Bright, Mechanosensitive Upconversion with Cubic-Phase Heteroepitaxial Core–Shell Nanoparticles
Abstract
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. Therefore, heteroepitaxial shelling significantly improves signal brightness without compromising the core's mechano-sensing capabilities and further, promotes core-shell cubic-phase nanoparticles as upcoming inmore »
- Authors:
-
- 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)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Light-Material Interactions in Energy Conversion (LMI); SLAC National Accelerator Lab., Menlo Park, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1464057
- Alternate Identifier(s):
- OSTI ID: 1532327
- Grant/Contract Number:
- AC02-05CH11231; AC02-76SF00515; SC0001293; FI 2042/1-1; 2013156180
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nano Letters
- Additional Journal Information:
- Journal Volume: 18; Journal Issue: 7; Journal ID: ISSN 1530-6984
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 77 NANOSCIENCE AND NANOTECHNOLOGY; core−shell; Heteroepitaxial; lanthanides; mechanosensitivity; quantum yield; upconversion
Citation Formats
Lay, Alice, Siefe, Chris, Fischer, Stefan, Mehlenbacher, Randy D., Ke, Feng, Mao, Wendy L., Alivisatos, A. Paul, Goodman, Miriam B., and Dionne, Jennifer A. Bright, Mechanosensitive Upconversion with Cubic-Phase Heteroepitaxial Core–Shell Nanoparticles. United States: N. p., 2018.
Web. doi:10.1021/acs.nanolett.8b01535.
Lay, Alice, Siefe, Chris, Fischer, Stefan, Mehlenbacher, Randy D., Ke, Feng, Mao, Wendy L., Alivisatos, A. Paul, Goodman, Miriam B., & Dionne, Jennifer A. Bright, Mechanosensitive Upconversion with Cubic-Phase Heteroepitaxial Core–Shell Nanoparticles. United States. https://doi.org/10.1021/acs.nanolett.8b01535
Lay, Alice, Siefe, Chris, Fischer, Stefan, Mehlenbacher, Randy D., Ke, Feng, Mao, Wendy L., Alivisatos, A. Paul, Goodman, Miriam B., and Dionne, Jennifer A. Thu .
"Bright, Mechanosensitive Upconversion with Cubic-Phase Heteroepitaxial Core–Shell Nanoparticles". United States. https://doi.org/10.1021/acs.nanolett.8b01535. https://www.osti.gov/servlets/purl/1464057.
@article{osti_1464057,
title = {Bright, Mechanosensitive Upconversion with Cubic-Phase Heteroepitaxial Core–Shell Nanoparticles},
author = {Lay, Alice and Siefe, Chris and Fischer, Stefan and Mehlenbacher, Randy D. and Ke, Feng and Mao, Wendy L. and Alivisatos, A. Paul and Goodman, Miriam B. and Dionne, Jennifer A.},
abstractNote = {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. Therefore, 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.},
doi = {10.1021/acs.nanolett.8b01535},
journal = {Nano Letters},
number = 7,
volume = 18,
place = {United States},
year = {Thu Jun 21 00:00:00 EDT 2018},
month = {Thu Jun 21 00:00:00 EDT 2018}
}
Web of Science
Figures / Tables:
Works referenced in this record:
Nanomaterials for in vivo imaging of mechanical forces and electrical fields
journal, December 2017
- Mehlenbacher, Randy D.; Kolbl, Rea; Lay, Alice
- Nature Reviews Materials, Vol. 3, Issue 2
Upconversion nanoparticles in biological labeling, imaging, and therapy
journal, January 2010
- Wang, Feng; Banerjee, Debapriya; Liu, Yongsheng
- The Analyst, Vol. 135, Issue 8
Stimuli responsive upconversion luminescence nanomaterials and films for various applications
journal, January 2015
- Tsang, Ming-Kiu; Bai, Gongxun; Hao, Jianhua
- Chemical Society Reviews, Vol. 44, Issue 6
Upconverting Nanoparticles as Optical Sensors of Nano- to Micro-Newton Forces
journal, June 2017
- Lay, Alice; Wang, Derek S.; Wisser, Michael D.
- Nano Letters, Vol. 17, Issue 7
Strain-Induced Modification of Optical Selection Rules in Lanthanide-Based Upconverting Nanoparticles
journal, February 2015
- Wisser, Michael D.; Chea, Maverick; Lin, Yu
- Nano Letters, Vol. 15, Issue 3
NIR-to-NIR Two-Photon Excited CaF 2 :Tm 3+ ,Yb 3+ Nanoparticles: Multifunctional Nanoprobes for Highly Penetrating Fluorescence Bio-Imaging
journal, October 2011
- Dong, Ning-Ning; Pedroni, Marco; Piccinelli, Fabio
- ACS Nano, Vol. 5, Issue 11
Neodymium(iii) doped fluoride nanoparticles as non-contact optical temperature sensors
journal, January 2012
- Wawrzynczyk, Dominika; Bednarkiewicz, Artur; Nyk, Marcin
- Nanoscale, Vol. 4, Issue 22
Upconversion Luminescence Properties of NaYF 4 :Yb:Er Nanoparticles Codoped with Gd 3+
journal, January 2015
- Klier, Dennis T.; Kumke, Michael U.
- The Journal of Physical Chemistry C, Vol. 119, Issue 6
High magnetic field and temperature tuning of up-conversion luminescence in Mn 2+ -doped (Er 3+ /Yb 3+ ): NaYF 4
journal, February 2015
- Wang, Ya-Lan; Zhang, Jun-Pei; Han, Jun-Bo
- Journal of Applied Physics, Vol. 117, Issue 8
Upconverting Nanoparticles
journal, May 2011
- Haase, Markus; Schäfer, Helmut
- Angewandte Chemie International Edition, Vol. 50, Issue 26
Direct Evidence of a Surface Quenching Effect on Size-Dependent Luminescence of Upconversion Nanoparticles
journal, August 2010
- Wang, Feng; Wang, Juan; Liu, Xiaogang
- Angewandte Chemie, Vol. 122, Issue 41
Direct Evidence for Coupled Surface and Concentration Quenching Dynamics in Lanthanide-Doped Nanocrystals
journal, February 2017
- Johnson, Noah J. J.; He, Sha; Diao, Shuo
- Journal of the American Chemical Society, Vol. 139, Issue 8
Precise Tuning of Surface Quenching for Luminescence Enhancement in Core–Shell Lanthanide-Doped Nanocrystals
journal, October 2016
- Fischer, Stefan; Bronstein, Noah D.; Swabeck, Joseph K.
- Nano Letters, Vol. 16, Issue 11
(α-NaYbF 4 :Tm 3+ )/CaF 2 Core/Shell Nanoparticles with Efficient Near-Infrared to Near-Infrared Upconversion for High-Contrast Deep Tissue Bioimaging
journal, August 2012
- Chen, Guanying; Shen, Jie; Ohulchanskyy, Tymish Y.
- ACS Nano, Vol. 6, Issue 9
Core–shell–shell heterostructures of α-NaLuF 4 :Yb/Er@NaLuF 4 :Yb@MF 2 (M = Ca, Sr, Ba) with remarkably enhanced upconversion luminescence
journal, January 2016
- Su, Yue; Liu, Xiuling; Lei, Pengpeng
- Dalton Transactions, Vol. 45, Issue 27
Selective Cation Exchange Enabled Growth of Lanthanide Core/Shell Nanoparticles with Dissimilar Structure
journal, December 2017
- Dong, Hao; Sun, Ling-Dong; Li, Lin-Dong
- Journal of the American Chemical Society, Vol. 139, Issue 51
Plasmon-Enhanced Upconversion
journal, November 2014
- Wu, Di M.; García-Etxarri, Aitzol; Salleo, Alberto
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 22
Silica Coated Upconversion Nanoparticles: A Versatile Platform for the Development of Efficient Theranostics
journal, June 2015
- Liu, Jia-Nan; Bu, Wen-Bo; Shi, Jian-Lin
- Accounts of Chemical Research, Vol. 48, Issue 7
Simultaneous Enhancement of Photoluminescence, MRI Relaxivity, and CT Contrast by Tuning the Interfacial Layer of Lanthanide Heteroepitaxial Nanoparticles
journal, July 2017
- He, Sha; Johnson, Noah J. J.; Nguyen Huu, Viet Anh
- Nano Letters, Vol. 17, Issue 8
Lanthanide-Based Heteroepitaxial Core–Shell Nanostructures: Compressive versus Tensile Strain Asymmetry
journal, October 2014
- Johnson, Noah J. J.; van Veggel, Frank C. J. M.
- ACS Nano, Vol. 8, Issue 10
Tuning the optical and electronic properties of colloidal nanocrystals by lattice strain
journal, December 2008
- Smith, Andrew M.; Mohs, Aaron M.; Nie, Shuming
- Nature Nanotechnology, Vol. 4, Issue 1
Absolute quantum yield measurements of colloidal NaYF4: Er3+, Yb3+ upconverting nanoparticles
journal, January 2010
- Boyer, John-Christopher; van Veggel, Frank C. J. M.
- Nanoscale, Vol. 2, Issue 8
Energy Migration Upconversion in Manganese(II)‐Doped Nanoparticles
journal, September 2015
- Li, Xiyan; Liu, Xiaowang; Chevrier, Daniel M.
- Angewandte Chemie, Vol. 127, Issue 45
Epitaxial Growth of Highly Luminescent CdSe/CdS Core/Shell Nanocrystals with Photostability and Electronic Accessibility
journal, July 1997
- Peng, Xiaogang; Schlamp, Michael C.; Kadavanich, Andreas V.
- Journal of the American Chemical Society, Vol. 119, Issue 30, p. 7019-7029
Stress relaxation and misfit dislocation nucleation in the growth of misfitting films: A molecular dynamics simulation study
journal, January 1998
- Dong, Liang; Schnitker, Jurgen; Smith, Richard W.
- Journal of Applied Physics, Vol. 83, Issue 1
Energetics and atomic mechanisms of dislocation nucleation in strained epitaxial layers
journal, October 2003
- Trushin, O.; Granato, E.; Ying, S. C.
- Physical Review B, Vol. 68, Issue 15
Works referencing / citing this record:
Accurate Control of Core–Shell Upconversion Nanoparticles through Anisotropic Strain Engineering
journal, August 2019
- Zhao, Jianxiong; Chen, Xian; Chen, Bing
- Advanced Functional Materials, Vol. 29, Issue 44
Stimuli‐Responsive Hybridized Nanostructures
journal, August 2019
- Guan, Guijian; Wu, Mingda; Han, Ming‐Yong
- Advanced Functional Materials, Vol. 30, Issue 2
Are lanthanide-doped upconversion materials good candidates for photocatalysis?
journal, January 2019
- Zhang, Qingzhe; Yang, Fan; Xu, Zhenhe
- Nanoscale Horizons, Vol. 4, Issue 3
Defect-induced abnormal enhanced upconversion luminescence in BiOBr:Yb 3+ /Er 3+ ultrathin nanosheets and its influence on visible-NIR light photocatalysis
journal, January 2020
- Li, Yongjin; Yao, Lu; Yin, Zhaoyi
- Inorganic Chemistry Frontiers, Vol. 7, Issue 2
Design of Layer‐Structured KAlF 4 :Yb/Er for Pressure‐Enhanced Upconversion Luminescence
journal, November 2019
- Zhang, Kun; Gao, Chao; Jiang, Zhang
- Advanced Optical Materials, Vol. 8, Issue 2
Figures / Tables found in this record: