SSPring-8/SACLA
Pring-8/SACLA ฼฼⏝◊✲ᡂᯝ㞟⏝◊✲ᡂᯝ㞟

SectionSection B

2013B3324                            BL08B2

ᩳධᑕ X ⥺ᅇᢡἲ࡟ࡼࡿ࣌ࣥࢱࢭࣥⷧ⭷ࡢᵓ㐀ゎᯒStructural Analysis of Pentacene Thin Films by Grazing Incident X-ray
Diffraction Measurements㧘ᶫỌḟᮾ㐶௓ᮎᗈ┬࿃
Eiji Takahashi, Yousuke Azuma, Shogo Suehiro㸦ᰴ㸧ఫ໬ศᯒࢭࣥࢱ࣮ ᢏ⾡㛤Ⓨࢭࣥࢱ࣮ Sumika Chemical Analysis Service, Ltd. Technology Innovation Center᭷ᶵⷧ⭷㸦࣌ࣥࢱࢭࣥ㸧ࡢ⵨╔⭷ᙧᡂ㐣⛬࡟࠾ࡅࡿࠊᡂ㛗ึᮇ㸦ᇶᯈ⏺㠃㸧࡜ᚋᮇ㸦᭷ᶵ⭷⾲㠃㸧࡛ࡢ࿘ᮇᵓ㐀ࡸศᏊ㓄ྥࢆゎᯒࡍࡿࡓࡵࠊᨺᑕග࡟ࡼࡿ㧗㍤ᗘ X ⥺ࢆ⏝࠸ࡓᅇᢡ ᐃࢆ⾜࠸ࠊ࣌ࣥࢱࢭࣥⷧ⭷ࡢᩓ஘ᅇᢡࣃࢱ࣮ࣥࢆᚓࡓࠋゎᯒࡢ⤖ᯝࠊ࣌ࣥࢱࢭࣥศᏊࡣ࢞ࣛࢫᇶᯈୖ࡛ᆶ┤㓄ྥࡍࡿࡀࠊ75 nm ௨ୖࡢⷧ⭷࡛ࡣࠊ⾲ᒙ௜㏆࡟ࣂࣝࢡ┦࡟ᖐᒓࡉࢀࡿᅇᢡࣆ࣮ࢡࡀ᪂ࡓ࡟᳨ฟࡉࢀࡓࠋ࣮࣮࢟࣡ࢻ㸸 ᭷ᶵⷧ⭷ࠊⷧ⭷ X ⥺ᅇᢡ⫼ᬒ࡜◊✲┠ⓗ㸸᭷ᶵ EL ࡸ᭷ᶵኴ㝧㟁ụ➼࡟฼⏝ࡉࢀࡿ᭷ᶵከᒙⷧ⭷࡛ࡣࠊྠࡌᮦᩱࢆ⏝࠸ࡓሙྜ࡛ࡶ〇⭷᪉ἲࡸ᮲௳࡟ࡼࡗ࡚ࠊ⣲Ꮚ࡟ࡋࡓ㝿ࡢᛶ⬟ࡀ኱ࡁࡃኚ໬ࡍࡿሙྜࡀ࠶ࡿࠋࡑࢀࡣࠊྛᒙࡈ࡜ࡢᮦᩱ⤌ᡂẚ࡜⭷ཌࡣྠࡌ࡛ࡶࠊ⭷ෆ࡛ࡢᆒ୍ᛶࡸᐦᗘࠊจ㞟≧ែ࠾ࡼࡧศᏊ㓄ྥ➼ࡀ␗࡞ࡿࡓࡵ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋࡑࢀᨾ࡟ࠊ᭷ᶵⷧ⭷⣲Ꮚࡢ㛤Ⓨ࡛ࡣࠊnm ࣞ࣋ࣝࡢ῝ࡉ᪉ྥ࡟ᑐࡋ࡚ࠊ෌⌧Ⰻࡃ⢭ᐦ࡞〇⭷ไᚚࡀồࡵࡽࢀࡿࡓࡵࠊⷧ⭷ホ౯࡟࠾࠸࡚ࡣ㧗࠸ᢏ⾡ࡀồࡵࡽࢀࠊ╔┠ࡍࡿ㡯┠࡟ᑐࡋ࡚ከ✀ከᵝ࡞᪉ἲࡀᥦ᱌ࡉࢀ࡚࠸ࡿ[1]ࠋࡉࡽ࡟㏆ᖺ࡛ࡣࠊศᏊ㓄ྥࡀᛶ⬟ྥୖ࡟⧅ࡀࡿ࡜࠸࠺ሗ
࿌౛[2,3]ࡀ࠶ࡾࠊពᅗⓗ࡟␗᪉ᛶࢆไᚚࡋࡓⷧ⭷ࡀὀ┠ࡉࢀ࡚࠸ࡿࠋࡇࡢࡼ࠺࡟ࠊホ౯ᢏ⾡ࡣ᪂つᮦᩱࡸࣉࣟࢭࢫ㛤Ⓨࡀ㐍ࡴ࡟ࡘࢀ࡚ࠊせồࣞ࣋ࣝࡀ㧗ࡃ࡞ࡿࠋࡑࡇ࡛ࠊ㧗㍤ᗘࡢᨺᑕග X ⥺ࢆ⏝࠸ࡓⷧ⭷ X ⥺ᅇᢡ ᐃࢆ฼⏝ࡋ࡚ࠊᗈ࠸ゅᗘ⠊ᅖ࡛ࡢᅇᢡ᝟ሗ࠿ࡽⷧ⭷῝ࡉ᪉ྥࡢᵓ㐀᝟ሗホ౯ࡢ᳨ウࢆᐇ᪋ࡋࡓࠋ
ᐇ㦂㸸
ᩳධᑕ X ⥺ᅇᢡἲࡣࠊX ⥺ࡢᅇᢡ⌧㇟ࢆ⏝࠸ࡿ᪉ἲ࡛࠶ࡾࠊⷧ⭷ヨᩱࡢ⤖ᬗᛶࠊ㓄ྥᛶࢆࡑࢀࡒࢀホ౯࡛ࡁࡿࠋཌࡉࡀᩘ 10–100 nm ࡢ᭷ᶵⷧ⭷ヨᩱࡢ ᐃ࡛ࡣࠊX ⥺ࡢධᑕゅᗘࢆ㠀ᖖ࡟ᑠࡉ࠸ゅᗘ⠊ᅖ࡜ࡍࡿ࡜ࠊⷧ⭷ࡢ῝ࡉ᪉ྥࡈ࡜࡟ホ౯࡛ࡁࡿࡓࡵࠊධᑕ X ⥺ࡢゅᗘ㑅ᢥࡀ㔜せ࡜࡞ࡿࠋ౛࠼ࡤࠊ᭷ᶵⷧ⭷ࡢ X ⥺඲཯ᑕ⮫⏺ゅࡼࡾὸ࠸ゅᗘ࡛ධᑕࡍࢀࡤࠊ᭷ᶵⷧ⭷⾲㠃࡛඲཯ᑕࡀ⏕ࡌࠊ⾲㠃㏆ഐࡢ᝟ሗࢆᚓࡿ஦ࡀฟ᮶ࡿࠋ୍᪉࡛ࠊᇶᯈᮦᩱࡢ඲཯ᑕゅࡼࡾࡶ῝࠸ゅᗘ࡛ධᑕࡍࡿ࡜ࠊᇶᯈࡢ᝟ሗࢆྵࡵࡓᩓ஘ᅇᢡࣃࢱ࣮ࣥ࡜࡞ࡿࠋᐇ㝿ࡢ ᐃ࡛ࡣࠊᇶᯈ࡜ヨᩱࡢᮦ㉁࠾ࡼࡧྲྀᚓࡋࡓ࠸᝟ሗ㡿ᇦ࠿ࡽ㐺ษ࡞ධᑕゅᗘࢆ㑅ᢥࡍࡿࠋ᭷ᶵⷧ⭷ࡣ㠀ᖖ࡟ⷧࡃࠊ࠿ࡘ୺ᡂศࡀ㍍ඖ⣲࡛ᵓᡂࡉࢀࡿࡓࡵࠊ᳨ฟឤᗘࡢపୗࡀ㢧ⴭ࡛࠶ࡿࠋࡉࡽ࡟ࠊヨᩱᖹ㠃࡟ᆶ┤࡞㠃እ㸦out of plane㸧᪉ྥࡢ ᐃ࡟ẚ࡭ࠊ㠃ෆ㸦in plane㸧᪉ྥࡢホ౯࡛ࡣᅇᢡᙉᗘࡀᙅ࠸ࡓࡵࠊ㧗㍤ᗘᨺᑕගࡢ฼⏝ࡀ᭷ຠ࡛࠶ࡿࠋヨᩱࡣࠊ࢞ࣛࢫᇶᯈୖ࡟࣌ࣥࢱࢭࣥࢆ⭷ཌ 5–150 nm ࡢཌࡉ࡟┿✵⵨╔ἲ࡛స〇ࡋࡓࠋX ⥺ᅇᢡᐃࡣ SPring-8 BL08B2 ࡛ࠊᅗ 1 ࡟♧ࡍࡼ࠺࡟ 2ș=5°ࡲ࡛ࡢẚ㍑ⓗపゅ㡿ᇦ࡜ 2ș=40°ࡲ࡛ࡢẚ㍑ⓗ
㧗ゅ㡿ᇦࢆูࠎ࡟ ᐃྍ⬟࡞ගᏛ⣔ࢆᵓ⠏ࡋࡓࠋ ᐃ᮲௳ࡣࠊపゅഃ࣓࢝ࣛ㛗ࡀ 1599 mm ࡛ࠊ㧗ゅഃ࣓࢝ࣛ㛗ࡀ 54.43 mm ࡛࠶ࡾࠊX ⥺Ἴ㛗ࡣ 0.1 nm ࡛࠶ࡿࠋヨᩱ࡬ࡢ X ⥺ධᑕゅࡣ 0.10–0.30°
࡛࠶ࡾࠊ㟢ග᫬㛫ࡣࠊపゅഃ᳨ฟࡀ 30–240 ⛊࡛ࠊ㧗ゅഃ᳨ฟࡀ 10 ⛊࡛࠶ࡿࠋ࡞࠾ࠊ࣓࢝ࣛ㛗ࡣ㏱㐣㓄⨨࡟࡚࣋࣊ࣥ㓟㖟࡛㍑ṇࡋࠊ࢚ࢿࣝࢠ࣮࡟ࡘ࠸࡚ࡣࠊCu-K ➃࡛㍑ṇࡋࡓࠋ䠉㻞㻜㻠䠉SSPring-8/SACLA
Pring-8/SACLA ฼฼⏝◊✲ᡂᯝ㞟⏝◊✲ᡂᯝ㞟

ᅗ 1

GI-SAXS/WAXS ྠ᫬Section
Section Bᐃྍ⬟࡞ගᏛ⣔⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸࢞ࣛࢫᇶᯈୖ࡟〇⭷ࡋࡓ࣌ࣥࢱࢭࣥ⵨╔⭷ࢆ⏝࠸࡚ࠊపゅഃ᳨ฟჾ࡛ᩓ஘ᅇᢡࣃࢱ࣮ࣥࢆ᳨ฟ
ࡋࡓ౛ࢆᅗ 2 ࡟♧ࡍࠋ⭷ཌ 150 nmࠊධᑕゅᗘ 0.3°ࡢ᮲௳࡛పゅ㡿ᇦ࠿ࡽࡢ ᐃࡀྍ⬟࡛ࠊ࣌ࣥࢱࢭࣥⷧ⭷ࡢ 001 ᅇᢡࣆ࣮ࢡࡀほ ࡉࢀࡓࠋࡑࡇ࡛ࠊධᑕゅᗘࢆ 0.3°㸦ᮏᐇ㦂᮲௳ࡢ࢞ࣛࢫࡢ⮫⏺
ゅᗘࡣ 0.14°㸧࡟ᅛᐃࡋ࡚ ᐃࡋࡓ㸦ᅗ 3(a)㸧ࠋᚓࡽࢀࡓᩓ஘ᅇᢡࣃࢱ࣮ࣥ࠿ࡽ out of plane ᪉ྥࡢᅇᢡࣃࢱ࣮ࣥࢆྲྀࡾฟࡋࠊゎᯒࡋࡓ⤖ᯝࠊᩥ⊩[4]࡜ྠᵝ࡟⭷ཌࡀ 50 nm ௨ୗࡢ࣌ࣥࢱࢭࣥⷧ⭷ࡣࠊd = 1.54 nm 㸦2ș = 3.75°㸧࡟ⷧ⭷┦࡜࿧ࡤࢀࡿࣆ࣮ࢡࡢࡳ᳨ฟࡉࢀࠊ75 nm ௨ୖࡢⷧ⭷ࡣ d = 1.45 nm
㸦2ș = 4.00°㸧࡟ࣂࣝࢡ┦࡜࿧ࡤࢀࡿࣆ࣮ࢡࡀ᪂ࡓ࡟᳨ฟࡉࢀࡓࠋࡇࢀࡽ࠿ࡽ࣌ࣥࢱࢭࣥศᏊࡀᇶᯈ࡟ᑐࡋ࡚ᆶ┤㓄ྥࡋ࡚࠸ࡿࡇ࡜ࡀ♧၀ࡉࢀࡿ[5]ࠋḟ࡟ 150 nm ࡢ࣌ࣥࢱࢭࣥⷧ⭷࡟ࡘ࠸࡚ࠊX ⥺ࡢධᑕゅᗘࢆኚ࠼࡚ ᐃࡋࡓ㸦ᅗ 3(b)㸧ࠋධᑕゅᗘࢆὸࡃࡍࡿ࡟ᚑ࠸ࠊࣂࣝࢡ┦⏤᮶ࡢࣆ࣮ࢡᙉᗘࡀ┦ᑐⓗ࡟㧗ࡃ࡞ࡗࡓࡇ࡜ࡼࡾࠊⷧ⭷⾲㠃㏆ഐࡢࣂࣝࢡᒙࡢᐤ୚ࡀ㧗࠸ࡇ࡜ࡀ☜ㄆ࡛ࡁࡓࠋ

ᅗ 2 ࢞ࣛࢫᇶᯈୖ࡟〇⭷ࡋࡓ࣌ࣥࢱࢭࣥⷧ⭷ࡢᩓ஘ᅇᢡࣃࢱ࣮ࣥ౛䠉㻞㻜㻡䠉SSPring-8/SACLA
Pring-8/SACLA ฼฼⏝◊✲ᡂᯝ㞟⏝◊✲ᡂᯝ㞟(a) ⭷ཌ౫Ꮡᛶ㸦ධᑕゅ 0.3°㸧

SectionSection B(b)ධᑕゅ౫Ꮡᛶᅗ 3 ࢞ࣛࢫᇶᯈୖ࡟〇⭷ࡋࡓ࣌ࣥࢱࢭࣥⷧ⭷ࡢᩓ஘ᅇᢡࣃࢱ࣮ࣥ (out of plane ᪉ྥ)ࠊ(a)X ⥺ࡢධᑕゅᗘࢆ୍ᐃ࡟ࡋࠊ⭷ཌࡀ␗࡞ࡿヨᩱࡢẚ㍑ࠊ(b)⭷ཌࡀ 150 nm ࡢヨᩱ࡟ᑐࡋ࡚ࠊX ⥺ࡢධᑕゅᗘࢆኚ࠼࡚ ᐃࡋࡓ㝿ࡢẚ㍑⥆࠸࡚ࠊX ⥺ධᑕゅᗘࢆ 0.1°ࠊヨᩱ⭷ཌ 150 nm ࡛ࡢ㧗ゅഃ ᐃ⤖ᯝࢆ♧ࡍ㸦ᅗ 4㸧ࠋゎᯒࡢ⤖ᯝࠊ
in plane ᪉ྥࠊࡍ࡞ࢃࡕ⤖ᬗࡢ▷㍈᪉ྥ࡟⏤᮶ࡍࡿࣆ࣮ࢡࡀ」ᩘ᳨ฟࡉࢀࡓ[6]ࠋࡍ࡞ࢃࡕࠊ࣌ࣥࢱ
ࢭࣥࡣᇶᯈ࡟ᑐࡋ࡚ᆶ┤᪉ྥ࡟㓄ิࡋ࡚࠸ࡿ஦ࢆ♧၀ࡍࡿ⤖ᯝࡀᚓࡽࢀࡓࠋ

1-10
110-110120020 1-21
0-21 -12-1

ᅗ 4 ࢞ࣛࢫᇶᯈୖ࡟〇⭷ࡋࡓ࣌ࣥࢱࢭࣥⷧ⭷㸦⭷ཌ 150 nm㸧ࡢ GI-WAXS᪉ྥࠊἼ㛗 0.1 nmࠊX ⥺ධᑕゅ 0.1°)

ᐃ⤖ᯝ (in plane௒ᚋࡢㄢ㢟㸸 」㞧࠿ࡘ⢭ᐦ໬ࡍࡿ᭷ᶵከᒙⷧ⭷࡟ᑐࡋ࡚ࠊࡑࡢ⭷ࡢ≧ែࢆホ౯࡛ࡁࡿ᪉ἲ࡜ࡋ࡚ࠊᨺᑕග㧗㍤ᗘ X ⥺ࢆ⏝࠸ࡓ X ⥺ᅇᢡ ᐃࡢ᳨ウࢆᐇ᪋ࡋࡓࠋࡑࡢ⤖ᯝࠊ᭷ᶵ࢚ࣞࢡࢺࣟࢽࢡࢫࢹࣂ࢖ࢫ࡟࠾ࡅࡿᐇ㝿ࡢ✚ᒙ⭷ࡢ⭷ཌ࡟㏆࠸ 20–150 nm ࡢཌࡉ࡛ࡢ᭷ᶵ⭷ᙧᡂ㏵ୖ࡛ࣂࣝࢡᒙ࠿ࡽⷧ⭷ᒙ࡬≧ែࡀኚ໬ࡍࡿ࣌ࣥࢱࢭࣥⷧ⭷ࡢᵓ㐀᝟ሗࡀྲྀᚓ࡛ࡁࡓࠋᮏ᪉ἲࡣࠊ〇⭷࣭⇕ฎ⌮➼ࡢࣉࣟࢭࢫ㐣⛬ࡢホ౯࡞࡝⤒᫬ኚ໬ࡢ ᐃ࡟ጾຊࢆⓎ᥹ࡍࡿ࡜⪃࠼ࡽࢀࡿࠋ୍᪉࡛ࠊ௒ᅇ ᐃࡋࡓヨᩱ࡟࠾࠸࡚ࠊ⭷ཌࡀⷧ࠸ヨᩱ࡛ࡣឤᗘࡀㄢ㢟࡜࡞ࡗࡓࠋ௚ࡢ ᐃᡭἲࡢ⤌ࡳྜࢃࡏࠊ ᐃ᮲௳࠾ࡼࡧゎᯒ᪉ἲࡢ᭱㐺໬࡟ࡼࡗ࡚㧗ឤᗘ໬ࢆᅗࡿࡇ࡜ࡀ࡛ࡁࢀࡤࠊ᭷ᶵ࢚ࣞࢡࢺࣟࢽࢡࢫᮦᩱࡢ㛤Ⓨ࡞ࡽࡧ࡟〇⭷᮲௳࡟ࡼࡿࢹࣂ࢖ࢫ≉ᛶࡢ㐪࠸ࢆ✲᫂ࡍࡿୖ࡛ࠊᙉຊ࡞ࢶ࣮ࣝ࡜࡞ࡿࠋ䠉㻞㻜㻢䠉SSPring-8/SACLA
Pring-8/SACLA ฼฼⏝◊✲ᡂᯝ㞟⏝◊✲ᡂᯝ㞟

SectionSection Bཧ⪃ᩥ⊩㸸
[1]  㔠ཎ⢤ ┘ಟ, ྜྷ⏣㈆ྐ ⦅㞟, ͆ⷧ⭷ࡢホ౯ᢏ⾡ࣁࣥࢻࣈࢵࢡ͇, ࢸࢡࣀࢩࢫࢸ࣒㸦2013㸧
[2]  D. Yokoyama, J. Mater. Chem., 21, 19187 (2011).
[3]  D. Yokoyama et al., Adv. Funct. Mater., 21, 1375 (2011).
[4]  H. Yoshida and N. Sato, J. Appl. Phys., 89, 101919 (2006).
[5]  R. B. Campbell, et al., Acta Cryst., 14, 705 (1961).
[6]  ྜྷᮏ๎அ ௚, ⾲㠃⛉Ꮫ 35, 190, (2014).

(Received: March 15, 2018; Early edition: April 10 2019;
Accepted: July 16, 2019; Published: August , 2019)䠉㻞㻜㻣䠉