light absorption in 1d and 2d nanostructured organic semiconductors
TRANSCRIPT
POUR L'OBTENTION DU GRADE DE DOCTEUR ÈS SCIENCES
acceptée sur proposition du jury:
Prof. F. Sorin, président du juryProf. H. Frauenrath, directeur de thèse
Prof. C. Lambert, rapporteurProf. R. Eelkema, rapporteurProf. F. Nüesch, rapporteur
Light absorption in 1D and 2D nanostructured organic semiconductors
THÈSE NO 6646 (2015)
ÉCOLE POLYTECHNIQUE FÉDÉRALE DE LAUSANNE
PRÉSENTÉE LE 22 MAI 2015
À LA FACULTÉ DES SCIENCES ET TECHNIQUES DE L'INGÉNIEURLABORATOIRE DES MATÉRIAUX ORGANIQUES ET MACROMOLÉCULAIRES
PROGRAMME DOCTORAL EN SCIENCE ET GÉNIE DES MATÉRIAUX
Suisse2015
PAR
Damien ROLLAND
δ
ε
Bulk Heteronjunction
First in 1995
c)
+−
Planar Heteronjunction
First in 1986
b)
+−
Single Layer
First in 1959
a)
Ordered Heteronjunction
d)
+−
*
*+−
5
21
5
34
+
−
a)
1
52
3 4
CT1
CS
CT*
(i)
(ii)
S0
S1
Energyb)
c)b)a)
a) b) c)0.3 μs
0.5 μs
1 μs
Energy (eV)
900 800 700 600
Wavelength (nm)
0
1
2
IQE
(nor
m. u
n.) Egap
500
1.4 1.6 1.8 2.0 2.2 2.4 2.6
S S
NS N
n
PCPDTBT
CTS
Polarons
38 fs
45 fs
38 fs
45 fs
100 fs
22 fs22 fs
S1
S2
S4
S0
a) b) c)
E (eV)
IQE
EQE
A by EL
A by PDS
CT 1
~N( E)
N(E) (a.u.)
10¬1
10¬2
10¬3
10¬4
10¬5
EQE(
E), A
(E),
IQE(
E)100
10¬61.2 1.4 1.6 1.8 2.42.22.0
1.38 eV
2.0 eV
2.48 eV
S
S
S
O
O
NO O
n
O
O
n
MEH-PPV PBDTTPD
IQE
EQE
A by EL
A by PDS
CT 1 ~N( E)
N(E) (a.u.)
E (eV)
EQE(
E), A
(E),
IQE(
E)
1.53 eV
2.0 eV10¬1
10¬2
10¬3
10¬4
10¬5
101
100
10¬7
10¬6
1.2 1.4 1.6 1.8 2.0
a) b)
D ANormal (25˚C)
Tilted (60-80˚C)
(trap)
c)
b)a)
d)
1: 2:
Voc =1e(EDONOR
HOMO − EAcceptorLUMO ) − 0 .3 V
c)
b)
a)
polymer polymer: PCBM (wt) processing solvent thickness (nm) Voc (V) Jsc (mA/cm2) FF η (%) IPCE (%) R s (Ω )
HMPNDT 1:1 CHCl 3 65 0.83 1.42 0.47 0.56 13.3 78.5PNDT-T 1:2 CB 55 0.73 3.25 0.50 1.18 20.1 133PNDT-BT 1:4 CB 70 0.83 2.90 0.53 1.27 16.8 68.5
c)
b)a)
c)
b)a)
(2EH/C8) (C14/C8)π–π π–π
f )
b)a)
polymerΔEDI(meV)
ΔEIM from CV(meV)
ΔEIM from UPS(meV)
RR-P3HT 150 110−140 200RRa-P3HT N/A 170 −360 230pBTTT N/A 240 −320 340pBnDT-FTAZ 130 120 110ZZ115 N/A N/A 130
c)
b)a) d)
e)
c)a) b)
PBDTTPD
stimulated emission
GS bleaching
polaron
polaron
0.5 μm 0.5 μm 2 μm
c)a) b)
c)b)a)BCP
Blend
PPV-b-PS/C60
SS
Br SS
NNN
O
O
m nH
c)
b)
a) d)
e)block random
blockrandom
BCP
P3HT-b-P3H/C60
TP3HT:PCBM
BCP P3HT:PCBM
c)
b)
a)
blend
BCP
blend
BCP
Solution Film
t t
RET 130(20) fs —CT state formation 2.7(2) ps 60(20) fsRec 1 — 1.1(2) psRec 2 55(8) ps 70(10) psRec 3 — 1.3(3) nsTriplet — >5 ns
TPT
c)
b)
a) d)
e)
Energytransfer
Chargeseparation
Chargerecomb.
Chargeseparation
Pump
Initial Dyad (n = 2–4)Improved Dyad
c)
b)
a)
d) e)
n
2.7%
c)
b)a)
c)b)a) d)
400 nm
c)
b)a)
d)
nwPBI
DA-n n = 1–4, x = 15
a)O N
H
HN
ONH
HN
O
O
O
On nX X
3289
3424
3290DA-4
DA-3tran
smis
sion
/ a.
u.
1693
1694
1692
1641
1669
tran
smis
sion
/ a.
u.
Amide A
DA-1 3423 1730
1725
1716
1729
1631
1630
1630DA-2
DA-4
DA-3
DA-1
DA-2
DA-4
DA-3
DA-1
DA-23290
3425
536
259
534
536
494
499
494
500 nm 500 nm 500 nm 500 nm
DA-1 DA-4DA-3DA-2
b) c)
d)
ε / 1
03 L m
ol-1
cm-1
0
3
2
1
0
2
1
0
2
1
0
2
1
Amide I UV/vis
800200 600400wavelength / nm
1800 1750 1700 1650 1600wavenumber / cm–1
3600 3500 3400 3300 3200 3100wavenumber / cm–1
19
NH
HN
O4
O
S NH
HN
O4
O
419
N
O
O
N
O
O19
NH
HN
O3
O
NH
HN
O3
O
19
PBI-A3
QT-A4
extended length ≈ 14–15 nm
b)
20 μm
2380 nm
2760 nm
2230 nm
c)PBI-A3 WAXSas spun
5 15 2010
inte
nsit
y / a
.u.
q / nm–1
d)6.2 Å
6.2 Å
6.2 Å
3.4 Å
3.4 Å
3.4 Å
4.6 Å
4.6 Å
4.6 Å
PBI-A3 WAXS
asspun
THFvapor
HV
fiber
PBI-A3
3.5 Å48°
89° 4.7 Å89°
a)
0
4
2
b)
Wavelength / nm
Abso
rptio
n
405372
200 300 500
10
0
-10
CD /
mde
g
407
377
400358
600
QT-A3 QT-A0
415 nm
452 nm
415
452
Magnetic field / G3460 3480 3500 3520
ESR
sign
al 1
0-4 (a
.u.)
6
3
0
-3
-6
QT-A3 in TCE
QT-A3 film
QT-A0 in TCE
d) e)24
20
16
12
8
4
0
Curr
ent /
10–
9 A
20016012080400
L = 2 μm
L = 5 μm
L = 10 μm
×10×10
QT-A3
Voltage / V
c)
Abso
rptio
n
600 800 1200 1400Wavelength / nm
702
1168
white light 0 min 180 min
10000
1.2QT-A3
QT-An (n = 0, 3)
NH
HN
O15 n n
O
S NH
HN
O 15
O
4
a)
•
•
•
d)Cl
Cl Cl
ClCl
Cl
NO
O OS
O75%, 19 g
ClCl Cl
ClCl
Cl
OO
O
ClCl Cl
ClCl
Cl
NO
O1 2
a) b)
OH
ClCl Cl
ClCl
Cl
NO
O OS
O92%, 103 g 99%, 95 g
3
c)Cl
Cl Cl
ClCl
Cl
NO
O OS
O81%, 89 g
S
c)Cl
Cl Cl
ClCl
Cl
NO
O OS
O98%, 21 g
S Br
4
5 6
Br
PdPPh3
PPh3
Ph3P
Pd
PPh3
Br
0
+2
BrSnBu3
S
R =
Br
S R/H
SBu3Sn
Ph3P
Pd
PPh3+2 S R/HS
SS
45
H/R
O
O
ClClCl
Cl Cl
Cl
NO
O
R
R/H
SS
SSR R R+
III
ClCl Cl
ClCl
Cl
NO
O OS
O
4
Br
a)Cl
Cl Cl
ClCl
Cl
NO
O OS
O39%, 16 g
S
8
S
b)Cl
Cl Cl
ClCl
Cl
NO
O OS
O79%, 13 g
S
9
S Br
a)
4
6
9
n = 1
n = 2
n = 3
12
13
14
15
16
17
n = 3 (from 4, 40%, 1.2 g)
n = 4 (from 4, 54%, 40 g)
n = 5 (from 6, 73%, 1.4 g)
n = 6 (from 6, 86%, 24 g)
n = 7 (from 9, 88%, 1.9 g)
n = 8 (from 9, 80%, 5.2 g)
ClCl Cl
ClCl
Cl
NO
O OS
n
O
O
O
ClClCl
ClCl
Cl
NO
O
Bu3Sn S SnBu3
nCl
Cl Cl
ClCl
Cl
NO
O OS Br
n
O
1011
n = 2n = 1
460 511 527370 43513 15 165 8
401 440 453309 36013 15 165 8
Normalized emission
in THF
Normalized absorption
in THF
300 400 800 nm500 600 700
a)
b)
1
10.80.40.2 0.6
2
3
4
concentration / mM0
0
700 nm300 400 500 600
25
30
20
15
10
5
0
abso
rban
ce /
a.u
.
norm
aliz
ed i
nten
sity
norm
aliz
ed i
nten
sity
norm
aliz
ed i
nten
sity
400
700 nm300 400 500 600
4
5
3
2
1
0
abso
rban
ce /
a.u
.
440
13
15
c)
d)
e)
f)
700 nm300 400 500 600
0.8
1
0.6
0.4
0.2
0
abso
rban
ce /
a.u
.
45316
0.4
0.2
1209030 60
0.6
0.8
1
concentration / μM0
0
760 1 2 3 54
25
30
20
15
10
5
0
concentration / mM
539384
13 Em.13 Abs.Absorbance
or Emission
on SiO2
300 400 800 nm500 600 700
624416
15 Em.15 Abs.Absorbance
or Emission
on SiO2
464
504
300 400 800 nm500 600 700
Absorbance
or Emission
on SiO2
300 400 800 nm500 600 700
62243016 Em.16 Abs.
487
525
300 400 800 nm500 600 700
53543817 Em.17 Abs.
359
Normalized
absorption
or emission
in THF
63737917 Em.17 Abs.
483
Normalized
absorption
or emission
on SiO2
Fmoc OHNH
O
R
FmocHN
NH
O
R
18a R = Me
18b R = H
O
O
R
FmocHN
NH
O
R
OH
O
R
FmocHN
NH
O
NH
O
O
O FmocHN
NH
O
NH
O
O
OH
21 22
18, 20 or 22
17
HN
H2N
R
Op
26, 27a, 28 p = 1, 2, 3; R = Me
27b p = 2; R = H
17
HN
NH
R
Op
23, 24a, 25 p = 1, 2, 3; R = Me
24b p = 2; R = H
Fmoc
20a + 27a
17
HN
H2N
Op
30 p = 4
17
HN
NH
Op
29 p = 4
Fmoc
i) ii)
i) ii)
iii) iv)
v) iv)
19a R = Me
19b R = H
20a R = Me
20b R = H
SNH
OHN
O17
NH
OHN
O174p p
NH
HHN
O17 p
THF
T4A0 p = 0 (600 mg, 48%)
T4A1 p = 1 (767 mg, 73%)
T4A2 p = 2 (1.39 g, 65%)
T4A3 p = 3 (474 mg, 84%)
T4A4 p = 4 (473 mg, 86%)
T6A0 p = 0 (203 mg, 73%)
T6A2 p = 2 (1.21 g, 86%) R = Me
T6A3 p = 3 (418 mg, 89%)
T6G2 p = 2 (578 mg, 79%) R = H
13
PIB-NH2 p = 0
26, 27a, 28, 30 p = 1–4
SNH
OHN
O17
R
NH
OHN
O17
R
6p p
NH
HHN
O17
R
p
THF15
PIB-NH2 p = 0
27a, 28 p = 2, 3 R = Me
27b p = 2 R = H
T7A0 p = 0 (200 mg, 78%)
T7A2 p = 2 (276 mg, 88%)
T7A3 p = 3 (255 mg, 95%)
SNH
OHN
O17
NH
OHN
O177p p
NH
HHN
O17 p
THF16
PIB-NH2 p = 0
27a, 28 p = 2, 3
T8A0 p = 0 (112 mg, 73%)
T8A2 p = 2 (751 mg, 91%)
T8A3 p = 3 (254 mg, 91%)
SNH
OHN
O17
NH
OHN
O178p p
NH
HHN
O17 p
THF17
PIB-NH2 p = 0
27a, 28 p = 2, 3
T3A0 p = 0 (63 mg, 40%)
T3A2 p = 2 (237 mg, 64%)
T3A3 p = 3 (215 mg, 63%)
SNH
OHN
O17
NH
OHN
O173p p
NH
HHN
O17 p
THF12
PIB-NH2 p = 0
27a, 28 p = 2, 3
T5A0 p = 0 (110 mg, 52%)
T5A2 p = 2 (350 mg, 77%)
T5A3 p = 3 (210 mg, 66%)
SNH
OHN
O17
NH
OHN
O175p p
NH
HHN
O17 p
THF14
PIB-NH2 p = 0
27a, 28 p = 2, 3
π
QT-A3 (m = 3, n = 4, p = 3)
TnAp (m = 2)
SHN
O
NH
O
17
HN
O
NH
O
17
pp n
m m
1800 1750 1700 1650 1600 cm–1
Amide I (νC=O
)
1626
1663
1667
1668
1667
1626
1627
1669
1627
1630
1667
1627
1629
1638
T4A0
T7A0
T4A1
T4A2
T4A3
T7A2
T6A0
T6A3
T8A0
T8A2
T7A3
T4A4
T5A0
T5A2
T5A3
T3A0
T3A2
T3A3
T6A2
T8A3
1626
1628
1630
1629
1626
1626
3600 3500 3300 3200 3100 cm–1
Amide A (νN–H
)
3400
3288
3431
3442
3287
3440 3304
3431
3443
3290
3286
3291
3290
34443306
3292
3292
3287
3287
3443
3286
3289
3291
Transmission / a.u.
T4A2
1 μm
T4A3
1 μm
T4A1
1 μm
T5A3
1 μm
T5A2
1 μm
T5A0
1 μm
T3A3
1 μm
T3A2
1 μm
T3A0
1 μm
T6A3
1 μm
T7A0
1 μm
T7A2
1 μm
T7A3
1 μm
T8A0
1 μm
T8A2
1 μm
T8A3
1 μm
T6A2
1 μm50 nm
height
phase
T6A0
1 μm
50 nm
T7A0
T4A2
T3A3
T4A3
T5A3
T7A2
T6A0
T6A2
T8A0
T8A2
T7A3
T6A3
T8A3
Milar®
5 10 15 20 25q / nm–1
WAXS
6.1 Å4.7 Å
6.1 Å
4.6 Å
3.20 Å3.9 Å
4.0 Å
6.1 Å
4.5 Å
3.42 Å
6.1 Å4.6 Å
3.24 Å4.0 Å
6.1 Å 4.5 Å
3.24 Å4.1 3.9
6.1 Å4.6 Å
3.21 Å4.0 Å
6.1 Å4.6 Å
3.20 Å3.9 Å
6.1 Å 4.6 Å
3.25 Å4.0 Å
6.2 Å 4.6 Å
3.22 Å4.0 Å
6.1 Å4.6 Å
3.20 Å4.0 Å
6.1 Å
4.6 Å
3.24 Å4.0 Å
6.1 Å
4.6 Å
3.20 Å3.9 Å
6.1 Å
4.6 Å
3.20 Å3.9 Å
0.2 1 5
SAXS
5.28 nm
6.59 nm
6.69 nm
7.59 nm
6.14 nm
6.06 nm
7.22 nm
6.69 nm
7.71 nm
7.85 nm
6.79 nm
7.34 nm
8.43 nm
q / nm–1
Heating 20˚C 100˚CT4A2 T4A2
0
4Ex
tinct
ion
/ 10
.000
L m
ol–
1 cm
-1
0.5
1.5
1
A(365nm)
A(413nm)
400300 500600 nm 4520 70
355
384
355
386
600 nm400300 500 100 ˚C
Mol
ar E
llipt
icit
y / 1
00 d
eg L
mol
–1
cm-1
Mol
ar E
llipt
icit
y / 1
00 d
eg L
mol
–1
cm-1
-13
0
13
-13
0
13
369368
401
372 373
401
Cooling 100˚C 20˚C Reversibility
heating
cooling
heating
cooling
T4A2T4A1 T4A3
T5A0 T5A2 T5A3
T3A0 T3A2 T3A3
x20
370
375
608
385425
381
421
407401
372
352
355
384
379
333
368
369
363
402
362
399
429
420
372
366369
366
410
0
12
-12
0
0
8
5
0
40
-40
4
0
3
-3
0
3
ε / 1
04 L m
ol–
1 cm
-1[θ
] / 1
00 d
eg L
mol
–1
cm-1
ε / 1
0.00
0 L
mol
–1
cm-1
[θ] /
100
deg
L m
ol–
1 cm
-1ε /
10.
000
L m
ol–
1 cm
-1[θ
] / 1
00 d
eg L
mol
–1
cm-1
400 500300 600 nm 400 500300 600 nm 400 500300 600 nm
T6A0 T6A2 T6A3
T7A0 T7A2 T7A3
T8A0 T8A2 T8A3
400 500300 600 nm 400 500300 600 nm 400 500300 600 nm
398
404
403
449
452405404
397
404
427447
403
438
385
419
374
411
382
422
383
426
384
422386
419
0
0
20
-20
5
070
-70
0
8
0
0
35
-35
8
ε / 1
0.00
0 L
mol
–1
cm-1
[θ] /
100
deg
L m
ol–
1 cm
-1ε /
10.
000
L m
ol–
1 cm
-1[θ
] / 1
00 d
eg L
mol
–1
cm-1
ε / 1
0.00
0 L
mol
–1
cm-1
[θ] /
100
deg
L m
ol–
1 cm
-1
20°C
100°C
Ellipticity / a.u.
T4A2 T4A3 T6A2L-Ala L-Ala L-Ala
400300 500 600 nm600 nm400300 500 400300 500 600 nm
D-Ala D-Ala D-Ala
T6G2
1 μm
T6G2
0
0
15
-15
5
ε / 1
0.00
0 L
mol
–1
cm-1
[θ] /
100
deg
L m
ol–
1 cm
-1
400 500300 600
Wavelength / nm
432386
1800 1750 1700 1650 1600
Amide I (νC=O
)
1648
Wavenumber / cm–1
3600 3500 3300 3200 3100
Amide A (νN–H
)
3400
3310
Wavenumber / cm–1
5 10 15 20 25
WAXS 6.1 Å
4.6 Å
3.23 Å3.9 Å
q / nm–1
0.2 1 5
SAXS 7.46 nm
q / nm–1
T6G2
T6G2
a)
b)
c) d)
50 nm
392
853
1751
1000 1500 2000 nm500
T6A3Light
Light
Abso
rptio
n / a
.u.
×10
P2
P1
+P1
P2
a) b)
400 500300 600 nm
T3A3
T5A3
T6A3
T4A3
T7A3
T8A3
402
400
396
385
372
353
TnA3
Absorption / a.u.
19001200500 2600 nm
7471154
1007
597
905
853
735
1755
1400
789 1495
1225
2110
1626
913780
943820
2407
1830
P2 P1
×20
×20
×20
×20
×20
×20
T3A3 T4A3 T5A3 T6A3 T7A3 T8A3
+ + + + + +
Aggregated
P2
P1
Blue-shift
Molecularly
dispersed
Kohn plots
1 / # thiophenes
Tran
sitio
n en
ergy
/ eV
3
2
1
01/7 1/6 1/5 1/4 1/31/8
a) b)
0-0.2 0.2 eV
P1
P1’
T3A3
T4A3
T5A3
T6A3
T7A3
T8A3
Nor
mal
ized
abs
orpt
ion
×
Α Α Α λ
⋅
45 min200
T3A3
T4A3
T5A3
T6A3
T7A3
T8A3
4%2.50
T3A3
T4A3
T5A3
T6A3
T7A3
T8A3
7 min20
T3A3
T4A3
T5A3
T6A3
T7A3
T8A3
3 h20
T3A3
T4A3
T5A3
T6A3
T7A3
T8A3
30 h200
T3A3
T4A3
T5A3
T6A3
T7A3
T8A3
a) b)
c)
τ1gen τ2
gen Asat
= A(P1) / A(λmax
)
τ1dec τ2
dec
50 h250
T6A2
T6A3
T7A2
T7A3
T8A2
T8A3
500 h2500
T6A2
T6A3
T7A2
T7A3
T8A2
T8A3
4%20
T6A2
T6A3
T7A2
T7A3
T8A2
T8A3
40 h200
T6A2
T6A3
T7A2
T7A3
T8A2
T8A3
4 h20
T6A2
T6A3
T7A2
T7A3
T8A2
T8A3
a) b)
c)
τ1gen τ2
gen Asat
= A(P1) / A(λmax
)
τ1dec τ2
dec
6040 800 20
T6A2
T6G2
100 min0
Abso
rptio
n / a
.u.
Abso
rptio
n / a
.u.
0.6
15100 5 20 h
T6A2
T6G2
0
0.6Illumination Decay
100 1500 50
T7A2
T7A0
200 min0
Abso
rptio
n / a
.u.
Abso
rptio
n / a
.u.
0.25
15100 5 20 h
T7A2
T7A0
0
0.25
Illumination Decay
1501000 50
T8A2
T8A0
200 min0
Abso
rptio
n / a
.u.
Abso
rptio
n / a
.u.
0.14
15100 5 20 h
T8A2
T8A0
0
0.14Illumination Decay
Glass substrate
N
O
O
O
On
SSS
S NN
O
O
O
O
n
N
PTP-n
PBI PBIT4
N
O
O
O
O
S
SS
SNN
O
O
O
O
N
N
O
O
O
O
ON
O
O
O
O
O
OO
O
O
O
O
O a)
c)
b)
31 33a n = 9 (12.7 g, 46%)33b n = 19 (430 mg, 60%)
34a n = 9 (8.77 g, 94%)34b n = 19 (277 mg, 98%)
PTP-9PTP-19
N
O
O
N
O
O
S
SS
S HN
PIB19NH
PIB19
O
O
n
PIBn =
PIBn
PIBn PIBn
PIB19 PIB19
PIBn
35
36
n = 9 (321 mg, 34%)n = 19 (54 mg, 42%)
⋅
PTP-19 in ODCB527
491
558
467440
398
500 600 700 800 nm
15
0300 400
ε / 1
04 L m
ol–
1 cm
–1
a)100˚C 20˚C PTP-19 on SiO
2
509542
467
610
500 600 700 800 nm
0.3
0300 400
Abso
rptio
n / O
D
b)25˚C 175˚C 300˚C
200 μm
Ra)
300 400 500 600 800 nm700
Abs /
a.u
. — = 6.4
b)
0.13
0.02
0
558 nm
A
A
PTP-9
0.2 1 5q / nm–1
Inte
nsit
y / a
.u.
q = 0.98
d = 6.40 nm
2.06
3.12
q = 0.84
d = 7.47 nm
1.56
3.13
a)SAXSPTP-9
PTP-19
5 10 15 20q / nm–1
Inte
nsit
y / a
.u.
9.45 Å
7.90 Å
6.67 Å
3.78 Å
7.90 Å
6.70 Å
3.78 Å
b)WAXS
PTP-9
PTP-19
100 nm
a) PTP-9 as deposited
100 nm
b) PTP-19 as deposited
100 nm
d) PTP-19 rubbed & annealed
100 nm
c) PTP-9 rubbed & annealed
100 nm
Height
100 nm
Phase
b) PTP-19 rubbed & annealedHeight
100 nm
Phase
a) PTP-9 rubbed & annealed
R
a) PTP-19
7.93
2.90
3.66 6.68
R
b) PTP-9
7.99
2.96
3.78
4.17
R
c) PTP-9, 23° tilt
7.93
7.092.95
3.77
300 400 500 600 800 nm700
Inte
nsit
y / a
.u.
531 539
493
576
531
461
PTP-19 absorption
PTP-19 emission x100
35/36 (2:1) emission x1
35/36 PTP-19
35/36 2:1 @ 530 nm
493
534
581
710
500 600 700 nm
40
0
-40
400
2 ps
1000 ps
ΔAbs
/ m
OD
b)
60
0
-60
PTP-19 @ 530 nm
535
495 579
717
690712
400 500 600 700
0.2 ps
8.8 ps
1000 ps
ΔAbs
/ m
OD
c)Global fit
400
680
530
495580
720
720685
500 600 700 nm
5.2 ps; Separation27 ps; Recombination
15
0
-15533
493578
715685
400 500 600 700
461
0 ps
9 ps
1000 psΔA
bs /
mO
D
PTP-19 @ 390 nmf)
493
463
531
706617
500 600 700 nm
5
0
-5
400
2 ps
1000 ps
ΔAbs
/ m
OD
35/36 2:1 @ 390 nme)
400
680530
490
460
580720
715685
500 600 700 nm
4.7 ps; Separation29 ps; Recombination
Global fit
20
0
-20
35 @ 530 nm
533
493580
709
400 500 600 700 nm
2 ps
1000 ps
a)
ΔAbs
/ m
OD
15
0
-15 528463493
618 694582
400 500 600 700 nm
36 @ 390 nm
2 ps
1000 ps
ΔAbs
/ m
OD
d)
b)
0
4
-12
ΔAbs
/ m
OD
35/36 2:1 @ 530 nm
482
559
400 500 600 700 nm
1 ps
1500 ps
e)
1
0
-1
ΔAbs
/ m
OD
35/36 2:1 @ 390 nm
485518
559
504
538
400 500 600 700 nm
0.2 ps
1500 ps
6
0
-6
ΔAbs
/ m
OD
PTP-19 @ 530 nm
471
443
558
708
400 500 600 700
c)
0.2 ps
5 ps
1500 ps
Global fit
400
565
440
470
710
500 600 700 nm
1.3 ps; Separation142 ps; Recombination1429 ps; Long-lived
475440
715
3
0
-3
PTP-19 @ 390 nm
471442
557
536505
713
400 500 600 700
f)
ΔAbs
/ m
OD
0.2 ps
6 ps
1500 ps
Global fit
400
470
440
715
555
720
480
445
505 535
500 600 700 nm
2 ps; Separation174 ps; Recombination2219 ps; Long-lived
d)
0.5
0
-2.5
ΔAbs
/ m
OD
35 @ 390 nm
519
480
560
539502
400 500 600 700 nm
0.2 ps
1500 ps
a)5
0
-15
ΔAbs
/ m
OD
35 @ 530 nm
482
400 500 600 700 nm
559
1 ps
1500 ps
Timedelay / ps
1.2
0.6
0.2
1Anisotropy =
0.8
0.4
0
-0.2
Anis
otro
py
Par. - Per.
0 300 600 900 1200 1500
Par. + 2∙Per.Film rubbed
Film as deposited
Timedelay / ps
Nor
mal
ized
ΔAb
s
0 200 400 600 800 1000
PTP-19 film (174 ps)
PTP-9 film (137 ps)
PTP-19 solution (30 ps)
Recombination dynamics at 710 nma) b)
•
•
•
•
×
μ
™
∼
μ
•
•
•
•