Photodiodes based in La0.7Sr0.3MnO3/single layer MoS2 hybrid vertical heterostructures

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

van der Waals-induced chromatic shifts in hydrogen-bonded two-dimensional porphyrin arrays on boron nitride

The fluorescence of a two-dimensional supramolecular network of 5,10,15,20-tetrakis(4-carboxylphenyl)porphyrin (TCPP) adsorbed on hexagonal boron nitride (hBN) is red shifted due to, primarily, adsorbate–substrate van der Waals interactions. TCPP is deposited from solution on hBN and forms faceted islands with typical dimensions of 100 nm and either square or hexagonal symmetry. The molecular arrangement is stabilized by in-plane hydrogen bonding as determined by a combination of molecular resolution atomic force microscopy performed under ambient conditions and density functional theory; a similar structure is observed on MoS2 and graphite. The fluorescence spectra of submonolayers of TCPP on hBN are red-shifted by ∼30 nm due to the distortion of the molecule arising from van der Waals interactions, in agreement with time-dependent density functional theory calculations. Fluorescence intensity variations are observed due to coherent partial reflections at the hBN interface, implying that such hybrid structures have potential in photonic applications

Triplet Excitation and Electroluminescence from a Supramolecular Monolayer Embedded in a Boron Nitride Tunnel Barrier

© 2019 American Chemical Society. We show that ordered monolayers of organic molecules stabilized by hydrogen bonding on the surface of exfoliated few-layer hexagonal boron nitride (hBN) flakes may be incorporated into van der Waals heterostructures with integral few-layer graphene contacts forming a molecular/two-dimensional hybrid tunneling diode. Electrons can tunnel through the hBN/molecular barrier under an applied voltage VSD, and we observe molecular electroluminescence from an excited singlet state with an emitted photon energy hν > eVSD, indicating upconversion by energies up to ∼1 eV. We show that tunneling electrons excite embedded molecules into singlet states in a two-step process via an intermediate triplet state through inelastic scattering and also observe direct emission from the triplet state. These heterostructures provide a solid-state device in which spin-triplet states, which cannot be generated by optical transitions, can be controllably excited and provide a new route to investigate the physics, chemistry, and quantum spin-based applications of triplet generation, emission, and molecular photon upconversion

Room temperature electroluminescence from mechanically formed van der Waals III–VI homojunctions and heterojunctions

Room temperature electroluminescence from semiconductor junctions is demonstrated. The junctions are fabricated by the exfoliation and direct mechanical adhesion of InSe and GaSe van der Waals layered crystals. Homojunction diodes formed from layers of p- and n-type InSe exhibit electroluminescence at energies close to the bandgap energy of InSe (Eg= 1.26 eV). In contrast, heterojunction diodes formed by combining layers of p-type GaSe and n-type InSe emit photons at lower energies, which is attributed to the generation of spatially indirect excitons and a staggered valence band lineup for the holes at the GaSe/InSe interface. These results demonstrate the technological potential of mechanically formed heterojunctions and homojunctions of direct-bandgap layered GaSe and InSe compounds with an optical response over an extended wavelength range, from the near-infrared to the visible spectrum

Ligand-induced control of photoconductive gain and doping in a hybrid graphene-quantum dot transistor

In graphene devices decorated with a layer of near-infrared colloidal PbS quantum dots (QDs), the choice of the QD capping ligands and the integrity of the QD layer have a strong influence on the doping, carrier mobility, and photoresponse. By using short (<1 nm) capping ligands, the photoresponsivity of the graphene devices is enhanced up to 109 A W−1

Ligand-induced control of photoconductive gain and doping in a hybrid graphene-quantum dot transistor

In graphene devices decorated with a layer of near-infrared colloidal PbS quantum dots (QDs), the choice of the QD capping ligands and the integrity of the QD layer have a strong influence on the doping, carrier mobility, and photoresponse. By using short (<1 nm) capping ligands, the photoresponsivity of the graphene devices is enhanced up to 109 A W−1

Fluorescence and Electroluminescence of J-Aggregated Polythiophene Monolayers on Hexagonal Boron Nitride

The photophysics of a semiconducting polymer is manipulated through molecular self-assembly on an insulating surface. Adsorption of polythiophene (PT) monolayers on hexagonal boron nitride (hBN) leads to a structurally induced planarization and a rebalancing of inter- and intrachain excitonic coupling. This conformational control results in a dominant 0–0 photoluminescence peak and a reduced Huang–Rhys factor, characteristic of J-type aggregates, and optical properties which are significantly different to both PT thin films and single polymer strands. Adsorption on hBN also provides a route to explore electroluminescence from PT monolayers though incorporation into hybrid van der Waals heterostructures whereby the polymer monolayer is embedded within a hBN tunnel diode. In these structures we observe up-converted singlet electroluminescence from the PT monolayer, with an excitation mechanism based upon inelastic electron scattering. We argue that surface adsorption provides a methodology for the study of fundamental optoelectronic properties of technologically relevant polymers

Highly responsive UV-photodetectors based on single electrospun TiO2 nanofibres

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, 201

Enhanced thermoelectricity in metal−[60]fullerene−graphene molecular junctions

The thermoelectric properties of molecular junctions consisting of a metal Pt electrode contacting [60]fullerene derivatives covalently bound to a graphene electrode have been studied by using a conducting-probe atomic force microscope (c-AFM). The [60]fullerene derivatives are covalently linked to the graphene via two meta-connected phenyl rings, two para-connected phenyl rings, or a single phenyl ring. We find that the magnitude of the Seebeck coefficient is up to nine times larger than that of Au-C60-Pt molecular junctions. Moreover, the sign of the thermopower can be either positive or negative depending on the details of the binding geometry and on the local value of the Fermi energy. Our results demonstrate the potential of using graphene electrodes for controlling and enhancing the thermoelectric properties of molecular junctions and confirm the outstanding performance of [60]fullerene derivativesThis work has been supported by the European Commission through FP7 ITN MOLESCO (Project Number 606728), the (MAD2D-CM)-UCM1-MRR project and through the EC H2020 FET Open Project Grant Agreement Number 767187 “QuIET”. The authors acknowledge support from the Spanish Ministry of Science and Innovation MCIN (Projects PID2020-114653RB-I00, PID2020-115120GB-I00, Centro de Excelencia Severo Ochoa SEV-2016-0686). L.R.-G. acknowledges support from Spanish MECD (Grant No. FPU14/03368) and, with N.A., funding from the Education and Research Council of the Comunidad de Madrid and the European Social Fund (ref. PEJD-2019-POST/IND-16353

Mechanical stiffening of porphyrin nanorings through supramolecular columnar stacking

Solvent-induced aggregates of nanoring cyclic polymers may be transferred by electrospray deposition to a surface where they adsorb as threedimensional columnar stacks. The observed stack height varies from single rings to four stacked rings with a layer spacing of 0.32 ± 0.04 nm as measured using scanning tunneling microscopy. The flexibility of the nanorings results in distortions from a circular shape, and we show, through a comparison withMonte Carlo simulations, that the bending stiffness increases linearly with the stack height. Our results show that noncovalent interactions may be used to control the shape and mechanical properties of artificial macromolecularaggregates offering a new route to solvent-induced control of two-dimensional supramolecular organization