Single-molecule junctions are ideal test beds for investigating the fundamentals of charge transport at the nanoscale. Conducting properties are strongly dependent on the metal-molecule interface geometry, which, however, is very poorly characterized due to numerous experimental challenges. We report on a new methodology for characterizing the adsorption site of single-molecule junctions through the combination of surface enhanced Raman scattering (SERS), current-voltage (I-V) curve measurements, and density functional theory simulations. This new methodology discriminates between three different adsorption sites for benzenedithiol and aminobenzenethiol junctions, which cannot be identified by solo measurements of either SERS or I-V curves. Using this methodology, we determine the interface geometry of these two prototypical molecules at the junction and its time evolution. By modulating the applied voltage, we can change and monitor the distribution of adsorption sites at the junction.

CD FMat National Institute of Advanced Industrial Science and Technology Central 2 Umezono 1 1 1 Tsukuba Ibaraki 305 8568 Japan Email

Department of Chemistry School of Science Tokyo Institute of Technology 2 12 1 W4 10 Ookayama Meguro ku Tokyo 152 8551 Japan Email

Graduate School of Engineering Nagoya Institute of Technology Gokiso Showa Nagoya 466 8555 Japan

Institute of Applied Physics University of Tsukuba Tennodai 1 1 1 Tsukuba 305 8573 Japan

Institute of Physics Academy of Sciences of the Czech Republic Cukrovarnicka 10 Prague CZ 162 00 Czech Republic Email

International Center for Materials Nanoarchitectonics National Institute for Materials Science Tsukuba Ibaraki 305 0044 Japan

Zobrazit více v PubMed

Aviram A., Ratner M. A. Chem. Phys. Lett. 1974;29:277–283.

Kiguchi M., Single-Molecule Electronics: An Introduction to Synthesis, Measurement and Theory, Springer, Singapore, 2016.

Song H., Reed M. A., Lee T. Adv. Mater. 2011;23:1583–1608. PubMed

Tao N. J. Nat. Nanotechnol. 2006;1:173–181. PubMed

Song H., Kim Y., Jang Y. H., Jeong H., Reed M. A., Lee T. Nature. 2009;462:1039–1043. PubMed

Fujii S., Marques-Gonzalez S., Shin J. Y., Shinokubo H., Masuda T., Nishino T., Arasu N. P., Vazquez H., Kiguchi M. Nat. Commun. 2017;8:15984. PubMed PMC

Venkataraman L., Klare J. E., Tam I. W., Nuckolls C., Hybertsen M. S., Steigerwald M. L. Nano Lett. 2006;6:458–462. PubMed

Kim Y., Pietsch T., Erbe A., Belzig W., Scheer E. Nano Lett. 2011;11:3734–3738. PubMed

Karimi M. A., Bahoosh S. G., Herz M., Hayakawa R., Pauly F., Scheer E. Nano Lett. 2016;16:1803–1807. PubMed

Isshiki Y., Fujii S., Nishino T., Kiguchi M. J. Am. Chem. Soc. 2018;140:3760–3767. PubMed

Leary E., Zotti L. A., Miguel D., Marquez I. R., Palomino-Ruiz L., Cuerva J. M., Rubio-Bollinger G., Gonzalez M. T., Agrait N. J. Phys. Chem. C. 2018;122:3211–3218.

Terada S., Yokoyama T., Sakano M., Imanishi A., Kitajima Y., Kiguchi M., Okamoto Y., Ohta T. Surf. Sci. 1998;414:107–117.

Haiss W., Wang C. S., Grace I., Batsanov A. S., Schiffrin D. J., Higgins S. J., Bryce M. R., Lambert C. J., Nichols R. J. Nat. Mater. 2006;5:995–1002. PubMed

Yoshinobu J., Takagi N., Kawai M. Chem. Phys. Lett. 1993;211:48–52.

Hihath J., Arroyo C. R., Rubio-Bollinger G., Tao N., Agrait N. Nano Lett. 2008;8:1673–1678. PubMed

Nie S. Science. 1997;275:1102–1106. PubMed

Phan-Quang G. C., Lee H. K., Teng H. W., Koh C. S. L., Yim B. Q., Tan E. K. M., Tok W. L., Phang I. Y., Ling X. Y. Angew. Chem., Int. Ed. 2018;57:5792–5796. PubMed

Ioffe Z., Shamai T., Ophir A., Noy G., Yutsis I., Kfir K., Cheshnovsky O., Selzer Y. Nat. Nanotechnol. 2008;3:727–732. PubMed

Liu Z., Ding S. Y., Chen Z. B., Wang X., Tian J. H., Anema J. R., Zhou X. S., Wu D. Y., Mao B. W., Xu X., Ren B., Tian Z. Q. Nat. Commun. 2011;2:305. PubMed PMC

Ward D. R., Corley D. A., Tour J. M., Natelson D. Nat. Nanotechnol. 2011;6:33–38. PubMed

Bi H., Palma C. A., Gong Y. X., Hasch P., Elbing M., Mayor M., Reichert J., Barth J. V. J. Am. Chem. Soc. 2018;140:4835–4840. PubMed

Kaneko S., Murai D., Marques-Gonzalez S., Nakamura H., Komoto Y., Fujii S., Nishino T., Ikeda K., Tsukagoshi K., Kiguchi M. J. Am. Chem. Soc. 2016;138:1294–1300. PubMed

Zotti L. A., Kirchner T., Cuevas J. C., Pauly F., Huhn T., Scheer E., Erbe A. Small. 2010;6:1529–1535. PubMed

Reed M. A., Zhou C., Muller C. J., Burgin T. P., Tour J. M. Science. 1997;278:252–254.

Kergueris C., Bourgoin J. P., Palacin S., Esteve D., Urbina C., Magoga M., Joachim C. Phys. Rev. B: Condens. Matter Mater. Phys. 1999;59:12505–12513.

Tsutsui M., Shoji K., Taniguchi M., Kawai T. Nano Lett. 2008;8:345–349. PubMed

Soler J. M., Artacho E., Gale J. D., Garcia A., Junquera J., Ordejon P., Sanchez-Portal D. J. Phys.: Condens. Matter. 2002;14:2745–2779. PubMed

Brandbyge M., Mozos J. L., Ordejon P., Taylor J., Stokbro K. Phys. Rev. B: Condens. Matter Mater. Phys. 2002;65:165401.

Perdew J. P., Burke K., Ernzerhof M. Phys. Rev. Lett. 1996;77:3865–3868. PubMed

Tian J. H., Liu B., Li X., Yang Z. L., Ren B., Wu S. T., Tao N., Tian Z. Q. J. Am. Chem. Soc. 2006;128:14748–14749. PubMed

Xiao X. Y., Xu B. Q., Tao N. J. Nano Lett. 2004;4:267–271.

Komoto Y., Fujii S., Kiguchi M. Adv. Nat. Sci.: Nanosci. Nanotechnol. 2017;8:025007.

Osawa M., Matsuda N., Yoshii K., Uchida I. J. Phys. Chem. 1994;98:12702–12707.

Xu P., Kang L. L., Mack N. H., Schanze K. S., Han X. J., Wang H. L. Sci. Rep. 2013;3:2997. PubMed PMC

Zheng J. T., Liu J. Y., Zhuo Y. J., Li R. H., Jin X., Yang Y., Chen Z. B., Shi J., Xiao Z. Y., Hong W. J., Tian Z. Q. Chem. Sci. 2018;9:5033–5038. PubMed PMC

Huang Y. F., Zhu H. P., Liu G. K., Wu D. Y., Ren B., Tian Z. Q. J. Am. Chem. Soc. 2010;132:9244–9246. PubMed

Lombardi J. R., Birke R. L., Lu T., Xu J. J. Chem. Phys. 1986;84:4174–4180.

Neaton J. B., Hybertsen M. S., Louie S. G. Phys.Phys. Rev. Lett.Rev. Lett. 2006;97:216405. PubMed

Flores F., Ortega J., Vazquez H. Phys. Chem. Chem. Phys. 2009;11:8658–8675. PubMed

Quek S. Y., Venkataraman L., Choi H. J., Louie S. G., Hybertsen M. S., Neaton J. B. Nano Lett. 2007;7:3477–3482. PubMed

Tsutsui M., Teramae Y., Kurokawa S., Sakai A. Appl. Phys. Lett. 2006;89:163111.

Sergueev N., Tsetseris L., Varga K., Pantelides S. Phys. Rev. B: Condens. Matter Mater. Phys. 2010;82:073106.

Pontes R. B., Rocha A. R., Sanvito S., Fazzio A., da Silva A. J. ACS Nano. 2011;5:795–804. PubMed

Komoto Y., Fujii S., Nakamura H., Tada T., Nishino T., Kiguchi M. Sci. Rep. 2016;6:26606. PubMed PMC

Todorov T. N. Philos. Mag. B. 1998;77:965–973.

Lü J.-T., Brandbyge M., Hedegård P., Todorov T. N., Dundas D. Phys. Rev. B: Condens. Matter Mater. Phys. 2012;85:245444.

Todorov T. N., Hoekstra J., Sutton A. P. Philos. Mag. B. 2000;80:421–455.

Zhang R. X., Rungger I., Sanvito S., Hou S. M. Phys. Rev. B: Condens. Matter Mater. Phys. 2011;84:085445.

Huang Z., Chen F., Bennett P. A., Tao N. J. Am. Chem. Soc. 2007;129:13225–13231. PubMed

Tsutsui M., Taniguchi M., Kawai T. Nano Lett. 2008;8:3293–3297. PubMed

Di Ventra M., Electrical Transport in Nanoscale Systems, Cambridge Univ. Press, Cambridge, 2008.

Resolving molecular frontier orbitals in molecular junctions with kHz resolution