Ab initio studies of polarization and piezoelectricity in vinylidene fluoride and BN-based polymers

Highly piezoelectric and pyroelectric phases of boron-nitrogen-based polymers have been designed from first principles. They offer excellent electrical and structural properties, with up to 100% improvement in the piezoelectic response and an enhanced thermal stability with respect to polyvinylidene fluoride (PVDF). Since methods for their synthesis are readily available, these polymers are extremely promising for numerous technological applications, rivaling the properties of ferroelectric ceramics and superseding PVDF-based materials in high-performance devices.     

Measurements of the thermal, dielectric, piezoelectric, pyroelectric and elastic properties of porous PZT samples

The introduction of porosity into ferroelectric ceramics has been of great interest in recent years. In particular, studies of porous lead-zirconate-titanate ceramic (PZT) have been made. In the research reported, samples of Ferroperm Pz27 with porosities of 20, 25 and 30% were studied. Very complete measurements were made of all of the physical properties relevant for ferroelectric applications including thermal conductivity and diffusivity, heat capacity, dielectric, pyroelectric, piezoelectric and elastic properties. Scanning electron micrographs indicated a change from 3-0 to 3-3 connectivity with increasing porosity. Although most of the physical properties are degraded by the presence of porosity, both piezoelectric and pyroelectric figures-of-merit are improved because of the markedly reduced relative permittivity. Porous ferroelectric ceramics are very promising materials for a number of applications.     

Processing,Structure, Properties,and Applications of PZT Thin Films

There has been a resurgence of complex oxides of late owing to their ferroelectric and ferromagnetic properties. Although these properties had been recognized decades ago, the renewed interest stems from modern deposition techniques that can produce high quality materials and attractive proposed device concepts. In addition to their use on their own, the interest is building on the use of these materials in a stack also. Ferroelectrics are dielectric materials that have spontaneous polarization in certain temperature range and show nonlinear polarization–electric field dependence called a hysteresis loop. The outstanding properties of the ferroelectrics are due to non-centro-symmetric crystal structure resulting from slight distortion of the cubic perovskite structure. The ferroelectric materials are ferroelastic also in that a change in shape results in a change in the electric polarization (thus electric field) developed in the crystal and vice versa. Therefore they can be used to transform acoustic waves to electrical signal in sonar detectors and convert electric field into motion in actuators and mechanical scanners requiring fine control. In a broader sense the ferroelectric materials can be used for pyroelectric and piezoelectric sensors, voltage tunable capacitors, infrared detectors, surface acoustic wave (SAW) devices, microactuators, and nonvolatile random-access memories (NVRAMs), including the potential production of one transistor memory cells, and applications requiring nonlinear optic components. Another set of potential applications seeks to exploit the ferroelastic properties in stacked templates where they are juxtaposed to ferromagnetic materials. Doing so would allow the control of magnetic properties with electric field, which is novel. Such templates taking advantage two or more properties acquired a new name and now goes by multiferroics. After a brief historical development, this article discusses technological issues such as growth and processing, electrical and optical properties, piezo, pyro, and ferroelectric properties, degradation, measurements methods, and application of mainly lead-zirconate-titanate (PZT = PbZr_1?xTi_xO₃). The focus on PZT stems from its large electromechanical constant, large saturation polarization and large dielectric constant.     

Study of the optoelectronic and piezoelectric properties of ZrO2 doped PVDF from quantum chemistry calculations

In this study, we have evaluated the optoelectronic and piezoelectric properties of doped PVDF. The electronic structures and the linear and non-linear optical properties of ZrO2-doped PVDF were calculated by adopting the LDA approximations for the exchange-correlation potential in the DFT method integrated in Gaussian 09. Optoelectronic parameters and ground state molecular geometry were calculated using B3LYP functional and LanL2DZ as the basis. We chose the calculation with the B3LYP functional because it is a relatively inexpensive and it is precise method to predict molecular structures, energies and frequencies. In this work, some optical parameters and constants such as refractive index, electrical susceptibility, dipole moment, average polarizability and hyperpolarizability, phase velocity have been calculated. Dielectric constants, ionization potentials, electronic affinities, electronegativities, hardness and flexibility were also calculated. Finally, the piezoelectric properties such as the piezoelectric coefficient and the pyroelectric coefficient are evaluated. The calculated electronic structures show that virgin PVDF, hybrid molecules PVDF/2ZrO2 and PVDF/3ZrO2 have an E_gap less than 3 eV. On the other hand, the hybrid PVDF/ZrO2 molecule is a good dielectric and therefore a good piezoelectric nanocomposite because its E_gap is 5.89 eV greater than 3 eV. Finally, the results show that the hybrid molecules PVDF-2ZrO2 could have potential applications not only as piezoelectric materials but also as semiconductor components, nonlinear optical materials and possible building materials for molecular electronics and photonic devices.     

New polymer-containing piezoelectric materials

A review is presented of the data on the design of polymer-containing piezoelectric materials: electrets exhibiting a piezoelectric effect, ferroelectric polymers, piezoelectric composites (piezoelectric ceramic + polymer), and new piezoelectric polymer materials, such as piezoelectrics based on porous polymers and elastic active dielectrics, whose piezoelectric properties considerably surpass the characteristics of conventional piezoelectric materials, as well as the characteristics of electromechanical and mechanoelectrical transducers operating in receiving, generating, and deformation-inducing modes.     

Large piezoelectric effects in charged, heterogeneous fluoropolymer electrets

Large piezoelectric d₃₃ coefficients around 600 pC/N are found in corona-charged non-uniform electrets consisting of elastically “soft” (microporous polytetrafluoroethylene PTFE) and “stiff” (perfluorinated cyclobutene PFCB) polymer layers. The piezoelectric activity of the two-layer fluoropolymer stack exceeds the d₃₃ coefficient of the ferroelectric ceramic lead zirconate titanate (PZT) by more than a factor of two and that of the ferroelectric polymer polyvinylidene fluoride (PVDF) by a factor of 20. Soft piezoelectric materials may become interesting for a large number of sensor and transducer applications, in areas such as security systems, medical diagnostics, and nondestructive testing. Accepted: 9 November 1999 / Published online: 3 December 1999     

高温压电材料、器件与应用

作为重要的功能材料,压电材料已经在国民经济的多个领域里有着重要应用.随着现代工业的快速发展,特别是新能源、交通和国防工业的高速发展,功能材料的应用已经从常规使用转向极端环境下的服役.本文综述了具有高居里点的压电材料,包括钙钛矿型压电陶瓷、铋层状结构氧化物压电陶瓷、钨青铜结构压电陶瓷以及非铁电压电单晶等;介绍了其晶体结构特征和高温压电性能、最新研究进展,并列举了一系列的高温压电器件和应用,包括高温压电探测器、传感器、换能器和驱动器等.另外,本文总结了高温压电材料的热点研究问题,并展望了今后的发展方向.     

磁电异质结及器件应用

磁电异质结是由铁磁和铁电材料通过连接层耦合而成,其磁电效应来源于铁电相的压电效应和铁磁相的磁致伸缩效应.相对于颗粒混相磁电复合材料,层状磁电异质结材料具有更高的磁电耦合系数和更低的介电损耗,使得其在磁场传感器、能量收集器、天线以及存储器等领域都有着巨大的应用前景.本综述重点总结了磁电异质结材料的发展历程以及相关应用领域的最新进展,最后评述了磁电异质结材料发展的挑战和前景展望.     

Novel nanostructures of ZnO for nanoscale photonics,optoelectronics, piezoelectricity,and sensing

Wurtzite-structured semiconductors such as ZnO, GaN, AlN, CdSe and ZnS are important materials for nanoscale devices. Zinc oxide, for example, is a unique material that exhibits semiconducting, piezoelectric, and pyroelectric properties. Using a solid–vapor phase thermal sublimation technique, nanocombs, nanorings, nanohelixes/nanosprings, nanobows, nanobelts, nanowires, and nanocages of ZnO have been grown under specific growth conditions. This paper is about the synthesis, structure, growth mechanisms, and potential applications of these nanostructures in optoelectronics, sensors, transducers, and biomedical science. PACS 81.07.-b; 78.67.-n; 85.35.-p     

A van der Waals density functional theory study of poly(vinylidene difluoride) crystalline phases

Ferroelectric polymers, such as poly(vinylidene difluoride) (PVDF), have many potential applications in flexible electronic devices. PVDF has six experimentally observed polymorphs, three of which are ferroelectric. In this work we use density functional theory to investigate the structural properties, energetics and polarisation of the stable α-phase, its ferroelectric analogue, the δ-phase, and the β-phase, which has the best ferroelectric properties. The results from a variety of exchange and correlation functionals were compared and it was found that van der Waals (vdW) interactions have an important effect on the calculated crystal structures and energetics, with the vdW-DF functional giving the best agreement with experimental lattice parameters. The spontaneous polarisation was found to strongly correlate with the unit cell volumes, which depend on the functional used. While the relative phase energies were not strongly dependent on the functional, the cohesive energies were significantly underestimated using the PBE functional. The inclusion of vdW interactions is, therefore, important to obtain the correct lattice structures, polarisation and energetics of PVDF polymorphs.     

感光栅极GaN基HEMT器件的制备与栅极优化

铁电材料作为感光功能薄膜的红外器件研究近年来十分活跃,其良好的压电、铁电、热释电、光电及非线性光学特性以及能够与半导体工艺相集成等特点,在微电子和光电子技术领域有着广阔的应用前景。实验将铁电材料锆钛酸铅作为感光层与GaN基高电子迁移率晶体管(HEMT)相结合,成功地制备出了感光栅极GaN基HEMT器件,并在波长为365 nm的光照下进行探测,经大量实验测试后发现器件在该波段的光照下饱和电流达到28 mA,相比无光照时饱和电流提高12 mA。另外,通过合理改变器件结构尺寸,包括器件栅长以及栅漏间距,发现随着栅长的增大,器件的饱和输出电流依次减小,而栅漏间距的变化对阈值电压以及饱和电流的影响并不大。由此可知,改变器件结构参数可以达到提高器件性能的目的并且可以提高探测效率。     

Effects of Sm substitution on ferroelectric domains and conductivity in bismuth ferrite ceramics

The large piezoelectric coefficient and multiferroicity of bismuth ferrite (BFO) make it an attractive candidate for lead-free ferroelectric devices. However, large leakage currents have limited broader applications. Rare-earth substitutions in BFO have been shown to improve ferroelectric and magnetic properties. In this work, we employed piezoresponse and conductive atomic force microscopy to study ferroelectric domains in Bi_1-xSm_xFeO₃ (x = 0–0.150) grown by the co-precipitation method. The combined piezoresponse and conductivity measurements can directly visualize the local ferroelectric domains under different sample bias. At Sm mol% > 7.5, Sm-substitution effectively lowers defect-generated conductivity. At Sm mol% < 7.5, conductivity increases due to conductive domain walls inside sample grains. The surfaces of these conductive samples exhibit a p-type rectifying behavior while the bulk is n-type. Our work details how the local piezoelectric properties and transport behaviors of BFO ceramics change as a function of Sm-substitution.     

Pressure effect on phase transition in ferroelectic polymers

Pressure effects of phase transition behaviour in two kinds of ferroelectric polymers of poly(vinylidene fluoride), PVDF, and copolymers of vinylidene fluoride and trifluoroethylene, (VDF/TrFE), are discussed. In the case of PVDF, several high-pressure treatments including a high-pressure annealing and a uniaxial compression were shown to induce a crystal transformation from a non-polar Form II crystal to a polar Form I crystal, which has ferroelectric characteristics and high piezoelectric activity. In addition, substantial pressure effects on ferroelectric phase transition points as well as crystal structures were observed for (VDF/TrFE) copolymers with different VDF contents. The most significant pressure effects were observed for copolymer samples with unstable ferroelectric structures at atmospheric pressure. From high-pressure X-ray and Raman scattering studies, these pressure effects were suggested to originate from the pressure-induced conformational transition from gauche to trans in the molecular chains.     

Piezo-/ferroelectric phenomena in biomaterials: A brief review of recent progress and perspectives

There have been overwhelming observations of piezo-/ferroelectric phenomena in many biological tissues and macromolecules,boosting the development of bio-based smart devices and the applications using electromechanical coupling phenomena in biological systems. The electromechanical coupling is believed to be responsible for various biophysical behaviors and remarkable biomaterial properties. Despite the abundant phenomenal observations, the fundamental understanding of the piezo-/ferroelectric effect in biomaterials/systems and the rational design of biobased macroscopic materials with desired piezoelectric responses are still scarce. In this review, we firstly present remarkable historical events on the development of piezo-/ferroelectricity in biomaterials, followed by a brief overview of the fundamental physics of piezo-/ferroelectricity. The developments of biopiezo-/bioferroelectricity in protein-based biomaterials and their implications are highlighted subsequently. In experimental studies, to identify the intrinsic piezo-/ferroelectric properties from other effects or artifacts is usually elusive. This issue is also addressed and discussed in detail, especially using piezoelectric force microscopy(PFM) and spectroscopy techniques to investigate the local piezo-/ferroelectric phenomena in nanostructured materials are highlighted emphatically.     

微型红外线传感技术的最新发展

综述了红外传感器技术的最新发展，由于应用了薄膜型红外探测器，衍射光学聚光镜和共振压电斩波器，红外传感器实现了微型化，在许多领域中获得了广泛的应用。     

Theoretical studies on the pyroelectric properties of two component composite ferroelectric thin film

Using a Ginzburg–Landau–Devonshire type model, the pyroelectric property and hysteresis loop are studied for a composite ferroelectric thin film that contains an insertion of a different type of ferroelectric material in parallel connection with the host ferroelectric film material. If these two types of ferroelectric materials are polarized along the same direction, there are two peaks occur in the pyroelectric coefficient vs temperature curve. If the two ferroelectric materials are polarized in opposite directions, one positive and one negative coefficient peaks occur in the temperature dependence of pyroelectric coefficient curve and the hysteresis loop appears to be a quasi-double loop. The effect of the external electric field on the pyroelectric coefficient is also investigated.     

Influences of thin Ni layer on the electrical and absorption properties of PZT thin film pyroelectric IR sensors

A solid precursor was used to prepare ferroelectric lead zirconate titanate (PZT) 30/70 thin films using the sol–gel deposition method. To apply PZT thin films for uncooled pyroelectric IR sensors, a Ni layer was deposited onto the PZT thin films, serving both as a selective absorption layer and as the top electrode. The absorption properties of such Ni coated multi-layered pyroelectric sensors were studied in the visible and infrared wavelength ranges. The maximum absorption coefficient of this type of IR sensor was measured to be 0.8 at 0.633 μm and 0.7 at 4 μm wavelength, respectively. A striking asymmetric polarization hysteresis loop in these PZT thin films with Ni as the top electrode was observed as a direct consequence. This asymmetric polarization was attributed to cause the difference in the dynamic pyroelectric responses in these Ni/PZT/Pt films, poled either positively or negatively before the measurement.     

Piezoelectricity in two‐dimensional group III–V buckled honeycomb monolayers

We studied the elastic and piezoelectric properties of buckled honeycomb group III–V monolayers (GaP, GaAs, GaSb, InP, InAs and InSb) by DFT calculations. Those buckled monolayers are ferroelectric and have nonzero e₁₁, e₃₁, d₁₁ and d₃₁ piezoelectric coefficients. Our calculations show that those monolayers are good piezoelectric materials and a pronounced periodic trend of the piezoelectric coefficients e₁₁, e₃₁, d₁₁ and d₃₁ was found. Group III–V monolayers are promising candidates for future atomically thin piezoelectric applications such as transducers, sensors, and energy harvesting devices.     

The strong piezoelectricity in polyvinylidene fluroide (PVDF)

Polymers have been playing an important role already for a long time in electronic engineering as dielectrics. Recently a search has been made for polymers with unusual properties: organic semiconductors or photoconductors, electrets, and polymeric piezo — and pyroelectrics have been developed. And now, polyvinylidene fluroide (PVDF), a new piezoelectric film material is being produced on an industrial scale.^1,2 In this article, recent developments and applications of piezoelectric polymers are surveyed.     

Effect of electrode on dielectric susceptibility and pyroelectric properties of a ferroelectric thin film capacitor using landau-khalatnikov theory

The influence of electrodes on the dielectric susceptibility and pyroelectric properties of a ferroelectric thin film with surface transition layers has been investigated within the framework of Landau-Khalatnikov dynamic theory. The contribution of the electrodes is reflected by the depolarization field in the free-energy function. The large electrode effect implies the strong depolarization field in ferroelectric thin films. The results show that the electrode materials can greatly impact the dynamic dielectric and pyroelectric properties of a ferroelectric thin film.