Wafer-Scale Two-Dimensional Semiconductors for Deep UV Sensing.

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.

Hydrogen-Induced Conversion of SnS2 into SnS or Sn: A Route to Create SnS2 /SnS Heterostructures.

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 SnS2 , where molecular hydrogen (H2 ) and H-ions induce a controlled chemical conversion into semiconducting-SnS or to ß-Sn. This hydrogen-driven reaction is facilitated by the different oxidation states of Sn and is successfully applied to form SnS2 /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.

Identifying carbon as the source of visible single-photon emission from hexagonal boron nitride.

Single-photon emitters (SPEs) in hexagonal boron nitride (hBN) have garnered increasing attention over the last few years due to their superior optical properties. However, despite the vast range of experimental results and theoretical calculations, the defect structure responsible for the observed emission has remained elusive. Here, by controlling the incorporation of impurities into hBN via various bottom-up synthesis methods and directly through ion implantation, we provide direct evidence that the visible SPEs are carbon related. Room-temperature optically detected magnetic resonance is demonstrated on ensembles of these defects. We perform ion-implantation experiments and confirm that only carbon implantation creates SPEs in the visible spectral range. Computational analysis of the simplest 12 carbon-containing defect species suggest the negatively charged [Formula: see text] defect as a viable candidate and predict that out-of-plane deformations make the defect environmentally sensitive. Our results resolve a long-standing debate about the origin of single emitters at the visible range in hBN and will be key to the deterministic engineering of these defects for quantum photonic devices.

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

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.

Lattice-Matched Epitaxial Graphene Grown on Boron Nitride.

Lattice-matched graphene on hexagonal boron nitride is expected to lead to the formation of a band gap but requires the formation of highly strained material and has not hitherto been realized. We demonstrate that aligned, lattice-matched graphene can be grown by molecular beam epitaxy using substrate temperatures in the range 1600-1710 °C and coexists with a topologically modified moiré pattern with regions of strained graphene which have giant moiré periods up to ∼80 nm. Raman spectra reveal narrow red-shifted peaks due to isotropic strain, while the giant moiré patterns result in complex splitting of Raman peaks due to strain variations across the moiré unit cell. The lattice-matched graphene has a lower conductance than both the Frenkel-Kontorova-type domain walls and also the topological defects where they terminate. We relate these results to theoretical models of band gap formation in graphene/boron nitride heterostructures.

Moiré-Modulated Conductance of Hexagonal Boron Nitride Tunnel Barriers.

Monolayer hexagonal boron nitride (hBN) tunnel barriers investigated using conductive atomic force microscopy reveal moiré patterns in the spatial maps of their tunnel conductance consistent with the formation of a moiré superlattice between the hBN and an underlying highly ordered pyrolytic graphite (HOPG) substrate. This variation is attributed to a periodc modulation of the local density of states and occurs for both exfoliated hBN barriers and epitaxially grown layers. The epitaxial barriers also exhibit enhanced conductance at localized subnanometer regions which are attributed to exposure of the substrate to a nitrogen plasma source during the high temperature growth process. Our results show clearly a spatial periodicity of tunnel current due to the formation of a moiré superlattice and we argue that this can provide a mechanism for elastic scattering of charge carriers for similar interfaces embedded in graphene/hBN resonant tunnel diodes.

Substrate-induced shifts and screening in the fluorescence spectra of supramolecular adsorbed organic monolayers.

We have investigated the influence of the substrate on the fluorescence of adsorbed organic molecules. Monolayer films of perylene-3,4,9,10-tetracarboxylic-3,4,9,10-diimide (PTCDI), a supramolecular network formed from PTCDI and melamine, and perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride have been deposited on hexagonal boron nitride (hBN). The principal peaks in the fluorescence spectra of these films were red-shifted by up to 0.37 eV relative to published measurements for molecules in helium droplets. Smaller shifts (∼0.03 eV) arising from interactions between neighbouring molecules are investigated by comparing the fluorescence of distinct arrangements of PTCDI, which are templated by supramolecular self-assembly and determined with molecular resolution using atomic force microscopy under ambient conditions. We compare our experimental results with red-shifts calculated using a combination of a perturbative model and density functional theory which account for, respectively, resonant and non-resonant effects of a dielectric hBN substrate. We show that the substrate gives rise to a red-shift in the fluorescence of an adsorbed molecule and also screens the interactions between neighbouring transition dipole moments; both these effects depend on the refractive index of the substrate.

Vernier templating and synthesis of a 12-porphyrin nano-ring.

Templates are widely used to arrange molecular components so they can be covalently linked into complex molecules that are not readily accessible by classical synthetic methods. Nature uses sophisticated templates such as the ribosome, whereas chemists use simple ions or small molecules. But as we tackle the synthesis of larger targets, we require larger templates-which themselves become synthetically challenging. Here we show that Vernier complexes can solve this problem: if the number of binding sites on the template, n(T), is not a multiple of the number of binding sites on the molecular building blocks, n(B), then small templates can direct the assembly of relatively large Vernier complexes where the number of binding sites in the product, n(P), is the lowest common multiple of n(B) and n(T) (refs 8, 9). We illustrate the value of this concept for the covalent synthesis of challenging targets by using a simple six-site template to direct the synthesis of a 12-porphyrin nano-ring with a diameter of 4.7 nm, thus establishing Vernier templating as a powerful new strategy for the synthesis of large monodisperse macromolecules.

Enhancement of CO2 Adsorption and Catalytic Properties by Fe-Doping of [Ga2(OH)2(L)] (H4L = Biphenyl-3,3',5,5'-tetracarboxylic Acid), MFM-300(Ga2).

Metal-organic frameworks (MOFs) are usually synthesized using a single type of metal ion, and MOFs containing mixtures of different metal ions are of great interest and represent a methodology to enhance and tune materials properties. We report the synthesis of [Ga2(OH)2(L)] (H4L = biphenyl-3,3',5,5'-tetracarboxylic acid), designated as MFM-300(Ga2), (MFM = Manchester Framework Material replacing NOTT designation), by solvothermal reaction of Ga(NO3)3 and H4L in a mixture of DMF, THF, and water containing HCl for 3 days. MFM-300(Ga2) crystallizes in the tetragonal space group I4122, a = b = 15.0174(7) Å and c = 11.9111(11) Å and is isostructural with the Al(III) analogue MFM-300(Al2) with pores decorated with -OH groups bridging Ga(III) centers. The isostructural Fe-doped material [Ga(1.87)Fe(0.13)(OH)2(L)], MFM-300(Ga(1.87)Fe(0.13)), can be prepared under similar conditions to MFM-300(Ga2) via reaction of a homogeneous mixture of Fe(NO3)3 and Ga(NO3)3 with biphenyl-3,3',5,5'-tetracarboxylic acid. An Fe(III)-based material [Fe3O(1.5)(OH)(HL)(L)(0.5)(H2O)(3.5)], MFM-310(Fe), was synthesized with Fe(NO3)3 and the same ligand via hydrothermal methods. [MFM-310(Fe)] crystallizes in the orthorhombic space group Pmn21 with a = 10.560(4) Å, b = 19.451(8) Å, and c = 11.773(5) Å and incorporates µ3-oxo-centered trinuclear iron cluster nodes connected by ligands to give a 3D nonporous framework that has a different structure to the MFM-300 series. Thus, Fe-doping can be used to monitor the effects of the heteroatom center within a parent Ga(III) framework without the requirement of synthesizing the isostructural Fe(III) analogue [Fe2(OH)2(L)], MFM-300(Fe2), which we have thus far been unable to prepare. Fe-doping of MFM-300(Ga2) affords positive effects on gas adsorption capacities, particularly for CO2 adsorption, whereby MFM-300(Ga(1.87)Fe(0.13)) shows a 49% enhancement of CO2 adsorption capacity in comparison to the homometallic parent material. We thus report herein the highest CO2 uptake (2.86 mmol g(-1) at 273 K at 1 bar) for a Ga-based MOF. The single-crystal X-ray structures of MFM-300(Ga2)-solv, MFM-300(Ga2), MFM-300(Ga2)·2.35CO2, MFM-300(Ga(1.87)Fe(0.13))-solv, MFM-300(Ga(1.87)Fe(0.13)), and MFM-300(Ga(1.87)Fe(0.13))·2.0CO2 have been determined. Most notably, in situ single-crystal diffraction studies of gas-loaded materials have revealed that Fe-doping has a significant impact on the molecular details for CO2 binding in the pore, with the bridging M-OH hydroxyl groups being preferred binding sites for CO2 within these framework materials. In situ synchrotron IR spectroscopic measurements on CO2 binding with respect to the -OH groups in the pore are consistent with the above structural analyses. In addition, we found that, compared to MFM-300(Ga2), Fe-doped MFM-300(Ga(1.87)Fe(0.13)) shows improved catalytic properties for the ring-opening reaction of styrene oxide, but similar activity for the room-temperature acetylation of benzaldehyde by methanol. The role of Fe-doping in these systems is discussed as a mechanism for enhancing porosity and the structural integrity of the parent material.

Adsorbate-induced curvature and stiffening of graphene.

The adsorption of the alkane tetratetracontane (TTC, C44H90) on graphene induces the formation of a curved surface stabilized by a gain in adsorption energy. This effect arises from a curvature-dependent variation of a moiré pattern due to the mismatch of the carbon-carbon separation in the adsorbed molecule and the period of graphene. The effect is observed when graphene is transferred onto a deformable substrate, which in our case is the interface between water layers adsorbed on mica and an organic solvent, but is not observed on more rigid substrates such as boron nitride. Our results show that molecular adsorption can be influenced by substrate curvature, provide an example of two-dimensional molecular self-assembly on a soft, responsive interface, and demonstrate that the mechanical properties of graphene may be modified by molecular adsorption, which is of relevance to nanomechanical systems, electronics, and membrane technology.

Surface-based supramolecular chemistry using hydrogen bonds.

CONSPECTUS: The arrangement of molecular species into extended structures remains the focus of much current chemical science. The organization of molecules on surfaces using intermolecular interactions has been studied to a lesser degree than solution or solid-state systems, and unanticipated observations still lie in store. Intermolecular hydrogen bonds are an attractive tool that can be used to facilitate the self-assembly of an extended structure through the careful design of target building blocks. Our studies have focused on the use of 3,4,9,10-perylene tetracarboxylic acid diimides (PTCDIs), and related functionalized analogues, to prepare extended arrays on surfaces. These molecules are ideal for such studies because they are specifically designed to interact with appropriate diaminopyridine-functionalized molecules, and related species, through complementary hydrogen bonds. Additionally, PTCDI species can be functionalized in the bay region of the molecule, facilitating modification of the self-assembled structures that can be prepared. Through a combination of PTCDI derivatives, sometimes in combination with melamine, porous two-dimensional arrays can be formed that can entrap guest molecules. The factors that govern the self-assembly processes of PTCDI derivatives are discussed, and the ability to construct suitable target arrays and host-specific molecular species, including fullerenes and transition metal clusters, is demonstrated.

Emergent rhombus tilings from molecular interactions with M-fold rotational symmetry.

We show that model molecules with particular rotational symmetries can self-assemble into network structures equivalent to rhombus tilings. This assembly happens in an emergent way, in the sense that molecules spontaneously select irregular fourfold local coordination from a larger set of possible local binding geometries. The existence of such networks can be rationalized by simple geometrical arguments, but the same arguments do not guarantee a network's spontaneous self-assembly. This class of structures must in certain regimes of parameter space be able to reconfigure into networks equivalent to triangular tilings.

Vernier-templated synthesis, crystal structure, and supramolecular chemistry of a 12-porphyrin nanoring.

Vernier templating exploits a mismatch between the number of binding sites in a template and a reactant to direct the formation of a product that is large enough to bind several template units. Here, we present a detailed study of the Vernier-templated synthesis of a 12-porphyrin nanoring. NMR and small-angle X-ray scattering (SAXS) analyses show that Vernier complexes are formed as intermediates in the cyclo-oligomerization reaction. UV/Vis/NIR titrations show that the three-component assembly of the 12-porphyrin nanoring figure-of-eight template complex displays high allosteric cooperativity and chelate cooperativity. This nanoring-template 1:2 complex is among the largest synthetic molecules to have been characterized by single-crystal analysis. It crystallizes as a racemate, with an angle of 27° between the planes of the two template units. The crystal structure reveals many unexpected intramolecular C-H⋅⋅⋅N contacts involving the tert-butyl side chains. Scanning tunneling microscopy (STM) experiments show that molecules of the 12-porphyrin template complex can remain intact on the gold surface, although the majority of the material unfolds into the free nanoring during electrospray deposition.

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 three-dimensional 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 with Monte 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 macromolecular aggregates offering a new route to solvent-induced control of two-dimensional supramolecular organization.

Cathodoluminescence spectroscopy of monolayer hexagonal boron nitride.

Cathodoluminescence (CL) spectroscopy is a suitable technique for studying the luminescent properties of optoelectronic materials because CL has no limitation on the excitable bandgap energy and eliminates ambiguous signals due to simple light scattering and resonant Raman scattering potentially involved in the photoluminescence spectra. However, direct CL measurements of atomically thin two-dimensional materials have been difficult due to the small excitation volume that interacts with high-energy electron beams. Herein, distinct CL signals from a monolayer hexagonal BN (hBN), namely mBN, epitaxial film grown on a graphite substrate are shown by using a CL system capable of large-area and surface-sensitive excitation. Spatially resolved CL spectra at 13 K exhibited a predominant 5.5-eV emission band, which has been ascribed to originate from multilayered aggregates of hBN, markedly at thicker areas formed on the step edges of the substrate. Conversely, a faint peak at 6.04 ± 0.01 eV was routinely observed from atomically flat areas, which is assigned as being due to the recombination of phonon-assisted direct excitons of mBN. The CL results support the transition from indirect bandgap in bulk hBN to direct bandgap in mBN. The results also encourage one to elucidate emission properties of other low-dimensional materials by using the present CL configuration.

Photosensitisation of inkjet printed graphene with stable all-inorganic perovskite nanocrystals.

All-inorganic perovskite nanocrystals (NCs) with enhanced environmental stability are of particular interest for optoelectronic applications. Here we report on the formulation of CsPbX3 (X is Br or I) inks for inkjet deposition and utilise these NCs as photosensitive layers in graphene photodetectors, including those based on single layer graphene (SLG) as well as inkjet-printed graphene (iGr) devices. The performance of these photodetectors strongly depends on the device structure, geometry and the fabrication process. We achieve a high photoresponsivity, R > 106 A W-1 in the visible wavelength range and a spectral response controlled by the halide content of the perovskite NC ink. By utilising perovskite NCs, iGr and gold nanoparticle inks, we demonstrate a fully inkjet-printed photodetector with R ≈ 20 A W-1, which is the highest value reported to date for this type of device. The performance of the perovskite/graphene photodetectors is explained by transfer of photo-generated charge carriers from the perovskite NCs into graphene and charge transport through the iGr network. The perovskite ink developed here enabled realisation of stable and sensitive graphene-based photon detectors. Compatibility of inkjet deposition with conventional Si-technologies and with flexible substrates combined with high degree of design freedom provided by inkjet deposition offers opportunities for partially and fully printed optoelectronic devices for applications ranging from electronics to environmental sciences.

Random and ordered phases of off-lattice rhombus tiles.

We study the covering of the plane by nonoverlapping rhombus tiles, a problem well studied only in the limiting case of dimer coverings of regular lattices. We go beyond this limit by allowing tiles to take any position and orientation on the plane, to be of irregular shape, and to possess different types of attractive interactions. Using extensive numerical simulations, we show that at large tile densities there is a phase transition from a fluid of rhombus tiles to a solid packing with broken rotational symmetry. We observe self-assembly of broken-symmetry phases, even at low densities, in the presence of attractive tile-tile interactions. Depending on the tile shape and interactions, the solid phase can be random, possessing critical orientational fluctuations, or crystalline. Our results suggest strategies for controlling tiling order in experiments involving "molecular rhombi."