Lanthanide-doped upconversion nanoparticles (UCNPs) are promising for applications as wide as biological imaging, multimodal imaging, photodynamic therapy, volumetric displays, and solar cells. Yet, the weak and narrow absorption of lanthanide ions poses a fundamental limit of UCNPs to withhold their brightness, creating a long-standing hurdle for the field. Dye-sensitized UCNPs are emerging to address this performance-limiting problem, yielding up to thousands-fold brighter luminescence than conventional UCNPs without dye sensitization. In their configuration, organic dyes with spectrally broad and intense absorption are anchored to the surface of UCNPs to harvest the excitation light energy, which is then transferred via Förster and/or Dexter mechanisms across the organic/inorganic interface to the lanthanides incorporated in UCNPs (with or devoid of a shell) to empower efficient upconversion. This tutorial review highlights recent progress in the development of dye sensitized UCNPs, with an emphasis on the theory of energy transfer, the geometric classification of the dye sensitized core and core/shell nanocrystals, and their emerging photonic and biophotonic applications. Opportunities and challenges offered by dye sensitized UCNPs are also discussed.

The ability to fabricate lanthanide-doped upconversion nanocrystals (UCNCs) with tailored size and emission profile has fuelled their uses in a broad spectrum of biological applications. Yet, limited success has been met in the preparation of sub-6 nm UCNCs with efficient upconversion photoluminescence (UCPL), which enable high contrast optical bioimaging with minimized adverse biological effects entailed by size-induced rapid clearance from the body. Here, we present a simple and reproducible approach to synthesize a set of monodispersed hexagonal-phase core NaGdF4:Yb/Ln (Ln = Er, Ho, Tm) of ∼3–4 nm and core/shell NaGdF4:Yb/Ln@NaGdF4 (Ln = Er, Ho, Tm) UCNCs of ∼5–6 nm. We show that the core/shell UCNCs can be up to ∼1000 times more efficient than the corresponding core UCNCs due to the effective suppression of surface-related quenching effects for the core. The observation of prolonged PL lifetime for the core/shell than that for the core UCNCs demonstrates the role of the inert shell layer for the protection of the core. The achievement of sub-6 nm NaGdF4 UCNCs with significantly improved luminescence efficiency constitutes a solid step towards high contrast UCPL optical imaging with secured biological safety.

The inability to utilize near infrared (NIR) light has posed a stringent limitation for the efficiencies of most single-junction photovoltaic cells such as dye-sensitized solar cells (DSSCs). Here, we describe a strategy to alleviate the NIR light harvesting problem by upconverting non-responsive NIR light in a broad spectral range (over 190 nm, 670–860 nm) to narrow solar-cell-responsive visible emissions through incorporated dye-sensitized upconversion nanoparticles (DSUCNPs). Unlike typically reported UCNPs with narrow and low NIR absorption, the organic dyes (IR783) anchored on the DSUCNP surface were able to harvest NIR photons broadly and efficiently, and then transfer the harvested energy to the inorganic UCNPs (typically reported), entailing an efficient visible upconversion. We show that the incorporation of DSUCNPs into the TiO2 photoanode of a DSSC is able to elevate its efficiency from 7.573% to 8.568%, enhancing the power conversion efficiency by about 13.1%. We quantified that among the relative efficiency increase, 7.1% arose from the contribution of broad-band upconversion in DSUCNPs (about ∼3.4 times higher than the highest previously reported value of ∼2.1%), and 6.0% mainly from the scattering effect of DSUCNPs. Our strategy has immediate implications for the use of DSUCNPs to improve the performance of other types of photovoltaic devices.

Lanthanide-doped upconversion nanoparticles (UCNPs) have attracted interest for use in bioimaging, biosensing, and therapeutic applications. These motivations are empowered by multicolor upconversion luminescence (UCL) under single near infrared wavelength excitation at ∼980 nm. However, this wavelength overlaps with the absorption peak of water that is dominant in the biological environment, eliciting a serious biological heating problem. This study reports tailored multicolor UCL from a Nd3+-sensitized sandwich-structure of core/shell/shell UCNPs of NaYbF4:0.5%Tm,1%Nd@ CaF2:30%Nd@CaF2:1%Nd,20%Yb,2%Er that can be excited at single wavelength of ∼800 nm without producing any local heating. Incorporation of substantial Nd3+ sensitizers in the middle shell region allows efficient harvesting of excitation light, with the excitation then migrating bidirectionally across the core/shell interfaces to simultaneously activate blue emission from Tm in the core as well as green and red emission from Er in the outermost shell layer. By precise control of the content of lanthanide ions in each domain, a palette of multicolor UCL can be produced, ranging from blue to white. The described Nd3+-sensitized multicolor UCNPs hold promises for a variety of multiplexed biological applications, without complications from heating effects.

We introduce a hybrid organic–inorganic system consisting of epitaxial NaYF4:Yb3+/X3+@NaYbF4@NaYF4:Nd3+ (X = null, Er, Ho, Tm, or Pr) core/shell/shell (CSS) nanocrystal with organic dye, indocyanine green (ICG) on the nanocrystal surface. This system is able to produce a set of narrow band emissions with a large Stokes-shift (>200 nm) in the second biological window of optical transparency (NIR-II, 1000–1700 nm), by directional energy transfer from light-harvesting surface ICG, via lanthanide ions in the shells, to the emitter X3+ in the core. Surface ICG not only increases the NIR-II emission intensity of inorganic CSS nanocrystals by ∼4-fold but also provides a broadly excitable spectral range (700–860 nm) that facilitates their use in bioapplications. We show that the NIR-II emission from ICG-sensitized Er3+-doped CSS nanocrystals allows clear observation of a sharp image through 9 mm thick chicken breast tissue, and emission signal detection through 22 mm thick tissue yielding a better imaging profile than from typically used Yb/Tm-codoped upconverting nanocrystals imaged in the NIR-I region (700–950 nm). Our result on in vivo imaging suggests that these ICG-sensitized CSS nanocrystals are suitable for deep optical imaging in the NIR-II region.

Lanthanide-doped upconversion nanoparticles hold promises for bioimaging, solar cells, and volumetric displays. However, their emission brightness and excitation wavelength range are limited by the weak and narrowband absorption of lanthanide ions. Here, we introduce a concept of multistep cascade energy transfer, from broadly infrared-harvesting organic dyes to sensitizer ions in the shell of an epitaxially designed core/shell inorganic nanostructure, with a sequential nonradiative energy transfer to upconverting ion pairs in the core. We show that this concept, when implemented in a core–shell architecture with suppressed surface-related luminescence quenching, yields multiphoton (three-, four-, and five-photon) upconversion quantum efficiency as high as 19% (upconversion energy conversion efficiency of 9.3%, upconversion quantum yield of 4.8%), which is about ∼100 times higher than typically reported efficiency of upconversion at 800 nm in lanthanide-based nanostructures, along with a broad spectral range (over 150 nm) of infrared excitation and a large absorption cross-section of 1.47 × 10–14 cm2 per single nanoparticle. These features enable unprecedented three-photon upconversion (visible by naked eye as blue light) of an incoherent infrared light excitation with a power density comparable to that of solar irradiation at the Earth surface, having implications for broad applications of these organic–inorganic core/shell nanostructures with energy-cascaded upconversion.

We report on heterogeneous core/shell CaF2:Yb3+/Ho3+@NaGdF4 nanocrystals of 17 nm with efficient upconversion (UC) photoluminescence (PL) for in vivo bioimaging. Monodisperse core/shell nanostructures were synthesized using a seed-mediated growth process involving two quite different approaches of liquid–solid-solution and thermal decomposition. They exhibit green emission with a sharp band around 540 nm when excited at ∼980 nm, which is about 39 times brighter than the core CaF2:Yb3+/Ho3+ nanoparticles. PL decays at 540 nm revealed that such an enhancement arises from efficient suppression of surface-related deactivation from the core nanocrystals. In vivo bioimaging employing water-dispersed core/shell nanoparticles displayed high contrast against the background.

Rational control over the uniform morphology and size of hexagonal NaYF4 has been achieved via a facile hydrothermal route. The evolution of particle morphology from peg-top-like to hexagonal microprisms with protruding centers and the long tubelike morphology with concave wedge and finally to solely microrods been demonstrated by increasing the F−/Ln3+ molar ratio, all other parameters being equal. Rationally controlling the shape of hexagonal NaYF4 is of great importance due to their strongly shape-dependent optical properties. Moreover, the systematic study on the photoluminescence of 20%Yb3+, 1%Er3+-doped β-NaYF4 with different shapes shows that the upconversion (UC) properties of these products are strongly dependent on the combined roles of morphologies, crystallinity, and particle sizes. In particular, the microrods evince a better PL signal as compared with others.Highlights► Uniform peg-top-like, microprisms, tubelike and microrod NaYF4 were synthesized. ► The evolution from peg-top-like to microrod NaYF4 is discovered. ► The as-synthesized NaYF4 shows outstanding impacts on output of UCL.

We present a simple method to gradually tune the size and to induce the shape change of CeO2 nanoparticlesvia increasing the content of Yb3+ doping.

We present a simple method to gradually tune the size and to induce the shape change of CeO2 nanoparticlesvia increasing the content of Yb3+ doping.

Lanthanide-doped upconversion nanoparticles (UCNPs) are promising for applications as wide as biological imaging, multimodal imaging, photodynamic therapy, volumetric displays, and solar cells. Yet, the weak and narrow absorption of lanthanide ions poses a fundamental limit of UCNPs to withhold their brightness, creating a long-standing hurdle for the field. Dye-sensitized UCNPs are emerging to address this performance-limiting problem, yielding up to thousands-fold brighter luminescence than conventional UCNPs without dye sensitization. In their configuration, organic dyes with spectrally broad and intense absorption are anchored to the surface of UCNPs to harvest the excitation light energy, which is then transferred via Förster and/or Dexter mechanisms across the organic/inorganic interface to the lanthanides incorporated in UCNPs (with or devoid of a shell) to empower efficient upconversion. This tutorial review highlights recent progress in the development of dye sensitized UCNPs, with an emphasis on the theory of energy transfer, the geometric classification of the dye sensitized core and core/shell nanocrystals, and their emerging photonic and biophotonic applications. Opportunities and challenges offered by dye sensitized UCNPs are also discussed.