TY - JOUR
T1 - Phenanthrodithiophene (PDT)-Difluorobenzothiadiazole (DFBT) Copolymers
T2 - Effect on Molecular Orientation and Solar Cell Performance of Alkyl Substitution onto a PDT Core
AU - Mori, Hiroki
AU - Takahashi, Ryosuke
AU - Hyodo, Keita
AU - Nishinaga, Shuhei
AU - Sawanaka, Yuta
AU - Nishihara, Yasushi
N1 - Funding Information:
This study was partly supported by ACT-C, JST Grant JPMJCR12YW, Japan, and Grant-in-Aid for Scientific Research on Innovative Areas, MEXT, Japan [#2401] FY2012-FY2017. The GIWAXS experiments were performed on beamline BL46XU of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposals 2015B1904, 2016A1542, 2016A1768, and 2016B1875). We gratefully thank Prof. Itaru Osaka (Hiroshima University) and Dr. Tomoyuki Koganezawa (JASRI) for the measurement of GIWAXS images, Prof. Koichi Mitsudo and Prof. Seiji Suga (Okayama University) for the CV measurements, Prof. Yoshihiro Kubozono (Okayama University) for the measurement of thickness, Prof. Naoshi Ikeda (Okayama University) for the AFM images, and Ms. Megumi Kosaka and Mr. Motonari Kobayashi at the Department of Instrumental Analysis, Advanced Science Research Center, Okayama University, for the elemental analyses.
Funding Information:
This study was partly supported by ACT-C, JST Grant JPMJCR12YW, Japan, and Grant-in-Aid for Scientific Research on Innovative Areas, MEXT, Japan [#2401] FY2012-FY2017. The GIWAXS experiments were performed on beamline BL46XU of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposals 2015B1904, 2016A1542, 2016A1768, and 2016B1875).
Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/2/27
Y1 - 2018/2/27
N2 - Synthesis, characterization, and solar cell application of three 4,7-dialkylated phenanthro[1,2-b:8,7-b′]dithiophene (PDT)-difluorobenzothiadiazole (DFBT copolymers (P1-P3) with different linear alkyl side chains to improve solubility, molecular weight, and molecular orientation are described. The utilization of Ir-catalyzed direct borylation and sequential functionalization can selectively afford the target 4,7-dialkylated PDT as the monomers. Migita-Kosugi-Stille coupling in the presence of CuI can accelerate polymerization to afford high-molecular-weight polymers along with their improved solubility. The effect of alkyl substitution at the 4,7-positions on the electronic structure of PDT-DFBT copolymers is negligible. By installation of additional alkyl chains at the 4,7-positions of PDT, the synthesized polymers P1-P3 have lower intermolecular interaction than that of nonalkylated P0, but they still maintained aggregation behavior in solution. In addition, they formed a favorable face-on orientation with a short π-stacking distance of 3.6 Å, which can enhance their carrier transport ability, resulting in high Jsc and FF. As a result, their fabricated solar cells reached a PCE exceeding 6%, which are about 1.7-fold higher than that of P0. Comparison of alkyl side chain length at the 4,7-positions of PDT revealed that all polymers formed a predominantly face-on orientation and have a similar face-on ratio in blended films, but their crystallinity was decreased as the carbon chains at the 4,7-positions of PDT became shorter. On the other hand, the polymers with short alkyl side chains tended to have low surface roughness and small domain size of active layers, which is an ideal phase separation structure for high-performance PSCs. From these results, it could be seen that the polymers have a trade-off relationship between their domain size and crystallinity, but the impact of alkyl side chain length on their photovoltaic properties is rather small. Thus, the construction of face-on orientation is highly important to achieve a high PCE. Among three polymers, the P3/PC61BM-based solar cell with an optimal nanoscale phase separation structure with bicontinuous domain showed the highest PCE of up to 6.6%.
AB - Synthesis, characterization, and solar cell application of three 4,7-dialkylated phenanthro[1,2-b:8,7-b′]dithiophene (PDT)-difluorobenzothiadiazole (DFBT copolymers (P1-P3) with different linear alkyl side chains to improve solubility, molecular weight, and molecular orientation are described. The utilization of Ir-catalyzed direct borylation and sequential functionalization can selectively afford the target 4,7-dialkylated PDT as the monomers. Migita-Kosugi-Stille coupling in the presence of CuI can accelerate polymerization to afford high-molecular-weight polymers along with their improved solubility. The effect of alkyl substitution at the 4,7-positions on the electronic structure of PDT-DFBT copolymers is negligible. By installation of additional alkyl chains at the 4,7-positions of PDT, the synthesized polymers P1-P3 have lower intermolecular interaction than that of nonalkylated P0, but they still maintained aggregation behavior in solution. In addition, they formed a favorable face-on orientation with a short π-stacking distance of 3.6 Å, which can enhance their carrier transport ability, resulting in high Jsc and FF. As a result, their fabricated solar cells reached a PCE exceeding 6%, which are about 1.7-fold higher than that of P0. Comparison of alkyl side chain length at the 4,7-positions of PDT revealed that all polymers formed a predominantly face-on orientation and have a similar face-on ratio in blended films, but their crystallinity was decreased as the carbon chains at the 4,7-positions of PDT became shorter. On the other hand, the polymers with short alkyl side chains tended to have low surface roughness and small domain size of active layers, which is an ideal phase separation structure for high-performance PSCs. From these results, it could be seen that the polymers have a trade-off relationship between their domain size and crystallinity, but the impact of alkyl side chain length on their photovoltaic properties is rather small. Thus, the construction of face-on orientation is highly important to achieve a high PCE. Among three polymers, the P3/PC61BM-based solar cell with an optimal nanoscale phase separation structure with bicontinuous domain showed the highest PCE of up to 6.6%.
UR - http://www.scopus.com/inward/record.url?scp=85042727563&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85042727563&partnerID=8YFLogxK
U2 - 10.1021/acs.macromol.7b02734
DO - 10.1021/acs.macromol.7b02734
M3 - Article
AN - SCOPUS:85042727563
VL - 51
SP - 1357
EP - 1369
JO - Macromolecules
JF - Macromolecules
SN - 0024-9297
IS - 4
ER -