Diamond is a wide bandgap semiconductor with excellent physical properties which allow it to operate under extreme conditions. However, the technological use of diamond was mostly conceived for the fabrication of ultraviolet, ionizing radiation and nuclear detectors, of electron emitters, and of power electronic devices. The use of nanosecond pulse excimer lasers enabled the microstructuring of diamond surfaces, and refined techniques such as controlled ablation through graphitization and etching by two-photon surface excitation are being exploited for the nanostructuring of diamond. On the other hand, ultrashort pulse lasers paved the way for a more accurate diamond microstructuring, due to reduced thermal effects, as well as an effective surface nanostructuring, based on the formation of periodic structures at the nanoscale. It resulted in drastic modifications of the optical and electronic properties of diamond, of which "black diamond" films are an example for future high-temperature solar cells as well as for advanced optoelectronic platforms. Although experiments on diamond nanostructuring started almost 20 years ago, real applications are only today under implementation.

Thermionic energy converters are heat engines based on the direct emission of electrons from a hot cathode toward a colder anode. Because the thermionic emission is unavoidably accompanied by photonic emission, radiative energy transfer is a significant source of losses in these devices. In this Letter, we provide the experimental demonstration of a hybrid thermionic−photovoltaic device that is able to produce electricity not only from the electrons but also from the photons that are emitted by the cathode. Thermionic electrons are injected in the valence band of a gallium arsenide semiconducting anode, then pumped to the conduction band by the photovoltaic effect, and finally extracted from the conduction band to produce useful energy before they are reinjected in the cathode. We show that such a hybrid device produces a voltage boost of ∼1 V with respect to a reference thermionic device made of the same materials and operating under the same conditions. This proof of concept paves the way to the development of efficient thermionic and photovoltaic devices for the direct conversion of heat into electricity.

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.

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Black diamond, obtained by femtosecond laser treatment of natively transparent diamond, is a promising material for solar applications. The enhancement of the interaction between the active material and the solar spectrum is obtained by a controlled texturing of the diamond surface at the nanoscale, the impact of which on the optical and electronic properties of the bulk material is strongly influenced by the laser parameters. In this work, the properties of black diamond samples obtained by using two different laser wavelengths (400 and 800 nm) are compared, showing that texturing periodicity (80 and 170 nm, respectively) is strictly related to the laser wavelength used. Conversely, a unique optimal accumulated absorbed laser fluence (2.10 kJ/cm²) demonstrated to return the best results in terms of responsivity in the solar spectrum, regardless of the wavelength used for laser treatment

Thin films of various borides, nitrides, and barium fluorides were tentatively deposited by pulsed laser deposition and by magnetron sputtering in order to develop the components of thermionic‐photovoltaic devices for the high‐temperature thermal to electrical conversion by solid state. To improve the device performance, the materials characterized by a low work function were selected. In the present work, the chemical composition and work function of obtained films were investigated by X‐ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy techniques. The values of work function were determined from the cut‐off in the He I valence band spectra. Different films were compared and estimated on the basis of X‐ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy results.

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