Ferroelectric Polymer Thin Films Research Articles

Role of Annealing with Electric Field Toward Improvement of Ferroelectric and Electroactive Properties of PVDF Copolymer and Terpolymer Thin Films.

The present study elucidates the role of annealing with electric field on lamellar crystalline structure and molecular orientation of polymer chains in ferroelectric copolymer (P(VDF-TrFE)) and ferroelectric terpolymer (P(VDF-TrFE-CFE)) spin-coated thin films. The ferroelectric polymer thin films annealed under an electric field support the growth of nanostructure with an "edge-on" lamellar crystalline structure having in-plane molecular chain orientation. The poled P(VDF-TrFE) thin films have higher remnant polarization (Pr) ≈6.2µCcm-2 and saturation polarization (Ps) ≈8.2µCcm-2 at an applied electric field of 250 MV/m compared to unpoled thin films having Pr ≈4.7 and Ps ≈6.2µCcm-2. Also, poled P(VDF-TrFE) thin films show lower coercive field (Ec) ≈94 MV/m compared to an unpoled thin film having Ec ≈105 MV/m. Similarly, poled PVDF-TrFE-CFE thin film shows better ferroelectric properties having Pr ≈0.4 and Ps ≈5.7µCcm-2 at an applied electric field of 200 MVm-1 compared to unpoled thin films having Pr ≈0.4 and Ps ≈4.1µCcm-2. The storage energy efficiency of unpoled and poled P(VDF-TrFE-CFE) thin films is measured to be ≈75% and 80%. Annealing of ferroelectric P(VDF-TrFE) polymer thin films under an electric field demonstrates improved ferroelectric and electroactive properties.

Solution-processed ferroelectric polymer nanocrystals

Since the first demonstrations of ferro- and piezoelectricity in solution-processed ferroelectric polymer thin films research activities have been stimulated in both academia and industry. Several applications have been reported using ferroelectric polymer thin films as bistable polarization switches in memory devices or as transducers in (micro-)electromechanical devices. In light of the continuing miniaturization of such devices, nanoscaled structures of ferroelectric polymers such as nanomesas are attracting increasing interest. However, nanopatterning ferroelectrics, to develop stable and reliable ferroelectric nanomesas remains challenging. In this work, we demonstrate the fabrication of solution-processed ferroelectric polymer nanocrystals, i.e. ferroelectric nanomesas, and verify their ferroelectric activity. By using the ferroelectric copolymer of vinylidene fluoride and trifluoroethylene (P(VDF-TrFE)), we are able to isolate crystalline domains. Morphology, molecular conformation, (nano-)mechanical and electromechanical properties of the nanocrystals are measured, yielding comparable results to those observed in uniform, continuous thin films. Therefore, synthesizing self-assembled ferroelectric polymer nanocrystals from polymer solution by spin-casting represents a promising approach for the realization of ferroelectric nanomesas.

Spherulite-like microstructure observed for spin-cast P(VDF-TrFE) thin films and their ferroelectric characteristics

Ferroelectric polymer thin films crystallize in different phases and microstructures depending on fabrication conditions such as annealing temperature or layer deposition technique. In this work, we demonstrate how the morphology of spin-cast poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) thin films changes as a function of annealing temperature from rice-like to spherulite-like microstructure, whereas the latter morphology is closer to the crystallization characteristic of poly(vinylidene-fluoride) (PVDF). Thin films of PVDF and P(VDF-TrFE) are analyzed at the nanometre-scale using atomic force microscopy. Chain conformation and crystallization characteristics are studied by Fourier transform infrared spectroscopy and X-ray diffraction. Furthermore, the electro-mechanical behavior of P(VDF-TrFE) thin films with a spherulite-like microstructure is measured and compared to other microstructures of PVDF-based polymers reported in literature. Our findings show that ferro- or piezoelectric properties of P(VDF-TrFE) thin films are less sensitive to the microstructure.

Self‐Assembled Patterns in Ferroelectric Polymer Thin Films: Formation and Implications

AbstractPatterned piezoelectric polymer films serve as a suitable template for exploring various applications based on the characteristic electrical and optical properties. Here, the large‐area spontaneous pattern formation in relaxor terpolymer, poly(vinylidene difluoride‐trifluoroethylene‐chlorofluoroethelene) (P(VDF‐TrFE‐CFE)) films, is demonstrated using the cost‐effective breath‐figure technique. The experimental parameters allowed for controlling the hemispheroidal patterns, with pore dimensions varying from a few ≈100 nm to ≈ mm range. Due to the increased charge accumulation region, these porous structures exhibit enhanced ferroelectric and piezoelectric responses. Additionally, the refractive index contrast in the patterned structures leads to improved diffused reflection and thermal emittance. Furthermore, in the presence of guest‐dye molecules, the dominant amorphous phase of the patterned films results in higher photoluminescence yield. These features enable patterned films for high‐efficiency piezoelectric generators and passive daytime radiators.

Ferroelectric polarization of β-polyvinylidene fluoride as control and mitigator of infectious organisms

In this work, Polyvinylidene fluoride (PVDF), a ferroelectric polymer thin film, was prepared by the solution casting method. The growth of polymer films was optimized to achieve the ferroelectric β–phase with PVDF and, most importantly, ferroelectric domains with dominant planar polarization components. The ferroelectric polarization of these polymers is known to hold surface charges with/without field. The polymer is expected to interact with microbial organisms whose physiological metabolism depends on surface charges. The current COVID-19 pandemic has motivated us to carry out a fundamental study of the interaction between the polarization of the ferroelectric polymers and microbes. The antimicrobial studies were performed, making these polymer films interact with bacterial, viral, and fungal growth environments. Electroded PVDF films were kept in contact with bacterial colonies, and a dc-voltage of 1.5 V was applied across the electrodes. The film was subjected to 1.5 V and kept in contact with the culture before the growth initiation, and the microbial growth was hindered entirely. It never occurred either beneath or over the surface of the films. Thus, in the presence of the electric field, the microbial growth was inhibited, even in a conducive environment.

Assembly of Close-Packed Ferroelectric Polymer Nanowires via Interface-Epitaxy with ReS2.

The flexible, transparent, and low-weight nature of ferroelectric polymers makes them promising for wearable electronic and optical applications. To reach the full potential of the polarization-enabled device functionalities, large-scale fabrication of polymer thin films with well-controlled polar directions is called for, which remains a central challenge. The widely exploited Langmuir-Blodgett, spin-coating, and electrospinning methods only yield polymorphous or polycrystalline films, where the net polarization is compromised. Here, an easily scalable approach is reported to achieve poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE) thin films composed of close-packed crystalline nanowires via interface-epitaxy with 1T'-ReS2 . Upon controlled thermal treatment, uniform P(VDF-TrFE) films restructure into about 10 and 35 nm-wide (010)-oriented nanowires that are crystallographically aligned with the underlying ReS2 , as revealed by high-resolution transmission electron microscopy. Piezoresponse force microscopy studies confirm the out-of-plane polar axis of the nanowire films and reveal coercive voltages as low as 0.1 V. Reversing the polarization can induce a conductance switching ratio of >108 in bilayer ReS2 , over six orders of magnitude higher than that achieved by an untreated polymer gate. This study points to a cost-effective route to large-scale processing of high-performance ferroelectric polymer thin films for flexible energy-efficient nanoelectronics.

Removable polytetrafluoroethylene template based epitaxy of ferroelectric copolymer thin films

In recent years ferroelectric polymers have shown their great potentials in organic and flexible electronics. To meet the requirements of high-performance and low energy consumption of novel electronic devices and systems, structural and electrical properties of ferroelectric polymer thin films are expected to be further optimized. One possible way is to realize epitaxial growth of ferroelectric thin films via removable high-ordered polytetrafluoroethylene (PTFE) templates. Here two key parameters in epitaxy process, annealing temperature and applied pressure, are systematically studied and thus optimized through structural and electrical measurements of ferroelectric copolymer thin films. Experimental results indicate that controlled epitaxial growth is realized via suitable combination of both parameters. Annealing temperature above the melting point of ferroelectric copolymer films is required, and simultaneously moderate pressure (around 2.0 MPa here) should be applied. Over-low pressure (around 1.0 MPa here) usually results in the failure of epitaxy process, while over-high pressure (around 3.0 MPa here) often results in residual of PTFE templates on ferroelectric thin films.

Epitaxy of Ferroelectric P(VDF-TrFE) Films via Removable PTFE Templates and Its Application in Semiconducting/Ferroelectric Blend Resistive Memory.

Ferroelectric polymer based devices exhibit great potentials in low-cost and flexible electronics. To meet the requirements of both low voltage operation and low energy consumption, thickness of ferroelectric polymer films is usually required to be less than, for example, 100 nm. However, decrease of film thickness is also accompanied by the degradation of both crystallinity and ferroelectricity and also the increase of current leakage, which surely degrades device performance. Here we report one epitaxy method based on removable poly(tetrafluoroethylene) (PTFE) templates for high-quality fabrication of ordered ferroelectric polymer thin films. Experimental results indicate that such epitaxially grown ferroelectric polymer films exhibit well improved crystallinity, reduced current leakage and good resistance to electrical breakdown, implying their applications in high-performance and low voltage operated ferroelectric devices. On the basis of this removable PTFE template method, we fabricated organic semiconducting/ferroelectric blend resistive films which presented record electrical performance with operation voltage as low as 5 V and ON/OFF ratio up to 105.

Facile patterning and transfer printing of ferroelectric P (VDF‐TrFE) microstructures by topographic dewetting and Rayleigh‐Plateau instability

ABSTRACTFacile microscale patterning of ferroelectric P(VDF‐TrFE) thin films are presented. Simple spin‐coating of the polymer solution on a patterned stamp has led to a variety of features due to the topographic dewetting. The effects of important experimental parameters, such as polymer solution concentration, spin speed, and stamp geometry, are systematically examined and the results are presented as morphological phase diagrams. Further, the dewetted cylindrical lines on the stamp protrusions are found to undergo Rayleigh‐Plateau instability, which leads to the break‐up of lines into dots in a row. The various pattern features formed on structured stamp has then been successfully transfer‐printed onto various substrates such as Si, glass, polymers. The P(VDF‐TrFE) micropatterns have shown more uniform ferroelectric performances than those of unpatterned film, due likely to confinement effect. The proposed simple patterning and transfer‐printing of ferroelectric polymer thin films can be found very useful in various emerging applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45028.

Flexible Polymer Transducers for Dynamic Recognizing Physiological Signals

Ferroelectric polymers are of interest as most promising electroactive materials. Flexible transducers from ferroelectric polymer thin film with underneath semiconducting polymer active layer for high sensitive and versatile detection of physiological signals are described. When attached directly on the wrist, the flexible transducers can distinguish the transient pulse waves non‐invasively and in situ, due to their fast response (milliseconds) and high sensitivity (down to several Pascal) to instantaneous change of blood pressure. High‐resolution picture of one pulse wave is available to provide two most common parameters for arterial stiffness diagnosis. The transducers are also suitable for dynamic recognizing physiological signals under both physical exercise and medicine treatment, demonstrating their enormous potential for warning the risk of cardiovascular disease, and evaluating the efficacy of heart medicines. The transducers are easy to carry around with an operating voltage of 1 V and the power consumption less than 1 μW. Thus, they are valuable for applications like electronic skin and mobile health monitoring.

Piezoresponse force microscopy study on ferroelectric polarization of ferroelectric polymer thin films with various structural configurations

Ferroelectric polymer-based memory devices have attracted much attention due to their potential in low-cost flexible memories. However, bad retention property of recorded logic states limited their applications. Though mechanisms of retention degradation in ferroelectric memories are complicated and still an open question, depolarization in ferroelectric polymer layer was regarded as the main influencing factor. Here we reported our piezoresponse force microscopy (PFM) study of retention property of polarization states on various ferroelectric polymer based structures. PFM results indicated that, as for ferroelectric/semiconductor structure and ferroelectric/insulator/semiconductor structure with thin insulating layer, both positive and negative polarization states could retain for a relatively long time. Mechanisms of good retention of polarization states were discussed. The discrepancy in bad retention of logic states and good polarization retention of ferroelectric layer was also analyzed.

Enhancement of local piezoresponse in polymer ferroelectrics via nanoscale control of microstructure.

Polymer ferroelectrics are flexible and lightweight electromechanical materials that are widely studied due to their potential application as sensors, actuators, and energy harvesters. However, one of the biggest challenges is their low piezoelectric coefficient. Here, we report a mechanical annealing effect based on local pressure induced by a nanoscale tip that enhances the local piezoresponse. This process can control the nanoscale material properties over a microscale area at room temperature. We attribute this improvement to the formation and growth of β-phase extended chain crystals via sliding diffusion and crystal alignment along the scan axis under high mechanical stress. We believe that this technique can be useful for local enhancement of piezoresponse in ferroelectric polymer thin films.

Ferroelectric Polymer Thin Films for Organic Electronics

The considerable investigations of ferroelectric polymer thin films have explored new functional devices for flexible electronics industry. Polyvinylidene fluoride (PVDF) and its copolymer with trifluoroethylene (TrFE) are the most commonly used polymer ferroelectric due to their well‐defined ferroelectric properties and ease of fabrication into thin films. In this study, we review the recent advances of thin ferroelectric polymer films for organic electronic applications. Initially the properties of ferroelectric polymer and fabrication methods of thin films are briefly described. Then the theoretical polarization switching models for ferroelectric polymer films are summarized and the switching mechanisms are discussed. Lastly the emerging ferroelectric devices based on P(VDF‐TrFE) films are addressed. Conclusions are drawn regarding future work on materials and devices.

Temperature dependence of flexoelectric response in ferroelectric and relaxor polymer thin films

We report the temperature dependence of the flexoelectric response in thin films of both ferroelectric and relaxor forms of vinylidene fluoride polymers. The ferroelectric samples were depoled to minimize piezoelectric response by heating them beyond their Curie temperature and then cooling in zero applied electric field. In both the relaxor ferroelectric polymer and the paraelectric state of the ferroelectric copolymer, the flexoelectric coefficient was proportional to the dielectric constant over a limited range of temperatures, in agreement with general theoretical principles. The enhancements in flexoelectric response were also observed near the Curie transition temperature for the ferroelectric polymer and near the dielectric relaxation temperature for the relaxors. The broad dielectric anomaly in these systems provides greater temperature stability for these enhancements.

Thin reduced graphene oxide interlayer with a conjugated block copolymer for high performance non-volatile ferroelectric polymer memory

Polymer ferroelectric-gate field effect transistors (Fe-FETs) employing ferroelectric polymer thin films as gate insulators are highly attractive as a next-generation non-volatile memory. For minimizing gate leakage current of a device which arises from electrically defective ferroelectric polymer layer in particular at low operation voltage, the materials design of interlayers between the ferroelectric insulator and gate electrode is essential. Here, we introduce a new solution-processed interlayer of conductive reduced graphene oxides (rGOs) modified with a conjugated block copolymer, poly(styrene-block-paraphenylene) (PS-b-PPP). A FeFET with a solution-processed p-type oligomeric semiconducting channel and ferroelectric poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) insulator exhibited characteristic source–drain current hysteresis arising from ferroelectric polarization switching of a PVDF-TrFE insulator. Our PS-b-PPP modified rGOs (PMrGOs) with conductive moieties embedded in insulating polymer matrix not only significantly reduced the gate leakage current but also efficiently lowered operation voltage of the device. In consequence, the device showed large memory gate voltage window and high ON/OFF source–drain current ratio with excellent data retention and read/write cycle endurance. Furthermore, our PMrGOs interlayers were successfully employed to FeFETs fabricated on mechanically flexible substrates with promising non-volatile memory performance under repetitive bending deformation.

Polarization imaging in ferroelectric polymer thin film capacitors by pyroelectric scanning microscopy

A Pyroelectric Scanning Microscopy system, which uses laser-induced thermal modulation for mapping the pyroelectric response, has been used to image a bipolar domain pattern in a ferroelectric polymer thin film capacitor. This system has achieved a resolution of 660 ± 28 nm by using a violet laser and high f-number microscope objective to reduce the optical spot size, and by operating at high modulation frequencies to reduce the thermal diffusion length. The results agree well with a thermal model implemented numerically using finite element analysis.

Measurement of the flexoelectric response in ferroelectric and relaxor polymer thin films

We report measurements of the flexoelectric response (electric polarization induced by a strain gradient) in thin films of both ferroelectric and relaxor forms of vinylidene fluoride polymers. By using a simple cantilever measurement technique, while monitoring remanent polarization through the pyroelectric response, we are able to measure the flexoelectric response in thin films as well as isolate and correct for piezoelectric contributions, which would otherwise dominate the flexoelectric measurement.

Induced magneto-electric coupling in ferroelectric/ferromagnetic heterostructures

Using an external magnetic field, we have demonstrated room temperature control of the electric polarization of a ferroelectric polymer, polyvinylidene fluoride (PVDF), in an artificial multiferroic structure. For ferroelectric PVDF polymer thin films in an iron-PVDF-iron heterostructure, both the ferroelectric coercivity and polarization display a hysteresis dependence on the external magnetic field. We also find that the thickness of the PVDF layer has an effect on the magnetoelectric coupling in our samples. We observe a giant magnetoelectric coupling with values as large as 3700 V/cm Oe to 41700 V/cm Oe.

High Performance Multi‐Level Non‐Volatile Polymer Memory with Solution‐Blended Ferroelectric Polymer/High‐k Insulators for Low Voltage Operation

AbstractPolymer ferroelectric‐gate field effect transistors (Fe‐FETs) employing ferroelectric polymer thin films as gate insulators are highly attractive as a next‐generation non‐volatile memory. Furthermore, polymer Fe‐FETs have been recently of interest owing to their capability of storing data in more than 2 states in a single device, that is, they have multi‐level cell (MLC) operation potential for high density data storage. However, among a variety of technological issues of MLC polymer Fe‐FETs, the requirement of high voltage for cell operation is one of the most urgent problems. Here, a low voltage operating MLC polymer Fe‐FET memory with a high dielectric constant (k) ferroelectric polymer insulator is presented. Effective enhancement of capacitance of the ferroelectric gate insulator layer is achieved by a simple binary solution‐blend of a ferroelectric poly(vinylidene fluoride‐co‐trifluoroethylene) (PVDF‐TrFE) (k ≈ 8) with a relaxer high‐k poly(vinylidene‐fluoride–trifluoroethylene–chlorotrifluoroethylene) (PVDF‐TrFE‐CTFE) (k ≈ 18). At optimized conditions, a ferroelectric insulator with a PVDF‐TrFE/PVDF‐TrFE‐CTFE (10/5) blend composition enables the discrete six‐level multi‐state operation of a MLC Fe‐FET at a gate voltage sweep of ±18 V with excellent data retention and endurance of each state of more than 104 s and 120 cycles, respectively.

Improving information density in ferroelectric polymer films by using nanoimprinted gratings

In this work, well-defined low aspect ratio nanostructures based on nanogratings on thin films of poly(vinylidene fluoride–trifluoroethylene) copolymers were prepared. By using these nanogratings, an improved management of writing and reading information of about 500 Gbit/in.2 (0.01 bit/nm2) can be reached as revealed by Piezoresponse Force Microscopy. Structural investigation by means of X-ray diffraction techniques indicates that the physical confinement generated by nanoimprint promotes the development of smaller and edge-on oriented crystals. Our results evidence that one-dimensional nanostructuring can be a straightforward approach to improve the control of the polarization in ferroelectric polymer thin films.