← Back to Search
The Impact Of Surface Coverage On The Kinetics Of Electron Transfer Through Redox Monolayers On A Silicon Electrode Surface
S. Ciampi, M. H. Choudhury, S. Ahmad, N. Darwish, A. L. Brun, J. Gooding
Published 2015 · Chemistry
Download PDFAnalyze on Scholarcy
The impact of the coverage of ferrocene moieties, attached to a silicon electrode modified via hydrosilylation of a dialkyne, on the kinetics of electron transfer between the redox species and the electrode is explored. The coverage of ferrocene is controlled by varying the coupling time between azidomethylferrocene and the distal alkyne of the monolayer via the copper assisted azide-alkyne cycloaddition reaction. All other variables in the surface preparation are maintained identical. What is observed is that the higher the surface coverage of the ferrocene moieties the faster the apparent rates of electron transfer. This surface coverage-dependent kinetic effect is attributed to electrons hopping between ferrocene moieties across the redox film toward hotspots for the electron transfer event. The origin of these hotspots is tentatively suggested to result from minor amounts of oxide on the underlying silicon surface that reduce the barrier for the electron transfer.
This paper references
Measurements of redox kinetics of adsorbed azobenzene by “a quasireversible maximum” in square-wave voltammetry
Š. Komorsky-Lovrič (1995)
Surface Functionalization of Electrodes with Molecular Reagents
M. Wrighton (1986)
Determination of flat-band potentials of silicon electrodes in HF by means of ac resistance measurements
S. Ottow (1998)
Heterogeneous Proton-Coupled Electron Transfer of an Aminoanthraquinone Self-Assembled Monolayer
Anusha D. Abhayawardhana (2009)
Ferrocene-terminated monolayers covalently bound to hydrogen-terminated silicon surfaces. Toward the development of charge storage and communication devices.
B. Fabre (2010)
A.C. Polarography and faradaic impedance of strongly adsorbed electroactive species: Part III. Theoretical complex plane analysis for a surface redox reaction
E. Laviron (1979)
Molecular engineering of semiconductor surfaces and devices.
G. Ashkenasy (2002)
Alkyl Monolayers on Silicon Prepared from 1-Alkenes and Hydrogen-Terminated Silicon
M. R. Linford (1995)
Measurement of Lateral Charge Propagation in Polyaniline Layers with the Scanning Electrochemical Microscope
and Daniel Mandler (2003)
Silicon still supreme
P. Ball (2005)
Influence of Doping Density on the Current−Voltage Characteristics of p-Type Silicon in Dilute Hydrofluoric Acid
T. Wijesinghe (2008)
Thermodynamic Potential for the Anodic Dissolution of n‐Type Semiconductors A Crucial Factor Controlling Durability and Efficiency in Photoelectrochemical Cells and an Important Criterion in the Selection of New Electrode/Electrolyte Systems
A. J. Bard (1977)
Grafting of 1-alkynes to hydrogen-terminated (100)silicon surfaces
G. Cerofolini (2005)
Alkyl monolayers covalently bonded to silicon surfaces
M. R. Linford (1993)
Single-component and mixed ferrocene-terminated alkyl monolayers covalently bound to Si(111) surfaces.
B. Fabre (2006)
Dynamics of electron hopping in assemblies of redox centers. Percolation and diffusion
D. Blauch (1992)
Tandem "click" reactions at acetylene-terminated Si(100) monolayers.
S. Ciampi (2011)
Charge transfer through DNA: A selective electrochemical DNA biosensor.
E. Wong (2006)
Functionalization of acetylene-terminated monolayers on Si(100) surfaces: a click chemistry approach.
S. Ciampi (2007)
Charge Transfer on the Nanoscale: Current Status
D. Adams (2003)
Silicon (100) electrodes resistant to oxidation in aqueous solutions: an unexpected benefit of surface acetylene moieties.
S. Ciampi (2009)
"Plugging into Enzymes": Nanowiring of Redox Enzymes by a Gold Nanoparticle
Yi Xiao (2003)
Nanoscale condensation of water on self-assembled monolayers
Michael James (2011)
Microscopic structure of the SiO2/Si interface.
Toward metal-organic insulator-semiconductor solar cells, based on molecular monolayer self-assembly on n-Si
Rotem Har-lavan (2009)
Microscopic structure of the SiO 2 /Si interface
F. J. Himpsel (1988)
Impedance Spectroscopy of Self-Assembled Monolayers on Au(111): Evidence for Complex Double-Layer Structure in Aqueous NaClO4 at the Potential of Zero Charge
Richard P. Janek and (1997)
Optimization of Click Chemistry of Ferrocene Derivatives on Acetylene‐Functionalized Silicon(100) Surfaces
S. Ciampi (2008)
Self-assembled monolayers of thiolates on metals as a form of nanotechnology.
J. Love (2005)
Synthesis and electrochemical properties of a series of ferrocene-containing alcohols
W. L. Davis (2005)
Co-refinement of multiple-contrast neutron/X-ray reflectivity data using MOTOFIT
A. Nelson (2006)
Rate of interfacial electron transfer through the 1,2,3-triazole linkage.
N. Devaraj (2006)
Coadsorption of ferrocene-terminated and unsubstituted alkanethiols on gold: electroactive self-assembled monolayers
C. Chidsey (1990)
Measurements of electron-transfer rates of charge-storage molecular monolayers on Si(100). Toward hybrid molecular/semiconductor information storage devices.
Kristian M. Roth (2003)
The molecular level modification of surfaces: from self-assembled monolayers to complex molecular assemblies.
J. Gooding (2011)
Surface-bound norbornylogous bridges as molecular rulers for investigating interfacial electrochemistry and as single molecule switches.
N. Darwish (2014)
Porphyrin anchoring on Si(100) using a beta-pyrrolic position.
H. Liu (2009)
ELECTRON TRANSFER RATES OF ALKYL-FERROCENE MOLECULES FORMING INCOMPLETE MONOLAYER ON SILICON ELECTRODES
G. Riveros (2010)
Ferrocene and porphyrin monolayers on Si(100) surfaces: preparation and effect of linker length on electron transfer.
K. Huang (2009)
Wet chemical routes to the assembly of organic monolayers on silicon surfaces via the formation of Si-C bonds: surface preparation, passivation and functionalization.
S. Ciampi (2010)
Comparison of the Electrical Properties and Chemical Stability of Crystalline Silicon(111) Surfaces Alkylated Using Grignard Reagents or Olefins with Lewis Acid Catalysts
L. Webb (2003)
A.C. polarography and faradaic impedance of strongly adsorbed electroactive species: Part I. Theoretical and experimental study of a quasi-reversible reaction in the case of a Langmuir isotherm
E. Laviron (1979)
Ac voltammetry studies of electron transfer kinetics for a redox couple attached via short alkanethiols to a gold electrode
Dmitri A. Brevnov (2001)
The detailed characterization of electrochemically switchable molecular assemblies on silicon electrodes.
S. Ciampi (2013)
Importance of monolayer quality for interpreting current transport through organic molecules: alkyls on oxide-free Si.
O. Seitz (2006)
Cu-catalyzed azide-alkyne cycloaddition.
M. Meldal (2008)
Multi-responsive photo- and chemo-electrical single-molecule switches.
N. Darwish (2014)
Reversible potential-induced structural changes of alkanethiol monolayers on gold surfaces
Nadim Darwish (2011)
pH sensitivity of Si--C linked organic monolayers on crystalline silicon surfaces.
E. Faber (2007)
Redox-active monolayers in mesoporous silicon
S. Ciampi (2012)
Silicon-based molecular nanotechnology
M. Hersam (2000)
Conformational disorder enhances electron transfer through alkyl monolayers: ferrocene on conductive diamond.
Rose E Ruther (2013)
Use of Diode Analogy in Explaining the Voltammetric Characteristics of Immobilized Ferrocenyl Moieties on a Silicon Surface
M. U. Herrera (2015)
Comparison of Electron-Transfer and Charge-Retention Characteristics of Porphyrin-Containing Self-Assembled Monolayers Designed for Molecular Information Storage
Kristian M. Roth (2002)
Self-Assembled Monolayers into the 21st Century: Recent Advances and Applications
J. Gooding (2003)
A New Way of Using ac Voltammetry To Study Redox Kinetics in Electroactive Monolayers
†‡ and Stephen E. Creager (1998)
This paper is referenced by
Expanding the Repertoire of Molecular Linkages to Silicon: Si-S, Si-Se, and Si-Te Bonds.
M. Hu (2016)
Electrocatalytic behavior of AgBr NPs as modifier of carbon past electrode in the presence of methanol and ethanol in aqueous solution: A kinetic study
Tahmineh Tamiji (2019)
Thermal Stability of Organic Monolayers Grafted to Si(111): Insights from ReaxFF Reactive Molecular Dynamics Simulations.
F. A. Soria (2017)
Coupled Thermodynamic and Kinetic Changes in the Electrochemistry of Ferrocenyl Monolayers Induced by Light.
Y. Yang (2017)
Electron Hopping between Fe 3d States in Ethynylferrocene-doped Poly(Methyl Methacrylate)-poly(Decyl Methacrylate) Copolymer Membranes
María Cuartero (2018)
Functionalization of Oxide-Free Silicon Surfaces with Redox-Active Assemblies.
B. Fabre (2016)
Stability of chemically passivated silicon electrodes in aqueous solutions: interplay between bias voltage and hydration of the electrolyte
V. R. Gonçales (2016)
Preparation, characterization, and protein-resistance of films derived from a series of α-oligo(ethylene glycol)-ω-alkenes on H–Si(111) surfaces
G. Qin (2017)
Voltammetric H/D Isotope Effects on Redox‐Active Small Molecules Conjugated with DNA Self‐Assembled Monolayers
Sarasi K. K. Galagedera (2019)
Forming Ferrocenyl Self‐Assembled Monolayers on Si(100) Electrodes with Different Alkyl Chain Lengths for Electron Transfer Studies
S. Ahmad (2019)
Click Coupling Reactions on Flat and Nanostructured Hydrogen‐Passivated Silicon Surfaces
A. Henriksson (2019)
Spontaneous S–Si bonding of alkanethiols to Si(111)–H: towards Si–molecule–Si circuits
Chandramalika R. Peiris (2020)
Towards molecular electronic devices based on 'all-carbon' wires.
A. Moneo (2018)