Transistor Paint: Environmentally Stable N‐alkyldithienopyrrole and Bithiazole‐Based Copolymer Thin‐Film Transistors Show Reproducible High Mobilities without Annealing

New solution processable 4-(2-hexyldecan)-4H-bisthieno[2,3-d:3',2'-b]pyrrole and 4,4'-dialkyl-2,2'-bithiazole-based copolymers (PBTzDTPs) are synthesized with excellent FET performance. These novel copolymers have considerable potential in printable electronics as they have high charge carrier mobilities, excellent air stability, good solution processibility, and no requirement for post-deposition thermal annealing, all requirements for this field of application. The thin film transistors fabricated from PBTzDTPs achieve field effect mobilities as high as 0.14 cm 2 V -1 s -1 with current on/off ratios up to 10 6 without thermal annealing. In addition, the devices exhibit stable performance in air, showing no significant degradation over 60 days. Moreover, the polymers described here provide an excellent example of the systems in which higher mobility performance does not require higher crystalline, long-range ordered structures. Such a system appears to be particularly promising for rapid fabrication techniques, where kinetic conditions usually prevent the development of long-range order.

[1]  Richard D. McCullough,et al.  THE CHEMISTRY OF CONDUCTING POLYTHIOPHENES , 1998 .

[2]  Howard E. Katz,et al.  Field-Effect Transistors Based on Thiophene Hexamer Analogues with Diminished Electron Donor Strength , 1999 .

[3]  H. Pan,et al.  Poly(2,5‐bis(2‐thienyl)‐3,6‐dialkylthieno [3,2‐b]thiophene)s—High‐Mobility Semiconductors for Thin‐Film Transistors , 2006 .

[4]  T. Kowalewski,et al.  High-lamellar ordering and amorphous-like pi-network in short-chain thiazolothiazole-thiophene copolymers lead to high mobilities. , 2009, Journal of the American Chemical Society.

[5]  N. Koch,et al.  Improving the Stability of Polymer FETs by Introducing Fixed Acceptor Units into the Main Chain: Application to Poly(alkylthiophenes) , 2007 .

[6]  H. Sirringhaus,et al.  Integrated optoelectronic devices based on conjugated polymers , 1998, Science.

[7]  K. Kubota,et al.  Extensive studies on pi-stacking of poly(3-alkylthiophene-2,5-diyl)s and poly(4-alkylthiazole-2,5-diyl)s by optical spectroscopy, NMR analysis, light scattering analysis, and X-ray crystallography , 1998 .

[8]  Donal D. C. Bradley,et al.  Mobility enhancement in conjugated polymer field-effect transistors through chain alignment in a liquid-crystalline phase , 2000 .

[9]  Zhenan Bao,et al.  High‐Performance Organic Semiconductors Based on Fluorene–Phenylene Oligomers with High Ionization Potentials , 2006 .

[10]  Bo Li,et al.  Nanostructure dependence of field-effect mobility in regioregular poly(3-hexylthiophene) thin film field effect transistors. , 2006, Journal of the American Chemical Society.

[11]  Ping Liu,et al.  High-performance semiconducting polythiophenes for organic thin-film transistors. , 2004, Journal of the American Chemical Society.

[12]  T. Verbiest,et al.  Improved synthesis of N-alkyl substituted dithieno[3,2-b:2′,3′-d]pyrroles , 2005 .

[13]  Youngsuk Jung,et al.  The Effect of Interfacial Roughness on the Thin Film Morphology and Charge Transport of High‐Performance Polythiophenes , 2008 .

[14]  F. Spano.  Erratum: “Modeling disorder in polymer aggregates: The optical spectroscopy of regioregular poly(3-hexylthiophene) thin films” [J. Chem. Phys. 122, 234701 (2005)] , 2007 .

[15]  Jean-Luc Brédas,et al.  Influence of Interchain Interactions on the Absorption and Luminescence of Conjugated Oligomers and Polymers: A Quantum-Chemical Characterization , 1998 .

[16]  Yang Yang,et al.  Polymer electroluminescent devices processed by inkjet printing: I. Polymer light-emitting logo , 1998 .

[17]  Yasuhiko Shirota,et al.  Photo- and electroactive amorphous molecular materials—molecular design, syntheses, reactions, properties, and applications , 2005 .

[18]  David Beljonne,et al.  Interchain Interactions in Organic π‐Conjugated Materials: Impact on Electronic Structure, Optical Response, and Charge Transport , 2001 .

[19]  Zhenan Bao,et al.  High-performance plastic transistors fabricated by printing techniques , 1997 .

[20]  S. Ng,et al.  Selective functionalization of 2,2'-bithiophenes , 1991 .

[21]  Takakazu Yamamoto,et al.  Copolymers of Thiophene and Thiazole. Regioregulation in Synthesis, Stacking Structure, and Optical Properties , 2003 .

[22]  C. M. Li,et al.  High-Performance Thin-Film Transistors from Solution-Processed Dithienothiophene Polymer Semiconductor Nanoparticles , 2008 .

[23]  B. Ong,et al.  Novel Peripherally Substituted Indolo[3,2‐b]carbazoles for High‐Mobility Organic Thin‐Film Transistors , 2005 .

[24]  Ullrich Scherf,et al.  Organic semiconductors for solution-processable field-effect transistors (OFETs). , 2008, Angewandte Chemie.

[25]  Henning Sirringhaus,et al.  Device Physics of Solution‐Processed Organic Field‐Effect Transistors , 2005 .

[26]  P. Liu,et al.  Benzodithiophene Copolymer—A Low‐Temperature, Solution‐Processed High‐Performance Semiconductor for Thin‐Film Transistors , 2007 .

[27]  Maxim Shkunov,et al.  Liquid-crystalline semiconducting polymers with high charge-carrier mobility , 2006, Nature materials.

[28]  Janos Veres,et al.  Gate Insulators in Organic Field-Effect Transistors , 2004 .

[29]  Y. Shirota.  Organic materials for electronic and optoelectronic devices , 2000 .

[30]  David C. Martin,et al.  Poly(alkylbithiazoles): A New Class of Variable-Bandgap, Conjugated Polymer , 1995 .

[31]  Rui Zhang,et al.  Novel Thiophene‐Thiazolothiazole Copolymers for Organic Field‐Effect Transistors , 2007 .

[32]  F. Spano,et al.  Modeling disorder in polymer aggregates: the optical spectroscopy of regioregular poly(3-hexylthiophene) thin films. , 2005, The Journal of chemical physics.

[33]  Jenny Clark,et al.  Role of intermolecular coupling in the photophysics of disordered organic semiconductors: aggregate emission in regioregular polythiophene. , 2007, Physical review letters.

[34]  Hiroshi Kageyama,et al.  Charge carrier transporting molecular materials and their applications in devices. , 2007, Chemical reviews.

[35]  K. Müllen,et al.  Field-effect transistors based on a benzothiadiazole-cyclopentadithiophene copolymer. , 2007, Journal of the American Chemical Society.

[36]  Jie Cao,et al.  Solid-state packing of conjugated oligomers: from pi-stacks to the herringbone structure. , 2004, Journal of the American Chemical Society.

[37]  Jean M. J. Fréchet,et al.  Controlling the Field‐Effect Mobility of Regioregular Polythiophene by Changing the Molecular Weight , 2003 .

[38]  G. Zanardi,et al.  Thermal decomposition of o-azidobithienyls , 1984 .

[39]  A. Yassar,et al.  All-Polymer Field-Effect Transistor Realized by Printing Techniques , 1994, Science.

[40]  R. Sarpeshkar,et al.  Large-scale complementary integrated circuits based on organic transistors , 2000, Nature.

[41]  Janos Veres,et al.  Low‐k Insulators as the Choice of Dielectrics in Organic Field‐Effect Transistors , 2003 .

[42]  E. W. Meijer,et al.  Two-dimensional charge transport in self-organized, high-mobility conjugated polymers , 1999, Nature.

[43]  J. Kampf,et al.  Intermolecular interactions in pi-stacked conjugated molecules. Synthesis, structure, and spectral characterization of alkyl bithiazole oligomers. , 2003, Journal of the American Chemical Society.

[44]  John A. Rogers,et al.  Printable organic and polymeric semiconducting materials and devices , 1999 .

[45]  T. Kowalewski,et al.  Highly disordered polymer field effect transistors: N-alkyl dithieno[3,2-b:2',3'-d]pyrrole-based copolymers with surprisingly high charge carrier mobilities. , 2008, Journal of the American Chemical Society.

[46]  Ping Liu,et al.  Effects of humidity on unencapsulated poly(thiophene) thin-film transistors , 2006 .

[47]  Zhenan Bao,et al.  Materials and Fabrication Needs for Low-Cost Organic Transistor Circuits , 2000 .

[48]  M. Kobashi,et al.  Alignment and Field-Effect Transistor Behavior of an Alternative π-Conjugated Copolymer of Thiophene and 4-Alkylthiazole , 2004 .

[49]  Maxim Shkunov,et al.  Stable polythiophene semiconductors incorporating thieno[2,3-b]thiophene. , 2005, Journal of the American Chemical Society.