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 and optical absorption properties of Au/NiO thin films

Au nanoparticles dispersed NiO composite films were prepared by a chemical solution method.The phase structure,microstructure,surface chemical state,and optical absorption properties of the films were characterized by X-ray diffraction,transmission electron microscopy,X-ray photoelectron spectroscopy,and Uv-vis spectrometer.The results indicate that Au particles with the average diameters of 35-42 nm are approximately spherical and disperse in the NiO matrix.The optical absorption peaks due to the surface plasmon resonance of Au particles shift to the shorter wavelength and intensify with the increase of Au content.The bandwidth narrows when the Au content increases from 8.4wt% to 45.2wt%,but widens by further increasing the Au content from 45.2wt% to 60.5wt%.The band gap Eg increases with the increase of Au contents from 8.4wt% to 45.2wt%,but decreases by further increasing the Au content.

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.

Effect of KNbO_3 content on the crystal structure and electrical properties of(1-x)PbZr_(0.54)Ti_(0.46)O_3-xKNbO_3 piezoelectric ceramics

（1 - x）PbZr0.54Tio.4603-xKNbO3 （0 〈 x 〈 25mo1%） （abbreviated as PZT-xKN） piezoelectric ceramics were successfully fabricated by a traditional sintering technique at 1225℃ for 30 min. The influence of KNbO3 content on the crystal structure and electrical properties of the PZT-xKN piezoelectric ceramics was studied. Samples with 0 〈 x 0.20 show a pure peroskite structure, indicating that ul KNbOdiffused ito the crystal lattice of PZT to form a single solid solution in this compositional range. A second Pb3Nb4013 phase is observed in the PZT-0.25KN sample, showing that the maximum solid solubility of KNbO3 in PZT matrix ceramic is less than 25mo1%. Compared with pure PZT piezoelectric ceramics, samples containing KNbO3 have smaller crystal grains. PZT-0.15KN exhibits excellent piezoelectric properties with d33 ： 209 pC/N.

Exceptional electrostrain with minimal hysteresis and superior temperature stability under low electric field in KNN-based lead-free piezoceramics

Over the past two decades,(K_(0.5)Na_(0.5))NbO_(3)(KNN)-based lead-free piezoelectric ceramics have made significant progress.However,attaining a high electrostrain with remarkable temperature stability and minimal hysteresis under low electric fields has remained a significant challenge.To address this long-standing issue,we have employed a collaborative approach that combines defect engineering,phase engineering,and relaxation engineering.The LKNNS-6BZH ceramic,when sintered at T_(sint)=1170℃,demonstrates an impressive electrostrain with a d_(33) value of 0.276%and 1379 pm·V^(-1)under 20 kV·cm^(-1),which is comparable to or even surpasses that of other lead-free and Pb(Zr,Ti)O_(3)ceramics.Importantly,the electrostrain performance of this ceramic remains stable up to a temperature of 125℃,with the lowest hysteresis observed at 9.73%under 40 kV·cm^(-1).These excellent overall performances are attributed to the presence of defect dipoles involving V′_(A)-V∙∙_(O) and B′_(Nb)-V∙∙O,the coexistence of R-O-T multiphase,and the tuning of the trade-off between long-range ordering and local heterogeneity.This work provides a lead-free alternative for piezoelectric actuators and a paradigm for designing piezoelectric materials with outstanding comprehensive performance under low electric fields.

BiAlO_(3)-modified BiFeO_(3)-BaTiO_(3) high Curie temperature lead-free piezoelectric ceramics with enhanced performance

BiFeO_(3)-BaTiO_(3)(BF-BT)lead-free piezoelectric ceramics have high piezoelectricity and high Curie temperature(T_(C)),but the mixed-valence Fe ions and Bi^(3+)volatilization would promote the formation of Bi_(25)FeO_(40)/Bi_(2)Fe_(4)O_9 and oxygen vacancy,which greatly degrade the insulation properties required for polarization.In this study,it was found that the modification of BiAlO_(3)(BA)in BF-BT ceramics could effectively solve these problems,reducing the leakage current to 1×10^(-9)A·cm^(-2)and transiting the space charge-limited conduction to ohmic conduction.Because of the enhanced insulation properties and appropriate rhombohedral-pseudocubic phase ratio(C_R/C_(PC)),BF-BT-xBA ceramics in an optimized composition obtain enhanced piezoelectric performance:piezoelectric charge coefficient(d_(33))=196 pC·N^(-1),planar electromechanical coupling coefficient(k_(p))=31.1%,T_(C)=487℃and depolarization temperature(T_d)=250°C;unipolar strain(S_(uni))=0.17%and piezoelectric strain coefficient(d_(33)^(*))=335 pm·V^(-1)at 100℃.Especially,d_(33)exceeds 283 pC·N^(-1)at 233℃and d_(33)^(*)is 335 pm·V^(-1)at100℃,showing an excellent high-temperature piezoelectricity and high depolarization temperature.The results are attributed to the domain structure of rhombohedral-pseudocubic phase coexistence and its high-temperature switching behavior.This work provides a feasible and effective approach to improve the high temperature piezoelectric properties of BF-BT-xBA ceramics,making them more suitable for high temperature applications.

Enhanced piezoelectricity in 0.7BiFeO_(3)-0.3BaTiO_(3)lead-free ceramics:Distinct effect of poling engineering

BiFeO_(3)-BaTiO_(3) based ceramics are considered to be the most promising lead-free piezoelectric ceramics due to their large piezoelectric response and high Curie temperature.Since the piezoelectric response of piezoelectric ceramics just appears after poling engineering,in this work,the domain evolution and microscopic piezoresponse were observed in-situ using piezoresponse force microscopy(PFM)and switching spectroscopy piezoresponse force microscopy(SS-PFM),which can effectively study the local switching characteristics of ferroelectric materials especially at the nanoscale.The new domain nucleation preferentially forms at the boundary of the relative polarization region and expands laterally with the increase of bias voltage and temperature.The maximum piezoresponse(Rs),remnant piezoresponse(Rrem),maximum displacement(Dmax)and negative displacement(Dneg)at 45 V and 120C reach 122,69,127 pm and 75 pm,respectively.Due to the distinct effect of poling engineering in full domain switching,the corresponding d33 at 50 kV/cm and 120C reaches a maximum of 205 pC/N,which is nearly twice as high as that at room temperature.Studying the evolution of ferroelectric domains in the poling engineering of BiFeO_(3)-BaTiO_(3)ceramics provides an insight into the relationship between domain structure and piezoelectric response,which has implications for other piezoelectric ceramics as well.

High-performance BiFeO_(3)eBaTiO_(3)lead-free piezoceramics insensitive to off-stoichiometry and processing temperature

It is well-known that the performance of BiFeO3eBaTiO3(BF-BT)ceramics is sensitive to composition,calcining and sintering temperature(Tcal and Tsint)due to the formation of Bi25FeO39 and/or Bi2Fe4O9 impurities and/or the volatilization of Bi_(2)O_(3).We report remarkably stable electrical properties over the range of
0.03≤x≤0.05 and 930℃≤Tsint≤970C in 0.7Bi(1þx)FeO_(3)-0.3BaTiO_(3)ceramics prepared by one-step process.This method avoids the thermodynamically unstable region of BiFeO_(3)and prevents the formation of Bi25FeO39 and/or Bi_(2)Fe_(4)O_(9)impurities even when the addition of a-Bi_(2)O_(3)raw material is intentionally deficient or rich to make off-stoichiometric BF-BT,thus greatly improving the robustness of compositional and processing.Rhombohedral-pseudocubic phase coexists in all ceramics,and their CR/CPC fraction are 48.0/52.0e50.6/49.4 and 55.9/44.1e56.6/43.4 when x increases from
0.05≤x≤0 to 0.01≤x≤0.05.The stable electrical properties of d33¼180e205 pC/N,Pr¼17.9e23.8 mC/cm^(2),and TC¼485e518℃are achieved.The maximum d_(33T)/d_(33RT)of BF-BT is twice that of soft PZT,superior to most the-state-of-art lead-free ceramics.Our results provide a synthesis strategy for designing high performance piezoelectric materials with good stability and easy industrialization.

Highly Textured N-Type SnSe Polycrystals with Enhanced Thermoelectric Performance

Thermoelectric materials,which directly convert heat into electricity based on the Seebeck effects,have long been investigated for use in semiconductor refrigeration or waste heat recovery.Among them,SnSe has attracted significant attention due to its promising performance in both p-type and n-type crystals;in particular,a higher out-of-plane ZT value could be achieved in ntype SnSe due to its 3D charge and 2D phonon transports.In this work,the thermoelectric transport properties of n-type polycrystalline SnSe were investigated with an emphasis on the out-of-plane transport through producing textural microstructure.The textures were fabricated using mechanical alloying and repeated spark plasma sintering(SPS),as a kind of hot pressing,aimed at producing strong anisotropic transports in n-type polycrystalline SnSe as that in crystalline SnSe.Results show that the lowest thermal conductivity of 0.36 Wm^(-1) K^(-1) was obtained at 783 K in perpendicular to texture direction.Interestingly,the electrical transport properties are less anisotropic and even nearly isotropic,and the power factors reach 681.3μWm^(-1) K^(-2) at 783 K along both parallel and perpendicular directions.The combination of large isotropic power factor and low anisotropic thermal conductivity leads to a maximum ZT of 1.5 at 783 K.The high performance elucidates the outstanding electrical and thermal transport behaviors in n-type polycrystalline SnSe,and a higher thermoelectric performance can be expected with future optimizing texture in n-type polycrystalline SnSe.

Optimal performance of Cu_(1.8)S_(1-x)Te_(x) thermoelectric materials fabricated via high-pressure process at room temperature

Cu_(1.8)S has been considered as a potential thermoelectric(TE)material for its stable electrical and thermal properties,environmental benignity,and low cost.Herein,the TE properties of nanostructured Cu_(1.8)S_(1-x)Te_(x)(0≤x≤0.2)bulks fabricated by a facile process combining mechanical alloying(MA)and room-temperature high-pressure sintering(RT-HPS)technique were optimized via eliminating the volatilization of S element and suppressing grain growth.Experimentally,a single phase of Cu_(1.8)S was obtained at x=0,and a second Cu_(1.96)S phase formed in all Cu_(1.8)S_(1-x)Te_(x) samples when 0.05≤x≤0.125.With further increasing x to 0.15≤x≤0.2,the Cu_(2-z)Te phase was detected and the samples consisted of Cu_(1.8)S,Cu_(1.96)S,and Cu_(2-z)Te phases.Benefiting from a modified band structure and the coexisted phases of Cu_(1.96)S and Cu_(2-z)Te,the power factor is enhanced in all Cu_(1.8)S_(1-x)Te_(x)(0.05≤x≤0.2)alloys.Combining with a drastic decrease in the thermal conductivity due to the strengthened phonon scatterings from multiscale defects introduced by Te doping and nano-grain boundaries,a maximum figure of merit(ZT)of 0.352 is reached at 623 K for Cu_(1.8)S_(0.875)Te_(0.125),which is 171%higher than that of Cu_(1.8)S(0.130).The study demonstrates that doping Te is an effective strategy to improve the TE performance of Cu_(1.8)S based materials and the proposed facile method combing MA and RT-HPS is a potential way to fabricate nanostructured bulks.

The Electronic Transport Channel Protection and Tuning in Real Space to Boost the Thermoelectric Performance of Mg_(3+δ)Sb_(2-y)Bi_(y) near Room Temperature

The optimization of thermoelectric materials involves the decoupling of the transport of electrons and phonons.In this work,an increased Mg_(1)-Mg_(2) distance,together with the carrier conduction network protection,has been shown as an effective strategy to increase the weighted mobility(U=μm∗3/2)and hence thermoelectric power factor of Mg_(3+δ)Sb_(2-y)Bi_(y) family near room temperature.Mg_(3+δ)Sb_(0.5)Bi_(1.5) has a high carrier mobility of 247 cm^(2)V^(-1) s^(-1) and a record power factor of 3470μWm^(-1) K^(-2) at room temperature.Considering both efficiency and power density,Mg_(3+δ)Sb_(1.0)Bi_(1.0) with a high average ZT of 1.13 and an average power factor of 3184μWm^(-1) K^(-2) in the temperature range of 50-250℃ would be a strong candidate to replace the conventional n-type thermoelectric material Bi_(2)Te_(2.7)Se_(0.3).The protection of the transport channel through Mg sublattice means alloying on Sb sublattice has little effect on electron while it significantly reduces phonon thermal conductivity,providing us an approach to decouple electron and phonon transport for better thermoelectric materials.

Enhanced photocatalytic activity in Ag-nanoparticle-dispersed BaTiO3 composite thin films: Role of charge transfer

Optical absorption and photocatalytic activity can be enhanced by surface plasmon resonance (SPR) effect,but the charge transfer (CT) mechanism between the dispersed noble metal nanoparticles (NPs) and the semiconductor matrix has been ignored.Herein,we adduce a direct and strong evidence in Ag-nanoparticle-dispersed BaTiO3 (Ag/BTO) composite films through X-ray photoelectron and photoluminescence spectra which reveals the CT from BTO trapped by Ag NPs under UV light and from Ag NPs to BTO under visible light.Owing to the broadened optical absorption and efficient CT from Ag NPs to BTO,the Ag25/BTO film manifests the optimal photocatalytic activity under the irradiation of visible light rather than UV-Vis light.Our work provides a helpful insight to design highly efficient plasmonic photocatalyst through considering the synergetic effect of the CT between metal and semiconductor on the enhanced photocatalytic activity.

Enhanced thermoelectric properties of Mn_(x)Cu_(1.8)S via tuning band structure and scattering multiscale phonons

Digenite(Cu_(1.8)S)as a potential p-type thermoelectric(TE)material has attracted extensive attention due to its environmental benign,abundant resources and low cost of component elements.In this study,the TE properties of MnxCu_(1.8)S bulk samples prepared by mechanical alloying(MA)combined with spark plasma sintering(SPS)were investigated.Doping Mn would initially substitute Cu and tune the band structure of Cu1.8S with an enlarged band gap Eg.However,if Mn content is beyond the solubility limit of x=0.01 in Cu1.8S will cause the formation of MnS,which contributes to the formation of Cu-rich phases at 0.02 ≤x≤ 0.08.Benefiting from the synergetic scattering effect of point defects(Mn Cu,V_(S))and MnS,Cu1.96S,Cu1.97S,Cu2S phases,the lowest thermal conductivity k value of 0.75 W m^(-1) K^(-1) was obtained at 773 K for Mn0.08Cu1.8S.Along with the decreased k,the highest figure of merit ZT value of 0.92 at 773 K achieved in Mn0.08Cu1.8S bulk sample.A maximum engineering ZTeng of 0.3 and its efficiency hmax of about 6%were obtained at 323e773 K,which is almost 3 times than that of the pristine Cu1.8S(ηmax=2.2%).Introducing Mn in Cu1.8S is an effective and convenient strategy to improve TE performance.

Enhanced energy storage properties and antiferroelectric stability of Mn-doped NaNbO_(3)-CaHfO_(3) lead-free ceramics:Regulating phase structure and tolerance factor

NaNbO_(3)-based ceramics usually show ferroelectric-like P-E loops at room temperature due to the irreversible transformation of the antiferroelectric orthorhombic phase to ferroelectric orthorhombic phase,which is not conducive to energy storage applications.Our previous work found that incorporating CaHfO_(3) into NaNbO_(3) can stabilize its antiferroelectric phase by reducing the tolerance factor(t),as indicated by the appearance of characteristic double P-E loops.Furthermore,a small amount of MnO_(2) addition effectively regulate the phase structure and tolerance factor of 0.94NaNbO_(3)-0.06CaHfO_(3)(0.94NN-0.06CH),which can further improve the stability of antiferroelectricity.The XRD and XPS results reveal that the Mn ions preferentially replace A-sites and then B-sites as increasing MnO_(2).The antiferroelectric orthorhombic phase first increases and then decreases,while the t shows the reversed trend,thus an enhanced antiferroelectricity and the energy storage density Wrec of 1.69 J/cm^(3) at 240 kV/cm are obtained for 0.94NN-0.06CH-0.5%MnO_(2)(in mass fraction).With the increase of Mn content to 1.0%from 0.5%,the efficiency increases to 81% from 45%,although the energy storage density decreases to 1.31 J/cm^(3) due to both increased tolerance factor and non-polar phase.

Room-temperature thermoelectric materials: Challenges and a new paradigm

Room-temperature thermoelectric materials provide promising solutions for energy harvesting from the environment,and deliver a maintenance-free power supply for the internet-of-things(IoTs).The currently available Bi_(2)Te_(3) family discovered in the 1950s,still dominates industrial applications,however,it has serious disadvantages of brittleness and the resource shortage of tellurium(1×10^(-3) ppm in the earth's crust).The novel Mg_(3)Sb_(2) family has received increasing attention as a promising alternative for room-temperature thermoelectric materials.In this review,the development timeline and fabrication strategies of the Mg 3 Sb 2 family are depicted.Moreover,an insightful comparison between the crystal-linity and band structures of Mg_(3)Sb_(2) and Bi_(2)Te_(3) is drawn.An outlook is presented to discuss challenges and new paradigms in designing room-temperature thermoelectric materials.