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Electron Transport at the Nanoscale - An Electrochemical Approach

English title Electron Transport at the Nanoscale - An Electrochemical Approach
Applicant Wandlowski Thomas
Number 124643
Funding scheme Project funding (Div. I-III)
Research institution Departement für Chemie und Biochemie Universität Bern
Institution of higher education University of Berne - BE
Main discipline Physical Chemistry
Start/End 01.09.2009 - 31.08.2012
Approved amount 571'418.00
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All Disciplines (2)

Discipline
Physical Chemistry
Other disciplines of Physics

Keywords (12)

Interfacial Electrochemistry; Charge Transport; Electrochemical Scanning Tunneling Microscopy; Molecular Electronics; Nanochemistry; Electron Transport; electrochemistry; single molecules; redox molecules; nanocrystals; scanning tunneling spectroscopy; break junction

Lay Summary (English)

Lead
Lay summary
The ability to measure and to control charge transport across nanometer scale metal?molecule?metal junctions represents a key step towards the realization of a molecular-based electronics. The present proposal aims at probing and understanding structure, electronic conductance, quantum transport and electrochemical charge transfer in active nanometer-scale molecular and nanocluster junctions at well-defined solid?liquid interfaces. We will focus on developing and applying the concept of an "electrolyte gate" and to integrate functionality in nanoscale molecule?electrode hybrid systems by tailoring both, the molecule (nanocluster) structure and the solid?liquid interface. We attempt to establish an electrochemical surface science based approach at the nanoscale with specific focus to address (1) metal-metal nanocontacts, (2) the electrolyte and (3) functional molecules or nanoclusters in confined space. The strategy is based on the following topology: A central functional unit F (molecule, nanocluster) to enable switching properties (conforma-tion, orientation, redox- or quantized charging) upon electrical or electrochemical stimulation is attached via spacer units S and anchoring groups A, either symmetrically or asymmetrically to contacting leads. The latter are represented either by the tip of a scanning tunnleing microscope (STM) and an adsorbate-modified single crystal metal substrate or a pair of microfabricated nanoelectrodes.We aim to explore fundamental aspects of electron transport as well as relationships between structural functionality and electronic conductivity of electrochemically stimulated nanojunctions. Specifically we will address the role of molecular length, conformation, conjugation, contact geometry, redox activity as well as the coupling of the transferring electrons with the metal leads, the polar (electrolyte) environment and local vibration modes of the active unit F. We identify the following specific working packages:WP 1:Electrochemical and structure characterization of metal-metal nanocontacts and tunneling junctionsWP 2:Electron transport in redox-inactive molecular nanojunctionWP 3:Fabrication and local addressing of redox-active nanojunctionsWP 4:Nanocrystal-mediated electron tunneling: An electrochemical approachWP 5:Combination of electron transport and near field Raman spectroscopyThe project will provide unique new insights into fundamental structure-property relationships of electron transport and switching processes in single molecular and nanocrystal assemblies, which are triggered by electrochemical stimuli.
Direct link to Lay Summary Last update: 21.02.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
Charge transport in single molecular junctions at the solid/liquid interface.
Li Chen, Mishchenko Artem, Wandlowski Thomas (2012), Charge transport in single molecular junctions at the solid/liquid interface., in Topics in current chemistry, 313, 121-88.
Cooperative and Noncooperative Assembly of Oligopyrenotides Resolved by Atomic Force Microscopy
Rudnev AV, Malinovskii VL, Nussbaumer AL, Mishchenko A, Haner R, Wandlowski T (2012), Cooperative and Noncooperative Assembly of Oligopyrenotides Resolved by Atomic Force Microscopy, in MACROMOLECULES, 45(15), 5986-5992.
Encyclopedia of Nanotechnology:“Electrochemical Scanning Tunneling Microscopy”
B. Bhushan (ed.) (2012), Encyclopedia of Nanotechnology:“Electrochemical Scanning Tunneling Microscopy”, Springer, Heidelberg.
An approach to measure electromechanical properties of atomic and molecular junctions
Pobelov IV, Meszaros G, Yoshida K, Mishchenko A, Gulcur M, Bryce MR, Wandlowski T (2012), An approach to measure electromechanical properties of atomic and molecular junctions, in JOURNAL OF PHYSICS-CONDENSED MATTER, 24(16), 164210 (0-164210 (15.
Correlations between Molecular Structure and Single-Junction Conductance: A Case Study with Oligo(phenylene-ethynylene)-Type Wires
Kaliginedi V, Moreno-Garcia P, Valkenier H, Hong WJ, Garcia-Suarez VM, Buiter P, Otten JLH, Hummelen JC, Lambert CJ, Wandlowski T (2012), Correlations between Molecular Structure and Single-Junction Conductance: A Case Study with Oligo(phenylene-ethynylene)-Type Wires, in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 134(11), 5262-5275.
Conduction mechanisms in biphenyl dithiol single-molecule junctions
Burkle M, Viljas JK, Vonlanthen D, Mishchenko A, Schon G, Mayor M, Wandlowski T, Pauly F (2012), Conduction mechanisms in biphenyl dithiol single-molecule junctions, in PHYSICAL REVIEW B, 85(7), 075417-1-075417-12.
Single Molecular Conductance of Tolanes: Experimental and Theoretical Study on the Junction Evolution Dependent on the Anchoring Group
Hong WJ, Manrique DZ, Moreno-Garcia P, Gulcur M, Mishchenko A, Lambert CJ, Bryce MR, Wandlowski T (2012), Single Molecular Conductance of Tolanes: Experimental and Theoretical Study on the Junction Evolution Dependent on the Anchoring Group, in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 134(4), 2292-2304.
Electrochemical scanning tunnelling spectroscopy of a ferrocene-modified n-Si(111)-surface: electrolyte gating and ambipolar FET behaviour
Mishchenko A, Abdualla M, Rudnev A, Fu YC, Pike AR, Wandlowski T (2011), Electrochemical scanning tunnelling spectroscopy of a ferrocene-modified n-Si(111)-surface: electrolyte gating and ambipolar FET behaviour, in CHEMICAL COMMUNICATIONS, 47(35), 9807-9809.
An MCBJ case study: The influence of pi-conjugation on the single-molecule conductance at a solid/liquid interface
Hong WJ, Valkenier H, Meszaros G, Manrique DZ, Mishchenko A, Putz A, Garcia PM, Lambert CJ, Hummelen JC, Wandlowski T (2011), An MCBJ case study: The influence of pi-conjugation on the single-molecule conductance at a solid/liquid interface, in BEILSTEIN JOURNAL OF NANOTECHNOLOGY, 2, 699-713.
Extraordinary Enhancement of Raman Scattering from Pyridine on Single Crystal Au and Pt Electrodes by Shell-Isolated Au Nanoparticles
Li JF, Ding SY, Yang ZL, Bai ML, Anema JR, Wang X, Wang A, Wu DY, Ren B, Hou SM, Wandlowski T, Tian ZQ (2011), Extraordinary Enhancement of Raman Scattering from Pyridine on Single Crystal Au and Pt Electrodes by Shell-Isolated Au Nanoparticles, in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 133(40), 15922-15925.
"Ligand-free" cluster quantized charging in an ionic liquid.
Mertens Stijn F L, Vollmer Christian, Held Alexander, Aguirre Myriam H, Walter Michael, Janiak Christoph, Wandlowski Thomas (2011), "Ligand-free" cluster quantized charging in an ionic liquid., in Angewandte Chemie (International ed. in English), 50(41), 9735-8.
Structural aspects of redox-mediated electron tunneling
Rudnev AV, Pobelov IV, Wandlowski T (2011), Structural aspects of redox-mediated electron tunneling, in JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 660(2), 302-308.
Redox-Switching in a Viologen-type Adlayer: An Electrochemical Shell-Isolated Nanoparticle Enhanced Raman Spectroscopy Study on Au(111)-(1 x 1) Single Crystal Electrodes
Liu B, Blaszczyk A, Mayor M, Wandlowski T (2011), Redox-Switching in a Viologen-type Adlayer: An Electrochemical Shell-Isolated Nanoparticle Enhanced Raman Spectroscopy Study on Au(111)-(1 x 1) Single Crystal Electrodes, in ACS NANO, 5(7), 5662-5672.
Electrochemical scanning tunnelling spectroscopy of a ferrocene-modified n-Si(111)-surface: electrolyte gating and ambipolar FET behaviour
Mishchenko A, Abdualla M, Rudnev A, Fu YC, Pike AR, Wandlowski T (2011), Electrochemical scanning tunnelling spectroscopy of a ferrocene-modified n-Si(111)-surface: electrolyte gating and ambipolar FET behaviour, in CHEMICAL COMMUNICATIONS, 47(35), 9807-9809.
Au@Hg nanoalloy formation through direct amalgamation: Structural, spectroscopic, and computational evidence for slow nanoscale diffusion
Mertens SFL, Gara M, Sologubenko AS, Mayer J, Szidat S, Krämer KW, Jacob T, Schiffrin DJ, Wandlowski T (2011), Au@Hg nanoalloy formation through direct amalgamation: Structural, spectroscopic, and computational evidence for slow nanoscale diffusion, in Advanced Functional Materials, 21(17), 3259-3267.
Conformationally Controlled Electron Delocalization in n-Type Rods: Synthesis, Structure, and Optical, Electrochemical, and Spectroelectrochemical Properties of Dicyanocyclophanes
Vonlanthen D, Rudnev A, Mishchenko A, Kaslin A, Rotzler J, Neuburger M, Wandlowski T, Mayor M (2011), Conformationally Controlled Electron Delocalization in n-Type Rods: Synthesis, Structure, and Optical, Electrochemical, and Spectroelectrochemical Properties of Dicyanocyclophanes, in CHEMISTRY-A EUROPEAN JOURNAL, 17(26), 7236-7250.
Conformationally Controlled Electron Delocalization in n-Type Rods: Synthesis, Structure, and Optical, Electrochemical, and Spectroelectrochemical Properties of Dicyanocyclophanes
Vonlanthen D, Rudnev A, Mishchenko A, Kaslin A, Rotzler J, Neuburger M, Wandlowski T, Mayor M (2011), Conformationally Controlled Electron Delocalization in n-Type Rods: Synthesis, Structure, and Optical, Electrochemical, and Spectroelectrochemical Properties of Dicyanocyclophanes, in CHEMISTRY-A EUROPEAN JOURNAL, 17(26), 7236-7250.
Synthesis, structures, redox and photophysical properties of benzodifuran-functionalised pyrene and anthracene fluorophores
Keller S, Yi CY, Li C, Liu SX, Blum C, Frei G, Sereda O, Neels A, Wandlowski T, Decurtins S (2011), Synthesis, structures, redox and photophysical properties of benzodifuran-functionalised pyrene and anthracene fluorophores, in ORGANIC & BIOMOLECULAR CHEMISTRY, 9(18), 6410-6416.
In Situ Gap-Mode Raman Spectroscopy on Single-Crystal Au(100) Electrodes: Tuning the Torsion Angle of 4,4 '-Biphenyldithiols by an Electrochemical Gate Field
Cui L, Liu B, Vonlanthen D, Mayor M, Fu YC, Li JF, Wandlowski T (2011), In Situ Gap-Mode Raman Spectroscopy on Single-Crystal Au(100) Electrodes: Tuning the Torsion Angle of 4,4 '-Biphenyldithiols by an Electrochemical Gate Field, in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 133(19), 7332-7335.
Atomic Force Microscopy-Scanning Electrochemical Microscopy: Influence of Tip Geometry and Insulation Defects on Diffusion Controlled Currents at Conical Electrodes
Leonhardt K, Avdic A, Lugstein A, Pobelov I, Wandlowski T, Wu M, Gollas B, Denuault G (2011), Atomic Force Microscopy-Scanning Electrochemical Microscopy: Influence of Tip Geometry and Insulation Defects on Diffusion Controlled Currents at Conical Electrodes, in ANALYTICAL CHEMISTRY, 83(8), 2971-2977.
Fabrication of cone-shaped boron doped diamond and gold nanoelectrodes for AFM-SECM.
Avdic A, Lugstein A, Wu M, Gollas B, Pobelov I, Wandlowski T, Leonhardt K, Denuault G, Bertagnolli E (2011), Fabrication of cone-shaped boron doped diamond and gold nanoelectrodes for AFM-SECM., in Nanotechnology, 22(14), 145306-145306.
Atomic force microscopy-scanning electrochemical microscopy: Influence of tip geometry and insulation defects on diffusion controlled currents at conical electrodes
Leonhardt K, Avdic A, Lugstein A, Pobelov I, Wandlowski T, Wu M, Gollas B, Denuault G (2011), Atomic force microscopy-scanning electrochemical microscopy: Influence of tip geometry and insulation defects on diffusion controlled currents at conical electrodes, in Analytical Chemistry, 83(8), 2971-2977.
Single-Molecule Junctions Based on Nitrile-Terminated Biphenyls: A Promising New Anchoring Group
Mishchenko A, Zotti LA, Vonlanthen D, Burkle M, Pauly F, Cuevas JC, Mayor M, Wandlowski T (2011), Single-Molecule Junctions Based on Nitrile-Terminated Biphenyls: A Promising New Anchoring Group, in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 133(2), 184-187.
Covalent versus Electrostatic Strategies for Nanoparticle Immobilisation
Mertens SFL, Bütikofer A, Siffert L, Wandlowski T (2010), Covalent versus Electrostatic Strategies for Nanoparticle Immobilisation, in Electroanalysis, 22(24), 2940-2946.
Dynamics of ionic liquid mediated quantised charging of monolayer-protected clusters
Mertens SFL, Mészáros G, Wandlowski T (2010), Dynamics of ionic liquid mediated quantised charging of monolayer-protected clusters, in Physical Chemistry Chemical Physics, 12(20), 5417-5424.
A Scanning Probe Microscopy Study of Annulated Redox-Active Molecules at a Liquid/Solid Interface: The Overruling of the Alkyl Chain Paradigm
Liu B, Ran YF, Li ZH, Liu SX, Jia CY, Decurtins S, Wandlowski T (2010), A Scanning Probe Microscopy Study of Annulated Redox-Active Molecules at a Liquid/Solid Interface: The Overruling of the Alkyl Chain Paradigm, in CHEMISTRY-A EUROPEAN JOURNAL, 16(17), 5008-5012.
Charge Transport with Single Molecules - An Electrochemical Approach
Li C, Mishchenko A, Pobelov I, Wandlowski T (2010), Charge Transport with Single Molecules - An Electrochemical Approach, in CHIMIA, 64(6), 383-390.
Charge Transport with Single Molecules - An Electrochemical Approach
Li C, Mishchenko A, Pobelov I, Wandlowski T (2010), Charge Transport with Single Molecules - An Electrochemical Approach, in CHIMIA, 64(6), 383-390.
Benzodifuran-Based pi-Conjugated Copolymers for Bulk Heterojunction Solar Cells
Li H, Jiang P, Yi CY, Li C, Liu SX, Tan ST, Zhao B, Braun J, Meier W, Wandlowski T, Decurtins S (2010), Benzodifuran-Based pi-Conjugated Copolymers for Bulk Heterojunction Solar Cells, in MACROMOLECULES, 43(19), 8058-8062.
From Redox Gating to Quantized Charging
Li ZH, Liu YQ, Mertens SFL, Pobelov IV, Wandlowski T (2010), From Redox Gating to Quantized Charging, in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 132(23), 8187-8193.
Influence of Conformation on Conductance of Biphenyl-Dithiol Single-Molecule Contacts
Mishchenko A, Vonlanthen D, Meded V, Burkle M, Li C, Pobelov IV, Bagrets A, Viljas JK, Pauly F, Evers F, Mayor M, Wandlowski T (2010), Influence of Conformation on Conductance of Biphenyl-Dithiol Single-Molecule Contacts, in NANO LETTERS, 10(1), 156-163.
Catechol-Based Macrocyclic Rods: En Route to Redox-Active Molecular Switches
Weibel N, Mishchenko A, Wandlowski T, Neuburger M, Leroux Y, Mayor M (2009), Catechol-Based Macrocyclic Rods: En Route to Redox-Active Molecular Switches, in EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, (35), 6140-6150.
Chemically Controlled Conductivity: Torsion-Angle Dependence in a Single-Molecule Biphenyldithiol Junction
Vonlanthen D, Mishchenko A, Elbing M, Neuburger M, Wandlowski T, Mayor M (2009), Chemically Controlled Conductivity: Torsion-Angle Dependence in a Single-Molecule Biphenyldithiol Junction, in ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 48(47), 8886-8890.
Chemically Controlled Conductivity: Torsion-Angle Dependence in a Single-Molecule Biphenyldithiol Junction
Vonlanthen David, Mishchenko A, Elbing M, Neuburger M, Wandlowski T, Mayor M (2009), Chemically Controlled Conductivity: Torsion-Angle Dependence in a Single-Molecule Biphenyldithiol Junction, in ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 48(47), 8886-8890.
Pronounced Electrochemical Amphotericity of a Fused Donor-Acceptor Compound: A Planar Merge of TTF with a TCNQ-Type Bithienoquinoxaline
Guegano X, Kanibolotsky AL, Blum C, Mertens SFL, Liu SX, Neels A, Hagemann H, Skabara PJ, Leutwyler S, Wandlowski T, Hauser A, Decurtins S (2009), Pronounced Electrochemical Amphotericity of a Fused Donor-Acceptor Compound: A Planar Merge of TTF with a TCNQ-Type Bithienoquinoxaline, in CHEMISTRY-A EUROPEAN JOURNAL, 15(1), 63-66.

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
12th International Fischer Symposium “Frontiers in Nanoelectrochemistry 03.07.2012 Lübeck, Germany
FUNMOLS Workshop IBM Zürich 15.01.2012 Rüschlikon, Switzerland
ECME2011 07.09.2011 Barcelona, Spain
German-French Workshop on Nano-Science 31.08.2011 Heidelberg, Germany
4th Heyrovsky Discussion 26.06.2011 Trest, Czech Republic
SNI-EMPA Workshop on Molecular Electronics 24.06.2011 Dübendorf, Switzerland
CUSO postgraduate school in Electrochemistry “Scanning Electrochemical” Microscopy” 22.06.2011 Lausanne, Switzerland
ISE Spring Meeting 08.05.2011 Turku, Finland
FUNMOLS Workshop 15.04.2011 Muggendorf, Germany
Chemical Nanoscience Symposium 30.03.2011 Newcastle-Upon-Tyne, UK
COST D 35 Meeting 13.01.2011 Brussels, Belgium
Nanoelectronic Days 2010, Jara, RWTH Aachen 07.10.2010 Aachen, RWTH, Germany
CECAM Workshop „Quantum Transport at the Molecualr Scale“ 14.09.2010 Zürich, Switzerland
FUNMOLS Workshop 07.09.2010 Copenhagen
CECAM Workshop “Transport Phenomena in Molecular Nanostructures 22.06.2010 Zürich, CH
HERODOT Meeting 27.05.2010 KU Leuven, Belgium
26th Annual Meeting of the Swiss Working Group on Surface and Interface Science 22.01.2010 Fribourgh, CH
International Conference on Molecular Electronics 05.01.2010 Emmetten, CH
1st Winter Workshop on Functional SPM in Bio and Chemical Physics 10.12.2009 Modena


Self-organised

Title Date Place
CUSO postgraduate school in Electrochemistry “Scanning Electrochemical Microscopy”, EPFL Lausanne 22.06.2011 Lausanne
FUNMOLS Workshop “Charge Transport with (Single) Molecules”, Bern 10.02.2011 Bern
CUSO Summer School “Nanoelectrochemistry”, Villars 05.09.2010 Villars

Knowledge transfer events

Active participation

Title Type of contribution Date Place Persons involved
BASF Vorstellung der Guppe, Diskusion Photovoltaic 08.07.2011 Basel
Open Day DCB Uni Bern 18.06.2011 Bern
NFP 62 Sommerschule 26.04.2011 Lugano
Perpektiven der Elektrochemischen Rastertunnelmikroskopie 25.02.2011 Liesthal


Communication with the public

Communication Title Media Place Year
Talks/events/exhibitions Open Day Uni Bern; Vortrag: Eine Reise in den Nanokosmos" German-speaking Switzerland 18.06.2011

Awards

Title Year
NF postdoctral fellowship in für Arbeiten im Labor von Prof. Geim, Liverpool 2011
Fakulty Price 2010 for best PhD thesis 2010

Associated projects

Number Title Start Funding scheme
144471 Electron Transport at the Nanoscale - An Electrochemical Approach II 01.09.2013 Project funding (Div. I-III)
121304 Purchase of a High-Performance Mass Spectrometer 01.09.2008 R'EQUIP
144471 Electron Transport at the Nanoscale - An Electrochemical Approach II 01.09.2013 Project funding (Div. I-III)

Abstract

The ability to measure and to control charge transport across nanometer scale metal¦molecule¦metal junctions represents a key step towards the realization of a molecular-based electronics. The present proposal aims at probing and understanding structure, electronic conductance, quantum transport and electrochemical charge transfer in active nanometer-scale molecular and nanocluster junctions at well-defined solid¦liquid interfaces. We will focus on developing and applying the concept of an “electrolyte gate” and to integrate functionality in nanoscale molecule¦electrode hybrid systems by tailoring both, the molecule (nanocluster) structure and the solid¦liquid interface. We attempt to establish an electrochemical surface science based approach at the nanoscale with specific focus to address (1) metal-metal nanocontacts, (2) the electrolyte and (3) functional molecules or nanoclusters in confined space. The strategy is based on the following topology: A central functional unit F (molecule, nanocluster) to enable switching properties (conforma-tion, orientation, redox- or quantized charging) upon electrical or electrochemical stimulation is attached via spacer units S and anchoring groups A, either symmetrically (A-S-F-S-A) or asymmetrically (A-S-F-S) to contacting leads. The latter are represented either by the tip of a STM and an adsorbate-modified single crystal metal substrate or a pair of microfabricated nanoelectrodes in a fixed or variable (mechanically controlled break junction, MCBJ) geometry.We aim to explore fundamental aspects of electron transport as well as relationships between structural functionality and electronic conductivity of electrochemically stimulated nanojunc-tions. Specifically we will address the role of molecular length, conformation, conjugation, contact geometry, redox activity as well as the coupling of the transferring electrons with the metal leads, the polar (electrolyte) environment and local vibration modes of the active unit F. Structure and chemical information on electrical and electrochemical processes in these nanojunctions is attempted to be explored by combination with near field Raman Spectroscopy (MJ-SERS). We identify the following specific working packages:WP 1:Electrochemical and structure characterization of metal-metal nanocontacts and tunneling junctionsWP 2:Electron transport in redox-inactive molecular nanojunctionWP 3:Fabrication and local addressing of redox-active nanojunctionsWP 4:Nanocrystal-mediated electron tunneling: An electrochemical approachWP 5:Combination of electron transport and near field Raman spectroscopyThe project will provide unique new insights into fundamental structure-property relationships of electron transport and switching processes in single molecular and nanocrystal assemblies, which are triggered by electrochemical stimuli. As an important methodological and topical development we aim to combine the nanoelectrochemical approach with local Raman spectros-copy. The proposed research represents an interdisciplinary approach and will benefit substantially from active collaborations with complementary teams representing expertise in molecular and supramolecular chemistry (S. Decurtins, Bern, M. Mayor, Basel, M. Ruben, Karlsruhe, F. Würthner, Würzburg), vibrational spectroscopy (Z. Tian, Xiamen, B. Hecht, Würzburg) electrical engineering (A. Lugstein, Vienna), and theoretical physics (F. Evers, Karlsruhe, E. Leiva, Cordoba).
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