High-entropy alloy screening for halide perovskites.

As the concept of high-entropy alloying (HEA) extends beyond metals, new materials screening methods are needed. Halide perovskites (HP) are a prime case study because greater stability is needed for photovoltaics applications, and there are 322 experimentally observed HP end-members, which leads to more than 1057 potential alloys. We screen HEAHP by first calculating the configurational entropy of 106 equimolar alloys with experimentally observed end-members. To estimate enthalpy at low computational cost, we turn to the delta-lattice parameter approach, a well-known method for predicting III-V alloy miscibility. To generalize the approach for non-cubic crystals, we introduce the parameter of unit cell volume coefficient of variation (UCV), which does a good job of predicting the experimental HP miscibility data. We use plots of entropy stabilization versus UCV to screen promising alloys and identify 102 HEAHP of interest.

Growth of Highly Oriented (VNbMoTaW)S2 Layers.

Compositional tunability, an indispensable parameter for modifying the properties of materials, can open up new applications for van der Waals (vdW) layered materials such as transition-metal dichalcogenides (TMDCs). To date, multielement alloy TMDC layers are obtained via exfoliation from bulk polycrystalline powders. Here, we demonstrate direct deposition of high-entropy alloy disulfide, (VNbMoTaW)S2, layers with controllable thicknesses on free-standing graphene membranes and on bare and hBN-covered Al2O3(0001) substrates via ultra-high-vacuum reactive dc magnetron sputtering of the VNbMoTaW target in Kr and H2S gas mixtures. Using a combination of density functional theory calculations, Raman spectroscopy, X-ray diffraction, scanning transmission electron microscopy coupled with energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy, we determine that the as-deposited layers are single-phase, 2H-structured, and 0001-oriented (V0.10Nb0.16Mo0.19Ta0.28W0.27)S2.44. Our synthesis route is general and applicable for heteroepitaxial growth of a wide variety of TMDC alloys and potentially other multielement alloy vdW compounds with the desired compositions.

Magnetotransport Signatures of Superconducting Cooper Pairs Carried by Topological Surface States in Bismuth Selenide.

As topological insulators (TIs) are becoming increasingly intriguing, the community is exploring transformative applications that require interfacing TIs with other materials such as ferromagnets or superconductors. Herein, we report on the manifestations of superconducting electrons carried by topological surface states (TSS) in Bi2Se3 films. As key signatures of TSS-carried Cooper pairs, we uncover the hysteresis of magnetoresistance (MR) and the switching behavior of anisotropic magnetoresistance (AMR). For in-plane fields perpendicular to the injected current, AMR shows negative switching (resistance drop) when the contacts become superconducting, which is consistent with a cooperative Zeeman effect enabled by the spin-momentum locking of TSS. The MR and AMR behaviors are robust, occurring reliably in multiple samples, from different sources, and with different defect concentrations. Our findings can guide novel developments in superconductor/TI quantum devices relying on supercurrent detection as well as lead to more refined transport signatures of Majorana zero-modes in the future.

Chirality and dislocation effects in single nanostructures probed by whispering gallery modes.

Nanostructures such as nanoribbons and -wires are of interest as components for building integrated photonic systems, especially if their basic functionality as dielectric waveguides can be extended by chiroptical phenomena or modifications of their optoelectronic properties by extended defects, such as dislocations. However, conventional optical measurements typically require monodisperse (and chiral) ensembles, and identifying emerging chiral optical activity or dislocation effects in single nanostructures has remained an unmet challenge. Here we show that whispering gallery modes can probe chirality and dislocation effects in single nanowires. Wires of the van der Waals semiconductor germanium(II) sulfide (GeS), obtained by vapor-liquid-solid growth, invariably form as growth spirals around a single screw dislocation that gives rise to a chiral structure and can modify the electronic properties. Cathodoluminescence spectroscopy on single tapered GeS nanowires containing joined dislocated and defect-free segments, augmented by numerical simulations and ab-initio calculations, identifies chiral whispering gallery modes as well as a pronounced modulation of the electronic structure attributed to the screw dislocation. Our results establish chiral light-matter interactions and dislocation-induced electronic modifications in single nanostructures, paving the way for their application in multifunctional photonic architectures.

Resolving the Subsurface Structure and Elastic Modulus of Layered Films via Contact Resonance Atomic Force Microscopy.

Since its discovery, atomic force microscopy (AFM) has become widely used for surface characterization, evolving from a tool for probing surface topography to a versatile method for characterizing mechanical, electrical, chemical, magnetic, and electro-optical properties of surfaces at the nanoscale. Developments of several AFM-based techniques have enabled even subsurface imaging, which is routinely being carried out at the qualitative level of feature detection for localized subsurface inhomogeneities. We surmise, however, that a quantitative three-dimensional (3D) subsurface characterization can emerge from the AFM mechanical response of flat buried interfaces, and present here a methodology for determining the depth of a film and its mechanical properties. Using load-dependent contact resonance atomic force microscopy (CR-AFM) and accurate modeling of the contact between the AFM tip and a layered sample, we determine the relationship between the measured resonance frequency of the AFM probe and the contact stiffness. Our subsequent statistical analysis reveals an intrinsic and sample-specific interdependence between the depth and modulus sensitivities of CR-AFM. This interdependence prevents the simultaneous accurate determination of both depth and modulus from measurements on a single-layered sample. If the elastic moduli of the sample components are predetermined from separate investigations of bulk samples (or otherwise known), then this methodology accurately yields the location of the interface between the layers of the sample; as such, it can serve as a nondestructive and robust technique for probing layer thickness, subsurface features, and elastic properties of materials used in semiconductor electronics, additive manufacturing, or biomaterials.

Doping of MoTe2 via Surface Charge Transfer in Air.

Doping is a key process by which the concentration and type of majority carriers can be tuned to achieve desired conduction properties. The common way of doping is via bulk impurities, as in the case of silicon. For van der Waals bonded semiconductors, control over bulk impurities is not as well developed, because they may either migrate between the layers or bond with the surfaces or interfaces becoming undesired scattering centers for carriers. Herein, we investigate by means of Kelvin probe force microscopy (KPFM) and density functional theory calculations (DFT) the doping of MoTe2 via surface charge transfer occurring in air. Using DFT, we show that oxygen molecules physisorb on the surface and increase its work function (compared to pristine surfaces) toward p-type behavior, which is consistent with our KPFM measurements. The surface charge transfer doping (SCTD) driven by adsorbed oxygen molecules can be easily controlled or reversed through thermal annealing of the entire sample. Furthermore, we also demonstrate local control of the doping by contact electrification. As a reversible and controllable nanoscale physisorption process, SCTD can thus open new avenues for the emerging field of 2D electronics.

Growth Kinetics of Two-Dimensional Hexagonal Boron Nitride Layers on Pd(111).

Using in situ variable-temperature scanning tunneling microscopy (300-673 K) during chemical vapor deposition of two-dimensional hexagonal boron nitride (hBN) on Pd(111) from borazine precursor at pressures up to 10-6 mbar, we identify the mechanisms leading to carpetlike uphill or downhill growth across the Pd steps. Deposition at a higher rate and lower temperature promotes uphill growth via preferential attachment at the ascending and descending step-edges, whereas a lower deposition rate and higher temperature lead to downhill growth via nucleation and growth of islands on Pd terraces. We attribute this unusual growth behavior to differences in temperature-dependent rates of hBN deposition at the steps versus on the Pd terraces. Our results illustrate how growth mechanisms can be activated by a pair of parameters (substrate temperature and partial pressure of borazine) and provide new insights into the mechanisms underlying carpetlike growth of hBN and other layered materials.

Recent Developments in Controlled Vapor-Phase Growth of 2D Group 6 Transition Metal Dichalcogenides.

An overview of recent developments in controlled vapor-phase growth of 2D transition metal dichalcogenide (2D TMD) films is presented. Investigations of thin-film formation mechanisms and strategies for realizing 2D TMD films with less-defective large domains are of central importance because single-crystal-like 2D TMDs exhibit the most beneficial electronic and optoelectronic properties. The focus is on the role of the various growth parameters, including strategies for efficiently delivering the precursors, the selection and preparation of the substrate surface as a growth assistant, and the introduction of growth promoters (e.g., organic molecules and alkali metal halides) to facilitate the layered growth of (Mo, W)(S, Se, Te)2 atomic crystals on inert substrates. Critical factors governing the thermodynamic and kinetic factors related to chemical reaction pathways and the growth mechanism are reviewed. With modification of classical nucleation theory, strategies for designing and growing various vertical/lateral TMD-based heterostructures are discussed. Then, several pioneering techniques for facile observation of structural defects in TMDs, which substantially degrade the properties of macroscale TMDs, are introduced. Technical challenges to be overcome and future research directions in the vapor-phase growth of 2D TMDs for heterojunction devices are discussed in light of recent advances in the field.

Characterization of Elastic Modulus Across the (Al1-xScx)N System Using DFT and Substrate-Effect-Corrected Nanoindentation.

Knowledge of accurate values of elastic modulus of (Al1-xScx)N is required for design of piezoelectric resonators and related devices. Thin films of (Al1-xScx)N across the entire composition space are deposited and characterized. Accuracy of modulus measurements is improved and quantified by removing the influence of substrate effects and by direct comparison of experimental results with density functional theory calculations. The 5%-30% Sc compositional range is of particular interest for piezoelectric applications and is covered at higher compositional resolution here than in previous work. The reduced elastic modulus is found to decrease by as much as 40% with increasing Sc concentration in the wurtzite phase according to both experimental and computational techniques, whereas Sc-rich rocksalt-structured films exhibit little variation in modulus with composition.

Carbon Capture by Metal Oxides: Unleashing the Potential of the (111) Facet.

Solid metal oxides for carbon capture exhibit reduced adsorption capacity following high-temperature exposure, due to surface area reduction by sintering. Furthermore, only low-coordinate corner/edge sites on the thermodynamically stable (100) facet display favorable binding toward CO2, providing inherently low capacity. The (111) facet, however, exhibits a high concentration of low-coordinate sites. In this work, MgO(111) nanosheets displayed high capacity for CO2, as well as a ∼65% increase in capacity despite a ∼30% reduction in surface area following sintering (0.77 mmol g-1 @ 227 m2 g-1 vs 1.28 mmol g-1 @ 154 m2 g-1). These results, unique to MgO(111), suggest intrinsic differences in the effects of sintering on basic site retention. Spectroscopic and computational investigations provided a new structure-activity insight: the importance of high-temperature activation to unleash the capacity of the polar (111) facet of MgO. In summary, we present the first example of a faceted sorbent for carbon capture and challenge the assumption that sintering is necessarily a negative process; here we leverage high-temperature conditions for facet-dependent surface activation.

Bias-Dependent Scanning Tunneling Microscopy Signature of Bridging-Oxygen Vacancies on Rutile TiO2(110).

The rutile TiO2(110) surface has long-served as a well-characterized, prototypical transition-metal oxide surface used in heterogeneous catalysis and photocatalytic water splitting. Naturally occurring defects on this surface, called bridging-oxygen (BO) vacancies, are important as they determine the overall reactivity of the surface. Herein, we report a bias-dependent, scanning tunneling microscopy (STM) signature of the BO vacancies on TiO2(110): for sample bias voltages past a threshold of +3 V, the bright vacancies are flanked on either side (along the oxygen row) by two dark spots approximately shaped like half-moons. The BO vacancies have a bright aspect below the threshold bias also but are not surrounded by half-moon dark depressions. Using generalized gradient approximation calculations with Hubbard correction (GGA + U) for projected density of states (DOS) and simulated STM images, we find that the bias-dependent STM signature originates from (i) local DOS maxima of all BOs (lighter background that occurs above the threshold bias) and (ii) the increased separation between the first and second BO atoms neighboring the vacancy which leads to an apparent dip between these neighboring oxygens. These results offer a new striking example of the STM signature that appears without switching the polarity of the bias. Similar approaches can be employed for seeking distinguishing features on the surfaces of other large band gap semiconductors and insulators.

Heterogeneous Pyrolysis: A Route for Epitaxial Growth of hBN Atomic Layers on Copper Using Separate Boron and Nitrogen Precursors.

Growth of hBN on metal substrates is often performed via chemical vapor deposition from a single precursor (e.g., borazine) and results in hBN monolayers limited by the substrates catalyzing effect. Departing from this paradigm, we demonstrate close control over the growth of mono-, bi-, and trilayers of hBN on copper using triethylborane and ammonia as independent sources of boron and nitrogen. Using density functional theory (DFT) calculations and reactive force field molecular dynamics, we show that the key factor enabling the growth beyond the first layer is the activation of ammonia through heterogeneous pyrolysis with boron-based radicals at the surface. The hBN layers grown are in registry with each other and assume a perfect or near perfect epitaxial relation with the substrate. From atomic force microscopy (AFM) characterization, we observe a moiré superstructure in the first hBN layer with an apparent height modulation and lateral periodicity of ∼10 nm. While this is unexpected given that the moiré pattern of hBN/Cu(111) does not have a significant morphological corrugation, our DFT calculations reveal a spatially modulated interface dipole layer which determines the unusual AFM response. These findings have improved our understanding of the mechanisms involved in growth of hBN and may help generate new growth methods for applications in which control over the number of layers and their alignment is crucial (such as tunneling barriers, ultrathin capacitors, and graphene-based devices).

Nanoscale Buckling of Ultrathin Low-k Dielectric Lines during Hard-Mask Patterning.

Commonly known in macroscale mechanics, buckling phenomena are now also encountered in the nanoscale world as revealed in today's cutting-edge fabrication of microelectronics. The description of nanoscale buckling requires precise dimensional and elastic moduli measurements, as well as a thorough understanding of the relationships between stresses in the system and the ensuing morphologies. Here, we analyze quantitatively the buckling mechanics of organosilicate fins that are capped with hard masks in the process of lithographic formation of deep interconnects. We propose an analytical model that quantitatively describes the morphologies of the buckled fins generated by residual stresses in the hard mask. Using measurements of mechanical properties and geometric characteristics, we have verified the predictions of the analytical model for structures with various degrees of buckling, thus putting forth a framework for guiding the design of future nanoscale interconnect architectures.

Shape-directional growth of Pt and Pd nanoparticles.

The design and synthesis of shape-directed nanoscale noble metal particles have attracted much attention due to their enhanced catalytic properties and the opportunities to study fundamental aspects of nanoscale systems. As such, numerous methods have been developed to synthesize crystals with tunable shapes, sizes, and facets by adding foreign species that promote or restrict growth on specific sites. Many hypotheses regarding how and why certain species direct growth have been put forward, however there has been no consensus on a unifying mechanism of nanocrystal growth. Herein, we develop and demonstrate the capabilities of a mathematical growth model for predicting metal nanoparticle shapes by studying a well known procedure that employs AgNO3 to produce {111} faceted Pt nanocrystals. The insight gained about the role of auxiliary species is then utilized to predict the shape of Pd nanocrystals and to corroborate other shape-directing syntheses reported in literature. The fundamental understanding obtained herein by combining modeling with experimentation is a step toward computationally guided syntheses and, in principle, applicable to predictive design of the growth of crystalline solids at all length scales (nano to bulk).

Self-assembly of collagen on flat surfaces: the interplay of collagen-collagen and collagen-substrate interactions.

Fibrillar collagens, common tissue scaffolds in live organisms, can also self-assemble in vitro from solution. While previous in vitro studies showed that the pH and the electrolyte concentration in solution largely control the collagen assembly, the physical reasons why such control could be exerted are still elusive. To address this issue and to be able to simulate self-assembly over large spatial and temporal scales, we have developed a microscopic model of collagen with explicit interactions between the units that make up the collagen molecules, as well as between these units and the substrate. We have used this model to investigate assemblies obtained via molecular dynamics deposition of collagen on a substrate at room temperature using an implicit solvent. By comparing the morphologies from our molecular dynamics simulations with those from our atomic-force microscopy experiments, we have found that the assembly is governed by the competition between the collagen-collagen interactions and those between collagen and the substrate. The microscopic model developed here can serve for guiding future experiments that would explore new regions of the parameter space.

Site-dependent activity of atomic Ti catalysts in Al-based hydrogen storage materials.

Doping catalytically inactive materials with dispersed atoms of an active species is a promising route toward realizing ultradilute binary catalyst systems. Beyond catalysis, strategically placed metal atoms can accelerate a wide range of solid-state reactions, particularly in hydrogen storage processes. Here we analyze the role of atomic Ti catalysts in the hydrogenation of Al-based hydrogen storage materials. We show that Ti atoms near the Al surface activate gas-phase H(2), a key step toward hydrogenation. By controlling the placement of Ti, we have found that the overall reaction, comprising H(2) dissociation and H spillover onto the Al surface, is governed by a pronounced trade-off between lowering of the H(2) dissociation barrier and trapping of the products near the active site, with a sharp maximum in the overall activity for Ti in the subsurface layer. Our findings demonstrate the importance of controlling the placement of the active species in optimizing the activity of dilute binary systems.

Real-time microscopy of graphene growth on epitaxial metal films: role of template thickness and strain.

Epitaxial transition metal films have recently been introduced as substrates for the scalable synthesis of transferable graphene. Here, real-time microscopy is used to study graphene growth on epitaxial Ru films on sapphire. At high temperatures, high-quality graphene grows in macroscopic (>100 µm) domains to full surface coverage. Graphene nucleation and growth characteristics on thin (100 nm) Ru films are consistent with a pure surface chemical vapor deposition process, without detectable contributions from C segregation. Experiments on thicker (1 µm) films show a systematic suppression of the C uptake into the metal to levels substantially below those expected from bulk C solubility data, consistent with a strain-induced reduction of the C solubility due to gas bubbles acting as stressors in the epitaxial Ru films. The results identify two powerful approaches--i) limiting the template thickness and ii) tuning the interstitial C solubility via strain--for controlling graphene growth on metals with high C solubility, such as Ru, Pt, Rh, Co, and Ni.

In situ gas-phase hydrosilylation of plasma-synthesized silicon nanocrystals.

Surface passivation of semiconductor nanocrystals (NCs) is critical in enabling their utilization in novel optoelectronic devices, solar cells, and biological and chemical sensors. Compared to the extensively used liquid-phase NC synthesis and passivation techniques, gas-phase routes provide the unique opportunity for in situ passivation of semiconductor NCs. Herein, we present a method for in situ gas-phase organic functionalization of plasma-synthesized, H-terminated silicon (Si) NCs. Using real-time in situ attenuated total reflection Fourier transform IR spectroscopy, we have studied the surface reactions during hydrosilylation of Si NCs at 160 °C. First, we show that, during gas-phase hydrosilylation of Si NCs using styrene (1-alkene) and acetylene (alkyne), the reaction pathways of the alkenes and alkynes chemisorbing onto surface SiH(x) (x = 1-3) species are different. Second, utilizing this difference in reactivity, we demonstrate a novel pathway to enhance the surface ligand passivation of Si NCs via in situ gas-phase hydrosilylation using the combination of a short-chain alkyne (acetylene) and a long-chain 1-alkene (styrene). The quality of surface passivation is further validated through IR and photoluminescence measurements of Si NCs exposed to air.

Experimental and DFT studies of gold nanoparticles supported on MgO(111) nano-sheets and their catalytic activity.

A wet chemical preparation of MgO with the (111) facet as the primary surface has recently been reported and with alternating layers of oxygen anions and magnesium cations, this material shows unique chemical and physical properties. The potential to utilize the MgO(111) surface for the immobilization of metal particles is intriguing because the surface itself offers a very different environment for the metal particle with an all oxygen interface, as opposed to the typical (100) facet that possesses alternating oxygen anion and magnesium cation sites on the surface. Gold nanoparticles have demonstrated a broad range of interesting catalytic properties, but are often susceptible to aggregation at high temperatures and are very sensitive to substrate effects. Here, we investigate gold-supported on MgO(111) nanosheets as a catalyst system for the aerobic oxidation of benzyl alcohol. Gold nanoparticles deposited on MgO(111) show an increased level of activity in the solvent-free benzyl alcohol aerobic oxidation as compared to gold nanoparticles deposited on a typical MgO aerogel. TEM studies reveal that the gold nanoparticles have a hemispherical shape while sitting on the main surface of MgO(111) nanosheets, with a large Au-MgO interface. Given that the gold nanoparticles deposited on the two types of MgO have similar size, and that the two types of unmodified MgO show almost the same activities in the blank reaction, we infer that the high activity of Au/MgO(111) is due to the properties of the (111) support and/or those of the gold-support interface. To understand the binding of Au on low-index MgO surfaces and the charge distribution at the surface of the support, we have performed density functional theory (DFT) calculations on all low-index MgO substrates (with and without gold), using a model Au(10) cluster. Due to similar lattice constants of Au(111) and MgO(111) planes, the Au cluster retains its structural integrity and binds strongly on MgO(111) with either oxygen or magnesium termination. Furthermore, we have found that for the (001) and (110) substrates the charges of the ions in the top surface layer have similar values as in bulk MgO, but that on (111) surfaces these charges are significantly different. This difference in surface charge determines the direction of the electronic transfer upon adsorption of gold, such transfer occurring so as to restore the bulk MgO charge values. Using the results from theoretical calculations, we provide an explanation of our observations of increased catalytic activity in the case of the Au/MgO(111) system.

Moiré superstructures of graphene on faceted nickel islands.

Using scanning tunneling microscopy and spectroscopy, in combination with density functional theory calculations, we investigated the morphology and electronic structure of monolayer graphene grown on the (111) and (110) facets of three-dimensional nickel islands on highly oriented pyrolytic graphite substrate. We observed graphene domains exhibiting hexagonal and striped moiré patterns with periodicities of 22 and 12 Å, respectively, on (111) and (110) facets of the Ni islands. Graphene domains are also observed to grow, as single crystals, across adjacent facets and over facet boundaries. Scanning tunneling spectroscopy data indicate that the graphene layers are metallic on both Ni(111) and Ni(110), in agreement with the calculations. We attribute this behavior to a strong hybridization between the d-bands on Ni and the π-bands of carbon. Our findings point to the possibility of preparing large-area epitaxial graphene layers even on polycrystalline Ni substrates.