Tuning the Electronic Response of Metallic Graphene by Potassium Doping.

Electron doping of graphene has been extensively studied on graphene-supported surfaces, where the metallicity is influenced by the substrate. Herewith we propose potassium adsorption on free-standing nanoporous graphene, thus eluding any effect due to the substrate. We monitor the electron migration in the π* downward-shifted conduction band. In this rigid band shift, we correlate the spectral density of the π* state in the upper Dirac cone with the associated plasmon, blue-shifted with increasing K dose, as deduced by electron energy loss spectroscopy. These results are confirmed by the Dirac plasmon activated by the C 1s emitted electrons, thanks to spatially resolved photoemission. This crosscheck constitutes a reference on the correlation between the electronic π* states in the conduction band and the Dirac plasmon evolution upon in situ electron doping of fully free-standing graphene.

Enhanced Field-Effect Control of Single-Layer WS2 Optical Features by hBN Full Encapsulation.

The field-effect control of the electrical and optical properties of two-dimensional (2D) van der Waals semiconductors (vdW) is one important aspect of this novel class of materials. Thanks to their reduced thickness and decreased screening, electric fields can easily penetrate in a 2D semiconductor and thus modulate their charge density and their properties. In literature, the field effect is routinely used to fabricate atomically thin field-effect transistors based on 2D semiconductors. Apart from the tuning of the electrical transport, it has been demonstrated that the field effect can also be used to modulate the excitonic optical emission of 2D transition metal dichalcogenides such as MoS2 or WSe2. In this paper, we present some recent experiments on the field-effect control of the optical and excitonic properties of the monolayer WS2. Using the deterministic transfer of van der Waals materials, we fabricate planar single-layer WS2 devices contacted by a gold electrode and partially sandwiched between two insulating hexagonal boron nitride (hBN) flakes. Thanks to the planar nature of the device, we can optically access both the hBN encapsulated and the unencapsulated WS2 regions and compare the field-effect control of the exciton population in the two cases. We find that the encapsulation strongly increases the range of tunability of the optical emission of WS2, allowing us to tune the photoluminescence emission from excitons-dominated to trions-dominated. We also discuss how the full encapsulation of WS2 with hBN helps reduce spurious hysteretic effects in the field-effect control of the optical properties, similar to what has been reported for 2D vdW field-effect transistors.

Broadband-tunable spectral response of perovskite-on-paper photodetectors using halide mixing.

Paper offers a low-cost and widely available substrate for electronics. It possesses alternative characteristics to silicon, as it shows low density and high flexibility, together with biodegradability. Solution processable materials, such as hybrid perovskites, also present light and flexible features, together with a huge tunability of the material composition with varying optical properties. In this study, we combine paper substrates with halide-mixed perovskites for the creation of low-cost and easy-to-prepare perovskite-on-paper photodetectors with a broadband-tunable spectral response. From the bandgap tunability of halide-mixed perovskites we create photodetectors with a cut-off spectral onset that ranges from the NIR to the green region, by increasing the bromide content on MAPb(I1-xBrx)3 perovskite alloys. The devices show a fast and efficient response. The best performances are observed for pure I and Br perovskite compositions, with a maximum responsivity of ∼400 mA W-1 on the MAPbBr3 device. This study provides an example of the wide range of possibilities that the combination of solution processable materials with paper substrates offers for the development of low-cost, biodegradable and easy-to-prepare devices.

Homogeneous Spatial Distribution of Deuterium Chemisorbed on Free-Standing Graphene.

Atomic deuterium (D) adsorption on free-standing nanoporous graphene obtained by ultra-high vacuum D2 molecular cracking reveals a homogeneous distribution all over the nanoporous graphene sample, as deduced by ultra-high vacuum Raman spectroscopy combined with core-level photoemission spectroscopy. Raman microscopy unveils the presence of bonding distortion, from the signal associated to the planar sp2 configuration of graphene toward the sp3 tetrahedral structure of graphane. The establishment of D-C sp3 hybrid bonds is also clearly determined by high-resolution X-ray photoelectron spectroscopy and spatially correlated to the Auger spectroscopy signal. This work shows that the low-energy molecular cracking of D2 in an ultra-high vacuum is an efficient strategy for obtaining high-quality semiconducting graphane with homogeneous uptake of deuterium atoms, as confirmed by this combined optical and electronic spectro-microscopy study wholly carried out in ultra-high vacuum conditions.

Paper-based broadband flexible photodetectors with van der Waals materials.

Layered metal chalcogenide materials are exceptionally appealing in optoelectronic devices thanks to their extraordinary optical properties. Recently, their application as flexible and wearable photodetectors have received a lot of attention. Herein, broadband and high-performance paper-based PDs were established in a very facile and inexpensive method by rubbing molybdenum disulfide and titanium trisulfide crystals on papers. Transferred layers were characterized by SEM, EDX mapping, and Raman analyses, and their optoelectronic properties were evaluated in a wavelength range of 405-810 nm. Although the highest and lowest photoresponsivities were respectively measured for TiS3 (1.50 mA/W) and MoS2 (1.13 µA/W) PDs, the TiS3-MoS2 heterostructure not only had a significant photoresponsivity but also showed the highest on/off ratio (1.82) and fast response time (0.96 s) compared with two other PDs. This advantage is due to the band offset formation at the heterojunction, which efficiently separates the photogenerated electron-hole pairs within the heterostructure. Numerical simulation of the introduced PDs also confirmed the superiority of TiS3-MoS2 heterostructure over the other two PDs and exhibited a good agreement with the experimental results. Finally, MoS2 PD demonstrated very high flexibility under applied strain, but TiS3 based PDs suffered from its fragility and experience a remarkable drain current reduction at strain larger than ± 0.33%. However, at lower strains, all PDs displayed acceptable performances.

Strongly Anisotropic Strain-Tunability of Excitons in Exfoliated ZrSe3.

The effect of uniaxial strain on the band structure of ZrSe3 , a semiconducting material with a marked in-plane structural anisotropy, is studied. By using a modified three-point bending test apparatus, thin ZrSe3 flakes are subjected to uniaxial strain along different crystalline orientations monitoring the effect of strain on their optical properties through micro-reflectance spectroscopy. The obtained spectra show excitonic features that blueshift upon uniaxial tension. This shift is strongly dependent on the direction along which the strain is being applied. When the flakes are strained along the b-axis, the exciton peak shifts at ≈60-95 meV %-1 , while along the a-axis, the shift only reaches ≈0-15 meV %-1 . Ab initio calculations are conducted to study the influence of uniaxial strain, applied along different crystal directions, on the band structure and reflectance spectra of ZrSe3 , exhibiting a remarkable agreement with the experimental results.

Integrating superconducting van der Waals materials on paper substrates.

Paper has the potential to dramatically reduce the cost of electronic components. In fact, paper is 10 000 times cheaper than crystalline silicon, motivating the research to integrate electronic materials on paper substrates. Among the different electronic materials, van der Waals materials are attracting the interest of the scientific community working on paper-based electronics because of the combination of high electrical performance and mechanical flexibility. Up to now, different methods have been developed to pattern conducting, semiconducting and insulating van der Waals materials on paper but the integration of superconductors remains elusive. Here, the deposition of NbSe2, an illustrative van der Waals superconductor, on standard copy paper is demonstrated. The deposited NbSe2 films on paper display superconducting properties (e.g. observation of Meissner effect and resistance drop to zero-resistance state when cooled down below its critical temperature) similar to those of bulk NbSe2.

Drawing WS2 thermal sensors on paper substrates.

Paper based thermoresistive sensors are fabricated by rubbing WS2 powder against a piece of standard copier paper, like the way a pencil is used to write on paper. The abrasion between the layered material and the rough paper surface erodes the material, breaking the weak van der Waals interlayer bonds, yielding a film of interconnected platelets. The resistance of WS2 presents a strong temperature dependence, as expected for a semiconductor material in which charge transport is due to thermally activated carriers. This strong temperature dependence makes the paper supported WS2 devices extremely sensitive to small changes in temperature. This exquisite thermal sensitivity, and their fast response times to sudden temperature changes, is exploited thereby demonstrating the usability of a WS2-on-paper thermal sensor in a respiration monitoring device.

Giant Piezoresistive Effect and Strong Bandgap Tunability in Ultrathin InSe upon Biaxial Strain.

The ultrathin nature and dangling bonds free surface of 2D semiconductors allow for significant modifications of their bandgap through strain engineering. Here, thin InSe photodetector devices are biaxially stretched, finding, a strong bandgap tunability upon strain. The applied biaxial strain is controlled through the substrate expansion upon temperature increase and the effective strain transfer from the substrate to the thin InSe is confirmed by Raman spectroscopy. The bandgap change upon biaxial strain is determined through photoluminescence measurements, finding a gauge factor of up to ≈200 meV %-1. The effect of biaxial strain on the electrical properties of the InSe devices is further characterized. In the dark state, a large increase of the current is observed upon applied strain which gives a piezoresistive gauge factor value of ≈450-1000, ≈5-12 times larger than that of other 2D materials and of state-of-the-art silicon strain gauges. Moreover, the biaxial strain tuning of the InSe bandgap also translates in a strain-induced redshift of the spectral response of the InSe photodetectors with ΔE cut-off ≈173 meV at a rate of ≈360 meV %-1 of strain, indicating a strong strain tunability of the spectral bandwidth of the photodetectors.

Microheater Actuators as a Versatile Platform for Strain Engineering in 2D Materials.

We present microfabricated thermal actuators to engineer the biaxial strain in two-dimensional (2D) materials. These actuators are based on microheater circuits patterned onto the surface of a polymer with a high thermal expansion coefficient. By running current through the microheater one can vary the temperature of the polymer and induce a controlled biaxial expansion of its surface. This controlled biaxial expansion can be transduced to biaxial strain to 2D materials, placed onto the polymer surface, which in turn induces a shift of the optical spectrum. Our thermal strain actuators can reach a maximum biaxial strain of 0.64%, and they can be modulated at frequencies up to 8 Hz. The compact geometry of these actuators results in a negligible spatial drift of 0.03 µm/°C, which facilitates their integration in optical spectroscopy measurements. We illustrate the potential of this strain engineering platform to fabricate a strain-actuated optical modulator with single-layer MoS2.

MoS2-on-paper optoelectronics: drawing photodetectors with van der Waals semiconductors beyond graphite.

We fabricate paper-supported semiconducting devices by rubbing a layered molybdenum disulfide (MoS2) crystal onto a piece of paper, similar to the action of drawing/writing with a pencil on paper. We show that the abrasion between the MoS2 crystal and the paper substrate efficiently exfoliates the crystals, breaking the weak van der Waals interlayer bonds and leading to the deposition of a film of interconnected MoS2 platelets. Employing this simple method, which can be easily extended to other 2D materials, we fabricate MoS2-on-paper broadband photodetectors with spectral sensitivity from the ultraviolet (UV) to the near-infrared (NIR) range. We also used these paper-based photodetectors to acquire pictures of objects by mounting the photodetectors in a homebuilt single-pixel camera setup.

Tunable Photodetectors via In Situ Thermal Conversion of TiS3 to TiO2.

In two-dimensional materials research, oxidation is usually considered as a common source for the degradation of electronic and optoelectronic devices or even device failure. However, in some cases a controlled oxidation can open the possibility to widely tune the band structure of 2D materials. In particular, we demonstrate the controlled oxidation of titanium trisulfide (TiS3), a layered semicon-ductor that has attracted much attention recently thanks to its quasi-1D electronic and optoelectron-ic properties and its direct bandgap of 1.1 eV. Heating TiS3 in air above 300 °C gradually converts it into TiO2, a semiconductor with a wide bandgap of 3.2 eV with applications in photo-electrochemistry and catalysis. In this work, we investigate the controlled thermal oxidation of indi-vidual TiS3 nanoribbons and its influence on the optoelectronic properties of TiS3-based photodetec-tors. We observe a step-wise change in the cut-off wavelength from its pristine value ~1000 nm to 450 nm after subjecting the TiS3 devices to subsequent thermal treatment cycles. Ab-initio and many-body calculations confirm an increase in the bandgap of titanium oxysulfide (TiO2-xSx) when in-creasing the amount of oxygen and reducing the amount of sulfur.

Symmetry Breakdown in Franckeite: Spontaneous Strain, Rippling, and Interlayer Moiré.

Franckeite is a naturally occurring layered mineral with a structure composed of alternating stacks of SnS2-like and PbS-like layers. Although this superlattice is composed of a sequence of isotropic two-dimensional layers, it exhibits a spontaneous rippling that makes the material structurally anisotropic. We demonstrate that this rippling comes hand in hand with an inhomogeneous in-plane strain profile and anisotropic electrical, vibrational, and optical properties. We argue that this symmetry breakdown results from a spatial modulation of the van der Waals interaction between layers due to the SnS2-like and PbS-like lattices incommensurability.

Superlattices based on van der Waals 2D materials.

Two-dimensional (2D) materials exhibit a number of improved mechanical, optical, and electronic properties compared to their bulk counterparts. The absence of dangling bonds in the cleaved surfaces of these materials allows combining different 2D materials into van der Waals heterostructures to fabricate p-n junctions, photodetectors, and 2D-2D ohmic contacts that show unexpected performances. These intriguing results are regularly summarized in comprehensive reviews. A strategy to tailor their properties even further and to observe novel quantum phenomena consists in the fabrication of superlattices whose unit cell is formed either by two dissimilar 2D materials or by a 2D material subjected to a periodic perturbation, each component contributing with different characteristics. Furthermore, in a 2D material-based superlattice, the interlayer interaction between the layers mediated by van der Waals forces constitutes a key parameter to tune the global properties of the superlattice. The above-mentioned factors reflect the potential to devise countless combinations of van der Waals 2D material-based superlattices. In the present feature article, we explain in detail the state-of-the-art of 2D material-based superlattices and describe the different methods to fabricate them, classified as vertical stacking, intercalation with atoms or molecules, moiré patterning, strain engineering and lithographic design. We also aim to highlight some of the specific applications of each type of superlattices.

Anisotropic buckling of few-layer black phosphorus.

When a two-dimensional material, adhered onto a compliant substrate, is subjected to compression it can undergo a buckling instability yielding to a periodic rippling. Interestingly, when black phosphorus (bP) flakes are compressed along the zig-zag crystal direction, the flake buckles forming ripples with a 40% longer period than that obtained when the compression is applied along the armchair direction. This anisotropic buckling stems from the puckered honeycomb crystal structure of bP and a quantitative analysis of the ripple period allows the determination of the Youngs's modulus of few-layer bP along the armchair direction (EbP_AC = 35.1 ± 6.3 GPa) and the zig-zag direction (EbP_ZZ = 93.3 ± 21.8 GPa).

InSe: a two-dimensional semiconductor with superior flexibility.

Two-dimensional indium selenide (InSe) has attracted extensive attention recently due to its record-high charge carrier mobility and photoresponsivity in the fields of electronics and optoelectronics. Nevertheless, the mechanical properties of this material in the ultra-thin regime have not been investigated yet. Here, we present our efforts to determine the Young's modulus of thin InSe (∼1-2 layers to ∼34 layers) flakes experimentally by using a buckling-based methodology. We find that the Young's modulus has a value of 23.1 ± 5.2 GPa, one of the lowest values reported to date for crystalline two-dimensional materials. This superior flexibility can be very attractive for different applications, such as strain engineering and flexible electronics.

Revisiting the Buckling Metrology Method to Determine the Young's Modulus of 2D Materials.

Measuring the mechanical properties of 2D materials is a formidable task. While regular electrical and optical probing techniques are suitable even for atomically thin materials, conventional mechanical tests cannot be directly applied. Therefore, new mechanical testing techniques need to be developed. Up to now, the most widespread approaches require micro-fabrication to create freely suspended membranes, rendering their implementation complex and costly. Here, a simple yet powerful technique is revisited to measure the mechanical properties of thin films. The buckling metrology method, that does not require the fabrication of freely suspended structures, is used to determine the Young's modulus of several transition metal dichalcogenides (MoS2 , MoSe2 , WS2 , and WSe2 ) with thicknesses ranging from 2 to 10 layers. The obtained values for the Young's modulus and their uncertainty are critically compared with previously published results, finding that this simple technique provides results which are in good agreement with those reported using other highly sophisticated testing methods. By comparing the cost, complexity, and time required for the different methods reported in the literature, the buckling metrology method presents certain advantages that make it an interesting mechanical test tool for 2D materials.

Thickness-Dependent Differential Reflectance Spectra of Monolayer and Few-Layer MoS2, MoSe2, WS2 and WSe2.

The research field of two dimensional (2D) materials strongly relies on optical microscopy characterization tools to identify atomically thin materials and to determine their number of layers. Moreover, optical microscopy-based techniques opened the door to study the optical properties of these nanomaterials. We presented a comprehensive study of the differential reflectance spectra of 2D semiconducting transition metal dichalcogenides (TMDCs), MoS2, MoSe2, WS2, and WSe2, with thickness ranging from one layer up to six layers. We analyzed the thickness-dependent energy of the different excitonic features, indicating the change in the band structure of the different TMDC materials with the number of layers. Our work provided a route to employ differential reflectance spectroscopy for determining the number of layers of MoS2, MoSe2, WS2, and WSe2.

Large birefringence and linear dichroism in TiS3 nanosheets.

TiS3 nanosheets have proven to be promising candidates for ultrathin optoelectronic devices due to their direct narrow band-gap and the strong light-matter interaction. In addition, the marked in-plane anisotropy of TiS3 is appealing for the fabrication of polarization sensitive optoelectronic devices. Herein, we study the optical contrast of TiS3 nanosheets of variable thickness on SiO2/Si substrates, from which we obtain the complex refractive index in the visible spectrum. We find that TiS3 exhibits very large birefringence, larger than that of well-known strong birefringent materials like TiO2 or calcite, and linear dichroism. These findings are in qualitative agreement with ab initio calculations that suggest an excitonic origin for the birefringence and linear dichroism of the material.

Quantum Transport through a Single Conjugated Rigid Molecule, a Mechanical Break Junction Study.

This Account provides an overview of our recent efforts to unravel charge transport characteristics of a metal-molecule-metal junction containing an individual π-conjugated molecule. The model system of our choice is an oligo(phenylene-ethynylene) consisting of three rings, in short OPE3, which represents a paradigmatic model system for molecular-scale electronics. Members of the OPE family are among the most studied in the field thanks to their simple and rigid structure, the possibility of chemically functionalizing them, and their clear transport characteristics. When investigating charge transport in molecular systems, two general directions can be distinguished: one in which assemblies composed of many molecules contacted in parallel are studied, while in the other a single molecule is investigated at a time. In the former approach, molecule-molecule interactions and ensemble-averaged quantities may play a role, thereby introducing broadening of spectral features and hindering the study of the behavior of individual molecules making it more difficult to deconvolute local and intrinsic molecular effects from collective ones. In contrast, single-molecule experiments directly probe individual molecular features and, when they are repeated many times, allow build up of a statistical representation of the changes introduced by, e.g., different junction configurations. Especially in recent years, experimental techniques have advanced such that now large sets of individual events can be measured and analyzed with statistical tools. To study individual single-molecule junctions, we use the break junction technique, in which two sharp movable electrodes are formed by breaking a thin metallic wire and used to contact a single or few molecules. By probing thousands of single-molecule junctions in different conditions, we show that their creation involves independent events justifying the statistical tools that are used. By combining room- and low-temperature data, we show that the dominant transport mechanism for electrons through the OPE3 molecule is off-resonant tunneling. The simplest model capturing transport details in this case is a single-level model characterized by three parameters: the level alignment of the frontier orbital with the Fermi energy of the leads and the electronic couplings to the leads. Variations in these parameters give a broad distribution (1 order of magnitude) in the observed conductance values, indicating that at the microscopic level both the hybridization with the metallic electrodes and the molecular electronic configuration can fluctuate. The low-temperature data show that these variations are due to abrupt changes in the configuration of the molecule in the junction leading to changes in either one of these parameters or both at the same time. The complementary information gained from different experiments is needed to build up a consistent and extended picture of the variability of molecular configurations, omnipresent in single-molecule studies. Knowledge of this variability can help one to better understand the behavior of molecules at the atomic level and at the metal-molecule interface in particular.