Dielectric and piezoelectric properties of [0 0 1] and [0 1 1]-poled relaxor ferroelectric PZN–PT and PMN–PT single crystals

The properties of PZN–PT and PMN–PT single crystals of varying compositions and orientations have been investigated. Among the various compositions studied, [0 0 1]-optimally poled PZN-(6–7)%PT and PMN-30%PT exhibit superior dielectric and piezoelectric properties, with K^T ≈ 6800–8000, d₃₃ ≈ 2800 pC/N, d₃₁ ≈ −(1200–1800) pC/N for PZN-(6–7)%PT; and K^T = 7500–9000, d₃₃ = 2200–2500 pC/N and d₃₁ = −(1100–1400) pC/N for PMN-30%PT. These two compositions are also fairly resistant to over-poling. The [0 0 1]-poled electromechanical coupling factors (k₃₃, k₃₁ and k_t) are relatively insensitive to crystal composition. [0 1 1]-optimally poled PZN-7%PT single crystal also exhibits extremely high d₃₁ values of up to −4000 pC/N with k₃₁ ≈ 0.90–0.96. While [0 1 1]-poled PZN-7%PT single crystal becomes over-poled with much degraded properties when poled at and above 0.6 kV/mm, PZN-6%PT crystal shows no signs of over-poling even when poled to 2.0 kV/mm. The presence of a certain amount (i.e., 10–15%) of orthorhombic phase in a rhombohedral matrix has been found to be responsible for the superior transverse piezoelectric properties of [0 1 1]-optimally poled PZN-(6–7)%PT. The present work shows that flux-grown PZN–PT crystals exhibit superior and consistent properties and improved over-poling resistance to flux-grown PMN–PT crystals and that, for or a given crystal composition, flux-grown PMN–PT crystals exhibit superior over-poling resistance to their melt-grown counterparts.     

Characterization of Pb(Zr,Ti)O3 thin films deposited on stainless steel substrates by RF-magnetron sputtering for MEMS applications

Piezoelectric Pb(Zr,Ti)O₃ (PZT) thin films with a composition near the morphotoropic phase boundary were deposited directly on cantilever-shaped stainless steel (SUS) substrates using RF-magnetron sputtering for application of micro-electromechanical systems (MEMS). X-ray diffraction measurements reveal that the PZT thin films have a polycrystalline perovskite structure with a preferential orientation of (1 0 1). Cross-section morphology – observed using a scanning electron microscope – indicates that the PZT films exhibit a dense columnar structure without pores or clacks. The films’ P–E hysteresis loops indicate clear ferroelectricity. Based on the deflection characteristics of the cantilever, the effective piezoelectric coefficient e₃₁ of the PZT films is measured to be −1.35 C/m².     

Ferroelectric properties of direct-patterned half-micron thick PZT film

Ferroelectric properties of direct-patterned PZT(PbZr_0.52Ti_0.48O₃) films with 460 μm × 460 μm size and 510 nm thick were analyzed for applying to micro-detecting devices. A photosensitive solution containing ortho-nitrobenzaldehyde was used for the preparation of direct-patterned PZT film. PZT solution was coated on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrate for three times to obtain half-micron thick film and three times of direct-patterning process were repeated to define a pattern on multi-layer PZT film. Through intermediate and final anneal procedure of direct-patterned PZT film, any shrinkage along horizontal direction was not observed within this experimental condition, i.e., the size of the pattern was preserved after annealing, only a thickness reduction was observed after each annealing treatment. Ferroelectric properties of direct-patterned PZT film with 460 μm × 460 μm size and 510 nm thick were compared with those of un-patterned conventional PZT film and shown to be almost the same. Through this work, the high potentiality of direct-patternable PZT film for applying to micro-devices without the introduction of physical damages from dry-etching could be confirmed.     

Effects of PbTiO3 seeding layer on electrical properties of PbZr0.4Ti0.6O3 thin films

Improvements in the ferroelectric properties were obtained by controlling process parameters of the lead titanate (PTO) seed layer. Highly oriented (1 1 1) perovskite lead zirconate titanate (PZT) films yielded the largest polarization switching charges, with an improved retention behavior, compared to those of PZT films without a PbTiO₃ seed layer. The degree of (1 1 1) orientation in a PZT perovskite film increased, when an additional heat treatment process was not applied during formation of the PTO seed layer. In addition, PTO seed layers showed the best results when 8% excess Pb was supplied.     

Red emitting MTiO3 (M = Ca or Sr) phosphors doped with Eu3+ or Pr3+ with some cations as co-dopants

Ca (or Sr)TiO₃:Eu³⁺, M (Li⁺ or Na⁺ or K⁺) and CaTiO₃:Pr³⁺, M (Li⁺ or Na⁺ or Ag⁺ or K⁺ or Gd³⁺ or La³⁺) powders were prepared by combustion synthesis method and the samples were further heated to ～1000 °C to improve the crystallinity. The structure and morphology of materials were examined by X-ray diffraction (XRD) and a scanning electron microscopy (SEM). The morphologies of SrTiO₃:Eu³⁺, CaTiO₃:Eu³⁺ or CaTiO₃:Pr³⁺ powders co-doped with other metal ions were very similar. Small and coagulated particles of nearly cubical shapes with small size distribution having smooth and regular surface were formed. Photo-luminescence spectra of CaTiO₃:Pr³⁺ and co-doped either with Li⁺, Na⁺, K⁺, Ag⁺, La³⁺ or Gd³⁺ ions showed red emissions at 613 nm due to the ¹D₂ → ³H₄ transition of Pr³⁺. The variation of intensity of emission peak with different co-doping follows the order: K⁺ > Ag⁺ > Na⁺ > Li⁺ > La³⁺ > Gd³⁺. The characteristic emissions of CaTiO₃:Eu³⁺ lattices had strong emission at 614 and 620 nm for ⁵D₀ → ⁷F₂ with other weak transitions observed at 580, 592, 654, 705 nm for ⁵D₀ → ⁷F_n transitions where n = 0, 1, 3, 4 respectively in all host lattices. Photoluminescence intensity in SrTiO₃:Eu³⁺ is more than CaTiO₃:Eu³⁺ lattices. A remarkable increase of photoluminescence intensity (in ⁵D₀ → ⁷F₂ transition) was observed if co-doped with Li⁺ ions in CaTiO₃:Eu³⁺ and SrTiO3:Eu³⁺.     

Doping effect of Ir(ppy)3 on white-light electrophosphorescent devices based on platinum(II) [1,3-difluoro-4,6-di(2-pyridinyl)benzene] chloride

Phosphorescent white organic light-emitting diodes (WOLEDs) based on single doped platinum(II) [1,3-difluoro-4,6-di(2-pyridinyl)benzene] chloride (Pt-4) emission layers were investigated in this paper. The devices exhibited electroluminescence spectra composed of bluish (λ_max = 480 nm) and reddish (λ_max = 660 nm) emission bands, which corresponding to monomer and excimer emission originated from Pt-4 dopants. With optimized device structures, a maximum current efficiency of 11.5 cd/A was obtained and remained above 10 cd/A even the brightness was over 6000 cd/m². Furthermore, by integrating the fac-tris(2-phenylpyridine) iridium(III) as a complementary emitter and an additional 2,2′,2″-(1,3,5-phenylene)-tris(1-phenyl-1H-benzimidazole) space layer, the device efficiency was further improved, which exhibited a maximum current efficiency of 20.4 cd/A at the luminance of 100 cd/m², and maintained the mild efficiency roll-off that similar to its single Pt-4 doped counterpart.     

Solutions to the functional equation I(x, y) = I(x, I(x, y)) for three types of fuzzy implications derived from uninorms

This paper investigates an iterative Boolean-like law with fuzzy implications derived from uninorms. More precisely, we characterize the solutions to the functional equation I(x, y) = I(x, I(x, y)) that involve RU-, (U, N)- and QLU-implications generated by the most usual classes of uninorms.     

Cationic P⋯N interaction in XH3P+⋯NCY complexes (X = H,F, CN,NH2, OH; Y = H,Li, F,Cl) and its cooperativity with hydrogen/lithium/halogen bond

The geometries, interaction energies and bonding properties of cationic pnicogen bond (CPB) interactions are studied in binary XH₃P⁺⋯NCY (X = H, F, CN, NH₂, OH; Y = H, Li, F, Cl) complexes by means of MP2/aug-cc-pVTZ calculations. Interaction energies of these binary complexes span a large range, from −16.36 kcal/mol in (NH₂)H₃P⁺⋯NCF to −71.36 kcal/mol in FH₃P⁺⋯NCLi complex. The spin–spin coupling constant across P⋯N interaction depends considerably on the nature of X and Y substituents. The characteristic of CPB interactions is analyzed in terms of parameters derived from quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analyses. The charge transfer from the nitrogen base to the cationic acid stabilizes these pnicogen–bonded complexes. For a given XH₃P⁺, the net charge transfer value increases as the interaction energy of the complex becomes more negative, i.e., NCLi > NCCl > NCH > NCF. Moreover, mutual influence between the CPB and hydrogen/halogen/lithium bond is studied in the ternary XH₃P⁺⋯NCY⋯NCH complexes. The results indicate that the formation of a Y⋯N interaction tends to strengthen CPB in the ternary systems.     

Magnetoelectric sensor for microtesla magnetic-fields based on (Fe80Co20)78Si12B10/PZT laminates

The magnetoelectric sensor based on (Fe₈₀Co₂₀)₇₈Si₁₂B₁₀/PZT laminates is designed, fabricated and characterized for determining dc and ac magnetic-field strengths as well as field orientations. At low dc magnetic-fields, a ME-voltage response (dV_ME/dH) as high as 2 mV/Oe is achieved. The linear relation V_ME(h_ac) with a slope of dV_ME/dh_ac of 17 mV/Oe shows a great ability to self-powered detecting low ac magnetic-fields. The field orientation can be detected by using the sinusoidal dependence of the magnetoelectric voltage. The sensor is promising not only for microtesla magnetic-field sensing but also for magnetic biosensor applications.     

Curves of Genus 2 with (N,N) Decomposable Jacobians

Let C be a curve of genus 2 and ψ₁: C  −  → E ₁  a map of degree n, from C to an elliptic curveE₁ , both curves defined over C. This map induces a degree n map φ₁:P¹  −  → P ¹  which we call a Frey–Kani covering. We determine all possible ramifications for φ₁. If ψ₁:C  −  → E ₁  is maximal then there exists a maximal map ψ₂: C  −  → E ₂  , of degree n, to some elliptic curveE₂ such that there is an isogeny of degree n²from the JacobianJ_C to E₁ × E₂. We say thatJ_C is (n, n)-decomposable. If the degree n is odd the pair (ψ₂, E₂) is canonically determined. For n =  3, 5, and 7, we give arithmetic examples of curves whose Jacobians are (n, n)-decomposable.     

Computing Modular Invariants of p-groups

Let V be a finite dimensional representation of a p -group, G, over a field,k , of characteristic p. We show that there exists a choice of basis and monomial order for which the ring of invariants, k [ V ]^G, has a finite SAGBI basis. We describe two algorithms for constructing a generating set for k [ V ] G. We use these methods to analyse k [2V₃ ]^U₃where U₃is the p -Sylow subgroup ofGL₃ (F_p) and 2 V₃is the sum of two copies of the canonical representation. We give a generating set for k [2 V₃]^U₃forp =  3 and prove that the invariants fail to be Cohen–Macaulay forp >  2. We also give a minimal generating set for k [mV₂ ]^Z / pwere V₂is the two-dimensional indecomposable representation of the cyclic group Z / p.     

Giant-grain silicon (GGS) and its application to stable thin-film transistor

We developed a giant-grain silicon (GGS) by Ni-mediated crystallization of amorphous silicon (a-Si) with a silicon-nitride (SiN_x) cap layer. Ni particles were sputtered onto the SiN_x/a-Si layer and then it was annealed at around 600 °C. The Ni diffuses through a SiN_x cap and then forms NiSi₂ crystallites in a-Si, which is able to induce crystallization. The grain size can be controlled from a few to 100 μm. The grain size can be increased with increasing the cap layer thickness or by decreasing the Ni density on the SiN_x. The p-channel GGS poly-Si TFT exhibited a field-effect mobility of 101 cm²/Vs and a threshold voltage of −3.6 V and is very stable under gate or hot carrier bias-stress. These superior performances may be due to the smooth surface of GGS poly-Si and solid-phase crystallization of a-Si.     

Evolution of structure,stability, and nonlinear optical properties of the heterodinuclear CNLin (n = 1–10) clusters

The lowest-energy structures and stabilities of the heterodinuclear clusters, CNLi_n (n = 1–10) and relevant CNLi_n⁺ (n = 1–10) cations, are studied using the density functional theory with the 6-311 + G(3df) basis set. The CNLi₆ and CNLi₅⁺ clusters are the first three-dimensional ones in the CNLi_n^0/+ series, respectively, and the CN group always caps the Li_n^0/+ moiety in the CNLi_n^0/+ (n = 1–9) configurations. The CN triple bond is found to be completely cleaved in the CNLi₁₀^0/+ clusters where the C and N atoms are bridged by two Li atoms. The CNLi_n (n = 2–10) clusters are hyperlithiated molecules with delocalized valence electrons and consequently possess low VIP values of 3.780–5.674 eV. Especially, the CNLi₈ and CNLi₁₀ molecules exhibit lower VIPs than that of Cs atom and can be regarded as heterobinuclear superalkali species. Furthermore, these two superalkali clusters show extraordinarily large first hyperpolarizabilities of 19,423 and 42,658 au, respectively. For the CNLi_n⁺ cationic species, the evolution of the energetic and electronic properties with the cluster size shows a special stability for CNLi₂⁺.     

Evaluation of response characteristics of resistive oxygen sensors based on porous cerium oxide thick film using pressure modulation method

In order to reduce the response time of resistive oxygen sensors using porous cerium oxide thick film, it is important to ascertain the factors controlling response. Pressure modulation method (PMM) was used to find the rate-limiting step of sensor response. This useful method measures the amplitude of sensor output (H(f)) for the sine wave modulation of oxygen partial pressure at constant frequency (f). In PMM, “break” response time, which is minimum period in which the sensor responds precisely, can be measured. Three points were examined: (1) simulated calculations of PMM were carried out using a model of porous thick film in which spherical particles are connected in a three-dimensional network; (2) sensor response speed was experimentally measured using PMM; and (3) the diffusion coefficient and surface reaction coefficient were estimated by comparison between experiment and calculation. The plot of log f versus log H(f) in the high f region was found to have a slope of approximately −0.5 for both porous thick film and non-porous thin film, when the rate-limiting step was diffusion. Calculations showed the response time of porous thick film was 1/20 that of non-porous thin film when the grain diameter of the porous thick film was the same as the thickness of non-porous thin film. At 973 K, “break” response time (t_b) of the resistive oxygen sensor was found by experiment to be 109 ms. It was concluded that the response of the resistive oxygen sensor prepared in this study was strongly controlled by diffusion at 923–1023 K, since the experiment revealed that the slope of plot of log f versus log H(f) in the high f region was approximately −0.5. At 923–1023 K, the diffusion coefficient of oxygen vacancy in porous ceria (D_V) was expressed as follows: D_V (m²s⁻¹) = 5.78 × 10⁻⁴ exp(−1.94 eV/kT). At 1023 K, the surface reaction coefficient (K) was found to exceed 10⁻⁴ m/s.     

Development of large-strain and low-powered electro-active polymers (EAPs) using conductive fillers

During the last decade, Electro Active Polymers (EAPs) have attracted much attention especially because of their high level of generated strain. Mainly ferroelectric materials are used as fillers with elevated volume percentages in order to create a reasonable strain level. Aggregation problems should also be considered. With silicone or acrylic elastomers as the matrix, very high strains, even more than 300%, can today be obtained, however this requires a very high electric induction, e.g., 120 MV/m. Such a high electric requirement prevents these materials from being utilized with other electric components. There exist intermediate materials between traditional actuator materials, such as PZTs, and EAPs. These materials can generate higher strain levels than traditional PZT materials, and are expected to be driven with a low electric level. The present paper shows the easy fabrication method of such intermediate materials. Conductive fillers were incorporated into the polymeric material. As opposed to for ferroelectric filler materials which have many dipoles, there was no electric field inside the conductive fillers. As a consequence, electric charges were distributed over the surface of the filler particle surfaces. This mechanism increased the electric coefficient so that a high strain level could be obtained more efficiently than in the case of ferroelectric fillers. The improvement of electrostriction by adding very small volume percentages of fillers, 0.1–2 Vol.%, was thus confirmed. The composite films, fabricated by a very easy method, could generate more than 20% of strain at 15 MV/m.     

Fluorescence detection of nitrogen dioxide with perylene/PMMA thin films

Thin films of polymethylmethacrylate (PMMA) doped with perylene provide selective, robust and easily prepared optical sensor films for NO₂ gas with suitable response times for materials aging applications. The materials are readily formed as 200 nm thin spin cast films on glass from chlorobenzene solution. The fluorescence emission of the films (λ_max=442 nm) is quenched upon exposure to NO₂ gas through an irreversible reaction forming non-fluorescent nitroperylene. Infrared, UV–VIS and fluorescence spectroscopies confirmed the presence of the nitro adduct in the films. In other atmospheres examined, such as air and 1000 ppm concentrations of SO₂, CO, Cl₂ and NH₃, the films exhibited no loss of fluorescence intensity over a period of days to weeks. Response curves were obtained for 1000, 100 and 10 ppm NO₂ at room temperature with equilibration times varying from hours to weeks. The response curves were fit using a numerical solution to the coupled diffusion and a nonlinear chemical reaction problem assuming that the situation is reaction limiting. The forward reaction constant fitted to experimental data was k_f∼0.06 (ppm min)⁻¹.     

Chromium(III)-selective sensor based on tri-o-thymotide in PVC matrix

Tri-o-thymotide (I) has been used as an electroactive material in PVC (poly(vinyl chloride)) matrix for fabrication of chromium(III)-selective sensor. The membrane containing tri-o-thymotide, sodium tetraphenyl borate (NaTPB), dibutyl phthalate (DBP) and PVC in the optimum ratio 5:1:75:100 (w/w) exhibits a working concentration range of 4.0 × 10⁻⁶ to 1.0 × 10⁻¹ M with a Nernstian slope of 20.0 ± 0.1 mV/decade of activity in the pH range of 2.8–5.1. The detection limit of this sensor is 2.0 × 10⁻⁷ M. The electrode exhibits a fast response time of 15 s, shows good selectivity towards Cr³⁺ over a number of mono-, bi- and trivalent cations and can also be used in partially non-aqueous medium (up to 15%, v/v) also. The assembly has been successfully used as an indicator electrode in the potentiometric titration of chromium(III) against EDTA and also to determine Cr(III) quantitatively in electroplating industry waste samples.     

Bounds for the Roots of Lacunary Polynomials

A polynomial P(X)  = X^d + a_d − 1X^d − 1 + ⋯ is called lacunary when a_d − 1 =  0. We give bounds for the roots of such polynomials with complex coefficients. These bounds are much smaller than for general polynomials.     

Fabrication and frequency response of dual-element ultrasonic transducer using PZT-5A thick film

Ultrasonic transducers based on PZT-5A thick films deposited onto polycrystalline Al₂O₃ substrates using screen-printing were successfully fabricated. Considering the relatively high sintering temperature of PZT-5A thick films and better impedance matching characteristics with PZT-5A, polished polycrystalline Al₂O₃ were used as substrates. For electrodes, high quality platinum (Pt) was deposited by a thin film process, because the surface state of electrodes greatly affects the quality of piezoelectric films. Applying Pt/PZT-5A/Pt/Al₂O₃ structures, dual-element ultrasonic transducers were assembled. The assembled transducers included a wear plate (normally alumina with 40.21 × 10⁶ kg/m² s of impedance), backing (tungsten carbide-epoxy), electrical matching, an epoxy glue layer, and a housing. The optimum measurement ranges of 5 and 10 MHz ultrasonic transducers were 2.51–300.2 and 2.50–250.1 mm, respectively. From the time and frequency response measurements of the assembled 10 MHz DEUTs, the value of −20 dB level waveform duration and the −6 dB bandwidth was 481.8 ns and 34.4%, respectively. Also, the measurement accuracies of both 5 and 10 MHz DEUTs assembled in this study were below 0.1 and 0.4%, respectively.