「有機EL素子の基礎及びその作製技術」‐材料科学の基礎 第1号
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- ふさこ そや
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1 Material Matters Basics Vol. 1, No. 1 EL EL EL
2 EL EL 1, yahiro@isit.or.jp 2 yahiro@cstf.kyushu-u.ac.jp 3 adachi@cstf.kyushu-u.ac.jp 1 EL EL EL EL EL EL EL EL EL ITO ITO EL Appendix EL A A A A A A A A Appendix Appendix A A EL 1-1 Mechanoluminescence Photo-luminescence Electroluminescence ELChemiluminescence EL 1-1 EL EL EL OLED Organic Light Emitting Diode 1-1 EL EL EL EL ma/cm 2 2 Tel: Fax: sialjpts@sial.com
3 EL ka/cm 2 EL Indium-Tin Oxide:ITO EL 1-2 EL -1- EL 1953 A. Bernanose EL EL New York M. Pope NRC Canada W. Helfrich W. Helfrich EL EL -2- C. W. Tang EL EL EL 1987 C. W. Tang 100 nm EL 11 ITO 75 nm Tris 8-quinolinolate aluminum Alq 3 60 nm MgAg ITO 10 V 1,000 cd/m 2 1 EL EL EL EL Organic Photoconductor OPC 5 6, 7 EL LB EL 8, S. Hayashi Alq 3 Diamine 1-4 C. W. Tang EL EL 1 EL C. W. Tang EL EL EL C. Adachi 1-5 C. W. Tang 12, 13 Tel: Fax: safcjp@sial.com 3
4 EL Mg PV Emitter TPD Au Glass ) 1990 EL C. Hosokawa Y. Hamada Alq 3 EL 15 ITO TPD 16 TPD 12 PBD 13 Alq EL 26, 27 EL NTT 30 EL 77 K EL 5 8 C. Adachi S. Tokito , EL EL EL ,4'-bis (2,2-diphenylethenyl) biphenyl π PPV EL 17 PAT 18 PF π EL EL XL EL PAT PF 1-7 PAT PF 625 nm 520 nm 460 nm EL EL EL 23, Princeton Southern California EL 4 Tel: Fax: sialjpts@sial.com
5 EL 2 EL 2-1 EL EL / EL EL 2-1 Appendix r f ext -3.3 ev -3.8 ev Mg 0.9 Ag 0.1 Al -4.3 ev Mg 0.9 Ag 0.1 Al LiF Al 0.5 nm 1.0 nm LiF Mg 0.9 Ag CuPc LiF EL EL 38 LUMO 5.0eV ITO 2.6eV α-npd 3.3eV Alq 3 3.8eV MgAg 5.5eV 6.0eV HOMO γ EL η ext η f η r EL 2-1 EL EL 2-2 ITO/ α-npd 50 nm / Alq 3 50 nm / MgAg 150 nm / Ag 10 nm α-npd -5.5 ev Highest Occupied Molecular Orbital HOMO ITO ITO α-npd HOMO ITO -4.7 ev UV- ITO -5.0 ev Ultraviolet Photoelectron Spectroscopy UPS 35 CuPc 15 nm CuPc UPS 36 Lowest Unoccupied Molecular Orbital LUMO Alq 3 LUMO EL cm/v s π-π EL Space Charge Limited Current, SCLC 39 SCLC J A/cm 2 cm/v/s L m V VF/m J 9 8 εε μv L 2 0 = (2.1) nm 10-3 cm/v s EL 10V 30 A/cm Ir EL Intersystem Crossing ISC 100 Tel: Fax: safcjp@sial.com 5
6 EL S T 1 / / - / ITO/ TPD 40 nm / CBP 6wt - Ir ppy 3 20 nm / BCP 10 nm / Alq 3 30 nm / LiF 0.5 nm / Al 100 nm / / / / / S HOMO LUMO DCM Alq 3 Alq 3 DCM 2-4 DCM DCM 1mol MgAg LiF/Al EL Finite-difference time-domain FDTD ITO ITO 44 EL EL EL ext EL η φ = γ η η η ( ext) r f ext Appendix A EL Alq 3 LUMO3.0 ev DCM LUMO3.5 ev DCM HOMO5.6eV Alq 3 HOMO6.0eV 2-4 EL HOMO-LUMO UPS HOMO-LUMO EL 520 nm Ir ppy 3 α-npd TPD EL (Web 製品リスト ) HOMO HOMO EL EL 3 C. W. Tang 2-2 ITO/α-NPD 50 nm / Alq 3 50 nm / MgAg 150 nm / Ag 10 nm / / / DCM ITO/α-NPD 50 nm / Alq 3 1mol - DCM 50 nm / MgAg 150 nm / Ag 10 nm CuPc PEDOT/PSS m-tdata 6 Tel: Fax: sialjpts@sial.com
7 EL TPD α-npd TCTA BCP DPvBi CBP π Alq 3 BCP t-bu-pbd Flrpic Ir(ppy) 3 (ppy) 2 Ir(acac) Alq Coumarin DCM PPV PPV EL PPV MEH-PPV PF Alq 3 Zn-PBO Web DMQ DCM2 Aldrich Materials Science Tel: Fax: safcjp@sial.com 7
8 EL 3 EL 3-1 C-C C-H 3-1 g 10-3 Pa Train Sublimation (a) (b) 3-2 CuPc 3-3 Train Sublimation Heat ITO EL ITO Indium-Tin Oxide 10Ω/ ITO (c) ITO (a) 40mm (b) 3-1 Train Sublimation abc mm (c) ITO 3mm 2mm 4mm 2mm 3mm EL (d) 8 Tel: Fax: sialjpts@sial.com
9 EL (e) 3:1 1:3 vol ratio ITO ITO 10 ITO ITO ITO ITO IPA 5 ITO ITO IPA EL ITO IPA UV/ mm (a) (b) 3-4 1mm 3-3 EL EL m P Pa T K D m 45 λ = T / PD (3.1) EL Alq 3 46 Alq /cm -3 Alq 3 Alq nm 300K 1Pa 0.5 mm 10-3 Pa 50 cm 10-3 Pa 50 cm 3 30 cm 10-4 Pa Zn /m 2 s P Pa T K M g/mol Zn = P /( MT ) (3.2) 10-4 Pa 300 K M /m nm Alq /m 2 1 C-C 10-4 Pa 10-3 Pa H. Aziz 47 T. Ikeda Pa 1 2 Tel: Fax: safcjp@sial.com 9
10 EL ppm UV FET FET / FET Ta Mo BN K- 30cm EL cm rpm 10 cm 3-6 Mg Ag Ca LiF W Ta V W Al Al Cu E- Al W Li Cs 2 10 V 100 A Pt Ta Ta Ta Ta Ta Mg W V Ag, Au, LiF W Al, Ca Tel: Fax: sialjpts@sial.com
11 EL 3-8 Z-ratio Tooling Factor Tooling Factor EL nm 30 mg 10 mg ( X mol M host W host R host M gest W gest R gest W M host Wgest M gest W + M host gest gest host 100 mol% 3.3 = X M gest X W gest = W M 100 X host (3.4) W : W = R : R (3.5) host host gest host gest M gest X R gest = R M 100 X host (3.6) X EL 1 5 /s wt M host = g/mol Alq 3 M gest = g/mol DCM 1mol R = (3.7) gest R host Alq 3 R host =5 /s R gest =0.033 /s Tooling Factor Y 3 Y 3 R host =15 /s R gest =0.099 /s10 1 Tooling Factor 3 R gest 1 /10s R host = 15 /s Tooling Factor 3 1/3 Mg Ag 10 1 wt ratio 3-4 EL EL 20 V EL 1 pa 100 ma 1A nw mw cd/m 2 lm/w 0.1V 0.5V 15V Tel: Fax: safcjp@sial.com 11
12 4 EL EL ext int η φ ( ext) = N photon = ( P E) N career ( I e) P λ = I 5 P λ = I (4.5) lm/w e cd/a c EL J-V ext -J EL EL ma/cm External quantum efficiency ext η φ ( ext ) 100 (4.1) EL EL PW/m 2 1 E J E hν = hc λ = (4.2) h J sv s -1 c m s -1 m P W/m 2 E N photon s -1 m -2 P( W ) E( J ) = P( J s ) E( J ) 1 N photon = (4.3) 1 W1 1 J J s -1 I A EL N career s -1 m -2 A/m 2 e C=A s N career ext = I( A) e( C) = I( A) e( A s 1 ) (4.4) Appendix Mlm/m 2 P W/m 2 y K m 683 lm/w M ( λ) P Km y( λ) = (4.6) EL EL M λ') = P K y( λ') F( λ') F( λ) dλ ( m (4.7) F( λ') M ( λ') dλ' = P K m y( λ') dλ' F( λ) dλ M M M = P K m F( λ') y( λ') dλ' F( λ) dλ (4.9) (4.8) EL M lm/m 2 M = P K L cd/m 2 m F( λ) y( λ) dλ F( λ) dλ M L = π (4.11) (4.10) EL EL W J/s EL EL W/m 2 W/m 2 L cd/m 2 M lm/m 2 P W/m Tel: Fax: sialjpts@sial.com
13 W 555nm 1 lm lm/m 2 cd cd/m 2 lx L-V 2.5 V EL 4 1 L cd/m 2 M lm/m 2 P W/m 2 1 L cd/m 2 1 π π /683 2 M lm/m 2 1/π 1 1/683 2 P W/m /π nm K m =683 lm/w 555 nm 4-2 EL ITO/α-NPD 50 nm / Alq 3 50 nm / MgAg 150 nm / Ag 10 nm J - V V 2.5 V EL EL V10V ma/cm L-J Ex - J Alq 3 α-npd J-V L - J EL Ex-J Tel: Fax: safcjp@sial.com 13
14 EL PL EL PL EL EL PL 5 EL EL EL EL Appendix EL PL UV-Vis UV-Vis PL Appendix PL 4-5 DCM Alq 3 1) A. Bernanose, M. Conte, P Vouauzx, J. Chim. Phys., 1953, 50, 64. 2) M. Pope, H. P. Kallmann, P. Magnante, J. Chem. Phys., 1963, 38, ) W. Herfrich and W. G. Schneider, Phys. Rev. Lett., 1965, 14, ) W. Herfrich and W. G. Schneider, J. Chem. Phys., 1965, 44, ) W. D. Gill, J. Appl. Phys., 1972, 43, ) G. Pfister, Phys. Rev., 1977, B 16, ) P. M. Borsenberger, W. Mey and A. Chowdy, J. Appl. Phys., 1978, 49, ) P. S. Vincett, W. A. Barlow and R. A. Hann, Thin Solid Films., 1982, 94, ) G. G. Roberts, M. M. McGinniity, W. A. Barlow, P. S. Vincett, Solid State Commun., 1979, 32, ) S. Hayashi, T. T. Wang, S. Matsuoka, S. Saito, Mol. Cryst. Liq. Cryst., 1986, 135, ) C. W. Tang and S. A. VanSlyke, Appl. Phys. Lett., 1987, 51, ) C. Adachi, S. Tokito, T. Tsutsui and S. Saito, Jpn. J. Appl. Phys., 1988, 27, L ) C. Adachi, S. Tokito, T. Tsutsui and S. Saito, Jpn. J. Appl. Phys., 1988, 27, L ) C. Hosokawa, H. Higashi, H. Nakamura, T. Kusumoto, Appl, Phys. Lett., 1995, 67, ) Y. Hamada, T. Sano, M. Fijita, T. Fujii, Y. Nishio and K. Shibata, Jpn. J. Appl. Phys., 1993, 32, L ) Y. Shirota, Y. Kuwabara and H. Inaba, Appl. Phys. Lett., 1994, 65, ) J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. Mackay, R. H. Friend, P. L. Burns and A. B. Holmes, Nature, 1990, 347, ) Y. Ohmori, M. Uchida, K. Muro and K. Yoshino, Jpn. J. Appl. Phys., 1991, 30, L ) Y. Ohmori, M. Uchida, K. Muro and K. Yoshino, Jpn. J. Appl. Phys., 1991, 30, L ) A. R. Brown, D. D. C. Bradley, J. H. Burroughes, R. H. Friend, N. C. Greenham, P. L. Burn, A. B. Holmes and A. Kraft, Appl. Phys. Lett., 1992, 61, ) J. Kido, H. Shionoya and K. Nagai, Appl. Phys. Lett., 1992, 67, ) T. Wakimoto, Y. Fukuda, K. Nagayama, A. Yokoi, H. Nakata, M. Tsuchida, IEEE Transactions Electron Devices, 1997, 44, ) N. Takada, T. Tsutsui and S. Saito, Appl. Phys. Lett., 1993, 63, ) 1998, 36, ) EL 19 p18. 26) M. A. Baldo, S. Lamansky, P. E. Burrows, M. E. Tompson, S. R. Forrest, Appl, Phys. Lett., 1999, 75, 4. 27) M. A. Baldo, D. F. O Brien, Y. You, A. Shoustikov, A. Aibley, M. E. Thompson and S. R. Forrest, Nature, 1998, 395, ) T. Tsutsui, M. Yang, M. Yahiro, K. Nakamura, T. Watanabe, T. Tsuji, Y. Fukuda, T. Wakimoto, S. Miyaguchi, Jpn. J. Appl. Phys., 1999, 38, L ) , p ) S. Hoshino and H. Suzuki, Appl. Phys. Lett., 1996, 69, ) C. Adachi, M. A. Baldo, S. R. Forrest and M. E. Tompson, Appl. Phys. Lett., 2000, 77, ) C. Adachi, M. A. Baldo, S. R. Forrest, S. Lamansky, M. E. Thopmson and R. C. Kwong, Appl. Phys. Lett., 2001, 78, ) C. Adachi, R. C. Kwong, P. Djurovich, V. Adamovich, M. A. Baldo, M. E. Thompson and S. R. Forrest, Appl. Phys. Lett., 2001, 79, ) S. Tokito, T. Iijima, Y. Suzuki and F. Sato, Appl. Phy, Lett,. 2003, 83, ) K. Sugiyama, H. Ishii, Y. Ouchi and K. Seki, J. Appl. Phys., 2000, 87, ) EL , p ) T. Wakimoto, Y. Fukuda, K. Nagayama, A. Yokoi, H. Nakada and M. Tsuchida, IEEE Trans. Electron Devices, 1997, 44, ) Y. Sato, T. Ogata, S.Ichisawa, M.Fugono and H. Kanai, Proc. SPIE, 1999, 3797, ) P. E. Burrows, Z. Shen, V. Bulovic, D. M. McCarty, S. R. Forrest, J. A. Cronin and S. R. Forrest, J. Appl. Phys., 1996, 79, ) N. C. Greenham, R. H. Friend and D. D. C. Bradlay, Adv. Mater., 1994, 6, ) 50 No3, 2003, ) G. Gu, D. Z. Garbuzov, P. E. Burrows, S. Venkatesh, S. R. Forrest and M. E. Thompson, Opt. Lett., 1997, 22, ) S. Moller and S. R. Forrest, J. Appl. Phys., 2002, 91, ) M. Fujita, T. Ueno, T. Asano, S. Noda, H. Ohhata, T. Tsuji, H. Nakada, N. Shimoji, Electron. Lett., 2003, 39, ) ) P. E. Burrows, Z. Shen, V. Bulobic D. M. McCarry, S. R. Forrest, J. A. Cronin, M.E. Tompson, J. Appl. Phys., 1996, 79, ) H. Aziz, Z. D. Popovic, S. Xie, A. M. Hor, N. X. Hu, C. Tripp, G. Xu, Appl. Phys. Lett., 1998, 72, ) T. Ikeda, H. Murata, Y. Kinoshita, J. Shike, Y. Ikeda, M. Kitano, Chem. Phys. Lett., 2006, 426, Tel: Fax: sialjpts@sial.com
15 EL Appendix EL M W A1-1 4 EL lm/w cd/a A1-1-1 int c L r f ext EL A1-2 A1-2-1 int r f A-2.1 N p N e A -1 I I e I h I e I h I r A-2.2 A-2.3 I A P W S m 2 m e C h J s Anode Organic layer Cathode A1-1-2 e A -1 EL Tel: Fax: safcjp@sial.com 15
16 EL I r I I = I h = I e I h = I e = 0 I = I h = I e = I r =1.0 I = I h > I e I h 0 I e = 0 I = I h = I e + I h I r = I e = I h - I h cm -3 A A-2.12 T S int 5 1 A-2.9A-2.14A-2.15 I = I e > I h I e 0 I h = 0 I = I e = I h + I e I r = I h = I e - I e I h 0, I e 0 A r r eh TS 3:1 r S dir S int 0.40 f f 1 EL 1 f f f f K r =1 / T r T r K t EL K nr f Triplet-Triplet annihilation A-2.10A-2.11A T* A A A-2.18 f = 1.0 K nr > K r f < Alq 3 1 EL Tel: Fax: sialjpts@sial.com
17 EL A1-2-2 A -2 ext 3 A -2 Rf: Rb: θc: Ωc: d: EL c c c Ω Ω ext c 1.7 A A m R f R b R f R b EL TE transverse electric modetm transverse magnetic mode 50 c R f R b R f 520 nm R b / 0.90 m = 0.95 ext =18 EL 80 n >1.0 ext n org c 1-cos θ sin 2 θ /2 n org 1.0 A-2.21 A-2.21 c R f EL / R b m ext r 0.25 f 1.0 A1-3 EL E ext ext P in W/m 2 P em W/m 2 E int P em / P in V V J A/m 2 P in = J V 1 hc / h c P em hc / F P em A-3.1 F 0 P em L U A-3.1 E int A-3.2 int Tel: Fax: safcjp@sial.com 17
18 EL N in N em N em / N in J / e - J / e J A/m 2 N in = J / e e int P W L cd/m 2 L cd/m 2 EL F y M lm/m 2 EL O R m 0 rad +d ds E p E p = P em / N em dsr EL I cdd dm lm A-3.2A-3.5 E int int A-3.6 M lm I 0 cd M lm E ext ext EL L 0 cd/m 2 M lm/m 2 A1-4 EL 0 π/2 = π/2 M lm/m nm W lm K m 680 lm/w EL M lm/m 2 A-3.2 A-4.8A-4.9 F 0 A-3.2A-3.7A-4.10 E ext A-3.4A-3.8 A-4.10 ext A-4.11A Tel: Fax: sialjpts@sial.com
19 EL A-4.11A-4.12 m A-4.11A CMY Cyan MagentaYellow 3 CMY A-4.13 A Appendix - 3 PL Alq 3 DCM DCM EL Appendix A3-1 2 RGB Red Green Blue 3 RGB 3 RGB A -1 A3-2 CRT CIE CIE CIE Commission Internationale de l Eclairage RGB 3 RGB RGB 1 R G B 2 xy CIE1931 NTSC National Television Standards Committee 1953 CRT NTSC CRT R 0.67,0.33G 0.21,0.71B 0.14,0.08 W 0.310,0.316 NTSC A -2 CIE1931 Tel: Fax: safcjp@sial.com 19
20 TM Aldrich TM TM Vol. 4, No. 1 Controlled Synthesis & Properties Morphing Materials into Meaning Alternative Energy the way to go Generation and Storage Vol. 3, No. 4 URL Material Matters sialjp@sial.com
有機電界発光素子
rganic Electroluminescent Device Shizuo Tokito, Yasunori Taga EL EL EL IT Mg Al EL Electroluminescent (EL) the devices based on organic materials have the potential to realize the full-color flatpanel
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6 2 T γ T B (6.4) (6.1) [( d nm + 3 ] 2 nt B )a 3 + nt B da 3 = 0 (6.9) na 3 = T B V 3/2 = T B V γ 1 = const. or T B a 2 = const. (6.10) H 2 = 8π kc2
![6 2 T γ T B (6.4) (6.1) [( d nm + 3 ] 2 nt B )a 3 + nt B da 3 = 0 (6.9) na 3 = T B V 3/2 = T B V γ 1 = const. or T B a 2 = const. (6.10) H 2 = 8π kc2](/thumbs/92/109118076.jpg "6 2 T γ T B (6.4) (6.1) [( d nm + 3 ] 2 nt B )a 3 + nt B da 3 = 0 (6.9) na 3 = T B V 3/2 = T B V γ 1 = const. or T B a 2 = const. (6.10) H 2 = 8π kc2")
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9 1. (Ti:Al 2 O 3 ) (DCM) (Cr:Al 2 O 3 ) (Cr:BeAl 2 O 4 ) Ĥ0 ψ n (r) ω n Schrödinger Ĥ 0 ψ n (r) = ω n ψ n (r), (1) ω i ψ (r, t) = [Ĥ0 + Ĥint (
9 1. (Ti:Al 2 O 3 ) (DCM) (Cr:Al 2 O 3 ) (Cr:BeAl 2 O 4 ) 2. 2.1 Ĥ ψ n (r) ω n Schrödinger Ĥ ψ n (r) = ω n ψ n (r), (1) ω i ψ (r, t) = [Ĥ + Ĥint (t)] ψ (r, t), (2) Ĥ int (t) = eˆxe cos ωt ˆdE cos ωt, (3)
1 Visible spectroscopy for student Spectrometer and optical spectrum phys/ishikawa/class/index.html
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1. 4cm 16 cm 4cm 20cm 18 cm L λ(x)=ax [kg/m] A x 4cm A 4cm 12 cm h h Y 0 a G 0.38h a b x r(x) x y = 1 h 0.38h G b h X x r(x) 1 S(x) = πr(x) 2 a,b, h,π
![1. 4cm 16 cm 4cm 20cm 18 cm L λ(x)=ax [kg/m] A x 4cm A 4cm 12 cm h h Y 0 a G 0.38h a b x r(x) x y = 1 h 0.38h G b h X x r(x) 1 S(x) = πr(x) 2 a,b, h,π](/thumbs/101/149329485.jpg "1. 4cm 16 cm 4cm 20cm 18 cm L λ(x)=ax [kg/m] A x 4cm A 4cm 12 cm h h Y 0 a G 0.38h a b x r(x) x y = 1 h 0.38h G b h X x r(x) 1 S(x) = πr(x) 2 a,b, h,π")
. 4cm 6 cm 4cm cm 8 cm λ()=a [kg/m] A 4cm A 4cm cm h h Y a G.38h a b () y = h.38h G b h X () S() = π() a,b, h,π V = ρ M = ρv G = M h S() 3 d a,b, h 4 G = 5 h a b a b = 6 ω() s v m θ() m v () θ() ω() dθ()
29 1 6 1 1 1.1 1.1 1.1( ) 1.1( ) 1.1: 2 1.2 1.2( ) 4 4 1 2,3,4 1 2 1 2 1.2: 1,2,3,4 a 1 2a 6 2 2,3,4 1,2,3,4 1.2( ) 4 1.2( ) 3 1.2( ) 1.3 1.3 1.3: 4 1.4 1.4 1.4: 1.5 1.5 1 2 1 a a R = l a l 5 R = l a +
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cm λ λ = h/p p ( ) λ = cm E pc [ev] 2.2 quark lepton u d c s t b e 1 3e electric charge e color charge red blue green qq
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2007 2007 7 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 1 2007 2 4 5 6 6 2 2.1 1: KEK Web page 1 1 1 10 16 cm λ λ = h/p p ( ) λ = 10 16 cm E pc [ev] 2.2 quark lepton 2 2.2.1 u d c s t b + 2 3 e 1 3e electric charge
2 FIG. 1: : n FIG. 2: : n (Ch h ) N T B Ch h n(z) = (sin ϵ cos ω(z), sin ϵ sin ω(z), cos ϵ), (1) 1968 Meyer [5] 50 N T B Ch h [4] N T B 10 nm Ch h 1 µ
![2 FIG. 1: : n FIG. 2: : n (Ch h ) N T B Ch h n(z) = (sin ϵ cos ω(z), sin ϵ sin ω(z), cos ϵ), (1) 1968 Meyer [5] 50 N T B Ch h [4] N T B 10 nm Ch h 1 µ](/thumbs/49/25515566.jpg "2 FIG. 1: : n FIG. 2: : n (Ch h ) N T B Ch h n(z) = (sin ϵ cos ω(z), sin ϵ sin ω(z), cos ϵ), (1) 1968 Meyer [5] 50 N T B Ch h [4] N T B 10 nm Ch h 1 µ")
: (Dated: February 5, 2016), (Ch), (Oblique Helicoidal) (Ch H ), Twist-bend (N T B ) I. (chiral: ) (achiral) (n) (Ch) (N ) 1996 [1] [2] 2013 (N T B ) [3] 2014 [4] (oblique helicoid) 2016 1 29 Electronic
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