Alkylsubstituted thienothiophene semiconducting materials: structure-property relationships.

A family of conjugated polymers with fused structures consisting of three to five thiophene rings and with the same alkyl side chains has been synthesized as a means to understand structure-property relationships. All three polymers showed well-extended conjugation through the polymer backbone. Ionization potentials (IP) ranged from 5.15 to 5.21 eV; these large values are indicative of their excellent oxidative stability. X-ray diffraction and AFM studies suggest that the polymer with the even number of fused thiophene rings forms a tight crystalline structure due to its tilted side chain arrangement. On the other hand, the polymers with the odd number of fused thiophene rings packed more loosely. Characterization in a field-effect transistor configuration showed that the mobility of the polymer with the even number of rings is 1 order of magnitude higher than its odd-numbered counterparts. Through this structure-property study, we demonstrate that proper design of the molecules and properly arranged side chain positions on the polymer backbone can greatly enhance polymer electronic properties.

[1]  M. He,et al.  Synthesis and structure of alkyl-substituted fused thiophenes containing up to seven rings. , 2007, The Journal of organic chemistry.

[2]  Keiji Kobayashi,et al.  Synthesis of tetrathieno-acene and pentathieno-acene: UV-spectral trend in a homologous series of thieno-acenes , 1989 .

[3]  R. J. Kline,et al.  Semiconducting Thienothiophene Copolymers: Design, Synthesis, Morphology, and Performance in Thin‐Film Organic Transistors , 2009 .

[4]  T. Kawase,et al.  High-mobility double-gate organic single-crystal transistors with organic crystal gate insulators , 2007 .

[5]  Eric K. Lin,et al.  Combinatorial screening of the effect of temperature on the microstructure and mobility of a high performance polythiophene semiconductor , 2007 .

[6]  Zhenan Bao,et al.  Effect of Mesoscale Crystalline Structure on the Field‐Effect Mobility of Regioregular Poly(3‐hexyl thiophene) in Thin‐Film Transistors , 2005 .

[7]  Eric K. Lin,et al.  Critical Role of Side-Chain Attachment Density on the Order and Device Performance of Polythiophenes , 2007 .

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

[9]  D. Kumaki,et al.  High-mobility and air-stable organic thin-film transistors with highly ordered semiconducting polymer films , 2007 .

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

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

[12]  J. Pflaum,et al.  Effect of Molecular Weight and Annealing of Poly(3‐hexylthiophene)s on the Performance of Organic Field‐Effect Transistors , 2004 .

[13]  S. Jenekhe,et al.  Electrochemical Properties and Electronic Structures of Conjugated Polyquinolines and Polyanthrazolines , 1996 .

[14]  Detlef-M. Smilgies,et al.  Grazing‐incidence small‐angle X‐ray scattering from thin polymer films with lamellar structures – the scattering cross section in the distorted‐wave Born approximation , 2006 .

[15]  Martin Heeney,et al.  Undoped polythiophene field-effect transistors with mobility of 1cm2V−1s−1 , 2007 .

[16]  J. Rogers,et al.  Elastomeric Transistor Stamps: Reversible Probing of Charge Transport in Organic Crystals , 2004, Science.

[17]  P. Bäuerle,et al.  The longest oligothiophene ever examined by X-ray structure analysis , 2006 .

[18]  Eric K. Lin,et al.  Significant dependence of morphology and charge carrier mobility on substrate surface chemistry in high performance polythiophene semiconductor films , 2007 .

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

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

[21]  Aram Amassian,et al.  Tetrathienoacene copolymers as high mobility, soluble organic semiconductors. , 2008, Journal of the American Chemical Society.

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

[23]  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.

[24]  J. Northrup,et al.  Atomic and electronic structure of polymer organic semiconductors: P3HT, PQT, and PBTTT , 2007 .

[25]  R. J. Kline,et al.  X-ray scattering study of thin films of poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene). , 2007, Journal of the American Chemical Society.

[26]  R. J. Kline,et al.  High Carrier Mobility Polythiophene Thin Films: Structure Determination by Experiment and Theory† , 2007 .

[27]  A. Facchetti,et al.  Air-stable, solution-processable n-channel and ambipolar semiconductors for thin-film transistors based on the indenofluorenebis(dicyanovinylene) core. , 2008, Journal of the American Chemical Society.

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

[29]  John E Anthony,et al.  Functionalized acenes and heteroacenes for organic electronics. , 2006, Chemical reviews.

[30]  Adam J. Matzger,et al.  Synthesis and Structure of Fused α-Oligothiophenes with up to Seven Rings , 2005 .

[31]  Wi Hyoung Lee,et al.  Liquid-crystalline semiconducting copolymers with intramolecular donor-acceptor building blocks for high-stability polymer transistors. , 2009, Journal of the American Chemical Society.

[32]  J A Rogers,et al.  Intrinsic charge transport on the surface of organic semiconductors. , 2004, Physical review letters.

[33]  O. Bunk,et al.  Simulating X-ray diffraction of textured films , 2008 .

[34]  A. Facchetti,et al.  A high-mobility electron-transporting polymer for printed transistors , 2009, Nature.

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

[36]  Iain McCulloch,et al.  Progress and Challenges in Commercialization of Organic Electronics , 2008 .

[37]  Hagen Klauk,et al.  Organic electronics : materials, manufacturing and applications , 2006 .

[38]  E. Cantatore,et al.  Plastic transistors in active-matrix displays , 2001, Nature.

[39]  S. Mannsfeld,et al.  Controlled Deposition of Crystalline Organic Semiconductors for Field‐Effect‐Transistor Applications , 2009 .

[40]  B. Ong,et al.  Polyindolo[3,2-b]carbazoles : A new class of p-channel semiconductor polymers for organic thin-film transistors , 2006 .

[41]  A. Facchetti,et al.  Design, synthesis, and characterization of ladder-type molecules and polymers. Air-stable, solution-processable n-channel and ambipolar semiconductors for thin-film transistors via experiment and theory. , 2009, Journal of the American Chemical Society.

[42]  Zhihua Chen,et al.  Naphthalenedicarboximide- vs perylenedicarboximide-based copolymers. Synthesis and semiconducting properties in bottom-gate N-channel organic transistors. , 2009, Journal of the American Chemical Society.