Nanointerfacial Layer Effect on Dielectric and Piezoelectric Responses in Chemical Solution-Derived Lead-Free Alkaline Niobate-Based Thin Films.

Since nonpiezoelectric interfacial layers even at the nanoscale significantly affect the performance of lead-free piezoelectric thin films, the quantitative characterization of property changes of thin films due to interfacial layers is of great importance and should be precisely undertaken for piezoelectric microelectromechanical system (MEMS) and nanoelectromechanical system (NEMS) devices. In contrast to widely accepted concepts for interfacial layer thickness estimation based on the existing series capacitor model, we find that the interfacial layer thickness at the top and the bottom interfaces is clearly different in chemical solution deposition (CSD)-derived (K0.5,Na0.5)(Mn0.005,Nb0.995)O3 (KNMN) thin films. Interestingly, the thickness of the bottom interface increases linearly with increasing thin-film thickness, while the thickness of the top interface is constant regardless of the thin-film thickness. In this work, nanointerfacial layer effects of CSD-derived KNMN thin films are theoretically and experimentally addressed in a combinatorial way using a modified series capacitor model. The obtained information is used to envisage the origins and the mechanisms of nonpiezoelectric interfacial layers and associated dielectric and ferroelectric properties of KNMN thin films. Our research connects macroscopic properties with microscopic origins and is greatly facilitated by separating intrinsic and extrinsic contributions to phenomenological behaviors, as well as engineering interface-related properties of the films. We believe these studies to be crucial for the further development and applications of KNN-based lead-free piezoelectric devices, which also open the door to future studies on other lead-free piezoelectric material systems for practical MEMS and NEMS applications.

Progress in lead-free piezoelectric nanofiller materials and related composite nanogenerator devices.

Current piezoelectric device systems need a significant reduction in size and weight so that electronic modules of increasing capacity and functionality can be incorporated into a great range of applications, particularly in energy device platforms. The key question for most applications is whether they can compete in the race of down-scaling and an easy integration with highly adaptable properties into various system technologies such as nano-electro-mechanical systems (NEMS). Piezoelectric NEMS have potential to offer access to a parameter space for sensing, actuating, and powering, which is inflential and intriguing. Fortunately, recent advances in modelling, synthesis, and characterization techniques are spurring unprecedented developments in a new field of piezoelectric nano-materials and devices. While the need for looking more closely at the piezoelectric nano-materials is driven by the relentless drive of miniaturization, there is an additional motivation: the piezoelectric materials, which are showing the largest electromechanical responses, are currently toxic lead (Pb)-based perovskite materials (such as the ubiquitous Pb(Zr,Ti)O3, PZT). This is important, as there is strong legislative and moral push to remove toxic lead compounds from commercial products. By far, the lack of viable alternatives has led to continuing exemptions to allow their temporary use in piezoelectric applications. However, the present exemption will expire soon, and the concurrent improvement of lead-free piezoelectric materials has led to the possibility that no new exemption will be granted. In this paper, the universal approaches and recent progresses in the field of lead-free piezoelectric nano-materials, initially focusing on hybrid composite materials as well as individual nanoparticles, and related energy harvesting devices are systematically elaborated. The paper begins with a short introduction to the properties of interest in various piezoelectric nanomaterials and a brief description of the current state-of-the-art for lead-free piezoelectric nanostructured materials. We then describe several key methodologies for the synthesis of nanostructure materials including nanoparticles, followed by the discussion on the critical current and emerging applications in detail.

Lead-Free Perovskite Nanowire-Employed Piezopolymer for Highly Efficient Flexible Nanocomposite Energy Harvester.

In the past two decades, mechanical energy harvesting technologies have been developed in various ways to support or power small-scale electronics. Nevertheless, the strategy for enhancing current and charge performance of flexible piezoelectric energy harvesters using a simple and cost-effective process is still a challenging issue. Herein, a 1D-3D (1-3) fully piezoelectric nanocomposite is developed using perovskite BaTiO3 (BT) nanowire (NW)-employed poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) for a high-performance hybrid nanocomposite generator (hNCG) device. The harvested output of the flexible hNCG reaches up to ≈14 V and ≈4 µA, which is higher than the current levels of even previous piezoceramic film-based flexible energy harvesters. Finite element analysis method simulations study that the outstanding performance of hNCG devices attributes to not only the piezoelectric synergy of well-controlled BT NWs and within P(VDF-TrFE) matrix, but also the effective stress transferability of piezopolymer. As a proof of concept, the flexible hNCG is directly attached to a hand to scavenge energy using a human motion in various biomechanical frequencies for self-powered wearable patch device applications. This research can pave the way for a new approach to high-performance wearable and biocompatible self-sufficient electronics.

Flexible Pb(Zr0.52Ti0.48)O3 Films for a Hybrid Piezoelectric-Pyroelectric Nanogenerator under Harsh Environments.

In spite of extremely high piezoelectric and pyroelectric coefficients, there are few reports on flexible ferroelectric perovskite film based nanogenerators (NGs). Here, we report the successful growth of a flexible Pb(Zr0.52Ti0.48)O3 (PZT) film and its application to hybrid piezoelectric-pyroelectric NG. A highly flexible Ni-Cr metal foil substrate with a conductive LaNiO3 bottom electrode enables the growth of flexible PZT film having high piezoelectric (140 pC/N) and pyroelectric (50 nC/cm(2)K) coefficients at room temperature. The flexible PZT-based NG effectively scavenges mechanical vibration and thermal fluctuation from sources ranging from the human body to the surroundings such as wind. Furthermore, it stably generates electric current even at elevated temperatures of 100 °C, relative humidity of 70%, and pH of 13 by virtue of its high Curie temperature and strong resistance for water and base. As proof of power generation under harsh environments, we demonstrate the generation of extremely high current at the exhaust pipe of a car, where hot CO and CO2 gases are rapidly expelled to air. This work expands the application of flexible PZT film-based NG for the scavenging mechanical vibration and thermal fluctuation energies even at extreme conditions.

Unveiling the Role of CNTs in the Phase Formation of One-Dimensional Ferroelectrics.

Carbon nanotubes (CNTs) have the potential to act as templates or bottom electrodes for three-dimensional (3D) capacitor arrays, which utilize one-dimensional (1D) ferroelectric nanostructures to increase the memory size and density. However, growing a ferroelectric on the surface of CNTs is nontrivial. Here, we demonstrate that multiwalled (MW) CNTs decrease the time and temperature for the formation of lead zirconium titanate Pb(Zr1-xTix)O3 (PZT) by ∼100 °C commensurate with a decrease in activation energy from 68 ± 15 to 27 ± 2 kJ/mol. As a consequence, monophasic PZT was obtained at 575 °C for MWCNTs/PZT, but for pure PZT, traces of pyrochlore were still present at 650 °C, where the PZT phase formed due to homogeneous nucleation. The piezoelectric nature of MWCNTs/PZT synthesized at 500 °C for 1 h was proven. Although further work is required to prove the concept of 3D capacitor arrays, our result suggests that it is feasible to utilize MWCNTs as templates/electrodes for the formation of 1D PZT nanoferroelectrics.

Electrophoretic deposition on nonconducting substrates: a demonstration of the application to microwave devices.

Through the use of a sacrificial carbon layer, this work reports a method of performing electrophoretic deposition (EPD) of thick films on fully nonconducting substrates, overcoming the restricting requirement for EPD of a conducting or partially conducting substrate. As a proof of concept, the method was applied to the development of microwave-thick films on insulating alumina substrates. The key parameter to be controlled is the thickness of the sacrificial carbon layer; this is expected to be a general result for the application of the processing method. The method allows direct patterning of the structure and leads to the potential use of EPD in a far wider range of electronic applications (multilayer ceramic capacitors (MLCCs), low-temperature cofired ceramics (LTTCs), and biotech devices). Furthermore, in conjunction with work reported elsewhere, the development of specific BaNd2Ti5O14 (BNT) thick-film microwave dielectrics opens up a technology platform for a range of high-quality factor (Q) devices. More specifically, 100-µm-thick BNT layers were achieved with a dielectric constant of 149 and Q of 1161 (10 GHz). These materials can now be integrated with tunable dielectrics or dielectrics on metal substrates to provide a platform for devices in the front end of communication systems and cellular base stations.

Activated solutions enabling low-temperature processing of functional ferroelectric oxides for flexible electronics.

Functional ferroelectric oxides for flexible electronics are achieved from activated solutions enabling low-temperature processing and large-area deposition directly on polymeric substrates. This processing technology reaches the lower limit temperature of crystallization at 300 °C, using a strategy that combines seeded diphasic precursors and photochemical solution deposition. Properties of these materials are comparable to those of high-temperature-processed counterparts and organic ferroelectrics.

Impact of Joule heating, roughness, and contaminants on the relative hardness of polycrystalline gold.

Asperities play a central role in the mechanical and electrical properties of contacting surfaces. Changes in trends of uniaxial compression of an asperity tip in contact with a polycrystalline substrate as a function of substrate geometry, compressive stress and applied voltage are investigated here by implementation of a coupled continuum and atomistic approach. Surprisingly, an unmodified Au polycrystalline substrate is found to be softer than one containing a void for conditions of high stress and an applied voltage of 0.2 V. This is explained in terms of the temperature distribution and weakening of Au as a function of temperature. The findings in this communication are important to the design of materials for electrical contacts because applied conditions may play a role in reversing relative hardness of the materials for conditions experienced during operation.

Critical role of suspension media in electrophoretic deposition: the example of low loss dielectric BaNd2Ti5O14 thick films.

The importance of electrophoretic deposition (EPD) is well recognized for thick film technology, but unfortunately there is no universal suspension medium for the EPD of oxides. Thus, the selection of the medium, the stability of the suspensions, and the control of the particle potentials, critical for a good deposition, need to be established for each new material being processed by EPD. In this article, we investigate the key parameters, studying the electrochemistry of BaNd(2)Ti(5)O(14) (BNT) suspensions, and establish relationships between suspension media, EPD process conditions, microstructure of the deposits, and resulting electrical properties of the BNT films. Suspension stability of water, ethanol, acetic acid, and acetone-based media was analyzed in terms of zeta potential, particle size distribution, UV transmittance, and inductively coupled plasma spectrometry. The highest absolute zeta potential values determined for acetone with I(2) and acetic acid media are in good agreement with the high stability, small and narrow particle size distribution, and low UV light transmittance measured for these suspensions. Very high quality thick deposits were consequently achieved. However, it was demonstrated that aging of the acetic acid-based suspension have serious negative effects on the EPD process for BNT materials, including leaching of the metallic elements with a consequent modification of the material stoichiometry, change of the conductivity of the suspension, and degradation of the films microstructure. These facts severely restrict the use of acetic acid. Our results clearly indicate that, besides the stability of the suspension, the electrochemistry and aging behavior are key aspects for the EPD of functional oxides. Our systematic approach could be viewed as providing a set of guidelines for the development of EPD of other oxides.

Scaling issues in ferroelectric barium strontium titanate tunable planar capacitors.

We report on the geometric limits associated with tunability of interdigitated capacitors, specifically regarding the impact of a parasitic non-tunable component that necessarily accompanies a ferroelectric surface capacitor, and can dominate the voltage-dependent response as capacitor dimensions are reduced to achieve the small capacitance values required for impedance matching in the X band. We present a case study of simple gap capacitors prepared and characterized as a function of gap width (i.e., the distance between electrodes) and gap length (i.e., the edge-to-edge gap distance). Our series of measurements reveals that for gap widths in the micrometer range, as gap lengths are reduced to meet sub-picofarad capacitance values, the non-tunable parasitic elements limit the effective tunability. These experimental measurements are supported by a companion set of microwave models that clarify the existence of parallel parasitic elements.

The impact of metallization thickness and geometry for X-band tunable microwave filters.

The impact of dc resistance on the performance of X-band filters with ferroelectric varactors was investigated. Two series of combline bandpass filters with specific geometries to isolate sources of conductor losses were designed and synthesized. Combining the changes in filter geometry with microwave measurements and planar filter solver (Sonnet software) simulations quantitatively identified the dependency of insertion loss on overall metallization thickness and local regions of thin metallization. The optimized 8-GHz bandpass filters exhibited insertion losses of 6.8 dB. These filters required 2.5 microm of metal thickness (or 3 effective skin depths) to achieve this loss. The trend of loss with thickness indicates diminishing return with additional metal. The integration scheme requires thin regions of metal in the immediate vicinity of the varactors. It is shown through experiment and simulation that short distances (i.e., 15 microm) of thin metallization can be tolerated provided that they are located in regions where the resonant microwave current is low.

Multiscale analysis of liquid lubrication trends from industrial machines to micro-electrical-mechanical systems.

An analytic multiscale expression is derived that yields conditions for effective liquid lubrication of oscillating contacts via surface flow over multiple time and length scales. The expression is a logistics function that depends on two quantities, the fraction of lubricant removed at each contact and a scaling parameter given by the logarithm of the ratio of the contact area to the product of the lubricant diffusion coefficient and the cycle time. For industrial machines the expression confirms the need for an oil mist. For magnetic disk drives, the expression predicts that existing lubricants are sufficient for next-generation data storage. For micro-electrical-mechanical systems, the expression predicts that a bound + mobile lubricant composed of tricresyl phosphate on an octadecyltrichlorosilane self-assembled monolayer will be effective only for temperatures greater than approximately 200 K and up to approximately MHz oscillation frequencies.