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Room-temperature optically detected magnetic resonance of triplet excitons in a pentacene-doped picene single crystal

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Abstract

The inclusion of functional molecules as substitutional dopants in single crystals of organic hosts with complementary optical properties provides a versatile strategy to tune optical and magnetic properties in view of their applications in opto-electronics and spintronics. Here, by combining electron spin resonance and optical spectroscopy, isolated triplet exciton states with distinct emission and absorptive resonance modes from two magnetically inequivalent sites of pentacene within the picene crystal are detected at room temperature. This is possible due to the incorporation of a low-doping, 1% mol/mol of pentacene into the monoclinic polymorph of picene high-quality single crystals. In addition, delayed fluorescence—optically detected magnetic resonance (ODMR) studies demonstrate efficient spin-dependent optical activities that are tuned by crystallographically oriented magnetic fields. These properties are particularly appealing for the exploitation of pentacene in room-temperature spin-driven opto-electronics, quantum sensing and in microwave amplification by stimulated emission of radiation (MASER).

Graphical abstract

Triplet excitons of pentacene molecules doped into a picene single crystal provide microwave emission and absorptive resonance modes as well as large optically detected magnetic resonance contrast which can be tuned by magnetic field strength and direction. These properties make pentacene-doped picene single crystals promising materials for spin-driven opto-electronics and, in particular, in microwave amplification by stimulated emission of radiation (MASER).

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Data availability

The datasets generated during and/or analysed during the current study are available in the Bicocca Open Archive Research Data repository, https://doi.org/10.17632/ncrnw9d3mg.1

References

  1. K.J. Baeg, M. Binda, D. Natali, M. Caironi, Y.Y. Noh, organic light detectors: photodiodes and phototransistors. Adv. Mater. 25(31), 4267 (2013)

    CAS  Google Scholar 

  2. V.A. Dediu, L.E. Hueso, I. Bergenti, C. Taliani, Spin routes in organic semiconductors. Nat. Mater. 8(9), 707 (2009)

    CAS  Google Scholar 

  3. K. Broch, J. Dieterle, F. Branchi, N.J. Hestand, Y. Olivier, H. Tamura, C. Cruz, V.M. Nichols, A. Hinderhofer, D. Beljonne, F.C. Spano, G. Cerullo, C.J. Bardeen, F. Schreiber, Robust singlet fission in pentacene thin films with tuned charge transfer interactions. Nat. Commun. (2018). https://doi.org/10.1038/s41467-018-03300-1

    Article  Google Scholar 

  4. D. Lubert-Perquel, E. Salvadori, M. Dyson, P.N. Stavrinou, R. Montis, H. Nagashima, Y. Kobori, S. Heutz, C.W.M. Kay, Identifying triplet pathways in dilute pentacene films. Nat. Commun. (2018). https://doi.org/10.1038/s41467-018-06330-x

    Article  Google Scholar 

  5. Y.X. Wang, Z. Liu, Y.H. Fang, S. Zhou, S.D. Jiang, S. Gao, Coherent manipulation and quantum phase interference in a fullerene-based electron triplet molecular qutrit. NPJ Quantum Inf. (2021). https://doi.org/10.1038/s41534-021-00362-w

    Article  Google Scholar 

  6. M.C. Hanna, A.J. Nozik, Solar conversion efficiency of photovoltaic and photoelectrolysis cells with carrier multiplication absorbers. J. Appl. Phys. 100(7), 074510 (2006)

    Google Scholar 

  7. H. Kraus, M.C. Heiber, S. Vath, J. Kern, C. Deibel, A. Sperlich, V. Dyakonov, Analysis of triplet exciton loss pathways in PTB7: PC71BM Bulk heterojunction solar cells. Sci. Rep. (2016). https://doi.org/10.1038/srep29158

    Article  Google Scholar 

  8. J.E. Anthony, The larger acenes: versatile organic semiconductors. Angew. Chem. Int. Ed. 47(3), 452 (2008)

    CAS  Google Scholar 

  9. H. Okamoto, N. Kawasaki, Y. Kaji, Y. Kubozono, A. Fujiwara, M. Yamaji, Air-assisted high-performance field-effect transistor with thin films of picene. J. Am. Chem. Soc. 130(32), 10470 (2008)

    CAS  Google Scholar 

  10. G.A. Artioli, F. Hammerath, M.C. Mozzati, P. Carretta, F. Corana, B. Mannucci, S. Margadonna, L. Malavasi, Superconductivity in Sm-doped n phenacenes (n=3,4,5). Chem. Commun. 51(6), 1092 (2015)

    CAS  Google Scholar 

  11. H.A. Galue, J. Oomens, W.J. Buma, B. Redlich, Electron-flux infrared response to varying pi-bond topology in charged aromatic monomers. Nat. Commun. 7, 1–12 (2016)

    Google Scholar 

  12. Y. Kubozono, H. Mitamura, X. Lee, X.X. He, Y. Yamanari, Y. Takahashi, Y. Suzuki, Y. Kaji, R. Eguchi, K. Akaike, T. Kambe, H. Okamoto, A. Fujiwara, T. Kato, T. Kosugi, H. Aoki, Metal-intercalated aromatic hydrocarbons: a new class of carbon-based superconductors. Phys. Chem. Chem. Phys. 13(37), 16476 (2011)

    CAS  Google Scholar 

  13. M. Bendikov, F. Wudl, D.F. Perepichka, Tetrathiafulvalenes, oligoacenenes, and their buckminsterfullerene derivatives: the brick and mortar of organic electronics. Chem. Rev. 104(11), 4891 (2004)

    CAS  Google Scholar 

  14. P. Cudazzo, M. Gatti, A. Rubio, Excitons in molecular crystals from first-principles many-body perturbation theory: picene versus pentacene. Phys. Rev. B. (2012). https://doi.org/10.1103/PhysRevB.86.195307

    Article  Google Scholar 

  15. J. Wrachtrup, C. Vonborczyskowski, J. Bernard, M. Orrit, R. Brown, Optically detected spin coherence of single molecues. Phys. Rev. Lett. 71(21), 3565 (1993)

    CAS  Google Scholar 

  16. M. Orrit, J. Bernard, Sinlge pentacene molecules detected by fluorescence in a para terphenyl crystal. Phys. Rev. Lett. 65(21), 2716 (1990)

    CAS  Google Scholar 

  17. K. Tateishi, M. Negoro, S. Nishida, A. Kagawa, Y. Morita, M. Kitagawa, Room temperature hyperpolarization of nuclear spins in bulk. Proc. Natl. Acad. Sci. USA 111(21), 7527 (2014)

    CAS  Google Scholar 

  18. M. Oxborrow, J.D. Breeze, N.M. Alford, Room-temperature solid-state maser. Nature 488(7411), 353 (2012)

    CAS  Google Scholar 

  19. D.J. Sloop, H.L. Yu, T.S. Lin, S.I. Weissman, Electron spin echoes of a photoexcited triplet pentacene in paraterphenyl crystals. J. Chem. Phys. 75(8), 3746 (1981)

    CAS  Google Scholar 

  20. A. Henstra, T.S. Lin, J. Schmidt, W.T. Wenckebach, High dynamic nuclear polarization at room temperature. Chem. Phys. Lett. 165(1), 6 (1990)

    CAS  Google Scholar 

  21. A. Kagawa, M. Negoro, R. Ohba, N. Ichijo, K. Takamine, Y. Nakamura, T. Murata, Y. Morita, M. Kitagawa, Dynamic nuclear polarization using photoexcited triplet electron spins in eutectic mixtures. J. Phys. Chem. A 122(50), 9670 (2018)

    CAS  Google Scholar 

  22. O.D. Jurchescu, J. Baas, T.T.M. Palstra, Effect of impurities on the mobility of single crystal pentacene. Appl. Phys. Lett. 84(16), 3061 (2004)

    CAS  Google Scholar 

  23. C. Reese, W.J. Chung, M.M. Ling, M. Roberts, Z.N. Bao, High-performance microscale single-crystal transistors by lithography on an elastomer dielectric. Appl. Phys. Lett. 89(20), 202108 (2006)

    Google Scholar 

  24. P.M. Zimmerman, Z.Y. Zhang, C.B. Musgrave, Singlet fission in pentacene through multi-exciton quantum states. Nat. Chem. 2(8), 648 (2010)

    CAS  Google Scholar 

  25. A. Rao, M.W.B. Wilson, J.M. Hodgkiss, S. Albert-Seifried, H. Bassler, R.H. Friend, Exciton fission and charge generation via triplet excitons in pentacene/C-60 bilayers. J. Am. Chem. Soc. 132(36), 12698 (2010)

    CAS  Google Scholar 

  26. H. Najafov, B. Lee, Q. Zhou, L.C. Feldman, V. Podzorov, Observation of long-range exciton diffusion in highly ordered organic semiconductors. Nat. Mater. 9(11), 938 (2010)

    CAS  Google Scholar 

  27. H. Okamoto, S. Hamao, R. Eguchi, H. Goto, Y. Takabayashi, P.Y.H. Yen, L.U. Liang, C.W. Chou, G. Hoffmann, S. Gohda, H. Sugino, Y.F. Liaos, H. Ishii, Y. Kubozono, Synthesis of the extended phenacene molecules, 10 phenacene and 11 phenacene, and their performance in a field-effect transistor. Sci. Rep. 9, 1–11 (2019)

    Google Scholar 

  28. R. Mitsuhashi, Y. Suzuki, Y. Yamanari, H. Mitamura, T. Kambe, N. Ikeda, H. Okamoto, A. Fujiwara, M. Yamaji, N. Kawasaki, Y. Maniwa, Y. Kubozono, Superconductivity in alkali-metal-doped picene. Nature 464(7285), 76 (2010)

    CAS  Google Scholar 

  29. S. Gottardi, T. Toccoli, S. Iannotta, P. Bettotti, A. Cassinese, M. Barra, L. Ricciotti, Y. Kubozono, Optimizing picene molecular assembling by supersonic molecular beam deposition. J. Phys. Chem. C 116(46), 24503 (2012)

    CAS  Google Scholar 

  30. Y. Shimo, T. Mikami, H.T. Murakami, S. Hamao, H. Goto, H. Okamoto, S. Gohda, K. Sato, A. Cassinese, Y. Hayashi, Y. Kubozono, Transistors fabricated using the single crystals of 8 phenacene. J. Mater. Chem. C 3(28), 7370 (2015)

    CAS  Google Scholar 

  31. T. Taguchi, F. Chiarella, M. Barra, F. Chianese, Y. Kubozono, A. Cassinese, Balanced ambipolar charge transport in phenacene/perylene heterojunction-based organic field-effect transistors. ACS Appl. Mater. Interfaces 13(7), 8631 (2021)

    CAS  Google Scholar 

  32. T. Hosokai, A. Hinderhofer, F. Bussolotti, K. Yonezawa, C. Lorch, A. Vorobiev, Y. Hasegawa, Y. Yamada, Y. Kubozoro, A. Gerlach, S. Kera, F. Schreiber, N. Ueno, Thickness and substrate dependent thin film growth of picene and impact on the electronic structure. J. Phys. Chem. C 119(52), 29027 (2015)

    CAS  Google Scholar 

  33. T. Toccoli, P. Bettotti, A. Cassinese, S. Gottardi, Y. Kubozono, M.A. Loi, M. Manca, R. Verucchi, Photophysics of pentacene-doped picene thin films. J. Phys. Chem. C 122(29), 16879 (2018)

    CAS  Google Scholar 

  34. A. De, R. Ghosh, S. Roychowdhury, P. Roychowdhury, Structural-analysis of picene, C22H14. Acta Crystallogr. Sect. C Cryst. Struct. Commun. 41(JUN), 907 (1985)

    Google Scholar 

  35. B. Mahns, O. Kataeva, D. Islamov, S. Hampel, F. Steckel, C. Hess, M. Knupfer, B. Buchner, C. Himcinschi, T. Hahn, R. Renger, J. Kortus, Crystal growth, structure, and transport properties of the charge-transfer salt picene/2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane. Cryst. Growth Des. 14(3), 1338 (2014)

    CAS  Google Scholar 

  36. Z.S. Zhao, L.H. Britt, G.K. Murphy, Oxidative, iodoarene-catalyzed intramolecular alkene arylation for the synthesis of polycyclic aromatic hydrocarbons. Chem.-Eur. J. 24(64), 17002 (2018)

    CAS  Google Scholar 

  37. J. Lang, D.J. Sloop, T.S. Lin, Orientational anisotropic studies by field rotation technique: near zero-field pulsed EPR experiments of pentacene doped in p-terphenyl. J. Magn. Reson. 176(2), 249 (2005)

    CAS  Google Scholar 

  38. J. Dieterle, K. Broch, A. Hinderhofer, H. Frank, J. Novak, A. Gerlach, T. Breuer, R. Banerjee, G. Witte, F. Schreibert, Structural properties of picene-perfluoropentacene and picene-pentacene blends: super lattice formation versus limited intermixing. J. Phys. Chem. C 119(47), 26339 (2015)

    CAS  Google Scholar 

  39. N. Hirota, M. Baba, Y. Hirata, S. Nagaoka, ODMR and EPR studies of the triplet-states of aliphatic and aromatic carbonyls. J. Phys. Chem. 83(26), 3350 (1979)

    CAS  Google Scholar 

  40. J. Kohler, A.C.J. Brouwer, E.J.J. Groenen, J. Schmidt, Fluorescence detecion of single-molecule magnetic-resonance for penatcene in p-terphenyl - the hyperfine interaction of a single triplet spin with a single C-13 nuclear spin. Chem. Phys. Lett. 228(1–3), 47 (1994)

    Google Scholar 

  41. T. Yago, G. Link, G. Kothe, T.S. Lin, Pulsed electron nuclear double resonance studies of the photoexcited triplet state of pentacene in p-terphenyl crystals at room temperature. J. Chem. Phys. 127(11), 114503 (2007)

    Google Scholar 

  42. T.C. Yang, D.J. Sloop, S.I. Weissman, T.S. Lin, Zero-field magnetic resonance of the photo-excited triplet state of pentacene at room temperature. J. Chem. Phys. 113(24), 11194 (2000)

    CAS  Google Scholar 

  43. S.S. Kim, Triplet state of picene in para terphenyl crystals by EPR. Chem. Phys. Lett. 61(2), 327 (1979)

    CAS  Google Scholar 

  44. H.L. Yu, T.S. Lin, S.I. Weissman, D.J. Sloop, Time resolved studies of pentacene triplets by electron spin echo spectroscopy. J. Chem. Phys. 80(1), 102 (1984)

    CAS  Google Scholar 

  45. T. Oyama, Y.S. Yang, K. Matsuo, T. Yasuda, Effects of chalcogen atom substitution on the optoelectronic and charge-transport properties in picene-type pi-systems. Chem. Commun. 53(27), 3814 (2017)

    CAS  Google Scholar 

  46. K. Marumoto, S. Kuroda, T. Takenobu, Y. Iwasa, Spatial extent of wave functions of gate-induced hole carriers in pentacene field-effect devices as investigated by electron spin resonance. Phys. Rev. Lett. (2006). https://doi.org/10.1103/PhysRevLett.97.256603

    Article  Google Scholar 

  47. P.G. Baranov, H.J. von Bardeleben, F. Jelezko, J. Wrachtrup, Magnetic Resonance of Semiconductors and Their Nanostructures: Basic and Advanced Applications (Springer, Vienna, 2017)

    Google Scholar 

  48. T.C. Yang, D.J. Sloop, S.I. Weissman, T.S. Lin, Magnetic effects on the dynamics of organic triplets in the level anti-crossing region. Mol. Phys. 100(9), 1333 (2002)

    CAS  Google Scholar 

  49. R. Brown, J. Wrachtrup, M. Orrit, J. Bernard, C. Vonborczyskowski, Kinetics of optically detected magnetic-resonance of single molecules. J. Chem. Phys. 100(10), 7182 (1994)

    CAS  Google Scholar 

  50. L.S. Swanson, P.A. Lane, J. Shinar, F. Wudl, Polarons and triplet excitons in poly(paraphenylene)(PPV) and substitued PPV. An optically detected magnetic resonance study. Phys. Rev. B. 44(19), 10617 (1991)

    CAS  Google Scholar 

  51. V. Dyakonov, N. Gauss, G. Rosler, S. Karg, W. Riess, Electron spin resonance in PPV photodiodes detection via photoinduced current. Chem. Phys. 189(3), 687 (1994)

    CAS  Google Scholar 

  52. J. De Ceuster, E. Goovaerts, A. Bouwen, V. Dyakonov, Recombination of triplet excitons and polaron pairs in a derived paraphenylene vinylene pentamer. Phys. Rev. B (2003). https://doi.org/10.1103/PhysRevB.68.125202

    Article  Google Scholar 

  53. J. Shinar, J. Partee, On the nature of trapped polarons in pi-conjugated polymers. Synth. Met. 84(1–3), 525 (1997)

    CAS  Google Scholar 

  54. P.A. Lane, L.S. Swanson, Q.X. Ni, J. Shinar, J.P. Engel, T.J. Barton, L. Jones, Dynamics of photoexticed states in C60. An optically deteced magnetic resonance, ESR and light induced ESR study. Phys. Rev. Lett. 68(6), 887 (1992)

    CAS  Google Scholar 

  55. J.F. Wang, J.M. Cui, F.F. Yan, Q. Li, Z.D. Cheng, Z.H. Liu, Z.H. Lin, J.S. Xu, C.F. Li, G.C. Guo, Optimization of power broadening in optically detected magnetic resonance of defect spins in silicon carbide. Phys. Rev. B (2020). https://doi.org/10.1103/PhysRevB.101.064

    Article  Google Scholar 

  56. E.V. Levine, M.J. Turner, P. Kehayias, C.A. Hart, N. Langellier, R. Trubko, D.R. Glenn, R.R. Fu, R.L. Walsworth, Principles and techniques of the quantum diamond microscope. Nanophotonics 8(11), 1945 (2019)

    CAS  Google Scholar 

  57. S. Fanetti, M. Citroni, R. Bini, L. Malavasi, G.A. Artioli, P. Postorino, HOMO-LUMO transitions in solvated and crystalline picene. J. Chem. Phys. 137(22), 224506 (2012)

    Google Scholar 

  58. T.D. Nguyen, E. Ehrenfreund, Z.V. Vardeny, Spin-polarized light-emitting diode based on an organic bipolar spin valve. Science 337(6091), 204 (2012)

    CAS  Google Scholar 

  59. T. Siegrist, C. Kloc, J.H. Schon, B. Batlogg, R.C. Haddon, S. Berg, G.A. Thomas, Enhanced physical properties in a pentacene polymorph. Angew. Chem. Int. Ed. 40(9), 1732 (2001)

    CAS  Google Scholar 

  60. J.A. Rackers, Z. Wang, C. Lu, M.L. Laury, L. Lagardere, M.J. Schnieders, J.P. Piquemal, P.Y. Ren, J.W. Ponder, Tinker 8: software tools for molecular design. J. Chem. Theory Comput. 14(10), 5273 (2018)

    CAS  Google Scholar 

  61. W.L. Jorgensen, D.S. Maxwell, J. Tirado-Rives, Development and testing of the OPLS all-atom force field on conformational energetics and properties of organic liquids. J. Am. Chem. Soc. 118(45), 11225 (1996)

    CAS  Google Scholar 

  62. W.L. Jorgensen, J. Tirado-Rives, Potential energy functions for atomic-level simulations of water and organic and biomolecular systems. Proc Natl. Acad. Sci. USA 102(19), 6665 (2005)

    CAS  Google Scholar 

  63. S. Stoll, A. Schweiger, EasySpin, a comprehensive software package for spectral simulation and analysis in EPR. J. Magn. Reson. 178(1), 42 (2006)

    CAS  Google Scholar 

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Acknowledgments

We thank the University of Milano-Bicocca, the Swedish Interdisciplinary Magnetic Resonance Centres (SIMARC) and the Italian MIUR through the Progetto Premiale 2012 "EOS: organic electronics for advanced research instrumentation". We thank Prof. W. M. Chen, Prof. M. Fanciulli and Dr T. Toccoli for reading the manuscript and useful comments.

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Moro, F., Moret, M., Ghirri, A. et al. Room-temperature optically detected magnetic resonance of triplet excitons in a pentacene-doped picene single crystal. Journal of Materials Research 37, 1269–1279 (2022). https://doi.org/10.1557/s43578-022-00536-y

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