Photovoltaic (PV) technologies for solar energy conversion represent promising routes to green and renewable energy generation. Despite relevant PV technologies being available for more than half a century, the production of solar energy remains costly, largely owing to low power conversion efficiencies of solar cells. The main difficulty in improving the efficiency of PV energy conversion lies in the spectral mismatch between the energy distribution of photons in the incident solar spectrum and the bandgap of a semiconductor material. In recent years, luminescent materials, which are capable of converting a broad spectrum of light into photons of a particular wavelength, have been synthesized and used to minimize the losses in the solar-cell-based energy conversion process. In this review, we will survey recent progress in the development of spectral converters, with a particular emphasis on lanthanide-based upconversion, quantum-cutting and down-shifting materials, for PV applications. In addition, we will also present technical challenges that arise in developing cost-effective high-performance solar cells based on these luminescent materials.

Enhancing solar cell efficiency: the search for luminescent materials as spectral converters

The use of lanthanide ions to convert photons to different, more useful, wavelengths is well-known from a wide range of applications (e.g. fluorescent tubes, lasers, white light LEDs). Recently, a new potential application has emerged: the use of lanthanide ions for spectral conversion in solar cells. The main energy loss in the conversion of solar energy to electricity is related to the so-called spectral mismatch: low energy photons are not absorbed by a solar cell while high energy photons are not used efficiently. To reduce the spectral mismatch losses both upconversion and downconversion are viable options. In the case of upconversion two low energy infrared photons that cannot be absorbed by the solar cell, are added up to give one high energy photon that can be absorbed. In the case of downconversion one high energy photon is split into two lower energy photons that can both be absorbed by the solar cell. The rich and unique energy level structure arising from the 4fn inner shell configuration of the trivalent lanthanide ions gives a variety of options for efficient up- and downconversion. In this perspective an overview will be given of recent work on photon management for solar cells. Three topics can be distinguished: (1) modelling of the potential impact of spectral conversion on the efficiency of solar cells; (2) research on up- and downconversion materials based on lanthanides; and (3) proof-of-principle experiments. Finally, an outlook will be given, including issues that need to be resolved before wide scale application of up- and downconversion materials can be anticipated.

Lanthanide ions as spectral converters for solar cells

Light emitting diodes (LEDs) are on the verge of a breakthrough in general lighting, due to their rapidly improving efficiency. Currently, white LEDs with high color rendering are mainly based on wavelength conversion by one or more phosphor materials. This Review first describes how to quantify the quality of a light source, discussing the color rendering index (CRI) and alternative color quality indices. Then, six main criteria are identified and discussed, which should be fulfilled by a phosphor candidate to be considered for actual application in LEDs. These criteria deal with the shape and position of the emission and the excitation spectra, the thermal quenching behavior, the quantum efficiency, the chemical and thermal stability and finally with the occurrence of saturation effects. Based on these criteria, the most common dopant ions (broad-band emitting Eu 2+ , Ce 3+ and Mn 2+ , line-emitting rare earth ions,...) and host compounds (garnets, sulfides, (oxy)nitrides,...) are evaluated. Although many phosphor materials have been proposed in literature in recent years, the number of phosphors effectively fulfilling all six requirements is relatively small.

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Selecting Conversion Phosphors for White Light-Emitting Diodes

Organic–inorganic perovskites are a class of interesting compound in the perovskite family due to their unique structures of alternately stacking sheets of organic and inorganic components on the molecular scale. In this highlight, the basic knowledge and recent advances in organic–inorganic perovskites are reviewed with particular emphasis on the feature work including: the novel - and -oriented perovskite structures, synthesis, film preparation, patterning methods and optoelectronic properties of hybrid perovskites. Moreover, the small functional organic molecules can be templated into a regular arrangement by the inorganic perovskite framework. This unique material with nature-formed lamellar structure has the potential to be used as a template to create novel derivatives and bring about unique physical properties. Some interesting examples, such as intercalated polymer and silica network by topochemical polymerisation, fabrication of disk-like semiconductor nanocrystals and metal nanoparticles by hybrid perovskite templates are described.

Layered organic-inorganic hybrid perovskites: structure, optical properties, film preparation, patterning and templating engineering

Treatment of large bone defects derived from bone tumor surgery is typically performed in multiple separate operations, such as hyperthermia to extinguish residual malignant cells or implanting bioactive materials to initiate apatite remineralization for tissue repair; it is very challenging to combine these functions into a material. Herein, we report the first photothermal (PT) effect in bismuth (Bi)-doped glasses. On the basis of this discovery, we have developed a new type of Bi-doped bioactive glass that integrates both functions, thus reducing the number of treatment cycles. We demonstrate that Bi-doped bioglasses (BGs) provide high PT efficiency, potentially facilitating photoinduced hyperthermia and bioactivity to allow bone tissue remineralization. The PT effect of Bi-doped BGs can be effectively controlled by managing radiative and non-radiative processes of the active Bi species by quenching photoluminescence (PL) or depolymerizing glass networks. In vitro studies demonstrate that such glasses are biocompatible to tumor and normal cells and that they can promote osteogenic cell proliferation, differentiation, and mineralization. Upon illumination with near-infrared (NIR) light, the bioglass (BG) can efficiently kill bone tumor cells, as demonstrated via in vitro and in vivo experiments. This indicates excellent potential for the integration of multiple functions within the new materials, which will aid in the development and application of novel biomaterials.

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Multi-functional bismuth-doped bioglasses: combining bioactivity and photothermal response for bone tumor treatment and tissue repair.

The reduction of Eu3+ to Eu2+ in air has been observed in a silicate matrix for the first time in BaMgSiO4∶Eu prepared by high-temperature solid-state reaction. Emission and excitation spectra were employed to detect the presence of Eu2+ ions in the compound and this reduction was explained by a charge compensation model proposed previously. In BaMgSiO4∶Eu2+, Eu2+ ions occupy three different lattice sites by substitution for Ba2+ ions. Eu2+ ions on Ba(1) and Ba(2) sites gave emissions at about 500 nm while that on Ba(3) site showed an emission band at 398 nm. All the emissions of Eu2+ ions in BaMgSiO4∶Eu2+ were not quenched at room temperature.

The reduction of Eu3+ to Eu2+ in BaMgSiO4∶Eu prepared in air and the luminescence of BaMgSiO4∶Eu2+ phosphor

Near infrared broadband emission characteristics of bismuth-doped aluminophosphate glass have been investigated. Broad infrared emissions peaking at 1210nm, 1173nm and 1300nm were observed when the glass was pumped by 405nm laser diode (LD), 514nm Ar+ laser and 808nm LD, respectively. The full widths at half maximum (FWHMs) are 235nm, 207nm and 300nm for the emissions at 1210nm, 1173nm and 1300nm, respectively. Based on the energy matching conditions, it is suggested that the infrared emission may be ascribed to 3P1→ 3P0 transition of Bi+. The broadband infrared luminescent characteristics of the glasses indicate that they are promising for broadband optical fiber amplifiers and tunable lasers.

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Near infrared broadband emission of bismuth-doped aluminophosphate glass

Broadband infrared luminescence from bismuth-doped germanium oxide glasses prepared by a conventional melting-quenching technique was discovered. The absorption spectrum of the glasses covered a wide range from the visible to the near-infrared wavelength regions and consisted of five broad peaks below 370, 500, 700, 800, and 1000 nm. The fluorescence spectrum exhibited broadband characteristics (FWHM) greater than 300 nm with a maximum at 1300 nm pumped by an 808-nm laser. The fluorescence lifetime at room temperature decreased with increasing Bi2O3 concentration in the glass. Codoping of aluminum and bismuth was indispensable for the broadband infrared luminescence in GeO2:Bi, Al glass.

Bismuth- and aluminum-codoped germanium oxide glasses for super-broadband optical amplification

We report near infrared broadband emission of bismuth-doped barium-aluminum-borate glasses. The broadband emission covers 1.3 mum window in optical telecommunication systems. And it possesses wide full width at half maximum (FWHM) of similar to 200nm and long lifetime as long as 350 mus. The luminescent properties are quite sensitive to glass compositions and excitation wavelengths. Based on energy matching conditions, we suggest that the infrared emission may be ascribed to P-3(1) --> P-3(0) transition of Bi+. The broad infrared emission characteristics of this material indicate that it might be a promising candidate for broadband optical fiber amplifiers and tunable lasers. (C) 2005 Optical Society of America.

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Infrared broadband emission of bismuth-doped barium-aluminum-borate glasses.

Near-infrared broadband emission from bismuth-tantalum-codoped germanium oxide glasses was observed at room temperature when the glasses were pumped by an 808 nm laser diode. The emission band covered the 0, E, S, C, and L bands (1260-1625 nm), with a maximum peak at similar to 1310 nm, a FWHM broader than 400 nm, and a lifetime longer than 200 lis. The observed broadband luminescence was attributed to bismuth clusters in the glasses. Bismuth-tantalum-codoped germanium oxide glass might be promising as amplification media for broadly tunable lasers and wideband amplifiers in optical communications. (c) 2005 Optical Society of America.

Mingying Peng

Papers

The reduction of Eu3+ to Eu2+ in BaMgSiO4∶Eu prepared in air and the luminescence of BaMgSiO4∶Eu2+ phosphor

Near infrared broadband emission of bismuth-doped aluminophosphate glass

Bismuth- and aluminum-codoped germanium oxide glasses for super-broadband optical amplification

Infrared broadband emission of bismuth-doped barium-aluminum-borate glasses.

Superbroadband 1310 nm emission from bismuth and tantalum codoped germanium oxide glasses