Synergistic Use of Pyridine and Selenophene in a Diketopyrrolopyrrole‐Based Conjugated Polymer Enhances the Electron Mobility in Organic Transistors

To achieve semiconducting materials with high electron mobility in organic field‐effect transistors (OFETs), low‐lying energy levels (the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO)) and favorable molecular packing and ordering are two crucial factors. Here, it is reported that the incorporation of pyridine and selenophene into the backbone of a diketopyrrolopyrrole (DPP)‐based copolymer produces a high‐electron‐mobility semiconductor, PDPPy‐Se. Compared with analogous polymers based on other DPP derivatives and selenophene, PDPPy‐Se features a lower LUMO that can decrease the electron transfer barrier for more effective electron injection, and simultaneously a lower HOMO that, however, can increase the hole transfer barrier to suppress the hole injection. Combined with thermal annealing at 240 °C for thin film morphology optimization to achieve large‐scale crystallite domains with tight molecular packing for effective charge transport along the conducting channel, OFET devices fabricated with PDPPy‐Se exhibit an n‐type‐dominant performance with an electron mobility (μe) as high as 2.22 cm2 V−1 s−1 and a hole/electron mobility ratio (μh/μe) of 0.26. Overall, this study demonstrates a simple yet effective approach to boost the electron mobility in organic transistors by synergistic use of pyridine and selenophene in the backbone of a DPP‐based copolymer.

[1]  Hang Yin,et al.  Recent progress of all-polymer solar cells – From chemical structure and device physics to photovoltaic performance , 2020 .

[2]  Wei Huang,et al.  All-acceptor polymers with noncovalent interactions for efficient ambipolar transistors , 2020 .

[3]  Hong Wang,et al.  Inducing Molecular Aggregation of Polymer Semiconductors in a Secondary Insulating Polymer Matrix to Enhance Charge Transport , 2020 .

[4]  Yun‐Hi Kim,et al.  Synthesis of Cyclopentadithiophene-Diketopyrrolopyrrole Donor-Acceptor Copolymers for High-Performance Nonvolatile Floating-Gate Memory Transistors with Long Retention Time. , 2019, ACS applied materials & interfaces.

[5]  S. Manzhos,et al.  Tuning the Charge Carrier Polarity of Organic Transistors by Varying the Electron Affinity of the Flanked Units in Diketopyrrolopyrrole‐Based Copolymers , 2019, Advanced Functional Materials.

[6]  Qian Liu,et al.  Developments of Diketopyrrolopyrrole‐Dye‐Based Organic Semiconductors for a Wide Range of Applications in Electronics , 2019, Advanced materials.

[7]  X. Gu,et al.  Pyrazine-Flanked Diketopyrrolopyrrole (DPP): A New Polymer Building Block for High-Performance n-Type Organic Thermoelectrics. , 2019, Journal of the American Chemical Society.

[8]  Ergang Wang,et al.  Star-Shaped Diketopyrrolopyrrole–Zinc Porphyrin that Delivers 900 nm Emission in Light-Emitting Electrochemical Cells , 2019, Chemistry of Materials.

[9]  Yongqian Shi,et al.  Fused Bithiophene Imide Oligomer and Diketopyrrolopyrrole Copolymers for n-Type Thin-Film Transistors. , 2019, Macromolecular rapid communications.

[10]  S. Manzhos,et al.  Naphthalene flanked diketopyrrolopyrrole: A new DPP family member and its comparative optoelectronic properties with thiophene- and furan- flanked DPP counterparts , 2019, Organic Electronics.

[11]  A. Jen,et al.  Recent advances in molecular design of functional conjugated polymers for high-performance polymer solar cells , 2019 .

[12]  Wei Huang,et al.  1300 nm absorption two-acceptor semiconducting polymer nanoparticles for NIR-II photoacoustic imaging system guided NIR-II photothermal therapy. , 2019, Chemical communications.

[13]  A. Priimagi,et al.  Thionation Enhances the Performance of Polymeric Dopant‐Free Hole‐Transporting Materials for Perovskite Solar Cells , 2019, Advanced Materials Interfaces.

[14]  Ming Hui Chua,et al.  Diversity of electron acceptor groups in donor–acceptor type electrochromic conjugated polymers , 2019, Solar Energy Materials and Solar Cells.

[15]  T. Shin,et al.  Improving the Electrical Connection of n-Type Conjugated Polymers through Fluorine-Induced Robust Aggregation , 2019, Chemistry of Materials.

[16]  Weiwei Li,et al.  Diketopyrrolopyrrole-based conjugated materials for non-fullerene organic solar cells , 2019, Journal of Materials Chemistry A.

[17]  Dezhi Yang,et al.  Precise regulation of the emissive layer for ultra-high performance white organic light-emitting diodes in an exciplex forming co-host system , 2019, Materials Chemistry Frontiers.

[18]  T. Michinobu,et al.  Significant Improvement of Unipolar n-Type Transistor Performances by Manipulating the Coplanar Backbone Conformation of Electron-Deficient Polymers via Hydrogen Bonding. , 2019, Journal of the American Chemical Society.

[19]  Daoben Zhu,et al.  Enhancing the n‐Type Conductivity and Thermoelectric Performance of Donor–Acceptor Copolymers through Donor Engineering , 2018, Advanced materials.

[20]  S. Manzhos,et al.  Naphthalene flanked diketopyrrolopyrrole based organic semiconductors for high performance organic field effect transistors , 2018 .

[21]  C. B. Nielsen,et al.  Performance Improvements in Conjugated Polymer Devices by Removal of Water‐Induced Traps , 2018, Advanced materials.

[22]  Zhongli Wang,et al.  Diketopyrrolopyrrole‐Based Conjugated Polymers Synthesized via Direct Arylation Polycondensation for High Mobility Pure n‐Channel Organic Field‐Effect Transistors , 2018, Advanced Functional Materials.

[23]  H. Sirringhaus,et al.  Charge Mobility Enhancement for Conjugated DPP-Selenophene Polymer by Simply Replacing One Bulky Branching Alkyl Chain with Linear One at Each DPP Unit , 2018 .

[24]  L. Toppare,et al.  A new NIR absorbing DPP-based polymer for thick organic solar cells , 2018 .

[25]  Wei Lin Leong,et al.  Diketopyrrolopyrrole based organic semiconductors with different numbers of thiophene units: symmetry tuning effect on electronic devices , 2018 .

[26]  M. Toney,et al.  Graphene induced electrical percolation enables more efficient charge transport at a hybrid organic semiconductor/graphene interface. , 2018, Physical chemistry chemical physics : PCCP.

[27]  H. Sirringhaus,et al.  Measurements of Ambipolar Seebeck Coefficients in High‐Mobility Diketopyrrolopyrrole Donor–Acceptor Copolymers , 2017 .

[28]  Jianqi Zhang,et al.  Bis‐Diketopyrrolopyrrole Moiety as a Promising Building Block to Enable Balanced Ambipolar Polymers for Flexible Transistors , 2017, Advanced materials.

[29]  Yun‐Hi Kim,et al.  Effect of alkyl chain spacer on charge transport in n-type dominant polymer semiconductors with a diketopyrrolopyrrole-thiophene-bithiazole acceptor–donor–acceptor unit , 2017 .

[30]  G. Yu,et al.  Thiazole-Flanked Diketopyrrolopyrrole Polymeric Semiconductors for Ambipolar Field-Effect Transistors with Balanced Carrier Mobilities. , 2016, ACS applied materials & interfaces.

[31]  Weiwei Li,et al.  Effect of Fluorination on Molecular Orientation of Conjugated Polymers in High Performance Field-Effect Transistors , 2016 .

[32]  Chain‐Shu Hsu,et al.  Synthesis of a 4,9-Didodecyl Angular-Shaped Naphthodiselenophene Building Block To Achieve High-Mobility Transistors , 2016 .

[33]  M. Toney,et al.  Reduced crystallinity and enhanced charge transport by melt annealing of an organic semiconductor on single layer graphene , 2016 .

[34]  H. Sirringhaus,et al.  Remarkable enhancement of charge carrier mobility of conjugated polymer field-effect transistors upon incorporating an ionic additive , 2016, Science Advances.

[35]  Guanxin Zhang,et al.  Significant Improvement of Semiconducting Performance of the Diketopyrrolopyrrole-Quaterthiophene Conjugated Polymer through Side-Chain Engineering via Hydrogen-Bonding. , 2016, Journal of the American Chemical Society.

[36]  Fosong Wang,et al.  High Mobility Ambipolar Diketopyrrolopyrrole‐Based Conjugated Polymer Synthesized Via Direct Arylation Polycondensation , 2015, Advanced materials.

[37]  T. Shin,et al.  Investigation of Structure–Property Relationships in Diketopyrrolopyrrole-Based Polymer Semiconductors via Side-Chain Engineering , 2015 .

[38]  S. Mannsfeld,et al.  Enhanced Vertical Charge Transport in a Semiconducting P3HT Thin Film on Single Layer Graphene , 2015 .

[39]  Yuning Li,et al.  A pyridine-flanked diketopyrrolopyrrole (DPP)-based donor–acceptor polymer showing high mobility in ambipolar and n-channel organic thin film transistors , 2015 .

[40]  Henning Sirringhaus,et al.  Chalcogenophene comonomer comparison in small band gap diketopyrrolopyrrole-based conjugated polymers for high-performing field-effect transistors and organic solar cells. , 2015, Journal of the American Chemical Society.

[41]  Bin Sun,et al.  Record High Electron Mobility of 6.3 cm2V−1s−1 Achieved for Polymer Semiconductors Using a New Building Block , 2014, Advanced materials.

[42]  P. Sonar,et al.  Synthesis of diketopyrrolopyrrole based copolymers via the direct arylation method for p-channel and ambipolar OFETs. , 2014, Physical chemistry chemical physics : PCCP.

[43]  Y. Yamaguchi,et al.  Terazulene: a high-performance n-type organic field-effect transistor based on molecular orbital distribution control. , 2013, Journal of the American Chemical Society.

[44]  T. Russell,et al.  Synthesis of pyridine-capped diketopyrrolopyrrole and its use as a building block of low band-gap polymers for efficient polymer solar cells. , 2013, Chemical communications.

[45]  P. Sonar,et al.  Isoindigo dye incorporated copolymers with naphthalene and anthracene: promising materials for stable organic field effect transistors , 2013 .

[46]  Soon-Ki Kwon,et al.  Effect of Selenophene in a DPP Copolymer Incorporating a Vinyl Group for High‐Performance Organic Field‐Effect Transistors , 2013, Advanced materials.

[47]  Changduk Yang,et al.  Solution-processable ambipolar diketopyrrolopyrrole-selenophene polymer with unprecedentedly high hole and electron mobilities. , 2012, Journal of the American Chemical Society.

[48]  Chain‐Shu Hsu,et al.  New Angular-Shaped and Isomerically Pure Anthradithiophene with Lateral Aliphatic Side Chains for Conjugated Polymers: Synthesis, Characterization, and Implications for Solution-Prossessed Organic Field-Effect Transistors and Photovoltaics , 2012 .

[49]  H. Sirringhaus,et al.  A new thiophene substituted isoindigo based copolymer for high performance ambipolar transistors. , 2012, Chemical communications.

[50]  T. Koganezawa,et al.  Synthesis, characterization, and transistor and solar cell applications of a naphthobisthiadiazole-based semiconducting polymer. , 2012, Journal of the American Chemical Society.

[51]  Henning Sirringhaus,et al.  High‐Performance Ambipolar Diketopyrrolopyrrole‐Thieno[3,2‐b]thiophene Copolymer Field‐Effect Transistors with Balanced Hole and Electron Mobilities , 2012, Advanced materials.

[52]  C. Luscombe,et al.  Oligoselenophene derivatives functionalized with a diketopyrrolopyrrole core for molecular bulk heterojunction solar cells. , 2011, ACS applied materials & interfaces.

[53]  Howard A. Padmore,et al.  A SAXS/WAXS/GISAXS Beamline with Multilayer Monochromator , 2010 .

[54]  A. Arias,et al.  Materials and applications for large area electronics: solution-based approaches. , 2010, Chemical reviews.

[55]  D. Figer.  An upper limit to the masses of stars , 2005, Nature.

[56]  G. Horowitz.  Organic Semiconductors for new electronic devices , 1990 .

[57]  N. Stingelin,et al.  Low band gap selenophene–diketopyrrolopyrrole polymers exhibiting high and balanced ambipolar performance in bottom-gate transistors , 2012 .