Lead-free piezoelectrics: Current status and perspectives

In the last few years,there has been tremendous effort to develop lead-free ferroelectric ceramics with high piezoelectric properties by various doping and alloying routes.Several material systems have been explored,however,no prominent alternative to the versatile lead zirconate titanate(PZT)system has been found yet.Despite the achieved improvement in piezoelectric properties,there are problems in the synthesis,processing and poling of the sintered ceramics.Various processing techniques including microwave,hydrothermal,sol
gel,Pechini and spark plasma sintering have been used to overcome the drawbacks related to synthesis issues.In this paper,an attempt is made to review recent developments on lead-free piezo materials emphasizing their preparation,structure
property relations,and consequent physical properties.In this context,both compositional and structural engineering approaches to achieve acceptable piezoelectric properties in lead-free materials are discussed.Piezoelectric properties of the most promising lead-free compositions/families including titanates,alkaline niobates and bismuth perovskites and their solid solutions,along with non-perovskites such as bismuth layer-structured ferroelectrics are reviewed in detail.A brief coverage of the recent developments in the area of piezoelectric energy harvesting is also encompassed.

Finite-size-effect on a very large length scale in NBT-based lead-free piezoelectrics

Na_(0.5)Bi_(0.5)TiO_(3)-based lead-free piezoelectrics are considered for potential replacement of the lead-based commercial piezoceramics in high-power transducer applications.We have examined the role of grain size in influencing the structural-polar inhomogeneity of stoichiometric and off-stoichiometric Na_(0.5)Bi_(0.5)TiO_(3)(NBT),and its morphotropic-phase-boundary(MPB)derivative 0.94Na_(0.5)Bi_(0.5)TiO_(3)-0.06BaTiO_(3)(NBT-6BT).Our study reveals that size effect comes into play in these systems on a very large length scale(on the scale of microns)considerably affecting its global structure and properties.

Manufacture and Cytotoxicity of a Lead-free Piezoelectric Ceramic as a Bone Substitute—Consolidation of Porous Lithium Sodium Potassium Niobate by Cold Isostatic Pressing

Aim The piezoelectric properties and cytotoxicity of a porous lead-free piezoelectric ceramic for use as a direct bone substitute were investigated. Methodology Cold isostatic pressing （CIP） was applied to fabricate porous lithium sodium potassium niobate （Li0.06Na0.5K0.44） NbO3 specimens using a pore-forming method. The morphologies of the CIP-processed specimens were characterized and compared to those of specimens made by from conventional pressing procedures. The effects of the ceramic on the attachment and proliferation of osteoblasts isolated from the cranium of 1-day-old Sprague- Dawley rats were examined by a scanning electron microscopy （SEM） and metbylthiazol tetrazolium （MTT） assay. Results The results showed that CIP enhanced piezoelectricity and biological performance of the niobate specimen, and also promoted an extracellular matrix-like topography of it. In vitro studies showed that the CIP-enhanced material had positive effects on the attachment and proliferation of osteoblasts. Conclusion Niobate ceramic generated by CIP shows a promise for being a piezoelectric composite bone substitute.

Effect of Li content on the microstructure and properties of lead-free piezoelectric(K_(0.5)Na_(0.5))_(1-x)Li_xNbO_3 ceramics prepared by SPS

Lead-free piezoelectric （K0.5sNa0.5）1-xLixNbO3 （x = 0at%-20at%） ceramics were synthesized by spark plasma sintering （SPS） at low temperature and the effects of LiNbO3 addition on its crystal structure and properties were also studied. When the Li content was less than 6at%, a single proveskite phase with the similar structure of （K0.5Na0.5）NbO3 was formed; and a secondary phase with K3Li2Nb5O15 structure was observed in the 6at% 〈 x 〈 20at% compositional range. Furthermore, LiNbO3 existed as the third phase when the Li content was higher than 8at%. The grain sizes increased from 200-500 nm to 5-8 μm when the K3Li2Nb5O15 and LiNbO3 like phases were formed. With increasing Li content, the relative density of the ceramics first decreased from 97% to 93% and then kept constant. The piezoelectric coefficient d33, dielectric constant, and planner electromechanical coupling factor exhibited a decreasing tendency with increasing Li content because of the decrease in density and the formation of the secondary phase such as K3Li2Nb5O15 and LiNbO3. The formation of dense microstructure with a single phase is necessary in improving the properties of the （K0.5Na0.5）1-xLixNbO3 ceramics.

Microstructure and electrical properties of Ti-modified (Na_(0.5)K_(0.5))(Ti_xNb_(1-x))O_3 lead-free piezoelectric ceramics

Ti-Modified (Na0.5K0.5)(TixNb1-x)O3 (NKNT) piezoelectric ceramics were fabricated by double-layer buried powder process at 1020°C for 2 h. The microstructures,and piezoelectric and dielectric properties of the lead-free NKNT ceramics were investigated. X-ray diffraction re-sults indicated that Ti4+ had diffused into the (Na0.5K0.5)NbO3 lattices to form a solid solution with a perovskite structure. The introducing of Ti into the (Na0.5K0.5)NbO3 solid solution effectively reduced the sintering temperature and...

Influence of Sb_2O_3 doping on the properties of KBT-NBT-BT lead-free piezoelectric ceramics

0.144（K0.5Bi0.5）TiO3-0.85（Na0.5Bi0.5）TiO3-0.006BaTiO3（KBT-NBT-BT） lead-free piezoelectric ceramics were prepared using a conventional solid state method.The influence of Sb2O3 doping on the crystal phase,surface microstructure and properties of the KBT-NBT-BT lead-free piezoelectric ceramics were investigated using X-ray diffraction（XRD）,scanning electron microscope（SEM） and other analytical methods.The results show that all compositions are of pure perovskite structure solid states.Sb2O3 doping does not influence the microstructure of KBT-NBT-BT lead-free piezoelectric ceramics obviously in the Sb2O3 doping range of 0.1-0.5 wt.%.Sb2O3 functions as a donor when doped small amount,while functions as a acceptor when doped large amount.The piezoelectric strain constant（d33） increases first and then decreases;the dielectric constant（ε33^T/ε0） and the dielectric loss（tanδ） decrease continuously when the amount of Sb2O3 dopant increases.When the doping amount of Sb2O3 is 0.1 wt.%,the KBT-NBT-BT piezoelectric ceramics with good comprehensive properties are obtained,whose d33,ε33^T/ε0 and tanδ are 147 pC/N,1510 and 4.2%,respectively.

Preparation and Piezoelectric Properties of CuO-added(Ag_(0.75)Li_(0.1)Na_(0.1)K_(0.05_)NbO_3 Lead-free Ceramics

CuO-doped（Ag0.75Li0.1Na0.1K0.05）NbO3（ALNKN-xCuO, x = 0.2mol%） lead-free piezoelectric ceramics were prepared by the solid-state reaction method in air atmosphere. The effects of CuO addition on the phase structure, microstructure, and piezoelectric properties of the ceramics were investigated. The experimental results show that the ALNKN ceramics without doping CuO possess rhombohedral phase along with K2NbrO16- type phase and metallic silver phase. For all of the CuO-doped ALNKN ceramics, a pure perovskite structure with the orthorhombic phase was obtained by enclosing the samples in a corundum tube. A homogeneous microstructure with＇the grain size of about 1 ~tm was formed for the ceramics with 0.5mo1% CuO. The grain size increases with increasing amount of CuO. The temperature dependence of dielectric properties indicates that the ferroelectric phase of the ALNKN-xCuO ceramics becomes less stable with the addition of CuO. The ceramics with x = lm01% exhibit relatively good electrical properties along with a high Curie temperature. These results will provide a helpful guidance to preparing other AN-based ceramics by solid-state reaction method in air atmosphere.

Modified phase transition and electrical properties of [Li_(0.05)(Na_(0.535)K_(0.48))_(0.95)]- (Nb_(0.94)Sb_(0.06))O_3 lead-free piezoelectric ceramic by sintering temperature

Li/Sb-doped (Na,K)NbO3 with a nominal composition of [Li0.05(Na0.535K0.48)0.95](Nb0.94Sb0.06)O3 ceramic was synthesized by normal sintering. The phase structure, microstructure, and electrical properties were investigated with a special emphasis on the influence of the sintering temperature. A polymorphic phase transition (PPT) from orthorhombic to tetragonal symmetry was observed when the sintering temperature was raised from 1040 to 1050 ℃, whereby the piezoelectric coefficient d33 and the electromechanical coupling coefficient kp reached the peak values of 245 pC·N-1 and 41.2%, respectively. The PPT induced by varying the sintering temperature is due to the different volatilization extents of alkali metals and appears to a lower sintering temperature with increasing Li content. The trace modifying of alkali metal content is more effective than doping B site element to enhance the d33 value.

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.

Effects of Na/K ratio on the phase structure and electrical properties of Na_xK_(1-x)NbO_3 lead-free piezoelectric ceramics

Lead-free piezoelectric NaxK1-xNbO3（x = 0.3-0.8）（NKN） ceramics were fabricated by normal sintering at 1060°C for 2 h.Microstructures and electrical properties of the ceramics were investigated with a special emphasis on the influence of Na content.The grain size of the produced dense ceramic was decreased by increasing Na content.A discontinuous change in the space distance was found at the composition close to Na0.7K0.3NbO3 ceramic, which indicates the presence of a transitional composition between two different orthorhombic phases, which is similar to the behavior of morphotropic phase boundary（MPB） in NaxK1-xNbO3 ceramics.Such MPB-like behavior contributes to the enhanced piezoelectric coefficient d33 of 122 pC/N, planar-mode electromechanical coupling coefficient kP of 28.6%, and dielectric constant εr of 703, respectively for the Na0.7K0.3NbO3 ceramic.Cubic temperature TC and the transitional temperature TO-T from orthorhombic to tetragonal phase are observed at around 420°C and 200°C, respectively.

Effect of doped Mn on piezoelectric properties of (Na_(0.5)Bi_(0.5))_ (0.92)Ba_(0.08)TiO_3 lead-free ceramics

Piezoelectric ceramics (Na0.5Bi0.5) （0.92）Ba0.08TiO3 +x%MnCO3（BNBT-Mn, x=0CD*21.6, mass fraction） were synthesized by conventional solid state reaction. The results show that when the addition of MnCO3 is 0CD*2 1.4%, BNBT-Mn ceramics exhibit a single-phase perovskite structure. With the increase of content of MnCO3, piezoelectric constant and electromechanical coupling factor increase rapidly when x is lower than 0.3. Then they both decrease when x is in the range of 0.3 and 1.6. When x=0.3, piezoelectric constant and electromechanical coupling factor reach the maximum value of 160pC/N and 58.5% respectively, which can improve the temperature stability of BNBT-Mn.

Influence of sintering temperature on the structure and piezoelectric properties of ZnO-modified (Li, Na, K)NbO_(3) lead-free ceramics

ZnO-modified (Li, Na, K)NbO3 lead-free ceramics with a nominal composition of Li0.06(Na0.535K0.48)0.94NbO3+0.7mol% ZnO (LNKN-ZT) was synthesized normally at 930-1000℃. The Zn ions incorporated into the A-site at a higher sintering temperaVare, which changed LNKN-Z7 to soft piezoelectric ceramics with the mechanical quality factor decreasing from 228 to 192. A phase transition from tetragonal to orthorhombic symmetry was identified by XRD analysis, and the corresponding calculation of lattice parameters was conducted at 970-980℃. Because of such transitional behavior and fine microstructure, the optimized values of piezoelectric coefficient, planar electromechanical coupling coefficient, and relative dielectric constant were obtained.

Microstructure,crystalline phase and electrical properties of Li_(0.06)(Na_(0.5)K_(0.5))_(0.94)Nb_(1-2x/5)Mg_xO_3 lead-free piezoelectric ceramics

MgO-modified Li0.06（Na0.5K0.5）0.94NbO3O3 （L6NKN） lead-free piezoelectric ceramics were synthesized by normal sintering at a rela- tively low temperature of 1000℃. The crystalline phase, microstructure, and electrical properties of the ceramics were investigated with a special emphasis on the influence of MgO content. The addition of MgO effectively improves the sintembility of the L6NKN ceramics. X-my diffr cfion analysis indicates that the morphotropic phase boundary （MPB） separating orthorhombic and tetragonal phases for the ceramics lies in the range of Mg doping content （x） from 0.3at% to 0.7at%. High electrical properties of the piezoelectric constant （d33=238 pC/N）, planar electromechanical coupling coefficient （kp=41.5%）, relative dielectric constant （εr=905）, and remanent polarization （Pr=38.3 μC/cm2） are obtained from the specimen with x=0.5at%, which suggests that the Li0.06（Na0.5K0.5）0.94Nb（1-2x/5）MgxO3 （x=0.5at%） ceramic is a promising lead-free piezoelectric material.

Lead-free Ce-doped perovskite scintillators with high figure of merit

Lead halide perovskite scintillators have recently received extensive research attention owing to their short fluorescence lifetimes,low detection limits,and ease of fabrication compared to traditional scintillators.The nontoxic cerium-doped lead-free perovskites with intrinsically efficient and short lifetime d–f transitions are a prospective replacement for the toxic Pb^(2+).Here,we demonstrated Ce-doped cesium lanthanide chloride perovskites (Cs_(3)LnCl_(6),Ln=Gd,Y,Lu) synthesized through a facile solution method for the first time.These perovskites exhibit blue-violet emission,which arises from Ce 5d→4f transitions.Among three types of Cs_(3)LnCl_(6) perovskites,Ce:Cs_(3)LuCl_(6) exhibited high photoluminescence quantum yield (PLQY) of 82%and a short excited-state lifetime of approximately 34 ns.When utilized as X-ray scintillators,Ce:Cs_(3)LuCl_(6) crystals display a high light yield of 8120 photons per MeV and a low detection limit of 36.8 n Gy air s^(-1).Importantly,the figure of merit (FoM),representing the ratio of light yield to decay time,reaches 239,which is the highest reported value for lead-free perovskite scintillators up to now.Additionally,the fabrication of perovskite/PMMA films was undertaken for practical demonstrations in X-ray imaging,resulting in the attainment of a resolution of up to 8.38 lp/mm.We anticipate that this work will inspire the utilization of Ce-doped Cs_(3)LnCl_(6) perovskites in ultrafast scintillation applications such as high-energy physics,nuclear reaction monitoring,and dynamic X-ray imaging.

Superflexible and Lead-Free Piezoelectric Nanogenerator as a Highly Sensitive Self-Powered Sensor for Human Motion Monitoring

For traditional piezoelectric sensors based on poled ceramics,a low curie tem-perature(T_(c))is a fatal flaw due to the depolarization phenomenon.However,in this study,we find the low T_(c) would be a benefit for flex-ible piezoelectric sensors because small alterations of force trig-ger large changes in polarization.BaTi_(0.88)Sn_(0.12)O_(3)(BTS)with high piezoelectric coefficient and low T_(c) close to human body temperature is taken as an example for materials of this kind.Continuous piezo-electric BTS films were deposited on the flexible glass fiber fabrics(GFF),self-powered sensors based on the ultra-thin,superflexible,and polarization-free BTS-GFF/PVDF composite piezoelectric films are used for human motion sensing.In the low force region(1-9 N),the sensors have the outstanding performance with voltage sensitivity of 1.23 V N^(−1) and current sensitivity of 41.0 nA N^(−1).The BTS-GFF/PVDF sensors can be used to detect the tiny forces of falling water drops,finger joint motion,tiny surface deformation,and fatigue driving with high sensitivity.This work provides a new paradigm for the preparation of superflexible,highly sensitive and wearable self-powered piezoelectric sensors,and this kind of sensors will have a broad application prospect in the fields of medical rehabilitation,human motion monitoring,and intelligent robot.

Ligand modulation of active center to promote lead-free Cs_(2)AgInCl_(6)photocatalytic CO_(2)reduction

Metal halide perovskites(MHP)are potential candidates for the photocatalytic reduction of CO_(2)due to their long photogenerated carrier lifetime and charge diffusion length.However,the conventional long-chain ligand impedes the adsorption and activation of CO_(2)molecules in practical applications.Here,a ligand modulation technology is employed to enhance the photocatalytic CO_(2)reduction activity of lead-free Cs_(2)AgInCl_(6)microcrystals(MCs).The Cs_(2)AgInCl_(6)MCs passivated by Oleic acid(OLA)and Octanoic acid(OCA)are used for photocatalytic CO_(2)reduction.The results show that the surface defects and electronic properties of Cs_(2)AgInCl_(6)MCs can be adjusted through ligand modulation.Compared with the OLA-Cs_(2)AgInCl_(6),the OCA-Cs_(2)AgInCl_(6)catalyst demonstrated a significant improvement in the catalytic yield of CO and CH_(4).The CO and CH_(4)catalytic yields of OCA-Cs_(2)AgInCl_(6)reached 171.88 and34.15μmol g^(-1)h^(-1)which were 2.03 and 12.98 times higher than those of OLA-Cs_(2)AgInCl_(6),and the total electron consumption rate of OCA-Cs_(2)AgInCl_(6)was 615.2μmol g^(-1)h^(-1)which was 3.25 times higher than that of OLA-Cs_(2)AgInCl_(6).Furthermore,in situ diffuse reflectance infrared Fourier transform spectra revealed the enhancement of photocatalytic activity in Cs_(2)AgInCl_(6)MCs induced by ligand modulation.This study illustrates the potential of lead-free Cs_(2)AgInCl_(6)MCs for efficient photocatalytic CO_(2)reduction and provides a ligand modulation strategy for the active promotion of MHP photocatalysts.

Microstructures and Electrical Properties of Bi_(0.5)-(Na_(1-x-y)K_xLi_y)_(0.5)TiO_3 Lead-free Piezoelectric Ceramics

The microstructures and electrical properties of Bi0.5（Na1-x-yKxLiy）0.5TiO3 lead-free piezoelectric ceramics were studied.These ceramics were prepared by conventional ceramic technique.XRD analysis reveals that the ceramics possess almost pure perovskite phase when y≤0.2.The SEM results show that,with more amounts of Li＋,the crystalline grain growing speed is accelerated,and the sintering temperature can effectively be decreased.The measurements of piezoelectric properties indicate that the ceramics with relatively low amount of Li＋ and high amount of K＋ have comparatively large piezoelectricity.The dielectric measurements show that the ceramics have properties like relaxor ferroelectrics and diffuse phase transition（DPT） at Td and Tc,respectively.The results of ferroelectric measurements reveal the system has relatively higher remanent polarization Pr（27.6 μC/cm2） and lower coercive field Ec（37.5 kV/cm）.

Effects of A-site non-stoichiometry on the structural and electrical properties of 0.96K_(0.5)Na_(0.5)NbO_3-0.04LiSbO_3 lead-free piezoelectric ceramics

Effects of A-site non-stoichiometry on the structural and electrical properties of 0.96K0.5＋xNa0.5＋xNbO3- 0.04LiSbO3 lead-free piezoelectric ceramics were examined for 0 ≤ x ≤0.02. The piezoelectric coefficients exhibited a maximum, d33 = 187 pC/N at x = 0.0075, coinciding with the maximum of the grain size and the apparent density at x = 0.0075. The apparent density and the piezoelectric coefficients decreased with increasing x at higher x which was likely due to the crystal geometrical distortion of 0.96K0.5＋xNa0.5＋xNbO3-0.04LiSbO3. In addition, super-large grains were found and this may be due to liquid phase sintering. Excess （K＋＋Na＋） attracted a sum of space charges to keep the charge neutral, resulting in charge leakage during the course of ceramic polarization, influencing the piezoelectric and ferroelectric properties. These findings are of importance for guiding the design of Ko.sNao.sNbO3-based lead-free ceramics with enhanced electrical properties.

Piezoelectric and dielectric properties of Li_x(K_(0.46)Na_(0.54))_(1-x)Nb_(0.86)Ta_(0.1)Sb_(0.04)O_3 lead-free ceramics

Lead-free piezoelectric ceramics Lix(K0.46Na0.54)1-xNb0.86Ta0.1Sb0.04O3 (with x ranging from 0 to 0.1) were synthesized by conventional solid state sintering method. The effect of cationic substitution of Li for K and Na in the A sites of perovskite lattice on the structure, phase transition behavior and electrical properties were investigated. Morphotropic phase boundaries(MPB) between orthorhombic and tetragonal phase are found in the composition range of 0.06≤x≤0.08. Analogous to Pb(Zr,Ti)O3, the dielectric and piezoelectric properties are enhanced for the composition near the morphotropic phase boundary. The Li0.06(K0.46Na0.54)0.94- Nb0.86Ta0.1Sb0.04O3 ceramics show excellent electrical properties, that is, piezoelectric constant d33=215 pC/N, planar electromechanical coupling factor kp=41%, dielectric constant ε 3T3 /ε0=1 303, and dielectric loss tan δ=2.45%. The results indicate that Lix(K0.46Na0.54)1-x Nb0.86 Ta0.1Sb0.04O3 ceramic is a promising lead-free piezoelectric material.

Research of Lead-free Na_(0.5)Bi_(0.5)TiO_(3)-BaTiO_(3)System Piezoelectric Ceramics

To reduce the coercive field of Na_(0.5)Bi_(0.5)TiO_(3),Ba TiO_(3)were added as dopant materials.Then the(1-x)Na_(0.5)Bi_(0.5)TiO_(3)-xBaTiO_(3)ceramic samples were produced in solid synthetic way.The optimum preparation condition and piezoelectric properties of the samples were investigated.The XRD results show that the fabric transites from rhombohedral to tetragonal gradually with the substitution of the Ba^(2+).The morphotropic phase boundaries(MPB)exists in the composition range of 0.06.