Reflection High-energy Electron Diffraction Research Articles

Predicting and Accelerating Nanomaterial Synthesis Using Machine Learning Featurization.

Materials synthesis optimization is constrained by serial feedback processes that rely on manual tools and intuition across multiple siloed modes of characterization. We automate and generalize feature extraction of reflection high-energy electron diffraction (RHEED) data with machine learning to establish quantitatively predictive relationships in small sets (∼10) of expert-labeled data, saving significant time on subsequently grown samples. These predictive relationships are evaluated in a representative material system (W1-xVxSe2 on c-plane sapphire (0001)) with two aims: 1) predicting grain alignment of the deposited film using pregrowth substrate data and 2) estimating vanadium dopant concentration using in situ RHEED as a proxy for ex situ methods (e.g., X-ray photoelectron spectroscopy). Both tasks are accomplished using the same materials-agnostic features, avoiding specific system retraining and leading to a potential 80% time saving over a 100-sample synthesis campaign. These predictions provide guidance to avoid doomed trials, reduce follow-on characterization, and improve control resolution for materials synthesis.

Design of an atomic layer deposition system with in situ reflection high energy electron diffraction.

We report the design, fabrication, and testing of an atomic layer deposition (ALD) system that is capable of reflection high energy electron diffraction (RHEED) in a single chamber. The details and specifications of the system are described and include capabilities of RHEED at varied accelerating voltages, sample rotation (azimuthal) control, sample height control, sample heating up to set temperatures of 1050 °C, and either single- or dual-differential pumping designs. Thermal and flow simulations were used to justify selected system dimensions as well as carrier gas/precursor mass flow rates. Temperature calibration was conducted to determine actual sample temperatures that are necessary for meaningful analysis of thermally induced transitions in ALD thin films. Several demonstrations of RHEED in the system are described. Calibration of the camera length was conducted using a gold thin film by analyzing RHEED images. Finally, RHEED conducted at a series of increasing temperatures was used to monitor the crystallization of an ALD HfO2 thin film. The crystallization temperature and the ring pattern were consistent with the monoclinic structure as determined by separate x-ray diffraction-based measurements.

Mechanistic study of β-Ga2O3 nitridation by RF nitrogen plasma for GaN heteroepitaxy

The transformation of 2¯01β-Ga2O3 to h-GaN under exposure to RF nitrogen plasma was monitored in situ by reflection high-energy electron diffraction. Analysis of the reaction kinetics reveals that the nitridation process is initiated by the formation of an oxynitride phase and proceeds via two-dimensional nucleation and growth of wurtzite GaN grains. X-ray photoelectron spectra suggest a Ga−(NxO1−x) type configuration dominates the surface early in the nitridation process. The surface restructuring is followed by a diffusion-fed phase transformation, which propagates the wurzite GaN structure into the substrate upon reaching 70% nitrogen anion site occupation, corresponding to the oxygen solubility in h-GaN. A direct correlation is observed between the nitridated film morphology and the epitaxial film crystallinity, demonstrating control of the residual strain, lateral coherence, and mosaicity in subsequent GaN epitaxy by the nitridation conditions. This study provides mechanistic details of the nitridation reaction of 2¯01β-Ga2O3 facilitating the optimization of the nitridation process toward improving GaN-2¯01β-Ga2O3 heterojunctions.

In-plane and out-of-plane domain orientation dispersions in 1 to 3 monolayers epitaxial WS2 and MoS2 films on GaN(0001) film/sapphire(0001)

Transition-metal dichalcogenides and their heterostructures have attractive potential applications in electronics and optoelectronics. Wafer scale 1 to 3 monolayers WS2 and MoS2 ultrathin films on GaN/sapphire substrates were grown by metal organic chemical vapor deposition. Azimuthal reflection high-energy electron diffraction (ARHEED) was used to characterize the long-range order of these TMDC ultrathin films. The RHEED patterns of WS2 and MoS2 show stripes and arcs but the MoS2 on GaN shows sharp spots in addition to stripes and arcs. The 2D map constructed from ARHEED patterns shows that WS2 is epitaxial and has an in-plane domain orientation dispersion. For the MoS2 on GaN/sapphire substrate, the 2D map shows concentric continuous rings for each diffraction order of MoS2 and GaN indicating that the in-plane MoS2 domain orientation and GaN nanocrystals are random. The out-of-plane orientation dispersion of MoS2 on the GaN substrate is larger than that of WS2 on the GaN substrate. The observations of stripes, arcs, and spots from RHEED patterns and the 2D maps reveal the deviation of ultrathin epitaxial films from its perfect epitaxy, especially the TMDC domain orientation dispersion over a large area. These rich findings from 2D maps broaden the application of ARHEED in more than one monolayer thick 2D materials.

Comprehensive study of SrF2 growth on highly oriented pyrolytic graphite (HOPG): Temperature-dependent van der Waals epitaxy

This study explores the molecular beam epitaxy (MBE) growth of SrF2 on highly oriented pyrolytic graphite (HOPG) highlighting the temperature-dependent variations in growth morphology, crystalline structure and electronic properties. The comprehensive characterization of SrF2/HOPG interfaces was carried out using atomic force microscopy (AFM), reflection high-energy electron diffraction (RHEED), ultraviolet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS). The spectroscopy data suggest that the chemical interaction of the fluoride with the substrate is weak at each deposited thickness and temperature of the substrate during the deposition, indicating a growth under a van der Waals epitaxial regime. SrF2 nanostructures deposited on HOPG depict a distinctive bulk-like character, concerning their crystallinity and composition, even at the very initial growth stage. Remarkably, temperature plays a crucial role in driving the growth patterns, moving from coalescence of dendritic islands at room temperature to induce nearly 1D rows along the step-edges of HOPG terraces at higher temperatures (400 °C).

GaN thickness dependence of GaN/AlN superlattices on face-to-face-annealed sputter-deposited AlN templates

Recently, deep-ultraviolet (DUV) light-emitting devices have attracted attention for various applications. GaN/AlN superlattices have emerged as a promising alternative for achieving high-efficiency DUV emission. To fabricate superlattices with high crystal quality and abrupt interfaces, we have utilized face-to-face-annealed sputter-deposited AlN template substrates characterized by a flat surface and low dislocation density. Furthermore, radio-frequency plasma-assisted molecular beam epitaxy with in situ reflection high-energy electron diffraction monitoring was employed for the growth process. The growth of the superlattices follows a specific sequence. Step 1: AlN growth, Step 2: conversion of Al droplets to AlN, Step 3: GaN growth, and Step 4: evaporation of Ga droplets. This study explored the impact of GaN thickness on the GaN/AlN superlattice. The GaN thickness was linearly controlled by changing the duration of Step 3. This approach allowed for the growth of a flat GaN layer up to 1 monolayer (ML) and achieved superlattices with abrupt interfaces. Single-peak cathodoluminescence (CL) emission at 240–245 nm was observed from the superlattices, with the peak shift toward longer wavelengths as the GaN thickness increased. In contrast, quantum dot-like GaN islands were generated with a thickness of over 1 ML, induced by compressive strain. Superlattices with thicker GaN exhibited broad CL emission with multiple peaks. However, the AlN barrier layer reduced the surface roughness and maintained abrupt interfaces within the superlattices. Therefore, to obtain sharp single-peak UV emission from GaN/AlN superlattices, the growth sequence should be controlled to obtain flat GaN layers without dots.

Nanometer-thick molecular beam epitaxy Al films capped with in situ deposited Al2O3—High-crystallinity, morphology, and superconductivity

Achieving high material perfection in aluminum (Al) films and their associated Al/AlOx heterostructures is essential for enhancing the coherence time in superconducting quantum circuits. We grew Al films with thicknesses ranging from 3 to 30 nanometers (nm) epitaxially on sapphire substrates using molecular beam epitaxy (MBE). An integral aspect of our work involved electron-beam (e-beam) evaporation to directly deposit aluminum oxide (Al2O3) films on the freshly grown ultrathin epitaxial Al films in an ultra-high-vacuum (UHV) environment. This in situ oxide deposition is critical for preventing the oxidation of parts of the Al films, avoiding the formation of undesired native oxides, and thereby preserving the nm-thick Al films in their pristine conditions. The thicknesses of our Al films in the study were accurately determined; for example, coherence lengths of 3.0 and 20.2 nm were measured in the nominal 3.0 and 20 nm thick Al films, respectively. These Al films were epitaxially grown on sapphire substrates, showing an orientational relationship, denoted as Al(111)⟨21¯1¯⟩∥sapphire(0001)[21¯1¯0]. The Al/sapphire interface was atomically ordered without any interfacial layers, as confirmed by in situ reflection high-energy electron diffraction (RHEED) and cross-sectional scanning transmission electron microscopy (STEM). All sample surfaces exhibited smoothness with a roughness in the range of 0.1–0.2 nm. The Al films are superconducting with critical temperatures ranging from 1.23 to around 2 K, depending on the film thickness.

Machine-learning-empowered identification of initial growth modes for 2D transition metal dichalcogenide thin films

In situ reflection high-energy electron diffraction (RHEED) is a powerful technique for monitoring surface states and offers invaluable insights into thin film growth. However, extracting hidden features and subtle changes from its vast data remains as a challenge. This work bridges the gap by employing machine learning (ML)-empowered RHEED analysis to elucidate the growth dynamics of two-dimensional (2D) transition metal dichalcogenide (TMDC) thin films grown under two distinct growth modes. Principal component analysis (PCA) and its modified processes were used to separate contributions of the graphene substrate and the MoSe2 film in the RHEED video. The ML-empowered RHEED analysis allowed us to effectively filter out the strong substrate signal and reconstructing RHEED videos solely for the MoSe2 films. This approach enabled detailed monitoring of film growth with unique features, and clearly distinguishing between the layer-by-layer growth mode and the island one. This work demonstrates the potentials of ML-empowered RHEED analysis for revealing complex growth dynamics of 2D TMDC materials, paving the way for advanced thin film monitoring and autonomous control in wider scope of thin film technologies.

Effect of changing the growth mechanism on the synthesis of two-dimensional germanium layers and quantum dots on silicon

Subject of study. The work studied the formation of germanium quantum dots on silicon with (100) crystallographic orientation under different growth regimes. Aim of study. The work is devoted to conducting experimental studies of the influence of growth mechanisms on the formation of germanium layers and quantum dots on a silicon (100) substrate for the production of optical elements based on silicon-germanium nanostructures. Methods. After pre-epitaxial cleaning of the Si substrate, germanium is synthesized on Si(100) through molecular beam epitaxy. The surface morphology is analyzed using reflection high-energy electron diffraction during synthesis and scanning electron microscopy after deposition. Main results. The work determines the temperature ranges at which the Si/Si(100) growth occurs due to the nucleation of islands, due to the movement of steps, and in combination. The effect of changing growth mechanisms on the size and density of Ge quantum dots on Si(100) is shown. Practical significance. The research results provide insight into the influence of growth mechanisms on the sizes of formed germanium quantum dots on silicon, which will make it possible to create nanophotonics and nanoelectronics elements with strictly specified parameters.

Abrupt ternary III–V metamorphic buffers

Emerging quantum materials as well as novel traditional electronic and photonic materials may enable a new generation of information science devices if they can be synthesized on suitable substrates. Additionally, material and device designs may benefit from tunable properties through engineered epitaxial strain for the manipulation of the electronic character. In this work, three series of III–V ternary alloys, GaInSb, AlInSb, and InAsSb, are grown via molecular beam epitaxy on GaAs (001) substrates to explore the flexibility of abrupt metamorphic epitaxial layers with tunable lattice parameters between 6.135 and 6.479 Å. Their deposition on both homomorphic GaAs and pseudomorphic AlAs buffers is also explored. The structures of these alloys are characterized via reflection high-energy electron diffraction, high-resolution x-ray diffraction, atomic force microscopy, and transmission electron microscopy to assess their suitability as stable buffer layers with wide variability of accessible lattice parameters.

In segregation influence on properties of InAs quantum dots in dots-in-a-well

We investigated the growth of InAs quantum dots (QDs) in a dots-in-a-well (DWELL) from the perspective of the influence of In segregation from the InGaAs layers in the DWELL. Reflection high-energy electron diffraction (RHEED) measurements during the growth of the lower InGaAs layer indicated that In segregation increased with the In composition of the InGaAs layer. The estimated In segregation values were consistent with the decreases in the critical thickness for the QDs growth and the total volume variations of the grown QDs. These results illustrate that the segregated In from the lower InGaAs layer contributes to the QD growth in the DWELL, and their density increases. Furthermore, RHEED measurements during the growth of the upper InGaAs layer indicated the suppression of the deformation of embedded QDs , which could partially contribute to the longer emission wavelength of the QDs in the DWELL.

Accommodating a hexagonal [formula omitted]- phase Mn2N film on a cubic MgO (001) substrate

The thin films of c-plane dominated hexagonal ζ- phase Mn2N were successfully grown on a cubic MgO (001) substrate directly using plasma-assisted molecular beam epitaxy. The surface was comprehensively studied through experimental and theoretical approaches. Reflection high energy electron diffraction revealed two pseudo-cubic domains along [100]MgO and [110]MgO, and one hexagonal domain, which is 30° apart from the [100]MgO direction. Scanning tunneling microscopy was used to image and resolve the high quality surface, revealing a distorted hexagonal surface structure. Furthermore, atomic resolution of the hexagonal domain with a 2 × 2 reconstructed surface is presented. For the c-plane surface, theoretical investigations were carried out using first-principle studies to determine the surface formation energy for various reconstructed surfaces. The theoretical study shows that the nitrogen terminated 2 × 2 structure with a manganese adatom on the surface is the most stable reconstruction that reproduces the experimental results. A corresponding simulated scanning tunneling microscopy model is also presented, providing strong support for the experimentally observed in-plane lattice structures. The manganese:nitrogen stoichiometry within the bulk and surface is in good agreement with the expected ratio of 2:1.

Epitaxial growth and magnetic properties of Mn5(SixGe1-x)3 thin films

Structural and magnetic properties of Mn5(SixGe1-x)3 thin films were investigated. Ferromagnetic Mn5Ge3 and anti-ferromagnetic Mn5Si3 thin films have been synthesized and characterized as these compounds exhibit interesting features for the development of spintronics. Here, Mn5(SixGe1-x)3 thin films were grown on Ge(111) substrates by co-deposition using molecular beam epitaxy. Crystalline thin films can be produced with controlled Si concentrations ranging from 0 to 1. The thin films were relaxed by dislocations at the interface with the substrate. A lattice parameter variation was observed as the Si content increased, which is comparable to previous works done in bulk. Reflection high-energy electron diffraction diagrams and X-ray diffraction profiles showed that lattice parameters a and c are shrinking and that the surface roughness and crystallinity degrade as the Si amount increases. Magnetometric measurements revealed a ferromagnetic behavior for all Si concentrations. The measured average ferromagnetic moment per manganese atom decreased from 2.33 to 0.05 μB/Mn atom. No ferro to anti-ferromagnetic transition was observed contrary to the bulk Mn5(SixGe1-x)3 compound.

Low-Temperature Synthesis of WSe2 by the Selenization Process under Ultrahigh Vacuum for BEOL Compatible Reconfigurable Neurons.

Low-temperature large-area growth of two-dimensional (2D) transition-metal dichalcogenides (TMDs) is critical for their integration with silicon chips. Especially, if the growth temperatures can be lowered below the back-end-of-line (BEOL) processing temperatures, the Si transistors can interface with 2D devices (in the back end) to enable high-density heterogeneous circuits. Such configurations are particularly useful for neuromorphic computing applications where a dense network of neurons interacts to compute the output. In this work, we present low-temperature synthesis (400 °C) of 2D tungsten diselenide (WSe2) via the selenization of the W film under ultrahigh vacuum (UHV) conditions. This simple yet effective process yields large-area, homogeneous films of 2D TMDs, as confirmed by several characterization techniques, including reflection high-energy electron diffraction, atomic force microscopy, transmission electron microscopy, and different spectroscopy methods. Memristors fabricated using the grown WSe2 film are leveraged to realize a novel compact neuron circuit that can be reconfigured to enable homeostasis.

RHEED Study of the Epitaxial Growth of Silicon and Germanium on Highly Oriented Pyrolytic Graphite

Two-dimensional silicon (silicene) and germanium (germanene) have attracted special attention from researchers in recent years. At the same time, highly oriented pyrolytic graphite (HOPG) and graphene are some of the promising substrates for growing silicene and germanene. However, to date, the processes occurring during the epitaxial growth of silicon and germanium on the surface of such substrates have been poorly studied. In this work, the epitaxial growth of silicon and germanium is studied directly during the process of the molecular beam epitaxy deposition of material onto the HOPG surface by reflection high-energy electron diffraction (RHEED). In addition, the obtained samples are studied by Raman spectroscopy and scanning electron microscopy. A wide range of deposition temperatures from 100 to 800 °C is considered and temperature intervals are determined for various growth modes of silicon and germanium on HOPG. Conditions for amorphous and polycrystalline growth are distinguished. Diffraction spots corresponding to the lattice constants of silicene and germanene are identified that may indicate the presence of areas of graphene-like 2D phases during epitaxial deposition of silicon and germanium onto the surface of highly oriented pyrolytic graphite.

Universal Deoxidation of Semiconductor Substrates Assisted by Machine Learning and Real-Time Feedback Control.

Substrate oxidation is inevitable when exposed to ambient atmosphere during semiconductor manufacturing, which is detrimental to the fabrication of state-of-the-art devices. Optimizing the deoxidation process in molecular beam epitaxy (MBE) for random substrates poses a multidimensional challenge and is sometimes controversial. Due to variations in substrates and growth processes, the determination of the deoxidation condition heavily relies on the individual's expertise, yielding inconsistent results. This study employs a machine learning model that integrates interpolation and vision transformer (Interpolation-ViT) techniques. The model utilizes reflection high-energy electron diffraction videos as input to predict the status of the substrate, enabling automated deoxidation within a controlled architecture for various substrates. Furthermore, we highlight the potential of models trained on data from specific MBE equipment to achieve high-accuracy deployment on different pieces of equipment. In contrast to traditional methods, our approach holds exceptional value, as it standardizes deoxidation temperatures across diverse equipment and substrates. This significantly advances the standardization of the semiconductor process. The concepts and methods presented are expected to revolutionize semiconductor manufacturing processes in the optoelectronic and microelectronic industries.

Molecular Beam Epitaxy Growth of GaN/InGaN Heterostructures under In‐Bilayer Stabilized Conditions

Molecular beam epitaxy is applied for the GaN/InGaN growth under In‐bilayer stabilized conditions, which require substrate temperatures above 580 °C for sufficient indium desorption. Under these conditions the indium content is limited to , as determined by a novel reflection high energy electron diffraction technique, which is based on indium adsorption and subsequent consumption at varying gallium flux. As‐grown structures show degraded surfaces after indium desorption. This effect is eliminated by applying excess gallium before and after InGaN growth, which results in morphologies and dislocation densities comparable to GaN/AlGaN structures.

Dislocation density as a factor compensating the polarization doping effect in graded p-AlGaN contact layers

One of the approaches to improve p-doping properties in (Al)GaN-based materials is using a method called polarization doping. In this study, the graded p-AlGaN contact layers were deposited using plasma-assisted molecular beam epitaxy with different III/N ratios. To study the influence of Ga flux on the structural and electrical properties of the grown graded p-AlGaN structures, the samples were investigated using reflection high-energy electron diffraction, atomic force microscopy, secondary ion mass spectrometry, X-ray diffraction, and Hall effect measurements. The electronic structure of the samples was investigated by X-ray absorption near edge spectroscopy, while the polarity of the layers was analyzed by means of transmission electron microscopy. Our study reveals that growing with a higher Ga flux increases Mg incorporation and changes its distribution in the graded layer. However, it was shown that the main factor drastically affecting the magnitude and the type of conductivity in the graded p-AlGaN structures is the dislocation density. The highest hole concentration of ∼3.0×1018 cm−3 was observed for sample grown with a low Ga flux.

Structural and surface characterizations of 2D β-In2Se3/3D β-Ga2O3 heterostructures grown on c-Sapphire substrates by molecular beam epitaxy

Integrating two-dimensional (2D) layered materials with wide bandgap β-Ga2O3 has unveiled impressive opportunities for exploring novel physics and device concepts. This study presents the epitaxial growth of 2D β-In2Se3/3D β-Ga2O3 heterostructures on c-Sapphire substrates by plasma-assisted molecular beam epitaxy. Firstly, we employed a temperature-dependent two-step growth process to deposit Ga2O3 and obtained a phase-pure (2¯01)\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$(\\overline{2 }01)$$\\end{document} β-Ga2O3 film on c-Sapphire. Interestingly, the in-situ reflective high-energy electron diffraction (RHEED) patterns observed from this heterostructure revealed the in-plane ‘b’ lattice constant of β-Ga2O3 ~ 3.038Å. In the next stage, for the first time, 2D In2Se3 layers were epitaxially realized on 3D β-Ga2O3 under varying substrate temperatures (Tsub) and Se/In flux ratios (RVI/III). The deposited layers exhibited (00l) oriented β-In2Se3 on (2¯01)\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$(\\overline{2 }01)$$\\end{document} β-Ga2O3/c-Sapphire with the epitaxial relationship of [112¯0]\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$[11\\overline{2 }0]$$\\end{document} β-In2Se3 || [010] β-Ga2O3 and [101¯0]\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$[10\\overline{1 }0]$$\\end{document} β-In2Se3 || [102] β-Ga2O3 as observed from the RHEED patterns. Also, the in-plane ‘a’ lattice constant of β-In2Se3 was determined to be ~ 4.027Å. The single-phase β-In2Se3 layers with improved structural and surface quality were achieved at a Tsub ~ 280 °C and RVI/III ~ 18. The microstructural and detailed elemental analysis further confirmed the epitaxy of 2D layered β-In2Se3 on 3D β-Ga2O3, a consequence of the quasi-van der Waals epitaxy. Furthermore, the β-Ga2O3 with an optical bandgap (Eg) of ~ 5.04 eV (deep ultraviolet) when integrated with 2D β-In2Se3, Eg ~ 1.43eV (near infra-red) can reveal potential applications in the optoelectronic field.

Post-annealing in ultra-high vacuum or nitrogen plasma for MoS2 thin films deposited by magnetron sputtering

The thin films of amorphous molybdenum disulfide were deposited at room temperature by magnetron sputtering technique. Post-annealing process in ultra-high vacuum (∼10−8 Pa) or nitrogen plasma environments at the temperatures of 300, 400, 500, and 700 °C have been first proposed to enhance the microstructure and optical properties of MoS2 thin films. The phase transformation of MoS2 thin films from amorphous to polycrystalline was characterized by in situ reflection high-energy electron diffraction during the post-annealing process. The microstructure of MoS2 thin films was also analyzed by Raman spectrum and X-ray diffractometer after the post-annealing process. In addition, the thermal analysis of the differential scanning calorimeter and optical measurement of photoreflectance confirmed the phase transformation of MoS2 thin films. The analysis of photoreflectance also estimated the exciton transition at the bandgap energy of 2.038 eV at 0 K, attributed by the crystalline MoS2 film annealed at 700 °C in ultra-high vacuum. The surface chemical composition of MoS2 thin films has been identified by X-ray photoelectron spectroscopy, but the desulfurization of MoS2 was observed after post-annealing in ultra-high vacuum. Moreover, the preferred orientation of (004) plane in the MoS2 films was performed as the increase in post-annealing temperature.