Search

The exfoliation of two naturally occurring van der Waals minerals, graphite and molybdenite, arouse an unprecedented level of interest by the scientific community and shaped a whole new field of research: 2D materials research. Several years later, the family of van der Waals materials that can be exfoliated to isolate 2D materials keeps growing, but most of them are synthetic. Interestingly, in nature plenty of naturally occurring van der Waals minerals can be found with a wide range of chemical compositions and crystal structures whose properties are mostly unexplored so far. This Perspective aims to provide an overview of different families of van der Waals minerals to stimulate their exploration in the 2D limit., Comment: Perspective article. 34 pages, 10 figures, 1 table, more than 170 references

Metal halide perovskites are known to suffer from rapid degradation, limiting their direct applicability. Here, the degradation of phenethylammonium lead iodide (PEA2PbI4) two-dimensional perovskites under ambient conditions is studied using fluorescence, absorbance and fluorescence lifetime measurements. It is demonstrated that a long-term stability of two-dimensional perovskites can be achieved through the encapsulation with hexagonal boron nitride. While un-encapsulated perovskite flakes degrade within hours, the encapsulated perovskites are stable for at least three months. In addition, encapsulation considerably improves the stability under laser irradiation. The environmental stability, combined with the improved durability under illumination, is a critical ingredient for thorough spectroscopic studies of the intrinsic opto-electronic properties of this material platform., Comment: 10 pages, 4 figures, and supporting information

We fabricate large-area atomically thin MoS$_2$ layers through the direct transformation of crystalline molybdenum MoS$_2$ (MoO$_3$) by sulfurization at relatively low temperatures. The obtained MoS2 sheets are polycrystalline (~10-20 nm single-crystal domain size) with areas of up to 300x300 um$^2$ with 2-4 layers in thickness and show a marked p-type behaviour. The synthesized films are characterized by a combination of complementary techniques: Raman spectroscopy, X-ray diffraction, transmission electron microscopy and electronic transport measurements., Comment: 6 figures in main text, 2 figures in supp. info

The exploration of electronic and optoelectronic properties of two-dimensional (2D) materials has become one of the most attractive line of research since the isolation of graphene. Such 'all-surface materials' present a strong sensitivity to environmental conditions and thus characterization of the devices based on these materials usually requires measurement systems operating in high-vacuum. However, conventional optoelectronic probe-station testing systems are are not compatible with high vacuum operation and vacuum-compatible versions are rather expensive. Here, we present a high-vacuum system specifically designed to test electronic and optoelectronic devices based on 2D materials. This system can be implemented with low budget and it is mostly based on the assembly of commercially available standard vacuum and optic components. Despite the simplicity of this system we demonstrate full capabilities to characterize optoelectronic devices in a broad range of wavelengths with fast pumping/venting speed and possibility of modulating the device temperature (room temperature to ~150deg)., Comment: Tables including all the part-numbers to replicate the setup are provided

The isolation of air-sensitive two-dimensional (2D) materials and the race to achieve a better control of the interfaces in van der Waals heterostructures has pushed the scientific community towards the development of experimental setups that allow to exfoliate and transfer 2D materials under inert atmospheric conditions. These systems are typically based on over pressurized N2 of Ar gloveboxes that require the use of very thick gloves to operate within the chamber or the implementation of several motorized micro-manipulators. Here, we set up a deterministic transfer system for 2D materials within a gloveless anaerobic chamber. Unlike other setups based on over-pressurized gloveboxes, in our system the operator can manipulate the 2D materials within the chamber with bare hands. This experimental setup allows us to exfoliate 2D materials and to deterministically place them at a desired location with accuracy in a controlled O2-free and very low humidity (<2% RH) atmosphere. We illustrate the potential of this system to work with air-sensitive 2D materials by comparing the stability of black phosphorus and perovskite flakes inside and outside the anaerobic chamber., Comment: 6 main text figures, 7 supp. info. figures. 1 main text table with all the part numbers needed to assemble the setup

The successful application of titanium oxide-graphene hybrids in the fields of photocatalysis, photovoltaics and photodetection strongly depends on the interfacial contact between both materials. The need to provide a good coupling between the enabling conductor and the photoactive phase prompted us to directly grow conducting graphenic structures on TiO2 crystals. We here report on the direct synthesis of tailored graphenic structures by using Plasma Assisted Chemical Vapour Deposition that present a clean junction with the prototypical titanium oxide (110) surface. Chemical analysis of the interface indicates chemical bonding between both materials. Photocurrent measurements under UV light illumination manifest that the charge transfer across the interface is efficient. Moreover, the influence of the synthesis atmosphere, gas precursor (C2H2) and diluents (Ar, O2), on the interface and on the structure of the as-grown graphenic material is assessed. The inclusion of O2 promotes vertical growth of partially oxidized carbon nanodots/rods with controllable height and density. The deposition with Ar results in continuous graphenic films with low resistivity (6.8x10-6 ohm x m). The synthesis protocols developed here are suitable to produce tailored carbon-semiconductor structures on a variety of practical substrates as thin films, pillars or nanoparticles., Comment: 24 pages, 8 figures, original research paper

Here, we propose a method to determine the thickness of the most common transition metal dichalcogenides (TMDCs) placed on the surface of transparent stamps, used for the deterministic placement of two-dimensional materials, by analyzing the red, green and blue channels of transmission-mode optical microscopy images of the samples. In particular, the blue channel transmittance shows a large and monotonic thickness dependence, making it a very convenient probe of the flake thickness. The method proved to be robust given the small flake-to-flake variation and the insensitivity to doping changes of MoS2. We also tested the method for MoSe2, WS2 and WSe2. These results provide a reference guide to identify the number of layers of this family of materials on transparent substrates only using optical microscopy., Comment: 4 figures in main text, 2 figures in supp. info

Strain engineering, which aims to tune the bandgap of a semiconductor by the application of strain, has emerged as an interesting way to control the electrical and optical properties of two-dimensional (2D) materials. Apart from the changes in the intrinsic properties of 2D materials, the application of strain can be also used to modify the characteristics of devices based on them. In this work, we study flexible and transparent photodetectors based on single-layer MoS2 under the application of biaxial strain. We find that by controlling the level of strain, we can tune the photoresponsivity (by 2-3 orders of magnitude), the response time (from <80 ms to 1.5 s) and the spectral bandwidth (with a gauge factor of 135 meV/% or 58 nm/%) of the device., Comment: 3 main text figures and 12 supporting information figures

Spatially periodic structures with a long range period, referred to as moir\'e pattern, can be obtained in van der Waals bilayers in the presence of a small stacking angle or of lattice mismatch between the monolayers. Theoretical predictions suggest that the resulting spatially periodic variation of the band structure modifies the optical properties of both intra and interlayer excitons of transition metal dichalcogenides heterostructures. Here, we report on the impact of the moir\'e pattern formed in a MoSe$_2$/MoS$_2$ heterobilayer encapsulated in hexagonal boron nitride. The periodic in-plane potential results in a splitting of the MoSe$_2$ exciton and trion in both emission and absorption spectra. The observed energy difference between the split peaks is fully consistent with theoretical predictions., Comment: just accepted in Nano Letters (10.1021/acs.nanolett.8b03266)

Gallium selenide (GaSe) is a novel two-dimensional material, which belongs to the layered III-VIA semiconductors family and attracted interest recently as it displays single-photon emitters at room temperature and strong optical non-linearity. Nonetheless, few-layer GaSe is not stable under ambient conditions and it tends to degrade over time. Here we combine atomic force microscopy, Raman spectroscopy and optoelectronic measurements in photodetectors based on thin GaSe to study its long-term stability. We found that the GaSe flakes exposed to air tend to decompose forming firstly amorphous selenium and Ga2Se3 and subsequently Ga2O3. While the first stage is accompanied by an increase in photocurrent, in the second stage we observe a decrease in photocurrent which leads to the final failure of GaSe photodetectors. Additionally, we found that the encapsulation of the GaSe photodetectors with hexagonal boron nitride (h-BN) can protect the GaSe from degradation and can help to achieve long-term stability of the devices., Comment: 23 pages, 5 figures, supporting information

We study mechanically exfoliated nanosheets of franckeite by quantitative optical microscopy. The analysis of transmission mode and epi-illumination mode optical microscopy images provides a rapid method to estimate the thickness of the exfoliated flakes at first glance. A quantitative analysis of the optical contrast spectra by means of micro-reflectance allows one to determine the refractive index of franckeite in a broad range of the visible spectrum through a fit of the acquired spectra to a Fresnel law based model., Comment: Main text (6 figures) + Supp. Info. (6 figures)

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., Comment: Main text (3 Figures) and Supp. Info. (23 Figures)

Hybrid organic-inorganic perovskites, MAPbX3 (X= halogen), containing methylammonium (MA: CH3-NH3+) in the large voids conformed by the PbX6 octahedral network, are the active absorption materials in the new generation of solar cells. CH3NH3PbBr3 is a promising alternative with a large band-gap that gives rise to a high open circuit voltage. A deep knowledge of the crystal structure and, in particular, the MA conformation inside the perovskite cage across the phase transitions undergone below room temperature, seems essential to establish structure-property correlations that may drive to further improvements. The presence of protons requires the use of neutrons, combined with synchrotron XRD data that help to depict subtle symmetry changes undergone upon cooling. We present a consistent picture of the structural features of this fascinating material, in complement with photocurrent measurements from a photodetector device, demonstrating the potential of MAPbBr3 in optoelectronics., Comment: Authors' version of the peer-reviewed manuscript. 19 pages, 7 figures

Designer heterostructures can now be assembled layer-by-layer with unmatched precision thanks to the recently developed deterministic placement methods to transfer two-dimensional (2D) materials. This possibility constitutes the birth of a very active research field on the so-called van der Waals heterostructures. Moreover, these deterministic placement methods also open the door to fabricate complex devices, which would be otherwise very difficult to achieve by conventional bottom-up nanofabrication approaches, and to fabricate fully-encapsulated devices with exquisite electronic properties. The integration of 2D materials with existing technologies such as photonic and superconducting waveguides and fiber optics is another exciting possibility. Here, we review the state-of-the-art of the deterministic placement methods, describing and comparing the different alternative methods available in the literature and we illustrate their potential to fabricate van der Waals heterostructures, to integrate 2D materials into complex devices and to fabricate artificial bilayer structures where the layers present a user-defined rotational twisting angle., Comment: Tutorial Review, 13 figures. Authors' pre-peer review version of the article

Two-dimensional semiconducting materials are particularly appealing for many applications. Although theory predicts a large number of two-dimensional materials, experimentally only a few of these materials have been identified and characterized comprehensively in the ultrathin limit. Lead iodide, which belongs to the transition metal halides family and has a direct bandgap in the visible spectrum, has been known for a long time and has been well characterized in its bulk form. Nevertheless, studies of this material in the nanometer thickness regime are rather scarce. In this article we demonstrate an easy way to synthesize ultrathin, highly crystalline flakes of PbI2 by precipitation from a solution in water. We thoroughly characterize the produced thin flakes with different techniques ranging from optical and Raman spectros-copy to temperature-dependent photoluminescence and electron microscopy. We compare the results to ab initio calculations of the band structure of the material. Finally, we fabricate photodetectors based on PbI2 and study their optoelectronic properties., Comment: main text 20 pages + 10 figures, supporting information 16 pages + 17 figures

The fabrication of artificial materials by stacking of individual two-dimensional (2D) materials is amongst one of the most promising research avenues in the field of 2D materials. Moreover, this strategy to fabricate new man-made materials can be further extended by fabricating hybrid stacks between 2D materials and other functional materials with different dimensionality making the potential number of combinations almost infinite. Among all these possible combinations, mixing 2D materials with transition metal oxides can result especially useful because of the large amount of interesting physical phenomena displayed separately by these two material families. We present a hybrid device based on the stacking of a single layer MoS2 onto a lanthanum strontium manganite (La0.7Sr0.3MnO3) thin film, creating an atomically thin device. It shows a rectifying electrical transport with a ratio of 103, and a photovoltaic effect with Voc up to 0.4 V. The photodiode behaviour arises as a consequence of the different doping character of these two materials. This result paves the way towards combining the efforts of these two large materials science communities., Comment: 1 table, 4 figures (+9 supp. info. figures)

We present a method to carry out electrical and opto-electronic measurements on 2D materials using carbon fiber microprobes to directly make electrical contacts to the 2D materials without damaging them. The working principle of this microprobing method is illustrated by measuring transport in MoS2 flakes in vertical (transport in the out-of-plane direction) and lateral (transport within the crystal plane) configurations, finding performances comparable to those reported for MoS2 devices fabricated by conventional lithographic process. We also show that this method can be used with other 2D materials., Comment: 7 main text figures + 11 Supp. Info. figures. Total 25 pages

Optical spectroscopy techniques such as differential reflectance and transmittance have proven to be very powerful techniques to study 2D materials. However, a thorough description of the experimental setups needed to carry out these measurements is lacking in the literature. We describe a versatile optical microscope setup to carry out differential reflectance and transmittance spectroscopy in 2D materials with a lateral resolution of ~1 micron in the visible and near-infrared part of the spectrum. We demonstrate the potential of the presented setup to determine the number of layers of 2D materials and to characterize their fundamental optical properties such as excitonic resonances. We illustrate its performance by studying mechanically exfoliated and chemical vapor-deposited transition metal dichalcogenide samples., Comment: 5 main text figures + 1 table with all the part numbers to replicate the experimental setup + 4 supp. info. figures

In this work we study the optoelectronic properties of individual TiO2 fibres produced through coupled sol-gel and electrospinning, by depositing them onto pre-patterned Ti/Au electrodes on SiO2/Si substrates. Transport measurements in the dark give a conductivity above 2*10^-5 S, which increases up to 8*10^-5 S in vacuum. Photocurrent measurements under UV-irradiation show high sensitivity (responsivity of 90 A/W for 375 nm wavelength) and a response time to illumination of ~ 5 s, which is superior to state-of-the-art TiO2-based UV photodetectors. Both responsivity and response speed are higher in air than in vacuum, due to oxygen adsorbed on the TiO2 surface which traps photoexcited free electrons in the conduction band, thus reducing the recombination processes. The photodetectors are sensitive to light polarization, with an anisotropy ratio of 12%. These results highlight the interesting combination of large surface area and low 1D transport resistance in electrospun TiO2 fibres. The simplicity of the sol-gel/electrospinning synthesis method, combined with a fast response and high responsivity makes them attractive candidates for UV-photodetection in ambient conditions. We anticipate their high (photo) conductance is also relevant for photocatalysis and dye-sensitized solar cells., Comment: 29 pages, 5 figures in the main text, 9 figures in the Supporting Information. in J. Mater. Chem. C, 2016