Photoreduction at illuminated p-type semiconducting silicon photoelectrodes. Evidence for Fermi level pinning

Bocarsly, Andrew Bruce; Bookbinder, Dana C.; Dominey, Raymond N.; Lewis, Nathan S.; Wrighton, Mark S.

doi:10.1021/ja00531a003

Cited by 156 publications

(127 citation statements)

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“…1 These data correspond to curves given in Fig. 7 Electrodes and Surface Derivatization with I. Electrodes were prepared by using procedures and materials described previously (2,24). Typical photoelectrode areas ranged from 5 to 15 mm2.…”

Section: Replacement Of Br-by Ptcl02-in Surfaces Treated Withsupporting

confidence: 56%

“…The surface modification light H20 > H2 + 1/202 [1] results in improved kinetics for H2 evolution from the p-type semiconductor. Kinetics for H2 evolution was previously identified as a major problem at p-semiconductor aqueous electrolyte interfaces (1)(2)(3). Surface modification of electrodes has recently been an active area of research, and examples of electrocatalysts are emerging (4).…”

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confidence: 99%

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Synthesis and characterization of a photosensitive interface for hydrogen generation: Chemically modified p-type semiconducting silicon photocathodes

Bookbinder

Bruce

Dominey

et al. 1980

Proc. Natl. Acad. Sci. U.S.A.

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results in improved kinetics for H2 evolution from the p-type semiconductor. Kinetics for H2 evolution was previously identified as a major problem at p-semiconductor aqueous electrolyte interfaces (1-3). Surface modification of electrodes has recently been an active area of research, and examples of electrocatalysts are emerging (4). To produce an efficient photosensitive interface from which to evolve H2 we take advantage of the light absorption and charge separating properties of a semiconductor (5-8). But additionally we employ surface modification to achieve good H2 evolution kinetics. A p-type semiconductor should serve as a photocathode, because the minority carrier is the electron, e-. As indicated in Fig. 1, the photoexcited electron becomes available at the interface as a reducing equivalent with reducing power no greater than the bottom of the conduction band at the interface ECB. Efficient solar-driven electrolysis requires: (i) use of a photocathode having a small Eg, 1-2 eV; (ii) optimization of the product of Ev and photocurrent; and (iii) a durable interface. Experiments show that Ev can be significant for small Eg photocathodes, but the kinetics for H2 evolution are so poor that little if any efficiency can be realized for p-type Si (Eg =

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Section: Replacement Of Br-by Ptcl02-in Surfaces Treated Withsupporting

confidence: 56%

mentioning

confidence: 99%

Synthesis and characterization of a photosensitive interface for hydrogen generation: Chemically modified p-type semiconducting silicon photocathodes

Bookbinder

Bruce

Dominey

et al. 1980

Proc. Natl. Acad. Sci. U.S.A.

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“…12,15,[51][52][53] The photogenerated electron or hole can transfer from the host photoelectrode to the corresponding catalyst, which will trap it and kinetically promote the water reduction or oxidation Noble metals, including Pt, Au, Pd, Ag, and Rh, and metal alloys, 12,15 have been widely used as catalysts for water reduction to improve reaction rates. RuO 2 , NiO, IrO 2 , and Co 3 O 4 12,15,19 are common useful catalysts for the water oxidation reaction.…”

Section: Catalyst Engineering For Photoelectrochemical Electrodesmentioning

confidence: 99%

Atomic layer deposition for electrochemical energy generation and storage systems

Peng

Lewis

Hoertz

et al. 2011

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

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Clean renewable energy sources (e.g., solar, wind, and hydro) offers the most promising solution to energy and environmental sustainability. On the other hand, owing to the spatial and temporal variations of renewable energy sources, and transportation and mobility needs, high density energy storage and efficient energy distribution to points of use is also critical. Moreover, it is challenging to scale up those processes in a cost-effective way. Electrochemical processes, including photoelectrochemical devices, batteries, fuel cells, super capacitors, and others, have shown promise for addressing many of the abovementioned challenges. Materials with designer properties, especially the interfacial properties, play critical role for the performance of those devices. Atomic layer deposition is capable of precise engineering material properties on atomic scale. In this review, we focus on the current state of knowledge of the applications, perspective and challenges of atomic layer deposition process on the electrochemical energy generation and storage devices and processes.

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“…3 for n-GaAs) systems whose Vredox span a range of 2.1 V. Moreover, the potential range over which Voc is independant of Vredox is considerably wider than the band gap energy values. This implies Fermi level pinning which is believed to be due to the presence of a high density of interface or surface states (36,38,40,41) or carrier injection due to a sufficient band bending to change the relative camer density (42)(43)(44). Analogous to other published data obtained in non-aqueous (36,38,41,44) and aqueous (35,40,(45)(46)(47) solvents, it could be concluded that a "surface-controlled model" appears to be appropriate to explain these experimental results.…”

Section: ( I ) Studies In Aqueous Acidic Mediummentioning

confidence: 99%

Fermi level pinning or semiconductor electrodes in aqueous and non aqueous electrolytes: influence of the modification of the electrode surface

Savadogo¹

1989

Can. J. Chem.

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Fermi level pinning or semiconductor electrodes in aqueous and non aqueous electrolytes:influence of the modification of the electrode surface Modification of several semiconductors material surfaces with H4SiW12040.~zH70 have been carried out to produce an increase in the open circuit photopotential at the semiconductor/electrolyte interface (V,,) without changing the flat-band potential. The augmentation of V, , is shown to be attributed to a decrease of the minority carriers recombination at the semiconductor/electrolyte interface along with the suppression of Fermi level pinning. The enhancement of V, and the electrocatalytic activity of the hydrogen evolution reaction in acidic medium of the derivatized electrodes is attributed to the Fermi level unpinning.Key words: photoelectrodes, photoelectrocatalysis, pinning, modification improvement.0 . SAVADOGO. Can. J. Chem. 67, 382 (1989).La modification des surfaces de matkriaux semiconducteurs avec H4SiW 12040.nHz0 conduit a une augmentation de la tension en circuit ouvert des cellules photoClectrochimiques (V,,) et a une diminution de la surtension des cellules photoClectrocatalytiques pour la rtaction de dCgagement d'hydrogene en milieu acide. Les potentiels de bandes plates des materiaux ne sont pas influencCs par cette modification. Ces rCsultats sont attribuis a une diminution du taux de recombinaison des porteurs minoritaires due a la suppression de l'ancrage du niveau de Fermi des materiaux.

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Photoreduction at illuminated p-type semiconducting silicon photoelectrodes. Evidence for Fermi level pinning

Cited by 156 publications

References 4 publications

Synthesis and characterization of a photosensitive interface for hydrogen generation: Chemically modified p-type semiconducting silicon photocathodes

Synthesis and characterization of a photosensitive interface for hydrogen generation: Chemically modified p-type semiconducting silicon photocathodes

Atomic layer deposition for electrochemical energy generation and storage systems

Fermi level pinning or semiconductor electrodes in aqueous and non aqueous electrolytes: influence of the modification of the electrode surface

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