Hybrid Molecular Beam Epitaxy Research Articles

Hybrid Molecular Beam Epitaxy for Single-Crystalline Oxide Membranes with Binary Oxide Sacrificial Layers.

The advancement in thin-film exfoliation for synthesizing oxide membranes has led to possibilities for creating artificially assembled heterostructures with structurally and chemically incompatible materials. The sacrificial layer method is a promising approach to exfoliate as-grown films from a compatible material system, allowing for their integration with dissimilar materials. Nonetheless, the conventional sacrificial layers often possess an intricate stoichiometry, thereby constraining their practicality and adaptability, particularly when considering techniques such as molecular beam epitaxy (MBE). This is where easy-to-grow binary alkaline-earth-metal oxides with a rock salt crystal structure are useful. These oxides, which include (Mg, Ca, Sr, Ba)O, can be used as a sacrificial layer covering a much broader range of lattice parameters compared to conventional sacrificial layers and are easily dissolvable in deionized water. In this study, we show the epitaxial growth of the single-crystalline perovskite SrTiO3 (STO) on sacrificial layers consisting of crystalline SrO, BaO, and Ba1-xCaxO films, employing a hybrid MBE method. Our results highlight the rapid (≤5 min) dissolution of the sacrificial layer when immersed in deionized water, facilitating the fabrication of millimeter-sized STO membranes. Using high-resolution X-ray diffraction, atomic-force microscopy, scanning transmission electron microscopy, impedance spectroscopy, and scattering-type near-field optical microscopy (SNOM), we demonstrate single-crystalline STO membranes with bulk-like intrinsic dielectric properties. The employment of alkaline earth metal oxides as sacrificial layers is likely to simplify membrane synthesis, particularly with MBE, thus expanding the research and application possibilities.

Thermogravimetric study of metal–organic precursors and their suitability for hybrid molecular beam epitaxy

Although metal–organic (MO) precursors are widely used in technologically relevant deposition techniques, reports on their temperature-dependent evaporation and decomposition behaviors are scarce. Here, MO precursors of the metals Ti, V, Al, Hf, Zr, Ge, Ta, and Pt were subjected to thermogravimetric analysis to experimentally determine their vapor pressure curves and to gain insight into their temperature-dependent decomposition kinetics. Benzoic acid was used as a calibration standard and vapor pressure curves were extracted from thermogravimetric measurements using the Langmuir equation. The obtained data is used to discuss the suitability of these MO precursors in chemical vapor deposition-based thin film growth approaches in general, and hybrid molecular beam epitaxy in particular. All MOs, except for Ta- and one Ti-based MOs, were deemed suitable for gas inlet systems. The Ta-based MO demonstrated suitability for an effusion cell, while all MOs showed compatibility with cracker usage.Graphical

Doping the Undopable: Hybrid Molecular Beam Epitaxy Growth, n-Type Doping, and Field-Effect Transistor Using CaSnO3.

The alkaline earth stannates are touted for their wide band gaps and the highest room-temperature electron mobilities among all of the perovskite oxides. CaSnO3 has the highest measured band gap in this family and is thus a particularly promising ultrawide band gap semiconductor. However, discouraging results from previous theoretical studies and failed doping attempts had described this material as "undopable". Here we redeem CaSnO3 using hybrid molecular beam epitaxy, which provides an adsorption-controlled growth for the phase-pure, epitaxial, and stoichiometric CaSnO3 films. By introducing lanthanum (La) as an n-type dopant, we demonstrate the robust and predictable doping of CaSnO3 with free electron concentrations, n3D, from 3.3 × 1019 cm-3 to 1.6 × 1020 cm-3. The films exhibit a maximum room-temperature mobility of 42 cm2 V-1 s-1 at n3D = 3.3 × 1019 cm-3. Despite having a comparable radius as the host ion, La expands the lattice parameter. Using density functional calculations, this effect is attributed to the energy gain by lowering the conduction band upon volume expansion. Finally, we exploit robust doping by fabricating CaSnO3-based field-effect transistors. The transistors show promise for CaSnO3's high-voltage capabilities by exhibiting low off-state leakage below 2 × 10-5 mA/mm at a drain-source voltage of 100 V and on-off ratios exceeding 106. This work serves as a starting point for future studies on the semiconducting properties of CaSnO3 and many devices that could benefit from CaSnO3's exceptionally wide band gap.

Temperature-dependent thermal conductivity of MBE-grown epitaxial SrSnO3 films

As an ultrawide bandgap (∼4.1 eV) semiconductor, single crystalline SrSnO3 (SSO) has promising electrical properties for applications in power electronics and transparent conductors. The device performance can be limited by heat dissipation issues. However, a systematic study detailing its thermal transport properties remains elusive. This work studies the temperature-dependent thermal properties of a single crystalline SSO thin film prepared with hybrid molecular beam epitaxy. By combining time-domain thermoreflectance and Debye–Callaway modeling, physical insight into thermal transport mechanisms is provided. At room temperature, the 350-nm SSO film has a thermal conductivity of 4.4 W m−1 K−1, ∼60% lower than those of other perovskite oxides (SrTiO3, BaSnO3) with the same ABO3 structural formula. This difference is attributed to the low zone-boundary frequency of SSO, resulting from its distorted orthorhombic structure with tilted octahedra. At high temperatures, the thermal conductivity of SSO decreases with temperature following a ∼T−0.54 dependence, weaker than the typical T−1 trend dominated by the Umklapp scattering. This work not only reveals the fundamental mechanisms of thermal transport in single crystalline SSO but also sheds light on the thermal design and optimization of SSO-based electronic applications.

Growing clean crystals from dirty precursors: Solid-source metal-organic molecular beam epitaxy growth of superconducting Sr2RuO4 films

Ultra-high purity elemental sources have long been considered a prerequisite for obtaining low impurity concentrations in compound semiconductors in the world of molecular beam epitaxy (MBE) since its inception in 1968. However, we demonstrate that a “dirty” solid precursor, ruthenium(III) acetylacetonate [also known as Ru(acac)3], can yield single-phase, epitaxial, and superconducting Sr2RuO4 films with the same ease and control as III–V MBE. A superconducting transition was observed at ∼0.9 K, suggesting a low defect density and a high degree of crystallinity in these films. In contrast to the conventional MBE, which employs the ultra-pure Ru metal evaporated at ∼2000 °C as a Ru source, along with reactive ozone to obtain Ru → Ru4+ oxidation, the use of the Ru(acac)3 precursor significantly simplifies the MBE process by lowering the temperature for Ru sublimation (less than 200 °C) and by eliminating the need for ozone. Combining these results with the recent developments in hybrid MBE, we argue that leveraging the precursor chemistry will be necessary to realize next-generation breakthroughs in the synthesis of atomically precise quantum materials.

High-efficiency InAs/GaAs quantum dot intermediate band solar cell achieved through current constraint engineering

In this work, a novel device concept for improving the efficiency and field operation of conventional InAs/GaAs quantum dot (QD) based intermediate band solar cell (IBSC) with the feature of current constraint (CC-QD-IBSC) was proposed and evaluated from both theoretical simulations and experimental demonstrations. The advantages of the proposed device concept including increasing efficiency, obtaining higher suitability for operation under concentrated photovoltaic (CPV) condition and more robust efficiency stability against intermediate band fluctuation were rigorously identified using the detailed balance theorem by comparing with conventional InAs/GaAs QD-IBSC. Furthermore, a hybrid molecular beam epitaxy (MBE) and metal organic chemical vapor deposition (MOCVD) shuttle growth of the proposed CC-QD-IBSC were adopted in this work for better preserving QD induced intermediate band feature and overcoming practical growth difficulties. By introducing a InGaP top cell for constraining the current of InAs/GaAs QD-IBSC, the short circuit current density of CC-QD-IBSC decreased to 13.0mA/cm2 under 1 sun illumination, a near 50 % reduction compared to the conventional InAs/GaAs QD-IBSC. On the contrary, by well adjusting the regrowth interface between MBE and MOCVD, we managed to reach the highest conversion efficiency of 22.8 % measured at an UL certified laboratory under light concentration ratio of 93 suns for the proposed CC-QD-IBSC with well-functioning QD and IB feature. It is our belief that our results pave the road for developing techniques geared towards higher efficiency and more practical field applications.

Monolithic integration of embedded III-V lasers on SOI

Silicon photonic integration has gained great success in many application fields owing to the excellent optical device properties and complementary metal-oxide semiconductor (CMOS) compatibility. Realizing monolithic integration of III-V lasers and silicon photonic components on single silicon wafer is recognized as a long-standing obstacle for ultra-dense photonic integration, which can provide considerable economical, energy-efficient and foundry-scalable on-chip light sources, that has not been reported yet. Here, we demonstrate embedded InAs/GaAs quantum dot (QD) lasers directly grown on trenched silicon-on-insulator (SOI) substrate, enabling monolithic integration with butt-coupled silicon waveguides. By utilizing the patterned grating structures inside pre-defined SOI trenches and unique epitaxial method via hybrid molecular beam epitaxy (MBE), high-performance embedded InAs QD lasers with monolithically out-coupled silicon waveguide are achieved on such template. By resolving the epitaxy and fabrication challenges in such monolithic integrated architecture, embedded III-V lasers on SOI with continuous-wave lasing up to 85 °C are obtained. The maximum output power of 6.8 mW can be measured from the end tip of the butt-coupled silicon waveguides, with estimated coupling efficiency of approximately -6.7 dB. The results presented here provide a scalable and low-cost epitaxial method for the realization of on-chip light sources directly coupling to the silicon photonic components for future high-density photonic integration.

Toward ultraclean correlated metal CaVO3

We report the synthesis and electronic properties of the correlated metal CaVO3, grown by hybrid molecular beam epitaxy. Films were grown on (100) LaAlO3 substrates at a temperature of 900 °C by supplying a flux of elemental Ca through a thermal effusion cell and metalorganic precursor, vanadium oxitriisopropoxide, as a source of vanadium. The presence of a self-regulated growth regime was revealed by the appearance of a specific surface reconstruction detected by reflection high-energy electron diffraction. Films grown within the growth window were characterized by atomically flat surfaces. X-ray reciprocal space maps revealed that the films were coherently strained to the substrate and inherited its twinned microstructure. Despite the presence of twin walls, CaVO3 thin films, grown within the stoichiometric growth window, revealed very low electrical resistivities at low temperatures, with residual resistivity ratios exceeding 90, while films grown at either Ca- or V-excess show deteriorated transport properties, attributed to the presence of extrinsic defects arising from the non-stoichiometry present in these films.

Stoichiometric Control and Optical Properties of BaTiO3 Thin Films Grown by Hybrid MBE

AbstractBaTiO3 is a technologically relevant material in the perovskite oxide class with above‐room‐temperature ferroelectricity and a very large electro‐optical coefficient, making it highly suitable for emerging electronic and photonic devices. An easy, robust, straightforward, and scalable growth method is required to synthesize epitaxial BaTiO3 thin films with sufficient control over the film's stoichiometry to achieve reproducible thin film properties. Here the growth of BaTiO3 thin films by hybrid molecular beam epitaxy is reported. A self‐regulated growth window is identified using complementary information obtained from reflection high energy electron diffraction, the intrinsic film lattice parameter, film surface morphology, and scanning transmission electron microscopy. Subsequent optical characterization of the BaTiO3 films by spectroscopic ellipsometry revealed refractive index and extinction coefficient values closely resembling those of stoichiometric bulk BaTiO3 crystals for films grown inside the growth window. Even in the absence of a lattice parameter change of BaTiO3 thin films, degradation of optical properties is observed, accompanied by the appearance of a wide optical absorption peak in the IR spectrum, attributed to optical transitions involving defect states present. Therefore, the optical properties of BaTiO3 can be utilized as a much finer and more straightforward probe to determine the stoichiometry level present in BaTiO3 films.

Growth of 28Si Quantum Well Layers for Qubits by a Hybrid MBE/CVD Technique

Isotopically enriched 28Si quantum well layers in SiGe/Si/SiGe heterostructures are an excellent material platform for electron spin qubits. In this work, we report the fabrication of 28SiGe/28Si/28SiGe heterostructures for qubits by a hybrid molecular beam epitaxy (MBE) / chemical vapour deposition (CVD) growth, where the thick relaxed SiGe substrates are realised by a reduced-pressure CVD and the 28SiGe/28Si/28SiGe stacks are grown by MBE Here, we achieve a fully strained 28Si quantum well layer in such heterostructures with a 29Si concentration as low as 200 ppm within the MBE grown layers. It concludes that 29Si primarily originates from the residual natural Si vapour in the MBE chamber. A reliable surface preparation combining ex situ wet chemical cleaning and in situ annealing and atomic hydrogen irradiation offers epitaxy ready CVD grown SiGe substrates with low carbon and oxygen impurities. Furthermore, we also present our studies about the growth temperature effect on the misfit dislocation formation in this heterostructure. It shows that the misfit dislocation formation is significantly suppressed at a low MBE growth temperature, such as 350 °C.

Sn-modified BaTiO3 thin film with enhanced polarization

Hybrid molecular beam epitaxy (MBE) growth of Sn-modified BaTiO3 films was realized with varying domain structures and crystal symmetries across the entire composition space. Macroscopic and microscopic structures and the crystal symmetry of these thin films were determined using a combination of optical second harmonic generation (SHG) polarimetry and scanning transmission electron microscopy (STEM). SHG polarimetry revealed a variation in the global crystal symmetry of the films from tetragonal (P4mm) to cubic (Pm3¯m) across the composition range, x = 0 to 1 in BaTi1−xSnxO3 (BTSO). STEM imaging shows that the long-range polar order observed when the Sn content is low (x = 0.09) transformed to a short-range polar order as the Sn content increased (x = 0.48). Consistent with atomic displacement measurements from STEM, the largest polarization was obtained at the lowest Sn content of x = 0.09 in Sn-modified BaTiO3 as determined by SHG. These results agree with recent bulk ceramic reports and further identify this material system as a potential replacement for Pb-containing relaxor-based thin film devices.

Freestanding epitaxial SrTiO 3 nanomembranes via remote epitaxy using hybrid molecular beam epitaxy

The epitaxial growth of functional oxides using a substrate with a graphene layer is a highly desirable method for improving structural quality and obtaining freestanding epitaxial nanomembranes for scientific study, applications, and economical reuse of substrates. However, the aggressive oxidizing conditions typically used in growing epitaxial oxides can damage graphene. Here, we demonstrate the successful use of hybrid molecular beam epitaxy for SrTiO3 growth that does not require an independent oxygen source, thus avoiding graphene damage. This approach produces epitaxial films with self-regulating cation stoichiometry. Furthermore, the film (46-nm-thick SrTiO3) can be exfoliated and transferred to foreign substrates. These results open the door to future studies of previously unattainable freestanding oxide nanomembranes grown in an adsorption-controlled manner by hybrid molecular beam epitaxy. This approach has potentially important implications for the commercial application of perovskite oxides in flexible electronics and as a dielectric in van der Waals thin-film electronics.

Hybrid molecular beam epitaxy of germanium-based oxides

Germanium-based oxides such as rutile GeO2 are garnering attention owing to their wide band gaps and the prospects of ambipolar doping for application in high-power devices. Here, we present the use of germanium tetraisopropoxide (GTIP), a metal-organic chemical precursor, as a source of germanium for the demonstration of hybrid molecular beam epitaxy for germanium-containing compounds. We use Sn1-xGexO2 and SrSn1-xGexO3 as model systems to demonstrate our synthesis method. A combination of high-resolution X-ray diffraction, scanning transmission electron microscopy, and X-ray photoelectron spectroscopy confirms the successful growth of epitaxial rutile Sn1-xGexO2 on TiO2(001) substrates up to x = 0.54 and coherent perovskite SrSn1-xGexO3 on GdScO3(110) substrates up to x = 0.16. Characterization and first-principles calculations corroborate that germanium occupies the tin site, as opposed to the strontium site. These findings confirm the viability of the GTIP precursor for the growth of germanium-containing oxides by hybrid molecular beam epitaxy, thus providing a promising route to high-quality perovskite germanate films.

Surface stability of SrNbO3+δ grown by hybrid molecular beam epitaxy

4d transition metal oxides have emerged as promising materials for numerous applications including high mobility electronics. SrNbO3 is one such candidate material, serving as a good donor material in interfacial oxide systems and exhibiting high electron mobility in ultrathin films. However, its synthesis is challenging due to the metastable nature of the d1 Nb4+ cation and the limitations in the delivery of refractory Nb. To date, films have been grown primarily by pulsed laser deposition (PLD), but development of a means to grow and stabilize the material via molecular beam epitaxy (MBE) would enable studies of interfacial phenomena and multilayer structures that may be challenging by PLD. To that end, SrNbO3 thin films were grown using hybrid MBE for the first time using a tris(diethylamido)(tert-butylimido) niobium precursor for Nb and an elemental Sr source on GdScO3 substrates. Varying thicknesses of insulating SrHfO3 capping layers were deposited using a hafnium tert-butoxide precursor for Hf on top of SrNbO3 films to preserve the metastable surface. Grown films were transferred in vacuo for x-ray photoelectron spectroscopy to quantify elemental composition, density of states at the Fermi energy, and Nb oxidation state. Ex situ studies by x-ray absorption near edge spectroscopy and scanning transmission electron microscopy illustrate that the SrHfO3 capping plays an important role in preserving the crystalline quality of the material and the Nb 4d1 metastable charge state under atmospheric conditions.

Probing electronic dead layers in homoepitaxial n-SrTiO3(001) films

We combine state-of-the-art oxide epitaxial growth by hybrid molecular beam epitaxy with transport, x-ray photoemission, and surface diffraction, along with classical and first-principles quantum mechanical modeling to investigate the nuances of insulating layer formation in otherwise high-mobility homoepitaxial n-SrTiO3(001) films. Our analysis points to charge immobilization at the buried n-SrTiO3/undoped SrTiO3(001) interface as well as within the surface contamination layer resulting from air exposure as the drivers of electronic dead-layer formation. As Fermi level equilibration occurs at the surface and the buried interface, charge trapping reduces the sheet carrier density (n2D) and renders the n-STO film insulating if n2D falls below the critical value for the metal-to-insulator transition.

Anomalous transport in high-mobility superconducting SrTiO3 thin films.

The study of subtle effects on transport in semiconductors requires high-quality epitaxial structures with low defect density. Using hybrid molecular beam epitaxy (MBE), SrTiO3 films with a low-temperature mobility exceeding 42,000 cm2 V−1 s−1 at a low carrier density of 3 × 1017 cm−3 were achieved. A sudden and sharp decrease in residual resistivity accompanied by an enhancement in the superconducting transition temperature were observed across the second Lifshitz transition where the third band becomes occupied, revealing dominant intraband scattering. These films further revealed an anomalous behavior in the Hall carrier density as a consequence of the antiferrodistortive (AFD) transition and the temperature dependence of the Hall scattering factor. Using hybrid MBE growth, phenomenological modeling, temperature-dependent transport measurements, and scanning superconducting quantum interference device imaging, we provide critical insights into the important role of inter- versus intraband scattering and of AFD domain walls on normal-state and superconducting properties of SrTiO3.

Stoichiometry-dependent surface electronic structure of SrTiO3 films grown by hybrid molecular beam epitaxy

We investigate the surface electronic structure of SrTiO3 (STO) films grown by a hybrid molecular beam epitaxy that are both stoichiometric and nonstoichiometric by means of x-ray photoelectron spectroscopy and electron energy loss spectroscopy. Increasing the fraction of the surface that is terminated with an SrO layer is correlated with a decrease in the chemical potential whereby the valence band maximum moves closer to the Fermi level, but without a significant change in the bandgap. Inasmuch as SrO-terminated STO (001) has previously been shown to act as an electron scavenger in which carriers from the bulk are trapped, we argue that the high fraction of SrO in the terminal layer is what lowers the chemical potential in Sr-rich STO. Our experimental results provide important insights into various physical phenomena that can occur on STO (001) surfaces and their effect on bulk electronic properties.

Quantitative Determination of Native Point‐Defect Concentrations at the ppm Level in Un‐Doped BaSnO3 Thin Films

AbstractThe high‐mobility, wide‐bandgap perovskite oxide BaSnO3 is taken as a model system to demonstrate that the native point defects present in un‐doped, epitaxial thin films grown by hybrid molecular beam epitaxy can be identified and their concentrations at the ppm level determined quantitatively. An elevated‐temperature, multi‐faceted approach is shown to be necessary: oxygen tracer diffusion experiments with secondary ion mass spectrometry analysis; molecular dynamics simulations of oxygen‐vacancy diffusion; electronic conductivity studies as a function of oxygen activity and temperature; and Hall‐effect measurements. The results indicate that the oxygen‐vacancy concentration cannot be lowered below 1017.3 cm−3 because of a background level of barium vacancies (of this concentration), introduced during film growth. The multi‐faceted approach also yields the electron mobility over a wide temperature range, coefficients of oxygen surface exchange and oxygen‐vacancy diffusion, and the reduction enthalpy. The consequences of the results for the lowest electron concentration achievable in BaSnO3 samples, for the ease of oxide reduction and for the stability of reduced films with respect to oxidation, are discussed.

Resonant x-ray scattering method for measuring cation stoichiometry in BaSnO3 thin films

We develop a resonant scattering technique to measure cation stoichiometry of lanthanum-doped BaSnO3 (BSO) thin films on a DyScO3 substrate. Samples are grown by a hybrid molecular beam epitaxy method and display high room-temperature carrier mobilities. The measured thin films are grown with widely differing cation arrival rates, with Ba being evaporated from an elemental source and Sn from a SnO2 source. Differences in mobilities in these films may arise from differences in Ba/Sn cation stoichiometry. Owing to the similar scattering strength of the Ba and Sn cations, odd-order Bragg peaks of BSO are particularly sensitive to the material's cation stoichiometry, i.e., the Ba/Sn ratio. Sensitivity to cation stoichiometry is further enhanced using the technique of resonant x-ray scattering, which changes the scattering strength of a single element across the Ba L absorption edges. We determine that the Ba/Sn cation stoichiometry varies from unity by less than 1% for films of mobility ranging from 84.8 to 144 cm2/(V s) and conclude that the mobility of these films scales with film thickness and growth rate rather than stoichiometry.

Correlating surface stoichiometry and termination in SrTiO3 films grown by hybrid molecular beam epitaxy

Hybrid oxide molecular beam epitaxy (hMBE), a thin-film deposition technique in which transition metal cations are delivered using a metal-organic precursor, has emerged as the state-of-the-art approach to the synthesis of electronic-grade complex oxide films with a stoichiometric growth window. However, numerous questions remain regarding the chemical mechanisms of the growth process and the surface properties of the resulting films. To examine these properties, thin film SrTiO3 (STO) was prepared by hMBE using a titanium tetraisopropoxide (TTIP) precursor for Ti delivery and an elemental Sr source on annealed STO and Nb-doped STO substrates with varying TTIP:Sr flux ratios to examine the conditions for the reported stoichiometric growth window. The films were transferred in vacuo to an x-ray photoelectron spectroscopy system to study the surface elemental composition. Samples were examined using x-ray diffraction to compare our surface sensitive results with previously reported measurements of the bulk of the films in the literature. Ex situ studies by atomic force microscopy, scanning tunneling microscopy, and low-energy electron microscopy confirmed the presence of surface reconstructions and an Ehrlich–Schwoebel barrier consistent with A-site SrO termination. We find that a surface exhibiting a mixture of SrO and TiO2 termination or a full SrO termination is necessary to obtain stoichiometric adsorption-controlled growth. These results indicate that surface Sr is necessary to maintain the chemical equilibrium for stoichiometric growth during the hMBE process, which is important for the design of future interfacial systems using this technique.