Ana M. Sanchez

Lateral heterojunctions within monolayer MoSe2–WSe2 semiconductors

Heterojunctions between three-dimensional (3D) semiconductors with different bandgaps are the basis of modern light-emitting diodes, diode lasers and high-speed transistors. Creating analogous heterojunctions between different 2D semiconductors would enable band engineering within the 2D plane and open up new realms in materials science, device physics and engineering. Here we demonstrate that seamless high-quality in-plane heterojunctions can be grown between the 2D monolayer semiconductors MoSe2 and WSe2. The junctions, grown by lateral heteroepitaxy using physical vapour transport, are visible in an optical microscope and show enhanced photoluminescence. Atomically resolved transmission electron microscopy reveals that their structure is an undistorted honeycomb lattice in which substitution of one transition metal by another occurs across the interface. The growth of such lateral junctions will allow new device functionalities, such as in-plane transistors and diodes, to be integrated within a single atomically thin layer.

Reducing carrier escape in the InAs/GaAs quantum dot intermediate band solar cell

Intermediate band solar cells (IBSCs) fabricated to date from In(Ga)As/GaAs quantum dot arrays (QD-IBSC) exhibit a quantum efficiency (QE) that extends to below bandgap energies. However, the production of sub-bandgap photocurrent relies often on the thermal and/or tunneling escape of carriers from the QDs, which is incompatible with preservation of the output voltage. In this work, we test the effectiveness of introducing a thick GaAs spacer in addition to an InAlGaAs strain relief layer (SRL) over the QDs to reduce carrier escape. From an analysis of the QE at different temperatures, it is concluded that escape via tunneling can be completely blocked under short-circuit conditions, and that carriers confined in QDs with an InAlGaAs SRL exhibit a thermal escape activation energy over 100 meV larger than in the case of InAs QDs capped only with GaAs.

Growth of III-nitrides on Si(1 1 1) by molecular beam epitaxy: Doping, optical, and electrical properties

The growth of high-quality III-nitrides by plasma-assisted molecular beam epitaxy on Si(1 1 1) substrates is addressed. A combination of optimized AIN buffer layers and a two-step growth process leads to GaN layers of high crystal quality (8 arcmin X-ray diffraction full-width at half-maximum) and flat surfaces (57 A rms). Low-temperature luminescence spectra, dominated by excitonic emissions at 3.465 ± 0.002 eV, reveal the presence of a biaxial tensile strain of thermal origin. AlGaN layers, grown within the alloy range 0.10 < x < 0.76, have flat surfaces and exhibit strong excitonic luminescence. Si-doping of GaN and AlGaN produces n-type films reaching electron densities up to 2 × 10 19 and 8 × 10 19 cm -3 , respectively. From photoluminescence and Hall data analysis a Si-donor ionization energy between 50 and 60 meV is derived in GaN. The exciton bound to Si neutral donors at 3.445 eV redshifts while the c-axis lattice parameter decreases as the Si-doping increases, indicating an enhancement of the biaxial tensile strain in the film. This strain increase is a consequence of a strong reduction of the density of dislocations reaching the free surface, due to a particular grain size and orientation governed by the presence of Si donors. Be-doping is also achieved on GaN giving the shallowest acceptor activation energy reported so far, around 90-100 meV. However, there is a severe limitation of the Be incorporation on substitutional sites, leading to the formation of complex, deep defects.

Room temperature emission at 1.6μm from InGaAs quantum dots capped with GaAsSb

Room temperature photoluminescence at 1.6μm is demonstrated from InGaAs quantum dots capped with an 8nm GaAsSb quantum well. Results obtained from various sample structures are compared, including samples capped with GaAs. The observed redshift in GaAsSb capped samples is attributed to a type II band alignment and to a beneficial modification of growth kinetics during capping due to the presence of Sb. The sample structure is discussed on the basis of transmission electron microscopy results.

Structural reorganization of cylindrical nanoparticles triggered by polylactide stereocomplexation

Co-crystallization of polymers with different configurations/tacticities provides access to materials with enhanced performance. The stereocomplexation of isotactic poly(L-lactide) and poly(D-lactide) has led to improved properties compared with each homochiral material. Herein, we report the preparation of stereocomplex micelles from a mixture of poly(L-lactide)-b-poly(acrylic acid) and poly(D-lactide)-b-poly(acrylic acid) diblock copolymers in water via crystallization-driven self-assembly. During the formation of these stereocomplex micelles, an unexpected morphological transition results in the formation of dense crystalline spherical micelles rather than cylinders. Furthermore, mixture of cylinders with opposite homochirality in either THF/H2O mixtures or in pure water at 65 °C leads to disassembly into stereocomplexed spherical micelles. Similarly, a transition is also observed in a related PEO-b-PLLA/PEO-b-PDLA system, demonstrating wider applicability. This new mechanism for morphological reorganization, through competitive crystallization and stereocomplexation and without the requirement for an external stimulus, allows for new opportunities in controlled release and delivery applications.

Physical Vapor Deposition of Metal Nanoparticles on Chemically Modified Graphene: Observations on Metal–Graphene Interactions

The growth of metallic nanoparticles formed on chemically modified graphene (CMG) by physical vapor deposition is investigated. Fine control over the size (down to ∼1.5 nm for Au) and coverage (up to 5 × 10(4) μm(-2) for Au) of nanoparticles can be achieved. Analysis of the particle size distributions gives evidence for Au nanocluster diffusion at room temperature, while particle size statistics differ clearly between metal deposited on single- and multilayer regions. The morphology of the nanoparticles varies markedly for different metals (Ag, Au, Fe, Pd, Pt, Ti), from a uniform thin film for Ti to a droplet-like growth for Ag. A simple model explains these morphologies, based only on consideration of 1) the different energy barriers to surface diffusion of metal adatoms on graphene, and 2) the ratio of the bulk cohesive energy of the metal to the metal-graphene binding energy. Understanding these interactions is important for controlling nanoparticle and thin-film growth on graphene, and for understanding the resultant charge transfer between metal and graphene.

Weak mismatch epitaxy and structural feedback in graphene growth on copper foil

AbstractGraphene growth by low-pressure chemical vapor deposition on low cost copper foils shows great promise for large scale applications. It is known that the local crystallography of the foil influences the graphene growth rate. Here we find an epitaxial relationship between graphene and copper foil. Interfacial restructuring between graphene and copper drives the formation of (n10) facets on what is otherwise a mostly Cu(100) surface, and the facets in turn influence the graphene orientations from the onset of growth. Angle resolved photoemission shows that the electronic structure of the graphene is decoupled from the copper indicating a weak interaction between them. Despite this, two preferred orientations of graphene are found, ±8° from the Cu[010] direction, creating a non-uniform distribution of graphene grain boundary misorientation angles. Comparison with the model system of graphene growth on single crystal Cu(110) indicates that this orientational alignment is due to mismatch epitaxy. Despite the differences in symmetry the orientation of the graphene is defined by that of the copper. We expect these observations to not only have importance for controlling and understanding the growth process for graphene on copper, but also to have wider implications for the growth of two-dimensional materials on low cost metal substrates.

A simple approach to characterizing block copolymer assemblies: graphene oxide supports for high contrast multi-technique imaging.

Block copolymers are well-known to self-assemble into a range of 3-dimensional morphologies. However, due to their nanoscale dimensions, resolving their exact structure can be a challenge. Transmission electron microscopy (TEM) is a powerful technique for achieving this, but for polymeric assemblies chemical fixing/staining techniques are usually required to increase image contrast and protect specimens from electron beam damage. Graphene oxide (GO) is a robust, water-dispersable, and nearly electron transparent membrane: an ideal support for TEM. We show that when using GO supports no stains are required to acquire high contrast TEM images and that the specimens remain stable under the electron beam for long periods, allowing sample analysis by a range of electron microscopy techniques. GO supports are also used for further characterization of assemblies by atomic force microscopy. The simplicity of sample preparation and analysis, as well as the potential for significantly increased contrast background, make GO supports an attractive alternative for the analysis of block copolymer assemblies.

The effect of Si doping on the defect structure of GaN/AlN/Si(111)

The effect of Si doping on the structural quality of wurtzite GaN layers grown by molecular beam epitaxy on AlN buffered (111) Si substrates is studied. The planar defect density in the grown GaN layer strongly increases with Si doping. The dislocation density at the free surface of GaN significantly decreases when Si doping overpasses a limit value. Si doping affects the misorientation of the subgrains that constitutes the mosaic structure of GaN. The increase of the planar defect density and out-plane misorientation angles of the GaN subgrains with Si doping explain the decrease of dislocations that reach the free surface of GaN. A redshift in the photoluminescence spectra together with a decrease in the c-axis lattice parameter as the Si doping increases point to an increase in the residual biaxial tensile strain in the GaN samples.

Exploiting nucleobase-containing materials – from monomers to complex morphologies using RAFT dispersion polymerization

The synthesis of nucleobase-containing polymers was successfully performed by RAFT dispersion polymerization in both chloroform and 1,4-dioxane and self-assembly was induced by the polymerizations. A combination of scattering and microscopy techniques were used to characterize the morphologies. It is found that the morphologies of self-assembled nucleobase-containing polymers are solvent dependent. By varying the DP of the core-forming block, only spherical micelles with internal structures were obtained in chloroform when using only adenine-containing methacrylate or a mixture of adenine-containing methacrylate and thymine-containing methacrylate as monomers. However, higher order structures and morphology transitions were observed in 1,4-dioxane. A sphere-rod-lamella-twisted bilayer transition was observed in this study. Moreover, the kinetics of the dispersion polymerizations were studied in both solvents, suggesting a different formation mechanism in these systems.