Discovery of a Magnetic Dirac System with a Large Intrinsic Nonlinear Hall Effect.

Magnetic materials exhibiting topological Dirac fermions are attracting significant attention for their promising technological potential in spintronics. In these systems, the combined effect of the spin-orbit coupling and magnetic order enables the realization of novel topological phases with exotic transport properties, including the anomalous Hall effect and magneto-chiral phenomena. Herein, we report experimental signature of topological Dirac antiferromagnetism in TaCoTe2 via angle-resolved photoelectron spectroscopy and first-principles density functional theory calculations. In particular, we find the existence of spin-orbit coupling-induced gaps at the Fermi level, consistent with the manifestation of a large intrinsic nonlinear Hall conductivity. Remarkably, we find that the latter is extremely sensitive to the orientation of the Néel vector, suggesting TaCoTe2 as a suitable candidate for the realization of non-volatile spintronic devices with an unprecedented level of intrinsic tunability.

Ultrasensitive Self-Driven Terahertz Photodetectors Based on Low-Energy Type-II Dirac Fermions and Related Van der Waals Heterojunctions.

The exotic electronic properties of topological semimetals (TSs) have opened new pathways for innovative photonic and optoelectronic devices, especially in the highly pursuit terahertz (THz) band. However, in most cases Dirac fermions lay far above or below the Fermi level, thus hindering their successful exploitation for the low-energy photonics. Here, low-energy type-II Dirac fermions in kitkaite (NiTeSe) for ultrasensitive THz detection through metal-topological semimetal-metal heterostructures are exploited. Furthermore, a heterostructure combining two Dirac materials, namely, graphene and NiTeSe, is implemented for a novel photodetector exhibiting a responsivity as high as 1.22 A W-1 , with a response time of 0.6 µs, a noise-equivalent power of 18 pW Hz-0.5 , with outstanding stability in the ambient conditions. This work brings to fruition of Dirac fermiology in THz technology, enabling self-powered, low-power, room-temperature, and ultrafast THz detection.

The advent of thermoplasmonic membrane distillation.

Freshwater scarcity is a vital societal challenge related to climate change, population pressure, and agricultural and industrial demands. Therefore, sustainable desalination/purification of salty/contaminated water for human uses is particularly relevant. Membrane distillation is an emerging hybrid thermal-membrane technology with the potential to overcome the drawbacks of conventional desalination by a synergic exploitation of the water-energy nexus. Although membrane distillation is considered a green technology, efficient heat management remains a critical concern affecting the cost of the process and hindering its viability at large scale. A multidisciplinary approach that involves materials chemistry, physical chemistry, chemical engineering, and materials and polymer science is required to solve this problem. The combination of solar energy with membrane distillation is considered a potentially feasible low-cost approach for providing high-quality freshwater with a low carbon footprint. In particular, recent discoveries about efficient light-to-heat conversion in nanomaterials have opened unprecedented perspectives for the implementation of sunlight-based renewable energy in membrane distillation. The integration of nanofillers enabling photothermal effects into membranes has been demonstrated to be able to significantly enhance the energy efficiency without impacting on economic costs. Here, we provide a comprehensive overview on the state of the art, the opportunities, open challenges and pitfalls of the emerging field of solar-driven membrane distillation. We also assess the peculiar physicochemical properties and synthesis scalability of photothermal materials, as well as the strategies for their integration into polymeric nanocomposite membranes enabling efficient light-to-heat conversion and freshwater.

The Quest for Green Solvents for the Sustainable Production of Nanosheets of Two-Dimensional (2D) Materials, a Key Issue in the Roadmap for the Ecology Transition in the Flatland.

The recent advent of two-dimensional (2D) materials has had a ground-breaking impact on science and technology. To exploit in technology their unique thickness-dependent physicochemical properties, the large-scale production of 2D materials is mandatory, but it represents an open challenge still due to various pitfalls and severe limitations including the toxicity of state-of-the-art solvents. Thus, liquid-phase exfoliation based on green and bioderived solvents represents an ideal methodology for massive production. This is particularly crucial for introducing 2D materials in technological applications such as the production of drinking water and agri-food industrial processes. Here, we assessed the production of 2D nanosheets (specifically, graphene, WS2, MoS2) with liquid-phase exfoliation assisted by eco-friendly solvents, with a comparative evaluation of green solvents in terms of the yield and, moreover, the aspect ratio, defectivity, and crystalline quality of the produced nanosheets. In particular, we focus on the most promising green solvents in terms of the yield and the crystalline quality of the produced nanosheets: Polarclean, Iris, and Cyrene, which were compared with acetone/water mixtures, isopropyl alcohol (IPA), triethanolamine (TEA), aqueous solutions of urea, and an ethanol/water mixture as well as two toxic solvents largely used for the production of 2D nanosheets: N-methyl-2-pyrrolidone (NMP) and N, N-dimethylformamide (DMF). Remarkably, the density of defects was particularly low in the liquid-phase exfoliation with Polarclean, as indicated by the Raman spectrum of graphene, with the I(D)/I(G) ratio below 0.1. Furthermore, Polarclean and Iris also enable ink-jet printing with functional inks of 2D materials based on green solvents due to their low dynamic viscosity at room temperature.

NiSe and CoSe Topological Nodal-Line Semimetals: A Sustainable Platform for Efficient Thermoplasmonics and Solar-Driven Photothermal Membrane Distillation.

The control of heat at the nanoscale via the excitation of localized surface plasmons in nanoparticles (NPs) irradiated with light holds great potential in several fields (cancer therapy, catalysis, desalination). To date, most thermoplasmonic applications are based on Ag and Au NPs, whose cost of raw materials inevitably limits the scalability for industrial applications requiring large amounts of photothermal NPs, as in the case of desalination plants. On the other hand, alternative nanomaterials proposed so far exhibit severe restrictions associated with the insufficient photothermal efficacy in the visible, the poor chemical stability, and the challenging scalability. Here, it is demonstrated the outstanding potential of NiSe and CoSe topological nodal-line semimetals for thermoplasmonics. The anisotropic dielectric properties of NiSe and CoSe activate additional plasmonic resonances. Specifically, NiSe and CoSe NPs support multiple localized surface plasmons in the optical range, resulting in a broadband matching with sunlight radiation spectrum. Finally, it is validated the proposed NiSe and CoSe-based thermoplasmonic platform by implementing solar-driven membrane distillation by adopting NiSe and CoSe nanofillers embedded in a polymeric membrane for seawater desalination. Remarkably, replacing Ag with NiSe and CoSe for solar membrane distillation increases the transmembrane flux by 330% and 690%, respectively. Correspondingly, costs of raw materials are also reduced by 24 and 11 times, respectively. The results pave the way for the advent of NiSe and CoSe for efficient and sustainable thermoplasmonics and related applications exploiting sunlight within the paradigm of the circular blue economy.

Setting the limit for the lateral thermal expansion of layered crystals via helium atom scattering.

The knowledge of the thermal expansion coefficient is of crucial importance to prevent the poor performance of devices, especially when these are made up of several layers of different materials, as in the case of 2D heterostructures. Helium atom scattering is a suitable tool for the direct measurement of the surface thermal expansion coefficient of materials. This information can be obtained directly from the position of the helium diffraction peaks, which allows determining the surface lattice constant at different temperatures by merely applying Bragg's law. We present new data for PdTe2 which confirm a trend observed for several 2D dichalcogenides, namely, that the in-plane lattice constant remains unchanged (within experimental error) in the temperature range of interest for applications, which enables setting an upper limit for the lateral thermal expansion coefficients of these materials.

On the fate of high-resolution electron energy loss spectroscopy (HREELS), a versatile probe to detect surface excitations: will the Phoenix rise again?

From its advent, high-resolution electron energy loss spectroscopy (HREELS) has emerged as one of the most versatile tools in surface science. In the last few decades, HREELS was widely used for the fundamental study of (i) chemical reactions at the surfaces of model catalysts (mostly single crystals), (ii) lattice dynamics (phonons), (iii) surface plasmons and (iv) magnons. However, HREELS has experienced a continuous decay of the number of daily users worldwide so far, due to several factors. However, the rise of Dirac materials (graphene, topological insulators, Dirac semimetals) offers new perspectives for HREELS, due to its unique features enabling ultrasensitive detection of (i) chemical modifications at their surfaces, (ii) Kohn anomalies arising from electron-phonon coupling and (iii) novel plasmonic excitations associated to Dirac-cone fermions, as well as their eventual mutual interplay with other plasmon resonances related to topologically trivial electronic states. By selected case-study examples, here we show that HREELS can uniquely probe these phenomena in Dirac materials, thus validating its outstanding relevance and its irreplaceability in contemporary solid-state physics, thus paving the way for a renewed interest. In addition, recent technological upgrades enable the combination of HREELS as an add-on to photoemission apparatuses for parallel readout of energy and momentum of surface excitations. Open issues for theoretical modelling of HREELS related to the dependence on primary electron beam energy and scattering geometry are also critically presented.

Chemical reactions on surfaces for applications in catalysis, gas sensing, adsorption-assisted desalination and Li-ion batteries: opportunities and challenges for surface science.

The study of chemical processes on solid surfaces is a powerful tool to discover novel physicochemical concepts with direct implications for processes based on chemical reactions at surfaces, largely exploited by industry. Recent upgrades of experimental tools and computational capabilities, as well as the advent of two-dimensional materials, have opened new opportunities and challenges for surface science. In this Perspective, we highlight recent advances in application fields strictly connected to novel concepts emerging in surface science. Specifically, we show for selected case-study examples that surface oxidation can be unexpectedly beneficial for improving the efficiency in electrocatalysis (the hydrogen evolution reaction and oxygen evolution reaction) and photocatalysis, as well as in gas sensing. Moreover, we discuss the adsorption-assisted mechanism in membrane distillation for seawater desalination, as well as the use of surface-science tools in the study of Li-ion batteries. In all these applications, surface-science methodologies (both experimental and theoretical) have unveiled new physicochemical processes, whose efficiency can be further tuned by controlling surface phenomena, thus paving the way for a new era for the investigation of surfaces and interfaces of nanomaterials. In addition, we discuss the role of surface scientists in contemporary condensed matter physics, taking as case-study examples specific controversial debates concerning unexpected phenomena emerging in nanosheets of layered materials, solved by adopting a surface-science approach.

Novel Undamped Gapless Plasmon Mode in a Tilted Type-II Dirac Semimetal.

We predict the existence of a novel long-lived gapless plasmon mode in a type-II Dirac semimetal (DSM). This gapless mode arises from the out-of-phase oscillations of the density fluctuations in the electron and the hole pockets of a type-II DSM. It originates beyond a critical wave vector along the direction of the tilt axis, owing to the momentum separation of the electron and hole pockets. A similar out-of-phase plasmon mode arises in other multicomponent charged fluids as well, but generally, it is Landau damped and lies within the particle-hole continuum. In the case of a type-II DSM, the open Fermi surface prohibits low-energy finite momentum single-particle excitations, creating a "gap" in the particle-hole continuum. The gapless plasmon mode lies within this particle-hole continuum gap and, thus, it is protected from Landau damping.

PtTe2 -Based Type-II Dirac Semimetal and Its van der Waals Heterostructure for Sensitive Room Temperature Terahertz Photodetection.

Recent years have witnessed rapid progresses made in the photoelectric performance of two-dimensional materials represented by graphene, black phosphorus, and transition metal dichalcogenides. Despite significant efforts, a photodetection technique capable for longer wavelength, higher working temperature as well as fast responsivity, is still facing huge challenges due to a lack of best among bandgap, dark current, and absorption ability. Exploring topological materials with nontrivial band transport leads to peculiar properties of quantized phenomena such as chiral anomaly, and magnetic-optical effect, which enables a novel feasibility for an advanced optoelectronic device working at longer wavelength. In this work, the direct generation of photocurrent at low energy terahertz (THz) band at room temperature is implemented in a planar metal-PtTe2 -metal structure. The results show that the THz photodetector based on PtTe2 with bow-tie-type planar contacts possesses a high photoresponsivity (1.6 A W-1 without bias voltage) with a response time less than 20 µs, while the PtTe2 -graphene heterostructure-based detector can reach responsivity above 1.4 kV W-1 and a response time shorter than 9 µs. Remarkably, it is already exploitable for large area imaging applications. These results suggest that topological semimetals such as PtTe2 can be ideal materials for implementation in a high-performing photodetection system at THz band.

Liquid-Phase Exfoliated Indium-Selenide Flakes and Their Application in Hydrogen Evolution Reaction.

Single- and few-layered InSe flakes are produced by the liquid-phase exfoliation of ß-InSe single crystals in 2-propanol, obtaining stable dispersions with a concentration as high as 0.11 g L-1 . Ultracentrifugation is used to tune the morphology, i.e., the lateral size and thickness of the as-produced InSe flakes. It is demonstrated that the obtained InSe flakes have maximum lateral sizes ranging from 30 nm to a few micrometers, and thicknesses ranging from 1 to 20 nm, with a maximum population centered at ≈5 nm, corresponding to 4 Se-In-In-Se quaternary layers. It is also shown that no formation of further InSe-based compounds (such as In2 Se3 ) or oxides occurs during the exfoliation process. The potential of these exfoliated-InSe few-layer flakes as a catalyst for the hydrogen evolution reaction (HER) is tested in hybrid single-walled carbon nanotubes/InSe heterostructures. The dependence of the InSe flakes' morphologies, i.e., surface area and thickness, on the HER performances is highlighted, achieving the best efficiencies with small flakes offering predominant edge effects. The theoretical model unveils the origin of the catalytic efficiency of InSe flakes, and correlates the catalytic activity to the Se vacancies at the edge of the flakes.

Phase-resolved terahertz self-detection near-field microscopy.

At terahertz (THz) frequencies, scattering-type scanning near-field optical microscopy (s-SNOM) based on continuous wave sources mostly relies on cryogenic and bulky detectors, which represents a major constraint for its practical application. Here, we devise a THz s-SNOM system that provides both amplitude and phase contrast and achieves nanoscale (60-70nm) in-plane spatial resolution. It features a quantum cascade laser that simultaneously emits THz frequency light and senses the backscattered optical field through a voltage modulation induced inherently through the self-mixing technique. We demonstrate its performance by probing a phonon-polariton-resonant CsBr crystal and doped black phosphorus flakes.

3D Dirac Plasmons in the Type-II Dirac Semimetal PtTe_{2}.

Transition-metal dichalcogenides showing type-II Dirac fermions are emerging as innovative materials for nanoelectronics. However, their excitation spectrum is mostly unexplored yet. By means of high-resolution electron energy loss spectroscopy and density functional theory, here, we identify the collective excitations of type-II Dirac fermions (3D Dirac plasmons) in PtTe_{2} single crystals. The observed plasmon energy in the long-wavelength limit is ∼0.5 eV, which makes PtTe_{2} suitable for near-infrared optoelectronic applications. We also demonstrate that interband transitions between the two Dirac bands in PtTe_{2} give rise to additional excitations at ∼1 and ∼1.4 eV. Our results are crucial to bringing to fruition type-II Dirac semimetals in optoelectronics.

Self-Assembly of Graphene Nanoblisters Sealed to a Bare Metal Surface.

The possibility to intercalate noble gas atoms below epitaxial graphene monolayers coupled with the instability at high temperature of graphene on the surface of certain metals has been exploited to produce Ar-filled graphene nanosized blisters evenly distributed on the bare Ni(111) surface. We have followed in real time the self-assembling of the nanoblisters during the thermal annealing of the Gr/Ni(111) interface loaded with Ar and characterized their morphology and structure at the atomic scale. The nanoblisters contain Ar aggregates compressed at high pressure arranged below the graphene monolayer skin that is decoupled from the Ni substrate and sealed only at the periphery through stable C-Ni bonds. Their in-plane truncated triangular shapes are driven by the crystallographic directions of the Ni surface. The nonuniform strain revealed along the blister profile is explained by the inhomogeneous expansion of the flexible graphene lattice that adjusts to envelop the Ar atom stacks.

Plasma-Wave Terahertz Detection Mediated by Topological Insulators Surface States.

Topological insulators (TIs) represent a novel quantum state of matter, characterized by edge or surface-states, showing up on the topological character of the bulk wave functions. Allowing electrons to move along their surface, but not through their inside, they emerged as an intriguing material platform for the exploration of exotic physical phenomena, somehow resembling the graphene Dirac-cone physics, as well as for exciting applications in optoelectronics, spintronics, nanoscience, low-power electronics, and quantum computing. Investigation of topological surface states (TSS) is conventionally hindered by the fact that in most of experimental conditions the TSS properties are mixed up with those of bulk-states. Here, we activate, probe, and exploit the collective electronic excitation of TSS in the Dirac cone. By engineering Bi2Te(3-x)Sex stoichiometry, and by gating the surface of nanoscale field-effect-transistors, exploiting thin flakes of Bi2Te2.2Se0.8 or Bi2Se3, we provide the first demonstration of room-temperature terahertz (THz) detection mediated by overdamped plasma-wave oscillations on the "activated" TSS of a Bi2Te2.2Se0.8 flake. The reported detection performances allow a realistic exploitation of TSS for large-area, fast imaging, promising superb impacts on THz photonics.

Manipulating the Topological Interface by Molecular Adsorbates: Adsorption of Co-Phthalocyanine on Bi2Se3.

Topological insulators are a promising class of materials for applications in the field of spintronics. New perspectives in this field can arise from interfacing metal-organic molecules with the topological insulator spin-momentum locked surface states, which can be perturbed enhancing or suppressing spintronics-relevant properties such as spin coherence. Here we show results from an angle-resolved photemission spectroscopy (ARPES) and scanning tunnelling microscopy (STM) study of the prototypical cobalt phthalocyanine (CoPc)/Bi2Se3 interface. We demonstrate that that the hybrid interface can act on the topological protection of the surface and bury the Dirac cone below the first quintuple layer.

Emergence of an Out-of-Plane Optical Phonon (ZO) Kohn Anomaly in Quasifreestanding Epitaxial Graphene.

In neutral graphene, two prominent cusps known as Kohn anomalies are found in the phonon dispersion of the highest optical phonon at q=Γ (LO branch) and q=K (TO branch), reflecting a significant electron-phonon coupling (EPC) to undoped Dirac electrons. In this work, high-resolution electron energy loss spectroscopy is used to measure the phonon dispersion around the Γ point in quasifreestanding graphene epitaxially grown on Pt(111). The Kohn anomaly for the LO phonon is observed at finite momentum q~2k_{F} from Γ, with a shape in excellent agreement with the theory and consistent with known values of the EPC and the Fermi level. More strikingly, we also observe a Kohn anomaly at the same momentum for the out-of-plane optical phonon (ZO) branch. This observation is the first direct evidence of the coupling of the ZO mode with Dirac electrons, which is forbidden for freestanding graphene but becomes allowed in the presence of a substrate. Moreover, we estimate the EPC to be even greater than that of the LO mode, making graphene on Pt(111) an optimal system to explore the effects of this new coupling in the electronic properties.

Environmentally Friendly Photothermal Membranes for Halite Recovery from Reverse Osmosis Brine via Solar-Driven Membrane Crystallization.

Modern society and industrial development rely heavily on the availability of freshwater and minerals. Seawater reverse osmosis (SWRO) has been widely adopted for freshwater supply, although many questions have arisen about its environmental sustainability owing to the disposal of hypersaline rejected solutions (brine). This scenario has accelerated significant developments towards the hybridization of SWRO with membrane distillation-crystallization (MD-MCr), which can extract water and minerals from spent brine. Nevertheless, the substantial specific energy consumption associated with MD-MCr remains a significant limitation. In this work, energy harvesting was secured from renewables by hotspots embodied in the membranes, implementing the revolutionary approach of brine mining via photothermal membrane crystallization (PhMCr). This method employs self-heating nanostructured interfaces under solar radiation to enhance water evaporation, creating a carefully controlled supersaturated environment responsible for the extraction of minerals. Photothermal mixed matrix photothermal membranes (MMMs) were developed by incorporating graphene oxide (GO) or carbon black (CB) into polyvinylidene fluoride (PVDF) solubilized in an eco-friendly solvent (i.e., triethyl phosphate (TEP)). MMMs were prepared using non-solvent-induced phase separation (NIPS). The effect of GO or GB on the morphology of MMMs and the photothermal behavior was examined. Light-to-heat conversion was used in PhMCr experiments to facilitate the evaporation of water from the SWRO brine to supersaturation, leading to sodium chloride (NaCl) nucleation and crystallization. Overall, the results indicate exciting perspectives of PhMCr in brine valorization for a sustainable desalination industry.

Evidence of confinement of the π plasmon in periodically rippled graphene on Ru(0001).

High-resolution electron energy loss spectroscopy has been used to study the electronic response of periodically rippled monolayer graphene grown on Ru(0001). A plasmonic mode, assigned to the π plasmon, has been observed at around 6 eV. The dispersion curve of this collective mode indicates plasmon confinement within the hills of the ripples. Moreover, we found that the corrugation of the graphene sheet also significantly affects the damping processes of the π plasmon.

The nature of free O-H stretching in water adsorbed on carbon nanosystems.

Motivated by the existence of several recent works claiming for unusual hydrogen bonds in water adsorbed or confined in carbon nanostructures, we have analyzed the nature of a sharp O-H stretching at 3700 cm(-1) in H2O/graphene recorded in vibrational measurements. The interpretation of such mode is rather controversial. On the basis of a careful inspection of our spectroscopic data and of literature, we suggest that the interpretation of this feature as a fingerprint of surface hydrophobicity, electronic effects or disorder is astray. Instead, it merely arises from interface effects.