Thiophene-Bithiazole Acceptor-Donor-Acceptor Unit ...

10
S1 Supplementary information Effect of Alkyl Chain Spacer on Charge Transport in n-Type Dominant Polymer Semiconductors with Diketopyrrolopyrrole- Thiophene-Bithiazole Acceptor-Donor-Acceptor Unit † Hojeong Yu, a,b,§ Hyong Nam Kim, c,§ Inho Song, a Yeon Hee Ha, c Hyungju Ahn, d Joon Hak Oh a,* , Yun-Hi Kim c,* a Department of Chemical Engineering, Pohang University of Science and Technology (POSTECH), Pohang, Gyeongbuk 790-784, South Korea. E-mail: [email protected] b School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 689-798, South Korea. c Department of Chemistry and RIGET, Gyeongsang National Univ, 900, Gajwa-dong, Jinju, Gyeongnam, 660-701, South Korea. *E-mail: [email protected] d Pohang Accelerator Laboratory, Pohang University of Science and Technology (POSTECH), Pohang, Gyeongbuk 790-784, South Korea. § Dual Contributors Table of Contents Page number S1. Materials and Methods S2-S3 Figure S1. H-NMR of P-24-DPPBTz and P-29-DPPBTz S4 Figure S2. Cyclovoltammetry curve of P-24-DPPBTz and P-29-DPPBTz S5 Figure S3. TGA and DSC thermograms of P-24-DPPBTz and P-29- DPPBTz S6 Figure S4. Out-of-plane X-ray diffraction (XRD) patterns of annealed P- 24-DPPBTz and P-29-DPPBTz thin films at 260 °C and 300 °C. S7 Figure S5. AFM phase images of annealed (a) P-24-DPPBTz and (b) P-29- DPPBTz films at 260 °C and 300 °C, respectively. S8 Figure S6. Average field-effect mobility variations with standard deviation values under various annealing temperatures S9 References S10 Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C. This journal is © The Royal Society of Chemistry 2017

Transcript of Thiophene-Bithiazole Acceptor-Donor-Acceptor Unit ...

Page 1: Thiophene-Bithiazole Acceptor-Donor-Acceptor Unit ...

S1

Supplementary information

Effect of Alkyl Chain Spacer on Charge Transport in n-Type

Dominant Polymer Semiconductors with Diketopyrrolopyrrole-

Thiophene-Bithiazole Acceptor-Donor-Acceptor Unit †

Hojeong Yu,a,b,§ Hyong Nam Kim,c,§ Inho Song,a Yeon Hee Ha,c Hyungju Ahn,d Joon Hak Oha,*, Yun-Hi Kimc,*

a Department of Chemical Engineering, Pohang University of Science and Technology (POSTECH), Pohang, Gyeongbuk 790-784, South Korea. E-mail: [email protected] School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 689-798, South Korea.c Department of Chemistry and RIGET, Gyeongsang National Univ, 900, Gajwa-dong, Jinju, Gyeongnam, 660-701, South Korea. *E-mail: [email protected] Pohang Accelerator Laboratory, Pohang University of Science and Technology (POSTECH), Pohang, Gyeongbuk 790-784, South Korea.§Dual Contributors

Table of Contents Page number

S1. Materials and Methods S2-S3

Figure S1. H-NMR of P-24-DPPBTz and P-29-DPPBTz S4

Figure S2. Cyclovoltammetry curve of P-24-DPPBTz and P-29-DPPBTz S5Figure S3. TGA and DSC thermograms of P-24-DPPBTz and P-29-DPPBTz S6

Figure S4. Out-of-plane X-ray diffraction (XRD) patterns of annealed P-24-DPPBTz and P-29-DPPBTz thin films at 260 °C and 300 °C. S7

Figure S5. AFM phase images of annealed (a) P-24-DPPBTz and (b) P-29-DPPBTz films at 260 °C and 300 °C, respectively. S8

Figure S6. Average field-effect mobility variations with standard deviation values under various annealing temperatures S9

References S10

Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.This journal is © The Royal Society of Chemistry 2017

Page 2: Thiophene-Bithiazole Acceptor-Donor-Acceptor Unit ...

S2

Experimental

Materials. All chemicals were purchased from Aldrich and Alpha : 2-bromothiazole, n-

butyllithium, N,N-dimethylformamide(DMF), tetrakis(triphenylphosphine) palladium (0) were

purchased from Aldrich. 3,6-Bis(5-bromothiophen-2-yl)-2,5-bis(2-

decyltetradecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione[1], 3,6-bis(5-bromothiophen-2-yl)-

2,5-bis(2-decylnonadecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione[2] and 5,5'-

bis(trimethylstannyl)-2,2'-bithiazole[3] were synthesized via published literature procedures.

Measurement. The 1H NMR spectra were recorded using a Bruker AM-300 spectrometer. The

thermal analysis was performed on a TA TGA 2100 thermogravimetric analyzer in a nitrogen.

The sample was heated at 20 ℃ min-1. Differential scanning calorimeter was conducted under

nitrogen on a TA instrument 2100 DSC. The sample was heated at 20 ℃ min-1 from 0 ℃ to

250 ℃. UV-vis absorption studies were carried out using Perkin-Elmer LAMBDA-900

UV/VIS/IR spectrophotometer. Cyclic voltammetry (CV) was performed on an EG and G Parc

model 273 Å potentiostat/galvanostat system with a three-electrode cell in a solution of

Bu4NCIO4 (0.1 M) in acetonitrile at a scan rate of 100 Mvs-1. The polymer films were coated

on a square Pt electrode (0.50 cm2) by dipping the electrode into the corresponding solvents

and 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.

Synthesis of 5,5'-bis(trimethylstannyl)-2,2'-bithiazole

5,5'-bis(trimethylstannyl)-2,2'-bithiazole was prepared according to the procedures reported in

the literature. [3] (1.3g, yield: 43%). 1H NMR (300 MHz, CDCl3) δ 7.819 (s, 2 H), 0.465 (s,

18H).

Page 3: Thiophene-Bithiazole Acceptor-Donor-Acceptor Unit ...

S3

Synthesis of P-24-DPPBTz : The polymer was prepared using a palladium-catalyzed Stille

coupling reaction. In a Schlenk flask 24-DPPBr (0.40 g, 0.35 mmol) and 5,5'-

bis(trimethylstannyl)-2,2'-bithiazole (0.175 g, 0.35 mmol) were dissolved in dry chlorobenzene

(6 mL). After degassing under nitrogen for 60 min, Pd2(dba)3 (6.4 mg) and P(oTol)3 (8.6 mg)

were added to the mixture, which was then stirred for 48 h at 110 °C. 2-Bromothiophen 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(2-decyltetradecyl)-3-(5-(5'-methyl-2,2'-bithiazol-5-yl)thiophen-2-yl)-6-(5-

methylthiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione] (P-24-DPPBTz) was obtained

by precipitation in methanol.

Synthesis of P-29-DPPBTz : The polymer was prepared using a palladium-catalyzed Stille

coupling reaction. In a Schlenk flask 29-DPPBr (0.4 g, 0.31 mmol) and 5,5'-

bis(trimethylstannyl)-2,2'-bithiazole (0.15 g, 0.31 mmol) were dissolved in dry chlorobenzene

(6 mL). After degassing under nitrogen for 60 min, Pd2(dba)3 (2.8 mg) and P(oTol)3 (2.8 mg)

were added to the mixture, which was then stirred for 48 h at 110 °C. 2-Bromothiophen 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)-3-(5-(5'-methyl-2,2'-bithiazol-5-yl)thiophen-2-yl)-6-(5-

methylthiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione) (P-29-DPPBTz) was obtained

by precipitation in methanol.

Page 4: Thiophene-Bithiazole Acceptor-Donor-Acceptor Unit ...

S4

Figure S1. H-NMR data of P-24-DPPBTz and P-29-DPPBTz

N

NO

O

SS

N

SN

S

R =C12H25

C10H21

nR

R

Page 5: Thiophene-Bithiazole Acceptor-Donor-Acceptor Unit ...

S5

-1.0 -0.5 0.00.000015

0.000010

0.000005

0.000000

Curr

ent (

A)

Potential (V vs Ag/Ag+)

P-24-DPPBTz

-1.0 -0.5 0.0

0.000000

Curre

nt (A

)

Potential (V vs Ag/Ag+)

P-29-DPPBTz

P-24-DPPBTz P-29-DPPBTz

Figure S2. Cyclovoltammetry curve of P-24-DPPBTz and P-29-DPPBTz

Page 6: Thiophene-Bithiazole Acceptor-Donor-Acceptor Unit ...

S6

100 150 200 250

-2

-1

0

1

2

3

Heat

ing

Flow

(w/g

)

Temperature (oC)

24DPP-BTz

100 150 200 250

-2

-1

0

1

2

3

Heat

ing

Flow

(w/g

)

Temperature (oC)

29DPP-BTz

0 100 200 300 400 500 600 700 800

0

20

40

60

80

100W

eigh

t (%

)

Temperature (oC)

24DPP-BTz

0 100 200 300 400 500 600 700 8000

20

40

60

80

100

Wei

ght (

%)

Temperature (oC)

29DPP-BTz

P-24-DPPBTz

P-24-DPPBTz

P-29-DPPBTz

P-29-DPPBTz(a) (b)

(c) (d)

Figure S3. TGA and DSC thermograms of P-24-DPPBTz and P-29-DPPBTz

Page 7: Thiophene-Bithiazole Acceptor-Donor-Acceptor Unit ...

S7

2 4 6 8 10 12 14 16 18 20 22 24 26

(500)

(300)

(400)

(200)

P-24-DPPBTz

Annealed film at 260 °C Annealed film at 300 °C

(100)

2 ( o)

Inte

nsity

(a.u

.)

2 4 6 8 10 12 14 16 18 20 22 24 26

(600)(500)

(400)

(300)

(200)

(100) P-29-DPPBTz

2 ( o)

Inte

nsity

(a.u

.)

Annealed film at 260 °C Annealed film at 300 °C

(a) (b)

Figure S4. Out-of-plane X-ray diffraction (XRD) patterns of annealed (a) P-24-DPPBTz and

(b) P-29-DPPBTz thin films at 260 °C and 300 °C.

Page 8: Thiophene-Bithiazole Acceptor-Donor-Acceptor Unit ...

S8

20 °

0 °1 µm

20 °

0 °1 µm

(b)(a)

Figure S5. AFM phase images of annealed (a) P-24-DPPBTz and (b) P-29-DPPBTz films on

OTS-treated SiO2/Si substrates.

Page 9: Thiophene-Bithiazole Acceptor-Donor-Acceptor Unit ...

S9

Figure S6. Average field-effect mobility variations with standard deviation values under

various annealing temperatures

0 220 240 260 280 30010-2

10-1

100 A

vera

ge m

obili

ty (c

m2 V

-1s-

1 )

Annealing temperature ( °C)

P-24-DPPBTz spin, h

spin, e

drop, h

drop, e

P-29-DPPBTz spin, h

spin, e

drop, h

drop, e

Page 10: Thiophene-Bithiazole Acceptor-Donor-Acceptor Unit ...

S10

References

[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.

[2] Il Kang, Hui-Jun Yun, Dae Sung Chung, Soon-Ki Kwon, and Yun-Hi Kim. J. Am. Chem.

Soc., 2013, 135, 14896-14899.

[3] B. Fu, C.-Y. Wang, B. D. Rose, Y. Jiang, M. Chang, P.-H. Chu, Z. Yuan, C. Fuentes-

Hernandez, B. Kippelen, J.-L. Brédas, D. M. Collard and E. Reichmanis, Chem. Mater.,

2015, 27, 2928-2937.