SrTiO3 Surface Research Articles

Strain effect on oxygen evolution reaction of the SrTiO3 (0 0 1) surface

Strontium titanate (SrTiO3) is one of the most promising photocatalysts for overall water splitting (OWS). Strains can be commonly introduced in SrTiO3 during the synthetic processes, for example, in pulsed laser deposition. However, the effect of the strains on the catalytic performance of OWS is still unclear to date. Herein, first-principles calculations were performed to evaluate the impact of biaxial strains applied in SrTiO3 (001) surface on the oxygen evolution reaction (OER), the bottleneck of OWS. It was found that the applied strains, especially the compressive strains, significantly affect the free energy changes for H2O dissociation and *OOH deprotonation of OER on SrTiO3 (001). More interestingly, the tensile strains reduce the surface energy and lower the OER overpotential through reducing the free energy change for the rate-determining step, i.e., the second step of OER (*OH deprotonation), while the compressive strains increase the surface energy and the OER overpotential. Consequently, it is probable to introduce the tensile strains in the synthetic process to enhance the OER performance on SrTiO3 (001) surface.

Unraveling the Impact of Graphene Addition to Thermoelectric SrTiO3 and La-Doped SrTiO3 Materials: A Density Functional Theory Study.

We present a detailed theoretical investigation of the interaction of graphene with the SrO-terminated (001) surface of pristine and La-doped SrTiO3. The adsorption of graphene is thermodynamically favorable with interfacial adsorption energies of −0.08 and −0.32 J/m2 to pristine SrTiO3 and La-doped SrTiO3 surfaces, respectively. We find that graphene introduces C 2p states at the Fermi level, rendering the composite semimetallic, and thus the electrical properties are predicted to be highly sensitive to the amount and quality of the graphene. An investigation of the lattice dynamics predicts that graphene adsorption may lead to a 60–90% reduction in the thermal conductivity due to a reduction in the phonon group velocities, accounting for the reduced thermal conductivity of the composite materials observed experimentally. This effect is enhanced by La doping. We also find evidence that both La dopant ions and adsorbed graphene introduce low-frequency modes that may scatter heat-carrying acoustic phonons, and that, if present, these effects likely arise from stronger phonon–phonon interactions.

Graphene probe to explore the surface polarization in SrTiO3 without damage

Graphene is utilized as a sensitive probe to explore the surface polarization phenomenon in SrTiO3 in this work. A ferroelectric-like hysteresis effect induced by the external electric field stimuli as well as a pyroelectric effect caused by the light stimuli is observed and discussed through the quasi-static/transient evolution of graphene current at a constant bias voltage. The existence of electric dipoles at the surface of SrTiO3 is confirmed. Dipoles are dependent on the external electric field, and there is an electric field induced remanent polarization after high electric field treatment. The pyroelectric phenomenon caused by the light illumination indicates that the electric dipoles naturally exist at the SrTiO3 surface even though there is no external electric field.

Photocatalytic overall water splitting without noble-metal: Decorating CoP on Al-doped SrTiO3

CoP, a noble-metal-free cocatalyst, was first introduced onto the surface of Al-doped SrTiO3 (Al:STO) via an in situ photodeposition-phosphorization method for photocatalytic overall water splitting (POWS) into stoichiometric H2 and O2. Compared with pure Al:STO, the POWS activity was enhanced by a factor of ~ 421 over 1.0%CoP/Al:STO, with the highest evolution rates of 2106 and 1002 μmol h−1 g−1 for H2 and O2, respectively. The mechanism for the remarkably boosted POWS activity was systematically analyzed based on the comprehensive characterization. On the one hand, benefiting from the in situ photodeposition process, CoP with metallic character were intimately decorated onto the surface of Al:STO and accelerated the separation and migration of photoinduced charge carriers. On the other hand, CoP, serving as reactive sites for H2 evolution reaction, lowered the overpotential and facilitated the surface reduction reaction, thereby enhancing the POWS activity. Furthermore, Cr2O3 was photodeposited on the surface of 1.0%CoP/Al:STO composite to suppress the undesired reverse reaction and the POWS activity was further enhanced up to 3558 and 1722 μmol h−1 g−1 for H2 and O2, respectively, with apparent quantum yield of 7.1% at 350 ± 10 nm. This work presents a new avenue for designing POWS system without noble-metal cocatalyst.

Generation and detection of 50 GHz surface acoustic waves by extreme ultraviolet pulses

We use femtosecond extreme ultraviolet pulses derived from a free electron laser to excite and probe surface acoustic waves (SAWs) on the (001) surface of single crystal SrTiO3. SAWs are generated by a pair of 39.9 nm pulses crossed at the sample with the crossing angle defining the SAW wavelength at 84 nm. Detection of SAWs is performed via diffraction of a time-delayed 13.3 nm probe pulse by SAW-induced surface ripples. Despite the low reflectivity of the sample in the extreme ultraviolet range, the reflection mode detection is found to be efficient because of an increase in the diffraction efficiency for shorter wavelengths. We describe a methodology for extracting the SAW attenuation in the presence of a thermal grating, which is based on measuring the decay of oscillations at twice the SAW frequency. The proposed approach can be used to study ultrahigh frequency SAWs in a broad range of materials and will bridge the wave vector gap in surface phonon spectroscopy between Brillouin scattering and He atom scattering.

The role of etching anisotropy in the fabrication of freestanding oxide microstructures on SrTiO3(100), SrTiO3(110), and SrTiO3(111) substrates

The release process for the fabrication of freestanding oxide microstructures relies on appropriate, controllable, and repeatable wet etching procedures. SrTiO3 (STO) is among the most employed substrates for oxide thin films growth and can be decomposed in HF:water solution. Such a process is strongly anisotropic and is affected by local defects and substrate cut-planes. We analyze the etching behavior of SrTiO3 substrates having (100), (110), and (111) cut-planes during immersion in a 5% HF:water solution. The etching process over the three substrates is compared in terms of pitting, anisotropy, macroscopic etch rate, and underetching effects around HF-resistant (La,Sr)MnO3 thin film micropatterns. The release of targeted structures, such as the reported (La,Sr)MnO3 freestanding microbridges, depends on the substrate crystallographic symmetry and on the in-plane orientation of the structures themselves along the planar directions. By comparing the etching evolution at two different length scales, we distinguish two regimes for the propagation of the etching front: an intrinsic one, owing to a specific lattice direction, and a macroscopic one, resulting from the mixing of different etching fronts. We report the morphologies of the etched SrTiO3 surfaces and the geometries of the underetched regions as well as of the microbridge clamping zones. The reported analysis will enable the design of complex MEMS devices by allowing to model the evolution of the etching process required for the release of arbitrary structures made of oxide thin films deposited on top of STO.

The role of surfaces in flexoelectricity

We develop the relationship between the strain derivative of the mean-inner potential and surface contributions to flexoelectricity, identifying the true surface-specific component of the flexoelectric response of finite samples. Density functional theory calculations on a range of experimentally observed, low energy SrTiO3, MgO, and Si surfaces demonstrate that the mean-inner potential and its contributions to flexoelectricity are sensitive to small differences in surface structure, chemistry, and adsorbates. We also introduce a method to estimate mean-inner potential contributions to flexoelectricity using electron scattering factors and use this approximation to predict total flexoelectric responses for a variety of insulators. Strategies to experimentally disentangle bulk and surface flexoelectric terms are also discussed.

Interface interaction of transition metal phthalocyanines with strontium titanate (100).

We study interface properties of CoPcFx and FePcFx (x = 0 or 16) on niobium-doped SrTiO3(100) surfaces using mainly X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy. For all studied molecules, a rather complex, bidirectional charge transfer with the oxide substrate was observed, involving both the macrocycle and the central metal atom. For molecules of the first monolayer, an electron transfer to the central metal atom is concluded from transition metal 2p core level photoemission spectra. The number of interacting molecules in the first monolayer on the oxide surface depends on the central metal atom of the phthalocyanine, whereas the substrate preparation has minor influence on the interaction between CoPc and SrTiO3(100). Differences of the interaction mechanism to related TiO2 surfaces are discussed.

Interface-enhanced thermoelectric output power in CrN/SrTiO3−x heterostructure

Thermoelectric devices enable direct conversion between thermal and electrical energy. Recent studies have indicated that the thin film/substrate heterostructure is effective in achieving high thermoelectric performance via decoupling the Seebeck coefficient and electrical conductivity otherwise adversely inter-dependent in homogenous bulk materials. However, the mechanism underlying the thin film/substrate heterostructure thermoelectricity remains unclear. In addition, the power output of the thin film/substrate heterostructure is limited to the nanowatt scale to date, falling short of the practical application requirement. Here, we fabricated the CrN/SrTiO3−x heterostructures with high thermoelectric output power and outstanding thermal stability. By varying the CrN film thickness and the reduction degree of SrTiO3−x substrate, the optimized power output and the power density have respectively reached 276 μW and 108 mW/cm2 for the 30 nm CrN film on a highly reduced surface of SrTiO3−x under a temperature difference of 300 K. The performance enhancement is attributed to the CrN/SrTiO3−x heterointerface, corroborated by the band bending as revealed by the scanning Kelvin probe microscopy. These results will stimulate further research efforts towards interface thermoelectrics.

Comparative Hybrid Hartree-Fock-DFT Calculations of WO2-Terminated Cubic WO3 as Well as SrTiO3, BaTiO3, PbTiO3 and CaTiO3 (001) Surfaces

We performed, to the best of our knowledge, the world’s first first-principles calculations for the WO2-terminated cubic WO3 (001) surface and analyzed the systematic trends in the WO3, SrTiO3, BaTiO3, PbTiO3 and CaTiO3 (001) surface ab initio calculations. According to our first principles calculations, all WO2 or TiO2-terminated WO3, SrTiO3, BaTiO3, PbTiO3 and CaZrO3 (001) surface upper-layer atoms relax inwards towards the crystal bulk, while all second-layer atoms relax upwards. The only two exceptions are outward relaxations of first layer WO2 and TiO2-terminated WO3 and PbTiO3 (001) surface O atoms. The WO2 or TiO2-terminated WO3, SrTiO3, BaTiO3, PbTiO3 and CaTiO3 (001) surface-band gaps at the Γ–Γ point are smaller than their respective bulk-band gaps. The Ti–O chemical bond populations in the SrTiO3, BaTiO3, PbTiO3 and CaTiO3 bulk are smaller than those near the TiO2-terminated (001) surfaces. Conversely, the W–O chemical bond population in the WO3 bulk is larger than near the WO2-terminated WO3 (001) surface.

The influence of piezoelectric effect on the heterogeneous photocatalytic hydrogen production of strontium titanate nanoparticles

Combining photocatalysis with the other physical-field is an efficient way to improve the performance of photocatalysis. The piezoelectric effect on the heterogeneous photocatalytic hydrogen production of SrTiO3 (STO) nanoparticles was studied in this paper. It was found that the piezoelectric effect generated by the ultrasonic cavitation (sonophotocatalysis) had a profound influence on heterogeneous photocatalytic hydrogen production with or without sacrificial agents. Notably, the sonophotocatalytic hydrogen production of STO was related to the viscosity of sacrificial agents and the position of the ultrasonic vibrators. The mechanism of the performance changes by sonophotocatalysis was investigated by in-situ deposition Pt nanoparticles, which were found to aggregate obviously on STO nanoparticles' surface. Thus, ultrasonic cavitation would build a piezoelectric potential on the local surface of STO that would inhibit photo-generated carriers migrating to the surface.

Dielectric properties of sub 20 nm homoepitaxial SrTiO3 thin film grown by molecular beam epitaxy using oxygen plasma

Epitaxial SrTiO 3 thin films were grown by molecular beam epitaxy (MBE) using an oxygen plasma source. SrO and TiO2 layers were alternately deposited on 0.5 wt% (001) Nb doped SrTiO3 substrates whose surface were terminated with TiO2. A two-dimensional (2-D) layer-by-layer growth mode was confirmed by the reflection high energy electron diffraction (RHEED) oscillation during the growth and the well-terraced SrTiO3 surface was obtained after growth. X-ray diffraction (XRD) and scanning transmission electron microscopy (STEM) analysis showed that the obtained SrTiO3 thin films had epitaxially (001) oriented and stoichiometric crystal structures without any interfacial layer. With simple MIS (Metal-Insulator-Semiconductor) capacitors using Ir top electrodes, the dielectric constants of the SrTiO3 thin film with 10, 15, 20, 100 nm were measured at room temperature, 10 kHz and zero bias.

Engineering of Electron Confinement through Defect‐Based Localized Polarization on SrTiO3 Surface

AbstractElectron behaviors are expected to differ in circumstances with polarization. Changes in electron dynamics further result in changes in the physical properties, especially at reduced dimensions. In this paper, threshold photoemission is used to image a 2D electron gas induced on a SrTiO3 surface with regions polarized by defect‐based localized dipolar moments. It is found that the induction of surface polarization results in decrease of the surface itinerant electron density and the magnetic moments at room temperature. Such effects are attributed to the polarization‐based trapping of the surface itinerant electrons. It is also demonstrated that those changes induced by surface polarization can be manipulated by varying temperature. These findings address the importance of polarization in low‐dimensional electron dynamics, which offers an alternative way to engineer the properties of the SrTiO3‐based 2D electron gas.

Intrinsic nanostructures on the (001) surface of strontium titanate at low temperatures

Atomically smooth (001) surfaces of SrTiO3 cut from the high-quality single crystals at two different miscut angles 0.9 and 7.0 deg between the real flat surfaces and crystallographic planes (001) were analyzed by means of the reflection high energy electron diffraction (RHEED) method from the room down to liquid helium temperatures. The diffraction patterns typical of the RHEED geometry close to ideal for a small miscut angle and those exhibiting distinct features of the specific periodicity associated with regular steps, which form due to the larger miscut angle, are presented. The surface symmetry and energetics were shown to impose differences in lattice parameters in parallel to a surface with respect to the bulk. This effect results in weak incommensurability between lattice parameters in surface layers and the bulk values relaxed due to step edges and misfit dislocations. The special surface nanostructures formed on the etched surfaces treated in chemically active solvents are also analyzed. The intrinsic nanostructures on single crystal surfaces open new prospects for applications when the ordered and controlled nanoscale architecture is required.

Unveiling Temperature-Induced Structural Domains and Movement of Oxygen Vacancies in SrTiO3 with Graphene.

Heterointerfaces coupling complex oxides exhibit coexisting functional properties such as magnetism, superconductivity, and ferroelectricity, often absent in their individual constituent. SrTiO3 (STO), a canonical band insulator, is an active constituent of such heterointerfaces. Temperature-, strain-, or mechanical stress-induced ferroelastic transition leads to the formation of narrow domains and domain walls in STO. Such ferroelastic domain walls have been studied using imaging or transport techniques and, often, the findings are influenced by the choice and interaction of the electrodes with STO. In this work, we use graphene as a unique platform to unveil the movement of oxygen vacancies and ferroelastic domain walls near the STO surface by studying the temperature and gate bias dependence of charge transport in graphene. By sweeping the back gate voltage, we observe antihysteresis in graphene typically observed in conventional ferroelectric oxides. Interestingly, we find features in antihysteresis that are related to the movement of domain walls and of oxygen vacancies in STO. We ascertain this by analyzing the time dependence of the graphene square resistance at different temperatures and gate bias. Density functional calculations estimate the surface polarization and formation energies of layer-dependent oxygen vacancies in STO. This corroborates quantitatively with the activation energies determined from the temperature dependence of the graphene square resistance. Introduction of a hexagonal boron nitride (hBN) layer, of varying thicknesses, between graphene and STO leads to a gradual disappearance of the observed features, implying the influence of the domain walls onto the potential landscape in graphene.

Optically Induced Three-Stage Picosecond Amorphization in Low-Temperature SrTiO3.

Photoexcitation can drastically modify potential energy surfaces of materials, allowing access to hidden phases. SrTiO3 (STO) is an ideal material for photoexcitation studies due to its prevalent use in nanostructured devices and its rich range of functionality-changing lattice motions. Recently, a hidden ferroelectric phase in STO was accessed through weak terahertz excitation of polarization-inducing phonon modes. In contrast, whereas strong laser excitation was shown to induce nanostructures on STO surfaces and control nanopolarization patterns in STO-based heterostructures, the dynamic pathways underlying these optically induced structural changes remain unknown. Here nonadiabatic quantum molecular dynamics reveals picosecond amorphization in photoexcited STO at temperatures as low as 10 K. The three-stage pathway involves photoinduced charge transfer and optical phonon activation followed by nonlinear charge and lattice dynamics that ultimately lead to amorphization. This atomistic understanding could guide not only rational laser nanostructuring of STO but also broader "quantum materials on demand" technologies.

Interfacial Polarons in van der Waals Heterojunction of Monolayer SnSe2 on SrTiO3 (001).

Interfacial polarons have been demonstrated to play important roles in heterostructures containing polar substrates. However, most of polarons found so far are diffusive large polarons; the discovery and investigation of small polarons at interfaces are scarce. Herein, we report the emergence of interfacial polarons in monolayer SnSe2 epitaxially grown on Nb-doped SrTiO3 (STO) surface using angle-resolved photoemission spectroscopy (ARPES) and scanning tunneling microscopy (STM). ARPES spectra taken on this heterointerface reveal a nearly flat in-gap band correlated with a significant charge modulation in real space as observed with STM. An interfacial polaronic model is proposed to ascribe this in-gap band to the formation of self-trapped small polarons induced by charge accumulation and electron-phonon coupling at the van der Waals interface of SnSe2 and STO. Such a mechanism to form interfacial polaron is expected to generally exist in similar van der Waals heterojunctions consisting of layered 2D materials and polar substrates.

Quantum well electronic states in spatially decoupled 2D Pb nanoislands on Nb-doped SrTiO3(0 0 1)

Two-dimensional (2D) Pb nanoisland has established an ideal platform for studying the quantum size effects on growth mechanism, electronic structures as well as high-temperature superconductivity. Here, we investigate the growth and quantum well electronic states of the 2D Pb nanoislands on Nb-doped SrTiO3(001) by scanning tunneling microscopy and spectroscopy. In contrast to Pb/Si(111), Pb/Cu(111) and Pb/Ag(111), there is no wetting layer of Pb formed on the Nb-doped SrTiO3(001) surface, resulting in isolated Pb nanoislands with an apparent height of 4 atomic layers as the building blocks for the island growth. According to the thickness-dependent quantum well states resolved in both occupied and unoccupied energy regions, the constant group velocity vg = 1.804 × 106 m/s and the Fermi wavevector kF = 1.575 Å−1, have been extracted from a linear fit of the Pb(111) band dispersion along the Γ-L direction. In addition, the energy-dependent scattering phase shift φ(E) obtained by means of the phase accumulation model shows a metallic-like scattering interface analogous to Pb/Ag(111). These spatially decoupled 2D Pb nanoislands thus realize an opportunity to explore the intrinsic quantum confinement phenomena in nanoscale superconductors on the doped titanium-oxide-type substrate.

Perovskite Oxides Tunable by Electromechanical and Electrothermal Couplings

Objectives: Oxides hold the great promise for emerging electronic applications (other than conventional CMOS components such as gate oxides) because they can significantly increase the operational range of temperature and bias voltage due to the much higher bandgap energy than semiconductors. However, using the oxides for such novel purposes requires their electronic properties to be properly tuned and tailored to specific device applications. Therefore, this work seeks to develop the way to address this challenge by focusing on the tunable characteristics of perovskite oxides driven by their unique electromechanical and electrothermal couplings. Among various types of oxides, crystalline perovskite titanate structures such as STO (SrTiO3) have been chosen as the representative material platform in this study, due to their multifunctional properties and well-established growth techniques. New Results: Previously, researchers have demonstrated the heat-induced tunable electrical characteristics of STO doped with various impurities [1-2]. Due to the complex chemistry where both the thermal and doping effects contribute to the observed change in electrical properties, accurate physical origin of the STO’s tunable behavior has not been clearly identified. In this work, we focused on an undoped, 1 mm-thick STO crystal to quantitatively measure its response when solely exposed to an external stimulus such as mechanical pressure.Fig. 1 depicts the C-AFM (conductive atomic force microscope) experimental setup to study the tunable behavior of STO driven by an electromechanical coupling. The commercially available conductive tip (Asyelec.01-R2) was used to apply a bias voltage (Vbias = 2V) while in contact with the top surface of the STO sample. This enables simultaneous measurement of electrical response during the experiment. The force was applied and varied by changing the set-point voltage (Vsetpoint, kept below 3V to prevent any possible damage to the measurement system) that is used to make the cantilever tip bent with the varying height. Conversion from the control parameter (Vsetpoint) to the mechanical pressure (N/m2) was conducted through precise calibration of the C-AFM measurement setup, including spring constant (0.92 N/m) and deflection sensitivity (0.0576 mm/V) (Table 1).Fig. 2 shows the measured electrical conductivity vs. applied pressure plot for the undoped STO sample used in the experiment. To ensure statistically meaningful data, each experiment was performed repetitively (at least 10 times) and both the mean (data points) and standard deviation (error bars) values were presented in the figure. A clear trend of increase in electrical conductivity with increasing pressure was observed, which is best attributed to creation of oxygen vacancies by mechanical stress in STO [3]. This will surely help researchers study the fundamental electromechanical coupling-driven behavior of perovskite oxide thin films. Fig. 3 further presents the C-AFM image when pressure was applied to the STO surface (the white particles are believed to be due to pile-up of electronic charges upon the application of localized electrical bias).We next studied the electrothermal coupling-driven conductance change in STO by performing a systematic study of thermal annealing (at temperatures ranging from 200°C to 800°C and in dry air). For this study, a sufficient amount of oxygen vacancies was purposely introduced when the STO thin film was prepared (see Fig. 4 for the device schematic). Because subsequent annealing annihilated oxygen vacancies, decrease in electrical conductivity was observed in STO samples annealed at high temperatures (Fig. 5). The reasoning of relating the observed trend in Fig. 5 to the change in the number of oxygen vacancies upon thermal annealing is well supported by measuring the hysteretic behavior of the STO thin film. Fig. 6 shows a measured butterfly curve that is typical for memristor devices where removal and restoration of oxygen vacancies play a key role as the switching mechanism. Significance: This work is of significant importance for the development of future electronic devices with significantly enhanced reliability features. By demonstrating that electrical characteristics of multifunctional oxide thin films can be largely tuned by external stimuli such as mechanical pressure and thermal annealing, it will spark various research initiatives in using the oxide for novel, more versatile applications.

Enhanced tunability of two-dimensional electron gas on SrTiO3 through heterostructuring

Two-dimensional electron gases (2DEGs) on the SrTiO3 (STO) surface or in STO-based heterostructures have exhibited many intriguing phenomena, which are strongly dependent on the 2DEG-carrier density. We report that the tunability of the 2DEG-carrier density is significantly enhanced by adding a monolayer LaTiO3 (LTO) onto the STO. Ultraviolet (UV) irradiation induced maximum carrier density of the 2DEG in LTO/STO is increased by a factor of ~4 times, compared to that of the bare STO. By oxygen gas exposure, it becomes 10 times smaller than that of the bare STO. This enhanced tunability is attributed to the drastic surface property change of a polar LTO layer by UV irradiation and O2 exposure. This indicates that the 2DEG controllability in LTO/STO is more reliable than that on the bare STO driven by defects, such an oxygen vacancy.