Orientation dependence on piezoresponse of lead-free piezoelectric sodium bismuth titanate epitaxial thin films

Lead-free piezoelectric sodium bismuth titanate((Bi0.5Na0.5)TiO3,BNT)thin films were epitaxially grown onto(001)-,(110)-,and(111)-oriented Nb:SrTiO3(STO)single crystal substrates prepared by sol-gel processing.Highly oriented growth in(001),(110),and(111)BNT thin films was obtained in this work benefiting from the lattice match between the BNT film and the STO substrate.The different growth models in thin films with various orientations result in various surface morphologies dependent on the film orientation.The piezoresponse of the BNT thin films was represented exhibiting a strong orientation dependence that(110)>(001)>(111).This is contributed by the various domain switching contribution related to the crystal symmetry and polarization distribution in the three oriented thin films.

Oxygen vacancy migration and its lattice structural origin in A-site non-stoichiometric bismuth sodium titanate perovskites

Off-stoichiometry of perovskite structural Bi0.5Na0.5TiO3(BNT)ferroelectrics can give rise to considerable oxide-ion conductivity.The inherent structural characteristics are urgent to be resolved due to its particular sensitivity of the conduction mechanism to the nominal composition and synthesis process.Herein,a thorough study of the temperature-dependent neutron,X-ray diffraction and Raman spectrum is carried out on a series of equivalently substituted A-site deficient non-stoichiometric and pristine BNT.Phase transition and defect association are systemically investigated in these dominated rhombohedral phases at room temperature,associated with well saturated ferroelectric states.Significant structural evolution identified by Rietveld refinements and the origin of the electrical performance are clarified at elevated temperatures,focusing on the subtle distortions of ionic displacements,oxygen octahedral tilts and local chemical environments for oxygen vacancies.The ion migration ability mediated by oxygen vacancies that are not energetically favorable in BNT mainly depends on the external substitutional disorder,and is strongly affected by the dopant concentration.Together with the lone pair substitution concept,superior oxide ionic conductivity is achieved,and an alternative strategy is provided in designing BNT based oxide ion conductors.

Investigation of Ceramic Based Composites by Using 2D Graphene Filler

The ceramic composites of sodium bismuth titanate with reduce graphene oxide NBT/rGO of different compositions were fabricated by solid state sintering method and characterized. In this work, the graphene oxide (GO) and reduce graphene oxide (rGO) was successfully synthesized by Hummer’s modified method which is confirmed by FTIR and XRD results. The reduce graphene oxide used as 2D filler in piezoelectric creamic material. The crystalline structure of NBT/rGO composite was confirmed by X-ray diffraction with rhombohedral symmetry. The dispersion of rGO in the ceramic can be detect by the optical microcopy images. The electrical conductivity of sodium bismuth titanate shows increase at higher values of frequency and conductivity nanocomposites of different wt% were start decreases up to certain value of frequency. The broadening of peaks in frequency explicit plots of electrical conductivity with the help of LCR Meter (Impedance Capacitance and Resistance). The crystalline size of reduced graphene oxide and NBT is calculated by Scherrer’s formula of XRD peaks.

Synthesis and Piezoelectric Properties of Lead-free (Bi_(0.5)Na_ (0.5))_ 1-x(Ba_aSr_b)_xTiO_3 Ceramics

A new group of lead-free piezoelectric ceramics,（Bi0.5 Na0.5）1-x（BaaSrb）xTiO3（abbreviated as BNBST[100x-100a/100b],0〈x〈1,a＋b=1）,was synthesized.The ceramics were prepared by conventional ceramic sintering technique,and the ceramics with density of 95% of the theoretical one can be sintered without the atmosphere control during the sintering process.The results of the X-ray diffraction（XRD） data show that the ceramics possess a single perovskite phase.The measurements of dielectric and piezoelectric properties reveal that the ceramics provide relatively high piezoelectric charge constant d33 and high planar electromechanical coupling factor kp.For the BNBST6-95/5 ceramics,d33 is equal to 170pC/N,and kp is equal to 32.0%.The fabrication technique for these ceramics is conventional and stable.

Structure and Electric Properties of (1-x)(Bi_(1/2)Na_(1/2)) TiO_3-xBaTiO_3 Systems

The structural, dielectric and piezoelectric properties of （1-x）（Bi1/2Na1/2） TiO3-xBaTiO3 ceramics were investigated for the compositional range, x=0.02, 0.04, 0.06, 0.08, 0.10. The samples were synthesized by a conventional solid-state reaction technique. All compositions show a single perovskite structure, and X-ray powder diffraction patterns can be indexed using a rhombohedral structure. Lattice constants and lattice distortion increase while the amount of BaTiO3 increases. The X-ray diffraction results show the morphotropic phase boundary （MPB） of （1-x）（Bi1/2Na12） TiO3-xBaTiO3 exists in near x=0.06-0.08. Temperature dependence of dielectric constant eT33/ε0 measurement reveals that all compositions experience one structural phase and two ferroelectric phases transition below 400℃： rhombohedral （or rhombohedral plus tetragonal） ferroelectric phase ←→ tetragonal antiferroelectric phase ←→ tetragonal paraelectric phase. Relaxor behaviors exist in the course of ferroelectric to antiferroelectric phase transition. Dielectric and piezoelectric properties are enhanced in the MPB range for （ 1-x）（Bi1/2Na1/2）TiO3-xBaTiO3.

A review:(Bi,Na)TiO_(3)(BNT)-based energy storage ceramics

Facing the increasingly serious energy and environmental problems,the research and development of new energy storage technology and environment-friendly energy storage materials are imminent.As a typical lead-free ferroelectric with excellent dielectric properties,(Bi,Na)TiO_(3)(BNT)is supposed to be the most potential and competitive environment-friendly ceramic material and has become a research hotspot for dielectric energy storage in recent years.This paper first briefly introduces the basic physical principles and energy storage performance evaluation parameters of dielectric energy storage materials,then summarizes the critical research systems and related progress of BNT-based lead-free energy storage materials(bulk ceramics,films and multilayer ceramics)from the aspects of ions doping modification and multi-component composite optimization,and finally looks forward to the improvement direction and energy storage application prospect of BNT-based lead-free relaxor ferroelectric materials.

Modulation of phase boundary and domain structures to engineer strain properties in BNT-based ferroelectrics

Bismuth sodium titanate(BNT)ceramics exhibit outstanding strain responses but are unfavorable for application in high-sensitivity displacement actuators due to the large negative strain resulting from irreversible changes in their phase transition and domain structure.Here,(1−x)Bi_(0.50)Na_(0.41)K_(0.09)TiO_(3)-xNaNbO_(3)(BNKT−xNN)solid solutions were prepared to improve the strain properties through the strategy of modulating the phase boundary and domain structures.The introduction of sodium niobate could effectively regulate the relative content of the tetragonal(P4bm)and rhombohedral(R3c)phases in the phase boundary region.The ferroelectric-to-relaxor phase transition(T_(F−R))was reduced,and the ergodic relaxor(ER)state was nurtured at room temperature.Excellent zero-negative strain properties of S=0.41%and d_(33)^(*)=742 pm/V were achieved from the reversible transition between the ER and ferroelectric states under an applied electric field(x=0.04).Additionally,understanding the domain states via piezoelectric force microscopy(PFM)and firstorder reversal curve(FORC)revealed that the superior strain responses originated from the reversible inter-transformation of substable macrodomains and polar nanoregions(PNRs)in the phase boundary.This study provides new insight into the interplay between the evolution of phase boundaries and domain structures and the strain properties of BNT-based ceramics.

Effect of rare earth on physical properties of Na_(0.5)Bi_(0.5)TiO_(3)system:A density functional theory investigation

Na_(0.5)(Bi_(3/4)RE_(1/4))_(0.5)TiO_(3)(RENBT,RE=Nd,Gd,Dy,and Ho)compounds were investigated in the framework of first-principles calculations using the full potential linearized augmented plane wave(FP-LAPW)method based on the spin-polarized density functional theory implemented in the WIEN2k code.Combined charge density distribution and Ti K-edge X-ray absorption spectra reveal that the RENBT compositions with high polarization values are accompanied by a higher TiO_(6)distortion,DyNBT,and NdNBT compounds.The effect of the rare-earth elements on the polarization is confirmed experimentally with the collection of the hysteresis loops.The investigation of the electronic properties of the compounds highlights the emergence of a magnetization owing to the 4f orbital effect of the rare-earth elements.Besides,the investigation of the chemical ordering shows a short-range chemical ordering for the pure composition and an increased A-site disorder for dysprosium doped NBT system.The increased disorder may speak for increased relaxor properties in the RE doped compositions.

Structure and Piezoelectric Properties of Lead-Free Na_(0.5)Bi_(0.5)TiO_3 Nanofibers Synthesized by Electrospinning

Lead-free Na0.5Bi0.5TiO 3（NBT） nanofibers with the perovskite structure were prepared by the electrospinning method.The nanofibers were about 200-300 nm in diameter and up to several hundred microns in length.The crystal structures and morphologies of the nanofibers were characterized by X-ray diffraction（XRD）,Raman spectroscopy,scanning electron microscopy（SEM）,and transmission electron microscopy（TEM）.The effective piezoelectric property of individual NBT nanofiber was examined by piezoresponse force microscopy（PFM）.The NBT nanofibers crystallized in pure perovskite phase after annealing above 700℃in air and comprised a great number of fine particles with size of 60-80 nm.In addition,the electromechanical energy conversion models for NBT nanofibers were built and demonstrated high voltage output as high as several millivolts.Such a result qualifies NBT nanofibers as a promising candidate for leadfree electromechanical conversion devices.

NaNbO_(3) modulated phase transition behavior and antiferroelectric stability evolution in 0.88(Bi_(0.5)Na_(0.5))TiO_(3)-0.12BaTiO_(3) lead-free ceramics

Giant strains in(Bi_(0.5)Na_(0.5))TiO_(3) based ceramics are usually attributed to electric field induced nonpolar to polar phase transition.Whether it is an ergodic relaxor R3c/P4mm ferroelectric(FE)to long-range ordered FE phase transformation or a reversible P4bm antiferroelectric(AFE)to FE phase transition is still unclear.Herein,lead-free(0.88-x)(Bi_(0.5)Na_(0.5))TiO_(3)-0.12BaTiO_(3-x)NaNbO_(3) ceramics exhibit a compositionmodulated FE tetragonal P4mm to relaxor AFE tetragonal P4bm phase transition,in which double hysteresis loop,sprout-shaped S-E curves,near-zero quasi-static d33 together with a large volume change suggest the AFE characteristics of P4bm phase.An interesting finding is that the reversibility of fieldinduced AFE P4bm phase to FE P4mm phase transition strongly depends on the NN content,from being completely irreversible at x=0.01e0.02,to partially reversible at x=0.03e0.05,and finally to completely reversible at x=0.06e0.08.It is indicated that the variation of reversibility should be attributed to the change of relative free energy caused by decreasing the FE to AFE phase transition temperature with increasing the NN content.

Structural and Dielectric Properties of ZnO Added (Na_(1/2)Bi_(1/2))TiO_3 Ceramics

Structural and dielectric properties of polycrystalline samples of lead-free （l-x）（Nal/2Bil/2）TiO3-xZnO, prepared using a high-temperature solid-state reaction method, were investigated in the composition range of 0≤x≤0.10. Rietveld analyses of X-ray diffraction data indicated the formation of a single-phase hexagonal structure with R3c symmetry. Williamson-Hall approach was applied to estimate the apparent particle size and lattice strain of the compounds. Temperature dependence of dielectric constant showed that the addition of ZnO to （Na1/2Bi1/2）TiO3 shifted the phase transition temperature towards higher side, a property favourable for practical applications of these ceramics. Further, temperature dependent permittivity data provided low temperature coefficient of capacitance （TCC〈8%） up to 100℃. Furthermore, a decrease in the value of dielectric loss with an increase in ZnO content was observed.

Structure and dielectric properties of NBT-xBT-ST lead-free ceramics for energy storage

(0:74-x)(Na_(0.5)Bi_(0.5))TiO_(3)-xBaTiO_(3)-0.26SrTiO_(3)(x=0~0.1)(abbreviated as NBT-xBT-ST)lead-free ceramics were fabricated by a solid-state reaction method.The effect of Ba doping amount x on the structure and energy storage properties of NBT-xBT-ST ceramics were investigated.All the NBT-xBT-ST ceramics showed single perovskite structure with a pseudocubic phase.Ba doping effectively suppressed grain growth,in favor of forming small and uniform grains.The ceramics with a composition of x=0.04,an optimized energy storage density(γ=0.47 J/cm^(3))and efficiency(η=48:67%),under an applied electric field of 50 kV/cm,should be a candidate for solid-state compact pulsed power capacitor materials.

Phase evolution in(1x)(Na_(0.5)Bi_(0.5))TiO_(3)-xSrTiO_(3) solid solutions:A study focusing on dielectric and ferroelectric characteristics

In the present work,the nature of phase evolution of(1x)(Na_(0.5)Bi_(0.5))TiO_(3)-xSrTiO_(3)(NBT-xST)solid solutions with x of 0e0.6 is revealed by characterizing the dielectric and ferroelectric properties.Two unique dielectric anomalies associated with high-temperature nanoregions(PNRs)in the ergodic relaxor(ER)state and low-temperature PNRs in the nonergodic relaxor(NR)state are identified.Characteristic temperatures,including TB,TRT*,Tm,Td and TT*,are determined in fresh and poled states on the basis of the characteristics of the evolution of these two dielectric anomalies.The whole evolution of the transition from the NR state to the ER state is reflected by the temperature-dependent polarization versus electric field(P-E)hysteresis loops,i.e.,from the square loops,via the double-like loops,to the slim loops.The characteristic temperatures,including TP-N,TN-R and TR-dis,are determined by the characteristics of the evolution of P-E loops.Accordingly,a phase diagram of NBT-xST was constructed according to these characteristic temperatures.Most importantly,the relationship between polarization responses and heterogeneous polar phase coexistence has been established and a schematic diagram is given.This work will help to understand the phase evolution and its impact on the macroscopic properties of NBT and the associated NBT-based solid solutions.

Progress and perspective of high strain NBT-based lead-free piezoceramics and multilayer actuators

In this review,the evolution of high strain Na_(0.5)Bi_(0.5)TiO_(3)-based lead-free piezoceramics and their multilayer actuators has been explored.First,in terms of Na_(0.5)Bi_(0.5)TiO_(3)-based ceramic materials,the origin of high strain,the typical chemical modification methods of obtaining large strain and extrinsic factors affecting the large strain are discussed.Then it briefly summarizes the problems existing in Na_(0.5)Bi_(0.5)TiO_(3)-based ceramics for multilayer actuator applications.Strategies to optimize strain performance by means of microstructure control and phase structure design are also discussed.Thereafter,in terms of multilayer actuator,we describe its characteristics,applications and preparation process systematically,as well as the recent development of Na_(0.5)Bi_(0.5)TiO_(3)-based multilayer actuator.At last,perspectives on directions of following work and promising fields for the applications of the materials and their devices are presented.

A REVIEW ON LEAD-FREE PIEZOELECTRIC CERAMICS STUDIES IN CHINA

There are a large number of research publications on the hot topic of environmental friendly leadfree piezoelectric materials worldwide in the last decade.The number of researchers and institutions involved from China is much larger than other countries or regions.The publications by Chinese researchers cover a broad spectrum on the preparations,structures,properties and applications of lead-free piezoelectric ceramics.This has motivated us to come out with a review on recent advances in development of lead-free piezoelectric ceramics in China.The emphases are especially on the preparation and electric properties of barium titanate-based materials,bismuth sodium titanate and related materials,alkaline niobate and related materials,bismuth layerstructured materials,as well as texture engineering of ceramics and some of their single crystals.Hopefully,this could give further impetus to the researchers to continue their e®orts in this promising area and also draw the attentions from legislature,research o±ce,industrial and publics.

Dielectric behaviors and relaxor characteristics in Bi_(0.5)Na_(0.5)TiO_(3)-BaTiO_(3) ceramics

Microstructure and dielectric behaviors of heating/cooling and bias-field were investigated in lead-free ceramics(1-x)Bi_(0.5)Na_(0.5)TiO_(3)-xBaTiO_(3)(BNT-xBT,x=0,0.02,0.04,0.06,0.08 and 0.10).The relaxor characters and the Vogel–Fulcher law of frequency-dependent dielectric properties were analyzed.Three dielectric anomalies with pronounced frequency dispersion at Td,a maximum dielectric with variable frequency-dispersion at Tm and a third Maxwell–Wagner-type relaxation over a wide temperature range in high-temperature region were observed.The significant dielectric thermal hysteresis,low barrier energy,high freezing temperature in heating process and the maximum dielectric tunability appeared in x=0.4 ceramic.

ENHANCED PIEZOELECTRIC PROPERTIES IN(Bi_(0.5)K_(0.5))TiO_(3)-(Bi_(0.5)Na_(0.5))TiO_(3)FERROELECTRIC SINGLE CRYSTALS

Single crystals of x(Bi,K)TiO_(3)-(1-x)(Bi,Na)TiO_(3)(0.11≤x≤0.47) were grown by a flux method and their polarization and piezoelectric properties were investigated along h100i cubic at 25℃.Rietveld analysis of powder X-ray diffraction data provides a tentative phase diagram in this system.rhombohedral R3c for x≤0.22,pseudocubic for 0.22<x<0.3 and tetragonal P4mm for 0.3≤x.Piezoelectric strain properties show that the crystals(x=0.38)exhibited an extremely large piezoelectric strain constant of 637 pm/V.

Correlations between structure,microstructure,density and dielectric properties of the lead-free ferroelectrics Bi_(0.5)(Na,K)_(0.5)TiO_(3)

Solid solutions of the lead-free ferroelectric oxides Bi_(0.5)Na_(0.5)TiO_(3)(BNT)and Bi_(0.5)Na_(0.5)TiO_(3)(BKT),represented as(1-x)BNT-xBKT,are studied for very close compositions in the range0≤x≤0.36 to understand the correlation between the structure and the properties.Compositions are varied in steps of △x=0.02 in the range0≤x≤0.1 and0.2≤x≤0.36 and△x=0.01 in the range 0.1≤x≤0.2,to precisely locate the structural transition as well as the morphotropic phase boundary(MPB)region and the compositional region of best performance.Rietveld refinement analysis of the powder X-ray diffraction patterns showed monoclinic phase up to x=0.17 and a mixture of monoclinic and tetragonal phases for x>0.17.Similarly,the density and the dielectric constant showed linear variation up to x=0.17 and a large increase above this composition,showing maximum values in the compositional range 0.22≤x≤0.26,corresponding to the MPB region.Microstructural features also showed corresponding changes,indicating close relationship between the structure,microstructure and properties of the different compositions.