Large-Area Intercalated Two-Dimensional Pb/Graphene Heterostructure as a Platform for Generating Spin-Orbit Torque.

A scalable platform to synthesize ultrathin heavy metals may enable high-efficiency charge-to-spin conversion for next-generation spintronics. Here, we report the synthesis of air-stable, epitaxially registered monolayer Pb underneath graphene on SiC (0001) by confinement heteroepitaxy (CHet). Diffraction, spectroscopy, and microscopy reveal that CHet-based Pb intercalation predominantly exhibits a mottled hexagonal superstructure due to an ordered network of Frenkel-Kontorova-like domain walls. The system's air stability enables ex situ spin torque ferromagnetic resonance (ST-FMR) measurements that demonstrate charge-to-spin conversion in graphene/Pb/ferromagnet heterostructures with a 1.5× increase in the effective field ratio compared to control samples.

Atomic Evolution Mechanism and Suppression of Edge Threading Dislocations in Nitride Remote Heteroepitaxy.

The majority of dislocations in nitride epilayers are edge threading dislocations (TDs), which diminish the performance of nitride devices. However, it is extremely difficult to reduce the edge TDs due to the lack of available slip systems. Here, we systematically investigate the formation mechanism of edge TDs and find that besides originating at the coalescence boundaries, these dislocations are also closely related to geometrical misfit dislocations at the interface. Based on this understanding, we propose a novel strategy to reduce the edge TD density of the GaN epilayer by nearly 1 order of magnitude via graphene-assisted remote heteroepitaxy. The first-principles calculations confirm that the insertion of graphene dramatically reduces the energy barrier required for interfacial sliding, which promotes a new strain release channel. This work provides a unique approach to directly suppress the formation of edge TDs at the source, thereby facilitating the enhanced performance of photoelectronic and electronic devices.

Expanded Stability of Layered SnSe-PbSe Alloys and Evidence of Displacive Phase Transformation from Rocksalt in Heteroepitaxial Thin Films.

Bulk PbSnSe has a two-phase region, or miscibility gap, as the crystal changes from a van der Waals-bonded orthorhombic 2D layered structure in SnSe-rich compositions to the related 3D-bonded rocksalt structure in PbSe-rich compositions. This structural transition drives a large contrast in the electrical, optical, and thermal properties. We realize low temperature direct growth of epitaxial PbSnSe thin films on GaAs via molecular beam epitaxy using an in situ PbSe surface treatment and show a significantly reduced two-phase region by stabilizing the Pnma layered structure out to Pb0.45Sn0.55Se, beyond the bulk limit around Pb0.25Sn0.75Se at low temperatures. Pushing further, we directly access metastable two-phase films of layered and rocksalt grains that are nearly identical in composition around Pb0.50Sn0.50Se and entirely circumvent the miscibility gap. We present microstructural and compositional evidence for an incomplete displacive transformation from a rocksalt to layered structure in these films, which we speculate occurs during the sample cooling to room temperature after synthesis. In situ temperature-cycling experiments on a Pb0.58Sn0.42Se rocksalt film reproduce characteristic attributes of a displacive transition and show a modulation in electronic properties. We find well-defined orientation relationships between the phases formed and reveal unconventional strain relief mechanisms involved in the crystal structure transformation using transmission electron microscopy. Overall, our work adds a scalable thin film integration route to harness the dramatic contrast in material properties in PbSnSe across a potentially ultrafast crystalline-crystalline structural transition.

Nanoscale-Confined Synthesis of 2D Metal Compounds for Electrochemical Applications.

2D metal compounds, such as transition metal dichalcogenides (TMDs), layered double hydroxides (LDHs), and MXenes, are emerging as important electrocatalyst materials in the transition to a sustainable energy future. Aided by their high surface area, electrical conductivity, and tunable electronic properties, these materials have provided a crucial research thrust in enhancing the efficiency of green hydrogen production, fuel cells, and carbon reduction processes. Most importantly, the synthesis of nanostructured 2D compounds, while challenging, is the key to optimizing their catalytic performance. Recent advancements in this field have highlighted the potential of 2D metal compounds in revolutionizing energy conversion technologies, which entails the discovery of new material compositions, the development of novel synthetic routes, and the integration of these materials into practical energy conversion systems. This review presents an overview of the distinctive characteristics of nanoscale-confined 2D metal compounds, the challenges encountered in their synthesis, and electrochemical applications.

Resurrected and Tunable Conductivity and Ferromagnetism in the Secondary Growth La0.7Ca0.3MnO3 on Transferred SrTiO3 Membranes.

To avoid the epitaxy dilemma in various thin films, such as complex oxide, silicon, organic, metal/alloy, etc., their stacking at an atomic level and secondary growth are highly desired to maximize the functionality of a promising electronic device. The ceramic nature of complex oxides and the demand for accurate and long-range-ordered stoichiometry face severe challenges. Here, the transport and magnetic properties of the La0.7Ca0.3MnO3 (LCMO) secondary growth on single-crystal freestanding SrTiO3 (STO) membranes are demonstrated. It has been experimentally found that on an only 10 nm thick STO membrane, the LCMO can offer a bulk-like Curie temperature (TC) of 253 K and negative magnetoresistance of -64%, with a weak dependence on the thickness. The resurrected conductivity and ferromagnetism in LCMO confirm the advantages of secondary growth, which benefits from the excellent flexibility and transferability. Additionally, this study explores the integration strategy of complex oxides with other functional materials.

Directed Self-Assembly of Oxide Nanocomposites by Ion-Beam Lithography.

Vertically aligned self-assembled nanocomposite films have provided a unique platform to study magnetoelectric effects and other forms of coupling between complex oxides. However, the distribution in the locations and sizes of the phase-separated nanostructures limits their utility. In this work, we demonstrate a process to template the locations of the self-assembled structure using ion lithography, which is effective for general insulating substrates. This process was used to produce a nanocomposite consisting of fin-shaped vertical nanostructures of ferroelectric BiFeO3 and ferrimagnetic CoFe2O4 with a feature size of 100 nm on (111)-oriented SrTiO3 substrates. Cross-sectional imaging of the three-phase perovskite-spinel-substrate epitaxial interface reveals the selective nucleation of CoFe2O4 in the trenches of the patterned substrate, and the magnetic domains of CoFe2O4 were manipulated by applying an external magnetic field.

Controlled Epitaxial Growth of (hk1)-Sb2Se3 Film on Cu9S5 Single Crystal via Post-Annealing Treatment for Photodetection Application.

Antimony selenide (Sb2Se3) is a promising semiconductor for photodetector applications due to its unique photovoltaic properties. Achieving optimal carrier transport in (001)-Sb2Se3 by the material of contacting substrate requires in-depth study. In this paper, the induced growth of Sb2Se3 films from (hk0) to (hk1) planes is achieved on digenite (Cu9S5) films by post-annealing treatment. The flake-like and flower-like morphologies on the surface of Sb2Se3 films are caused by different thicknesses of the Cu9S5 films, which are related to the (hk0) and (hk1) planes of Sb2Se3 surface. The epitaxial growth of Sb2Se3 films on (105)-Cu9S5 surfaces exhibits thickness dependence. The results inform research into the controlled induced growth of low-dimensional materials. The device of Sb2Se3/Cu9S5/Si has good broadband response (visible to near-infrared), self-powered characteristics, and stability. As the crystalline quality of the Sb2Se3 film increases along the (hk1) plane, the carrier transport is enhanced correspondingly. Under the 980 nm light irradiation, the device has an excellent switching ratio of 2 × 104 at 0 bias, with responsivity, detectivity, and response time up to 17 µA W-1, 1.48 × 107 Jones, and 355/490 µs, respectively. This suggests that Sb2Se3 is suitable for self-powered photodetectors and related optical and optoelectronic devices.

Atomic Layer Deposition and Strain Analysis of Epitaxial GaN-ZnO Core-Shell Nanowires.

We demonstrate the epitaxial coating of GaN NWs with an epitaxial ZnO shell by atomic layer deposition at 300 °C. Scanning transmission electron microscopy proves a sharp and defect-free coherent interface. The strain in the core-shell structure due to the lattice mismatch and different thermal expansion coefficients of GaN and ZnO was analyzed using 4D-STEM strain mapping and Raman spectroscopy and compared to theoretical calculations. The results highlight the outstanding advantages of epitaxial shell growth using atomic layer deposition, e.g., conformal coating and precise thickness control.

Freestanding Oxide Membranes for Epitaxial Ferroelectric Heterojunctions.

Since facile routes to fabricate freestanding oxide membranes were previously established, tremendous efforts have been made to further improve their crystallinity, and fascinating physical properties have been also reported in heterointegrated freestanding membranes. Here, we demonstrate our synthetic recipe to manufacture highly crystalline perovskite SrRuO3 freestanding membranes using new infinite-layer perovskite SrCuO2 sacrificial layers. To accomplish this, SrRuO3/SrCuO2 bilayer thin films are epitaxially grown on SrTiO3 (001) substrates, and the topmost SrRuO3 layer is chemically exfoliated by etching the SrCuO2 template layer. The as-exfoliated SrRuO3 membranes are mechanically transferred to various nonoxide substrates for the subsequent BaTiO3 film growth. Finally, freestanding heteroepitaxial junctions of ferroelectric BaTiO3 and metallic SrRuO3 are realized, exhibiting robust ferroelectricity. Intriguingly, the enhancement of piezoelectric responses is identified in freestanding BaTiO3/SrRuO3 heterojunctions with mixed ferroelectric domain states. Our approaches will offer more opportunities to develop heteroepitaxial freestanding oxide membranes with high crystallinity and enhanced functionality.

Thin-Film Organic Heteroepitaxy.

Incorporating crystalline organic semiconductors into electronic devices requires understanding of heteroepitaxy given the ubiquity of heterojunctions in these devices. However, while rules for commensurate epitaxy of covalent or ionic inorganic material systems are known to be dictated by lattice matching constraints, rules for heteroepitaxy of molecular systems are still being written. Here, it is found that lattice matching alone is insufficient to achieve heteroepitaxy in molecular systems, owing to weak intermolecular forces that describe molecular crystals. It is found that, in addition, the lattice matched plane also must be the lowest energy surface of the adcrystal to achieve one-to-one commensurate molecular heteroepitaxy over a large area. Ultraviolet photoelectron spectroscopy demonstrates the lattice matched interface to be of higher electronic quality than a disordered interface of the same materials.

Stability of Graphene and Influence of AlN Surface Pits on GaN Remote Heteroepitaxy for Exfoliation.

Remote epitaxy is a promising technology that has recently attracted considerable attention, which enables the growth of thin films that copy the crystallographic characteristics of the substrate through two-dimensional material interlayers. The grown films can be exfoliated to form freestanding membranes, although it is often challenging to apply this technique if the substrate materials are prone to damage under harsh epitaxy conditions. For example, remote epitaxy of GaN thin films on graphene/GaN templates has not been achieved by a standard metal-organic chemical vapor deposition (MOCVD) method due to such damages. Here, we report GaN remote heteroepitaxy on graphene/AlN templates by MOCVD and investigate the influence of surface pits in AlN on the growth and exfoliation of GaN thin films. We first show the thermal stability of graphene before GaN growth, based on which two-step growth of GaN on graphene/AlN is developed. The GaN samples are successfully exfoliated after the first step of the growth at 750 °C, whereas the exfoliation failed after the second step at 1050 °C. In-depth analysis confirms that the pits in AlN templates lead to the degradation of graphene near the area and thus the alteration of growth modes and the failure of exfoliation. These results exemplify the importance of chemical and topographic properties of growth templates for successful remote epitaxy. It is one of the key factors for III-nitride-based remote epitaxy, and these results are expected to be of great help in realizing complete remote epitaxy using only MOCVD.

The Heteroepitaxy of Thick ß-Ga2O3 Film on Sapphire Substrate with a ß-(AlxGa1-x)2O3 Intermediate Buffer Layer.

A high aluminum (Al) content ß-(AlxGa1-x)2O3 film was synthesized on c-plane sapphire substrate using the gallium (Ga) diffusion method. The obtained ß-(AlxGa1-x)2O3 film had an average thickness of 750 nm and a surface roughness of 2.10 nm. Secondary ion mass spectrometry results indicated the homogenous distribution of Al components in the film. The Al compositions in the ß-(AlxGa1-x)2O3 film, as estimated by X-ray diffraction, were close to those estimated by X-ray photoelectron spectroscopy, at ~62% and ~61.5%, respectively. The bandgap of the ß-(AlxGa1-x)2O3 film, extracted from the O 1s core-level spectra, was approximately 6.0 ± 0.1 eV. After synthesizing the ß-(AlxGa1-x)2O3 film, a thick ß-Ga2O3 film was further deposited on sapphire substrate using carbothermal reduction and halide vapor phase epitaxy. The ß-Ga2O3 thick film, grown on a sapphire substrate with a ß-(AlxGa1-x)2O3 buffer layer, exhibited improved crystal orientation along the (-201) plane. Moreover, the scanning electron microscopy revealed that the surface quality of the ß-Ga2O3 thick film on sapphire substrate with a ß-(AlxGa1-x)2O3 intermediate buffer layer was significantly improved, with an obvious transition from grain island-like morphology to 2D continuous growth, and a reduction in surface roughness to less than 10 nm.

Heteroepitaxy of 2D CuCr2 Te4 with Robust Room-temperature Ferromagnetism.

Magnetic materials in 2D have attracted widespread attention for their intriguing magnetic properties. 2D magnetic heterostructures can provide unprecedented opportunities for exploring fundamental physics and novel spintronic devices. Here, the heteroepitaxial growth of ferromagnetic CuCr2 Te4 nanosheets is reported on Cr2 Te3 and mica by chemical vapor deposition. Magneto-optical Kerr effect measurements reveal the thickness-dependent ferromagnetism of CuCr2 Te4 nanosheets on mica, where a decrease of Curie temperature (TC ) from 320 to 260 K and an enhancement of perpendicular magnetic anisotropy with reducing thickness are observed. Moreover, lattice-matched heteroepitaxial ultrathin CuCr2 Te4 on Cr2 Te3 exhibits an enhanced robust ferromagnetism with TC up to 340 K due to the interfacial charge transfer. Stripe-type magnetic domains and single magnetic domain are discovered in this heterostructure with different thicknesses. The work provides a way to construct robust room-temperature 2D magnetic heterostructures for functional spintronic devices.

Temperature cycling-induced formation of crystalline coatings.

The surface of particles is the hotspot of interaction with their environment and is therefore a major target for particle engineering. Particles with tailored coatings are greatly desired for a range of different applications. Amorphous coatings applied via film coating or microencapsulation have frequently been described in the pharmaceutical context and usually result in homogeneous surfaces. In the present study we have been exploring the feasibility of coating core particles with crystalline substances, a matter that has rarely been investigated. The expansion of the range of possible coating materials to include small organic molecules enables completely new product properties to be achieved. We present an approach based on temperature cycles performed in a tubular crystallizer to result in engineered crystalline coatings on excipient core particles. By manipulating the process settings and by the choice of coating substance we are able to tailor surface roughness, topography as well as surface chemistry. Benefits of our approach are demonstrated by using resulting particles as carriers in dry-powder-inhaler formulations. Depending on the resulting surface chemistry and surface roughness, coated carrier particles show varying fitness for delivering the model API salbutamol sulphate to the lung.

Heteroepitaxy Growth and Characterization of High-Quality AlN Films for Far-Ultraviolet Photodetection.

The ultra-wide bandgap (~6.2 eV), thermal stability and radiation tolerance of AlN make it an ideal choice for preparation of high-performance far-ultraviolet photodetectors (FUV PDs). However, the challenge of epitaxial crack-free AlN single-crystalline films (SCFs) on GaN templates with low defect density has limited its practical applications in vertical devices. Here, a novel preparation strategy of high-quality AlN films was proposed via the metal organic chemical vapor deposition (MOCVD) technique. Cross-sectional transmission electron microscopy (TEM) studies clearly indicate that sharp, crack-free AlN films in single-crystal configurations were achieved. We also constructed a p-graphene/i-AlN/n-GaN photovoltaic FUV PD with excellent spectral selectivity for the FUV/UV-C rejection ratio of >103, a sharp cutoff edge at 206 nm and a high responsivity of 25 mA/W. This work provides an important reference for device design of AlN materials for high-performance FUV PDs.

Multiscale Kinetic Monte Carlo Simulation of Self-Organized Growth of GaN/AlN Quantum Dots.

A three-dimensional kinetic Monte Carlo methodology is developed to study the strained epitaxial growth of wurtzite GaN/AlN quantum dots. It describes the kinetics of effective GaN adatoms on an hexagonal lattice. The elastic strain energy is evaluated by a purposely devised procedure: first, we take advantage of the fact that the deformation in a lattice-mismatched heterostructure is equivalent to that obtained by assuming that one of the regions of the system is subjected to a properly chosen uniform stress (Eshelby inclusion concept), and then the strain is obtained by applying the Green's function method. The standard Monte Carlo method has been modified to implement a multiscale algorithm that allows the isolated adatoms to perform long diffusion jumps. With these state-of-the art modifications, it is possible to perform efficiently simulations over large areas and long elapsed times. We have taylored the model to the conditions of molecular beam epitaxy under N-rich conditions. The corresponding simulations reproduce the different stages of the Stranski-Krastanov transition, showing quantitative agreement with the experimental findings concerning the critical deposition, and island size and density. The influence of growth parameters, such as the relative fluxes of Ga and N and the substrate temperature, is also studied and found to be consistent with the experimental observations. In addition, the growth of stacked layers of quantum dots is also simulated and the conditions for their vertical alignment and homogenization are illustrated. In summary, the developed methodology allows one to reproduce the main features of the self-organized quantum dot growth and to understand the microscopic mechanisms at play.

Nanopore-Patterned CuSe Drives the Realization of the PbSe-CuSe Lateral Heterostructure.

Monolayer PbSe has been predicted to be a two-dimensional (2D) topological crystalline insulator (TCI) with crystalline symmetry-protected Dirac-cone-like edge states. Recently, few-layered epitaxial PbSe has been grown on the SrTiO3 substrate successfully, but the corresponding signature of the TCI was only observed for films not thinner than seven monolayers, largely due to interfacial strain. Here, we demonstrate a two-step method based on molecular beam epitaxy for the growth of the PbSe-CuSe lateral heterostructure on the Cu(111) substrate, in which we observe a nanopore-patterned CuSe layer that acts as the template for lateral epitaxial growth of PbSe. This further results in a PbSe-CuSe lateral heterostructure with an atomically sharp interface. Scanning tunneling microscopy and spectroscopy measurements reveal a fourfold symmetric square lattice of such PbSe with a quasi-particle band gap of 1.8 eV, a value highly comparable with the theoretical value of freestanding PbSe. The weak monolayer-substrate interaction is further supported by both density functional theory (DFT) and projected crystal orbital Hamilton population, with the former predicting the monolayer's anti-bond state to reside below the Fermi level. Our work demonstrates a practical strategy to fabricate a high-quality in-plane heterostructure, involving a monolayer TCI, which is viable for further exploration of the topology-derived quantum physics and phenomena in the monolayer limit.

Atomic Mechanism of Strain Alleviation and Dislocation Reduction in Highly Mismatched Remote Heteroepitaxy Using a Graphene Interlayer.

Remote heteroepitaxy is known to yield semiconductor films with better quality. However, the atomic mechanisms in systems with large mismatches are still unclear. Herein, low-strain single-crystalline nitride films are achieved on highly mismatched (∼16.3%) sapphire via graphene-assisted remote heteroepitaxy. Because of a weaker interface potential, the in-plane compressive strain at the interface releases by 30%, and dislocations are prevented. Meanwhile, the lattice distortions in the epilayer disappear when the structure climbs over the atomic steps on substrates because graphene renders the steps smooth. In this way, the density of edge dislocations in as-grown nitride films reduces to the same level as that of the screw dislocations, which is rarely observed in heteroepitaxy. Further, the indium composition in InxGa1-xN/GaN multiquantum wells increases to ∼32%, enabling the fabrication of a yellow light-emitting diode. This study demonstrates the advantages of remote heteroepitaxy for bandgap tuning and opens opportunities for photoelectronic and electronic applications.

Review of Highly Mismatched III-V Heteroepitaxy Growth on (001) Silicon.

Si-based group III-V material enables a multitude of applications and functionalities of the novel optoelectronic integration chips (OEICs) owing to their excellent optoelectronic properties and compatibility with the mature Si CMOS process technology. To achieve high performance OEICs, the crystal quality of the group III-V epitaxial layer plays an extremely vital role. However, there are several challenges for high quality group III-V material growth on Si, such as a large lattice mismatch, highly thermal expansion coefficient difference, and huge dissimilarity between group III-V material and Si, which inevitably leads to the formation of high threading dislocation densities (TDDs) and anti-phase boundaries (APBs). In view of the above-mentioned growth problems, this review details the defects formation and defects suppression methods to grow III-V materials on Si substrate (such as GaAs and InP), so as to give readers a full understanding on the group III-V hetero-epitaxial growth on Si substrates. Based on the previous literature investigation, two main concepts (global growth and selective epitaxial growth (SEG)) were proposed. Besides, we highlight the advanced technologies, such as the miscut substrate, multi-type buffer layer, strain superlattice (SLs), and epitaxial lateral overgrowth (ELO), to decrease the TDDs and APBs. To achieve high performance OEICs, the growth strategy and development trend for group III-V material on Si platform were also emphasized.

Flexible Plasmonics Using Aluminum and Copper Epitaxial Films on Mica.

We demonstrate here the growth of aluminum (Al), copper (Cu), gold (Au), and silver (Ag) epitaxial films on two-dimensional, layered muscovite mica (Mica) substrates via van der Waals (vdW) heteroepitaxy with controllable film thicknesses from a few to hundreds of nanometers. In this approach, the mica thin sheet acts as a flexible and transparent substrate for vdW heteroepitaxy, which allows for large-area formation of atomically smooth, single-crystalline, and ultrathin plasmonic metals without the issue of film dewetting. The high-quality plasmonic metal films grown on mica enable us to design and fabricate well-controlled Al and Cu plasmonic nanostructures with tunable surface plasmon resonances ranging from visible to the near-infrared spectral region. Using these films, two kinds of plasmonic device applications are reported, including (1) plasmonic sensors with high effective index sensitivities based on surface plasmon interferometers fabricated on the Al/Mica film and (2) Cu/Mica nanoslit arrays for plasmonic color filters in the visible and near-infrared regions. Furthermore, we show that the responses of plasmonic nanostructures fabricated on the Mica substrates remain unaltered under large substrate bending conditions. Therefore, the metal-on-mica vdW heteroepitaxy platform is suitable for flexible plasmonics based on their bendable properties.