BaTiO3 Nanocubes Research Articles

Data quality in laboratory convergent-beam X-ray total scattering

Measurement of laboratory atomic pair distribution function data has improved with contemporary X-ray sources, optics and detectors, with acquisition times of the order of minutes for ideal samples. This paper examines resolution effects in pair distribution function data obtained using a convergent-beam configuration and an Ag X-ray tube from standard silicon powder and from 10 nm BaTiO3 nanocubes. The elliptical multilayer X-ray mirror reflects a non-trivial X-ray spectrum and introduces resolution effects not commonly treated in ordinary parafocusing divergent-beam laboratory diffraction. These resolution effects are modeled using the fundamental parameters approach, and the influence this has on interpretation and modeling of the resulting reduced atomic pair distribution function data is demonstrated.

Biomimetic piezoelectric nanomaterial-modified oral microrobots for targeted catalytic and immunotherapy of colorectal cancer.

Lactic acid (LA) accumulation in the tumor microenvironment poses notable challenges to effective tumor immunotherapy. Here, an intelligent tumor treatment microrobot based on the unique physiological structure and metabolic characteristics of Veillonella atypica (VA) is proposed by loading Staphylococcus aureus cell membrane-coating BaTiO3 nanocubes (SAM@BTO) on the surface of VA cells (VA-SAM@BTO) via click chemical reaction. Following oral administration, VA-SAM@BTO accurately targeted orthotopic colorectal cancer through inflammatory targeting of SAM and hypoxic targeting of VA. Under in vitro ultrasonic stimulation, BTO catalyzed two reduction reactions (O2 → •O2- and CO2 → CO) and three oxidation reactions (H2O → •OH, GSH → GSSG, and LA → PA) simultaneously, effectively inducing immunogenic death of tumor cells. BTO catalyzed the oxidative coupling of VA cells metabolized LA, effectively disrupting the immunosuppressive microenvironment, improving dendritic cell maturation and macrophage M1 polarization, and increasing effector T cell proportions while decreasing regulatory T cell numbers, which facilitates synergetic catalysis and immunotherapy.

Synthesis of BaTiO3-CaTiO3 and BaTiO3-SrTiO3 Core-Shell Nanocubes via the Surface Reconstruction of BaTiO3 Nanocubes.

BaTiO3-CaTiO3 and SrTiO3-BaTiO3 core-shell nanocubes were synthesized through the surface reconstruction of BaTiO3 nanocubes, which involved the reaction of titanium oxide with Ca(OH)2, Sr(OH)2, or Sr(OH)2·8H2O in water at 100 °C. The core-shell structure comprised a BaTiO3 nanocube core and a CaTiO3 or SrTiO3 shell. The outermost layer with a perovskite structure also comprised CaTiO3 or SrTiO3, and its thickness was several hundred picometers. The thinnest layer was constructed of only one layer of CaTiO3 or SrTiO3. This is the first presented work on a core-shell nanocube with the outermost layer consisting of only CaTiO3 or SrTiO3 surrounding the BaTiO3 nanocube. The shells of CaTiO3 and SrTiO3 comprise a layer thickness of only one unit cell of ∼0.4 nm (400 pm). Thus, we demonstrate new research on nanocube surfaces on the picometer scale.

Construction of Millimeter-Wide Monolayers of Ordered Nanocubes as a Stain of “Wineglass Tears” Driven by the Marangoni Flow

We constructed millimeter-wide monolayers consisting of tetragonally ordered BaTiO3 (BT) nanocubes through the liquid film formation caused by the Marangoni flow in a toluene-hexane binary liquid containing oleic acid. A thin liquid film containing BT nanocubes was overspread on a standing silicon substrate through the condensation of toluene at the advancing front after the preferential evaporation of hexane. Then, the oscillatory droplet formation like "wineglass tears" occurred on the substrate. Finally, two-dimensionally ordered BT nanocubes were observed as a stain of "wineglass tears" on the substrate after the liquid film receded through evaporation. The presence of a thin liquid film in the binary system is essential for the production of millimeter-wide monolayers on the substrate because multilayer deposition occurs without the formation of a thin liquid film in monocomponent systems. We improved the regularity of the ordered arrays of nanocubes by adjusting the liquid component and evaporation conditions.

Critical Roles of Impurities and Imperfections in Various Phases of Materials.

In many materials, impurities and imperfections play a critical role on the physical and chemical properties. In the present review, some examples of such materials are discussed. A bulk nanobubble (an ultrafine bubble) is stabilized against dissolution by hydrophobic impurities attached to the bubble surface. An acoustic cavitation threshold in various liquids decreases significantly by the presence of impurities such as solid particles, etc. The strength of brittle ceramics is determined by the size and number of pre-existing microcracks (imperfections) in the specimen. The size effect of a BaTiO3 nanocrystal is influenced by the amount and species of adsorbates (impurities) on its surface as adsorbate-induced charge-screening changes the free energy. The dielectric constant of an assembly of BaTiO3 nanocubes is influenced by a small tilt angle (imperfection) between two attached nanocubes, which induces strain inside a nanocube, and is also influenced by the spatial strain-relaxation due to defects and dislocations (imperfections), resulting in flexoelectric polarization.

Piezoelectric effect enhanced plasmonic photocatalysis in the Pt/BaTiO3 heterojunctions

The use of piezoelectric internal field to assist in photocatalysis is important for inexpensive and high-efficiency catalytic techniques. In this study, novel Pt/BaTiO3 heterojunctions were prepared via decoration of Pt nanoparticles (PtNPs) on the surface of piezoelectric BaTiO3 nanocubes through a facile photoreduction process. The photocatalytic, piezo-catalytic, and piezo-photocatalytic activities of the Pt/BaTiO3 heterojunctions for methyl orange (MO) degradation were investigated under ultrasonic excitation and/or full-spectrum light irradiation. The weight percentage of PtNPs, piezoelectric internal field of BaTiO3, and plasmonic effect have been proven important for the photocatalytic activity of the heterojunctions. The Pt0.25/BaTiO3 with 0.25 wt% PtNPs exhibited an optimum photocatalytic degradation performance of 92.5% for MO in 50 min under full-spectrum light and ultrasonic co-excitation, and this value was about 1.35 times higher than the degradation rate under full-spectrum light irradiation alone. Well-dispersed PtNPs in the Pt/BaTiO3 heterojunction can be excited by incident light to generate an electromagnetic field caused by the surface plasmon resonance (SPR) effect, which drives the collective oscillation of electrons and generate hot electron–hole pairs. The piezoelectric internal field generated in BaTiO3 due to ultrasonic excitation can improve the separation efficiency of SPR-induced hot charge carriers and contribute to the production of highly reactive oxidation radicals, thereby enhancing the catalytic capability of the heterojunction to oxidize organic dyes. This study introduces the piezoelectric effect of BaTiO3 into plasma photocatalysis to enhance the photocatalytic activity of Ptx/BaTiO3 heterojunction, and this effect can be extended to other piezoelectric material systems to provide an effective technology for environmental purification.

Ferroelectric properties of BaTiO3 nanocube self-assembled monolayers: an investigation using piezoresponse force microscopy

We investigated the ferroelectric properties of barium titanate (BTO) nanocube self-assembled monolayers with and without heat treatment using piezoresponse force microscopy (PFM). Observations of polarization switching behavior confirmed that BTO nanocube monolayers about 15 nm thick are ferroelectric, even without heat treatment. Vertical PFM phase imaging of the monolayers revealed that heat treatment changed the ferroelectric polarization distribution in the monolayers at 800 °C. Atomic force microscopy and transmission electron microscopy suggested that this change originated from the residual stress caused by mechanical interactions between neighboring BTO nanocubes and between the monolayers and the substrate.

Self-powered flexible piezoelectric sensors based on self-assembled 10 nm BaTiO₃ nanocubes on glass fiber fabric

Hardness or brittleness limits the broad applications of currently available high-performance piezoelectric sensors in emerging fields like human-machine interface and wearable electronics, while existing technologies for fabricating flexible piezoelectric sensors often require high-temperature sintering or complex processes. Here, we reported flexible piezoelectric sensors based on 10 nm BaTiO3 nanocubes self-assembled on glass fiber fabric (GFF). The simple self-assembly process avoids high temperature sintering process which can well maintain the mechanical performance of GFF. Owing to the superior piezoelectric performance of BaTiO3 nanocubes and robust mechanical properties of GFF, the integrally fabricated flexible piezoelectric sensors achieved high sensitivity (101.09 nA kPa−1 and 3.31 V kPa−1 in the low pressure range of 0–10 N) and short response time (19 ms). The sensors can intelligently identify handwriting or recognize the user of keyboard, and the initially collected electrical signals are essentially the same as those after 3000 bending cycles. This work provides a novel self-assembly process to develop fabric-based flexible electronics, which promotes the development of self-powered piezoelectric sensors and creates advancements in human-machine interfaces.

Stretchable Unsymmetrical Piezoelectric BaTiO3 Composite Hydrogel for Triboelectric Nanogenerators and Multimodal Sensors.

Improving output performance of triboelectric nanogenerators (TENGs) is crucial for expanding their applications in smart devices, especially for flexible and wearable bioelectronics. In this study, we design and fabricate a flexible, stretchable, and highly transparent TENG based on an unsymmetrical PAM/BTO composite film, made of polyacrylamide (PAM) hydrogel and BaTiO3 nanocubes (BTO NCs, BTO), and the TENG performance can be tailored by adjusting the amount and distribution location of BTO. The stretchable hydrogel electrode could bear over 8 times stretching. By changing the content and distribution location of BTO in the unsymmetrical hydrogel film, the output of the fabricated TENGs could be improved, acting as pressure sensors with high sensitivity to distinguish a spectrum of forces (0.25-6 N) at the low frequency. The mechanism of the enhanced output performance of the PAM/BTO composite hydrogel-based TENG is discussed in detail. By integrating piezoresistive, piezoelectric, and triboelectric effects, the optimized TENG and piezoresistive sensors are used as multimodal biomechanical sensors for detecting the motions of human bodies, pressure, and curvature with high sensitivity.

Hydrophilic porous PVDF membrane embedded with BaTiO3 featuring controlled oxygen vacancies for piezocatalytic water cleaning

High-efficient and recyclable piezocatalysts are promising to utilize natural mechanical energy in piezocatalytic degradation for environmental purification. Herein, a new piezoelectric membrane with dual piezoelectric potentials was fabricated by embedding piezoelectric BaTiO3 nanocubes in piezoelectric PVDF polymeric film. In particular, the pre-modified controlled oxygen vacancies in BaTiO3 nanocubes (BTO-OVs) enhanced the adsorption and activation of dissolved oxygen in water, promoting the generation of reactive radicals. And the PVDF film embedded by BTO-OVs had boosted piezoelectric property and improved hydrophilicity and porosity after socking. Thus, the hydrophilic porous composite membrane (HPVDF/BTO-OVs) had efficient adsorption and piezocatalytic degradation of Bisphenol A in water under ultrasonic vibration and the removal efficiency is 14 times higher than that of pure PVDF film. In addition, the HPVDF/BTO-OVs membrane adhered on impeller can effectively remove BPA under 900 rpm stirring, which provided a promising material for water purification utilizing low-frequency mechanical energy from nature.

Coexistence of Flexo- and Ferro-Electric Effects in an Ordered Assembly of BaTiO3 Nanocubes.

It has been reported that the flexoelectric effect could be dominant in the nanoscale. The discrepancy between theory and experiments on the frequency dependence of the dielectric constant of an ordered assembly of BaTiO3 nanocubes is nearly resolved by assuming the coexistence of flexo- and ferro-electric effects. Although flexoelectric polarizations perpendicular to the applied alternating electric field contribute to the dielectric constant, those parallel to the electric field do not contribute because the magnitude of the flexoelectric polarization does not change due to the mismatch of strain at the interface of the nanocubes. On the other hand, some dielectric response is possible for the ferroelectric component of the polarization parallel to the electric field.

Temperature dependent local structure coherence of surface-modified BaTiO3 nanocubes

BaTiO3 nanocubes capped by polar tetrafluoroborate (BF4−) ligands are shown to have enhanced ferroelectric order and undergo sharper ferroelectric to paraelectric phase transitions relative to nanocubes capped with nonpolar oleic acid (OA) ligands.

Optimizing TiO2 through Water-Soluble Ti Complexes as Raw Material for Controlling Particle Size and Distribution of Synthesized BaTiO3 Nanocubes

Barium titanate (BaTiO3) nanocubes with a narrow particle size distribution were synthesized using a three-step approach. First, a water-soluble Ti complex was synthesized using a hydrolysis method. Next, the titanium dioxide (TiO2) raw material was synthesized via a hydrothermal method using various water-soluble titanium (Ti) complexes. The TiO2 exhibited various particle sizes and crystal structures (anatase, rutile, or brookite) depending on the water-soluble Ti complex and the hydrothermal conditions used in its synthesis. Finally, BaTiO3 nanocubes were subsequently created through a hydrothermal method using the synthesized TiO2 particles and barium hydroxide octahydrate [Ba(OH)2·8H2O] as raw materials. The present study clarifies that the particle size of the BaTiO3 nanocubes depends on the particle size of the TiO2 raw material. BaTiO3 particles with a narrow size distribution were obtained when the TiO2 particles exhibited a narrow size distribution. We found that the best conditions for the creation of BaTiO3 nanocubes using TiO2 involved using lactic acid as a complexing agent, which resulted in a particle size of 166 nm on average. This particle size is consistent with an average of the width of the cubes measured from corner to corner diagonally, which corresponds to a side length of 117 nm. In addition, surface reconstruction of the BaTiO3 was clarified via electron microscopy observations, identifying the outermost surface as a Ti layer. Electron tomography using high-angle annular dark-field (HAADF)-scanning transmission electron microscopy (STEM) confirmed the three-dimensional (3D) structure of the obtained BaTiO3 nanocubes.

In situ TEM measurement of electrical properties of individual BaTiO3 nanocubes

We report on the measurement of the electrical properties of individual pristine and doped BaTiO3 nanocubes by using in situ transmission electron microscopy with a two-electrode configuration. The dimensions of the nanocubes tested are between 10 and 20 nm, which rendered their in situ electrical characterization challenging. We characterized 4%Cr and 5%La (atomic percentage) doped BaTiO3 nanocubes and compared them with the properties of pristine BaTiO3 nanocubes synthesized by the same solvothermal method. We found that the resistance of all three types of nanocubes when displayed in log-scale shows a nearly linear dependence on the applied electric field (R2 ≥ 0.95) over a wide range of electric fields (50–900 kV/cm). Compared with pristine BaTiO3 nanocubes, the resistance of both 4%Cr and 5%La doped nanocubes showed reduced variation rates with respect to the electric field, with 5%La doping, demonstrating a better reduction in the variation rate. By developing techniques capable of evaluating the properties of individual BaTiO3 nanocubes, we expect that our work to open the door to the use of BaTiO3 nanomaterials in the design of future multilayer ceramic capacitors with improved volumetric efficiency and ferroelectrics-enabled nanodevices with advanced functionality.

Effect of Ligand Polarity on the Internal Dipoles and Ferroelectric Distortion in BaTiO3 Nanocubes.

Surface adsorbates and surrounding matrix species have been demonstrated to affect the properties of nanoscale ferroelectrics and nanoscale ferroelectric composites; potentially counteracting performance losses that can occur in small particle sizes. In this work, the effects of nonpolar oleic acid (OA) and polar tetrafluoroborate (BF4 - ) ligand capping on the surface of various sizes of BaTiO3 nanocubes have been investigated with combined neutron diffraction and neutron pair distribution function (PDF), density functional theory (DFT), and ab initio molecular dynamics (AIMD) methods. The low real space PDF region provides an unobstructed view of rhombohedral (split short and long) Ti-O distances in BaTiO3 nanocubes, mimicking the well-established order-disorder local structure found in bulk BaTiO3 . Interestingly, the intermediate-range order in nanocubes is found to be orthorhombic, rather than tetragonal. It is concluded that polar ligands adsorbed at BaTiO3 surfaces stabilize the correlation length scale of local rhombohedral distortions in ferroelectric nanoparticles relative to nonpolar ligands.

Stabilization of Size-Controlled BaTiO3 Nanocubes via Precise Solvothermal Crystal Growth and Their Anomalous Surface Compositional Reconstruction.

Crystal growth of barium titanate (BaTiO3) using a wet chemical reaction was investigated at various temperatures. BaTiO3 nanoparticles were obtained at an energy-efficient temperature of 80 °C. However, BaTiO3 nanocubes with a preferred size and shape could be synthesized using a solvothermal method at 200 °C via a reaction involving titanium tetraisopropoxide [(CH3)2CHO]4Ti for nucleation and fine titanium oxide (TiO2) nanoparticles for crystal growth. The BaTiO3 nanocubes showed a high degree of dispersion without the use of dispersants or surfactants. The morphology of BaTiO3 was found to depend on the reaction medium. The size of the BaTiO3 particles obtained using water as the reaction medium was the largest among the particles synthesized using various reaction media. In the case of alcohol reaction media, the BaTiO3 particle size increased in the order methanol, ethanol, 1-propanol, 1-butanol, and 1-pentanol. Furthermore, BaTiO3 powder obtained using alcohol reaction media resulted in cubic shapes as opposed to the round shapes obtained when water was used as the medium. We found that the optimal condition for the synthesis of BaTiO3 nanocubes involved the use of 1-butanol as the reaction medium, resulting in an average particle size of 52 nm, which is the average distance of the cubes measured diagonally from corner to corner, and gives an average side length of 37 nm, and a tetragonal crystal system as evidenced by the powder X-ray diffraction pattern obtained using high-energy synchrotron X-rays. The origin of the spontaneous polarization of the BaTiO3 tetragonal crystal structure was clarified by a pair distribution function analysis. In addition, surface reconstruction of BaTiO3 nanocubes led to an outermost surface comprising two layers of Ti columns.

Effect of heat treatment on internal stress in barium titanate nanocube assemblies and their dielectric property

Heat treatment is a key process to determine the dielectric properties of nanocrystalline barium titanate (BaTiO3) ceramics, which are a prospective candidate to realize further miniaturization of dielectric components in electric devices. Here, we use Raman spectroscopy and scanning microwave impedance microscopy to investigate the dependence of the internal stress and the relative permittivity of BaTiO3 nanocube three-dimensional assemblies on heat treatment temperature. We show that heat treatment in the temperature range from 700 °C to 1000 °C causes internal compressive stress in the nanocube assemblies without grain growth. The internal compressive stress is caused by formation of tight attachments between neighboring BaTiO3 nanocubes and of Ti-rich phases in the nanocube assemblies in the lower and higher temperature ranges, respectively. We also show that the relative permittivity of the nanocube assemblies at 3 GHz shows a positive correlation with the internal compressive stress. The result indicates that the internal compressive stress enhances the relative permittivity of BaTiO3 nanocubes.

Turbulence enhanced ferroelectric-nanocrystal-based photocatalysis in urchin-like TiO2/BaTiO3 microspheres for hydrogen evolution.

The application of a built-in electric field due to piezoelectric potential is one of the most efficient approaches for photo-induced charge transport and separation. However, the efficiency of converting mechanical energy to chemical energy is still very low, and the enhancement of photocatalysis, thus, is limited. To overcome this problem, here, we propose sonophotocatalysis based on a new hybrid photocatalyst, which combines ferroelectric nanocrystals (BaTiO3) and dendritic TiO2 to form an urchin-like TiO2/BaTiO3 hybrid photocatalyst. Under periodic ultrasonic excitation, a spontaneous polarization potential of BaTiO3 nanocrystals in response to ultrasonic waves can act as an alternating built-in electric field to separate photoinduced carriers incessantly, which can significantly enhance the photocatalytic activity and cyclic performance of the urchin-like TiO2/BaTiO3 catalyst. More importantly, the significant enhancement of photocatalytic hydrogen evolution is due to the coupling effect of two types of piezoelectric potential in the presence of BaTiO3 nanocubes as well as the semiconductor and optical properties of TiO2 nanowires of the urchin-like TiO2/BaTiO3 hybrid structure under simulated sunlight and periodic ultrasonic irradiation, which can significantly improve the efficiency of converting mechanical energy to chemical energy.

Dynamic dielectric-response model of flexoelectric polarization from kHz to MHz range in an ordered assembly of BaTiO3 nanocubes

Due to the strain gradient near each surface of a BaTiO3 nanocube in their ordered assembly, electric polarization appears due to flexoelectric effect. The magnitude of the flexoelectric polarization could be one order of magnitude larger than that of ferroelectric spontaneous polarization of BaTiO3. Thus, dielectric response of an assembly could be dominated by that of the flexoelectric polarization if there is no ferroelectric domain-wall motion. Numerical simulations of the dielectric response of a BaTiO3 nanocube in an ordered assembly are performed from kHz to MHz range based on a dynamic model of flexoelectric polarization assuming anharmonic potential. The calculated temperature dependence of the dielectric constant is consistent with the experimental data of high dielectric constant with nearly-flat temperature dependence. It is suggested that high dielectric constant with nearly-flat temperature dependence is not originated in ferroelectric nature of BaTiO3 nanocubes but originated in flexoelectric polarization in nanocubes which is also seen in non-ferroelectric materials.

High refractive index and dielectric properties of BaTiO3 nanocube/polymer composite films

Single-crystalline BaTiO3 nanocube (BT NC) dispersed polymethyl methacrylate (PMMA) nanocomposite films were fabricated using a spin-coating process. Thermogravimetry indicated that volume fraction of BT NCs in nanocomposite film was achieved above 64% with keeping transparency. Refractive index of BT NC/PMMA composite film was 1.89 at 550 nm. The microstructure of BT NC/PMMA composite films was characterized by homogeneous dispersion of BT NC with high occupancy. Dielectric constant of BT NC/PMMA film was about 41 corresponding to 13 times as high as that of PMMA with low loss below 4%.