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Excitonic processes in molecular crystalline materials

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Abstract

This article provides an overview of the basic aspects of the structure and dynamics of excitons in molecular crystals that give rise to their unique spectroscopic behavior. The two different types of optically accessible excitons, charge-transfer and Frenkel, are described and their different properties discussed. Particular attention is paid to the spin properties of Frenkel excitons (i.e., singlet and triplet) and also to their coupling to intramolecular vibrations. Experimental challenges in the study of molecular crystal optical properties are also reviewed, including their high optical density, complex refractive index behavior, and issues with sample crystallinity and chemical purity. Once created, excitons in molecular crystals can exhibit interesting dynamical behavior, including diffusion over large length scales and ionization into electron–hole pairs. Exciton–exciton interactions are also important, ranging from fusion or annihilation (two excitons combine into one exciton) to fission (one exciton splits into two excitons). The long-range diffusion and exciton fission effects have particular relevance for the design of organic photovoltaic materials.

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References

  1. A.S. Davydov, Theory of Molecular Excitons (Plenum Press, New York, 1971).

    Book  Google Scholar 

  2. M.R. Philpott, Adv. Chem. Phys. 23, 227 (1973).

    CAS  Google Scholar 

  3. G.W. Robinson, Ann. Rev. Phys. Chem. 21, 429 (1970).

    Article  CAS  Google Scholar 

  4. D.P. Craig, S.H. Walmsley, Excitons in Molecular Crystals (W.A. Benjamin, New York, 1968).

    Google Scholar 

  5. E.A. Silinsh, Organic Molecular Crystals: Their Electronic States (Springer-Verlag, Heidelberg, 1980).

    Book  Google Scholar 

  6. V.M. Agranovich, M.D. Galanin, Electronic Excitation Energy Transfer in Condensed Matter (North-Holland, New York, 1982).

    Google Scholar 

  7. G.D. Scholes, G. Rumbles, Nature Mater. 5, 683 (2006).

    Article  CAS  Google Scholar 

  8. J.N. Murrell, J. Tanaka, Molec. Phys. 7, 363 (1964).

    Article  CAS  Google Scholar 

  9. M. Kasha, H.R. Rawls, M.A. El-Bayoumi, Pure Appl. Chem. 11, 371 (1965).

    Article  CAS  Google Scholar 

  10. P.J. Bounds, P. Petelenz, W. Siebrand, Chem. Phys. 63, 303 (1981).

    Article  CAS  Google Scholar 

  11. M. Pope, C.E. Swenberg, Electronic Processes in Organic Crystals and Polymers (Oxford University Press, New York, 1999).

    Google Scholar 

  12. R.S. Knox, Theory of Excitons (Academic Press, New York, 1963).

    Google Scholar 

  13. Z. Shen, S.R. Forrest, Phys. Rev. B 55, 10578 (1997).

    Article  CAS  Google Scholar 

  14. T. Wagersreiter, S. Mukamel, Chem. Phys. 210, 171 (1996).

    Article  CAS  Google Scholar 

  15. D. Beljonne, J. Cornil, R. Silbey, P. Millie, J.L. Brédas, J. Chem. Phys. 112, 4749 (2000).

    Article  CAS  Google Scholar 

  16. A.E. Clark, C. Qin, A.D. Q. Li, J. Am. Chem. Soc. 129, 7586 (2007).

    Article  CAS  Google Scholar 

  17. F.C. Spano, Ann. Rev. Phys. Chem. 57, 217 (2006).

    Article  CAS  Google Scholar 

  18. H. Yamagata, F.C. Spano, J. Chem. Phys. 135, 054906 /1 (2011).

    Article  CAS  Google Scholar 

  19. R. Schuster, M. Knupfer, H. Berger, Phys. Rev. Lett. 98, 037402 /1 (2007).

    Article  CAS  Google Scholar 

  20. H. Yamagata, J. Norton, E. Hontz, Y. Olivier, D. Beljonne, J.L. Brédas, R.J. Silbey, F.C. Spano, J. Chem. Phys. 134, 204703 /1 (2011).

    Article  CAS  Google Scholar 

  21. I.N. Levine, Quantum Chemistry (Prentice-Hall, Upper Saddle River, NJ, 2000).

    Google Scholar 

  22. H. Yersin, A.F. Rausch, R. Czerwieniec, T. Hofbeck, T. Fischer, Coord. Chem. Rev. 255, 2622 (2011).

    Article  CAS  Google Scholar 

  23. M.A. Baldo, D.F. O’Brien, Y. You, A. Shoustikov, S. Sibley, M.E. Thompson, S.R. Forrest, Nature 305, 151 (1998).

    Article  Google Scholar 

  24. R.W.I. d. Boer, M.E. Gershenson, A.F. Morpurgo, V. Podzorov, Phys. Stat. Solid. A 201, 1302 (2004).

    Article  Google Scholar 

  25. S. Tavazzi, M. Campione, M. Laicini, L. Raimondo, A. Borghesi, P. Spearman, J. Chem. Phys. 124, 194710 /1 (2006).

    Article  CAS  Google Scholar 

  26. M.R. Philpott, Ann. Rev. Phys. Chem. 31, 97 (1980).

    Article  CAS  Google Scholar 

  27. M. Baldo, M. Deutsch, P. Burrows, H. Gossenberger, M. Gerstenberg, V. Ban, S. Forrest, Adv. Mater. 10, 1505 (1998).

    Article  CAS  Google Scholar 

  28. H.S. Nalwa, H. Kasai, S. Okada, H. Oikawa, H. Matsuda, A. Kakuta, A. Mukoh, H. Nakanishi, Adv. Mater. 5, 758 (1993).

    Article  CAS  Google Scholar 

  29. E. Kwon, H. Oikawa, H. Kasai, H. Nakanishi, Cryst. Growth Des. 7, 600 (2007).

    Article  CAS  Google Scholar 

  30. T. Asahi, T. Sugiyama, H. Masuhara, Acc. Chem. Res. 41, 1790 (2008).

    Article  CAS  Google Scholar 

  31. S. Kostler, A. Rudorfer, A. Haase, V. Satzinger, G. Jakopic, V. Ribitsch, Adv. Mater. 21, 2505 (2009).

    Article  Google Scholar 

  32. R.M. Hochstrasser, Rev. Mod. Phys. 34, 531 (1962).

    Article  CAS  Google Scholar 

  33. G. Lanzani, S.V. Frolov, P.A. Lane, Z.V. Vardeny, M. Nisoli, S.D. Silvestri, Phys. Rev. Lett. 79, 3066 (1997).

    Article  CAS  Google Scholar 

  34. A. Matsui, J. Opt. Soc. Am. B 7, 1615 (1990).

    Article  CAS  Google Scholar 

  35. T. Yago, Y. Tamaki, A. Furube, R. Katoh, Phys. Chem. Chem. Phys. 10, 4435 (2008).

    Article  CAS  Google Scholar 

  36. J. Tanaka, Bull. Chem. Soc. Jap. 36, 1237 (1963).

    Article  CAS  Google Scholar 

  37. M. Muccini, M. Schneider, C. Taliani, M. Sokolowski, E. Umbach, D. Beljonne, J. Cornil, J. L. Bredas, Phys. Rev. B 62, 6296 (2000).

    Article  CAS  Google Scholar 

  38. E.E. Jelley, Nature 138, 1009 (1936).

    Article  CAS  Google Scholar 

  39. A. Eisfeld, J.S. Briggs, Chem. Phys. 324, 376 (2006).

    Article  CAS  Google Scholar 

  40. R.H. Dicke, Phys. Rev. 93, 99 (1954).

    Article  CAS  Google Scholar 

  41. M.J. Stephen, J. Chem. Phys. 40, 669 (1964).

    Article  CAS  Google Scholar 

  42. F.C. Spano, S. Mukamel, J. Chem. Phys. 91, 683 (1989).

    Article  CAS  Google Scholar 

  43. A. Camposeo, M. Polo, S. Tavazzi, L. Silvestri, P. Spearman, R. Cingolani, D. Pisignano, Phys. Rev. B 81, 033306 /1 (2010).

    Article  Google Scholar 

  44. S.H. Lim, T.G. Bjorklund, F.C. Spano, C.J. Bardeen, Phys. Rev. Lett. 92, 107402 /1 (2004).

    Article  Google Scholar 

  45. M. Voigt, A. Langner, P. Schouwink, J.M. Lupton, R.F. Mahrt, M. Sokolowski, J. Chem. Phys. 127, 114705 /1 (2007).

    Article  CAS  Google Scholar 

  46. F.C. Spano, Acc. Chem. Res. 43, 429 (2010).

    Article  CAS  Google Scholar 

  47. T.S. Ahn, A.M. Muller, R.O. Al-Kaysi, F.C. Spano, J.E. Norton, D. Beljonne, J.L. Brédas, C.J. Bardeen, J. Chem. Phys. 128, 054505 /1 (2008).

    Article  Google Scholar 

  48. F. Meinardi, M. Cerminara, A. Sassella, A. Borghesi, P. Spearman, G. Bongiovanni, A. Mura, R. Tubino, Phys. Rev. Lett. 89, 157403 /1 (2002).

    Article  CAS  Google Scholar 

  49. H. Sun, Z. Zhao, F.C. Spano, D. Beljonne, J. Cornil, Z. Shuai, J.L. Brédas, Adv. Mater. 15, 818 (2003).

    Article  CAS  Google Scholar 

  50. R. Osterbacka, C.P. An, X.M. Jiang, Z.V. Vardeny, Science 287, 839 (2000).

    Article  CAS  Google Scholar 

  51. J. Clark, C. Silva, R.H. Friend, F.C. Spano, Phys. Rev. Lett. 98, 206406 /1 (2007).

    Article  Google Scholar 

  52. J.L. Brédas, J.E. Norton, J. Cornil, V. Coropceanu, Acc. Chem. Res. 42, 1691 (2009).

    Article  Google Scholar 

  53. B.A. Gregg, J. Phys. Chem. B 107, 4688 (2003).

    Article  CAS  Google Scholar 

  54. P. Peumans, S. Uchida, S.R. Forrest, Nature 425, 158 (2003).

    Article  CAS  Google Scholar 

  55. R.R. Lunt, J.B. Benziger, S.R. Forrest, Adv. Mater. 22, 1233 (2010).

    Article  CAS  Google Scholar 

  56. S. Jang, M.D. Newton, R.J. Silbey, Phys. Rev. Lett. 92, 218301 /1 (2004).

    Article  Google Scholar 

  57. E.V. Emelianova, S. Athanasopoulos, R.J. Silbey, D. Beljonne, Phys. Rev. Lett. 104, 206405 /1 (2010).

    Article  CAS  Google Scholar 

  58. G.S. Engel, T.R. Calhoun, E.L. Read, T.K. Ahn, T. Mancal, Y.C. Cheng, R.E. Blankenship, G.R. Fleming, Nature 446, 782 (2007).

    Article  CAS  Google Scholar 

  59. G.D. Scholes, J. Phys. Chem. Lett. 1, 2 (2010).

    Article  CAS  Google Scholar 

  60. T.S. Rose, R. Righini, M.D. Fayer, Chem. Phys. Lett. 106, 13 (1984).

    Article  CAS  Google Scholar 

  61. H. Najafov, B. Lee, Q. Zhou, L.C. Feldman, V. Podzorov, Nat. Mater. 9, 938 (2010).

    Article  CAS  Google Scholar 

  62. R.C. Powell, Z.G. Soos, J. Luminescence 11, 1 (1975).

    Article  CAS  Google Scholar 

  63. D.M. Adams, J. Kerimo, D.B. O’Connor, P.F. Barbara, J. Phys. Chem. A 103, 10138 (1999).

    Article  CAS  Google Scholar 

  64. A.M. Muller, C.J. Bardeen, J. Phys. Chem. C 111, 12483 (2007).

    Article  Google Scholar 

  65. P. Irkhin, I. Biaggio, Phys. Rev. Lett. 107, 017402 /1 (2011).

    Article  Google Scholar 

  66. E.A. Silinsh, H. Inokuchi, Chem. Phys. 149, 373 (1991).

    Article  CAS  Google Scholar 

  67. P. Petelenz, D. Mucha, J. Chem. Phys. 100, 4607 (1994).

    Article  CAS  Google Scholar 

  68. Y. Yi, V. Coropceanu, J.L. Brédas, J. Am. Chem. Soc. 131, 15777 (2009).

    Article  CAS  Google Scholar 

  69. M. Kleinerman, L. Azarraga, S.P. McGlynn, J. Chem. Phys. 37, 1825 (1962).

    Article  CAS  Google Scholar 

  70. K. Hummer, P. Puschnig, C. Ambrosch-Draxl, Phys. Rev. Lett. 92, 147402 /1 (2004).

    Article  Google Scholar 

  71. N. Sai, M.L. Taigo, J.R. Chelikowski, F.A. Reboredo, Phys. Rev. B 77, 161306 /1 (2008).

    Article  Google Scholar 

  72. D. Moses, C. Soci, X. Chi, A.P. Ramirez, Phys. Rev. Lett. 97, 067401/1 (2006).

    Article  Google Scholar 

  73. O. Ostroverkhova, D.G. Cooke, F.A. Hegmann, J.E. Anthony, V. Podzorov, M.E. Gershenson, O.D. Jurchescu, T.T.M. Palstra, Appl. Phys. Lett. 88, 162101 /1 (2006).

    Article  Google Scholar 

  74. V.K. Thorsmolle, R.D. Averitt, X. Chi, D.J. Hilton, D.L. Smith, A.P. Ramirez, A.J. Taylor, Appl. Phys. Lett. 84, 891 (2004).

    Article  CAS  Google Scholar 

  75. G. Horowitz, F. Kouki, P. Valat, P. Delannoy, J. Roussel, Phys. Rev. B 59, 10651 (1999).

    Article  CAS  Google Scholar 

  76. H. Najafov, I. Biaggio, V. Podzorov, M.F. Calhoun, M.E. Gershenson, Phys. Rev. Lett. 96, 056604 /1 (2006).

    Article  Google Scholar 

  77. D.R. Kearns, J. Chem. Phys. 39, 2697 (1963).

    Article  CAS  Google Scholar 

  78. M. Silver, D. Olness, M. Swicord, R.C. Jarnagin, Phys. Rev. Lett. 10, 12 (1963).

    Article  CAS  Google Scholar 

  79. G.H. Gelinck, J.J. Piet, B.R. Wegewijs, K. Mullen, J. Wildeman, G. Hadziioannou, J.M. Warman, Phys. Rev. B 62, 1489 (2000).

    Article  CAS  Google Scholar 

  80. B.I. Greene, R.R. Millard, Phys. Rev. Lett. 55, 1331 (1985).

    Article  CAS  Google Scholar 

  81. D.L. Andrews, D.S. Bradshaw, J. Chem. Phys. 121, 2445 (2004).

    Article  CAS  Google Scholar 

  82. C.A. Parker, C.G. Hatchard, T.A. Joyce, Nature 205, 1282 (1965).

    Article  CAS  Google Scholar 

  83. A. Ryansnyanskiy, I. Biaggio, Phys. Rev. B 84, 193203 /1 (2011).

    Article  Google Scholar 

  84. R.R. Insangulov, D.V. Kozlov, F.N. Castellano, Chem. Commun. (30), 3776 (2005).

  85. S. Baluschev, T. Miteva, V. Yakutkin, G. Nelles, A. Yasuda, G. Wegner, Phys. Rev. Lett. 97, 13903 /1 (2006).

    Google Scholar 

  86. M.B. Smith, J. Michl, Chem. Rev. 110, 6891 (2010).

    Article  CAS  Google Scholar 

  87. S. Singh, W.J. Jones, W. Siebrand, B.P. Stoicheff, W.G. Schneider, J. Chem. Phys. 42, 330 (1965).

    Article  CAS  Google Scholar 

  88. C.E. Swenberg, W.T. Stacy, Chem. Phys. Lett. 2, 327 (1968).

    Article  CAS  Google Scholar 

  89. J.J. Burdett, D. Gosztola, C.J. Bardeen, J. Chem. Phys. 135, 214508/1 (2011).

    Article  Google Scholar 

  90. J.J. Burdett, C.J. Bardeen, J. Am. Chem. Soc. 134, 8597 (2012).

    Article  CAS  Google Scholar 

  91. W.L. Chan, M. Ligges, X.Y. Zhu, Nat. Chem. 4, 840 (2012).

    Article  CAS  Google Scholar 

  92. A. Rao, M.W.B. Wilson, J.M. Hodgkiss, S. Albert-Seifried, H. Bassler, R.H. Friend, J. Am. Chem. Soc. 132, 12698 (2010).

    Article  CAS  Google Scholar 

  93. M.W.B. Wilson, A. Rao, J. Clark, R.S.S. Kumar, D. Brida, G. Cerullo, R.H. Friend, J. Am. Chem. Soc. 133, 11830 (2011).

    Article  CAS  Google Scholar 

  94. W.L. Chan, M. Ligges, A. Jailaubekov, L. Kaake, L. Miaja-Avila, X.Y. Zhu, Science 334, 1541 (2011).

    Article  CAS  Google Scholar 

  95. J.C. Johnson, A.J. Nozik, J. Michl, J. Am. Chem. Soc. 132, 16302 (2010).

    Article  CAS  Google Scholar 

  96. C. Wang, M.J. Tauber, J. Am. Chem. Soc. 132, 13988 (2010).

    Article  CAS  Google Scholar 

  97. G. Lanzani, G. Cerullo, M. Zavelani-Rossi, S.D. Silvestri, Phys. Rev. Lett. 87, 187402 /1 (2001).

    Article  Google Scholar 

  98. I. Paci, J.C. Johnson, X. Chen, G. Rana, D. Popovic, D.E. David, A.J. Nozik, M.A. Ratner, J. Michl, J. Am. Chem. Soc. 128, 16546 (2006).

    Article  CAS  Google Scholar 

  99. P.J. Jadhav, A. Mohanty, J. Sussman, J. Lee, M.A. Baldo, Nano Lett. 11, 1495 (2011).

    Article  CAS  Google Scholar 

  100. B. Ehrler, M.W.B. Wilson, A. Rao, R.H. Friend, N.C. Greenham, Nano Lett. 12, 1053 (2012).

    Article  CAS  Google Scholar 

  101. W. Shockley, H.J. Queisser, J. Appl. Phys. 32, 510 (1961).

    Article  CAS  Google Scholar 

  102. M.C. Hanna, A.J. Nozik, J. Appl. Phys. 100, 074510 /1 (2006).

    Article  Google Scholar 

  103. H. Shpaisman, O. Niitsoo, I. Lubomirsky, D. Cahen, Sol. Energy Mater. Sol. Cells 92, 1541 (2008).

    Article  CAS  Google Scholar 

  104. S. Liu, W.M. Wang, A.L. Briseno, S.C.B. Mannsfeld, Z. Bao, Adv. Mater. 21, 1217 (2009).

    Article  CAS  Google Scholar 

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Acknowledgment

This work was supported by the National Science Foundation under Grant CHE-1152677.

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  1. Department of Chemistry, University of California, Riverside, USA

    Christopher J. Bardeen

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Bardeen, C.J. Excitonic processes in molecular crystalline materials. MRS Bulletin 38, 65–71 (2013). https://doi.org/10.1557/mrs.2012.312

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