Interplay of Bias-Driven Charging and the Vibrational Stark Effect in Molecular Junctions

Li, Yajing; Zolotavin, Pavlo; Doak, Peter; Kronik, Leeor; Neaton, Jeffrey B.; Natelson, Douglas

doi:10.1021/acs.nanolett.5b04340

Title: Interplay of Bias-Driven Charging and the Vibrational Stark Effect in Molecular Junctions

Journal Article · Wed Jan 27 00:00:00 EST 2016 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.5b04340· OSTI ID:1393883

Li, Yajing ^[1]; Zolotavin, Pavlo ^[1];

^[2]; Kronik, Leeor ^[3]; Neaton, Jeffrey B. ^[4]; Natelson, Douglas ^[5]

Rice Univ., Houston, TX (United States). Dept. of Physics and Astronomy
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
Weizmann Inst. of Science, Rehovoth (Israel). Dept. of Materials and Interfaces
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Univ. of California, Berkeley, CA (United States). Dept. of Physics; Kavli Energy Nanosciences Inst. at Berkeley, CA (United States)
Rice Univ., Houston, TX (United States). Dept. of Physics and Astronomy; Rice Univ., Houston, TX (United States). Dept. of Electrical and Computer Engineering; Rice Univ., Houston, TX (United States). Dept of Materials Science and Nanoengineering

We observe large, reversible, bias driven changes in the vibrational energies of PCBM based on simultaneous transport and surface-enhanced Raman spectroscopy (SERS) measurements on PCBM-gold junctions. A combination of linear and quadratic shifts in vibrational energies with voltage is analyzed and compared with similar measurements involving C 60 -gold junctions. A theoretical model based on density functional theory (DFT) calculations suggests that both a vibrational Stark effect and bias-induced charging of the junction contribute to the shifts in vibrational energies. In the PCBM case, a linear vibrational Stark effect is observed due to the permanent electric dipole moment of PCBM. The vibrational Stark shifts shown here for PCBM junctions are comparable to or larger than the charging effects that dominate in C 60 junctions.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725; AC02-05CH11231

OSTI ID:: 1393883

Alternate ID(s):: OSTI ID: 1439985

Journal Information:: Nano Letters, Vol. 16, Issue 2; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 34 works

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