材料科学の基礎 - Sigma-Aldrich: Analytical, Biology ... ??活性層とするFET の報告である1)。しかしながら、本報告では、電 流の増幅率である相互コンダクタンスは述べられているものの、移 動度の見積まではなされていない。 1984年になってKudoらのグ ループは、有機太陽電池で用いた 10

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  • Materials Science

    6

  • 1.

    Organic Thin-Film TransistorOTFTOrganic Field-Effect TransistorOFET

    195019801983FET 1

    1984KudoFET10-5 10-7 cm2/Vs 2

    FETFET1 cm2/Vs 350 cm2/VsFET 4

    20106EL 5 6RFID 7 8 9

    2. 2.1

    2-1

    (A)

    (B)

    Gate

    Gate

    Gate

    Gate

    Gate

    Gate

    Gate

    Gate

    (A)

    (A)

    Gate

    Gate

    Gate

    Gate

    Gate

    Gate

    Gate

    Gate

    Gate

    Gate

    Gate

    Gate

    Gate

    Gate

    Gate

    Gate

    (C) (D)

    ABC

    D1 , 2 , 3 , 4 , 5 , 6

    2-1

    2-1AC

    1

    2

    3

    4

    5

    2,3 2,4 2,5 1,2 4 2 1,2

    1. ............................................................................................................ 22. .................................................. 2 2.1 .................................................................. 2 2.2 ................................. 3 2.3FETMOS-FET......................................... 3 2.4 ......................................................... 43. .......................................................................... 5 3.1 .................................................................................. 5 3.2 ........................................................................ 6 3.3 TFT ............................................... 64. .........................................................................13 4.1Cr/Au .................13 4.2 ......................14 4.3 .......................................................................15 4.4FET .......................................................................165. ...........................................................................................................166. ...........................................................................................................17

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  • 2-1BD / -ABCD

    4MISMetal Insulator SemiconductorABCD

    10 11

    /Chemical Vapor DepositionCVD 12,13

    2.2 2.1

    MIS-FET

    FET /FET / /

    30 mSUS

    14 2-2 15,16

    Gate

    Gate

    Gate

    Gate

    FloatingMetal

    Gate

    Gate

    Floating Metal

    Gate

    Gate

    Gate

    Gate

    Gate

    Gate

    (B)

    (A)

    (C)

    p

    n

    Base

    Emitter

    Collectorp

    n

    Base

    Emitter

    Collector

    A -BC

    2-2

    2.3 FETMOS-FETFET

    MOSMetal-Oxide-SemiconductorMOS-FET2-3

    n-

    p

    n-p

    OFFn-p-n pn

    OFF pp

    2-3FETMOS-FET

    MOS-FET /pnAsPOFFn-p-nOFF

    FET /OFF

    FETFETppMOS-FETpn

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  • 2.4

    Organic FETOFET / /MIS3

    Ld

    2-4FET

    /WLFET

    Id

    Vg

    MIS2-51 Vg 0 VVd

    Vg 2-52Vg VthVd Vg-VthVg VsgroundVth Vg VthVg Vd Id2-53Vg VthVd Vg-Vth Vd

    Vd Vg-VthVd Vd Vg-Vth 2-54VdLLVd Id

    G

    DS

    -0.7

    -0.6

    -0.5

    -0.4

    -0.3

    -0.2

    -0.1

    0-120-100-80-60-40-200

    Dra

    in c

    urre

    nt (n

    A)

    Drain voltage (V)

    Vg0 V

    G

    DS

    -250

    -200

    -150

    -100

    -50

    0-120-100-80-60-40-200

    Dra

    in c

    urre

    nt (

    A)

    Drain voltage (V)

    DS

    G

    -250

    -200

    -150

    -100

    -50

    0-120-100-80-60-40-200

    Dra

    in c

    urre

    nt (

    A)

    Drain voltage (V)

    DS

    G

    -250

    -200

    -150

    -100

    -50

    0-120-100-80-60-40-200

    Dra

    in c

    urre

    nt (

    A)

    Drain voltage (V)

    Id-VdW2 mmL100 m

    1Vg0 V

    3VgVthVdVg -Vth 4VgVthVdVg -Vth

    2VgVthVd Vg -Vth

    VgVs

    Vd

    Vg-100 V

    VdId

    Vg-100 V

    Vg-100 V

    Vd

    Vg

    W

    L

    2-4FET

    2-5

    4 Tel:03-5796-7330Fax:03-5796-7335 E-mail : sialjpts@sial.com

  • 3. 3.1

    3

    p

    npnpnp

    pHOMOHighest Occupied Molecular Orbital5.0 eVLUMOLowest Unoccupied Molecular Orbital3.2 eV / -5.1 eV -4.9 eVAuHOMOpCa

    -2.9 eVLUMOn

    ambipolar 173.2

    p50 cm2/Vs 4n pn 18,19

    n0.2 cm2/Vsnp3 cm2/Vsn 20,21ppn1 cm2/Vs

    Sinn-C60 1.5 cm2/Vsn 22

    10,00010,000

    1980Processability10-2 cm2/VsFET

    poly9,9-dioctylfluorene-co-bithiophene F8T223poly-3-hexylthiopheneP3HT24,25P3HT0.1 cm2/Vs1 cm2/Vs

    2009Facchetti 26nn0.85 cm2/Vspnpn

    3

    1980OFETp 27,281990 29,301 cm2/Vs19971 cm2/Vs 31

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  • 19801510-5 cm2/Vs1 cm2/Vs53-1

    S

    S

    S

    1985 1990 1995 2000

    2005 2010 2015

    103

    102

    10-1

    10-2

    10-3

    10-4

    10-5

    10

    1

    2004216P111

    cm2 /

    Vs

    3-1TFT

    2000TIPS-Pentacene 32 33,34,351 cm2/Vs 36,37,38,39,40,41

    3.2

    pnELp 42,43,44,45

    p /n /pn

    pn3-2

    /EL 46,47

    48

    3-2

    3.3 FETFET

    FET3

    /

    AuAu

    AuCu49Ag50Ca51 ITOIndium Tin Oxide52 53 54PEDOT-PSS 55,56 5758

    Au4.9 eVnpHOMO 59 60,61,62,63

    6 Tel:03-5796-7330Fax:03-5796-7335 E-mail : sialjpts@sial.com

  • SiO2 64,65Al2O366Ta2O567OFETSiO2 HexamethyldisilazaneHMDSOctadecyltrichlorosilanOTSOTSPFOTS

    -6T -CYEPL

    PVAPVCPMMA 68PIPVP 69,70

    FETFET1 2

    2-1p2-2n2-33 4

    1 1FET

    1-1Aldrich 55111250 cm2/Vs1-2Aldrich 698423Vth OPV1-3DNTT1-4

    1

    1-1 RubreneAldrich 551112

    Podzorov, V. Sysoev, S.E. Loginova, E. Pudalov, V. M. Gershenson, M.E., Appl. Phys. Lett., 2003, 83, 3504.Podzorov, V. Pudalov, V.M. Gershenson, M.E., Appl. Phys. Lett., 2003, 82, 1739.Sundar, V.C. Zaumseil, J. Podzorov, V. Menard, E. Willett, R.L. Someya, T. Gershenson, M.E. Rogers, J.A., Science, 2004, 303, 1644.Takeya, J. Yamagishi, M. Tominari, Y. Hirahara, R. Nakazawa, Y. Nishikawa, T. Kawase, T. Shimoda, T. Ogawa, S., Appl. Phys. Lett., 2007, 90, 102120.Pernstich, K.P. Haas, S. Oberhoff, D. Goldmann, C. Gundlach, D.J. Batlogg, B. Rashid, A.N. Schitter, G., J. Appl. Phys., 2004, 96, 6431.

    1-2 PentaceneAldrich 698423

    Takeya, J. Goldmann, C. Haas, S. Pernstich, K.P. Ketterer, B. Batlogg, B., J. Appl. Phys., 2003, 94, 5800.Jurchescu, O.D. Popinciuc, M. Wees, B.J. Palstra, T.T.M., Adv. Mater., 2007, 19. 688.

    1-3 Oligop-phenylenevinyleneOPV

    Nakanotani, H. Saito, M. Nakamura, H. Adachi, C., Appl. Phys. Lett., 2009, 95, 033308.

    1-4 Dinaphtho2,3-b:2',3'-f thiopheno3,2-bthiopheneDNTT

    Uno, M. Tominari, Y. Yamagishi, M. Doi, I. Miyazaki, E. Takimiya, K. Takeya, J., Appl. Phys. Lett., 2009, 94, 223308.Haas, S. Takahashi, Y. Takimiya, K. Hasegawa, T., Appl. Phys. Lett., 2009, 95, 022111.

    !Aldrich !WEB :

    DNTT : Dinaphtho2,3-b:2',3'-f thiopheno3,2-bthiophene

    DPh-BDT : 2,6-Diphenylbenzo1,2-b:4,5-bdithiophene

    DPh-BTBT: 2,7-Dipheny1benzothieno3,2-bbenzothiophene

    DT-BDT: 2,6-Ditolylbenzo1,2-b:4,5-bdithiophene

    7Tel:03-5796-7340Fax:03-5796-7345 E-mail : safcjp@sial.com

  • 2 2-1 p2

    2-1PentaceneAldrich P1802, 684848, 698423p 71,72 73 741 cm2/Vs2-20.3 cm2/Vs

    2-3CopperII phthalocyanineCuPcAldrich 546674, 702854ELpFET0.02 cm2/VsFET

    FET 752-4FET

    P3HTFET 76

    2-5BDT2-6BTBT2.0 cm2/VsHOMOBTBTDNTT2-7DNTT2.9 cm2/Vs7.9 cm2/Vs 77

    2p

    2-1 PentaceneAldrich P1802, 684848,

    698423

    Klauk, H. Gundlach, D.J. Nichols, J.A. Jackson, T.N., IEEEE Trans. Electron Devices, 1999, 46, 1258.,Laquindanum, J.G. Katz, H.E. Lovinger, A.J. Dodabalapur, A., Chem. Mater., 1996, 8, 2542.,Dimitrakopoulos, C.D. Brown, A.R. Pomp, A., J. Apply. Phys., 1996, 80, 2501.,Dimitrakopoulos, C.D. Mascaro, D.J., IBM J. Res. & Dev., 2001, 45, 11.

    2-2 2,3,9,10-TetramethylpentaceneMe4PENT

    Meng, H. Bendikov, M. Mitchell, G. Helgeson, R. Wudl, F. Bao, Z. Siegrist, T. Kloc, C. Chen, C.-H., Adv. Mater., 2003, 15, 1090

    2-3 CopperII phthalocyanineCuPc

    Aldrich 546674, 702854

    Bao, Z. Lovinger, A.J. Dodabalapur, A., Appl. Phys. Lett., 1996, 69, 3066.

    2-4 Aldrich

    Horowitz, G. Fichou, D. Peng, X. Xu, Z. Garnier, F., Solid State Commum. 1989, 72, 381.

    2-5 2,6-Diphenylbenzo1,2-b:4,5-bdichalcogenopheneDPh-BDX

    Takimiya, K.Kunugi, Y. Konda, Y. Niihara, N. Otsubo, T., J. Am. Chem. Soc., 2004, 126, 5084.

    2-6 2,7-Diphenyl1benzothieno3,2-bbenzothiopheneDPh-BTBT

    Takimiya, K.Kunugi, Y. Konda, Y. Ebata, H. Toyoshima, Y. Otsubo, T., J. Am. Chem. Soc., 2006, 128, 3044.,Takimiya, K. Ebata, H. Sakamoto, K. Izawa, T. Otsubo, T. Kunugi, Y., J. Am. Chem. Soc., 2006, 128, 12604.

    2-7 Dinaphtho2,3-b:2,3-f thieno3,2-bthiopheneDNTT

    Yamamoto, T. Takimiya, K., J. Am. Chem. Soc., 2007, 129, 2224.Uno, M. Doi, I. Takimiya, K. Takeya, J. Appl. Phys. Lett., 2009, 94, 103307.Zschieschang, U. Ante, F. Yamamoto, T. Takimiya, K. Kuwabara, H.Ikeda, M. Sekitani, T. Someya, T. Kern, K. Klauk, H. Adv.Mater., 2010, 22, 982.

    2-4

    Name Structure Cat. No.

    -Sexithiophene (6T)

    SS

    SS

    SS

    594687-1G

    5,5-Dihexyl-2,2:5,2:5,2:5,2:5,2-sexithiophene (DH-6T)

    S S

    S S S

    SCH2(CH2)4CH3

    CH3(CH2)4CH2

    633216-500MG

    sigma-aldrich.com/organicelectronics-jp

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  • 2-2 n3

    2-8N,N'-dioctyl-3,4,9,10-perylene tetracarboxylic diimideAldrich 663913n0.6 cm2/Vs

    nHOMO2-9CopperII 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro-29H,31H-phthalocyanineAldrich 4466530.03 cm2/VsnCMOSn

    2-10nFETSiO2 OTS0.1 cm2/VsFETn

    n2-111.8 cm2/VsVth2-120.2 cm2/Vs

    FETC602-13Fullerene -C60Aldrich 572500, 379646, 483036n3 cm2/VsPCBM2-14Aldrich 684457, 684449, 684430n0.2 cm2/Vs 78 79

    3n

    2-8 N,N'-dioctyl-3,4,9,10-perylene tetracarboxylic diimidePTCDI-C8HPTCDI-C8

    Aldrich 663913

    Malenfant, P.R.L. Dimitrakopoulos, C.D. Gelorme, J.D. Kosbar, L.L. Graham, T.O. Curioni, A. Andreoni, W., Appl. Phys. Lett., 2002, 80, 2517.

    2-9 CopperII 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro-29H,31H-phthalocyanineF16CuPc

    Aldrich 446653

    Bao, Z. Lovinger, A.J. Brown, L., J. Am. Chem. Soc., 1998, 120, 207.

    2-10 Perfluoropentacene Sakamoto, Y. Suzuki, T. Kobayashi, M. Gao, Y. Fukai, Y. Inoue, Y. Sato, F. Tokito, S., J. Am. Chem. Soc., 2004, 126, 8138.

    2-11 2,2'-Bis4-trifluoromethylphenyl-5,5'-bithiazole

    Ando, S. Murakami, R. Nishida, J. Tada, H. Inoue, Y. Tokito, S. Yamashita, Y., J. Am. Chem. Soc., 2005, 127, 14996.

    2-12 4,7-Bis5-4'-trifluoromethylphenylthiophen-2-ylbenzo1,2,5thiadiazole

    Kono, T. Kumaki, D. Nishida, J. Sakanoue, T. Kakita, M. Tada, H. Tokito, S. Yamashita. Y., Chem. Mater., 2007, 19, 1218.

    2-13 Fullerene-C60C60

    Aldrich 572500, 379646, 483036

    Haddon, R.C. Perel, A.S. Morris, R.C. Palstra, T.T.M. Hebard, A.F. Fleming, R.M., Appl. Phys. Lett., 1995, 67, 121.Anthopoulos, T.D. Singh, B. Marjanov, N. Sariciftci, N.S. Ramil, A.M. Sitter, H. Clle, M. Leeuw, D.M., Appl. Phys. Lett., 2005, 89, 213504.Kinoshita, S. Sakanoue, T. Yahiro, M. Takimiya, K. Ebata, H. Ikeda, M. Kuwabara, H. Adachi, C., Solid State Commum., 2008, 145, 114.Haddock, J.N. Zhang, X. Domercq, B. Kippelen, B., Org. Electronics, 2005, 6, 182.

    2-14 6,6-Phenyl C61 butyric acid methyl esterPCBM60PCBM

    Aldrich 684457, 684449, 684430

    Chikamatsu, M. Itakura, A. Yoshida, Y. Azumi, R. Yase, K., Chem. Mater., 2008, 20, 7366.

    9Tel:03-5796-7340Fax:03-5796-7345 E-mail : safcjp@sial.com

  • 2-3 42-15TIPS-PentaceneAldrich 716006

    TIPS0.17 cm2/Vs1 cm2/Vs 802-161 cm2/Vs

    BTBT2-171 cm2/VsC132.8 cm2/VsHOMO

    3 3-1 5

    3-1H0.1 cm2/VsMllenp3-2PR-TRMCPulse-Radiolysis Time-Resolved Microwave Conductivity0.1 1 cm2/Vs3-3Colr Colh10-1

    cm2/VsTOFTime of FlightFET

    3-2 6903-4

    3-5ASmA10-4 cm2/VsESmE10-2 cm2/Vs3-6

    Lcol10-3 cm2/Vs3-7SmHTOFSmH0.1 cm2/Vs

    3-8FET0.14 cm2/Vs3-90.5 cm2/Vson/off10715

    4 7FET90

    4-13-P3RT

    4

    2-15 6,13-Bistriisopropylsilylethynyl pentaceneTIPS-pentacene

    Aldrich 716006

    Anthony, J.E. Brooks, J.S. Eaton, D.L. Parkin, S.R., J. Am. Chem. Soc., 2001, 123, 9482.Payne, M.M. Delcamp, J.H. Parkin, S.R. Anthony, J.E., Org. Lett., 2004, 6, 1609.Payne, M.M. Odom, S.A. Parkin, S.R. Anthony, J.E., Org. Lett., 2004, 6, 3325.

    2-16 5,11-Bistriethylsilylethynylanthra2,3-b:6,7-b' dithiopheneTES anthradithiophene

    Payne, M.M. Parkin, S.R. Anthony, J.E. Kuo, C.C. Jackson, T.N., J. Am. Chem. Soc., 2005, 127, 4986.

    2-17 2,7-Dialkyl1benzothieno3,2-bbenzothiophenealkyl-BTBT

    Ebata, H. Izawa, T. Miyazaki, E. Takimiya, K. Ikeda, M. Kuwabara, H. Yui, T., J. Am. Chem. Soc., 2007, 129, 15732.Izawa, T. Miyazaki, E. Takimiya, K. Adv. Mater., 2008, 20, 3388.Kang, M.J. Doi, I. Mori, H. Miyazaki, E. Takimiya, K. Ikeda, M. Kuwabara, H., Adv. Mater., 2011, 23, 1222.

    10 Tel:03-5796-7330Fax:03-5796-7335 E-mail : sialjpts@sial.com

  • 5

    3-1 2,3,6,7,10,11-HexahexylthiotriphenyleneHHTT

    Adam, D. Schuhmacher, P. Simmerer, J. Hussling, L. Siemensmeyer, K. Nature 1994, 371, 141.

    3-2 Alkyl-hexabenzocoroneneHBC

    van de Craats, A.M. Warman, J. M. Fechtenktter, A. Brand, J. D. Harbison, M. A., Mllen, K. Adv.Mater. 1999, 11, 1469.

    3-3 1,4,8,11,15,18,22,25-Octaoctylphthalocyanine

    Iino, H. Hanna, J. Bushby, R. J. Movaghar, B. Whitaker, B. J. Cook, M. J. Appl.Phys.Lett. 2005, 87, 132102.

    6

    3-4 2-4'-heptyloxyphenyl-6-dodecylthiobenzothiazole

    Funahashi, M. Hanna, J. Phys. Rev. Lett. 1997, 78, 2184.

    3-5 2-4'-octylphenyl-6-dodecyloxynaphthalene8-PNP-O12

    Funahashi, M. Hanna, J. Appl. Phys. Lett. 1997, 71, 602.

    3-6 1Benzothieno3,2-b1benzothiophene-2,7-dicarboxylateBTBT

    Mry, S. Haristoy, D. Nicoud, J.-F. Guillon, D. Diele, S. Monobe, H. Shimizu, Y. J. Mater. Chem. 2002, 12, 37.

    3-7 5-Propyl-5''''-henynyl-2,2':5',2'':5'',2'''-quanterthiophene3-QTP-yne-4

    Funahashi, M. Hanna, J. Adv.Mater. 2005, 17, 594.

    3-8 5,5'-Bis7-hexyl-9H-fluoren-2-yl-2,2'-bithiopheneDHFTTF

    Meng, H. Zheng, J. Lovinger, A. J. Wang, B.-C. Van Patten, P. G. Bao, Z. Chem.Mater. 2003, 15, 1778.

    3-9 Bis-5'-hexylthiophen-2'-yl-2,6-anthraceneDHTAnt

    Meng, H. Sun, F. Goldfinger, M.B. Jaycox, G. D. Li, Z. Marshall, W. J. Blackman, G. S. J. Am. Chem. Soc. 2005, 127, 2406.

    TM

    www.sigma-aldrich.com/sacatalog-jp

    TIPSJohn E. AnthonyTobin MarksIain McCullochMartin HeeneyThomas Bjrnholm

    Vol.4 No.3

    11Tel:03-5796-7340Fax:03-5796-7345 E-mail : safcjp@sial.com

  • FET0.1 cm2/VsP3RTXMEH-PPVP3RTFET-LED4-20.1 cm2/Vs4-3

    FET5 m0.15 cm2/Vs14-40.6 cm2/Vs4-54-4FET0.08 cm2/VsTg150 0.25 cm2/Vs

    PFPF4-6265 4-6

    FET0.1 0.2 cm2/Vs5 8PF4-7TOFFET0.01 cm2/VsPF4-8PF0.01 cm2/Vs

    7

    4-1 Poly3-alkylthiopheneP3RT

    Sirringhaus, H. Tessler, N. Friend, R.H. Science 1998, 280, 1741.Bao, Z. Dodabalapur, A. Lovinger, A. J. Appl. Phys. Lett. 1996, 69, 4108.

    4-2 Poly3,3'''-dialkyl-quaterthiophenePQT

    Ong, B. S. Wu, Y. Liu, P. Gardner, S. J. Am. Chem. Soc. 2004, 126, 3378.

    4-3 Poly2,5-bis3-decylthiophen-2-ylthieno2,3-bthiophene

    Heeney, M. Bailey, C. Genevicius, K. Shkunov, M. Sparrowe, D. Tierney, S. McCulloch, I. J. Am. Chem. Soc. 2005, 127, 1078.

    4-4 Poly2,5-bis3-alkylthiophen-2-ylthieno3,2-bthiophene

    McCulloch, I. Heeney, M. Bailey, C.Genevicius, K. MacDonald, I.Shkunov,M. Sparrowe, D. Tierney, S. Wagner, R. Zhang, W. Chabinyc, M.L. Kline, R. J. McGehee, M. D. Toney M. F. Nat.Mater. 2006, 5, 328.

    4-5 Poly2,5-bis2-thienyl-3,6-dialkylthieno 3,2-bthiophene

    Li, Y. Wu, Y. Liu, P. Birau , M. Pan, H. Ong, B.S. Adv. Mater. 2006, 18, 3029.

    4-6 Poly-9,9'-dioctyl-fluorene-co-bithiopheneF8T2

    Aldrich 685070

    Sirringhaus, H. Wilson, R. J. Friend, R. H. Inbasekaran, M. Wu, W. Woo, E. P. Grell, M., Bradley, D. D. C. Appl. Phys. Lett. 2000, 77, 406.

    4-7 PolytriarylaminePTAA

    Aldrich702471

    Veres, J.Ogier, S.D. Leeming, S.W. Cupertino, D.C. Khaffaf, S. M. Adv. Funct. Mater. 2003, 13, 199.

    4-8 Poly9,9-dioctylfluorenyl-2,7-diyl-co-4,4-N-4-sec-butylphenyl diphenylamineTFB

    Fong, H. H. Papadimitratos, A. Malliaras, G. G. Appl.Phys.Lett. 2006, 89, 172116.

    4-13-

    Name S-tructure Mobility Average Molecular Weight Cat. No.

    Poly(3-hexylthiophene-2,5-diyl) (P3HT)

    S

    CH2(CH2)4CH3

    n

    regioregular 445703-1G

    104 - 101 cm2/Vs average Mn 25,000-35,000regioregular, electronic grade, Plex-core OS 1100

    698989-250MG698989-1G698989-5G

    104 - 101 cm2/Vs average Mn 45,000-65,000regioregular, electronic grade, Plex-core OS 2100

    698997-250MG698997-1G

    *Plexcore is a registered trademark of Plextronics, Inc.

    sigma-aldrich.com/organicelectronics-jp

    12 Tel:03-5796-7330Fax:03-5796-7335 E-mail : sialjpts@sial.com

  • 4. 4.1 Cr/Au

    TFTphotolithography

    1 300 nm

    n++-Si

    2

    350ml

    15mm100Orientation Flat4-1

    100

    4-1

    11145

    50 ml10 ml40 ml14vol ratio

    70 1010dangling bond

    32pHpH

    IPAisopropyl alcohol3IPAIPA

    3 HMDS1,1,1,3,3,3-

    H...

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