SrTiO3 Single Crystal Substrates Research Articles

Pulsed laser deposition and structural analysis of Ba2Ti6O13 epitaxial thin film on the (210) surface of SrTiO3 single crystal

Abstract A single crystalline thin film of Ba2Ti6O13 was grown on the (210) surface of a SrTiO3 single-crystal substrate by pulsed laser deposition. Scanning transmission electron microscopy shows that the Ba2Ti6O13 thin film grew epitaxially with the a-plane, and the b-/c-axes of Ba2Ti6O13 parallel to the (210) plane and the [00-1]/[-120] directions of SrTiO3, respectively. The electrical conductance of the Ba2Ti6O13 film was approximately one order larger than that of reduced SrTiO3-δ single crystal with oxygen deficiency of roughly δ = 0.05. Electronic structure calculations predict that δ is an n-type degenerate semiconductor with spin-split states primarily of Ti 3d orbital.

A novel method to enhance the superconducting properties of Bi2Sr2CaCu2O8+δ superconducting thin films by self-assembly NiO nanorods

The utilization of Bi-based superconductors in magnetic field environments is limited due to their anisotropic structure and lack of efficient magnetic flux pinning sites. Therefore, to enhance the performance of Bi-based superconductors in a magnetic field, this study presents the preparation of Bi2212 high-temperature superconducting thin films with varying NiO doping levels on SrTiO3 (STO) single crystal substrates with different concentrations of NiO seed layers via the self-assembly method. Additionally, phase purity, crystal structure, surface morphology, and transport properties were thoroughly analyzed. According to the results, the NiO seed layers prepared on the STO substrates presented epitaxial growth characteristics, with the NiO second phase in the Bi2212 matrix growing epitaxially along the seed layers. As NiO doping slightly broadens the phase formation temperature range of Bi2212 superconducting thin films, the self-assembly method can be utilized to prepare NiO nanorods with epitaxial growth in Bi2212 thin films. Notably, the self-assembled NiO-doped Bi2212 thin film demonstrated higher critical current carrying capacity, with its Jc reaching 6.28 × 104 A/cm2 at 10 K in self-field. This provides a technical reference for improving the performance of high-temperature superconducting thin films under a high magnetic field.

Patterning and epitaxy of large-area arrays of nanoscale complex oxide epitaxial heterostructures

A combination of block copolymer (BCP) lithography and solid-phase epitaxy can be employed to form large areas, on the order of square centimeters, of a high density of epitaxial crystalline complex oxide nanostructures. We have used BCP lithography with a poly(styrene-block-methyl methacrylate) (PS-b-PMMA) copolymer to template a nanohole array either directly on an (001)-oriented SrTiO3 (STO) single crystal substrate or on a 20 nm-thick Si3N4 layer deposited on the STO substrate. BCPs with the selected compositions assembled in a cylindrical phase with 16 nm diameter PMMA cylinders and a cylinder-to-cylinder spacing of 32 nm. The substrate was modified with an energetically non-preferential polymer layer to allow for the vertical alignment of the cylinders. The PMMA cylinders were removed using a subtractive process, leaving an array of cylindrical holes. For BCPs assembled on Si3N4/STO, the pattern was transferred to the Si3N4 layer using reactive ion etching, exposing the underlying STO substrate in the nanoholes. An amorphous LaAlO3 (LAO) layer was deposited on the patterned Si3N4/STO at room temperature. The amorphous LAO epitaxially crystallized within the nanoscale-patterned holes with fully relaxed lattice parameters through solid phase epitaxy, resulting in the formation of nanoscale LAO/STO epitaxial heterostructures.

Enhanced energy storage performance in Bi4Ti3O12 thin films with oxygen depletion layers

The imprint effect in ferroelectric materials can significantly enhance the performance of energy storage devices. Bi4Ti3O12 (BTO) and oxygen-deficient Bi4Ti3O11.2 (DBTO) thin films were deposited on single-crystal Nb-doped SrTiO3 substrates using pulsed laser deposition. In stark contrast, multilayer DBTO/BTO thin films incorporating an oxygen-deficient layer were also fabricated, with the DBTO layers having thicknesses of 5 nm and 10 nm, respectively. Both BTO and DBTO thin films exhibited epitaxial growth and c-axis-oriented crystallinity. Regarding ferroelectric properties, DBTO/BTO capacitors with an oxygen-deficient layer demonstrated a pronounced imprint effect in their ferroelectric hysteresis loops, compared to the BTO and DBTO capacitors. This effect was particularly noticeable in the DBTO/BTO capacitor with a 10 nm oxygen-deficient layer, as opposed to the thin film with a 5 nm oxygen-deficient layer. We suggest that the imprint effect can be attributed to localized electric field variations and imbalances in charge transport at the interface between the oxygen-depleted layer and the remaining thin film. Consequently, the imprint effect observed in the DBTO/BTO capacitors contributed to an enhancement in energy storage density and efficiency, compared to BTO and DBTO capacitors. This study demonstrates the potential of multilayer DBTO/BTO thin films in advancing capacitive energy storage systems.

Structural and resistive properties of Pt/BiFeO3/La0.5Sr0.5CoO3 heterostructure for storage application

BiFeO3 has promissing application in non-volatile ferroelectric memory, but the dominant mechanism has not been unified. Here, Pt/BiFeO3 (100 nm)/La0.5Sr0.5CoO3 (Pt/BFO/LSCO) heterostructures have been fabricated on (001) SrTiO3 (STO) single crystal substrates by off-axis magnetron sputtering. Both XRD and TEM analyses confirm that the (001) oriented BFO/LSCO heterostructures have been epitaxially grown on STO. In addition, XRD, TEM along with XPS analyses further indicate that the BFO film (001) presents epitaxial perovskite structure. On the basis of electric field regulation of Pt/BFO and BFO/LSCO interface barrier, the switching interface state is controlled by charge filling and trapping in interface potential well, which is responsible for I–V resistance and G-V hysteretic curve. Based on the fitting results of the conduction mechanism of I–V characteristic curve, it proves that the space charges limiting current play a dominant role, and the filling and trapping of interface traps are considered as the main resistance mechanisms. Moreover, ultraviolet irradiation can modulate the I–V resistance curve but does not change its conduction mechanism. This work provides experimental data for the practical application of integrated BFO resistive memories.

Quantum interference in a high-transition-temperature superconductor based on nanoslits on SrTiO3 substrate

The Josephson junction, a key component of superconducting quantum circuits, is much less mature, especially for the high-transition (high-Tc) temperature cuprate superconductors. Herein, we report on the realization of high-Tc Josephson junction based on nanoslits on a SrTiO3 substrate. We demonstrate the ability to manipulate the current–voltage characteristics of YBa2Cu3O7−x bridges continuously from superconducting current-dominated to Josephson junction behavior by changing the irradiation parameters of the focused Ga+ ion beam on a single-crystal SrTiO3 substrate. The periodic critical current that depends on the magnetic flux coupled into the superconducting quantum interference devices was observed, which exactly reflects the effects of quantum tunneling and flux quantization. To some extent, this weak link within the framework of the semiconductor manufacturing process shows the potential to provide a cost-effective, highly efficient, and reliable pathway for scaling up quantum mechanical superconducting circuits, which is promising for the fabrication process.

Navigating the magnetic contribution of the commonly used single-crystal substrates SrTiO3 (100) and LaAlO3 (100) in weak magnetic thin films

In recent years, thin films of weak ferromagnetic materials have been in huge demand; however, probing their magnetic characteristics has been difficult due to contributions from underlying substrates. In the present study, we have analyzed the magnetic properties of the commonly used single-crystal SrTiO3 (100) and LaAlO3 (100) substrates and performed a time-dependent annealing protocol in vacuum and ambient oxygen pressure to mitigate the intrinsic weak ferromagnetic contributions from these substrates arising due to the presence of disorder or defects such as vacancies in the pristine substrates. It is shown that after proper air annealing, the substrate magnetic background becomes diamagnetic. When such air-annealed diamagnetic substrates are used for the deposition of low-thickness films carrying low magnetic moments such as SrRuO3 and SrMnO3 thin films, their magnetic transitions are explicitly observed. The proposed annealing protocols help to improve the signal from weak magnetic samples. This allows us to analyze the film’s magnetic properties without worrying about the contribution from the substrate.

Texture in atomic layer deposited Hf0.5Zr0.5O2 ferroelectric thin films

HfO2-based ferroelectric materials have excellent CMOS compatibility and polarization even in ultrathin films, which is regarded as promising candidate material for memory devices and related electronic devices. However, as the ferroelectric layer thickness scaling down, the consistency of device performance is inevitably affected by the complex polyphase and polycrystalline nature of HfO2-based ferroelectric thin films. Therefore, obtaining and controlling the texture of HfO2-based ferroelectric thin films is extremely important for regulating polarization orientation and improving ferroelectric polarization. In this work, 10 nm Hf0.5Zr0.5O2 (HZO) films were prepared by atomic layer deposition (ALD) on Nb-doped SrTiO3 (NSTO) single crystal substrates. The texture and orientation of HZO films were analyzed through the state-of-the-art spherical aberration corrected transmission electron microscope (Cs-TEM) technique. The domain matching epitaxy between HZO films and NSTO substrate helps eliminate lattice mismatch and residual misfit strain, and ultimately leads to the formation of <112> texture in HZO ferroelectric films. The obtained results represent lattice and interface play an extremely important role in regulating the ferroelectricity of HfO2-based films, which provides a way to design ultra-thin HfO2-based materials with excellent ferroelectric polarization by controlling the crystal structure and orientation.

Preparation of p/n-type YBa2Cu3O7−δ/Nd1.85Ce0.15CuO4 superconducting heterostructures

Due to the great differences in electron pairing characteristics between the hole-type (p-type) high-temperature superconductor (HTS) and the electron-type (n-type) HTS, when the Cooper pairs enter from a p-type to an n-type HTS or an n-type to a p-type HTS, pairing adjustment or even the recombination of them will inevitably occur at the interface, and the superconducting current dominated by them will be bound to change. Therefore, it is possible to better understand the electron pairing mechanism of the HTS and develop new HTS junction devices by studying these changes. In this paper, p-/n-type YBa2Cu3O7−δ/Nd1.85Ce0.15CuO4 (YBCO/NCCO) heterostructures were prepared via pulsed laser deposition on (00l)-oriented single-crystal SrTiO3 substrates. X-ray diffraction measurements indicate that the NCCO films prepared on YBCO do not exhibit good c-axis epitaxial growth, while excellent c-axis epitaxial growth is obtained for YBCO/NCCO heterostructures with NCCO at the bottom. Due to the high-temperature oxygen atmosphere and the deoxygenation process, the superconducting electrical properties of the bilayer structure are seriously degraded, and it is not possible to obtain good superconducting electrical properties for both the upper and lower layers using the traditional preparation process based on an oxygen atmosphere. Subsequently, the effects of different growth atmospheres on the electrical properties of the YBCO superconductors were studied, and high-quality YBCO superconducting films could be grown in oxygen, nitrous oxide, and nitrogen atmospheres. However, the oxygen and nitrous oxide atmospheres degrade the superconducting electrical properties of the underlying NCCO layer, while the nitrogen atmosphere does not seem to affect it significantly. YBCO/NCCO superconducting bilayers with critical transition temperatures of 85 and 8 K for YBCO and NCCO, respectively, were finally prepared by growing NCCO in an oxygen atmosphere and YBCO in a nitrogen atmosphere using a low-temperature oxygenation process. The successful preparation of the p-/n-type HTS heterostructure will help further study on the HTS.

Ferroelectric Resistance Switching in Epitaxial BiFeO3/La0.7Sr0.3MnO3 Heterostructures.

BiFeO3/La0.7Sr0.3MnO3 (BFO/LSMO) epitaxial heterostructures were successfully synthesized by pulsed laser deposition on (001)-oriented SrTiO3 single-crystal substrates with Au top electrodes. Stable bipolar resistive switching characteristics regulated by ferroelectric polarization reversal was observed in the Au/BFO/LSMO heterostructures. The conduction mechanism was revealed to follow the Schottky emission model, and the Schottky barriers in high-resistance and low-resistance states were estimated based on temperature-dependent current-voltage curves. Further, the observed memristive behavior was interpreted via the modulation effect on the depletion region width and the Schottky barrier height caused by ferroelectric polarization reversal, combining with the oxygen vacancies migration near the BFO/LSMO interface.

Effect of heat treatment on resistive switching memory characteristics of NiO nanodots of tens of nanometers shattered by AFM tips

The characteristics of resistive random access memory (RRAM) at the nanometer scale are increasingly important for RRAM cells with further miniaturization. We report the RRAM characteristics of NiO nanodots in the order of tens of nanometers. NiO nanodots of approximately 70 nm were created on a single-crystal Nb-doped SrTiO3 (Nb:STO) substrate by dip-pen nanolithography. For comparison, a NiO thin film was also deposited on the Nb:STO substrate by spin coating. To reduce the size of NiO nanodots, they were shattered by an atomic force microscope tip, obtaining nanodots of approximately 10 nm. Using a conductive atomic force microscope, we characterized the current according to the applied electric field of the NiO nanodots on the Nb:STO substrate with a capacitor configured of Pt/NiO/Nb:STO substrate. When compared with the NiO thin film, the forming voltage of the NiO nanodots decreased. In addition, the shattered NiO nanodots exhibited unipolar switching characteristics, and the forming and set/reset voltages decreased with the reduction in nanodot size. Furthermore, the NiO nanodots exhibited a substantially reduced forming and set/reset voltages after heat treatment in vacuum. We suggest that the oxygen-depleted layer formed on the surface of NiO nanodots by heat treatment plays a crucial role in the reduction of the forming and operation voltages.

Energy storage and multiferroic properties of La-doped epitaxial BiFeO3 thin films according to La doping concentration

La-doped epitaxial BiFeO3 (LBFO) thin films with La doping concentrations of 0, 10, 20, 25, and 30 % were deposited by pulsed laser deposition on Nb-doped single-crystal SrTiO3 substrates. The LBFO thin films doped with a La doping concentration of 10 % showed the best ferroelectric properties due to a large c/a ratio of about 1.04. As the concentration of La increased, the ferroelectric polarizations of the LBFO films decreased while the ferromagnetic properties steadily improved. In particular, the LBFO thin films tended to increase energy storage efficiency as the concentration of La increased, and the LBFO thin films with a La doping concentration of 30 % showed a high energy storage density of about 30.7 J/cm3.

Magnetotransport, spin reorientation, and anomalous ferrimagnetic-to-antiferromagnetic phase transition in epitaxial Mn2Sb alloy thin films

High-quality ferrimagnetic Mn2Sb epitaxial thin films have been successfully grown on SrTiO3 (001) single-crystal substrates via systematically optimizing the growth parameters using molecular beam epitaxy. Magnetotransport and magnetic measurements reveal that a spin reorientation transition occurs in the 260–150 K region where the direction of spins rotates from out-of-plane to in-plane upon cooling, resulting in the ferrimagnetic(II) phase, followed by a giant magnetoresistance associated anomalous ferrimagnetic(II)-to-canted antiferromagnetic (c-AFM) phase transition in the 150–115 K region, resulting in the c-AFM ground state, both of which are completely absent and have yet not been previously observed in Mn2Sb bulk and thin films. Temperature-dependent X-ray diffraction measurements reveal that the low-temperature c-AFM phase originates from the contraction of the out-of-plane lattice constant c, which would increase the exchange interaction between neighbouring magnetic sublattices and thus stabilize the c-AFM phase. DFT calculations reveal that substrate clamping is the cause of the unique c-axis contraction in Mn2Sb films. For the 24-nm films, there is almost no out-of-plane magnetization in the ground state, but exists a weak in-plane remanent magnetization (∼0.4 μB/f.u.) and anomalous Hall effects, implying spin canting within the ab plane. With decreasing film thickness from 64 to 8 nm, the out-of-plane saturation magnetization at 10 K increases by approximately 10 times, and for the 8-nm film, its saturation magnetization (4.8 μB/f.u.) is 2.8 times larger than that of Mn2Sb bulk (∼1.74 μB/f.u.), both of which are attributed to the interfacial strain effect. Our work demonstrates that Mn2Sb films grown on perovskite oxide substrates show anomalous spin-charge-lattice coupling phenomena, which may inspire more study of its basic properties and potential device applications.

Local piezoelectric properties of Bi3TaTiO9 thin films: The role of grain crystallinity

We report the relationship between grain shape and local piezoelectric coefficient (d33) hysteresis loops in a Bi-layered perovskite Bi3TaTiO9 (BTTO) thin film, fabricated via pulsed laser deposition. The BTTO thin film, deposited on a single-crystal Nb-doped SrTiO3 substrate, exhibited a polycrystalline structure with both elongated and round grains identified through atomic force microscopy. Local d33 hysteresis loops measurements in the BTTO thin film revealed that elongated grains exhibited higher d33 value compared to round grains. Intriguingly, the highest d33 value was measured at the areas where elongated and round grains are adjacent. These findings suggest that piezoelectricity is enhanced when a- and c-oriented crystallinity are present simultaneously in Bi-layered perovskite thin films. This observation parallels the phenomenon of phase coexistence observed near the morphotropic phase boundary in systems such as lead zirconate titanate.

Epitaxial Bi5Ti3FeO15 thin films on Nb‐doped SrTiO3 substrates

AbstractWe investigated the ferroelectric switching dynamics as well as the multiferroic and piezoelectric properties of highly a‐oriented epitaxial Bi5Ti3FeO15 (BTFO) thin films on Nb‐doped SrTiO3 single crystal substrates. The BTFO thin films favored highly a‐oriented crystallinity because c‐oriented crystallinity decreased under deposition conditions in which substrate temperature and thin film deposition rate were simultaneously lowered. The highly a‐oriented epitaxial BTFO thin films showed the best ferroelectric properties, whereas the highly c‐oriented epitaxial BTFO thin films showed the best ferromagnetic properties. In particular, the BTFO thin films in which a‐ and c‐oriented crystallinity were properly mixed showed the best piezoelectric properties.

Process-Gas-Influenced Anti-Site Disorder and Its Effects on Magnetic and Electronic Properties of Half-Metallic Sr2FeMoO6 Thin Films

Anti-site disorder, arising due to the similar size of Fe and Mo ions in Sr2FeMoO6 (SFMO) double perovskites, hampers spintronic applicability by deteriorating the magnetic response of this double perovskite system. A higher degree of anti-site disorder can also completely destroy the half-metallicity of the SFMO system. To study the effects of different process gas conditions on the anti-site disorder, we have prepared a series of SFMO thin films on SrTiO3 (001) single-crystal substrate using a pulsed laser deposition (PLD) technique. The films are grown either under vacuum or under N2/O2 partial gas pressures. The vacuum-grown SFMO film shows the maximum value of saturation magnetization (MS) and Curie temperature (TC), signaling the lowest anti-site disorder in this series. In other words, there is a long-range Fe/Mo-O-Mo/Fe ferrimagnetic exchange in the vacuum-grown thin film, thereby enhancing the magnetization. Further, all the SFMO films show a semiconducting state with a systematic increase in overall resistivity with the increased anti-site disorder. The electrical conduction mechanism is defined by the variable-range hopping model at low temperatures. Raman spectra show a weak Fano peak, suggesting the presence of electron–phonon coupling in SFMO thin films. These results show the significance of the process gas in causing anti-site disorder, tuning the degree of this disorder and therefore its influence on the structural, magnetic, electrical, and vibrational properties of SFMO thin films.

Preparation and electrical properties of ultra-thin Bi2212 films by sol-gel method

In order to achieve flexible applications of superconducting thin film materials in devices, the surface quality of the film is critical. The thickness of the film is one of the important factors affecting its surface quality. In this paper, Bi2212 superconducting thin films of different thicknesses were prepared on LaAlO3(100) and SrTiO3(100) single crystal substrates by sol-gel method and the effects of film thickness and different heterogeneous structures on their crystallographic, morphological and superconducting properties were investigated. The results showed that the roughness gradually increased with increasing Bi2212 thickness at the initial stage of film growth and stabilized after reaching a certain thickness, while the superconducting properties were destroyed at very small sample thickness, which was consistent in both single-crystal substrate films. In the Bi2212/LaAlO3 structure, the surface quality of the sample was excellent with a roughness of 5.4 nm at a thickness of about 18 nm for Bi2212, and the growth of the precipitated phase was inhibited to a greater extent. The film also had good superconductivity. This work provided a further research basis for the preparation of high quality Bi2212 films and offers further possibilities for their practical application.

Control of resistive switching type in BaTiO3 thin films grown by high and low laser fluence

A ferroelectric memristor has attracted much attention due to convenient controlling by polarization switching, but the resistive switching has been attributed to the drift or charge trapping of defects. To distinguish the resistive switching mechanism between ferroelectric polarization switching and the normal resistive switching mechanism such as the drift or charge trapping of defects, BaTiO3 (BTO) thin films were grown on a (001) Nb:SrTiO3 single crystal substrate by pulsed laser deposition with high and low laser energy density. Based on a piezoelectric force microscope, ferroelectricity is found in BTO thin films grown at high laser energy density. X-ray photoelectron spectroscopy further confirms the existence of defects in the BTO films grown at low laser energy density. The high energy sample with low density of defects exhibits a resistance hysteresis loop but little current hysteresis loop, while the low energy sample with high density of defects shows a significant resistance and current hysteresis loop simultaneously. These results provide a deep understanding about the resistive switching from ferroelectric polarization switching and the drift or charge trapping of defects.

Preparation by chemical solution deposition and transparent conducting properties of LaRh1-xNixO3 thin films

Transparent conducting thin films have been widely used in lots of fields. The absence of high-performance hole-type transparent conducting thin films, however, seriously limits the wider applications. LaRhO3 as a type of perovskite material shows hole-type conduction with semiconductor-like properties and no investigations have been carried out about transparent conducting properties on LaRhO3 thin films. Here, LaRh1-xNixO3 (x = 0, 0.05, 0.1) thin films were firstly deposited by chemical solution deposition, showing epitaxial growth on single crystal SrTiO3 (001) substrates with the epitaxial relationship of LaRhO3(001)[110]||SrTiO3(001)[110]. With the doping of Ni element, the surface morphology became denser. Hall measurements confirmed that the hole concentration was enhanced with Ni doping, resulting in the decreased resistivity. Low resistivity of 17.3 mΩ cm at 300K was obtained for the LaRh0.9Ni0.1O3 thin films. The electrical transport mechanisms were investigated, showing thermal activation at high temperatures and variable range hopping model for the doped thin films at low temperatures. The transmittance within the visible range for all thin films was higher than 50%. The results will provide a feasible route to deposit hole-type transparent conducting LaRhO3-based thin films.

Solution epitaxy of polarization-gradient ferroelectric oxide films with colossal photovoltaic current

Solution growth of single-crystal ferroelectric oxide films has long been pursued for the low-cost development of high-performance electronic and optoelectronic devices. However, the established principles of vapor-phase epitaxy cannot be directly applied to solution epitaxy, as the interactions between the substrates and the grown materials in solution are quite different. Here, we report the successful epitaxy of single-domain ferroelectric oxide films on Nb-doped SrTiO3 single-crystal substrates by solution reaction at a low temperature of ~200 oC. The epitaxy is mainly driven by an electronic polarization screening effect at the interface between the substrates and the as-grown ferroelectric oxide films, which is realized by the electrons from the doped substrates. Atomic-level characterization reveals a nontrivial polarization gradient throughout the films in a long range up to ~500 nm because of a possible structural transition from the monoclinic phase to the tetragonal phase. This polarization gradient generates an extremely high photovoltaic short-circuit current density of ~2.153 mA/cm2 and open-circuit voltage of ~1.15 V under 375 nm light illumination with power intensity of 500 mW/cm2, corresponding to the highest photoresponsivity of ~4.306×10−3 A/W among all known ferroelectrics. Our results establish a general low-temperature solution route to produce single-crystal gradient films of ferroelectric oxides and thus open the avenue for their broad applications in self-powered photo-detectors, photovoltaic and optoelectronic devices.