Compression of cross-linked poly(vinylidene fluoride-co-trifluoro ethylene) films for facile ferroelectric polarization

In this study, we demonstrated a facile route for enhancing the ferroelectric polarization of a chemically cross-linked poly(vinylidene fluoride-co-trifluoro ethylene) (PVDF-TrFE) film. Our method is based on thermally induced cross-linking of a PVDF-TrFE film with a 2,2,4-trimethyl-1,6-hexanediamine (THDA) agent under compression. The remanent polarization (P(r)) of a metal/ferroelectric/metal capacitor containing a cross-linked PVDF-TrFE film increased with pressure up to a certain value, whereas no change in the P(r) value was observed in the absence of THDA. A film cross-linked with 10 wt % THDA with respect to PVDF-TrFE under a pressure of 100 kPa exhibited a P(r) of approximately 5.61 μC/cm(2), which is 1.6 times higher than that in the absence of pressure. The enhanced ferroelectric polarization was attributed to highly ordered 20-nm-thick edge-on crystalline lamellae whose c-axes are aligned parallel to the substrate. The lamellae were effective for ferroelectric switching of the PVDF-TrFE when a cross-linked film was recrystallized under pressure. Furthermore, compression of a PVDF-TrFE film with a topographically prepatterned poly(dimethyl siloxane) mold gave rise to a chemically cross-linked micropattern in which edge-on crystalline lamellae were globally oriented over a very large area.     

Nonvolatile polymer memory with nanoconfinement of ferroelectric crystals

We demonstrate significantly improved performance of a nonvolatile polymeric ferroelectric field effect transistor (FeFET) memory using nanoscopic confinement of poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) within self-assembled organosilicate (OS) lamellae. Periodic OS lamellae with 30 nm in width and 50 nm in periodicity were templated using block copolymer self-assembly. Confined crystallization of PVDF-TrFE not only significantly reduces gate leakage current but also facilitates ferroelectric polarization switching. These benefits are due to the elimination of structural defects and the development of an effective PVDF-TrFE crystal orientation through nanoconfinement. A bottom gate FeFET fabricated using a single-crystalline triisopropylsilylethynyl pentacene channel and PVDF-TrFE/OS hybrid gate insulator shows characteristic source-drain current hysteresis that is fully saturated at a programming voltage of ±8 V with an ON/OFF current ratio and a data retention time of approximately 10(2) and 2 h, respectively.     

Growth and the microstructural and ferroelectric characterization of oriented BaMgF(4) thin films

The growth of ferroelectric BaMgF(4) thin films on Si(100), sapphire, and other substrates under ultrahigh vacuum (UHV) conditions is reported. Microstructural characterization of the films using transmission electron microscopy (TEM) revealed that they were oriented crystalline films, although not epitaxial. Ferroelectric hysteresis measurements yielded spontaneous polarization and coercivity values of almost 1.0 muC/cm(2) and 160 kV/cm, respectively. The discrepancy with the bulk ferroelectric values were attributed to the electrical contacts, impurities in the film, and lack of polar axis orientation. Preliminary capacitance-voltage (C-V) hysteresis measurements on a 480-nm-thick BaMgF(4) film yielded a 10.8-V threshold shift (memory window) in response to a +/-10-V programming voltage for a MIS gate structure similar to that of the ferroelectric memory field-effect transistor (FEMFET).     

Electric characteristics of organic thin-film transistors and logic circuits with a ferroelectric gate insulator

Organic electronic devices using a pentacene have improved importantly in the last several years. We fabricated pentacene organic thin-film transistors (OTFTs) with dielectric SiO₂ and ferroelectric Pb(Zr_0.3,Ti_0.7)O₃ (PZT) gate insulators. The organic devices using SiO₂ and PZT films had the field-effect mobility of approximately 0.1 and 0.004 cm²/V s, respectively. The drain current in the transfer curve of pentacene/PZT transistors showed a hysteresis behavior originated in a ferroelectric polarization switching. In order to investigate the polarization effect of PZT gate dielectrics in a logic circuit, the simple voltage inverter using SiO₂ and PZT films was fabricated and measured by an output-input measurement. The gain of inverter at the poling-down state was approximately 7.2 and it was three times larger than the value measured at the poling-up state.     

结构设计对铁电薄膜系统电滞回线的影响

为制备符合Si集成铁电器件要求的高质量Si基铁电薄膜，采用溶胶—凝胶(sol—gel)工艺，制备了MFM及MFS结构的铁电薄膜系统，研究了不同结构及不同衬底对铁电薄膜系统铁电性能及电滞回线的影响，并对这些差异产生的主要影响因素进行了分析，在此基础上，提出并制备了Ag／Pb(Zr0.52Ti0.48)O3／Bi4Ti3O12／p—Si多层结构，该结构铁电薄膜系统的铁电性能及电滞回线的对称性有明显改善，有望应用于Si集成铁电器件。     

Integration of BiFeO3 thin films on Si wafer via a simple sol-gel method

Integration of BiFeO₃ (BFO) films on Si substrate is desirable from an application point of view. The growth of (110)-textured BFO thin films with high quality on Si(100) substrate was realized by a seeding technique via a simple sol-gel method. Obviously switchable ferroelectric domains were observed, and in the meantime, the BFO films also exhibited a weak magnetization which somewhat showed dependence on the film thickness. Such an integration of the BFO films on Si constructed a metal/ferroelectric/insulator/semiconductor structure, which presented a memory feature as evidenced by capacitance-voltage hysteresis.     

Ba0.6Sr0.4TiO3薄膜的微结构及铁电性能研究

采用射频磁控溅射法制备了Ba0.6Sr0.4TiO3(简称BST)薄膜材料,研究了BST薄膜的组成、晶体结构、表面形貌及介电性能.介电偏压特性曲线和电滞回线都表明其具有铁电性,厚度为500 nm、晶粒尺寸为30 nm的BST薄膜,介电系数电压变化率(介电调谐率)为29.4%,矫顽场强(EC)约为12.1 kV/cm,并讨论了介电偏压特性曲线和电滞回线之间的联系,解释了电滞回线不对称的原因.     

Interfacial reaction and electrical properties of HfO2 film gate dielectric prepared by pulsed laser deposition in nitrogen: role of rapid thermal annealing and gate electrode

The high-k dielectric HfO(2) thin films were deposited by pulsed laser deposition in nitrogen atmosphere. Rapid thermal annealing effect on film surface roughness, structure and electrical properties of HfO(2) film was investigated. The mechanism of interfacial reaction and the annealing atmosphere effect on the interfacial layer thickness were discussed. The sample annealed in nitrogen shows an amorphous dominated structure and the lowest leakage current density. Capacitors with high-k HfO(2) film as gate dielectric were fabricated, using Pt, Au, and Ti as the top gate electrode whereas Pt constitutes the bottom side electrode. At the gate injection case, the Pt- and Au-gated metal oxide semiconductor devices present a lower leakage current than that of the Ti-gated device, as well as similar leakage current conduction mechanism and interfacial properties at the metal/HfO(2) interface, because of their close work function and chemical properties.     

Electrical properties of AlNx/Al/Mo composite film prepared for use in thin-film transistors

In the present study, AlN_x/Al/Mo composite films with various thicknesses of AlN_x and Al layers were prepared to replace commercial AlNd/Mo composite film as the gate metal of the two metal layers (namely the gate metal and the source-drain metal) in thin-film transistor (TFT) specimens. The prerequisite for the TFT device is that no hillock is formed. The electrical properties of the AlN_x/Al/Mo TFT device rival those of the AlNd/Mo TFT device. One of eight kinds of AlN_x/Al/Mo composite films (0.05 µm/0.2 µm/0.07 µm) without hillocks was compared with the AlNd/Mo (0.25 µm/0.07 µm) composite film. The line width after development and strip inspections, the I_g (gate leakage current)-V_g (gate voltage) curve, the coating film resistance to electricity, the contact resistance between the indium tin oxide (ITO) film and the metal film, the I_d-V_g curve, and the critical dimension loss (CD loss) were compared. The experimental results indicate that the metal line widths for these two composite films are similar. The coating film resistance, the contact resistance between the ITO film and the metal film, and the I_d-V_g curve for the AlN_x/Al/Mo TFT device were similar to those for the AlNd/Mo TFT device. The CD loss shown in the AlN_x/Al/Mo TFT device was lower than that for the AlNd/Mo TFT device.     

Preparation and Characterization of the Ferroelectric Potassium Nitrate: Poly(vinyl alcohol) Composite Films

The composite films of ferroelectric potassium nitrate (KNO₃):poly(vinyl alcohol) (PVA) with different weight percentages of KNO₃ have been prepared at 200°C using the spray-deposition technique. The remanent polarization (P_r) and peak current density for all composite films was estimated by tracing the polarization-electric field (P-E) hysteresis loop and current density-electric field (J-E) loop, respectively, using a modified Sawyer-Tower circuit. Pure KNO₃ is known not to exhibit any ferroelectricity under ambient conditions, but the X-ray diffraction (XRD) studies of PVA:KNO₃ composite films reveal the presence of a ferroelectric phase III of KNO₃ in the composite films at room temperature. The composite film containing KNO₃:PVA in equal proportions shows maximum Pr and peak intensity ratio of approximately 20.10 μC/ cm² and 2.67, respectively, at room temperature. The J-E and capacitance voltage (C-V) characteristics exhibit butterfly features that supports the presence of a ferroelectric phase in the composite films. The field emission scanning electron microscopy (FE-SEM) image of the composite film containing equal proportions of KNO₃ and PVA shows the homogenous distribution of spherical grains of KNO3 of size ~225 nm.     

Ag/Bi4Ti3O12/p-Si异质结的制备及其C-V特性研究

为制备符合铁电存储器件要求的高质量铁电薄膜,采用溶胶-凝胶(Sol-Gel)工艺,制备了Si基Bi4Ti3O12铁电薄膜及MFS结构的Ag/Bi4Ti3O12/P-Si异质结,对Bi4Ti3O12薄膜的相结构特征及异质结的C-V特性进行了测试与分析.XRD图谱显示,Si基Bi4Ti3O12薄膜具有沿c-轴择优取向生长的趋势,而Ag/Bi4Ti3O12/p-Si异质结顺时针回滞的C-V特性曲线则表明,该异质结可实现电极化存储.此外,对该异质结C-V特性曲线的非对称及向负偏压方向偏移的产生原因也进行了分析.在此基础上,为提高铁电薄膜的铁电性能及改善其C-V特性提出了合理的结构设想.     

铅过量PLZT铁电薄膜的制备及其电学性质研究

采用Sol Gel法 ,在Pt TiO2 Si基片上制备了具有不同铅过量 (0— 2 0mol% )的PLZT铁电薄膜。分析了薄膜的晶相结构 ,研究了铅过量对PLZT铁电薄膜的介电性能和铁电性能的影响。结果表明 ,各薄膜均具有钙钛矿型结构 ,且各薄膜均呈 (110 )择优取向。PLZT铁电薄膜的介电性能和铁电性能随铅过量的变化而改变。铅过量为 10mol%的薄膜具有最佳的的介电性能和铁电性能。     

Morphology controlled fabrication and ferroelectric properties of vertically aligned one-dimensional lead titanate nanoarrays

Vertically aligned nanowires and highly uniform nanoporous array thin films of PbTiO(3) are synthesized by varying anodic oxidation conditions of Ti foil followed by hydrothermal reaction in an aqueous Pb(II) acetate trihydrate solution. As-synthesized samples have single crystalline nanowire structure and polycrystalline nanoporous structure, although both are pure PbTiO(3) with a tetragonal phase. The structure of intermediate TiO(2) films obtained from different anodic oxidation conditions determines the structure of the product PbTiO(3). The relationships between these morphological structures and ferroelectric properties are investigated. Piezoresponse force microscopy reveals that both these films show ferroelectricity with clear phase contrast and well-defined hysteresis loops. The saturated longitudinal piezoelectric coefficient field (E(c)) of the nanowire sample is smaller than that of nanoporous thin film. Thus, polarization of nanowire thin film is larger in magnitude and easier to flip than that of nanoporous film.     

Fabrication and characterization of direct patterning ferroelectric Sr0.9Bi2.1Ta2O9 thin films by photosensitive sol–gel solution

Photosensitive ferroelectric Sr_0.9Bi_2.1Ta₂O₉ (SBT) precursor solutions were synthesized using strontium ethoxide chelated with ethylacetoacetone, tetramethylheptanedionato bismuth and tantalum ethoxide chelated with ethylacetoacetone. SBT thin films with 200 nm thickness were prepared on Pt/TiO₂/SiO₂/Si substrates using the spin coating method. As UV light exposure time to the SBT thin film increased, the intensity of the UV absorption peak of the metal β-diketonate decreased due to metal–oxygen–metal bond formation, which led to decreased solubility of SBT thin film. The solubility difference enabled direct patterning of thin films that had ferroelectric properties. The ferroelectric properties of the UV irradiated SBT thin films were superior to those of the non-UV irradiated films. Pr/Ps and 2 Pr values (at 3 V) of SBT thin films improved approximately 8% and 5%, respectively, with UV irradiation.     

Comprehensive characterization of PVDF-TrFE thin films for microelectromechanical system applications

This paper presents a comprehensive characterization of a polyvinylidene fluoride-trifluoroethylene (PVDF-TrFE) thin film with 75/25 molar ratio for piezoelectric MEMS applications. PVDF-TrFE film was deposited on a silicon substrate using spin coating, and electrodes were formed using sputtering. Dielectric constant and dielectric loss factor were measured at different frequencies. Frequency and temperature dependence of the ferroelectric response was examined to investigate required poling conditions and maximum operating temperature. The lower limit for the coercive field was measured as 55 V/μm at room temperature. Coercive field decreased with temperature with a slope of ?0.1 V/μm K, and ferroelectric to paraelectric transition occurred between 100? and 108?°C. Piezoelectric displacement measurements were performed using an atomic force microscope based method. Average value of the effective piezoelectric d₃₃ coefficient was measured as ?23.9 pm/V. No degradation was observed in this value after 2?×?10⁵ unipolar excitation cycles. On the other hand, significant fatigue was observed in the piezoelectric response due to polarization switching; 1.8?×?10⁵ cycles caused an average reduction of 33% in the effective d₃₃. Presented data corroborates with the previous studies in the literature and can be used in the design of PVDF-TrFE based MEMS devices utilizing its dielectric, ferroelectric, and piezoelectric properties.     

Epitaxially Grown Ferroelectric PVDF‐TrFE Film on Shape‐Tailored Semiconducting Rubrene Single Crystal

Epitaxial crystallization of thin poly(vinylidene fluoride‐co‐trifluoroethylene) (PVDF‐TrFE) films is important for the full utilization of their ferroelectric properties. Epitaxy can offer a route for maximizing the degree of crystallinity with the effective orientation of the crystals with respect to the electric field. Despite various approaches for the epitaxial control of the crystalline structure of PVDF‐TrFE, its epitaxy on a semiconductor is yet to be accomplished. Herein, the epitaxial growth of PVDF‐TrFE crystals on a single‐crystalline organic semiconductor rubrene grown via physical vapor deposition is presented. The epitaxy results in polymer crystals globally ordered with specific crystal orientations dictated by the epitaxial relation between the polymer and rubrene crystal. The lattice matching between the c‐axis of PVDF‐TrFE crystals and the (210) plane of orthorhombic rubrene crystals develops two degenerate crystal orientations of the PVDF‐TrFE crystalline lamellae aligned nearly perpendicular to each other. Thin PVDF‐TrFE films with epitaxially grown crystals are incorporated into metal/ferroelectric polymer/metal and metal/ferroelectric polymer/semiconductor/metal capacitors, which exhibit excellent nonvolatile polarization and capacitance behavior, respectively. Furthermore, combined with a printing technique for micropatterning rubrene single crystals, the epitaxy of a PVDF‐TrFE film is formed selectively on the patterned rubrene with characteristic epitaxial crystal orientation over a large area.     

Effect of compositional variations on electrical properties in phase switching (Pb,La)(Zr,Ti,Sn)O3 thin and thick films

The composition-dependent electrical properties in (Pb,La)(Zr,Ti,Sn)O₃ antiferroelectric-ferroelectric phase switching thin and thick films have been systematically studied and compared with bulk ceramics. The films were deposited on Pt-buffered silicon substrates by a sol-gel method. The results show that the dependence of low-field dielectric properties on compositions in the films is similar to that in bulk ceramics but the variation of high field properties (polarization or hysteresis loops) is quite different, which may be attributed to the special mechanical boundary condition of the films. While all the films with compositions in the antiferroelectric tetragonal region in the phase diagram demonstrate the existence of remanent polarization in the hysteresis loops, the films with zero remanent polarization can be obtained in the antiferroelectric orthorhombic region. This is because the films are under high tensile stress due to the thermal mismatch between the film and substrate, which tends to stabilize the ferroelectric phase and causes the retention of ferroelectric phase for the films in the antiferroelectric tetragonal region because of their relatively small free energy difference between the antiferroelectric phase and ferroelectric phase.     

Thickness dependence of ferroelectricity in Langmuir-Blodgett multilayer films of hemicyanine dyes

The thickness dependence of ferroelectricity in hemicyanine Langmuir-Boldgett multilayer films was reported in this paper. By the observed ferroelectric hysteresis loop, it was found that the coercive field decreased with increasing of film thickness monotonously and may be approximated by a power law Ec infinity N(-4/3) in the range from 30 to 200 nm, which is consistent with other conventional ferroelectric materials. The measurement of dielectric properties give the optimum thickness about 60 nm of hemicyanine LB films and their optimum value as ferroelectric storage-devices has the same order of magnitude as copolymer's P(VDF-TrFE) (70:30 mol%).     

Dependence of ferroelectric and magnetic properties on measuring temperatures for polycrystalline BiFeO(3) films

A multiferroic BiFeO(3) film was fabricated on a Pt/Ti/SiO(3)/Si(100) substrate by a chemical solution deposition (CSD) method, and this was followed by postdeposition annealing at 923 K for 10 min in air. X-ray diffraction analysis indicated the formation of the polycrystalline single phase of the BiFeO(3) film. A high remanent polarization of 89 microC/cm(2) was observed at 90 K together with a relatively low electric coercive field of 0.32 MV/cm, although the ferroelectric hysteresis loops could not be observed at room temperature due to a high leakage current density. The temperature dependence of the ferroelectric hysteresis loops indicated that these hysteresis loops lose their shape above 165 K, and the nominal remanent polarization drastically increased due to the leakage current. Magnetic measurements indicated that the saturation magnetization was less than 1 emu/cm(3) at room temperature and increased to approximately 2 emu/cm(3) at 100 K, although the spontaneous magnetization could not appear. The magnetization curves of polycrystalline BiFeO3 film were nonlinear at both temperatures, which is different with BiFeO3 single crystal.     

The domain switching and structural characteristics of PLZT bulk ceramics and thin films chemically prepared from the same acetate precursor solutions

Lead lanthanum zirconate titanate (PLZT) ferroelectrics were produced in bulk ceramic and thin-film form from the same acetate precursor solutions in order to compare their electrical and physical properties. Bulk ceramics were hot pressed from chemically coprecipitated powders, and thin films were fabricated by spin coating on silver foil and platinum-coated silicon wafer substrates. A number of PLZT compositions were investigated, including ferroelectric memory materials near the morphotropic phase boundary with 2% La, memory and slim-loop ferroelectric x/65/35 (La/Zr/Ti) compositions with up to 12% La, as well as some antiferroelectric thin-film materials. Internal film stress from thermal expansion mismatch between films and substrates was found to contribute to differences in electrical properties and Curie temperatures between the thin film and bulk materials, as were interface layers between the films and substrates, mechanical clamping from the substrates and grain size.