Piezoresponse Force Microscopy Hysteresis Loops Research Articles

Role of Bi3+ ion substitution on the piezocatalytic degradation performance of lead-free BaTi0·89Sn0·11O3 at low vibrational energy

Harnessing low ultrasonic vibration energy to initiate piezocatalytic-based reactions is increasingly becoming a significant focus due to the current environmental energy crisis. In this study, we report on the potential of heterovalent ion substitution in improving piezocatalytic degradation of Rhodamine B dye (RhB) under the application of low-power ultrasonic vibration. For this purpose, bismuth ions Bi3+ are substituted into the lead-free ferroelectric BaTi0·89Sn0·11O3 (BTSn11-xBi, x = 0, 0.02, 0.04) submicrocubes synthesized using sol-gel method. The structural, morphological, optical and piezocatalytic properties of the prepared materials appear to be significantly influenced by the substituting content. Compared to pure BTSn11 and BTSn11-0.04Bi, BTSn11-0.02Bi exhibits the lowest band gap energy value of 3.22 eV, the smallest particle size value of 283 nm, the strongest piezoelectric current of about 8 μA/cm2, and the lowest required applied field for piezoresponse force microscopy hysteresis loops. The degradation efficiency and the kinetic rate constant are substantially higher for BTSn11-0.02Bi, indicating its enhanced piezocatalytic efficiency. Total organic carbon (TOC) measurements revealed good RhB mineralization using BTSn11-xBi piezocatalysts. Furthermore, the BTSn11-0.02Bi sample demonstrates good reusability and stability by maintaining effective RhB dye degradation for five consecutive cycling tests. These findings suggest that the BTSn11-0.02Bi piezocatalytic system holds significant potential for environmental remediation applications.

Room temperature multiferroicity in a transition metal dichalcogenide

The coexistence of multiple ferroic orders, i.e., multiferroicity, is a scarce property to be found in materials. Historically, this state has been found mainly in 3-dimensional complex oxides, but so far, this state has still been elusive for the most widely studied and characterized family of 2-dimensional compounds, the transition metal dichalcogenides. In this study, we report the experimental realization of multiferroic states in this family of materials, at room temperature, in bulk single crystals of Te-doped WSe2. We observe the coexistence of ferromagnetism and ferroelectricity, evidenced in the presence of magnetization and piezoresponse force microscopy hysteresis loops. These findings open the possibility of widening the use and study of van der Waals-based multifunctional devices for nanoelectronics and spintronics applications.

Changing the polarization and mechanical response of flexible PVDF-nickel ferrite films with nickel ferrite additives

Polymer-based flexible nanocomposite films, of nickel ferrite nanoparticles in a polyvinylidene fluoride (PVDF) polymer matrix, were fabricated using a blade coating technique. A two-step process is used to prepare nanocomposite films. The first process involves the synthesis of nickel ferrite (NiFe2O4) nanoparticles using sonochemical method, and then incorporation of various weight percentage (5, 10, 20, and 30%) of nickel ferrite nanoparticles into the PVDF to form polymer nanocomposites. Nickel ferrite nanoparticles demonstrated a magnetization of 37.3 emu/g at magnetic field of 5 kOe while 30% Nickel-ferrite-PVDF nanocomposite shows 23.8 emu/g. Finally, the ferroelectric and local polarization switching properties of pure PVDF and nanocomposite films were investigated via piezoresponse force microscopy (PFM) measurements. The pure PVDF film demonstrates a negative piezoelectric coefficient from the PFM hysteresis loop measurement whereas the nanocomposite film shows a positive piezoelectric coefficient with an opposite PFM signal.

Piezoresponse amplitude and phase quantified for electromechanical characterization

Piezoresponse force microscopy (PFM) is a powerful characterization technique to readily image and manipulate the ferroelectric domains. PFM gives an insight into the strength of local piezoelectric coupling and polarization direction through PFM amplitude and phase, respectively. Converting measured arbitrary units into units of effective piezoelectric constant remains a challenge, and insufficient methods are often used. While most quantification efforts have been spent on quantifying the PFM amplitude signal, little attention has been given to the PFM phase, which is often arbitrarily adjusted to fit expectations. This is problematic when investigating materials with unknown or negative sign of the probed effective electrostrictive coefficient or strong frequency dispersion of electromechanical responses, because assumptions about the PFM phase cannot be reliably made. The PFM phase can, however, provide important information on the polarization orientation and the sign of the effective electrostrictive coefficient probed by PFM. Most notably, the orientation of the PFM hysteresis loop is determined by the PFM phase. Moreover, when presenting PFM data as a combined signal, the resulting response can be artificially lowered or asymmetric if the phase data have not been correctly processed. Here, we explain the PFM amplitude quantification process and demonstrate a path to identify the phase offset required to extract correct meaning from the PFM phase data. We explore different sources of phase offsets including the experimental setup, instrumental contributions, and data analysis. We discuss the physical working principles of PFM and develop a strategy to extract physical meaning from the PFM amplitude and phase.

Electrostatic effect on off-field ferroelectric hysteresis loop in piezoresponse force microscopy

Piezoresponse force microscopy (PFM) has been extensively utilized as a versatile and an indispensable tool to understand and analyze nanoscale ferro-/piezoelectric properties by detecting the local electromechanical response on a sample surface. However, it has been discovered that the electromechanical response originates not only from piezoelectricity but also from other factors such as the electrostatic effect. In this study, we explore the dependence of off-field PFM hysteresis loops on the surface-potential-induced electrostatic effect in a prototypical ferroelectric thin film by applying an external voltage to the bottom electrode during the measurement. We simplify the situation by equating the surface potential to the direct current voltage waveform variations and predicting the contribution of the surface-potential-induced electrostatic effect to the PFM hysteresis loops. The experimental results approximately match our prediction—the coercive voltage linearly decreases with the surface potential, whereas the saturated amplitude and piezoresponse remain nearly constant owing to the relatively large piezoelectric coefficient of the ferroelectric thin film.

Enhanced ferromagnetism in BaNiF4 film

BaMF4 (M = Mn, Ni, Co, etc.) are typical multiferroic materials with above room temperature ferroelectricity, but the antiferromagnetic ordering temperature is quite low. We report the epitaxial growth of BaNiF4 films on Al2O3 substrates by pulsed laser deposition. The epitaxial growth of BaNiF4 films is confirmed by the observation of only (040), (080) and (0120) diffraction peaks in X ray diffraction patterns. Using piezoresponse force microscopy (PFM), the ferroelectricity at room temperature has been inferred from the observation of PFM hysteresis loops. The wasp-wasted hysteresis loops are clearly observed below 10 K, which is due to the weak antiferromagnetic nature of the canted spins. Clear weak ferromagnetism has been observed up to 300 K, which is considered to be due to the epitaxial strains.

Nanoscale Bubble Domains and Topological Transitions in Ultrathin Ferroelectric Films.

Observation of a new type of nanoscale ferroelectric domains, termed as "bubble domains"-laterally confined spheroids of sub-10 nm size with local dipoles self-aligned in a direction opposite to the macroscopic polarization of a surrounding ferroelectric matrix-is reported. The bubble domains appear in ultrathin epitaxial PbZr0.2 Ti0.8 O3 /SrTiO3 /PbZr0.2 Ti0.8 O3 ferroelectric sandwich structures due to the interplay between charge and lattice degrees of freedom. The existence of the bubble domains is revealed by high-resolution piezoresponse force microscopy (PFM), and is corroborated by aberration-corrected atomic-resolution scanning transmission electron microscopy mapping of the polarization displacements. An incommensurate phase and symmetry breaking is found within these domains resulting in local polarization rotation and hence impart a mixed Néel-Bloch-like character to the bubble domain walls. PFM hysteresis loops for the bubble domains reveal that they undergo an irreversible phase transition to cylindrical domains under the electric field, accompanied by a transient rise in the electromechanical response. The observations are in agreement with ab-initio-based calculations, which reveal a very narrow window of electrical and elastic parameters that allow the existence of bubble domains. The findings highlight the richness of polar topologies possible in ultrathin ferroelectric structures and bring forward the prospect of emergent functionalities due to topological transitions.

Identifying intrinsic ferroelectricity of thin film with piezoresponse force microscopy

Piezoresponse force microscopy (PFM) is a powerful technique to characterize ferroelectric thin films by measuring the dynamic electromechanical response. The ferroelectricity is commonly demonstrated by the PFM hysteresis loops and a 180o phase difference of PFM images before and after poling. Such ferroelectric-like behaviors, however, recently are also found in many non-ferroelectrics. Consequently, it is still a challenge to identify intrinsic ferroelectricity in various kinds of thin films. Here, using PFM, we systematically studied the electromechanical responses in ferroelectric thin films with fast (BaTiO3) and slow (PVDF) switch dynamics, and also in the non-ferroelectric (Al2O3) thin films. It is found that both of the ac voltage (Vac) and pulsed dc voltage (Vdc) play an important role in the PFM measurement. When the Vac amplitude is higher than a explicit threshold voltage (Vc), collapse of the PFM hysteresis loops is observed for the films with fast switch dynamics. By measuring PFM hysteresis loops at various Vdc frequencies, an explicit Vc could be found in ferroelectric rather than in non-ferroelectric. The existence of an explicit Vc as well as nonvolatile behavior is proposed as an important approach to unambiguously identify intrinsic ferroelectricity in materials regardless of switch dynamics.

Mechanical stress-induced switching kinetics of ferroelectric thin films at the nanoscale

We investigate ferroelectric domain structure and piezoelectric response under variable mechanical compressive stress in Pb(Zr0.2TiO0.8)O3 (PZT) thin films using high-resolution piezoresponse force microscopy (PFM) and an in situ sample bending stage. Measurements reveal a drastic change in the ferroelectric domain structure which is presented along with details of the mediating switching process involving domain wall motion, nucleation, and domain wall roughening under an applied external mechanical stimulus. Furthermore, local PFM hysteresis loops reveal significant changes in the observed coercive biases under applied stress. The PFM hysteresis loops become strongly imprinted under increasing applied compressive stress.

Current and surface charge modified hysteresis loops in ferroelectric thin films

Polarization domains in ferroelectric materials and the ability to orient them with an external electric field lead to the development of a variety of applications from information storage to actuation. The development of piezoresponse force microscopy (PFM) has enabled researchers to investigate ferroelectric domains and ferroelectric domain switching on the nanoscale, which offers a pathway to study structure-function relationships in this important material class. Due to its commercial availability and ease of use, PFM has become a widely used research tool. However, measurement artifacts, i.e., alternative signal origins besides the piezoelectric effect are barely discussed or considered. This becomes especially important for materials with a small piezoelectric coefficient or materials with unknown ferroelectric properties, including non-ferroelectric materials. Here, the role of surface charges and current flow during PFM measurements on classical ferroelectrics are discussed and it will be shown how they alter the PFM hysteresis loop shape. This will help to better address alternative signal origins in PFM-type experiments and offer a pathway to study additional phenomena besides ferroelectricity.

Magnetic interactions in BiFe₀.₅Mn₀.₅O₃ films and BiFeO₃/BiMnO₃ superlattices.

The clear understanding of exchange interactions between magnetic ions in substituted BiFeO3 is the prerequisite for the comprehensive studies on magnetic properties. BiFe0.5Mn0.5O3 films and BiFeO3/BiMnO3 superlattices have been fabricated by pulsed laser deposition on (001) SrTiO3 substrates. Using piezoresponse force microscopy (PFM), the ferroelectricity at room temperature has been inferred from the observation of PFM hysteresis loops and electrical writing of ferroelectric domains for both samples. Spin glass behavior has been observed in both samples by temperature dependent magnetization curves and decay of thermo-remnant magnetization with time. The magnetic ordering has been studied by X-ray magnetic circular dichroism measurements, and Fe-O-Mn interaction has been confirmed to be antiferromagnetic (AF). The observed spin glass in BiFe0.5Mn0.5O3 films has been attributed to cluster spin glass due to Mn-rich ferromagnetic (FM) clusters in AF matrix, while spin glass in BiFeO3/BiMnO3 superlattices is due to competition between AF Fe-O-Fe, AF Fe-O-Mn and FM Mn-O-Mn interactions in the well ordered square lattice with two Fe ions in BiFeO3 layer and two Mn ions in BiMnO3 layer at interfaces.

Epitaxial PbxZr1−xTiO3 on GaN

Epitaxial integration of PbxZr1−xTiO3 (PZT) (111) with GaN (0002) presents the possibility of polarity coupling across a functional-oxide/nitride heteropolar interface. This work describes the synthesis and characterization of such thin film heterostructures by magnetron sputtering, with specific attention given to process optimization. Using x-ray diffraction and electrical characterization, the growth of epitaxial PZT (∼250 nm) on GaN and PZT on MgO/GaN stacks was verified. A two-stage growth process was developed for epitaxial PZT with a deposition temperature of 300 °C and an ex-situ anneal at 650 °C, which was effective in mitigating interfacial reactions and promoting phase-pure perovskite growth. Electrical analysis of interdigital capacitors revealed a nonlinear and hysteretic dielectric response consistent with ferroelectric PZT. Piezoresponse force microscopy (PFM) characterization shows clear evidence of ferroelectric switching, and PFM hysteresis loop analysis shows minimal evidence for direct polarity coupling, but suggests that band offsets which accompany the oxide-nitride heterostructures influence switching.

Ferroelectric switching in Bi4Ti3O12nanorods

We report the piezoelectric and ferroelectric properties of individual one-dimensional objects made of Bi(4)Ti(3)O(12) (BiT). The nanorods and nanowires investigated in this study were fabricated by a two-step process: 1) preparation of reactive templates using hydrothermal-like synthesis and colloidal chemistry and 2) transformation of the reactive templates in Bi(4)Ti(3)O(12) by solid-state reaction, overcoming the morphological instability problem of 1-D templates. Using piezoresponse force microscopy (PFM) with both out-of-plane and in-plane detection capability, we show that both types of objects exhibit strong piezoelectric activity and good switching ferroelectric behavior. Analysis of the PFM hysteresis loops obtained revealed that the coercive voltage of the in-plane PFM signal can be either equal to or different from that of the out-of-plane response. We associate these situations with two types of polarization switching mechanisms: direct 180° switching, and via rotation of polarization, resulting from the independent switching of the components along the a- and ccrystallographic axes. In a few instances, we observe a negative piezoelectric coefficient, which we explain by the specific shape of the piezoelectric surface of Bi(4)Ti(3)O(12).