• Energy Research

The structural and optical properties of thin layers based on 70%SiO2–30%HfO2 doped with different concentration of rare earth ions (terbium and ytterbium) have been studied with a view to integrating them in a photovoltaic cell as a spectral conversion layer in order to improve its efficiency, by using down-conversion process. These thin films were synthesized by using sol gel technique and deposited on the pure silica substrate by dip-coating method. The DC layer can be placed on the front side of a solar cell and can enhance the current by converting ultraviolet (UV) photons into a large number of visible photons.In present study two series of samples are compared, the first series corresponds to samples treated at 900 °C (glass- S) while the second series concerns samples treated at 1000 °C (glass-ceramic- SC). These series are based on 70SiO2–30HfO2 activated by different molar concentrations of rare earths [Tb + Yb]/[Si + Hf] = 7%, 9%, 12%, 15%, 17%, 19% and 21%.Photoluminescence results of reference samples (without Yb3+) showed an emission from 5D4 to 7FJ (J = 3, 4, 5, 6) level characteristic transitions of Tb3+, with a maximum peak in the green centered at 543.5 nm corresponding to the 5D4→7F5 transition. For the co-doped samples a clear NIR PL emission around 980 nm was detected, due to the 2F5/2→2F7/2 transition of Yb3+ ions. From luminescence decay curves of Tb3+ maximum emission peak (7F5→5D4 transition at 543.5 nm) we have identified the energy transfer efficiency. The quantum efficiency increases by increasing the total [Tb + Yb] concentration. The most significant yield was achieved with [Tb + Yb]=19%, the maximum quantum transfer efficiency obtained was 190% for glass-ceramic samples and 161% for glassy one.

The efficiency of photovoltaic solar cells is strongly related to the spectral absorption and photo-conversion properties of the cell's active material, which does not exploit the whole broadband solar spectrum. This mismatch between the spectrum of the solar light and the wavelength dependent cell's response can be partially overcome by using luminescent conversion layers in front or in the back of the solar cell. In this paper, the investigation of Tb3+-Yb3+ co-doped SiO2-HfO2 glass and glass-ceramic waveguides is presented. Due to a down-conversion process based on cooperative energy transfer between one Tb3+ ion and two Yb3+ ions, a blue photon at 488 nm can be divided in two NIR photons at 980 nm. Films with different molar concentrations of rare earths, up to a total amount of [Tb + Yb] = 15%, were prepared by a sol-gel route, using dip-coating deposition on SiO2 substrates. For all the films, the molar ratio [Yb]/[Tb] was taken equal to 4. The comparison of the energy-transfer efficiency between Tb3+ and Yb3+ ions in the glass and in the glass-ceramic materials demonstrated the higher performance of the glass-ceramic, with a maximum quantum transfer efficiency of 179% for the highest rare earth doping concentration. Moreover, experimental results and comparison with proper rate equations modelling showed a linear dependence of the photoluminescence emission intensity for the Yb3+ ions 2F5/2 -> 2F7/2 transition at 980 nm on the excitation power, indicating a direct transfer process from Tb3+ to Yb3+ ions. The reported waveguides could find applications not only as downconverting filters in transmission but also as efficient solar concentrators in the near-IR spectral region.

We investigate the photoelectron transfer rate from PbS@CdS core@shell QDs to wide bandgap mesoporous films using photoluminescence lifetime spectroscopy, which is strongly size, shell thickness and oxide dependent.

AbstractThe need to develop sustainable energy solutions is an urgent requirement for society, with the additional requirement to limit dependence on critical raw materials, within a virtuous circular economy model. In this framework, it is essential to identify new avenues for light‐conversion into clean energy and fuels exploiting largely available materials and green production methods. Metal oxide semiconductors (MOSs) emerge among other species for their remarkable environmental stability, chemical tunability, and optoelectronic properties. MOSs are often key constituents in next generation energy devices, mainly in the role of charge selective layers. Their use as light harvesters is hitherto rather limited, but progressively emerging. One of the key strategies to boost their properties involves doping, that can improve charge mobility, light absorption and tune band structures to maximize charge separation at heterojunctions. In this review, effective methods to dope MOSs and to exploit the derived benefits in relation to performance enhancement in different types of devices are identified and critically compared. The work is focused specifically on the best opportunities coming from the use of non‐critical raw materials, so as to contribute in defining an economically feasible roadmap for light conversion technologies based on these highly stable and widely available compounds.

The optical photoluminescent (PL) emission of Yb3+ ions in the near infrared (NIR) spectral region at about 950–1100 nm has many potential applications, from photovoltaics to lasers and visual devices. However, due to their simple energy-level structure, Yb3+ ions cannot directly absorb UV or visible light, putting serious limits on their use as light emitters. In this paper we describe a broadband and efficient strategy for sensitizing Yb3+ ions by Ag codoping, resulting in a strong 980 nm PL emission under UV and violet-blue light excitation. Yb-doped silica–zirconia–soda glass–ceramic films were synthesized by sol-gel and dip-coating, followed by annealing at 1000 °C. Ag was then introduced by ion-exchange in a molten salt bath for 1 h at 350 °C. Different post-exchange annealing temperatures for 1 h in air at 380 °C and 430 °C were compared to investigate the possibility of migration/aggregation of the metal ions. Studies of composition showed about 1–2 wt% Ag in the exchanged samples, not modified by annealing. Structural analysis reported the stabilization of cubic zirconia by Yb-doping. Optical measurements showed that, in particular for the highest annealing temperature of 430 °C, the potential improvement of the material’s quality, which would increase the PL emission, is less relevant than Ag-aggregation, which decreases the sensitizers number, resulting in a net reduction of the PL intensity. However, all the Ag-exchanged samples showed a broadband Yb3+ sensitization by energy transfer from Ag aggregates, clearly attested by a broad photoluminescence excitation spectra after Ag-exchange, paving the way for applications in various fields, such as solar cells and NIR-emitting devices.

A set of samples co-doped with Er and Ag were prepared with a combined sol-gel and ion-exchange route. This multistep process sytnthesizes samples in which the silver atoms are dispersed in the matrix and/or aggregated in Ag multimers or nanoclusters. The samples exhibit a different photo-luminescence response depending on the sensitizing effect due to silver atoms. The spectroscopic properties were correlated with the structural properties investigated by extended x-ray absorption fine structure (EXAFS) spectroscopy and x-ray diffraction. The Er 3+ excitation via energy transfer, obtained in a wide range of wavelengths, has been clearly related to the presence in the sample of Ag multimers.