Roadmap on thermoelectricity.

The increasing energy demand and the ever more pressing need for clean technologies of energy conversion pose one of the most urgent and complicated issues of our age. Thermoelectricity, namely the direct conversion of waste heat into electricity, is a promising technique based on a long-standing physical phenomenon, which still has not fully developed its potential, mainly due to the low efficiency of the process. In order to improve the thermoelectric performance, a huge effort is being made by physicists, materials scientists and engineers, with the primary aims of better understanding the fundamental issues ruling the improvement of the thermoelectric figure of merit, and finally building the most efficient thermoelectric devices. In this Roadmap an overview is given about the most recent experimental and computational results obtained within the Italian research community on the optimization of composition and morphology of some thermoelectric materials, as well as on the design of thermoelectric and hybrid thermoelectric/photovoltaic devices.

Deep-Subwavelength 2D Periodic Surface Nanostructures on Diamond by Double-Pulse Femtosecond Laser Irradiation.

Two-dimensional laser-induced periodic surface structures with a deep-subwavelength periodicity (80 nm ≈ λ/10) are obtained for the first time on diamond surfaces. The distinctive surface nanotexturing is achieved by employing a single step technique that relies on irradiation with two temporally delayed and cross-polarized femtosecond-laser pulses (100 fs duration, 800 nm wavelength, 1 kHz repetition rate) generated with a Michelson-like interferometer configuration, followed by chemical etching of surface debris. In this Letter, we demonstrate that, if the delay between two consecutive pulses is ≤2 ps, the 2D periodicity of nanostructures can be tuned by controlling the number of pulses irradiating the surface. Under scanning mode, the method is effective in treating uniformly large areas of diamond, so to induce remarkable antireflection properties able to enhance the absorptance in the visible up to 50 times and to pave the route toward the creation of metasurfaces for future diamond-based optoelectronic devices.

Metal-Halide Perovskite Submicrometer-Thick Films for Ultra-Stable Self-Powered Direct X-Ray Detectors.

Metal-halide perovskites are revolutionizing the world of X-ray detectors, due to the development of sensitive, fast, and cost-effective devices. Self-powered operation, ensuring portability and low power consumption, has also been recently demonstrated in both bulk materials and thin films. However, the signal stability and repeatability under continuous X-ray exposure has only been tested up to a few hours, often reporting degradation of the detection performance. Here it is shown that self-powered direct X-ray detectors, fabricated starting from a FAPbBr3 submicrometer-thick film deposition onto a mesoporous TiO2 scaffold, can withstand a 26-day uninterrupted X-ray exposure with negligible signal loss, demonstrating ultra-high operational stability and excellent repeatability. No structural modification is observed after irradiation with a total ionizing dose of almost 200 Gy, revealing an unexpectedly high radiation hardness for a metal-halide perovskite thin film. In addition, trap-assisted photoconductive gain enabled the device to achieve a record bulk sensitivity of 7.28 C Gy-1 cm-3 at 0 V, an unprecedented value in the field of thin-film-based photoconductors and photodiodes for "hard" X-rays. Finally, prototypal validation under the X-ray beam produced by a medical linear accelerator for cancer treatment is also introduced.

Structural and Photoelectronic Properties of κ-Ga2O3 Thin Films Grown on Polycrystalline Diamond Substrates.

Orthorhombic κ-Ga2O3 thin films were grown for the first time on polycrystalline diamond free-standing substrates by metal-organic vapor phase epitaxy at a temperature of 650 °C. Structural, morphological, electrical, and photoelectronic properties of the obtained heterostructures were evaluated by optical microscopy, X-ray diffraction, current-voltage measurements, and spectral photoconductivity, respectively. Results show that a very slow cooling, performed at low pressure (100 mbar) under a controlled He flow soon after the growth process, is mandatory to improve the quality of the κ-Ga2O3 epitaxial thin film, ensuring a good adhesion to the diamond substrate, an optimal morphology, and a lower density of electrically active defects. This paves the way for the future development of novel hybrid architectures for UV and ionizing radiation detection, exploiting the unique features of gallium oxide and diamond as wide-bandgap semiconductors.

Multi-Scale Femtosecond-Laser Texturing for Photothermal Efficiency Enhancement on Solar Absorbers Based on TaB2 Ceramics.

Tantalum boride is an ultra-refractory and ultra-hard ceramic known so far for its favorable high-temperature thermo-mechanical properties and also characterized by a low spectral emittance, making it interesting for novel high-temperature solar absorbers for Concentrating Solar Power. In this work, we investigated two types of TaB2 sintered products with different porosities, and on each of them, we realized four femtosecond laser treatments differing in the accumulated laser fluence. The treated surfaces were then characterized by SEM-EDS, roughness analysis, and optical spectrometry. We show that, depending on laser processing parameters, the multi-scale surface textures produced by femtosecond laser machining can greatly increase the solar absorptance, while the spectral emittance increase is significantly lower. These combined effects result in increased photothermal efficiency of the absorber, with interesting perspectives for the application of these ceramics in Concentrating Solar Power and Concentrating Solar Thermal. To the best of our knowledge, this is the first demonstration of successful photothermal efficiency enhancement of ultra-hard ceramics using laser machining.

A Highly Versatile X-ray and Electron Beam Diamond Dosimeter for Radiation Therapy and Protection.

Radiotherapy is now recognized as a pillar in the fight against cancer. Two different types are currently used in clinical practice: (1) external beam radiotherapy, using high-energy X-rays or electron beams, both in the MeV-range, and (2) intraoperative radiotherapy, using low-energy X-rays (up to 50 keV) and MeV-range electron beams. Versatile detectors able to measure the radiation dose independently from the radiation nature and energy are therefore extremely appealing to medical physicists. In this work, a dosimeter based on a high-quality single-crystal synthetic diamond sample was designed, fabricated and characterized under low-energy X-rays, as well as under high-energy pulsed X-rays and electron beams, demonstrating excellent linearity with radiation dose and dose-rate. Detector sensitivity was measured to be 0.299 ± 0.002 µC/Gy under 6 MeV X-ray photons, and 0.298 ± 0.004 µC/Gy under 6 MeV electrons, highlighting that the response of the diamond dosimeter is independent of the radiation nature. Moreover, in the case of low-energy X-rays, an extremely low limit of detection (23 nGy/s) was evaluated, pointing out the suitability of the device to radiation protection dosimetry.

Etching Kinetics of Nanodiamond Seeds in the Early Stages of CVD Diamond Growth.

We present an experimental study on the etching of detonation nanodiamond (DND) seeds during typical microwave chemical vapor deposition (MWCVD) conditions leading to ultra-thin diamond film formation, which is fundamental for many technological applications. The temporal evolution of the surface density of seeds on the Si(100) substrate has been assessed by scanning electron microscopy (SEM). The resulting kinetics have been explained in the framework of a model based on the effect of the particle size, according to the Young-Laplace equation, on both chemical potential of carbon atoms in DND and activation energy of the reaction with atomic hydrogen. The model describes the experimental kinetics of seeds' disappearance by assuming that nanodiamond particles with a size smaller than a "critical radius," r*, are etched away while those greater than r* can grow. Finally, the model allows to estimate the rate coefficients for growth and etching from the experimental kinetics.

Femtosecond-Laser Nanostructuring of Black Diamond Films under Different Gas Environments.

Irradiation of diamond with femtosecond (fs) laser pulses in ultra-high vacuum (UHV) conditions results in the formation of surface periodic nanostructures able to strongly interact with visible and infrared light. As a result, native transparent diamond turns into a completely different material, namely "black" diamond, with outstanding absorptance properties in the solar radiation wavelength range, which can be efficiently exploited in innovative solar energy converters. Of course, even if extremely effective, the use of UHV strongly complicates the fabrication process. In this work, in order to pave the way to an easier and more cost-effective manufacturing workflow of black diamond, we demonstrate that it is possible to ensure the same optical properties as those of UHV-fabricated films by performing an fs-laser nanostructuring at ambient conditions (i.e., room temperature and atmospheric pressure) under a constant He flow, as inferred from the combined use of scanning electron microscopy, Raman spectroscopy, and spectrophotometry analysis. Conversely, if the laser treatment is performed under a compressed air flow, or a N2 flow, the optical properties of black diamond films are not comparable to those of their UHV-fabricated counterparts.

Laser-Induced Periodic Surface Structures (LIPSS) on Heavily Boron-Doped Diamond for Electrode Applications.

Diamond is known as a promising electrode material in the fields of cell stimulation, energy storage (e.g., supercapacitors), (bio)sensing, catalysis, etc. However, engineering its surface and electrochemical properties often requires costly and complex procedures with addition of foreign material (e.g., carbon nanotube or polymer) scaffolds or cleanroom processing. In this work, we demonstrate a novel approach using laser-induced periodic surface structuring (LIPSS) as a scalable, versatile, and cost-effective technique to nanostructure the surface and tune the electrochemical properties of boron-doped diamond (BDD). We study the effect of LIPSS on heavily doped BDD and investigate its application as electrodes for cell stimulation and energy storage. We show that quasi-periodic ripple structures formed on diamond electrodes laser-textured with a laser accumulated fluence of 0.325 kJ/cm2 (800 nm wavelength) displayed a much higher double-layer capacitance of 660 µF/cm2 than the as-grown BDD (20 µF/cm2) and that an increased charge-storage capacity of 1.6 mC/cm2 (>6-fold increase after laser texturing) and a low impedance of 2.74 Ω cm2 turn out to be appreciable properties for cell stimulation. Additional morphological and structural characterization revealed that ripple formation on heavily boron-doped diamond (2.8 atom % [B]) occurs at much lower accumulated fluences than the 2 kJ/cm2 typically reported for lower doping levels and that the process involves stronger graphitization of the BDD surface. Finally, we show that the exposed interface between sp2 and sp3 carbon layers (i.e. the laser-ablated diamond surface) revealed faster kinetics than the untreated BDD in both ferrocyanide and RuHex mediators, which can be used for electrochemical (bio)sensing. Overall, our work demonstrates that LIPSS is a powerful single-step tool for the fabrication of surface-engineered diamond electrodes with tunable material, electrochemical, and charge-storage properties.