• Domain wall free polar structure enhanced photodegradation activity in nanoscale ferroelectric BaxSr1-xTiO3

      Wang, Yaqiong; Zhang, Man; Jianguo, Liu; Zhang, Haibin; Li, Feng; Tseng, Chiao-Wei; Yang, Bin; Smith, Graham C.; Zhai, Jiwei; Zhang, Zhen; et al.
      Ferroelectric materials exhibit anomalous behavior due to the presence of domains and domain walls which are related to the spontaneous polarization inherent in the crystal structure. Control of ferroelectric domains and domain walls has been used to enhance device performances in ultrasound, pyroelectric detectors and photovoltaic systems with renewed interest in nanostructuring for energy applications. It is also known that the ferroelectric including domain walls can double photocatalytic rate and increase carrier lifetime from μs to ms[1] However, there remains a lack of understanding on the different contributions of the domain and domain walls to photo-catalytic activities. Herein it is found, by comparing samples of nanostructured BaxSr1 xTiO3 with and without a polar domain, that the material with polar domains has a faster reaction rate (k=0.18 min-1) than the non polar one (k = 0.11 min-1). It is further revealed that the observed enhanced photoactivity of perovskite ferroelectric materials stems from the inherent polarization of the domain instead of domain walls. Here, the new understanding of the underlying physics of materials with a spontaneous dipole opens a door to enhance the performance of light induced energy harvesting systems.
    • Isolation of a Ferroelectric Intermediate Phase in Antiferroelectric Dense Sodium Niobate Ceramics

      Yang, Bin; Zhang, Hangfeng; Yan, Haixue; Abrahams, Isaac (Elsevier, 2019-08-22)
      Switchable ferroelectric/antiferroelectric ceramics are of significant interest for high power energy storage applications. Grain size control of this switching is an interesting approach to controlling polarization and hence dielectric properties. However, the use of this approach in technologically relevant ceramics is hindered by difficulty in fabricating dense ceramics with small grain sizes. Here an intermediate polar ferroelectric phase (P21ma) has been isolated in dense bulk sodium niobate ceramics by grain size control through spark plasma sintering methods. Our findings, supported by XRD, DSC, P-E (I-E) loops and dielectric characterization, provide evidence that the phase transition from the antiferroelectric (AFE) R-phase, in space group Pnmm, above 300 C, to the AFE P-phase, in space group Pbma, at room temperature, always involves the polar intermediate P21ma phase and that the P21ma to Pbma transition can be suppressed by reducing grain size.
    • Microstructure and broadband dielectric properties of Zn2SiO4 ceramics with nano-sized TiO2 addition

      Weng, Zhangzhao; Song, Chunxiao; Xiong, Zhaoxian; Xue, Hao; Sun, Wenfeng; Zhang, Yan; Yang, Bin; Reece, Michael J.; Yan, Haixue; Xiamen University; Capital Normal University; University of Chester; Queen Mary, University of London; China Electronic Product Reliability and Environmental Testing Research Institute (Elsevier, 2019-04-06)
      Zn2SiO4 ceramics with nano-sized TiO2 addition (ZST) were synthesized by conventional solid state method. The association between the new composite’s microstructures and dielectric properties reveals that reduced pores, increased density and average grain sizes with increasing sintering temperatures, have contributed to the increased permittivities at kHz and microwave bands; the decrease of the permittivities at 1275 0C is due to the form of twin planes. At the terahertz band, the competition of generating oxygen vacancies and forming them into twin crystallographic shear planes dominates the change of permittivities: the crystallographic shear planes decrease the permittivity at the sintering temperature 12250C and 12500C, and the high-rate generation of oxygen vacancies at 1275 0C increases the permittivities. The ZST ceramics demonstrate stable permittivity and low dielectric losses (<10-3 from 10 kHz to microwave band; and < 10-2 at THz range); and the temperature coefficient of resonant frequency is optimized to close zero. These advanced dielectric properties and low sintering temperature (<13000C) provide the ZST ceramics great potential in designing microwave and THz devices.
    • Microwave and terahertz dielectric properties of MgTiO3–CaTiO3 ceramics

      Huang, Jinbao; Yang, Bin; Yu, Chuying; Zhang, Guang; Xue, Hao; Xiong, Zhaoxian; Viola, Giuseppe; Donnan, Robert S.; Yan, Haixue; Reece, Michael J.; et al. (Elsevier, 2015-10-05)
      The THz dielectric properties of MgTiO3–CaTiO3 ceramics are reported. The ceramics were prepared via a solid-state reaction route and the sintering conditions were optimized to obtain ceramics with high permittivity and low loss in the terahertz frequency domain. The amount of impurities (MgTi2O5) and grain size increased with increasing sintering temperature. The dielectric properties improved with increasing density, and the best terahertz dielectric performance was obtained at 1260 °C, with a permittivity of 17.73 and loss of 3.07×10−3. Ceramics sintered above 1260 °C showed a sharp increase in loss, which is ascribed to an increase in the impurity content.
    • Perovskite Srx(Bi1-xNa0.97-xLi0.03)0.5TiO3 ceramics with polar nano regions for high power energy storage

      Wu, Jiyue; Mahajan, Amit; Riekehr, Lars; Zhang, Hangfeng; Yang, Bin; Meng, Nan; Zhang, Zhen; Yan, Haixue; Queen Mary University of London; Uppsala University; University of Chester (Elsevier, 2018-06-06)
      Dielectric capacitors are very attractive for high power energy storage. However, the low energy density of these capacitors, which is mainly limited by the dielectric materials, is still the bottleneck for their applications. In this work, lead-free single-phase perovskite Srx(Bi1-xNa0.97-xLi0.03)0.5TiO3 (x=0.30 and 0.38) bulk ceramics, prepared using solid-state reaction method, were carefully studied for the dielectric capacitor application. Polar nano regions (PNRs) were created in this material using co-substitution at A-site to enable relaxor behaviour with low remnant polarization (Pr) and high maximum polarization (Pmax). Moreover, Pmax was further increased due to reversible electric field induced phase transitions. Comprehensive structural and electrical studies were performed to confirm the PNRs and the reversible phase transitions. And finally a high energy density (1.70 J/cm3) with an excellent efficiency (87.2%) was achieved using the contribution of PNRs and field-induced transitions in this material, making it among the best performing lead-free dielectric ceramic bulk material for high energy storage.
    • SrFe12O19 based ceramics with ultra-low dielectric loss in the millimetre-wave band

      Yu, Chuying; Zeng, Yang; Yang, Bin; Wylde, Richard; Donnan, Robert S.; Wu, Jiyue; Xu, Jie; Gao, Feng; Abrahams, Isaac; Reece, Michael J.; et al. (AIP Publishing, 2018-04-02)
      Non-reciprocal devices such as isolators and circulators, based mainly on ferromagnetic materials, require extremely low dielectric loss in order for strict power-link budgets to be met for millimetre (mm)-wave and terahertz (THz) systems. The dielectric loss of commercial SrFe12O19 hexaferrite was significantly reduced to below 0.002 in the 75 - 170 GHz band by thermal annealing. While the overall concentration of Fe2+ and oxygen vacancy defects is relatively low in the solid, their concentration at the surface is significantly higher, allowing for a surface sensitive technique such as XPS to monitor the Fe3+/Fe2+ redox reaction. Oxidation of Fe2+ and a decrease in oxygen vacancies is found at the surface on annealing, which is reflected in the bulk sample by a small change in unit cell volume. The significant decrease in dielectric loss property can be attributed to the decreased concentration of charged defects such as Fe2+ and oxygen vacancies through annealing process, which demonstrated that thermal annealing could be effective in improving the dielectric performance of ferromagnetic materials for various applications.
    • Structure and dielectric properties of double A-site doped bismuth sodium titanate relaxor ferroelectrics for high power energy storage applications

      Yang, Bin; Zhang, Hangfeng; Fortes, Dominic; Yan, Haixue; Abrahams, Isaac; University of Chester; Queen Mary University of London; Rutherford Appleton Laboratory
      The structural and dielectric properties of barium/strontium substituted Bi0.5Na0.5TiO3 were examined in compositions of general formula (Ba0.4Sr0.6TiO3)x(Bi0.5Na0.5TiO3)1-x. An average classic cubic perovskite structure is maintained from x = 0.5 to 1.0. The temperature dependence of dielectric properties of studied compositions shows relaxor-ferroelectric behaviour attributed to the existence of polar nano-regions. Ferroelectric measurements under variable temperature demonstrated two transitions from normal ferroelectric to relaxor-ferroelectric and relaxor-ferroelectric to paraelectric, at the dipole freezing temperature, Tf, and temperature of maximum permittivity, Tm, respectively. The obtained value of Tf coincides with the onset of linear thermal expansion of the cubic unit cell parameter obtained from high resolution powder neutron diffraction data. Careful analysis of the neutron diffraction data revealed no significant change in the average cubic structure from -263 to 150 C. However, changes in the Gaussian variance component of the neutron peak shape, reveal three distinct regions with transitions at about -100 and 100 C corresponding to the beginning and end of the dielectric dispersion seen in the permittivity and loss spectra. This variation in the Gaussian variance parameter is attributed to the activity of the polar nano-regions. The composition (Ba0.4Sr0.6)0.5(Bi0.5Na0.5)0.5TiO3 was found to exhibit the maximum recoverable energy storage density, with a value of 1.618 J cm-3 and 76.9% storage efficiency at a field of 17 kV mm-1.
    • Terahertz reading of ferroelectric domain wall dielectric switching

      Zhang, Man; Chen, Zhe; Yue, Yajun; Chen, Tao; Yan, Zhongna; Jiang, Qinghui; Yang, Bin; Eriksson, Mirva; Tang, Jianhua; Zhang, Dou; et al.
      Ferroelectric domain walls (DWs) are important nano scale interfaces between two domains. It is widely accepted that ferroelectric domain walls work idly at terahertz (THz) frequencies, consequently discouraging efforts to engineer the domain walls to create new applications that utilise THz radiation. However, the present work clearly demonstrates the activity of domain walls at THz frequencies in a lead free Aurivillius phase ferroelectric ceramic, Ca0.99Rb0.005Ce0.005Bi2Nb2O9, examined using THz time domain spectroscopy (THz-TDS). The dynamics of domain walls are different at kHz and THz frequencies. At low frequencies, domain walls work as a group to increase dielectric permittivity. At THz frequencies, the defective nature of domain walls serves to lower the overall dielectric permittivity. This is evidenced by higher dielectric permittivity in the THz band after poling, reflecting decreased domain wall density. An elastic vibrational model has also been used to verify that a single frustrated dipole in a domain wall represents a weaker contribution to the permittivity than its counterpart within a domain. The work represents a fundamental breakthrough in understanding dielectric contributions of domain walls at THz frequencies. It also demonstrates that THz probing can be used to read domain wall dielectric switching.
    • Titanium Dioxide Engineered for Near-dispersionless High Terahertz Permittivity and Ultra-low-loss

      Chuying, Yu; Zeng, Yang; Yang, Bin; Donnan, Robert S.; Huang, Jinbao; Xiong, Zhaoxian; Mahajan, Amit; Shi, Baogui; Ye, Haitao; Binions, Russell; et al. (Nature Publishing Group, 2017-07-26)
      Realising engineering ceramics to serve as substrate materials in high-performance terahertz(THz) that are low-cost, have low dielectric loss and near-dispersionless broadband, high permittivity, is exceedingly demanding. Such substrates are deployed in, for example, integrated circuits for synthesizing and converting nonplanar and 3D structures into planar forms. The Rutile form of titanium dioxide (TiO2) has been widely accepted as commercially economical candidate substrate that meets demands for both low-loss and high permittivities at sub-THz bands. However, the relationship between its mechanisms of dielectric response to the microstructure have never been systematically investigated in order to engineer ultra-low dielectric-loss and high value, dispersionless permittivities. Here we show TiO2 THz dielectrics with high permittivity (ca. 102.30) and ultra-low loss (ca. 0.0042). These were prepared by insight gleaned from a broad use of materials characterisation methods to successfully engineer porosities, second phase, crystallography shear-planes and oxygen vacancies during sintering. The dielectric loss achieved here is not only with negligible dispersion over 0.2 - 0.8 THz, but also has the lowest value measured for known high-permittivity dielectrics. We expect the insight afforded by this study will underpin the development of subwavelength-scale, planar integrated circuits, compact high Q-resonators and broadband, slow-light devices in the THz band.
    • Ultrafast Electric Field-induced Phase Transition in Bulk Bi0.5Na0.5TiO3 under High Intensity Terahertz Irradiation

      Yang, Bin; Zhang, Man; McKinnon, Ruth A.; Viola, Giuseppe; Zhang, Dou; Reece, Michael J.; Abrahams, Isaac; Yan, Haixue; University of Chester; Queen Mary University of London; Central South University
      Ultrafast polarization switching is being considered for the next generation of ferroelectric based devices. Recently, the dynamics of the field-induced transitions associated with this switching have been difficult to explore, due to technological limitations. The advent of terahertz (THz) technology has now allowed for the study of these dynamic processes on the picosecond (ps) scale. In this paper, intense terahertz (THz) pulses were used as a high-frequency electric field to investigate ultrafast switching in the relaxor ferroelectric, Bi0.5Na0.5TiO3. Transient atomic-scale responses, which were evident as changes in reflectivity, were captured by THz probing. The high energy THz pulses induce an increase in reflectivity, associated with an ultrafast field-induced phase transition from a weakly polar phase (Cc) to a strongly polar phase (R3c) within 20 ps at 200 K. This phase transition was confirmed using X-ray powder diffraction and by electrical measurements which showed a decrease in the frequency dispersion of relative permittivity at low frequencies.