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Mehlenbacher, Randy D.

Publications and source records attributed to Mehlenbacher, Randy D..

4 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Sub-20 nm Core–Shell–Shell Nanoparticles for Bright Upconversion and Enhanced Förster Resonant Energy Transfer

Upconverting nanoparticles provide valuable benefits as optical probes for bioimaging and Förster resonant energy transfer (FRET) due to their high signal-to-noise ratio, photostability, and biocompatibility; yet, making nanoparticles small yields a significant decay in brightness due to increased surface quenching. Approaches to improve the brightness of UCNPs exist but often require increased nanoparticle size. Here we present a unique core-shell-shell nanoparticle architecture for small (sub-20 nm), bright upconversion with several key features: (1) maximal sensitizer concentration in the core for high near-infrared absorption, (2) efficient energy transfer between core and interior shell for strong emission, and (3) emitter localization near the nanoparticle surface for efficient FRET. This architecture consists of β-NaYbF 4 (core) @NaY 0.8-x Er x Gd 0.2 F 4 (interior shell) @NaY 0.8 Gd 0.2 F 4 (exterior shell), where sensitizer and emitter ions are partitioned into core and interior shell, respectively. Emitter concentration is varied (x = 1, 2, 5, 10, 20, 50, and 80%) to investigate influence on single particle brightness, upconversion quantum yield, decay lifetimes, and FRET coupling. We compare these seven samples with the field-standard core-shell architecture of β-NaY 0.58 Gd 0.2 Yb 0.2 Er 0.02 F 4 (core) @NaY 0.8 Gd 0.2 F 4 (shell), with sensitizer and emitter ions codoped in the core. At a single particle level, the core-shell-shell design was up to 2-fold brighter than the standard core-shell design. Further, by coupling a fluorescent dye to the surface of the two different architectures, we demonstrated up to 8-fold improved emission enhancement with the core-shell-shell compared to the core-shell design. Finally, we show how, given proper consideration for emitter concentration, we can design a unique nanoparticle architecture to yield comparable or improved brightness and FRET coupling within a small volume.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Small Alkaline-Earth-based Core/Shell Nanoparticles for Efficient Upconversion

The optical efficiency of lanthanide-based upconversion is intricately related to the crystalline host lattice. Different crystal fields interacting with the electron clouds of the lanthanides can significantly affect transition probabilities between the energy levels. Here, we investigate six distinct alkaline-earth rare-earth fluoride host materials (M 1- x Ln x F 2+ x , MLnF) for infrared-to-visible upconversion, focusing on nanoparticles of CaYF, CaLuF, SrYF, SrLuF, BaYF, and BaLuF doped with Yb 3+ and Er 3+ . We first synthesize ~5 nm upconverting cores of each material via a thermal decomposition method. Then we introduce a dropwise hot-injection method to grow optically inert MYF shell layers around the active cores. Five distinct shell thicknesses are considered for each host material, resulting in 36 unique, monodisperse upconverting nanomaterials each with size below ~15 nm. The upconversion quantum yield (UCQY) is measured for all core/shell nanoparticles as a function of shell thickness and compared with hexagonal (β-phase) NaGdF 4 , a traditional upconverting host lattice. While the UCQY of core nanoparticles is below the detection limit (<10-5%), it increases by 4 to 5 orders of magnitude as the shell thickness approaches 4-6 nm. The UCQY values of our cubic MLnF nanoparticles meet or exceed the β-NaGdF 4 reference sample. Across all core/shell samples, SrLuF nanoparticles are the most efficient, with UCQY values of 0.53% at 80 W/cm 2 for cubic nanoparticles with ~11 nm edge length. This efficiency is 5 times higher than our β-NaGdF 4 reference material with comparable core size and shell thickness. Our work demonstrates efficient and bright upconversion in ultrasmall alkaline-earth-based nanoparticles, with applications spanning biological imaging and optical sensing.

36 MATERIALS SCIENCE↗
DOE OSTI2018

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

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-NaYF 4 :Yb,Er cores are shelled with an optically inert surface passivation layer of ~4.5 nm thickness. Using different shell materials, including NaGdF 4 , NaYF 4 , and NaLuF 4 , 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/cm 2 , 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.

77 NANOSCIENCE AND NANOTECHNOLOGY↗