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Solid phase epitaxy (SPE) has been widely employed for various thin-film materials, making it valuable for industrial applications due to its scalability. In complex oxides, SPE has been limited to a few materials because of the challenges in maintaining stoichiometric control during growth, particularly when volatile phases are present at high temperatures. Here, we investigate the impact of encapsulation layers on the SPE of complex oxides, using SrRuO3 (SRO) as a model system. An amorphous SRO layer was deposited on a SrTiO3 (STO) substrate, followed by the transfer of a single-crystalline STO membrane as an encapsulation layer in order to suppress the evaporation of volatile species (RuO2) during the SPE process. Whereas both encapsulated and unencapsulated SRO layers were successfully crystallized, the unencapsulated films suffered a substantial loss of Ru ions—exceeding 20%—compared to their encapsulated counterparts. This loss of Ru ions led to a loss of metallicity in the unencapsulated SRO layers, whereas the encapsulated layers retained their metallic ferromagnetic properties. This study demonstrates that the encapsulation provided by oxide membranes effectively suppresses stoichiometric loss during SPE, presenting a new strategy in stabilizing a broader class of functional oxides as epitaxial thin films.
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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.
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- Award ID(s):
- 2004326
- PAR ID:
- 10428910
- Date Published:
- Journal Name:
- Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films
- Volume:
- 39
- Issue:
- 5
- ISSN:
- 0734-2101
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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We investigate the surface electronic structure of SrTiO 3 (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.more » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1116/6.0001159
