Reflection High-energy Electron Diffraction Oscillations Research Articles

Canonical approach to cation flux calibration in oxide molecular-beam epitaxy

Molecular-beam epitaxy (MBE) is the gold standard for the epitaxial growth of complex oxides with the best material properties as determined by respective figures of merit. Unfortunately, once more than one cation is involved in the material desired, MBE growth often becomes plagued by difficulties in stoichiometry control. Instead of relying on a quartz crystal microbalance to measure the fluxes of the individual molecular beams, which lacks accuracy, or reflection high-energy electron diffraction oscillations of the targeted multication oxide in layer-by-layer growth, which lacks general applicability, here, we describe a canonical approach based on the growth of films of the constituent binary oxides or metals individually for cation flux calibration. This method can calibrate the flux of each molecular beam with an absolute accuracy of \ifmmode\pm\else\textpm\fi{}1%. After describing the growth parameters of binary oxides or metals enabling the individual fluxes of 39 elements of the periodic table to be determined, we demonstrate the efficacy of this approach by applying it to the growth of the quaternary ferromagnetic metal ${\mathrm{La}}_{0.5}{\mathrm{Sr}}_{0.5}\mathrm{Co}{\mathrm{O}}_{3\ensuremath{-}\ensuremath{\delta}}$ to achieve films with transport properties rivalling the best reported using thin-film growth techniques providing stoichiometric transfer.

Specific cation stoichiometry control of SrMnO3-δ thin films via RHEED oscillations

Cubic heteroepitaxial (001) SrMnO3-δ (SMO) films were grown on SrTiO3 substrates by atomic alternating layer molecular beam epitaxy. Precise control of cation stoichiometry was achieved by in situ reflection high-energy electron diffraction (RHEED) oscillation. During SMO film growth, a correlation between RHEED oscillation features and the cation stoichiometry/monolayer dose was established. In non-stoichiometric films, there were out-of-plane lattice expansions due to off-stoichiometry-dependent defects, including Ruddlesden–Popper SrO planar faults in Sr-rich films and Sr vacancy defect clusters in Mn-rich films.

In situ x-ray and electron scattering studies of oxide molecular beam epitaxial growth

We perform in situ synchrotron x-ray ray diffraction (SXRD)/reflection high energy electron diffraction (RHEED) studies on the growth of complex oxide thin films by molecular beam epitaxy. The unique deposition chamber, located at the Advanced Photon Source, allows the preparation of complex oxide samples with monolayer precision and facilitates the formation of direct correlations between in situ x-ray studies and the more prevalent RHEED investigations. Importantly, because SXRD and RHEED probe different atomic-scale processes during thin film synthesis, their concomitant use enables the extraction of details concerning growth behavior that one cannot determine from either probe alone. We describe the results of such in situ studies on the epitaxial growth of perovskite LaNiO3 on (La0.18Sr0.82)(Al0.59Ta0.41)O3 (001). We find that during the earliest stages of growth, the RHEED and x-ray signals do not agree with each other, demonstrating that while regular RHEED oscillations may imply high quality growth, the film–substrate interface can undergo significant changes during deposition due to the occurrence of interdiffusion at the growth temperature.

Movable holder for a quartz crystal microbalance for exact growth rates in pulsed laser deposition.

Controlling the amount of material deposited by pulsed laser deposition (PLD) down to fractions of one atomic layer is crucial for nanoscale technologies based on thin-film heterostructures. Albeit unsurpassed for measuring growth rates with high accuracy, the quartz crystal microbalance (QCM) suffers from some limitations when applied to PLD. The strong directionality of the PLD plasma plume and its pronounced dependence on deposition parameters (e.g., background pressure and fluence) require that the QCM is placed at the same position as the substrate during growth. However, QCM sensors are commonly fixed off to one side of the substrate. This also entails fast degradation of the crystal, as it is constantly exposed to the ablated material. The design for a movable QCM holder discussed in this work overcomes these issues. The holder is compatible with standard transfer arms, enabling easy insertion and transfer between a PLD chamber and other adjoining vacuum chambers. The QCM can be placed at the same position as the substrate during PLD growth. Its resonance frequency is measured in vacuum at any location where it can be in contact with an electrical feedthrough, before and after deposition. We tested the design for the deposition of hematite (Fe2O3), comparing the rates derived from the QCM and from reflection high-energy electron diffraction oscillations during homoepitaxial growth.

Multi-cycle RHEED oscillation under nitrogen supply in alternative source supply AlN growth by rf-MBE

An alternative source supply sequence was applied to aluminum nitride (AlN) growth by rf-plasma-assisted molecular-beam epitaxy on silicon carbide (SiC) substrates with a high-quality AlN template layer. Under a nitrogen-only source supply after aluminum source supply, multi-cycle oscillations of reflection high-energy electron diffraction (RHEED) intensity were observed, which were due to layer-by-layer growth of the AlN layer. The RHEED oscillation under nitrogen-only supply indicates that excess aluminum exists on the surface as a few-monolayer-thick wetting layer along with microdroplets. By repeating the sequence, a 105 nm thick high-quality AlN layer was coherently grown on a SiC substrate without aluminum droplets.

Overlapping growth windows to build complex oxide superlattices

Perovskite oxide superlattices are of particular interest due to novel phenomena emerging at interfaces which are beyond the bulk properties of the constituent layers. However, building perovskite superlattices comprised of stoichiometric layers with sharp interfaces has proven challenging. Here, the synthesis of a series of high quality (SrTiO3)n/(CaTiO3)n superlattice structures grown on LSAT substrates is demonstrated by employing hybrid molecular beam epitaxy, where Ti was supplied using metal-organic titanium tetraisopropoxide (TTIP), and Sr and Ca were supplied using conventional effusion cells. By careful adjustment of the cation fluxes of Sr and Ca with respect to the TTIP flux, the growth windows of SrTiO3 and CaTiO3 were overlapped, allowing us to grow the individual superlattice layers with self-regulated stoichiometry. Stable and repeatable reflection high-energy electron diffraction oscillations during the entire ∼2.5 h growth period indicated good source flux stability. The structural quality of the superlattice films were determined by scanning transmission electron microscopy and synchrotron-based X-ray diffraction, revealing periodic, phase pure, homogenous superlattice structures with abrupt interfaces. Utilization of perovskite stoichiometric growth windows offers great potential for accessing and realizing interface driven phenomena in versatile perovskite superlattice materials with chemistries beyond titanates.

Chemically specific termination control of oxide interfaces via layer-by-layer mean inner potential engineering

Creating oxide interfaces with precise chemical specificity at the atomic layer level is desired for the engineering of quantum phases and electronic applications, but highly challenging, owing partially to the lack of in situ tools to monitor the chemical composition and completeness of the surface layer during growth. Here we report the in situ observation of atomic layer-by-layer inner potential variations by analysing the Kikuchi lines during epitaxial growth of strontium titanate, providing a powerful real-time technique to monitor and control the chemical composition during growth. A model combining the effects of mean inner potential and step edge density (roughness) reveals the underlying mechanism of the complex and previously not well-understood reflection high-energy electron diffraction oscillations observed in the shuttered growth of oxide films. General rules are proposed to guide the synthesis of atomically and chemically sharp oxide interfaces, opening up vast opportunities for the exploration of intriguing quantum phenomena at oxide interfaces.

In situ determination of the growth conditions of GaSbBi alloys

We have grown by molecular-beam epitaxy (MBE) GaSb1−xBix layers at different temperatures and fluxes to observe their influence on the Bi incorporation rate. All growth runs were monitored by in situ reflection high-energy electron diffraction (RHEED). Strong intensity oscillations were observed during the MBE growth of all GaSbBi and GaSb layers at very low temperatures, down to 170 °C (thermocouple temperature). We demonstrate that a detailed analysis of these RHEED oscillations gives an excellent insight into the variation of the Bi incorporation rate over the whole 2–13% composition range. While identifying the conditions to grow high quality GaSbBi alloys is a challenge generally addressed via a cumbersome trial and error approach, we demonstrate that RHEED oscillations is a powerful method to set the optimized growth conditions for the epitaxy of III-V-Bi alloys.

RHEED oscillations in spinel ferrite epitaxial films grown by conventional planar magnetron sputtering

Real-time in situ reflection high energy electron diffraction (RHEED) observations of Fe3O4, γ-Fe2O3, and (Co,Fe)3O4 films on MgO(001) substrates grown by a conventional planar magnetron sputtering was studied. The change in periodical intensity of the specular reflection spot in the RHEED images of three different spinel ferrite compounds grown by two different sputtering systems was examined. The oscillation period was found to correspond to the 1/4 unit cell of each spinel ferrite, similar to that observed in molecular beam epitaxy (MBE) and pulsed laser deposition (PLD) experiments. This suggests that the layer-by-layer growth of spinel ferrite (001) films is general in most physical vapor deposition (PVD) processes. The surfaces of the films were as flat as the surface of the substrate, consistent with the observed layer-by-layer growth process. The observed RHEED oscillation indicates that even a conventional sputtering method can be used to control film thickness during atomic layer depositions.

Wafer-scale two-dimensional ferromagnetic Fe3GeTe2 thin films grown by molecular beam epitaxy

Recently, layered two-dimensional ferromagnetic materials (2D FMs) have attracted a great deal of interest for developing low-dimensional magnetic and spintronic devices. Mechanically exfoliated 2D FMs were discovered to possess ferromagnetism down to monolayer. It is therefore of great importance to investigate the distinct magnetic properties at low dimensionality. Here, we report the wafer-scale growth of 2D ferromagnetic thin films of Fe3GeTe2 via molecular beam epitaxy, and their exotic magnetic properties can be manipulated via the Fe composition and the interface coupling with antiferromagnetic MnTe. A 2D layer-by-layer growth mode has been achieved by in situ reflection high-energy electron diffraction oscillations, yielding a well-defined interlayer distance of 0.82 nm along {002} surface. The magnetic easy axis is oriented along c-axis with a Curie temperature of 216.4 K. Remarkably, the Curie temperature can be enhanced when raising the Fe composition. Upon coupling with MnTe, the coercive field dramatically increases 50% from 0.65 to 0.94 Tesla. The large-scale layer-by-layer growth and controllable magnetic properties make Fe3GeTe2 a promising candidate for spintronic applications. It also opens up unprecedented opportunities to explore rich physics when coupled with other 2D superconductors and topological matters.

Homoepitaxial Growth of Metal Halide Crystals Investigated by Reflection High-Energy Electron Diffraction

We report the homoepitaxial growth of a metal halide on single crystals investigated with in situ reflection high-energy electron diffraction (RHEED) and ex situ atomic force microscopy (AFM). Epitaxial growth of NaCl on NaCl (001) is explored as a function of temperature and growth rate which provides the first detailed report of RHEED oscillations for metal halide growth. Layer-by-layer growth is observed at room temperature accompanied by clear RHEED oscillations while the growth mode transitions to an island (3D) mode at low temperature. At higher temperatures (>100 °C), RHEED oscillations and AFM data indicate a transition to a step-flow growth mode. To show the importance of such metal halide growth, green organic light-emitting diodes (OLEDs) are demonstrated using a doped NaCl film with a phosphorescent emitter as the emissive layer. This study demonstrates the ability to perform in situ and non-destructive RHEED monitoring even on insulating substrates and could enable doped single crystals and crystalline substrates for a range of optoelectronic applications.

Monitoring surface roughness during film growth using modulated RHEED intensity oscillations

Separation of the high- and low-frequency components of Reflection High-Energy Electron Diffraction (RHEED) intensity oscillations during pulsed deposition allows the extraction of a signal that is in phase with the cyclic surface morphology evolution during layer-by-layer growth. Similar to a biased impedance measurement in electricity, the periodic modulation of surface roughness induced by the pulsed deposition probes the differential response of the growth front to changes in step density. This signal does not follow the complex variation of the RHEED oscillation phase with diffraction conditions and surface reconstruction and therefore allows a direct detection of monolayer completion. Off-Laue Circle oscillations show promise to probe the surface morphology evolution at sharply defined in-plane spatial frequencies.

Discussion of the importance of the refraction effects for RHEED

The preparation of nanostructured materials is quite often controlled with the help of reflection high energy electron diffraction (RHEED). However, the interpretation of RHEED results should be carried out with some care because electrons strongly interact with atoms. Here, the importance of the refraction effects is shown theoretically. Results of dynamical and kinematical calculations of RHEED rocking curves are compared for diamond and gallium arsenide. Dynamical calculations are carried by solving the Schrödinger equation. For kinematical calculations respective analytical formulas are used. RHEED intensities for growing surfaces are analyzed. In particular, it discussed why the refraction effects are very important for the appearance of RHEED oscillations.

Algorithms for determining the phase of RHEED oscillations

Oscillations of reflection high-energy electron diffraction (RHEED) intensities are computed using dynamical diffraction theory. The phase of the oscillations is determined using two different approaches. In the first, direct, approach, the phase is determined by identifying the time needed to reach the second oscillation minimum. In the second approach, the phase is found using harmonic analysis. The two approaches are tested by applying them to oscillations simulated using dynamical diffraction theory. The phase of RHEED oscillations observed experimentally is also analysed. Experimental data on the variation of the phase as a function of the glancing angle of incidence, derived using the direct method, are compared with the values computed using both the direct and harmonic methods. For incident-beam azimuths corresponding to low-symmetry directions, both approaches produce similar results.

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.

Arrayed van der Waals Vertical Heterostructures Based on 2D GaSe Grown by Molecular Beam Epitaxy

Vertically stacking two-dimensional (2D) materials can enable the design of novel electronic and optoelectronic devices and realize complex functionality. However, the fabrication of such artificial heterostructures on a wafer scale with an atomically sharp interface poses an unprecedented challenge. Here, we demonstrate a convenient and controllable approach for the production of wafer-scale 2D GaSe thin films by molecular beam epitaxy. In situ reflection high-energy electron diffraction oscillations and Raman spectroscopy reveal a layer-by-layer van der Waals epitaxial growth mode. Highly efficient photodetector arrays were fabricated, based on few-layer GaSe on Si. These photodiodes show steady rectifying characteristics and a high external quantum efficiency of 23.6%. The resultant photoresponse is super-fast and robust, with a response time of 60 μs. Importantly, the device shows no sign of degradation after 1 million cycles of operation. We also carried out numerical simulations to understand the underlying device working principles. Our study establishes a new approach to produce controllable, robust, and large-area 2D heterostructures and presents a crucial step for further practical applications.

Complex oxide growth using simultaneous in situ reflection high-energy electron diffraction and x-ray reflectivity: When is one layer complete?

During layer-by-layer homoepitaxial growth, both the Reflection High-Energy Electron Diffraction (RHEED) intensity and the x-ray reflection intensity will oscillate, and each complete oscillation indicates the addition of one monolayer of material. However, it is well documented, but not well understood, that the phase of the RHEED oscillations varies from growth to growth and thus the maxima in the RHEED intensity oscillations do not necessarily occur at the completion of a layer. We demonstrate this by using simultaneous in situ x-ray reflectivity and RHEED to characterize layer-by-layer growth of SrTiO3. We show that we can control the RHEED oscillation phase by changing the pre-growth substrate annealing conditions, changing the RHEED oscillation phase by as much as 137°. In addition, during growth via pulsed laser deposition, the relaxation times between each laser pulse can be used to determine when a layer is complete, independent of the phase of the RHEED oscillation.

Surface reconstructions in molecular beam epitaxy of SrTiO3

We show that reflection high-energy electron diffraction (RHEED) can be used as a highly sensitive tool to track surface and resulting film stoichiometry in adsorption-limited molecular beam epitaxy of (001) SrTiO3 thin films. Even under growth conditions that yield films with a lattice parameter that is identical to that of stoichiometric bulk crystals within the detection limit of high-resolution x-ray diffraction (XRD), changes in surface reconstruction occur from (1 × 1) to (2 × 1) to c(4 × 4) as the equivalent beam pressure of the Ti metalorganic source is increased. These surface reconstructions are correlated with a shift from mixed SrO/TiO2 termination to pure TiO2 termination. The crossover to TiO2 surface termination is also apparent in a phase shift in RHEED oscillations observed at the beginning of growth. Comparison with prior results for carrier mobilities of doped films shows that the best films are grown under conditions of a TiO2-saturated surface [c(4 × 4) reconstruction] within the XRD growth window.

RHEED intensities from two-dimensional heteroepitaxial nanoscale systems

A practical computing algorithm has been developed for calculating the reflection high-energy electron diffraction (RHEED) from the molecular beam epitaxy growing surface. The calculations are based on the use of the dynamical diffraction theory in which the electrons are taken to be diffracted by a potential, which is periodic in the dimension perpendicular to the surface. The computer program presented in this paper enables calculations for three basic types of diffuse potential for crystalline heteroepitaxial structures, including the possible existence of various diffuse scattering models through the layer parallel to the surface. Program SummaryProgram title: RHEED_DIFFCatalogue identifier: AETW_v1_0Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AETW_v1_0.htmlProgram obtainable from: CPC Program Library, Queen’s University, Belfast, N. IrelandLicensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.htmlNo. of lines in distributed program, including test data, etc.: 68483No. of bytes in distributed program, including test data, etc.: 480831Distribution format: tar.gzProgramming language: C++.Computer: Intel i7-based PC.Operating system: Windows, Linux.RAM: The presented algorithm belongs to the linear memory class of the computational complexity O(n).Word size: 64 bitsClassification: 4.6, 6.2, 7.2.Nature of problem:RHEED rocking curves (the specular beam intensities versus the glancing angle) recorded from heteroepitaxial layers are used for the non-destructive evaluation of epilayer thickness and composition with a high degree of accuracy. Rocking curves from such heterostructures are often very complex because the thickness fringes from every layer beat together. Simulations based on the dynamical diffraction theory are generally used to interpret the rocking curves of such structures from which very small changes in thickness and composition can be obtained. Rocking curves are also used to determine the level of strain and its relaxation mechanism in a lattice-mismatched system.Solution method:RHEED intensities are calculated within the framework of the general matrix formulation described in Ref. [1] under the one-beam condition [2,3]. The dynamical diffraction calculations presented in this paper utilize the systematic reflection case in RHEED, in which the atomic potential in the planes parallel to the surface are projected onto the surface normal, so that the results are insensitive to the atomic arrangement in the layers parallel to the surface. In this paper, an approach in which oscillating changes in the intensity appear as a combined effect of changes in the refraction conditions and changes in diffuse scattering for different models of the scattering potential is implemented.Running time:Numerically, the problem of calculating the changes in RHEED oscillation intensity from growing layers is an NP problem. The time computational complexity of the presented algorithm depends on the number of layers for both the substrate and the growing layers included in the calculations. The time-computational complexity of the presented solution is O(n2), where n is the total number of layers used in the calculations.

Tuning cationic composition of La:EuTiO3−δ films

Eu1−xLaxTiO3−δ (x = 0, 0.3, 0.5) films were deposited in a p(Ar(96%)/H2(4%)) = 4 × 10−4 mbar atmosphere on (LaAlO3)0.3-(Sr2AlTaO6)0.7 vicinal substrates (0.1°). Reflection high-energy electron diffraction oscillation characteristics of a layer-by-layer growth mode were observed for stoichiometric and Ti-rich films and the laser fluence suited to deposit stoichiometric films was identified to be 1.25 J/cm2 independent of the La content. The variety of resulting film compositions follows the general trend of Eu-enrichment for low laser and Ti-enrichment for high laser fluence. X-ray diffraction confirms that all the films are compressively strained with a general trend of an increase of c-axis elongation for non-stoichiometric films. The surfaces of non-stoichiometric films have an increased roughness, the highest sheet resistances, exhibit the presence of islands, and are Eu3+ rich for films deposited at low laser fluence.