CaltechAUTHORS
  A Caltech Library Service

Energetics and Kinetics of Interfacial Electron-Transfer Processes at Chemically Modified InP/Liquid Junctions

Prokopuk, Nicholas and Lewis, Nathan S. (2004) Energetics and Kinetics of Interfacial Electron-Transfer Processes at Chemically Modified InP/Liquid Junctions. Journal of Physical Chemistry B, 108 (14). pp. 4449-4456. ISSN 1520-6106. doi:10.1021/jp0223049. https://resolver.caltech.edu/CaltechAUTHORS:20170619-064106321

Full text is not posted in this repository. Consult Related URLs below.

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20170619-064106321

Abstract

The electrochemical behavior of freshly etched (111)B-oriented InP surfaces was compared to that of (111)B-oriented InP surfaces that had been chemically modified by reaction with p-BrCH_2C_6H_4CF_3. Differential capacitance versus potential and current density versus potential techniques were used to measure the energetics and kinetics of interfacial electron-transfer reactions in contact with a 70:30 (v:v) mixture of CH_3CN−tetrahydrofuran that contained either 1,1‘-dimethylferrrocene^(+/0) or decamethylferrocene^(+/0). For both the etched and modified (111)B InP contacts, plots of differential capacitance versus potential measurements indicated a linear dependence of the equilibrium voltage drop (V_(bi)) in the semiconductor space-charge region, as a function of the redox potential (E(A/A-)) of the solution, with the slope of V_(bi) vs E(A/A-) ≈ 1.0, as expected for ideal behavior of a semiconductor/liquid junction. The barrier heights calculated for the chemically modified InP/liquid junctions were 100 ± 20 mV higher than the barrier heights of freshly etched, unmodified (111)B InP surfaces in contact with the same electrolyte solutions. The higher barrier heights of the chemically modified surfaces are consistent with a shift in the InP band-edge energies induced by the surface modification process. The modified and etched surfaces both displayed interfacial electron-transfer kinetics that were first order in the concentration of acceptors in solution and first order in the concentration of electrons at the semiconductor surface. The interfacial electron-transfer rate constants for these systems were determined to be ∼10^(-17)−10^(-18) cm^4 s^(-1).


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jp0223049DOIArticle
http://pubs.acs.org/doi/full/10.1021/jp0223049PublisherArticle
ORCID:
AuthorORCID
Lewis, Nathan S.0000-0001-5245-0538
Additional Information:© 2004 American Chemical Society. Received 24 October 2002. Published online 16 March 2004. Published in print 1 April 2004. We acknowledge the Department of Energy, Office of Basic Energy Sciences, for support of this work.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)UNSPECIFIED
Issue or Number:14
DOI:10.1021/jp0223049
Record Number:CaltechAUTHORS:20170619-064106321
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170619-064106321
Official Citation:Energetics and Kinetics of Interfacial Electron-Transfer Processes at Chemically Modified InP/Liquid Junctions Nicholas Prokopuk and Nathan S. Lewis The Journal of Physical Chemistry B 2004 108 (14), 4449-4456 DOI: 10.1021/jp0223049
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:78310
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:19 Jun 2017 16:33
Last Modified:15 Nov 2021 17:38

Repository Staff Only: item control page