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

Abstract

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.

Authors:
 [1];  [1]; ORCiD logo [2];  [3];  [4];  [5]
+ Show Author Affiliations
  1. Rice Univ., Houston, TX (United States). Dept. of Physics and Astronomy
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
  3. Weizmann Inst. of Science, Rehovoth (Israel). Dept. of Materials and Interfaces
  4. 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)
  5. 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
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1393883
Alternate Identifier(s):
OSTI ID: 1439985
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 16; Journal Issue: 2; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Li, Yajing, Zolotavin, Pavlo, Doak, Peter, Kronik, Leeor, Neaton, Jeffrey B., and Natelson, Douglas. Interplay of Bias-Driven Charging and the Vibrational Stark Effect in Molecular Junctions. United States: N. p., 2016. Web. doi:10.1021/acs.nanolett.5b04340.
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Li, Yajing, Zolotavin, Pavlo, Doak, Peter, Kronik, Leeor, Neaton, Jeffrey B., & Natelson, Douglas. Interplay of Bias-Driven Charging and the Vibrational Stark Effect in Molecular Junctions. United States. https://doi.org/10.1021/acs.nanolett.5b04340
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Li, Yajing, Zolotavin, Pavlo, Doak, Peter, Kronik, Leeor, Neaton, Jeffrey B., and Natelson, Douglas. Wed . "Interplay of Bias-Driven Charging and the Vibrational Stark Effect in Molecular Junctions". United States. https://doi.org/10.1021/acs.nanolett.5b04340. https://www.osti.gov/servlets/purl/1393883.
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@article{osti_1393883,
title = {Interplay of Bias-Driven Charging and the Vibrational Stark Effect in Molecular Junctions},
author = {Li, Yajing and Zolotavin, Pavlo and Doak, Peter and Kronik, Leeor and Neaton, Jeffrey B. and Natelson, Douglas},
abstractNote = {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.},
doi = {10.1021/acs.nanolett.5b04340},
journal = {Nano Letters},
number = 2,
volume = 16,
place = {United States},
year = {Wed Jan 27 00:00:00 EST 2016},
month = {Wed Jan 27 00:00:00 EST 2016}
}
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https://doi.org/10.1021/acs.nanolett.5b04340
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