2009A1773                        BL46XU

ȝ-Contact Print ἲ࡟ࡼࡿ⮬ᕫ⤌⧊໬⭷ࢆୗᆅᒙ࡜ࡋࡓ Regioregularpoly㻔3-hexylthiophene㻕ⷧ⭷ࡢ㓄ྥ≧ែࡢゎᯒ
Analysis on Orientation of Regioregular Poly㻔3-hexylthiophene㻕 with
Self-Assembled Underlayer Prepared by ȝ-Contact Printing୵⏣ ᑦ a, బ⸨ ࿴ᙪ b, ᇼෆ ೺ b, ᮡᮏ ೺஧ b
Takashi Kushidaa, Kazuhiko Satob, Ken Horiuchib, Kenji Sugimotobaᖇே㻔ᰴ㻕᪂஦ᴗ㛤Ⓨࢢ࣮ࣝࣉ ⼥ྜᢏ⾡◊✲ᡤ ➨஧◊✲ᐊ,bᖇே㻔ᰴ㻕᪂஦ᴗ㛤Ⓨࢢ࣮ࣝࣉ ᵓ㐀ゎᯒ◊✲ᡤa Research Laboratories II, Integrated Technology Research Institute, New Business Development Group,TEIJIN LIMITEDb
Material Analysis Research Laboratories, New Business Development Group, TEIJIN LIMITED.
ࣅ࣮࣒ࣛ࢖ࣥ BL46XU ࢆ⏝࠸ࡓ GIXD㻔ࡍࢀࡍࢀධᑕ X ⥺ᅇᢡ㻕࡟ࡼࡿ in-plane ཬࡧ out of planeᅇᢡ࡟ࡼࡾࠊ᭷ᶵ༙ᑟయࡢୗᆅᒙ࡜ࡋ࡚⏝࠸ࡽࢀࡿ octadecyltrichlorosilane㻔OTS㻕ⷧ⭷ࡢ〇⭷ἲ࡟ࡼࡾࠊࡑࡢୖ࡟ᙧᡂࡉࢀࡿ regioregular poly㻔3-hexylthiophen㻕㻌㻔P3HT㻕ࡢ㓄ྥ≧ែࡀ␗࡞ࡿࡇ࡜ࢆ᫂ࡽ࠿࡜ࡋࡓࠋᾮ┦ἲ㻔LPD ἲ㻕࡛స〇ࡉࢀࡓ OTS ⮬ᕫ⤌⧊໬⭷ୖࡢ P3HT ࡣᚑ᮶ሗ࿌ࡢ㏻ࡾᇶᯈ࡟ᑐࡋ
࡚ edge on 㓄ྥࢆ♧ࡍࠋ୍᪉ȣ-ࢥࣥࢱࢡࢺࣉࣜࣥࢺἲ㻔PCP ἲ㻕࡛స〇ࡉࢀࡓ OTS ⮬ᕫ⤌⧊໬⭷ୖ
ࡢ P3HT ࡣప㓄ྥࡢ⤖ᬗᵓ㐀ࢆ࡜ࡗ࡚࠸ࡿࡇ࡜ࡀุ᫂ࡋࡓࠋ࣮࣮࢟࣡ࢻ㸸 ࣏ࣜ㻔3㸫࣊࢟ࢩࣝࢳ࢜ࣇ࢙ࣥ㻕ࠊ࣐࢖ࢡࣟࢥࣥࢱࢡࢺࣉࣜࣥࢺࠊ⮬ᕫ⤌⧊໬ࠊGIXD⫼ᬒ࡜◊✲┠ⓗ㸸᭷ᶵ༙ᑟయࢆ⏝࠸ࡓⷧ⭷ࢺࣛࣥࢪࢫࢱ㻔TFT㻕ࡢ◊✲ࡀ㏆ᖺ┒ࢇ࡟⾜ࢃࢀ࡚࠸ࡿࠋ᭷ᶵ༙ᑟయࢆ⏝࠸ࡿࡇ࡜࡟ࡼࡾࠊᰂ㌾ᛶ࡟ඃࢀሬᕸ༳ๅ࡟ࡼࡾ〇㐀ྍ⬟࡞ TFT ᅇ㊰ࡀྍ⬟࡜࡞ࡾࠊࣇࣞ࢟ࢩࣈࣝ࠿ࡘ࣮ࣟࢥࢫࢺࡢࢹ࢕ࢫࣉࣞ࢖㥑ືᅇ㊰ࡸ↓⥺ࢱࢢᅇ㊰࡬࡜ᛂ⏝ࡉࢀࡿࡇ࡜ࡀᮇᚅࡉࢀ࡚࠸ࡿࠋ᭷ᶵ༙ᑟయࡢ≉ᛶࡣ⤖ᬗᵓ㐀ࠊ㓄ྥᗘ➼࡟኱ࡁࡃᙳ㡪ࢆཷࡅࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋ౛࠼ࡤ௦⾲ⓗ࡞᭷ᶵ༙ᑟయ࡛࠶ࡿ P3HT ࡣࠊㄏ㟁య⾲㠃ࢆ SAM㻔self-assembled monolayer㻕ฎ⌮➼࡟ࡼࡾ␯Ỉ໬ࡍࡿࡇ࡜࡟ࡼࡾ⮬ᕫจ㞟ⓗ࡟ edge on 㓄ྥࢆ࡜ࡾࡸࡍࡃ࡞ࡿࠋࡑࢀ࡟ࡼࡾ㠃ෆSSࢫࢱࢵ࢟ࣥࢢࡀቑຍࡋࠊ⛣ືᗘࡀྥୖࡍࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿ[1]ࠋ୍⯡࡟ୗᆅᒙ࡜ࡋ࡚⏝࠸ࡿ SAM ࡢ✀㢮࡟ࡼ
ࡾ P3HT ࡢ㓄ྥ≧ែࡀ␗࡞ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠾ࡾ[2]ࠊ[3]ࠊ୺࡜ࡋ࡚ SAM ࡢ⾲㠃࢚ࢿࣝࢠ࣮ࡀᙳ㡪ࢆཬࡰࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋᡃࠎࡣࡇࢀࡲ࡛ࡢࣛ࣎ᐇ㦂࡟ࡼࡾࠊྠ୍ࡢ⮬ᕫ⤌⧊໬⭷㻔self-assembled layer: SAL㻕ࢆ⏝࠸ࡓሙྜ࡟࠾࠸࡚ࡶࠊࡑࡢᙧᡂἲ࡟ࡼࡾ P3HT ࡢ㓄ྥᣲືࡀኚ໬ࡋ࡚࠸ࡿྍ⬟ᛶࢆぢฟࡋࡓࠋ௒ᅇࡣࡑࢀࢆ☜ㄆࡍࡿࡓࡵ BL46XU ࢆ⏝࠸࡚ in-plane ࠾ࡼࡧ out of plane ࡢ GIXD ᐃࢆ⾜ࡗࡓࠋᐇ㦂㸸ࢧࣥࣉࣝᇶᯈ࡜ࡋ࡚ 300nm ཌࡢ⇕㓟໬⭷௜ n-ࢻ࣮ࣉࢩࣜࢥ࢚ࣥ࢘ࣁࢆ⏝࠸ࠊUV-࢜ࢰࣥὙίࢆ 30 ศ⾜ࡗࡓࡶࡢࢆ⏝࠸ࡓࠋOTS SAL ࡢస〇ࡣPCP ἲࠊLPD ἲඹ࡟‵ᗘ 3%⛬ᗘ࡟ㄪᩚࡋࡓࢻࣛ࢖࣎ࢵࢡࢫ୰࡛⾜ࡗࡓࠋPCP ἲࡣࠊ50mM OTS ࡢ࣊࢟ࢧࣥ⁐ᾮ࡟ poly㻔dimethylsiloxane㻕ࡢࢩ࣮ࢺࢆᾐₕࡋࠊ❅⣲Ẽὶୗ࡛ 10 ศ㛫஝⇱ࡉࡏࡓᚋ࡟ࠊୖグᇶᯈ࡟ 2 ᫬㛫᥋ゐࡉࡏస〇ࡋࡓࠋLPD ἲ SAL ࡣࠊ20mMOTS ࡢࢺ࢚ࣝࣥ⁐ᾮ࡟ᇶᯈࢆ 7 ᪥㛫ᾐₕࡋࡓࠋ཯ᛂᚋࠊࡑࢀࡒࢀ࣊࢟ࢧࣥࠊࢺ࢚࡛ࣝࣥὙίࡋࠊ
࢚ࢱࣀ࣮ࣝ୰࡛ 1 ศ㛫㉸㡢ἼὙίࢆᐇ᪋ࡋࡓࠋࡑࡢᚋࠊ኱Ẽୗ࡟ฟࡋ࡚⣧Ỉ࡛Ὑίࡋࠊ100Υ࡛ 5ศ㛫⇕ฎ⌮ࢆ࠾ࡇ࡞࠸ SAL ௜ᇶᯈࢆస〇ࡋࡓࠋ
P3HT ࡣ Plextronics ♫〇ࡢ Plexcore OS 1100 ࢆࡑࡢࡲࡲ⏝࠸ࠊ1%ࡢࢺ࢚ࣝࣥ⁐ᾮࢆ⏝࠸࡚ࠊୖグ SAL ௜ᇶᯈ࡟ࢫࣆࣥࢥ࣮ࢺࡋࡓࠋ〇⭷ᚋࠊ┿✵ୗ࡛ 150Υ࡛ 1 ᫬㛫࢔ࢽ࣮ࣝࢆ࠾ࡇ࡞ࡗࡓࠋ⭷ཌࡣ࢚ࣜࣉࢯ࣓࣮ࢱ࣮࡛ࠊ᥋ゐゅࡣ⣧Ỉࢆ⏝࠸࡚ࡑࢀࡒࢀ ᐃࡋࡓࠋGIXD ᐃ
BL46XU ࣅ࣮࣒ࣛ࢖ࣥ࡟࠾࠸࡚ HUBER 〇 8 ㍈ᅇᢡィࢆ⏝࠸ࠊX ⥺࢚ࢿࣝࢠ࣮10KeVࠊධᑕゅ
0.14rࡢ᮲௳࡛ in-plane ࠾ࡼࡧ out of plane ᐃࢆᐇ᪋ࡋࡓࠋ⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸
⾲ 1 ࡟ LPD ἲ࠾ࡼࡧPCP ἲ࡛స〇ࡋࡓ OTS SAL ࡢ⭷ཌࠊ⣧Ỉࡢ᥋ゐゅࢆ♧ࡍࠋOTS ࢆ⏝࠸ࡓ
SAM ࡢ⭷ཌࡣ 28Å ⛬ᗘ࡛࠶ࡿࡇ࡜ࡀሗ࿌ࡉࢀ࡚࠾ࡾ[4]ࠊ[5]ࠊ௒ᅇస〇ࡋࡓ SAL ࡣ࠸ࡎࢀࡶ࡯ࡰ༢ศᏊ⭷ࡢཌࡳࢆ᭷ࡋ࡚࠸ࡿࠋࡲࡓ᥋ゐゅࡶ࡯ࡰྠ୍ࡢ್࡛࠶ࡾࠊ⾲㠃࢚ࢿࣝࢠ࣮࡟኱ࡁ࡞ᕪ␗ࡣ࡞࠸ࡇ࡜ࡀࢃ࠿ࡿࠋࡲࡓ 20Pm ゅࡢど㔝࡛ AFM ࡟࡚ ᐃࡋࡓᖹᆒ஧஌⢒ࡉ㻔RMS㻕ࡢ್࠿ࡽࡣPCP ἲ SAL ࡢ᪉ࡀᖹᆠᛶࡀ㧗࠸ࡇ࡜ࡀࢃ࠿ࡿࠋ
⾲ 1㸬PCP ࠾ࡼࡧ LPD SAL ࡢ≉ᛶ
SALPCP SALLPD SAL⭷ཌ
31.8Å
29.3Å

᥋ゐゅ108º108ºRMS4.7Å
5.7Å

Fig.1 ࡟PCP ἲ࠾ࡼࡧ LPD ἲ SAL ࢆୗᆅᒙ࡜ࡋࡓሙྜࡢ P3HT ⷧ⭷ࡢ out of plane GIXD ࡢࣉࣟࣇ࢓࢖ࣝࢆ♧ࡍࠋ࠸ࡎࢀࡢࢧࣥࣉࣝࡶ᫂☜࡞㻔100㻕ࠊ㻔200㻕ࠊ㻔300㻕ࡢᅇᢡࣆ࣮ࢡࡀほ ࡉࢀࡓࠋࡇࢀ
ࡣ P3HT ࡢ࣓ࣛࣛᵓ㐀࡟⏤᮶ࡋ࡚࠾ࡾࠊP3HT ࡢ࢔ࣝ࢟ࣝ㙐ࡀᇶᯈ࡟ᑐࡋ࡚ᆶ┤࡟❧ࡗࡓ edge on㓄ྥࡀᏑᅾࡋ࡚࠸ࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿࠋࡲࡓPCP ἲ SAL ࡢሙྜࡣࠊ㻔n00㻕࡜ేࡏ࡚㻔010㻕ࡢࣆ࣮ࢡࡀᏑᅾࡍࡿࠋࡇࢀࡣࢳ࢜ࣇ࢙ࣥ⎔ࡢSSࢫࢱࢵ࢟ࣥࢢ࡟⏤᮶ࡋ࡚࠾ࡾࠊࢳ࢜ࣇ࢙ࣥ⎔ࡀᇶᯈ࡜ᖹ⾜࡞㓄⨨ࢆྲྀࡿ face on ᵓ㐀ࢆ࡜ࡗ࡚࠸ࡿࡇ࡜ࢆព࿡ࡋ࡚࠸ࡿࠋࡘࡲࡾPCP ἲ SAL ࢆ⏝࠸ࡓሙྜࡣࠊedge on 㓄ྥ⤖ᬗ࡜ face on 㓄ྥ⤖ᬗࡀඹ࡟Ꮡᅾࡍࡿẚ㍑ⓗࣛࣥࢲ࣒࡞㓄ྥ≧ែࢆྲྀࡗ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋ

Fig.1.

P3HT ࡢ out of plane GIXD 㻔ྑୖࡣ㒊ศᣑ኱ᅗ㻕ࡘࡂ࡟ Fig.2 ࡟ྛࢧࣥࣉࣝࡢ in-plane GIXD ࡢࣉࣟࣇ࢓࢖ࣝࢆ♧ࡍࠋ࠸ࡎࢀࡢࢧࣥࣉࣝࡶ out ofplane GIXD ࡜ẚ㍑ࡋ࡚㻔n00㻕ࡢࣆ࣮ࢡࡣᑠࡉࡃ࡞ࡗ࡚࠸ࡿࠋ୍᪉ LPD ἲ SAL ࡢሙྜࡣ㻔010㻕ࡢࣆ࣮ࢡࡀほ ࡉࢀࠊ㠃ෆ࡟SSࢫࢱࢵ࢟ࣥࢢࡀᏑᅾࡋ࡚࠸ࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࢀࡣ out of plane ࡢ⤖ᯝ࡜ేࡏࡿ࡜ࠊ㠃ෆ࡟SSࢫࢱࢵ࢟ࣥࢢࠊ㠃እ࡟࣓ࣛࣛᵓ㐀ࢆ᭷ࡍࡿ edge on 㓄ྥࡋࡓᚑ᮶ࡢሗ࿌࡝࠾ࡾࡢ㓄ྥᣲືࢆ࡜ࡗ࡚࠸ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋ୍᪉PCP ἲ SAL ࡣࠊࣆ࣮ࢡᙉᗘࡀᙅ࠸ࡇ࡜ࡶ࠶ࡾࠊ㻔010㻕ࡢࣆ࣮ࢡࡣほ ࡉࢀ࡞࠿ࡗࡓࠋࡋࡓࡀࡗ࡚ࡇࢀࡶྠᵝ࡟ edge on 㓄ྥ⤖ᬗ࡜ face on 㓄ྥ⤖ᬗࡀඹ࡟Ꮡᅾࡍࡿẚ㍑ⓗࣛࣥࢲ࣒࡞㓄ྥ≧ែࢆྲྀࡗ࡚࠸ࡿࡇ࡜⿬௜ࡅࡿ࡜⪃࠼ࡽࢀࡿࠋ

Fig.2. P3HT ࡢ in-plane GIXD 㻔ྑୖࡣ㒊ศᣑ኱ᅗ㻕㻌ྠ୍໬Ꮫ✀ࢆ⏝࠸࡚⾲㠃ฎ⌮࡛ୗᆅᒙࡢ SAL ࡢ〇⭷ἲ࡛㓄ྥᣲືࡀኚࢃࡿ⌮⏤࡟ࡘ࠸࡚ࡣ⌧ᅾ᳨ウ୰࡛࠶ࡿࠋࡋ࠿ࡋ⾲㠃ᖹᆠᛶࡢ㧗࠸PCP ἲ SAL ࡢ᪉ࡀ P3HT ࡀప㓄ྥ࡟࡞ࡗ࡚ᢡࡾࠊ⾲㠃ᙧ≧ࡢᙳ㡪ࡢࡳ࡛ࡇࡢ⌧㇟ࡀ⏕ࡌ࡚࠸ࡿࢃࡅ࡛ࡣ࡞࠸࡜ᛮࢃࢀࡿࠋ௒ᚋࡢㄢ㢟㸸௒ᅇ ᐃ᮲௳ࡢタᐃࡀ᭱㐺࡛࡞ࡃࠊrocking curve ➼ࡢࢹ࣮ࢱࢆᚓࡿࡇ࡜ࡀ࡛ࡁ࡞࠿ࡗࡓࠋ௒ᚋ
ࡑࡢ௚ࡢ SAL ࡢሙྜࢆྵࡵ࡚ࠊヲ⣽࡞ࢹ࣮ࢱࢆྲྀᚓࡍࡿᚲせࡀ࠶ࡿࠋPCP ἲ SAL ࢆ⏝࠸ࡿࡇ࡜
࡟ࡼࡾࠊP3HT ࡢ㓄ྥࡀప࠸࡟ࡶ࠿࠿ࢃࡽࡎࠊ༙ᑟయ≉ᛶ࡟ඃࢀࡿྍ⬟ᛶࢆぢฟࡋ࡚࠾ࡾࠊ௒ᚋ㟁Ẽ≉ᛶ࡜㓄ྥ≧ែࡢ┦㛵࡟ࡘ࠸࡚⢭ᰝࡍࡿࠋཧ⪃ᩥ⊩㸸[1] H. Sirringhous, N. Tessler, and R. H. Friend, Science, 280, 12, 1741-1744 㻔1998㻕
[2] D. H. Kim, Y. Yang, Y. D. Park, and K. Cho, Langmuir, 21, 8, 3203-3206 㻔2005㻕
[3] R. J. Kline, M. D. McGehee, and M. F. Toney, Nature Mater., 5, 222-228 㻔2006㻕
[4] S. R. Wasserman, Y. T. Tao, and G. M. Whitesides, Langmuir, 5, 1074-1087 㻔1989㻕
[5] A. Y. Fadeev, and T. J. McCarthy, Langmuir, 16, 7268-7274 㻔2000㻕