This application claims priority to Taiwan Application Serial Number 102148724, filed Dec. 27, 2013, which is herein incorporated by reference.
1. Technical Field
The present disclosure relates to a method of fabricating a piezoelectric/conductive polymer hybrid polymer thin film and its performance boosting in electric output.
2. Description of Related Art
The piezoelectric material is one kind of the electric material with a characteristic of electric to mechanical energy conversion. It is applied to the sensor, energy converter, and actuator based on the converse piezoelectric effect which is about a mechanical transformation with an electric field, and on the direct piezoelectric effect which is about converting mechanical energy to electric energy.
The piezoelectric material can be classified in two categories as polymer and inorganic. At present, the main research direction in the piezoelectric polymer material is focus on PDF (polyvinylidene fluoride), The PVDF-based member group of the piezoelectric polymer material has the advantage of low resistance, low density, and high malleability, which the point is its easy processing and low cost result in rapid development. But the PVDF-based member group of the piezoelectric polymer material has the lower piezoelectricity compared with the piezoelectric inorganic material.
For the reason to promote the piezoelectricity of the piezoelectric polymer material, In 2008 Chunyan Li et al, issued a paper entitled “Flexible dome and bump shape piezoelectric tactile sensors using pvdf-trfe copolymer” (Journal of Microelectromechanical Systems, Vol. 17, pp. 334-341, 2008), which reports a PVDF-TrFE (poly(vinylidenefluoride-co-trifluoroethylene)) thin film, and formed a dome and bump micro-structure on the PVDF-TrFE thin film for promoting the piezoelectricity of PVDF-TrFE.
In 2012, Rachid Hadi et al, issued a paper entitled “Preparation and Characterization of P(VDF-TrFE)/Al2O3 Nanocomposite” (IEEE TRANSACTIONS ON ULTRASONICS, FERROELECTRICS, AND FREQUENCY CONTROL, Vol. 59, No. 1, pp. 163-167, 2012), which reports a method for mixing PVDF-TrFE and Al2O3 nanocomposite so as to promote the piezoelectricity of PVDF-TrFE.
Furthermore, the fact that mixing PVDF-TrFE and ZnO nanoparticle can also promote the piezoelectricity of PVDF-TrFE, which is disclosed via John S. Dodds et al. on “Piezoelectric Characterization of PVDF-TrFE Thin Films Enhanced With ZnO Nanoparticles” (IEEE SENSORS JOURNAL, Vol. 12, No. 6, pp. 1889-1890, 2012).
However, the piezoelectric material itself has no piezoelectricity when it is in steady-state condition. Since the crystal lattices of the piezoelectric material has spontaneous dipole moments which are mostly arranged in unfixed direction result in the cancellation between the dipole moment. Thus, it is necessary to utilize a polarize process for enhancing or generating the piezoelectricity of the piezoelectric material. Otherwise, the unpolarized piezoelectric material only regards as a dielectric material.
Generally speaking, the polarize process of the piezoelectric material thin film is utilized by the method with high electric field parallel plate, in which the electric field of polarization of the piezoelectric material thin film is about 40-100 MV/m. But the over-thick piezoelectric material thin film makes the higher electric field intensity, it is difficult to provide high electric field to polarize the piezoelectric material thin film with the higher electric field intensity. By contrast, it is an easy way to apply the lower electric field on the thinner piezoelectric material thin film. Even though, the following process of micro/nanostructure on the surface of the thinner piezoelectric material thin film makes the thinner piezoelectric material thin film punctured easily, and that generates the problem of the short between the top and bottom electrode which on the piezoelectric material thin film.
At previously demonstrated, the purpose of all forgoing disclosures is promoting the piezoelectricity of PVDF-TrFE composite by mixing the inorganic piezoelectric powder and PVDF-TrFE powder. In this way, the dried powder is difficult to uniformly mixed with each other, and cannot be controlled the internal electric property (such as capacitive and resistive character) of the PVDF-TrFE composite.
According to one embodiment of the present disclosure, a method for promoting an electric output of a piezoelectric/conductive hybrid polymer is provided, the method includes the following step: the piezoelectric/conductive hybrid polymer is performed by mixing a poly(vinylidene fluoride-trifluoroethylene) (PVDF-TrFE) and poly(3,4-ethylenedioxythiophene):po;y(styrenesulfonate) (PEDOT:PSS) so as to increase an output current and an output power of the piezoelectric/conductive hybrid polymer; and a surface structure of the piezoelectric/conductive hybrid polymer is changed by a nano-imprint process for promoting a piezoelectricity of the piezoelectric/conductive hybrid polymer, thereby, an output voltage, the output current and the output power of the piezoelectric/conductive hybrid polymer can be further increased.
According to another embodiment of the present disclosure, a method of fabricating a piezoelectric/conductive hybrid polymer thin film is provided, which is promoting an electric output of a piezoelectric polymer. The method includes a mixing step, a filming step, and an annealing step. The mixing step includes: a piezoelectric solution is formed by dissolving a PVDF-TrFE in an active solvent; a conductive solution is formed by dissolving a PEDOT:PSS in a water; and a piezoelectric/conductive hybrid polymer solution is formed by mixing the piezoelectric solution and the conductive solution. In the filming step, the piezoelectric/conductive hybrid polymer solution is heated, thus the piezoelectric/conductive hybrid polymer thin film is formed. In the annealing step, the piezoelectric/conductive hybrid polymer thin film is recrystallized and a nano-sized protruding structure is formed on a surface of the piezoelectric/conductive hybrid polymer thin film.
The present disclosure can be more fully understood by reading the following detailed description of the embodiment, with reference made to the accompanying drawings as follows:
The mixing step 100 includes a step 110, a step 120 and a step 130. In the step 110, a piezoelectric solution is formed by dissolving a PVDF-TrFE in an active solvent, wherein PVDF-TrFE is heated at a temperature within a range of 70° C. to 80° C. and is stirred to be dissolved in the active solvent. In the step 120, a conductive solution is formed by dissolving a PEDOT:PSS in a water, wherein a weight percentage of the PEDOT:PSS is 4.3% to 5.2% based on a weight percentage of the conductive solution being 100%. In the step 130, a piezoelectric/conductive hybrid polymer solution is formed by mixing the piezoelectric solution and the conductive solution, wherein a weight percentage range of the PEDOT:PSS is 0.78% to 2% based on a weight percentage of the piezoelectric/conductive hybrid polymer solution being 100%.
In detail PEDOT:PSS is mixed into PVDF-TrFE according to the like dissolve like principle. In the “like dissolve like” principle, the polarity of the solvent determines whether a substance or a solvent is dissolved therein or not. The permittivity of butanone is 18.5 by a measurement of the dielectric constant or the electric dipole moment. The mutual solubility between PEDOT:PSS and PVDF-TrFE is poor when PEDOT:PSS is mixed directly with PVDF-TrFE. However, the permittivity of water is 80.1, which makes PEDOT:PSS and water can completely be dissolved with each other, and the fact is known that water and butaone can completely be dissolved with each other. Therefore, the piezoelectric solution is formed by dissolving PVDF-TrFE in butaone and water as a third-party solvent to solve the problem butaone and PEDOT:PSS cannot be dissolved with each other, thereby, the piezoelectric/conductive hybrid polymer solution can be formed with mixing PEDOT:PSS and PVF-TrFE.
In the filming step 200, the piezoelectric/conductive hybrid polymer solution is heated, thus the piezoelectric/conductive hybrid polymer thin film is formed by a vaporization of the active solvent and the water, wherein the active solvent can be abovementioned butanone solvent. The filming step 200 is performed by a casting process to heat and cure the piezoelectric/conductive hybrid polymer solution, thereby the piezoelectric/conductive hybrid polymer thin film is formed. An insulating substrate is covered an electrode as a carrier of the casting process for the follow-up experiment. Specifically, the piezoelectric/conductive hybrid polymer solution is cast on the carrier, heated to 80° C. for 1 minute for the vaporization of the butaone solvent, and gradiently heated to 100° C. for the vaporization of the water, in which the piezoelectric/conductive hybrid polymer thin film is formed for 30 seconds to 3 minutes. The above are based on film forming abilities of PVDF-TrFE and the differences of the boiling point between the butaone solvent and the water. The method of gradiently heating after the vaporization of the butaone solvent is performed that the piezoelectric/conductive hybrid polymer solutions is heated slowly form 80° C. to 90° C. for 1 minute, and then heated to 100° C. for 1 minute by soft-baking for a vaporization of the water, in order to solve the problem of forming film on the surface of the piezoelectric/conductive hybrid polymer thin film caused by boiling with vapor-liquid phase transition.
In the annealing step 300, the piezoelectric/conductive hybrid polymer thin film is recrystallized at a recrystallization temperature between a Curie point (Tc) 120° C. and a melting point (Tm) 142° C. for 2 hour to 5 hour, thereby changing a crystallinity of the piezoelectric/conductive hybrid polymer thin film.
The following describes an analysis of experiment date according to the abovementioned embodiments, thereby proving an efficacy of the present disclosure fabricating process of the piezoelectric/conductive hybrid polymer thin film. It must be explained first, the experimental samples are made of the method of fabricating the piezoelectric/conductive hybrid polymer thin film according to the present disclosure, and the fabricating parameters and conditions are stated as follows: the formation time of the piezoelectric/conductive hybrid polymer thin film is 3 minute in the filming step 200, the recrystallization temperature is 140° C. and the recrystallization time is 2 hour in the annealing step 300, but only a mixing concentration of the piezoelectric solution and the conductive solution as a variance in the step 130.
From
The crystallinity of the piezoelectric/conductive hybrid polymer thin film with variable concentration conditions (weight percentage) of PEDOT:PSS is analyzed by XRD (X-ray Diffraction). The technology of XRD is well known to those of ordinary skill in the art, and will not be described particularly herein. The results in diffraction analysis with XRD are listed in TABLE 2 and TABLE 3 below:
According to TABLE 2, no peak is expressed as 2θ angle position of sample D and sample E, that is, sample D and sample E are not crystallized with a beta crystalline phase. All of sample A, sample B, sample C and sample F have peak as the same angle position (2θ, is about 20°) that is sample A, sample B, sample C and sample F are crystallized with the beta crystalline phase. The magnitude and the shift of the peak changes with the weight percentage of PEDOT:PSS in the piezoelectric/conductive hybrid polymer thin film.
According to TABLE 3, the larger grain size of the crystal is, the narrower FWHM (Full Width half Maximum) of the peak is, that is, the higher crystallinity of the piezoelectric/conductive hybrid polymer thin film is obtained.
The piezoelectricity of the piezoelectric/conductive hybrid polymer thin film with variable concentration conditions (weight percentage) of PEDOT:PSS is analyzed by PFM (Piezorespnse Force Microscopy).
The following analysis is about measuring of direct piezoelectric signals and output current signals of the piezoelectric/conductive hybrid polymer thin film with a vibration of a motor which with adjustment of the voltage to control the vibration frequency, thereby, the piezoelectricity of the piezoelectric/conductive hybrid polymer thin film can be measured.
The vibration frequency of the motor is set as 250 Hz, and the additional samples apart from abovementioned sample A-F are listed in the table 4 below:
In addition, the best concentration condition (weight percentage) of the PEDOT:PSS in the piezoelectric/conductive hybrid polymer thin film can be obtained by a EA (Electrochemical Analyzer).
The following analysis is about measuring of direct piezoelectric signals of the piezoelectric/conductive hybrid polymer thin film by a preset force from a cantilever applying on thereof, as the piezoelectric/conductive hybrid polymer thin film is forced by the cantilever which with adjustment of a height between the cantilever and the piezoelectric/conductive hybrid polymer thin film to control the preset force, thereby, the piezoelectricity of the piezoelectric/conductive hybrid polymer thin film can be obtained. To perform this analysis must set a predetermined height between the cantilever and the piezoelectric/conductive hybrid polymer thin film. While the cantilever is lifted to the predetermined height and then released, a potential energy of the cantilever is converted to a kinetic energy as the preset force on the piezoelectric/conductive hybrid polymer thin film.
A maximum of the preset force which the cantilever provided herein is 99.86 mN, the maximum force is forced on sample B, sample F, and sample K.
A specific implement of the thermal nanoimprinting mold process applies on sample B as sample B′ is following; performing a fluorination for an mold with nanograss structure, and then imprinting the mold on the surface of the piezoelectric/conductive hybrid polymer thin film with uniform heating and pressurizing, thereby forming the piezoelectric/conductive hybrid polymer thin film with nanograss. The mold surface has a cover layer of fluorine, a contact angle between the mole and the piezoelectric/conductive hybrid polymer thin film becomes larger, so that an adhesive force between the mole and the piezoelectric/conductive hybrid polymer thin film will be decreased.
Furthermore, the output current and the output voltage piezoelectric/conductive hybrid polymer thin film with nanograss on the nano-sized protrusive on the surface are analyzed by the abovementioned method with the vibration of the motor.
Although the present invention has been described in considerable detail with reference to certain embodiments thereof, other embodiments are possible. Therefore, the spirit and scope of the appended claims should not be limited to the description of the embodiments contained herein.
It will be apparent to those skilled in the art that various modifications and variations can be made to the structure of the present invention without departing from the scope or spirit of the invention. In view of the foregoing, it is intended that the present invention cover modifications and variations of this invention provided they fall within the scope of the following claims.
Number | Date | Country | Kind |
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102148724 | Dec 2013 | TW | national |