Radiative Cooling Properties of Portlandite and Tobermorite: Two Cementitious Minerals of Great Relevance in Concrete Science and Technology.

Although concrete and cement-based materials are the most engineered materials employed by mankind, their potential for use in daytime radiative cooling applications has yet to be fully explored. Due to its complex structure, which is composed of multiple phases and textural details, fine-tuning of concrete is impossible without first analyzing its most important ingredients. Here, the radiative cooling properties of Portlandite (Ca(OH)2) and Tobermorite (Ca5Si6O16(OH)2·4H2O) are studied due to their crucial relevance in cement and concrete science and technology. Our findings demonstrate that, in contrast to concrete (which is a strong infrared emitter but a poor sun reflector), both Portlandite and Tobermorite exhibit good radiative cooling capabilities. These results provide solid evidence that, with the correct optimization of composition and porosity, concrete can be transformed into a material suitable for daytime radiative cooling.

Cementitious materials as promising radiative coolers for solar cells.

Nowadays, radiative coolers are extensively investigated for the thermal management of solar cells with the aim of improving their performance and lifetime. Current solutions rely on meta-materials with scarce elements or complex fabrication processes, or organic polymers possibly affected by UV degradation. Here, the potential of innovative cement-based solutions as a more sustainable and cost-effective alternative is reported. By combining chemical kinetics, molecular mechanics and electromagnetic simulations, it is shown that the most common cements, i.e., Portland cements, can be equipped with excellent radiative cooling properties, which might enable a reduction of the operating temperature of solar cells by up to 20 K, with outstanding efficiency and lifetime gains. This study represents a first step toward the realization of a novel class of energy-efficient, economically viable and robust radiative coolers, based on cheap and available cementitious materials.

Application of Floquet theory to dynamical systems with memory.

We extend the recently developed generalized Floquet theory [Phys. Rev. Lett. 110, 170602 (2013)] to systems with infinite memory, i.e., a dependence on the whole previous history. In particular, we show that a lower asymptotic bound exists for the Floquet exponents associated to such cases. As examples, we analyze the cases of an ideal 1D system, a Brownian particle, and a circuit resonator with an ideal transmission line. All these examples show the usefulness of this new approach to the study of dynamical systems with memory, which are ubiquitous in science and technology.

Thin-film InAs/GaAs quantum dot solar cell with planar and pyramidal back reflectors.

Quantum dot solar cells are promising for next-generation photovoltaics owing to their potential for improved device efficiency related to bandgap tailoring and quantum confinement of charge carriers. Yet implementing effective photon management to increase the absorptivity of the quantum dots is instrumental. To this end, the performance of thin-film InAs/GaAs quantum dot solar cells with planar and structured back reflectors is reported. The experimental thin-film solar cells with planar reflectors exhibited a bandgap-voltage offset of 0.3 V with an open circuit voltage of 0.884 V, which is one of the highest values reported for quantum dot solar cells grown by molecular beam epitaxy to our knowledge. Using measured external quantum efficiency and current-voltage characteristics, we parametrize a simulation model that was used to design an advanced reflector with diffractive pyramidal gratings revealing a 12-fold increase of the photocurrent generation in the quantum dot layers.

Droplet epitaxy quantum dot based infrared photodetectors.

The fabrication and characterization of an infrared photodetector based on GaAs droplet epitaxy quantum dots embedded in Al0.3Ga0.7As barrier is reported. The high control over dot electronic properties and the high achievable number density allowed by droplet epitaxy technique permitted us to realize a device using a single dot layer in the active region. Moreover, thanks to the independent control over dot height and width, we were able to obtain a very sharp absorption peak in the thermal infrared region (3-8 µm). Low temperature photocurrent spectrum was measured by Fourier spectroscopy, showing a narrow peak at 198 meV (∼6.3 µm) with a full width at half maximum of 25 meV. The observed absorption is in agreement with theoretical prediction based on effective mass approximation of the dot electronic transition.

Comparison of metal/polymer back reflectors with half-sphere, blazed, and pyramid gratings for light trapping in III-V solar cells.

We report on the fabrication of diffraction gratings for application as back contact reflectors. The gratings are designed for thin-film solar cells incorporating absorbers with bandgap slightly lower than GaAs, i.e. InAs quantum dot or GaInNAs solar cells. Light trapping in the solar cells enables the increase of the absorption leading to higher short circuit current densities and higher efficiencies. We study metal/polymer back reflectors with half-sphere, blazed, and pyramid gratings, which were fabricated either by photolithography or by nanoimprint lithography. The gratings are compared in terms of the total and the specular reflectance, which determine their diffraction capabilities, i.e. the feature responsible for increasing the absorption. The pyramid grating showed the highest diffuse reflection of light compared to the half-sphere structure and the blazed grating. The diffraction efficiency measurements were in agreement with the numerical simulations. The validated model enables designing such metal/polymer back reflectors for other type of solar cells by refining the optimal dimensions of the gratings for different wavelength ranges.

Guided-mode resonance gratings for enhanced mid-infrared absorption in quantum dot intermediate-band solar cells.

Achieving strong absorption of low-energy photons is one of the key issues to demonstrate quantum dot solar cells working in the intermediate band regime at practical concentration factors and operating temperatures. Guided-mode resonance effects may enable large enhancement of quantum dot intraband optical transitions. We propose quantum dot thin-film cells designed to have significant field waveguiding in the quantum dot stack region and patterned at the rear-side with a sub-wavelength diffraction grating. Remarkable increase of the optical path length at mid-infrared wavelengths is shown owing to guided-mode resonances. Design guidelines are presented for energy and strength of the second-photon absorption for III-V quantum dots, such as InAs/GaAs and GaSb/GaAs, whose intraband and intersubband transitions roughly extends over the 2 - 8 µm range. The proposed design can also be applied to quantum dot infrared detectors. Angle-selectivity is discussed in view of applications in concentrator photovoltaic systems and infrared imaging systems.

Consistent static and small-signal physics-based modeling of dye-sensitized solar cells under different illumination conditions.

A numerical device-level model of dye-sensitized solar cells (DSCs) is presented, which self-consistently couples a physics-based description of the photoactive layer with a compact circuit-level description of the passive parts of the cell. The opto-electronic model of the nanoporous dyed film includes a detailed description of photogeneration and trap-limited kinetics, and a phenomenological description of nonlinear recombination. Numerical simulations of the dynamic small-signal behavior of DSCs, accounting for trapping and nonlinear recombination mechanisms, are reported for the first time and validated against experiments. The model is applied to build a consistent picture of the static and dynamic small-signal performance of nanocrystalline TiO2-based DSCs under different incident illumination intensity and direction, analyzed in terms of current-voltage characteristic, Incident Photon to Current Efficiency, and Electrochemical Impedance Spectroscopy. This is achieved with a reliable extraction and validation of a unique set of model parameters against a large enough set of experimental data. Such a complete and validated description allows us to gain a detailed view of the cell collection efficiency dependence on different operating conditions. In particular, based on dynamic numerical simulations, we provide for the first time a sound support to the interpretation of the diffusion length, in the presence of nonlinear recombination and non-uniform electron density distribution, as derived from small-signal characterization techniques and clarify its correlation with different estimation methods based on spectral measurements.

Charge transport improvement employing TiO2 nanotube arrays as front-side illuminated dye-sensitized solar cell photoanodes.

TiO(2) nanotube (NT) arrays with different lengths were fabricated by anodic oxidation of Ti foil and free-standing NT membranes were detached by the metal substrate and bonded on the fluorine-doped tin oxide surface implementing an easy procedure. Morphology of the as-grown material and of the prepared photoanode was investigated by means of electron microscopy, deepening the investigation on the thermal treatment effect. Crystalline orientation and exposed surface area were studied by X-ray diffraction and Brunauer-Emmett-Teller measurements, showing suitable characteristics for the application in dye-sensitized solar cells (DSCs). DSCs were assembled employing a microfluidic housing system. The cell performances and the electron transport properties as a function of the tube length, before and after a TiCl(4) treatment, were characterized by I-V electrical measurements, incident photon-to-electron conversion efficiency, electrochemical impedance spectroscopy and open circuit voltage decay. Fitting the impedance spectra with an equivalent circuit, it was possible to obtain information on the electron diffusion properties into the TiO(2) nanotubes. A comparison with the charge transport properties evaluated in nanoparticle-based photoanodes witnesses a noteworthy increase of electron lifetime and diffusion length, yielding an overall power conversion efficiency up to 7.56%.

High efficiency dye-sensitized solar cells exploiting sponge-like ZnO nanostructures.

Sponge-like nanostructured ZnO layers were successfully employed as photoanodes for the fabrication of highly efficient dye-sensitized solar cells. The sponge-like ZnO layers were obtained by room temperature radio-frequency magnetron sputtering deposition of metallic zinc, followed by thermal oxidation treatment in an ambient atmosphere. The porous films show a 3D branched nanomorphology, with a feature similar to natural coral. The morphological and optical properties of these layers were studied through field emission scanning electron microscopy, specific surface area measurements, ultraviolet-visible transmittance and absorption spectroscopy. The sponge-like ZnO film presents a high density of branches, with a relatively high specific surface area value, and fine optical transmittance. The morphology of the porous structure provides a high number of adsorption sites for the anchoring of sensitizer molecules, making it suitable for the fabrication of ZnO-based photoanodes for dye-sensitized solar cells. The light harvesting performance of the sensitized semiconductor was evaluated by current density vs. voltage measurements, incident photon-to-electron conversion efficiency, open circuit voltage decay and impedance spectroscopy. The modelling of the electrical characteristics evidences a higher electron lifetime and a longer charge diffusion length, if compared to standard TiO(2) nanoparticle based photoanodes. For ZnO films with a thickness up to 18 µm, a photoconversion efficiency as high as 6.67% and a maximum value of the incident photon-to-electron collection efficiency equal to 87% at 530 nm were demonstrated.