Chun-sheng Zhou, Huan Shan, Bin Li, Ai-di Zhao. Imaging Molecular Orbitals of Single Picene Molecules Adsorbed on Cu(111) Surface: a Combined Experimental and Theoretical Study[J]. Chinese Journal of Chemical Physics , 2017, 30(1): 29-35. doi: 10.1063/1674-0068/30/cjcp1606123
Citation: Chun-sheng Zhou, Huan Shan, Bin Li, Ai-di Zhao. Imaging Molecular Orbitals of Single Picene Molecules Adsorbed on Cu(111) Surface: a Combined Experimental and Theoretical Study[J]. Chinese Journal of Chemical Physics , 2017, 30(1): 29-35. doi: 10.1063/1674-0068/30/cjcp1606123

Imaging Molecular Orbitals of Single Picene Molecules Adsorbed on Cu(111) Surface: a Combined Experimental and Theoretical Study

doi: 10.1063/1674-0068/30/cjcp1606123
  • Received Date: 2016-06-08
  • Rev Recd Date: 2016-08-04
  • Picene, which attracts the great interest of researchers, not only can be used to fabricate thin film transistors with high hole mobilities, but also is the parent material of a new type organic superconductor. Here, we investigate the electronic properties of individual picene molecules directly adsorbed on Cu(111) surface by a combination of experimental scanning tunneling microscopy/spectroscopy measurements and theoretical calculations based on the density functional theory. At low coverage, the picene molecules exhibit mono-dispersed adsorption behavior with the benzene ring planes parallel to the surface. The highest occupied state around-1.2 V and the lowest unoccupied state around 1.6 V with an obvious energy gap of the singly adsorbed picene molecule are identified by the dI/dV spectra and maps. In addition, we observe the strong dependence of the dI/dV signal of the unoccupied states on the intramolecular positions. Our first-principles calculations reproduce the above experimental results and interpret them as a specific molecule-substrate interaction and energy/spatial distributions of hybrid states mainly derived from different molecular orbitals of picene with some intermixing between them. This work provides direct information on the local electronic structure of individual picene on a metallic substrate and will facilitate the understanding the dependence of electron transport properties on the coupling between molecules and metal electrodes in single-molecule devices.
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  • [1] M. Perrin, E. Burzurí, and H. S. J. van der Zant, Chem. Soc. Rev. 44, 902(2015).
    [2] K. Moth-Poulsen and T. Bjørnholm, Nat. Nanotechnol. 4, 551(2009).
    [3] E. Goiri, P. Borghetti, A. El-Sayed, J. Enrique Ortega, and D. G. de Oteyza, Adv. Mater. 28, 1340(2016).
    [4] J. Repp, G. Meyer, S. M. Stojković, A. Gourdon, and C. Joachim, Phys. Rev. Lett. 94, 026803(2005).
    [5] W. H. Soe, C. Manzano, A. De Sarkar, N. Chandrasekhar, and C. Joachim, Phys. Rev. Lett. 102, 176102(2009).
    [6] J. B. Neaton, M. S. Hybertsen, and S. G. Louie, Phys. Rev. Lett. 97, 216405(2006).
    [7] X. Lu, M. Grobis, K. H. Khoo, S. G. Louie, and M. F. Crommie, Phys. Rev. Lett. 90, 096802(2003).
    [8] K. Wang, J. Zhao, S. Yang, L. Chen, Q. Li, B. Wang, S. Yang, J. G. Hou, and Q. Zhu, Phys. Rev. Lett. 91, 185504(2003).
    [9] X. Lu, M. Grobis, K. H. Khoo, S. G. Louie, and M. F. Crommie, Phys. Rev. B 70, 115418(2004).
    [10] M. Feng, J. Zhao, and H. Petek, Science 320, 359(2008).
    [11] S. Müllegger, W. Schöfberger, M. Rashidi, L. M. Reith, and R. Koch, J. Am. Chem. Soc. 131, 17740(2009).
    [12] H. Okamoto, N. Kawasaki, Y. Kaji, Y. Kubozono, A. Fujiwara, and M. Yamaji, J. Am. Chem. Soc. 130, 10470(2008).
    [13] N. Kawasaki, Y. Kubozono, H. Okamoto, A. Fujiwara, and M. Yamaji, Appl. Phys. Lett. 94, 043310(2009).
    [14] Y. Kaji, N. Kawasaki, X. Lee, H. Okamoto, Y. Sugawara, S. Oikawa, A. Ito, H. Okazaki, T. Yokoya, A. Fujiwara, and Y. Kubozono, Appl. Phys. Lett. 95, 183302(2009).
    [15] Y. Kaji, R. Mitsuhashi, X. Lee, H. Okamoto, T. Kambe, N. Ikeda, A. Fujiwara, M. Yamaji, K. Omote, and Y. Kubozono, Org. Electron. 10, 432(2009).
    [16] N. Kawasaki, W. L. Kalb, T. Mathis, Y. Kaji, R. Mitsuhashi, H. Okamoto, Y. Sugawara, A. Fujiwara, Y. Kubozono, and B. Batlogg, Appl. Phys. Lett. 96, 113305(2010).
    [17] Y. Sugawara, Y. Kaji, K. Ogawa, R. Eguchi, S. Oikawa, H. Gohda, A. Fujiwara, and Y. Kubozono, Appl. Phys. Lett. 98, 013303(2011).
    [18] N. Komura, H. Goto, X. He, H. Mitamura, R. Eguchi, Y. Kaji, H. Okamoto, Y. Sugawara, S. Gohda, K. Sato, and Y. Kubozono, Appl. Phys. Lett. 101, 083301(2012).
    [19] N. Kawai, R. Eguchi, H. Goto, K. Akaike, Y. Kaji, T. Kambe, A. Fujiwara, and Y. Kubozono, J. Phys. Chem. C 116, 7983(2012).
    [20] X. He, R. Eguchi, H. Goto, E. Uesugi, S. Hamao, Y. Takabayashi, and Y. Kubozono, Org. Electron. 14, 1673(2013).
    [21] R. Mitsuhashi, Y. Suzuki, Y. Yamanari, H. Mitamura, T. Kambe, N. Ikeda, H. Okamoto, A. Fujiwara, M. Yamaji, N. Kawasaki, Y. Maniwa, and Y. Kubozono, Nature 464, 76(2010).
    [22] Y. Kubozono, H. Mitamura, X. Lee, X. He, Y. Yamanari, Y. Takahashi, Y. Suzuki, Y. Kaji, R. Eguchi, K. Akaike, T. Kambe, H. Okamoto, A. Fujiwara, T. Kato, T. Kosugi, and H. Aoki, Phys. Chem. Chem. Phys. 13, 16476(2011).
    [23] X. F. Wang, R. H. Liu, Z. Gui, Y. L. Xie, Y. J. Yan, J. J. Ying, X. G. Luo, and X. H. Chen, Nat. Commun. 2, 507(2011).
    [24] X. F. Wang, Y. J. Yan, Z. Gui, R. H. Liu, J. J. Ying, X. G. Luo, and X. H. Chen, Phys. Rev. B 84, 214523(2011).
    [25] X. F. Wang, X. G. Luo, J. J. Ying, Z. J. Xiang, S. L. Zhang, R. R. Zhang, Y. H. Zhang, Y. J. Yan, A. F. Wang, P. Cheng, G. J. Ye, and X. H. Chen, J. Phys:Condens. Matter 24, 345701(2012).
    [26] M. Xue, T. Cao, D. Wang, Y. Wu, H. Yang, X. Dong, J. He, F. Li, and G. F. Chen, Sci. Rep. 2, 389(2012).
    [27] Q. Xin, S. Duhm, F. Bussolotti, K. Akaike, Y. Kubozono, H. Aoki, T. Kosugi, S. Kera, and N. Ueno, Phys. Rev. Lett. 108, 226401(2012).
    [28] H. Okazaki, T. Wakita, T. Muro, Y. Kaji, X. Lee, H. Mitamura, N. Kawasaki, Y. Kubozono, Y. Yamanari, T. Kambe, T. Kato, M. Hirai, Y. Muraoka, and T. Yokoya, Phys. Rev. B 82, 195114(2010).
    [29] F. Roth, B. Mahns, B. Büchner, and M. Knupfer, Phys. Rev. B 83, 144501(2011).
    [30] A. Ruff, M. Sing, R. Claessen, H. Lee, M. Tomić, H. O. Jeschke, and R. Valent, Phys. Rev. Lett. 110, 216403(2013).
    [31] T. Kato, T. Kambe, and Y. Kubozono, Phys. Rev. Lett. 107, 077001(2011).
    [32] M. Casula, M. Calandra, G. Profeta, and F. Mauri, Phys. Rev. Lett. 107, 137006(2011).
    [33] M. Kim, B. I. Min, G. Lee, H. J. Kwon, Y. M. Rhee, and J. H. Shim, Phys. Rev. B 83, 214510(2011).
    [34] T. Kosugi, T. Miyake, S. Ishibashi, R. Arita, and H. Aoki, Phys. Rev. B 84, 214506(2011).
    [35] Y. Yoshida, H. Yang, H. Huang, S. Guan, S. Yanagisawa, T. Yokosuka, M. Lin, W. Su, C. Chang, G. Hoffmann, and Y. Hasegawa, J. Chem. Phys. 141, 114701(2014).
    [36] C. Zhou, H. Shan, B. Li, A. Zhao, and B. Wang, Appl. Phys. Lett. 108, 171601(2016).
    [37] J. P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett. 77, 3865(1996).
    [38] B. Delley, J. Chem. Phys. 113, 7756(2000).
    [39] W. Kohn and L. J. Sham, Phys. Rev. 140, A1133(1965).
    [40] L. J. Sham and W. Kohn, Phys. Rev. 145, 561(1966).
    [41] A. Tkatchenko and M. Scheffler, Phys. Rev. Lett. 102, 073005(2009).
    [42] D. R. Hamann, M. Schluter, and C. Chiang, Phys. Rev. Lett. 43, 1494(1979).
    [43] J. Tersoff and D. R. Hamann, Phys. Rev. Lett. 50, 1998(1983).
    [44] J. Tersoff and D. R. Hamann, Phys. Rev. B 31, 805(1985).
    [45] J. Kliewer, R. Berndt, E. V. Chulkov, V. M. Silkin, P. M. Echenique, and S. Crampin, Science 288, 1399(2000).
    [46] L. Scudiero, D. E. Barlow, U. Mazur, and K. W. Hipps, J. Am. Chem. Soc. 123, 4073(2001).
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Imaging Molecular Orbitals of Single Picene Molecules Adsorbed on Cu(111) Surface: a Combined Experimental and Theoretical Study

doi: 10.1063/1674-0068/30/cjcp1606123

Abstract: Picene, which attracts the great interest of researchers, not only can be used to fabricate thin film transistors with high hole mobilities, but also is the parent material of a new type organic superconductor. Here, we investigate the electronic properties of individual picene molecules directly adsorbed on Cu(111) surface by a combination of experimental scanning tunneling microscopy/spectroscopy measurements and theoretical calculations based on the density functional theory. At low coverage, the picene molecules exhibit mono-dispersed adsorption behavior with the benzene ring planes parallel to the surface. The highest occupied state around-1.2 V and the lowest unoccupied state around 1.6 V with an obvious energy gap of the singly adsorbed picene molecule are identified by the dI/dV spectra and maps. In addition, we observe the strong dependence of the dI/dV signal of the unoccupied states on the intramolecular positions. Our first-principles calculations reproduce the above experimental results and interpret them as a specific molecule-substrate interaction and energy/spatial distributions of hybrid states mainly derived from different molecular orbitals of picene with some intermixing between them. This work provides direct information on the local electronic structure of individual picene on a metallic substrate and will facilitate the understanding the dependence of electron transport properties on the coupling between molecules and metal electrodes in single-molecule devices.

Chun-sheng Zhou, Huan Shan, Bin Li, Ai-di Zhao. Imaging Molecular Orbitals of Single Picene Molecules Adsorbed on Cu(111) Surface: a Combined Experimental and Theoretical Study[J]. Chinese Journal of Chemical Physics , 2017, 30(1): 29-35. doi: 10.1063/1674-0068/30/cjcp1606123
Citation: Chun-sheng Zhou, Huan Shan, Bin Li, Ai-di Zhao. Imaging Molecular Orbitals of Single Picene Molecules Adsorbed on Cu(111) Surface: a Combined Experimental and Theoretical Study[J]. Chinese Journal of Chemical Physics , 2017, 30(1): 29-35. doi: 10.1063/1674-0068/30/cjcp1606123
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