Reactive Molecular Beam Epitaxy Research Articles

Structure-Related Electronic and Magnetic Properties in Ultrathin Epitaxial NixFe3-xO4 Films on MgO(001).

Off-stoichiometric NixFe3-xO4 ultrathin films (x < 2.1) with varying Ni content x and thickness 16 (±2) nm were grown on MgO(001) by reactive molecular beam epitaxy. Synchrotron-based high-resolution X-ray diffraction measurements reveal vertical compressive strain for all films, resulting from a lateral pseudomorphic adaption of the film to the substrate lattice without any strain relaxation. Complete crystallinity with smooth interfaces and surfaces is obtained independent of the Ni content x. For x < 1 an expected successive conversion from Fe3O4 to NiFe2O4 is observed, whereas local transformation into NiO structures is observed for films with Ni content x > 1. However, angle-resolved hard X-ray photoelectron spectroscopy measurements indicate homogeneous cationic distributions without strictly separated phases independent of the Ni content, while X-ray absorption spectroscopy shows that also for x > 1, not all Fe2+ cations are substituted by Ni2+ cations. The ferrimagnetic behavior, as observed by superconducting quantum interference device magnetometry, is characterized by decreasing saturation magnetization due to the formation of antiferromagnetic NiO parts.

Time-resolved high-energy X-ray diffraction studies of ultrathin Ni ferrite films on MgO(001)

Time-resolved high-energy X-ray diffraction was used during growth of ultrathin Ni x Fe3−x O4 films with varying Ni content (0 ≤ x ≤ 1.5) deposited on MgO(001) substrates by reactive molecular beam epitaxy, providing an insight into the growth dynamics of these films. In order to obtain structural information, reciprocal-space maps were recorded and the temporal evolution of the Bragg peaks specific to the octahedral and tetrahedral lattice sites of the inverse spinel structure of Ni x Fe3−x O4 was observed during growth of the films. A time delay, corresponding to a coverage of 1.2–1.8 nm, between the appearance of the Bragg reflections originating from octahedral sites and reflections originating exclusively from tetrahedral sites indicates that the ferrite films grow in two stages. In the initial growth phase, a rock salt interface layer is formed. Afterwards, a structural transition occurs and the films grow in an inverse spinel structure. The thickness of the initial rock salt phase was found to increase with Ni content and to be responsible for atypical strain in the thin films. Films with Ni contents x &gt; 1 do not show a structural transition. These films remain in a (deficient) rock salt structure consisting of a mixed Ni–Fe oxide and do not form a spinel structure at all. They show an increased number of NiO clusters as detected by X-ray photoelectron spectroscopy of the valence band, accompanied by a significant roughening of the films.

Initial Optimization of the Growth Conditions of GaAs Homo-Epitaxial Layers after Cleaning and Restarting the Molecular Beam Epitaxy Reactor.

The molecular beam epitaxy (MBE) technique is renowned as the most suitable for the growth of high-quality crystalline materials and nanostructures such as GaAs. However, once established, optimal growth parameters required for repeatability of top-quality structures may be easily lost as MBE is highly sensitive to any changes in the system. Especially, routine servicing procedures, which include any activity which requires unsealing of the growth chamber, are devastating for developed growth parameters and force the necessity of recalibration. In this work, we present the process of growth parameter pre-optimization for obtaining homoepitaxial GaAs layers after servicing and restarting the MBE system. Namely, we present how each step of reestablishing optimal growth condition influences various characteristics of obtained GaAs layers. Those include in situ, structural, and spectral measurement techniques. An additional aspect was to compare the optimal conditions for the growth of homoepitaxial GaAs layers from two growth campaigns in which the main difference is the addition of an ion pump and increasing the temperature gradient on the Ga cell.

Synthesis of Chemically Sharp Interface in NdNiO3/SrTiO3 Heterostructures

The nickel-based superconductivity provides a fascinating new platform to explore high-T c superconductivity. As the infinite-layer nickelates are obtained by removing the apical oxygens from the precursor perovskite phase, the crystalline quality of the perovskite phase is crucial in synthesizing high quality superconducting nickelates. Especially, cation-related defects, such as the Ruddlesden–Popper-type (RP-type) faults, are unlikely to disappear after the topotactic reduction process and should be avoided during the growth of the perovskite phase. Herein, using reactive molecular beam epitaxy, we report the atomic-scale engineering of the interface structure and demonstrate its impact in reducing crystalline defects in Nd-based nickelate/SrTiO3 heterostructures. A simultaneous deposition of stoichiometric Nd and Ni directly on SrTiO3 substrates results in prominent Nd vacancies and Ti diffusion at the interface and RP-type defects in nickelate films. In contrast, inserting an extra [NdO] monolayer before the simultaneous deposition of Nd and Ni forms a sharp interface and greatly eliminates RP-type defects in nickelate films. A possible explanation related to the polar discontinuity is also discussed. Our results provide an effective method to synthesize high-quality precursor perovskite phase for the investigation of the novel superconductivity in nickelates.

Synthesis of Chemically Sharp Interface in NdNiO3/SrTiO3 Heterostructures

Abstract The nickel-based superconductivity provides a fascinating new platform to explore the high-T c superconductivity. As the infinite-layer nickelates are obtained by removing the apical oxygens from the precursor perovskite phase, the crystalline quality of the perovskite phase is crucial in synthesizing high quality superconducting nickelates. Especially, cation-related defects, such as the Ruddlesden-Popper-type (RP-type) faults, are unlikely to disappear after the topotactic reduction process and should be avoided during the growth of the perovskite phase. Herein, using reactive molecular beam epitaxy, we report the atomic-scale engineering of the interface structure and demonstrate its impact in reducing crystalline defects in Nd-based nickelate/SrTiO3 heterostructures. A simultaneous deposition of stoichiometric Nd and Ni directly on SrTiO3 substrate results in prominent Nd vacancies and Ti diffusion at the interface and RP-type defects in nickelate films. In contrast, inserting an extra [NdO] monolayer before the simultaneous deposition of Nd and Ni forms a sharp interface and greatly eliminates RP-type defects in nickelate films. A possible explanation related to the polar discontinuity is also discussed. Our results provide an effective method to synthesize high-quality precursor perovskite phase for the investigation of the novel superconductivity in nickelates.

Nanoporous GaN by selective area sublimation through an epitaxial nanomask: AlN versus Si x N y

Nanoporous GaN layers were fabricated using selective area sublimation through a self-organized AlN nanomask in a molecular beam epitaxy reactor. The obtained pore morphology, density and size were measured using plan-view and cross-section scanning electron microscopy experiments. It was found that the porosity of the GaN layers could be adjusted from 0.04 to 0.9 by changing the AlN nanomask thickness and sublimation conditions. The room temperature photoluminescence properties as a function of the porosity were analysed. In particular, a strong improvement (>100) of the room temperature photoluminescence intensity was observed for porous GaN layers with a porosity in the 0.4–0.65 range. The characteristics of these porous layers were compared to those obtained with a Si x N y nanomask. Furthermore, the regrowth of p-type GaN on light emitting diode structures made porous by using either an AlN or a Si x N y nanomask were compared.

Inverse tunnel magnetoresistance of magnetic tunnel junctions with a NiCo2O4 electrode

Inverse spinel oxide NiCo2O4 (NCO) is known to exhibit ferrimagnetic characteristics and electrical conductivity. First-principles calculations predict NCO to be a half-metal with a negative polarization of −100%. In this study, we fabricated epitaxial NCO/MgO/Fe magnetic tunnel junctions by reactive molecular beam epitaxy and observed an inverse tunnel magnetoresistance (TMR) effect of −19.1% at 14 K, indicating that NCO has negative spin polarization. The TMR ratio monotonically decreased with increasing temperature, which was attributed to the temperature dependence of the NCO surface magnetization due to the thermal excitation of spin waves. In addition, the TMR ratio displayed strong bias voltage dependence, decreasing to less than half of the maximum value at +20 and −30 mV. These findings support the use of NCO in spintronic devices and should lead to further developments in oxide spintronics.

Influence of Oxygen Plasma on the Growth and Stability of Epitaxial NiCo2O4 Ultrathin Films on Various Substrates.

In this work, we investigated the influence of oxygen plasma on the growth of nickel cobaltite (NiCo2O4) thin films compared to growth in a molecular oxygen atmosphere. The films were grown on MgO(001), MgAl2O4(001) and SrTiO3(001) substrates by oxygen plasma (atmosphere of activated oxygen)-assisted and reactive molecular beam epitaxy (molecular oxygen atmosphere). Soft X-ray photoelectron spectroscopy showed that only the use of oxygen plasma led to a spectrum characteristic of (NiCo2O4). Low energy electron diffraction measurements were conducted to obtain information on the structure of the film surfaces. The results proved the formation of a spinel surface structure for films grown with oxygen plasma, while the formation of a rock salt structure was observed for growth with molecular oxygen. To determine the film thickness, X-ray reflectivity measurements were performed. If oxygen plasma were used to grow (NiCo2O4) films, this would result in lower film thicknesses compared to growth using molecular oxygen although the cation flux was kept constant during deposition. Additional X-ray diffraction experiments delivered structural information about the bulk structure of the film. All films had a rock salt bulk structure after exposure to ambient conditions. Angle-resolved hard X-ray photoelectron spectroscopy revealed a homogeneous depth distribution of cations of the grown film, but no typical (NiCo2O4) spectrum anymore. Thus, on the one hand, (NiCo2O4) films with a spinel structure prepared using activated oxygen were not stable under ambient conditions. The structure of these films was transformed into NiCo oxide with a rock salt structure. On the other hand, it was not possible to form (NiCo2O4) films using molecular oxygen. These films had a rock salt structure that was stable under ambient conditions.

Percolative superconductivity in electron-doped Sr1−xEuxCuO2+y films

Electron-doped infinite-layer Sr$_{1-x}$Eu$_{x}$CuO$_{2+y}$ films over a wide doping range have been prepared epitaxially on SrTiO$_3$(001) using reactive molecular beam epitaxy. In-plane transport measurements of the single crystalline samples reveal a dome-shaped nodeless superconducting phase centered at $x$ $\sim$ 0.15, a Fermi-liquid behavior and pronounced upturn in low temperature resistivity. We show that the resistivity upturn follows square-root temperature dependence, suggesting the emergence of superconductivity via a three-dimensional percolation process. The percolative superconductivity is corroborated spectroscopically by imaging the electronic phase separation between superconducting and metallic phases with low-temperature scanning tunneling microscopy. Furthermore, we visualize interstitial and apical oxygen anions that rapidly increase in number as $x>$ 0.12, and elucidate their impacts on the superconductivity and normal-state resistivity.

Evolving surface morphology during epitaxy of NiO on Ag(001)

Reactive molecular beam epitaxy of NiO on Ag(001) has been characterized by high-resolution low energy electron diffraction performed during deposition of Ni on Ag(001) in molecular oxygen atmosphere for deposition temperatures of 300–420 K. The initial stage of film growth at high deposition temperature is determined by competing processes of Ni oxidation and Ni interdiffusion into Ag(001) with Ni-Ag alloying. Ni oxidation is favored at low deposition temperatures. Thus, NiO bilayers are immediately formed. At high deposition temperatures, however, alloying with Ag is enhanced and the formation of the initial NiO bilayer is delayed. After formation of a closed NiO bilayer, alloying is prevented and all deposited Ni is oxidized and NiO growth proceeds in the layer-by-layer growth mode. Later stages of epitaxy are governed by relaxation processes induced by the formation of mosaics due to interface dislocations. The tilt angle of the mosaic decreases with increasing film thickness due to elastic deformation of the NiO lattice. Dislocation related mosaics are paired and form grooves. Postdeposition characterization shows periodic arrangement of grooves related to the formation of a regular dislocation network.

Real-Time Monitoring the Growth of Epitaxial CoxFe3-xO4 Ultrathin Films on Nb-Doped SrTiO3(001) via Reactive Molecular Beam Epitaxy by Means of Operando HAXPES.

In this work, we present a comprehensive study on real-time monitoring the growth of epitaxial CoxFe3−xO4 thin films grown on SrTiO3(001) substrates via reactive molecular beam epitaxy. The growth process was monitored during evaporation by means of time resolved operando hard X-ray photoelectron spectroscopy (HAXPES). We prepared ultrathin ferrite films using different oxygen partial pressures, showing pure metallic, light oxidic, and cobalt ferrite-like growth. Additional X-ray diffraction measurements confirm HAXPES results.

Time-resolved x-ray diffraction and photoelectron spectroscopy investigation of the reactive molecular beam epitaxy of Fe3O4 ultrathin films

We present time-resolved high energy x-ray diffraction (tr-HEXRD), time-resolved hard x-ray photoelectron spectroscopy (tr-HAXPES) and time-resolved grazing incidence small angle x-ray scattering (tr-GISAXS) data of the reactive molecular beam epitaxy (RMBE) of $\mathrm{Fe_3O_4}$ ultrathin films on various substrates. Reciprocal space maps are recorded during the deposition of $\mathrm{Fe_3O_4}$ on $\mathrm{SrTiO_3(001)}$, MgO(001) and NiO/MgO(001) in order to observe the temporal evolution of Bragg reflections sensitive to the octahedral and tetrahedral sublattices of the inverse spinel structure of $\mathrm{Fe_3O_4}$. A time delay between the appearance of rock salt and spinel-exclusive reflections reveals that first, the iron oxide film grows with $\mathrm{Fe_{1-\delta}O}$ rock salt structure with exclusive occupation of octahedral lattice sites. When this film is 1.1$\,$nm thick, the further growth of the iron oxide film proceeds in the inverse spinel structure, with both octahedral and tetrahedral lattice sites being occupied. In addition, iron oxide on $\mathrm{SrTiO_3(001)}$ initially grows with none of these structures. Here, the formation of the rock salt structure starts when the film is 1.5$\,$nm thick. This is confirmed by tr-HAXPES data obtained during growth of iron oxide on $\mathrm{SrTiO_3(001)}$, which demonstrate an excess of $\mathrm{Fe^{2+}}$ cations in growing films thinner than 3.2$\,$nm. This rock salt phase only appears during growth and vanishes after the supply of the Fe molecular beam is stopped. Thus, it can be concluded the rock salt structure of the interlayer is a property of the dynamic growth process. The tr-GISAXS data link these structural results to an island growth mode of the first 2-3$\,$nm on both MgO(001) and $\mathrm{SrTiO_3(001)}$ substrates.

Epitaxial growth of metastable La0.67Sr0.33MnO3−δ films by using Sr3Al2O6 as multifunctional buffer layers

In doped manganites, a substantial tuning of the magnetic and electrical transport properties can be realized by engineering the concentration of oxygen vacancies. To date, most oxygen-deficient La1−xSrxMnO3−δ (0 ≤ x ≤ 1) films are synthesized by after-growth treatments. However, the direct growth of La1−xSrxMnO3−δ films remains challenging due to the metastability of this material. Here, we report the epitaxial growth of high quality single crystalline La0.67Sr0.33MnO3−δ films with an extremely large out-of-plane lattice parameter of 4.26 Å by reactive oxide molecular beam epitaxy. To stabilize this metastable phase, Sr3Al2O6 buffer layers are used to block the oxygen diffusion from the SrTiO3 substrate to the film during the growth process. This work provides an efficient way to obtain metastable La0.67Sr0.33MnO3−δ films.

Electronic and transport properties in Ruddlesden-Popper neodymium nickelates Ndn+1NinO3n+1 ( n=1–5 )

A series of Ruddlesden-Popper nickelates, Nd$_{n+1}$Ni$_{n}$O$_{3n+1}$ (${n}$ = 1-5), have been stabilized in thin film form using reactive molecular-beam epitaxy. High crystalline quality has been verified by X-ray diffraction and scanning transmission electron microscopy. X-ray photoelectron spectroscopy indicates the ${n}$-dependent valence states of nickel in these compounds. Metal-insulator transitions show clear ${n}$ dependence for intermediate members (${n}$ = 3-5), and the low-temperature resistivities of which show logarithmic dependence, resembling the Kondo-scattering as observed in the parent compounds of superconducting infinite-layer nickelates.

Growth-mode and interface structure of epitaxial ultrathin MgO/Ag(001) films

MgO ultrathin films are of great technological importance as electron tunneling barrier in electronics and spintronics, and as template for metallic clusters in catalysis and for molecular networks for 2D electronics. The wide band-gap of MgO allows for a very effective decoupling from the substrate. The films morphology and the detailed structure of the interface are crucial for applications, controlling the electronic transfer. Using surface x-ray diffraction, we studied the growth-mode and the structure of MgO/Ag(001) ultrathin films elaborated by reactive molecular beam epitaxy as function of the substrate temperature. We observed that deposition of about 1 monolayer results in an MgO(001) film in coherent epitaxy, with the oxygen atoms on top of silver as predicted by DFT calculations, and an interlayer distance at the interface of about 270 pm. Under well-defined conditions, a sharp MgO bilayer is formed covering a fraction of the substrate surface.

Co-deposition growth and superconductivity of La2−xSrxCuO4 films by reactive molecular beam epitaxy

Reactive molecular beam epitaxy has been employed to prepare ${\mathrm{La}}_{2\ensuremath{-}x}{\mathrm{Sr}}_{x}\mathrm{Cu}{\mathrm{O}}_{4}$ cuprate films via a Co-deposition method. Precise control of flux ratios among the solid sources leads us to establish a very narrow growth window for the cation stoichiometry. The hole doping by divalent ${\mathrm{Sr}}^{2+}$ cation is found to occur in a substitution-limited manner, accompanied by partial oxidation of Sr flux into peroxide $\mathrm{Sr}{\mathrm{O}}_{2}$ on the top surface. Through interface engineering, we explore the impact of substrate strain on the crystal parameters and superconductivity of ${\mathrm{La}}_{2\ensuremath{-}x}{\mathrm{Sr}}_{x}\mathrm{Cu}{\mathrm{O}}_{4}$ thin films. The present study provides a time-saving, effective approach to preparing high-quality cuprate films, and further understanding the effect of surface/interface microstructures on cuprate superconductivity.

Spectroscopic ellipsometry as an in-situ monitoring tool for Bi2Se3 films grown by molecular beam epitaxy

In-operando spectroscopic ellipsometry (SE) was used to measure the optical response of Bi2Se3 films grown on sapphire substrates in a molecular beam epitaxy (MBE) reactor during cool-down from a growth temperature of 225 °C. A temperature dependent dielectric model was refined for the topological insulator Bi2Se3 by taking SE spectra at different temperatures and fitting the amplitude ratio and phase difference of orthogonally polarized light using Bi2Se3 films with varying thickness. In-operando SE demonstrated here enabled determining the dielectric function of substrate and growing film unobscured by surface or interface reactions. Its sensitivity to sample temperature and film thickness variations allows determining growth temperature, absolute film thickness, and growth rate in real time, rendering it a reliable and universal approach for a direct comparison of growth conditions between different growth campaigns, thus offering the potential to improve reproducibility of the growth conditions for Bi2Se3 based films and heterostructures.

Epitaxial growth and transport properties of compressively-strained Ba2IrO4 films* *Project supported by the National Natural Science Foundation of China (Grant Nos. 11774153, 11861161004, 51772143, 11974163, and 51672125), the National Key Research and Development Program of China (Grant No. 2016YFA0201104), the Fundamental Research Funds for the Central Universities, China (Grant Nos. 0213-14380167 and 0213-14380198), and the Hong Kong Research Grants Council

Ba2IrO4 is a sister compound of the widely investigated Sr2IrO4 and has no IrO6 octahedral rotation nor net canted antiferromagnetic moment, thus it acts as a system more similar to the high-T c cuprate. In this work, we synthesize the Ba2IrO4 epitaxial films by reactive molecular beam epitaxy and study their crystalline structure and transport properties under biaxial compressive strain. High resolution scanning transmission electron microscopy and x-ray diffraction confirm the high quality of films with partial strain relaxation. Under compressive epitaxial strain, the Ba2IrO4 exhibits the strain-driven enhancement of the conductivity, consistent with the band gap narrowing and the stronger hybridization of Ir-t2g and O-2p orbitals predicted in the first-principles calculations.

Epitaxial growth and electronic structure of Ruddlesden–Popper nickelates (Lan+1NinO3n+1, n = 1–5)

We report the epitaxial growth of Ruddlesden–Popper nickelates, Lan+1NinO3n+1, with n up to 5 by reactive molecular beam epitaxy. X-ray diffractions indicate high crystalline quality of these films, and transport measurements show strong dependence on the n values. Angle-resolved photoemission spectroscopy reveals the electronic structure of La5Ni4O13, showing a large hole-like pocket centered around the Brillouin zone corner with a (π, π) back-folded copy.

Strain relaxation induced transverse resistivity anomalies in SrRuO3 thin films

Here, we report a magnetotransport study of high-quality $\mathrm{Sr}\mathrm{Ru}{\mathrm{O}}_{3}$ thin films with high residual resistivity ratios grown by reactive oxide molecular-beam epitaxy. The transverse resistivity exhibits clear anomalies which are typically believed to be signatures of the topological Hall effect and the presence of magnetic skyrmions. By systematically investigating these anomalies as a function of temperature, field, film thickness, and excitation currents we verify that these anomalies originate from a two-channel anomalous Hall effect arising from magnetic inhomogeneities in the samples and not from an intrinsic topological Hall effect. Using a combination of magnetic circular dichroism, scanning transmission electron microscopy, x-ray diffraction, and magnetotransport, we discover that strain relaxation effects in the films are the origin of these inhomogeneities. Our results shed light on the recently reported Hall effect anomalies in $\mathrm{Sr}\mathrm{Ru}{\mathrm{O}}_{3}$ thin films and heterostructures and provide an approach to determine whether such anomalies arise from an intrinsic topological Hall effect or from extrinsic mechanisms.