High-performance organic electrochemical transistors(OECTs)with sustainable processes are crucial for bioelectronics and integration applications,but still face challenges in molecular design,as well as solvent-device...High-performance organic electrochemical transistors(OECTs)with sustainable processes are crucial for bioelectronics and integration applications,but still face challenges in molecular design,as well as solvent-device compatibility.Herein,we introduced a unique synthetic protocol focused on regioselective chemistry for the development of a donor-acceptor polymeric mixed ionic-electronic conductor(PMIEC)with a well-defined side chain arrangement and demonstrated the superiority of side chain regioregularity in enhancing OECT performance.Furthermore,we pioneered the utilization of a green solvent,2-methyl tetrahydrofuran(MeTHF),for depositing the active OECT channel layers.We found that the regioregular copolymer exhibited over three times higherμC*of up to 810 F cm^(-1)V^(-1)s^(-1)compared to its regioirregular counterpart,thanks to improved crystallinity,reduced trap density of states(tDOS),and enhanced OECT hole mobility.Notably,this was achieved without the need for additional film posttreatments or specialized polymer fractionation techniques and stood among the highest values reported to date for green-solvent-processed OECTs.Our work represents a significant advancement in sustainable OECTs and highlights the importance of precise control over side chain regioregularity in developing high-performance PMIECs.展开更多
A series of donor-acceptor oligomer OBTThn （n = 1- 7） and polymer PBTThl and PBTTh2 composed of al- ternative 2,1,3-benzothiadiazole and 3-hexylthiophene have been designed and synthesized for the purpose of in- ves...A series of donor-acceptor oligomer OBTThn （n = 1- 7） and polymer PBTThl and PBTTh2 composed of al- ternative 2,1,3-benzothiadiazole and 3-hexylthiophene have been designed and synthesized for the purpose of in- vestigation on the effect of chain length and side-chain regioregularity on their basic properties and photovoltaic performance. In the OBTThn oligomers and PBTThl polymer, all the hexyl side chains on thienyl units orient to- ward the same direction. Upon elongation of the chain length, the intramolecular charge transfer （ICT） absorption band in solution gradually redshifts from 398 nm for OBTThl to 505 nm for OBTThT, then to 512 nm for PBTThl polymer. Meanwhile, the HOMO energy level increases from -5.45 eV （OBTTh0 to -5.08 eV （OBTThT） and -5.09 eV （PBTThl）, and the LUMO energy level decreases from -3.11 eV （OBTTh0 to -3.30 eV （OBTThT） and -3.33 eV （PBTThl）, thus giving a smaller and smaller energy bandgap for higher oligomers and polymers. Theo- retical calculation suggests straight line-like backbone geometry for this series of oligomers and polymer. On the other hand, polymer PBTTh2 possesses a different side-chain regioregularity, in which every two neighbor hexyl side chains are arranged in different orienting direction. It is theoretically suggested to have curved line-like back- bone geometry. In solution, it shows similar photophysical and electrochemical properties as PBTThl. However in film state, it displays a less redshift in the ICT band as refer to that in solution than PBTThl. In combination with [6,6]-phenyl-C61-butyric acid methyl ester （PC61BM）, these oligomers and polymers were used as donor material to fabricate organic bulk heterojunction solar cells. Again, chain length-dependent device photovoltaic performance was observed. The device based on OBTTh4 showed a power conversion efficiency of 0.16%, while it increased to 0.36% and 0.49% for the devices based on OBTTh6 and PBTThb respectively. However, the side-chain regio- regularity has less influence on the device photovoltaic output since the device based on PBTTh~ displayed an effi- ciency of 0.52%, comparable to that of PBTThl.展开更多
Introduction of asymmetric units into conjugated polymers is an important strategy to regulate the photophysical and electronic properties of polymers,as asymmetric units can not only regulate solubility and energy le...Introduction of asymmetric units into conjugated polymers is an important strategy to regulate the photophysical and electronic properties of polymers,as asymmetric units can not only regulate solubility and energy levels,but also molecular stacking and orientation,thus giving much higher optoelectronic properties.However,very few studies have been reported in this field.The semiconducting properties of conjugated polymers could be regulated through regioregularity adjustment.Here,we took the asymmetric thiophene/pyridine side group DPP as core and developed the regioregular monomer T-Py-DPP through three steps:alkyl chain introduction,tin monomer coupling and NBS double bromination.The T-Py-DPP monomer was polymerized into reg-PPy TDPP-2FBT with a head-to-head structure.The regioregularity of T-Py-DPP unit endowed reg-PPy TDPP-2FBT with backbone planarity,self-assembly orientation,network-like morphology and high crystallinity in films,thus the superior bipolar transport properties.The highest hole and electron mobilities of reg-PPy TDPP-2FBT were 0.93 and 0.57 cm^(2)·V^(-1)·s^(-1),respectively,with 40%improvement relative to the regiorandom polymer.展开更多
A new bis(aroylacetylene) containing tfiazole and fluorene moieties is synthesized by click chemistry. Polycyclotrimerization of the monomer is catalyzed by piperidine in refluxed dioxane,furnishing a regioregular pol...A new bis(aroylacetylene) containing tfiazole and fluorene moieties is synthesized by click chemistry. Polycyclotrimerization of the monomer is catalyzed by piperidine in refluxed dioxane,furnishing a regioregular poly(aroylarylene) in a satisfactory yield.The hyperbranched structure of the polymer is characterized spectroscopically with satisfactory results.The polymer enjoys no metal detriment and is soluble in common organic solvents such as tetrahydrofuran (THF),chloroform,dichloromethane (DCM),and N,N-...展开更多
In order to enhance the performance of regioregular poly（3-hexylthiophene） （RR-P3HT） field-effect transistors （FETs）, RR-P3HT FETs are prepared by the spin-coating method followed by vacuum placement and anneali...In order to enhance the performance of regioregular poly（3-hexylthiophene） （RR-P3HT） field-effect transistors （FETs）, RR-P3HT FETs are prepared by the spin-coating method followed by vacuum placement and annealing. This paper reports that the crystal structure, the molecule interconnection, the surface morphology, and the charge carrier mobility of RR-P3HT films are affected by vacuum relaxation and annealing. The results reveal that the field-effect mobility of RR-P3HT FETs can reach 4.17×10^-2m^2/（V·s） by vacuum relaxation at room temperature due to an enhanced local self-organization. Furthermore, it reports that an appropriate annealing temperature can facilitate the crystal structure, the orientation and the interconnection of polymer molecules. These results show that the field-effect mobility of device annealed at 150 ℃ for 10 minutes in vacuum at atmosphere and followed by placement for 20 hours in vacuum at room temperature is enhanced dramatically to 9.00×10^-2m^2/（V·s）.展开更多
This paper investigates the effects of concentration on the crystalline structure, the morphology, and the charge carrier mobility of regioregular poly（3-hexylthiophene） （RR-P3HT） field-effect transistors （FETs）...This paper investigates the effects of concentration on the crystalline structure, the morphology, and the charge carrier mobility of regioregular poly（3-hexylthiophene） （RR-P3HT） field-effect transistors （FETs）. The RR-P3HT FETs with RR-P3HT as an active layer with different concentrations of RR-P3HT solution from 0.5 wt% to 2 wt% are prepared. The results indicate that the performance of RR-P3HT FETs improves drastically with the increase of RR-P3HT weight percentages in chloroform solution due to the formation of more microcrystalline lamellae and bigger nanoscale islands. It finds that the field-effect mobility of RR-P3HT FET with 2 wt% can reach 5.78×10^-3 cm^2/Vs which is higher by a factor of 13 than that with 0.5 wt%. Further, an appropriate thermal annealing is adopted to improve the performance of RR-P3HT FETs. The field-effect mobility of RR-P3HT FETs increases drastically to 0.09 cm^2/Vs by thermal annealing at 150 ℃, and the value of on/off current ratio can reach 104.展开更多
All-polymer solar cells(all-PSCs)have received attention due to their morphological stability under thermal and mechanical stresses.Currently,the highest reported power conversion efficiency of all-PSCs is over 17%,ac...All-polymer solar cells(all-PSCs)have received attention due to their morphological stability under thermal and mechanical stresses.Currently,the highest reported power conversion efficiency of all-PSCs is over 17%,achieved by utilizing polymerized small molecular acceptors(PSMAs).However,the need for higher regiospecificity to avoid forming isomers during polymerization of SMAs still challenges the further applications of all-PSCs.From this perspective,we focus on some recent studies and highlight the importance of controlling the regioregularity of PSMAs.In particular,integrating PSMAs with regioregularity endows the polymer acceptors with good absorption,superior backbone ordering,and optimal blend morphology compared with those obtained from regiorandom one.Moreover,the distinctive features that are derived from these regioregular PSMAs,such as the possibility of repeatable synthesis and reproducible device performance,herald a brighter future for scaling-up and commercializing all-PSCs.We expect this integrated strategy will inspire researchers to devote more efforts to further narrow the efficiency gap between the PSCs based on SMAs and PSMAs.Finally,we discuss the existing challenges and future prospects of PSMAs as new platform for further advancing all-PSCs.展开更多
Comprehensive Summary The regioregularity induced by the isomers of the end-groups has been widely recognized as a key factor that determines the photovoltaic properties of polymerized small molecular acceptors(PSMAs)...Comprehensive Summary The regioregularity induced by the isomers of the end-groups has been widely recognized as a key factor that determines the photovoltaic properties of polymerized small molecular acceptors(PSMAs)in all-polymer solar cells(all-PSCs).However,the influence of regioregularity on the photovoltaic properties of non-fused PSMAs has not been explored yet.In this contribution,two regioregular non-fused PSMAs,PFBTz-T-γand PFBTz-T-δ,were synthesized for the first time by using the monomers with isomeric pure end-groups.Compared with PFBTz-T-δ,PFBTz-T-γhas more compact and more ordered packing in solid state,which results in a more red-shifted optical absorption and a higher electron mobility.More remarkably,PFBTz-T-γand PFBTz-T-δexhibited huge difference in photovoltaic performance in all-PSCs,which offered the power conversion efficiencies(PCEs)of 9.72%and 0.52%,respectively.Further studies have unveiled that the higher PCE of PFBTz-T-γis due to more efficient exciton dissociation,higher and more balanced electron/hole mobility,and less charge recombination as a result of favorable morphology of the blend film.This work demonstrates that the development of regioregular non-fused PSMAs by tuning the polymerization sites is an effective strategy for obtaining high-efficiency all-PSCs.展开更多
A series of model polymerization are carried out via the one-pot externally initiated Kumada catalyst-transfer polycondensation （KCTP） of 2-bromo-5-chloromagne- slum thiophene monomers, and the excess amount of init...A series of model polymerization are carried out via the one-pot externally initiated Kumada catalyst-transfer polycondensation （KCTP） of 2-bromo-5-chloromagne- slum thiophene monomers, and the excess amount of initiators or catalysts are found no need to be isolated during the polycondensation process. Especially, the impacts of the nickel catalyst loading variation on regioregularity （rr）, yield, molecular weight （Mn）, polydispersity （PDI） and initiation efficiency of poly（3-hexylthiophene） （P3HT） are systematically investigated. The IH NMR, size-exclusion chromatography （SEC）, and MALDI-TOF mass spectroscopy results indicated that an excess amount of catalyst does not influence yield, rr, Mn, and PDI of P3HT, nor the initiation efficiency. However, the PDI of the product is broad, and the Mn and rr values decreased in the absence of 1,3-bis （diphenylphosphino）propane （dppp）. It can be concluded that the in-situ KCTP polymerization of P3HT is a practical and effective process. These results are especially valuable for the synthesis of all-conjugated block copolymers where macroinitiators are used.展开更多
The design and synthesis of high-mobility n-type near-amorphous conjugated polymers(NACPs)represent a prominent research focus in organic semiconductors.The diketopyrrolopyrrole(DPP)unit is a widely used building bloc...The design and synthesis of high-mobility n-type near-amorphous conjugated polymers(NACPs)represent a prominent research focus in organic semiconductors.The diketopyrrolopyrrole(DPP)unit is a widely used building block for constructing high-mobility conjugated polymers.However,DPP-based polymers often exhibit semi-crystalline structures and inherent p-type charge-transport characteristics,which hinder their application in n-type flexible electronic devices.To overcome these challenges,this study employs acceptor modulation and terpolymerization by integrating pyridine-flanked DPP with 3,4-difluorothiophene(2FT)and selenophene(Se)as comonomers.Besides,the incorporation of oligo(ethylene glycol)side chains is strategically designed to enhance polymer solubility and favorably modulate the morphology.Thus,a series of polymers,P2FTx(x=100–0),are synthesized via Stille polycondensation,enabling systematic investigation of the composition-structure-property relationships.It reveals that optimal Se incorporation minimizes torsional barriers and reduces backbone regularity,inducing a near-amorphous phase with locally ordered domains while maintaining suitable energy levels for efficient electron transport.Notably,P2FT90 achieves the highest electron mobility of 0.47 cm^(2)·V^(-1)·s^(-1),highlighting the efficacy of this compositional engineering approach.This study exemplifies a synergistic approach that combines precise control of backbone regioregularity and energy-level engineering to realize high-performance n-type NACPs.展开更多
基金financial support from the National Natural Science Foundation of China(NSFCgrant nos.52203251 and 22275212)+3 种基金the Guangzhou Basic and Applied Basic Research Foundation,China(grant no.202201011508)National Key R&D Program(grant no.2022YFA1206600)Fundamental Research Funds for the Central Universities,Sun Yat-sen University,China(grant no.23yxqntd002)State Key Laboratory of Optoelectronic&Materials and Technologies,Sun Yat-Sen University(grant no.OEMT-2023-KF-03).
文摘High-performance organic electrochemical transistors(OECTs)with sustainable processes are crucial for bioelectronics and integration applications,but still face challenges in molecular design,as well as solvent-device compatibility.Herein,we introduced a unique synthetic protocol focused on regioselective chemistry for the development of a donor-acceptor polymeric mixed ionic-electronic conductor(PMIEC)with a well-defined side chain arrangement and demonstrated the superiority of side chain regioregularity in enhancing OECT performance.Furthermore,we pioneered the utilization of a green solvent,2-methyl tetrahydrofuran(MeTHF),for depositing the active OECT channel layers.We found that the regioregular copolymer exhibited over three times higherμC*of up to 810 F cm^(-1)V^(-1)s^(-1)compared to its regioirregular counterpart,thanks to improved crystallinity,reduced trap density of states(tDOS),and enhanced OECT hole mobility.Notably,this was achieved without the need for additional film posttreatments or specialized polymer fractionation techniques and stood among the highest values reported to date for green-solvent-processed OECTs.Our work represents a significant advancement in sustainable OECTs and highlights the importance of precise control over side chain regioregularity in developing high-performance PMIECs.
基金the National Natural Science Foundation of China，Chinese Academy of Sciences,and Shanghai Science and Technology Commission
文摘A series of donor-acceptor oligomer OBTThn （n = 1- 7） and polymer PBTThl and PBTTh2 composed of al- ternative 2,1,3-benzothiadiazole and 3-hexylthiophene have been designed and synthesized for the purpose of in- vestigation on the effect of chain length and side-chain regioregularity on their basic properties and photovoltaic performance. In the OBTThn oligomers and PBTThl polymer, all the hexyl side chains on thienyl units orient to- ward the same direction. Upon elongation of the chain length, the intramolecular charge transfer （ICT） absorption band in solution gradually redshifts from 398 nm for OBTThl to 505 nm for OBTThT, then to 512 nm for PBTThl polymer. Meanwhile, the HOMO energy level increases from -5.45 eV （OBTTh0 to -5.08 eV （OBTThT） and -5.09 eV （PBTThl）, and the LUMO energy level decreases from -3.11 eV （OBTTh0 to -3.30 eV （OBTThT） and -3.33 eV （PBTThl）, thus giving a smaller and smaller energy bandgap for higher oligomers and polymers. Theo- retical calculation suggests straight line-like backbone geometry for this series of oligomers and polymer. On the other hand, polymer PBTTh2 possesses a different side-chain regioregularity, in which every two neighbor hexyl side chains are arranged in different orienting direction. It is theoretically suggested to have curved line-like back- bone geometry. In solution, it shows similar photophysical and electrochemical properties as PBTThl. However in film state, it displays a less redshift in the ICT band as refer to that in solution than PBTThl. In combination with [6,6]-phenyl-C61-butyric acid methyl ester （PC61BM）, these oligomers and polymers were used as donor material to fabricate organic bulk heterojunction solar cells. Again, chain length-dependent device photovoltaic performance was observed. The device based on OBTTh4 showed a power conversion efficiency of 0.16%, while it increased to 0.36% and 0.49% for the devices based on OBTTh6 and PBTThb respectively. However, the side-chain regio- regularity has less influence on the device photovoltaic output since the device based on PBTTh~ displayed an effi- ciency of 0.52%, comparable to that of PBTThl.
基金financially supported by the Ministry of Science and Technology of China(Nos.2018YFA0703200 and 2022YFB3603800)the National Natural Science Foundation of China(Nos.21875259,52233010,51725304,61890943,52103245 and 22021002)+2 种基金the CAS Project for Young Scientists in Basic Research(No.YSBR-053)the Youth Innovation Promotion Association of the Chinese Academy of Sciences,the National Program for Support of Top-notch Young Professionals,the Beijing National Laboratory for Molecular Sciences(No.BNLMS-CXXM-202012)the Key Research Program of the Chinese Academy of Sciences(Nos.XDPB13 and 121111KYSB20200004)。
文摘Introduction of asymmetric units into conjugated polymers is an important strategy to regulate the photophysical and electronic properties of polymers,as asymmetric units can not only regulate solubility and energy levels,but also molecular stacking and orientation,thus giving much higher optoelectronic properties.However,very few studies have been reported in this field.The semiconducting properties of conjugated polymers could be regulated through regioregularity adjustment.Here,we took the asymmetric thiophene/pyridine side group DPP as core and developed the regioregular monomer T-Py-DPP through three steps:alkyl chain introduction,tin monomer coupling and NBS double bromination.The T-Py-DPP monomer was polymerized into reg-PPy TDPP-2FBT with a head-to-head structure.The regioregularity of T-Py-DPP unit endowed reg-PPy TDPP-2FBT with backbone planarity,self-assembly orientation,network-like morphology and high crystallinity in films,thus the superior bipolar transport properties.The highest hole and electron mobilities of reg-PPy TDPP-2FBT were 0.93 and 0.57 cm^(2)·V^(-1)·s^(-1),respectively,with 40%improvement relative to the regiorandom polymer.
基金supported by the National Natural Science Foundation of China (Nos.20634020 and 50703033)the Ministry of Science & Technology (No.2009CB623605)+2 种基金the Research Grants Council of Hong Kong (Nos.603008,602707 and 602706)A.J.Q.acknowledges the support from the China Postdoctoral Science Foundation (No.20070420228)B.Z.T.thanks the support from the Cao Guangbiao Foundation of Zhejiang University.
文摘A new bis(aroylacetylene) containing tfiazole and fluorene moieties is synthesized by click chemistry. Polycyclotrimerization of the monomer is catalyzed by piperidine in refluxed dioxane,furnishing a regioregular poly(aroylarylene) in a satisfactory yield.The hyperbranched structure of the polymer is characterized spectroscopically with satisfactory results.The polymer enjoys no metal detriment and is soluble in common organic solvents such as tetrahydrofuran (THF),chloroform,dichloromethane (DCM),and N,N-...
基金Project supported by the National Natural Science Foundation of China (Grant Nos 10774013 and 10804006)the National High Technology Research and Development Program of China (Grant No 2006AA03Z0412)+4 种基金the Research Fund for the Doctoral Program of Higher Education of China (Grant No 20070004024)the Research Fund for the Youth Scholars of the Doctoral Program of Higher Education (Grant No 20070004031)the Beijing NOVA program (Grant No 2007A024)the the 111 of China (Grant No B08002)the research grants from the Academy of Sciences for the Developing World
文摘In order to enhance the performance of regioregular poly（3-hexylthiophene） （RR-P3HT） field-effect transistors （FETs）, RR-P3HT FETs are prepared by the spin-coating method followed by vacuum placement and annealing. This paper reports that the crystal structure, the molecule interconnection, the surface morphology, and the charge carrier mobility of RR-P3HT films are affected by vacuum relaxation and annealing. The results reveal that the field-effect mobility of RR-P3HT FETs can reach 4.17×10^-2m^2/（V·s） by vacuum relaxation at room temperature due to an enhanced local self-organization. Furthermore, it reports that an appropriate annealing temperature can facilitate the crystal structure, the orientation and the interconnection of polymer molecules. These results show that the field-effect mobility of device annealed at 150 ℃ for 10 minutes in vacuum at atmosphere and followed by placement for 20 hours in vacuum at room temperature is enhanced dramatically to 9.00×10^-2m^2/（V·s）.
基金supported by the National Natural Science Foundation of China (Grant Nos 10774013,10804006)the National High Technology Research and Development Program of China (Grant No 2006AA03Z0412)+3 种基金the Research Fund for the Doctoral Program of Higher Education of China (Grant No 20070004024)The Research Fund for the Youth Scholars of the Doctoral Program of Higher Education (Grant No 20070004031)the Beijing NOVA Program (Grant No 2007A024)the 111 Project(Grant No B08002)
文摘This paper investigates the effects of concentration on the crystalline structure, the morphology, and the charge carrier mobility of regioregular poly（3-hexylthiophene） （RR-P3HT） field-effect transistors （FETs）. The RR-P3HT FETs with RR-P3HT as an active layer with different concentrations of RR-P3HT solution from 0.5 wt% to 2 wt% are prepared. The results indicate that the performance of RR-P3HT FETs improves drastically with the increase of RR-P3HT weight percentages in chloroform solution due to the formation of more microcrystalline lamellae and bigger nanoscale islands. It finds that the field-effect mobility of RR-P3HT FET with 2 wt% can reach 5.78×10^-3 cm^2/Vs which is higher by a factor of 13 than that with 0.5 wt%. Further, an appropriate thermal annealing is adopted to improve the performance of RR-P3HT FETs. The field-effect mobility of RR-P3HT FETs increases drastically to 0.09 cm^2/Vs by thermal annealing at 150 ℃, and the value of on/off current ratio can reach 104.
基金Natural Science Foundation of Jiangsu Province,Grant/Award Number:BK20211598National Key Research and Development Program of China,Grant/Award Number:2017YFA0206600+2 种基金Outstanding Youth Science and Technology Foundation of Xi'an University of Science and Technology,Grant/Award Number:2019YQ3-03Science and Technology Program of Shaanxi Province,Grant/Award Number:2019JQ-244National Natural Science Foundation of China,Grant/Award Numbers:21961160720,51922032,21772030,51773045,51803144,52073198,21905225。
文摘All-polymer solar cells(all-PSCs)have received attention due to their morphological stability under thermal and mechanical stresses.Currently,the highest reported power conversion efficiency of all-PSCs is over 17%,achieved by utilizing polymerized small molecular acceptors(PSMAs).However,the need for higher regiospecificity to avoid forming isomers during polymerization of SMAs still challenges the further applications of all-PSCs.From this perspective,we focus on some recent studies and highlight the importance of controlling the regioregularity of PSMAs.In particular,integrating PSMAs with regioregularity endows the polymer acceptors with good absorption,superior backbone ordering,and optimal blend morphology compared with those obtained from regiorandom one.Moreover,the distinctive features that are derived from these regioregular PSMAs,such as the possibility of repeatable synthesis and reproducible device performance,herald a brighter future for scaling-up and commercializing all-PSCs.We expect this integrated strategy will inspire researchers to devote more efforts to further narrow the efficiency gap between the PSCs based on SMAs and PSMAs.Finally,we discuss the existing challenges and future prospects of PSMAs as new platform for further advancing all-PSCs.
基金supported by the Ministry of Science and Technology of China(2019YFA0705900)the National Natural Science Foundation of China(21875072,22275058,and U20A6002)Guangdong Innovative and Entrepreneurial Research Team Program(2019ZT08L075).
文摘Comprehensive Summary The regioregularity induced by the isomers of the end-groups has been widely recognized as a key factor that determines the photovoltaic properties of polymerized small molecular acceptors(PSMAs)in all-polymer solar cells(all-PSCs).However,the influence of regioregularity on the photovoltaic properties of non-fused PSMAs has not been explored yet.In this contribution,two regioregular non-fused PSMAs,PFBTz-T-γand PFBTz-T-δ,were synthesized for the first time by using the monomers with isomeric pure end-groups.Compared with PFBTz-T-δ,PFBTz-T-γhas more compact and more ordered packing in solid state,which results in a more red-shifted optical absorption and a higher electron mobility.More remarkably,PFBTz-T-γand PFBTz-T-δexhibited huge difference in photovoltaic performance in all-PSCs,which offered the power conversion efficiencies(PCEs)of 9.72%and 0.52%,respectively.Further studies have unveiled that the higher PCE of PFBTz-T-γis due to more efficient exciton dissociation,higher and more balanced electron/hole mobility,and less charge recombination as a result of favorable morphology of the blend film.This work demonstrates that the development of regioregular non-fused PSMAs by tuning the polymerization sites is an effective strategy for obtaining high-efficiency all-PSCs.
文摘A series of model polymerization are carried out via the one-pot externally initiated Kumada catalyst-transfer polycondensation （KCTP） of 2-bromo-5-chloromagne- slum thiophene monomers, and the excess amount of initiators or catalysts are found no need to be isolated during the polycondensation process. Especially, the impacts of the nickel catalyst loading variation on regioregularity （rr）, yield, molecular weight （Mn）, polydispersity （PDI） and initiation efficiency of poly（3-hexylthiophene） （P3HT） are systematically investigated. The IH NMR, size-exclusion chromatography （SEC）, and MALDI-TOF mass spectroscopy results indicated that an excess amount of catalyst does not influence yield, rr, Mn, and PDI of P3HT, nor the initiation efficiency. However, the PDI of the product is broad, and the Mn and rr values decreased in the absence of 1,3-bis （diphenylphosphino）propane （dppp）. It can be concluded that the in-situ KCTP polymerization of P3HT is a practical and effective process. These results are especially valuable for the synthesis of all-conjugated block copolymers where macroinitiators are used.
基金supported by the National Natural Science Foundation of China(Grant Nos.22375051 and 52203216)the Shanghai Rising-Star Program(24YF2702800).
文摘The design and synthesis of high-mobility n-type near-amorphous conjugated polymers(NACPs)represent a prominent research focus in organic semiconductors.The diketopyrrolopyrrole(DPP)unit is a widely used building block for constructing high-mobility conjugated polymers.However,DPP-based polymers often exhibit semi-crystalline structures and inherent p-type charge-transport characteristics,which hinder their application in n-type flexible electronic devices.To overcome these challenges,this study employs acceptor modulation and terpolymerization by integrating pyridine-flanked DPP with 3,4-difluorothiophene(2FT)and selenophene(Se)as comonomers.Besides,the incorporation of oligo(ethylene glycol)side chains is strategically designed to enhance polymer solubility and favorably modulate the morphology.Thus,a series of polymers,P2FTx(x=100–0),are synthesized via Stille polycondensation,enabling systematic investigation of the composition-structure-property relationships.It reveals that optimal Se incorporation minimizes torsional barriers and reduces backbone regularity,inducing a near-amorphous phase with locally ordered domains while maintaining suitable energy levels for efficient electron transport.Notably,P2FT90 achieves the highest electron mobility of 0.47 cm^(2)·V^(-1)·s^(-1),highlighting the efficacy of this compositional engineering approach.This study exemplifies a synergistic approach that combines precise control of backbone regioregularity and energy-level engineering to realize high-performance n-type NACPs.
