Harvesting Sub-Bandgap IR Photons by Photothermionic Hot Electron Transfer in a Plasmonic p-n Junction

Wenxing Yang; Yawei Liu; David A. Cullen; James R. McBride; Tianquan Lian

doi:10.1021/acs.nanolett.1c00932

Harvesting Sub-Bandgap IR Photons by Photothermionic Hot Electron Transfer in a Plasmonic p-n Junction

Wenxing Yang, Yawei Liu, David A. Cullen, James R. McBride, Tianquan Lian

Materials MicroAnalysis

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19 Scopus citations

Abstract

Plasmonic semiconductors are an emerging class of low-cost plasmonic materials, and the presence of a bandgap and band-bending in these materials offer new opportunities to overcome some of the limitations of plasmonic metals. Here, we demonstrate that in a plasmonic p-n heterojunction (Cu2-xSe-CdSe) the near-IR excitation (1.1 eV) of the hole plasmon in the p-Cu2-xSe phase results in rapid hot electron transfer to n-CdSe, with an energy 2.2 eV above the Fermi level. This hot electron generation and energy upconversion process can be well-described by a photothermionic mechanism, where the presence of a bandgap in p-Cu2-xSe facilitates the generation of energetic photothermal electrons. The lifetime of the transferred electrons in Cu2-xSe-CdSe can reach ∼130 ps, which is nearly 100× longer than that of its metal-semiconductor counterpart. This result demonstrates a novel approach for harvesting the sub-bandgap near IR photons using plasmonic p-n junctions and the potential advantages of plasmonic semiconductors for hot carrier-based devices.

Original language	English
Pages (from-to)	4036-4043
Number of pages	8
Journal	Nano Letters
Volume	21
Issue number	9
DOIs	https://doi.org/10.1021/acs.nanolett.1c00932
State	Published - May 12 2021

Funding

This material is based on work supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Solar Photochemistry Program under Award no. DE- DE-SC0008798 (to T.L.). Transient absorption measurements were conducted in a multiuser facility funded by an NSF MRI grant CHE-1726536 (T.L.). W.Y. acknowledges financial support from the Swedish Research Council (Vetenskapsrådet) for an International Postdoc Fellowship (2017-00449). Electron microscopy experiments were conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. A portion of the STEM-EDS experiments were performed at the Vanderbilt Institute of Nanoscale Science and Engineering. Dr. Leif Hammarström is acknowledged for his helpful discussions on the spectroscopic interpretations.

Funders	Funder number
NSF MRI	CHE-1726536
U.S. Department of Energy
Office of Science
Basic Energy Sciences	DE- DE-SC0008798
Vetenskapsrådet	2017-00449

Keywords

cation exchange
copper selenide
hot carrier transfer
photothermal
plasmonic photocatalysis
transient heating

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10.1021/acs.nanolett.1c00932

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title = "Harvesting Sub-Bandgap IR Photons by Photothermionic Hot Electron Transfer in a Plasmonic p-n Junction",

abstract = "Plasmonic semiconductors are an emerging class of low-cost plasmonic materials, and the presence of a bandgap and band-bending in these materials offer new opportunities to overcome some of the limitations of plasmonic metals. Here, we demonstrate that in a plasmonic p-n heterojunction (Cu2-xSe-CdSe) the near-IR excitation (1.1 eV) of the hole plasmon in the p-Cu2-xSe phase results in rapid hot electron transfer to n-CdSe, with an energy 2.2 eV above the Fermi level. This hot electron generation and energy upconversion process can be well-described by a photothermionic mechanism, where the presence of a bandgap in p-Cu2-xSe facilitates the generation of energetic photothermal electrons. The lifetime of the transferred electrons in Cu2-xSe-CdSe can reach ∼130 ps, which is nearly 100× longer than that of its metal-semiconductor counterpart. This result demonstrates a novel approach for harvesting the sub-bandgap near IR photons using plasmonic p-n junctions and the potential advantages of plasmonic semiconductors for hot carrier-based devices.",

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author = "Wenxing Yang and Yawei Liu and Cullen, {David A.} and McBride, {James R.} and Tianquan Lian",

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AU - Yang, Wenxing

AU - Liu, Yawei

AU - Cullen, David A.

AU - McBride, James R.

AU - Lian, Tianquan

PY - 2021/5/12

Y1 - 2021/5/12

N2 - Plasmonic semiconductors are an emerging class of low-cost plasmonic materials, and the presence of a bandgap and band-bending in these materials offer new opportunities to overcome some of the limitations of plasmonic metals. Here, we demonstrate that in a plasmonic p-n heterojunction (Cu2-xSe-CdSe) the near-IR excitation (1.1 eV) of the hole plasmon in the p-Cu2-xSe phase results in rapid hot electron transfer to n-CdSe, with an energy 2.2 eV above the Fermi level. This hot electron generation and energy upconversion process can be well-described by a photothermionic mechanism, where the presence of a bandgap in p-Cu2-xSe facilitates the generation of energetic photothermal electrons. The lifetime of the transferred electrons in Cu2-xSe-CdSe can reach ∼130 ps, which is nearly 100× longer than that of its metal-semiconductor counterpart. This result demonstrates a novel approach for harvesting the sub-bandgap near IR photons using plasmonic p-n junctions and the potential advantages of plasmonic semiconductors for hot carrier-based devices.

AB - Plasmonic semiconductors are an emerging class of low-cost plasmonic materials, and the presence of a bandgap and band-bending in these materials offer new opportunities to overcome some of the limitations of plasmonic metals. Here, we demonstrate that in a plasmonic p-n heterojunction (Cu2-xSe-CdSe) the near-IR excitation (1.1 eV) of the hole plasmon in the p-Cu2-xSe phase results in rapid hot electron transfer to n-CdSe, with an energy 2.2 eV above the Fermi level. This hot electron generation and energy upconversion process can be well-described by a photothermionic mechanism, where the presence of a bandgap in p-Cu2-xSe facilitates the generation of energetic photothermal electrons. The lifetime of the transferred electrons in Cu2-xSe-CdSe can reach ∼130 ps, which is nearly 100× longer than that of its metal-semiconductor counterpart. This result demonstrates a novel approach for harvesting the sub-bandgap near IR photons using plasmonic p-n junctions and the potential advantages of plasmonic semiconductors for hot carrier-based devices.

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Harvesting Sub-Bandgap IR Photons by Photothermionic Hot Electron Transfer in a Plasmonic p-n Junction

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