Epitaxial SrTiO3 Thin Films Research Articles

Laser-induced transverse voltage effect in c-axis inclined La x Sr1−x TiO3 thin films prepared by MOCVD

Light and thermal detectors based on the laser-induced transverse voltage (LITV) effect have garnered significant interest for their rapid and broad spectral response. In this study, we prepared the La-doped SrTiO3 (STO) epitaxial thin films on the 12° inclined single crystal LaAlO3 (LAO) (100) substrates using our home-designed metal–organic chemical vapor deposition system. Under the illumination of a 248 nm laser, the LITV signals of La x Sr1−x TiO3 films were observed and showed dependence on the La doping level, which can be explained by the changes in the light absorption coefficient, thermal conductivity, and optical penetration depth. The optimized LITV signal was observed with a peak voltage of 23.25 V and a decay time of 106 ns under the laser power density of 1.0 mJ mm−2. The high peak voltage and fast response time of La x Sr1−x TiO3 show great potential in the field of light and thermal detection.

Impact of Cationic Stoichiometry on Physical, Optical and Electrical Properties of SrTiO3 Thin Films Grown on (001)-Oriented Si Substrates.

In this study, we investigate the changes in the crystalline structure of MBE-deposited SrTiO3 layers on Si with different deviations from Sr/Ti stoichiometry as deposited but also after annealing at high temperatures (>600 °C). We show that as-grown 15 nm thick non-stochiometric SrTiO3 layers present surprisingly lower FWHM values of the (002) omega diffraction peak compared to fully stoichiometric layers of similar thickness. This can misleadingly point to superior crystalline quality of such non-stochiometric layers. However, thermal post-deposition anneals of these layers at temperatures up to 850 °C in oxygen show strong detrimental effects on the crystalline structure, surface and interface with the Si (001) substrate. On the contrary, the post-deposition anneals applied to the stoichiometric samples strongly improve the physical, optical and electrical properties of the epitaxial SrTiO3 thin films.

Surface triggered stabilization of metastable charge-ordered phase in SrTiO3

Charge ordering (CO), characterized by a periodic modulation of electron density and lattice distortion, has been a fundamental topic in condensed matter physics, serving as a potential platform for inducing novel functional properties. The charge-ordered phase is known to occur in a doped system with high d-electron occupancy, rather than low occupancy. Here, we report the realization of the charge-ordered phase in electron-doped (100) SrTiO3 epitaxial thin films that have the lowest d-electron occupancy i.e., d1-d0. Theoretical calculation predicts the presence of a metastable CO state in the bulk state of electron-doped SrTiO3. Atomic scale analysis reveals that (100) surface distortion favors electron-lattice coupling for the charge-ordered state, and triggering the stabilization of the CO phase from a correlated metal state. This stabilization extends up to six unit cells from the top surface to the interior. Our approach offers an insight into the means of stabilizing a new phase of matter, extending CO phase to the lowest electron occupancy and encompassing a wide range of 3d transition metal oxides.

Thickness-dependent flexoresistance in SrTiO3 thin films

We report a thickness-dependent flexoresistance effect caused by strain gradient in SrTiO3 (STO) epitaxial thin films. The strain gradient in STO was induced by using an atomic force microscope diamond-coated tip. The depolarization field caused by the strain gradient changes the electrical state of the film, resulting in a decrease in the resistance of the films by 4–6 orders of magnitude. By testing the current–voltage (I–V) curves of STO films with different thicknesses, it is found that the flexoresistance behavior of STO films is obvious thickness dependent: the thicker the film, the higher the force threshold to trigger the film to enter a highly conductive state. The comparison of the surface morphology before and after the I–V test with loading shows that only when the thickness of the STO film is below 8 nm, the film can enter the conductive state from the insulating state without damaging the surface. During the electrical state switching process, the strain gradient caused by tip loading play an important role in the modification of the film barrier.

Examining imprinted ferroelectric hysteresis loops and improved energy storage properties of Mn-doped epitaxial SrTiO3 thin films using heat treatment

This study investigated imprinted ferroelectric hysteresis loops and energy storage properties of Mn-doped epitaxial SrTiO3 (MSTO) thin films using heat treatment. The crystallinity of MSTO thin films was improved by reducing the deposition rates of epitaxial (001) MSTO thin films on single-crystal (100) Rh substrates from 0.15 to 0.03 nm/pulse. The polarization of MSTO thin films, with improved polarization by Mn doping, was further enhanced by improving film crystallinity. MSTO thin films exhibited an energy storage efficiency of approximately 90 % and an increase in energy storage density from 23 to 34 J/cm3. The energy storage density increased further to 39 J/cm3 using imprinted ferroelectric hysteresis loops and heat treatment.

Effect of Oxygen Partial Pressure on Crystal Structure, Oxygen Vacancy, and Surface Morphology of Epitaxial SrTiO3 Thin Films Grown by Ion Beam Sputter Deposition

Epitaxial SrTiO3 (STO) thin films were grown on (001)-oriented LaAlO3 (LAO) substrates at 800 °C by an ion beam sputter deposition (IBSD). Oxygen partial pressure (PO2) was varied at 1.5 × 10−5, 1.5 × 10−4, and 1.5 × 10−3 Torr during the growth. The effects of PO2 on crystal structure, oxygen vacancy, and surface morphology of the STO films were investigated and are discussed to understand their correlation. It was found that PO2 played a significant role in influencing the crystal structure, oxygen vacancy, and surface morphology of the STO films. All STO films grew on the LAO substrates under a compressive strain along an in-plane direction (a- and b-axes) and a tensile strain along the growth direction (c-axis). The crystalline quality of STO films was slightly improved at higher PO2. Oxygen vacancy was favorably created in the STO lattice grown at low PO2 due to a lack of oxygen during growth and became suppressed at high PO2. The existence of oxygen vacancy could result in a lattice expansion in both out-of-plane and in-plane directions due to the presence of Ti3+ instead of Ti4+ ions. The surface roughness of the STO films gradually decreased and was nearly close to that of the bare LAO substrate at high PO2, indicating a two-dimensional (2D) growth mode. The results presented in this work provide a correlation among crystal structure, oxygen vacancy, and surface morphology of the epitaxial STO films grown by IBSD, which form a useful guideline for further study.

Synthesis of Stoichiometric SrTiO3 and Its Carrier Doping from Air-Stable Bimetallic Complexes.

We demonstrate the synthesis of perovskite oxide SrTiO3 with ideal cation stoichiometry and homogeneous La doping using air-stable Sr-Ti and La-Ti bimetallic peroxo complexes with a 1:1 cation ratio. Phase-pure SrTiO3, La2Ti2O7, and LaTiO3 were successfully synthesized by thermal decomposition of those complexes. La-doped SrTiO3 was obtained by mixing the Sr-Ti and La-Ti complexes in an acid solution, followed by thermal decomposition. La-doped SrTiO3 showed systematic chemical trends in the lattice constant and electrical conduction. Not only those bulk polycrystals but also cation-stoichiometric SrTiO3 epitaxial thin films were grown with an atomically flat surface from the Sr-Ti complex.

Self-assembled gold nanostructures in complex oxide thin films

Recently, noble metal- complex oxide nanocomposites with a high interface-to-volume ratio have attracted considerable interest for their potential applications in advanced devices. In this work, Nb:SrTiO3 epitaxial thin films embedded with different ratios of Au nanophase were fabricated using pulsed laser deposition. Detailed heterostructures at an atomic scale have been investigated based on advanced transmission electron microscopy. The results reveal that the pattern tunability of Au nanostructures can be realized by controlling the volume ratios between Au and Nb:SrTiO3, resulting in the manipulation of absorption characteristics in the visible light region. It is suggested that elastic energy and surface energy anisotropy are important factors to control the growth of the present Au/Nb:SrTiO3 heterostructures. This work offers a desirable platform to design nanocomposites with novel optical properties.

Ferroelectricity in SrTiO3 epitaxial thin films via Sr-vacancy-induced tetragonality

SrTiO3 is one of the most widely studied perovskite oxides that exhibit quantum paraelectric behavior. Being at the border of the paraelectric-ferroelectric transition, SrTiO3 is known to become ferroelectric at a finite temperature by exploiting various approaches including epitaxial strain, oxygen isotope exchange, and dimensionality. In this study, owing to the state-of-the-art pulsed laser epitaxy, a selective engineering of elemental vacancies is proposed for the emergence and systematic control of the ferroelectricity in SrTiO3 thin films. Therein, Sr vacancy plays an essential role in inducing the cubic-to-tetragonal transition, resulting in the inversion symmetry breaking necessary for the switchable electric polarization. Furthermore, the tetragonality is enhanced with the increase in the Sr vacancies, eventually strengthening the ferroelectricity. Our research summarizes the tetragonality-induced ferroelectricity in SrTiO3 and provides facile growth control of the behavior.

(Invited) Impact of Stoichiometry and Interface Configuration on the Time Stability and the Speed-Limiting Step in Memristive SrTiO3 Cells

Resistive switching oxides are promising candidates for future non-volatile memory and for functional units of neuromorphic computing. Epitaxial SrTiO3 thin films can be regarded as model system for resistive switching thin films due to their well-known defect chemistry and the absence of grain boundaries. We have recently shown that so-called eightwise switching in SrTiO3 can be attributed to the release and reincorporation oxygen at the interface to a Pt electrode [1,2]. In the light of this knowledge, we studied in detail the impact of the Sr/Ti stoichiometry on the filament formation process, the filament stability [3] and the switching kinetics. We observed that Sr rich thin films exhibit an improved retention of the low resistive state (LRS) at low current compliance values with respect to the stoichiometric thin films. In order to identify the underlying processes, we investigated the filament formation process of SrTiO3 thin films with different stoichiometry by photoelectron emission microscopy. Stoichiometric thin films form a stable LRS state as soon as the current compliance is sufficient to trigger SrO segregation at the surface [4]. We attribute this to the impeded reoxidation of the oxygen deficient filament by the presence of the SrO at the surface. We could mimic this effect by intentionally depositing additional SrO, or other oxygen blocking layers such as Al2O3 on the surface of stoichiometric thin films and were thereby able to improve the memory window as well as the LRS retention. We furthermore investigated the switching kinetics of the SET process for different Sr/Ti stoichiometries and interface layers. We compared these results to analytical models for the switching kinetics based on ion movement, modeled by the Mott-Gurney-Law, and an oxygen exchange reaction at the interface, modeled by the Butler-Volmer-Equation, as the rate-determining steps in combination with simulated temperature and electrical potential data from finite element simulations, as shown in Figures 1 ((a) stoichiometric, (b) Sr rich). For stoichiometric SrTiO3 cells, oxygen transfer at the oxide-metal interface is determined as the rate-determining step. In contrast, for Sr-rich STO cells we propose oxygen diffusion within the SrO layer at the metal-STO interface as rate-limiting. We will discuss possible reasons for the different rate-determining steps, such as different vacancy concentrations and exchange probabilities.

Effect of Nb concentration on the spin-orbit coupling strength in Nb-doped SrTiO3 epitaxial thin films

Several oxide materials have attracted much interest for the application in spintronic devices due to unusual properties originating from the strongly correlated orbital and spin degrees of freedom. One missing part in oxide spintronics is a good spin channel featured by strong spin-orbit coupling (SOC) which enables an efficient control of the electron’s spin. We have systematically investigated the dependence of the SOC strength of Sr(NbxTi1−x)O3 thin films on Nb concentration (nNb = 2~20 at. %) as a deeper exploration of a recent finding of the strong SOC in a heavily Nb-doped SrTiO3 (Sr(Nb0.2Ti0.8)O3) epitaxial film. Apart from a finding of a proportionality of the SOC to nNb, we have observed an intriguing temperature dependence of the SOC strength and the anisotropic magnetoresistance (MR) in the intermediate nNb region. These phenomena are associated with the temperature dependence of Landé g-factor and the change of the band structure, which is consistent with the result of density functional theory (DFT) calculation.

Strain-induced nanostructure of Pb(Mg1/3Nb2/3)O3–PbTiO3 on SrTiO3 epitaxial thin films with low PbTiO3 concentration

The singularity of the structure in (1 − x)Pb(Mg1/3Nb2/3)O3–xPbTiO3 (PMN–xPT) (x = 0–50 mol %) epitaxial thin films of 100 nm thickness was investigated from the viewpoint of the localized residual strain in the nanoscale. The films were deposited on SrTiO3 (STO) (001) single-crystal substrates by chemical solution deposition (CSD) using metallo-organic decomposition (MOD) solutions. X-ray and electron diffraction patterns revealed that PMN–xPT thin films included a single phase of the perovskite-type structure with the cube-on-cube orientation relationship between PMN–xPT and STO: (001)Film ∥ (001)Sub, [100]Film ∥ [100]Sub. X-ray reciprocal space maps showed an in-plane tensile strain in all the compositional ranges considered. Unit cells in the films were strained from the rhombohedral (pseudocubic) (R) phase to a lower symmetry crystal system, the monoclinic (MB) phase. The morphotropic phase boundary (MPB) that split the R and tetragonal (T) phases was observed at x = 30–35 for bulk crystals of PMN–xPT, whereas the strain suppressed the transformation from the R phase to the T phase in the films up to x = 50. High-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) analysis and its related local strain analysis revealed that all of the films have a bilayer morphology. The nanoscale strained layer formed only above the film/substrate semi-coherent interface. The misfit dislocations generated the localized and periodic strain fields deformed the unit cells between the dislocation cores from the R to an another type of the monoclinic (MA) phase. Thus, the singular and localized residual strains in the PMN–xPT/STO (001) epitaxial thin films affect the phase stability around the MPB composition and result in the MPB shift phenomena.

Optical investigation of oxygen defect states in SrTiO3 epitaxial thin films

We investigated oxygen defect states in SrTiO3 (STO) thin films by using photoluminescence spectroscopy and spectroscopic ellipsometry. The oxygen-deficient STO homoepitaxial films were fabricated by using different oxygen partial pressures and flow rates for controlling the amount of oxygen vacancies systematically. The visible emission and absorption increased simultaneously with increasing oxygen vacancy concentration in the STO thin films. Given the absolute values of the optical constants, we discussed the origins of the visible absorption features in the STO thin films, in relation to the defect formation and related electronic reconstruction.

Large linear magnetoresistance in heavily-doped Nb:SrTiO3 epitaxial thin films.

Interaction between electrons has long been a focused topic in condensed-matter physics since it has led to the discoveries of astonishing phenomena, for example, high-Tc superconductivity and colossal magnetoresistance (CMR) in strongly-correlated materials. In the study of strongly-correlated perovskite oxides, Nb-doped SrTiO3 (Nb:SrTiO3) has been a workhorse not only as a conducting substrate, but also as a host possessing high carrier mobility. In this work, we report the observations of large linear magnetoresistance (LMR) and the metal-to-insulator transition (MIT) induced by magnetic field in heavily-doped Nb:STO (SrNb0.2Ti0.8O3) epitaxial thin films. These phenomena are associated with the interplay between the large classical MR due to high carrier mobility and the electronic localization effect due to strong spin-orbit coupling, implying that heavily Nb-doped Sr(Nb0.2Ti0.8)O3 is promising for the application in spintronic devices.

Growth of Epitaxial Oxide Thin Films on Graphene.

The transfer process of graphene onto the surface of oxide substrates is well known. However, for many devices, we require high quality oxide thin films on the surface of graphene. This step is not understood. It is not clear why the oxide should adopt the epitaxy of the underlying oxide layer when it is deposited on graphene where there is no lattice match. To date there has been no explanation or suggestion of mechanisms which clarify this step. Here we show a mechanism, supported by first principles simulation and structural characterisation results, for the growth of oxide thin films on graphene. We describe the growth of epitaxial SrTiO3 (STO) thin films on a graphene and show that local defects in the graphene layer (e.g. grain boundaries) act as bridge-pillar spots that enable the epitaxial growth of STO thin films on the surface of the graphene layer. This study, and in particular the suggestion of a mechanism for epitaxial growth of oxides on graphene, offers new directions to exploit the development of oxide/graphene multilayer structures and devices.

Electrical and Optical Properties of Transparent Conducting p‐Type SrTiO3 Thin Films

We report a systematic study of the electrical and optical properties of epitaxial perovskite p‐type In‐doped SrTiO3 thin films (SrInxTi1−xO3, 0 ≤ x ≤ 0.15) grown on single‐crystal (100)‐oriented LaAlO3 substrates using a hybrid method which combines pulsed laser deposition and molecular beam epitaxy in a range of deposition conditions. X‐ray diffraction analysis confirms the epitaxial growth of high crystal quality films. Four‐point probe and Hall Effect measurements demonstrate that the films are p‐type semiconductors with a low resistivity of ~10−2 Ω·cm and a high carrier concentration of ~1019 cm−3. The optical transmittance spectra reveal that the films are highly transparent (˃70%) in the visible region.

Band alignment of epitaxial SrTiO3 thin films with (LaAlO3)0.3-(Sr2AlTaO6)0.7 (001)

SrTiO3 (STO) epitaxial thin films and heterostructures are of considerable interest due to the wide range of functionalities they exhibit. The alloy perovskite (LaAlO3)0.3-(Sr2AlTaO6)0.7 (LSAT) is commonly used as a substrate for these material structures due to its structural compatibility with STO and the strain-induced ferroelectric response in STO films grown on LSAT. However, surprisingly little is known about the electronic properties of the STO/LSAT interface despite its potentially important role in affecting the overall electronic structure of system. We examine the band alignment of STO/LSAT heterostructures using x-ray photoelectron spectroscopy for epitaxial STO films deposited using two different molecular beam epitaxy approaches. We find that the valence band offset ranges from +0.2(1) eV to −0.2(1) eV depending on the film surface termination. From these results, we extract a conduction band offset from −2.4(1) eV to −2.8(1) eV, indicating that the conduction band edge is more deeply bound in STO and that LSAT will not act as a sink or trap for electrons in the supported film or multilayer.

Defect Chemistry of Perovskite Titanates: From Bulk Materials to Nanostructured Materials

To describe the electrical conductivities of perovskite titanates (e.g. SrTiO3 and BaTiO3) and the relation to parameters like temperature, oxygen partial pressure or acceptor- or donor-type dopants, the defect chemistry has been extensively studied since the late 1960s. The studies finally lead to the formulation of the point defect chemistry on the basis of defect chemical reactions, exchange processes with the atmosphere and changes of the valence state regarding their individual thermal activation and thermo­dynamic equilibriums. Comparing with microstructured counterparts, nanostructured materials have significantly higher interface (surface and/or grain boundary) to bulk fraction, which leads to some unique effects in nanostructured perovskite titanates. One effect is that the space charge layer becomes increasingly important. Owing to the high surface-to-volume ratio, the surface space charge layer plays an important role in thin films. For example, the p-type conductivity of the epitaxial SrTiO3 thin films decreases, and the n-type conductivity increases with decreasing film thickness. This phenomenon is attributed to the charge carrier redistribution in the space charge layer. Moreover, the defect thermodynamics at nanometer-scale is different. E.g. the oxidation enthalpy of nanocrystalline BaTiO3 ceramics is found to be about one-third of that of microcrystalline BaTiO3. As a result, the p-type electrical conductivity of nanocrystalline BaTiO3 is about 2 orders of magnitude higher than that of microcrystalline BaTiO3.

A novel, layered phase in Ti-rich SrTiO3 epitaxial thin films.

Sr2Ti7O14, a new phase, is synthesized by leveraging the innate chemical and thermo-dynamic instabilities in the SrTiO3-TiO2 system and non-equilibrium growth techniques. The chemical composition, epitaxial relationships, and orientation play roles in the formation of this novel layered phase, which, in turn, possesses unusual charge ordering, anti-ferromagnetic ordering, and low, glass-like thermal conductivity.

Band-Gap Reduction and Dopant Interaction in Epitaxial La,Cr Co-doped SrTiO3 Thin Films

We show that by co-doping SrTiO3 (STO) epitaxial thin films with equal amounts of La and Cr, it is possible to produce films with an optical band gap ∼0.9 eV lower than that of undoped STO. Sr1–xLaxTi1–xCrxO3 thin films were deposited by molecular beam epitaxy and characterized using X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy to show that the Cr dopants are almost exclusively in the Cr3+ oxidation state. Extended X-ray absorption fine structure measurements and theoretical modeling suggest that it is thermodynamically preferred for La and Cr dopants to occupy nearest-neighbor A- and B-sites in the lattice. Transport measurements show that the material exhibits variable-range hopping conductivity with high resistivity. These results create new opportunities for the use of doped STO films in photovoltaic and photocatalytic applications.