Record High Hole Mobility in Polymer Semiconductors via Side-Chain ...
Supplementary information
Record High Hole Mobility in Polymer Semiconductors via Side-Chain Engineering Il Kang,† Hui-Jun Yun,† Dae Sung Chung,*,§ Soon-Ki Kwon,*,† and Yun-Hi Kim,*,‡ †
School of Materials Science and Engineering & REGET, Gyeongsang National University, Jinju 660-701, South Korea. ‡ Department of Chemistry and RINS, Gyeongsang National University, Jinju, 660-701, South Korea. § School of Chemical Engineering and Material Science, Chung-Ang University, Seoul 156–756, South Korea.
Contents
S1. Materials and Methods S2. NMR spectra of Materials. S3. Differential scanning calorimetry of Polymers. S4. Thermogravimetric analysis of Polymers. S5. Cyclic voltammetry of Polymers. S6. X-ray diffaction patterns of Polymers. S7.Electrical Characteristics of the DPP-Based OFETs.
S1
S1. Materials and Methods All chemicals were purchased from Aldrich and Alpha : thiophene-2-carbonitrile, dimethyl succinate, 11-(6’-bromohexyl)tricosane, DMF, THF, NBS, n-BuLi, and were used without further purification. 3,6-Bis(5-bromothiophen-2-yl)-2,5-bis(2-decyltetradecyl)pyrrolo[3,4c]pyrrole-1,4(2H,5H)-dione[1] and (E)-1,2-di(selenophen-2-yl)ethene[2] were synthesized via published literature procedures. 1
H-NMR spectra were recorded using a BrukerAM-200 spectrometer. The melting points
were determined using an Electrothermal Mode 1307 digital analyzer. Molecular weights and polydispersities of the copolymers were determined by gel permeation chromatography (GPC) analysis with polystyrene standard calibration (waters high-pressure GPC assembly Model M515 pump, u-Styragel columns of HR4, HR4E, HR5E, with 500 and 100 Å , refractive index detectors, solvent Chloroform). Thermal analysis was performed using a TA TGA 2100 thermogravimetric analyzer under a nitrogen atmosphere at a heating rate of 10°C/min. Differential scanning calorimeter (DSC) was conducted under nitrogen using a TA instrument 2100 DSC. The sample was heated at 10°C /min from 30°C to 250°C. UV–vis absorption
spectra
were
measured
using
a
Perkin-Elmer
LAMBDA-900
UV
spectrophotometer. Cyclic voltammetry (CV) was performed using an EG and G Parc model 273 Å potentiostat/galvanostat system with a three-electrode cell in a solution containing Bu4NClO4 (0.1 M) in acetonitrile at a scan rate of 100 mV/s. The polymer films were coated on a square carbon electrode (0.50 cm2) by dipping the electrode into the corresponding solvents then drying in air. A Pt wire was used as the counter electrode, and an Ag/AgNO3 (0.1 M) electrode was used as the reference electrode.
S2
Experimental Section Synthesis
of
29-DPP:
3,6-Dithiophen-2-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione
(1.00 g, 3.33 mmol) and anhydrous potassium carbonate (2.50 g, 0.013 mol) were dissolved into N,N-dimethylformamide (50 mL) in a three-neck round flask and heated to 120 °C. 11(6’-bromohexyl)tricosane (8.3 g, 0.017 mol) was injected two portion by syringe. The reaction was stirred for 48 h at 120 °C. This mixture was extracted with diethyl ether, the organic phase was dried over anhydrous magnesium sulfate (MgSO4) and removed solvent. The crude product was purified by silica gel chromatography (hexane–methylenechloride (MC), gradient from 10:1 to 3:1). The residue was recrystallized from ethyl alcohol and MC to get a purple solid powder (1.3 g, 35%). 1H-NMR (300 MHz, CDCl3, ppm): δ 8.96 (d, 2H), 7.64 (d, 2H), 7.32 (d, 2H), 4.11-4.06 (t, 4H), 1.81-1.72 (t, 4H), 1.44-1.27 (m, 98H), 0.92-0.81 (m, 12H), 13C- NMR (125 MHz, CDCl3, ppm): 161.78, 140.42, 135.62, 130.97, 130.22, 128.98, 108.16, 42.65, 37.82, 34.10, 32.32, 30.55, 30.39, 30.113, 30.054, 29.75, 27.34, 27.12, 27.05, 23.08, 14.49. Synthesis of 29-DPPBr : Protected from light, N-bromosuccinimide (NBS) (0.33 g, 1.89 mmol) was added to a 29-DPP (1.00 g, 0.90 mmol) in CHCl3 (75 mL) at room temperature. The solution was stirred for 12 h, the mixture was extracted with chloroform, the organic phase was dried over anhydrous magnesium sulfate (MgSO4) and removed solvent. The crude product was purified by silica gel chromatography (hexane–MC, 3:1). The residue was recrystallized from MC and ethyl alcohol to get a purple solid powder (0.98 g,
86%). 1H-
NMR (300 MHz, CDCl3, ppm): δ 8.71 (d, 2H), 7.26 (d, 2H), 4.02-3.97 (t, 4H), 1.78-1.71 (t, 4H), 1.44-1.27(m, 98H), 0.92-0.87 (m, 12H), 13C- NMR (125 MHz, CDCl3, ppm): 161.43, 139.38, 135.72, 132.04, 131.56, 119.50, 108.26, 42.71, 37.82, 34.09, 32.32, 30.56, 30.41, 30.11, 30.05, 29.75, 27.28, 27.12, 27.01, 23.08, 14.49.
S3
Synthesis of P-29-DPPDBTE : The polymer was prepared using a palladium-catalyzed Stille coupling reaction. In a Schlenk flask 29-DPPBr (0.50 g, 0.4 mmol) and 1,2-(E)-Bis(5(trimethylstannanyl-2(-C-thienyl)ethene (0.229 g, 0.4 mmol) were dissolved in dry chlorobenzene (7.5 mL). After degassing under nitrogen for 60 min, Pd2(dba)3 (8 mg) and P(oTol)3 (11 mg) were added to the mixture, which was then stirred for 48 h at 110 °C. 2Bromothiophen and tributyl(thiophen-2-yl)stannane were injected sequentially into the reaction mixture for end-capping, and the solution was stirred for 6 h after each addition. The polymer was precipitated in methanol. The crude polymer was collected by filtration and purified by Soxhlet extraction with methanol, acetone, hexane, toluene, and chloroform, successively. The final product, poly[2,5-bis-(7-decylnonadecyl)pyrrolo[3,4-c]pyrrole1,4(2H,5H)-dione-(E)-1,2-di(2,2'-bithiophen-5-yl)ethene] (P-29-DPPDBTE) was obtained by precipitation in methanol. Yield : 0.52g. (Mn =33,369, Mw =60,781, PDI = 1.82). 1H NMR (CDCl3, 500MHz), δ(ppm) : δ8.96 (broad, 4H), 7.4-6.75 (broad, 6H), 4.01 (broad, 4H), 1.8-1.25 (broad, 102H), 0.85 (broad,12H). Synthesis of P-29-DPPDTSE : The polymer was prepared using a palladium-catalyzed Stille coupling reaction. In a Schlenk flask 29-DPPBr (0.5 g, 0.4 mmol) and 1,2-(E)-bis(5(trimethylstannyl)selenophen-2-yl)ethene (0.27 g, 0.4 mmol) were dissolved in dry chlorobenzene (7.5 mL). After degassing under nitrogen for 60 min, Pd2(dba)3 (8 mg) and P(oTol)3 (11 mg) were added to the mixture, which was then stirred for 48 h at 110 °C. 2Bromothiophen and tributyl(thiophen-2-yl)stannane were injected sequentially into the reaction mixture for end-capping, and the solution was stirred for 6 h after each addition. The polymer was precipitated in methanol. The crude polymer was collected by filtration and purified by Soxhlet extraction with methanol, acetone, hexane, toluene, and chloroform, successively.
The
final
product,
poly[2,5-bis(7-decylnonadecyl)pyrrolo[3,4-c]pyrrole-
1,4(2H,5H)-dione-(E)-(1,2-bis(5-(thiophen-2-yl)selenophen-2-yl)ethene) (P-29-DPPDTSE) S4
was obtained by precipitation in methanol. Yield : 0.49g. (Mn = 35,826, Mw = 58,038, PDI =1.62). 1H NMR (CDCl3, 500MHz), δ(ppm) : δ8.78 (broad, 4H), 7.4-6.75 (broad, 6H), 4.02 (broad, 4H), 1.95-1.26 (broad, 102H), 0.85 (broad,12H).
OFET fabrication : Top-contact OFETs were fabricated on a common gate of highly ndoped silicon with a 100 nm thick thermally grown SiO2 dielectric layer. The octadecyltrichlorosilane monolayer was treated in toluene for 1 h. Thin layer of CytopTM was spin-coated onto SiO2 dielectric layer (~20 nm). Capacitance of such dielectric layer was measured using an SR 720 LCR meter at frequencies ranging from 100 Hz to 100 kHz. (MIM device structure was used.) Solutions containing the organic semiconductors were spincoated at 2000 rpm from 0.2 wt% chloroform solutions with a nominal thickness of 30 nm, as confirmed using a surface profiler (Alpha Step 500, Tencor). The films were annealed at 200 °C for 10 min under a nitrogen atmosphere. Gold source and drain electrodes were evaporated on top of the semiconductor layers (60 nm). For all measurements, typical channel widths (W) and lengths (L) were 1000 µm and 50 µm, respectively. Characterization : The electrical characteristics of the OFETs were measured under ambient condition using Keithley 2400 and 236 source/measure units. Field-effect mobilities were extracted in the saturation regime from the slope of the source–drain current. The capacitance of OTS-treated and Cytop-treated SiO2 were measured to be 10.5 nF/cm2 and 9.6 nF/cm2, respectively. The gate voltage sweep rate was fixed to be 2V/s
Reference [1] T. L. Nelson, T. M. Young, J. Y. Liu, S. P. Mishra, J. A. Belot, C. L. Balliet, A. E. Javier, T. Kowalewski,R. D. McCullough. Adv. Mater. 2010, 22, 4617
S5
[2] S. C. Ng, H. S. O. Chan, T. T. Ong, K. Kumura, Y. Mazaki, K. Kobayashi Macromolecules. 1988, 31, 1221
S2. NMR spectra of Materials
Figure S1. 1H-NMR spectrum of 29-DPP in CDCl3.
S6
Figure S2. 13C-NMR spectrum of 29-DPP in CDCl3.
S7
Figure S3. 1H-NMR spectrum of 29-DPPBr in CDCl3.
S8
Figure S4. 13C-NMR spectrum of 29-DPPBr in CDCl3.
S9
Figure S5. 1H-NMR spectrum of P-29-DPPDBTE in CDCl3.
S10
C12H 25
C10H 21 Se n
O
S
S
N
N
Se
O
Figure S6. 1H-NMR spectrum of P-29-DPPDTSE in CDCl3. C 10H 21
C12H 25
S3. Differential scanning calorimetry of Polymers
Figure S6. Thermogravimetric analysis plot for P-29-DPPDBTE, P-29-DPPDTSE
S11
S3. Differential scanning calorimetry of Polymers
1st Heat Cool
1st Heat Cool
P-29-DPPDTSE
Heating Flow(w/g)
Heating Flow(w/g)
P-29-DPPDBTE
50
100
150
200
250
300 100
200
300
o
Temperature ( C)
o
Temperature ( C)
Figure S7. Differential scanning calorimetry plot for polymers. Scan rate = 10 °C/min from 0 to 300 °C.
S12
S4. Thermogravimetric analysis of Polymers
100
100
P-29-DPPDBTE
80
Weight (%)
Weight (%)
80
P-29-DPPDTSE
60 40 20
60 40 20
0
0 0
200
400
600
800
0
o
200
400
600
800
o
Temperature ( C)
Temperature ( C)
Figure S8. Thermogravimetric analysis plot for P-29-DPPDBTE, P-29-DPPDTSE. Scan rate = 10 °C/min from 10 to 800 °C.
S13
S5. Cyclic voltammetry of Polymers
P-29-DPPDTSE
Current (A)
Current (A)
P-24-DPPDBTE
-0.5
0.0
0.5
1.0
1.5
-0.5
Potential (V vs Ag/Ag+)
0.0
0.5
1.0
1.5
Potential (V vs Ag/Ag+)
Figure S9. Cyclic voltammetry plots of P-29-DPPDBTE and acetonitrile solution.
S14
P-29-DPPDBE obtained in an
S6. X-ray diffaction patterns of Polymers
Figure S10. The out-of-plane XRD patterns of polymers as a function of thermal annealing temperature.
S15
S7. Electrical Characteristics of the DPP-Based OFETs
Figure S11. Transfer characteristics of FETs based on (a) P-24-DPPDBTE, (b) P-24-DPPDTSE fabricated with OTS-modified SiO2/Si substrate. (c) and (d) correspond to Cytop-modified substrate for P-24-DPPDBTE and P-24DPPDTSE, respectively. Output characteristics of FETs based on (e) P-24-DPPDBTE, (f) P-24-DPPDTSE fabricated with OTS-modified SiO2/Si substrate. (g) and (h) correspond to Cytop-modified substrate for P-24-DPPDBTE and P24-DPPDTSE, respectively.
S16
S8.Temperature dependences of 2D-GIXD patterns Temperature dependences of crystalline structure of P-24-DPPDTSE and P-29-DPPDTSE were directly compared using two-dimensional grazing-incidence X-ray diffraction (2DGIXD) technique. (Figure S10, S11) Interestingly, P-29-DPPDTSE, whose branching position in the side chain is adjusted, show very well developed crystalline structure even in as-cast condition. As shown in Figure S11, highly ordered diffraction patterns are observed along the direction of out of plane (qz). Furthermore, quite distinct & intense (010) diffraction (qxy) is also observed in as cast film. Note that further thermal annealing results in only slight increase of intensity of diffraction patterns which already appeared in as cast film. On the other hand, (Figure S10) in the case of P-24-DPPDTSE, the as cast film show very weak Bragg diffraction patterns together with distinct diffraction amorphous halos. Only films processed by high temperature annealing show highly ordered (001) patterns as well as (010) diffraction. This can support the reason why P-29s have such high mobility even without high temperature thermal annealing.
Figure S12. 2-D GIXD patterns of P-24-DPPDTSE deposited onto Cytop/SiO2 substrate. (a) as cast (b) annealed at 100 ºC (c) annealed at 150 ºC and (d) annealed at 200 ºC
S17
Figure S13. 2-D GIXD patterns of P-29-DPPDTSE deposited onto Cytop/SiO2 substrate. (a) as cast (b) annealed at 100 ºC (c) annealed at 150 ºC and (d) annealed at 200 ºC
S18
Table S1. Assignment of the peaks in the XRD spectra Thermal annealing Lamella distance (Å)
π- π stacking distance (Å)
P-24DPPDBTE
P-24DPPDTSE
P-29DPPDBTE
P-29DPPDTSE
RT
21.9
21.8
27.3
27.4
200
21.5
21.5
26.9
26.9
RT
N/A
N/A
3.64
3.60
200
3.72
3.71
3.62
3.58
S19
Record High Hole Mobility in Polymer Semiconductors via Side-Chain Engineering Il Kang,† Hui-Jun Yun,† Dae Sung Chung,*,§ Soon-Ki Kwon,*,† and Yun-Hi Kim,*,‡ †
School of Materials Science and Engineering & REGET, Gyeongsang National University, Jinju 660-701, South Korea. ‡ Department of Chemistry and RINS, Gyeongsang National University, Jinju, 660-701, South Korea. § School of Chemical Engineering and Material Science, Chung-Ang University, Seoul 156–756, South Korea.
Contents
S1. Materials and Methods S2. NMR spectra of Materials. S3. Differential scanning calorimetry of Polymers. S4. Thermogravimetric analysis of Polymers. S5. Cyclic voltammetry of Polymers. S6. X-ray diffaction patterns of Polymers. S7.Electrical Characteristics of the DPP-Based OFETs.
S1
S1. Materials and Methods All chemicals were purchased from Aldrich and Alpha : thiophene-2-carbonitrile, dimethyl succinate, 11-(6’-bromohexyl)tricosane, DMF, THF, NBS, n-BuLi, and were used without further purification. 3,6-Bis(5-bromothiophen-2-yl)-2,5-bis(2-decyltetradecyl)pyrrolo[3,4c]pyrrole-1,4(2H,5H)-dione[1] and (E)-1,2-di(selenophen-2-yl)ethene[2] were synthesized via published literature procedures. 1
H-NMR spectra were recorded using a BrukerAM-200 spectrometer. The melting points
were determined using an Electrothermal Mode 1307 digital analyzer. Molecular weights and polydispersities of the copolymers were determined by gel permeation chromatography (GPC) analysis with polystyrene standard calibration (waters high-pressure GPC assembly Model M515 pump, u-Styragel columns of HR4, HR4E, HR5E, with 500 and 100 Å , refractive index detectors, solvent Chloroform). Thermal analysis was performed using a TA TGA 2100 thermogravimetric analyzer under a nitrogen atmosphere at a heating rate of 10°C/min. Differential scanning calorimeter (DSC) was conducted under nitrogen using a TA instrument 2100 DSC. The sample was heated at 10°C /min from 30°C to 250°C. UV–vis absorption
spectra
were
measured
using
a
Perkin-Elmer
LAMBDA-900
UV
spectrophotometer. Cyclic voltammetry (CV) was performed using an EG and G Parc model 273 Å potentiostat/galvanostat system with a three-electrode cell in a solution containing Bu4NClO4 (0.1 M) in acetonitrile at a scan rate of 100 mV/s. The polymer films were coated on a square carbon electrode (0.50 cm2) by dipping the electrode into the corresponding solvents then drying in air. A Pt wire was used as the counter electrode, and an Ag/AgNO3 (0.1 M) electrode was used as the reference electrode.
S2
Experimental Section Synthesis
of
29-DPP:
3,6-Dithiophen-2-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione
(1.00 g, 3.33 mmol) and anhydrous potassium carbonate (2.50 g, 0.013 mol) were dissolved into N,N-dimethylformamide (50 mL) in a three-neck round flask and heated to 120 °C. 11(6’-bromohexyl)tricosane (8.3 g, 0.017 mol) was injected two portion by syringe. The reaction was stirred for 48 h at 120 °C. This mixture was extracted with diethyl ether, the organic phase was dried over anhydrous magnesium sulfate (MgSO4) and removed solvent. The crude product was purified by silica gel chromatography (hexane–methylenechloride (MC), gradient from 10:1 to 3:1). The residue was recrystallized from ethyl alcohol and MC to get a purple solid powder (1.3 g, 35%). 1H-NMR (300 MHz, CDCl3, ppm): δ 8.96 (d, 2H), 7.64 (d, 2H), 7.32 (d, 2H), 4.11-4.06 (t, 4H), 1.81-1.72 (t, 4H), 1.44-1.27 (m, 98H), 0.92-0.81 (m, 12H), 13C- NMR (125 MHz, CDCl3, ppm): 161.78, 140.42, 135.62, 130.97, 130.22, 128.98, 108.16, 42.65, 37.82, 34.10, 32.32, 30.55, 30.39, 30.113, 30.054, 29.75, 27.34, 27.12, 27.05, 23.08, 14.49. Synthesis of 29-DPPBr : Protected from light, N-bromosuccinimide (NBS) (0.33 g, 1.89 mmol) was added to a 29-DPP (1.00 g, 0.90 mmol) in CHCl3 (75 mL) at room temperature. The solution was stirred for 12 h, the mixture was extracted with chloroform, the organic phase was dried over anhydrous magnesium sulfate (MgSO4) and removed solvent. The crude product was purified by silica gel chromatography (hexane–MC, 3:1). The residue was recrystallized from MC and ethyl alcohol to get a purple solid powder (0.98 g,
86%). 1H-
NMR (300 MHz, CDCl3, ppm): δ 8.71 (d, 2H), 7.26 (d, 2H), 4.02-3.97 (t, 4H), 1.78-1.71 (t, 4H), 1.44-1.27(m, 98H), 0.92-0.87 (m, 12H), 13C- NMR (125 MHz, CDCl3, ppm): 161.43, 139.38, 135.72, 132.04, 131.56, 119.50, 108.26, 42.71, 37.82, 34.09, 32.32, 30.56, 30.41, 30.11, 30.05, 29.75, 27.28, 27.12, 27.01, 23.08, 14.49.
S3
Synthesis of P-29-DPPDBTE : The polymer was prepared using a palladium-catalyzed Stille coupling reaction. In a Schlenk flask 29-DPPBr (0.50 g, 0.4 mmol) and 1,2-(E)-Bis(5(trimethylstannanyl-2(-C-thienyl)ethene (0.229 g, 0.4 mmol) were dissolved in dry chlorobenzene (7.5 mL). After degassing under nitrogen for 60 min, Pd2(dba)3 (8 mg) and P(oTol)3 (11 mg) were added to the mixture, which was then stirred for 48 h at 110 °C. 2Bromothiophen and tributyl(thiophen-2-yl)stannane were injected sequentially into the reaction mixture for end-capping, and the solution was stirred for 6 h after each addition. The polymer was precipitated in methanol. The crude polymer was collected by filtration and purified by Soxhlet extraction with methanol, acetone, hexane, toluene, and chloroform, successively. The final product, poly[2,5-bis-(7-decylnonadecyl)pyrrolo[3,4-c]pyrrole1,4(2H,5H)-dione-(E)-1,2-di(2,2'-bithiophen-5-yl)ethene] (P-29-DPPDBTE) was obtained by precipitation in methanol. Yield : 0.52g. (Mn =33,369, Mw =60,781, PDI = 1.82). 1H NMR (CDCl3, 500MHz), δ(ppm) : δ8.96 (broad, 4H), 7.4-6.75 (broad, 6H), 4.01 (broad, 4H), 1.8-1.25 (broad, 102H), 0.85 (broad,12H). Synthesis of P-29-DPPDTSE : The polymer was prepared using a palladium-catalyzed Stille coupling reaction. In a Schlenk flask 29-DPPBr (0.5 g, 0.4 mmol) and 1,2-(E)-bis(5(trimethylstannyl)selenophen-2-yl)ethene (0.27 g, 0.4 mmol) were dissolved in dry chlorobenzene (7.5 mL). After degassing under nitrogen for 60 min, Pd2(dba)3 (8 mg) and P(oTol)3 (11 mg) were added to the mixture, which was then stirred for 48 h at 110 °C. 2Bromothiophen and tributyl(thiophen-2-yl)stannane were injected sequentially into the reaction mixture for end-capping, and the solution was stirred for 6 h after each addition. The polymer was precipitated in methanol. The crude polymer was collected by filtration and purified by Soxhlet extraction with methanol, acetone, hexane, toluene, and chloroform, successively.
The
final
product,
poly[2,5-bis(7-decylnonadecyl)pyrrolo[3,4-c]pyrrole-
1,4(2H,5H)-dione-(E)-(1,2-bis(5-(thiophen-2-yl)selenophen-2-yl)ethene) (P-29-DPPDTSE) S4
was obtained by precipitation in methanol. Yield : 0.49g. (Mn = 35,826, Mw = 58,038, PDI =1.62). 1H NMR (CDCl3, 500MHz), δ(ppm) : δ8.78 (broad, 4H), 7.4-6.75 (broad, 6H), 4.02 (broad, 4H), 1.95-1.26 (broad, 102H), 0.85 (broad,12H).
OFET fabrication : Top-contact OFETs were fabricated on a common gate of highly ndoped silicon with a 100 nm thick thermally grown SiO2 dielectric layer. The octadecyltrichlorosilane monolayer was treated in toluene for 1 h. Thin layer of CytopTM was spin-coated onto SiO2 dielectric layer (~20 nm). Capacitance of such dielectric layer was measured using an SR 720 LCR meter at frequencies ranging from 100 Hz to 100 kHz. (MIM device structure was used.) Solutions containing the organic semiconductors were spincoated at 2000 rpm from 0.2 wt% chloroform solutions with a nominal thickness of 30 nm, as confirmed using a surface profiler (Alpha Step 500, Tencor). The films were annealed at 200 °C for 10 min under a nitrogen atmosphere. Gold source and drain electrodes were evaporated on top of the semiconductor layers (60 nm). For all measurements, typical channel widths (W) and lengths (L) were 1000 µm and 50 µm, respectively. Characterization : The electrical characteristics of the OFETs were measured under ambient condition using Keithley 2400 and 236 source/measure units. Field-effect mobilities were extracted in the saturation regime from the slope of the source–drain current. The capacitance of OTS-treated and Cytop-treated SiO2 were measured to be 10.5 nF/cm2 and 9.6 nF/cm2, respectively. The gate voltage sweep rate was fixed to be 2V/s
Reference [1] T. L. Nelson, T. M. Young, J. Y. Liu, S. P. Mishra, J. A. Belot, C. L. Balliet, A. E. Javier, T. Kowalewski,R. D. McCullough. Adv. Mater. 2010, 22, 4617
S5
[2] S. C. Ng, H. S. O. Chan, T. T. Ong, K. Kumura, Y. Mazaki, K. Kobayashi Macromolecules. 1988, 31, 1221
S2. NMR spectra of Materials
Figure S1. 1H-NMR spectrum of 29-DPP in CDCl3.
S6
Figure S2. 13C-NMR spectrum of 29-DPP in CDCl3.
S7
Figure S3. 1H-NMR spectrum of 29-DPPBr in CDCl3.
S8
Figure S4. 13C-NMR spectrum of 29-DPPBr in CDCl3.
S9
Figure S5. 1H-NMR spectrum of P-29-DPPDBTE in CDCl3.
S10
C12H 25
C10H 21 Se n
O
S
S
N
N
Se
O
Figure S6. 1H-NMR spectrum of P-29-DPPDTSE in CDCl3. C 10H 21
C12H 25
S3. Differential scanning calorimetry of Polymers
Figure S6. Thermogravimetric analysis plot for P-29-DPPDBTE, P-29-DPPDTSE
S11
S3. Differential scanning calorimetry of Polymers
1st Heat Cool
1st Heat Cool
P-29-DPPDTSE
Heating Flow(w/g)
Heating Flow(w/g)
P-29-DPPDBTE
50
100
150
200
250
300 100
200
300
o
Temperature ( C)
o
Temperature ( C)
Figure S7. Differential scanning calorimetry plot for polymers. Scan rate = 10 °C/min from 0 to 300 °C.
S12
S4. Thermogravimetric analysis of Polymers
100
100
P-29-DPPDBTE
80
Weight (%)
Weight (%)
80
P-29-DPPDTSE
60 40 20
60 40 20
0
0 0
200
400
600
800
0
o
200
400
600
800
o
Temperature ( C)
Temperature ( C)
Figure S8. Thermogravimetric analysis plot for P-29-DPPDBTE, P-29-DPPDTSE. Scan rate = 10 °C/min from 10 to 800 °C.
S13
S5. Cyclic voltammetry of Polymers
P-29-DPPDTSE
Current (A)
Current (A)
P-24-DPPDBTE
-0.5
0.0
0.5
1.0
1.5
-0.5
Potential (V vs Ag/Ag+)
0.0
0.5
1.0
1.5
Potential (V vs Ag/Ag+)
Figure S9. Cyclic voltammetry plots of P-29-DPPDBTE and acetonitrile solution.
S14
P-29-DPPDBE obtained in an
S6. X-ray diffaction patterns of Polymers
Figure S10. The out-of-plane XRD patterns of polymers as a function of thermal annealing temperature.
S15
S7. Electrical Characteristics of the DPP-Based OFETs
Figure S11. Transfer characteristics of FETs based on (a) P-24-DPPDBTE, (b) P-24-DPPDTSE fabricated with OTS-modified SiO2/Si substrate. (c) and (d) correspond to Cytop-modified substrate for P-24-DPPDBTE and P-24DPPDTSE, respectively. Output characteristics of FETs based on (e) P-24-DPPDBTE, (f) P-24-DPPDTSE fabricated with OTS-modified SiO2/Si substrate. (g) and (h) correspond to Cytop-modified substrate for P-24-DPPDBTE and P24-DPPDTSE, respectively.
S16
S8.Temperature dependences of 2D-GIXD patterns Temperature dependences of crystalline structure of P-24-DPPDTSE and P-29-DPPDTSE were directly compared using two-dimensional grazing-incidence X-ray diffraction (2DGIXD) technique. (Figure S10, S11) Interestingly, P-29-DPPDTSE, whose branching position in the side chain is adjusted, show very well developed crystalline structure even in as-cast condition. As shown in Figure S11, highly ordered diffraction patterns are observed along the direction of out of plane (qz). Furthermore, quite distinct & intense (010) diffraction (qxy) is also observed in as cast film. Note that further thermal annealing results in only slight increase of intensity of diffraction patterns which already appeared in as cast film. On the other hand, (Figure S10) in the case of P-24-DPPDTSE, the as cast film show very weak Bragg diffraction patterns together with distinct diffraction amorphous halos. Only films processed by high temperature annealing show highly ordered (001) patterns as well as (010) diffraction. This can support the reason why P-29s have such high mobility even without high temperature thermal annealing.
Figure S12. 2-D GIXD patterns of P-24-DPPDTSE deposited onto Cytop/SiO2 substrate. (a) as cast (b) annealed at 100 ºC (c) annealed at 150 ºC and (d) annealed at 200 ºC
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Figure S13. 2-D GIXD patterns of P-29-DPPDTSE deposited onto Cytop/SiO2 substrate. (a) as cast (b) annealed at 100 ºC (c) annealed at 150 ºC and (d) annealed at 200 ºC
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Table S1. Assignment of the peaks in the XRD spectra Thermal annealing Lamella distance (Å)
π- π stacking distance (Å)
P-24DPPDBTE
P-24DPPDTSE
P-29DPPDBTE
P-29DPPDTSE
RT
21.9
21.8
27.3
27.4
200
21.5
21.5
26.9
26.9
RT
N/A
N/A
3.64
3.60
200
3.72
3.71
3.62
3.58
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