FB 161030142400

MEH-PPV
The Synthesis and Characterization of

Electroluminescent Materials of
MEH-PPV
Copolymers
(Wei-Chin Chiu)
(Dr. Wen-Chung Ou-Yang)
MEH-PPV (poly(2-methoxy-5-(2`-ethyl
-hexyloxy)-1,4-phenylene-vinylene) MEH
-PPV PL (380 ~ 600 nm)
MEH-PPV
MEH-PPV
MEH-PPV
phenothiazinecarbazolepyridine thiophene
MEH-PPV
wittig reaction
(Polymeric light-emitting diodesPLED)
300 (
Tdca. 300 )
UV-vis
PL
(red-shift)
thiophene
LUMO
thiophene
EL CIE
II
III

......I
II
.......III
.......IV
...................IV
...1
1-1..1
1-2..3
1-2-1...3
1-2-25
1-2-36
1-2-4MEH-PPV.8
1-2-5..9
1-2-6 ......11
1-2-6 ..12
IV
...15
2-1..15
2-216
...17
3-117
3-218
3-3 ...21
3-4MEH-PPV 24
3-4-1Methoxy-4-(2-ethylhexyloxy)benzene.24
3-4-2,-Dibromo-2-methoxy-5-(2-ethylhexyloxy)xylene.24
3-4-3(MEH-PPV )..25
3-525
3-5-11-(2-ethylhexyloxy)-2,5-bis(chloromethyl)-4-methoxybenzene25
3-5-21-(2-Ethylhexyloxy)-4-methoxy-2,5-xylenebis(triphenylphos
-phonium chloride)... 26
3-5-39-hexyl-9H-carbazole-3,6-dicarbaldehyde.26
2-5-410-hexyl-10H-phenothiazine-3,7-dicarbaldehyde..27
2-5-52,6-Pyridinedicarboxaldehyde28
V
3-5-6PPzCzMEH-PPV.29
3-5-7PPyCzMEH-PPV.30
3-5-8PPyPzMEH-PPV..31
3-5-9PPzTpMEH-PPV..32
3-5-10PCzTpMEH-PPV33
3-5-11PPyTpMEH-PPV34
...35
4-1 ..35
4-2 ..42
4-3..48
...50
5-1.50
5-2..51
5-2(GPC)..55
5-3(POM).61
...65
VI
6-1 MEH-PPV ...65

6-1-1 ..65
6-1-2 ..65
6-2 PL ...66
6-3 MEH-PPV ...73
6-3-1 ..73
6-3-2 PL 73
6-4MEH-PPV Copolymers ....81
6-4-1MEH-PPV Copolymers -81
6-4-2MEH-PPV Copolymers THF 86
6-4-2MEH-PPV Copolymers Tol 91
6-4-4.96
6-4-5CIE 100
.105
7-1..105
7-1-1108
7-2..114
VII
7-2-1ITO 114
7-2-2 ITO .115
7-2-3115
7-2-4117
7-2-5117
.....125
...133
VIII

1-1LED...7
4-1MEH-PPV ..49
5-154
5-260
6-1 MEH-PPV (4-MP )65
6-2 MEH-PPV (t-BuOk )..66
6-3-...82
6-4 CIE ..101
7-1MEH-PPV Copolymers 112
7-2...118
7-3PL EL ..122
IX

1-1[poly(p-phenylenevinylene)].2
1-2-5-(2--)-1,4-(MEH-PPV)..2
1-32
1-4Perrin-jablonski diagram4
1-55
1-6PPV6
1-7MEH-PPV(C17H24O2)n8
1-8(a) MEH-PPV
(b) MEH-PPV ...10
1-9MEH-PPVDCB
THFa...11
1-1012
4-1 PPh3 MEH-PPV FTIR ..36
4-2 carbazole FTIR .36
4-3 phenothiazine FTIR .37
4-4 pyridine FTIR ...37
4-5 thiophene FTIR 38

4-6 PPzCzMEH-PPV FTIR 38
4-7 PPyPzMEH-PPV FTIR 39
4-8 PCzTpMEH-PPV FTIR 39
4-9 PPzTpMEH-PPV FTIR 40
4-10 PPyCzMEH-PPV FTIR ..40
4-11 PPyTpMEH-PPV FTIR ..41
4-12 pyridine 1H-NMR 43
4-13 thiophene 1H-NMR 44
4-14 phenothiazine 1H-NMR ..44
4-15 carbazole 1H-NMR 45
4-16 PPyPzMEH-PPV 1H-NMR 45
4-17PCzPzMEH-PPV 1H-NMR 46
4-18 PPyCzMEH-PPV 1H-NMR 46
4-19 PCzTpMEH-PPV 1H-NMR 47
4-20 PPzTpMEH-PPV 1H-NMR ...47
4-21 PPyTpMEH-PPV 1H-NMR 48
5-1MEH-PPV TGA 53
XI
5-2MEH-PPV TGA 53
5-3PPyCzMEH-PPV GPC ..56
5-4PCzTpMEH-PPVGPC..57
5-5PPyTpMEH-PPVGPC57
5-6PCzPzMEH-PPV GPC .58
5-7PPyPzMEH-PPV GPC ..58
5-8PTpPzMEH-PPV GPC ..59
5-9PPyCzMEH-PPV POM .62
5-10PCzTpMEH-PPV POM ..62
5-11PPyTpMEH-PPV POM 63
5-12PCzPzMEH-PPV POM ..63
5-13PPyPzMEH-PPV POM ..64
5-14PTpPzMEH-PPV POM ..64
6-1Z1~Z5 THF (PL)(Ex 480 nm).67
6-2T1 THF (PL)(Ex 480 nm)..67
6-3T2 THF (PL)(Ex 340380480 nm).. 69
6-4T3 THF (PL)(Ex 340 nm)..69
6-5T4 THF (PL)(Ex 340380 nm).70
XII
6-6T5 THF (PL)(Ex 340380 nm, Em 560

nm)70
6-7T6 THF (PL)(Ex 340380480 nm). 71
6-8T7 THF (PL)(Ex 340380480 nm).. 71
6-9T8 THF (PL)(Ex 340380480 nm).. 72
6-10MEH-PPV DCB 0.05 %(Ex 270 nm).76
6-11MEH-PPV THF 0.05%(Ex 301 nm)...77
6-12MEH-PPV DCB THF 0.05 %Ex 299
nmDCB ()THF ()77
nmTHF ()DCB ().78
6-14MEH-PPV DCB (33%) THF (66%)
0.05%(Ex 270 nm)..78
6-15MEH-PPV DCB(66%) THF(33%)
0.05 %(Ex 270 nm)79
6-16MEH-PPV DCBTHFTol
0.05 %(Ex 295 nm)..79
4-17MEH-PPV DCBTHFCF
0.05 %(Ex 264 nm)..80
6-18PPyCzMEH-PPV THF -..83
6-19PCzTpMEH-PPV THF -..83
6-20PPyTpMEH-PPV THF -..84
6-21PPzCzMEH-PPV THF -...84
6-22PPyPzMEH-PPV THF -..85
XIII
6-23PPzTpMEH-PPV THF -......85

6-24PPyCzMEH-PPV THF 88
6-25PCzTpMEH-PPV THF 88
6-26PPyTpMEH-PPV THF ....89
6-27PPzCzMEH-PPV THF .89
6-28PPyPzMEH-PPV THF 90
6-29PPzTpMEH-PPV THF 90
6-30PPyCzMEH-PPV Toluene ..93
6-31PCzTpMEH-PPV Toluene .93
6-32PPyTpMEH-PPV Toluene ..94
6-33PPzCzMEH-PPV Toluene ..94
6-34PPyPzMEH-PPV Toluene ..95
6-35PPzTpMEH-PPV Toluene ..95
6-36PPyCzMEH-PPV Tol THF PL ..97
6-37PCzTpMEH-PPV Tol THF PL ..97
6-38PPyTpMEH-PPV Tol THF PL ..98
6-39PPzCzMEH-PPV Tol THF PL ..98
6-40PPyPzMEH-PPV Tol THF PL ..99
XIV
6-41PPzTpMEH-PPV Tol THF PL ..99

6-42PPyCzMEH-PPV CIE 101
6-43PCzTpMEH-PPV CIE 102
6-44PPyTpMEH-PPV CIE 102
6-45PPzCzMEH-PPV CIE 103
6-46PPyPzMEH-PPV CIE 103
6-47PPzTpMEH-PPV CIE 104
7-1..107
7-2..107
7-3PPyCzMEH-PPV .109
7-4PCzTpMEH-PPV .109
7-5PPyTpMEH-PPV ...110
7-6PPzCzMEH-PPV ..110
7-7PPyPzMEH-PPV ..111
7-8PPzTpMEH-PPV ..111
7-9MEH-PPV Copolymers 112
7-10MEH-PPV Copolymers ..113
7-11..116
XV
7-12PPyCzMEH-PPV I-V-L .119

7-13PCzTpMEH-PPV I-V-L .119
7-14PPyTpMEH-PPV I-V-L .120
7-15PPzCzMEH-PPV I-V-L 120
7-16PPyPzMEH-PPV I-V-L .121
7-17PPzTpMEH-PPV I-V-L .121
7-18PPyCzMEH-PPV EL 122
7-19PCzTpMEH-PPV EL 123
7-20PPyTpMEH-PPV EL 123
7-21PPzCzMEH-PPV EL 124
7-22PPyPzMEH-PPV EL .124
7-23PPzTpMEH-PPV EL .125
7-24PPyCzMEH-PPV CIE 125
7-25PCzTpMEH-PPV CIE ...126
7-26PPyTpMEH-PPV CIE ..126
7-27PPzCzMEH-PPV CIE 127
7-28PPyPzMEH-PPV CIE 127
7-29PPzTpMEH-PPV CIE 128
XVI

1-1
[1] (delocalized)
(hoping)

[poly(p-phenylenevinylene)PPV] ( 1-1)
(spin
coating) (ITO)
PPV
Heeger
[poly(2-methoxy-5-(2`-ethyl-hexyloxy)-1,4-phenylene
vinylene)
MEH-PPV( 1-2)
max 610 nm 1% MEH-PPV
[2] ( 1-3) MEH-PPV
MEH-PPV

[3-5]
n
1-1. [poly(p-phenylenevinylene)]
H3CO
n
O
poly(2-methoxy-5-(2`-ethyl-hexyloxy)-1,4-phenylene-vinylene
1-2. -5-(2--)-1,4-(MEH-PPV)
*
*
Polyacetylene (PA)
Poly(p-phenylene) (PPA)
Poly(pyrrole) (PPy)
Polythiophene (PT)
poly(thienylene vinylene) (PTV)
1-3.
2
1-2
1-2-1
PhotoluminescencePL[6]
ElectroluminescenceEL[7]
highest occupied molecular orbitalHOMO

lowest unoccupied molecular
orbitalLUMOsinglet(exciton)
S0S1
S1 S0
fluorescenceS1
intersystem crossingTripletT1
S0
S-T[9]T-S
phosphorescence[8]1-4
forbidden
T110-4 ~S110-5 ~10-8
S-TT-SS-S (1-5)
ITO
3
negative polaron
(positive polaron)
S1S0
1-4Perrin-jablonski diagram.
1-5
1-2-2
1-6.
ITO(work function)PPV
(ionization potential, IP)[10](Fermi level)PPV
(highest occupied molecular orbital, HOMO)
Al Ca PPV (lowest unoccupied
molecular orbital, LUMO)1-6
1-6PPV
1-2-3
/(Electroluminescence,
EL)
LEDOLEDPLED
PHPLEDOLEDALq3
450~700 nm(apex wavelength)550 nm[11]PLED
(conjugated polymer)
(spin coating)
1990CavendishBurroughws
LED PPV(Poly para-phenylene vinylene)
ITO/PPV/AlPLED(EL)max550 nm
6
(quantum efficiency)0.05 %[12]PPV
PPVMEH-PPVPoly(fluorine)
(PLED)
(flexible)
[13~15](1-1)
1-1LED
1-2-4
MEH-PPV
1999HeegerApplied Physics Letters[16]

MEH-PPV (1-7.) (EL) 610
nm2.0 eV1 %[17~19]MEH-PPV
MEH-PPV
MEH-PPV
(energy gap)
[20,21][22,23]
[24][2,26][27]LEDs
1-7MEH-PPV(C17H24O2)n
8
1-2-5
(aggregation)
- (rigid-rod)
(28-31)
(32)
(hopping)
3.5-4 [33,34]
(agglomeration)(35)
(red-shift peak)(36~39)
(luminescence efficiency)(40)
(collapse)(41,42)
UCLABenjamin J. Schwartz[43]MEH-PPVCB
tol (turn-on
voltage) (working current)
(solution) (solid
film) (memory effect)

(classification of aggregation)[44]
MEH-PPVTHF
(zipper aggregation effect)
(deaggregate). Y. YangMEH-PPV
[45]
MEH-PPV(
1-8)MEH-PPV(
1-9)
(a)
(b)
1-8(a) MEH-PPV
(b) MEH-PPV
10
1-9MEH-PPVDCB
THF
1-2-6
S. A. Chen (NTHU) Electroluminescent

(EL)(46,47)(48,49)
(50,51)
(excimers) (self-quench) PPV
(2-2,5-) (Alkoxy)(52)
(Alkylsilyl)
(53)
(phenyl)
(54)
triphenylamine(55) fluorene(56) 9,
10-diphenylanthracene(57)
PPV
11
(host, H) (guest, G)
(quenching)
life time
(overlap)
(carrier)
1-2-6
90
Poly(p-phenylenes) (PPP)
(Conjugation length)
(Oligomer)
12
[58]
(1)(dye)
(2)
13
(3)
(4)
1-10
14
2-1
MEH-PPV
MEH-PPV
MEH-PPV
MEH-PPV
MEH-PPMEH-PPV
MEH-PPVMEH-PPV
wittig reaction random
15
2-2
MEH-PPV
MEH-PPV
MEH-PPV CopolymersMEH-PPV
16

3-1
17
3-2
(1) p-methoxyphenol (HOC6H4OCH3) Lancaster>98%
(2) Sodium methylate (CH3ONa) LancasterAldrich

98%-20
(3) Sodium hydroxide (NaOH) 95%
(4) Sodium (Na)
(5) (C2H5OH) 99.5%
(6) 2-Ethylhexyl bromide (BrCH2CH(C2H5)C4H9) Lancaster96%
(7) Ether (C2H10O) 95%

(8) Magnesium sulfate anhydrous (MgSO4) Showa
99%
(9) para(formaldehyde) ((CH2)n) Lancaster
(10) 1,4-dioxane (C4H8O2)Tedia99.98%
(11) Hydrochloric acid (HCl) >35%
(12) Hydrobromic acid (HBr) >47%
18
(13) Acetic acid, Glacial (CH3COOH) >99%
(14) Tetrahydrofuran (C4H8O) KOH Na

(15) Potassium tert-butoxide (t-BuOK) Lancaster98%
(16) 4-(tert-butyl)benzyl bromide (C11H15Br) Aldrich97%
(17) Methanol (CH3OH) L.C. grade99% 65
(18) Chloroform (CHCl3) TEDIAHPLC99.98%

(19) n-Hexane (C6H14) TediaHPLC95%
(20) Camphour sulfonic acid (C10H16O4S) Riedel-dehaenen
98%
(21) m-Cresol (C7H8O) Riedel-deHen98%
(22) Hydrochloric acidclass1037-38%
(23) Ethyl acetateTedia99.9 %
(24) TolueneTedia99.9%
(25) Phosphorus oxychlorideAcros99%
19
(26) 1,1,2-trichloroethaneAcros99.8%
(27) N-MethylformanilideAcros99%
(28) Sodium acetateAldrich98%
(29) CarbazoleAcros96%
(30) N,N-Dimethylformamide(DMF)TediaLC grade
20
3-3
3-3-1
(Nuclear Magnetic Resonance, NMR)
Bruker, Model AMX-400 ppm

Hz.S (singlet)d (doublet)t (triplet)m
(multiplet)
3-3-2
(Elemental Analyzer, EA)
Heraus CHN-rapid Acetanilide
950
N2CO2
H20
3-3-3
(Thermogravimetric Analysis, TGA)
Dupont TA Instrument Co.-TGA 2050(TGA)
(Td)
5~10 mg 20 /min 20
21
ml/min 200~800
3-3-4
(Photoluminescence, PL)
Hitachi F-4500 Fluorescence Spectrophotometer Xe Lamp

240 nm/min 300~700 nm
3-3-5
(Infrared Spectrophotometer, FT-IR)
Perkin-Elmer 16 PC FT-IR(KBr)
Jasco Fourier Transform Infrared Spectrometer Volar III
cm-1
400~4000 cm-1
3-3-6
-
(Ultraviolet-visible Spectrophotometer,
UV-vis)
Jasco V-550 UV-vis Spectrophotometer
( 2 c.c.)
UV-vis
22
3-3-7
(Gel Permeation Chromatography, GPC)
Water-717tlus Auto-Sampler 0.7 mg 1.5 ml THF

(Mw)
(Mn)(PDI)
3-3-8
(Polarizing Optical Microscope
POM)
MINOLTA CS-100A THF
x125
3-3-9
(Vacuum Coater)
ULVAC SINKU-KIKI CO. VPC-060

3-3-10
(Spin Coater)
SWIENCO TYPE PM 4908
23
3-4
MEH-PPV
H3CO
H3CO
Br
NaOCH3
H3CO
750C 72h
OH
ONa
(1)
H3CO
H3CO
(CH2O)n
HBr
700C 4h
BrH2C
CH2Br
O
(2)
H3CO
H3CO
BrH2C
CH2Br
t-BuOK
*
*
THF
O
(3)
3-4-1
Methoxy-4-(2-ethylhexyloxy)benzene (1)
p-methoxy phenol 100 gKOH 56 g tetrabutylammonium
b r o mi d e 5 g 1 50 ml
2 - eth yl h ex yl b romi d e 1 54 g
24
3-4-2
,-Dibromo-2-methoxy-5-(2-ethylhexyloxy)xylene (2)
50 g (1)para-formaldehyde 30 g 100 ml
HBr 100 ml 70
NaHCO3
MgSO4
n-hexane
3-4-3
(MEH-PPV
)
(3)
2 g80 ml THF p-methoxy phenol 1.5 g
potassium tert-butoxide ( 20 ml THF 1 M)
16 THF n-hexane
THF
3-5
3-5-1
1-(2-ethylhexyloxy)-2,5-bis(chloromethyl)-4-methoxybenzene (4)
H3CO
H3CO
HCl 1,4-dioxane
90 oC , 72 hr
ClH2C
CH2Cl
O
Mol. Wt.: 333.29
Mol. Wt.: 236.35
(4)
25
50 g (1)para-formaldehyde 30 g (130 mmol)HCl 100 ml

1,4-dioxane 100 ml 90 72
71 %
3-5-2
1-(2-Ethylhexyloxy)-4-methoxy-2,5-xylenebis(triphenylphos
-phonium chloride) (5)
(5)
1,4-bis(chloromethyl)-5-(2-ethylhexyloxy)-2-methoxybenzene 5 g
(15 mmol)triphenylphosphine 8.7 g (33 mmol) 60 ml DMF
24 diethyl ether
87 %
26
3-5-3
9-hexyl-9H-carbazole-3,6-dicarbaldehyde (6)
(6)
250 ml DMF 16.7 ml(220
mmol) Phosphorus oxychloride 16.8 ml (180 mmol)
9-hexyl-9H-carbazole 5 g (18 mmol) 1,1,2-trichloroethane
30 ml 90 48
NaOH pH 6 ~ 8
ethyl acetate
Silica gel 60,230-400 mesh (n-hexane/ethyl
acetate) 48 %
27
2-5-4
10-hexyl-10H-phenothiazine-3,7-dicarbaldehyde (7)
(7)
N-methylformanilide 5.0g (37 mmol) Toluene 20 ml
Phosphorus oxychloride 4.4 ml (28.5 mmol)
10-hexyl-10H-phenothiazine 6.9 g (28.4 mmol) 95 12
20 % Sodium acetate 30 ml 10
ethyl ether 100 ml 50 ml
K2CO3 Silica gel 60,230-400 mesh
(n-hexane 90 %/ethyl acetate 10 %)
51%
28
2-5-5
2,6-Pyridinedicarboxaldehyde (8)
(8)
2,6-pyridinedimethanol 5 g dioxane 60 ml
SeO2 3.98 g 4
Soxhlet Silica gel60,230-400 mesh
Chloroform
70 %
3-5-6
PPzCzMEH-PPV
H3CO
+
OHC
t-BuOK
CHCl3 / EtOH
CH2PPh3
Cl-
N
OHC
Ph3PH2C
+
Cl-
N
S
CHO
H3CO
H3CO
S
O
29
10-hexyl-10H-phenothiazine-3,7-dicarbaldehyde
0.328 g (1.06 mmol)9-hexyl-9H-carbazole-3,6-dicarbaldehyde 0.324 g
(1.06 mmol)1-(2-Ethylhexyloxy)-4-methoxy-2,5-xylenebis (triphenylphos
-phonium chloride) 2 g (2.11mmol) THF 15 ml
potassium tert-butoxide 1.5 g
THF 15 ml 12
41 %1H NMR (400 MHz, CDCl3)

:8.42-8.20 (m, 20H), 4.37-3.29 (m, 18H), 2.84 (s, 2H), 2.22(s, 1H),
1.59-0.59(m, 45H)elemental analysis calcd. (%) for C92H111N3O4S2C,
79.67 %; H, 8.07 %; N, 3.03 %. Found: C, 75.20 %; H, 8.15 %; N, 2.20 %
3-5-7
PPyCzMEH-PPV
H3CO
+
N
OHC
Ph3HPH2C
+
ClOHC
CHO
CHO
30
CH2PPh3
ClO
t-BuOK
CHCl3 / EtOH
H3CO
H3CO
2,6-Pyridinedicarboxaldehyde 0.142 g (1.06

mmol)9-hexyl-9H-carbazole-3,6-dicarbaldehyde 0.324 g (1.06 mmol)
1-(2-Ethylhexyloxy)-4-methoxy-2,5-xylenebis
(triphenylphos-phonium
chloride) 2 g (2.11 mmol) THF 15 ml

potassium tert-butoxide 1.5 g THF 15 ml
12
40 %1H NMR (400 MHz, CDCl3) :8.42-8.20 (m,

14H), 4.37-3.29 (m, 10H), 2.84 (s, 1H), 2.22(s, 6H), 1.59-0.59(m, 39H)
elemental analysis calcd. (%) for C61H74N2O4C, 81.47 %; H, 8.29 %; N,
3.12 %. Found: C, 79.59 %; H, 8.25 %; N, 2.45 %
31
3-5-8
PPyPzMEH-PPV
H3CO
+
OHC
N
OHC
Ph3PH2C
ClCHO +
CH2PPh3
ClO
H3CO
t-BuOK
H3CO
N
CHCl3 / EtOH
10-hexyl-10H-phenothiazine-3,7-dicarbaldehyde
0.328 g (1.06 mmol) 2,6-Pyridinedicarboxaldehyde 0.142 g (1.06
mmol)1-(2-Ethylhexyloxy)-4-methoxy-2,5-xylenebis(triphenylphos-phoniu
m chloride) 2 g (2.11 mmol) THF 15 ml
potassium tert-butoxide 1.5 g THF 15
ml 12
35%1H NMR (400 MHz, CDCl3) :8.42-8.20 (m,

10H), 4.37-3.29 (m, 6H), 2.84 (s, 1H), 2.22(s, 1H), 1.59-0.59(m, 25H)
32
elemental analysis calcd. (%) for C79H95N3O4S2C, 78.11 %; H, 7.88 %; N,

3.46 %. Found: C, 74.8 %; H, 7.70 %; N, 2.90 %
3-5-9
PPzTpMEH-PPV
H3CO
+
N
OHC
OHC
CHO
Ph3PH2C
Cl-
CH2PPh3
ClO
t-BuOK
S H3CO
H3CO
N
CHCl3 / EtOH
10-hexyl-10H-phenothiazine-3,7-dicarbal
Dehyde 0.328 g (1.06 mmol)2,5-thiophenedicarboxaldehyde 0.148 g (1.06
mmol)1-(2-Ethylhexyloxy)-4-methoxy-2,5-xylenebis(triphenylphos
-phonium chloride) 2 g (2.11mmol) THF 15 ml
potassium tert-butoxide 1.5 g
THF 15 ml 12
33

36 %1H NMR (400 MHz, CDCl3)
:8.42-8.20 (m, 21H), 4.37-3.29 (m, 16H), 2.84 (s, 4H), 2.22(s, 52H),
1.59-0.59(m, 57H)elemental analysis calcd. (%) for C78H94N2O4S3C,
76.8 %; H, 7.77 %; N, 2.3 %. Found: C, 71.72 %; H, 7.85 %; N, 1.00 %
3-5-10
PCzTpMEH-PPV
H3CO
+
N
OHC
OHC
CHO +
Ph3PH2C
Cl-
CH2PPh3
ClO
CHO
H3CO
N
t-BuOK
CHCl3 / EtOH
H3CO
9-hexyl-9H-carbazole-3,6-dicarbaldehyde0.324 g
(1.06 mmol) 2,5-thiophenedicarboxaldehyde 0.148 g (1.06 mmol)
1-(2-Ethylhexyloxy)-4-methoxy-2,5-xylenebis(triphenylphos-phonium
chloride) 2 g (2.11mmol) THF 15 ml
34
12
40 %1H NMR (400 MHz, CDCl3) :8.42-8.20 (m,

50H), 4.37-3.29 (m, 47H), 2.84 (s, 11H), 2.22(s, 24H), 1.59-0.59(m,
109H)elemental analysis calcd. (%) for C60H73NO4SC, 80.54 %; H,
8.22%; N, 2.54 %. Found: C, 75.09 %; H, 8.00 %; N, 2.20 %
3-5-11
PPyTpMEH-PPV
H3CO
+
OHC
t-BuOK
CHO
OHC
CHO +
CH2PPh3
ClO
H3CO
CHCl3 / EtOH
Ph3PH2C
Cl-
H3CO
*
2,6-Pyridinedicarboxaldehyde0.142 g (1.06
mmol) 2,5-thiophenedicarboxaldehyde0.148 g (1.06 mmol)
1-(2-Ethylhexyloxy)-4-methoxy-2,5-xylenebis(triphenylphos-phonium
chloride) 2 g (2.11mmol) THF 15 ml
35

12
45 %1H NMR (400 MHz, CDCl3) :8.42-8.20 (m, 9H),

4.37-3.29 (m, 7H), 2.84 (s, 1H), 2.22(s, 4H), 1.59-0.59(m, 26H)elemental
analysis calcd. (%) for C47H57NO4SC, 77.12 %; H, 7.85%; N, 1.91 %.
Found:
C,
74.19
%;
H,
36
7.56
%;
N,
1.43
(FTIR)(NMR)(EA)
4-1
FTIR 4-1 4-5
4-1 MEH-PPV
4-1 4-5 1593 cm-1 1475 cm-1 C-C
2935 cm-1 C-H sp3 4-2
4-4 1315 cm-1 1375 cm-1 C-N
4-6 4-11 MEH-PPV
FTIR
MEH-PPV triphenylphosphine wittig
reaction MEH-PPV
37
Transmittance
H3CO
C-H sp3
+
Ph3PH2C
Cl-
+
CH2PPh3
ClO
C=C
Mol. Wt.: 946.77
4000
3500
3000
2500
2000
1500
1000
500
-1
Wavenumber (cm )
Transmittance
4-1 PPh3 MEH-PPV FTIR
C-H sp3
C=C C-N
N
OHC
C=O
CHO
Mol. Wt.: 307.39
4000
3500
3000
2500
2000
1500
1000
500
-1
Wavenumber (cm )
4-2 carbazole FTIR
38
Transmittance
C-H sp3
OHC
C=O
Mol. Wt.: 311.44
4000
3500
3000
2500
C=C C-N
2000
1500
1000
500
-1
Wavenumber (cm )
4-3 phenothiazine FTIR
120
C=O
Transmittance
100
80
60
40
C=C C-N
O
4000
O
N
20
2,6-Pyridinedicarboxaldehyde
3500
3000
2500
2000
1500
1000
500
-1
Wavenumber (cm )
4-4 pyridine FTIR
39
Transmittance
OHC
CHO
2,5-thiophenedicarboxaldehyde
Mol. Wt.: 140.16
C=O
4000
3500
3000
2500
2000
1500
1000
500
-1
Wavenumber (cm )
Transmittance
4-5 thiophene FTIR
C-H sp3
H3CO
H3CO
C=C C-N
PPzCzMEH-PPV
4000
3500
3000
2500
2000
1500
1000
500
-1
Wavenumber (cm )
4-6 PPzCzMEH-PPV FTIR

40
102
100
98
T%
96
94
C-H
92
H3CO
H3CO
N
S
90
PPyPzMEH-PPV
88
4000
3500
C=C C-N
3000
2500
2000
1500
1000
500
-1
wavenumber (cm )
Transmittance
4-7 PPyPzMEH-PPV FTIR
C=C C-N
C-H sp3
H3CO
H3CO
*
N
*
PCzTpMEH-PPV
4000
3500
3000
2500
2000
-1
1500
1000
500
Wavenumber (cm )
4-8 PCzTpMEH-PPV FTIR

41
Transmittance
C-H sp3
H 3CO
H3CO
N
S
C=C C-N
PPzTpMEH-PPV
4000
3500
3000
2500
2000
1500
1000
500
-1
Wavenumber (cm )
Transmittance
4-9 PPzTpMEH-PPV FTIR
C-H sp3
N
H3CO
C=C C-N
H3CO
*
PPyCzMEH-PPV
4000
3500
3000
2500
2000
1500
1000
500
-1
Wavenumber (cm )
4-10 PPyCzMEH-PPV FTIR

42
Transmittance
C-H sp3
C=C C-N
*
H3CO
H3CO
*
4000
3500
3000
2500
2000
1500
1000
500
-1
Wavenumber (cm )
4-11 PPyTpMEH-PPV FTIR
43
4-2
5 mg 0.5 ml D-DMSO NMR
Tube 1H-NMR 4-12 4-15
4-16 4-21
4-12 pyridine 1H-NMR 7.85~8.14
10.09~10.21
4-13 thiophene 1H-NMR 7.75~8.85
thiophene 9.93~10.04
4-14 phenothiazine 1H-NMR 0.83

-CH3 1.25 1.72~1.81 -CH2 3.82~3.86 -NCH2-
6.62~7.14 7.53~7.60 9.74
4-15 carbazole 1H-NMR 0.79~0.84

-CH3 1.21~1.33 1.79~1.89
-CH2- 4.27~4.36 -NCH2-
7.40~7.52 7.95~8.12 8.57~8.62
44
10.05~10.09
4-16 4-21 1H-NMR MEH-PPV
=10 MEH-PPV
1H-NMR
reaction MEH-PPV
4-12 pyridine 1H-NMR

45
4-13 thiophene 1H-NMR
4-14 phenothiazine 1H-NMR

46
4-15 carbazole 1H-NMR
4-16 PPyPzMEH-PPV 1H-NMR

47
4-17PCzPzMEH-PPV 1H-NMR
4-18 PPyCzMEH-PPV 1H-NMR

48
4-19 PCzTpMEH-PPV 1H-NMR
4-20 PPzTpMEH-PPV 1H-NMR

49
4-21 PPyTpMEH-PPV 1H-NMR
4-3
(EA)
EA 4-1 4-1
H 0.5 % N
1 %C
5 %C
wittig reaction
C
50
EA MEH-PPV
triphenylphosphine wittig reaction
MEH-PPV
4-1MEH-PPV
Sample
Formula
PPyCzMEH-PPV
C61H74N2O4
PCzTpMEH-PPV
C60H73NO4S
PPyTpMEH-PPV
C47H57NO4S
PCzPzMEH-PPV
C92H111N3O4S2
PPyPzMEH-PPV
C79H95N3O4S2
PTpPzMEH-PPV
C78H94N2O4S3
51
N%
C%
H%
Calc.
3.12
81.47
8.29
Found
2.45
79.59
8.50
Calc.
2.54
80.54
8.22
Found
2.20
75.09
8.00
Calc.
1.91
77.12
7.85
Found
1.43
74.19
7.56
Calc.
3.03
79.67
8.07
Found
2.20
75.20
8.15
Calc.
3.46
78.11
7.88
Found
2.90
74.10
7.70
Calc.
2.30
76.80
7.77
Found
1.00
71.32
7.85
wittig reaction Electroluminescence Polymers

(Mw)
(Mn) (PDI)
5-1
(Gel Permeation Chromatograph GPC)

Polystyrence 7 mg 1.5 mL NMP
0.5 ~ 1 % (Mw)
(Mn) (PDI)
(Thermogravimeteric AnalysisTGA) 3 ~ 5 mg
20 /min 35
850 100 15 (Td)
(char yield)
(Polarization MicroscopyPOM) 0.01 g
1 mL 1 w/v %
x125
52
5-2
(TGA)
(thermal
decomposition temperatureTd) (char yield)
Electroluminescence Polymers
20 /min Tr Td
(rapid weight loss) 5-1~ 5-2
(Td 5 %) (Tr)
5-1 5-1 PPyCzMEH-PPV (Td)
283 MEH-PPV (Td) 300
300
500 ~ 600
(TGA) MEH-PPV
triphenylphosphine wittig reaction
53
MEH-PPV
MEH-PPV ( 5%
) 300
54
120
PCzTpMEH-PPV
PPyCzMEH-PPV
100
PPyTpMEH-PPV
Weight (%)
80
60
40
20
0
100
200
300
400
500
600
700
800
Temperature ( C)
5-1MEH-PPV TGA
120
PPyPzMEH-PPV
PTpPzMEH-PPV
100
PCzPzMEH-PPV
Weight (%)
80
60
40
20
0
100
200
300
400
500
600
700
800
Temperature ( C)
5-2MEH-PPV TGA
55
5-1
Tda ()
Sample
Char
Yield at
Trb ()
650
5%
10%
50% Step 1 Step 2 Step 3 (wt.%)
PPyCzMEH-PPV
295
330
553
283
411
773
PCzTpMEH-PPV
330
370
535
286
536
701
24
PPyTpMEH-PPV
363
400
521
302
453
561
PCzPzMEH-PPV
336
362
481
328
557
760
11
PPyPzMEH-PPV
316
340
727
312
451
772
PTpPzMEH-PPV
314
339
455
289
406
512
10
aTemplerature resulting in n% weight loss based on initial weight

bTemperature at which rapid weight loss occur, the temperature was obtained by taking first
derivative.
56
5-2
(GPC)
(Mw) (Mn)
(PDI)
5-3 5-8
(Electroluminescent polymers) MEH-PPV GPC
5-2 MwMn Mw/Mn
PDI 5-2 wittig reaction
(electroluminescent polymers)
MEH-PPV
MEH-PPV PDI 1~1.3
PDI 1
5-3 5-8
(GPC)
reaction MEH-PPV
57
5-3PPyCzMEH-PPV GPC
58
5-4PCzTpMEH-PPV GPC
5-5PPyTpMEH-PPV GPC
59
5-6PCzPzMEH-PPV GPC
5-7PPyPzMEH-PPV GPC
60
5-8PTpPzMEH-PPV GPC
61
Table 5-2
Sample
Mw
Mn
PDI
PPyCzMEH-PPV
4438
3731
1.19
PCzTpMEH-PPV
3515
3333
1.05
PPyTpMEH-PPV
4505
3834
1.18
PCzPzMEH-PPV
3731
3344
1.12
PPyPzMEH-PPV
3347
3185
1.05
PTpPzMEH-PPV
3624
3308
1.10
Mw
Mn
PDI(Mw/Mn)
62
5-3
(POM)
(amophorus)
Toluene 1 w/v %
POM x125
5-9 5-14
electroluminescent polymers
(POM)
MEH-PPV triphenylphosphine
wittig reaction MEH-PPV
63
5-9PPyCzMEH-PPV POM
5-10PCzTpMEH-PPV POM
64
5-11PPyTpMEH-PPV POM
5-12PCzPzMEH-PPV POM
65
5-13PPyPzMEH-PPV POM
5-14PTpPzMEH-PPV POM
66

6-1 MEH-PPV
6-1-1
MEH-PPV
6-1-2
P-methoxyphenol(4-MP) Potassium tert-butoxide
(t-BuOk) ( 6-1 6-2 )
6-1. MEH-PPV (4-MP )

Name
monome t-BuOK 4-MP

(g)
r (g)
(g)
THF
(ml)
reaction Temp. Weight

time (t) ()
(g)
Yield
(%)
Z1
1.68
180
5 min
25
1.5366 78.52%
Z2
1.68
0.011
180
5 min
25
1.3237 67.64%
Z3
1.68
0.022
180
5 min
25
1.6099 82.26%
Z4
1.68
0.044
180
16 min
25
1.3597 69.48%
Z5
1.68
0.088
180
30 min
25
0.5658 28.91%
67
6-2. MEH-PPV (t-BuOk )

Name
Monomer t-BuOK 4-MP

(g)
(g)
(g)
THF Reaction Temp. Weight

(ml) time (t) ()
(g)
Yield
(%)
T1
1.2609
180
5 min
25
0.7171 36.64%
T2
1.0205
180
5 min
25
0.7063 36.09%
T3
0.9020
180
5 min
25
0.6699 34.23%
T4
0.8721
180
5 min
25
0.6574 33.59%
T5
0.8568
180
5 min
25
0.3780 19.32%
T6
0.8415
180
5 min
25
0.7463 38.14%
T7
0.7809
180
5 min
25
0.1801 9.20%
T8
0.3310
180
5 min
25
0.0379 1.94%
6-2 PL
6-1. MEH-PPV P-methoxyphenol(4-MP)
Z1~Z2 MEH-PPV
Ex 480 nm 0.001 %
551 nm 600 nm
(red-shift) (aggregate)
Z1~Z2 P-methoxyphenol
P-methoxyphenol MEH-PPV
68
6-1. Z1~Z5 THF (PL)(Ex 480 nm)
6-2. T1 THF (PL)(Ex 480 nm)

69
P-methoxyphenol MEH-PPV
Potassium tert-butoxide (t-BuOk)
T1~T8 6-2 6-9 t-BuOk MEH-PPV
Ex 480 nm 0.001 %
t-BuOk
(551 nm)(409431460 550 nm) MEH-PPV
T-BuOk
MEH-PPVT-BuOk
MEH-PPV t-BuOk MEH-PPV
6-6 PLE 480 nm
550 nm peak
340 nm
380 nm 340 nm
380 nm 409 nm
MEH-PPV T5 Ex 340
pack
70
6-3T2 THF (PL)(Ex 340380480 nm)
6-4T3 THF (PL)(Ex 340 nm)
71
6-5T4 THF (PL)(Ex 340380 nm)
6-6T5 THF (PL)(Ex 340380 nm, Em 560 nm)
72
6-7T6 THF (PL)(Ex 340380480 nm)
6-8T7 THF (PL)(Ex 340380480 nm)

73
6-9T8 THF (PL)(Ex 340380480 nm)
74
6-3 MEH-PPV
6-3-1
MEH-PPV
THF()DCB() 1 %
(spin coating)
PL
1
2
3
4
6-3-2 PL
6-10 T5 MEH-PPV DCB
0.5 % PL
PLE 267 nm
PL 499 nm peak
400~600 nm T5 PL
6-11 THF
75
PLE 301 nm 360 nm

PL 558 nm peak PL
THF
DCB
T5 MEH-PPV THF DCB

6-12 DCB ()THF
() PLE 299 nm 362 nm
299 nm PL 557 nm
THF ()DCB () 6-13
PLE 265 nm PL
499 nm 557 nm
DCB THF THF
DCB THF DCB
499 nm THF DCB
76
DCB DCB MEH-PPV THF

THF
( 6-14 ) T5 MEH-PPV 1 c.c.
(DCB 33 %THF 66 %) Ex 270 nm
PL 499 nm 557 nm 6-15
(DCB 66 %THF 33 %) Ex
270 nm PL 499
nm 557 nm 557 nm
DCB THF
THF
peak 557 nm peak
THF
6-16
DCBTHFTol T5 MEH-PPV
0.5 % PLE 295 nm 362 nm
295 nm PL 499 nm 543
nm DCBTHFCF ( 6-17 )
PLE 264 nm
77
PL 498 nm ( 499 nm )
543 nm CF THF
543 nm
498 nm 543 nm
6-10MEH-PPV DCB 0.05 %(Ex 270 nm)
78
6-11MEH-PPV THF 0.05%(Ex 301 nm)

nmDCB ()THF ()
79

nmTHF ()DCB ()
6-14MEH-PPV DCB (33%) THF (66%)

0.05%(Ex 270 nm)
80
6-15MEH-PPV DCB(66%) THF(33%)

0.05 %(Ex 270 nm)
6-16MEH-PPV DCBTHFTol
0.05 %(Ex 295 nm)
81
4-17MEH-PPV DCBTHFCF
0.05 %(Ex 264 nm)
82
6-4
MEH-PPV Copolymers
THF 0.0001 w/v % UV
THF Toluene
0.000010.00010.0010.010.1 1 w/v % PL
Toluene THF 1 w/v %
6-4-1
MEH-PPV Copolymers -

THF -
6-18 6-23 MEH-PPV Copolymers -
( max ) Table 5-3 5-3
PPyCzMEH-PPV 347 nm
PPyCzMEH-PPV pyridine carbazole
PPyCzMEH-PPV pyridine carbazole

PCzTpMEH-PPVPPyTpMEH-PPV 423470
83
nm thiophene thiophene
MEH-PPV
PPzCzMEH-PPV PPyPzMEH-PPV
PPzTpMEH-PPV 423 426 446 nm
phenothiazine end cap phenothiazine
MEH-PPV
6-3-
Polymer
max (nm)
PPyCzMEH-PPV
347
PCzTpMEH-PPV
423
PPyTpMEH-PPV
470
PPzCzMEH-PPV
423
PPyPzMEH-PPV
426
PPzTpMEH-PPV
446
84
1.5
PPyCzMEH-PPV
N
H3CO
H3CO
Normalized absorbance (a.u.)
*
*
347
0.5
0
300
350
400
450
500
550
600
650
700
Wavelength (nm)
6-18PPyCzMEH-PPV THF -
1.5
H3CO
PCzTpMEH-PPV
H3CO
423
1
0.5
0
350
400
450
500
550
600
650
700
Wavelength (nm)
6-19PCzTpMEH-PPV THF -
85
1.5
*
H3CO
H3CO
*
PPyTpMEH-PPV
470
1
0.5
0
350
400
450
500
550
600
650
700
Wavelength (nm)
6-20PPyTpMEH-PPV THF -
1.5
PPzCzMEH-PPV
H3CO
H3CO
423
1
0.5
0
350
400
450
500
550
600
650
700
Wavelength (nm)
6-21PPzCzMEH-PPV THF -
86
1.5
PPyPzMEH-PPV
H3CO
H3CO
N
426
1
0.5
0
350
400
450
500
550
600
650
700
Wavelength (nm)
6-22PPyPzMEH-PPV THF -
1.5
PPzTpMEH-PPV
H3CO
H3CO
N
N
S
446
1
0.5
0
350
400
450
500
550
600
650
700
Wavelength (nm)
6-23PPzTpMEH-PPV THF -
87
6-4-2
MEH-PPV Copolymers THF
THF()
1x100 w/v % 1x10-12 w/v %
6-24 6-29 MEH-PPV THF

6-24 PPyCzMEH-PPV
472 nm510 nm541 nm
(aggregate)
(red-shift) 1x10-8 w/v % 472 nm
510 nm 541 nm 6-25
PCzTpMEH-PPV
414 nm470 nm499 nm 572 nm 1x10-7 w/v %
414 nm 499 nm 572 nm
600 nm 615 nm 572 nm
6-26 PPyTpMEH-PPV
464 nm 508 nm
(aggregate) 1x10-8 w/v % 464 nm
510 nm (red-shift) 572 nm 607 nm
88
6-27 PPzCzMEH-PPV
470 nm 502 nm 1x10-7 w/v % 470 nm
502 nm 527 nm
6-28 PPyPzMEH-PPV
462 nm 550 nm 1x10-9 w/v % 462 nm
550 nm 521 nm
528 nm 6-29 PPzTpMEH-PPV
529 nm 1x10-8 w/v
% 529 nm 610 nm
MEH-PPV Copolymer THF () 1x10-12
w/v % 1 w/v % (aggregate)
Copolymer
(red-shift)
89
1.5
PPyCzMEH-PPV
H3CO
-9
H3CO
1x10 %
Normalized PL Intensity
1x10 %
472
-8
-7
1x10 %
510
-6
1x10 %
-5
1x10 %
-4
1x10 %
541
-3
1x10 %
-2
1x10 %
0.5
-1
1x10 %
0
1x10 %
0
400
450
500
550
600
650
Wavelength (nm)
6-24PPyCzMEH-PPV THF
1.5
PCzTpMEH-PPV
H3CO
1x10-12 %
H3CO
Normalized PL Intensity (a.u.)
N
*
414
1x10-11 %
-10
1x10 %
600 615
470
1x10-9%
1x10-8%
-7
1x10 %
499
1x10-6%
572
1x10-5%
1x10-4%
1x10-3%
0.5
1x10-2%
1x10-1%
1x10-0%
0
350
400
450
500
550
600
650
700
750
Wavelength (nm)
6-25PCzTpMEH-PPV THF
90
1.5
H3CO
PPyTpMEH-PPV
H3CO
1x10-12%
1x10-11%
1x10-10%
510
572
1x10-9%
607
464
1x10-8%
1x10-7%
1x10-6%
1x10-5%
1x10-4%
-3
1x10 %
0.5
1x10-2%
-1
1x10 %
0
1x10 %
0
400
500
600
700
800
Wavelength (nm)
6-26PPyTpMEH-PPV THF
1.5
PPzCzMEH-PPV
H3CO
Normalized PL intensity (a.u.)
H3CO
1x10-8 %
1x10-7 %
-6
470
502
1x10 %
527
1x10-5 %
-4
1x10 %
-3
1x10 %
-2
1x10 %
-1
1x10 %
0
1x10 %
0.5
0
450
500
550
600
650
Wavelength (nm)
6-27PPzCzMEH-PPV THF
91
1.5
PPyPzMEH-PPV
H3CO
H3CO
N
S
1x10-11 %
1x10-10 %
1x10-9%
462
500 528
1x10-8%
-7
1x10 %
1x10-6%
-5
1x10 %
-4
1x10 %
1x10-3%
1x10-2%
0.5
1x10-1%
0
1x10 %
0
400
450
500
550
600
650
Wavelength (nm)
6-28PPyPzMEH-PPV THF
1.5
PPzTpMEH-PPV
H3CO
N
S
504
529
-11
-10
1x10
H3CO
565
1x10
-9
1x10 %
1x10-8 %
597 610
-7
1x10 %
1x10-6 %
1x10-5 %
1x10-4 %
1x10-3 %
-2
1x10 %
1x10-1 %
0.5
1x10 %
0
450
500
550
600
Wavelength (nm)
650
700
6-29PPzTpMEH-PPV THF
92
6-4-2
MEH-PPV Copolymers Tol
Toluene ()
1x100 w/v % 1x10-12 w/v %
6-30 6-35 MEH-PPV Toluene

6-30 PPyCzMEH-PPV
472 nm506 nm543 nm
(aggregate)
(red-shift) 1x10-7 w/v % 472 nm
506 nm 543 nm 6-31
PCzTpMEH-PPV
471nm502nm 545 nm 1x10-9 w/v % 502 nm
545 nm 545 nm 601 nm 615 nm
6-32 PPyTpMEH-PPV
466 nm 511 nm (aggregate)
1x10-8 w/v % 466 nm 511 nm
(red-shift) 533 nm566 nm 592 nm 6-33
PPzCzMEH-PPV
93
473 nm 503nm 1x10-10 w/v % 473 nm

503 nm 522 nm 6-34
PPyPzMEH-PPV
462 nm 504 nm 1x10-10 w/v % 462 nm
504 nm 515 nm
526nm 6-35 PPzTpMEH-PPV
510nm 1x10-11 w/v %
510 nm 612 nm
MEH-PPV Copolymer Toluene () 1x10-12
w/v % 1x100 w/v %(aggregate)
(red-shift)
94
1.5
PPyCzMEH-PPV
H3CO
H3CO
-8
1x10 %
*
*
472
-7
1x10 %
-6
1x10 %
506
-5
1x10 %
-4
1x10 %
-3
1x10 %
543
-2
1x10 %
-1
1x10 %
0.5
1x10 %
0
450
500
550
600
650
Wavelength (nm)
6-30PPyCzMEH-PPV Toluene
1.5
PCzTpMEH-PPV
H3CO
H3CO
471
1x10-12 %
1x10-11 %
1x10-10 %
1x10-9 %
601 615
1x10-8 %
1x10-7 %
502
1x10-6 %
-5
1x10 %
1x10-4 %
-3
1x10 %
0.5
-2
1x10 %
-1
1x10 %
1x100%
0
440
480
520
560
600
640
680
720
Wavelength (nm)
6-31PCzTpMEH-PPV Toluene
95
1.5
N
H3CO
H3CO
PPyTpMEH-PPV
1x10-12 %
1x10-11 %
1x10-9%
511
533
1x10-10 %
566 592
1x10-8%
-7
1x10 %
466
1x10-6%
1x10-5%
1x10-4%
1x10-3%
0.5
-2
1x10 %
1x10-1%
0
450
500
550
600
650
700
Wavelength (nm)
6-32PPyTpMEH-PPV Toluene
1.5
PPzCzMEH-PPV
H3CO
H3CO
-12
1x10 %
1x10-11 %
-10
503
1x10 %
522
1x10-9%
1x10-8%
473
1x10-7%
1x10-6%
1x10-5%
-4
1x10 %
1x10-3%
0.5
-2
1x10 %
1x10-1%
1x100%
480
520
560
600
Wavelength (nm)
6-33PPzCzMEH-PPV Toluene
96
1.5
PPyPzMEH-PPV
H3CO
H3CO
Normalized absorption (a.u.)
N
S
1x10-12 %
1x10-11 %
1x10-10 %
504 515 526
1x10-9%
1x10-8%
1x10-7%
462
-6
1x10 %
1x10-5%
1x10-4%
1x10-3%
0.5
1x10-2%
1x10-1%
1x100%
0
450
500
550
600
650
Wavelength (nm)
6-34PPyPzMEH-PPV Toluene
1.5
PPzTpMEH-PPV
H3CO
H3CO
N
Normalized Intensity (a.u.)
1x10-12%
-11
1x10 %
-10
510
555
1x10 %
594 612
1x10-9%
1x10-8%
-7
1x10 %
-6
1x10 %
1x10-5%
1x10-4%
-3
1x10 %
0.5
-2
1x10 %
1x10-1%
1x100%
0
440
480
520
560
600
640
680
720
Wavelength (nm)
6-35PPzTpMEH-PPV Toluene
97
6-4-4
MEH-PPV Copolymers
6-36 6-41 THF Toluene
(solution)(solid film)
THF Toluene THF

Toluene THF
Toluene
Toluene THF
Toluene
98
1.5
PPyCzMEH-PPV
1% THF
Intensity (a.u.)
1% Tol
0.5
0
400
450
500
550
600
650
700
Wavelength (nm)
6-36PPyCzMEH-PPV Tol THF PL

1.5
PCzTpMEH-PPV
1% THF
Intensity (a.u.)
1% Tol
0.5
0
450
500
550
600
650
700
750
800
Wavelength (nm)
6-37PCzTpMEH-PPV Tol THF PL
99
1.5
1.5
PPyTpMEH-PPV
1% THF
1% Tol
Intensity (a.u.)
0.5
0.5
0
450
500
550
600
650
700
750
0
800
Wavelength (nm)
6-38PPyTpMEH-PPV Tol THF PL

1.5
PPzCzMEH-PPV
1% THF
Intensity (a.u.)
1% Tol
0.5
0
400
450
500
550
600
650
700
Wavelength (nm)
6-39PPzCzMEH-PPV Tol THF PL

100
1.5
PPyPzMEH-PPV
1% THF
Intensity (a.u.)
1% Tol
0.5
0
400
450
500
550
600
650
700
Wavelength (nm)
6-40PPyPzMEH-PPV Tol THF PL

1.5
PPzTpMEH-PPV
1% THF
1% Tol
Intensity (nm)
0.5
0
500
550
600
650
700
750
Wavelength (nm)
6-41PPzTpMEH-PPV Tol THF PL

101
6-4-5
CIE
MEH-PPV Copolymers 0.01 mg 1 mL THF
Toluene UV 365 nm
CIE
6-42 6-47
MEH-PPV Copolymers CIE 6-42 PPyCzMEH-PPV
6-43 6-44
PCzTpMEH-PPV PPyTpMEH-PPV
6-45 6-46 PPzCzMEH-PPV PPyPzMEH-PPV
6-47
PPzTpMEH-PPV CIE
CIE 6-4
102
6-4 CIE
CIE
Sample
PPyCzMEH-PPV
PCzTpMEH-PPV
PPyTpMEH-PPV
PPzCzMEH-PPV
PPyPzMEH-PPV
PPzTpMEH-PPV
THF
Tol
THF
Tol
THF
Tol
THF
Tol
THF
Tol
THF
Tol
x
0.308
0.364
0.552
0.517
0.571
0.559
0.392
0.405
0.418
0.440
0.504
0.505
y
0.532
0.521
0.342
0.359
0.328
0.351
0.566
0.537
0.552
0.524
0.375
0.335
6-42PPyCzMEH-PPV CIE
103
6-43PCzTpMEH-PPV CIE
6-44PPyTpMEH-PPV CIE
104
6-45PPzCzMEH-PPV CIE
6-46PPyPzMEH-PPV CIE
105
6-47PPzTpMEH-PPV CIE
106
7-1
[59,60] 7-1
(Working electrode) (Reference electrode)
(Auxiliary electrode) ITO (0.5 cm 5 cm)
ITO ( 5 mg
1 mL ) ITO (dip-coating)
50 0.1 M
(n-Bu)4NClO4 acetonitrile
(Supporting electrolyte) Ag/AgCl
100 mV/s0~2.5 mV
Ferrocene / Ferrocenium (Fc/Fc+)
FOC
(IP) 4.8 eV 25 (100 mV/s)
107
6-2E1/2 = (Epc+Epa) / 2(Epa

Epc ) Ag/AgCl
EFOC = 0.45 V Eonset(ox)
HOMO
HOMO = -e(Eox vs Ag/AgCl E1/2, ferrocene) + -4.8 eV
LUMO UV
HOMO LUMO
Eg(eV) = hc / onset = 1241 / onset(nm)
HOMO = LUMO - ( 1241/onset)
108
7-1
Ferrocene
30
pa
20
= 0.34
Current (
A)
10
-10
-20
-30
-40
0.2
0.4
0.6
pa
= 0.56
0.8
E (V vs. Ag/AgCl , Acetonitrile with 0.1M TBAP)
7-2
109
7-1-1
7-3~ 7-8 MEH-PPV Copolymers CV 0 V

2.5 V PPyCzMEH-PPV
1.60 VPCzTpMEH-PPV 1.25 V 1.83 V
PPyTpMEH-PPV 0.96 V 1.46 V
PPzCzMEH-PPV 1.48 V PPyPzMEH-PPV
1.74 V PPzTpMEH-PPV
0.98 V1.19 V 1.58 V
MEH-PPV Copolymers PPyCzMEH-PPV onset =
465 nmPCzTpMEH-PPV onset = 573 nmPPyTpMEH-PPV onset = 567
nmPPzCzMEH-PPV onset = 475 nmPPyPzMEH-PPV onset = 478 nm
PPzTpMEH-PPV onset = 568 nm (Egopt) 2.69 eV
2.17 eV2.19 eV2.61 eV2.60 eV 2.18 eV LUMO
HOMO 7-1 7-9 7-10 MEH-PPV
Copolymers thiophene LUMO -2.82 eV
-2.90eV
Copolymers
110
140
PPyCzMEH-PPV
120
Current (
A)
100
80
1.60
60
40
20
onset : 0.69
0
0
0.5
1.5
2.5
Potential (V)
7-3PPyCzMEH-PPV
250
PCzTpMEH-PPV
Current (
A)
200
150
1.83
100
1.25
50
onset : 0.64
0
0
0.5
1.5
2.5
Potential / V
7-4PCzTpMEH-PPV
111
100
PPyTpMEH-PPV
80
Current (
A)
1.46
60
40
0.96
20
onset : 0.66
0
0
0.5
1.5
2.5
Potential (V)
7-5PPyTpMEH-PPV
1400
PPzCzMEH-PPV
1200
Current (
A)
1000
800
1.48
600
400
200
onset : 0.72
0
0
0.5
1.5
2.5
Potential (V)
7-6PPzCzMEH-PPV
112
200
PPzPyMEH-PPV
Current (
A)
150
1.74
100
50
onset : 0.99
0
0
0.5
1.5
2.5
Potential (V)
7-7PPyPzMEH-PPV
300
PPzTpMEH-PPV
250
Current (
A)
200
1.58
150
1.19
0.98
100
50
onset : 0.68
0
0
0.5
1.5
2.5
Potential (V)
7-8PPzTpMEH-PPV
113
7-1MEH-PPV Copolymers
Eonset(ox) vs.a)
HOMO (eV) LUMO (eV) Egopt (ev)
Material
Eonset(ox)
PPyCzMEH-PPV
0.69
0.24
-5.04
-2.35
2.69
PCzTpMEH-PPV
0.64
0.19
-4.99
-2.82
2.17
PPyTpMEH-PPV
0.66
0.21
-5.01
-2.82
2.19
PPzCzMEH-PPV
0.72
0.27
-5.07
-2.46
2.61
PPyPzMEH-PPV
0.99
0.54
-5.34
-2.74
2.60
PPzTpMEH-PPV
0.68
0.23
-5.03
-2.84
2.18
EFOC(V)
a. EFOC = 0.45 V vs Ag/AgCl
114
115
7-2
(EL)
(PL)
7-2-1
ITO
ITO 70
60~90
116
7-2-2
ITO
ITO
UV-ozone ITO
(1) ITO
(2) ITO : = 3:1
20
(3) 20
(4) 20
(5) 20
(6) 20
40
7-2-3
ITO
PEDOT:PSS (HTL) ITO
10 mg 1 mL
117
1000 rpm PEDOT:PSS Ca

Al Ca
ITO
10-6 torr
20 mm x 20mm 4 mm x 2
mm 7-11
7-11
118
7-2-4
-(I-V)
(Luminance)(EL)
1. --(I-V-L)
(Exciton)
I-V-L
2. (EL)
Shutter Xe
EL
7-2-5
7-12 7-17 MEH-PPV Copolymers I-V-L I-V-L

PPzCzMEH-PPV 2463 cd/m2
Copolymer
Copolymer thiophene
1127 ~ 1269 cd/m2 thiophene
119

7-27-18~7-23MEH-PPV CopolymersELMEH-PPV
CopolymersELPL
ELPLEL7-3
7-24~7-29MEH-PPV CopolymersCIE
PPyCzMEH-PPVPPzCzMEH-PPVPPyPzMEH-PPV
PCzTpMEH-PPVPPyTpMEH-PPVPPzTpMEH-PPV
7-2
Material
a)
Max
Turn-on
Luminance
EL
Voltage Luminance Efficiency max
(nm)
(V)
(cd/m2)
(cd/A)
C.I.E
(x,y)
PPyCzMEH-PPV
7.62
1909
0.33
510
(0.27,0.41)
PCzTpMEH-PPV
3.56
1127
0.19
599
(0.59,0.40)
PPyTpMEH-PPV
5.08
1130
0.20
629
(0.62,0.36)
PPzCzMEH-PPV
5.42
2463
0.43
526
(0.36,0.59)
PPyPzMEH-PPV
15.25
1683
0.29
524
(0.33,0.56)
PPzTpMEH-PPV
5.59
1269
0.23
584
(0.57,0.42)
a) Device structure was ITO/PEDOT/Copolymer/Ca/Al.
120
2500
15
PPyCzMEH-PPV
I-V
2000
Current density (mA/cm )
V-L
Luminance (cd/m )
10
Al
Al
1500
Al
Ca
PPyCzMEH-PPV
1000
PEDOT
ITO
Glass
500
0
25
0
0
10
15
20
Bias (V)
7-12PPyCzMEH-PPV I-V-L
12
1500
PCzTpMEH-PPV
I-V
V-L
8
Luminance (cd/m )
1000
Al
Al
Al
Ca
PCzTpMEH-PPV
PEDOT
ITO
500
Glass
2
0
0
Bias
7-13PCzTpMEH-PPV I-V-L
121
10
1500
PyTpMEH-PPV
I-V
V-L
1.5
Luminance (cd/m )
1000
Al
Al
Al
Ca
PPyTpMEH-PPV
PEDOT
500
ITO
Glass
0.5
0
0
0
15
10
Bias (V)
7-14PPyTpMEH-PPV I-V-L
3500
PPzCzMEH-PPV
I-V
3000
2500
Al
Al
Al
2000
Ca
PPzCzMEH-PPV
1500
PEDOT
ITO
1000
Glass
500
0
0
Luminance (cd/m )
Current density (mA/cm2)
V-L
10
Bias (V)
7-15PPzCzMEH-PPV I-V-L
122
2500
PPyPzMEH-PPV
I-V
2000
V-L
1500
Al
Al
Al
Ca
PPyPzMEH-PPV
1000
PEDOT
Luminance (cd/m )
ITO
500
Glass
0
0
10
15
Bias (V)
20
0
25
7-16PPyPzMEH-PPV I-V-L
14
PPzTpMEH-PPV
1600
I-V
12
V-L
10
Luminance (cd/m )
1200
Al
Al
Al
Ca
800
PPzTpMEH-PPV
PEDOT
ITO
Glass
400
0
0
10
Bias (V)
7-17PPzTpMEH-PPV I-V-L
123
7-3PL EL
max PL
(nm)
506
601
592
522
526
612
Material
PPyCzMEH-PPV
PCzTpMEH-PPV
PPyTpMEH-PPV
PPzCzMEH-PPV
PPyPzMEH-PPV
PPzTpMEH-PPV
max EL
(nm)
510
599
629
526
524
619
1.5
PPyCzMEH-PPV
N
H 3CO
H 3CO
*
Normaized EL Intensity (a.u.)
510
0.5
0
350
400
450
500
550
600
650
700
Wavelenght (nm)
7-18PPyCzMEH-PPV EL
124
750
1.5
PTpCzMEH-PPV
H3CO
H3CO
*
Normaized EL intensity (a.u.)
599
0.5
0
450
500
550
600
650
700
750
800
Wavelength (nm)
7-19PCzTpMEH-PPV EL
1.5
*
H3CO
H3CO
Normaized EL intensity (a.u.)
PPyTpMEH-PPV
629
1
0.5
500
600
700
800
Wavelength (nm)
7-20PPyTpMEH-PPV EL
125
900
1.5
PPzCzMEH-PPV
H3CO
Normalized EL intensity (a.u.)
H3CO
526
0.5
0
450
500
550
600
650
700
Wavelength (nm)
7-21PPzCzMEH-PPV EL
1.5
PPyPzMEH-PPV
H3CO
H3CO
N
N
S
524
0.5
0
400
450
500
550
600
650
700
Wavelength (nm)
7-22PPyPzMEH-PPV EL
126
750
1.5
PPzTpMEH-PPV
H3CO
H3CO
N
584
619
0.5
0
450
500
550
600
650
700
750
Wavelength (nm)
7-23PPzTpMEH-PPV EL
7-24PPyCzMEH-PPV CIE
127
800
7-25PCzTpMEH-PPV CIE
7-26PPyTpMEH-PPV CIE
128
7-27PPzCzMEH-PPV CIE
7-28PPyPzMEH-PPV CIE
129
7-29PPzTpMEH-PPV CIE
130

MEH-PPV
MEH-PPV P-methoxyphenol(4-MP)
MEH-PPV
t-BuOK MEH-PPV
(T5)T5 0.001% Ex340 PL
409431460489 549 nm
MEH-PPV
phenothiazinecarbazolepyridine
thiopheneMEH-PPV
wittig reaction
(FT-IR) (1H-NMR)
(EA) MEH-PPV Copolymers
GPCMEH-PPV
3000 ~ 5000
PDI1.3300
131
(POM)
UV-vis
(PL)
(red-shift)
HOMOLUMO
thiophenethiophene
2.17 ~ 2.19 eVthiophene
2.60 ~ 2.69 eVMEH-PPV Copolymers
1909 1127 1130 2463 1683
1269 cd/m2
PPzCzMEH-PPV 0.43 cd/APCzTpMEH-PPV

0.19 cd/A2.2
thiophene
thiophene
132

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MEH-PPV

The Synthesis and Characterization of

(Dr. Wen-Chung Ou-Yang)

6-1 MEH-PPV ...65

4-5 thiophene FTIR 38

6-6T5 THF (PL)(Ex 340380 nm, Em 560

6-23PPzTpMEH-PPV THF -......85

6-41PPzTpMEH-PPV Tol THF PL ..99

7-12PPyCzMEH-PPV I-V-L .119

poly(thienylene vinylene) (PTV)

highest occupied molecular orbitalHOMO

(quantum efficiency)0.05 %[12]PPV

1999HeegerApplied Physics Letters[16]

S. A. Chen (NTHU) Electroluminescent

wittig reaction random

(2) Sodium methylate (CH3ONa) LancasterAldrich

(6) 2-Ethylhexyl bromide (BrCH2CH(C2H5)C4H9) Lancaster96%

(7) Ether (C2H10O) 95%

(13) Acetic acid, Glacial (CH3COOH) >99%

(14) Tetrahydrofuran (C4H8O) KOH Na

(16) 4-(tert-butyl)benzyl bromide (C11H15Br) Aldrich97%

(17) Methanol (CH3OH) L.C. grade99% 65

(18) Chloroform (CHCl3) TEDIAHPLC99.98%

Bruker, Model AMX-400 ppm

Heraus CHN-rapid Acetanilide

Dupont TA Instrument Co.-TGA 2050(TGA)

Hitachi F-4500 Fluorescence Spectrophotometer Xe Lamp

Jasco V-550 UV-vis Spectrophotometer

Water-717tlus Auto-Sampler 0.7 mg 1.5 ml THF

MINOLTA CS-100A THF

ULVAC SINKU-KIKI CO. VPC-060

SWIENCO TYPE PM 4908

Mol. Wt.: 333.29

Mol. Wt.: 236.35

50 g (1)para-formaldehyde 30 g (130 mmol)HCl 100 ml

41 %1H NMR (400 MHz, CDCl3)

2,6-Pyridinedicarboxaldehyde 0.142 g (1.06

chloride) 2 g (2.11 mmol) THF 15 ml

40 %1H NMR (400 MHz, CDCl3) :8.42-8.20 (m,

35%1H NMR (400 MHz, CDCl3) :8.42-8.20 (m,

elemental analysis calcd. (%) for C79H95N3O4S2C, 78.11 %; H, 7.88 %; N,

40 %1H NMR (400 MHz, CDCl3) :8.42-8.20 (m,

potassium tert-butoxide 1.5 g THF 15 ml

45 %1H NMR (400 MHz, CDCl3) :8.42-8.20 (m, 9H),

4-1 PPh3 MEH-PPV FTIR

4-2 carbazole FTIR

Mol. Wt.: 311.44

4-3 phenothiazine FTIR

4-4 pyridine FTIR

4-5 thiophene FTIR

4-6 PPzCzMEH-PPV FTIR

4-7 PPyPzMEH-PPV FTIR

4-8 PCzTpMEH-PPV FTIR

4-9 PPzTpMEH-PPV FTIR

4-10 PPyCzMEH-PPV FTIR

4-11 PPyTpMEH-PPV FTIR

4-14 phenothiazine 1H-NMR 0.83

4-15 carbazole 1H-NMR 0.79~0.84

4-12 pyridine 1H-NMR

4-13 thiophene 1H-NMR

4-14 phenothiazine 1H-NMR

4-15 carbazole 1H-NMR

4-16 PPyPzMEH-PPV 1H-NMR