Core-shell rare-earth-doped nanostructures in biomedicine

The current status of the use of core-shell rare-earth-doped nanoparticles in biomedical applications is reviewed in detail. The different core-shell rare-earth-doped nanoparticles developed so far are described and the most relevant examples of their application in imaging, sensing, and therapy are summarized. In addition, the advantages and disadvantages they present are discussed. Finally, a critical opinion of their potential application in real life biomedicine is givenThis work has been partially supported by the Ministerio de Economía y Competitividad de España (MINECO) (MAT2016-75362-C3-1-R), by the Instituto de Salud Carlos III (PI16/ 00812), by the Comunidad Autónoma de Madrid (B2017/ BMD-3867RENIM-CM), by the European Comission (NanoTBTech), and co-financed by European Structural and Investment Fund. This work has also been partially supported by COST action CM1403. L. L. P. thanks the Universidad Autónoma de Madrid for the “Formación de personal investi-gador (FPI-UAM)” program. P. R. S. thanks MINECO and the Fondo Social Europeo (FSE) for the “Promoción del talento y su Empleabilidad en I+D+i” statal program (BES-2014-069410). D. H. O. is grateful to the Instituto de Salud Carlos III for a Sara Borrell Fellowship (CD17/00210

Rare earth based nanostructured materials: Synthesis, functionalization, properties and bioimaging and biosensing applications

Rare earth based nanostructures constitute a type of functional materials widely used and studied in the recent literature. The purpose of this review is to provide a general and comprehensive overview of the current state of the art, with special focus on the commonly employed synthesis methods and functionalization strategies of rare earth based nanoparticles and on their different bioimaging and biosensing applications. The luminescent (including downconversion, upconversion and permanent luminescence) and magnetic properties of rare earth based nanoparticles, as well as their ability to absorb X-rays, will also be explained and connected with their luminescent, magnetic resonance and X-ray computed tomography bioimaging applications, respectively. This review is not only restricted to nanoparticles, and recent advances reported for in other nanostructures containing rare earths, such as metal organic frameworks and lanthanide complexes conjugated with biological structures, will also be commented on.European Union 267226Ministerio de Economía y Competitividad MAT2014-54852-

Temperature dependent NIR emitting lanthanide-PMO/silica hybrid materials

Two materials - a mesoporous silica (MS) and a periodic mesoporous organosilica (PMO) functionalized with dipyridyl-pyridazine (dppz) units were grafted with near-infrared (NIR) emitting lanthanide (Nd3+, Er3+, Yb3+) complexes in an attempt to obtain hybrid NIR emitting materials. The parent materials: dppz-vSilica and dppz-ePMO were prepared by a hetero Diels-Alder reaction between 3,6-di(2-pyridyl)-1,2,4,5- tetrazine (dptz) and the double bonds of either ethenylene-bridged PMO (ePMO) or vinyl-silica (vSilica) and subsequent oxidation. The dppz-vSilica is reported here for the first time. The prepared lanthanide-PMO/silica hybrid materials were studied in depth for their luminescence properties at room temperature and chosen Nd3+ and Yb3+ samples also at low temperature (as low as 10 K). We show that both the dppz-vSilica and dppz-ePMO materials can be used as "platforms" for obtaining porous materials showing NIR luminescence. To obtain NIR emission these materials can be excited either in the UV or Vis region (into the pi -> pi* transitions of the ligands or directly into the f-f transitions of the Ln(3+) ions). More interestingly, when functionalized with Nd3+ or Yb3+ beta-diketonate complexes these materials showed interesting luminescence properties over a wide temperature range (10-360 K). The Yb3+ materials were investigated for their potential use as ratiometric temperature sensors

Designing a Broadband Pump for High-Quality Micro-Lasers via Modified Net Radiation Method

High-quality micro-lasers are key ingredients in non-linear optics, communication, sensing and low-threshold solar-pumped lasers. However, such micro-lasers exhibit negligible absorption of free-space broadband pump light. Recently, this limitation was lifted by cascade energy transfer, in which the absorption and quality factor are modulated with wavelength, enabling non-resonant pumping of high-quality micro-lasers and solar-pumped laser to operate at record low solar concentration. Here, we present a generic theoretical framework for modeling the absorption, emission and energy transfer of incoherent radiation between cascade sensitizer and laser gain media. Our model is based on linear equations of the modified net radiation method and is therefore robust, fast converging and has low complexity. We apply this formalism to compute the optimal parameters of low-threshold solar-pumped lasers. It is revealed that the interplay between the absorption and self-absorption of such lasers defines the optimal pump absorption below the maximal value, which is in contrast to conventional lasers for which full pump absorption is desired. Numerical results are compared to experimental data on a sensitized Nd[superscript 3+]:YAG cavity, and quantitative agreement with theoretical models is found. Our work modularizes the gain and sensitizing components and paves the way for the optimal design of broadband-pumped high-quality micro-lasers and efficient solar-pumped lasers.Russell Berrie Nanotechnology InstituteTechnion, Israel Institute of Technology. Grand Technion Energy ProgramIsrael Strategic Alternative Energy Foundatio

Theoretical investigation of the more suitable rare earth to achieve high gain in waveguide based on silica containing silicon nanograins doped with either Nd3+ or Er3+ ions

We present a comparative study of the gain achievement in a waveguide whose active layer is constituted by a silica matrix containing silicon nanograins acting as sensitizer of either neodymium ions (Nd3+) or erbium ions (Er3+). By means of an auxiliary differential equation and finite difference time domain (ADE-FDTD) approach that we developed, we investigate the steady states regime of both rare earths ions and silicon nanograins levels populations as well as the electromagnetic field for different pumping powers ranging from 1 to 104 mW/mm2. Moreover, the achievable gain has been estimated in this pumping range. The Nd3+ doped waveguide shows a higher gross gain per unit length at 1064 nm (up to 30 dB/cm) than the one with Er3+ doped active layer at 1532 nm (up to 2 dB/cm). Taking into account the experimental background losses we demonstrate that a significant positive net gain can only be achieved with the Nd3+ doped waveguide

Lanthanide upconversion luminescence at the nanoscale: fundamentals and optical properties

First published online: 26 Feb 2016Upconversion photoluminescence is a nonlinear effect where multiple lower energy excitation photons produce higher energy emission photons. This fundamentally interesting process has many applications in biomedical imaging, light source and display technology, and solar energy harvesting. In this review we discuss the underlying physical principles and their modelling using rate equations. We discuss how the understanding of photophysical processes enabled a strategic influence over the optical properties of upconversion especially in rationally designed materials. We subsequently present an overview of recent experimental strategies to control and optimize the optical properties of upconversion nanoparticles, focussing on their emission spectral properties and brightness.Annemarie Nadort, Jiangbo Zhao and Ewa M. Goldy

Modeling of optical amplifier waveguide based on silicon nanostructures and rare earth ions doped silica matrix gain media by a finite-difference time-domain method: comparison of achievable gain with Er3+ or Nd3+ ions dopants

A comparative study of the gain achievement is performed in a waveguide optical amplifier whose active layer is constituted by a silica matrix containing silicon nanograins acting as sensitizer of either neodymium ions (Nd 3+) or erbium ions (Er 3+). Due to the large difference between population levels characteristic times (ms) and finite-difference time step (10 --17 s), the conventional auxiliary differential equation and finite-difference time-domain (ADE-FDTD) method is not appropriate to treat such systems. Consequently, a new two loops algorithm based on ADE-FDTD method is presented in order to model this waveguide optical amplifier. We investigate the steady states regime of both rare earth ions and silicon nanograins levels populations as well as the electromagnetic field for different pumping powers ranging from 1 to 10 4 mW.mm-2. Furthermore, the three dimensional distribution of achievable gain per unit length has been estimated in this pumping range. The Nd 3+ doped waveguide shows a higher gross gain per unit length at 1064 nm (up to 30 dB.cm-1) than the one with Er 3+ doped active layer at 1532 nm (up to 2 dB.cm-1). Considering the experimental background losses found on those waveguides we demonstrate that a significant positive net gain can only be achieved with the Nd 3+ doped waveguide. The developed algorithm is stable and applicable to optical gain materials with emitters having a wide range of characteristic lifetimes.Comment: Photonics West , Feb 2015, San Francisco, United States. S, SPIE Proceedings, 9357 (935709), 2015, Physics and Simulation of Optoelectronic Devices XXIII. arXiv admin note: text overlap with arXiv:1405.533

Effectively realizing broadband spectral conversion of UV/visible to near-infrared emission in (Na,K)Mg(La,Gd)TeO6:Mn4+,Nd3+,Yb3+ materials for c-Si solar cells via efficient energy transfer

In this work, a series of (Na,K)Mg(La,Gd)TeO6:Mn4+,Nd3+,Yb3+ materials were prepared via a high-temperature solid-state reaction method. As reported before, certain Mn4+ singly doped samples present good red luminescence properties, showing emission bands at around 700 nm upon excitation with UV/n-UV/blue light. When Mn4+ and Nd3+ were co-doped into the same host, effective energy transfer from Mn4+ to Nd3+ ions was inferred from the spectral overlap of the Mn4+ emission and Nd3+ excitation bands. The variation of the emission bands upon 365 nm UV excitation with fixed Mn4+ concentration and varying Nd3+ concentration in phosphors can validate this energy transfer process from Mn4+ to Nd3+ ions. In addition, comparison of the excitation spectra monitored at the Nd3+ emission peaks to those monitored at the Mn4+ emission bands and the decrease of the Mn4+ decay times supplied more evidence for the energy transfer phenomenon from Mn4+ to Nd3+ ions in these Mn4+,Nd3+ co-doped samples. Since the energy transfer from Nd3+ to Yb3+ ions has been well reported before, we co-doped Yb3+ in our Mn4+,Nd3+ co-doped samples to show that Nd3+ can be a bridging ion to regulate the energy transfer from Mn4+ to Yb3+ ions for the first time, which was confirmed from the analysis of the excitation spectra and decay times. This can be considered as a novel method to enhance the energy transfer from Mn4+ to Yb3+ ions. Based on the energy transfer from Mn4+ to Nd3+ and then to Yb3+, UV/visible luminescence can be effectively converted into near-infrared emission, allowing a better spectral response for c-Si solar cells, which suggests a possible enhancement of the conversion efficiency of such c-Si solar cells

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-NaYbF4 (core) @NaY0.8-xErxGd0.2F4 (interior shell) @NaY0.8Gd0.2F4 (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-NaY0.58Gd0.2Yb0.2Er0.02F4 (core) @NaY0.8Gd0.2F4 (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. 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

Spectroscopic investigation of the Cr to Tm energy transfer in Yttrium Aluminum Garnet (YAG) crystals

New and interesting schemes have recently been considered for the efficient operation of solid-state ionic laser systems. Often the available data on these systems were obtained only because they seemed directly related to the laser performance and provide no insight into the physical processes. A more systematic approach is desirable, where more attention is devoted to the elementary basic processes and to the nature of the mechanisms at work. It is with this aim that we have undertaken the present study. Yttrium Aluminum Garnet (Y4Al5O12), called YAG, has two desirable properties as host for rare earth impurities: (1) trivalent rare earth ions can replace the yttrium without any charge compensation problem, and (2) YAG crystals have high cutoff energies. The results of measurements and calculations indicate that the Cr(3+) ion in YAG can be used to sensitize efficiently the Tm(3+) ion