Dual-Gated Graphene Devices for Near-Field Nano-imaging.

Graphene-based heterostructures display a variety of phenomena that are strongly tunable by electrostatic local gates. Monolayer graphene (MLG) exhibits tunable surface plasmon polaritons, as revealed by scanning nano-infrared experiments. In bilayer graphene (BLG), an electronic gap is induced by a perpendicular displacement field. Gapped BLG is predicted to display unusual effects such as plasmon amplification and domain wall plasmons with significantly larger lifetime than MLG. Furthermore, a variety of correlated electronic phases highly sensitive to displacement fields have been observed in twisted graphene structures. However, applying perpendicular displacement fields in nano-infrared experiments has only recently become possible [Li, H.; Nano Lett. 2020, 20, 3106-3112]. In this work, we fully characterize two approaches to realizing nano-optics compatible top gates: bilayer MoS2 and MLG. We perform nano-infrared imaging on both types of structures and evaluate their strengths and weaknesses. Our work paves the way for comprehensive near-field experiments of correlated phenomena and plasmonic effects in graphene-based heterostructures.

Optical Modeling of Plasmonic Nanoparticles with Electronically Depleted Layers.

Doped metal oxide (MO) nanocrystals (NCs) are well-known for the localized surface plasmon resonance in the infrared range generated by free electrons in the conduction band of the material. Owing to the intimate connection between plasmonic features and the NC's carrier density profile, proper modeling can unveil the underlying electronic structure. The carrier density profile in MO NCs is characterized by the presence of an electronically depleted layer as a result of the Fermi level pinning at the surface of the NC. Moreover, the carrier profile can be spatially engineered by tuning the dopant concentrations in core-shell architectures, generating a rich plethora of plasmonic features. In this work, we systematically studied the influence of the simulation parameters used for optical modeling of representative experimental absorption spectra by implementing multilayer models. We highlight in particular the importance of minimizing the fit parameters by support of experimental results and the importance of interparameter relationships. We show that, in all cases investigated, the depletion layer is fundamental to correctly describe the continuous spectra evolution. We foresee that this multilayer model can be used to design the optoelectronic properties of core-shell systems in the framework of energy band and depletion layer engineering.

Energy transfer and charge transfer between semiconducting nanocrystals and transition metal dichalcogenide monolayers.

Nowadays, as a result of the emergence of low-dimensional hybrid structures, the scientific community is interested in their interfacial carrier dynamics, including charge transfer and energy transfer. By combining the potential of transition metal dichalcogenides (TMDs) and nanocrystals (NCs) with low-dimensional extension, hybrid structures of semiconducting nanoscale matter can lead to fascinating new technological scenarios. Their characteristics make them intriguing candidates for electronic and optoelectronic devices, like transistors or photodetectors, bringing with them challenges but also opportunities. Here, we will review recent research on the combined TMD/NC hybrid system with an emphasis on two major interaction mechanisms: energy transfer and charge transfer. With a focus on the quantum well nature in these hybrid semiconductors, we will briefly highlight state-of-the-art protocols for their structure formation and discuss the interaction mechanisms of energy versus charge transfer, before concluding with a perspective section that highlights novel types of interactions between NCs and TMDs.

Control of electronic band profiles through depletion layer engineering in core-shell nanocrystals.

Fermi level pinning in doped metal oxide (MO) nanocrystals (NCs) results in the formation of depletion layers, which affect their optical and electronic properties, and ultimately their application in smart optoelectronics, photocatalysis, or energy storage. For a precise control over functionality, it is important to understand and control their electronic bands at the nanoscale. Here, we show that depletion layer engineering allows designing the energetic band profiles and predicting the optoelectronic properties of MO NCs. This is achieved by shell thickness tuning of core-shell Sn:In2O3-In2O3 NCs, resulting in multiple band bending and multi-modal plasmonic response. We identify the modification of the band profiles after the light-induced accumulation of extra electrons as the main mechanism of photodoping and enhance the charge storage capability up to hundreds of electrons per NC through depletion layer engineering. Our experimental results are supported by theoretical models and are transferable to other core-multishell systems as well.

Liquid-Phase Exfoliation of Bismuth Telluride Iodide (BiTeI): Structural and Optical Properties of Single-/Few-Layer Flakes.

Bismuth telluride halides (BiTeX) are Rashba-type crystals with several potential applications ranging from spintronics and nonlinear optics to energy. Their layered structures and low cleavage energies allow their production in a two-dimensional form, opening the path to miniaturized device concepts. The possibility to exfoliate bulk BiTeX crystals in the liquid represents a useful tool to formulate a large variety of functional inks for large-scale and cost-effective device manufacturing. Nevertheless, the exfoliation of BiTeI by means of mechanical and electrochemical exfoliation proved to be challenging. In this work, we report the first ultrasonication-assisted liquid-phase exfoliation (LPE) of BiTeI crystals. By screening solvents with different surface tension and Hildebrandt parameters, we maximize the exfoliation efficiency by minimizing the Gibbs free energy of the mixture solvent/BiTeI crystal. The most effective solvents for the BiTeI exfoliation have a surface tension close to 28 mN m-1 and a Hildebrandt parameter between 19 and 25 MPa0.5. The morphological, structural, and chemical properties of the LPE-produced single-/few-layer BiTeI flakes (average thickness of ∼3 nm) are evaluated through microscopic and optical characterizations, confirming their crystallinity. Second-harmonic generation measurements confirm the non-centrosymmetric structure of both bulk and exfoliated materials, revealing a large nonlinear optical response of BiTeI flakes due to the presence of strong quantum confinement effects and the absence of typical phase-matching requirements encountered in bulk nonlinear crystals. We estimated a second-order nonlinearity at 0.8 eV of |χ(2)| ∼ 1 nm V-1, which is 10 times larger than in bulk BiTeI crystals and is of the same order of magnitude as in other semiconducting monolayers (e.g., MoS2).

Influence of Magnetic Scaffold Loading Patterns on Their Hyperthermic Potential Against Bone Tumors.

Magnetic scaffolds have been investigated as promising tools for the interstitial hyperthermia treatment of bone cancers, to control local recurrence by enhancing radio- and chemotherapy effectiveness. The potential of magnetic scaffolds motivates the development of production strategies enabling tunability of the resulting magnetic properties. Within this framework, deposition and drop-casting of magnetic nanoparticles on suitable scaffolds offer advantages such as ease of production and high loading, although these approaches are often associated with a non-uniform final spatial distribution of nanoparticles in the biomaterial. The implications and the influences of nanoparticle distribution on the final therapeutic application have not yet been investigated thoroughly. In this work, poly-caprolactone scaffolds are magnetized by loading them with synthetic magnetic nanoparticles through a drop-casting deposition and tuned to obtain different distributions of magnetic nanoparticles in the biomaterial. The physicochemical properties of the magnetic scaffolds are analyzed. The microstructure and the morphological alterations due to the reworked drop-casting process are evaluated and correlated to static magnetic measurements. THz tomography is used as an innovative investigation technique to derive the spatial distribution of nanoparticles. Finally, multiphysics simulations are used to investigate the influence on the loading patterns on the interstitial bone tumor hyperthermia treatment.

Two-dimensional BiTeI as a novel perovskite additive for printable perovskite solar cells.

Hybrid organic-inorganic perovskite solar cells (PSCs) are attractive printable, flexible, and cost-effective optoelectronic devices constituting an alternative technology to conventional Si-based ones. The incorporation of low-dimensional materials, such as two-dimensional (2D) materials, into the PSC structure is a promising route for interfacial and bulk perovskite engineering, paving the way for improved power conversion efficiency (PCE) and long-term stability. In this work, we investigate the incorporation of 2D bismuth telluride iodide (BiTeI) flakes as additives in the perovskite active layer, demonstrating their role in tuning the interfacial energy-level alignment for optimum device performance. By varying the concentration of BiTeI flakes in the perovskite precursor solution between 0.008 mg mL-1 and 0.1 mg mL-1, a downward shift in the energy levels of the perovskite results in an optimal alignment of the energy levels of the materials across the cell structure, as supported by device simulations. Thus, the cell fill factor (FF) increases with additive concentration, reaching values greater than 82%, although the suppression of open circuit voltage (V oc) is reported beyond an additive concentration threshold of 0.03 mg mL-1. The most performant devices delivered a PCE of 18.3%, with an average PCE showing a +8% increase compared to the reference devices. This work demonstrates the potential of 2D-material-based additives for the engineering of PSCs via energy level optimization at perovskite/charge transporting layer interfaces.

Photodoping of metal oxide nanocrystals for multi-charge accumulation and light-driven energy storage.

The growing demand for self-powered devices has led to the study of novel energy storage solutions that exploit green energies whilst ensuring self-sufficiency. In this context, doped metal oxide nanocrystals (MO NCs) are interesting nanosized candidates with the potential to unify solar energy conversion and storage into one set of materials. In this review, we aim to present recent and important developments of doped MO NCs for light-driven multi-charge accumulation (i.e., photodoping) and solar energy storage. We will discuss the general concept of photodoping, the spectroscopic and theoretical tools to determine the charging process, together with unresolved open questions. We conclude the review by highlighting possible device architectures based on doped MO NCs that are expected to considerably impact the field of energy storage by combining in a unique way the conversion and storage of solar power and opening the path towards competitive and novel light-driven energy storage solutions.

Two-Dimensional Gallium Sulfide Nanoflakes for UV-Selective Photoelectrochemical-type Photodetectors.

Two-dimensional (2D) transition-metal monochalcogenides have been recently predicted to be potential photo(electro)catalysts for water splitting and photoelectrochemical (PEC) reactions. Differently from the most established InSe, GaSe, GeSe, and many other monochalcogenides, bulk GaS has a large band gap of ∼2.5 eV, which increases up to more than 3.0 eV with decreasing its thickness due to quantum confinement effects. Therefore, 2D GaS fills the void between 2D small-band-gap semiconductors and insulators, resulting of interest for the realization of van der Waals type-I heterojunctions in photocatalysis, as well as the development of UV light-emitting diodes, quantum wells, and other optoelectronic devices. Based on theoretical calculations of the electronic structure of GaS as a function of layer number reported in the literature, we experimentally demonstrate, for the first time, the PEC properties of liquid-phase exfoliated GaS nanoflakes. Our results indicate that solution-processed 2D GaS-based PEC-type photodetectors outperform the corresponding solid-state photodetectors. In fact, the 2D morphology of the GaS flakes intrinsically minimizes the distance between the photogenerated charges and the surface area at which the redox reactions occur, limiting electron-hole recombination losses. The latter are instead deleterious for standard solid-state configurations. Consequently, PEC-type 2D GaS photodetectors display a relevant UV-selective photoresponse. In particular, they attain responsivities of 1.8 mA W-1 in 1 M H2SO4 [at 0.8 V vs reversible hydrogen electrode (RHE)], 4.6 mA W-1 in 1 M Na2SO4 (at 0.9 V vs RHE), and 6.8 mA W-1 in 1 M KOH (at 1.1. V vs RHE) under 275 nm illumination wavelength with an intensity of 1.3 mW cm-2. Beyond the photodetector application, 2D GaS-based PEC-type devices may find application in tandem solar PEC cells in combination with other visible-sensitive low-band-gap materials, including transition-metal monochalcogenides recently established for PEC solar energy conversion applications.