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

•

•

•

•