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    Szarko, Jodi M. Rolczynski, Brian S. Lou, Sylvia J. Xu, Tao Strzalka, Joseph Marks, Tobin J. Yu, Luping and Chen, Lin X. 2014. Photovoltaic Function and Exciton/Charge Transfer Dynamics in a Highly Efficient Semiconducting Copolymer. Advanced Functional Materials, Vol. 24, Issue. 1, p. 10.

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Length-dependent self-assembly of oligothiophene derivatives in thin films

  • Brian S. Rolczynski (a1), Jodi M. Szarko (a2), Byeongdu Lee (a3), Joseph Strzalka (a3), Jianchang Guo (a4), Yongye Liang (a5), Luping Yu (a6) and Lin X. Chen (a7)
  • DOI:
  • Published online: 19 January 2011

Thin-film aggregation characteristics of a series of oligothiophenes with a central thieno[3,4-b]thiophene ester unit and 4 (M5), 8 (M9), and 16 (M17) regioregular hexylthiophene units were investigated. These oligomers exhibited length-dependent self-assembly characteristics upon spin coating. M9 formed long fibers, while M5 and M17 formed random domains. Grazing incidence x-ray diffraction was performed to understand the reason for this length dependence. The M5 had a dominant ester–ester interaction that disrupted long-range order. The M9 morphology was due to a balance of orthogonal backbone and ester effects, which imposed long-range order on the M9 aggregates. Meanwhile, the M17 ester chain had a smaller relative contribution to packing and functioned as a molecular defect, disrupting long-range order. As a result, though the local self-assembly between monomers was very similar for the molecules, backbone length dependent changes in intermolecular forces dominated long-range structure. The analysis of self-assembly characteristics in these materials provides guidance in the design of organic conjugated materials for use in semiconductor devices.

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1.Y. Liang , D. Feng , J. Guo , J.M. Szarko , C. Ray , L.X. Chen , and L. Yu : Regioregular oligomer and polymer containing thieno[3,4-b]thiophene moiety for efficient organic solar cells. Macromolec. 42, 1091 (2009).

2.G. Dennler , M. Scharber , and C. Brabec : Polymer-fullerene bulk-heterojunction solar cells. Adv. Mater. 27, 1 (2009).

3.S. Holdcroft : Patterning π-conjugated polymers. Adv. Mater. 13, 7154 (2001).

4.R.H. Friend , R.W. Gymer , A.B. Holmes , J.H. Burroughes , R.N. Marks , C. Taliani , D. Bradley , D.A.D. Santos , J.L. Brédas , M. Lögdlund , and W.R. Salaneck : Electroluminescence in conjugated polymers. Nature 397, 121 (1999).

5.A.C. Mayer , M.F. Toney , S.R. Scully , J. Rivnay , C. Brabec , M. Scharber , M. Koppe , M.H. McCulloch , and M.D. McGehee : Bimolecular crystals of fullerenes in conjugated polymers and the implications of molecular mixing for solar cells. Adv. Funct. Mater. 19, 1173 (2009).

6.G.R. Desiraju : Crystal engineering: A holistic view. Angew. Chem. 46, 8342 (2007).

7.M.C. Etter : Encoding and decoding hydrogen-bond patterns of organic compounds. Acc. Chem. Res. 23, 120 (1990).

8.A. Gavezzotti : Molecular Aggregation: Structure Analysis and Molecular Simulation of Crystals and Liquids (Oxford University Press, New York, NY, 2007), pp. 367418.

10.M. Dante , J. Peet , and T. Nguyen : Nanoscale charge transport and internal structure of bulk heterojunction conjugated polymer/fullerene solar cells by scanning-probe microscopy. J. Phys. Chem. C 112, 7241 (2008).

11.L. Pingree , O.G. Reid , and D. Ginger : Electrical scanning-probe microscopy on active organic electronic devices. Adv. Mater. 21, 19 (2009).

12.J. Peet , J.Y. Kim , N.E. Coates , W.L. Ma , D. Moses , A.J. Heeger , and G.C. Bazan : Efficiency enhancement in low-bandgap polymer solar cells by processing with alkane dithiols. Nat. Mater. 6, 497 (2007).

13.I. Hwang , D. Moses , and A. Heeger : Photoinduced carrier generation in P3HT/PCBM bulk heterojunction materials. J. Phys. Chem. C 112, 4350 (2008).

14.M.J. Winokur , D. Spiegel , Y. Kim , S. Hotta , and A.J. Heeger : Structural and absorption studies of the thermochromic transition in poly(3-hexylthiophene). Synth. Met. 28, C419 (1989).

15.A. Gavezzotti and G. Filippini : Crystal packing and lattice energies of polythienyls: Calculations and predictions. Synth. Met. 40, 257 (1991).

16.R. Azumi , M. Goto , K. Honda , and M. Matsumoto : Conformation and packing of odd-numbered alpha-oligothiophenes in single crystals. Bull. Chem. Soc. Jpn. 76, 1561 (2003).

17.J. Cornil , D. Beljonne , J. Calbert , and J. Brédas : Interchain interactions in organic p-conjugated materials: Impact on electronic structure, optical response, and charge transport. Adv. Mater. 13, 1053 (2001).

18.D. Fichou : Structural order in conjugated oligothiophenes and its implications on opto-electronic devices. J. Mater. Chem. 10, 571 (2000).

19.J. Lehn : Toward self-organization and complex matter. Science 295, 2400 (2002).

20.A. Schenning and E. Meijer : Supramolecular electronics: Nanowires from self-assembled π-conjugated systems. Chem. Commun. 3245 (2005).

21.J. Guo , Y. Liang , J. Szarko , B. Lee , H.J. Son , B.S. Rolczynski , L. Yu , and L.X. Chen : Structure, dynamics, and power conversion efficiency correlations in a new low bandgap polymer: PCBM solar cell. J. Phys. Chem. B 114, 742 (2010).

22.J.M. Szarko , B.S. Rolczynski , J. Guo , Y. Liang , F. He , M.W. Mara , L. Yu , and L.X. Chen : Electronic processes in conjugated diblock oligomers mimicking low band-gap polymers: Experimental and theoretical spectral analysis. J. Phys. Chem. B 114, 14505 (2010).

23.D. Beljonne , Z. Shuai , G. Pourtois , and J.L. Bredas : Spin-orbit coupling and intersystem crossing in conjugated polymers: A configuration interaction description. J. Phys. Chem. A 105, 3899 (2001).

24.M. Chabinyc : X-ray scattering from films of semiconducting polymers. Pol. Rev. 48, 463 (2008).

25.Y. Kim , S. Cook , S.M. Tuladhar , S.A. Choulis , J. Nelson , J.R. Durrant , D.D.C. Bradley , M. Giles , I. McCulloch , C-s. Ha , and M. Ree : A strong regioregularity effect in self-organizing conjugated polymer films and high-efficiency polythiophene: Fullerene solar cells. Nat. Mater. 5, 198 (2006).

26.S. Joshi , S. Grigorian , and U. Pietsch : X-ray structural and crystallinity studies of low and high molecular weight poly(3-hexylthiophene). Phys. Status Solidi, A Appl. Mater. Sci. 205, 488 (2008).

27.A. Raudino and B. Pignataro : Supra-aggregates of fiber-forming anisotropic molecules. J. Phys. Chem. B 110, 2116 (2006).

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Journal of Materials Research
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