Efficient organic solar cells processed from hydrocarbon ...€¦ · Efficient organic solar cells...
Transcript of Efficient organic solar cells processed from hydrocarbon ...€¦ · Efficient organic solar cells...
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
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
F2 - Processing parametersSI 32768SF 100.6127533 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
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
F2 - Processing parametersSI 65536SF 400.1300073 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
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
F2 - Processing parametersSI 32768SF 100.6127542 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
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
======== CHANNEL f1 ========SFO1 400.1324710 MHzNUC1 1HP1 14.30 usecPLW1 9.10000038 W
F2 - Processing parametersSI 65536SF 400.1300093 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
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
======== CHANNEL f1 ========SFO1 100.6228298 MHzNUC1 13CP1 9.60 usecPLW1 31.98900032 W
======== CHANNEL f2 ========SFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 90.00 usecPLW2 9.10000038 WPLW12 0.24608000 WPLW13 0.19933000 W
F2 - Processing parametersSI 32768SF 100.6127546 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
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
F2 - Acquisition ParametersDate_ 20141221Time 20.12INSTRUM 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 294.2 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.60 usecPL1 -1.00 dBSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1300086 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
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
F2 - Acquisition ParametersDate_ 20141221Time 20.19INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 113DS 2SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 2050DW 20.800 usecDE 6.00 usecTE 294.9 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
F2 - Processing parametersSI 32768SF 100.6127544 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
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
F2 - Acquisition ParametersDate_ 20150127Time 21.47INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 8012.820 HzFIDRES 0.122266 HzAQ 4.0894465 secRG 45.67DW 62.400 usecDE 6.50 usecTE 296.5 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========SFO1 400.1324710 MHzNUC1 1HP1 14.50 usecPLW1 11.99499989 W
F2 - Processing parametersSI 65536SF 400.1300101 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
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
F2 - Acquisition ParametersDate_ 20150127Time 21.58INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgpg30TD 65536SOLVENT CDCl3NS 186DS 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
F2 - Processing parametersSI 32768SF 100.6127551 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
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-
thienyl)-2,1,3-benzothiadiazole (compound S6).
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
======== CHANNEL f1 ========SFO1 400.1324710 MHzNUC1 1HP1 14.30 usecPLW1 9.10000038 W
F2 - Processing parametersSI 65536SF 400.1300113 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
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
Current Data ParametersNAME JZhao-ffBT2T-C9C13EXPNO 2PROCNO 1
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
======== CHANNEL f1 ========SFO1 100.6228298 MHzNUC1 13CP1 9.60 usecPLW1 31.98900032 W
======== CHANNEL f2 ========SFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 90.00 usecPLW2 9.10000038 WPLW12 0.24608000 WPLW13 0.19933000 W
F2 - Processing parametersSI 32768SF 100.6127547 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
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-
thienyl)-2,1,3-benzothiadiazole (compound S6).
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
Current Data ParametersNAME JZhao-ffBT2T-C9C13EXPNO 3PROCNO 1
F2 - Acquisition ParametersDate_ 20150126Time 22.42INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgpg30TD 65536SOLVENT CDCl3NS 15DS 2SWH 93750.000 HzFIDRES 1.430511 HzAQ 0.3495253 secRG 196.92DW 5.333 usecDE 6.50 usecTE 297.3 KD1 2.00000000 secD11 0.03000000 secTD0 1
======== CHANNEL f1 ========SFO1 376.4607162 MHzNUC1 19FP1 14.70 usecPLW1 15.99600029 W
======== CHANNEL f2 ========SFO2 400.1316005 MHzNUC2 1HCPDPRG[2 waltz16PCPD2 90.00 usecPLW2 11.99499989 WPLW12 0.34213999 WPLW13 0.27713001 W
F2 - Processing parametersSI 32768SF 376.4983660 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
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-
nonyltridecyl)-2-thienyl)-2,1,3-benzothiadiazole (compound S7).
Supplementary Figure 33. 19F NMR spectrum of 5,6-difluoro-4,7-bis(5-bromo-4-(2-
nonyltridecyl)-2-thienyl)-2,1,3-benzothiadiazole (compound S7).
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
Current Data Parameters
NAME JZhao-ffBT2TBr-C9C13
EXPNO 2
PROCNO 1
F2 - Acquisition Parameters
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
F2 - Processing parameters
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
Current Data Parameters
NAME JZhao-ffBT2TBr-C9C13
EXPNO 3
PROCNO 1
F2 - Acquisition Parameters
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
F2 - Processing parameters
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
======== CHANNEL f1 ========SFO1 400.1324710 MHzNUC1 1HP1 14.50 usecPLW1 11.99499989 W
F2 - Processing parametersSI 65536SF 400.1305182 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
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
F2 - Acquisition ParametersDate_ 20140512Time 0.06INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 1DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9845889 secRG 64DW 60.800 usecDE 6.00 usecTE 294.6 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========NUC1 1HP1 13.60 usecPL1 -1.00 dBSFO1 400.1324710 MHz
F2 - Processing parametersSI 32768SF 400.1300046 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
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)-
2-thienyl)-2,1,3-benzothiadiazole (compound S8).
Supplementary Figure 37. 19F NMR spectrum of 5,6-difluoro-4,7-bis(5-bromo-4-(2-hexyldecyl)-
2-thienyl)-2,1,3-benzothiadiazole (compound S8).
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
Current Data ParametersNAME JZhao-ffBT2TBr-C6C10EXPNO 2PROCNO 1
F2 - Acquisition ParametersDate_ 20140512Time 10.20INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 10741DS 2SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 2050DW 20.800 usecDE 6.00 usecTE 294.3 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1
======== CHANNEL f1 ========NUC1 13CP1 8.60 usecPL1 -3.00 dBSFO1 100.6228298 MHz
======== CHANNEL f2 ========CPDPRG[2 waltz16NUC2 1HPCPD2 80.00 usecPL12 14.33 dBPL13 18.00 dBPL2 -1.00 dBSFO2 400.1316005 MHz
F2 - Processing parametersSI 32768SF 100.6127532 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
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
Current Data ParametersNAME JZhao-ffBT2TBr-C6C10EXPNO 3PROCNO 1
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
F2 - Processing parametersSI 65536SF 376.4983660 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
S
C6H13 C8H17
S
C6H13C8H17
NS
N
FF
Br
Br
Supplementary Figure 38. 1H NMR spectrum of PffBT4T-C6C10 at 130 °C.
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
Current Data ParametersNAME JZhao-PffBT4T-C6C10EXPNO 1PROCNO 1
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
======== CHANNEL f1 ========SFO1 400.1324710 MHzNUC1 1HP1 14.30 usecPLW1 9.10000038 W
F2 - Processing parametersSI 65536SF 400.1305182 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
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
Current Data ParametersNAME JZhao-ffBT2TBr-C7C11EXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20150524Time 22.35INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 8012.820 HzFIDRES 0.122266 HzAQ 4.0894465 secRG 62.93DW 62.400 usecDE 6.50 usecTE 298.0 KD1 1.00000000 secTD0 1
======== CHANNEL f1 ========SFO1 400.1324710 MHzNUC1 1HP1 14.50 usecPLW1 11.99499989 W
F2 - Processing parametersSI 65536SF 400.1300104 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
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-
heptylundecyl)-2-thienyl)-2,1,3-benzothiadiazole (compound S9).
Supplementary Figure 41. 19F NMR spectrum of 5,6-difluoro-4,7-bis(5-bromo-4-(2-
heptylundecyl)-2-thienyl)-2,1,3-benzothiadiazole (compound S9).
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
Current Data Parameters
EXPNO 2PROCNO 1
F2 - Acquisition ParametersDate_ 20150525Time 12.12INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgpg30TD 65536SOLVENT CDCl3NS 14245DS 2SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631488 secRG 196.92DW 20.800 usecDE 6.50 usecTE 298.8 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
F2 - Processing parametersSI 32768SF 100.6127538 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40
NAME JZhao-ffBT2TBr-C7C11
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
Current Data ParametersNAME JZhao-ffBT2TBr-C7C11EXPNO 3PROCNO 1
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
F2 - Processing parametersSI 65536SF 376.4983660 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
S
C7H15 C9H19
S
C7H15C9H19
NS
N
FF
Br
Br
Supplementary Figure 42. 1H NMR spectrum of PffBT4T-C7C11 at 120 °C.
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
Current Data ParametersNAME JZhao-PffBT4T-C7C11EXPNO 1PROCNO 1
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
======== CHANNEL f1 ========SFO1 400.1324710 MHzNUC1 1HP1 14.50 usecPLW1 11.99499989 W
F2 - Processing parametersSI 65536SF 400.1305181 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00
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).
Elem. Anal. Calcd for C54H72F2N2S5: C, 68.45; H, 7.66; N, 2.96. Found: C, 68.23; H, 7.79; N, 2.89.
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).
Elem. Anal. Calcd for C58H80F2N2S5: C, 69.41; H, 8.04; N, 2.79. Found: C, 69.43; H, 7.99; N, 2.87.
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).