Before the 1960s, all anti-Stokes emissions, which were known to exist, involved emission energies in excess of excitation energies by only a few kT. They were linked to thermal population of energy states above excitation states by such an energy amount. It was the well-known case of anti-Stokes emission for the so-called thermal bands or in the Raman effect for the well-known anti-Stokes sidebands. Thermoluminescence, where traps are emptied by excitation energies of the order of kT, also constituted a field of anti-Stokes emission of its own. Superexcitation, i.e., raising an already excited electron to an even higher level by excited-state absorption (ESA), was also known but with very weak emissions. These types of well-known anti-Stokes processes have been reviewed in classical textbooks on luminescence.1 All fluorescence light emitters usually follow the well-known principle of the Stokes law which simply states that excitation photons are at a higher energy than emitted ones or, in other words, that output photon energy is weaker than input photon energy. This, in a sense, is an indirect statement that efficiency cannot be larger than 1. This principle is

Upconversion and Anti-Stokes Processes with f and d Ions in Solids

Lanthanide ions possess fascinating optical properties and their discovery, first industrial uses and present high technological applications are largely governed by their interaction with light. Lighting devices (economical luminescent lamps, light emitting diodes), television and computer displays, optical fibres, optical amplifiers, lasers, as well as responsive luminescent stains for biomedical analysis, medical diagnosis, and cell imaging rely heavily on lanthanide ions. This critical review has been tailored for a broad audience of chemists, biochemists and materials scientists; the basics of lanthanide photophysics are highlighted together with the synthetic strategies used to insert these ions into mono- and polymetallic molecular edifices. Recent advances in NIR-emitting materials, including liquid crystals, and in the control of luminescent properties in polymetallic assemblies are also presented. (210 references.)

Taking advantage of luminescent lanthanide ions

Recent startling interest for lanthanide luminescence is stimulated by the continuously expanding need for luminescent materials meeting the stringent requirements of telecommunication, lighting, electroluminescent devices, (bio-)analytical sensors and bio-imaging set-ups. This critical review describes the latest developments in (i) the sensitization of near-infrared luminescence, (ii) “soft” luminescent materials (liquid crystals, ionic liquids, ionogels), (iii) electroluminescent materials for organic light emitting diodes, with emphasis on white light generation, and (iv) applications in luminescent bio-sensing and bio-imaging based on time-resolved detection and multiphoton excitation (500 references).

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Lanthanide luminescence for functional materials and bio-sciences

Doping is a widely applied technological process in materials science that involves incorporating atoms or ions of appropriate elements into host lattices to yield hybrid materials with desirable properties and functions. For nanocrystalline materials, doping is of fundamental importance in stabilizing a specific crystallographic phase, modifying electronic properties, modulating magnetism as well as tuning emission properties. Here we describe a material system in which doping influences the growth process to give simultaneous control over the crystallographic phase, size and optical emission properties of the resulting nanocrystals. We show that NaYF(4) nanocrystals can be rationally tuned in size (down to ten nanometres), phase (cubic or hexagonal) and upconversion emission colour (green to blue) through use of trivalent lanthanide dopant ions introduced at precisely defined concentrations. We use first-principles calculations to confirm that the influence of lanthanide doping on crystal phase and size arises from a strong dependence on the size and dipole polarizability of the substitutional dopant ion. Our results suggest that the doping-induced structural and size transition, demonstrated here in NaYF(4) upconversion nanocrystals, could be extended to other lanthanide-doped nanocrystal systems for applications ranging from luminescent biological labels to volumetric three-dimensional displays.

Simultaneous phase and size control of upconversion nanocrystals through lanthanide doping

Lanthanide ions exhibit unique luminescent properties, including the ability to convert near infrared long-wavelength excitation radiation into shorter visible wavelengths through a process known as photon upconversion. In recent years lanthanide-doped upconversion nanocrystals have been developed as a new class of luminescent optical labels that have become promising alternatives to organic fluorophores and quantum dots for applications in biological assays and medical imaging. These techniques offer low autofluorescence background, large anti-Stokes shifts, sharp emission bandwidths, high resistance to photobleaching, and high penetration depth and temporal resolution. Such techniques also show potential for improving the selectivity and sensitivity of conventional methods. They also pave the way for high throughput screening and miniaturization. This tutorial review focuses on the recent development of various synthetic approaches and possibilities for chemical tuning of upconversion properties, as well as giving an overview of biological applications of these luminescent nanocrystals.

Recent advances in the chemistry of lanthanide-doped upconversion nanocrystals

Highly Efficient Multicolour Upconversion Emission in Transparent Colloids of Lanthanide-Doped NaYF4 Nanocrystals

Novel materials doped with trivalent lanthanides and transition metal ions showing near-infrared to visible photon upconversion

Blue, Green, and Red Upconversion Emission from Lanthanide‐Doped LuPO4 and YbPO4 Nanocrystals in a Transparent Colloidal Solution

Visible light emission upon near-infrared excitation in a transparent solution of nanocrystalline β-NaGdF4: Yb3+, Er3+

This work reports on the structural characterization and on the low-temperature upconversion spectroscopy of the Y2O3:2%Er,1%Yb nanophosphor prepared by thermal decomposition of a polymeric resin (Pechini’s method [U.S. Patent No. 3,330,697 (July 11 1967)]). The average particle size evaluated from transmission electron microscopy lies in the range of 05–25nm. The high-resolution upconversion luminescence spectrum at 10K in the ultraviolet to near infrared (UV-NIR) spectral regions shows narrow lines, characteristic of Er3+ transitions occupying both Y3+ sites with point symmetries C2 and C3i in the oxide cubic system. The excitation spectrum at 10K in the IR region was used to monitor the green upconversion and IR luminescences and it displayed Er and Yb lines. Power dependence measurements at 298 and 10K indicate that the main upconversion mechanism is a two-photon excitation process. The temperature dependence of the upconversion luminescence shows a decrease in the emission intensity with increasing t...

Stephan Heer

Papers

Highly Efficient Multicolour Upconversion Emission in Transparent Colloids of Lanthanide-Doped NaYF4 Nanocrystals

Novel materials doped with trivalent lanthanides and transition metal ions showing near-infrared to visible photon upconversion

Blue, Green, and Red Upconversion Emission from Lanthanide‐Doped LuPO4 and YbPO4 Nanocrystals in a Transparent Colloidal Solution

Visible light emission upon near-infrared excitation in a transparent solution of nanocrystalline β-NaGdF4: Yb3+, Er3+

Low-temperature upconversion spectroscopy of nanosized Y2O3:Er,Yb phosphor