人工调控微结构压电驻极体的热稳定性和电荷动态特性

利用表面带有周期性结构的硬质模板,通过冷压工艺将周期结构图案复制到多孔聚四氟乙烯(PTFE)薄膜表面,再经过热黏合工艺与致密氟化乙丙烯共聚物(FEP)薄膜复合,制备出了高度有序的微孔结构复合膜,并用电晕充电的方法对复合膜进行极化处理,最终获得氟聚合物复合膜压电驻极体.借助对这类复合膜压电驻极体介电谐振谱的测量,得到了材料的杨氏模量.并利用等温热老化工艺对它们的压电系数d33的热稳定性进行了考察.最后通过短路热刺激放电谱的测量和分析,讨论了该复合膜在热老化处理后的电荷动态 关键词： 有序结构 压电驻极体 压电性 电荷动态特性     

聚四氟乙烯和氟化乙丙烯共聚物复合膜的压电性

以多孔PTFE膜为骨架,而以致密（非多孔）FEP膜为储电介质层的孔洞结构复合压电驻极体膜的制备方法.利用正压电效应,测量了复合膜的准静态压电系数d₃₃;研究了压电系数的热稳定性和复合膜中空间电荷的动态特性;并通过介电谐振谱的分析,比较了这类复合膜的准静态和动态压电系数.结果表明：FEP和PTFE复合膜压电驻极体的准静态压电系数d₃₃可以达到300 pC/N.经90℃老化20 h 后的d₃₃仍保持在初 关键词： 压电驻极体 压电性 多孔聚四氟乙烯 致密氟化乙丙烯共聚物     

Polarization and piezoelectricity in polymer films with artificial void structure

Laminated polymer-film systems with well-defined void structures were prepared from fluoroethylenepropylene (FEP) and polytetrafluoroethylene (PTFE) layers. First the PTFE films were patterned and then fusion-bonded with the FEP films. The laminates were subjected to either corona or contact charging in order to obtain the desired piezoelectricity. The build-up of the “macro-dipoles” in the laminated films was studied by recording the electric hysteresis loops. The resulting electro-mechanical properties were investigated by means of dielectric resonance spectroscopy (DRS) and direct measurements of the stress-strain relationship. Moreover, the thermal stability of the piezoelectric d ₃₃ coefficient was investigated at elevated temperatures and via thermally stimulated discharge (TSD) current measurements in short circuit. For 150 μm thick laminated films, consisting of one 25 μm thick PTFE layer, two 12.5 μm thick FEP layers, and a void of 100 μm height, the critical voltage necessary for the build-up of the “macro-dipoles” in the inner voids was approximately 1400 V, which agrees with the value calculated from the Paschen Law. A quasi-static piezoelectric d ₃₃ coefficient up to 300 pC/N was observed after corona charging. The mechanical properties of the film systems are highly anisotropic. At room temperature, the Young’s moduli of the laminated film system are around 0.37 MPa in the thickness direction and 274 MPa in the lateral direction, respectively. Using these values, the theoretical shape anisotropy ratio of the void was calculated, which agrees well with experimental observation. Compared with films that do not exhibit structural regularity, the laminates showed improved thermal stability of the d ₃₃ coefficients. The thermal stability of d ₃₃ can be further improved by pre-aging. E.g., the reduction of the d ₃₃ value in the sample pre-aged at 150°C for 5 h was less than 5% after annealing for 30 h at a temperature of 90°C.     

Fluoroethylenepropylene ferroelectrets with patterned microstructure and high, thermally stable piezoelectricity

Layered fluoroethylenepropylene (FEP) ferroelectret films were prepared from sheets of FEP films by template-patterning followed by a fusion-bonding process and contact charging. The layered ferroelectret films show consistency and regularity in their void structures and good bonding of the layers. For films composed of two 12.5???m thick FEP layers and a typical void of 60???m height, the critical voltage necessary for the built-up of the ??macro-dipoles?? in the inner voids is approximately 800 V. At room temperature, Young??s modulus in the thickness direction, determined from dielectric resonance spectra of the fabricated films with a typical thickness of 85???m, is about 0.21 MPa. Initial quasistatic piezoelectric d ₃₃ coefficients of samples contact charged at a peak voltage of 1500 V are in the range of 1000?C3000 pC/N. From these, ferroelectrets with high quasistatic and dynamic (up to 20 kHz) d ₃₃ coefficients of up to 1000 pC/N and 400 pC/N, respectively, which are thermally stable at 120°C, can be obtained by proper annealing treatment. This constitutes a significant improvement compared to previous results.     

Polytetrafluoroethylene piezoelectrets prepared by sintering process

Polytetrafluoroethylene (PTFE) films with a void structure are prepared by a sintering process. Such void PTFE films are piezoelectric after proper corona charging. The quasi-static piezoelectric d ₃₃ coefficients up to 250 pC/N are achieved for the samples which were made of compact and biaxial-tension porous PTFE layers. Pre-ageing treatment is an effective method to further improve the thermal stability. For the samples with pre-ageing treatment, the reduction of the d ₃₃ coefficients is around 2% per day when exposed to 120 °C.     

Improvement of piezoelectric coefficient of cellular polypropylene films by repeated expansions

Pressure expansion can be used to improve the piezoelectric d₃₃-coefficients of customary cellular polypropylene (PP) films. In the present paper, the experimental procedure for a double expansion process is described and experimental results of d₃₃-coefficients that can be achieved by choosing expansion pressures from 0.2 to 2 MPa and expansion temperatures from 20 to 120 °C for the two processes are discussed. For example, expansion pressures of 2 MPa, a temperature of 90 to 100 °C for the first expansion and 60 °C for the second expansion, and exposure times of the order of 1 h result in quasistatic d₃₃-coefficients of more than 1000 pC/N which are relatively stable at room temperature.     

Combined effects of Li content and sintering temperature on?polymorphic phase boundary and electrical properties of Li/Ta co-doped (Na, K)NbO3 lead-free piezoceramics

Crystallographic structure, phase transition and electrical properties of lead-free (Na_0.535K_0.485)_1−x Li _x (Nb_0.942Ta_0.058)O₃ (x=0.042–0.098) (NKL _x NT) piezoelectric ceramics were investigated. The experimental results show that both Li content and sintering temperature strongly affect the orthorhombic–tetragonal polymorphic phase boundary (PPB), which results in remarkable differences of the piezoelectric property and its temperature stability in the NKL _x NT ceramics. Chemical analysis indicates that sodium volatilizes more seriously than potassium and lithium with increasing sintering temperature. Due to the comprehensively optimized effects of Li content and sintering temperature, an enhanced piezoelectric constant d ₃₃ (276 pC/N) was obtained at room temperature in the ceramics with x=0.074 sintered at 1000°C. In the same composition, a further high d ₃₃ up to 354 pC/N was obtained at 43°C, which is close to its T _o−t temperature. Furthermore, better temperature stability can be obtained when x=0.082 sintered at 1000°C, whose piezoelectric constant d ₃₃ (236 pC/N) keeps almost constant from room temperature to 100°C. Such a temperature-independent piezoelectric property is available in the NKL _x NT ceramics with high Li content because its T _o−t was moved below room temperature.     

Thermally stable fluorocarbon ferroelectrets with high piezoelectric coefficient

Fused layers of polytetrafluoroethylene (PTFE) and fluoroethylenepropylene (FEP) films with small interfacial cellular gas voids show large quasistatic piezoelectric d₃₃-coefficients of more than 1000 pC/N. After annealing at a temperature of 90 °C for 4 days, d₃₃ amounts to about 400 pC/N and thereafter changes by less than 10 percent over a period of 5 days at this temperature. The piezoelectric coefficient is independent of applied pressure in the range up to 20 kPa. Its frequency response shows a small decrease up to the vicinity of the thickness resonance frequency at 40 to 150 kHz. PACS 77.65.Bn; 77.55.+f; 77.84.Jd     

氟聚合物压电驻极体的压电性及其电荷的动态行为

描述了一种可控微结构的多孔聚合物压电功能膜的制备方法,讨论了采用该工艺制备的聚四氟乙烯(PTFE)和全氟乙丙烯共聚物(FEP)复合膜压电驻极体的压电性能及其热稳定性.通过等温压电系数衰减和短路热刺激放电(TSD)方法,研究了氟聚合物复合膜压电活性热稳定性改善的根源,以及脱阱电荷输运和复合的特性.结果表明,这类氟聚合物压电驻极体膜的准静态压电系数d₃₃可高达2200pC/N;压电系数d₃₃的压强特性在直到20kPa的压强范围内呈现良好的 关键词： 氟聚合物 压电驻极体 热稳定性 电荷动态特性     

Optimization of calcination temperature of lead-free BiFeO3–BaTiO3 high-temperature piezoceramics

0.7BiFeO₃-0.3BaTiO₃+1mol% MnO₂(0.7BFO-0.3BTO) ceramics were synthesized by conventional solid-state powder method under different calcination temperatures (T_cal) between 770 and 830 °C. The phase structure, microstructure, and ferroelectric and piezoelectric properties changed greatly depending on the applied T_cal. Benefitting from the formation of low defect levels and large grain size and an appropriate morphotropic phase boundary (MPB) with the rhombohedral-to-pseudocubic phase ratio = 49.1 : 50.9, BFO-BTO ceramics calcined at 785 °C showed the best ferroelectric, piezoelectric, and insulating properties (P_r = 23.1 μC/cm², E_C = 25.8 kV/cm, d₃₃ = 167.8 pC/N, k_p = 0.342%). Above T_cal = 800 °C, however, the ferroelectric and piezoelectric properties deteriorated because volatilization of Bi and reduction of Fe caused a poor insulating property and high degree of chemical inhomogeneity. Moreover, the ceramics calcined at 785 °C showed a high Curie temperature (T_C) of 509.2 °C and excellent thermal aging resistance of d₃₃ up to 450 °C, demonstrating great potential for use in high-temperature applications.     

Ordering of SiO<Subscript>x</Subscript>H<Subscript>y</Subscript>C<Subscript>z</Subscript> islands deposited by atmospheric pressure microwave plasma torch on Si(100) substrates patterned by nanoindentation

SiO _x H _y C _z nanometric layers are deposited from hexamethyldisiloxane by atmospheric pressure microwave plasma torch on Si(100) substrates submitted to temperatures varying on the range [0 °C; 120 °C]. Atomic force microscopy (AFM) characterizations of samples grown at intermediate substrate temperatures (~30 °C) demonstrate a layer-by-layer growth (Frank van der Merwe growth) leading to smooth flat and compact films while films deposited at lower and higher substrates temperatures show an island-like growth (Volmer-Weber growth) generating a high surface roughness. Concomitantly, a detailed infrared spectroscopy analysis of the growing films evidences structural modifications due to changes in the bond types, Si-O-Si conformation and stoichiometry correlated with scanning electron microscopy and AFM characterizations. Then, deposition conditions and specific microstructure are selected with the aim of generating 3-dimensional SiO _x H _y C _z nanostructure arrays on nanoindented Si (100) templates. The first results are discussed.     

Pyroelectric properties of BiFeO3 ceramics prepared by a modified solid-state-reaction method

BiFeO₃ (BFO) ceramics were prepared by a modified solid-state-reaction method which adopts a higher heating/cooling rate during the sintering process than usually used. It was found that the calcination temperature T _cal (from 400 to 750°C) does not influence the BFO phase formation, while the sintering temperature T _sin (from 815 to 845°C) dominates the phase purity. The optimum sintering temperature was in the range from 825 to 835°C. The optimized samples exhibit saturated ferroelectric hysteresis loops with a remnant polarization of 13.2 μC/cm². The measured piezoelectric coefficient d ₃₃ was 45 pC/N. No remnant magnetization was observed in all of the samples. The pyroelectric properties were studied as a function of temperature and frequency. A pyroelectric coefficient as high as 90 μC/m² K was obtained at room temperature in the optimized sample. An abrupt decrease of the pyroelectric coefficient was observed at temperatures between 70 and 80°C. On the basis of our results, BFO may have the potential for pyroelectric applications.     

Pulsed laser deposition of high temperature protonic films

Pulsed laser deposition has been used to fabricate nanostructured BaCe_0.85Y_0.15O_3−δ films. Protonic conduction of the fabricated BaCe_0.85Y_0.15O_3−δ films was compared to the sintered BaCe_0.85Y_0.15O_3−δ. Sintered samples and laser targets were prepared by sintering BaCe_0.85Y_0.15O_3−δ powders derived by solid state synthesis. Films 1 to 8 μm thick were deposited by KrF excimer laser on porous Al₂O₃ substrates. Thin films were fabricated at deposition temperatures of 700 to 950 °C at O₂ pressures up to 200 mTorr using laser pulse energy densities of 1.4–3 J/cm². Fabricated films were characterized by X-ray diffraction, electron microscopy and electrical impedance spectroscopy. Single phase BaCe_0.85Y_0.15O_3−δ films with a columnar growth morphology are observed with preferred crystal growth along the [100] or [001] direction. Results indicate [100] growth dependence upon laser pulse energy. Electrical conductivity of bulk samples produced by solid state sintering and thin film samples were measured over a temperature range of 100 to 900 °C. Electrical conduction behavior was dependent upon film deposition temperature. Maximum conductivity occurs at deposition temperature of 900 °C; the electrical conductivity exceeds the sintered specimen. All other deposited films exhibit a lower electrical conductivity than the sintered specimen. Activation energy for electrical conduction showed dependence upon deposition temperature, it varied from 115 to 54 kJ. Film microstructure was attributed to the difference in electrical conductivity of the BaCe_0.85Y_0.15O_3−δ films.     

Synthesis and electrical transport of SrHfO3 thin films grown on a SrTiO3 (001) substrate using a pulsed laser deposition

We report the deposition of epitaxial SrHfO₃ thin films on a SrTiO₃ (001) substrate in different substrate temperatures by using a pulsed laser deposition (PLD) method. We carried out X-ray diffraction (XRD), X-ray reflectivity (XRR), reciprocal space mapping (RSM), atomic force microscopy (AFM), resistivity, and Hall measurements to examine the crystallinity, morphology and electrical properties of these films. All films showed smooth and uniform morphology with small root mean square (RMS) roughness. While the SrHfO₃ sample grown at 750 °C is metallic, the films deposited at 600 °C, 650 °C, and 700 °C show an upturn at low temperatures. The temperature dependence of the metallic parts was analyzed based on the parallel resistor model that includes resistivity saturation. On the other hand, the low-temperature upturn was found to be well described by a weak localization mechanism. We also observed the possible emergence of non-Fermi liquid behavior when the upturn disappeared. All SrHfO₃ films have p-type charge carriers.     

Transition temperature reduction for CdS nanoparticles under high pressure

The structure transition of nanoparticles has a significant effect on their practical applications. In this study, the transition temperature of CdS nanoparticles with the size of 3–5 nm from sphalerite to wurtzite structure is significantly reduced to 150 °C under a high pressure of 1 GPa, much lower than that 300–400 °C for CdS nanoparticles and 600 °C for bulk CdS under room pressure. The lower transition temperature leads to an ultrafine grain size d = 5 nm for the formed wurtzite phase as compared with that d = 33 nm yielded under room pressure with a similar transition volume fraction of ~80%. The underlying physical mechanism is discussed.     

Er:YAB nanoparticles and vitreous thin films by the polymeric precursor method

The synthesis of Y_0.9Er_0.1Al₃(BO₃)₄ crystalline powders and vitreous thin films were studied. Precursor solutions were obtained using a modified polymeric precursor method using d-sorbitol as complexant agent. The chemical reactions were described. Y_0.9Er_0.1Al₃(BO₃)₄ composition presents good thermal stability with regard to crystallization. The Y_0.9Er_0.1Al₃(BO₃)₄ crystallized phase can be obtained at 1,150 °C, in agreement with other authors. Crack- and porosity-free films were obtained with very small grain size and low RMS roughness. The films thickness revealed to be linearly dependent on precursor solution viscosity, being the value of 25 mPa s useful to prepare high-quality amorphous multi-layers (up to ∼ 800 nm) at 740 °C during 2 h onto silica substrates by spin coating with a gyrset technology.     

Structural, electrical, and surface characteristics of La0.5Sr0.5CoO3 thin films prepared by pulsed-laser deposition

A parametric study of the growth of La_0.5Sr_0.5CoO₃ (LSCO) thin films on (100) MgO substrates by pulsed-laser deposition (PLD) is reported. Films are grown under a wide range of substrate temperature (450–800 °C), oxygen pressure (0.1–0.9 mbar), and incident laser fluence (0.8–2.6 J/cm²). The optimum ranges of temperature, oxygen pressure, and laser fluence to produce c-axis oriented films with smooth surface morphology and high metallic conductivity are identified. Films deposited at low temperature (500 °C) and post-annealed in situ at higher temperatures (600–800 °C) are also investigated with respect to their structure, surface morphology, and electrical conductivity. Received: 20 November 1998 / Accepted: 6 July 1999 / Published online: 21 October 1999     

Orientation dependence of electrical properties of 0.96Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-0.04BaTiO<Subscript>3</Subscript> lead-free piezoelectric single crystal

In this paper, a single crystal of 0.96Na_0.5Bi_0.5TiO₃-0.04BaTiO₃ with dimensions of Φ 30×10 mm was grown by the top-seeded-solution growth method. X-ray powder diffraction results show that the as-grown crystal possesses the rhombohedral perovskite-type structure. The dielectric, piezoelectric and electrical conductivity properties were systematically investigated with 〈001〉, 〈110〉 and 〈111〉 oriented crystal samples. The room-temperature dielectric constants for the 〈001〉, 〈110〉 and 〈111〉 oriented crystal samples are found to be 650, 740 and 400 at 1 kHz. The (T _m, ε _m) values of the dielectric temperature spectra are almost independent of the crystal orientations; they are (306°C, 3718), (305°C, 3613) and (307°C, 3600) at 1 kHz for the 〈001〉, 〈110〉 and 〈111〉 oriented crystal. The optimum poling conditions were obtained by investigating the piezoelectric constants d ₃₃ as a function of poling temperature and poling electric field. For the 〈001〉 and 〈110〉 crystal samples, the maximum d ₃₃ values of 146 and 117 pC/N are obtained when a poling electric field of 3.5 kV/mm and a poling temperature of 80°C were applied during the poling process. The as-grown 0.96Na_0.5Bi_0.5TiO₃-0.04BaTiO₃ crystal possesses a relatively large dc electrical conductivity, especially at higher temperature, having a value of 1.98×10⁻¹¹ Ω⁻¹⋅m⁻¹ and 3.95×10⁻⁹ Ω⁻¹⋅m⁻¹ at 25°C and 150°C for the 〈001〉 oriented crystal sample.     

Thermal tuning of surface plasmon resonance: Ag gratings on barium strontium titanate thin films

Surface plasmon tuning via thermally induced refractive index changes in ferroelectrics is investigated. Epitaxial (Ba_0.7Sr_0.3)TiO₃ (BST) thin films were deposited on MgO (001) substrates by pulsed laser deposition. The refractive index of BST thin films measured by the prism-coupling technique was found to increase from 2.3932 (TE)/1.9945 (TM) at room temperature to 2.3949 (TE)/1.9965 (TM) at 66°C. Then 30-nm-Ag gratings with periodicity 750 nm and width 300 nm were fabricated on BST by soft ultraviolet nanoimprint lithography and subsequent lift-off process. The reflection spectra from 500 to 1000 nm with incident angle from 5° to 60° were measured at room temperature and 66°C, with a collimated and p-polarized light incident perpendicularly to the grating direction. Several modes were observed from the spectra. At 66°C, a red shift of a dip at about 850 nm by 2 nm was obtained at an incident angle of 15°. Calculations confirmed that the observed modes belong to the (−1), (2), (−2) and (3) surface plasmon modes from the Ag and BST interfaces and localized mode; the red shift by thermal tuning is also confirmed. The results indicate the feasibility of active modulation in surface plasmon resonance in solid-state structures.     

Structural and magnetic properties of thin epitaxial Fe films on (1 1 0) GaAs prepared by metalorganic chemical vapor deposition

Iron films have been grown on (1 1 0) GaAs substrates by atmospheric pressure metalorganic chemical vapor deposition at substrate temperatures (T_s) between 135°C and 400°C. X-ray diffraction (XRD) analysis showed that the Fe films grown at T_s between 200°C and 330°C were single crystals. Amorphous films were observed at T_s below 200°C and it was not possible to deposit films at T_s above 330°C. The full-width at half-maximum of the rocking curves showed that crystalline qualities were improved at T_s above 270°C. Single crystalline Fe films grown at different substrate temperature showed different structural behaviors in XRD measurements. Iron films grown at T_s between 200°C and 300°C showed bulk α-Fe like behavior regardless of film thickness (100–6400 Å). Meanwhile, Fe films grown at 330°C (144 and 300 Å) showed a biaxially compressed strain between substrate and epilayer, resulting in an expanded inter-planar spacing along the growth direction. Magnetization measurements showed that Fe films (>200 Å) grown at 280°C and 330°C were ferromagnetic with the in-plane easy axis along the [1 1 0] direction. For the thinner Fe films (⩽200 Å) regardless of growth temperature, square loops along the [1 0 0] easy axis were very weak and broad.