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Two-dimensional van der Waals ferroelectric materials play an important role in a wide spectrum of semiconductor technologies and device applications. Integration of ferroelectrics into 2D-layered material-based devices is expected to offer intriguing working principles and add desired functionalities for next-generation electronics. Here, we investigate the electric and thermoelectric properties of thin layers of the 2H and 3R polymorphs of α -In2Se3 embedded in solid-state three-terminal devices. Charge transport measurements reveal a hysteretic behavior that can be ascribed to the effect of ferroelectric polarization at the metal electrode/2D semiconductor interfaces. The thermoelectric investigation of the same devices unveils a well-defined negative signal of the order of 100–200 μ V/K in absolute value for the 2H polymorph, showing a slight modulation as a function of the gate voltage. An analogous but noisy thermoelectric voltage is measured for devices based on the 3R polymorph, where indeed a constant finite transversal offset in the 100 μ V-few mV range is detected, which does not depend on the applied temperature gradient. We argue that these experimental observations are related to a strong residual in-plane ferroelectric polarization in the 3R α -In2Se3 polymorph thin layer. Our results show that the thermoelectric response is a fine probe of the ferroelectric character of 2D layered α -In2Se3. [ABSTRACT FROM AUTHOR]

Two-dimensional van der Waals ferroelectric materials play an important role in a wide spectrum of semiconductor technologies and device applications. Integration of ferroelectrics into 2D-layered material-based devices is expected to offer intriguing working principles and add desired functionalities for next-generation electronics. Here, we investigate the electric and thermoelectric properties of thin layers of the 2H and 3R polymorphs of α -In2Se3 embedded in solid-state three-terminal devices. Charge transport measurements reveal a hysteretic behavior that can be ascribed to the effect of ferroelectric polarization at the metal electrode/2D semiconductor interfaces. The thermoelectric investigation of the same devices unveils a well-defined negative signal of the order of 100–200 μ V/K in absolute value for the 2H polymorph, showing a slight modulation as a function of the gate voltage. An analogous but noisy thermoelectric voltage is measured for devices based on the 3R polymorph, where indeed a constant finite transversal offset in the 100 μ V-few mV range is detected, which does not depend on the applied temperature gradient. We argue that these experimental observations are related to a strong residual in-plane ferroelectric polarization in the 3R α -In2Se3 polymorph thin layer. Our results show that the thermoelectric response is a fine probe of the ferroelectric character of 2D layered α -In2Se3. [ABSTRACT FROM AUTHOR]

Two-dimensional (2D) material resonators have emerged as promising platforms for advanced nanomechanical applications due to their exceptional mechanical properties, tunability, and nonlinearities. We explored the strong mechanical mode coupling between two adjacent 3R-WSe 2 nanodrums at room temperature. Combining a piezoelectric material, as noncentrosymmetric 3R-WSe 2 , and vibration manipulation is the building block for phononic experiments with 2D materials. By strategically placing gate grids beneath each resonator and mapping the spatial distribution of these modes, we demonstrate the ability to transit between localized modes in individual membranes to delocalized, strongly coupled modes that span the entire suspended region. The coherent coupling is strongly tunable with simple gate voltage, and remarkable resonance splitting was achieved, corresponding to up to 5% of the vibration frequency. These results showcase the potential of 2D material resonators for efficient information exchange, paving the way for novel applications in quantum technologies and nanoscale sensing.

The growth of bilayers of two-dimensional (2D) materials on conventional 3D semiconductors results in 2D/3D hybrid heterostructures, which can provide additional advantages over more established 3D semiconductors while retaining some specificities of 2D materials. Understanding and exploiting these phenomena hinge on knowing the electronic properties and the hybridization of these structures. Here, we demonstrate that a rhombohedral-stacked bilayer (AB stacking) can be obtained by molecular beam epitaxy growth of tungsten diselenide (WSe 2 ) on a gallium phosphide (GaP) substrate. We confirm the presence of 3R-stacking of the WSe 2 bilayer structure using scanning transmission electron microscopy (STEM) and micro-Raman spectroscopy. Also, we report high-resolution angle-resolved photoemission spectroscopy (ARPES) on our rhombohedral-stacked WSe 2 bilayer grown on a GaP(111)B substrate. Our ARPES measurements confirm the expected valence band structure of WSe 2 with the band maximum located at the Γ point of the Brillouin zone. The epitaxial growth of WSe 2 /GaP(111)B helps to understand the fundamental properties of these 2D/3D heterostructures, toward their implementation in future devices.

Two-dimensional (2D) ferroelectric (FE) materials are promising compounds for next-generation nonvolatile memories due to their low energy consumption and high endurance. Among them, α-In 2 Se 3 has drawn particular attention due to its in- and out-of-plane ferroelectricity, whose robustness has been demonstrated down to the monolayer limit. This is a relatively uncommon behavior since most bulk FE materials lose their ferroelectric character at the 2D limit due to the depolarization field. Using angle resolved photoemission spectroscopy (ARPES), we unveil another unusual 2D phenomenon appearing in 2H α-In 2 Se 3 single crystals, the occurrence of a highly metallic two-dimensional electron gas (2DEG) at the surface of vacuum-cleaved crystals. This 2DEG exhibits two confined states, which correspond to an electron density of approximately 10 13 electrons/cm 2 , also confirmed by thermoelectric measurements. Combination of ARPES and density functional theory (DFT) calculations reveals a direct band gap of energy equal to 1.3 ± 0.1 eV, with the bottom of the conduction band localized at the center of the Brillouin zone, just below the Fermi level. Such strong n-type doping further supports the quantum confinement of electrons and the formation of the 2DEG.

Nanowires are widely used for energy harvesting, sensors, and solar cells. We report a study on the role of buffer layer in the growth of zinc oxide (ZnO) nanowires (NWs) synthesised by a chemical bath deposition (CBD) method. To control the thickness of the buffer layer, multilayer coatings corresponding to one layer (100 nm thick), three layers (300 nm thick), and six layers (600 nm thick) of ZnO sol-gel thin-films were used. The evolution of the morphology and structure of ZnO NWs was characterized by scanning electron microscopy, X-ray diffraction, photoluminescence, and Raman spectroscopy. Highly C-oriented ZnO (002)-oriented NWs were obtained on both substrates, silicon and ITO, when the thickness of the buffer layer was increased. The role of ZnO sol-gel thin films used as a buffer layer for the growth of ZnO NWs with (002)-oriented grains also resulted in a significant change in surface morphology on both substrates. The successful deposition of ZnO NWs on a variety of substrates, as well as the promising results, open up a wide range of applications., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

In two dimensional materials, substitutional doping during growth can be used to alter the electronic properties. Here, we report on the stable growth of p-type hexagonal boron nitride (h-BN) using Mg-atoms as substitutional impurities in the h-BN honeycomb lattice. We use micro-Raman spectroscopy, angle-resolved photoemission measurements (nano-ARPES) and Kelvin probe force microscopy (KPFM) to study the electronic properties of Mg-doped h-BN grown by solidification from a ternary Mg-B-N system. Besides the observation of a new Raman line at ∼1347 cm -1 in Mg-doped h-BN, nano-ARPES reveals p-type carrier concentration. Our nano-ARPES experiments demonstrate that the Mg dopants can significantly alter the electronic properties of h-BN by shifting the valence band maximum about 150 meV toward higher binding energies with respect to pristine h-BN. We further show that, Mg doped h-BN exhibits a robust, almost unaltered, band structure compared to pristine h-BN, with no significant deformation. Kelvin probe force microscopy (KPFM) confirms the p-type doping, with a reduced Fermi level difference between pristine and Mg-doped h-BN crystals. Our findings demonstrate that conventional semiconductor doping by Mg as substitutional impurities is a promising route to high-quality p-type doped h-BN films. Such stable p-type doping of large band h-BN is a key feature for 2D materials applications in deep ultra-violet light emitting diodes or wide bandgap optoelectronic devices., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Multilayers based on quantum materials (complex oxides, topological insulators, transition-metal dichalcogenides, etc.) have enabled the design of devices that could revolutionize microelectronics and optoelectronics. However, heterostructures incorporating quantum materials from different families remain scarce, while they would immensely broaden the range of possible applications. Here we demonstrate the large-scale integration of compounds from two highly multifunctional families: perovskite oxides and transition-metal dichalcogenides (TMDs). We couple BiFeO 3 , a room-temperature multiferroic oxide, and WSe 2 , a semiconducting two-dimensional material with potential for photovoltaics and photonics. WSe 2 is grown by molecular beam epitaxy and transferred on a centimeter-scale onto BiFeO 3 films. Using angle-resolved photoemission spectroscopy, we visualize the electronic structure of 1 to 3 monolayers of WSe 2 and evidence a giant energy shift as large as 0.75 eV induced by the ferroelectric polarization direction in the underlying BiFeO 3 . Such a strong shift opens new perspectives in the efficient manipulation of TMD properties by proximity effects.

Atomically thin two-dimensional (2D) layered semiconductors such as transition metal dichalcogenides have attracted considerable attention due to their tunable band gap, intriguing spin-valley physics, piezoelectric effects and potential device applications. Here we study the electronic properties of a single layer WS 1.4 Se 0.6 alloys. The electronic structure of this alloy, explored using angle resolved photoemission spectroscopy, shows a clear valence band structure anisotropy characterized by two paraboloids shifted in one direction of the k -space by a constant in-plane vector. This band splitting is a signature of a unidirectional Rashba spin splitting with a related giant Rashba parameter of 2.8 ± 0.7 eV Å. The combination of angle resolved photoemission spectroscopy with piezo force microscopy highlights the link between this giant unidirectional Rashba spin splitting and an in-plane polarization present in the alloy. These peculiar anisotropic properties of the WS 1.4 Se 0.6 alloy can be related to local atomic orders induced during the growth process due the different size and electronegativity between S and Se atoms. This distorted crystal structure combined to the observed macroscopic tensile strain, as evidenced by photoluminescence, displays electric dipoles with a strong in-plane component, as shown by piezoelectric microscopy. The interplay between semiconducting properties, in-plane spontaneous polarization and giant out-of-plane Rashba spin-splitting in this 2D material has potential for a wide range of applications in next-generation electronics, piezotronics and spintronics devices., (© 2022 IOP Publishing Ltd.)

Nearly localized moiré flat bands in momentum space, arising at particular twist angles, are the key to achieve correlated effects in transition-metal dichalcogenides. Here, we use angle-resolved photoemission spectroscopy (ARPES) to visualize the presence of a flat band near the Fermi level of van der Waals WSe 2 /MoSe 2 heterobilayer grown by molecular beam epitaxy. This flat band is localized near the Fermi level and has a width of several hundred meVs. By combining ARPES measurements with density functional theory calculations, we confirm the coexistence of different domains, namely the reference 2H stacking without layer misorientation and regions with arbitrary twist angles. For the 2H-stacked heterobilayer, our ARPES results show strong interlayer hybridization effects, further confirmed by complementary micro- Raman spectroscopy measurements. The spin-splitting of the valence band at K is determined to be 470 meV. The valence band maximum (VBM) position of the heterobilayer is located at the Γ point. The energy difference between the VBM at Γ and the K point is of -60 meV, which is a stark difference compared to individual single monolayer WSe 2 and monolayer WSe 2 , showing both a VBM at K ., (© 2022 IOP Publishing Ltd.)

GeSn alloys are promising materials for CMOS-compatible mid-infrared lasers manufacturing. Indeed, Sn alloying and tensile strain can transform them into direct bandgap semiconductors. This growing laser technology however suffers from a number of limitations, such as poor optical confinement, lack of strain, thermal, and defects management, all of which are poorly discussed in the literature. Herein, a specific GeSn-on-insulator (GeSnOI) stack using stressor layers as dielectric optical claddings is demonstrated to be suitable for a monolithically integration of planar Group-IV semiconductor lasers on a versatile photonic platform for the near- and mid-infrared spectral range. Microdisk-shape resonators on mesa structures were fabricated from GeSnOI, after bonding a Ge 0.9 Sn 0.1 alloy layer grown on a Ge strain-relaxed-buffer, itself on a Si(001) substrate. The GeSnOI microdisk mesas exhibited significantly improved optical gain as compared to that of conventional suspended microdisk resonators formed from the as-grown layer. We further show enhanced vertical out-coupling of the disk whispering gallery mode in-plane radiation, with up to 30% vertical out-coupling efficiency. As a result, the GeSnOI approach can be a valuable asset in the development of silicon-based mid-infrared photonics that combine integrated sources in a photonic platform with complex lightwave engineering., (© 2021. The Author(s).)

The strain in hybrid van der Waals heterostructures, made of two distinct two-dimensional van der Waals materials, offers an interesting handle on their corresponding electronic band structure. Such strain can be engineered by changing the relative crystallographic orientation between the constitutive monolayers, notably, the angular misorientation, also known as the "twist angle". By combining angle-resolved photoemission spectroscopy with density functional theory calculations, we investigate here the band structure of the WS 2 /graphene heterobilayer for various twist angles. Despite the relatively weak coupling between WS 2 and graphene, we demonstrate that the resulting strain quantitatively affects many electronic features of the WS 2 monolayers, including the spin-orbit coupling strength. In particular, we show that the WS 2 spin-orbit splitting of the valence band maximum at K can be tuned from 430 to 460 meV. Our findings open perspectives in controlling the band dispersion of van der Waals materials.

Zinc oxide (ZnO) is a II-VI group semiconductor with a wide direct bandgap and is an important material for various fields of industry and high-technological applications. The effects of thickness, annealing process in N 2 and air, optical properties, and morphology of ZnO thin-films are studied. A low-cost sol-gel spin-coating technique is used in this study for the simple synthesis of eco-friendly ZnO multilayer films deposited on (100)-oriented silicon substrates ranging from 150 to 600 nm by adjusting the spin coating rate. The ZnO sol-gel thin-films using precursor solutions of molarity 0.75 M exhibit an average optical transparency above 98%, with an optical band gap energy of 3.42 eV. The c -axis (002) orientation of the ZnO thin-films annealed at 400 °C were mainly influenced by the thickness of the multilayer, which is of interest for piezoelectric applications. These results demonstrate that a low-temperature method can be used to produce an eco-friendly, cost-effective ZnO sol-gel that is compatible with a complementary metal-oxide-semiconductor (CMOS) and integrated-circuits (IC)., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

HgTe nanocrystals (NCs) enable broadly tunable infrared absorption, now commonly used to design light sensors. This material tends to grow under multipodic shapes and does not present well-defined size distributions. Such point generates traps and reduces the particle packing, leading to a reduced mobility. It is thus highly desirable to comprehensively explore the effect of the shape on their performance. Here, we show, using a combination of electron tomography and tight binding simulations, that the charge dissociation is strong within HgTe NCs, but poorly shape dependent. Then, we design a dual-gate field-effect-transistor made of tripod HgTe NCs and use it to generate a planar p-n junction, offering more tunability than its vertical geometry counterpart. Interestingly, the performance of the tripods is higher than sphere ones, and this can be correlated with a stronger Te excess in the case of sphere shapes which is responsible for a higher hole trap density.

Semiconducting monolayers of a 2D material are able to concatenate multiple interesting properties into a single component. Here, by combining opto-mechanical and electronic measurements, we demonstrate the presence of a partial 2H-1T' phase transition in a suspended 2D monolayer membrane of MoS 2 . Electronic transport shows unexpected memristive properties in the MoS 2 membrane, in the absence of any external dopants. A strong mechanical softening of the membrane is measured concurrently and may only be related to the 2H-1T' phase transition, which imposes a 3% directional elongation of the topological 1T' phase with respect to the semiconducting 2H. We note that only a few percent 2H-1T' phase switching is sufficient to observe measurable memristive effects. Our experimental results combined with first-principles total energy calculations indicate that sulfur vacancy diffusion plays a key role in the initial nucleation of the phase transition. Our study clearly shows that nanomechanics represents an ultrasensitive technique to probe the crystal phase transition in 2D materials or thin membranes. Finally, a better control of the microscopic mechanisms responsible for the observed memristive effect in MoS 2 is important for the implementation of future devices.

Nanocrystals are promising building blocks for the development of low-cost infrared optoelectronics. Gating a nanocrystal film in a phototransistor geometry is commonly proposed as a strategy to tune the signal-to-noise ratio by carefully controlling the carrier density within the semiconductor. However, the performance improvement has so far been quite marginal. With metallic electrodes, the gate dependence of the photocurrent follows the gate-induced change of the dark current. Graphene presents key advantages: (i) infrared transparency that allows back-side illumination, (ii) vertical electric field transparency, and (iii) carrier selectivity under gate bias. Here, we investigate a configuration of 2D/0D infrared photodetectors taking advantage of a high capacitance ionic glass gate, large-scale graphene electrodes, and a HgTe nanocrystals layer of high carrier mobility. The introduction of graphene electrodes combined with ionic glass enables one to reconfigure selectively the HgTe nanocrystals and the graphene electrodes between electron-doped (n) and hole-doped (p) states. We unveil that this functionality enables the design a 2D/0D p-n junction that expands throughout the device, with a built-in electric field that assists charge dissociation. We demonstrate that, in this specific configuration, the signal-to-noise ratio for infrared photodetection can be enhanced by 2 orders of magnitude, and that photovoltaic operation can be achieved. The detectivity now reaches 10 9 Jones, whereas the device only absorbs 8% of the incident light. Additionally, the time response of the device is fast (<10 μs), which strongly contrasts with the slow response commonly observed for 2D/0D mixed-dimensional heterostructures, where larger photoconduction gains come at the cost of slower response.

Semiconducting two-dimensional (2D) materials, such as transition-metal dichalcogenides (TMDs), are emerging in nanomechanics, optoelectronics, and thermal transport. In each of these fields, perfect control over 2D material properties including strain, doping, and heating is necessary, especially on the nanoscale. Here, we study clean devices consisting of membranes of single-layer MoS 2 suspended on pillar arrays. Using Raman and photoluminescence spectroscopy, we have been able to extract, separate, and simulate the different contributions on the nanoscale and to correlate these to the pillar array design. This control has been used to design a periodic MoS 2 mechanical membrane with a high reproducibility and to perform optomechanical measurements on arrays of similar resonators with a high-quality factor of 600 at ambient temperature, hence opening the way to multiresonator applications with 2D materials. At the same time, this study constitutes a reference for the future development of well-controlled optical emissions within 2D materials on periodic arrays with reproducible behavior. We measured a strong reduction of the MoS 2 band gap induced by the strain generated from the pillars. A transition from direct to indirect band gap was observed in isolated tent structures made of MoS 2 and pinched by a pillar. In fully suspended devices, simulations were performed allowing both the extraction of the thermal conductance and doping of the layer. Using the correlation between the influences of strain and doping on the MoS 2 Raman spectrum, we have developed a simple, elegant method to extract the local strain in suspended and nonsuspended parts of a membrane. This opens the way to experimenting with tunable coupling between light emission and vibration.

A combination of sol-gel chemistry and the electrospinning process leads to unprecedented versatility in the design of nano-Magnéli phases. Adjusting experimental levers provides an efficient route for tuning the composition, the crystal structure, and the nano- and microstructure of titanium sub-oxides, thus paving the way to functional membranes and tissues., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Quantum interference in cross-conjugated molecules embedded in solid-state devices was investigated by direct current-voltage and differential conductance transport measurements of anthraquinone (AQ)-based large area planar junctions. A thin film of AQ was grafted covalently on the junction base electrode by diazonium electroreduction, while the counter electrode was directly evaporated on top of the molecular layer. Our technique provides direct evidence of a large quantum interference effect in multiple CMOS compatible planar junctions. The quantum interference is manifested by a pronounced dip in the differential conductance close to zero voltage bias. The experimental signature is well developed at low temperature (4 K), showing a large amplitude dip with a minimum >2 orders of magnitude lower than the conductance at higher bias and is still clearly evident at room temperature. A temperature analysis of the conductance curves revealed that electron-phonon coupling is the principal decoherence mechanism causing large conductance oscillations at low temperature.

A hallmark of mechanical resonators made from a single nanotube is that the resonance frequency can be widely tuned. Here, we take advantage of this property to realize parametric amplification and self-oscillation. The gain of the parametric amplification can be as high as 18.2 dB and tends to saturate at high parametric pumping due to nonlinear damping. These measurements allow us to determine the coefficient of the linear damping force. The corresponding damping rate is lower than the one obtained from the line shape of the resonance (without pumping), supporting the recently reported scenario that describes damping in nanotube resonators by a nonlinear force. The possibility to combine nanotube resonant mechanics and parametric amplification holds promise for future ultralow force sensing experiments.