材料科学の基礎 - Sigma-Aldrich: Analytical, Biology .... 1, No. 1 有機EL の動作機構および構造有機EL の作製方法測定データの整理有機EL の効率に

Vol. 1, No. 1

EL

EL

EL

EL

Material Matters Basics

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EL

Tel:03-5796-7330Fax:03-5796-7335 E-mail : [email protected] Tel:03-5796-7330Fax:03-5796-7335 E-mail : [email protected]

1 EL

1-1MechanoluminescencePhoto-luminescenceElectroluminescenceELChemiluminescenceEL1-1EL EL ELOLEDOrganic Light Emitting Diode

1-1 EL

EL EL ELmA/cm2

1,2 3

1E-mail [email protected] [email protected] [email protected]

- -1 EL .............................................................................. 2 1-1 ..................................................................... 2 1-2 EL -1- ............................................ 3 1-3 EL -2- ............................................ 32 EL .......................................... 5 2-1 EL ......................................................... 5 2-2 EL ......................................................... 6 2-2-1 EL ................................ 6 2-2-2 EL ......................... 63 EL ............................................................ 8 3-1 .......................................................... 8 3-2ITO .................................................... 8 3-2-1ITO ................................................. 8 3-2-2 .............................................................. 9 3-3 EL ........................ 9 3-3-1 ....................................................... 9 3-3-2 .............................................. 11 3-4 ................................................................... 114 ................................................................... 12 4-1 ............................ 12 4-2 ................................................. 135 .......................................................................... 146 .......................................................................... 14

Appendix EL ................. 15 A1-1 ................................................................. 15 A1-1-1 .......................................................... 15 A1-1-2 ............................................ 15 A1-2 ........................................... 15 A1-2-1 ................................................... 15 A1-2-2 ................................................... 17 A1-3 ........................................... 17 A1-4 ......................... 18Appendix ................................. 19Appendix ......................................... 19 A3-1 ............................................... 19 A3-2 ............ 19

EL

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EL

Tel:03-5796-7340Fax:03-5796-7345 E-mail : [email protected]

3Tel:03-5796-7340Fax:03-5796-7345 E-mail : [email protected]

kA/cm2

EL

1

234

1-2 EL -1- EL1953 A. Bernanose EL EL 11960New YorkM. Pope NRC CanadaW. Helfrich 1-2 2-4W. Helfrich EL

1-2

EL1970 1980 EL

Organic PhotoconductorOPC 5 6, 7

ELLB EL 8, 91980S. Hayashi

-Indium-Tin Oxide:ITO 1-3 10 EL

1-3

1-3 EL -2- C. W. Tang EL EL

EL1987 C. W. Tang 100 nm EL 11ITO 75 nm Tris8-quinolinolatealuminumAlq360 nmMgAg ITO10 V 1,000 cd/m2 1 EL EL 1-4

Alq3 Diamine

1-4C. W. Tang EL

EL

1

EL C. W. Tang EL EL ELC. Adachi 1-5C. W. Tang 12, 13

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EL


Mg

PV

Emitter

TPD

Au

Glass

1-5 12)

1990 ELC. Hosokawa 1-6 14Y. Hamada Alq3 EL 15 ITOTPD 16TPD12PBD13 Alq311 14 EL

1-64,4'-bis (2,2-diphenylethenyl) biphenyl

PPV EL 17PAT18PF19 1-7 EL 20

PAT PF

1-7PAT PF

625 nm 520 nm 460 nm EL 21 22 EL EL 23, 24 25

Princeton Southern CaliforniaEL

26, 27 EL 28 29 NTT30 EL77 K EL 5 8C. Adachi S. Tokito 19 31 12 32 620 33, 34

1990 EL1987 10 EL2007 12 EL 1-8 1-9

1-8 EL XL-1

1-9 EL

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EL


5

2 EL

2-1 EL EL / EL EL 2-1Appendix

r

f

ext

25 75

EL

r

f

ext

2-1 EL

EL 2-2

ITO/ -NPD50 nm/ Alq350 nm/ MgAg150 nm/ Ag10 nm

-NPD -5.5 eVHighest Occupied Molecular OrbitalHOMO ITOITO -NPD HOMOITO -4.7 eVUV- ITO -5.0 eVUltraviolet Photoelectron SpectroscopyUPS 35CuPc 15 nmCuPcUPS 36Lowest Unoccupied Molecular OrbitalLUMOAlq3 LUMO

-3.3 eV-3.8 eVMg0.9Ag0.1Al -4.3 eVMg0.9Ag0.1 AlLiF Al 0.5 nm 1.0 nm LiFMg0.9Ag0.1 22CuPcLiFEL EL 38

2.6eV

-NPD

5.5eV

3.3eV

Alq3

6.0eV

5.0eVITO

3.8eVMgAg

LUMO

HOMO

2-22 EL

EL 10-3 10-6 cm/Vs- ELSpace Charge Limited Current, SCLC39 SCLC JA/cm2cm/V/s Lm VVF/m

3

20

89

LVJ = (2.1)

100 nm 10-3 cm/Vs EL 10V 30 A/cm2

1 3 2-3 2775 Ir ELIntersystem CrossingISC 100

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EL


S1

S0

T1

25

75

2-3

EL20 80 40Finite-difference time-domainFDTD41 42 43 ITO ITO 44 EL

EL ELext EL

extfrext =)( 2.2

5 20 Appendix A1-2.

2-2 EL

2-2-1 EL EL 3

C. W. Tang 2-2ITO/-NPD50 nm/ Alq350 nm/ MgAg150 nm/Ag10 nm / / /

DCMITO/-NPD50 nm/ Alq31mol - DCM50 nm/MgAg150 nm/ Ag10 nm

/ / -/

ITO/ TPD40 nm/ CBP6wt - Irppy320 nm/ BCP10 nm/ Alq330 nm/ LiF0.5 nm/ Al100nm / / / / /

HOMOLUMO DCMAlq3 Alq3DCM 2-4DCM DCM1molMgAg LiF/Al

Alq3LUMO3.0 eV

DCMLUMO3.5 eV

DCMHOMO5.6eV

Alq3HOMO6.0eV

2-4

ELHOMO-LUMOUPSHOMO-LUMO EL520 nm Irppy3 -NPD TPD

2-2-2 EL HOMO HOMO

CuPc PEDOT/PSS

m-TDATA

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(Web)

https://www.sigmaaldrich.com/japan/materialscience/org-electronics.html?utm_source=redirect&utm_medium=promotional&utm_campaign=mm-pdf-jp

EL


7

TPD -NPD

TCTA

BCP

Alq3BCP

t-Bu-PBD

Alq3 100 Coumarin DCM

DMQ DCM2

Alq3 Zn-PBO

DPvBi CBP

Flrpic Ir(ppy)3 (ppy)2Ir(acac)

PPVPPV EL

PPV MEH-PPV PF

www.sigma-aldrich.com/ms-jpwww.ssiiggmmaa--aalllddddrrrrriiiiiccccchhhhh....cccccooooommmmm////mmmmssss---jjjjppppp

Web

Aldrich Materials Science

www.sigma-aldrich.com/ms-jpwww.sigma-aldrich.com/ms-jp

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https://www.sigmaaldrich.com/japan/materialscience.html?utm_source=redirect&utm_medium=promotional&utm_campaign=mm-pdf-jp

EL


3 EL

3-1C-C C-H

3-1 g10-3 PaTrain Sublimation

(a)

(c)

(b)

3-1Train Sublimationabc

3-2

3-2CuPc

3-3 Train Sublimation

Heat

3-3

3-2ITO EL ITOIndium-Tin Oxide 10/ ITO

3-2-1ITO

(a)

(d)

(b)

(c)

40mm

ITO

EL

14mm

3mm2mm4mm2mm3mm

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EL


9

(e)

1:3 vol ratioITO ITO

10 ITO

ITO ITO

ITO

3-2-2 3-4 5 5IPA 5ITO

ITO IPA

EL ITOIPA

UV/ 10 15

15mm

(a)

(b)

1mm

3-4

3-3 EL

3-3-1 ELm

PPa TK Dm 45

224 /101.3 PDT= (3.1) EL Alq3 46 Alq3 2 1021

/cm-3 Alq3Alq3 1.4 nm300K1Pa 0.5 mm10-3 Pa 50 cm10-3 Pa 50 cm 3 30 cm10-4 Pa Zn /m2s PPa TKMg/mol 45

2124 )/(106.2 MTPZn = (3.2)

10-4 Pa 300 KM02 322.7 1018 /m2 1.4 nm Alq3 6.5 1017 /m21

C-C

10-4 Pa10-3 Pa H. Aziz 47 T. Ikeda 48

10-4 Pa

1 2

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3:1

EL


3-5 0.1 ppm UVFET FET /FET

3-5

3-6 EL22 30 cm10 12 rpm10 cm

TaMoBN K-

30cm

8

3-6

Mg AgCa LiFW Ta VWAlAl CuE-AlWLiCs 2 10 V100 APt Ta 450 3-7

Ta

Ta

Ta

Ta

Mg

WAl, Ca

WV

Ag, Au, LiF

3-7

.indd 10 2009/10/19 14:46:47

EL


11

3-8

Z-ratioTooling Factor Tooling Factor

EL 10 100 nm 30 mg 10 mg

(

3-8

3-3-2X molMhostWhost RhostMgestWgest Rgest

X

MW

MW

MW

gest

gest

host

host

gest

gest

=+

100 mol% 3.3

hosthost

gestgest WX

XMM

W

=100

(3.4)

gesthostgesthost RRWW :: = (3.5)

hosthost

gestgest RX

XMM

R

=100

(3.6)

X EL 1 5/swtMhost=459.44 g/mol Alq3Mgest=303.36 g/mol DCM 1mol3.6

hostgest RR =31067.6 (3.7)

Alq3 Rhost=5 /s Rgest=0.033 /s10 0.33 Tooling Factor Y 3 Y 3Rhost=15 /s Rgest=0.099 /s10 1 Tooling Factor 3 Rgest 1 /10s Rhost= 15 /sTooling Factor 3 1/3MgAg101 wt ratio

3-4 EL EL20 V EL1 pA 100 mA 1AnWmWcd/m2lm/W 0.1V 0.5V15V

.indd 11 2009/10/19 14:46:49


4 EL EL

extint

lm/Wecd/Ac

EL

J-Vext-J

EL ELmA/cm2

4-1 External quantum effi ciencyext

ext )( 100 (4.1)

EL ELPW/m2 1 EJ

hchE == (4.2)

h6.626 10-34Jsvs-1c2.998 108ms-1m PW/m2 E Nphotons-1 m-2

)()()()( 1 JEsJPJEWPNphoton== (4.3)

1W1 1JJs-1

IA EL Ncareers-1 m-2A/m2 e1.60210-19C=As

)()()()( 1== sAeAICeAINcareer (4.4)

ext

IP

IP

eIEPNN careerphotonext

=

=

=

=

5

834

19

)(

1006.8

10998.210626.610602.1

)()(

(4.5)

Appendix

Mlm/m2PW/m2yKm 683lm/W

)()( yKPM m = (4.6)

EL EL

=

dF

FyKPM m)()'()'()'( (4.7)

')()'()'(')'(

ddF

FyKPdM m = (4.8)

MM

=

dF

dyFKPM m

)(

')'()'((4.9)

ELMlm/m2

=

dF

dyFKPM m

)(

)()((4.10)

Lcd/m2

ML = (4.11)

EL ELW J/s EL ELW/m2W/m2 Lcd/m2Mlm/m2 PW/m2 1

.indd 12 2009/10/19 14:46:49


13

W

555nm

1lm lm/m2

cd cd/m2

lx

4

1Lcd/m2 Mlm/m2 PW/m2 1

Lcd/m2 1 /683 2

Mlm/m2 1/ 1 1/683 2

PW/m2 1 683/ 683 1 1 555 nm 2 683

Km=683lm/W 555 nm

4-2 EL

ITO/-NPD50 nm/ Alq350 nm/ MgAg150 nm/ Ag10 nm

J - V 0 2.5 V 2.5 V EL EL 2.4 2.6 V10V80100 mA/cm2

4-1 -J-V

L - JEL

L-V 2.5 V EL

4-2 -L-J

Ex - J Alq3 -NPD

4-3 -Ex-J

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EL PLEL PL ELEL PL

4-4EL

PL UV-VisUV-Vis PLAppendix PL

4-5DCM Alq3

5 EL EL EL ELAppendix

61) 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, 2042.3) W. Herfrich and W. G. Schneider, Phys. Rev. Lett., 1965, 14, 229.4) W. Herfrich and W. G. Schneider, J. Chem. Phys., 1965, 44, 2902.5) W. D. Gill, J. Appl. Phys., 1972, 43, 5033.6) G. Pfi ster, Phys. Rev., 1977, B 16, 3676.7) P. M. Borsenberger, W. Mey and A. Chowdy, J. Appl. Phys., 1978, 49, 273.8) P. S. Vincett, W. A. Barlow and R. A. Hann, Thin Solid Films., 1982, 94, 171.9) G. G. Roberts, M. M. McGinniity, W. A. Barlow, P. S. Vincett, Solid State Commun., 1979,

32, 683.10) S. Hayashi, T. T. Wang, S. Matsuoka, S. Saito, Mol. Cryst. Liq. Cryst., 1986, 135, 355.11) C. W. Tang and S. A. VanSlyke, Appl. Phys. Lett., 1987, 51, 913.12) C. Adachi, S. Tokito, T. Tsutsui and S. Saito, Jpn. J. Appl. Phys., 1988, 27, L269.13) C. Adachi, S. Tokito, T. Tsutsui and S. Saito, Jpn. J. Appl. Phys., 1988, 27, L713.14) C. Hosokawa, H. Higashi, H. Nakamura, T. Kusumoto, Appl, Phys. Lett., 1995, 67, 3853.15) Y. Hamada, T. Sano, M. Fijita, T. Fujii, Y. Nishio and K. Shibata, Jpn. J. Appl. Phys., 1993,

32, L514.16) Y. Shirota, Y. Kuwabara and H. Inaba, Appl. Phys. Lett., 1994, 65, 807.17) 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, 539.18) Y. Ohmori, M. Uchida, K. Muro and K. Yoshino, Jpn. J. Appl. Phys., 1991, 30, L1938.19) Y. Ohmori, M. Uchida, K. Muro and K. Yoshino, Jpn. J. Appl. Phys., 1991, 30, L1941.20) 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, 2793.21) J. Kido, H. Shionoya and K. Nagai, Appl. Phys. Lett., 1992, 67, 2281.22) T. Wakimoto, Y. Fukuda, K. Nagayama, A. Yokoi, H. Nakata, M. Tsuchida, IEEE

Transactions Electron Devices, 1997, 44, 1245.23) N. Takada, T. Tsutsui and S. Saito, Appl. Phys. Lett., 1993, 63, 2032.24) 1998, 36, 479.25) EL 19p18.26) 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, 151.28) T. Tsutsui, M. Yang, M. Yahiro, K. Nakamura, T. Watanabe, T. Tsuji, Y. Fukuda, T.

Wakimoto, S. Miyaguchi, Jpn. J. Appl. Phys., 1999, 38, L1502.29) 51

1990, p1041.30) S. Hoshino and H. Suzuki, Appl. Phys. Lett., 1996, 69, 224.31) C. Adachi, M. A. Baldo, S. R. Forrest and M. E. Tompson, Appl. Phys. Lett., 2000, 77,

904.32) C. Adachi, M. A. Baldo, S. R. Forrest, S. Lamansky, M. E. Thopmson and R. C. Kwong,

Appl. Phys. Lett., 2001, 78, 1622.33) C. Adachi, R. C. Kwong, P. Djurovich, V. Adamovich, M. A. Baldo, M. E. Thompson and S.

R. Forrest, Appl. Phys. Lett., 2001, 79, 2082.34) S. Tokito, T. Iijima, Y. Suzuki and F. Sato, Appl. Phy, Lett,. 2003, 83, 569.35) K. Sugiyama, H. Ishii, Y. Ouchi and K. Seki, J. Appl. Phys., 2000, 87, 295.36) EL 72001, p.103.37) T. Wakimoto, Y. Fukuda, K. Nagayama, A. Yokoi, H. Nakada and M. Tsuchida, IEEE Trans.

Electron Devices, 1997, 44, 1245.38) Y. Sato, T. Ogata, S.Ichisawa, M.Fugono and H. Kanai, Proc. SPIE, 1999, 3797, 198.39) 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, 7991.40) N. C. Greenham, R. H. Friend and D. D. C. Bradlay, Adv. Mater., 1994, 6, 491.41)

50No3, 2003, 1408.42) G. Gu, D. Z. Garbuzov, P. E. Burrows, S. Venkatesh, S. R. Forrest and M. E. Thompson,

Opt. Lett., 1997, 22, 396.43) S. Moller and S. R. Forrest, J. Appl. Phys., 2002, 91, 3324.44) M. Fujita, T. Ueno, T. Asano, S. Noda, H. Ohhata, T. Tsuji, H. Nakada, N. Shimoji, Electron.

Lett., 2003, 39, 1750.45) 1977.46) P. E. Burrows, Z. Shen, V. Bulobic D. M. McCarry, S. R. Forrest, J. A. Cronin, M.E.

Tompson, J. Appl. Phys., 1996, 79, 7991.47) H. Aziz, Z. D. Popovic, S. Xie, A. M. Hor, N. X. Hu, C. Tripp, G. Xu, Appl. Phys. Lett.,

1998, 72, 756.48) T. Ikeda, H. Murata, Y. Kinoshita, J. Shike, Y. Ikeda, M. Kitano, Chem. Phys. Lett., 2006,

426, 111.

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EL


15

Appendix EL

A1-14 ELlm/Wcd/A

A1-1-1int

rf

ext EL

Np Ne

IA PW Sm2m

eC hJs

A1-1-2e

MW

c

L

A1-2

A1-2-1intrfA-2.1

A-1 I IeIh IeIh IrA-2.2A-2.3

Organic layerAnode Cathode

A-1 EL

.indd 15 2009/10/19 14:46:57

EL


Ir I

I = Ih = IeIh = Ie = 0 I = Ih = Ie = Ir=1.0

I = Ih > IeIh 0Ie = 0

I = Ih = Ie + IhIr = Ie = Ih - Ih

I = Ie > IhIe 0Ih = 0 I = Ie = Ih + IeIr = Ih = Ie - Ie

Ih 0, Ie 0 A-2.7

1.0

rrehTS 3:1

Triplet-Triplet annihilationA-2.10A-2.11A-2.102 1T*

A-2.11 2 0A-2.10

1

03 3

1012 cm-3A-2.1281 3

A-2.12 T Sint

51A-2.9A-2.14A-2.15

r Sdir 0.25 -Sint 0.40

ff 1EL 1ffff Kr=1 / TrTr Kt EL Knr

f

A-2.18f = 1.0Knr > Krf < 1.0 1.0 Alq3 1EL 100

.indd 16 2009/10/19 14:47:00

EL


17

A1-2-2 A-2ext3

A-2

Rf:Rb:c:c:d:

ELccc

norg

c 1-cos sin2/2 norg 1.0A-2.21

A-2.21

c Rf EL

/ Rb

m

ext

c1.7A-2.19 19A-2.21 17

m RfRb RfRb ELTEtransverse electric modeTMtransverse magnetic mode 50cRfRb Rf 520 nm 0.014 Rb / 0.90m = 0.95

ext =18 EL 80 n>1.0

ext

0.05 1.00.2

ext 0.2 1.0r 0.25f 1.0

A1-3 ELEextextPinW/m2 PemW/m2Eint Pem / Pin VV JA/m2 Pin = J V 1 hc / hcPem hc / F PemA-3.1

F0 PemLUA-3.1EintA-3.2

int

.indd 17 2009/10/19 14:47:03

EL


Nin Nem Nem / Nin

J / e - J / e JA/m2Nin = J / eeint

EpEp = Pem / Nem

A-3.2A-3.5EintintA-3.6

Eextext

A1-4

PW Lcd/m2

Lcd/m2 EL F yMlm/m2

ELO Rm 0rad+d dS

dsr

EL Icdd dMlm

Mlm

I0cd

Mlm

ELL0cd/m2Mlm/m2

EL 0 /2= /2Mlm/m2

555 nmW lmKm680 lm/W ELMlm/m2A-3.2

A-4.8A-4.9 F0

A-3.2A-3.7A-4.10EextA-3.4A-3.8A-4.10extA-4.11A-4.12

.indd 18 2009/10/19 14:47:08

EL


19

A-4.11A-4.12

mA-4.11A-4.12

A-4.13A-4.14 20 30

Appendix - 3

PL

Alq3 DCM DCM EL

AppendixA3-1 2

RGB RedGreenBlue 3 RGB 3RGB 3100

0

CMY CyanMagentaYellow 3CMY 3 100

A-1

A3-2

CRT CIECIE CIECommission Internationale de lEclairage 1931 3 RGB 3 RGBRGB 1 R G B2 xy CIE1931

NTSCNational Television Standards Committee 1953CRTNTSCCRTR0.67,0.33G0.21,0.71B0.14,0.08W0.310,0.316NTSC

A-2CIE1931

.indd 19 2009/10/19 14:47:11

2-12-22-32-4 33-13-23-33-44-14-2

URL

http://www.sigma-aldrich.com/mscatalog-jpMaterial [email protected]

Aldrich

TM

SAJ1146 2009.10

2009101Websigma-aldrich.com/japan

TM

Generation and Storage

Vol. 3, No. 4

Alternative Energythe way to go

Material Matters 3-4.indd 1

Alternative Ener

TM

Vol. 4, No. 1

Morphing Materials into Mea

ning

Controlled Synthesis & Proper

ties

2009/07/13 15:49:0

.indd 20 2009/10/19 14:47:14

Documents

材料科学の基礎 - Sigma-Aldrich: Analytical, Biology .... 1, No. 1 有機EL の動作機構 および構造 有機EL の作製方法 測定データの整理 有機EL の効率に

材料科学の基礎 - Sigma-Aldrich: Analytical, Biology .... 1, No. 1 有機EL の動作機構および構造有機EL の作製方法測定データの整理有機EL の効率に