Violation of Boltzmann Equipartition Theorem in Angular Phonon Phase Space Slows down Nanoscale Heat Transfer in Ultrathin Heterofilms.

Heat transfer through heterointerfaces is intrinsically hampered by a thermal boundary resistance originating from the discontinuity of the elastic properties. Here, we show that with shrinking dimensions the heat flow from an ultrathin epitaxial film through atomically flat interfaces into a single crystalline substrate is significantly reduced due to violation of Boltzmann equipartition theorem in the angular phonon phase space. For films thinner than the phonons mean free path, we find phonons trapped in the film by total internal reflection, thus suppressing heat transfer. Repopulation of those phonon states, which can escape the film through the interface by transmission and refraction, becomes the bottleneck for cooling. The resulting nonequipartition in the angular phonon phase space slows down the cooling by more than a factor of 2 compared to films governed by phonons diffuse scattering. These allow tailoring of the thermal interface conductance via manipulation of the interface.

Defects in GaSe grown by Bridgman method.

Optical quality GaSe crystals have been grown by vertical Bridgman method. The structural properties and micromorphology of a cleaved GaSe(001) surface have been evaluated by RHEED, SEM and AFM. The cleaved GaSe(001) is atomically flat with as low roughness as ∼0.06 nm excepting local hillock type defects. The hillock-type formations are round-shaped with a bottom diameter of ∼200 nm and a height of ∼20-35 nm. The drastic depletion of the hillock material by gallium has been indicated by EDX measurements.

Identification of Kikuchi lines in electron diffraction patterns collected in small-angle geometry.

It is demonstrated that Kikuchi features become clearly visible if reflection high-energy electron diffraction (RHEED) patterns are filtered using digital image processing software. The results of such pattern transformations are shown for SrTiO3 with mixed surface termination for data collected at different azimuths of the incident electron beam. A simplified analytical approach for the theoretical description of filtered Kikuchi patterns is proposed and discussed. Some examples of raw and filtered patterns for thin films are shown. RHEED patterns may be treated as a result of coherent and incoherent scattering of electron waves. The effects of coherent scattering may be considered as those occurring due to wave diffraction by an idealized crystal and, usually, only effects of this type are analysed to obtain structural information on samples investigated with the use of RHEED. However, some incoherent scattering effects mostly caused by thermal vibrations of atoms, known as Kikuchi effects, may also be a source of valuable information on the arrangements of atoms near the surface. Typically, for the case of RHEED, Kikuchi features are hidden in the intensity background and researchers cannot easily recognize them. In this paper, it is shown that the visibility of features of this type can be substantially enhanced using computer graphics methods.

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

Integrating two-dimensional (2D) layered materials with wide bandgap ß-Ga2O3 has unveiled impressive opportunities for exploring novel physics and device concepts. This study presents the epitaxial growth of 2D ß-In2Se3/3D ß-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 ) ß-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 ß-Ga2O3 ~ 3.038Å. In the next stage, for the first time, 2D In2Se3 layers were epitaxially realized on 3D ß-Ga2O3 under varying substrate temperatures (Tsub) and Se/In flux ratios (RVI/III). The deposited layers exhibited (00l) oriented ß-In2Se3 on ( 2 ¯ 01 ) ß-Ga2O3/c-Sapphire with the epitaxial relationship of [ 11 2 ¯ 0 ] ß-In2Se3 || [010] ß-Ga2O3 and [ 10 1 ¯ 0 ] ß-In2Se3 || [102] ß-Ga2O3 as observed from the RHEED patterns. Also, the in-plane 'a' lattice constant of ß-In2Se3 was determined to be ~ 4.027Å. The single-phase ß-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 ß-In2Se3 on 3D ß-Ga2O3, a consequence of the quasi-van der Waals epitaxy. Furthermore, the ß-Ga2O3 with an optical bandgap (Eg) of ~ 5.04 eV (deep ultraviolet) when integrated with 2D ß-In2Se3, Eg ~ 1.43eV (near infra-red) can reveal potential applications in the optoelectronic field.

Machine-learning-assisted analysis of transition metal dichalcogenide thin-film growth.

In situ reflective high-energy electron diffraction (RHEED) is widely used to monitor the surface crystalline state during thin-film growth by molecular beam epitaxy (MBE) and pulsed laser deposition. With the recent development of machine learning (ML), ML-assisted analysis of RHEED videos aids in interpreting the complete RHEED data of oxide thin films. The quantitative analysis of RHEED data allows us to characterize and categorize the growth modes step by step, and extract hidden knowledge of the epitaxial film growth process. In this study, we employed the ML-assisted RHEED analysis method to investigate the growth of 2D thin films of transition metal dichalcogenides (ReSe2) on graphene substrates by MBE. Principal component analysis (PCA) and K-means clustering were used to separate statistically important patterns and visualize the trend of pattern evolution without any notable loss of information. Using the modified PCA, we could monitor the diffraction intensity of solely the ReSe2 layers by filtering out the substrate contribution. These findings demonstrate that ML analysis can be successfully employed to examine and understand the film-growth dynamics of 2D materials. Further, the ML-based method can pave the way for the development of advanced real-time monitoring and autonomous material synthesis techniques.

Epitaxial CdSe/PbSe Heterojunction Growth and MWIR Photovoltaic Detector.

A novel Epitaxial Cadmium Selenide (CdSe) on Lead Selenide (PbSe) type-II heterojunction photovoltaic detector has been demonstrated by Molecular Beam Epitaxy (MBE) growth of n-type CdSe on p-type PbSe single crystalline film. The use of Reflection High-Energy Electron Diffraction (RHEED) during the nucleation and growth of CdSe indicates high-quality single-phase cubic CdSe. This is a first-time demonstration of single crystalline and single phase CdSe growth on single crystalline PbSe, to the best of our knowledge. The current-voltage characteristic indicates a p-n junction diode with a rectifying factor over 50 at room temperature. The detector structure is characterized by radiometric measurement. A 30 µm × 30 µm pixel achieved a peak responsivity of 0.06 A/W and a specific detectivity (D*) of 6.5 × 108 Jones under a zero bias photovoltaic operation. With decreasing temperature, the optical signal increased by almost an order of magnitude as it approached 230 K (with thermoelectric cooling) while maintaining a similar level of noise, achieving a responsivity of 0.441 A/W and a D* of 4.4 × 109 Jones at 230 K.

An Analysis of Kikuchi Lines Observed with a RHEED Apparatus for a TiO2-Terminated SrTiO3 (001) Crystal.

In this study, electron diffraction patterns observed under high vacuum conditions for an SrTiO3 surface were interpreted in detail while paying special attention to the features of inelastic effects. The surface of the SrTiO2 was carefully prepared to enforce its termination with single domains of TiO2 layers at the top. The inelastic patterns were interpreted using analytical models. Two types of Kikuchi lines are recognized in this paper: those which can be described with the Bragg law and those which appear due to surface wave resonance effects. However, we also discuss that there exists a formal connection between the two types of the Kikuchi lines observed.

Substrate Modification during Chemical Vapor Deposition of hBN on Sapphire.

A comparison of hexagonal boron nitride (hBN) layers grown by chemical vapor deposition on C-plane (0001) versus A-plane (112̅0) sapphire (α-Al2O3) substrate is reported. The high deposition temperature (>1200 °C) and hydrogen ambient used for hBN deposition on sapphire substantially alters the C-plane sapphire surface chemistry and leaves the top layer(s) oxygen deficient. The resulting surface morphology due to H2 etching of C-plane sapphire is inhomogeneous with increased surface roughness which causes non-uniform residual stress in the deposited hBN film. In contrast to C-plane, the A-plane of sapphire does not alter substantially under a similar high temperature H2 environment, thus providing a more stable alternative substrate for high quality hBN growth. The E2g Raman mode full width at half-maximum (FWHM) for hBN deposited on C-plane sapphire is 24.5 ± 2.1 cm-1 while for hBN on A-plane sapphire is 24.5 ± 0.7 cm-1. The lesser FWHM standard deviation on A-plane sapphire indicates uniform stress distribution across the film due to reduced undulations on the surface. The photoluminescence spectra of the hBN films at 300 and 3 K, obtained on C-plane and A-plane sapphire exhibit similar characteristics with peaks at 4.1 and 5.3 eV reported to be signature peaks associated with defects for hBN films deposited under lower V/III ratios. The dielectric breakdown field of hBN deposited on A-plane sapphire was measured to be 5 MV cm-1, agreeing well with reports on mechanically exfoliated hBN flakes. Thus, under the typical growth conditions required for high crystalline quality hBN growth, A-plane sapphire provides a more chemically stable substrate.

Strain Relaxation in "2D/2D and 2D/3D Systems": Highly Textured Mica/Bi2Te3, Sb2Te3/Bi2Te3, and Bi2Te3/GeTe Heterostructures.

Strain engineering as a method to control functional properties has seen in the last decades a surge of interest. Heterostructures comprising 2D-materials and containing van der Waals(-like) gaps were considered unsuitable for strain engineering. However, recent work on heterostructures based on Bi2Te3, Sb2Te3, and GeTe showed the potential of a different type of strain engineering due to long-range mutual straining. Still, a comprehensive understanding of the strain relaxation mechanism in these telluride heterostructures is lacking due to limitations of the earlier analyses performed. Here, we present a detailed study of strain in two-dimensional (2D/2D) and mixed dimensional (2D/3D) systems derived from mica/Bi2Te3, Sb2Te3/Bi2Te3, and Bi2Te3/GeTe heterostructures, respectively. We first clearly show the fast relaxation process in the mica/Bi2Te3 system where the strain was generally transferred and confined up to the second or third van der Waals block and then abruptly relaxed. Then we show, using three independent techniques, that the long-range exponentially decaying strain in GeTe and Sb2Te3 grown on the relaxed Bi2Te3 and Bi2Te3 on relaxed Sb2Te3 as directly observed at the growth surface is still present within these three different top layers a long time after growth. The observed behavior points at immediate strain relaxation by plastic deformation without any later relaxation and rules out an elastic (energy minimization) model as was proposed recently. Our work advances the understanding of strain tuning in textured heterostructures or superlattices governed by anisotropic bonding.

Reentrant Behavior of the Density vs. Temperature of Indium Islands on GaAs(111)A.

We show that the density of indium islands on GaAs(111)A substrates have a non-monotonic, reentrant behavior as a function of the indium deposition temperature. The expected increase in the density with decreasing temperature, indeed, is observed only down to 160 ∘C, where the indium islands undertake the expected liquid-to-solid phase transition. Further decreasing the temperature causes a sizable reduction of the island density. An additional reentrant increasing behavior is observed below 80 ∘C. We attribute the above complex behavior to the liquid-solid phase transition and to the complex island-island interaction which takes place between crystalline islands in the presence of strain. Indium solid islands grown at temperatures below 160 ∘C have a face-centered cubic crystal structure.

New Findings on Multilayer Silicene on Si(111)√3×√3R30°-Ag Template.

We report new findings on multilayer silicene grown on Si(111)√3 × âˆš3 R30°-Ag template, after the recent first compelling experimental evidence of its synthesis. Low-energy electron diffraction, reflection high-energy electron diffraction, and energy-dispersive grazing incidence X-ray diffraction measurements were performed to show up the fingerprints of √3 × âˆš3 multilayer silicene. Angle-resolved photoemission spectroscopy displayed new features in the second surface Brillouin zone, attributed to the multilayer silicene on Si(111)√3 × âˆš3 R30°-Ag. Band-structure dispersion theoretical calculations performed on a model of three honeycomb stacked layers, silicene grown on Si(111)√3 × âˆš3 R30°-Ag surface confirm the experimental results.

Tuning the Surface Morphologies and Properties of ZnO Films by the Design of Interfacial Layer.

Wurtzite ZnO films were grown on MgO(111) substrates by plasma-assisted molecular beam epitaxy (MBE). Different initial growth conditions were designed to monitor the film quality. All the grown ZnO films show highly (0001)-oriented textures without in-plane rotation, as illustrated by in situ reflection high-energy electron diffraction (RHEED) and ex situ X-ray diffraction (XRD). As demonstrated by atomic force microscopy (AFM) images, "ridge-like" and "particle-like" surface morphologies are observed for the ZnO films grown in a molecular O2 atmosphere with and without an initial deposition of Zn adatoms, respectively, before ZnO growth with oxygen plasma. This artificially designed interfacial layer deeply influences the final surface morphology and optical properties of the ZnO film. From room-temperature photoluminescence (PL) measurements, a strong defect-related green luminescence band appears for the ZnO film with a "particle-like" morphology but was hardly observed in the films with flat "ridge-like" surface morphologies. Our work suggests that the ZnO crystallinity can be improved and defect luminescence can be reduced by designing interfacial layers between substrates and epilayers.

Revealing the Crystalline Integrity of Wafer-Scale Graphene on SiO2/Si: An Azimuthal RHEED Approach.

The symmetry of graphene is usually determined by a low-energy electron diffraction (LEED) method when the graphene is on the conductive substrates, but LEED cannot handle graphene transferred to SiO2/Si substrates due to the charging effect. While transmission electron microscopy can generate electron diffraction on post-transferred graphene, this method is too localized. Herein, we employed an azimuthal reflection high-energy electron diffraction (RHEED) method to construct the reciprocal space mapping and determine the symmetry of wafer-size graphene both pre- and post-transfer. In this work, single-crystalline Cu(111) films were prepared on sapphire(0001) and spinel(111) substrates with sputtering. Then the graphene was epitaxially grown on single-crystalline Cu(111) films with a low pressure chemical vapor deposition. The reciprocal space mapping using azimuthal RHEED confirmed that the graphene grown on Cu(111) films was single-crystalline, no matter the form of the monolayer or multilayer structure. While the Cu(111) film grown on sapphire(0001) may occasionally consist of 60° in-plane rotational twinning, the reciprocal space mapping revealed that the in-plane orientation of graphene grown atop was not affected. The proposed method for checking the crystalline integrity of the post-transferred graphene sheets is an important step in the realization of the graphene as a platform to fabricate electronic and optoelectronic devices.

Orientation of FePt nanoparticles on top of a-SiO2/Si(001), MgO(001) and sapphire(0001): effect of thermal treatments and influence of substrate and particle size.

Texture formation and epitaxy of thin metal films and oriented growth of nanoparticles (NPs) on single crystal supports are of general interest for improved physical and chemical properties especially of anisotropic materials. In the case of FePt, the main focus lies on its highly anisotropic magnetic behavior and its catalytic activity, both due to the chemically ordered face-centered tetragonal (fct) L10 phase. If the c-axis of the tetragonal system can be aligned normal to the substrate plane, perpendicular magnetic recording could be achieved. Here, we study the orientation of FePt NPs and films on a-SiO2/Si(001), i.e., Si(001) with an amorphous (a-) native oxide layer on top, on MgO(001), and on sapphire(0001) substrates. For the NPs of an approximately equiatomic composition, two different sizes were chosen: "small" NPs with diameters in the range of 2-3 nm and "large" ones in the range of 5-8 nm. The 3 nm thick FePt films, deposited by pulsed laser deposition (PLD), served as reference samples. The structural properties were probed in situ, particularly texture formation and epitaxy of the specimens by reflection high-energy electron diffraction (RHEED) and, in case of 3 nm nanoparticles, additionally by high-resolution transmission electron microscopy (HRTEM) after different annealing steps between 200 and 650 °C. The L10 phase is obtained at annealing temperatures above 550 °C for films and 600 °C for nanoparticles in accordance with previous reports. On the amorphous surface of a-SiO2/Si substrates we find no preferential orientation neither for FePt films nor nanoparticles even after annealing at 630 °C. On sapphire(0001) supports, however, FePt nanoparticles exhibit a clearly preferred (111) orientation even in the as-prepared state, which can be slightly improved by annealing at 600-650 °C. This improvement depends on the size of NPs: Only the smaller NPs approach a fully developed (111) orientation. On top of MgO(001) the effect of annealing on particle orientation was found to be strongest. From a random orientation in the as-prepared state observed for both, small and large FePt NPs, annealing at 650 °C for 30 min reorients the small particles towards a cube-on-cube epitaxial orientation with a minor fraction of (111)-oriented particles. In contrast, large FePt NPs keep their as-prepared random orientation even after doubling the annealing period at 650 °C to 60 min.

Theoretical analysis of reflection high-energy electron diffraction (RHEED) and reflection high-energy positron diffraction (RHEPD) intensity oscillations expected for the perfect layer-by-layer growth.

Predictions from two theoretical models, allowing one to determine the phase of intensity oscillations, are compared for reflected beams of electrons and positrons. Namely, results of the precise dynamical calculations are compared with results obtained using a simplified approach. Within the simplified model, changes in the specularly reflected beam intensity, expected to occur during the deposition of new atoms, are described with the help of interfering waves and the effect of refraction, and respective approximate analytical formulas are employed to determine the phase of the oscillations. It is found that the simplified model is very useful for understanding the physics ruling the appearance of intensity oscillations. However, it seems that the model with the realistic potential is more suitable for carrying out interpretations of experimental data.

Reliable synthesis of self-running Ga droplets on GaAs (001) in MBE using RHEED patterns.

Self-running Ga droplets on GaAs (001) surfaces are repeatedly and reliably formed in a molecular beam epitaxial (MBE) chamber despite the lack of real-time imaging capability of a low-energy electron microscope (LEEM) which has so far dominated the syntheses and studies of the running droplets phenomenon. Key to repeatability is the observation and registration of an appropriate reference point upon which subsequent sublimation conditions are based. The reference point is established using reflection high-energy electron diffraction (RHEED), not the noncongruent temperature used in LEEM where temperature discrepancies up to 25°C against MBE is measured. Our approach removes instrumental barriers to the observation and control of this complex dynamical system and may extend the usefulness of many droplet-related processes.

Big-data reflection high energy electron diffraction analysis for understanding epitaxial film growth processes.

Reflection high energy electron diffraction (RHEED) has by now become a standard tool for in situ monitoring of film growth by pulsed laser deposition and molecular beam epitaxy. Yet despite the widespread adoption and wealth of information in RHEED images, most applications are limited to observing intensity oscillations of the specular spot, and much additional information on growth is discarded. With ease of data acquisition and increased computation speeds, statistical methods to rapidly mine the data set are now feasible. Here, we develop such an approach to the analysis of the fundamental growth processes through multivariate statistical analysis of a RHEED image sequence. This approach is illustrated for growth of La(x)Ca(1-x)MnO(3) films grown on etched (001) SrTiO(3) substrates, but is universal. The multivariate methods including principal component analysis and k-means clustering provide insight into the relevant behaviors, the timing and nature of a disordered to ordered growth change, and highlight statistically significant patterns. Fourier analysis yields the harmonic components of the signal and allows separation of the relevant components and baselines, isolating the asymmetric nature of the step density function and the transmission spots from the imperfect layer-by-layer (LBL) growth. These studies show the promise of big data approaches to obtaining more insight into film properties during and after epitaxial film growth. Furthermore, these studies open the pathway to use forward prediction methods to potentially allow significantly more control over growth process and hence final film quality.

Crystal structure evolution of individual graphene islands during CVD growth on copper foil.

Single-crystal percentage of graphene islands on Cu foil is associated with island sizes and shapes. In polycrystalline islands, certain grain boundary types are favored. There is no obvious relation between the number of lobes and grain orientations. An observed structure evolution and surface disorder of Cu grains can be possible factors for the formation of grain boundaries within graphene islands.

A look inside epitaxial cobalt-on-fluorite nanoparticles with three-dimensional reciprocal space mapping using GIXD, RHEED and GISAXS.

In this work epitaxial growth of cobalt on CaF2(111), (110) and (001) surfaces has been extensively studied. It has been shown by atomic force microscopy that at selected growth conditions stand-alone faceted Co nanoparticles are formed on a fluorite surface. Grazing-incidence X-ray diffraction (GIXD) and reflection high-energy electron diffraction (RHEED) studies have revealed that the particles crystallize in the face-centered cubic lattice structure otherwise non-achievable in bulk cobalt under normal conditions. The particles were found to inherit lattice orientation from the underlying CaF2 layer. Three-dimensional reciprocal space mapping carried out using X-ray and electron diffraction has revealed that there exist long bright 〈111〉 streaks passing through the cobalt Bragg reflections. These streaks are attributed to stacking faults formed in the crystal lattice of larger islands upon coalescence of independently nucleated smaller islands. Distinguished from the stacking fault streaks, crystal truncation rods perpendicular to the {111} and {001} particle facets have been observed. Finally, grazing-incidence small-angle X-ray scattering (GISAXS) has been applied to decouple the shape-related scattering from that induced by the crystal lattice defects. Particle faceting has been verified by modeling the GISAXS patterns. The work demonstrates the importance of three-dimensional reciprocal space mapping in the study of epitaxial nanoparticles.

Structure, morphology, and magnetic properties of Fe nanoparticles deposited onto single-crystalline surfaces.

BACKGROUND: Magnetic nanostructures and nanoparticles often show novel magnetic phenomena not known from the respective bulk materials. In the past, several methods to prepare such structures have been developed - ranging from wet chemistry-based to physical-based methods such as self-organization or cluster growth. The preparation method has a significant influence on the resulting properties of the generated nanostructures. Taking chemical approaches, this influence may arise from the chemical environment, reaction kinetics and the preparation route. Taking physical approaches, the thermodynamics and the kinetics of the growth mode or - when depositing preformed clusters/nanoparticles on a surface - the landing kinetics and subsequent relaxation processes have a strong impact and thus need to be considered when attempting to control magnetic and structural properties of supported clusters or nanoparticles. RESULTS: In this contribution we focus on mass-filtered Fe nanoparticles in a size range from 4 nm to 10 nm that are generated in a cluster source and subsequently deposited onto two single crystalline substrates: fcc Ni(111)/W(110) and bcc W(110). We use a combined approach of X-ray magnetic circular dichroism (XMCD), reflection high energy electron diffraction (RHEED) and scanning tunneling microscopy (STM) to shed light on the complex and size-dependent relation between magnetic properties, crystallographic structure, orientation and morphology. In particular XMCD reveals that Fe particles on Ni(111)/W(110) have a significantly lower (higher) magnetic spin (orbital) moment compared to bulk iron. The reduced spin moments are attributed to the random particle orientation being confirmed by RHEED together with a competition of magnetic exchange energy at the interface and magnetic anisotropy energy in the particles. The RHEED data also show that the Fe particles on W(110) - despite of the large lattice mismatch between iron and tungsten - are not strained. Thus, strain is most likely not the origin of the enhanced orbital moments as supposed before. Moreover, RHEED uncovers the existence of a spontaneous process for epitaxial alignment of particles below a critical size of about 4 nm. STM basically confirms the shape conservation of the larger particles but shows first indications for an unexpected reshaping occurring at the onset of self-alignment. CONCLUSION: The magnetic and structural properties of nanoparticles are strongly affected by the deposition kinetics even when soft landing conditions are provided. The orientation of the deposited particles and thus their interface with the substrate strongly depend on the particle size with consequences regarding particularly the magnetic behavior. Spontaneous and epitaxial self-alignment can occur below a certain critical size. This may enable the obtainment of samples with controlled, uniform interfaces and crystallographic orientations even in a random deposition process. However, such a reorientation process might be accompanied by a complex reshaping of the particles.