Tuning Confinement in Colloidal Silicon Nanocrystals with Saturated Surface Ligands

Carroll, Gerard M.; Limpens, Rens; Neale, Nathan R.

doi:10.1021/acs.nanolett.8b00680

Tuning Confinement in Colloidal Silicon Nanocrystals with Saturated Surface Ligands

Journal Article · Mon Apr 16 00:00:00 EDT 2018 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.8b00680· OSTI ID:1436402

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

The optical properties of silicon nanocrystals (Si NCs) are a subject of intense study and continued debate. In particular, Si NC photoluminescence (PL) properties are known to depend strongly on the surface chemistry, resulting in electron-hole recombination pathways derived from the Si NC band-edge, surface-state defects, or combined NC-conjugated ligand hybrid states. In this Letter, we perform a comparison of three different saturated surface functional groups - alkyls, amides, and alkoxides - on nonthermal plasma-synthesized Si NCs. We find a systematic and size-dependent high-energy (blue) shift in the PL spectrum of Si NCs with amide and alkoxy functionalization relative to alkyl. Time-resolved photoluminescence and transient absorption spectroscopies reveal no change in the excited-state dynamics between Si NCs functionalized with alkyl, amide, or alkoxide ligands, showing for the first time that saturated ligands - not only surface-derived charge-transfer states or hybridization between NC and low-lying ligand orbitals - are responsible for tuning the Si NC optical properties. To explain these PL shifts we propose that the atom bound to the Si NC surface strongly interacts with the Si NC electronic wave function and modulates the Si NC quantum confinement. Furthermore, these results reveal a potentially broadly applicable correlation between the optoelectronic properties of Si NCs and related quantum-confined structures based on the interaction between NC surfaces and the ligand binding group.

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) (SC-22)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1436402

Report Number(s):: NREL/JA--5900-71481

Journal Information:: Nano Letters, Journal Name: Nano Letters Journal Issue: 5 Vol. 18; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Tuning Confinement in Colloidal Silicon Nanocrystals with Saturated Surface Ligands

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