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Symmetrically functionalized diketopyrrolopyrrole with alkylated thiophene moiety: from synthesis to electronic devices applications

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Abstract

A symmetrically conjugated molecular semiconductor derived from diketopyrrolopyrrole (DPP), i.e., 2,5-dihexadecyl-3,6-bis(5-(3-hexylthiophen-2-yl)thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione [DPP(3HT) 2 ], has been synthesized using the Stille coupling reaction. The optical band gap of DPP(3HT) 2 is found to be 1.65 eV with HOMO energy level of −5.13 eV. DPP(3HT) 2 is thermally stable up to 348 °C exhibiting only 5 % weight loss. X-ray diffraction analysis revealed the DPP(3HT) 2 to be polycrystalline with a high degree of crystallinity. It showed highly narrow and strong diffraction peaks with a d-spacing of ca. 30.18 Å (at 2θ = 2.09°, full width at half maximum: 2θ = 0.126°) indicating an end-to-end packing distance with the long alkyl chains (along the a-axis) being slightly tilted and partially interdigitated for effective packing. Field-effect transistors and complementary inverters employing DPP(3HT) 2 as a p-channel semiconductor have been fabricated and characterized.

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References

  1. Jager CM, Schmaltz T, Novak M, Khassanov A, Vorobiev A, Hennemann M, Krause A, Dietrich H, Zahn D, Hirsch A, Halik M, Clark T (2013) Improving the charge transport in self-assembled monolayer field-effect transistors: from theory to devices. J Am Chem Soc 135:4893–4900

    Article  Google Scholar 

  2. Tarabella G, Mohammadi FM, Coppede N, Barbero F, Iannotta S, Santato C, Cicoira F (2013) New opportunities for organic electronics and bioelectronics: ions in action. Chem Sci 4:1395–1409

    Article  Google Scholar 

  3. Roelofs WSC, Adriaans WH, Janssen RAJ, Kemerink M, de Leeuw DM (2013) Light emission in the unipolar regime of ambipolar organic field-effect transistors. Adv Funct Mater 23:4133–4139

    Article  Google Scholar 

  4. Magliulo M, Mallardi A, Mulla MY, Cotrone S, Pistillo BR, Favia P, Vikholm-Lundin I, Palazzo G, Torsi L (2013) Electrolyte-gated organic field-effect transistor sensors based on supported biotinylated phospholipid bilayer. Adv Mater 25:2090–2094

    Article  Google Scholar 

  5. Kang MS, Frisbie CD (2013) A pedagogical perspective on ambipolar FETs. Chem Phys Chem 14:1547–1552

    Article  Google Scholar 

  6. Mukherjee B, Sim K, Shin TJ, Lee J, Mukherjee M, Ree M, Pyo S (2012) Organic phototransistors based on solution grown, ordered single crystalline arrays of a π-conjugated molecule. J Mater Chem 22:3192–3200

    Article  Google Scholar 

  7. Mas-Torrent M, Rovira C (2011) Role of molecular order and solid-state structure in organic field-effect transistors. Chem Rev 111:4833–4856

    Article  Google Scholar 

  8. Klauk H (2010) Organic thin-film transistors. Chem Soc Rev 39:2643–2666

    Article  Google Scholar 

  9. Ko JB, Hong J-H (2010) Electrical property of pentacene organic thin-film transistors with a complementary-gated structure. J Mater Sci 45:2839–2842.doi:10.1007/s10853-009-4194-0

    Article  Google Scholar 

  10. Mei J, Diao Y, Appleton AL, Fang L, Bao Z (2013) Integrated materials design of organic semiconductors for field-effect transistors. J Am Chem Soc 135:6724–6746

    Article  Google Scholar 

  11. Khim D, Lee W-H, Baeg K-J, Kim D-Y, Kang I-N, Noh Y–Y (2012) Highly stable printed polymer field-effect transistors and inverters via polyselenophene conjugated polymers. J Mat Chem 22:12774–12783

    Article  Google Scholar 

  12. Shahid M, McCarthy-Ward T, Labram J, Rossbauer S, Domingo EB, Watkins SE, Stingelin N, Anthopoulos TD, Heeney M (2012) Low band gap selenophene-diketopyrrolopyrrole polymers exhibiting high and balanced ambipolar performance in bottom-gate transistors. Chem Sci 3:181–185

    Article  Google Scholar 

  13. Wen Y, Liu Y, Guo Y, Yu G, Hu W (2011) Experimental techniques for the fabrication and characterization of organic thin films for field-effect transistors. Chem Rev 111:3358–3406

    Article  Google Scholar 

  14. Arias AC, MacKenzie JD, McCulloch I, Rivnay J, Salleo A (2010) Materials and applications for large area electronics: solution-based approaches. Chem Rev 110:3–24

    Article  Google Scholar 

  15. Ortiz RP, Facchetti A, Marks TJ (2010) High-k organic, inorganic and hybrid dielectrics for low-voltage organic field-effect transistors. Chem Rev 110:205–239

    Article  Google Scholar 

  16. Glowatzki H, Sonar P, Singh SP, Mak AM, Sullivan MB, Chen W, Wee ATS, Dodabalapur A (2013) Band gap tunable N-type molecules for organic field effect transistors. J Phys Chem C 117:11530–11539

    Article  Google Scholar 

  17. Li J, Chang J–J, Tan HS, Jiang H, Chen X, Chen Z, Zhang J, Wu J (2012) Disc-like 7,14-dicyano-ovalene-3,4:10,11-bis(dicarboximide) as a solution-processible n-type semiconductor for air stable field-effect transistors. Chem Sci 3:846–850

    Article  Google Scholar 

  18. Ruiz C, Garcia-Frutos EM, Hennrich G, Gomez-Lor B (2012) Organic semiconductors toward electronic devices: high mobility and easy processability. J Phys Chem Lett 3:1428–1436

    Article  Google Scholar 

  19. Li L, Tang Q, Li H, Yang X, Hu W, Song Y, Shuai Z, Xu W, Liu Y, Zhu D (2007) An ultra closely π-stacked organic semiconductor for high performance field-effect transistors. Adv Mater 19:2613–2617

    Article  Google Scholar 

  20. Liscio F, Albonetti C, Broch K, Shehu A, Quiroga SD, Ferlauto L, Frank C, Kowarik S, Nervo R, Gerlach A, Milita S, Schreiber F, Biscarini F (2013) Molecular reorganization in organic field-effect transistors and its effect on two-dimensional charge transport pathways. ACS Nano 7:1257–1264

    Article  Google Scholar 

  21. Zaumseil J, Sirringhaus H (2007) Electron and ambipolar transport in organic field-effect transistors. Chem Rev 107:1296–1323

    Article  Google Scholar 

  22. Holcombe TW, Yum J-H, Yoon J, Gao P, Marszalek M, Censo DD, Rakstys K, Nazeeruddin MdK, Graetzela M (2012) A structural study of DPP-based sensitizers for DSC applications. Chem Commun 48:10724–10726

    Article  Google Scholar 

  23. Palai AK, Lee J, Das S, Lee J, Cho H, Park S-U, Pyo S (2012) A diketopyrrolopyrrole containing molecular semiconductor: synthesis, characterization and solution-processed 1D-microwire based electronic devices. Org Electron 13:2553–2560

    Article  Google Scholar 

  24. Burckstummer H, Weissenstein A, Bialas D, Wurthner F (2011) Synthesis and characterization of optical and redox properties of bithiophene-functionalized diketopyrrolopyrrole chromophores. J Org Chem 76:2426–2432

    Article  Google Scholar 

  25. Kim Y, Song CE, Cho A, Kim J, Eom Y, Ahn J, Moon S-J, Lim E (2014) Synthesis of diketopyrrolopyrrole (DPP)-based small molecule donors containing thiophene or furan for photovoltaic applications. Mater Chem Phys 143:825–829

    Article  Google Scholar 

  26. Lee OP, Yiu AT, Beaujuge PM, Woo CH, Holcombe TW, Millstone JE, Douglas JD, Chen MS, Fréchet JMJ (2011) Efficient small molecule bulk heterojunction solar cells with high fill factors via pyrene-directed molecular self-assembly. Adv Mater 23:5359–5363

    Article  Google Scholar 

  27. Loser S, Bruns CJ, Miyauchi H, Ortiz RP, Facchetti A, Stupp SI, Marks TJ (2011) A naphthodithiophene-diketopyrrolopyrrole donor molecule for efficient solution-processed solar cells. J Am Chem Soc 133:8142–8145

    Article  Google Scholar 

  28. Qu S, Wu W, Hua J, Kong C, Long Y, Tian H (2010) New diketopyrrolopyrrole (DPP) dyes for efficient dye-sensitized solar cells. J Phys Chem C 114:1343–1349

    Article  Google Scholar 

  29. Matthews JR, Niu W, Tandia A, Wallace AL, Hu J, Lee W-Y, Giri G, Mannsfeld SCB, Xie Y, Cai S, Fong HH, Bao Z, He M (2013) Scalable synthesis of fused thiophene-diketopyrrolopyrrole semiconducting polymers processed from nonchlorinated solvents into high Performance thin film transistors. Chem Mater 25:782–789

    Article  Google Scholar 

  30. Mei J, Graham KR, Stalder R, Tiwari SP, Cheun H, Shim J, Yoshio M, Nuckolls C, Kippelen B, Castellano RK, Reynolds JR (2011) Self-assembled amphiphilic diketopyrrolopyrrole-based oligothiophenes for field-effect transistors and solar cells. Chem Mater 23:2285–2288

    Article  Google Scholar 

  31. Lu C, Chen W-C (2013) Diketopyrrolopyrrole-thiophene-based acceptor-donor-acceptor conjugated materials for high-performance field-effect transistors. Chem Asian J 8:2813–2821

    Article  Google Scholar 

  32. Tantiwiwat M, Tamayo A, Luu N, Dang X-D, Nguyen T-Q (2008) Oligothiophene derivatives functionalized with a diketopyrrolopyrrolo core for solution-processed field effect transistors: effect of alkyl substituents and thermal annealing. J Phys Chem C 112:17402–17407

    Article  Google Scholar 

  33. Qiao Y, Guo Y, Yu C, Zhang F, Xu W, Liu Y, Zhu D (2012) Diketopyrrolopyrrole-containing quinoidal small molecules for high-performance, air-stable, and solution-processable n-channel organic field-effect transistors. J Am Chem Soc 134:4084–4087

    Article  Google Scholar 

  34. Zhong H, Smith J, Rossbauer S, White AJP, Anthopoulos TD, Heeney M (2012) Air-stable and high-mobility n-channel organic transistors based on small-molecule/polymer semiconducting blends. Adv Mater 24:3205–3211

    Article  Google Scholar 

  35. Zhang Y, Kim C, Lin J, Nguyen T-Q (2012) Solution-processed ambipolar field-effect transistor based on diketopyrrolopyrrole functionalized with benzothiadiazole. Adv Funct Mater 22:97–105

    Article  Google Scholar 

  36. Song B, Wei H, Wang Z, Zhang X, Smet M, Dehaen W (2007) Supramolecular nanofibers by self-organization of bola-amphiphiles through a combination of hydrogen bonding and π–π stacking interactions. Adv Mater 19:416–420

    Article  Google Scholar 

  37. Kong H, Chung DS, Kang I-N, Lim E, Jung YK, Park J-H, Park CE, Shim H-K (2007) Fluorene-based conjugated copolymers containing hexyl-thiophene derivatives for organic thin film transistors. Bull Korean Chem Soc 28:1945–1950

    Article  Google Scholar 

  38. Palai AK, Cho H, Cho S, Shin T, Jang S, Park S-U, Pyo S (2013) Non-functionalized soluble diketopyrrolopyrrole: simplest p-channel core for organic field-effect transistors. Org Electron 14:1396–1406

    Article  Google Scholar 

  39. Zou Y, Gendron D, Badrou-Aich R, Najari A, Tao Y, Lecrerc M (2009) A high-mobility low-bandgap poly(2,7-carbazole) derivative for photovoltaic applications. Macromolecules 42:2891–2894

    Article  Google Scholar 

  40. Spartan’10 Wavefunction, Inc. Irvine, CA

  41. Sonar P, Ng G-M, Lin TT, Dodabalapur A, Chen Z-K (2010) Solution processable low bandgap diketopyrrolopyrrole (DPP) based derivatives: novel acceptors for organic solar cells. J Mater Chem 20:3626–3636

    Article  Google Scholar 

  42. Sonar P, Singh SP, Leclere P, Surin M, Lazzaroni R, Lin TT, Dodabalapur A, Sellinger A (2009) Synthesis, characterization and comparative study of thiophene-benzothiadiazolebased donor–acceptor–donor (D–A–D) materials. J Mater Chem 19:3228–3237

    Article  Google Scholar 

  43. Leontie L, Danac R, Girtan M, Carlescu A, Rambu AP, Rusu GI (2012) Electron transport properties of some new 4-tert-butylcalix[4]arene derivatives in thin films. Mater Chem Phys 135:123–129

    Article  Google Scholar 

  44. Seju U, Kumar A, Sawant KK (2011) Development and evaluation of olanzapine-loaded PLGA nanoparticles for nose-to-brain delivery: in vitro and in vivo studies. Acta Biomater 7:4169–4176

    Article  Google Scholar 

  45. Kuwabara J, Yamagata T, Kanbara T (2010) Solid-state structure and optical properties of highly fluorescent diketopyrrolopyrrole derivatives synthesized by cross-coupling reaction. Tetrahedron 66:3736–3741

    Article  Google Scholar 

  46. Huang J, Jia H, Li L, Lu Z, Zhang W, He W, Jiang B, Tang A, Tan Z, Zhan C, Li Y, Yao J (2012) Fine-tuning device performances of small molecule solar cells via the more polarized DPP-attached donor units. Phys Chem Chem Phys 14:14238–14242

    Article  Google Scholar 

  47. Menard E, Podzorov V, Hur S-H, Gaur A, Gershenson ME, Rogers JA (2004) High-performance n- and p-type single-crystal organic transistors with free-space gate dielectrics. Adv Mater 16:2097–2101

    Article  Google Scholar 

  48. Kim SH, Jang M, Kim J, Choi H, Baek K-Y, Park CE, Yang H (2012) Complementary photo and temperature cured polymer dielectrics with high-quality dielectric properties for organic semiconductors. J Mater Chem 22:19940–19947

    Article  Google Scholar 

  49. Gundlach DJ, Pernstich KP, Wilckens G, Grüter M, Haas S, Batlogg B (2005) High mobility n-channel organic thin-film transistors and complementary inverters. J Appl Phys 98:064502(1–8)

  50. Kim S, Lim T, Sim K, Kim H, Choi Y, Park K, Pyo S (2011) Light sensing in a photoresponsive, organic-based complementary inverter. ACS Appl Mater Interfaces 3:1451–1456

    Article  Google Scholar 

  51. Kim SH, Kang I, Kim YG, Hwang HR, Kim Y-H, Kwon S-K, Jang J (2013) High performance ink-jet printed diketopyrrolopyrrole-based copolymer thin-film transistors using a solution-processed aluminium oxide dielectric on a flexible substrate. J Mater Chem C 1:2408–2411

    Article  Google Scholar 

  52. Li J, Zhao Y, Tan HS, Guo Y, Di C-A, Yu G, Liu Y, Lin M, Lim SH, Zhou Y, Su H, Ong BS (2012) A stable solution-processed polymer semiconductor with record high-mobility for printed transistors. Scintific reports 2:754. doi:10.1038/srep00754

    Google Scholar 

  53. Roelofs WSC, Mathijssen SGJ, Bijleveld JC, Raiteri D, Geuns TCT, Kemerink M, Cantatore E, Janssen RAJ, de Leeuw DM (2011) Fast ambipolar integrated circuits with poly(diketopyrrolopyrrole-terthiophene). Appl Phys Lett 98:203301(1–3)

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Acknowledgements

This work was supported by the National Research Foundation (NRF) funded by Korea government (MEST) (R11-2008-052-03,003, 2012R1A2A2A01045694). A.K.P. acknowledges financial support from the 2012 KU Brain Pool Program of Konkuk University.

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Authors and Affiliations

  1. Department of Chemistry, Konkuk University, 120 Neungdong-ro, Gwangjin-gu, Seoul, 143-701, Republic of Korea

    Akshaya K. Palai, Jihee Lee, Minkyung Jea, Hanah Na, Seung-Un Park & Seungmoon Pyo

  2. Pohang Accelerator Laboratory, Pohang, 790-784, Republic of Korea

    Tae Joo Shin

  3. Department of Chemistry, Sejong University, 209 Neungdong-ro, Gwangjin-gu, Seoul, 143-747, Republic of Korea

    Soonmin Jang

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  1. Akshaya K. Palai
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  2. Jihee Lee
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Correspondence to Seungmoon Pyo.

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Akshaya K. Palai and Jihee Lee contributed equally to this work.

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Palai, A.K., Lee, J., Jea, M. et al. Symmetrically functionalized diketopyrrolopyrrole with alkylated thiophene moiety: from synthesis to electronic devices applications. J Mater Sci 49, 4215–4224 (2014). https://doi.org/10.1007/s10853-014-8116-4

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