溶液プロセスによる有機半導体膜の構造制御とデバイス応用

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九州大学学術情報リポジトリ

Kyushu University Institutional Repository

溶液プロセスによる有機半導体膜の構造制御とデバイス応用

青木, 陽一

https://doi.org/10.15017/1866323

出版情報：Kyushu University, 2017, 博士（工学）, 課程博士

バージョン：

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1 EL

(4)

1 2

1.1 . . . 2

1.2 EL . . . 3

1.3 . . . 5

1.4 . . . 6

1.5 . . . 10

2 EL 11 2.1 EL . . . 11

2.2 EL . . . 14

2.3 EL . . . 18

2.4 EL . . . 21

3 24 3.1 . . . 24

3.2 . . . 24

3.3 . . . 28

3.4 . . . 34

4 ESDUS 40 4.1 . . . 40

4.2 ESDUS . . . 40

4.3 . . . 41

4.4 . . . 42

4.5 . . . 51

5 ESDUS EL 54 5.1 . . . 54

5.2 ESDUS . . . 54

5.3 EL . . . 58

6 59 6.1 . . . 59

6.2 . . . 62

6.3 EL . . . 69

6.4 EL . . . 71

6.5 . . . 82

7 85 7.1 . . . 85

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1

1.1

1987

C.W.Tang nm

[1] 2005

RGB 40 EL

EL

2003 4 20 TFT

40 EL

1,000∼2,000 1997

EL ^{[2, 3]}

EL

1.1:

EL

×

× ×

×

(6)

1.2 EL

EL 1987 C.W.Tang

Alq₃ tris(8-hydroxyquinoline)aluminum

Mg Ag nm

10 V ≥1000 cd/m² 1%

1.1 ^[1]

[4] 1988

EL

[5, 6] EL 5

RGB 40

Glass substrate ITO

Diamine Alq3 Mg:Ag

h㱙

-

+

N Al O N

N O

O N N

CH3

H3C

CH3

S Alq³

Diamine

1.1: Tang EL

(7)

C.W.Tang

[10]

1990 J.H.Burroughes

poly(p-phenylenevinylene) PPV PPV

EL

1.2 ^[11–13] 1983

[14, 15]

π

[8]

PPV polyacteylene PA poly(p-phenylene) PPP poly(p- phenylenevinylene) PPV poyfluorene PF polyaniline PAni polypyrrole PPy polythiophene PT

PPV poly[2-methoxy-5-(2-ethylhexyloxy)-p-phenylenevinylene] MEH-PPV

ITO/PAni/MEH-PPV/Ca 2∼2.5% 3∼4.5 lmW⁻¹

[9] PAni poly(3,4-ethylenedioxythiophene)

PEDOT

CH2Cl

ClH2C S

CH3OH,heat S

S

+Cl^-

S+Cl^-

n n

250 ,vacuum

1. ^-OH 2. H⁺ 3. Dialysis

(8)

1.3 EL

2

wt%

1.3

1 2 µm

3 4

High-speed rotation Droplet

Substrate

Spincoater

Organic thin layer

1.3:

(9)

1.4

Flat panel display

RGB sub-pixel matrix

R

G B

M Y

C W

1.4:

R G B

1.4 EL

RGB RGB

EL RGB

RGB

EL RGB

RGB RGB

RGB

µm

RGB 1 RGB

[7, 16–19]

RGB

EL RGB

[20–22] [23, 24] [25–27]

[28–31] [32, 33] [34] 1.6

1pL

(10)

1.5

50mPa·sec 50mN/m

Polymer droplet

1.5:

EL RGB

π

ITO electrode Insulator Bulk Inkjet Nozzle

Film substrate

Drum

Ink

(11)

Glass Substrate Organic Layer Metal Cathode

ITO Anode

Driver IC

1.7: EL

EL

1.7

EL FET

1.8 1

2 3

4 5

EL

•

• nm

•

(12)

Glass substrate ITO Anode

Emissive polymer (ETL/EL) Cathode

R

- +

G B

Glass substrate ITO anode

White-Emissive polymer (EL) Cathode

- +

R G B

Color filter

Glass substrate ITO anode

Blue-Emissive polymer (EL) Cathode

-

+

R G B

Fluorescent material

Glass substrate ITO Anode

Emissive polymer (ETL/EL) Cathode

R

-

+

GB RGB RGB

Transparent electrode

1.8: EL RGB RGB

RGB

(13)

1.5

ppm Evaporative Spray Deposition from Ultra-dilute Solution ESDUS

1.9 ESDUS

ESDUS EL

EL

[35, 36]

EL EL

ESDUS

Glass sbstrate

Polymer solution particle

Photoresist film Metal mask

Glass sbstrate

Glass sbstrate Glass sbstrate

１２

４３

1.9: ESDUS

(14)

2 EL

2.1 EL

Glass substrate Anode Organic layer Cathode

-

+ ^hole

electron

hν

ーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーーー

Anode Ec

S1

Ev

Organic layer Cathode S0

hʚ

ーーーーー

2.1: EL

EL

2.1 100 nm

Highest Occupied Molcular Orbital HOMO Lowest Occupied Molcular Orbital LUMO

Indium Tin

Oxide ITO UV 4.8 eV

5.0∼6.5 eV HOMO 1 eV

π π

meV

1 3

2.2

(15)

- S1 T1 100%

100%

π

25% 60% ^{[37, 38]}

ηint

N_in N_em

η_int= N_em

N_in (2.1)

ηint γ

η_r φ_f

η_int=γ·η_r·φ_f (2.2)

γ

1.0 1.0

1 η_r

1 3

η_r 0.25

φ_f

1.0

ηint = γ·ηr·φ_f

= 1.0×0.25×1.0

= 0.25 (2.3)

η_ext η_ext η_int

χ

ηext=χ×ηint (2.4)

n 1.0

χ

χ= 1

2n² (2.5)

EL 1.7 χ 0.2

(16)

η_int γ

η_r φ_f χ

η_ext=η_int·γ·η_r·φ_f ·χ (2.6) 5%

非発光性三重項励起子正孔・電子の結合

発光性一重項励起子

発光

外部への発光内部消光

余剰な正孔・電子

正孔電子

熱失活 η

ext

η

f

η

r

γ

2.2:

Glass substrate

Forward-Scatterd Light Waveguided Light

OLED

Glass substrate

Forward-Scatterd Light Glass Mesa

OLED

2.3:

(17)

2.2 EL EL

(lm)

η_e(lm/W) EL L(cd/m²)

P_i(W/m²) η_e(lm/W)

η_e(lm/W) =π× L(cd/m²)

Pi(W/m²) (2.7)

EL η_c(cd/A)

ηc(cd/A) = L(cd/m²)

J(A/m²) (2.8)

P_in(W/m²) P_emis(W/m²)

λ hc/λ

hc/λ λ_L λ_U P_emis

P_emis =F₀

! _λ_U

λL

F(λ)hc

λdλ (2.9)

EL F(λ)

F₀

ηint Nin

N_emis N_emis/N_in

J e N_in=J/e

N_emis

N_emis =F₀

! _λ_U

λL

F(λ)dλ (2.10)

η_int

η_int = N_emis N_in

= eF₀ J

! λU

λ

F(λ)dλ (2.11)

(18)

K_m(683lm/W) y(λ) χ

M =χF₀

! λU

λL

hc

λF(λ)K_my(λ)dλ (2.12)

M =πL (2.13)

F₀

F₀ = πL χK_mhc

! _λ_U 1

λL

F(λ)

λ y(λ)dλ

(2.14)

η_ext L(cd/m²)

J(A/m²) λ EL F(λ) 2.7 y(λ)

e 1.602×10⁻¹⁹ C h 6.6261×10⁻³⁴ J·s c 2.99×10⁸ m/s² K_m 683 lm/W

η_ext= πLE K_mhcJ

! _λ_U

λL

F(λ)dλ

! _λ_U

λ_L

F(λ)

λ y(λ)dλ

(2.15)

EL η_ext

EL EL Keithley

238 Topcom BM-5A ADVANTESR 6817E-DC

2.4 2.5 2.6

(19)

OLED hν

Current source

Computer Digital multimeter

GPIP in-out put Cryostat

+ - Spectrometer

649025794 cd

649025794 mA

Computer Spectra analyzer

SCSI

649025794 cd

2.4: - - I-V-L

OLED hν

Current source

Computer Digital multimeter

GPIP in-out put Cryostat

+ - Luminance colorimeter

649025794 cd

649025794 mA

2.5: EL

(20)

OLED hǵ

Cryostat

+-

Mesurement system

2.6: EL

0 0.2 0.4 0.6 0.8 1 1.2

200 300 400 500 600 700 800

2.7:

(21)

2.3 EL

EL

ITO 150nm

10Ω/ ITO 4.6∼5.0eV HOMO

5.0∼5.5eV ITO

300

ITO nm

PEDOT:PSS poly(3,4-ethylene dioxythiophene) : poly(styrene sul-

fonate) PEDOT:PSS

PEDOT

2.0 cm²V⁻¹S⁻¹ 600 Scm⁻¹

[41, 42] PEDOT:PSS ITO

[43]

ITO ITO

PEDOT:PSS Chloroform Toluen

S O O

n SO3H

n

PEDOT PSS

(22)

RGB R MEH- PPV Poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene-vinylene] - End capped with DMP M_w(GPC vs PS)=1000000 American Dye Source Inc. ADS100RE Lot♯04B008PA G CN-PDHFV Poly[(9,9-dihexyl-2,7-(2-cyanodivinylene)- fluorenylene)] M_w(GPC vs PS)=120000 American Dye Source Inc. ADS127GE Lot♯04G058PA B PFO Poly(9,9-dioctylfluorenyl-2,7-diyl) - End capped with DMP M_w(GPC vs PS)=140000 American Dye Source Inc. ADS129BE Lot♯021029W 2.8

H₃CO

O

n

C₈H₁₇ C₈H₁₇

CN

n ^C⁸^H¹⁷ ^C⁸^H¹⁷ ⁿ

MEH-PPV CN-PDHFV PFO

2.8: EL

(23)

LiF 0.5nm

2.9

I-V-L

EL

Mg Ag Mg:Ag=9:1 LiF

0.5nm /Al 80nm EL

EL

LiF Al CsCO₃

CsCO3

EL

Vaccum pump Chamber

Substrate

Heat board Sublimed material Quartz oscillator

Reagent

Shutter

2.9:

(24)

2.4 EL

EL ITO

2.10

ITO SLR

OFPR-800 NMD-3 Hydrochloric acid

Nitric acid

7-NL Aceton

Ethanol Chloroform Toluene THF

Lithium Fluoride Cesium carbonate Alminium

0.5µm 13JP050AN ADVANTEC

0.45µm 13HP045AN ADVANTEC

SS-1-10 K-359 S-1

UV ROBOLIGHT MODEL BOX-7

UV NL-UV253

ULVAC

(25)

㪧㪜㪛㪦㪫㪑㪧㪪㪪㩷㪪㫇㫀㫅㪄㪺㫆㪸㫋㫀㫅㪾㪈㪉㪇㷄㩷㪘㫅㫅㪼㪸㫃㫀㫅㪾㩽

㪜㫄㫀㫊㫊㫀㫍㪼㩷㫇㫆㫃㫐㫄㪼㫉㪪㫇㫀㫅㪄㪺㫆㪸㫋㫀㫅㪾㩷㫆㫉㩷㪪㫇㫉㪸㫐㪄㫆㫅㪍㪇㷄㪃㪍㪇㫄㫀㫅㩷㪘㫅㫅㪼㪸㫃㫀㫅㪾㩷㫀㫅㩷㫍㪸㪺㫌㫌㫄㩷㩽

㪣㫀㪝㩷㪸㫅㪻㩷㪘㫃㪭㪸㪺㫌㫌㫄㩷㪻㪼㫇㫆㫊㫀㫋㫀㫆㫅㪤㪼㫋㪸㫃㩷㪚㪸㫋㪿㫆㪻㪼

㪜㫄㫀㫊㫊㫀㫍㪼㩷㪧㫆㫃㫐㫄㪼㫉

㪧㪜㪛㪦㪫㪑㪧㪪㪪㪪㫋㫉㫀㫇㪼㪄㫇㪸㫋㫋㪼㫉㫅㪼㪻㩷㪠㪫㪦㩷㫆㫅㩷㪾㫃㪸㫊㫊㩷㫊㫌㪹㫊㫋㫉㪸㫋㪼

2.10: EL

ITO ITO

1. ITO 100 mm×100 mm

2.

1st : 800 rpm,10sec 2nd : 1200 rpm,20sec

3. 90 30

4. 2mm UV 10

5 5. ITO

6. : : 1:1:3

8 - 12 7.

8. ITO 20 mm 20 mm

1. ITO 5

2. 3% 15 ×2

3. 15 ×2

×

(26)

1.

2. UV UV 20

PEDOT:PSS

1. 0.45µm PEDOT:PSS

2. PEDOT:PSS ITO 1500rpm,30sec

3. 120

1. Chloroform 1wt% 6

2. 0.5µm

3. 500∼3000rpm,30sec

4. 60 60

ESDUS

1. THF 4ppm

2. ESDUS 3.

LiF Al

1. LiF 1mg Al 100mg

2. 2mm ITO 2mm

3. 2.0∼4.0×10⁻⁶Torr LiF 1.0nm Al 80nm 0.1˚A/s

(27)

3

3.1

RGB

ESDUS EL

RGB

3.2

RGB 500∼3000rpm

3.1

EL 3.2 3.3 3.4

100nm

Glass substrate ITO (Anode) PEDOT:PSS (HTL) Emissive polymer (ETL/EL) LiF

Al (Cathode)

hν

- +

PEDOT:PSS ITO

4.2 eV

5.0 eV 4.8 eV

LiF / Al 5.1 eV

PFO 3.5 eV

6.0 eV 5.8 eV

2.9 eV 2.9 eV

CN-PDHFV

MEH-PPV or or

Emissive polymer layer

3.1: ITO/PEDOT:PSS(30nm)/Emissive polymer/LiF(1.0nm)/Al(80nm)

(28)

- V-I - V-L

- I-Q EL

3.2: ITO/PEDOT:PSS(30nm)/MEH-PPV(Xnm)/LiF(1.0nm)/Al(80nm) -

- I-V-L - I-Q EL

90nm 130nm 150nm 220nm

(29)

- V-I - V-L

- I-Q EL

3.3: ITO/PEDOT:PSS(30nm)/CN-PDHFV(Xnm)/LiF(1.0nm)/Al(80nm)

- - I-V-L - I-Q EL

80nm 120nm 150nm 200nm

(30)

- V-I - V-L

- I-Q EL

3.4: ITO/PEDOT:PSS(30nm)/PFO(Xnm)/LiF(1.0nm)/Al(80nm) - -

I-V-L - I-Q EL

70nm 100nm 180nm 270nm

(31)

3.3

Tg

ESDUS 120∼140

30∼120 T_g

75 MEH-PPV

CN-PDHFV PFO

500∼3000rpm 140 5

RGB

130nm 60 60

140 5 3.5

3.1 I-V-L

Q 3.6 3.7 3.8 3.9

I-V-L

100nm

Al (Cathode)

hν

- +

3.5: EL

3.1: EL

V [V] I [mA/cm²] L [cd/m²] Q [%]

MEH-PPV(not Annealed) 7.00 382.5 305.2 0.059

MEH-PPV(Annealed) 10 389.7 209.8 0.102

CN-PDHFV(not Annealed) 9.25 299.1 2066 0.27 CN-PDHFV(Annealed) 10.00 385.8 2633 0.30

(32)

MEH-PPV

CN-PDHFV PFO

3.6: EL EL :MEH-PPV :CN-

PDHFV :PFO

(33)

- V-I - V-L

- I-L - I-Q

3.7: ITO/PEDOT:PSS(30nm)/Annealed MEH-PPV(Xnm)/LiF(1.0)/Al(80nm)

- - I-V-L - I-Q

100nm 140nm 170nm 270nm

(34)

- V-I - V-L

- I-L - I-Q

3.8: ITO/PEDOT:PSS(30nm)/Annealed CN-PDHFV(Xnm)/LiF(1.0nm)/Al(80nm)

- - I-V-L - I-Q

60nm 80nm 100nm 120nm

(35)

- V-I - V-L

- I-L - I-Q

3.9: ITO/PEDOT:PSS(30nm)/Annealed PFO(Xnm)/LiF(1.0nm)/Al(80nm)

- - I-V-L - I-Q

130nm 150nm 170nm 200nm

(36)

3.4

CsCO3

[55]

2-ethoxyethanol 0.1∼0.5wt%

2000rpm 30 60 60

LiF Lithium fluoride 2-ethoxyehanol

LiF 2-ethoxyehanol CsCO3

EL 3.10

3.2 I-V-L

Q 3.4 3.12 3.13

I-V-L

LiF CsCO3

CsCO₃ LiF

LiF

Glass substrate ITO (Anode) PEDOT:PSS (HTL) Emissive polymer (ETL/EL) Cs²CO³

Al (Cathode)

hν

-

+

3.10: ITO/PEDOT:PSS(30nm)/CN-PDHFV or PFO(80nm)/X/Al

3.2: ITO/PEDOT:PSS(30nm)/CN-PDHFV or PFO(80nm)/X/Al

V [V] I [mA/cm²] L [cd/m²] Q [%] EL [nm]

CN-PDHFV LiF : V.D. 7.5 486.0 3591.0 0.45 499.8, 532.7 LiF : Spincoat 6.75 89.6 340 0.30 500.2, 535.7 CsCO₃ 6.75 377.2 635 0.09 498.8, 535.2

Non 8.5 47.0 80.44 0.08 539.1

PFO LiF : V.D. 8.5 596.5 163 0.12 447.4

LiF : Spincoat 7.0 375.5 429.4 0.06 480.4

CsCO₃ 7.75 291.0 92.7 0.03 480.4

Non 8.0 124.8 51.6 0.03 479.9

(37)

CN-PDHFV

PFO

3.11: ITO/PEDOT:PSS(30nm)/Emissive polymer(Variable thickness)/X/Al(80nm)

EL :CN-PDHFV :PFO

LiF LiF Cs(carbo)

(38)

- V-I - V-L

- I-L - I-Q

3.12: ITO/PEDOT:PSS(30nm)/CN-PDHFV(80nm)/X/Al(80nm) - -

I-V-L - I-Q EL

LiF

LiF Cs(carbo)

(39)

- V-I - V-L

- I-L - I-Q

3.13: ITO/PEDOT:PSS(30nm)/PFO(90nm)/X/Al(80nm) - - I-

V-L - I-Q

LiF LiF

Cs(carbo)

(40)

ITO EL

EL 3.14 ITO µm

ITO ITO

1st:300rpm,3s 2nd:2000rpm,20s 3rd:5000rpm,0.5s OFPR-800

N-HC600 1µm 80 20

30

N-A5 60 3.15 120 5

6 ITO

ITO 3.16

Development UV irradiation

Glass substarate

Photosensitive film (Nega-type) Shadow mask

UV irradiation

Glass substarate

Photosensitive film (Posi-type) Shadow mask

Development

3.14:

3.15: : :

(41)

3.16: ITO

ITO PEDOT:PSS 1500rpm,30sec

120 CN-

PDHFV 2000rpm,30sec

60 60

2.0∼4.0×10⁻⁶Torr LiF 1.0nm Al 80nm 0.1˚A/s

3.17 OLED ITO

3.17: ITO EL

(42)

4 ESDUS

4.1

ppm

ESDUS ESDUS

ESDUS nm EL I-V-L

[56]

4.2 ESDUS

4.1 ESDUS ( 60cm

120cm) ( 40cm 80cm)

8mm 5mm 4mm 3mm 20mm

Ceramic heater Glass substrate

Exhaust

Sample solution 0.5μm filter

Heater

N2 Gas

Nebulizer Heater

Chamber

X-Y positioner Nozzle

Deposition room

Heater

4.1: ESDUS

(43)

4.3

4ppm THF NP-KX-700

120ml/min

0.5µm CRF-2

AKI37 N₂ 120 - 160l/min

N₂ 10µm

N2

MS-1 4.2 ESDUS

UV-Vis-NIR UV-3150 Xe900,M300,S300 Edinburgh Instruments

Nanopics 100 SII

R_ave P-V R_{RM S}

Glass sbstrate

Polymer solution particle

Diffusion

Stable nuclide

4.2: ESDUS

(44)

4.4

MEH-PPV 4ppm THF ESDUS

60cm 120cm 8mm

20mm N₂ 155l/min

120ml/min 40 120 4

120

THF (a)40 (b)80

(c)120 (d)160 (e)200 40

THF

80 THF

THF THF

30 (f)40 (g)80

(h)120 (i)160 4.1

AFM 4.4 R_ave

P-V RRM S 20µm×20µm

T h 4 ref

Toluene 1wt%

4.1: ESDUS

T [ ] h [nm] R_ave [nm] P-V [nm] R_{RM S} [nm]

(a) 40 10 2.16 117.4 3.65

(b) 80 99.9 6.67 221.7 10.42

(c) 120 60 5.42 249.7 10.17

(d) 160 298.5 4.23 130.1 6.28

(e) 200 113.9 4.85 145.9 6.93

(f) 40 - - - -

(g) 80 115.9 6.13 163.1 8.47

(h) 120 203.9 6.02 121.3 7.99

(i) 160 123.0 70.71 501.4 86.51

ref - 70 0.61 66.7 1.38

(45)

4.4

80 120

160 120

(h)

EL ITO/PEDOT:PSS(30nm)/MEH-PPV(90nm)/LiF(0.5nm)/Al(80nm)

4.3 I-V-L

I-V

ESDUS L=8.89cd/m²

120

THF THF 1-Butanol %

1-Butanol

MEH-PPV T_g 75

50

4.3: I-V-L ESDUS

(46)

(a) (b) (c)

(d) (e) (f)

(g) (h) (i)

4.4: 80µm×80µm

40 (a) - (e) 30 (f) - (i)

(a)40 (b)80 (c)120 (d)160 (e)200 (f)40 (g)80 (h)120 (i)160

(47)

50

MEH-PPV THF MEH-PPV

MEH-PPV THF

THF MEH-PPV

MEH-PPV

MEH-PPV 4ppm

THF ESDUS

40cm 80cm 8mm 20mm

N₂ 120l/min 120ml/min

50 40 50 120

(a) - (f)

4.2 MEH-PPV

R_ave P-V R_{RM S}

AFM 4.5 4.6

4.2: MEH-PPV

(a) 80 34.9 2.82 142.0 5.1

(b) 100 95.2 3.19 220.9 9.54

(c) 120 102.8 7.42 213.2 10.35

(d) 140 92.1 9.12 239.1 12.57

(e) 160 95.7 11.53 168.1 14.9

(f) 180 130.1 11.5 256.6 17.0

(48)

(a) (b) (c)

(d) (e) (f)

4.5: MEH-PPV 20µm×20µm

(a)80 (b)100 (c)120 (d)140 (e)160 (f)180

(a) (b) (c)

(49)

4.5 AFM ESDUS MEH-PPV 120

nm P-V

CN-PDHFV 140

PFO

60 1nm

80 100 N₂

4.3 AFM 4.7

4.8 PFO 120 ESDUS

4.3: PFO

(a) 80 - - - -

(b) 100 - - - -

(c) 120 89.9 1.50 19.7 1.92

(d) 140 45 1.06 30.0 1.47

(e) 160 126 2.91 24.4 3.54

(f) 180 379 12.55 77.5 15.14

ESDUS -

4.4 4.9 THF

MEH-PPV π

ESDUS THF ESDUS

(50)

4.4:

polymer state P L_max [nm] UV_max [nm]

MEH-PPV ESDUS 567.0 509.6

Spincoat 606.5 486.5

in THF 556.5 501.5

CN-PDHFV ESDUS 535.0 441.5

Spincoat 501.0 443.5

in THF 486.0 442.0

PFO ESDUS 448.5, 489.5 399.0 Spincoat 440.0 382.0

in THF 421.0 393.0

(51)

(a) (b) (c)

(d) (e) (f)

4.7: PFO 20µm× 20µm

(a)80 (b)100 (c)120 (d)140 (e)160 (f)180

(a) (b) (c)

(52)

MEH-PPV - MEH-PPV

CN-PDHFV - CN-PDHFV

(53)

4.5 ESDUS

[57] 4.10 4.11

R 40µm 100µm 10µm

ESDUS THF

THF

4.12 a

b c

d

4.14

4.10: ESDUS

4.11:

(54)

(a) (b)

(c) (d)

4.12: (a) (b)

(c) (d)

4.13: ESDUS

(55)

R G

R G 2

R G

4.14 ESDUS

Photosensitive film Shadow mask

Remove the mask

Overlay the mask Remove the mask

Glass substarate

Spray-on Spray-on

4.14:

PL

(56)

5 ESDUS EL

5.1

ESDUS FET EL

EL

THF

5.2 ESDUS

RGB EL

5.1 I-V-L

Q EL

5.1 5.2 5.3 ESDUS

THF

5.1 ESDUS MEH-PPV EL EL

MEH-PPV π

X

5.1: EL I-V-L

V [V] I [mA/cm²] L [cd/m²] Q [%]

MEH-PPV(Spincoat) 7.0 382.5 305.2 0.059 MEH-PPV(ESDUS) 9.25 369.3 158.1 0.056 CN-PDHFV(Spincoat) 6.50 322.0 2479.0 0.27 CN-PDHFV(ESDUS) 8.0 666.6 2869.0 0.29 PFO(Spincoat) 10.75 363.3 588.0 0.097

PFO(ESDUS) 12.75 756.7 900.3 0.064

(57)

- V-I - V-L - V-L

- I-Q EL

5.1: ITO/PEDOT:PSS(30nm)/MEH-PPV(130nm)/LiF(1.0nm)/Al(80nm)

- - I-V-L - I-Q EL

ESDUS

(58)

- V-I - V-L - V-L

- I-Q EL

5.2: ITO/PEDOT:PSS(30nm)/CN-PDHFV(80nm)/LiF(1.0nm)/Al(80nm)

- - I-V-L - I-Q EL

ESDUS

(59)

- V-I - V-L - V-L

- I-Q EL

5.3: ITO/PEDOT:PSS(30nm)/PFO(140nm)/LiF(1.0nm)/Al(80nm) - -

I-V-L - I-Q EL

ESDUS

(60)

5.3 EL

ESDUS R G EL

5mm ITO

PEDOT:PSS ESDUS

Li/Al 5.4

5.5

EL

R G

ー

+

Light-sensitive film

hν

Al (Cathode)

hν

5.4: EL

5.5: EL EL

(61)

6

6.1

1989 C.W.Tang Alq3 DCM

EL 2

6.1 0.1 - mol%

[44]

k_H∗→G

H^∗+G−→H+G^∗ (6.1)

S T

I. S_H∗+S_G−→S_H +S_G∗ (6.2) II. T_H∗+S_G −→S_H+T_G∗ (6.3) III. TH^∗+SG−→SH +SG^∗ (6.4) IV. S_H∗+S_G −→S_H+T_G∗ (6.5)

I -

-

II

III IV. -

-

v f_H^′ (v) ε_G(v)

N R -

K² 0 - 4

K²= 2/3

k_H∗→G= 9000K²ln10 128π⁵n⁴Nτ₀R⁶

! f_H^′ (v)ε_G(v)

v⁴ dv (6.6)

(62)

2.

3. -

τ₀

τ φF L

τ₀ =τ/φ_{F L}

k_H∗→G = 9000K²ln10φ_{F L} 128π⁵n⁴NτR⁶

! f_H^′ (v)ε_G(v) v⁴ dv

=

"

1 τ

# "

R₀ R

#6

(6.7)

R⁶₀ = 9000K²ln10φ_{F L} 128π⁵n⁴N

! f_H^′ (v)ε_G(v)

v⁴ dv (6.8)

R = R₀ k_H∗→G = 1/τ

R

R0 R0 R

6 R0

k_H∗→G=

"

2π h

# K²exp

"

−2R L

# !

f_H^′ (v)ε^′_G(v)dv (6.9)

K R L

- 6.2

-

EL

[58, 59]

EL PFO

MEH-PPV PFV

(63)

H*

H

G*

R〜10nm R〜1nm

TH* SG SH TG*

-

6.1:

(1)

(2)

H*

H

G*

Host Guest

H*

H

G*

6.2: EL

1 EL

(64)

6.2

MEH-PPV

[16, 45–48]

poly(N-vinylcalbazole) PVK

[49] PFO

wt% MEH-PPV

EL PFO MEH-PPV

1.3eV

[50]

CN-PDHFV

3 6.3

EL

CN-PDHFV MEH-PPV

MEH-PPV R CN-PDHFV G PFO B

R5G20B75 R5B95 R5B95 R100

6.4 MEH-PPV 6.5

6.6 6.7 ME-PPV

R5G20B75

PFO CN-PDHFV MEH-PPV

Energy Energy

PFO CN-PDHFV MEH-PPV

Energy level

hν

6.3: EL MEH-PPV

CN-PDHFV PFO

(65)

R5G20B75 R5B95

R5B95 R100

6.4: EL EL

R5G20B75 50nm 100nm 130nm 170nm R5B95

70nm 110nm 150nm R5B95 100nm 130nm

220nm 340nm R100 90nm 130nm 150nm

220nm

(66)

- V-I - V-L

- I-L - I-Q

6.5: ITO/PEDOT:PSS(30nm)/R5G20B75(Xnm)/LiF(1.0nm)/Al(80nm) -

- I-V-L - I-Q 50nm

100nm 130nm 170nm

(67)

- V-I - V-L

- I-L - I-Q

6.6: ITO/PEDOT:PSS(30nm)/R5G95(Xnm)/LiF(1.0nm)/Al(80nm) -

- I-V-L - I-Q 70nm

110nm 150nm

(68)

- V-I - V-L

- I-L - I-Q

6.7: ITO/PEDOT:PSS(30nm)/R5B95(Xnm)/LiF(1.0nm)/Al(80nm) -

- I-V-L - I-Q 100nm

130nm 220nm 340nm

(69)

MEH-PPV

MEH-PPV Chroloform

6.9 - 6.8

PMA-11 UV-Vis-NIR

UV-3150 Xe900,M300,S300 Edinburgh Instruments

MEH-PPV CN-PDHFV PFO

6.1 I-V-L

Q φ_f 380nm

6.1: EL

V [V] I [mA/cm²] L [cd/m²] Q [%] φ_f [%]

R5G20B75 13.75 154.1 1616 1.16 45

R5G95 13.25 448.75 829.0 0.93 22

R5B95 23.00 346.7 2273 0.39 34

R100 7.00 382.5 305.2 0.06 9

6.8:

(70)

6.9: R100 G100

B100 R5G95 R5B95 R5G20B75

120nm(R100) 90nm(G100) 85nm(B100) 108nm(R5G95) 147nm(R5B95) 90nm(R5G20B75) 6.9

MEH-PPV

R5G95 R5B95 R5G20B75 EL

R5G20B75

PFO CN-PDHFV

EL

6.8 R5B95 EL

R5G95

R5B95 1.3eV

Ca

(71)

6.3 EL

EL EL

EL

PVK RGB

[51–53] RGB

G B

R

RGB

EL ^[54]

RGB

CIE¹ CT color temperature CRI the

color rendering index CIE 0.333

0.333

6.10 EL

R5G10B90 6.11

R5G10B90 MEH-PPV R1G5B95 R1G1B100 6.12

Glass substrate ITO (Anode) PEDOT:PSS (HTL) Mixed RGB (ETL/EL) LiF

Al (Cathode)

Jǵ

PEDOT:PSS ITO

4.2 eV

5.0 eV 4.8 eV

LiF / Al 5.1 eV

PFO / CN-PDHFV / MEH-PPV 3.5 eV

6.0 eV 5.8 eV 2.9 eV

(72)

6.11: EL R5G10B90 EL EL R5G10B90(240nm) EL

6.12: EL ITO/PEDOT:PSS(30nm)/Bulk

RGB(Xnm)/LiF(1.0nm)/Al(80nm) EL R1G5B95 R1G1B100

(73)

6.4 EL EL

Anode

Organic layer

Cathode

I_h'

I_e' I_e

I_h'

I

6.13:

EL

2 γ

I I_e

I_h I^′_h I^′_e

(6.10) (6.11)

I = I_h+I_e^′ =I_h^′ +I_e (6.10) I = I_h−I_h^′ =I_e^′ −Ie (6.11)

γ I_r I

γ = I_r

I (6.12)

1

I=I_h=I_e I^′_h=I^′_e=0 I=I_h=I_e=I_r γ=1.0

2

I=I_h≥I_e I^′_e̸=0 I^′_h=0 2 I=I_e=I_h+I^′_e I_r=I_h=I_e-I^′_e

(74)

3 I^′_e̸=0 I^′_hI^′_e̸=0

I^′_h=0 δ

δ = I_h+I_e^′

I_h^′ +I_e (6.14)

γ = 1−δ

1 +δ (6.15)

δ 1.0 γ

EL

ITO/TPD/Alq₃/LiF/Al TPD

Alq₃ TPD Alq3

1%

EL

[61–64]

p n

Alq₃

[65, 66] MEH-PPV EL ITO

MEH-PPV π

[67]

[19, 68]

[69–71]

UV ^[72]

ESDUS

ITO/PEDOT:PSS/PFO/CN-

PDHFV/LiF/Al 0.7%

[73]

RGB EL

ESDUS

(75)

EL

MEH-PPV CN-PDHFV PFO PEDOT:PSS EL

EL

4.0×10⁻⁴cm²/V·s MEH-PPV 1.0×10⁻⁶cm²/V·s MEH-PPV

MEH-PPV LUMO 5.1eV

CN-PDHFV

[60] nm

PEDOT:PSS

PFO MEH-PPV CN-PDHFV

EL

ITO LiF(1.0nm)/Al(80nm)

Layered B/R/G 6.2 6.14

CN-PDHFV Layered B/R PFO

Layered R/G CN-PDHFV 5%MEH-PPV

Layered B/GdR Blend R5G20B75

PEDOT:PSS PFO

ESDUS ESDUS

ESDUS

6.3 I-V-L

Q

6.2: EL

Layered B/R/G PEDOT:PSS/PFO/MEH-PPV/CN-PDHFV Layered B/R PEDOT:PSS/PFO/MEH-PPV

Layered R/G PEDOT:PSS/MEH-PPV/CN-PDHFV

Layered B/GdR PEDOT:PSS/PFO/CN-PDHFV doped 5% MEH-PPV Blend RGB PEDOT:PSS/MEH-PPV & CN-PDHFV & PFO Single R PEDOT:PSS/MEH-PPV

(76)

6.3: EL

V [V] I [mA/cm²] L[cd/m²] Q [%]

Layered B/R/G 22.25 338.5 1204 0.77 Layered B/R 18.0 60.12 27.15 0.11 Layered R/G 9.75 175.7 477.4 0.48 Layered B/GdR 11.0 248.0 2665 1.15 Blend R5G20B75 24.5 152.5 452.3 1.20

Single R 7.0 382.5 305.2 0.06

Glass substrate ITO (Anode) PEDOT:PSS (HIL) PFO (HTL) LiF Al (Cathode)

-

+

MEH-PPV (EL) CN-PDHFV (ETL)

hǵ

Glass substrate ITO (Anode) PEDOT:PSS (HIL) LiF

Al (Cathode)

-

+

MEH-PPV (EL) CN-PDHFV (ETL)

hν

Layered B/R/G Layered R/G

-

+

MEH-PPV (EL)

hǵ

-

+

CN-PDHFV dope 5% MEH-PPV (ETL)

h㱙

Layered B/R Layered B/GdR

Glass substrate ITO (Anode) PEDOT:PSS (HIL) LiF

Al (Cathode)

- +

Bulk RGB (ETL)

h㱙

Al (Cathode)

hν

- +

Blend RGB Single R

6.14: EL

(77)

Layered B/R/G Layered B/R

Layered B/GdR Blend RGB

6.15: EL EL Layered

B/R/G 70nm/35nm/35nm 70nm/65nm/65nm 130nm/40nm/40nm 130nm/55nm/55nm Layered B/R 130nm/70nm 130nm/90nm

Layered B/GdR 70nm/80nm 70nm/110nm 130nm/90nm

130nm/120nm Blend RGB 220nm 110nm 200nm 110nm

100nm

(78)

- V-I - V-L

- I-L - I-Q

6.16: EL Layered B/R/G Layered

B/R/G 70nm/35nm/35nm 70nm/65nm/65nm 130nm/40nm/40nm 130nm/55nm/55nm

(79)

- V-I - V-L

- I-L - I-Q

6.17: EL Layered B/R Layered B/R

130nm/70nm 130nm/90nm

(80)

- V-I - V-L

- I-L - I-Q

6.18: EL Layered R/G Layered R/G

35nm/15nm 35nm/65nm 80nm/45nm 135nm/15nm

(81)

- V-I - V-L

- I-L - I-Q

6.19: EL Layered B/G doped R Layered

B/GdR 70nm/80nm 70nm/110nm 130nm/90nm 130nm/120nm

(82)

- V-I - V-L

- I-L - I-Q

6.20: ESDUS EL ITO/PEDOT:PSS(50nm)/Blend

RGB(Xnm)/LiF(1.0nm)/Al(80nm) Blend RGB 220nm

110nm 200nm 110nm 100nm

(83)

- UV-Vis-NIR UV-3150

Xe900,M300,S300 Edinburgh Instruments EL

6.21 R G B

6.22 R5G10B75

RGB

R ESUDS

R G B

6.21: -

(84)

6.5

6.23: - EL

RGB RGB

6.20 R5G20B75

1%

RGB R

G

R5G20B75 3

1. PFO

CN-PDHFV MEH-PPV

2. CN-PDHFV

MEH-PPV

3. MEH-PPV

B R R5B95 6.7

B R

B R 1.3eV

G R

(85)

1 EL

EL R100

R5G20B75 70nm 6.5 G EL

RGB RGB

ESDUS

EL ESDUS

RGB RGB ESDUS

RGB

Layered B/GdR

EL Layered B/R/G 6.16

0.8% Layered

B/R/G PFO I-L

PFO

PFO 0.8eV

poly(3-methylthiophene) PHT polyaniline PA

Layered R/G 6.18 0.5%

MEH-PPV

PFO Layered B/R/G

Layered B/R/G

CN-PDHFV Layered

B/R

6.17 0.1%

I-V-L 6.23

MEH-PPV

(86)

EL Layered

B/R/G Layered R/G EL 6.23

6.24 ² ^{[74, 75]}

Friend

Layered B/R/G Layered R/G MEH-PPV

CN-PDHFV

EL

MEH-PPV CN-PDHFV PPV

ESDUS

MEH-PPV CN-PDHFV Blend R5G95 EL

LUMO

HOMO㪂㪂㪂

㪄

㪂

LUMO

HOMO

㪄

㪂 hv

LUMO

HOMO㪂㪂

㪄 LUMO

HOMO 㪄

㪂

hv

HTL ETL HTL ETL

(a) (b)

HTL ETL HTL ETL

6.24: a /

b

(87)

7

7.1

ESDUS RGB

nm ESDUS

EL

R G

ESDUS

EL ESDUS

PEDOT:PSS

PFO MEH-PPV CN-PDHFV

MEH-PPV

22 MEH-PPV CN-PDHFV 7.1

RGB

MEH-PPV 19

ESDUS

PEDOT:PSS ITO

4.2 eV

5.0 eV 4.8 eV

LiF / Al 5.1 eV

PFO

3.5 eV

6.0 eV 5.8 eV

2.9 eV 2.9 eV

CN-PDHFV MEH-PPV

㻎

㻎㻎㻎㻎㻎

㻎㻐

㻐㻐㻐㻐

㻐㻔

㻕

7.1: MEH-PPV CN-PDHFV

(88)

7.2 ESDUS

ESDUS EL

µm

EL

-

X

ESDUS EL

THF

120 L/min

ESDUS

EL

polymer light-emitting cell

PLEC MEH-PPV poly(ethylene oxide)

PEO lithium trifluoromethanesulfonate LiCF₃SO₃

EL ^{[76, 77]} PLEC

MEH-PPV Anode Cathode

ESDUS

+ +

[78, 79]

EL MEH-PPV

[80]

EL

(89)

ESDUS EL

-

+ ^hole

electron

hν

-

+ ^hole

electron

hν

Charge Generation Layer

7.2: EL EL

EL

HTL/EML/ETL Charge Generation Layer(CGL)

EL Anode/HTL/EML/ETL/CGL/HTL/EML/ETL/CGL....

CGL V₂O₅ Alq₃

[81]

7.2 EL

EL ESDUS

CGL PLEC

(90)

ESDUS EL

Glass substrate Anode

Hole Transport Layer (HTL) Emissive Layer (EML) - Blue Electron Transport Layer (ETL) Cathode

-

+

Charge Generation Layer (CGL) Emissive Layer (EML) - Red

Hole Transport Layer (HTL) Emissive Layer (EML) - Green Electron Transport Layer (ETL) Cathode

-

+

Ultra-thin Emissive Layer (EML) - Red Ultra-thin Emissive Layer (EML) - Blue

RB2 RGB3

Hole Transport Layer (HIL) Electron Transport Layer (HTL) Cathode

-

+

Mixed RGB Emissive Layer (EML)

Hole Transpot Layer (HTL) Emissive Layer (EML) Electron Transport Layer (ETL) Cathode

-

+

RGB RGB

Hole Transport Layer (HTL) Emissive Layer (EML) - Red Electron Transport Layer (ETL) Cathode

-

+

Transparent Electrode Emissive Layer (EML) - Green Emissive Layer (EML) - Blue

Hole Transport Layer (HTL) Emissive Layer (EML) - Red Electron Transport Layer (ETL) Cathode

-

+

Charge Generation Layer (CGL) Emissive Layer (EML) - Green Emissive Layer (EML) - Blue

RGB CGL RGB

7.3: EL

EL

7.3

RGB ESDUS

RGB

ESDUS

RGB S×S(side by side)

(91)

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(96)

2

(97)

1 95 1.1 . . . 95

1.2 . . . 95

1.3 . . . 97

1.4 . . . 97

2 99

2.1 . . . 99

2.2 . . . 100

2.3 . . . 101

2.4 . . . 104

2.5 . . . 104

2.6 . . . 108

3 111

4 ESDUS 114

4.1 . . . 114 4.2 ESDUS . . . 115

4.3 ESDUS . . . 117

4.4 ESDUS . . . 120

5 124

5.1 OPV . . . 125

5.2 . . . 126

5.3 OPV . . . 127 5.4 OPV . . . 131 5.5 OPV . . . 132

5.6 OPV . . . 134

5.7 OPV . . . 136

5.7.1 . . . 136

5.7.2 IoT/ . . . 138

5.7.3 . . . 140

6 141

(98)

1

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1000 2020 9

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溶液プロセスによる有機半導体膜の構造制御とデバ イス応用

九州大学学術情報リポジトリ

Kyushu University Institutional Repository