Energy Transfer Networks within Upconverting Nanoparticles Are Complex Systems with Collective, Robust, and History-Dependent Dynamics
Abstract
Applications of photon upconverting nanoparticles (UCNPs) in biological imaging and solar energy conversion demand that their anti-Stokes luminescence be both tunable and efficient. Rational design of more efficient UCNPs requires an understanding of energy transfer (ET) between their lanthanide dopants, dynamics that are typically characterized by measuring luminescence lifetimes. Existing knowledge, however, cannot explain basic observations in lifetime experiments, such as their dependence on excitation power, significantly limiting the generality and reliability of lifetime measurements. Here in this paper, we elucidate the origins of the ET dynamics and luminescence lifetimes of Yb3+-, Er3+-co-doped NaYF4 UCNPs using time-resolved luminescence and novel applications of rate equations and stochastic simulations. Experiments and calculations consistently show that at high concentrations of Er3+, the luminescence lifetimes of UCNPs decrease as much as six-fold when excitation power densities are increased over 6 orders of magnitude. Since power-dependent lifetimes cannot be explained by intrinsic relaxation rates of individual transitions, we analyze lifetime data by treating each UCNP as a complex ET network. We find that UCNP ET networks exhibit four distinguishing characteristics of complex systems: collectivity, nonlinear feedback, robustness, and history dependence. We conclude that power-dependent lifetimes are the consequence of thousands of minor relaxation pathways thatmore »
- Authors:
-
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Dalian Maritime Univ., Dalian, Liaoning (China)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Columbia Univ., New York, NY (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Research Foundation of Korea (NRF)
- OSTI Identifier:
- 1580361
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 123; Journal Issue: 4; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Teitelboim, Ayelet, Tian, Bining, Garfield, David J., Fernandez-Bravo, Angel, Gotlin, Adam C., Schuck, P. James, Cohen, Bruce E., and Chan, Emory M.. Energy Transfer Networks within Upconverting Nanoparticles Are Complex Systems with Collective, Robust, and History-Dependent Dynamics. United States: N. p., 2019.
Web. doi:10.1021/acs.jpcc.9b00161.
Teitelboim, Ayelet, Tian, Bining, Garfield, David J., Fernandez-Bravo, Angel, Gotlin, Adam C., Schuck, P. James, Cohen, Bruce E., & Chan, Emory M.. Energy Transfer Networks within Upconverting Nanoparticles Are Complex Systems with Collective, Robust, and History-Dependent Dynamics. United States. https://doi.org/10.1021/acs.jpcc.9b00161
Teitelboim, Ayelet, Tian, Bining, Garfield, David J., Fernandez-Bravo, Angel, Gotlin, Adam C., Schuck, P. James, Cohen, Bruce E., and Chan, Emory M.. Tue .
"Energy Transfer Networks within Upconverting Nanoparticles Are Complex Systems with Collective, Robust, and History-Dependent Dynamics". United States. https://doi.org/10.1021/acs.jpcc.9b00161. https://www.osti.gov/servlets/purl/1580361.
@article{osti_1580361,
title = {Energy Transfer Networks within Upconverting Nanoparticles Are Complex Systems with Collective, Robust, and History-Dependent Dynamics},
author = {Teitelboim, Ayelet and Tian, Bining and Garfield, David J. and Fernandez-Bravo, Angel and Gotlin, Adam C. and Schuck, P. James and Cohen, Bruce E. and Chan, Emory M.},
abstractNote = {Applications of photon upconverting nanoparticles (UCNPs) in biological imaging and solar energy conversion demand that their anti-Stokes luminescence be both tunable and efficient. Rational design of more efficient UCNPs requires an understanding of energy transfer (ET) between their lanthanide dopants, dynamics that are typically characterized by measuring luminescence lifetimes. Existing knowledge, however, cannot explain basic observations in lifetime experiments, such as their dependence on excitation power, significantly limiting the generality and reliability of lifetime measurements. Here in this paper, we elucidate the origins of the ET dynamics and luminescence lifetimes of Yb3+-, Er3+-co-doped NaYF4 UCNPs using time-resolved luminescence and novel applications of rate equations and stochastic simulations. Experiments and calculations consistently show that at high concentrations of Er3+, the luminescence lifetimes of UCNPs decrease as much as six-fold when excitation power densities are increased over 6 orders of magnitude. Since power-dependent lifetimes cannot be explained by intrinsic relaxation rates of individual transitions, we analyze lifetime data by treating each UCNP as a complex ET network. We find that UCNP ET networks exhibit four distinguishing characteristics of complex systems: collectivity, nonlinear feedback, robustness, and history dependence. We conclude that power-dependent lifetimes are the consequence of thousands of minor relaxation pathways that act collectively to depopulate and repopulate Er3+ emitting levels. These ET pathways are dependent on past excitation power because they originate from excited donors and excited acceptors; however, each transition has an unexpectedly small impact on lifetimes due to negative feedback in the network. This robustness is determined by systematically “knocking out”, or disabling, ET transitions in kinetic models. Our classification of UCNP ET networks as complex systems explains why UCNP luminescence lifetimes do not match the intrinsic lifetimes of emitting states. In the future, UCNP networks may be engineered to rival the complexity of biological networks that pattern features with unmatched precision.},
doi = {10.1021/acs.jpcc.9b00161},
journal = {Journal of Physical Chemistry. C},
number = 4,
volume = 123,
place = {United States},
year = {Tue Jan 08 00:00:00 EST 2019},
month = {Tue Jan 08 00:00:00 EST 2019}
}
Web of Science
Works referenced in this record:
Perspectives for Upconverting Nanoparticles
journal, September 2017
- Wilhelm, Stefan
- ACS Nano, Vol. 11, Issue 11
Controlling upconversion nanocrystals for emerging applications
journal, November 2015
- Zhou, Bo; Shi, Bingyang; Jin, Dayong
- Nature Nanotechnology, Vol. 10, Issue 11
Combinatorial approaches for developing upconverting nanomaterials: high-throughput screening, modeling, and applications
journal, January 2015
- Chan, Emory M.
- Chemical Society Reviews, Vol. 44, Issue 6
Long-Term Real-Time Tracking of Lanthanide Ion Doped Upconverting Nanoparticles in Living Cells
journal, May 2011
- Nam, Sang Hwan; Bae, Yun Mi; Park, Yong Il
- Angewandte Chemie, Vol. 123, Issue 27
Energy-Looping Nanoparticles: Harnessing Excited-State Absorption for Deep-Tissue Imaging
journal, September 2016
- Levy, Elizabeth S.; Tajon, Cheryl A.; Bischof, Thomas S.
- ACS Nano, Vol. 10, Issue 9
Non-blinking and photostable upconverted luminescence from single lanthanide-doped nanocrystals
journal, June 2009
- Wu, S.; Han, G.; Milliron, D. J.
- Proceedings of the National Academy of Sciences, Vol. 106, Issue 27, p. 10917-10921
Near-infrared deep brain stimulation via upconversion nanoparticle–mediated optogenetics
journal, February 2018
- Chen, Shuo; Weitemier, Adam Z.; Zeng, Xiao
- Science, Vol. 359, Issue 6376
Dye-Sensitized Core/Active Shell Upconversion Nanoparticles for Optogenetics and Bioimaging Applications
journal, December 2015
- Wu, Xiang; Zhang, Yuanwei; Takle, Kendra
- ACS Nano, Vol. 10, Issue 1
In vivo photodynamic therapy using upconversion nanoparticles as remote-controlled nanotransducers
journal, September 2012
- Idris, Niagara Muhammad; Gnanasammandhan, Muthu Kumara; Zhang, Jing
- Nature Medicine, Vol. 18, Issue 10
Amplified stimulated emission in upconversion nanoparticles for super-resolution nanoscopy
journal, February 2017
- Liu, Yujia; Lu, Yiqing; Yang, Xusan
- Nature, Vol. 543, Issue 7644
(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
Multi-photon near-infrared emission saturation nanoscopy using upconversion nanoparticles
journal, August 2018
- Chen, Chaohao; Wang, Fan; Wen, Shihui
- Nature Communications, Vol. 9, Issue 1
Low irradiance multiphoton imaging with alloyed lanthanide nanocrystals
journal, August 2018
- Tian, Bining; Fernandez-Bravo, Angel; Najafiaghdam, Hossein
- Nature Communications, Vol. 9, Issue 1
Single upconversion nanoparticle imaging at sub-10 W cm−2 irradiance
journal, August 2018
- Liu, Qian; Zhang, Yunxiang; Peng, Chunte Sam
- Nature Photonics, Vol. 12, Issue 9
Thermal Scanning at the Cellular Level by an Optically Trapped Upconverting Fluorescent Particle
journal, January 2016
- Rodríguez-Sevilla, Paloma; Zhang, Yuhai; Haro-González, Patricia
- Advanced Materials, Vol. 28, Issue 12
Far-field optical nanothermometry using individual sub-50 nm upconverting nanoparticles
journal, January 2016
- Kilbane, Jacob D.; Chan, Emory M.; Monachon, Christian
- Nanoscale, Vol. 8, Issue 22
Optical Torques on Upconverting Particles for Intracellular Microrheometry
journal, November 2016
- Rodríguez-Sevilla, Paloma; Zhang, Yuhai; de Sousa, Nuno
- Nano Letters, Vol. 16, Issue 12
Tunable lifetime multiplexing using luminescent nanocrystals
journal, December 2013
- Lu, Yiqing; Zhao, Jiangbo; Zhang, Run
- Nature Photonics, Vol. 8, Issue 1
Temporal full-colour tuning through non-steady-state upconversion
journal, January 2015
- Deng, Renren; Qin, Fei; Chen, Runfeng
- Nature Nanotechnology, Vol. 10, Issue 3
Continuous-wave upconverting nanoparticle microlasers
journal, June 2018
- Fernandez-Bravo, Angel; Yao, Kaiyuan; Barnard, Edward S.
- Nature Nanotechnology, Vol. 13, Issue 7
Spectroscopic Imaging and Power Dependence of Near-Infrared to Visible Upconversion Luminescence from NaYF 4 :Yb 3+ ,Er 3+ Nanoparticles on Nanocavity Arrays
journal, October 2015
- Fisher, Jon; Zhao, Bo; Lin, Cuikun
- The Journal of Physical Chemistry C, Vol. 119, Issue 44
Upconverting Nanoparticle Relays for Resonance Energy Transfer Networks
journal, March 2016
- LaBoda, Craig D.; Dwyer, Chris L.
- Advanced Functional Materials, Vol. 26, Issue 17
Upconversion for Photovoltaics - a Review of Materials, Devices and Concepts for Performance Enhancement
journal, April 2015
- Goldschmidt, Jan Christoph; Fischer, Stefan
- Advanced Optical Materials, Vol. 3, Issue 4
Rationally Designed Energy Transfer in Upconverting Nanoparticles
journal, March 2015
- Chan, Emory M.; Levy, Elizabeth S.; Cohen, Bruce E.
- Advanced Materials, Vol. 27, Issue 38
Concentrating and Recycling Energy in Lanthanide Codopants for Efficient and Spectrally Pure Emission: The Case of NaYF 4 :Er 3+ /Tm 3+ Upconverting Nanocrystals
journal, May 2012
- Chan, Emory M.; Gargas, Daniel J.; Schuck, P. James
- The Journal of Physical Chemistry B, Vol. 116, Issue 35
Assembling programmable FRET-based photonic networks using designer DNA scaffolds
journal, December 2014
- Buckhout-White, Susan; Spillmann, Christopher M.; Algar, W. Russ
- Nature Communications, Vol. 5, Issue 1
Excitation migration in trimeric cyanobacterial photosystem I
journal, June 2004
- Şener, Melih K.; Park, Sanghyun; Lu, Deyu
- The Journal of Chemical Physics, Vol. 120, Issue 23
Nanoscale Optical Computing Using Resonance Energy Transfer Logic
journal, November 2008
- Pistol, Constantin; Dwyer, Chris; Lebeck, Alvin R.
- IEEE Micro, Vol. 28, Issue 6
Self-Assembled Resonance Energy Transfer Keys for Secure Communication over Classical Channels
journal, October 2015
- Nellore, Vishwa; Xi, Sam; Dwyer, Chris
- ACS Nano, Vol. 9, Issue 12
Spatiotemporal dynamics in optical energy transfer on the nanoscale and its application to constraint satisfaction problems
journal, September 2012
- Naruse, Makoto; Aono, Masashi; Kim, Song-Ju
- Physical Review B, Vol. 86, Issue 12
Complex networks: Structure and dynamics
journal, February 2006
- Boccaletti, S.; Latora, V.; Moreno, Y.
- Physics Reports, Vol. 424, Issue 4-5
Upconversion Luminescence of β-NaYF 4 : Yb 3+ , Er 3+ @β-NaYF 4 Core/Shell Nanoparticles: Excitation Power Density and Surface Dependence
journal, April 2009
- Wang, Yu; Tu, Langping; Zhao, Junwei
- The Journal of Physical Chemistry C, Vol. 113, Issue 17
Explaining the Nanoscale Effect in the Upconversion Dynamics of β-NaYF 4 :Yb 3+ , Er 3+ Core and Core–Shell Nanocrystals
journal, July 2017
- Hossan, Md Yeathad; Hor, Amy; Luu, QuocAnh
- The Journal of Physical Chemistry C, Vol. 121, Issue 30
Upconversion luminescence with tunable lifetime in NaYF 4 :Yb,Er nanocrystals: role of nanocrystal size
journal, January 2013
- Zhao, Jiangbo; Lu, Zhenda; Yin, Yadong
- Nanoscale, Vol. 5, Issue 3
Revisiting the NIR-to-Visible Upconversion Mechanism in β-NaYF 4 :Yb 3+ ,Er 3+
journal, December 2013
- Anderson, Robert B.; Smith, Steve J.; May, P. Stanley
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 1
Er:Yb:NaY 2 F 5 O up-converting nanoparticles for sub-tissue fluorescence lifetime thermal sensing
journal, January 2014
- Savchuk, Ol. A.; Haro-González, P.; Carvajal, J. J.
- Nanoscale, Vol. 6, Issue 16
Apparent self-heating of individual upconverting nanoparticle thermometers
journal, November 2018
- Pickel, Andrea D.; Teitelboim, Ayelet; Chan, Emory M.
- Nature Communications, Vol. 9, Issue 1
Enrichment of molecular antenna triplets amplifies upconverting nanoparticle emission
journal, April 2018
- Garfield, David J.; Borys, Nicholas J.; Hamed, Samia M.
- Nature Photonics, Vol. 12, Issue 7
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
Engineering bright sub-10-nm upconverting nanocrystals for single-molecule imaging
journal, March 2014
- Gargas, Daniel J.; Chan, Emory M.; Ostrowski, Alexis D.
- Nature Nanotechnology, Vol. 9, Issue 4
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
Precisely Tailoring Upconversion Dynamics via Energy Migration in Core-Shell Nanostructures
journal, February 2018
- Zuo, Jing; Sun, Dapeng; Tu, Langping
- Angewandte Chemie International Edition, Vol. 57, Issue 12
Upconversion Nanoparticles: Design, Nanochemistry, and Applications in Theranostics
journal, March 2014
- Chen, Guanying; Qiu, Hailong; Prasad, Paras N.
- Chemical Reviews, Vol. 114, Issue 10
Near-Infrared-Triggered Azobenzene-Liposome/Upconversion Nanoparticle Hybrid Vesicles for Remotely Controlled Drug Delivery to Overcome Cancer Multidrug Resistance
journal, August 2016
- Yao, Chi; Wang, Peiyuan; Li, Xiaomin
- Advanced Materials, Vol. 28, Issue 42
Achieving high-efficiency emission depletion nanoscopy by employing cross relaxation in upconversion nanoparticles
journal, October 2017
- Zhan, Qiuqiang; Liu, Haichun; Wang, Baoju
- Nature Communications, Vol. 8, Issue 1
Fluorescence Lifetime Measurements and Biological Imaging
journal, May 2010
- Berezin, Mikhail Y.; Achilefu, Samuel
- Chemical Reviews, Vol. 110, Issue 5
The Ecology of Collective Behavior
journal, March 2014
- Gordon, Deborah M.
- PLoS Biology, Vol. 12, Issue 3
Controlled Synthesis and Single-Particle Imaging of Bright, Sub-10 nm Lanthanide-Doped Upconverting Nanocrystals
journal, February 2012
- Ostrowski, Alexis D.; Chan, Emory M.; Gargas, Daniel J.
- ACS Nano, Vol. 6, Issue 3
Successive Layer-by-Layer Strategy for Multi-Shell Epitaxial Growth: Shell Thickness and Doping Position Dependence in Upconverting Optical Properties
journal, December 2012
- Li, Xiaomin; Shen, Dengke; Yang, Jianping
- Chemistry of Materials, Vol. 25, Issue 1
Exact stochastic simulation of coupled chemical reactions
journal, December 1977
- Gillespie, Daniel T.
- The Journal of Physical Chemistry, Vol. 81, Issue 25
Modeling Energy Migration for Upconversion Materials
journal, December 2017
- Ledoux, G.; Amans, D.; Joubert, M. -F.
- The Journal of Physical Chemistry C, Vol. 122, Issue 1
Autocatalytic, bistable, oscillatory networks of biologically relevant organic reactions
journal, September 2016
- Semenov, Sergey N.; Kraft, Lewis J.; Ainla, Alar
- Nature, Vol. 537, Issue 7622
Two-Photon Upconversion Laser (Scanning and Wide-Field) Microscopy Using Ln 3+ -Doped NaYF 4 Upconverting Nanocrystals: A Critical Evaluation of their Performance and Potential in Bioimaging
journal, September 2011
- Pichaandi, Jothirmayanantham; Boyer, John-Christopher; Delaney, Kerry R.
- The Journal of Physical Chemistry C, Vol. 115, Issue 39
Testing Turing's theory of morphogenesis in chemical cells
journal, March 2014
- Tompkins, N.; Li, N.; Girabawe, C.
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 12
Differential Diffusivity of Nodal and Lefty Underlies a Reaction-Diffusion Patterning System
journal, April 2012
- Muller, P.; Rogers, K. W.; Jordan, B. M.
- Science, Vol. 336, Issue 6082
Colloidal Double Quantum Dots
journal, April 2016
- Teitelboim, Ayelet; Meir, Noga; Kazes, Miri
- Accounts of Chemical Research, Vol. 49, Issue 5
Colloidal Nanoparticles for Intermediate Band Solar Cells
journal, June 2015
- Vörös, Márton; Galli, Giulia; Zimanyi, Gergely T.
- ACS Nano, Vol. 9, Issue 7
Quantifying Microsecond Transition Times Using Fluorescence Lifetime Correlation Spectroscopy
journal, December 2017
- Ghosh, Arindam; Isbaner, Sebastian; Veiga-Gutiérrez, Manoel
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 24
Emission Intensity Dependence and Single-Exponential Behavior In Single Colloidal Quantum Dot Fluorescence Lifetimes
journal, December 2003
- Fisher, Brent R.; Eisler, Hans-Jürgen; Stott, Nathan E.
- The Journal of Physical Chemistry B, Vol. 108, Issue 1
Excitation density dependence of radiative and nonradiative recombination lifetimes in InGaN/GaN multiple quantum wells: Excitation density dependence of recombination lifetimes in InGaN/GaN MQWs
journal, December 2014
- Murotani, Hideaki; Yamada, Yoichi; Honda, Yoshio
- physica status solidi (b), Vol. 252, Issue 5
Materials Integrating Photochemical Upconversion
journal, March 2016
- McCusker, Catherine E.; Castellano, Felix N.
- Topics in Current Chemistry, Vol. 374, Issue 2
Works referencing / citing this record:
Ultralow-threshold, continuous-wave upconverting lasing from subwavelength plasmons
journal, September 2019
- Fernandez-Bravo, Angel; Wang, Danqing; Barnard, Edward S.
- Nature Materials, Vol. 18, Issue 11
Concentration-regulated photon upconversion and quenching in NaYF 4 :Yb 3+ ,Er 3+ nanocrystals: nonexponentiality revisited
journal, January 2019
- Sun, Liyuan; Gao, Rongyao; Pan, Tingting
- Nanoscale, Vol. 11, Issue 39
Sharpening upconversion nanoparticles to reduce surface quenching
journal, January 2020
- Zhu, Jingyi; Zhao, Pingping; Yang, Junxing
- Dalton Transactions, Vol. 49, Issue 2