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2D semiconductors can drive advances in quantum science and technologies. However, they should be free of any contamination; also, the crystallographic ordering and coupling of adjacent layers and their electronic properties should be well-controlled, tunable, and scalable. Here, these challenges are addressed by a new approach, which combines molecular beam epitaxy and in situ band engineering in ultra-high vacuum of semiconducting gallium selenide (GaSe) on graphene. In situ studies by electron diffraction, scanning probe microscopy, and angle-resolved photoelectron spectroscopy reveal that atomically-thin layers of GaSe align in the layer plane with the underlying lattice of graphene. The GaSe/graphene heterostructure, referred to as 2semgraphene, features a centrosymmetric (group symmetry D 3d ) polymorph of GaSe, a charge dipole at the GaSe/graphene interface, and a band structure tunable by the layer thickness. The newly-developed, scalable 2semgraphene is used in optical sensors that exploit the photoactive GaSe layer and the built-in potential at its interface with the graphene channel. This proof of concept has the potential for further advances and device architectures that exploit 2semgraphene as a functional building block., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Two-dimensional semiconductors (2DSEM) based on van der Waals crystals offer important avenues for nanotechnologies beyond the constraints of Moore's law and traditional semiconductors, such as silicon (Si). However, their application necessitates precise engineering of material properties and scalable manufacturing processes. The ability to oxidize Si to form silicon dioxide (SiO 2 ) was crucial for the adoption of Si in modern technologies. Here, we report on the thermal oxidation of the 2DSEM gallium selenide (GaSe). The nanometer-thick layers are grown by molecular beam epitaxy on transparent sapphire (Al 2 O 3 ) and feature a centro-symmetric polymorph of GaSe. Thermal annealing of the layers in an oxygen-rich environment promotes the chemical transformation and full conversion of GaSe into a thin layer of crystalline Ga 2 O 3 , paralleled by the formation of coherent Ga 2 O 3 /Al 2 O 3 interfaces. Versatile functionalities are demonstrated in photon sensors based on GaSe and Ga 2 O 3 , ranging from electrical insulation to unfiltered deep ultraviolet optoelectronics, unlocking the technological potential of GaSe nanostructures and their amorphous and crystalline oxides., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

2D semiconductors (2SEM) can transform many sectors, from information and communication technology to healthcare. To date, top-down approaches to their fabrication, such as exfoliation of bulk crystals by "scotch-tape," are widely used, but have limited prospects for precise engineering of functionalities and scalability. Here, a bottom-up technique based on epitaxy is used to demonstrate high-quality, wafer-scale 2SEM based on the wide band gap gallium selenide (GaSe) compound. GaSe layers of well-defined thickness are developed using a bespoke facility for the epitaxial growth and in situ studies of 2SEM. The dominant centrosymmetry and stacking of the individual van der Waals layers are verified by theory and experiment; their optical anisotropy and resonant absorption in the UV spectrum are exploited for photon sensing in the technological UV-C spectral range, offering a scalable route to deep-UV optoelectronics., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

Indium selenides (In x Se y ) have been shown to retain several desirable properties, such as ferroelectricity, tunable photoluminescence through temperature-controlled phase changes, and high electron mobility when confined to two dimensions (2D). In this work we synthesize single-layer, ultrathin, subnanometer-wide In x Se y by templated growth inside single-walled carbon nanotubes (SWCNTs). Despite the complex polymorphism of In x Se y we show that the phase of the encapsulated material can be identified through comparison of experimental aberration-corrected transmission electron microscopy (AC-TEM) images and AC-TEM simulations of known structures of In x Se y . We show that, by altering synthesis conditions, one of two different stoichiometries of sub-nm In x Se y , namely InSe or β-In 2 Se 3 , can be prepared. Additionally, in situ AC-TEM heating experiments reveal that encapsulated β-In 2 Se 3 undergoes a phase change to γ-In 2 Se 3 above 400 °C. Further analysis of the encapsulated species is performed using X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), energy dispersive X-ray analysis (EDX), and Raman spectroscopy, corroborating the identities of the encapsulated species. These materials could provide a platform for ultrathin, subnanometer-wide phase-change nanoribbons with applications as nanoelectronic components.

We use phenomenological modelling and detailed experimental studies of charge carrier transport to investigate the dependence of the electrical resistivity, ρ , on gate voltage, V g , for a series of monolayer graphene field effect transistors with mobilities, μ , ranging between 5000 and 250 000 cm 2 V -1 s -1 at low-temperature. Our measurements over a wide range of temperatures from 4 to 400 K can be fitted by the universal relationμ=4/eδnmaxfor all devices, whereρmaxis the resistivity maximum at the neutrality point and δn is an 'uncertainty' in the bipolar carrier density, given by the full width at half maximum of the resistivity peak expressed in terms of carrier density, n . This relation is consistent with thermal broadening of the carrier distribution and the presence of the disordered potential landscape consisting of so-called electron-hole puddles near the Dirac point. To demonstrate its utility, we combine this relation with temperature-dependent linearised Boltzmann transport calculations that include the effect of optical phonon scattering. This approach demonstrates the similarity in the temperature-dependent behaviour of carriers in different types of single layer graphene transistors with widely differing carrier mobilities. It can also account for the relative stability, over a wide temperature range, of the measured carrier mobility of each device., (Creative Commons Attribution license.)

Strain engineering can be used to control the physical properties of two-dimensional van der Waals (2D-vdW) crystals. Coherent phonons, which carry dynamical strain, could push strain engineering to control classical and quantum phenomena in the unexplored picosecond temporal and nanometer spatial regimes. This intriguing approach requires the use of coherent GHz and sub-THz 2D phonons. Here, we report on nanostructures that combine nanometer thick vdW layers and nanogratings. Using an ultrafast pump-probe technique, we generate and detect in-plane coherent phonons with frequency up to 40 GHz and hybrid flexural phonons with frequency up to 10 GHz. The latter arises from the periodic modulation of the elastic coupling of the vdW layer at the grooves and ridges of the nanograting. This creates a new type of a tailorable 2D periodic phononic nanoobject, a flexural phononic crystal, offering exciting prospects for the ultrafast manipulation of states in 2D materials in emerging quantum technologies.

The family of van der Waals (vdW) materials is large and diverse with applications ranging from electronics and optoelectronics to catalysis and chemical storage. However, despite intensive research, there remains significant knowledge-gaps pertaining to their properties and interactions. One such gap is the interaction between these materials and hydrogen, a potentially vital future energy vector and ubiquitous processing gas in the semiconductor industry. This work reports on the interaction of hydrogen with the vdW semiconductor SnS 2 , where molecular hydrogen (H 2 ) and H-ions induce a controlled chemical conversion into semiconducting-SnS or to β-Sn. This hydrogen-driven reaction is facilitated by the different oxidation states of Sn and is successfully applied to form SnS 2 /SnS heterostructures with uniform layers, atomically flat interfaces and well-aligned crystallographic axes. This approach is scalable and offers a route for engineering materials at the nanoscale for semiconductor technologies based on the earth-abundant elements Sn and S, a promising result for a wide range of potential applications., (© 2022 The Authors. Small published by Wiley-VCH GmbH.)

2D layered chalcogenide semiconductors have been proposed as a promising class of materials for low-dimensional electronic, optoelectronic, and spintronic devices. Here, all-2D van der Waals vertical spin-valve devices, that combine the 2D layered semiconductor InSe as a spacer with the 2D layered ferromagnetic metal Fe 3 GeTe 2 as spin injection and detection electrodes, are reported. Two distinct transport behaviors are observed: tunneling and metallic, which are assigned to the formation of a pinhole-free tunnel barrier at the Fe 3 GeTe 2 /InSe interface and pinholes in the InSe spacer layer, respectively. For the tunneling device, a large magnetoresistance (MR) of 41% is obtained under an applied bias current of 0.1 µA at 10 K, which is about three times larger than that of the metallic device. Moreover, the tunneling device exhibits a lower operating bias current but a more sensitive bias current dependence than the metallic device. The MR and spin polarization of both the metallic and tunneling devices decrease with increasing temperature, which can be fitted well by Bloch's law. These findings reveal the critical role of pinholes in the MR of all-2D van der Waals ferromagnet/semiconductor heterojunction devices., (© 2021 Wiley-VCH GmbH.)

The 2D semiconductor indium selenide (InSe) has attracted significant interest due its unique electronic band structure, high electron mobility, and wide tunability of its band gap energy achieved by varying the layer thickness. All these features make 2D InSe a potential candidate for advanced electronic and optoelectronic applications. Here, the discovery of new polymorphs of InSe with enhanced electronic properties is reported. Using a global structure search that combines artificial swarm intelligence with first-principles energetic calculations, polymorphs that consist of a centrosymmetric monolayer belonging to the point group D 3 d are identified, distinct from well-known polymorphs based on the D 3 h monolayers that lack inversion symmetry. The new polymorphs are thermodynamically and kinetically stable, and exhibit a wider optical spectral response and larger electron mobilities compared to the known polymorphs. Opportunities to synthesize these newly discovered polymorphs and viable routes to identify them by X-ray diffraction, Raman spectroscopy, and second harmonic generation experiments are discussed., Competing Interests: The authors declare no conflict of interest., (© 2020 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.)

Most of the studied two-dimensional (2D) materials have been obtained by exfoliation of van der Waals crystals. Recently, there has been growing interest in fabricating synthetic 2D crystals which have no layered bulk analogues. These efforts have been focused mainly on the surface growth of molecules in high vacuum. Here, we report an approach to making 2D crystals of covalent solids by chemical conversion of van der Waals layers. As an example, we used 2D indium selenide (InSe) obtained by exfoliation and converted it by direct fluorination into indium fluoride (InF 3 ), which has a nonlayered, rhombohedral structure and therefore cannot  possibly be obtained by exfoliation. The conversion of InSe into InF 3 is found to be feasible for thicknesses down to three layers of InSe, and the obtained stable InF 3 layers are doped with selenium. We study this new 2D material by optical, electron transport, and Raman measurements and show that it is a semiconductor with a direct bandgap of 2.2 eV, exhibiting high optical transparency across the visible and infrared spectral ranges. We also demonstrate the scalability of our approach by chemical conversion of large-area, thin InSe laminates obtained by liquid exfoliation, into InF 3 films. The concept of chemical conversion of cleavable thin van der Waals crystals into covalently bonded noncleavable ones opens exciting prospects for synthesizing a wide variety of novel atomically thin covalent crystals.

Despite important advances in the synthesis of inorganic perovskite nanocrystals (NCs), the long-term instability and degradation of their quantum yield (QY) over time need to be addressed to enable the further development and exploitation of these nanomaterials. Here we report stable CsPbI 3 perovskite NCs and their use in hybrid light emitting diodes (LEDs), which combine in one system the NCs and a blue GaN-based LED. Nanocrystals with improved morphological and optical properties are obtained by optimizing the post-synthesis replacement of oleic acid ligands with iminodibenzoic acid: the NCs have a long shelf-life (>2 months), stability under different environmental conditions, and a high QY, of up to 90%, in the visible spectral range. Ligand replacement enables the engineering of the morphological and optical properties of the NCs. Furthermore, the NCs can be used to coat the surface of a GaN-LED to realize a stable diode where they are excited by blue light from the LED under low current injection conditions, resulting in emissions at distinct wavelengths in the visible range. The high QY and fluorescence lifetime in the nanosecond range are key parameters for visible light communication, an emerging technology that requires high-performance visible light sources for secure, fast energy-efficient wireless transmission.

Two dimensional III-VI metal monochalcogenide materials, such as GaSe and InSe, are attracting considerable attention due to their promising electronic and optoelectronic properties. Here, an investigation of point and extended atomic defects formed in mono-, bi-, and few-layer GaSe and InSe crystals is presented. Using state-of-the-art scanning transmission electron microscopy, it is observed that these materials can form both metal and selenium vacancies under the action of the electron beam. Selenium vacancies are observed to be healable: recovering the perfect lattice structure in the presence of selenium or enabling incorporation of dopant atoms in the presence of impurities. Under prolonged imaging, multiple point defects are observed to coalesce to form extended defect structures, with GaSe generally developing trigonal defects and InSe primarily forming line defects. These insights into atomic behavior could be harnessed to synthesize and tune the properties of 2D post-transition-metal monochalcogenide materials for optoelectronic applications.

Indium selenide, a post-transition metal chalcogenide, is a novel two-dimensional (2D) semiconductor with interesting electronic properties. Its tunable band gap and high electron mobility have already attracted considerable research interest. Here we demonstrate strong quantum confinement and manipulation of single electrons in devices made from few-layer crystals of InSe using electrostatic gating. We report on gate-controlled quantum dots in the Coulomb blockade regime as well as one-dimensional quantization in point contacts, revealing multiple plateaus. The work represents an important milestone in the development of quality devices based on 2D materials and makes InSe a prime candidate for relevant electronic and optoelectronic applications.

The controlled manipulation of the spin and charge of electrons in a semiconductor has the potential to create new routes to digital electronics beyond Moore's law, spintronics, and quantum detection and imaging for sensing applications. These technologies require a shift from traditional semiconducting and magnetic nanostructured materials. Here, a new material system is reported, which comprises the InSe semiconductor van der Waals crystal that embeds ferromagnetic Fe-islands. In contrast to many traditional semiconductors, the electronic properties of InSe are largely preserved after the incorporation of Fe. Also, this system exhibits ferromagnetic resonances and a large uniaxial magnetic anisotropy at room temperature, offering opportunities for the development of functional devices that integrate magnetic and semiconducting properties within the same material system.

The integration of different two-dimensional materials within a multilayer van der Waals (vdW) heterostructure offers a promising technology for high performance opto-electronic devices such as photodetectors and light sources. Here we report on the fabrication and electronic properties of vdW heterojunction diodes composed of the direct band gap layered semiconductors InSe and GaSe and transparent monolayer graphene electrodes. We show that the type II band alignment between the two layered materials and their distinctive spectral response, combined with the short channel length and low electrical resistance of graphene electrodes, enable efficient generation and extraction of photoexcited carriers from the heterostructure even when no external voltage is applied. Our devices are fast (∼2 μs), self-driven photodetectors with multicolor photoresponse ranging from the ultraviolet to the near-infrared and offer new routes to miniaturized optoelectronics beyond present semiconductor materials and technologies.

Photodetectors for the ultraviolet (UV) range of the electromagnetic spectrum are in great demand for several technologies, but require the development of novel device structures and materials. Here we report on the high detectivity of UV photodetectors based on well-ordered laterally mesoporous GaN. The specific detectivity of our devices under UV-illumination reaches values of up to 5.3 × 10 14 Jones. We attribute this high specific detectivity to the properties of the mesoporous GaN/metal contact interface: the trapping of photo-generated holes at the interface lowers the Schottky barrier height thus causing a large internal gain. High detectivity along with a simple fabrication process endows these laterally mesoporous GaN photodetectors with great potential for applications that require selective detection of weak optical signals in the UV range.

A decade of intense research on two-dimensional (2D) atomic crystals has revealed that their properties can differ greatly from those of the parent compound. These differences are governed by changes in the band structure due to quantum confinement and are most profound if the underlying lattice symmetry changes. Here we report a high-quality 2D electron gas in few-layer InSe encapsulated in hexagonal boron nitride under an inert atmosphere. Carrier mobilities are found to exceed 10 3  cm 2  V -1  s -1 and 10 4  cm 2  V -1  s -1 at room and liquid-helium temperatures, respectively, allowing the observation of the fully developed quantum Hall effect. The conduction electrons occupy a single 2D subband and have a small effective mass. Photoluminescence spectroscopy reveals that the bandgap increases by more than 0.5 eV with decreasing the thickness from bulk to bilayer InSe. The band-edge optical response vanishes in monolayer InSe, which is attributed to the monolayer's mirror-plane symmetry. Encapsulated 2D InSe expands the family of graphene-like semiconductors and, in terms of quality, is competitive with atomically thin dichalcogenides and black phosphorus.

Magnetic interactions of Mn 2+ ions in lead sulfide (PbS) nanocrystals with protons in water are probed by NMR and MRI. A thin layer of capping molecules enables free solvent diffusion to the nanocrystal surface resulting in a decrease of proton relaxation times. Magnetic resonance imaging of neuronal cell pellets exposed to (PbMn)S at non-toxic concentrations demonstrates their prospects as MRI-labels.

The nanoscale design of quantum dots (QDs) requires advanced analytical techniques. However, those that are commonly used do not have sufficient sensitivity or spatial resolution. Here, we use magnetic resonance techniques combined with paramagnetic Mn impurities in PbS QDs for sensitive probing of the QD surface and environment. In particular, we reveal inequivalent proton spin relaxations of the capping ligands and solvent molecules, strengths and anisotropies of the Mn nuclear spin interactions, and Mn nuclei distances with ∼1 Å sensitivity. These findings demonstrate the potential of magnetically doped QDs as sensitive magnetic nanoprobes and the use of electron spins for surface sensing.

Van der Waals (vdW) layered crystals and heterostructures have attracted substantial interest for potential applications in a wide range of emerging technologies. An important, but often overlooked, consideration in the development of implementable devices is phonon transport through the structure interfaces. Here we report on the interface properties of exfoliated InSe on a sapphire substrate. We use a picosecond acoustic technique to probe the phonon resonances in the InSe vdW layered crystal. Analysis of the nanomechanics indicates that the InSe is mechanically decoupled from the substrate and thus presents an elastically imperfect interface. A high degree of phonon isolation at the interface points toward applications in thermoelectric devices, or the inclusion of an acoustic transition layer in device design. These findings demonstrate basic properties of layered structures and so illustrate the usefulness of nanomechanical probing in nanolayer/nanolayer or nanolayer/substrate interface tuning in vdW heterostructures.

High broad-band photoresponsivity of mechanically formed InSe-graphene van der Waals heterostructures is achieved by exploiting the broad-band transparency of graphene, the direct bandgap of InSe, and the favorable band line up of InSe with graphene. The photoresponsivity exceeds that for other van der Waals heterostructures and the spectral response extends from the near-infrared to the visible spectrum., (© 2015 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We report on an example of confined magnetic ions with long spin coherence near room temperature. This was achieved by confining single Mn(2+) spins in colloidal semiconductor quantum dots (QDs) and by dispersing the QDs in a proton-spin free matrix. The controlled suppression of Mn-Mn interactions and minimization of Mn-nuclear spin dipolar interactions result in unprecedentedly long phase memory (TM ~ 8 μs) and spin-lattice relaxation (T1 ~ 10 ms) time constants for Mn(2+) ions at T = 4.5 K, and in electron spin coherence observable near room temperature (TM ~ 1 μs).

Colorectal carcinoma (CRC) is the 3 rd most common cancer worldwide, thus development of novel therapeutic strategies is imperative. Herein potent, selective dose-dependent antitumor activity of horse spleen apoferritin encapsulated PbS quantum dots (AFt-PbS) against two human-derived colorectal carcinoma cell lines is reported (GI 50 ∼ 70 μg mL -1 ). Following in vitro exposure to AFt-PbS, CRC cells fail to recover proliferative capacity, and undergo apoptosis triggered by the generation of reactive oxygen species (ROS). In stark contrast, the AFt-PbS nanocomposites do not affect the growth and cell cycle of non-tumor human microvessel endothelial HMEC-1 cells (GI 50 > 500 μg mL -1 ). In vivo, AFt-PbS QDs are well tolerated by mice. Neither adverse health nor behavioral indicators were observed throughout the 15 day study. The photoluminescence of AFt-PbS combined with selective antitumor activity offer potential development of AFt-PbS for simultaneous non-invasive imaging and treatment of malignant tissue.

Strong quantization effects and tuneable near-infrared photoluminescence emission are reported in mechanically exfoliated crystals of γ-rhombohedral semiconducting InSe. The optical properties of InSe nanosheets differ qualitatively from those reported recently for exfoliated transition metal dichalcogenides and indicate a crossover from a direct to an indirect band gap semiconductor when the InSe flake thickness is reduced to a few nanometers., (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A superlattice (SL) is an artificial crystal in which alternating nanometre-thick layers of two or more different semiconductor materials provide a periodic potential for conduction electrons. Strong magnetic and electric fields applied to this type of structure provide a means of exploring novel regimes of electron dynamics. The applied fields lower the dimensionality of the electronic states and lead to qualitative changes in the electronic conduction. This discovery is of fundamental interest and highly relevant to the properties of other low-dimensional conductors, such as nanowires and quantum dot SLs, which are presently attracting the attention of the physics and device communities. In addition, a rare type of chaotic electron dynamics, called non-Kolmogorov-Arnold-Moser (KAM) chaotic motion, which has been theoretically studied for several decades, is observed experimentally in SLs. The onset of chaos at discrete values of the applied electric and magnetic fields is observed as a large increase in the current flow due to the creation of unbound electron orbits, which propagate through intricate web patterns in phase space. Therefore, non-KAM chaos could provide a new mechanism for controlling the electrical conductivity of the electronic devices with extreme sensitivity.