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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 Abstract

 

Among ABO3 perovskites, SrMoO3 possesses the lowest electrical resistivity in addition to having high optical transparency in the visible spectrum. This unusual combination of material properties allows it to be a potential replacement for indium tin oxide as a transparent electrode. Thus far, its thin film synthesis has been challenging and limited primarily to pulsed laser deposition and sputtering. Here, we report the growth of SrMoO3 thin films by suboxide molecular beam epitaxy. We demonstrate that optically transparent and conductive SrMoO3 films can be grown by supplying elemental strontium via a conventional effusion cell and thermally evaporating MoO3 pellets as a molybdenum source. The direct supply of a molecular oxygen flux to the MoO3 charge was utilized to prevent reduction to lower oxidation states of the charge to ensure congruent evaporation and, thus, a stable MoO3 molecular flux. The optimal growth conditions were found by varying the Sr to MoO3 flux ratio determined from quartz crystal microbalance measurements and monitoring the growth by reflection high-energy electron diffraction. SrMoO3 thin films with 21 nm thickness were confirmed to be optically transparent with transmission between 75 and 91% throughout the visible spectral range and electrically conducting with a room temperature resistivity of 5.0 × 10−5 Ω cm. This realization of this thin film growth method can be further expanded to the growth of other transition metal perovskites in which cations have extremely low vapor pressure and cannot be evaporated in elemental forms.

 

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.

 

BaTiO₃is 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 BaTiO₃thin films with sufficient control over the film's stoichiometry to achieve reproducible thin film properties. Here the growth of BaTiO₃thin 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 BaTiO₃films by spectroscopic ellipsometry revealed refractive index and extinction coefficient values closely resembling those of stoichiometric bulk BaTiO₃crystals for films grown inside the growth window. Even in the absence of a lattice parameter change of BaTiO₃thin 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 BaTiO₃can be utilized as a much finer and more straightforward probe to determine the stoichiometry level present in BaTiO₃films.

 

The temperature-dependent desorption behavior of selenium and tellurium is investigated using a heated quartz crystal microbalance. Prior to heating the quartz crystal microbalance, selenium and tellurium films with varying thickness were deposited using thermal effusion cells in a molecular beam epitaxy system for subsequent determination of temperature-dependent mass loss of the deposited films. The desorption rate for tellurium was found to exhibit one sharp peak around 190 °C, indicating the loss of the entire film irrespective of film thickness within a temperature window of 20 °C, which was completely evaporated at 200 °C. Similar experiments for selenium revealed that the thermal desorption took place via a two-stage process with a smaller portion of the material desorbing within an even narrower temperature window of 5 °C at a much lower peak temperature of 65 °C, while most selenium desorbed within a temperature range of 10 °C around 90 °C. This two-stage behavior indicated the presence of at least two chemically distinct selenium species or binding states. The direct and quantitative determination of the chalcogen desorption process provides important insights into the kinetics of chalcogenide-based film growth and is in addition of applied benefit to the research community in the area of Se/Te capping and decapping of air sensitive materials as it provides temperature ranges and rates at which full desorption is achieved. Our work furthermore points toward the need for a more detailed understanding of the chemical composition state of atomic and molecular beams supplied from thermal evaporation sources during growth.

 

Abstract The structural properties of co-deposited ultrathin PtSe 2 films grown at low temperatures by molecular beam epitaxy on c-plane Al 2 O 3 are studied. By simultaneously supplying a Se flux from a Knudsen cell and Pt atoms from an electron-beam evaporator, crystalline (001)-oriented PtSe 2 films were formed between 200 °C and 300 °C. The long separation between substrate and electron beam evaporator of about 60 cm ensured minimal thermal load. At optimum deposition temperatures, a ten times or even higher supply rate of Se compared to Pt ensured that the pronounced volatility of the Se was compensated and the PtSe 2 phase was formed and stabilized at the growth front. Postgrowth anneals under a Se flux was found to dramatically improve the crystalline quality of the films. Even before the postgrowth anneal in Se, the crystallinity of PtSe 2 films grown with the co-deposition method was superior to films realized by thermal assisted conversion. Postgrowth annealed films showed Raman modes with narrower peaks and more than twice the intensity. Transmission electron microscopy investigations revealed that the deposited material transitioned to a two-dimensional layered structure only after the postgrowth anneal. PtSe 2 growth was found to start as single layer islands that preferentially nucleated at atomic steps of the substrate and progressed in a layer-by-layer like fashion. A close to ideal wetting behavior resulted in coalesced PtSe 2 films after depositing about 1.5 PtSe 2 layers. Detailed Raman investigation of the observed PtSe 2 layer breathing modes of films grown under optimized co-deposition conditions revealed an interlayer coupling force constant of 5.0–5.6 × 10 19 N m −3 . 

The drive toward non‐von Neumann device architectures has led to an intense focus on insulator‐to‐metal (IMT) and the converse metal‐to‐insulator (MIT) transitions. Studies of electric field‐driven IMT in the prototypical VO₂thin‐film channel devices are largely focused on the electrical and elastic responses of the films, but the response of the corresponding TiO₂substrate is often overlooked, since it is nominally expected to be electrically passive and elastically rigid. Here, in‐operando spatiotemporal imaging of the coupled elastodynamics using X‐ray diffraction microscopy of a VO₂film channel device on TiO₂substrate reveals two new surprises. First, the film channel bulges during the IMT, the opposite of the expected shrinking in the film undergoing IMT. Second, a microns thick proximal layer in the substrate also coherently bulges accompanying the IMT in the film, which is completely unexpected. Phase‐field simulations of coupled IMT, oxygen vacancy electronic dynamics, and electronic carrier diffusion incorporating thermal and strain effects suggest that the observed elastodynamics can be explained by the known naturally occurring oxygen vacancies that rapidly ionize (and deionize) in concert with the IMT (MIT). Fast electrical‐triggering of the IMT via ionizing defects and an active “IMT‐like” substrate layer are critical aspects to consider in device applications.