Modulating donor–acceptor transition energies in phosphorus–boron co-doped silicon nanocrystals via X- and L-type ligands

Pach, Gregory; Carroll, Gerard; Zhang, Hanyu; Neale, Nathan

doi:10.1039/c9fd00106a

Modulating donor–acceptor transition energies in phosphorus–boron co-doped silicon nanocrystals via X- and L-type ligands

Journal Article · Mon Jan 06 00:00:00 EST 2020 · Faraday Discussions

DOI:https://doi.org/10.1039/c9fd00106a· OSTI ID:1603926

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National Renewable Energy Lab. (NREL), Golden, CO (United States)

In this work, we explore the effect of ligand binding groups on the visible and NIR photoluminescent properties within phophorus-boron co-doped silicon nanocrystals (PB:Si NCs) by exploiting both the X-type (covalent) and L-type (Lewis donor molecule) bonding interactions. We find that the cooperative nature of both X-and L-type bonding from alkoxide/alcohol, alkylamide/alkylamine, and alkylthiolate/alkylthiol on PB:Si NCs results in photoluminescence (PL) energy blue shifts from the as-synthesized, hydride-terminated NCs (PB:Si–H) in excess of 0.4 eV, depending on the surface termination. These PL blue shifts appear greatestin the most strongly confined samples with diameters <4 nm where the surface-to-volume ratio is high and, therefore, the ligand effects are most pronounced. A correlation between thedonor group strength (either X-type or L-type) and the degree of D–A state modulation is found, and the proportion of the PL blue shift from the X-and L-type interactionsis quantified.Raman spectroscopy is used to provide additional evidence of the strength of the L-type donor groups. Additionally, we probe how the nature of the ligand chemistry affects the radiative lifetime and PL efficiency and find that the ligands do not significantly change the D–A emission dynamics, and all samples retain the long 50–130 μs lifetimes characteristic of these transitions.Finally, we describethree mechanisms that operate to effect the D–A recombination energies: (1) X-type ligands that modulate the PB:Si–X NC wavefunction; (2) L-type ligands that perturb the donor and acceptor states via a molecular orbital theory picture; and (3) X-and L-type ligands that cause a dielectric increase around the PB:Si NC core, which provides Coulomb screening and modulates the donor and acceptor states even further.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1603926

Alternate ID(s):: OSTI ID: 1602081

Report Number(s):: NREL/JA-5900-75122; MainId:23375; UUID:e2b72a34-dce9-e911-9c29-ac162d87dfe5; MainAdminID:11851

Journal Information:: Faraday Discussions, Journal Name: Faraday Discussions Vol. 222; ISSN 1359-6640

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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transition energies

Modulating donor–acceptor transition energies in phosphorus–boron co-doped silicon nanocrystals via X- and L-type ligands

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