Piezoresponse Force Microscopy Response Research Articles

Ferroelectric Texture of Individual Barium Titanate Nanocrystals.

Ferroelectric materials display exotic polarization textures at the nanoscale that could be used to improve the energetic efficiency of electronic components. The vast majority of studies were conducted in two dimensions on thin films that can be further nanostructured, but very few studies address the situation of individual isolated nanocrystals (NCs) synthesized in solution, while such structures could have other fields of applications. In this work, we experimentally and theoretically studied the polarization texture of ferroelectric barium titanate (BaTiO3, BTO) NCs attached to a conductive substrate and surrounded by air. We synthesized NCs of well-defined quasicubic shape and 160 nm average size that conserve the tetragonal structure of BTO at room temperature. We then investigated the inverse piezoelectric properties of such pristine individual NCs by vector piezoresponse force microscopy (PFM), taking particular care to suppress electrostatic artifacts. In all of the NCs studied, we could not detect any vertical PFM signal, and the maps of the lateral response all displayed larger displacement amplitude on the edges with deformations converging toward the center. Using field phase simulations dedicated to ferroelectric nanostructures, we were able to predict the equilibrium polarization texture. These simulations revealed that the NC core is composed of 180° up and down domains defining the polar axis that rotate by 90° in the two facets orthogonal to this axis, eventually lying within these planes forming a layer of about 10 nm thickness mainly composed of 180° domains along an edge. From this polarization distribution, we predicted the lateral PFM response, which was revealed to be in very good qualitative agreement with the experimental observations. This work positions PFM as a relevant tool to evaluate the potential of complex ferroelectric nanostructures to be used as sensors.

Correlating Crystallographic Orientation and Ferroic Properties of Twin Domains in Metal Halide Perovskites.

Metal halide perovskite (MHP) solar cells have attracted worldwide research interest. Although it has been well established that grain, grain boundary, and grain facet affect MHPs optoelectronic properties, less is known about subgrain structures. Recently, MHP twin stripes, a subgrain feature, have stimulated extensive discussion due to the potential for both beneficial and detrimental effects of ferroelectricity on optoelectronic properties. Connecting the ferroic behavior of twin stripes in MHPs with crystal orientation will be a vital step to understand the ferroic nature and the effects of twin stripes. In this work, we studied the crystallographic orientation and ferroic properties of CH3NH3PbI3 twin stripes, using electron backscatter diffraction (EBSD) and advanced piezoresponse force microscopy (PFM), respectively. Using EBSD, we discovered that the orientation relationship across the twin walls in CH3NH3PbI3 is a 90° rotation about ⟨1̅1̅0⟩, with the ⟨030⟩ and ⟨111⟩ directions parallel to the direction normal to the surface. By careful inspection of CH3NH3PbI3 PFM results including in-plane and out-of-plane PFM measurements, we demonstrate some nonferroelectric contributions to the PFM responses of this CH3NH3PbI3 sample, suggesting that the PFM signal in this CH3NH3PbI3 sample is affected by nonferroelectric and nonpiezoelectric forces. If there is piezoelectric response, it is below the detection sensitivity of our interferometric displacement sensor PFM (<0.615 pm/V). Overall, this work offers an integrated picture describing the crystallographic orientations and the origin of PFM signal of MHPs twin stripes, which is critical to understanding the ferroicity in MHPs.

Calibration of the in-plane PFM response by the lateral force curves

Calibration technique for lateral piezoresponse force microscopy (PFM) based on lateral force curves measurements is introduced and discussed in terms of relative error connected with experimental realization. Dependences of lateral calibration coefficient on the tip motion velocity, normal loading force, humidity environment, and position of laser spot on the cantilever beam are considered. The maximal error of the measurements does not exceed 10%, which is close to the error of typical vertical PFM signal calibration based on force-distance curves. Proposed calibration technique is easy and accurate, which is important for the future development of quantitative PFM method.

Efficiency Enhancement with the Ferroelectric Coupling Effect Using P(VDF-TrFE) in CH3NH3PbI3 Solar Cells.

A novel ferroelectric coupling photovoltaic effect is reported to enhance the open‐circuit voltage (V OC) and the efficiency of CH3NH3PbI3 perovskite solar cells. A theoretical analysis demonstrates that this ferroelectric coupling effect can effectively promote charge extraction as well as suppress combination loss for an increased minority carrier lifetime. In this study, a ferroelectric polymer P(VDF‐TrFE) is introduced to the absorber layer in solar cells with a proper cocrystalline process. Piezoresponse force microscopy (PFM) is used to confirm that the P(VDF‐TrFE):CH3NH3PbI3 mixed thin films possess ferroelectricity, while the pure CH3NH3PbI3 films have no obvious PFM response. Additionally, with the applied external bias voltages on the ferroelectric films, the devices begin to show tunable photovoltaic performance, as expected for the polarization in the poling process. Furthermore, it is shown that through the ferroelectric coupled effect, the efficiency of the CH3NH3PbI3‐based perovskite photovoltaic devices is enhanced by about 30%, from 13.4% to 17.3%. And the open‐circuit voltages (V OC) reach 1.17 from 1.08 V, which is reported to be among the highest V OCs for CH3NH3PbI3‐based devices. It should be noted in particular that the thickness of the layer is less than 160 nm, which can be regarded as semi‐transparent.

Electrostatic contribution to hysteresis loop in piezoresponse force microscopy

In piezoresponse force microscopy (PFM), ideally, electromechanical strain is induced only by the converse piezoelectric effect. In reality, however, the obtained experimental PFM signal is a combination of many other factors. In particular, the concurrent electrostatic effect between the tip/cantilever and a sample surface can be significant because the electrostatic effect induced by surface potential is inevitable in some cases. However, most previous reports dealt with the extreme case of the electrostatic effect, such as the on-field state. That is, the contributions to the hysteresis loop of electrostatic effects from different sources have not yet been clearly understood. In the present work, we study the electrostatic effect on the hysteresis loop in relation to various measurement parameters. The results indicate that the PFM response is strongly affected by the electrostatic effect caused by external charge injection. This work can provide a guideline for determining the PFM response in a hysteresis loop.

Decoding Apparent Ferroelectricity in Perovskite Nanofibers.

Ferroelectric perovskites are an important group of materials underpinning a wide variety of devices ranging from sensors and transducers to nonvolatile memories and photovoltaic cells. Despite the progress in material synthesis, ferroelectric characterization of nanoscale perovskites is still a challenge. Piezoresponse force microscopy (PFM) is one of the most popular tools for probing and manipulating nanostructures to study the ferroelectric properties. However, the interpretation of hysteresis data and alternate signal origins are critical. Here, we use a family of scanning probe microscopy (SPM) techniques to systematically investigate the ferroelectric behavior of electrospun potassium niobate (KNbO3) nanofibers. Band Excitation (BE) SPM scans reveal that PFM signals are dominated by changes in resonant frequency due to rough nanofiber surfaces, rather than the actual local piezoelectric strength. We investigate the bias-induced charge injection properties and electrostatic interactions on the PFM response of the nanofiber using contact mode Kelvin probe force microscopy (cKPFM). Furthermore, the impact of relative humidity on the KNbO3 nanofiber's piezoresponse, switching behavior, and tip-induced charges are explored. The resultant data from BE scans were utilized to estimate the piezoelectric constants of the KNO nanofiber. These observations will provide clarity in studying newly developed ferroelectric nanostructures and unambiguously interpreting the PFM data.

Effects of Thickness on the Responses of Piezoresponse Force Microscopy for Piezoelectric Film/Substrate Systems

Piezoresponse force microscopy (PFM) extends the conventional nano-indentation technique and has become one of the most widely used methods to determine the properties of small scale piezoelectric materials. Its accuracy depends largely on whether a reliable analytical model for the corresponding properties is available. Based on the coupled theory and the image charge model, a rigorous analysis of the film thickness effects on the electromechanical behaviors of PFM for piezoelectric films is presented. When the film is very thick, analytical solutions for the surface displacement, electric potential, image charge, image charge distance, and effective piezoelectric coefficient are obtained. For the infinitely thin (IT) film case, the corresponding closed-form solutions are derived. When the film is of finite thickness, a single parameter semi-empirical formula agreeing well with the numerical results is proposed for the effective piezoelectric coefficient. It is found that if the film thickness effect is not taken into account, PFM can significantly underestimate the effective piezoelectric coefficient compared to the half space result. The effects of the ambient dielectric property on PFM responses are also explored. Humidity reduces the surface displacement, broadens the radial distribution peak, and greatly enlarges the image charge, resulting in reduced effective piezoelectric coefficient. The proposed semi-empirical formula is also suitable to describe the thickness effects on the effective piezoelectric coefficient of thin films in humid environment. The obtained results can be used to quantitatively interpret the PFM signals and enable the determination of intrinsic piezoelectric coefficient through PFM measurement for thin films.

Enhancement of local piezoelectric properties of a perforated ferroelectric thin film visualized via piezoresponse force microscopy

The local piezoresponse in a Ba0.8Sr0.2TiO3 epitaxial ferroelectric film perforated by cylindrical channels has been investigated experimentally by means of piezoresponse force microscopy (PFM). A large enhancement of the effective values for both lateral and vertical components of piezoelectric tensor was experimentally detected in the perforated film as compared to non-perforated structure—by a factor of 8 for the lateral and by a factor 2 for the vertical piezoresponse. This result is consistent with the previously reported enhancement of the optical second harmonic generation over perforated films observed in macroscopic experiments. We assume that a possible mechanism for the increased PFM response is due to reduction of stress and clamping in the film imposed by the substrate. The obtained insight is critical for understanding nanoscale piezo- and ferroelectric responses in photonic crystals fabricated by focused ion beam milling.

Substrate effects on piezoresponse force microscopy electromechanical responses of piezoelectric thin films

To explore substrate influences on piezoresponse force microscopy (PFM) responses, the coupled theory is extended to investigate the electromechanical responses of PFM on piezoelectric films bonded to rigid and dielectric, rigid and insulating, elastic and conducting and elastic and dielectric substrates. It is found that all responses transit to the half space results when the normalized thickness (film thickness to tip curvature radius t/R0) is larger than about 0.08 for PZT4, and degenerate to the dielectric half space solutions as expected for rigid and dielectric substrate case, when the normalized thickness approaches zero verifying the calculations. PFM responses are greatly reduced by substrate dielectric permittivity thus a conducting substrate is recommended to eliminate the dielectric constant influences and the dielectric “dead layer” should be avoided or carefully dealt with. For elastic substrates, the tip induced surface displacement for a relatively thick film, image charge and image charge distance are slightly affected by the change of the substrate Young's modulus and Poisson's ratio. And the effective piezoelectric coefficient is remarkably decreased when t/R0 < 0.001. However as t/R0 > 0.001 in which region a practical PFM experiment would fall, so long as the substrate is matched or harder, the substrate could be deemed as a rigid one and the investigation of PFM responses would be greatly facilitated. Then effective piezoelectric coefficients from the decoupled and coupled theories of films on elastically matched, conducting or dielectric substrates are compared indicating that the decoupled theory tends to overestimate effective piezoelectric coefficient for thin films, the same as that for half space case. The obtained influences of substrate properties may serve as a primary experimental guidance for the choosing a proper substrate and supply useful information for the quantitative interpretation of the PFM signals.

Ferroelectric-like hysteresis loop originated from non-ferroelectric effects

Piezoresponse force microscopy (PFM) has provided advanced nanoscale understanding and analysis of ferroelectric and piezoelectric properties. In PFM-based studies, electromechanical strain induced by the converse piezoelectric effect is probed and analyzed as a PFM response. However, electromechanical strain can also arise from several non-piezoelectric origins that may lead to a misinterpretation of the observed response. Among them, electrostatic interaction can significantly affect the PFM response. Nonetheless, previous studies explored solely the influence of electrostatic interaction on the PFM response under the situation accompanied with polarization switching. Here, we show the influence of the electrostatic interaction in the absence of polarization switching by using unipolar voltage sweep. The obtained results reveal that the electromechanical neutralization between piezoresponse of polarization and electrostatic interaction plays a crucial role in the observed ferroelectric-like hysteresis loop despite the absence of polarization switching. Thus, our work can provide a basic guideline for the correct interpretation of the hysteresis loop in PFM-based studies.

The role of substrates and environment in piezoresponse force microscopy: A case study with regular glass slides

Piezoresponse force microscopy (PFM) is a powerful tool for probing nanometer-scale ferroelectric and piezoelectric properties. Hysteretic switching of the phase and amplitude of the PFM response are believed to be the hallmark of ferroelectric and piezoelectric behavior respectively. However, the application of PFM is limited by the fact that similar hysteretic effects may also arise from mechanisms not related to ferroelectricity or piezoelectricity. In this paper we report our studies on regular glass slides that show ferroelectric-like signal without being ferroelectric and frequently used as a substrate in PFM experiments. We demonstrate how the substrates and other environmental factors like relative humidity and experimental conditions may influence the PFM results on novel materials.

Electro-mechanical response of top-gated LaAlO3/SrTiO3

LaAlO3/SrTiO3 heterostructures are known to exhibit a sharp, hysteretic metal-insulator transition (MIT) with large enhanced capacitance near depletion. To understand the physical origin of this behavior, the electromechanical response of top-gated LaAlO3/SrTiO3 heterostructures is probed using two simultaneous measurement techniques: piezoresponse force microscopy (PFM) and capacitance spectroscopy. The observed hysteretic PFM responses show strong correlation with the capacitance signals, suggesting an interfacial carrier-mediated structural distortion associated with the gate-tuned MIT. In addition, the frequency dependence of the capacitance enhancement in LaAlO3/SrTiO3 is found to be well-matched to local PFM measurements. Our experimental results provide a fuller understanding of the top-gate tuned MIT in oxide heterostructure, which could be helpful for the development of future oxide-based nanoelectronics.

In-situ piezoresponse force microscopy cantilever mode shape profiling

The frequency-dependent amplitude and phase in piezoresponse force microscopy (PFM) measurements are shown to be a consequence of the Euler-Bernoulli (EB) dynamics of atomic force microscope (AFM) cantilever beams used to make the measurements. Changes in the cantilever mode shape as a function of changes in the boundary conditions determine the sensitivity of cantilevers to forces between the tip and the sample. Conventional PFM and AFM measurements are made with the motion of the cantilever measured at one optical beam detector (OBD) spot location. A single OBD spot location provides a limited picture of the total cantilever motion, and in fact, experimentally observed cantilever amplitude and phase are shown to be strongly dependent on the OBD spot position for many measurements. In this work, the commonly observed frequency dependence of PFM response is explained through experimental measurements and analytic theoretical EB modeling of the PFM response as a function of both frequency and OBD spot location on a periodically poled lithium niobate sample. One notable conclusion is that a common choice of OBD spot location—at or near the tip of the cantilever—is particularly vulnerable to frequency dependent amplitude and phase variations stemming from dynamics of the cantilever sensor rather than from the piezoresponse of the sample.

Differentiating Ferroelectric and Nonferroelectric Electromechanical Effects with Scanning Probe Microscopy.

Ferroelectricity in functional materials remains one of the most fascinating areas of modern science in the past several decades. In the last several years, the rapid development of piezoresponse force microscopy (PFM) and spectroscopy revealed the presence of electromechanical hysteresis loops and bias-induced remnant polar states in a broad variety of materials including many inorganic oxides, polymers, and biosystems. In many cases, this behavior was interpreted as the ample evidence for ferroelectric nature of the system. Here, we systematically analyze PFM responses on ferroelectric and nonferroelectric materials and demonstrate that mechanisms unrelated to ferroelectricity can induce ferroelectric-like characteristics through charge injection and electrostatic forces on the tip. We will focus on similarities and differences in various PFM measurement characteristics to provide an experimental guideline to differentiate between ferroelectric material properties and charge injection. In the end, we apply the developed measurement protocols to an unknown ferroelectric material.

Top electrode size effect on hysteresis loops in piezoresponse force microscopy of Pb(Zr,Ti)O3-film on silicon structures

Experimental and theoretical studies of hysteresis loops in piezoresponse force microscopy (PFM) directed on elucidating the influence of top electrode lateral sizes on loop peculiarities were performed for Pt/Pb(Zr, Ti)O3/Pt/TiOx/SiO2/Si-substrate structures. The set of top Pt electrodes (50 nm to 10 μm of lateral size) was deposited on the Pb(ZrxTi1−x)O3 film (x = 0.54, thickness ≈1 μm) by RF magnetron sputtering. Under approaching the top electrode lateral size to the film thickness, the transition-like behaviour of PFM response amplitude and coercive tip voltage was observed. The existence of the critical value of dimensionless electrode size parameter γd/h ≈ 1 (γ is the dielectric anisotropy factor, d is the electrode size parameter, and h is the film thickness) was interpreted in the framework of the model based on Landau-Ginzburg-Devonshire theory combined with the decoupling approximation subject to the nonlinear electric field dependence of the ferroelectric polarization and dielectric permittivity.

Analyzing piezoresponse force microscopy for reconstruction of probed ferroelectric structures

Piezoresponse force microscopy (PFM) has emerged as the tool of choice for characterizing piezoelectric and ferroelectric materials at nanoscale, yet the interpretation of PFM remains to be difficult and sometimes ambiguous. Built on earlier works, we developed a numerical integration scheme to analyze the expected PFM response in ferroelectrics with arbitrary domain configurations, with the ultimate goal to accurately reconstruct the underlying ferroelectric structure from PFM measurements. Using such technique, we demonstrated that the relationship between the effective and intrinsic piezoelectric coefficients is sensitive to a variety of factors that are intrinsic to the probed materials, and showed that the PFM mapping is not only influenced by polarization distribution on the sample surface but also three-dimensional polarization distribution inside the material. While relatively simple domain structures were used for demonstration, the approach is general, and can be applied to ferroelectrics with arbitrary polarization distributions.

Real-space phase-field simulation of piezoresponse force microscopy accounting for stray electric fields

Piezoresponse force microscopy (PFM) is a powerful scanning-probe technique used to characterize important aspects of the microstructure in ferroelectrics. It has been widely applied to understand domain patterns, domain nucleation and the structure of domain walls. In this paper, we apply a real-space phase-field model to consistently simulate various PFM configurations. We model the PFM tip as a charged region that is external to the ferroelectric, and implement a boundary element method to efficiently and accurately account for the external stray fields that mediate the interactions between the tip and the ferroelectric. Our phase-field model and the solution method together are able to account for the electrical fields both within the specimen as well as those outside, and also consistently solve for the resulting electromechanical response with the same phase-field model. We apply this to various problems: first, the effect of crystal lattice orientation on the induced tip displacement and rotation; second, PFM scanning of a 90° domain wall that emerges at a free surface; third, the effect of closure domain microstructure on PFM response; fourth, the effect of surface modulations on PFM response; and fifth, the effect of surface charge compensation on PFM response.

Depth resolution of piezoresponse force microscopy

Given that a ferroelectric domain is generally a three dimensional entity, the determination of its area as well as its depth is mandatory for full characterization. Piezoresponse force microscopy (PFM) is known for its ability to map the lateral dimensions of ferroelectric domains with high accuracy. However, no depth profile information has been readily available so far. Here, we have used ferroelectric domains of known depth profile to determine the dependence of the PFM response on the depth of the domain, and thus effectively the depth resolution of PFM detection.

Electromechanical detection in scanning probe microscopy: Tip models and materials contrast

The rapid development of nanoscience and nanotechnology in the last two decades was stimulated by the emergence of scanning probe microscopy techniques capable of accessing local material properties, including transport, mechanical, and electromechanical behaviors, on the nanoscale. Here, we analyze the general principles of electromechanical probing by piezoresponse force microscopy (PFM), a scanning probe technique applicable to a broad range of piezoelectric and ferroelectric materials. The relationship between vertical and lateral PFM signals and material properties is derived analytically for two cases: transversally isotropic piezoelectric materials in the limit of weak elastic anisotropy, and anisotropic piezoelectric materials in the limit of weak elastic and dielectric anisotropies. The integral representations for PFM response for fully anisotropic material are also obtained. The image formation mechanism for conventional (e.g., sphere and cone) and multipole tips corresponding to emerging shielded and strip-line-type probes is analyzed. Possible applications for orientation imaging on the nanoscale and molecular resolution imaging are discussed.

Indentation plasticity of barium titanate single crystals: Dislocation influence on ferroelectric domain walls

The plastic behaviors of barium titanate (0 0 1) and (1 1 0) single crystals are studied with atomic force microscopy and piezoresponse force microscopy (PFM) following nanoindendation damage. Plastic deformation mechanisms of ferroelectric barium titanate single crystals are discussed with a focus on the interaction between PFM response and dislocation activities. Nanoindentation tests indicate that the theoretical strength is approached prior to the first pop-in event, consistent with the creation of dislocation nucleation sites required for the onset of plasticity. Surface topographic and piezoelectric analyses indicate that pile-ups around indents result from dislocation activities on the primary slip system, { 1 1 0 } pc 〈 1 1 ¯ 0 〉 pc . The more complex indentation-induced domain patterns observed on (1 1 0) barium titanate are also discussed.