journal article·2018-03-28Open access

Graphene wrinkle effects on molecular resonance states

Peter N. Nirmalraj, Kishan Thodkar, Sarah Guerin, Michel Calame, Damien Thompson

Abstract

Abstract Wrinkles are a unique class of surface corrugations present over diverse length scales from Kinneyia-type wrinkles in Archean-era sedimentary fossils to nanoscopic crinkling in two-dimensional crystals. Lately, the role of wrinkles on graphene has been subject to debate as devices based on graphene progress towards commercialization. While the topology and electronic structure of graphene wrinkles is known, data on wrinkle geometrical effects on molecular adsorption patterns and resonance states is lacking. Here, we report molecular superstructures and enhancement of free-molecular electronic states of pentacene on graphene wrinkles. A new trend is observed where the pentacene energy gap scales with wrinkle height, as wrinkles taller than 2 nm significantly screen metal induced hybridization. Combined with density functional theory calculations, the impact of wrinkles in tuning molecular growth modes and electronic structure is clarified at room-temperature. These results suggest the need to rethink wrinkle engineering in modular devices based on graphene and related 2D materials interfacing with electronically active molecules.
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Research context

OpenAlex topics: Graphene research and applications · Advanced Materials and Mechanics · 2D Materials and Applications

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References (73)

Show source-provided references
1. Tapaszto, L. et al. Breakdown of continuum mechanics for nanometre-wavelength rippling of graphene. Nat. Phys. 8, 739–742 (2012).10.1038/nphys2389 ↗
2. Zhu, W. et al. Structure and electronic transport in graphene wrinkles. Nano Lett. 12, 3431–3436 (2012).10.1021/nl300563h ↗
3. Zang, J. et al. Multifunctionality and control of the crumpling and unfolding of large-area graphene. Nat. Mater. 12, 321–325 (2013).10.1038/nmat3542 ↗
4. Banhart, F., Kotakoski, J. & Krasheninnikov, A. V. Structural defects in graphene. ACS Nano 5, 26–41 (2011).10.1021/nn102598m ↗
5. Yu, Q. et al. Control and characterization of individual grains and grain boundaries in graphene grown by chemical vapour deposition. Nat. Mater. 10, 443–449 (2011).10.1038/nmat3010 ↗
6. Deng, S. & Berry, V. Wrinkled, rippled and crumpled graphene: an overview of formation mechanism, electronic properties, and applications. Mater. Today 19, 197–212 (2016).10.1016/j.mattod.2015.10.002 ↗
7. Cerda, E. & Mahadevan, L. Geometry and physics of wrinkling. Phys. Rev. Lett. 90, 074302 (2003).10.1103/PhysRevLett.90.074302 ↗
8. Nicholl, R. J. T. et al. The effect of intrinsic crumpling on the mechanics of free-standing graphene. Nat Commun. 6, 8789 (2015).10.1038/ncomms9789 ↗
9. Verma, A. & Parashar, A. The effect of STW defects on the mechanical properties and fracture toughness of pristine and hydrogenated graphene. Phys. Chem. Chem. Phys. 19, 16023–16037 (2017).10.1039/C7CP02366A ↗
10. Kim, K. S. et al. Large-scale pattern growth of graphene films for stretchable transparent electrodes. Nature 457, 706–710 (2009).10.1038/nature07719 ↗
11. Bao, W. et al. Controlled ripple texturing of suspended graphene and ultrathin graphite membranes. Nat. Nano 4, 562–566 (2009).10.1038/nnano.2009.191 ↗
12. Eun-Ah, K. & Neto, A. H. C. Graphene as an electronic membrane. EPL 84, 57007 (2008).10.1209/0295-5075/84/57007 ↗
13. Guinea, F., Katsnelson, M. I. & Vozmediano, M. A. H. Midgap states and charge inhomogeneities in corrugated graphene. Phys. Rev. B 77, 075422 (2008).10.1103/PhysRevB.77.075422 ↗
14. Zurutuza, A. & Marinelli, C. Challenges and opportunities in graphene commercialization. Nat. Nano 9, 730–734 (2014).10.1038/nnano.2014.225 ↗
15. Liu, Z. et al. The application of highly doped single-layer graphene as the top electrodes of semitransparent organic solar cells. ACS Nano 6, 810–818 (2012).10.1021/nn204675r ↗
16. Seo, S., Min, M., Lee, S. M. & Lee, H. Photo-switchable molecular monolayer anchored between highly transparent and flexible graphene electrodes. Nat. Commun. 4, 1920 (2013).10.1038/ncomms2937 ↗
17. Zhang, Q. et al. Graphene as a promising electrode for low-current attenuation in nonsymmetric molecular junctions. Nano Lett. 16, 6534–6540 (2016).10.1021/acs.nanolett.6b03180 ↗
18. Nef, C. et al. High-yield fabrication of nm-size gaps in monolayer CVD graphene. Nanoscale 6, 7249–7254 (2014).10.1039/C4NR01838A ↗
19. El Abbassi, M. et al. From electroburning to sublimation: substrate and environmental effects in the electrical breakdown process of monolayer graphene. Nanoscale 9, 17312–17317 (2017).10.1039/C7NR05348G ↗
20. Pósa, L. et al. Multiple physical time scales and dead time rule in few-nanometers sized graphene–siox-graphene memristors. Nano Lett. 17, 6783–6789 (2017).10.1021/acs.nanolett.7b03000 ↗
21. Prins, F. et al. Room-temperature gating of molecular junctions using few-layer graphene nanogap electrodes. Nano Lett. 11, 4607–4611 (2011).10.1021/nl202065x ↗
22. Martinez, A., Fuse, K. & Yamashita, S. Mechanical exfoliation of graphene for the passive mode-locking of fiber lasers. Appl. Phys. Lett. 99, 121107 (2011).10.1063/1.3641419 ↗
23. Cho, J. et al. Structural and electronic decoupling of C60 from epitaxial graphene on SiC. Nano Lett. 12, 3018–3024 (2012).10.1021/nl3008049 ↗
24. Kiraly, B. et al. Solid-source growth and atomic-scale characterization of graphene on Ag(111). Nat. Commun. 4, 2804 (2013).10.1038/ncomms3804 ↗
25. Wu, R. et al. Quasi-free-standing graphene nano-islands on Ag(110), grown from solid carbon source. Appl. Phys. Lett. 110, 213107 (2017).10.1063/1.4984093 ↗
26. Wan, X., Chen, K. & Xu, J. Interface engineering for CVD graphene: current status and progress. Small 10, 4443–4454 (2014).10.1002/smll.201401458 ↗
27. Wu, X. et al. Growth of continuous monolayer graphene with millimeter-sized domains using industrially safe conditions. Sci. Rep. 6, 21152 (2016).10.1038/srep21152 ↗
28. Lara-Avila, S. et al. Non-volatile photochemical gating of an epitaxial graphene/polymer heterostructure. Adv. Mater. 23, 878–882 (2011).10.1002/adma.201003993 ↗
29. Li, X. et al. Large-area synthesis of high-quality and uniform graphene films on copper foils. Science 324, 1312–1314 (2009).10.1126/science.1171245 ↗
30. Wan, X. et al. High-quality large-area graphene from dehydrogenated polycyclic aromatic hydrocarbons. Chem. Mater. 24, 3906–3915 (2012).10.1021/cm301993z ↗
31. Lee, Y. et al. Wafer-scale synthesis and transfer of graphene films. Nano Lett. 10, 490–493 (2010).10.1021/nl903272n ↗
32. Wang, Q. H. & Hersam, M. C. Room-temperature molecular-resolution characterization of self-assembled organic monolayers on epitaxial graphene. Nat. Chem. 1, 206–211 (2009).10.1038/nchem.212 ↗
33. Jung, M. et al. Atomically resolved orientational ordering of C60 molecules on epitaxial graphene on Cu(111). Nanoscale 6, 11835–11840 (2014).10.1039/C4NR03249G ↗
34. MacLeod, J. M. & Rosei, F. Molecular self-assembly on graphene. Small 10, 1038–1049 (2014).10.1002/smll.201301982 ↗
35. Pshenichnyuk, I. A., Coto, P. B., Leitherer, S. & Thoss, M. Charge transport in pentacene–graphene nanojunctions. J. Phys. Chem. Lett. 4, 809–814 (2013).10.1021/jz400025q ↗
36. Pacakova, B. et al. Mastering the wrinkling of self-supported graphene. Sci. Rep. 7, 10003 (2017).10.1038/s41598-017-10153-z ↗
37. Gehring, P. et al. Distinguishing lead and molecule states in graphene-based single-electron transistors. ACS Nano 11, 5325–5331 (2017).10.1021/acsnano.7b00570 ↗
38. Ahn, E. & Kim, B.-S. Multidimensional thin film hybrid electrodes with MoS2 multilayer for electrocatalytic hydrogen evolution reaction. ACS Appl. Mater. Interfaces 9, 8688–8695 (2017).10.1021/acsami.6b15251 ↗
39. Nirmalraj, P. N., Lutz, T., Kumar, S., Duesberg, G. S. & Boland, J. J. Nanoscale mapping of electrical resistivity and connectivity in graphene strips and networks. Nano Lett. 11, 16–22 (2011).10.1021/nl101469d ↗
40. Wang, W., Yang, S. & Wang, A. Observation of the unexpected morphology of graphene wrinkle on copper substrate. Sci. Rep. 7, 8244 (2017).10.1038/s41598-017-08159-8 ↗
41. Chae, S. J. et al. Synthesis of large-area graphene layers on poly-nickel substrate by chemical vapor deposition: wrinkle formation. Adv. Mater. 21, 2328–2333 (2009).10.1002/adma.200803016 ↗
42. Xu, K., Cao, P. & Heath, J. R. Scanning tunneling microscopy characterization of the electrical properties of wrinkles in exfoliated graphene monolayers. Nano Lett. 9, 4446–4451 (2009).10.1021/nl902729p ↗
43. Bettis Homan, S. et al. Ultrafast exciton dissociation and long-lived charge separation in a photovoltaic pentacene–MoS2 van der Waals heterojunction. Nano Lett. 17, 164–169 (2017).10.1021/acs.nanolett.6b03704 ↗
44. Chhikara, M., Pavlica, E. & Bratina, G. Grafold-driven nucleation of pentacene on graphene. Surf. Sci. 609, L5–L8 (2013).10.1016/j.susc.2012.11.001 ↗
45. Khokhar, F. S. et al. The influence of substrate temperature on growth of para-sexiphenyl thin films on Ir{111} supported graphene studied by LEEM. Surf. Sci. 606, 475–480 (2012).10.1016/j.susc.2011.11.012 ↗
46. Zhang, B. et al. Low-temperature chemical vapor deposition growth of graphene from toluene on electropolished copper foils. ACS Nano 6, 2471–2476 (2012).10.1021/nn204827h ↗
47. Kaur, I. et al. Substituent effects in pentacenes: gaining control over HOMO−LUMO gaps and photooxidative resistances. J. Am. Chem. Soc. 130, 16274–16286 (2008).10.1021/ja804515y ↗
48. Zhang, G. & Musgrave, C. B. Comparison of DFT methods for molecular orbital eigenvalue calculations. J. Phys. Chem. A 111, 1554–1561 (2007).10.1021/jp061633o ↗
49. Faber, C., Boulanger, P., Attaccalite, C., Duchemin, I. & Blase, X. Excited states properties of organic molecules: from density functional theory to the GW and Bethe–SalpeterGreen’s function formalisms. Philos. Trans. R. Soc. A 372, 20130271 (2014).10.1098/rsta.2013.0271 ↗
50. Koslowski, S. et al. Adsorption and electronic properties of pentacene on thin dielectric decoupling layers. Beilstein J. Nanotechnol. 8, 1388–1395 (2017).10.3762/bjnano.8.140 ↗
51. Repp, J., Meyer, G., Stojković, S. M., Gourdon, A. & Joachim, C. Molecules on Insulating films: scanning-tunneling microscopy imaging of individual molecular orbitals. Phys. Rev. Lett. 94, 026803 (2005).10.1103/PhysRevLett.94.026803 ↗
52. Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132, 154104 (2010).10.1063/1.3382344 ↗
53. Thodkar, K. et al. Restoring the electrical properties of CVD graphene via physisorption of molecular adsorbates. ACS Appl. Mater. Interfaces 9, 25014–25022 (2017).10.1021/acsami.7b05143 ↗
54. Zhang, Y. et al. Probing carrier transport and structure-property relationship of highly ordered organic semiconductors at the two-dimensional limit. Phys. Rev. Lett. 116, 016602 (2016).10.1103/PhysRevLett.116.016602 ↗
55. Lin, Z. et al. Controllable growth of large–size crystalline MoS2 and resist-free transfer assisted with a Cu thin film. Scientific Reports 5, 18596 (2015).10.1038/srep18596 ↗
56. Maassen, J., Ji, W. & Guo, H. First principles study of electronic transport through a Cu (111)∣ graphene junction. Appl. Phys. Lett. 97, 142105 (2010).10.1063/1.3496490 ↗
57. Ferretti, A. et al. Mixing of electronic states in pentacene adsorption on copper. Phys. Rev. Lett. 99, 046802 (2007).10.1103/PhysRevLett.99.046802 ↗
58. Xu, Z. & Buehler, M. J. Interface structure and mechanics between graphene and metal substrates: a first-principles study. J. Phys. Condens. Matter 22, 485301 (2010).10.1088/0953-8984/22/48/485301 ↗
59. Toyoda, K. et al. First-principles study of the pentacene/Cu (111) interface: adsorption states and vacuum level shifts. J. Electron Spectrosc. Relat. Phenom. 174, 78–84 (2009).10.1016/j.elspec.2009.04.005 ↗
60. Toyoda, K., Hamada, I., Lee, K., Yanagisawa, S. & Morikawa, Y. Density functional theoretical study of pentacene/noble metal interfaces with van der Waals corrections: vacuum level shifts and electronic structures. J. Chem. Phys. 132, 134703 (2010).10.1063/1.3373389 ↗
61. Lagoute, J., Kanisawa, K. & Fölsch, S. Manipulation and adsorption-site mapping of single pentacene molecules on Cu (111). Phys. Rev. B 70, 245415 (2004).10.1103/PhysRevB.70.245415 ↗
62. Smerdon, J., Bode, M., Guisinger, N. & Guest, J. Monolayer and bilayer pentacene on Cu (111). Phys. Rev. B 84, 165436 (2011).10.1103/PhysRevB.84.165436 ↗
63. Paramonov, P. B., Coropceanu, V. & Brédas, J.-L. Electronic and vibronic interactions at weakly bound organic interfaces: The case of pentacene on graphite. Phys. Rev. B 78, 041403 (2008).10.1103/PhysRevB.78.041403 ↗
64. Vanin, M. et al. Graphene on metals: a van der Waals density functional study. Phys. Rev. B 81, 081408 (2010).10.1103/PhysRevB.81.081408 ↗
65. Giovannetti, G. et al. Doping graphene with metal contacts. Phys. Rev. Lett. 101, 026803 (2008).10.1103/PhysRevLett.101.026803 ↗
66. Chen, W., Huang, H., Thye, A. & Wee, S. Molecular orientation transition of organic thin films on graphite: the effect of intermolecular electrostatic and interfacial dispersion forces. Chem. Commun. 4276–4278 (2008).10.1039/b805788e ↗
67. Lee, W. H. et al. Surface-directed molecular assembly of pentacene on monolayer graphene for high-performance organic transistors. J. Am. Chem. Soc. 133, 4447–4454 (2011).10.1021/ja1097463 ↗
68. Bae, S.-H. et al. Unveiling the carrier transport mechanism in epitaxial graphene for forming wafer-scale, single-domain graphene. Proc. Natl Acad. Sci. 114, 4082–4086 (2017).10.1073/pnas.1620176114 ↗
69. Thodkar, K. et al. Comparative study of single and multi domain CVD graphene using large-area Raman mapping and electrical transport characterization. Phys. Status Solidi 10, 807–811 (2016).10.1002/pssr.201600211 ↗
70. Nirmalraj, P. et al. Nanoelectrical analysis of single molecules and atomic-scale materials at the solid/liquid interface. Nat. Mater. 13, 947–953 (2014).10.1038/nmat4060 ↗
71. Schneir, J. & Hansma, P. K. Scanning tunneling microscopy and lithography of solid surfaces covered with nonpolar liquids. Langmuir 3, 1025–1027 (1987).10.1021/la00078a025 ↗
72. Schneir, J. et al. Scanning tunneling microscopy and atomic force microscopy of the liquid–solid interface. J. Vac. Sci. Technol. A 6, 283–286 (1988).10.1116/1.575426 ↗
73. Nirmalraj, P. et al. Fingerprinting electronic molecular complexes in liquid. Sci. Rep. 6, 19009 (2016).10.1038/srep19009 ↗