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Titolo: Distance dependence of the electron-transfer rate across covalently bondedmonolayers on silicon
Autore: Cheng, J; Robinson, DB; Cicero, RL; Eberspacher, T; Barrelet, CJ; Chidsey, CED;
- Indirizzi:
- Stanford Univ, Dept Chem, Stanford, CA 94305 USA Stanford Univ Stanford CA USA 94305 iv, Dept Chem, Stanford, CA 94305 USA
- Titolo Testata:
- JOURNAL OF PHYSICAL CHEMISTRY B
fascicolo: 44,
volume: 105,
anno: 2001,
pagine: 10900 - 10904
- SICI:
- 1520-6106(20011108)105:44<10900:DDOTER>2.0.ZU;2-M
- Fonte:
- ISI
- Lingua:
- ENG
- Soggetto:
- ORGANIZED MOLECULAR ASSEMBLIES; ALKANETHIOL MONOLAYERS; ALKYL MONOLAYERS; THIOL MONOLAYERS; RATE CONSTANTS; SI SURFACES; FREE-ENERGY; GOLD; KINETICS; ELECTROCHEMISTRY;
- Tipo documento:
- Article
- Natura:
- Periodico
- Settore Disciplinare:
- Physical, Chemical & Earth Sciences
- Citazioni:
- 33
- Recensione:
- Indirizzi per estratti:
- Indirizzo: Chidsey, CED Stanford Univ, Dept Chem, Stanford, CA 94305 USA Stanford Univ Stanford CA USA 94305 , Stanford, CA 94305 USA
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- Citazione:
- J. Cheng et al., "Distance dependence of the electron-transfer rate across covalently bondedmonolayers on silicon", J PHYS CH B, 105(44), 2001, pp. 10900-10904
Abstract
Alkyl monolayers covalently bonded directly to n-type Si(111) surfaces have been prepared by UV illumination of the H-Si(111) surface while immersed in CH2=CH-(CH2)(n-3)CH3 (n = 5-8) under high vacuum. The characterization by ellipsometry, infrared spectroscopy, and X-ray photoelectron spectroscopyshows that I-alkenes form dense monolayers on the silicon surface. The electron-transfer rates from the surface of the electrode through the alkyl monolayers; to decamethylferricenium acceptors in tetrahydrofuran have been measured. The rates are proportional to the decamethylferricenium concentration and also to the dopant density as determined from capacitance measurements. The rates show an exponential distance dependence with a decay constant of 1.00 +/- 0.05 per CH2, similar to known behavior with alkanethiol monolayers on metal electrodes. The dependence of the rates on applied potential has a logarithmic slope of about 0.25 F/RT at potentials negative of the flat-band potential derived from capacitance measurements. This slope is qualitatively consistent with the expected potential dependence of the activation energy of electron transfer. The slope increases as expected at potentials positive of the flat-band potential, where a space-charge region forms.
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Documento generato il 19/06/13 alle ore 06:43:20