Nanomechanical characterization of soft bioelectronic interfaces via modeling-informed atomic force microscopy

The field of bioelectronics involves the use of electrodes to exchange electrical signals with biological systems for diagnostic and therapeutic purposes in biomedical devices and healthcare applications. However, the mechanical compatibility of implantable devices with the human body has been a challenge, particularly with long-term implantation into target organs. Current rigid bioelectronics can trigger inflammatory responses and cause unstable device functions due to the mechanical mismatch with the surrounding soft tissue. Recent advances in flexible and stretchable electronics have shown promise in making bioelectronic interfaces more biocompatible. To fully achieve this goal, material science and engineering of soft electronic devices must be combined with quantitative characterization and modeling tools to understand the mechanical issues at the interface between electronic technology and biological tissue. Local mechanical characterization is crucial to understand the activation of failure mechanisms and optimizing the devices. Experimental techniques for testing mechanical properties at the nanoscale are emerging, and the Atomic Force Microscope (AFM) is a good candidate for in situ local mechanical characterization of soft bioelectronic interfaces. In this work, in situ experimental techniques with solely AFM supported by interpretive models for the characterization of planar and three-dimensional devices suitable for in vivo and in vitro biomedical experimentations are reported. The combination of the proposed models and experimental techniques provides access to the local mechanical properties of soft bioelectronic interfaces. The study investigates the nanomechanics of hard thin gold films on soft polymeric substrates (Poly(dimethylsiloxane) PDMS) and 3D inkjet-printed micropillars under different deformation states. The proposed characterization methods provide a rapid and precise determination of mechanical properties, thus giving the possibility to parametrize the microfabrication steps and investigate their impact on the final device.

Determination of local density of states in amorphous oxide semiconductors with Kelvin Probe Force Microscopy

Amorphous semiconductors are important materials as they can be deposited by physical deposition techniques on large areas and even on plastic substrates. Therefore, they are crucial for transistors in large active matrices for imaging and transparent wearable electronics. The most widely applied candidate for amorphous thin film transistors production is Indium Gallium Zinc Oxide (IGZO). It is attracting much interest because of its optical transparency, facile processing by sputtering deposition and notable improved charge carrier mobility with respect to hydrogenated amorphous silicon a-Si:H. Degradation of the device and long-term performance issues have been observed if IGZO thin film transistors are subjected to electrical stress, leading to a modification of IGZO channel properties and subthreshold slope. Therefore, it is of great interest to have a reliable and precise method to study the conduction band tail, and the density of states in amorphous semiconductors. The aim of this thesis is to develop a local technique using Kelvin Probe Force Microscopy to study the evolution of IGZO DOS properties. The work is divided into three main parts. First, solutions to the non-linear Poisson-Boltzmann equation of a metal-insulator-semiconductor junction describing the charge accumulation and its relation to DOS properties are elaborated. Second macroscopic techniques such as capacitance voltage (CV) measurements and photocurrent spectroscopy are applied to obtain a non-local estimate of band-tail DOS properties in thin film transistor samples. The third part of my my thesis is dedicated to the KPFM measurements. By fitting the data to the developed numerical model, important parameters describing the amorphous conduction band tail are obtained. The results are in excellent agreement with the macroscopic characterizations. KPFM result is comparable also with non-local optoelectronic characterizations, such as photocurrent spectroscopy.

Local piezoelectric response of single poly(vinylidene fluoride) electrospun fibers

It is shown that electrospun poly(vynilidene fluoride) nanofibers are fully poled right after preparation and show b-phase contents of 70%, therefore being able to be implemented into electroactive devices without further processing steps. Further,the local piezoelectric properties of individual electrospun fibers have been studied by piezoresponse force microscopy. Piezoelectric response, polarization switching, and nanoscale patterning of the fibers have been demonstrated.

The self-polarization effect in Pb(Zr0.50Ti0.50)O-3 thin films with no preferential orientation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Nanoscale electromechanical properties of CaCu3Ti4O12 ceramics

Piezoresponse Force Microscopy (PFM) is used to characterize the nanoscale electromechanical properties of centrosymmetric CaCu3Ti4O12 ceramics with giant dielectric constant. Clear PFM contrast both in vertical (out-of-plane) and lateral (in-plane) modes is observed on the ceramic surface with varying magnitude and polarization direction depending on the grain crystalline orientation. Lateral signal changes its sign upon 180 degrees rotation of the sample thus ruling out spurious electrostatic contribution and confirming piezoelectric nature of the effect. Piezoresponse could be locally reversed by suitable electrical bias (local poling) and induced polarization was quite stable showing long-time relaxation (similar to 3 hrs). The electromechanical contrast in unpoled ceramics is attributed to the surface flexoelectric effect (strain gradient induced polarization) while piezoresponse hysteresis and ferroelectric-like behavior are discussed in terms of structural instabilities due to Ti off-center displacements and structural defects in this material. (C) 2011 American Institute of Physics. [doi:10.1063/1.3623767]

Electromechanical properties of calcium bismuth titanate films: A potential candidate for lead-free thin-film piezoelectrics

CaBi4Ti4O15 (CBTi144) thin films were evaluated for use as lead-free thin-film piezoelectrics in microelectromechanical systems. The films were grown by the polymeric precursor method on (100)Pt/Ti/SiO2/Si substrates. The a/b-axis orientation of the ferroelectric film is considered to be associated with the preferred orientation of the Pt bottom electrode. The P-r and E-c were 14 mu C/cm(2) and 64 kV/cm, respectively, for a maximum applied field of 400 kV/cm. The domain structure was investigated by piezoresponse force microscopy. The film has a piezoelectric coefficient, d(33), equal to 60 pm/V and a current density of 0.7 mA/cm(2).

Ferroelectric and piezoelectric properties of bismuth titanate thin films grown on different bottom electrodes by soft chemical solution and microwave annealing

Bismuth titanate (Bi4Ti3O12, BIT) films were evaluated for use as lead-free piezoelectric thin films in micro-electromechanical systems. The films were grown by the polymeric precursor method on LaNiO3/SiO2/Si (1 0 0) (LNO), RuO2/SiO2/Si (1 0 0) (RuO2) and Pt/Ti/SiO2/Si (1 0 0) (Pt) bottom electrodes in a microwave furnace at 700 degrees C for 10 min. The domain structure was investigated by piezoresponse force microscopy (PFM). Although the converse piezoelectric coefficient, d(33), regardless of bottom electrode is around (similar to 40 pm/V), those over RuO2 and LNO exhibit better ferroelectric properties, higher remanent polarization (15 and 10 mu C/cm(2)), lower drive voltages (2.6 and 1.3 V) and are fatigue-free. The experimental results demonstrated that the combination of the polymeric precursor method assisted with a microwave furnace is a promising technique to obtain films with good qualities for applications in ferroelectric and piezoelectric devices. (c) 2006 Elsevier Ltd. All rights reserved.

Piezoelectric properties of Bi4Ti3O12 thin films annealed in different atmospheres

Bismuth titanate (Bi4Ti3O12-BIT) films were evaluated for use as lead-free piezoelectric thin-films in micro-electromechanical systems. The films were grown by the polymeric precursor method on Pt/Ti/SiO2/Si (1 0 0) (Pt) bottom electrodes at 700 degrees C for 2 h in static air and oxygen atmospheres. The domain structure was investigated by piezoresponse force microscopy (PFM). Annealing in static air leads to better ferroelectric properties, higher remanent polarization, lower drive voltages and higher piezoelectric coefficient. on the other hand, oxygen atmosphere favors the imprint phenomenon and reduces the piezoelectric coefficient dramatically. Impedance data, represented by means of Nyquist diagrams, show a dramatic increase in the resistivity for the films annealed in static air atmopshere. (c) 2006 Elsevier Ltd. All rights reserved.

Structure, microstructure, ferroelectric/electromechanical properties and retention characteristics of [Bi1-x Nb (x) ]FeO3 thin films

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Structure, ferroelectric/magnetoelectric properties and leakage current density of (Bi0.85Nd0.15)FeO3 thin films

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Rietveld analyses and piezoelectric properties of niobium doped bismuth titanate systems

Bi 4Ti 3- xNbxO 12 (BITNb) samples, with × ranging from 0 to 0.40 were obtained using a polymeric precursor solution. Rietveld analyses confirmed that the powders crystallize in an orthorhombic structure free of secondary phases with space group Fmmm. Raman analysis evidenced a sharp increase in the bands intensity located at 129 cm -1 and 190 cm -1 due the lattice distortion in BIT02Nb and BIT04Nb compositions. UV-vis spectra indicated that addition of niobium causes a reduction of defects in the BIT lattice due the suppression of oxygen vacancies located at BO-6 octahedral. Size and morphology of particles as well as electrical behavior of BIT ceramics were affected by addition of donor dopant. Polarization reversal was investigated by applying dc voltage through a conductive tip during the area scanning and was investigated by piezoresponse force microscopy (PFM). PFM measurements revealed a decrease in piezoelectric response with increasing Nb concentration originating from a reduced polarizability along the a-axis. High spontaneous polarization is noted for the less doped sample due the reduction of strain energy and pin charged defects after niobium addition. Copyright © 2010 American Scientific Publishers.

Polymer Matrix-Based Piezoelectric Composite for Structural Health Monitoring

Structural health monitoring (SHM) refers to the procedure of assessing the structure conditions continuously so it is an alternative to conventional nondestructive evaluation (NDE) techniques [1]. With the growing developments in sensor technology acoustic emission (AE) technology has been attracting attention in SHM applications. AE are characterized by waves produced by the sudden internal stress redistribution caused by the changes in the internal structure, such as fatigue, crack growth, corrosion, etc. Piezoelectric materials such as Lead Zirconate Titanate (PZT) ceramic have been widely used as sensor due to its high electromechanical coupling factor and piezoelectric d coefficients. Because of the poor mechanical characteristic and the lack in the formability of the ceramic, polymer matrix-based piezoelectric composites have been studied in the last decade in order to obtain better properties in comparison with a single phase material. In this study a composite film made of polyurethane (PU) and PZT ceramic particles partially recovered with polyaniline (PAni) was characterized and used as sensor for AE detection. Preliminary results indicate that the presence of a semiconductor polymer (PAni) recovering the ceramic particles, make the poling process easier and less time consuming. Also, it is possible to observe that there is a great potential to use such type of composite as sensor for structure health monitoring.

Measurement of Radiant Energy using Pyroelectric Polymer/Ceramic Composite

Monitoring non-ionizing radiant energy is increasingly demanded for many applications such as automobile, biomedical and security system. Thermal type infrared (IR) sensors can operate at room temperature and pyroelectric materials have high sensitivity and accuracy for that application. Working as thermal transducer pyroelectric sensor converts the non-quantified thermal flux into the output measurable quantity of electrical charge, voltage or current. In the present study the composite made of poly(vinylidene fluoride) -PVDF and lead zirconate titanate (PZT) partially recovered with polyaniline (PAni) conductor polymer has been used as sensor element. The pyroelectric coefficient p(T) was obtained by measuring the pyroelectric reversible current, i.e., measuring the thermally stimulated depolarization current (TSDC) after removing all irreversible contribution to the current such as injected charge during polarization of the sample. To analyze the sensing property of the pyroelectric material, the sensor is irradiated by a high power light source (halogen lamp of 250 W) that is chopped providing a modulated radiation. A device assembled in the laboratory is used to change the light intensity sensor, an aluminum strip having openings with diameters ranging from 1 to 10 mm incremented by one millimeter. The sensor element is assembled between two electrodes while its frontal surface is painted black ink to maximize the light absorption. The signal from the sensor is measured by a Lock-In amplifier model SR530 -Stanford Research Systems. The behavior of the output voltage for an input power at several frequencies for PZT-PAni/PVDF (30/ 70 vol%) composite follows the inverse power law (1/ f) and the linearity can be observed in the frequency range used.

Fabrication and Characterization of PZT-PAni/PVDF Based Nanocomposite

This work presents the preparation and characterization of PZT ceramic obtained by the polymeric precursor method (PPM). The influence of the synthesis method on the grain size and the morphology are also object of study. The fabrication and characterization of composite films with 0-3 connectivity, immersing nanoparticles of PZT into the non-polar poly(vinylidene fluoride) -PVDF as the polymer matrix were presented. For comparison there are results obtained with composite samples made of ceramic particles unrecovered and recovered with a conducting polymer, the polyaniline (PAni).

Nanoscale switching characteristics of nearly tetragonal BiFeO3 thin films

We have investigated the nanoscale switching properties of strain-engineered BiFeO(3) thin films deposited on LaAlO(3) substrates using a combination of scanning probe techniques. Polarized Raman spectral analysis indicates that the nearly tetragonal films have monoclinic (Cc) rather than P4mm tetragonal symmetry. Through local switching-spectroscopy measurements and piezoresponse force microscopy, we provide clear evidence of ferroelectric switching of the tetragonal phase, but the polarization direction, and therefore its switching, deviates strongly from the expected (001) tetragonal axis. We also demonstrate a large and reversible, electrically driven structural phase transition from the tetragonal to the rhombohedral polymorph in this material, which is promising for a plethora of applications.