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Title: Ferrocene-Based Nanoelectronics

Abstract

Ferrocene-based molecular components for nanoelectronics offer a number of distinct advantages relative to all carbon frameworks due to metal-centered molecular states that should be closer in energy to the Fermi levels of the metal electrodes in metal / molecule / metal heterojunctions. Given this, the overall goal of the project was to investigate the conduction physics of a variety of proposed ferrocene diode / transistor designs in order to address the fundamental question; can electron transport within nm-length scale structures be modulated in a controlled fashion? During the funded period, substantial progress towards achieving this goal was made by surmounting a number of scientific and technical obstacles. More specifically, a concise and general synthetic route to several mono- and diferrocene dithiols and monothiols was achieved that now allows for the directed and controlled assembly of a variety of metal / molecule /metal test structures for the single molecule conductance measurements and the fabrication of self-assembled monolayers (SAMs) on Au(111) that are amenable to quantitative electrochemical characterization of electron-transfer rates. Most importantly, by using an electromigrated test structure, reproducible I/V data for one of the ferrocene dithiol molecules have been collected which exhibit surprisingly high conductance. Exceptional agreement of this resultmore » with theory serves to substantiate the original hypothesis that metal-centered states within a molecular bridge can indeed serve to establish higher conductance relative to all-organic molecular bridges. Overall, the successful demonstration of the ability of ferrocene-molecular frameworks to serve as exceptional molecular conductors will play an important role in the continued evolution in design of molecular components for nanoelectronic devices, which in turn, will have a positive impact on the science and potential technologies associated with these systems.« less

Authors:
Publication Date:
Research Org.:
University of Maryland, College Park
Sponsoring Org.:
USDOE - Office of Energy Research (ER)
OSTI Identifier:
876179
Report Number(s):
Final Report
TRN: US200712%%158
DOE Contract Number:
FG02-01ER15258
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CARBON; DESIGN; DITHIOLS; ELECTRODES; ELECTRON TRANSFER; ELECTRONS; FABRICATION; FERMI LEVEL; FERROCENE; HETEROJUNCTIONS; HYPOTHESIS; PHYSICS; TRANSPORT; molecular electronics, nanoelectronics, ferrocene

Citation Formats

Lawrence R. Sita. Ferrocene-Based Nanoelectronics. United States: N. p., 2006. Web. doi:10.2172/876179.
Lawrence R. Sita. Ferrocene-Based Nanoelectronics. United States. doi:10.2172/876179.
Lawrence R. Sita. Wed . "Ferrocene-Based Nanoelectronics". United States. doi:10.2172/876179. https://www.osti.gov/servlets/purl/876179.
@article{osti_876179,
title = {Ferrocene-Based Nanoelectronics},
author = {Lawrence R. Sita},
abstractNote = {Ferrocene-based molecular components for nanoelectronics offer a number of distinct advantages relative to all carbon frameworks due to metal-centered molecular states that should be closer in energy to the Fermi levels of the metal electrodes in metal / molecule / metal heterojunctions. Given this, the overall goal of the project was to investigate the conduction physics of a variety of proposed ferrocene diode / transistor designs in order to address the fundamental question; can electron transport within nm-length scale structures be modulated in a controlled fashion? During the funded period, substantial progress towards achieving this goal was made by surmounting a number of scientific and technical obstacles. More specifically, a concise and general synthetic route to several mono- and diferrocene dithiols and monothiols was achieved that now allows for the directed and controlled assembly of a variety of metal / molecule /metal test structures for the single molecule conductance measurements and the fabrication of self-assembled monolayers (SAMs) on Au(111) that are amenable to quantitative electrochemical characterization of electron-transfer rates. Most importantly, by using an electromigrated test structure, reproducible I/V data for one of the ferrocene dithiol molecules have been collected which exhibit surprisingly high conductance. Exceptional agreement of this result with theory serves to substantiate the original hypothesis that metal-centered states within a molecular bridge can indeed serve to establish higher conductance relative to all-organic molecular bridges. Overall, the successful demonstration of the ability of ferrocene-molecular frameworks to serve as exceptional molecular conductors will play an important role in the continued evolution in design of molecular components for nanoelectronic devices, which in turn, will have a positive impact on the science and potential technologies associated with these systems.},
doi = {10.2172/876179},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Wed Feb 15 00:00:00 EST 2006},
month = {Wed Feb 15 00:00:00 EST 2006}
}

Technical Report:

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  • Recent work has shown that graphene, a 2D electronic material amenable to the planar semiconductor fabrication processing, possesses tunable electronic material properties potentially far superior to metals and other standard semiconductors. Despite its phenomenal electronic properties, focused research is still required to develop techniques for depositing and synthesizing graphene over large areas, thereby enabling the reproducible mass-fabrication of graphene-based devices. To address these issues, we combined an array of growth approaches and characterization resources to investigate several innovative and synergistic approaches for the synthesis of high quality graphene films on technologically relevant substrate (SiC and metals). Our work focused onmore » developing the fundamental scientific understanding necessary to generate large-area graphene films that exhibit highly uniform electronic properties and record carrier mobility, as well as developing techniques to transfer graphene onto other substrates.« less
  • Ferrocene (5%) inhibits treeing and raises the needle-plane breakdown voltage by approximately 100%. However, it is unstable (oxidizes) both in air and in the presence of dicumylperoxide. None of the antioxidants investigated stabilized ferrocene. The effectiveness of ferrocene is not due to an increase in intrinsic dielectric stength, or electron scavenging properties, but seems to be related to the low ionization potential of the compound. The mechanisms are discussed. Nine other related compounds have been found to be ineffective or oxidatively unstable. Low-frequency dielectric studies indicate that the lack of effectiveness of most of the ionic compounds investigated previously wasmore » due to an unexpected frequency dependence of field-enhanced dissociation. A new ionic compound, ..cap alpha..-bromolauric acid, has been found to be effective in steel-needle breakdown tests at 60 Hz. Although it is oxidatively stable, results suggest that its performance may be specific to systems where field enhancement occurs at iron imperfections. Long-term tests at room temperature show a large improvement in breakdown voltage; however, at 85/sup 0/C reactions involving iron result in the formation of large voids that completely bridge the needle-to-plane test gap. The most important result of the two studies into additives for inhibiting tree growth in solid extruded cable insulation has been the finding, backed by supporting information on the mechanisms involved, that one can significantly inhibit treeing and raise the breakdown stength. Unfortunately, the materials identified have all suffered from thermal and oxidative instability.« less
  • A treatment of ionic-atmosphere effects upon symmetrical electron-transfer reactions resulting from added electrolyte is outlined. Relationships are derived on the basis of the extended Debye-Huckel model for the increase in the activation free energy, associated with reorganization of the ionic atmosphere for homogeneous-phase reactions involving a pair of spherical reactants with varying internuclear distance R. Similar relationships apply to the energetics of symmetrical optical electron transfer, since the increase in the optical transition energy, should equal the corresponding ionic atmosphere reorganization energy, under the anticipated linear response conditions.
  • Results of a test program to evaluate the feasibility of utilizing the smoke suppressant fuel additive, ferrocene, during post overhaul performance checks of gas turbine engines at Naval Air Rework Facilities (NARF's) and other lower level maintenance test facilities to reduce test cell exhaust smoke plumes to environmentally acceptable levels are presented. This test program was conducted on the following gas turbine engines: J52-P-6B, J57-P-10, J79-GE-8D, TF30-P-6C and TF41-A-2A.