Enhanced ferroelectric properties of (Pb0.90La0.10)Ti0.975O3 multilayered thin films prepared by RF magnetron sputtering

The (Pb_0.90La_0.10)Ti_0.975O₃/PbTiO₃ (PLT/PT), PbTiO₃/(Pb_0.90La_0.10)Ti_0.975O₃/PbTiO₃ (PT/PLT/PT) multilayered thin films with a PbO_x buffer layer were in situ deposited by RF magnetron sputtering at the substrate temperature of 600 °C. With this method, highly (1 0 0)-oriented PLT/PT and PT/PLT/PT multilayered thin films were obtained. The PbO_x buffer layer leads to the (1 0 0) orientation of the films. The dielectric, ferroelectric and pyroelectric properties of the PLT multilayered thin films were investigated. It is found that highly (1 0 0)-oriented PT/PLT/PT multilayered thin films possess higher remnant polarization 2P_r (44.1 μC/cm²) and better pyroelectric coefficient at room temperature p (p = 2.425 × 10⁻⁸ C/cm² K) than these of PLT and PLT/PT thin films. These results indicate that the design of the PT/PLT/PT multilayered thin films with a PbO_x buffer layer should be an effective way to enhance the dielectric, ferroelectric and pyroelectric properties. The mechanism of the enhanced ferroelectric properties was also discussed.     

(111)取向(Pb,La)TiO3铁电薄膜中90°纳米带状畴与热释电性能的研究

采用射频磁控溅射技术在Pt/Ti/SiO₂/Si(100)衬底上生长了掺镧钛酸铅(PLT)铁电薄膜.用X射线衍射技术(XRD)研究了PLT薄膜结晶性能，结果表明PLT薄膜为 (111)择优取向钙钛矿相织构.使用原子力显微镜(AFM)和压电响应力显微镜(PFM) 分别观察了PLT薄膜的表面形貌和对应区域的电畴结构.PFM观察显示PLT薄膜中存在90°纳米带状畴，电畴的极化为首尾相接的低能量的排列方式，带状畴的宽度为20—60nm.研究了PLT10铁电薄膜的制备条件与性能之间的关系.发现在优化条件下制备的PLT10铁电薄膜的介电常数ε_r为365、介电损耗tgδ为0.02，热释电系数γ为2.18×10^-8C·(cm²·K)^-1，可以满足制备非制冷红外探测器的需要. 关键词： PLT薄膜 电畴 PFM 极化     

Leakage current, ferroelectric and structural properties in Pb1−xBaxTiO3 thin films prepared by chemical route

Single-phase perovskite structure Pb_1−xBa_xTiO₃ thin films (x=0.30, 0.50 and 0.70) were deposited on Pt/Ti/SiO₂/Si substrates by the spin-coating technique. The dielectric study reveals that the thin films undergo a diffuse type ferroelectric phase transition, which shows a broad peak. An increase of the diffusivity degree with the increasing Barium contents was observed, and it was associated to a grain decrease in the studied composition range. The temperature dependence of the phonon frequencies was used to characterize the phase transition temperatures. Raman modes persist above tetragonal to cubic phase transition temperature, although all optical modes should be Raman inactive. The origin of these modes was interpreted in terms of breakdown of the local cubic symmetry by chemical disorder. The absence of a well-defined transition temperature and the presence of broad bands in some interval temperature above FE-PE phase transition temperature suggested a diffuse type phase transition. This result corroborates the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in these thin films. The leakage current density of the PBT thin films was studied at different temperatures and the data follow the Schottky emission model. Through this analysis the Schottky barrier height values 0.75, 0.53 and 0.34 eV were obtained to the PBT70, PBT50 and PBT30 thin films, respectively.     

Glass transition and dynamics of single and stacked thin films of poly(2-chlorostyrene)

The glass transition temperature and the dynamics of the α-process have been investigated using dielectric relaxation spectroscopy for single and stacked thin films of poly(2-chlorostyrene) (P2CS). The stacked film consists of 10 layers of single thin films with thickness of 12 nm or 18 nm. The glass transition temperature T _g of the single thin films of P2CS is found to decrease with decreasing film thickness in a similar way as observed for polystyrene thin films. The magnitude of the depression of T _g for the stacked thin films is larger than that of the single thin films with corresponding thickness. The depression of the temperature at which the dielectric loss shows a peak due to the α-process at a given frequency, T _α, is larger than that of the single thin films, although the magnitude is smaller than that of T _g . Annealing at a high temperature could cause the T _g and T _α of the stacked thin films to approach the values of the bulk system.     

Ti-doping induced antiferroelectric to ferroelectric phase transition and electrical properties in Sm-PbZrO3 thin films

The antiferroelectric (Pb_0.985Sm_0.01) (Zr_1-xTi_x)O₃ (Ti-PSZO) thin films were synthesized on Pt(111)/Ti/SiO₂/Si substrates using a chemical solution deposition method. The films were crystallized in the perovskite phase with a preferential orientation along (111) direction. With Ti doping in PSZO, a gradual transformation from antiferroelectric to ferroelectric phase transition was noticed at room temperature owing to the Ti doping induced lattice distortion. The phase transition has been confirmed through the P - E hysteresis loops, X-ray diffraction (peak shifting), capacitance-voltage measurements, and Raman scattering analysis. The thin film with Ti = 0.15 doping displayed a ferroelectric behavior with high dielectric constant and large dielectric tunability of about 62%. Also, Ti doping altered the Curie temperature (T_c) and enhanced the order of dielectric diffuseness. It is believed that Ti-doping in PSZO is an effective way to induce an antiferroelectric - ferroelectric phase transition and to tailor the electrical characteristics of PSZO thin films.     

Synthesis and characteristics of KTa0.5Nb0.5O3 thin films

KTa_0.5Nb_0.5O₃ thin films were synthesized via a metal-organic solution. Characteristics were measured, such as X-ray diffraction pattern, surface morphology and roughness, and electric properties. The synthesized films have a (100) preferential growth orientation on Si (100) substrate. The homogeneous microstructure and smooth surface benefit to the good electric properties of the thin films. The current density-voltage characteristic shows an unexpected feature of the transition from linear to nonlinear, which can be explained by the space-charge-limited mode. Dielectric constant and loss of the thin films decrease with the increase of frequency. The decrease of dielectric loss is related to the decrease of net polarization in material. The decrease of dielectric constant can be explained by Debye formula. The phase transition temperature T _c is about 102 °C for KTa_0.5Nb_0.5O₃ materials.     

Film structure and ferroelectric properties of in situ grown SrBi2Ta2O9 films

Ferroelectric SrBi₂Ta₂O₉ (SBT) films were grown by pulsed-laser deposition (PLD) at different substrate temperatures and fluences. A correlation between film structure and ferroelectric properties is established. The dielectric function ε^′ of thin SBT films shows a Curie–Weiss behavior well below the peak temperature T_max and relaxor-like behavior in the vicinity of T_max. Domain walls have a strong influence on the dielectric and ferroelectric properties and on the polarization fatigue of SBT films below 100 °C. The formation of ferroelectric phases is favored at lower substrate temperatures by incorporating Bi₂O₃ template layers into the structure. Received: 18 March 1999 / Accepted: 19 March 1999 / Published online: 5 May 1999     

Dielectric characterization of semiconducting ZnPc films sandwiched between Gold or Aluminum electrodes

The dependencies of complex dielectric functions (the dielectric constant, ε ₁, and the dielectric loss, ε ₂), on frequency and temperature of zinc phthalocyanine (ZnPc) thin films sandwiched between either gold or aluminum Ohmic-electrode contacts have been investigated in the temperature range of 93–470 K and frequency range 0.1–20 kHz. It is found that both values of ε ₁ and ε ₂ decrease with increasing frequency and increase with decreasing temperature. The rate of change depends greatly on the temperature and frequency ranges under consideration. Around room temperature, neither ε ₁ nor ε ₂ show any appreciable change through the whole range of frequencies. Thus, the dielectric dispersion is found to include of both dipolar and interfacial polarizations. The dependencies of both dielectric functions on frequency at different temperatures were found to follow a universal power law of the form ω ⁿ , where the index 0<n≤?1. This indicates that the correlated barrier hopping (CBH) model is a suitable mechanism to describe the dielectric behavior in ZnPc films. Furthermore, the results of the dielectric response indicate that polarization in these films could be in the form of non-Debye polarization. However, the Debye polarization can be traced below room temperature. The obtained results of the relaxation-time, τ, dependency on temperature have shown that a thermally-activated process may be dominated in ZnPc thin films conduction at high temperatures. Partial phase transition (from α- to β-phase) has been observed around 400 K in molecular relaxation-time, τ, and optical dielectric constant, ε _∞. Arrhenius behavior has been observed for all the dielectric loss and conductivity relaxation-times above room temperature and their activation energies are explained and reported. The optical dielectric constant ε _∞ was found to increase with temperature.     

Structure and dielectric behavior of TlSbS2

A comparison of structure and dielectric properties of TlSbS₂ thin films, deposited in different thicknesses (400–4100 Å) by thermal evaporation of TlSbS₂ crystals that were grown by the Stockbarger–Bridgman technique and the bulk material properties of TlSbS₂ are presented. Dielectric constant ε ₁ and dielectric loss ε ₂ have been calculated by measuring capacitance and dielectric loss factor in the frequency range 20 Hz–10 KHz and in the temperature range 273–433 K. It is observed that at 1 kHz frequency and 293 K temperature the dielectric constant of TlSbS₂ thin films is ε ₁=1.8–6 and the dielectric loss of TlSbS₂ thin films is ε ₂=0.5–3 depending on film thickness. In the given intervals, both of dielectric constant and dielectric loss decrease with frequency, but increase with temperature. The maximum barrier height W _m is calculated from the dielectric measurements. The values of W _m for TlSbS₂ films and bulk are obtained as 0.56 eV and 0.62 eV at room temperature, respectively. The obtained values agree with those proposed by the theory of hopping over the potential barrier. The temperature variation of ac conductivity can be reasonably interpreted in terms of the correlated barrier hopping model since it obeys the ω ^s law with a temperature dependent s (s<1) and going down as the temperature is increased. The temperature coefficient of capacitance (TCC) and permittivity (TCP) are evaluated for both thin films and bulk material of TlSbS₂.     

Dielectric properties and phase transitions of (Pb0.87La0.02Ba0.1)(Zr0.6Sn0.4−xTix)O3 ceramics with compositions near AFE/RFE phase boundary

The electrical properties and phase transition behavior of (Pb_0.87La_0.02Ba_0.1)(Zr_0.6Sn_0.4−xTi_x)O₃ solid solutions (PLBZST, 0.04≤x0.2) were investigated by the X-ray diffraction, permittivity, pyroelectric current, and P-E electric hysterisis loops. As the composition x increased from 0.04 to 0.2, the antiferroelectric ceramics (x≤0.07, AFE) with tetragonal phase changed to the ferroelectric relaxors (RFE, 0.09≤x). AFE ceramics showed a peculiar diffuse phase transition and dielectric relaxation at the low temperature (down to −100 °C) due to a frustration between AFE and FE state. With an increase in composition x, electrically field-induced AFE-FE switching field (E_AFE-FE) and AFE-paraelectric (PE) phase transition temperature (T_c) are depressed in the temperature (T)-Ti composition (x) phase diagram, a FE-AFE-PE triple phase point (T_tr) with the lowest transition temperature occurred at x=0.09. The pyroelectric currents under an application of various external electric field (E) were measured to identify a T-E phase diagram of the PLBZST compound.     

Effect of dispersion degree of orientation on dielectric properties of (100)-oriented PST thin film

(100) Oriented (Pb_xSr_1−x)TiO₃ (PST) thin films were prepared on indium tin oxide coated glass substrates by sol–gel technique with rapid thermal processing. The dielectric permittivity and tunability of the thin films with different dispersion degrees of orientation were investigated in detail by characterizing the full width at half maximum of their (100) peak based on rocking curves at different annealing temperatures. Influence of orientation dispersion on dielectric properties was exhibited in the tunable dielectric thin films. It shows that the dielectric constant and hence the tunability of the sol–gel derived PST thin films are improved with the decrease in the dispersion degree of orientation of the perovskite phase other than the increase in the content of crystalline phase in the thin films. The dielectric constant (capacitance) and figure of merit of the oriented thin films are 3–6 times and 1 times higher than that of randomly oriented thin film respectively.     

Dielectric properties of deuterated ammonium Rochelle salt

The dielectric constant of deuterated ammonium Rochelle salt along the three crystallographic axes as well as the pyroelectric charge density developed on the crystal surface perpendicularly to the b-axis have been measured with a high temperature resolution. The para- to ferroelectric transition at T_c = ?159°C shows a thermal hysteresis of ΔT = 0.15°C. This and the discontinuities in the dielectric constant along all three axes show that the phase transition is of the first-order. No phase intermediate between the para- and the ferroelectric phases could be detected.     

Modification of the charge ordering transition in the quasi-one-dimensional conductor (TMTTF)2SbF6 under pressure

We have measured the temperature dependences of the conductance G and the dielectric permittivity ε′ of the (TMTTF)₂SbF₆ compound under a moderate pressure. The maximum of G(T) associated with the Mott-Hubbard localization disappears under pressure. With increasing pressure the peak in ε′(T), corresponding to the charge ordering (CO) phase transition, shifts to lower temperatures and broadens. At pressures above 0.24 GPa, ε′(T) becomes strongly frequency dependent. These modifications are explained in the frame of the extended Hubbard model and a slowing down behavior.     

The effects of substrate temperatures on the electrical properties of CaZrO3 thin films prepared by RF magnetron sputtering

The radio frequency magnetron sputtering technology (RFMS) was employed to deposit perovskite structure orthogonal phase CaZrO₃ thin films on Pt/Ti/SiO₂/Si substrates. The effects of substrate temperatures on structure and electrical properties of these films were investigated in detail. The CaZrO₃ thin films were systematically characterized by means of X-ray diffraction (XRD), Scanning electron microscope (SEM), Multi-frequency LCR meter (HP4294A) and Radiant Precision Workstation to study the phase structure, cross-section morphology, dielectric and ferroelectric properties at different substrate temperatures. The result indicates that these films can withstand 80 V DC Bias voltage and have excellent stability of frequency, voltage and temperature. The CaZrO₃ thin film prepared at 550 °C turned out to be mainly orthorhombic CaZrO₃ phase with high permittivity, low dielectric loss, extremely low leakage current (at 1 MHz, the dielectric constant is 39.42, the dielectric loss is 0.00455, the quality factor is 220 and the leakage current density is 9.11 × 10⁻⁷A/cm² at 80 V applied voltage.). This work demonstrates that higher substrate temperature can boost the formation of orthorhombic CaZrO₃ phase and the CaZrO₃ thin film prepared by RF magnetron sputtering is a very promising paraelectric material in the application of thin film capacitor.     

Na1−xLixNbO3 ceramics studied by X-ray diffraction, dielectric, pyroelectric, piezoelectric and Raman spectroscopy

Na_1−xLi_xNbO₃ ceramics with composition 0.05≤x≤0.30 were prepared by solid-state reaction method and sintered in the temperature range 1100-1150 °C. These ceramics were characterised by X-ray diffraction as well as dielectric permittivity measurements and Raman spectroscopy. Dielectric properties of ceramics belonging to the whole composition domain were investigated in a broad range of temperatures from 300 to 750 K and frequencies from 0.1 to 200 kHz. The Rietveld refinement powder X-ray diffraction analysis showed that these ceramics have a single phase of perovskite structure with orthorhombic symmetry for x≤0.15 and two phases coexistence of rhombohedral and orthorhombic above x=0.20. The evolution of the permittivity as a function of temperature and frequency showed that these ceramics Na_1−xLi_xNbO₃ with composition 0.05≤x≤0.15 present the classical ferroelectric character and the phase transition temperature T_C increases as x content increases. The polarisation state was checked by pyroelectric and piezoelectric measurements. For x=0.05, the piezoelectric coefficient d₃₁ is of 2pC/N. The evolution of the Raman spectra was studied as a function of temperatures and compositions. The results of the Raman spectroscopy study confirm our dielectric measurements, and they indicate clearly the transition from the polar ferroelectric phase to the non-polar paraelectric one.     

Lead-free ferroelectric thin films obtained by pulsed laser deposition

Na_0.5Bi_0.5TiO₃-BaTiO₃ (NBT-BT) thin films grown by pulsed laser deposition have been investigated by X-ray diffraction, scanning electron microscopy, and dielectric spectroscopy in order to clarify the role of substrate temperature on crystalline structure, grain morphology, and dielectric properties. We have shown that the structural and dielectric properties of NBT-BT thin films with composition at morphotropic phase boundary (6% BT) critically depend on the substrate temperature: small variations of this parameter induce structural changes, shifting the morphotropic phase boundary toward tetragonal or rhombohedral side. Higher deposition temperature (1000 K) favor the formation of rhombohedral phase, films deposited at 923 K and 973 K have tetragonal symmetry at room temperature. Grains morphology depends also on the deposition temperature. Atomic force micrographs show grains with square or rectangular shape in a compact structure for films grown at lower temperatures, while grains with triangular shape in a porous structure are observed for films grown at 1000 K. Dielectric spectroscopy measurements evidenced the phase transition between ferroelectric and antiferroelectric phase at 370 K. Films grown at 1000 K shown low electrical resistivity due to their porous structure. High dielectric constant values (about 800 at room temperature and 2700 at 570 K) have been obtained for films grown at temperatures up to 973 K.     

Dielectric properties of a triglycine sulfate crystal grown with a transition through the Curie point

The dielectric properties of the triglycine sulfate (TGS) crystal grown by lowering the temperature with a transition through Curie point T_C during its growth are studied. The greatest values of low-frequency dielectric permittivity ε_max(T = T_C) and effective dielectric permittivity ε_eff(E₀) correspond to the layer of crystal formed at the temperature of the phase transition.     

Magnetic-field-induced phase transition in Tb0.95Bi0.05MnO3+δ multiferroic

The effect of a magnetic field on the dielectric properties of Tb_0.95Bi_0.05MnO_3+δ single crystals has been analyzed. It has been shown that the state of the crystal for temperatures of 5–440 K is inhomogeneous and restricted domains of polar and spin correlations are exhibited in it. A phase transition in which the inhomogeneous state of the crystal changes substantially has been observed at a temperature of T ? 180 and 225 K (in the absence and presence of a magnetic field, respectively). The high-temperature phase contains large dielectric domains with a high dielectric constant (ε ～ 10⁵) and thin conducting layers at the boundaries of these domains. The magnetic field significantly affects the state of both low-and high-temperature phases of the crystal, shifting the temperature of the phase transition between them, and induces an additional phase transition at T ? 441 K.     

Sputtered magnesium diboride thin films: Growth conditions and surface morphology

Magnesium diboride (MgB₂) thin films were deposited on C-plane sapphire substrates by sputtering pure B and Mg targets at different substrate temperatures, and were followed by in situ annealing. A systematic study about the effects of the various growth and annealing parameters on the physical properties of MgB₂ thin films showed that the substrate temperature is the most critical factor that determines the superconducting transition temperature (T_c), while annealing plays a minor role. There was no superconducting transition in the thin films grown at room temperature without post-annealing. The highest T_c of the samples grown at room temperature after the optimized annealing was 22 K. As the temperature of the substrate (T_s) increased, T_c rose. However, the maximum T_s was limited due to the low magnesium sticking coefficient and thus the T_c value was limited as well. The highest T_c, 29 K, was obtained for the sample deposited at 180 °C, annealed at 620 °C, and was subsequently annealed a second time at 800 °C. Three-dimensional (3D) AFM images clearly demonstrated that the thin films with no transition, or very low T_c, did not have the well-developed MgB₂ grains while the films with higher T_c displayed the well-developed grains and smooth surface. Although the T_c of sputtered MgB₂ films in the current work is lower than that for the bulk and ex situ annealed thin films, this work presents an important step towards the fabrication of MgB₂ heterostructures using rather simple physical vapor deposition method such as sputtering.     

Molecular dynamics in thin films of isotactic poly(methyl methacrylate)

The molecular dynamics in thin films (18 nm-137 nm) of isotactic poly(methyl methacrylate) (i-PMMA) of two molecular weights embedded between aluminium electrodes are measured by means of dielectric spectroscopy in the frequency range from 50 mHz to 10 MHz at temperatures between 273 K and 392 K. The observed dynamics is characterized by two relaxation processes: the dynamic glass transition (α-relaxation) and a (local) secondary β-relaxation. While the latter does not depend on the dimensions of the sample, the dynamic glass transition becomes faster (≤2 decades) with decreasing film thickness. This results in a shift of the glass transition temperature T _g to lower values compared to the bulk. With decreasing film thickness a broadening of the relaxation time distribution and a decrease of the dielectric strength is observed for the α-relaxation. This enables to deduce a model based on immobilized boundary layers and on a region displaying a dynamics faster than in the bulk. Additionally, T _g was determined by temperature-dependent ellipsometric measurements of the thickness of films prepared on silica. These measurements yield a gradual increase of T _g with decreasing film thickness. The findings concerning the different thickness dependences of T _g are explained by changes of the interaction between the polymer and the substrates. A quantitative analysis of the T _g shifts incorporates recently developed models to describe the glass transition in thin polymer films. Received 12 August 2001 and Received in final form 16 November 2001