Surface-Functionalization of Oleate-Capped Nano-Emitters for Stable Dispersion in 3D-Printable Polymers

Akhilesh Kumar Pathak; Sachin Prashant Kulkarni; Rachel R. Chan; Chad A. Mirkin; Koray Aydin; Sridhar Krishnaswamy

doi:10.1002/adfm.202412064

Surface-Functionalization of Oleate-Capped Nano-Emitters for Stable Dispersion in 3D-Printable Polymers

Akhilesh Kumar Pathak, Sachin Prashant Kulkarni, Rachel R. Chan, Chad A. Mirkin, Koray Aydin^*, Sridhar Krishnaswamy^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

Two-photon polymerization 3D-printing is a well-known technique for fabricating passive micro/nanoscale structures, such as microlenses and inversely designed polarization splitters. The integration of light emitting nanoparticle (NP) dopants, such as quantum dots (QDs) and rare-earth doped nanoparticles (RENPs), into a polymer resist would enable 3D printing of active polymer micro-photonic devices, including sensors, lasers, and solid-state displays. Many NPs contain oleic acid ligands to prevent degradation, but oleate-capped NPs (oc-NPs) tend to agglomerate in nonpolar media despite the hydrophobicity of the ligand. This results in an uneven nanoparticle distribution and increased optical extinction. In this work, a general approach is proposed for dispersing oc-NPs in commercial 3D printable polymers. Controlled growth of small carbon chains around the oc-NPs is achieved by functionalizing them with methyl-methacrylate monomers. The proposed approach is validated on RENPs (≈65 nm) and CdSe/ZnS quantum dots (≈12 nm) using commercial polymer resists (IP-Dip and IP-Visio). Dispersions of functionalized NPs (f-NPs) have improved the NP density by an order of magnitude and are shown to be stable for several weeks with minimal impact on printing quality. The approach is generalizable to other oc-NPs, enabling synthesis of functional resins for high-quality polymer-based optical and electronic devices.

Original language	English (US)
Article number	2412064
Journal	Advanced Functional Materials
Volume	35
Issue number	1
DOIs	https://doi.org/10.1002/adfm.202412064
State	Published - Jan 2 2025

Funding

A.K.P. and S.P.K. contributed equally to this work. S.K. acknowledges support from the Office of Naval Research through award numbers N00014-23-1-2529 and N00014-21-1-2233. K.A. and C.A.M. acknowledge support from the Air Force Office of Scientific Research under award number FA9550-22-1-0300. R.R.C. gratefully acknowledges support by the National Science Foundation Graduate Research Fellowship Program under grant DGE-2234667. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the funding agencies. This work made use of the two-photon 3D printer at the Center for Smart Structures and Materials at Northwestern acquired with support from the ONR through award number N00014-15-1-2935. This work made use of the EPIC and BioCryo facilities of Northwestern University's NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), the IIN, and Northwestern's MRSEC Program (NSF DMR-1720139). This work made use of the IMSERC\u00A0(RRID:SCR_017874)\u00A0MS facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), the State of Illinois, and the International Institute for Nanotechnology (IIN). A.K.P. and S.P.K. contributed equally to this work. S.K. acknowledges support from the Office of Naval Research through award numbers N00014\u201023\u20101\u20102529 and N00014\u201021\u20101\u20102233. K.A. and C.A.M. acknowledge support from the Air Force Office of Scientific Research under award number FA9550\u201022\u20101\u20100300. R.R.C. gratefully acknowledges support by the National Science Foundation Graduate Research Fellowship Program under grant DGE\u20102234667. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the funding agencies. This work made use of the two\u2010photon 3D printer at the Center for Smart Structures and Materials at Northwestern acquired with support from the ONR through award number N00014\u201015\u20101\u20102935. This work made use of the EPIC and BioCryo facilities of Northwestern University's NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS\u20102025633), the IIN, and Northwestern's MRSEC Program (NSF DMR\u20101720139). This work made use of the IMSERC ( RRID:SCR_017874 ) MS facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS\u20102025633), the State of Illinois, and the International Institute for Nanotechnology (IIN).

Keywords

3D printing
dispersion
functionalization
nano-emitters
two-photon polymerization

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
General Chemistry
Biomaterials
General Materials Science
Condensed Matter Physics
Electrochemistry

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10.1002/adfm.202412064

Cite this

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abstract = "Two-photon polymerization 3D-printing is a well-known technique for fabricating passive micro/nanoscale structures, such as microlenses and inversely designed polarization splitters. The integration of light emitting nanoparticle (NP) dopants, such as quantum dots (QDs) and rare-earth doped nanoparticles (RENPs), into a polymer resist would enable 3D printing of active polymer micro-photonic devices, including sensors, lasers, and solid-state displays. Many NPs contain oleic acid ligands to prevent degradation, but oleate-capped NPs (oc-NPs) tend to agglomerate in nonpolar media despite the hydrophobicity of the ligand. This results in an uneven nanoparticle distribution and increased optical extinction. In this work, a general approach is proposed for dispersing oc-NPs in commercial 3D printable polymers. Controlled growth of small carbon chains around the oc-NPs is achieved by functionalizing them with methyl-methacrylate monomers. The proposed approach is validated on RENPs (≈65 nm) and CdSe/ZnS quantum dots (≈12 nm) using commercial polymer resists (IP-Dip and IP-Visio). Dispersions of functionalized NPs (f-NPs) have improved the NP density by an order of magnitude and are shown to be stable for several weeks with minimal impact on printing quality. The approach is generalizable to other oc-NPs, enabling synthesis of functional resins for high-quality polymer-based optical and electronic devices.",

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Surface-Functionalization of Oleate-Capped Nano-Emitters for Stable Dispersion in 3D-Printable Polymers

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