Thiophene-Bithiazole Acceptor-Donor-Acceptor Unit ...
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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: joonhoh@postech.ac.krb 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: ykim@gnu.ac.krd 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
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).
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.
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
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
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
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.
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.
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
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.
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