Photon upconversion

Upconversion Fluorescence. Optical fiber that contains infrared light shines with a blue color in the dark

Photon upconversion (UC) is a process in which the sequential absorption of two or more photons leads to the emission of light at shorter wavelength than the excitation wavelength. It is an anti-Stokes type emission. An example is the conversion of infrared light to visible light. Materials by which upconversion can take place often contain ions of d-block and f-block elements. Examples of these ions are Ln³⁺, Ti²⁺, Ni²⁺, Mo³⁺, Re⁴⁺, Os⁴⁺, and so on.

Three basic mechanisms are energy transfer upconversion, excited-state absorption (ESA) and photon avalanche (PA). Upconversion should be distinguished from two-photon absorption and second-harmonic generation. An early proposal (a solid-state IR quantum counter) was made by N. Bloembergen in 1959 and the process was first observed by F. Auzel in 1966. In particular, recent big progress in synthesis of high-quality nano-structured crystals has enabled some new pathways for photon upconversion, such as Tb-mediated interfacial energy transfer.

Thermal upconversion mechanism has also been proposed. This mechanism is based on the absorption of photons with low energies in the upconverter, which heats up and re-emits photons with higher energies. To make this process possible, the density of optical states of the upconverter has to be carefully engineered to provide frequency- and angularly-selective emission characteristics. For example, a planar thermal upconverting platform can have a front surface that absorbs low-energy photons incident within a narrow angular range, and a back surface that efficiently emits only high-energy photons. These surface properties can be realized through designs of photonic crystal, and theories and experiments have been demonstrated on thermophotovoltaics and radiation cooling. Under best criterion, energy conversion efficiency from solar radiation to electricity by introducing up-converter can go up to 73% using AM1.5D spectrum and 76% considering sun as a black body source at 6000K for a single junction cell.

Upconversion nanoparticles

Lanthanide-doped nanoparticles

Lanthanide-doped nanoparticles emerged in the late 1990s due to the prevalent work on nanotechnology, marking a turning point in the landscape of modern lanthanide research. Although the optical transitions in lanthanide-doped nanoparticles essentially resemble those in bulk materials, the nanostructure amenable to surface modifications provides new opportunities for research. Particularly, these nanoparticles are promising alternatives to molecular fluorophores for biological applications. Their unique optical properties, such as large Stokes shift and nonblinking, have enabled them to rival conventional luminescent probes in challenging tasks including single-molecule tracking and deep tissue imaging. Despite the promising aspects of these nanomaterials, one urgent task that confronts materials chemists lies in the synthesis of nanoparticles with tunable emissions, which are essential for applications in multiplexed imaging and sensing.

The development of a reproducible, high yield synthetic route that allows controlled growth of rare earth halide nanoparticles has enabled the development and commercialization of upconversion nanoparticles in many different bioapplications described above. The first worldwide, commercially available upconversion nanoparticles were developed by Intelligent Material Solutions, Inc. and distributed through Sigma-Aldrich.

Semiconductor nanoparticles

The use of semiconductor nanoparticles, such as CdSe, PbS and PbSe, has recently been shown as a new strategy for photon upconversion. They are being used to upconvert 980 nm infrared light to 600 nm visible light. This technique benefits from a very high upconverting capability. Especially, these materials can be used to capture the infrared region of sunlight to electricity and enhance the efficiency of photovoltaic solar cells.

Upconversion Nanocapsules for Differential Cancer Bioimaging in vivo

Early diagnosis of tumor malignancy is crucial for timely cancer treatment aimed at imparting desired clinical outcomes. The traditional fluorescence-based imaging is unfortunately faced with challenges such as low tissue penetration and background autofluorescence. Upconversion (UC)-based bioimaging can overcome these limitations as their excitation occurs at lower frequencies and the emission at higher frequencies. Recently, Kwon et al developed multifunctional silica-based nanocapsules, synthesized to encapsulate two distinct triplet-triplet annihilation UC chromophore pairs. Each nanocapsule emits different colors, blue or green, following a red light excitation. These nanocapsules were further conjugated with either antibodies or peptides to selectively target breast or colon cancer cells, respectively. Both in vitro and in vivo experimental results demonstrated cancer-specific and differential-color imaging from single wavelength excitation as well as far greater accumulation at targeted tumor sites than that due to the enhanced permeability and retention effect. This approach can be used to host a variety of chromophore pairs for various tumor-specific, color-coding scenarios and can be employed for diagnosis of a wide range of cancer types within the heterogeneous tumor microenvironment.

Applications and examples

At present, there is great interest in luminescent materials for efficient frequency conversion from infrared to visible radiation, mainly because a visible source pumped by a near infrared laser is useful for high-capacity data storage optical devices. This process can be obtained by upconversion mechanisms, where several infrared photons can be absorbed by the material doped with rare earth (RE) ions in order to populate more energetic levels. Therefore, both the fluorescence lifetime and the stimulated emission cross-section of the RE excited level should be maximized, whereas the nonradiative decay mechanisms should be minimized.

Oxyfluoride glass ceramics are ambivalent materials. Despite the fact that they are mainly oxide glasses, they can exhibit optical properties of fluoride single crystals when they are doped with rare earth ions. They are often called nanocomposite materials. Their weird character is obtained by a classical melting and quenching preparation in air followed by an adapted thermal treatment during which fluoride phases are crystallized. The size, size distribution, and volume concentration of fluoride crystallites are crucial for photonic applications. For example, to be a promising optical functional material, the size of the crystallites should be smaller than at least half of the wavelength of the light used while the size distribution should be narrow and the crystallites should possess a homogeneous spatial distribution. In this way, according to Rayleigh scattering, complete transparency of a light transmitting material can be attained. A refractive index difference between the amorphous and crystalline phases of less than 0.1 is also required. However, according to Beall and Pinckney, based on Hopper’s model, crystal sizes of 30 nm and differences in refractive index of 0.3 may be acceptable, provided that the crystal spacing is not larger than six times the average crystal size. Transparent Glass Ceramic (TGC) can also be obtained with even larger crystal sizes if optical isotropy is achieved within the glass ceramic. Consequently, the selection of the oxide glass composition and the fluoride phase composition is the key factor in obtaining the desired glass ceramic materials. The Er³⁺ ions are specially interesting due to their emission at 1.5 μm and the green upconversion obtained under near infrared excitation. In order to improve these emissions, the sensitization of this nanocomposite with Yb³⁺ ions may be a good choice because of the efficient energy transfer process from Yb³⁺ to Er³⁺ ions.