supporting information - royal society of chemistry · 2016-05-31 · supporting information novel...
TRANSCRIPT
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)
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)