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).

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