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Title: Energetic effects of hybrid organic/inorganic interfacial architecture on nanoporous black silicon photoelectrodes

Abstract

Photoelectrochemical cells have been the subject of great interest in the research community as a route for fuel formation directly from sunlight. Interfacial layers are frequently employed on the surface of light-absorbing semiconductor photoelectrodes to enhance the activity and stability of the semiconductor. Here we consider the energetic effects of such layers on a nanoporous ‘black’ silicon photocathode. We construct hybrid organic/inorganic films by growing an oxide-nucleating molecular monolayer on the nanostructured Si surface and burying this molecular monolayer under TiO2 deposited by atomic layer deposition. We examine the energetic effects of this hybrid interfacial architecture via our recently developed intensity-modulated high-frequency resistivity (IMHFR) impedance spectroscopy technique and quantify the change in thermodynamic flatband potential as the oxide thickness is increased from 0–15 nm. By comparing the IMHFR data with traditional voltammetry, we are able to deconvolute the thermodynamic and kinetic contributions that determine the observed proton reduction onset potential. We also study these photoelectrodes with Pt nanoparticles either (i) deposited on top of the molecular/TiO2 interfacial layer or (ii) etched into the Si surface. In the first architecture, a beneficial positive shift in the thermodynamic flatband potential is achieved from the Si|molecular|TiO2 p-n junction, but the lack of amore » direct Si|Pt contact results in large kinetic charge transfer losses. In contrast, the second architecture allows for facile charge transfer due to the direct Si|Pt contact but negates any benficial thermodynamic effect of the molecular/TiO2 bilayer. Despite the lack of thermodynamic effect of the hybrid molecular/TiO2 interfacial layer, we find that there is still a significant kinetic benefit from this layer. This work demonstrates the sensitive nature of the thermodynamics and kinetics on the interfacial architecture and yields critical insights into the design of photoelectrochemical interfaces.« less

Authors:
ORCiD logo [1];  [2];  [2]; ORCiD logo [2]
+ Show Author Affiliations
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Texas, Austin, TX (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1506615
Alternate Identifier(s):
OSTI ID: 1499820
Report Number(s):
NREL/JA-5900-73052
Journal ID: ISSN 2398-4902; MainId:24354;UUID:f5cf7b9c-4b10-e911-9c1a-ac162d87dfe5;MainAdminID:12830
Grant/Contract Number:  
AC36-08GO28308; SC0014664
Resource Type:
Accepted Manuscript
Journal Name:
Sustainable Energy & Fuels
Additional Journal Information:
Journal Volume: 3; Journal Issue: 7; Journal ID: ISSN 2398-4902
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; photoelectrochemical cells; energetics; interfacial layers; black silicon photoelectrodes; nanostructure

Citation Formats

Pekarek, Ryan T., Christensen, Steven T., Liu, Jun, and Neale, Nathan R. Energetic effects of hybrid organic/inorganic interfacial architecture on nanoporous black silicon photoelectrodes. United States: N. p., 2019. Web. doi:10.1039/c9se00032a.
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Pekarek, Ryan T., Christensen, Steven T., Liu, Jun, & Neale, Nathan R. Energetic effects of hybrid organic/inorganic interfacial architecture on nanoporous black silicon photoelectrodes. United States. https://doi.org/10.1039/c9se00032a
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Pekarek, Ryan T., Christensen, Steven T., Liu, Jun, and Neale, Nathan R. Fri . "Energetic effects of hybrid organic/inorganic interfacial architecture on nanoporous black silicon photoelectrodes". United States. https://doi.org/10.1039/c9se00032a. https://www.osti.gov/servlets/purl/1506615.
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@article{osti_1506615,
title = {Energetic effects of hybrid organic/inorganic interfacial architecture on nanoporous black silicon photoelectrodes},
author = {Pekarek, Ryan T. and Christensen, Steven T. and Liu, Jun and Neale, Nathan R.},
abstractNote = {Photoelectrochemical cells have been the subject of great interest in the research community as a route for fuel formation directly from sunlight. Interfacial layers are frequently employed on the surface of light-absorbing semiconductor photoelectrodes to enhance the activity and stability of the semiconductor. Here we consider the energetic effects of such layers on a nanoporous ‘black’ silicon photocathode. We construct hybrid organic/inorganic films by growing an oxide-nucleating molecular monolayer on the nanostructured Si surface and burying this molecular monolayer under TiO2 deposited by atomic layer deposition. We examine the energetic effects of this hybrid interfacial architecture via our recently developed intensity-modulated high-frequency resistivity (IMHFR) impedance spectroscopy technique and quantify the change in thermodynamic flatband potential as the oxide thickness is increased from 0–15 nm. By comparing the IMHFR data with traditional voltammetry, we are able to deconvolute the thermodynamic and kinetic contributions that determine the observed proton reduction onset potential. We also study these photoelectrodes with Pt nanoparticles either (i) deposited on top of the molecular/TiO2 interfacial layer or (ii) etched into the Si surface. In the first architecture, a beneficial positive shift in the thermodynamic flatband potential is achieved from the Si|molecular|TiO2 p-n junction, but the lack of a direct Si|Pt contact results in large kinetic charge transfer losses. In contrast, the second architecture allows for facile charge transfer due to the direct Si|Pt contact but negates any benficial thermodynamic effect of the molecular/TiO2 bilayer. Despite the lack of thermodynamic effect of the hybrid molecular/TiO2 interfacial layer, we find that there is still a significant kinetic benefit from this layer. This work demonstrates the sensitive nature of the thermodynamics and kinetics on the interfacial architecture and yields critical insights into the design of photoelectrochemical interfaces.},
doi = {10.1039/c9se00032a},
journal = {Sustainable Energy & Fuels},
number = 7,
volume = 3,
place = {United States},
year = {Fri Mar 01 00:00:00 EST 2019},
month = {Fri Mar 01 00:00:00 EST 2019}
}
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https://doi.org/10.1039/c9se00032a
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