Efficient organic solar cells processed from hydrocarbon ...€¦ · Efficient organic solar cells processed from hydrocarbon solvents Jingbo Zhao, Yunke Li, Guofang Yang, Kui Jiang,

SUPPLEMENTARY INFORMATIONARTICLE NUMBER: 15027 | DOI: 10.1038/NENERGY.2015.27

NATURE ENERGY | www.nature.com/natureenergy 1

Efficient organic solar cells processed from hydrocarbon solvents

Jingbo Zhao, Yunke Li, Guofang Yang, Kui Jiang, Haoran Lin, Harald Ade, Wei Ma and He Yan

http://dx.doi.org/10.1038/nenergy.2015.27

Supplementary Tables

Supplementary Table 1. A comparison of DIO and several potential hydrocarbon additives. The

unit for temperatures is ºC

Classification Example Boiling

point

Melting

point Note

State-of-the-art additive DIO ~332 ~20 Halogenated, unstable

Aliphatic hydrocarbons Octadecane 317 ~30 Poor solvents

for fullerenes Alkylbenzenes 1-Phenyldodecane 331 3

Polycyclic arenes

1,2-Dimethylnaphthalene 270 ~-2 Low boiling point

Anthracene 340 210 High melting point

2-Phenylnaphthalene 346 103

PN 325 40* Ideal choice

* Although a reported melting point of PN is slightly higher than room temperature1, commercially

available products of PN from different vendors all exist as liquids. Several reports also show that

PN (purity > 99.5%) is difficult to crystallize at room temperature.2, 3

Supplementary Table 2. Hole and electron mobilities of PffBT4T-C9C13:PC71BM blend films

processed from TMB-PN and TMB.

Processing solvents Hole mobility (cm2 V-1 s-1) Electron mobility (cm2 V-1 s-1)

TMB-PN 7.0×10-3 3.4×10-3

TMB 6.6×10-3 1.2×10-4

Supplementary Table 3. Solar cell performance of PffT2-FTAZ-C10C14 processed from TMB-PN

or CB-DIO. The statistics are from 10 devices.

Solvents VOC (mV) Jsc (mA cm-2) FF (%) PCE (%)

TMB-PN 827 ± 7 14.3 ± 0.4 71 ± 2 8.4 ± 0.3 (8.7)

CB-DIO 819 ± 3 13.3 ± 0.6 68 ± 3 7.4 ± 0.1 (7.7)

Supplementary Table 4. Summary of morphology parameters and solar cell performance processed

from TMB-PN or CB-DIO of the two polymers.

Polymer Processing

system PCE (%)

Domain

spacing (nm)

Domain

purity

Anisotropy

parameter

PffBT4T-C9C13 TMB-PN 11.3 ± 0.1 (11.7) 38 1.00* 0.26

CB-DIO 9.1 ± 0.2 (9.6) 40 0.90 0.14

PffT2-FTAZ-

C10C14

TMB-PN 8.4 ± 0.3 (8.7) 38 1.00* 0.26

CB-DIO 7.4 ± 0.1 (7.7) 45 0.92 0.17

* The domain purity was compared between two solvent systems for each material and does NOT

indicate a same purity level of the two polymers processed from TMB-PN.

Supplementary Table 5. Solar cell performance processed from different solvents of PTB7 and

PTB7-Th. The statistics are from 10 devices.

Polymer Solvents VOC (mV) Jsc (mA cm-2) FF (%) PCE (%)

PTB7 CB-DIO 752 ± 2 16.4 ± 0.3 0.63 ± 0.01 7.7 ± 0.2 (7.9)

TMB-PN 778 ± 2 16.1 ± 0.2 0.65 ± 0.01 8.2 ± 0.1 (8.4)

PTB7-Th CB-DIO 790 ± 7 16.2 ± 0.3 0.61 ± 0.03 7.8 ± 0.3 (8.4)

TMB-PN 787 ± 5 16.2 ± 0.2 0.64 ± 0.01 8.1 ± 0.1 (8.3)

Supplementary Figures

Supplementary Figure 1. Structural comparison of 1-phenylnaphthalene and 2-phenylnaphthalene.

The values of dihedral angle between the phenyl ring and the naphthyl ring are cited from a previous

report.4

400 500 600 700 8000.0

0.2

0.4

0.6

0.8

1.0

1.2

No

rmaliz

ed a

bsorp

tion (

a.u

.)

Wavelength (nm)

30

40

50

60

70

80

90

100

Supplementary Figure 2. UV-Vis absorption spectra of PffBT4T-C9C13 at elevated temperatures in

a 0.02 mg mL-1 TMB solution. The insets indicate temperatures (units: °C).

Supplementary Figure 3. Independent certification by Newport Corporation confirming a power

conversion efficiency of 11.48%.

Supplementary Figure 4. AFM (1×1 μm) images of PffBT4T-C9C13:PC71BM blend films processed from a, TMB-PN and b, TMB. The height and phase images are displayed on the left and right sides, respectively.

Supplementary Figure 5. J1/2~V characteristics of a, hole only and b, electron only devices. Dash lines are fits.

Supplementary Figure 6. PSoXS profiles for PffBT4T-C9C13:PC71BM films processed from various solvents at 285.2 eV. a, TMB-PN. b, TMB. c, CB-DIO. The red line represents the fully integrated average data; blue and green lines are 10° scattering sector averages at the direction perpendicular and parallel to the electric field of X-rays, respectively.

20°

0°0 nm

50 nm10°

0°0 nm

20 nm a b

100 nm 100 nm

RMS = 2.0 nm RMS = 5.2 nm

a b

1.5 2.0 2.5 3.0 3.5 4.00

10

20

30

40

50

TMB-PN 320 nm slope = 17.5 TMB 250 nm slope = 4.81

J 0.

5 (A0.

5 m-1)

Voltage (V)1.0 1.5 2.0 2.5 3.0 3.5 4.0

0

20

40

60

80

100

TMB-PN 410 nm slope = 16.9 TMB 380 nm slope = 19.5

J 0.

5 (A0.

5 m-1)

Voltage (V)

a b c

0.0 0.1 0.2 0.3 0.4 0.50.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

ytisnetnIq

2 (10-7

nm

-2)

q (nm-1)

TMB A (E) = 0.29

0.0 0.1 0.2 0.3 0.4 0.50.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

ytisnetnIq

2 (10-7

nm

-2)

q (nm-1)

TMB-PN A (E) = 0.26

0.0 0.1 0.2 0.3 0.4 0.50.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

ytisnetnIq

2 (10-7

nm

-2)

q (nm-1)

CB-DIO A (E) = 0.14

400 500 600 700 8000.0

0.2

0.4

0.6

0.8

1.0

1.2

No

rma

lize

d a

bso

rptio

n (

a.u

.)

Wavelength (nm)

PffBT4T-C9C

13 TMB-PN

PffBT4T-C8C

12 CB-DIO

PffBT4T-C9C

13 CB-DIO

Supplementary Figure 7. UV-Vis absorption spectra of PffBT4T-C9C13:PC71BM films processed

from CB-DIO and TMB-PN, as well as PffBT4T-C8C12:PC71BM film processed from CB-DIO.

Supplementary Figure 8. Solar cell performance of polymer:PC71BM processed from CB-DIO. a,

J–V curves of the solar cells. b, EQE spectra of the cells.

Supplementary Figure 9. Solar cell performance of polymer:PC71BM processed from TMB-PN.

a, J–V curves of the solar cells. b, EQE spectra of the cells.

a b

-0.2 0.0 0.2 0.4 0.6 0.8 1.0-25

-20

-15

-10

-5

0

5

Cu

rren

t de

nsity (

mA

cm

-2)

Voltage (V)

PffBT4T-C8C

12

PffBT4T-C9C

13

PffBT4T-C10

C14

300 400 500 600 700 8000

20

40

60

80

100

EQ

E (

%)

Wavelength (nm)

PffBT4T-C8C

12

PffBT4T-C9C

13

PffBT4T-C10

C14

a b

-0.2 0.0 0.2 0.4 0.6 0.8 1.0-25

-20

-15

-10

-5

0

5

Voltage (V)

Cu

rren

t de

nsity (

mA

cm

-2)

PffBT4T-C8C

12

PffBT4T-C9C

13

PffBT4T-C10

C14

300 400 500 600 700 8000

20

40

60

80

100

Wavelength (nm)

EQ

E (

%)

PffBT4T-C8C

12

PffBT4T-C9C

13

PffBT4T-C10

C14

Supplementary Figure 10. RSoXS profile of polymer:PC71BM films processed from TMB-PN. The inset indicates the relative domain purity.

Supplementary Figure 11. Chemical structures and 2D GIWAXS images of PffBT4T-C6C10 and PffBT4T-C7C11 blended with PC71BM and processed from CB-DIO.

Supplementary Figure 12. Chemical structures of PffT2-FTAZ-C10C14, PTB7 and PTB7-Th.

0.0 0.1 0.2 0.3 0.4 0.5 0.60.0

0.2

0.4

0.6

0.8

1.0 PffBT4T-C8C12 1.04 PffBT4T-C9C13 1.00 PffBT4T-C10C14 0.88

ytisnetnIq

2 (10-6

nm

-2)

q (nm-1)

q zÅ(

1-)

0.25.1

0.15.0

0.00.0 -0.5 -1.0 -1.5

qxy (Å-1)

q zÅ(

1-)

0.25.1

0.15.0

0.00.0 -0.5 -1.0 -1.5

qxy (Å-1)

C7C11CB-DIO

C6C10CB-DIO

Supplementary Figure 13. Solar cell performance of PffT2-FTAZ-C10C14:PC71BM processed from TMB-PN and CB-DIO. a, J–V curves of the solar cells. b, EQE spectra of the cells.

Supplementary Figure 14. RSoXS and PSoXS profiles for PffT2-FTAZ-C10C14:PC71BM films processed from various solvents. a, RSoXS plots of the blend films. The inset indicates the relative domain purity. b, PSoXS profile of a film processed from TMB-PN. c, PSoXS profile of a film processed from CB-DIO. The red line represents the fully integrated average data; blue and green lines are 10° scattering sector averages at the direction perpendicular and parallel to the electric field of X-rays, respectively.

Supplementary Figure 15. Solar cell performance of PTB7:PC71BM processed from TMB-PN and CB-DIO. a, J–V curves of the solar cells. b, EQE spectra of the cells.

a b

-0.2 0.0 0.2 0.4 0.6 0.8 1.0-15

-10

-5

0

5

Voltage (V)

mc A

m( ytisned tnerruC

-2)

TMB-PN CB-DIO

300 400 500 600 700 8000

20

40

60

80

100

Wavelength (nm)

)%(

EQ

E

TMB-PN CB-DIO

a b c

0.0 0.1 0.2 0.3 0.4 0.5 0.60.0

0.2

0.4

0.6

0.8

q (nm-1)

ytisnetnIq

2 (10-6

mn -2) TMB-PN 1.00

CB-DIO 0.92

0.0 0.1 0.2 0.3 0.4 0.50.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

ytisnetnIq

2 (10-7

nm

-2)

q (nm-1)

TMB-PN A (E) = 0.26

0.0 0.1 0.2 0.3 0.4 0.50.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

ytisnetnIq

2 (10-7

nm

-2)

q (nm-1)

CB-DIO A (E) = 0.17

a b

-0.2 0.0 0.2 0.4 0.6 0.8 1.0-20

-15

-10

-5

0

5

Voltage (V)

mc A

m( ytisned tnerruC

-2)

TMB-PN CB-DIO

300 400 500 600 700 8000

20

40

60

80

100

Wavelength (nm)

)%(

EQ

E

TMB-PN CB-DIO

Supplementary Figure 16. Solar cell performance of PTB7-Th:PC71BM processed from TMB-PN

and CB-DIO. a, J–V curves of the solar cells. b, EQE spectra of the cells.

7 8 9 10 11 120.0

0.2

0.4

0.6

0.8

1.0

Re

lative A

bundance

Time (min)

Annealed

As cast

Supplementary Figure 17. GC-MS spectra of active layers (as cast or annealed) processed from

TMB-PN. The peak at 8.03 min has an m/z of 204 and corresponds to PN.

a b

300 400 500 600 700 8000

20

40

60

80

100

Wavelength (nm)

EQ

E (

%)

TMB-PN

CB-DIO

-0.2 0.0 0.2 0.4 0.6 0.8 1.0-20

-15

-10

-5

0

5

Voltage (V)

Cu

rre

nt d

en

sity (

mA

cm

-2)

TMB-PN

CB-DIO

Supplementary Figure 18. 1H NMR spectrum of ethyl 2-nonyltridecanoate (compound S1).

Supplementary Figure 19. 13C NMR spectrum of ethyl 2-nonyltridecanoate (compound S1).

10 9 8 7 6 5 4 3 2 1 ppm

0.879

0.895

1.253

1.395

1.410

1.430

1.444

1.559

1.580

1.594

2.264

2.277

2.287

2.299

2.312

2.322

2.335

4.107

4.124

4.142

4.160

6.1

2

36.3

5

2.7

9

2.1

9

0.9

9

2.0

0

Current Data ParametersNAME JZhao-C9C13-EsterEXPNO 1PROCNO 1

F2 - Acquisition ParametersDate_ 20141130Time 21.43INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9845889 secRG 64DW 60.800 usecDE 6.00 usecTE 294.3 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 13.60 usecPL1 -1.00 dBSFO1 400.1324710 MHz

F2 - Processing parametersSI 32768SF 400.1300019 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

C11H23 COOEt

C9H19

200 180 160 140 120 100 80 60 40 20 ppm

14.251

14.496

22.830

27.584

29.451

29.498

29.633

29.701

29.729

29.781

32.039

32.066

32.673

45.922

60.048

176.793

Current Data ParametersNAME JZhao-C9C13-EsterEXPNO 2PROCNO 1

F2 - Acquisition ParametersDate_ 20141130Time 22.07INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 302DS 2SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 2050DW 20.800 usecDE 6.00 usecTE 295.3 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1

======== CHANNEL f1 ========NUC1 13CP1 9.25 usecPL1 -3.00 dBSFO1 100.6228298 MHz

======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 80.00 usecPL12 12.45 dBPL13 18.00 dBPL2 -1.00 dBSFO2 400.1316005 MHz


C11H23 COOEt

C9H19

Supplementary Figure 20. 1H NMR spectrum of 2-nonyltridecanol (compound S2).

Supplementary Figure 21. 13C NMR spectrum of 2-nonyltridecanol (compound S2).

10 9 8 7 6 5 4 3 2 1 ppm

0.864

0.881

0.898

1.263

1.376

1.441

1.454

3.527

3.541

6.1

1

40.1

9

2.0

0

Current Data ParametersNAME JZhao-C9C13-OHEXPNO 1PROCNO 1

F2 - Acquisition ParametersDate_ 20150304Time 11.01INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 8012.820 HzFIDRES 0.122266 HzAQ 4.0894465 secRG 31.55DW 62.400 usecDE 6.50 usecTE 296.4 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 400.1324710 MHzNUC1 1HP1 14.50 usecPLW1 11.99499989 W


C11H23

C9H19

OH

200 180 160 140 120 100 80 60 40 20 ppm

14.254

22.837

27.044

29.506

29.806

29.829

30.224

31.084

32.073

40.687

65.892

Current Data ParametersNAME JZhao-C9C13-OHEXPNO 2PROCNO 1

F2 - Acquisition ParametersDate_ 20150304Time 11.38INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgpg30TD 65536SOLVENT CDCl3NS 647DS 2SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 196.92DW 20.800 usecDE 6.50 usecTE 297.7 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========SFO1 100.6228298 MHzNUC1 13CP1 9.70 usecPLW1 46.98899841 W

======== CHANNEL f2 ========SFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 90.00 usecPLW2 11.99499989 WPLW12 0.34213999 WPLW13 0.27713001 W


C11H23

C9H19

OH

Supplementary Figure 22. 1H NMR spectrum of 2-nonyltridecyl bromide (compound S3).

Supplementary Figure 23. 13C NMR spectrum of 2-nonyltridecyl bromide (compound S3).

10 9 8 7 6 5 4 3 2 1 ppm

0.865

0.882

0.898

1.264

1.579

1.592

3.441

3.453

6.3

9

37.3

0

0.9

8

2.0

0

Current Data ParametersNAME JZhao-C9C13-BrEXPNO 1PROCNO 1

F2 - Acquisition ParametersDate_ 20141209Time 21.17INSTRUM spectPROBHD 5 mm DUL 13C-1PULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 8012.820 HzFIDRES 0.122266 HzAQ 4.0894465 secRG 4.51DW 62.400 usecDE 6.50 usecTE 295.7 KD1 1.00000000 secTD0 1



Br

C9H19

C11H23

200 180 160 140 120 100 80 60 40 20 ppm

14.276

22.846

26.709

29.489

29.511

29.748

29.793

29.825

29.937

32.076

32.704

39.644

39.910

Current Data ParametersNAME JZhao-C9C13-BrEXPNO 2PROCNO 1

F2 - Acquisition ParametersDate_ 20141209Time 21.22INSTRUM spectPROBHD 5 mm DUL 13C-1PULPROG zgpg30TD 65536SOLVENT CDCl3NS 83DS 2SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 196.92DW 20.800 usecDE 6.50 usecTE 296.6 KD1 2.00000000 secD11 0.03000000 secTD0 1




Br

C9H19

C11H23

Supplementary Figure 24. 1H NMR spectrum of 3-(2-nonyltridecyl)thiophene (compound S4).

Supplementary Figure 25. 13C NMR spectrum of 3-(2-nonyltridecyl)thiophene (compound S4).

10 9 8 7 6 5 4 3 2 1 ppm

0.864

0.881

0.898

1.250

1.589

1.603

2.544

2.561

6.885

6.899

7.208

7.215

7.219

7.227

6.3

0

38.4

8

1.0

6

2.0

8

2.0

4

1.0

0

Current Data ParametersNAME JZhao-C9C13-TEXPNO 1PROCNO 1




S

C9H19

C11H23

200 180 160 140 120 100 80 60 40 20 ppm

14.282

22.854

26.765

29.516

29.792

29.830

30.160

32.082

33.465

34.854

39.083

120.773

124.904

128.959

142.068

Current Data ParametersNAME JZhao-C9C13-TEXPNO 2PROCNO 1





S

C9H19

C11H23

Supplementary Figure 26. 1H NMR spectrum of 3-(2-nonyltridecyl)thiophene-2-boronic acid

pinacol ester (compound S5).

Supplementary Figure 27. 13C NMR spectrum of 3-(2-nonyltridecyl)thiophene-2-boronic acid

pinacol ester (compound S5).

10 9 8 7 6 5 4 3 2 1 ppm

0.863

0.880

0.897

1.253

1.343

1.591

2.536

2.553

7.172

7.174

7.430

7.433

6.6

9

42.2

9

13.2

1

1.8

7

2.1

2

1.0

3

1.0

0

Current Data ParametersNAME JZhao-C9C13-T-BpinEXPNO 1PROCNO 1




S

C9H19

C11H23

B

O

O

200 180 160 140 120 100 80 60 40 20 ppm

14.268

22.840

24.911

26.747

29.504

29.779

29.826

30.142

32.072

33.429

34.634

39.152

84.111

128.515

139.160

143.628

Current Data ParametersNAME JZhao-C9C13-T-BpinEXPNO 2PROCNO 1





S

C9H19

C11H23

B

O

O

Supplementary Figure 28. 1H NMR spectrum of 5,6-difluoro-4,7-bis(4-(2-nonyltridecyl)-2-

thienyl)-2,1,3-benzothiadiazole (compound S6).

Supplementary Figure 29. 13C NMR spectrum of 5,6-difluoro-4,7-bis(4-(2-nonyltridecyl)-2-


10 9 8 7 6 5 4 3 2 1 ppm

0.851

0.868

0.884

1.245

1.304

1.691

1.704

2.639

2.656

7.168

8.087

12.1

2

74.1

3

2.0

5

3.9

9

1.9

9

2.0

0

Current Data ParametersNAME JZhao-ffBT2T-C9C13EXPNO 1PROCNO 1

F2 - Acquisition ParametersDate_ 20150122Time 22.43INSTRUM spectPROBHD 5 mm DUL 13C-1PULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 8012.820 HzFIDRES 0.122266 HzAQ 4.0894465 secRG 4.51DW 62.400 usecDE 6.50 usecTE 296.1 KD1 1.00000000 secTD0 1



S

C9H19C11H23

S

C9H19 C11H23

NS

N

F F

200 180 160 140 120 100 80 60 40 20 ppm

14.268

22.847

26.797

29.525

29.818

29.858

30.184

32.079

33.486

35.023

39.110

111.778

111.821

111.870

111.911

124.986

131.147

132.966

133.003

142.515

148.516

148.721

149.051

149.092

149.133

151.098

151.302


F2 - Acquisition ParametersDate_ 20150123Time 9.23INSTRUM spectPROBHD 5 mm DUL 13C-1PULPROG zgpg30TD 65536SOLVENT CDCl3NS 11215DS 2SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 196.92DW 20.800 usecDE 6.50 usecTE 297.3 KD1 2.00000000 secD11 0.03000000 secTD0 1




S

C9H19C11H23

S

C9H19 C11H23

NS

N

F F

Supplementary Figure 30. 19F NMR spectrum of 5,6-difluoro-4,7-bis(4-(2-nonyltridecyl)-2-


Supplementary Figure 31. 1H NMR spectrum of 5,6-difluoro-4,7-bis(5-bromo-4-(2-

nonyltridecyl)-2-thienyl)-2,1,3-benzothiadiazole (compound S7).

-180-160-140-120-100-80-60-40-200 ppm

-128.202

2.0

0



======== CHANNEL f1 ========SFO1 376.4607162 MHzNUC1 19FP1 14.70 usecPLW1 15.99600029 W



S

C9H19C11H23

S

C9H19 C11H23

NS

N

F F

10 9 8 7 6 5 4 3 2 1 ppm

0.844

0.849

0.861

0.867

0.878

0.883

1.237

1.298

1.311

1.740

2.567

2.585

7.907

12.2

3

74.2

4

2.0

3

4.0

0

2.0

0

Current Data Parameters

NAME JZhao-ffBT2TBr-C9C13

EXPNO 1

PROCNO 1

F2 - Acquisition Parameters

Date_ 20150118

Time 23.32

INSTRUM spect

PROBHD 5 mm DUL 13C-1

PULPROG zg30

TD 65536

SOLVENT CDCl3

NS 16

DS 2

SWH 8012.820 Hz

FIDRES 0.122266 Hz

AQ 4.0894465 sec

RG 62.93

DW 62.400 usec

DE 6.50 usec

TE 297.9 K

D1 1.00000000 sec

TD0 1

======== CHANNEL f1 ========

SFO1 400.1324710 MHz

NUC1 1H

P1 14.30 usec

PLW1 9.10000038 W

F2 - Processing parameters

SI 65536

SF 400.1300111 MHz

WDW EM

SSB 0

LB 0.30 Hz

GB 0

PC 1.00

S

C9H19 C11H23

S

C9H19C11H23

NS

N

FF

Br

Br

Supplementary Figure 32. 13C NMR spectrum of 5,6-difluoro-4,7-bis(5-bromo-4-(2-


Supplementary Figure 33. 19F NMR spectrum of 5,6-difluoro-4,7-bis(5-bromo-4-(2-


200 180 160 140 120 100 80 60 40 20 ppm

14.271

22.849

26.702

29.528

29.820

29.866

30.168

32.081

33.518

34.280

38.684

111.092

111.133

111.182

111.222

115.246

115.280

131.173

132.467

132.509

132.554

141.934

148.412

148.570

148.612

150.999

151.203



EXPNO 2

PROCNO 1


Date_ 20150119

Time 11.10

INSTRUM spect

PROBHD 5 mm DUL 13C-1

PULPROG zgpg30

TD 65536

SOLVENT CDCl3

NS 12224

DS 2

SWH 24038.461 Hz

FIDRES 0.366798 Hz

AQ 1.3631488 sec

RG 196.92

DW 20.800 usec

DE 6.50 usec

TE 297.0 K

D1 2.00000000 sec

D11 0.03000000 sec

TD0 1

======== CHANNEL f1 ========

SFO1 100.6228298 MHz

NUC1 13C

P1 9.60 usec

PLW1 31.98900032 W

======== CHANNEL f2 ========

SFO2 400.1316005 MHz

NUC2 1H

CPDPRG[2 waltz16

PCPD2 90.00 usec

PLW2 9.10000038 W

PLW12 0.24608000 W

PLW13 0.19933000 W


SI 32768

SF 100.6127545 MHz

WDW EM

SSB 0

LB 1.00 Hz

GB 0

PC 1.40

S

C9H19 C11H23

S

C9H19C11H23

NS

N

FF

Br

Br

-180-160-140-120-100-80-60-40-200 ppm

-128.018

2.0

0



EXPNO 3

PROCNO 1


Date_ 20150126

Time 22.36

INSTRUM spect

PROBHD 5 mm PABBO BB/

PULPROG zgpg30

TD 65536

SOLVENT CDCl3

NS 16

DS 2

SWH 93750.000 Hz

FIDRES 1.430511 Hz

AQ 0.3495253 sec

RG 196.92

DW 5.333 usec

DE 6.50 usec

TE 297.3 K

D1 2.00000000 sec

D11 0.03000000 sec

TD0 1

======== CHANNEL f1 ========

SFO1 376.4607162 MHz

NUC1 19F

P1 14.70 usec

PLW1 15.99600029 W

======== CHANNEL f2 ========

SFO2 400.1316005 MHz

NUC2 1H

CPDPRG[2 waltz16

PCPD2 90.00 usec

PLW2 11.99499989 W

PLW12 0.34213999 W

PLW13 0.27713001 W


SI 32768

SF 376.4983660 MHz

WDW EM

SSB 0

LB 1.00 Hz

GB 0

PC 1.40

S

C9H19 C11H23

S

C9H19C11H23

NS

N

FF

Br

Br

Supplementary Figure 34. 1H NMR spectrum of PffBT4T-C9C13 at 120 °C.

Supplementary Figure 35. 1H NMR spectrum of 5,6-difluoro-4,7-bis(5-bromo-4-(2-hexyldecyl)-

2-thienyl)-2,1,3-benzothiadiazole (compound S8).

10 9 8 7 6 5 4 3 2 1 ppm

0.921

0.935

0.938

0.952

1.334

1.353

1.405

1.417

1.435

1.460

1.471

1.919

1.934

1.947

2.935

2.951

7.271

8.209

5.3

5

32.3

7

1.2

0

2.0

4

1.9

5

1.0

0

Current Data ParametersNAME JZhao-PffBT4T-C9C13EXPNO 1PROCNO 1

F2 - Acquisition ParametersDate_ 20150326Time 13.28INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 65536SOLVENT C2D2Cl4NS 128DS 2SWH 8012.820 HzFIDRES 0.122266 HzAQ 4.0894465 secRG 196.92DW 62.400 usecDE 6.50 usecTE 393.2 KD1 1.00000000 secTD0 1



NS

N

F F

S SS

S n

C9H19C11H23C9H19

C11H23

10 9 8 7 6 5 4 3 2 1 ppm

0.841

0.853

0.858

0.870

0.886

1.262

1.299

1.313

1.744

2.581

2.599

7.926

12.6

5

50.1

5

2.1

3

3.9

5

2.0

0

Current Data ParametersNAME JZhao-ffBT2TBr-C6C10EXPNO 1PROCNO 1




S

C6H13 C8H17

S

C6H13C8H17

NS

N

FF

Br

Br

Supplementary Figure 36. 13C NMR spectrum of 5,6-difluoro-4,7-bis(5-bromo-4-(2-hexyldecyl)-


Supplementary Figure 37. 19F NMR spectrum of 5,6-difluoro-4,7-bis(5-bromo-4-(2-hexyldecyl)-


200 180 160 140 120 100 80 60 40 20 ppm

14.264

22.835

26.672

29.504

29.776

29.842

30.160

32.060

33.490

33.533

34.270

38.700

111.165

111.209

111.246

111.297

115.176

115.213

115.249

131.175

132.508

132.550

132.596

141.963

148.460

148.596

148.635

148.664

151.052

151.256






S

C6H13 C8H17

S

C6H13C8H17

NS

N

FF

Br

Br

-200-180-160-140-120-100-80-60-40-200 ppm

-128.136

2.0

0


F2 - Acquisition ParametersDate_ 20140513Time 18.30INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgflqnTD 131072SOLVENT CDCl3NS 16DS 4SWH 89285.711 HzFIDRES 0.681196 HzAQ 0.7340032 secRG 1290DW 5.600 usecDE 6.00 usecTE 293.0 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========NUC1 19FP1 19.50 usecPL1 -4.00 dBSFO1 376.4607164 MHz


S

C6H13 C8H17

S

C6H13C8H17

NS

N

FF

Br

Br


Supplementary Figure 39. 1H NMR spectrum of 5,6-difluoro-4,7-bis(5-bromo-4-(2-

heptylundecyl)-2-thienyl)-2,1,3-benzothiadiazole (compound S9).

10 9 8 7 6 5 4 3 2 1 ppm

0.918

0.927

0.936

0.944

0.953

1.365

1.387

1.439

1.465

1.477

1.923

1.937

1.949

2.938

2.956

7.272

8.209

6.2

5

28.1

4

1.0

9

1.9

9

2.0

2

1.0

0


F2 - Acquisition ParametersDate_ 20140512Time 19.00INSTRUM spectPROBHD 5 mm DUL 13C-1PULPROG zg30TD 65536SOLVENT C2D2Cl4NS 16DS 2SWH 8012.820 HzFIDRES 0.122266 HzAQ 4.0894465 secRG 4.51DW 62.400 usecDE 6.50 usecTE 404.2 KD1 1.00000000 secTD0 1



NS

N

F F

S SS

S n

C6H13C8H17C6H13

C8H17

10 9 8 7 6 5 4 3 2 1 ppm

0.846

0.861

0.864

0.877

1.263

1.299

1.312

1.740

2.569

2.587

7.907

12.6

2

59.3

2

2.0

8

4.0

3

2.0

0





S

C7H15 C9H19

S

C7H15C9H19

NS

N

FF

Br

Br

Supplementary Figure 40. 13C NMR spectrum of 5,6-difluoro-4,7-bis(5-bromo-4-(2-


Supplementary Figure 41. 19F NMR spectrum of 5,6-difluoro-4,7-bis(5-bromo-4-(2-


200 180 160 140 120 100 80 60 40 20 ppm

14.249

22.836

26.713

26.723

29.498

29.516

29.806

29.830

30.138

30.161

32.069

33.527

33.554

34.290

38.701

111.116

111.158

111.206

111.246

115.202

115.236

115.272

131.179

132.481

132.522

132.569

141.941

148.427

148.551

148.592

148.631

151.015

151.218


EXPNO 2PROCNO 1






S

C7H15 C9H19

S

C7H15C9H19

NS

N

FF

Br

Br

-180-160-140-120-100-80-60-40-200 ppm

-128.074

2.0

0


F2 - Acquisition ParametersDate_ 20150524Time 22.37INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgflqnTD 131072SOLVENT CDCl3NS 16DS 4SWH 89285.711 HzFIDRES 0.681196 HzAQ 0.7340032 secRG 196.92DW 5.600 usecDE 6.50 usecTE 298.0 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 376.4607164 MHzNUC1 19FP1 14.70 usecPLW1 15.99600029 W


S

C7H15 C9H19

S

C7H15C9H19

NS

N

FF

Br

Br


10 9 8 7 6 5 4 3 2 1 ppm

0.917

0.934

0.951

1.339

1.353

1.360

1.418

1.436

1.461

1.472

1.919

1.933

2.935

2.952

7.270

8.208

10.3

3

51.1

8

2.1

8

3.8

0

3.7

7

2.0

0


F2 - Acquisition ParametersDate_ 20150529Time 19.49INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 65536SOLVENT C2D2Cl4NS 128DS 2SWH 8012.820 HzFIDRES 0.122266 HzAQ 4.0894465 secRG 196.92DW 62.400 usecDE 6.50 usecTE 393.2 KD1 1.00000000 secTD0 1



NS

N

F F

S SS

S n

C7H15C9H19C7H15

C9H19

Supplementary Notes

The selection of the halogenated solvent processing system. In our previous report, a 1:1 mixture

of CB:DCB with the DIO additive was used as the processing solvents for PffBT4T-C8C12.5 In this

paper, however, a processing system based on CB-DIO is used as the reference halogenated solvent

processing system. The CB-DIO system was selected as the reference due to the following three

reasons. First, the polymer PffBT4T-C8C12 showed similar performance when processed from CB-

DIO (Table 2) compared with the previous reported from CB:DCB-DIO. Thus, the CB:DCB-DIO

system has no significant advantages over CB-DIO. Second, the best polymer in this work,

PffBT4T-C9C13 showed even poorer performance when processed from CB:DCB-DIO (VOC = 0.778

V, JSC = 15.2 mA cm-2, FF = 0.63, PCE = 7.4%). Third, it is more reasonable to compare two binary

solvent systems (CB-DIO and TMB-PN) rather than a binary solvent system (TMB-PN) and a

ternary solvent system (CB-DCB-DIO).

Supplementary Methods

AFM analysis. AFM measurements were performed by using a Scanning Probe Microscope-

Dimension 3100 in tapping mode. All film samples were spin-cast on ITO/ZnO substrates.

Optical characterizations. Film UV-Vis absorption spectra were acquired on a Perkin Elmer

Lambda 20 UV/VIS Spectrophotometer. All film samples were spin-cast on ITO/ZnO substrates.

Solution UV-Vis absorption spectra at elevated temperatures were collected on a Perkin Elmer

Lambda 950 UV/VIS/NIR Spectrophotometer. The temperature of the cuvette was controlled with

a Perkin Elmer PTP 6+6 Peltier System, which is supplied by a Perkin Elmer PCB 1500 Water

Peltier System. Before each measurement, the system was held for at least 10 min at the target

temperature to reach thermal equilibrium. A cuvette with a stopper (Sigma Z600628) was used to

avoid volatilization during the measurement.

Hole mobility measurements. The hole mobilities were measured using the SCLC method,

employing a device architecture of ITO/V2O5/blend film/V2O5/Al. The mobilities were obtained by

taking current-voltage curves and fitting the results to a space charge limited form, where the SCLC

is described by:

𝐽 =9𝜀0𝜀r𝜇𝑉

2

8𝐿3

Where ε0 is the permittivity of free space, εr is the relative permittivity of the material (assumed to

be 3), μ is the hole mobility and L is the thickness of the film. From the plots of J1/2 vs V, hole

mobilities can be deduced.

Electron mobility measurements. The electron mobilities were measured using the SCLC method,

employing a device architecture of ITO/ZnO/blend film/Ca/Al. The mobilities were obtained by

taking current-voltage curves and fitting the results to a space charge limited form, where the SCLC

is described by:

𝐽 =9𝜀0𝜀r𝜇𝑉

2

8𝐿3

Where ε0 is the permittivity of free space, εr is the relative permittivity of the material (assumed to

be 3), μ is the hole mobility and L is the thickness of the film. From the plots of J1/2 vs V, electron

mobilities can be deduced.

Synthetic Work: General Information. Microwave reactions were carried out on a CEM Discover

system (Model No. 908010). 1H and 13C NMR spectra were recorded on a Bruker AV-400 MHz

NMR spectrometer. Chemical shifts are reported in parts per million (ppm, δ). 1H NMR spectra

were referenced to tetramethylsilane (0 ppm) for CDCl3, or solvent residual peak (5.98 ppm) for

C2D2Cl4 as internal standard. 13C NMR spectra were referenced to solvent residual peak (77.16 ppm)

as internal standard. 19F NMR spectra were referenced to 0.05% α,α,α-trifluorotoluene in CDCl3 (-

64 ppm) as external standard. Mass spectra were collected on a MALDI Micro MX mass

spectrometer, or an API QSTAR XL System. GC-MS spectra were collected on an Agilent GC/MS

5975C system. Elemental analysis was performed by Midwest Microlab, LLC. Polymer molecular

weights were determined on a Polymer Laboratories PL-GPC 220 using trichlorobenzene as eluent

at 170 ºC vs polystyrene standards.

Materials. PffBT4T-C8C12 (Mn = 47.5 kDa, Mw = 93.7 kDa, PDI = 1.97) and PffBT4T-C10C14 (Mn

= 56.2 kDa, Mw = 100 kDa, PDI = 1.78) were synthesized according to previous reports.5 PffT2-

FTAZ-C10C14 was synthesized according to previous reports.6 PTB7 and PTB7-Th were purchased

from 1-Material Inc. PC71BM was purchased from Sigma-Aldrich. TMB was purchased from Acros

Organics. PN was purchased from Tokyo Chemical Industry (TCI). Tetrahydrofuran and toluene

were freshly distilled before use from sodium using benzophenone as indicator. All other reagents

and chemicals were purchased from commercial sources and used without further purification.

Synthesis of PffBT4T-C9C13. Synthetic route to PffBT4T-C9C13.

Synthetic procedures.

Ethyl 2-nonyltridecanoate (S1). A lithium diisopropylamide solution (2 M, 4.5 mL, 8.9 mmol) was

diluted with tetrahydrofuran (15 mL) under nitrogen atmosphere. The solution was cooled to -78 °C

and ethyl tridecanoate (Alfa Aesar B25242, 1.8 mL, 7.4 mmol) was added dropwise. The reaction

mixture was stirred at the same temperature for 1 h before 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-

pyrimidinone (0.27 mL, 2.2 mmol) was added in one portion. 1-Iodononane (TCI I0493, 2.72 g,

9.67 mmol) was added dropwise. The mixture was warmed to -40 °C and stirred for 2 h before

returned to r.t. overnight. A saturated ammonium chloride aqueous solution was added and the

mixture was extracted with diethyl ether for three times. The combined organic extracts were

washed with hydrochloric acid (1M aqueous solution) for three times, dried over sodium sulfate,

and concentrated in vacuum. The residue was purified by flash column chromatography on silica

gel (eluent: n-hexane: dichloromethane = 6:1, stained with phosphomolybdic acid) to get the product

as colorless oil (2.2 g, 80%).

1H NMR (400 MHz, CDCl3) δ 4.13 (q, J = 7.2 Hz, 2H), 2.35 – 2.25 (m, 1H), 1.62 – 1.19 (m, 39H),

0.88 (t, J = 6.4 Hz, 6H).

13C NMR (100 MHz, CDCl3) δ 176.79, 60.05, 45.92, 32.67, 32.07, 32.04, 29.78, 29.73, 29.70, 29.63,

29.50, 29.45, 27.58, 22.83, 14.50, 14.25.

HRMS (CI+) Calcd for C24H49O2 (M+H+): 369.3733, Found: 369.3727.

2-Nonyltridecanol (S2). A solution of compound S1 (310 mg, 0.842 mmol) in tetrahydrofuran (3

mL) was cooled to 0 °C under nitrogen atmosphere, and a lithium aluminium hydride solution (0.70

mL, 1.7 mmol) was added dropwise. The reaction mixture was warmed to r.t. and refluxed overnight.

The reaction mixture was then cooled to 0 °C and quenched with water. Hydrochloric acid (37%)

was then added until the solution became clear. The mixture was extracted with diethyl ether for

three times. The organic extracts were combined, washed with water followed by brine. Then the

solution was dried over sodium sulfate and concentrated in vacuum to get the product as colorless

oil (272 mg, 99%).

1H NMR (400 MHz, CDCl3) δ 3.53 (d, J = 5.6 Hz, 2H), 1.51 – 1.19 (m, 38H), 0.88 (t, J = 6.8 Hz,

6H).

13C NMR (100 MHz, CDCl3) δ 65.89, 40.69, 32.07, 31.08, 30.22, 29.83, 29.81, 29.51, 27.04, 22.84,

14.25.

HRMS (CI-) Calcd for C22H45O (M-H-): 325.3470, Found: 325.3486.

2-Nonyltridecyl bromide (S3). A solution of compound S2 (427 mg, 1.31 mmol) and

triphenylphosphine (377 mg, 1.44 mmol) in dichloromethane (10 mL) was cooled to 0 °C, and N-

bromosuccinimide (256 mg, 1.44 mmol) was added in portions. The reaction mixture was warmed

to r.t. and stirred overnight. The reaction mixture was concentrated in vacuum and suspended in

hexane. The mixture was filtered and washed with hexane. The filtrate was concentrated in vacuum

and the residue was purified by flash column chromatography (eluent: n-hexane, stained with

phosphomolybdic acid) to get the product as colorless oil (478 mg, 94%).

1H NMR (400 MHz, CDCl3) δ 3.45 (d, J = 4.8 Hz, 2H), 1.65 – 1.55 (m, 1H), 1.45 – 1.20 (m, 36H),

0.88 (t, J = 6.4 Hz, 6H).

13C NMR (100 MHz, CDCl3) δ 39.91, 39.64, 32.70, 32.08, 29.94, 29.83, 29.79, 29.75, 29.51, 29.49,

26.71, 22.85, 14.28.

HRMS (CI+) Calcd for C22H45 (M-Br+): 309.3521, Found: 309.3522.

3-(2-Nonyltridecyl)thiophene (S4). In an oven-dried three-neck flask equipped with a condenser

and a dropping funnel, a suspension of magnesium (323 mg, 13.3 mmol) and a drop of 1,2-

dibromoethane in tetrahydrofuran (15 mL) was stirred and heated to reflux under nitrogen

atmosphere. Compound S3 (4.3 g, 11 mmol) was dissolved in tetrahydrofuran (10 mL) and added

drop-wise via the funnel. The mixture was refluxed overnight, diluted with tetrahydrofuran (20 mL)

and cooled to room temperature. The solution was transferred via syringe to another oven-dried

flask, where there is a mixture of 3-bromothiophene (2.2 g, 13 mmol) and Ni(dppp)Cl2 (150 mg,

0.277 mmol) in tetrahydrofuran (20 mL) cooled with an ice/water bath. The mixture was stirred and

return to r.t. overnight before quenched with hydrochloric acid (1M). The mixture was then extracted

with diethyl ether for three times. The combined extracts was washed with water and then brine,

dried over sodium sulfate and concentrated under reduced pressure. The crude product was purified

by repeated flash column chromatography (eluent: n-hexane) to get the product as colorless oil (690

mg, 16%).

1H NMR (400 MHz, CDCl3) δ 7.22 (dd, J = 4.8, 3.2 Hz, 1H), 6.90 – 6.85 (m, 2H), 2.55 (d, 2H, J =

6.8 Hz), 1.65 – 1.55 (m, 1H), 1.45 – 1.15 (m, 36H), 0.88 (t, J = 6.4 Hz, 6H).

13C NMR (100 MHz, CDCl3) δ 142.07, 128.96, 124.90, 120.77, 39.08, 34.85, 33.47, 32.08, 30.16,

29.83, 29.79, 29.52, 26.77, 22.85, 14.28.

HRMS (CI+) Calcd for C26H49S (M+H+): 393.3555, Found: 393.3546.

3-(2-Nonyltridecyl)thiophene-2-boronic acid pinacol ester (S5). A solution of compound S4

(1.17 g, 2.99 mmol) in tetrahydrofuran (10 mL) was cooled to -78 °C under nitrogen atmosphere,

and a lithium diisopropylamide solution (2 M, 1.8 mL, 3.6 mmol) was added dropwise. The reaction

mixture was warmed to 0 °C and stirred for 1h before cooled again to -78 °C. 2-Isopropoxy-4,4,5,5-

tetramethyl-1,3,2-dioxaborolane (0.91 mL, 4.48 mmol) was added in one portion. The reaction

mixture was warmed to r.t. and stirred overnight before quenched with a saturated ammonium

chloride aqueous solution. The mixture was extracted with diethyl ether for three times. The organic

extracts were combined, washed with water and then brine, dried over sodium sulfate, and

concentrated in vacuum. The residue was purified by flash column chromatography (eluent: n-

hexane: dichloromethane = 10:1) to get the product as pale yellow oil (1.42 g, 92%).

1H NMR (400 MHz, CDCl3) δ 7.43 (d, J = 1.2 Hz, 1H), 7.17 (d, J = 0.8 Hz, 1H), 2.54 (d, J = 6.8

Hz, 2H), 1.66 – 1.55 (m, 1H), 1.34 (s, 12H), 1.50 – 1.15 (m, 36H), 0.88 (t, J = 6.8 Hz, 6H).

13C NMR (100 MHz, CDCl3) δ 143.63, 139.16, 128.52, 84.11, 39.15, 34.63, 33.43, 32.07, 30.14,

29.83, 29.78, 29.50, 26.75, 24.91, 22.84, 14.27.

HRMS (CI+) Calcd for C32H59BO2S (M+): 518.4329, Found: 518.4322.

5,6-Difluoro-4,7-bis(4-(2-nonyltridecyl)-2-thienyl)-2,1,3-benzothiadiazole (S6). Compound S5

(327 mg, 0.630 mmol), 4,7-dibromo-5,6-difluoro-2,1,3-benzothiadiazole (Derthon BT112, 94.5 mg,

0.286 mmol), potassium carbonate (396 mg, 2.86 mmol), Pd(dba)2 (16.5 mg, 0.0286 mmol) and 2-

dicyclohexylphosphino-2',6'-dimethoxybiphenyl (11.8 mg, 0.0286 mmol) were mixed under

nitrogen atmosphere. Toluene (6 mL) and water (2 mL) were added. The mixture was refluxed

overnight before cooled to r.t.. The mixture was diluted with diethyl ether and water. The organic

layer was separated and washed with a saturated ammonium chloride aqueous solution, dried over

sodium sulfate, and concentrated in vacuum. The residue was purified by flash column

chromatography (eluent: n-hexane) to get the product as yellow solid (233 mg, 85%).

1H NMR (400 MHz, CDCl3) δ 8.09 (s, 2H), 7.17 (s, 2H), 2.65 (d, J = 6.8 Hz, 4H) 1.80 – 1.62 (m,

2H), 1.45 – 1.15 (m, 72H), 0.87 (t, J = 6.4 Hz, 12H).

13C NMR (100 MHz, CDCl3) δ 149.91 (dd, J = 261, 20.6 Hz), 149.09 (t, J = 4.1 Hz), 142.52, 133.00,

132.98 (d, J = 3.7 Hz), 131.15, 124.99, 111.84 (dd, J = 9.1, 4.1 Hz), 39.11, 35.02, 33.49, 32.08,

30.18, 29.86, 29.82, 29.53, 26.80, 22.85, 14.27.

19F NMR (376 MHz, CDCl3) δ -128.20 (s, 2F).

HRMS (MALDI+) Calcd for C58H94F2N2S3 (M+): 952.6547, Found: 952.6525.

5,6-Difluoro-4,7-bis(5-bromo-4-(2-nonyltridecyl)-2-thienyl)-2,1,3-benzothiadiazole (S7). A

suspension of compound S6 (3.07 g, 3.22 mmol) and a small amount of silica gel in chloroform (50

mL) was cooled to 0 °C in dark. N-bromosuccinimide (1.26 g, 7.07 mmol) was added in one portion.

The reaction mixture was warmed to r.t., stirred overnight and concentrated in vacuum. The residue

was purified by flash column chromatography (eluent: n-hexane) to get the product as orange solid

(3.34 g, 93%).

1H NMR (400 MHz, CDCl3) δ 7.91 (s, 2H), 2.58 (d, J = 7.2 Hz, 4H) 1.82 – 1.68 (m, 2H), 1.45 –

1.15 (m, 72H), 0.92 – 0.80 (m, 12H).

13C NMR (100 MHz, CDCl3) δ 149.81 (dd, J = 261, 20.4 Hz), 148.57 (t, J = 4.3 Hz), 141.93, 132.51

(t, J = 4.5 Hz), 131.17, 115.25 (t, J = 3.4 Hz), 111.16 (dd, J = 9.0, 4.0 Hz), 38.68 , 34.28 , 33.52 ,

32.08 , 30.17 , 29.87 , 29.82 , 29.53 , 26.70 , 22.85 , 14.27.

19F NMR (376 MHz, CDCl3) δ -128.02 (s, 2F).

HRMS (MALDI+) Calcd for C58H92Br2F2N2S3 (M+): 1108.4757, Found: 1108.4775.

PffBT4T-C9C13. A mixture of monomer S7 (104 mg, 0.0939 mmol), 5,5'-bis(trimethylstannyl)-2,2'-

bithiophene (Sunatech IN1207, 46.2 mg, 0.0939 mmol), Pd2(dba)3 (1 mg, 0.001 mmol) and P(o-

tol)3 (2 mg, 0.007 mmol) was placed in a microwave tube. Toluene (0.4 mL) was added in a glove

box which is filled with nitrogen. The tube was sealed and heated to 140 °C for 1 h in a microwave

reactor. The obtained deep green gel was diluted with 20 mL hot xylene and the deep red solution

was precipitated into methanol. The solid was collected by filtration, and loaded into a thimble in a

Soxhlet extractor. The crude polymer was extracted successively with acetone, dichloromethane and

chloroform. The chloroform solution was concentrated by evaporation, re-dissolved in hot toluene

and precipitated into methanol. The solid was collected by filtration and dried in vacuo to get the

polymer as deep green solid (77 mg, 74%).

1H NMR (400 MHz, C2D2Cl4, 393 K). δ 8.21 (s, 2H), 7.27 (br, 4H), 2.94 (d, J = 6.4 Hz, 4H), 1.98-

1.86 (m, 2H), 1.58 – 1.12 (m, 72H), 1.02 – 0.84 (m, 12H).

Elem. Anal. Calcd for C66H96F2N2S5: C, 71.05; H, 8.67; N, 2.51. Found: C, 71.24; H, 8.79; N, 2.40.

HT-GPC: Mn = 68.4 kDa, Mw = 111 kDa, PDI = 1.62.

Synthesis of PffBT4T-C6C10 and PffBT4T-C7C11.

5,6-Difluoro-4,7-bis(5-bromo-4-(2-hexyldecyl)-2-thienyl)-2,1,3-benzothiadiazole (S8) was

synthesized according to the method for S7.

1H NMR (400 MHz, CDCl3) δ 7.92 (s, 2H), 2.59 (d, J = 7.1 Hz, 4H), 1.81 – 1.66 (m, 2H), 1.45 –

1.10 (m, 48H), 0.94 – 0.75 (m, 12H).

13C NMR (100 MHz, CDCl3) δ 149.07 (dd, J = 258.9, 20.4 Hz), 147.83 (d, J = 4.0 Hz), 141.17,

131.76 (t, J = 4.5 Hz), 130.39, 114.42, 110.44 (dd, J = 8.6, 4.6 Hz), 37.91, 33.48, 32.74, 32.70, 31.27,

29.37, 29.05, 28.99, 28.71, 25.90, 25.88, 22.04, 13.47.

19F NMR (376 MHz, CDCl3) δ -128.15 (s, 2F).

HRMS (MALDI+) Calcd for C46H68Br2F2N2S3 (M+): 940.2879, Found: 940.2907.

PffBT4T-C6C10. A mixture of monomer S8 (35.0 mg, 0.0371 mmol), 5,5'-bis(trimethylstannyl)-

2,2'-bithiophene (18.6 mg, 0.0379 mmol), Pd2(dba)3 (0.6 mg, 0.0007 mmol) and P(o-tol)3 (1.2 mg,

0.004 mmol) was placed in a microwave tube. Chlorobenzene (0.15 mL) was added in a glove box

which is filled with nitrogen. The tube was sealed and heated to 160 °C for 1 h in a microwave

reactor. The obtained deep green gel was diluted with 20 mL hot 1,2-dichlorobenzene and the deep

red solution was precipitated into methanol. The solid was collected by filtration, and loaded into a

thimble in a Soxhlet extractor. The crude polymer was extracted successively with acetone,

dichloromethane, chloroform and chlorobenzene. The chlorobenzene solution was concentrated by

evaporation, re-dissolved in hot 1,2-dichlorobenzene and precipitated into methanol. The solid was

collected by filtration and dried in vacuo to get the polymer as deep green solid (6.7 mg, 19%).

1H NMR (400 MHz, C2D2Cl4, 403 K). δ 8.21 (s, 2H), 7.27 (s, 4H), 2.95 (d, J = 6.9 Hz, 4H), 1.94

(br, 2H), 1.59 – 1.27 (m, 48H), 0.99 – 0.90 (m, 12H).


HT-GPC: Mn = 22.3 kDa, Mw = 35.4 kDa, PDI = 1.59.

5,6-Difluoro-4,7-bis(5-bromo-4-(2-heptylundecyl)-2-thienyl)-2,1,3-benzothiadiazole (S9) was

synthesized according to the method for S7.

1H NMR (400 MHz, CDCl3) δ 7.91 (s, 2H), 2.58 (d, J = 7.2 Hz, 4H), 1.83 – 1.68 (m, 2H), 1.50 –

1.10 (m, 56H), 0.92 – 0.78 (m, 12H).

13C NMR (100 MHz, CDCl3) δ 149.82 (dd, J = 260.4, 20.4 Hz), 148.59, 141.94, 132.52 (t, J = 4.5

Hz), 131.18, 115.24 (t, J = 3.5 Hz), 111.18 (dd, J = 8.9, 4.1 Hz), 38.70, 34.29, 33.55, 33.53, 32.07,

30.16, 30.14, 29.83, 29.81, 29.52, 29.50, 26.72, 26.71, 22.84, 14.25.

19F NMR (376 MHz, CDCl3) δ -128.07 (s, 2F).

HRMS (MALDI+) Calcd for C50H7679Br81BrF2N2S3 (M+): 998.3485, Found: 998.3460.

PffBT4T-C7C11. A mixture of monomer S9 (64.9 mg, 0.065 mmol), 5,5'-bis(trimethylstannyl)-2,2'-

bithiophene (31.9 mg, 0.065 mmol), Pd2(dba)3 (0.5 mg, 0.0005 mmol) and P(o-tol)3 (1 mg, 0.003

mmol) was placed in a microwave tube. Chlorobenzene (0.3 mL) was added in a glove box which

is filled with nitrogen. The tube was sealed and heated to 140 °C for 1 h in a microwave reactor.

The obtained deep green gel was diluted with 20 mL hot 1,2-dichlorobenzene and the deep red

solution was precipitated into methanol. The solid was collected by filtration, and loaded into a

thimble in a Soxhlet extractor. The crude polymer was extracted successively with ethyl acetate,

chloroform, toluene and chlorobenzene. The chlorobenzene solution was concentrated by

evaporation, re-dissolved in hot chlorobenzene and precipitated into methanol. The solid was

collected by filtration and dried in vacuo to get the polymer as deep green solid (42.1 mg, 65%).

1H NMR (400 MHz, C2D2Cl4, 393 K). δ 8.21 (s, 2H), 7.27 (s, 4H), 2.94 (d, J = 6.8 Hz, 4H), 2.00 –

1.86 (m, 2H), 1.55 – 1.10 (m, 56H), 0.99 – 0.85 (m, 12H).


HT-GPC: Mn = 39.6 kDa, Mw = 55.4 kDa, PDI = 1.40.

Supplementary References

1. Molander, G. A., Beaumard, F. Nickel-Catalyzed C−O Activation of Phenol Derivatives with

Potassium Heteroaryltrifluoroborates. Org. Lett., 12, 4022-4025 (2010).

2. Chirico, R. D., Steele, W. V., Kazakov, A. F. Thermodynamic properties of 1-phenylnaphthalene

and 2-phenylnaphthalene. J. Chem. Thermodyn., 73, 241-254 (2014).

3. Rocha, M. A. A., Lima, C. F. R. A. C., Santos, L. M. N. B. F. Phase transition thermodynamics

of phenyl and biphenyl naphthalenes. J. Chem. Thermodyn., 40, 1458-1463 (2008).

4. Lima, C. F. R. A. C., et al. Phenylnaphthalenes: Sublimation Equilibrium, Conjugation, and

Aromatic Interactions. J. Phys. Chem. B, 116, 3557-3570 (2012).

5. Liu, Y., et al. Aggregation and morphology control enables multiple cases of high-efficiency

polymer solar cells. Nature Commun., 5, 5293 (2014).

6. Li, Z., et al. Dramatic performance enhancement for large bandgap thick-film polymer solar

cells introduced by a difluorinated donor unit. Nano Energy, 15, 607-615 (2015).

Documents

Efficient organic solar cells processed from hydrocarbon ...€¦ · Efficient organic solar cells processed from hydrocarbon solvents Jingbo Zhao, Yunke Li, Guofang Yang, Kui Jiang,