݁থ֨ࢠ໘๏ઢͷͳ֯͢ Ψ ͱճં֯ͷؔ܎ΛධՁ͢Δ

sin2 Ψ ๏͕༗ޮͰ͋Δ [1–3]ɽͨͱ͑͹थࢷ/Cu ք໘ʹҾுԠྗ͕ଘࡏ͢Δ৔߹ͷ Cu ݁থ֨ࢠͷঢ়ଶΛߟ͑ΔͱɼΨ = 0◦ ʹରԠ͢Δ֨ࢠ໘ͷִؒ͸ແ࿪ঢ়ଶʹରͯ͠ϙΞιϯൺʹै͍খ͘͞ͳΓɼΨ ͕େ͖͘ͳ
ΔͭΕ໘ִؒ͸޿͕ΓɼΨ = 90◦ Ͱ࠷େͱͳΔɽզʑ͸͜Ε·Ͱʹଟ࣠ճં‫ ͱܭ‬0 ࣍‫ݩ‬γϯνϨʔͷք໘ʹ͸೤Ԡྗ͕࢒ཹԠྗͱͯ͠஝ੵ͢Δɽ࢒ཹԠγϣϯΧ΢ϯλʔΛ༻͍ɼsin2 Ψ ๏ʹΑΔ൒ಋମύοྗ͸൒ಋମύοέʔδͷ࿪Έ΍൓Γͱͳͬͯ‫ݱ‬Εɼքέʔδʹ͓͚Δथࢷ/Cu ք໘ͷ࢒ཹԠྗධՁΛ‫ݕ‬౼໘ണ཭ͱ͍͏൒ಋମύοέʔδʹ͓͚Δக໋తͳෆྑ

͖ͯͨ͠ [4–6]ɽ͔͠͠ͳ͕Βɼෳ਺ͷ Ψ ʹର͢ΔճϞʔυͷཁҼͱͳΔɽ൒ಋମύοέʔδʹ͓͚Δ഑ઢ

ંϓϩϑΟʔϧΛεΩϟϯ͢Δඞཁ͕͋ΔͨΊɼ1 ଌ–7–

Status Report of Hyogo-Beamlines with Research Results, Vol. 5 (2016)ఆʹ਺े෼ؒ΋ͷ࣌ؒΛཁ͠ɼ਺–਺े෼Φʔμʔͷ࣮‫ݧ‬೤ϓϩηεͷ֤޻ఔʹ͓͚ΔԠྗมԽΛৄࡉʹղੳ͢ΔͨΊʹ͸ɼଌఆ࣌ؒΛ਺෼Φʔμʔʹ୹ॖ͢Δ͜ͱ
͕՝୊Ͱ͋Δɽͦ͜Ͱɼ0 ࣍‫ݕݩ‬ग़‫ث‬Λ༻͍ͨ sin2 Ψ๏ʹ୅ΘΔ ୹࣌ؒͰͷԠྗධՁख๏ͱͯ͠ɼ2 ࣍‫ݕݩ‬ग़‫ث‬Λ༻͍ͨ cos α ๏ʹ஫໨ͨ͠ [1, 7, 8]ɽcos α ๏͸

2 ࣍‫ݕݩ‬ग़‫Ͱث‬ಘΒΕΔճં‫؀‬શମͷ࿪৘ใΑΓԠྗΛࢉग़͢Δख๏Ͱ͋Γɼߋʹ 1 छྨͷ X ઢೖࣹ֯Ͱ
ͷճંσʔλͷΈͰղੳՄೳͰ͋ΔͨΊɼେ෯ͳଌఆ
࣌ؒ୹ॖ͕‫ظ‬଴͞ΕΔɽࠓճɼcos α ๏Λ༻͍ͨ൒ಋ
ମύοέʔδ෧ࢭ༻೤ߗԽੑथࢷ/Cu ք໘ʹ͓͚Δ࢒
ཹԠྗධՁٕज़ͷ‫ূݕ‬ɼ͓Αͼ೤࣌ͷ࢒ཹԠྗͦͷ৔‫ݕ͍ͯͭʹ࡯؍‬౼ͨ͠ɽ൒ಋମύοέʔδͷϞσϧࡐྉͱͯ͠ɼCu ഩ (12µm)/൒ಋମύοέʔδ෧ࢭ༻೤ߗԽੑथࢷ (1.3 mm)/Cu ഩ (12 µm) ͷࡾ૚ߏ଄͔ΒͳΔฏ൘ঢ়ࢼྉΛ 200◦ CͰͷՃ೤ѹॖ੒‫ʹܗ‬ΑΓ࡞੡͠ɼ20 mm × 20 mm ʹ੾ग़ͨ͠ (Fig. 1a, b)ɽ೤ߗԽੑथࢷͱͯ͠थࢷ a ͓Αͼथࢷ b Λ༻͍ͯ࡞੡ͨ͠ϞσϧࡐྉΛ֤ʑsample-

Aɼsample-B ͱ͢Δɽ͜͜Ͱɼ൒ಋମύοέʔδͷྫྷ೤িܸࢼ‫͚͓ʹݧ‬Δ Cu ͱͷք໘ີண৴པੑ͸थࢷ aΑΓ΋थࢷ b ͕༏ΕΔɽ·ͨɼ͍ͣΕͷथࢷ΋γϦΧϑΟϥʔΛ໿ 70 wt%‫ؚ‬Έ (Fig. 1c)ɼߗԽथࢷͷ CTE
͸ 200◦ C ҎԼʹ͓͍ͯ Cu ͱ΄΅ಉ౳ͷ஋Λࣔ͢Α͏ʹઃ‫͞ܭ‬Ε͍ͯΔ͕ɼ200◦ C Ҏ্ʹ͓͍ͯ͸େ͖͘มԽ͠ɼथࢷ b ͸थࢷ a ΑΓେ͖ͳ஋Λࣔ͢ (Fig. 2)ɽ
ଌఆͷϨΠΞ΢τΛ Fig. 3 ʹࣔ͢ɽࢼྉՃ೤࿍ʹ͸ϏʔϜϥΠϯอ༗ͷখ‫ܕ‬ηϥϛοΫώʔλʔΛ༻͍ɼೖࣹ X ઢͱࢼྉද໘๏ઢͷͳ֯͢ (ϕ) ͕ 30◦ ͱͳΔΑ͏ʹઃஔͨ͠ɽද໘ Cu ഩ͔Βͷճં X ઢ͸ɼࢼྉΑΓ্ྲྀଆʹઃஔͨ͠ X ઢಁա݀Λ༗͢ΔΠϝʔδϯάϓϨʔτ (IP)(BAS-SR2025) Λ༻͍ͯഎ໘൓ࣹ
഑ஔͰଌఆͨ͠ɽଓ͚ͯಉ͡ IP ʹແ࿪ճં‫͓؀‬ΑͼϏʔϜηϯλʔΛ‫ٻ‬ΊΔͨΊͷඪ४ࢼྉͱͯ͠Ξϧϛχ΢Ϝค຤ͷճં‫؀‬Λଟॏ࿐ޫͨ͠ɽଌఆࢼྉͱඪ४
ࢼྉͷަ‫࡞ૢ׵‬͸ࣗಈ X ࣠εςʔδΛར༻͢Δ͜ͱͰϋον֎ΑΓߦͬͨɽ

Fig. 1. (a) Schematic image of semiconductor package model for residual stress analysis comprising of
Cu/Resin/Cu three-layered sample. (b) Photo image of the specimen for the residual stress analysis.
(c) X-ray CT image of a semiconductor encapsulation resin containing SiO2 -fillers (pale-colored region) by using CCD detector measured at BL08B2

a function of temperature obtained by TMA analy-

beamlineses. The value of copper (16.8 ppm/K) is from liter-Fig. 2. CTE of resin-a and resin-b cured at 250◦ C as

ature data.

–8–ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू

(2) தͷ ∆L ͸ఴࣈͰࣔ͢ํҐ֯ʹ͓͚Δඪ४ࢼྉͱ
ଌఆࢼྉͷճંϐʔΫτοϓͷಈ‫͋Ͱࠩ཭ڑܘ‬ΓɼํҐ֯ α ʹ͓͚ΔճંϐʔΫτοϓ͸ɼํҐ֯ α ± 0.5◦ͷൣғͰηΫλʔฏ‫ͯ͠ۉ‬ಘͨ 1 ࣍‫ݩ‬ϓϩϑΟʔϧͷϩʔϨϯπؔ਺ϑΟοςΟϯάʹΑΓࢉग़ͨ͠ɽ

∆L =(∆lα − ∆lπ+α ) + (∆l−α − ∆lπ−α )2(2)ղੳʹ͸ Al(422) ໘ͱ Cu(331) ໘ͷճં‫؀‬Λ༻͍ɼ8.0

keV ʹ͓͚Δແ࿪ঢ়ଶͰͷճં֯Λ֤ʑ139.0◦ ͓Αͼ
138.0◦ ͱͨ͠ɽࢼྉ–‫ݕ‬ग़‫཭ڑؒث‬͸ɼଌఆࢼྉ 74mm ͓Αͼඪ४ค຤ 66 mm ͱ͠ɼࣜ (1) ʹ͓͚Δඪ
४ค຤ͷճં֯ 2θ0,std ͸ɼඪ४ค຤–‫ݕ‬ग़‫཭ڑؒث‬Λ

Fig. 3. Instrumental setup for residual stress measurements with an imaging plate detector by using

74 mm ͱԾఆͨ͠‫ֻ͚ݟ‬ͷճં֯ 142.5◦ Λ༻͍ͨɽcos α method.

ͷϐΫηϧαΠζ͸ɼIP ΛαΠζ‫ط‬஌ͷ Al ഩͰϚεIP σʔλͷಡऔΓʹ͸ BAS-1800II Λ༻͍ɼಡऔը૾
Ϋͨ͠ঢ়ଶͰ X ઢΛ࿐ޫͯ͠ಘͨը૾σʔλ͔Βࢉଌఆʹ༻͍ͨ X ઢͷΤωϧΪʔ͸ 8.0 keVɼϏʔϜαΠζ͸ 0.4 mm × 0.4 mm ͱ͠ɼX ઢরࣹ࣌ؒ

ग़ͨ͠ߍਖ਼஋ (49.88 µm/pixel × 49.49 µm/pixel) Λ࢖༻ͨ͠ɽ͸ଌఆࢼྉ 2 minɼඪ४ࢼྉ 3 min ͱͨ͠ɽՃ೤ϓϩηε͸ɼ40◦ C ͔Β 250◦ C ΁ͷঢԹɼ250◦ C อ࣋ɼ◦݁Ռ͓Αͼߟ࡯

◦250 C ͔Β 40 C ΁ͷ߱ԹͷαΠΫϧΛ 2 ճ‫܁‬Γฦͨ͠ɽ250◦ C Ͱͷอ࣋࣌ؒ͸ɼ1 αΠΫϧ໨͸൒ಋମύοέʔδ੒‫ޙܗ‬ͷ೤ߗԽॲཧΛ૝ఆͨ͠ 1 h อ࣋ɼ

2 αΠΫϧ໨͸ߗԽॲཧ‫ޙ‬ͷ೤ϓϩηεΛ૝ఆͨ͠ 30
min อ࣋ͱͨ͠ (Fig. 7)ɽࢼྉશମΛ‫ۉ‬ҰՃ೤͢Δͨ

Fig. 4 ʹ sample-A ͷߗԽॲཧ‫ ޙ‬40◦ C ʹ͓͚Δ 2
࣍‫ݩ‬ճંϓϩϑΟʔϧΛࣔ͢ɽߋʹɼFig. 5 ʹ Al(422)໘͓Αͼ Cu(331) ໘͔ΒͷճંϓϩϑΟʔϧʹ͍ͭ
ͯ 1 ࣍‫ݩ‬Խͨ͠΋ͷΛ α ͷؔ਺ͱͯࣔ͢͠ɽࢼྉ͸ΊʹɼࢼྉͱώʔλʔΛΧϓτϯϑΟϧϜͰ෴͍ɼࢼ
ྉԹ౓͸γʔτঢ়೤ిରΛ༻͍ͯ Cu ഩ্ͷԹ౓ͱͯ͠‫ܭ‬ଌͨ͠ɽ
थࢷ/Cu ք໘ͷ࢒ཹԠྗ (σ) ͸ࣜ (1) Λ༻͍ͯࢉग़
ͨ͠ [5]ɽԠྗූ߸͕ਖ਼ͷ৔߹͸ҾுԠྗɼෛͷ৔߹͸ѹॖԠྗͰ͋Δɽ E
cos2 2θ0 tan 2θ0,std·
σ=
2Lstd tan θ0
1+


 ν
1
d∆L
·
(1)
·
d cos αsin2 (ϕ − η) − sin2 (ϕ + η)͜͜Ͱɼ2θ0 ͓Αͼ 2θ0,std ͸ଌఆࢼྉ (Cu) ͓Αͼඪ४ค຤ (Al) ͷແ࿪ঢ়ଶͷճં֯ɼLstd ͸ඪ४ค຤ճ
ં‫؀‬൒‫ܘ‬ɼE ͓Αͼ ν ͸ Cu ഩͷ஄ੑ཰ (65.0 GPa) ͓ΑͼϙΞιϯൺ (0.343)ɼ2η ͸ଌఆࢼྉͷճં֯ 2θ0ͷิ֯Ͱ͋Δɽα ͸ Fig. 3 ͓Αͼ Fig. 4 ʹ −η ଆͱͯࣔͨ͠͠‫ݕ‬ग़໘ʹ͓͚Δ 9 ࣌ํ޲͔Β࣌‫ܭ‬ճΓͷํҐ

Fig. 4. Two-dimensional diffraction profiles of Cu(cured sample-A at 40◦ C before second heating process) and Al-powder measured on a single imaging
plate at different sample-to-detector distances of 74
and 66 mm, respectively.

֯ɼ∆L ͸ࣜ (2) Ͱఆٛ͞ΕΔύϥϝʔλͰ͋Γɼࣜ

–9–

Status Report of Hyogo-Beamlines with Research Results, Vol. 5 (2016)

Fig. 5.

Diffraction peak profiles of Cu(311) andAl(422) as a function of azimutial angle α for cured
sample-A at 40◦ C before second heating process.

Fig. 7. Change in residual stress at the resin/Cu
interface during heating process.

࣍ʹɼՃ೤ϓϩηεաఔʹ͓͚Δ sample-A ͓Αͼsample-B ͷथࢷ/Cu ք໘ͷ࢒ཹԠྗมԽͷղੳ݁ՌΛ Fig. 7 ʹࣔ͢ɽՃ೤ϓϩηε࣌ؒ (t) ʹ൐͏໌ྎͳԠྗมԽ͕ಘΒΕͨɽ͜ΕΒͷ‫ڍ‬ಈΛɼथࢷͷ೤๲ுɼߗԽऩॖɼCTE ͳͲͷ‫఺؍‬ΑΓҎԼͷΑ͏ʹߟ࡯ͨ͠ɽ(i) t = 0 min (Ճ೤ϓϩηεલ): sample-A ͱ sampleB ͱ΋ʹະߗԽࢼྉ͸ѹॖԠྗΛࣔͨ͠ɽϞσϧࡐྉͷ੒‫ܗ‬Թ౓ (200◦ C) ʹ͓͍ͯथࢷ͕೤๲ுͨ͠ঢ়ଶͰ
ք໘͕‫ܗ‬੒͞ΕΔͨΊɼ40◦ C ΁ͷྫྷ٫ʹ൐͏ະߗԽ
थࢷͷ೤ऩॖ͕थࢷ/Cu ք໘ʹѹॖԠྗΛ΋ͨΒͨ͠

Fig. 6. ∆L − cos α plot for cured sample-A at 40◦ C
before second heating process.

ͱਪఆ͞ΕΔɽ(ii) t = 0 − 40 min (ߗԽԹ౓·ͰͷঢԹաఔ):250◦ C ΁ͷঢԹաఔʹ͓͍ͯɼsample-A ͱ sample-B
Cu ഩ/थࢷ/Cu ഩͷࡾ૚ߏ଄Ͱ͋Δ͕ɺϐʔΫ෼྾ͷͱ΋ʹԠྗ͕૿Ճ͠ɼѹॖԠྗ͔ΒҾுԠྗ΁ͱมԽͳ͍໌ྎͳ Cu ͷճં‫͕؀‬ಘΒΕͯΔ͜ͱΑΓɼཪ໘ͨ͠ɽ͜Ε͸ɼՃ೤ʹΑΔະߗԽथࢷͷ೤๲ுʹΑͬCu ഩ͔Βͷ X ઢճંͷ‫د‬༩͸γϦΧϑΟϥʔΛ‫ؚ‬༗ͯथࢷ/Cu ք໘ʹҾுํ޲ͷԠྗ͕ՃΘͬͨͨΊͱਪ

͢Δथࢷ૚Ͱͷ X ઢ‫ٵ‬ऩʹΑͬͯແࢹͰ͖Δͱߟ͑ఆ͞ΕΔɽΒΕΔɽFig. 5 ͓Αͼࣜ (2) ΑΓ‫ٻ‬Ίͨ ∆L − cos α ઢ(iii) t = 40 − 100 min (ߗԽաఔ):͍ͣΕͷथࢷ΋ਤΛ Fig. 6 ʹࣔ͢ɽ∆L − cos α ઢਤ͸શͯͷํҐ֯

250◦ C ౸ୡ͔࣌Βอ࣋աఔʹ͓͍ͯҾுԠྗ͕໿ 10αɼ͢ͳΘͪ cos α = 0 ∼ 1 ͷൣғͰΑ͍௚ઢੑΛࣔMPa ‫ݮ‬গ͠ɼ࠷ऴతʹ sample-Aɼsample-B ͷԠྗ͠ɼઢ‫ܗ‬ϑΟοςΟϯάΑΓ‫ٻ‬Ίͨ܏͖ 0.221±0.005

͸֤ʑ27, 24 MPa ͱͳͬͨɽथࢷͷ೤ߗԽ൓Ԡਐߦ

mm ͓Αͼࣜ (1) ΑΓ࢒ཹԠྗ͸ 26.1±0.6 MPa ͱࢉʹΑΔߗԽऩॖʹΑͬͯɼҾுԠྗ͕؇࿨͞ΕͨͨΊग़͞Εͨɽ͜ͷ݁ՌΑΓɼथࢷ/Cu ք໘ʹ͸ҾுԠྗͱਪఆ͞ΕΔɽ(iv) t = 100 − 140 min (ߗԽऴྃ‫ޙ‬ͷྫྷ٫աఔ):͕ଘࡏ͢Δ͜ͱ͕໌Β͔ͱͳͬͨɽIP ͓Αͼ cos α ๏Λ༻͍ͨຊख๏ʹΑΓɼथࢷ/Cu ഩք໘ʹ͓͚Δ਺े

sample-A ͸ 250◦ C ͔Β 200◦ C (t = 110min) ΁ͷྫྷ

MPa Φʔμʔͷ࢒ཹԠྗΛ਺෼ΦʔμʔͰଌఆ͢Δ

٫աఔͰԠྗ͸ 27 MPa ͔Β 14 MPa ʹ‫ݮ‬গ͠ɼͦͱ͍͏՝୊ʹର͠ɼࢼྉ΁ͷ X ઢরࣹ࣌ؒ 2 min ͱͷ‫ޙ‬͸΄΅ҰఆͱͳͬͨɽҰํɼsample-B ͸ 250◦ C͍͏୹࣌ؒͰͷԠྗղੳ͕Մೳͱͳͬͨɽ

͔Β 150◦ C (t = 120min) ΁ͷྫྷ٫աఔͰԠྗ͸ 24– 10 –

ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू

MPa ͔Β 3 MPa ʹ‫ݮ‬গ͠ɼͦͷ‫ޙ‬͸΄΅Ұఆͱͳͬࣄ‫΁ۀ‬ͷߩ‫ݙ‬ͨɽ͜ΕΒͷ‫ڍ‬ಈ͸ɼFig. 2 ʹࣔ͢ߗԽथࢷ୯ಠͷ

CTE มԽ͔Βઆ໌͕Ͱ͖Δɽ͢ͳΘͪɼ250◦ C ͔Βͷྫྷ٫աఔʹ͓͍͍ͯͣΕͷथࢷ΋ CTE ͕௿Լ͢Δ
͕ɼथࢷ a ͸ 200◦ C ෇ۙͰɼथࢷ b ͸ 230◦ C ෇ۙͰͦΕͧΕ CTE ͕ Cu ͱҰக͠ɼͦΕҎԼͷԹ౓Ͱ͸Cu ͱಉ͡ CTE Λҡ࣋͢Δɽߋʹ CTE ͷ஋ΑΓɼ250◦

C ͔Βͷྫྷ٫աఔʹ͓͍ͯ͸थࢷ a ΑΓ΋थࢷ b ͷํ͕೤ऩॖྔ͸େ͖͘ͳΔͱਪ࡯͞ΕΔɽ͜ͷߗԽथࢷ୯ಠͷ CTE มԽ͕थࢷ/Cu ෳ߹ࡐྉʹ΋΄΅൓ө͞Ε͓ͯΓɼsample-A ΑΓ sample-B ͷํ͕ߗԽॲ

ࠓճ‫ݕ‬౼ͨ͠ cos α ๏ʹΑΔ࢒ཹԠྗධՁٕज़͸ɼ൒ಋମύοέʔδ༻෧ࢭथࢷ/Cu ք໘ͷঢ়ଶΛඇഁյͰղੳ͢Δ͜ͱ͕Մೳͳ‫ۃ‬Ίͯ༗ޮͳख๏Ͱ͋Δɽߋʹ਺෼Φʔμʔͱ͍͏୹࣌ؒ‫ܭ‬ଌ͕ՄೳͰ͋ΔͨΊɼຊ‫ݕ‬౼ʹΑͬͯ൒ಋମύοέʔδͷີண৴པੑʹେ͖͘Ө‫͢ڹ‬Δͱਪఆ͞ΕΔ೤িܸԼͷԠྗมԽΛਝ଎ʹଊ͑Δٕज़໨ॲཱ͕ͬͨɽࠓ‫ޙ‬ɼຊධՁٕज़Λ౰ࣾͷ൒ಋମύοέʔδ༻थࢷࡐྉ։ൃʹ޿͘ల։͍ͯ͘͠༧ఆͰ͋Δɽ

ཧ‫ޙ‬ͷྫྷ٫աఔʹ͓͚Δ೤ऩॖྔ͕େ͖͘ɼҾுԠྗँ͕ࣙେ͖͘؇࿨͞Εͨͱਪఆ͞ΕΔɽ(v) t = 140 − 250 min (ߗԽ඼ͷՃ೤ྫྷ٫աఔ): ԠྗͱԹ౓ͷؔ܎͸ɼt = 100−140 min ʹ͓͚ΔߗԽऴྃ‫ޙ‬ͷྫྷ٫աఔͱ΄΅ಉ༷ͷ݁Ռ͕ಘΒΕɼՄ‫ٯ‬తͳมԽͰ͋Δͱਪఆ͞ΕΔɽߗԽॲཧ‫ޙ‬ͷϞσϧࡐྉͷथࢷ/Cu ք໘ͷԠྗมԽ͸ɼߗԽथࢷͱ Cu ͷ CTE
ࠩ (CTE ϛεϚον) ͷԹ౓ґଘੑʹΑͬͯઆ໌͕Մ
ೳͰ͋Δ͜ͱ͕֬ೝ͞ΕͨɽҎ্ΑΓɼࠓճ‫ݕ‬౼ͨ͠൒ಋମύοέʔδ༻෧ࢭथࢷʹ͓͚Δथࢷ/Cu ք໘ͷԠྗൃੜϝΧχζϜ͸ߗԽथࢷͱ Cu ͷ CTE ϛεϚον͕ཁҼͷͻͱͭͱͯ͠ਪఆ͞ΕΔɽ·ͨɼsample-A ͸ৗʹҾுԠྗֻ͕͔͍ͬͯΔঢ়ଶͰ͋Γɼsample-B ͸ࣨԹ෇ۙͰ͸ҾுԠྗ͕؇࿨͞Εͨঢ়ଶͱͳΔ͜ͱ͕໌Β͔ͱͳΓɼ͜ΕΒ͕൒ಋମύοέʔδͷ೤αΠΫϧ৴པੑʹӨ‫ڹ‬Λ‫͍ͯ͠΅ٴ‬ΔՄೳੑ͕ࣔࠦ͞Εͨɽࠓ‫ޙ‬ͷ՝୊
ࠓճಘΒΕͨԠྗͷଥ౰ੑ͸ɼಉ༷ʹ X ઢճં๏Λ༻͍ͨධՁख๏Ͱ͋Δ sin2 Ψ ๏ʹΑΔղੳ΍༗‫ݶ‬ཁૉຊଌఆΛߦ͏ʹ͋ͨΓɼฌ‫ཱݝݿ‬େֶ์ࣹޫφϊςΫηϯλʔͷ‫܂‬ຊ࣎ੜത࢜ɼ࣫‫ྑݪ‬ণത࢜ɼཥཕത࢜ɼ
ͦͷଞؔ܎ऀͷօ༷ΑΓଟ਺ͷٕज़‫ݴॿ͝ͱྗڠ‬Λ͍͖ͨͩ·ͨ͠ɽ·ͨɼ࢒ཹԠྗղੳʹ͋ͨΓɼਆ‫ށ‬େֶɾ੢໺޹‫ڭ‬तʹ͝ࢦಋ͍͖ͨͩ·ͨ͠ɽ‫ँײ‬ਃ্͛͠·͢ɽࢀߟจ‫ݙ‬[1] ాத‫ܒ‬հɹଞɿʮ์ࣹޫʹΑΔԠྗͱͻͣΈͷධՁʯཆ‫ݡ‬ಊ, ౦‫( ژ‬2009).
[2] K. Nakamae et al.: J. Appl. Polym. Sci. 40, 2231
(1990).
[3] T. Nishino et al.: J. Appl. Polym. Sci. 45, 1239
(1992).
[4] एྛΈͲΓ ଞɿSPring-8/SACLA ར༻‫ڀݚ‬੒Ռू
3, 589 (2015).
[5] एྛΈͲΓ ଞɿSPring-8/SACLA ར༻‫ڀݚ‬੒Ռू
4, 275 (2016).
[6] एྛΈͲΓ ଞɿSPring-8/SACLA ར༻‫ڀݚ‬੒Ռू
4, 294 (2016).
[7] ࠤʑ໦හ඙ ଞɿࡐྉ 44, 1138 (1995).
[8] Ԧ ଞɿ೔ཱධ࿦ 95, 454 (2013).

๏ʹΑΔγϛϡϨʔγϣϯͳͲଞͷධՁख๏ʹΑΔ݁
Ռͱͷൺֱ‫͕ূݕ‬ඞཁͰ͋Δɽ·ͨɼຊ‫ݕ‬౼Ͱ͸ࣨԹ͔Β 250◦ C ͔Βʹ͓͚Δ೤࣌ͷՃ೤ϓϩηεʹؔͯ͠ධՁΛߦ͕ͬͨɼ൒ಋମύοέʔδͷྫྷ೤িܸࢼ‫Ͱݧ‬͸ −40◦ C ͰͷධՁ΋࣮ࢪ͞ΕΔͨΊɼ−40 ∼+250◦ CͰͷྫྷ೤ଌఆ͕Մೳͳࢼྉεςʔδ։ൃɼ͓Αͼྫྷ೤࣌ͷ࢒ཹԠྗͦͷ৔‫ٕ࡯؍‬ज़։ൃ͕ࠓ‫ޙ‬ͷ՝୊Ͱ͋Δɽߋʹɼࠓ‫ޙ‬͸ྫྷ೤িܸࢼ‫ݧ‬Λ 100, 500, 1000 αΠΫϧͳͲ࣮ࢪͨ͠‫ޙ‬ͷϞσϧࡐྉΛ༻͍ɼथࢷ/Cu ք໘ͷີண৴པੑͱԠྗมԽͷ૬ؔղ໌Λ໨ࢦ͢ɽ– 11 –

Status Report of Hyogo-Beamlines with Research Results, Vol. 5 (2016)

BL24XU

2015B3231

Li ΠΦϯి஑ਖ਼‫ࡐۃ‬அ໘ͷ X ઢϚΠΫϩϏʔϜʹΑΔ൓Ԡ෼෍ղੳ
Reaction Distribution Analysis of Cathode Material of Lithium
Ion Battery by X-ray Micro-Beam Imaging Methodࡾࠜੜ ৾ 1 ɼट౻ େ‫ ث‬2 ɼ஛ా ৾‫ ޗ‬2 ɼԣࢁ ࿨࢘ 2 ɼॅా ߂༞ 1 ,Susumu Mineoi1 , Motoki Sudo2 , Shingo Takeda2 , Kazushi Yokoyama2 , Hirosuke Sumida111Ϛπμ‫ࣜג‬ձࣾ ٕज़‫ॴڀݚ‬ɼ2 ฌ‫ཱݝݿ‬େֶ์ࣹޫφϊςΫηϯλʔ

Mazda Motor Corporation Technical Research Center, 2 Synchrotron Radiation Nanotechnology
Laboratory, University of Hyogo֓ཁɿαΠΫϧࢼ‫ݧ‬લ͓Αͼࢼ‫ޙݧ‬ͷϦν΢ϜΠΦϯి஑͔Β࠾औͨ͠ਖ਼‫ۃ‬Λ༻͍ͯɼॆ์ిաఔʹ͓͚Δ߹
ࡎஅ໘ͷ൓Ԡ෼෍Λ X ઢϚΠΫϩϏʔϜʹΑΓධՁͨ͠ɽॆ์ిϨʔτΛ 0.5 C ͱͨ͠৔߹ɼࢼ‫ࢼޙݧ‬ྉͰ͸γάφϧ‫౓ڧ‬มԽͷఔ౓͸ηύϨʔλͱ઀͢Δද໘ͱूిഩͱ઀͢Δ಺෦Ͱҟͳ͍ͬͯͨɽҰํɼࢼ‫ݧ‬લࢼྉͰ͸ද໘ͱ಺෦ͷγάφϧ‫౓ڧ‬มԽ͕ಉఔ౓ʹੜͨ͡ɽαΠΫϧࢼ‫ࢼޙݧ‬ྉ͸ɼ߹ࡎ಺෦ͰͷϦν΢ϜΠΦ
ϯ‫ٵ‬ଂɾ์ग़ͷ൓Ԡ્͕֐͞Ε͍ͯΔͱ෼͔ͬͨ
ΩʔϫʔυɿX ઢϚΠΫϩϏʔϜ, Πϝʔδϯά෼ੳ, XAFSഎ‫ڀݚͱܠ‬໨తஅ໘͸ɼ੾Γग़ͨ͠ਖ਼‫ۃ‬ද໘ʹରͯ͠ਨ௚ํ޲΁ӶརϦν΢ϜΠΦϯి஑ʢLithium Ion BatteryɿLIBʣ
͸ΤωϧΪʔີ౓ͱೖग़ྗಛੑΛόϥϯεͤ͞Δ͜ͱʹΑΓɼখ‫͔ثػܕ‬Βେ‫ܕ‬Ҡಈମ·Ͱ෯޿͘ద༻͕ਐ
ΊΒΕ͍ͯΔɽLIB Λ༻͍ͨ੡඼͕ɼ͓٬༷ͷ΋ͱͰඞཁͱ͞ΕΔ‫ػ‬ೳΛҡ࣋͢ΔͨΊʹ͸ɼ֤੡඼Ͱಛ௃
తͳ LIB ͷ࢖͍ํͱͦΕʹΑΔੑೳมԽͷ‫ݪ‬ҼΛे෼ʹཧղͯ͠੡඼ઃ‫͢ܭ‬Δ͜ͱ͕‫ٻ‬ΊΒΕΔ. ஶऀΒ͸ɼ2014B ‫ʹظ‬αΠΫϧࢼ‫ޙݧ‬ͷ 18650 αΠζ LIB
͔Β࠾औͨ͠ਖ਼‫ۃ‬Λ༻͍, ෼ੳηϧΛॆ์ి͠ͳ͕Βਖ਼‫ࡎ߹ۃ‬அ໘Λ X ઢϚΠΫϩϏʔϜͰΠϝʔδϯά෼ੳͯ͠ɼ‫׆‬෺࣭͕ঢ়ଶมԽ͢Δ༷ࢠΛใࠂͨ͠ [1, 2].
ຊऔ૊ΈͰ͸ɼαΠΫϧࢼ‫ݧ‬લ‫ޙ‬ͷ LIB ͔Β࠾औͨ͠ਖ਼‫ۃ‬Λ༻͍ͯ X ઢϚΠΫϩϏʔϜͰͷ෼ੳΛߦ͍ɼ߹ࡎஅ໘Ͱͷ൓Ԡ෼෍ʹ͍ͭͯൺֱղੳ͢Δ͜ͱΛ໨తͱͨ͠ɽͳਕ෺Ͱ੾அ͢Δํ๏Ͱ࡞੡ͨ͠ɽ෼ੳηϧ͸੾அՃ޻‫ޙ‬ͷਖ਼‫ࡐۃ‬Λ࡞༻‫ۃ‬, ۚଐ Li ഩΛର‫ͯ͠ͱۃ‬άϩʔϒϘοΫε಺Ͱ૊Έཱͯɼ࣮‫͍ͨ༻ʹݧ‬ɽ࣮‫ݧ‬͸ SPring-8 ฌ‫ݝݿ‬ϏʔϜϥΠϯ BL24XU ʹ࣮ͯࢪͨ͠. ࣮‫࣌ݧ‬ͷϏʔϜ৚݅͸, ϏʔϜ‫ ౓ڧ‬5×109

photons/sec. (at 8333 eV), ϏʔϜαΠζ͸Ԗ௚ํ޲
1.6 µm, ਫฏํ޲ 4.2 µm Ͱ͋ͬͨ. ‫ݕ‬ग़‫ʹث‬͸ Lytle‫ݕ‬ग़‫ث‬Λ࢖༻͠, ‫ޫܬ‬๏ʢAr ΨεϑϩʔʣͰଌఆΛߦͬͨɽΠϝʔδϯά෼ੳ͸, ࢼྉεςʔδΛ 1 µm
εςοϓͰ࡞ಈͤͯ͞ X ઢϚΠΫϩϏʔϜͷরࣹҐஔΛ੍‫͕ͳ͠ޚ‬Βి‫ ʹ޲ํ͞ްۃ‬80 µmɼ໘಺ํ޲
ʹ 32 µm ͷΠϝʔδϯά૾Λಘͨ. ͜ͷͱ͖֤఺ͷacquisition λΠϜ͸ 0.1 ඵɼ1 ը૾ͷऔಘ࣌ؒ͸໿ 7෼Ͱ͋ͬͨɽը૾σʔλͷ‫֨ن‬Խॲཧํ๏͸લใ [2]ͷ௨ΓͰ͋Δɽ݁Ռ͓Αͼߟ࡯࣮‫ݧ‬ਖ਼‫ۃ‬͸, ࿐఺؅ཧ͞ΕͨάϩʔϒϘοΫε಺Ͱ LIB
ʢ18650 αΠζʣΛղମͯ͠࠾औ͠ɼδϝνϧΧʔϘωʔτͰͷચড়ɼ‫ס‬૩Λߦͬͨɽ෼ੳର৅ͱ͢Δ߹ࡎ

αΠΫϧࢼ‫ݧ‬લͷࢼྉʹ͍ͭͯɼ0.5 C Ͱॆ์ి͠
ͨ৔߹ͷॆ์ి‫ۂ‬ઢͱ‫֨ن‬Խॲཧ‫ޙ‬ͷΠϝʔδϯά෼ੳ݁ՌΛ Fig. 1 ʹࣔ͢ɽͳ͓ɼFig. 1 தͷఴࣈ 1∼10͸෼ੳΛ࣮ࢪͨ͠λΠϛϯάɼFig. 1(C) ͸ి‫ࡎ߹ۃ‬– 12 –

ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू

Fig. 1. Imaging results of cathode cross section at 0.5 C : (A) sample setting, (B) voltage curve and (C)normalized images.

෦෼ͷΈΛ੾Γग़ͨ͠ը૾Ͱ͋ΔɽॆిΛ։࢝͢Δͱɼ

ͨλΠϛϯάͰ͋ΔɽϥΠϯϓϩϑΝΠϧԽͷৄࡉ͸ઌͣηύϨʔλଆͰγάφϧ‫͕౓ڧ‬௿Լͨ͠ɽॆిΛ

Fig. 3 ʹࣔ͢Α͏ʹηύϨʔλଆ͔Βूిഩଆʹֻ‫ܧ‬ଓ͢Δͱɼి‫ࡐۃ‬ͷηύϨʔλଆ͔Β Al ूిഩଆ͚ͯσʔλΛಡΈऔΓɼ͜ΕΛฏ‫ۉ‬Խͨ͠ɽʹֻ͚ͯશମతʹγάφϧ‫౓ڧ‬ͷ௿Լ͍༷ͯ͘͠ࢠ͕

αΠΫϧࢼ‫ݧ‬લࢼྉ͓Αͼࢼ‫ࢼޙݧ‬ྉͷϥΠϯϓϩ

֬ೝ͞Εͨɽॆిఀࢭ‫ޙ‬ͷ։ճ࿏อ࣋தɼγάφϧ‫ڧ‬ϑΝΠϧΛ Fig. 4 ʹࣔ͢ɽॆిΛ։࢝͢ΔͱɼαΠ౓ͷ෼෍ʹ͸‫ݦ‬ஶͳมԽ͕‫ݟ‬ΒΕͳ͔ͬͨɽ͍࣍Ͱ์

Ϋϧࢼ‫ݧ‬લɼࢼ‫ͪͲޙݧ‬Βͷࢼྉ΋ઌͣηύϨʔλଆిΛ։࢝͢Δͱɼγάφϧ‫͕౓ڧ‬શମతʹ্ঢͨ͠ɽ

Ͱγάφϧ‫͕౓ڧ‬௿Լ͍ͯ͠Δɽ

αΠΫϧࢼ‫ݧ‬લࢼྉͱࢼ‫ࢼޙݧ‬ྉͷॆ์ిաఔͰͷ൓Ԡ෼෍Λղੳ͢ΔͨΊɼΠϝʔδϯά෼ੳʹΑΓऔಘͨ͠σʔλΛϥΠϯϓϩϑΝΠϧԽͯ͠ɼͦͷ‫ܗ‬ঢ়มԽΛൺֱͨ͠ɽαΠΫϧࢼ‫ࢼޙݧ‬ྉΛ 0.5 C Ͱॆ์ిͨ͠৔߹ͷॆ์ి‫ۂ‬ઢΛ Fig. 2 ʹࣔ͢ɽFig. 2தͷఴࣈ 11∼20 ͸Πϝʔδϯά෼ੳσʔλΛऔಘ͠Fig. 2. Voltage curve of cycle tested cathode at 0.5
C.

– 13 –

Fig. 3. Line profiling from imaging results.

Status Report of Hyogo-Beamlines with Research Results, Vol. 5 (2016)

Fig. 4. Line profiles of imaging results at 0.5 C : (A) new cathode during charging, (B) new cathode during
discharging, (C) cycled cathode during charging and (D)cycled cathode during discharging.

ॆిΛ‫ܧ‬ଓ͢Δͱࢼ‫ݧ‬લࢼྉ͸γάφϧ‫͕౓ڧ‬શମ෼ੳΛద༻͢Δ͜ͱͰɼ߹ࡎ಺෦ͰͷϦν΢ϜΠΦϯ

తʹ௿Լ͢Δ༷ࢠ͕֬ೝ͞ΕͨɽҰํɼࢼ‫ࢼޙݧ‬ྉͰ‫ٵ‬ଂɾ์ग़ͷ൓Ԡ્͕֐͞Ε͍ͯΔͱ෼͔ͬͨɽߋʹ͸ి‫ࡐۃ‬ද໘ͷγάφϧ‫͕౓ڧ‬௿Լ͠ɼి‫಺ࡐۃ‬෦ͷߴϨʔτʹ͓͍ͯ΋ɼσʔλͷਫ਼౓Λ֬อͭͭ͠෼ੳ

γάφϧ‫౓ڧ‬௿Լ͸খ͍͞ɽ͍࣍Ͱ์ిΛ։࢝͢Δͱɼ

Մೳͱ͢Δ͜ͱͰɼి஑ࡐྉͷม࣭΍ঢ়ଶධՁΛৄࡉࢼ‫ݧ‬લࢼྉ͓Αͼࢼ‫ࢼޙݧ‬ྉͱ΋γάφϧ‫ిॆ͕౓ڧ‬ʹ‫ূݕ‬ՄೳͱͳΔ͜ͱ͕‫ظ‬଴͞ΕΔ.

લͷঢ়ଶ·Ͱ্ঢͨ͠ɽ͜ͷϥΠϯϓϩϑΝΠϧൺֱ͔ΒɼαΠΫϧࢼ‫ޙݧ‬ͷਖ਼‫Ͱࡎ߹ۃ‬͸ɼूిഩʹ͍ۙ߹ࡎ಺෦ͰϦν΢ϜΠΦϯͷ‫ٵ‬ଂɾ์ग़൓Ԡ્͕֐͞

ࣄ‫΁ۀ‬ͷߩ‫ݙ‬Ε͍ͯΔͱߟ͑ΒΕΔɽ·ͨɼαΠΫϧࢼ‫ݧ‬લࢼྉͷຊ‫͔ڀݚ‬ΒಘΒΕٕͨज़ʹΑΓ, Ϧν΢ϜΠΦϯೋϥΠϯϓϩϑΝΠϧΛॆి࣌ͱ์ి࣌Ͱൺֱ͢Δͱɼ࣍ి஑ͷి‫಺ࡎ߹ۃ‬෦ʹ͓͚Δ൓Ԡ෼෍Λղੳ͢Δ͜

์ి࣌͸ϓϩϑΝΠϧ‫ܗ‬ঢ়Λ΄΅อͬͨ··γάφϧͱ͕Ͱ͖Δ. ं͔྆Β‫ٻ‬ΊΒΕΔ෯޿͍ೖग़ྗ৚݅Լ

‫౓ڧ‬มԽ͍ͯ͠Δ͕ɼॆి࣌͸΍΍ి‫಺ࡎ߹ۃ‬෦ͷγͰͷ൓Ԡ‫ڍ‬ಈΛղੳ͠, ੍‫ޚ‬Ҽࢠͷ໌֬Խ΍ϝΧχζ

άφϧ‫౓ڧ‬มԽ͕খ͍͞ɽຊऔ૊ΈͰ༻͍ͨਖ਼‫ۃ‬͸ॆϜղ໌ʹར༻͢Δ༧ఆͰ͋Δ.

ి࣌ʹ൓Ԡ෼෍͕ൃੜ͠ɼද໘ଆʹଘࡏ͢Δ‫׆‬෺࣭ʹෛՙֻ͕͔ΔՄೳੑ͕ߟ͑ΒΕΔɽ

ࢀߟจ‫ݙ‬·ͱΊͱࠓ‫ޙ‬ͷ՝୊

LIB ͔Β࠾औͨ͠ਖ਼‫಺ࡎ߹ۃ‬෦Ͱͷ൓Ԡ෼෍Λղੳ
͢ΔͨΊʹ, X ઢϚΠΫϩϏʔϜʹΑΔΠϝʔδϯά[1] ॅ ా ߂ ༞ɿSPring-8 ར ༻ ՝ ୊ ࣮ ‫ ݧ‬ใ ࠂ ॻ
2014B3231.
[2] ࡾࠜੜ৾ɿฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू 4, 18(2015).

– 14 –

ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू

2013B3320, 2014A3320,2014B3320,2015A3320

BL08B2In-situ XAFS/SAXS ಉ࣌ଌఆʹΑΔ Au φϊཻࢠੜ੒աఔղੳ
Formulation Process Analysis of Au Nano-particle by Coupled
In-situ XAFS and SAXS౦‫ޫ ޱ‬੖ɼࡔຊ ௚‫ل‬
Mitsuharu Higashiguchi, Naoki Sakamoto1ѴԽ੒‫ࣜג‬ձࣾ
Asashi Kasei Corporation֓ཁɿӷ૬͔Βͷφϊཻࢠͷੜ੒աఔΛධՁ͢Δख๏ͱͯ͠ɼՁ਺มԽͱཻࢠ੒௕աఔΛ XAFS/SAXS ಉ࣌ଌఆʹͯ‫͢࡯؍‬Δख๏ཱ֬Λ໨ࢦͨ͠ɽHAuCl4 ༹ӷͷؐ‫ʹݩ‬ΑΔ Au φϊཻࢠੜ੒Λྫͱͯ͠ɼۚଐ΁ͷՁ਺มԽɼཻࢠੜ੒ɼ༹ӷͷ‫ͨݟ‬໨ͷมԽ͕ରԠͨ͠Ұ࿈ͷղੳ݁ՌΛऔಘ͢Δ͜ͱ͕Ͱ͖ɼφϊཻࢠͷੜ੒աఔΛ၆ᛌ͢Δଌఆٕज़ͷཱ֬Λୡ੒ͨ͠ɽ
ΩʔϫʔυɿφϊཻࢠɼXAFSɼSAXSɼin-situഎ‫ڀݚͱܠ‬໨తࠓճɼۚଐφϊཻࢠͷதͰ΋ɼଟ͘ͷใࠂྫ͕͋Δ

ۚଐφϊཻࢠ͸ɼൺද໘ੵ͕‫ۃ‬Ίͯେ͖͍͜ͱ΍ɼిࢠͷด͡ࠐΊʹ༝དྷͨ͠ྔࢠޮՌʹΑΓ௨ৗͷࡐྉͱ͸ҟͳΔޫֶಛੑ౳Λࣔ͢͜ͱ͔Βɼ৮ഔɼృྉɼ
ߏ଄վ࣭ࡎɼిࢠࡐྉ౳༷ʑͳ෼໺Ͱ༻͍ΒΕ͍ͯ
Δ [1]ɽۚଐφϊཻࢠͷಛ௃ͱͯ͠ɼཻ‫ܘ‬΍෼෍ɼϞϧϑΥϩδʔͷҧ͍͕෺ੑʹ௚݁͢ΔͨΊɼ͜ΕΒཻࢠಛੑͷਫ਼ີ੍‫ۀ޻͕ޚ‬తʹॏཁͳ՝୊ͱͳΔɽۚଐφϊཻࢠ͸ӷ૬๏΍‫ؾ‬૬๏Ͱ࡞ΒΕΔ͕ [1]ɼӷAu φϊཻࢠͷੜ੒աఔΛར༻͠ɼXAFS/SAXS ಉ࣌ଌఆʹΑΓɼφϊཻࢠͷੜ੒աఔʹॏཁͳؐ‫ࢠཻͱݩ‬੒௕աఔΛಉ࣌ʹ‫͢࡯؍‬Δख๏ͷཱ֬Λ໨ࢦͨ͠ɽຊ
ख๏͸ɼAu Ҏ֎ͷφϊཻࢠ΁ͷల։΍ɼՁ਺มԽͱ
ߏ଄มԽ͕‫͜ى‬Δ৮ഔ൓Ԡʹ΋ల։͕‫·ࠐݟ‬ΕΔͨ
Ίɼଟ͘ͷ੡඼։ൃʹ‫د‬༩Ͱ͖Δͱ‫ظ‬଴͍ͯ͠Δɽ࣮‫ݧ‬૬๏͸େྔੜ࢈ʹద͓ͯ͠Γɼ·ͨೱ౓΍Թ౓ͷ؅ཧ

Au φϊཻࢠͷ࡞੒͸ɼҰൠతʹ༻͍ΒΕ͍ͯΔɼ

͕༰қͰ͋ΔͨΊ޿͘༻͍ΒΕ͍ͯΔɽӷ૬๏ͷத

HAuCl4 ༹ӷʹΫΤϯࢎφτϦ΢ϜΛՃ͑ɼؐ‫ʹݩ‬ΑͰ΋ؐ‫ࡎݩ‬Λ༻͍ͯɼۚଐΠΦϯΛ࠶ੳग़ͤ͞Δؐ‫ݩ‬Γੳग़ͤ͞Δํ๏Λબ୒ͨ͠ɽHAuCl4 ༹ӷͱΫΤϯ๏͸ɼख๏ͷ؆ศ͔͞Β޻‫ۀ‬తʹ΋ར༻͠΍͍͢ɽۚࢎ༹ӷͷೱ౓͸ɼա‫ڈ‬ͷྨࣅͷଌఆͷจ‫ݙ‬Λࢀߟʹͦଐφϊཻࢠͷੜ੒͸ɼۚଐΠΦϯ༹ӷ΁ؐ‫ࡎݩ‬Λ౤ೖΕͧΕɼ0.25 mmol/L ͱ 2.5 mmol/L ͱͨ͠ [2]ɽࢼ

‫ʹ͙͢ޙ‬͸‫͜ى‬Βͣɼ༠ಋ‫ؒظ‬Λ‫ࢠཻͯܦ‬ͷੜ੒͕ੜྉͷௐ੔͸ɼ์ࣹޫϋον֎Ͱߦ͍ɼ༹྆ӷΛόΠΞ

͡Δɽ༠ಋ‫ʹظ‬͸ɼۚଐΠΦϯͷؐ‫֩ͱݩ‬ͷੜ੒͕‫ى‬ϧළதͰྑࠞ͘߹ͤͨ͞‫ޙ‬ɼφ2mm ͷੴӳΩϟϐϥ

͍ͬͯ͜Δͱߟ͑ΒΕΔ͕ɼ੡଄ͰͷධՁ͸ɼੜ੒‫ޙ‬ϦʔʹೖΕଌఆʹ‫ͨ͠ڙ‬ɽࢼༀྨ͸ɼࠞ߹௚લ·ͰྫྷͷۚଐφϊཻࢠͰߦ͏ͨΊɼ༠ಋ‫ؔ͢ʹظ‬Δ஌‫ݟ‬͸গଂ͓͖ͯ͠ɼࠞ߹͸ࣨԹͰߦ͍ͬͯΔɽ

ͳ͍ɽͦͷͨΊɼ৽‫ن‬ͷཻࢠಛੑΛ࣋ͭɼۚଐφϊཻ

XAFS/SAXS ಉ࣌ଌఆ͸ɼฌ‫ݝݿ‬ϏʔϜϥΠϯࢠΛ੡଄͢Δࡍʹ͸ɼͦͷ౎౓ɼ੡଄৚݅ͷ‫ݟ‬௚͕͠

BL08B2 ͷୈ 2 ϋονʹ࣮ͯࢪͨ͠ɽFig. 1 ʹଌఆͷඞཁͱͳΔɽ༠ಋ‫ظ‬Λཧղ͠ɼཻࢠͷੜ੒ɼ੒௕͕Ͳ

ηοτΞοϓਤΛࣔ͢ɽࢼྉԹ౓͸ࣨԹʢ25◦ Cʣͱ͠ͷΑ͏ͳλΠϛϯάͰ‫͍ͯͬ͜ى‬Δ͔஌Δ͜ͱ͕Ͱ͖

ͨɽXAFS ଌఆ͸ɼSi(111)-2 ݁থ෼ޫ‫ث‬Λ࢖༻͠ɼAu-Ε͹ɼࢼ࡞࣌ؒͷ୹ॖʹ‫د‬༩Ͱ͖Δͱ‫ظ‬଴͞ΕΔɽ

LIII ୺ (11920 eV) ʹͯ‫ޫܬ‬๏ͷ Q-XAFS Λߦͬͨɽ‫ ޫܬ‬X ઢͷ‫ݕ‬ग़‫ʹث‬͸ Lytle ‫ݕ‬ग़‫ث‬Λ༻͍ͨɽSAXS– 15 –

Status Report of Hyogo-Beamlines with Research Results, Vol. 5 (2016)

Fig. 1. Schematic view of coupled in-situ XAFS andSAXS experimental set-up.

ଌఆ͸ɼࢼྉ͔ΒͷΧϝϥ௕ 1940 mm ͱ͠ɼ‫ݕ‬ग़‫ث‬ʹ͸ PILATUS-100k Λར༻ͨ͠ɽAu ‫ٵ‬ऩ୺ͷӨ‫ڹ‬Λආ͚ΔͨΊɼଌఆ͸‫ٵ‬ऩ୺ΑΓΤωϧΪʔͷ௿͍

11810 eVʢ೾௕ɿ0.105 nmʣͱͨ͠ɽಘΒΕͨ̎࣍‫ ݩ‬SAXS ύλʔϯ͸ಁա཰ɼۭηϧࢄཚิਖ਼Λ͓͜ͳ͏ͱͱ΋ʹɼԁ‫؀‬ฏ‫ʹۉ‬ΑΓ̍࣍‫ݩ‬Խͯ͠ղੳʹ‫͠ڙ‬ͨɽۭηϧࢄཚͱͯ͠͸ະ൓ԠͷӷͷࢄཚΛ༻͍ͨɽຊ࣮‫Ͱݧ‬͸ۚφϊཻࢠੜ੒ʹ൐͍ɼ༹ӷ͕ೱ͍੺৭Λ

Fig. 2. Normalized Au-LIII -edge X-ray absorption spectra during formulation process of Au nanoparticle.

ఄͯ͘͠Δɽͦ͜ͰɼੴӳΩϟϐϥϦʔʹࢼྉΛηοτͨ͠‫ʹޙ‬όΠΞϧϏϯʹ࢒༹ͬͨӷʹ͍ͭͯϏσΦ͓Γۚଐ·Ͱؐ‫͕ݩ‬ਐΜͰ͍Δͱਪଌ͞Εͨɽؐ‫ݩ‬աࡱӨΛߦ͍ɼ໨ࢹͰண৭͢Δ࣌ؒΛ‫ܭ‬ଌͨ͠ɽ·ͨɼఔΛ͞Βʹৄ͘͠‫ݟ‬ΔͨΊʹɼ‫ٵ‬ऩ୺ͷ‫࣌ܦ‬มԽΛಋ

XAFS/SAXS ಉ࣌ଌఆʹ‫ͨ͠ڙ‬ੴӳΩϟϐϥϦʔதग़ͨ͠ɽ‫ٵ‬ऩ୺ͷҐஔ͸ɼεϖΫτϧ‫֨ن‬Խ‫ޙ‬ͷΤοͷ༹ӷͷ৭ͷมԽʹ͍ͭͯ΋ΧϝϥʹΑΓϞχλʔδδϟϯϓͷ‫ ౓ڧ‬0.5 ͱͳΔΤωϧΪʔͰఆٛͨ͠ɽ

ͨ͠ɽ

Fig. 3 ʹ Fig. 2 ͷεϖΫτϧ͔Βಋग़ͨ͠‫ٵ‬ऩ୺Τωຊ࣌෼ׂ XAFS/SAXS ಉ࣌ଌఆʹ͓͚ΔଌఆαΠϧΪʔͷ‫࣌ܦ‬มԽΛࣔ͢ɽԣ࣠͸༹ӷΛࠞ߹͔ͨ࣌͠

Ϋϧ͸ɼ3.5 ෼Ͱ͋ΔɽԼ‫֤ʹه‬αΠΫϧͰ͸ҎԼͷΒͷ࣌ࠁͱ͍ͯ͠Δɽ࠷ऴతʹۚଐ·Ͱؐ‫͕ݩ‬ਐΉͱॱʹࢼྉͷ֎‫؍‬ɼSAXSɼXAFS ଌఆΛ࣮ࢪͨ͠ɽ

ͯ͠ɼՁ਺มԽ͕Ұఆͱͳͬͨͱ͜ΖΛ+0 ՁɼAuCl
ඪ४ࢼྉͷ‫ٵ‬ऩ୺ҐஔΛ+1 Ձͱͯ͠ਤʹࣔͨ͠ɽࠞ

1 ༹ӷͷը૾ࡱӨ

2 XAFS ։࢝ΤωϧΪʔʹͯ SAXS Λ 10 ඵ࿐ޫͰ߹͔Βͷ࣌ؒΛθϩʹ֎૷ͯ͠ɼ͓Αͦ 1 Ձ෼ɼՁ਺

3 Q-XAFS ଌఆ‫ޙ‬Ҏ߱͸ɼ‫ٵ‬ऩ୺Ґஔ͸΄΅ҰఆͰɼͦΕҎ্ؐ‫͕ݩ‬ଌఆมԽ͍ͯ͠Δͱਪଌ͞Εͨɽ·ͨɼࠞ߹͔Β 50-60 ෼ࠞ߹͔Βଌఆ·ͰͷλΠϜϥά͕ൃੜ͢ΔͨΊɼผ్ਐߦ͍ͯ͠ͳ͍ͱਪଌ͞ΕΔɽ‫ݪ‬ྉͷ HAuCl4 ͸ɼ+3࣌ࠁΛ‫ܭ‬ଌ݁͠Ռʹ൓ө͍ͤͯ͞Δɽ

ՁͰ͋ΔͨΊɼࠞ߹‫ʹ͙͢ޙ‬+1 Ձ·Ͱ‫͕ݩؐʹܹٸ‬ਐΈɼͦͷ‫ޙ‬؇΍͔ʹ+0 Ձʹ޲͚ؐ‫͕ݩ‬ਐΉͷͰ͸ͳ͍͔ͱਪଌ͞ΕΔɽ

݁Ռ͓Αͼߟ࡯

Fig. 2 ʹ Au φϊཻࢠੜ੒աఔͷ Au-LIII ୺ XAFSεϖΫτϧͷॏͶॻ͖Λࣔ͢ɽ੺͔Β੨΁ͱ͕࣌ؒ‫ܦ‬ա͍ͯ͠Δɽ໼ҹͰࣔͨ͠ɼ11923 eV ෇ۙͷ Au-LIII‫ٵ‬ऩ୺εϖΫτϧϐʔΫ͕ɼ࣌ؒͱ‫ݮʹڞ‬গ͍ͯ͠

Fig. 4 ʹ Au φϊཻࢠੜ੒աఔʹ͓͚Δ SAXS ϓϩϑΟʔϧมԽΛࣔ͢ɽԣ࣠͸ࣜ 1 Ͱද͞ΕΔࢄཚϕΫτϧͷઈର஋Ͱ͋Δɽͳ͓ɼθ ͸ Bragg ֯ɼλ ͸ Xઢ೾௕Ͱ͋Δɽ༷͘ࢠ͕‫؍‬ଌ͞Ε͍ͯΔɽࢀরࢼྉ (HAuCl4 (Au3+ )ɼ

AuCl(Au

1+)ɼAu ഩ (Au0+)) ͷଌఆ͔ΒɼAu-LIII ‫ٵ‬ऩ୺εϖΫτϧϐʔΫ͸ɼߴՁ਺΄ͲӶ͘ɼҰํͰۚଐʹͳΔͱফࣦ͢Δ܏޲͕‫ݟ‬ΒΕͨɽͦͷͨΊɼFig.

1 ͷมԽ͸ɼؐ‫ݩ‬աఔΛ‫͍ͯݟ‬Δͱߟ͑ΒΕΔɽ·ͨɼ‫࣌ܦ‬มԽͷ࠷ऴεϖΫτϧ͸ɼAu ഩͱ΄΅Ұகͯ͠q = 4π sin θ/λ(1)൓Ԡ։࢝‫ޙ‬ɼ40 ෼ఔ౓·Ͱ͸΄ͱΜͲࢄཚ͕‫؍‬ଌ͞Ε͓ͯΒͣɼSAXS Ͱଊ͑ΒΕΔΑ͏ͳφϊߏ଄͸‫ܗ‬੒͞Ε͍ͯͳ͍ͱߟ͑Β͑ΔɽҰํɼ40 ෼Ҏ߱ Au φϊཻࢠ༝དྷͷࢄཚ‫౓ڧ‬ͷ૿େ͕‫؍‬ଌ͞Ε͍ͯΔɽͳ͓ɼ– 16 –

ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू

Fig. 3. Time-dependent absorption-edge energyof Au-LIII , in which energy of Au-foil(+0) andAuCl(+1) are also represented as references.

ΑΓৄ͘͠ SAXS ϓϩϑΟʔϧมԽΛ‫ݟ‬Δͱ 40 ෼Ҏ߱ 47 ෼ఔ౓·Ͱখ֯ྖҬͷࢄཚ͕૿Ճͨ͠‫ޙ‬ɼ54 ෼
ఔ౓·ͰҰ౓ࢄཚ‫ݮ͕౓ڧ‬গ͍ͯ͠Δɽ͞Βʹɼͦͷ‫ࢄͼ࠶ޙ‬ཚ‫౓ڧ‬͸૿Ճʹస͡Δ͕ɼࢄཚγϣϧμʔͷҐஔ͸ 40-51 ෼ͷ΋ͷΑΓ΋޿֯ʹଘࡏ͍ͯ͠Δɽ‫ܗ‬੒͞ΕΔ Au φϊཻࢠͷαΠζΛఆྔతʹߟ࡯͢Δͨ
ΊʹɼFig. 4 ͷ 40 ෼Ҏ߱ͷ SAXS ϓϩϑΟʔϧΛࣜ̎Ͱද͞ΕΔ൒‫ܘ‬෼෍Λߟྀͨ͠ϥϯμϜ഑޲γϦϯμʔߏ଄Λ࣋ͭ‫ࢠཱཻݽ‬ͷཧ࿦ࢄཚࣜͰϑΟοςΟ
ϯά͠ɼ֤छύϥϝʔλΛಘͨɽ൒‫ܘ‬ͷ෼෍͸ମੵ෼
཰͕ Schultz-Zimm ෼෍ʹै͍ͬͯΔͱԾఆͨ͠ɽͳ
͓ɼ∆ρe ͸༹ഔͱཻۚࢠͷిࢠີ౓ࠩɼN ͸ཻࢠͷ਺ີ౓ɼrɼl ͸γϦϯμʔʢͻ΋ʣঢ়ߏ଄ͷ൒‫ͱܘ‬௕͞ɼσ ͸൒‫ ܘ‬r ͷඪ४ภࠩɼJ1 ͸̍࣍ͷϕοηϧؔ

Fig. 4. SAXS profiles during formulation process of
Au nano-particle.

ͳ͓ɼFig. 4 ͷ SAXS ϓϩϑΟʔϧ͸‫ٿ‬ঢ়ཻࢠΛԾఆͨ͠ཧ࿦ࢄཚࣜͰ͸͏·͘ϑΟοςΟϯάͰ͖ͣɼͻ΋ঢ়ߏ଄ΛԾఆͨ͠΄͏͕Α࣮͘ଌ SAXS ϓϩϑΟʔϧΛ࠶‫͖ͨͰݱ‬ɽFig. 4 ʹ͸ࣜ (2) ʹΑΓߦͬͨϑΟοςΟϯάͷ݁Ռʹ͍ͭͯ΋߹Θ͍ͤͯࣔͯ͠Δɽ࣮ࡍͷཻࢠ‫ܗ‬ঢ়ʹ͍ͭͯిࢠ‫ݦ‬ඍ‫ʹڸ‬ΑΔ֬ೝ͸ߦ͍ͬͯͳ͍͕ɼจ‫Ͱݙ‬͸ͻ΋ঢ়ͷߏ଄͕‫ܗ‬੒͞ΕΔྫ΋ใࠂ͞Ε͓ͯΓ [3]ɼ͜͜Ͱ͸ͻ΋ঢ়ߏ଄ΛԾఆͯ͠ղੳ
Λߦͬͨɽ·ͨɼAu φϊཻࢠͷྔʢମੵʣͷࢦඪͱͯ͠ɼࣜ (3) Ͱද͞ΕΔ Invariant Q Λ‫ͨ͠ࢉܭ‬ɽͳ͓ɼੵ෼ൣғ͸ɹ 0.07 < q < 1.2 nm−1 ͱͨ͠ɽಛʹখ֯ྖҬͷੵ෼ൣғ͕ෆे෼͕ͩɼੜ੒ͨ͠ Au φϊཻࢠͷྔʢମੵʣͷ܏޲͸௥͑Δͱߟ͑ΒΕΔɽ
͜͏ͯ͠‫͞ࢉܭ‬Εͨͻ΋ঢ়ߏ଄ͷฏ‫ۉ‬௚‫ ܘ‬dɼ‫ͼٴ‬

਺ɺSi(x) ͸ੵ෼ਖ਼‫͋Ͱ਺ؔݭ‬Δɽl  r ΛԾఆͯ͠

Invariant Q ͷ࣌ؒมԽΛ Fig. 5 ʹࣔ͢ɽ ൓Ԡ‫ ޙ‬40

 ∞

(2)

͍Δɽ

I(q)
2

=

F (q, r, l)

=

P (r)

=

P  (r)=M=∆ρ2e NP (r)F 2 (q, r, l)dr

0

2


2
1 − cos(ql) J1 (qr)8(πr2 l)Si(ql)−
ɹql
qlqr
P  (r)/V (r)ɹP  (r)/V (r)dr


MM
M
M −1
r
exp − r ɹ
r0
Γ(M )r0M

σ −0.5 ɹ– 17 –

Status Report of Hyogo-Beamlines with Research Results, Vol. 5 (2016)૿Ճ͍ͯ͠ΔՄೳੑ΋͋Δɽd ͱ Q ͷ࣌ؒมԽ͸ɼ40෼Ҏ߱ʹ‫ܗ‬੒͞Εͨφϊཻࢠ͸‫ߏूڽ‬଄Λ‫ܗ‬੒͓ͯ͠ΓɼͦΕ͕Ұ౓ɼ෼྾ͨ͠‫ޙ‬ɼ࠶ͼ੒௕͢Δͱ͍͏աఔΛ͍ࣔͯ͠Δͷ͔΋͠Εͳ͍ɽ40 ෼Ҏ߱͸ɼՁ਺มԽ͕΄΅ۚଐͱͯ͠Ұఆʹͳ͍ͬͯΔ͜ͱ͔Βɼۚଐঢ়ଶͷ༹͕֩ӷશମʹੜ੒ͨ͠ͷͪɼঃʑʹͦΕΒ͕݁߹ͯ͠φϊཻࢠͱͯ͠੒௕͢ΔաఔΛ‫͍ͯݟ‬ΔՄ
ೳੑ͕ਪଌ͞ΕΔɽͳ͓ɼࠓճɼSAXS ͷղੳͰ͸ͻ΋ঢ়ͷߏ଄͕‫ܗ‬੒͞ΕΔͱԾఆͯ͠ߦ͕ͬͨɼFig. 4
ͷ SAXS ϓϩϑΟʔϧͷ‫ܗ‬ঢ়มԽ͔Βߟ͑ͯɼԾʹ࣮ࡍͷ Au ཻࢠͷ‫ܗ‬ঢ়͕ผͷϞϧϑΥϩδʔͰ͋ͬͨ
ͱͯ͠΋ Fig. 5 ͷ d ͷมԽ͸ఆੑతʹ͸ਖ਼͍͠ͱߟ

Fig. 5. Time-dependent diameter of particles (leftaxis) and Invariant Q (right axis), assume that shapeof nano-particle is wire.

͑Β͑Δɽ࠷‫ʹޙ‬ɼόΠΞϧϏϯʹ࢒༹ͬͨӷʹ͍ͭͯϏσΦࡱӨ݁Ռʹ͍ͭͯ‫͢ٴݴ‬ΔɽFig. 6 ʹϏσΦ͔ΒΩϟϓνϟʔͨ͠ը૾Λࣔͨ͠ɽ਺ࣈ͸ࠞ߹͔Βͷ࣌ؒΛ෼ͷ SAXS ϓϩϑΟʔϧʹ͍ͭͯ͸͏·ࣜ͘ (2) Ͱ͍ࣔͯ͠Δɽ͓Αͦ 30 ෼‫ޙ‬ఔ౓͔Β༹ӷͷ৭͕มԽϑΟοςΟϯάͰ͖͓ͯΒͣɼಘΒΕͨฏ‫ۉ‬௚‫ ܘ‬d ͷ࢝͠Ίɼ45 ෼ఔ౓ʹ͸ɼ΄΅ӷશମ͕ࠇ͘ม৭͠ɼφਫ਼౓͕௿͍ͱߟ͑ΒΕΔ͜ͱʹ஫ҙͯ͠ཉ͍͠ɽ
 ∞1
Q=
I(q)q 2 dq
(3)
2π 0

ϊཻࢠ͕ੳग़ͨ͜͠ͱ͕ਪଌ͞ΕΔɽ͜ͷ৭ͷมԽ͕

Fig. 2∼5 Λ‫ݟ‬Δͱɼ·ͣɼXAFS ͔ΒಘΒΕΔ Au‫ݩ‬ૉͷՁ਺มԽͱ SAXS ͔ΒಘΒΕΔφϊཻࢠ੒௕ͱͰ࣌ؒมԽ͕ҟͳΔ͜ͱ͕Θ͔ΔɽFig. 3ɼ5 ΑΓɼAu ‫ࢠݪ‬ͷؐ‫ݩ‬͸൓Ԡ։࢝௚‫͔ޙ‬Βਐߦ͢Δ͕ɼφϊཻࢠͷ‫ܗ‬੒͸͔ͳΓ Au ‫ࢠݪ‬ͷؐ‫͕ݩ‬ਐߦͨ͠‫ॳʹޙ‬Ίͯ։࢝͢Δ͜ͱ͕Θ͔Δɽ͞ΒʹɼFig. 5 ͷ d ͱ Q‫͜ى‬ΔλΠϛϯά͸ɼXAFS ͷՁ਺มԽ͕΄΅Ұఆ஋ʹམͪண͖ɼSAXS ͷࢄཚ͕‫؍‬ଌ͞Ε࢝ΊΔ࣌ࠁͱ͓ΑͦҰக͢ΔɽҎ্ͷࣄ͔Βɼ༹ӷͷ‫ͨݟ‬໨ͷมԽɼՁ਺มԽɼཻࢠੜ੒ΛରԠ෇͚Δ͜ͱ͕Ͱ͖ɼຊख๏
͕໨త௨Γؐ‫ࢠཻͱݩ‬੒௕աఔΛಉ࣌ʹ‫͢࡯؍‬Δख๏
ͱཱͯ֬͠͞Εͨͱͨ͠ɽ
ࠓ‫ޙ‬ͷ՝୊

ͷมԽΛ‫ͯݟ‬ΈΔͱɼd ͸Ұ౓ 15 nm ఔ౓·Ͱ૿Ճ͠ࠓճɼXAFS/SAXS ಉ࣌ଌఆख๏ͷཱ֬Λ໨తʹͨ‫ޙ‬ɼҰ౓ 8 nm ఔ౓·Ͱখ͘͞ͳͬͨ‫ޙ‬ɼ࠶ͼ૿Ճ࣮‫ݧ‬Λߦ͍ɼ਺े෼ఔ౓Ͱ‫͜ى‬Δཻࢠੜ੒աఔͷ‫࡯؍‬ʹస͍ͯ͡ΔɽҰํɼQ ʹ͍ͭͯ͸ಉ༷ʹ్தͰҰ౓͕ՄೳͰ͋Δ͜ͱΛ֬ೝͨ͠ɽҰํͰɼ‫ر‬ऍ༹ӷͷͨ‫ݮ‬গ͍ͯ͠Δ͕ɼͦͷ‫ݮ‬গͷఔ౓͸খ͍͞ɽInvariant

Ί XAFS ଌఆͷ‫͕౓ײ‬খ͘͞ɼͦΕ͕࣌ؒ෼ղೳͷΛ‫ٻ‬ΊΔࡍͷখ֯ଆͷੵ෼ൣғ͕ෆे෼Ͱ͋Δ͜ͱΛ཯଎ʹͳ͍ͬͯΔࣄ΍ɼ์ࣹޫϋον֎Ͱͷࣄલͷ‫ۉ‬ߟྀ͢Δͱ Invariant ʹ͍ͭͯ͸΄΅࣌ؒͱ‫ʹڞ‬୯ௐҰࠞ߹͕ඞཁͳ͜ͱ͔ΒɼՁ਺มԽͷॳ‫͔ظ‬Βͷଌఆ

Fig. 6. Time-dependent color of residue in a vial container (Numbers show time from mixing).

– 18 –

ฌ‫ݝݿ‬ϏʔϜϥΠϯ೥ใɾ੒Ռू
͸‫ݱ‬ঢ়Ͱ͖ͳ͍͜ͱ͕՝୊ͱͯ͠‫͛ڍ‬ΒΕΔɽ޻‫ۀ‬తँࣙͳԠ༻Λ೦಄ʹͨ͠৔߹ɼϓϩηε্ɼਝ଎ͳཻࢠ੒
௕աఔ΍ࠞ߹λΠϛϯά͕՝୊ͱͳΔΑ͏ͳ‫͕ܥ‬ଘࡏ͢ΔɽࠓճͷଌఆͰɼφϊཻࢠੜ੒աఔΛ‫͢࡯؍‬Δ
ͷʹద੾ͳख๏Ͱ͋Δ͜ͱ͕෼͔ͬͨͨΊɼࠓ‫ޙ‬͸ɼ

XAFS ‫౓ײ‬ΛߴΊΔํ๏΍์ࣹޫϋον಺Ͱͷ༹ӷࠞ߹ख๏Λ։ൃ͢Δ͜ͱ΋೦಄ʹख๏ͷ։ൃΛਐΊ͍ͨɽࠓճͷ‫ڀݚ‬Λߦ͏ʹ౰ͨΓɼฌ‫ཱݝݿ‬େֶ࢈ֶ࿈‫ܞ‬ɾ‫ڀݚ‬ਪਐ‫ޫࣹ์ߏػ‬φϊςΫηϯλʔͷ‫܂‬ຊ࣎ੜࢯɼ
໺੉૜ࢢࢯɼཥཕࢯΛ͸͡Ίଟ͘ͷํʑʹ͓ੈ࿩ʹͳ
Γ·ͨ͠ɽ͜ͷ৔ΛआΓ͓ͯྱΛਃ͋͛͠·͢ɽࢀߟจ‫ݙ‬

ࣄ‫΁ۀ‬ͷߩ‫ݙ‬ฐࣾͰ͸ɼ‫ܦ‬Ӧଟ֯Խʹ൐͍ɼ༷ʑͳ঎඼ΛऔΓѻ͍ͬͯΔɽࠓճղੳର৅ͱͨ͠ӷதͷཻࢠੜ੒աఔ
Λ༻͍Δ޻‫ۀ‬੡඼΋৮ഔɼృྉɼߏ଄վ࣭ࡎɼిࢠࡐ
ྉ౳ଟ‫ʹذ‬ΘͨΔҝɼͦΕΒͷ੡඼։ൃΛՃ଎͢ΔͨΊɼੜ੒ϝΧχζϜͷఏ‫͖ͰݙߩͰܗ͏͍ͱڙ‬Δͱߟ
͍͑ͯΔɽ

– 19 –[1] খੴᚸ७ɼੴҪจ༝ஶɿʮφϊཻࢠͷ͸ͳ͠ʯॳ൛ୈ 1 ࡮ɼ೔‫৽ۀ޻ץ‬ฉࣾ (2006).
[2] J. Polte et al.: J. Am. Chem. Soc. 132, 12961301 (2010).
[3] X. Ji et al.: J. Am. Chem. Soc. 129, 1393913948 (2007).

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Vol. 5 20162017 ೥ 3 ݄ 22 ೔ ΦϯϥΠϯ ൃ ߦฤूɹฌ‫ݝݿ‬ϏʔϜϥΠϯ੒Ռूฤूҕһձɹฤूҕһ௕ɹɹ࿜ౡɹ༃
ɹฤू෭ҕһ௕ɹԣࢁ࿨࢘
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