Supporting Information

Novel DonorndashAcceptor Polymer Containing o-Fluoro-p-alkoxyphenyl- Substituted Benzo[12-b45-bprime]dithiophene Unit for Polymer Solar Cells with Power Conversion Efficiency Exceeding 9 Ning WangDaggera Weichao ChenDaggera Wenfei Shena Linrui Duana Meng Qiua Junyi Wang a Chunming Yangb Zhengkun Dua Renqiang Yangac a CAS Key Laboratory of Bio-based Materials Qingdao Institute of Bioenergy and Bioprocess Technology Chinese Academy of Sciences Qingdao 266101 China E-mail yangrqqibebtaccn

b Shanghai Synchrotron Radiation Facility Shanghai Institute of Applied Physics Chinese Academy of Sciences Shanghai 201204 China E-mail yangchunmingsinapaccn

c State Key Laboratory of Luminescent Materials and Devices South China University of Technology Guangzhou 510641 China

DaggerN Wang and W Chen contributed equally to this work

Materials

All reagents were bought from commercial sources and were used without

further purification The solvents were purified with standard methods All air and

water sensitive reactions were performed under an argon atmosphere Silica gel (200-

300 mesh) was used for column chromatography New monomers were characterized

by 1H NMR 13C NMR and Atmospheric Pressure Chemical Ionization-Time of

Flight (APCI-TOF) high resolution mass spectra (HRMS)

Characterization

1H NMR and 13C NMR spectra were recorded on a Bruker DRX-600

spectrometer APCI-TOF HRMS were performed on Bruker Maxis UHR-TOF (both

positive and negative ion reflector mode) The molecular weight and polydispersity

were determined by gel permeation chromatography (GPC) analysis using an ELEOS

System Thermogravimetric analysis (TGA) measurements were performed using a

TA-Q600 analyzer with a heating rate of 10 oC min-1 under a nitrogen atmosphere

Electronic Supplementary Material (ESI) for Journal of Materials Chemistry AThis journal is copy The Royal Society of Chemistry 2016

The ultraviolet-visible (UV-Vis) spectra were measured on a Varian Cary 50 The

electrochemical behaviors of the fullerene derivatives were investigated by cyclic

voltammograms (CV) The CV was performed in a solution of tetrabutylammonium

hexafluorophosphate (Bu4NPF6) (01 M) in acetonitrile A three-electrode cell

consisting of a glassy carbon working electrode a Pt counter electrode and an

AgAgCl reference electrode was used The scan rate was 100 mVs The polymer

films were coated on a glassy carbon electrode by dipping the corresponding solutions

onto the electrode The potential of ferroceneferrocenium (FcFc+) was measured to

be 040 V compared to the AgAgCl electrode under the same conditions It is

assumed that the redox potential of FcFc+ has an absolute energy level of -48 eV to

vacuum Ultraviolet photoelectron spectroscopy (UPS) was perfromed on the Thermo

Scientific ESCALab 250Xi The gas discharge lamp was used for UPS with helium

gas admitted and the He I (2122 eV) emission line employed The helium pressure in

the analysis chamber during analysis was about 2times10minus8 mbar The data were acquired

with -10 V bias Atomic force microscopy (AFM) images were obtained on an

Agilent 5400 scanning probe microscope using AC mode The blend films of

conjugated polymer and PC71BM were prepared under the same experimental

conditions as that of optimized photovoltaic devices fabrication Transmission

electron microscopy (TEM) images were obtained on a JEOL JEM-1011 at an

accelerating voltage of 100 kV The GIWAXS data were obtained at beam line

BL16B1 of the Shanghai Synchrotron Radiation Facility (SSRF)

Fabrication of photovoltaic devices

Photovoltaic devices with a layered structure of

ITOPEDOTPSSpolymersPC71BM Ca (10 nm)Al (100 nm) were fabricated on

ITO coated glass substrates (15 mmtimes15 mm) The ITO coated glasses were cleaned in

an ultrasonic bath with detergent ultra pure water acetone and isopropyl alcohol

sequentially for 20 min and then oxygen plasma treated for 20 min The substrates

were spin-coated with PEDOTPSS at 5000 rpm and dried at 120 oC for 20 min in air

The copolymers and PC71BM were dissolved in deoxygenated anhydrous o-

dichlorobenzene in the weight ratios of 11 115 and 12 respectively and stirred

overnight in glovebox An active layer consisting of the blend of the copolymer and

PC71BM was then spin coated on PEDOTPSS A typical concentration of the

polymerPC71BM blending solution was 20 mgmL Subsequently Ca (10 nm) and Al

(100 nm) were thermally evaporated in a vacuum of 2times10-4 Pa on top of the active

layer as cathode A shadow mask with the area of 01 cm2 was used to define the

device area when evaporating the cathode Photovoltaic performance was

characterized under illumination with an AM 15G (100 mW cm-2) and the currentndash

voltage curves were recorded using a Keithley 2400 source meter The external

quantum efficiencies (EQE) of solar cells were analyzed using a certified Newport

incident photon conversion efficiency (IPCE) measurement system

Synthesis of compound 1

To the solution of 4-bromo-3-fluorophenol (950 g 50 mmol) anhydrous

potassium carbonate (1380 g 100 mmol) in dry DMF (150 ml) 7-

(bromomethyl)pentadecane (152 g 50 mmol) was added in one portion The reaction

mixture was stirred at 100 oC for 24 h and then was cooled to room temperature

Thereafter it was poured into water (100 mL) and exacted three times with hexane

The organic layers were combined and dried over Na2SO4 The solvent was removed

under reduced pressure The crude product was purified by silica gel flash column

chromatography using petroleum ether as an eluent to afford compound 1 as colorless

oil (1760 g 4249 mmol) in 85 yield 1H NMR (600 MHz CDCl3) δ (ppm) = 741

(t 2H) 671 (dd 2H) 663 (dd 2H) 381 (t 4H) 178 (m 2H) 148ndash124 (m 48H)

096ndash087 (m 12H)

Synthesis of compound 2

Compound 1 (1035 g 25 mmol) was dissolved in dry THF (50 mL) in the

argon atmosphene and then n-butyllithium solution (25 mmol 1000 mL 25 M in

hexane) was added dropwise at -78 oC After addition the reaction mixture was

maintained at this temperature for 2 h followed by the addition of benzo[12-b45-

bprime]dithiophene-48-dione (220 g 10 mmol) and allowed to warm to 55 oC for 2 h The

solution was cooled down to room temperature and then SnCl22H2O (1805 g 80

mmol) in 10 aqueous HCl (200 mL) was added The solution was refluxed for 2 h

and then the cooled mixture was poured into water and extracted with hexane The

combined organic phase was dried over Na2SO4 and evaporated to obtain the crude

product as pale yellow oil which was purified on a silica gel column eluting with

petroleum ether as eluent Compound 2 was obtained as a pale yellow solid (387 g

450 mmol) in 45 yield 1H NMR (600 MHz CDCl3) δ(ppm) 757ndash749 (m 2H)

740 (dd 2H) 718ndash715 (m 2H) 691ndash686 (m 2H) 684 (d 2H) 392 (d 4H)

187ndash180 (m 2H) 152ndash124 (m 48H) 093ndash086 (m 12H)

Synthesis of compound 3

Compound 2 (344 g 40 mmol) was dissolved into 50 mL of methylene chloride

in a 100 mL flask Bromine (128 g 80 mmol) was dissolved into 20 mL of

methylene chloride in a funnel and slowly dropped into the flask under an ice-water

bath and then the reactant was stirred at 40 oC over night Then the reaction mixture

was cooled to room temperature The solvent was removed under vacuum to afford

crude product as yellow solid which was purified on a silica gel column eluting with

petroleum ether as eluent to afford compound 3 as a pale yellow solid (220 g 216

mmol) in 54 yield 1H NMR (600 MHz CDCl3) δ(ppm) 748ndash740 (m 2H) 712 (t

2H) 689ndash685 (m 2H) 683 (d 2H) 392 (d 4H) 188ndash181 (m 2H) 152ndash124 (m

48H) 094ndash086 (m 12H)

Synthesis of o-FBDTP

Compound 3 (203 g 200 mmol) was added in a 50 mL dry flack After purging

with argon fresh distilled THF (30 mL) was added The reaction mixture was cooled

down to -78 oC and n-butyllithium (25 M in hexane 168 mL 420 mmol) was

added dropwise After 1 h of stirring at this temperature the neat trimethylstannyl

chloride (10 M in hexane 42 mL 42 mmol) was added The solution was allowed

to warm to room temperature and stirred for another 12 h followed by dilution with

hexane and washing with brine The organic layer was collected and dried over

anhydrous Na2SO4 then the solvent was removed in vacuo The recrystallization of

the crude product using isopropanol afforded o-FBDTP as pale yellow solid (185 g

156 mmol) in 78 yield 1H NMR (600 MHz CDCl3) δ (ppm) = 757ndash750 (m 2H)

722ndash714 (m 2H) 693ndash688 (m 2H) 686 (d 2H) 394 (d 4H) 188ndash180 (m 2H)

155ndash125 (m 48H) 095ndash085 (m 12H) 035 (s 18H) 13C NMR (150 MHz CDCl3)

δ(ppm) 16123 16085 16077 15957 14294 14193 13762 13211 13197

13073 12286 11880 11869 11080 10266 10249 7132 3800 3192 3188

3140 3137 3004 2971 2961 2935 2934 2690 2687 2270 2269 1413 -

835 HRMS (APCI-TOF) Calcd for C60H92F2O2S2Sn2 (M+H+) 11854636 found

11854635

Synthesis of compound 4

1-Bromo-4-(2-hexylhexadecyloxy)benzene (991 g 25 mmol) was dissolved in

dry THF (50 mL) in the argon atmosphene and then n-butyllithium solution (25

mmol 1000 mL 25 M in hexane) was added dropwise at -78 oC After addition the

reaction mixture was maintained at this temperature for 2 h followed by the addition

of benzo[12-b45-bprime]dithiophene-48-dione (220 g 10 mmol) and allowed to warm

to 55 oC for 2 h The solution was cooled down to room temperature and then

SnCl22H2O (1805 g 80 mmol) in 10 aqueous HCl (200 mL) was added The

solution was refluxed for 2 h and then the cooled mixture was poured into water and

extracted with hexane The combined organic phase was dried over Na2SO4 and

evaporated to obtain the crude product as pale yellow oil which was purified on a

silica gel column eluting with petroleum ether as eluent Compound 4 was obtained

as a white solid (510 g 620 mmol) in 62 yield 1H NMR (600 MHz CDCl3) δ

(ppm) = 762 (d 4H) 738 (d 2H) 734 (d 2H) 708 (d 4H) 394 (d 4H) 188ndash180

(m 2H) 155ndash122 (m 48H) 095ndash084 (m 12H)

Synthesis of BDTP

Compound 4 (165 g 200 mmol) was added in a 50 mL dry flack After

purging with argon fresh distilled THF (30 mL) was added The reaction mixture was

cooled down to 0 oC and n-butyllithium (25 M in hexane 168 mL 420 mmol) was

added dropwise After 1 h of stirring at this temperature the neat trimethylstannyl

chloride (10 M in hexane 42 mL 42 mmol) was added The solution was allowed

to warm to room temperature and stirred for another 12 h followed by dilution with

hexane and washing with brine The organic layer was collected and dried over

anhydrous Na2SO4 then the solvent was removed in vacuo The recrystallization of

the crude product using isopropanol afforded BDTP as yellow solid (186 g 162

mmol) in 81 yield 1H NMR (600 MHz CDCl3) δ (ppm) = 764 (d 4H) 738 (s

2H) 710 (d 4H) 395 (d 4H) 188ndash181 (m 2H) 152ndash124 (m 48H) 094ndash086 (m

12H) 035 (s 18H) 13C NMR (150 MHz CDCl3) δ(ppm) 15908 14261 14162

13709 13206 13088 13058 12847 11466 7093 3812 3194 3191 3148

31423008 2975 2964 2937 2932 2694 2692 2273 2271 1415 -836

HRMS (APCI-TOF) Calcd for C60H94O2S2Sn2 (M+H+) 11494825 found

11494778

General polymerization procedure

All the polymers were synthesized by applying Stille polymerization The

representative procedure for the synthesis of polymer P1 is as following To a 25 mL

flask compound BDTP (17242 mg 015 mmol) and C8DTBTff (10779 mg 015

mmol) Pd2(dba)3 (275 mg 2 mol) and P(o-tol)3 (550 mg 12 mol) were

dissolved in anhydrous toluene (5 mL) After being purged with argon for another 30

min the reaction mixture was heated to 110 oCand stirred for 12 h under an argon

atmosphere Then the mixture was cooled down to ambient temperature and the

polymer was precipitated by the addition of 150 mL methanol The crude polymer

product was then subjected to Soxhlet extraction with methanol hexane and

chlorobenzene The polymer recovered from chlorobenzene was precipitated by

addition of 150 mL methanol Then the product was dried under vacuum for 1 day to

give the target polymer P1 as a dark solid

Table S1 The yield GPC results and thermal stability of the polymers

Solubility (mgml)polymer Yield ()

Mn

(Kda)PDI Td (oC)

chloroform chlorobenzene o-dichlorobenzene

P1 62 161 14 334 15 45 79

P2 66 170 16 337 26 68 95

P3 70 160 18 336 20 60 85

Figure S1 Thermal stability of the polymers

Figure S2 Cyclic voltammogram (a) UPS spectrum of the onset (b) amplified spectrum of the onset (c) and the secondary edge region (d) of the polymers P1 P2 and P3

Figure S3 (a) the two possible conformations of the compound 2 and the totle energy difference (b) the calculated distributions of the frontier molecular orbitals and the HOMO and LUMO energy levels of the polymers

Table S2 Calculated Bond Angles of the Repeat Units of the Copolymersa

NSN

SS

R

S

S

O

O

θ1

θ2 θ3

θ4

θ5FF

X

X

polymer X R θ1 (deg) θ2 (deg) θ3 (deg) θ4 (deg) θ5 (deg)

P1 H 2-ethyl-hexyl 5869 5741 3773 066 053

P2 F 2-ethyl-hexyl 5931 6039 4246 099 051

P3 F hexyl 5974 5920 418 071 009

aillustration of θ1 θ2 θ3 θ4 and θ5 is given in graphic

Figure S4 UV-vis absorption spectra of P1 (a) P2 (b) P3 (c) in chlorobenzene solution at different temperature

Table S3 the performance of the devices with different raito and amount of DIOPolymer RatioaAddditive Voc (V) Jsc (mA cm-2) FF () PCEmax (PCEave)b ()

P1 110 DIO 089 910 5344 433 (421)

1150 DIO 088 1127 4696 467 (450)

120 DIO 088 964 4367 369 (352)

1151 DIO 084 1117 4924 464 (454)

1152 DIO 084 1181 4943 491 (472)

1153 DIO 084 1092 4891 449 (414)

P2 110 DIO 102 619 4176 264 (261)

1150 DIO 103 730 4376 329 (315)

120 DIO 101 684 4229 294 (290)

1151 DIO 094 792 5682 424 (401)

1152 DIO 094 1248 6903 810 (805)

1153 DIO 094 1212 6432 730 (712)

P3 110 DIO 093 1129 6675 701 (698)

1150 DIO 093 1297 7449 902 (896)

120 DIO 093 1149 6776 725 (711)

1151 DIO 090 1286 7120 823 (801)

1152 DIO 089 1243 5761 639 (622)

1153 DIO 088 1240 4881 531 (510)

a) The weight ratio of polymer to PC71BM b)The average PCE is obtained from 20 devices

Figure S5 the J-V curves of polymer P1 P2 P3 with different weight ratio to PC71BM (a c e) and different amount of DIO (b d f) as additive

Figure S6 J-V plots for the devices ITOPEDOTPSSpolymerPC71BMAu The solid line is the fittig of the data points (the thicknesses of the polymer films were 100 nm) The graphs a b c represent P1 P2 P3 respectively

Figure S7 AFM phase images of the active layers of P1PC71BM (a) P1PC71BM with 2 DIO (b) P2PC71BM (c) P2PC71BM with 2 DIO (d) P3PC71BM (e) and P3PC71BM with 2 DIO (f)

Photovoltaic devices with a layered structure of

ITOPEDOTPSSpolymersPC71BM Ca (10 nm)Al (100 nm) were fabricated on

ITO coated glass substrates (15 mmtimes15 mm) The ITO coated glasses were cleaned in

an ultrasonic bath with detergent ultra pure water acetone and isopropyl alcohol

sequentially for 20 min and then oxygen plasma treated for 20 min The substrates

were spin-coated with PEDOTPSS at 5000 rpm and dried at 120 oC for 20 min in air

The copolymers and PC71BM were dissolved in deoxygenated anhydrous o-

dichlorobenzene in the weight ratios of 11 115 and 12 respectively and stirred

overnight in glovebox An active layer consisting of the blend of the copolymer and

PC71BM was then spin coated on PEDOTPSS A typical concentration of the

polymerPC71BM blending solution was 20 mgmL Subsequently Ca (10 nm) and Al

(100 nm) were thermally evaporated in a vacuum of 2times10-4 Pa on top of the active

layer as cathode A shadow mask with the area of 01 cm2 was used to define the

device area when evaporating the cathode Photovoltaic performance was

characterized under illumination with an AM 15G (100 mW cm-2) and the currentndash

voltage curves were recorded using a Keithley 2400 source meter The external

quantum efficiencies (EQE) of solar cells were analyzed using a certified Newport

incident photon conversion efficiency (IPCE) measurement system

Synthesis of compound 1

To the solution of 4-bromo-3-fluorophenol (950 g 50 mmol) anhydrous

potassium carbonate (1380 g 100 mmol) in dry DMF (150 ml) 7-

(bromomethyl)pentadecane (152 g 50 mmol) was added in one portion The reaction

mixture was stirred at 100 oC for 24 h and then was cooled to room temperature

Thereafter it was poured into water (100 mL) and exacted three times with hexane

The organic layers were combined and dried over Na2SO4 The solvent was removed

under reduced pressure The crude product was purified by silica gel flash column

chromatography using petroleum ether as an eluent to afford compound 1 as colorless

oil (1760 g 4249 mmol) in 85 yield 1H NMR (600 MHz CDCl3) δ (ppm) = 741

(t 2H) 671 (dd 2H) 663 (dd 2H) 381 (t 4H) 178 (m 2H) 148ndash124 (m 48H)

096ndash087 (m 12H)

Synthesis of compound 2

Compound 1 (1035 g 25 mmol) was dissolved in dry THF (50 mL) in the

argon atmosphene and then n-butyllithium solution (25 mmol 1000 mL 25 M in

hexane) was added dropwise at -78 oC After addition the reaction mixture was

maintained at this temperature for 2 h followed by the addition of benzo[12-b45-

bprime]dithiophene-48-dione (220 g 10 mmol) and allowed to warm to 55 oC for 2 h The

solution was cooled down to room temperature and then SnCl22H2O (1805 g 80

mmol) in 10 aqueous HCl (200 mL) was added The solution was refluxed for 2 h

and then the cooled mixture was poured into water and extracted with hexane The

combined organic phase was dried over Na2SO4 and evaporated to obtain the crude

product as pale yellow oil which was purified on a silica gel column eluting with

petroleum ether as eluent Compound 2 was obtained as a pale yellow solid (387 g

450 mmol) in 45 yield 1H NMR (600 MHz CDCl3) δ(ppm) 757ndash749 (m 2H)

740 (dd 2H) 718ndash715 (m 2H) 691ndash686 (m 2H) 684 (d 2H) 392 (d 4H)

187ndash180 (m 2H) 152ndash124 (m 48H) 093ndash086 (m 12H)

Synthesis of compound 3

Compound 2 (344 g 40 mmol) was dissolved into 50 mL of methylene chloride

in a 100 mL flask Bromine (128 g 80 mmol) was dissolved into 20 mL of

methylene chloride in a funnel and slowly dropped into the flask under an ice-water

bath and then the reactant was stirred at 40 oC over night Then the reaction mixture

was cooled to room temperature The solvent was removed under vacuum to afford

crude product as yellow solid which was purified on a silica gel column eluting with

petroleum ether as eluent to afford compound 3 as a pale yellow solid (220 g 216

mmol) in 54 yield 1H NMR (600 MHz CDCl3) δ(ppm) 748ndash740 (m 2H) 712 (t

2H) 689ndash685 (m 2H) 683 (d 2H) 392 (d 4H) 188ndash181 (m 2H) 152ndash124 (m

48H) 094ndash086 (m 12H)

Synthesis of o-FBDTP

Compound 3 (203 g 200 mmol) was added in a 50 mL dry flack After purging

with argon fresh distilled THF (30 mL) was added The reaction mixture was cooled

down to -78 oC and n-butyllithium (25 M in hexane 168 mL 420 mmol) was

added dropwise After 1 h of stirring at this temperature the neat trimethylstannyl

chloride (10 M in hexane 42 mL 42 mmol) was added The solution was allowed

to warm to room temperature and stirred for another 12 h followed by dilution with

hexane and washing with brine The organic layer was collected and dried over

anhydrous Na2SO4 then the solvent was removed in vacuo The recrystallization of

the crude product using isopropanol afforded o-FBDTP as pale yellow solid (185 g

156 mmol) in 78 yield 1H NMR (600 MHz CDCl3) δ (ppm) = 757ndash750 (m 2H)

722ndash714 (m 2H) 693ndash688 (m 2H) 686 (d 2H) 394 (d 4H) 188ndash180 (m 2H)

155ndash125 (m 48H) 095ndash085 (m 12H) 035 (s 18H) 13C NMR (150 MHz CDCl3)

δ(ppm) 16123 16085 16077 15957 14294 14193 13762 13211 13197

13073 12286 11880 11869 11080 10266 10249 7132 3800 3192 3188

3140 3137 3004 2971 2961 2935 2934 2690 2687 2270 2269 1413 -

835 HRMS (APCI-TOF) Calcd for C60H92F2O2S2Sn2 (M+H+) 11854636 found

11854635

Synthesis of compound 4

1-Bromo-4-(2-hexylhexadecyloxy)benzene (991 g 25 mmol) was dissolved in

dry THF (50 mL) in the argon atmosphene and then n-butyllithium solution (25

mmol 1000 mL 25 M in hexane) was added dropwise at -78 oC After addition the

reaction mixture was maintained at this temperature for 2 h followed by the addition

of benzo[12-b45-bprime]dithiophene-48-dione (220 g 10 mmol) and allowed to warm

to 55 oC for 2 h The solution was cooled down to room temperature and then

SnCl22H2O (1805 g 80 mmol) in 10 aqueous HCl (200 mL) was added The

solution was refluxed for 2 h and then the cooled mixture was poured into water and

extracted with hexane The combined organic phase was dried over Na2SO4 and

evaporated to obtain the crude product as pale yellow oil which was purified on a

silica gel column eluting with petroleum ether as eluent Compound 4 was obtained

as a white solid (510 g 620 mmol) in 62 yield 1H NMR (600 MHz CDCl3) δ

(ppm) = 762 (d 4H) 738 (d 2H) 734 (d 2H) 708 (d 4H) 394 (d 4H) 188ndash180

(m 2H) 155ndash122 (m 48H) 095ndash084 (m 12H)

Synthesis of BDTP

Compound 4 (165 g 200 mmol) was added in a 50 mL dry flack After

purging with argon fresh distilled THF (30 mL) was added The reaction mixture was

cooled down to 0 oC and n-butyllithium (25 M in hexane 168 mL 420 mmol) was

added dropwise After 1 h of stirring at this temperature the neat trimethylstannyl

chloride (10 M in hexane 42 mL 42 mmol) was added The solution was allowed

to warm to room temperature and stirred for another 12 h followed by dilution with

hexane and washing with brine The organic layer was collected and dried over

anhydrous Na2SO4 then the solvent was removed in vacuo The recrystallization of

the crude product using isopropanol afforded BDTP as yellow solid (186 g 162

mmol) in 81 yield 1H NMR (600 MHz CDCl3) δ (ppm) = 764 (d 4H) 738 (s

2H) 710 (d 4H) 395 (d 4H) 188ndash181 (m 2H) 152ndash124 (m 48H) 094ndash086 (m

12H) 035 (s 18H) 13C NMR (150 MHz CDCl3) δ(ppm) 15908 14261 14162

13709 13206 13088 13058 12847 11466 7093 3812 3194 3191 3148

31423008 2975 2964 2937 2932 2694 2692 2273 2271 1415 -836

HRMS (APCI-TOF) Calcd for C60H94O2S2Sn2 (M+H+) 11494825 found

11494778

General polymerization procedure

All the polymers were synthesized by applying Stille polymerization The

representative procedure for the synthesis of polymer P1 is as following To a 25 mL

flask compound BDTP (17242 mg 015 mmol) and C8DTBTff (10779 mg 015

mmol) Pd2(dba)3 (275 mg 2 mol) and P(o-tol)3 (550 mg 12 mol) were

dissolved in anhydrous toluene (5 mL) After being purged with argon for another 30

min the reaction mixture was heated to 110 oCand stirred for 12 h under an argon

atmosphere Then the mixture was cooled down to ambient temperature and the

polymer was precipitated by the addition of 150 mL methanol The crude polymer

product was then subjected to Soxhlet extraction with methanol hexane and

chlorobenzene The polymer recovered from chlorobenzene was precipitated by

addition of 150 mL methanol Then the product was dried under vacuum for 1 day to

give the target polymer P1 as a dark solid

Table S1 The yield GPC results and thermal stability of the polymers

Solubility (mgml)polymer Yield ()

Mn

(Kda)PDI Td (oC)

chloroform chlorobenzene o-dichlorobenzene

P1 62 161 14 334 15 45 79

P2 66 170 16 337 26 68 95

P3 70 160 18 336 20 60 85

Figure S1 Thermal stability of the polymers

Figure S2 Cyclic voltammogram (a) UPS spectrum of the onset (b) amplified spectrum of the onset (c) and the secondary edge region (d) of the polymers P1 P2 and P3

Figure S3 (a) the two possible conformations of the compound 2 and the totle energy difference (b) the calculated distributions of the frontier molecular orbitals and the HOMO and LUMO energy levels of the polymers

Table S2 Calculated Bond Angles of the Repeat Units of the Copolymersa

NSN

SS

R

S

S

O

O

θ1

θ2 θ3

θ4

θ5FF

X

X

polymer X R θ1 (deg) θ2 (deg) θ3 (deg) θ4 (deg) θ5 (deg)

P1 H 2-ethyl-hexyl 5869 5741 3773 066 053

P2 F 2-ethyl-hexyl 5931 6039 4246 099 051

P3 F hexyl 5974 5920 418 071 009

aillustration of θ1 θ2 θ3 θ4 and θ5 is given in graphic

Figure S4 UV-vis absorption spectra of P1 (a) P2 (b) P3 (c) in chlorobenzene solution at different temperature

Table S3 the performance of the devices with different raito and amount of DIOPolymer RatioaAddditive Voc (V) Jsc (mA cm-2) FF () PCEmax (PCEave)b ()

P1 110 DIO 089 910 5344 433 (421)

1150 DIO 088 1127 4696 467 (450)

120 DIO 088 964 4367 369 (352)

1151 DIO 084 1117 4924 464 (454)

1152 DIO 084 1181 4943 491 (472)

1153 DIO 084 1092 4891 449 (414)

P2 110 DIO 102 619 4176 264 (261)

1150 DIO 103 730 4376 329 (315)

120 DIO 101 684 4229 294 (290)

1151 DIO 094 792 5682 424 (401)

1152 DIO 094 1248 6903 810 (805)

1153 DIO 094 1212 6432 730 (712)

P3 110 DIO 093 1129 6675 701 (698)

1150 DIO 093 1297 7449 902 (896)

120 DIO 093 1149 6776 725 (711)

1151 DIO 090 1286 7120 823 (801)

1152 DIO 089 1243 5761 639 (622)

1153 DIO 088 1240 4881 531 (510)

a) The weight ratio of polymer to PC71BM b)The average PCE is obtained from 20 devices

Figure S5 the J-V curves of polymer P1 P2 P3 with different weight ratio to PC71BM (a c e) and different amount of DIO (b d f) as additive

Figure S6 J-V plots for the devices ITOPEDOTPSSpolymerPC71BMAu The solid line is the fittig of the data points (the thicknesses of the polymer films were 100 nm) The graphs a b c represent P1 P2 P3 respectively

Figure S7 AFM phase images of the active layers of P1PC71BM (a) P1PC71BM with 2 DIO (b) P2PC71BM (c) P2PC71BM with 2 DIO (d) P3PC71BM (e) and P3PC71BM with 2 DIO (f)

mixture was stirred at 100 oC for 24 h and then was cooled to room temperature

Thereafter it was poured into water (100 mL) and exacted three times with hexane

The organic layers were combined and dried over Na2SO4 The solvent was removed

under reduced pressure The crude product was purified by silica gel flash column

chromatography using petroleum ether as an eluent to afford compound 1 as colorless

oil (1760 g 4249 mmol) in 85 yield 1H NMR (600 MHz CDCl3) δ (ppm) = 741

(t 2H) 671 (dd 2H) 663 (dd 2H) 381 (t 4H) 178 (m 2H) 148ndash124 (m 48H)

096ndash087 (m 12H)

Synthesis of compound 2

Compound 1 (1035 g 25 mmol) was dissolved in dry THF (50 mL) in the

argon atmosphene and then n-butyllithium solution (25 mmol 1000 mL 25 M in

hexane) was added dropwise at -78 oC After addition the reaction mixture was

maintained at this temperature for 2 h followed by the addition of benzo[12-b45-

bprime]dithiophene-48-dione (220 g 10 mmol) and allowed to warm to 55 oC for 2 h The

solution was cooled down to room temperature and then SnCl22H2O (1805 g 80

mmol) in 10 aqueous HCl (200 mL) was added The solution was refluxed for 2 h

and then the cooled mixture was poured into water and extracted with hexane The

combined organic phase was dried over Na2SO4 and evaporated to obtain the crude

product as pale yellow oil which was purified on a silica gel column eluting with

petroleum ether as eluent Compound 2 was obtained as a pale yellow solid (387 g

450 mmol) in 45 yield 1H NMR (600 MHz CDCl3) δ(ppm) 757ndash749 (m 2H)

740 (dd 2H) 718ndash715 (m 2H) 691ndash686 (m 2H) 684 (d 2H) 392 (d 4H)

187ndash180 (m 2H) 152ndash124 (m 48H) 093ndash086 (m 12H)

Synthesis of compound 3

Compound 2 (344 g 40 mmol) was dissolved into 50 mL of methylene chloride

in a 100 mL flask Bromine (128 g 80 mmol) was dissolved into 20 mL of

methylene chloride in a funnel and slowly dropped into the flask under an ice-water

bath and then the reactant was stirred at 40 oC over night Then the reaction mixture

was cooled to room temperature The solvent was removed under vacuum to afford

crude product as yellow solid which was purified on a silica gel column eluting with

petroleum ether as eluent to afford compound 3 as a pale yellow solid (220 g 216

mmol) in 54 yield 1H NMR (600 MHz CDCl3) δ(ppm) 748ndash740 (m 2H) 712 (t

2H) 689ndash685 (m 2H) 683 (d 2H) 392 (d 4H) 188ndash181 (m 2H) 152ndash124 (m

48H) 094ndash086 (m 12H)

Synthesis of o-FBDTP

Compound 3 (203 g 200 mmol) was added in a 50 mL dry flack After purging

with argon fresh distilled THF (30 mL) was added The reaction mixture was cooled

down to -78 oC and n-butyllithium (25 M in hexane 168 mL 420 mmol) was

added dropwise After 1 h of stirring at this temperature the neat trimethylstannyl

chloride (10 M in hexane 42 mL 42 mmol) was added The solution was allowed

to warm to room temperature and stirred for another 12 h followed by dilution with

hexane and washing with brine The organic layer was collected and dried over

anhydrous Na2SO4 then the solvent was removed in vacuo The recrystallization of

the crude product using isopropanol afforded o-FBDTP as pale yellow solid (185 g

156 mmol) in 78 yield 1H NMR (600 MHz CDCl3) δ (ppm) = 757ndash750 (m 2H)

722ndash714 (m 2H) 693ndash688 (m 2H) 686 (d 2H) 394 (d 4H) 188ndash180 (m 2H)

155ndash125 (m 48H) 095ndash085 (m 12H) 035 (s 18H) 13C NMR (150 MHz CDCl3)

δ(ppm) 16123 16085 16077 15957 14294 14193 13762 13211 13197

13073 12286 11880 11869 11080 10266 10249 7132 3800 3192 3188

3140 3137 3004 2971 2961 2935 2934 2690 2687 2270 2269 1413 -

835 HRMS (APCI-TOF) Calcd for C60H92F2O2S2Sn2 (M+H+) 11854636 found

11854635

Synthesis of compound 4

1-Bromo-4-(2-hexylhexadecyloxy)benzene (991 g 25 mmol) was dissolved in

dry THF (50 mL) in the argon atmosphene and then n-butyllithium solution (25

mmol 1000 mL 25 M in hexane) was added dropwise at -78 oC After addition the

reaction mixture was maintained at this temperature for 2 h followed by the addition

of benzo[12-b45-bprime]dithiophene-48-dione (220 g 10 mmol) and allowed to warm

to 55 oC for 2 h The solution was cooled down to room temperature and then

SnCl22H2O (1805 g 80 mmol) in 10 aqueous HCl (200 mL) was added The

solution was refluxed for 2 h and then the cooled mixture was poured into water and

extracted with hexane The combined organic phase was dried over Na2SO4 and

evaporated to obtain the crude product as pale yellow oil which was purified on a

silica gel column eluting with petroleum ether as eluent Compound 4 was obtained

as a white solid (510 g 620 mmol) in 62 yield 1H NMR (600 MHz CDCl3) δ

(ppm) = 762 (d 4H) 738 (d 2H) 734 (d 2H) 708 (d 4H) 394 (d 4H) 188ndash180

(m 2H) 155ndash122 (m 48H) 095ndash084 (m 12H)

Synthesis of BDTP

Compound 4 (165 g 200 mmol) was added in a 50 mL dry flack After

purging with argon fresh distilled THF (30 mL) was added The reaction mixture was

cooled down to 0 oC and n-butyllithium (25 M in hexane 168 mL 420 mmol) was

added dropwise After 1 h of stirring at this temperature the neat trimethylstannyl

chloride (10 M in hexane 42 mL 42 mmol) was added The solution was allowed

to warm to room temperature and stirred for another 12 h followed by dilution with

hexane and washing with brine The organic layer was collected and dried over

anhydrous Na2SO4 then the solvent was removed in vacuo The recrystallization of

the crude product using isopropanol afforded BDTP as yellow solid (186 g 162

mmol) in 81 yield 1H NMR (600 MHz CDCl3) δ (ppm) = 764 (d 4H) 738 (s

2H) 710 (d 4H) 395 (d 4H) 188ndash181 (m 2H) 152ndash124 (m 48H) 094ndash086 (m

12H) 035 (s 18H) 13C NMR (150 MHz CDCl3) δ(ppm) 15908 14261 14162

13709 13206 13088 13058 12847 11466 7093 3812 3194 3191 3148

31423008 2975 2964 2937 2932 2694 2692 2273 2271 1415 -836

HRMS (APCI-TOF) Calcd for C60H94O2S2Sn2 (M+H+) 11494825 found

11494778

General polymerization procedure

All the polymers were synthesized by applying Stille polymerization The

representative procedure for the synthesis of polymer P1 is as following To a 25 mL

flask compound BDTP (17242 mg 015 mmol) and C8DTBTff (10779 mg 015

mmol) Pd2(dba)3 (275 mg 2 mol) and P(o-tol)3 (550 mg 12 mol) were

dissolved in anhydrous toluene (5 mL) After being purged with argon for another 30

min the reaction mixture was heated to 110 oCand stirred for 12 h under an argon

atmosphere Then the mixture was cooled down to ambient temperature and the

polymer was precipitated by the addition of 150 mL methanol The crude polymer

product was then subjected to Soxhlet extraction with methanol hexane and

chlorobenzene The polymer recovered from chlorobenzene was precipitated by

addition of 150 mL methanol Then the product was dried under vacuum for 1 day to

give the target polymer P1 as a dark solid

Table S1 The yield GPC results and thermal stability of the polymers

Solubility (mgml)polymer Yield ()

Mn

(Kda)PDI Td (oC)

chloroform chlorobenzene o-dichlorobenzene

P1 62 161 14 334 15 45 79

P2 66 170 16 337 26 68 95

P3 70 160 18 336 20 60 85

Figure S1 Thermal stability of the polymers

Figure S2 Cyclic voltammogram (a) UPS spectrum of the onset (b) amplified spectrum of the onset (c) and the secondary edge region (d) of the polymers P1 P2 and P3

Figure S3 (a) the two possible conformations of the compound 2 and the totle energy difference (b) the calculated distributions of the frontier molecular orbitals and the HOMO and LUMO energy levels of the polymers

Table S2 Calculated Bond Angles of the Repeat Units of the Copolymersa

NSN

SS

R

S

S

O

O

θ1

θ2 θ3

θ4

θ5FF

X

X

polymer X R θ1 (deg) θ2 (deg) θ3 (deg) θ4 (deg) θ5 (deg)

P1 H 2-ethyl-hexyl 5869 5741 3773 066 053

P2 F 2-ethyl-hexyl 5931 6039 4246 099 051

P3 F hexyl 5974 5920 418 071 009

aillustration of θ1 θ2 θ3 θ4 and θ5 is given in graphic

Figure S4 UV-vis absorption spectra of P1 (a) P2 (b) P3 (c) in chlorobenzene solution at different temperature

Table S3 the performance of the devices with different raito and amount of DIOPolymer RatioaAddditive Voc (V) Jsc (mA cm-2) FF () PCEmax (PCEave)b ()

P1 110 DIO 089 910 5344 433 (421)

1150 DIO 088 1127 4696 467 (450)

120 DIO 088 964 4367 369 (352)

1151 DIO 084 1117 4924 464 (454)

1152 DIO 084 1181 4943 491 (472)

1153 DIO 084 1092 4891 449 (414)

P2 110 DIO 102 619 4176 264 (261)

1150 DIO 103 730 4376 329 (315)

120 DIO 101 684 4229 294 (290)

1151 DIO 094 792 5682 424 (401)

1152 DIO 094 1248 6903 810 (805)

1153 DIO 094 1212 6432 730 (712)

P3 110 DIO 093 1129 6675 701 (698)

1150 DIO 093 1297 7449 902 (896)

120 DIO 093 1149 6776 725 (711)

1151 DIO 090 1286 7120 823 (801)

1152 DIO 089 1243 5761 639 (622)

1153 DIO 088 1240 4881 531 (510)

a) The weight ratio of polymer to PC71BM b)The average PCE is obtained from 20 devices

Figure S5 the J-V curves of polymer P1 P2 P3 with different weight ratio to PC71BM (a c e) and different amount of DIO (b d f) as additive

Figure S6 J-V plots for the devices ITOPEDOTPSSpolymerPC71BMAu The solid line is the fittig of the data points (the thicknesses of the polymer films were 100 nm) The graphs a b c represent P1 P2 P3 respectively

Figure S7 AFM phase images of the active layers of P1PC71BM (a) P1PC71BM with 2 DIO (b) P2PC71BM (c) P2PC71BM with 2 DIO (d) P3PC71BM (e) and P3PC71BM with 2 DIO (f)

740 (dd 2H) 718ndash715 (m 2H) 691ndash686 (m 2H) 684 (d 2H) 392 (d 4H)

187ndash180 (m 2H) 152ndash124 (m 48H) 093ndash086 (m 12H)

Synthesis of compound 3

Compound 2 (344 g 40 mmol) was dissolved into 50 mL of methylene chloride

in a 100 mL flask Bromine (128 g 80 mmol) was dissolved into 20 mL of

methylene chloride in a funnel and slowly dropped into the flask under an ice-water

bath and then the reactant was stirred at 40 oC over night Then the reaction mixture

was cooled to room temperature The solvent was removed under vacuum to afford

crude product as yellow solid which was purified on a silica gel column eluting with

petroleum ether as eluent to afford compound 3 as a pale yellow solid (220 g 216

mmol) in 54 yield 1H NMR (600 MHz CDCl3) δ(ppm) 748ndash740 (m 2H) 712 (t

2H) 689ndash685 (m 2H) 683 (d 2H) 392 (d 4H) 188ndash181 (m 2H) 152ndash124 (m

48H) 094ndash086 (m 12H)

Synthesis of o-FBDTP

Compound 3 (203 g 200 mmol) was added in a 50 mL dry flack After purging

with argon fresh distilled THF (30 mL) was added The reaction mixture was cooled

down to -78 oC and n-butyllithium (25 M in hexane 168 mL 420 mmol) was

added dropwise After 1 h of stirring at this temperature the neat trimethylstannyl

chloride (10 M in hexane 42 mL 42 mmol) was added The solution was allowed

to warm to room temperature and stirred for another 12 h followed by dilution with

hexane and washing with brine The organic layer was collected and dried over

anhydrous Na2SO4 then the solvent was removed in vacuo The recrystallization of

the crude product using isopropanol afforded o-FBDTP as pale yellow solid (185 g

156 mmol) in 78 yield 1H NMR (600 MHz CDCl3) δ (ppm) = 757ndash750 (m 2H)

722ndash714 (m 2H) 693ndash688 (m 2H) 686 (d 2H) 394 (d 4H) 188ndash180 (m 2H)

155ndash125 (m 48H) 095ndash085 (m 12H) 035 (s 18H) 13C NMR (150 MHz CDCl3)

δ(ppm) 16123 16085 16077 15957 14294 14193 13762 13211 13197

13073 12286 11880 11869 11080 10266 10249 7132 3800 3192 3188

3140 3137 3004 2971 2961 2935 2934 2690 2687 2270 2269 1413 -

835 HRMS (APCI-TOF) Calcd for C60H92F2O2S2Sn2 (M+H+) 11854636 found

11854635

Synthesis of compound 4

1-Bromo-4-(2-hexylhexadecyloxy)benzene (991 g 25 mmol) was dissolved in

dry THF (50 mL) in the argon atmosphene and then n-butyllithium solution (25

mmol 1000 mL 25 M in hexane) was added dropwise at -78 oC After addition the

reaction mixture was maintained at this temperature for 2 h followed by the addition

of benzo[12-b45-bprime]dithiophene-48-dione (220 g 10 mmol) and allowed to warm

to 55 oC for 2 h The solution was cooled down to room temperature and then

SnCl22H2O (1805 g 80 mmol) in 10 aqueous HCl (200 mL) was added The

solution was refluxed for 2 h and then the cooled mixture was poured into water and

extracted with hexane The combined organic phase was dried over Na2SO4 and

evaporated to obtain the crude product as pale yellow oil which was purified on a

silica gel column eluting with petroleum ether as eluent Compound 4 was obtained

as a white solid (510 g 620 mmol) in 62 yield 1H NMR (600 MHz CDCl3) δ

(ppm) = 762 (d 4H) 738 (d 2H) 734 (d 2H) 708 (d 4H) 394 (d 4H) 188ndash180

(m 2H) 155ndash122 (m 48H) 095ndash084 (m 12H)

Synthesis of BDTP

Compound 4 (165 g 200 mmol) was added in a 50 mL dry flack After

purging with argon fresh distilled THF (30 mL) was added The reaction mixture was

cooled down to 0 oC and n-butyllithium (25 M in hexane 168 mL 420 mmol) was

added dropwise After 1 h of stirring at this temperature the neat trimethylstannyl

chloride (10 M in hexane 42 mL 42 mmol) was added The solution was allowed

to warm to room temperature and stirred for another 12 h followed by dilution with

hexane and washing with brine The organic layer was collected and dried over

anhydrous Na2SO4 then the solvent was removed in vacuo The recrystallization of

the crude product using isopropanol afforded BDTP as yellow solid (186 g 162

mmol) in 81 yield 1H NMR (600 MHz CDCl3) δ (ppm) = 764 (d 4H) 738 (s

2H) 710 (d 4H) 395 (d 4H) 188ndash181 (m 2H) 152ndash124 (m 48H) 094ndash086 (m

12H) 035 (s 18H) 13C NMR (150 MHz CDCl3) δ(ppm) 15908 14261 14162

13709 13206 13088 13058 12847 11466 7093 3812 3194 3191 3148

31423008 2975 2964 2937 2932 2694 2692 2273 2271 1415 -836

HRMS (APCI-TOF) Calcd for C60H94O2S2Sn2 (M+H+) 11494825 found

11494778

General polymerization procedure

All the polymers were synthesized by applying Stille polymerization The

representative procedure for the synthesis of polymer P1 is as following To a 25 mL

flask compound BDTP (17242 mg 015 mmol) and C8DTBTff (10779 mg 015

mmol) Pd2(dba)3 (275 mg 2 mol) and P(o-tol)3 (550 mg 12 mol) were

dissolved in anhydrous toluene (5 mL) After being purged with argon for another 30

min the reaction mixture was heated to 110 oCand stirred for 12 h under an argon

atmosphere Then the mixture was cooled down to ambient temperature and the

polymer was precipitated by the addition of 150 mL methanol The crude polymer

product was then subjected to Soxhlet extraction with methanol hexane and

chlorobenzene The polymer recovered from chlorobenzene was precipitated by

addition of 150 mL methanol Then the product was dried under vacuum for 1 day to

give the target polymer P1 as a dark solid

Table S1 The yield GPC results and thermal stability of the polymers

Solubility (mgml)polymer Yield ()

Mn

(Kda)PDI Td (oC)

chloroform chlorobenzene o-dichlorobenzene

P1 62 161 14 334 15 45 79

P2 66 170 16 337 26 68 95

P3 70 160 18 336 20 60 85

Figure S1 Thermal stability of the polymers

Figure S2 Cyclic voltammogram (a) UPS spectrum of the onset (b) amplified spectrum of the onset (c) and the secondary edge region (d) of the polymers P1 P2 and P3

Figure S3 (a) the two possible conformations of the compound 2 and the totle energy difference (b) the calculated distributions of the frontier molecular orbitals and the HOMO and LUMO energy levels of the polymers

Table S2 Calculated Bond Angles of the Repeat Units of the Copolymersa

NSN

SS

R

S

S

O

O

θ1

θ2 θ3

θ4

θ5FF

X

X

polymer X R θ1 (deg) θ2 (deg) θ3 (deg) θ4 (deg) θ5 (deg)

P1 H 2-ethyl-hexyl 5869 5741 3773 066 053

P2 F 2-ethyl-hexyl 5931 6039 4246 099 051

P3 F hexyl 5974 5920 418 071 009

aillustration of θ1 θ2 θ3 θ4 and θ5 is given in graphic

Figure S4 UV-vis absorption spectra of P1 (a) P2 (b) P3 (c) in chlorobenzene solution at different temperature

Table S3 the performance of the devices with different raito and amount of DIOPolymer RatioaAddditive Voc (V) Jsc (mA cm-2) FF () PCEmax (PCEave)b ()

P1 110 DIO 089 910 5344 433 (421)

1150 DIO 088 1127 4696 467 (450)

120 DIO 088 964 4367 369 (352)

1151 DIO 084 1117 4924 464 (454)

1152 DIO 084 1181 4943 491 (472)

1153 DIO 084 1092 4891 449 (414)

P2 110 DIO 102 619 4176 264 (261)

1150 DIO 103 730 4376 329 (315)

120 DIO 101 684 4229 294 (290)

1151 DIO 094 792 5682 424 (401)

1152 DIO 094 1248 6903 810 (805)

1153 DIO 094 1212 6432 730 (712)

P3 110 DIO 093 1129 6675 701 (698)

1150 DIO 093 1297 7449 902 (896)

120 DIO 093 1149 6776 725 (711)

1151 DIO 090 1286 7120 823 (801)

1152 DIO 089 1243 5761 639 (622)

1153 DIO 088 1240 4881 531 (510)

a) The weight ratio of polymer to PC71BM b)The average PCE is obtained from 20 devices

Figure S5 the J-V curves of polymer P1 P2 P3 with different weight ratio to PC71BM (a c e) and different amount of DIO (b d f) as additive

Figure S6 J-V plots for the devices ITOPEDOTPSSpolymerPC71BMAu The solid line is the fittig of the data points (the thicknesses of the polymer films were 100 nm) The graphs a b c represent P1 P2 P3 respectively

Figure S7 AFM phase images of the active layers of P1PC71BM (a) P1PC71BM with 2 DIO (b) P2PC71BM (c) P2PC71BM with 2 DIO (d) P3PC71BM (e) and P3PC71BM with 2 DIO (f)

the crude product using isopropanol afforded o-FBDTP as pale yellow solid (185 g

156 mmol) in 78 yield 1H NMR (600 MHz CDCl3) δ (ppm) = 757ndash750 (m 2H)

722ndash714 (m 2H) 693ndash688 (m 2H) 686 (d 2H) 394 (d 4H) 188ndash180 (m 2H)

155ndash125 (m 48H) 095ndash085 (m 12H) 035 (s 18H) 13C NMR (150 MHz CDCl3)

δ(ppm) 16123 16085 16077 15957 14294 14193 13762 13211 13197

13073 12286 11880 11869 11080 10266 10249 7132 3800 3192 3188

3140 3137 3004 2971 2961 2935 2934 2690 2687 2270 2269 1413 -

835 HRMS (APCI-TOF) Calcd for C60H92F2O2S2Sn2 (M+H+) 11854636 found

11854635

Synthesis of compound 4

1-Bromo-4-(2-hexylhexadecyloxy)benzene (991 g 25 mmol) was dissolved in

dry THF (50 mL) in the argon atmosphene and then n-butyllithium solution (25

mmol 1000 mL 25 M in hexane) was added dropwise at -78 oC After addition the

reaction mixture was maintained at this temperature for 2 h followed by the addition

of benzo[12-b45-bprime]dithiophene-48-dione (220 g 10 mmol) and allowed to warm

to 55 oC for 2 h The solution was cooled down to room temperature and then

SnCl22H2O (1805 g 80 mmol) in 10 aqueous HCl (200 mL) was added The

solution was refluxed for 2 h and then the cooled mixture was poured into water and

extracted with hexane The combined organic phase was dried over Na2SO4 and

evaporated to obtain the crude product as pale yellow oil which was purified on a

silica gel column eluting with petroleum ether as eluent Compound 4 was obtained

as a white solid (510 g 620 mmol) in 62 yield 1H NMR (600 MHz CDCl3) δ

(ppm) = 762 (d 4H) 738 (d 2H) 734 (d 2H) 708 (d 4H) 394 (d 4H) 188ndash180

(m 2H) 155ndash122 (m 48H) 095ndash084 (m 12H)

Synthesis of BDTP

Compound 4 (165 g 200 mmol) was added in a 50 mL dry flack After

purging with argon fresh distilled THF (30 mL) was added The reaction mixture was

cooled down to 0 oC and n-butyllithium (25 M in hexane 168 mL 420 mmol) was

added dropwise After 1 h of stirring at this temperature the neat trimethylstannyl

chloride (10 M in hexane 42 mL 42 mmol) was added The solution was allowed

to warm to room temperature and stirred for another 12 h followed by dilution with

hexane and washing with brine The organic layer was collected and dried over

anhydrous Na2SO4 then the solvent was removed in vacuo The recrystallization of

the crude product using isopropanol afforded BDTP as yellow solid (186 g 162

mmol) in 81 yield 1H NMR (600 MHz CDCl3) δ (ppm) = 764 (d 4H) 738 (s

2H) 710 (d 4H) 395 (d 4H) 188ndash181 (m 2H) 152ndash124 (m 48H) 094ndash086 (m

12H) 035 (s 18H) 13C NMR (150 MHz CDCl3) δ(ppm) 15908 14261 14162

13709 13206 13088 13058 12847 11466 7093 3812 3194 3191 3148

31423008 2975 2964 2937 2932 2694 2692 2273 2271 1415 -836

HRMS (APCI-TOF) Calcd for C60H94O2S2Sn2 (M+H+) 11494825 found

11494778

General polymerization procedure

All the polymers were synthesized by applying Stille polymerization The

representative procedure for the synthesis of polymer P1 is as following To a 25 mL

flask compound BDTP (17242 mg 015 mmol) and C8DTBTff (10779 mg 015

mmol) Pd2(dba)3 (275 mg 2 mol) and P(o-tol)3 (550 mg 12 mol) were

dissolved in anhydrous toluene (5 mL) After being purged with argon for another 30

min the reaction mixture was heated to 110 oCand stirred for 12 h under an argon

atmosphere Then the mixture was cooled down to ambient temperature and the

polymer was precipitated by the addition of 150 mL methanol The crude polymer

product was then subjected to Soxhlet extraction with methanol hexane and

chlorobenzene The polymer recovered from chlorobenzene was precipitated by

addition of 150 mL methanol Then the product was dried under vacuum for 1 day to

give the target polymer P1 as a dark solid

Table S1 The yield GPC results and thermal stability of the polymers

Solubility (mgml)polymer Yield ()

Mn

(Kda)PDI Td (oC)

chloroform chlorobenzene o-dichlorobenzene

P1 62 161 14 334 15 45 79

P2 66 170 16 337 26 68 95

P3 70 160 18 336 20 60 85

Figure S1 Thermal stability of the polymers

Figure S2 Cyclic voltammogram (a) UPS spectrum of the onset (b) amplified spectrum of the onset (c) and the secondary edge region (d) of the polymers P1 P2 and P3

Figure S3 (a) the two possible conformations of the compound 2 and the totle energy difference (b) the calculated distributions of the frontier molecular orbitals and the HOMO and LUMO energy levels of the polymers

Table S2 Calculated Bond Angles of the Repeat Units of the Copolymersa

NSN

SS

R

S

S

O

O

θ1

θ2 θ3

θ4

θ5FF

X

X

polymer X R θ1 (deg) θ2 (deg) θ3 (deg) θ4 (deg) θ5 (deg)

P1 H 2-ethyl-hexyl 5869 5741 3773 066 053

P2 F 2-ethyl-hexyl 5931 6039 4246 099 051

P3 F hexyl 5974 5920 418 071 009

aillustration of θ1 θ2 θ3 θ4 and θ5 is given in graphic

Figure S4 UV-vis absorption spectra of P1 (a) P2 (b) P3 (c) in chlorobenzene solution at different temperature

Table S3 the performance of the devices with different raito and amount of DIOPolymer RatioaAddditive Voc (V) Jsc (mA cm-2) FF () PCEmax (PCEave)b ()

P1 110 DIO 089 910 5344 433 (421)

1150 DIO 088 1127 4696 467 (450)

120 DIO 088 964 4367 369 (352)

1151 DIO 084 1117 4924 464 (454)

1152 DIO 084 1181 4943 491 (472)

1153 DIO 084 1092 4891 449 (414)

P2 110 DIO 102 619 4176 264 (261)

1150 DIO 103 730 4376 329 (315)

120 DIO 101 684 4229 294 (290)

1151 DIO 094 792 5682 424 (401)

1152 DIO 094 1248 6903 810 (805)

1153 DIO 094 1212 6432 730 (712)

P3 110 DIO 093 1129 6675 701 (698)

1150 DIO 093 1297 7449 902 (896)

120 DIO 093 1149 6776 725 (711)

1151 DIO 090 1286 7120 823 (801)

1152 DIO 089 1243 5761 639 (622)

1153 DIO 088 1240 4881 531 (510)

a) The weight ratio of polymer to PC71BM b)The average PCE is obtained from 20 devices

Figure S5 the J-V curves of polymer P1 P2 P3 with different weight ratio to PC71BM (a c e) and different amount of DIO (b d f) as additive

Figure S6 J-V plots for the devices ITOPEDOTPSSpolymerPC71BMAu The solid line is the fittig of the data points (the thicknesses of the polymer films were 100 nm) The graphs a b c represent P1 P2 P3 respectively

Figure S7 AFM phase images of the active layers of P1PC71BM (a) P1PC71BM with 2 DIO (b) P2PC71BM (c) P2PC71BM with 2 DIO (d) P3PC71BM (e) and P3PC71BM with 2 DIO (f)

(ppm) = 762 (d 4H) 738 (d 2H) 734 (d 2H) 708 (d 4H) 394 (d 4H) 188ndash180

(m 2H) 155ndash122 (m 48H) 095ndash084 (m 12H)

Synthesis of BDTP

Compound 4 (165 g 200 mmol) was added in a 50 mL dry flack After

purging with argon fresh distilled THF (30 mL) was added The reaction mixture was

cooled down to 0 oC and n-butyllithium (25 M in hexane 168 mL 420 mmol) was

added dropwise After 1 h of stirring at this temperature the neat trimethylstannyl

chloride (10 M in hexane 42 mL 42 mmol) was added The solution was allowed

to warm to room temperature and stirred for another 12 h followed by dilution with

hexane and washing with brine The organic layer was collected and dried over

anhydrous Na2SO4 then the solvent was removed in vacuo The recrystallization of

the crude product using isopropanol afforded BDTP as yellow solid (186 g 162

mmol) in 81 yield 1H NMR (600 MHz CDCl3) δ (ppm) = 764 (d 4H) 738 (s

2H) 710 (d 4H) 395 (d 4H) 188ndash181 (m 2H) 152ndash124 (m 48H) 094ndash086 (m

12H) 035 (s 18H) 13C NMR (150 MHz CDCl3) δ(ppm) 15908 14261 14162

13709 13206 13088 13058 12847 11466 7093 3812 3194 3191 3148

31423008 2975 2964 2937 2932 2694 2692 2273 2271 1415 -836

HRMS (APCI-TOF) Calcd for C60H94O2S2Sn2 (M+H+) 11494825 found

11494778

General polymerization procedure

All the polymers were synthesized by applying Stille polymerization The

representative procedure for the synthesis of polymer P1 is as following To a 25 mL

flask compound BDTP (17242 mg 015 mmol) and C8DTBTff (10779 mg 015

mmol) Pd2(dba)3 (275 mg 2 mol) and P(o-tol)3 (550 mg 12 mol) were

dissolved in anhydrous toluene (5 mL) After being purged with argon for another 30

min the reaction mixture was heated to 110 oCand stirred for 12 h under an argon

atmosphere Then the mixture was cooled down to ambient temperature and the

polymer was precipitated by the addition of 150 mL methanol The crude polymer

product was then subjected to Soxhlet extraction with methanol hexane and

chlorobenzene The polymer recovered from chlorobenzene was precipitated by

addition of 150 mL methanol Then the product was dried under vacuum for 1 day to

give the target polymer P1 as a dark solid

Table S1 The yield GPC results and thermal stability of the polymers

Solubility (mgml)polymer Yield ()

Mn

(Kda)PDI Td (oC)

chloroform chlorobenzene o-dichlorobenzene

P1 62 161 14 334 15 45 79

P2 66 170 16 337 26 68 95

P3 70 160 18 336 20 60 85

Figure S1 Thermal stability of the polymers

Figure S2 Cyclic voltammogram (a) UPS spectrum of the onset (b) amplified spectrum of the onset (c) and the secondary edge region (d) of the polymers P1 P2 and P3

Figure S3 (a) the two possible conformations of the compound 2 and the totle energy difference (b) the calculated distributions of the frontier molecular orbitals and the HOMO and LUMO energy levels of the polymers

Table S2 Calculated Bond Angles of the Repeat Units of the Copolymersa

NSN

SS

R

S

S

O

O

θ1

θ2 θ3

θ4

θ5FF

X

X

polymer X R θ1 (deg) θ2 (deg) θ3 (deg) θ4 (deg) θ5 (deg)

P1 H 2-ethyl-hexyl 5869 5741 3773 066 053

P2 F 2-ethyl-hexyl 5931 6039 4246 099 051

P3 F hexyl 5974 5920 418 071 009

aillustration of θ1 θ2 θ3 θ4 and θ5 is given in graphic

Figure S4 UV-vis absorption spectra of P1 (a) P2 (b) P3 (c) in chlorobenzene solution at different temperature

Table S3 the performance of the devices with different raito and amount of DIOPolymer RatioaAddditive Voc (V) Jsc (mA cm-2) FF () PCEmax (PCEave)b ()

P1 110 DIO 089 910 5344 433 (421)

1150 DIO 088 1127 4696 467 (450)

120 DIO 088 964 4367 369 (352)

1151 DIO 084 1117 4924 464 (454)

1152 DIO 084 1181 4943 491 (472)

1153 DIO 084 1092 4891 449 (414)

P2 110 DIO 102 619 4176 264 (261)

1150 DIO 103 730 4376 329 (315)

120 DIO 101 684 4229 294 (290)

1151 DIO 094 792 5682 424 (401)

1152 DIO 094 1248 6903 810 (805)

1153 DIO 094 1212 6432 730 (712)

P3 110 DIO 093 1129 6675 701 (698)

1150 DIO 093 1297 7449 902 (896)

120 DIO 093 1149 6776 725 (711)

1151 DIO 090 1286 7120 823 (801)

1152 DIO 089 1243 5761 639 (622)

1153 DIO 088 1240 4881 531 (510)

a) The weight ratio of polymer to PC71BM b)The average PCE is obtained from 20 devices

Figure S5 the J-V curves of polymer P1 P2 P3 with different weight ratio to PC71BM (a c e) and different amount of DIO (b d f) as additive

Figure S6 J-V plots for the devices ITOPEDOTPSSpolymerPC71BMAu The solid line is the fittig of the data points (the thicknesses of the polymer films were 100 nm) The graphs a b c represent P1 P2 P3 respectively

Figure S7 AFM phase images of the active layers of P1PC71BM (a) P1PC71BM with 2 DIO (b) P2PC71BM (c) P2PC71BM with 2 DIO (d) P3PC71BM (e) and P3PC71BM with 2 DIO (f)

flask compound BDTP (17242 mg 015 mmol) and C8DTBTff (10779 mg 015

mmol) Pd2(dba)3 (275 mg 2 mol) and P(o-tol)3 (550 mg 12 mol) were

dissolved in anhydrous toluene (5 mL) After being purged with argon for another 30

min the reaction mixture was heated to 110 oCand stirred for 12 h under an argon

atmosphere Then the mixture was cooled down to ambient temperature and the

polymer was precipitated by the addition of 150 mL methanol The crude polymer

product was then subjected to Soxhlet extraction with methanol hexane and

chlorobenzene The polymer recovered from chlorobenzene was precipitated by

addition of 150 mL methanol Then the product was dried under vacuum for 1 day to

give the target polymer P1 as a dark solid

Table S1 The yield GPC results and thermal stability of the polymers

Solubility (mgml)polymer Yield ()

Mn

(Kda)PDI Td (oC)

chloroform chlorobenzene o-dichlorobenzene

P1 62 161 14 334 15 45 79

P2 66 170 16 337 26 68 95

P3 70 160 18 336 20 60 85

Figure S1 Thermal stability of the polymers

Figure S2 Cyclic voltammogram (a) UPS spectrum of the onset (b) amplified spectrum of the onset (c) and the secondary edge region (d) of the polymers P1 P2 and P3

Figure S3 (a) the two possible conformations of the compound 2 and the totle energy difference (b) the calculated distributions of the frontier molecular orbitals and the HOMO and LUMO energy levels of the polymers

Table S2 Calculated Bond Angles of the Repeat Units of the Copolymersa

NSN

SS

R

S

S

O

O

θ1

θ2 θ3

θ4

θ5FF

X

X

polymer X R θ1 (deg) θ2 (deg) θ3 (deg) θ4 (deg) θ5 (deg)

P1 H 2-ethyl-hexyl 5869 5741 3773 066 053

P2 F 2-ethyl-hexyl 5931 6039 4246 099 051

P3 F hexyl 5974 5920 418 071 009

aillustration of θ1 θ2 θ3 θ4 and θ5 is given in graphic

Figure S4 UV-vis absorption spectra of P1 (a) P2 (b) P3 (c) in chlorobenzene solution at different temperature

Table S3 the performance of the devices with different raito and amount of DIOPolymer RatioaAddditive Voc (V) Jsc (mA cm-2) FF () PCEmax (PCEave)b ()

P1 110 DIO 089 910 5344 433 (421)

1150 DIO 088 1127 4696 467 (450)

120 DIO 088 964 4367 369 (352)

1151 DIO 084 1117 4924 464 (454)

1152 DIO 084 1181 4943 491 (472)

1153 DIO 084 1092 4891 449 (414)

P2 110 DIO 102 619 4176 264 (261)

1150 DIO 103 730 4376 329 (315)

120 DIO 101 684 4229 294 (290)

1151 DIO 094 792 5682 424 (401)

1152 DIO 094 1248 6903 810 (805)

1153 DIO 094 1212 6432 730 (712)

P3 110 DIO 093 1129 6675 701 (698)

1150 DIO 093 1297 7449 902 (896)

120 DIO 093 1149 6776 725 (711)

1151 DIO 090 1286 7120 823 (801)

1152 DIO 089 1243 5761 639 (622)

1153 DIO 088 1240 4881 531 (510)

a) The weight ratio of polymer to PC71BM b)The average PCE is obtained from 20 devices

Figure S5 the J-V curves of polymer P1 P2 P3 with different weight ratio to PC71BM (a c e) and different amount of DIO (b d f) as additive

Figure S6 J-V plots for the devices ITOPEDOTPSSpolymerPC71BMAu The solid line is the fittig of the data points (the thicknesses of the polymer films were 100 nm) The graphs a b c represent P1 P2 P3 respectively

Figure S7 AFM phase images of the active layers of P1PC71BM (a) P1PC71BM with 2 DIO (b) P2PC71BM (c) P2PC71BM with 2 DIO (d) P3PC71BM (e) and P3PC71BM with 2 DIO (f)

Figure S2 Cyclic voltammogram (a) UPS spectrum of the onset (b) amplified spectrum of the onset (c) and the secondary edge region (d) of the polymers P1 P2 and P3

Figure S3 (a) the two possible conformations of the compound 2 and the totle energy difference (b) the calculated distributions of the frontier molecular orbitals and the HOMO and LUMO energy levels of the polymers

Table S2 Calculated Bond Angles of the Repeat Units of the Copolymersa

NSN

SS

R

S

S

O

O

θ1

θ2 θ3

θ4

θ5FF

X

X

polymer X R θ1 (deg) θ2 (deg) θ3 (deg) θ4 (deg) θ5 (deg)

P1 H 2-ethyl-hexyl 5869 5741 3773 066 053

P2 F 2-ethyl-hexyl 5931 6039 4246 099 051

P3 F hexyl 5974 5920 418 071 009

aillustration of θ1 θ2 θ3 θ4 and θ5 is given in graphic

Figure S4 UV-vis absorption spectra of P1 (a) P2 (b) P3 (c) in chlorobenzene solution at different temperature

Table S3 the performance of the devices with different raito and amount of DIOPolymer RatioaAddditive Voc (V) Jsc (mA cm-2) FF () PCEmax (PCEave)b ()

P1 110 DIO 089 910 5344 433 (421)

1150 DIO 088 1127 4696 467 (450)

120 DIO 088 964 4367 369 (352)

1151 DIO 084 1117 4924 464 (454)

1152 DIO 084 1181 4943 491 (472)

1153 DIO 084 1092 4891 449 (414)

P2 110 DIO 102 619 4176 264 (261)

1150 DIO 103 730 4376 329 (315)

120 DIO 101 684 4229 294 (290)

1151 DIO 094 792 5682 424 (401)

1152 DIO 094 1248 6903 810 (805)

1153 DIO 094 1212 6432 730 (712)

P3 110 DIO 093 1129 6675 701 (698)

1150 DIO 093 1297 7449 902 (896)

120 DIO 093 1149 6776 725 (711)

1151 DIO 090 1286 7120 823 (801)

1152 DIO 089 1243 5761 639 (622)

1153 DIO 088 1240 4881 531 (510)

a) The weight ratio of polymer to PC71BM b)The average PCE is obtained from 20 devices

Figure S5 the J-V curves of polymer P1 P2 P3 with different weight ratio to PC71BM (a c e) and different amount of DIO (b d f) as additive

Figure S6 J-V plots for the devices ITOPEDOTPSSpolymerPC71BMAu The solid line is the fittig of the data points (the thicknesses of the polymer films were 100 nm) The graphs a b c represent P1 P2 P3 respectively

Figure S7 AFM phase images of the active layers of P1PC71BM (a) P1PC71BM with 2 DIO (b) P2PC71BM (c) P2PC71BM with 2 DIO (d) P3PC71BM (e) and P3PC71BM with 2 DIO (f)

Figure S3 (a) the two possible conformations of the compound 2 and the totle energy difference (b) the calculated distributions of the frontier molecular orbitals and the HOMO and LUMO energy levels of the polymers

Table S2 Calculated Bond Angles of the Repeat Units of the Copolymersa

NSN

SS

R

S

S

O

O

θ1

θ2 θ3

θ4

θ5FF

X

X

polymer X R θ1 (deg) θ2 (deg) θ3 (deg) θ4 (deg) θ5 (deg)

P1 H 2-ethyl-hexyl 5869 5741 3773 066 053

P2 F 2-ethyl-hexyl 5931 6039 4246 099 051

P3 F hexyl 5974 5920 418 071 009

aillustration of θ1 θ2 θ3 θ4 and θ5 is given in graphic

Figure S4 UV-vis absorption spectra of P1 (a) P2 (b) P3 (c) in chlorobenzene solution at different temperature

Table S3 the performance of the devices with different raito and amount of DIOPolymer RatioaAddditive Voc (V) Jsc (mA cm-2) FF () PCEmax (PCEave)b ()

P1 110 DIO 089 910 5344 433 (421)

1150 DIO 088 1127 4696 467 (450)

120 DIO 088 964 4367 369 (352)

1151 DIO 084 1117 4924 464 (454)

1152 DIO 084 1181 4943 491 (472)

1153 DIO 084 1092 4891 449 (414)

P2 110 DIO 102 619 4176 264 (261)

1150 DIO 103 730 4376 329 (315)

120 DIO 101 684 4229 294 (290)

1151 DIO 094 792 5682 424 (401)

1152 DIO 094 1248 6903 810 (805)

1153 DIO 094 1212 6432 730 (712)

P3 110 DIO 093 1129 6675 701 (698)

1150 DIO 093 1297 7449 902 (896)

120 DIO 093 1149 6776 725 (711)

1151 DIO 090 1286 7120 823 (801)

1152 DIO 089 1243 5761 639 (622)

1153 DIO 088 1240 4881 531 (510)

a) The weight ratio of polymer to PC71BM b)The average PCE is obtained from 20 devices

Figure S5 the J-V curves of polymer P1 P2 P3 with different weight ratio to PC71BM (a c e) and different amount of DIO (b d f) as additive

Figure S6 J-V plots for the devices ITOPEDOTPSSpolymerPC71BMAu The solid line is the fittig of the data points (the thicknesses of the polymer films were 100 nm) The graphs a b c represent P1 P2 P3 respectively

Figure S7 AFM phase images of the active layers of P1PC71BM (a) P1PC71BM with 2 DIO (b) P2PC71BM (c) P2PC71BM with 2 DIO (d) P3PC71BM (e) and P3PC71BM with 2 DIO (f)

Table S2 Calculated Bond Angles of the Repeat Units of the Copolymersa

NSN

SS

R

S

S

O

O

θ1

θ2 θ3

θ4

θ5FF

X

X

polymer X R θ1 (deg) θ2 (deg) θ3 (deg) θ4 (deg) θ5 (deg)

P1 H 2-ethyl-hexyl 5869 5741 3773 066 053

P2 F 2-ethyl-hexyl 5931 6039 4246 099 051

P3 F hexyl 5974 5920 418 071 009

aillustration of θ1 θ2 θ3 θ4 and θ5 is given in graphic

Figure S4 UV-vis absorption spectra of P1 (a) P2 (b) P3 (c) in chlorobenzene solution at different temperature

Table S3 the performance of the devices with different raito and amount of DIOPolymer RatioaAddditive Voc (V) Jsc (mA cm-2) FF () PCEmax (PCEave)b ()

P1 110 DIO 089 910 5344 433 (421)

1150 DIO 088 1127 4696 467 (450)

120 DIO 088 964 4367 369 (352)

1151 DIO 084 1117 4924 464 (454)

1152 DIO 084 1181 4943 491 (472)

1153 DIO 084 1092 4891 449 (414)

P2 110 DIO 102 619 4176 264 (261)

1150 DIO 103 730 4376 329 (315)

120 DIO 101 684 4229 294 (290)

1151 DIO 094 792 5682 424 (401)

1152 DIO 094 1248 6903 810 (805)

1153 DIO 094 1212 6432 730 (712)

P3 110 DIO 093 1129 6675 701 (698)

1150 DIO 093 1297 7449 902 (896)

120 DIO 093 1149 6776 725 (711)

1151 DIO 090 1286 7120 823 (801)

1152 DIO 089 1243 5761 639 (622)

1153 DIO 088 1240 4881 531 (510)

a) The weight ratio of polymer to PC71BM b)The average PCE is obtained from 20 devices

Figure S5 the J-V curves of polymer P1 P2 P3 with different weight ratio to PC71BM (a c e) and different amount of DIO (b d f) as additive

Figure S6 J-V plots for the devices ITOPEDOTPSSpolymerPC71BMAu The solid line is the fittig of the data points (the thicknesses of the polymer films were 100 nm) The graphs a b c represent P1 P2 P3 respectively

Figure S7 AFM phase images of the active layers of P1PC71BM (a) P1PC71BM with 2 DIO (b) P2PC71BM (c) P2PC71BM with 2 DIO (d) P3PC71BM (e) and P3PC71BM with 2 DIO (f)

Figure S4 UV-vis absorption spectra of P1 (a) P2 (b) P3 (c) in chlorobenzene solution at different temperature

Table S3 the performance of the devices with different raito and amount of DIOPolymer RatioaAddditive Voc (V) Jsc (mA cm-2) FF () PCEmax (PCEave)b ()

P1 110 DIO 089 910 5344 433 (421)

1150 DIO 088 1127 4696 467 (450)

120 DIO 088 964 4367 369 (352)

1151 DIO 084 1117 4924 464 (454)

1152 DIO 084 1181 4943 491 (472)

1153 DIO 084 1092 4891 449 (414)

P2 110 DIO 102 619 4176 264 (261)

1150 DIO 103 730 4376 329 (315)

120 DIO 101 684 4229 294 (290)

1151 DIO 094 792 5682 424 (401)

1152 DIO 094 1248 6903 810 (805)

1153 DIO 094 1212 6432 730 (712)

P3 110 DIO 093 1129 6675 701 (698)

1150 DIO 093 1297 7449 902 (896)

120 DIO 093 1149 6776 725 (711)

1151 DIO 090 1286 7120 823 (801)

1152 DIO 089 1243 5761 639 (622)

1153 DIO 088 1240 4881 531 (510)

a) The weight ratio of polymer to PC71BM b)The average PCE is obtained from 20 devices

Figure S5 the J-V curves of polymer P1 P2 P3 with different weight ratio to PC71BM (a c e) and different amount of DIO (b d f) as additive

Figure S6 J-V plots for the devices ITOPEDOTPSSpolymerPC71BMAu The solid line is the fittig of the data points (the thicknesses of the polymer films were 100 nm) The graphs a b c represent P1 P2 P3 respectively

Figure S7 AFM phase images of the active layers of P1PC71BM (a) P1PC71BM with 2 DIO (b) P2PC71BM (c) P2PC71BM with 2 DIO (d) P3PC71BM (e) and P3PC71BM with 2 DIO (f)

Table S3 the performance of the devices with different raito and amount of DIOPolymer RatioaAddditive Voc (V) Jsc (mA cm-2) FF () PCEmax (PCEave)b ()

P1 110 DIO 089 910 5344 433 (421)

1150 DIO 088 1127 4696 467 (450)

120 DIO 088 964 4367 369 (352)

1151 DIO 084 1117 4924 464 (454)

1152 DIO 084 1181 4943 491 (472)

1153 DIO 084 1092 4891 449 (414)

P2 110 DIO 102 619 4176 264 (261)

1150 DIO 103 730 4376 329 (315)

120 DIO 101 684 4229 294 (290)

1151 DIO 094 792 5682 424 (401)

1152 DIO 094 1248 6903 810 (805)

1153 DIO 094 1212 6432 730 (712)

P3 110 DIO 093 1129 6675 701 (698)

1150 DIO 093 1297 7449 902 (896)

120 DIO 093 1149 6776 725 (711)

1151 DIO 090 1286 7120 823 (801)

1152 DIO 089 1243 5761 639 (622)

1153 DIO 088 1240 4881 531 (510)

a) The weight ratio of polymer to PC71BM b)The average PCE is obtained from 20 devices

Figure S5 the J-V curves of polymer P1 P2 P3 with different weight ratio to PC71BM (a c e) and different amount of DIO (b d f) as additive

Figure S6 J-V plots for the devices ITOPEDOTPSSpolymerPC71BMAu The solid line is the fittig of the data points (the thicknesses of the polymer films were 100 nm) The graphs a b c represent P1 P2 P3 respectively

Figure S7 AFM phase images of the active layers of P1PC71BM (a) P1PC71BM with 2 DIO (b) P2PC71BM (c) P2PC71BM with 2 DIO (d) P3PC71BM (e) and P3PC71BM with 2 DIO (f)

Figure S5 the J-V curves of polymer P1 P2 P3 with different weight ratio to PC71BM (a c e) and different amount of DIO (b d f) as additive

Figure S6 J-V plots for the devices ITOPEDOTPSSpolymerPC71BMAu The solid line is the fittig of the data points (the thicknesses of the polymer films were 100 nm) The graphs a b c represent P1 P2 P3 respectively

Figure S7 AFM phase images of the active layers of P1PC71BM (a) P1PC71BM with 2 DIO (b) P2PC71BM (c) P2PC71BM with 2 DIO (d) P3PC71BM (e) and P3PC71BM with 2 DIO (f)

Figure S6 J-V plots for the devices ITOPEDOTPSSpolymerPC71BMAu The solid line is the fittig of the data points (the thicknesses of the polymer films were 100 nm) The graphs a b c represent P1 P2 P3 respectively

Figure S7 AFM phase images of the active layers of P1PC71BM (a) P1PC71BM with 2 DIO (b) P2PC71BM (c) P2PC71BM with 2 DIO (d) P3PC71BM (e) and P3PC71BM with 2 DIO (f)

Figure S7 AFM phase images of the active layers of P1PC71BM (a) P1PC71BM with 2 DIO (b) P2PC71BM (c) P2PC71BM with 2 DIO (d) P3PC71BM (e) and P3PC71BM with 2 DIO (f)