Bright, Mechanosensitive Upconversion with Cubic-Phase Heteroepitaxial Core–Shell Nanoparticles

Lay, Alice; Siefe, Chris; Fischer, Stefan; Mehlenbacher, Randy D.; Ke, Feng; Mao, Wendy L.; Alivisatos, A. Paul; Goodman, Miriam B.; Dionne, Jennifer A.

doi:10.1021/acs.nanolett.8b01535

Bright, Mechanosensitive Upconversion with Cubic-Phase Heteroepitaxial Core–Shell Nanoparticles

Journal Article · Thu Jun 21 00:00:00 EDT 2018 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.8b01535· OSTI ID:1464057

^[1]; Siefe, Chris ^[1]; Fischer, Stefan ^[1]; Mehlenbacher, Randy D. ^[1]; Ke, Feng ^[1]; Mao, Wendy L. ^[1]; ^[2]; Goodman, Miriam B. ^[1]; Dionne, Jennifer A. ^[1]

Stanford Univ., Stanford, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kavli Energy NanoScience Institute, Berkeley, CA (United States)

Lanthanide-doped nanoparticles are an emerging class of optical sensors, exhibiting sharp emission peaks, high signal-to-noise ratio, photostability, and a ratiometric color response to stress. The same centrosymmetric crystal field environment that allows for high mechanosensitivity in the cubic-phase (α), however, contributes to low upconversion quantum yield (UCQY). In this work, we engineer brighter mechanosensitive upconverters using a core–shell geometry. Sub-25 nm α-NaYF₄:Yb,Er cores are shelled with an optically inert surface passivation layer of ~4.5 nm thickness. Using different shell materials, including NaGdF₄, NaYF₄, and NaLuF₄, we study how compressive to tensile strain influences the nanoparticles’ imaging and sensing properties. All core–shell nanoparticles exhibit enhanced UCQY, up to 0.14% at 150 W/cm², which rivals the efficiency of unshelled hexagonal-phase (β) nanoparticles. Additionally, strain at the core–shell interface can tune mechanosensitivity. In particular, the compressive Gd shell results in the largest color response from yellow-green to orange or, quantitatively, a change in the red to green ratio of 12.2 ± 1.2% per GPa. For all samples, the ratiometric readouts are consistent over three pressure cycles from ambient to 5 GPa. Furthermore, heteroepitaxial shelling significantly improves signal brightness without compromising the core’s mechano-sensing capabilities and further, promotes core–shell cubic-phase nanoparticles as upcoming in vivo and in situ optical sensors.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Light-Material Interactions in Energy Conversion (LMI); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

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

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515; SC0001293

OSTI ID:: 1464057

Alternate ID(s):: OSTI ID: 1532327

Journal Information:: Nano Letters, Journal Name: Nano Letters Journal Issue: 7 Vol. 18; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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