Abstract
An ab initio approach was utilized to explore the electronic transport properties of 4′-thiolate-biphenyl-4-dithiocarboxylate (TBDT) sandwiched between two electrodes made of various materials X (X = Cu, Ag, and Au). Analysis of current–voltage (I–V) characteristics, rectification performance, transmission functions, and the projected density of states (PDOS) under various external voltage biases showed that the transport properties of these constructed systems are markedly impacted by the choice of electrode materials. Further, Cu electrodes yield the best rectifying behavior, followed by Ag and then Au electrodes. Interestingly, the rectification effects can be tuned by changing the torsion angle between the two phenyl rings, as well as by stretching the contact distances between the end group and the electrodes. For Cu, the maximum rectifying ratio increases by 37 % as the contact distance changes from 1.7 Å to 1.9 Å. This is due to an increase in coupling strength asymmetry between the molecule and the electrodes. Our findings are compared with the results reported for other systems. The present calculations are helpful not only for predicting the optimal electrode material for practical applications but also for achieving better control over rectifying performance in molecular devices.
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References
Nitzan A, Ratner MA (2003) Electron transport in molecular wire junctions. Science 300:1384–1389. doi:10.1126/science.1081572
Halbritter A, Csonka S, Mihaly G, Jurdik E, Kolesnychenko OY, Shklyarevskii OI, Speller S, van Kempen H (2003) Transition from tunneling to direct contact in tungsten nanojunctions. Phys Rev B 68:035417. doi:10.1103/PhysRevB.68.035417
Ulman A (1996) Formation and structure of self-assembled monolayers. Chem Rev 96:1533–1554. doi:10.1021/cr9502357
Reed MA, Zhou C, Muller CJ, Burgin TP, Tour JM (1997) Conductance of a molecular junction. Science 278:25–2254. doi:10.1126/science.278.5336.252
Chen J, Reed MA, Rawlett AM, Tour JM (1999) Large on-off ratios and negative differential resistance in molecular electronic device. Science 286:1550–1552. doi:10.1126/science.286.5444.1550
Aviram A, Ratner MA (1974) Molecular rectifiers. Chem Phys Lett 29:277–283. doi:10.1016/0009-2614(74)85031-1, DOI:10.1016/0009-2614(74)85031-1
Metzger RM (2003) Unimolecular electrical rectifiers. Chem Rev 103:3803–3834. doi:10.1021/cr020413d
Zeng J, Chen KQ, He J, Zhang XJ, Sun CQ (2011) Edge hydrogenation-induced spin-filtering and rectifying behaviors in graphene nanoribbon heterojunctions. J Phys Chem C 115:25072–25076. doi:10.1021/jp208248v
Du Y, Pan H, Wang S, Wu T, Feng YP, Pan J, Wee ATS (2012) Symmetrical negative differential resistance behavior of a resistive switching device. ACS Nano 6:2517–2523. doi:10.1021/nn204907t
Zheng X, Lu W, Abtew TA, Meunier V, Bernholc J (2010) Negative differential resistance in C60-based electronic devices. ACS Nano 4:7205–7210. doi:10.1021/nn101902r
Zeng J, Chen KQ, He J, Zhang XJ, Hu WP (2011) Rectifying and successive switch behaviors induced by weak intermolecular interaction. Org Electron 12:1606–1611. doi:10.1016/j.orgel.2011.06.010, DOI:10.1016/j.orgel.2011.06.010
Poirier GE, Pylant ED (1996) The self-assembly mechanism of alkanedithiols on Au(111). Science 272:1145–1148. doi:10.1126/science.272.5265.1145
Hong JP, Park AY, Lee S, Kang J, Shin N, Yoon DY (2008) Tuning of Ag work functions by self-assembled monolayers of aromatic thiols for an efficient hole injection for solution processed triisopropylsilylethynyl pentacene organic thin film transistors. Appl Phys Lett 92:143311. doi:10.1063/1.2907691
Matsushita R, Kaneko S, Nakazumi T, Kinguchi M (2011) Effect of metal–molecule contact on electron-vibration interaction in single hydrogen molecule junction. Phys Rev B 84:245412. doi:10.1103/PhysRevB.84.245412
Meng FX, Ming C, Zhuang J, Ning XJ (2013) Dependence of electronic rectification in carbon nanocone devices upon electrode materials. J Phys D Appl Phys 46:055309. doi:10.1088/0022-3727/46/5/055309
Yaliraki SN, Kemp M, Ratner MA (1999) Conductance of molecular wires: influence of molecule-electrode binding. J Am Chem Soc 121:3428–3434. doi:10.1021/ja982918k
Kondo H, Nara J, Kino H, Ohno T (2009) Transport properties of a biphenyl-based molecular junction system—the electrode metal dependence. J Phys Condens Matter 21:064220. doi:10.1088/0953-8984/21/6/064220
Taylor J, Brandbyge M, Stokbro K (2002) Theory of rectification in tour wires: the role of electrode coupling. Phys Rev Lett 89:138301. doi:10.1103/PhysRevLett.89.138301
Venkataraman L, Klare JE, Nuckolls C, Hybertsen MS, Steigerwald ML (2006) Dependence of single-molecule junction conductance on molecular conformation. Nature (London) 442:904–907. doi:10.1038/nature05037
Burkle M, Viljas JK, Vonlanthen D, Mishchenko A, Schon G, Mayor M, Wandlowski T, Pauly F (2012) Conductance mechanisms in biphenyl dithiol single-molecule junctions. Phys Rev B 85:075417. doi:10.1103/PhysRevB.85.075417
Wang LH, Guo Y, Tian CF, Song XP, Ding BJ (2010) Torsion angle dependence of the rectifying performance in molecular device with asymmetrical anchoring groups. Phys Lett A 374:4876–4879. doi:10.1016/j.physleta.2010.09.068
Li Z, Kosov DS (2006) Orbital interaction mechanisms of conductance enhancement and rectification by dithiocaboxylate anchoring group. J Phys Chem B 110:19116–19120. doi:10.1021/jp065120t
QuantumWise A/S (2011) AtomistixToolKit version 2011.2.8 (http://quantumwise.com)
Wang YF, Kroger J, Berndt R, Vazquez H, Brandbyge M, Paulsson M (2010) Atomic-scale control of electron transport through single molecules. Phys Rev Lett 104:176802. doi:10.1103/PhysRevLett.104.176802
Lindsay SM, Ratner MA (2007) Molecular transport junctions: clearing mists. Adv Mater 19:23–31. doi:10.1002/adma.200601140
Landauer R (1970) Electrical resistance of disordered one-dimensional lattices. Philos Mag 21:863–867. doi:10.1080/14786437008238472
Buttiker M (1986) Four-terminal phase-coherent conductance. Phys Rev Lett 57:1761. doi:10.1103/PhysRevLett57.1761
George CB, Ratner MA, Lambert JB (2009) Strong conductance in conformationally constrained oligosilane tunnel junctions. J Phys Chem A 113:3876–3880. doi:10.1021/jp809963r
Perdew JP, Zunger A (1981) Self-interaction correction to density-functional approximations for many-electron systems. Phys Rev B 23:5048–5079. doi:10.1103/PhysRevB.23.5048
Gonzalez MT, Wu S, Huber R, Wolen SJVD, Schonenberger C, Calame M (2006) Electrical conductance of molecular junctions by a robust statistical analysis. Nano Lett 6:2238–2242. doi:10.1021/nl061581e
Geng WT, Nara J, Ohno T (2004) Adsorption of benzene thiolate on the (111) surface of M (M = Pt, Ag, Cu) and the conductance of M/benzene dithiolate/M molecular junctions: a first-principles study. Thin Solid Films 464:379–383. doi:10.1016/j.tsf.2004.06.083
Nara J, Kino H, Kobayashi N, Tsukada, Ohno T (2003) Theoretical investigation of contact effects in conductance of single organic molecule. Thin Solid Films 438:221–224. doi:10.1016/S0040-6090(03)00774-0
Tivanski AV, He Y, Borguet E, Liu H, Walker GC, Waldeck DH (2005) Conjugated thiol linker for enhanced electrical conduction of gold-molecule contacts. J Phys Chem B 109:5398–5402. doi:10.1021/jp50022d
Pan JB, Zhang ZH, Ding KH, Deng XQ, Guo C (2011) Current rectification induced by asymmetrical electrode materials in a molecular device. Appl Phys Lett 98:092102. doi:10.1063/1.3556278
Wang GM, Sandberg WC, Kenny SD (2006) Density functional study of a typical thiol tethered on a gold surface: ruptures under normal or parallel stretch. Nanotechnology 17:4819–4824. doi:10.1088/0957-4484/17/19/006
Datta S, Tian W, Hong S, Reifenberger, Henderson JI, Kubiak CP (1997) Current–voltage characteristics of self-assembled monolayers by scanning tunneling microscopy. Phys Rev Lett 79:2530–2533. doi:10.1103/PhysRevLett.79.2530
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The authors thank the Computational Nanoscience & Technology Laboratory (CNTL), Atal Bihari Vajpayee (ABV)–Indian Institute of Information Technology & Management, Gwalior (India) for providing the computational and infrastructural facilities.
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Parashar, S., Srivastava, P. & Pattanaik, M. Electrode materials for biphenyl-based rectification devices. J Mol Model 19, 4467–4475 (2013). https://doi.org/10.1007/s00894-013-1938-1
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DOI: https://doi.org/10.1007/s00894-013-1938-1