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

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

Solar energy represents one of the most abundant and yet least harvested sources of renewable energy. In recent years, tremendous progress has been made in developing photovoltaics that can be potentially mass deployed. Of particular interest to cost-effective solar cells is to use novel device structures and materials processing for enabling acceptable efficiencies. In this regard, here, we report the direct growth of highly regular, single-crystalline nanopillar arrays of optically active semiconductors on aluminium substrates that are then configured as solar-cell modules. As an example, we demonstrate a photovoltaic structure that incorporates three-dimensional, single-crystalline n-CdS nanopillars, embedded in polycrystalline thin films of p-CdTe, to enable high absorption of light and efficient collection of the carriers. Through experiments and modelling, we demonstrate the potency of this approach for enabling highly versatile solar modules on both rigid and flexible substrates with enhanced carrier collection efficiency arising from the geometric configuration of the nanopillars.

http://nano.eecs.berkeley.edu/publications/NatureMat_2009_SNOPcell.pdf

Three-dimensional nanopillar-array photovoltaics on low-cost and flexible substrates

Photon upconversion of near-infrared photons is a promising way to overcome the Shockley–Queisser efficiency limit of 32% of a single-junction solar cell. However, the practical applicability of the most efficient known upconversion materials at moderate light intensities is limited by their extremely weak and narrowband near-infrared absorption. Here, we introduce the concept of an upconversion material where an organic near-infrared dye is used as an antenna for the b-NaYF4:Yb,Er nanoparticles in which the upconversion occurs. The overall upconversion by the dye-sensitized nanoparticles is dramatically enhanced (by a factor of ∼3,300) as a result of increased absorptivity and overall broadening of the absorption spectrum of the upconverter. The proposed concept can be extended to cover any part of the solar spectrum by using a set of dye molecules with overlapping absorption spectra acting as an extremely broadband antenna system, connected to suitable upconverters.

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Broadband dye-sensitized upconversion of near-infrared light

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

Low cost surface passivation for p-type mc-Si based on pseudobinary alloys (Al2O3)x(TiO2)1−x

One of the main challenges in the ongoing development of thin film crystalline silicon solar cells on a supporting silicon substrate is the implementation of a long-wavelength reflector at the interface between the epitaxial layer and the substrate. IMEC has developed such a reflector based on electrochemical anodization of silicon to create a multi-layer porous silicon stack with alternating high and low porosity layers. This innovation results in a 1–2% absolute increase in efficiency for screenprinted epitaxial cells with a record of 13� 8%. To reach a better understanding of the reflector and to aid in its continued optimization, several extensive optical simulations have been performed using an in-house-developed optical software programme. This software is written as a Microsoft Excel workbook to make use of its user-friendliness and modular structure. It can handle up to 15 individual dielectric layers and is used to determine the influence of the number and the sequence of the layers on the internal reflection. A sensitivity analysis is also presented. A study of the angle at which the light strikes the reflector shows separate regions in the physical working of the reflector which include a region where the Bragg effect is dominant as well as a region where total internal reflection plays the largest role. The existence of these regions is proved using reflection measurements. Based on these findings, an estimate is made for the achievable current gain with an ideal reflector and the potential of epitaxial silicon solar cells is determined. Copyright # 2008 John Wiley & Sons, Ltd.

Simulation and Implementation of a Porous Silicon Reflector for Epitaxial Silicon Solar Cells

Poly-Si films prepared by rapid thermal CVD on boron and phosphorus silicate glass coated ceramic substrates

Epitaxially grown emitters for thin film crystalline silicon solar cells

A considerable cost reduction in photovoltaics could be achieved if efficient solar cells could be made from thin polycrystalline-silicon (pc-Si) films. Although hydrogen passivation of pc-Si films is crucial to obtain good solar cells, the exact mechanism of hydrogen diffusion through pc-Si layers is not yet understood. In this letter, the influence of the junction and the grain size are investigated. We find that the presence of a p-n junction acts as a barrier for hydrogen diffusion in thin-film polysilicon solar cells. Therefore, pc-Si solar cells should preferably be passivated before junction formation. Furthermore, pc-Si layers with large grains retain less hydrogen after passivation than layers with small grains. This indicates that hydrogen atoms get mainly trapped at the grain boundaries.

Guy Beaucarne

Papers

Low cost surface passivation for p-type mc-Si based on pseudobinary alloys (Al2O3)x(TiO2)1−x

Simulation and Implementation of a Porous Silicon Reflector for Epitaxial Silicon Solar Cells

Poly-Si films prepared by rapid thermal CVD on boron and phosphorus silicate glass coated ceramic substrates

Epitaxially grown emitters for thin film crystalline silicon solar cells

Study of the hydrogenation mechanism by rapid thermal anneal of SiN:H in thin-film polycrystalline-silicon solar cells