DE112021006131T5 - Layered electronic component and method for producing the layered electronic component - Google Patents

Abstract

A layered electronic device, for example a flexible haptic feedback device, is disclosed. The layered electronic device may include a stack with first and second electroactive polymer (EAP) layers. Each of the first and second EAP layers may contain an EAP material. A substantial portion of each of the first and second EAP layers may be particle-free. The stack may further include an electroactive composite layer disposed between the first and second EAP layers, the electroactive composite layer having a thickness along a first direction. The electroactive composite layer may contain a polymer matrix, which may also contain particles. Furthermore, a method for producing a layered electronic component is disclosed. The method may include providing a substrate and forming a stack. The stack may be formed by: applying a first EAP layer material, applying an EAP composite layer composition, and applying a second EAP layer material.

Description

Technical area

Various aspects of this disclosure relate to a layered electronic device and a method of manufacturing the layered electronic device.

State of the art

Conventional electronic components can have electrically active layers between electrodes. The electrically active layers may contain composite layers with high dielectric constant fillers to improve the dielectric properties of the device. However, such fillers cause local amplification of an applied electric field due to the Maxwell-Wagner-Sillars effect (MWS) at the filler/matrix interface, resulting in severe degradation of dielectric strength and premature failure of the device.

Therefore, there is a need to provide an improved layered electronic device that has high dielectric strength.

Short presentation

It is therefore the subject of the invention to provide an improved layered electronic component, e.g. B. to provide an electromechanical actuator or actuator.

Various embodiments may provide a layered electronic device. The layered electronic device may include a stack, which may further include first and second electroactive polymer (EAP) layers. Each of the first and second EAP layers may contain an EAP material. A significant part of it can be particle-free. The stack may further include an electroactive composite layer, which may be disposed between the first and second EAP layers and may have a thickness along a first direction. The electroactive composite layer may contain a polymer matrix and may also contain particles.

Various embodiments may provide a method of manufacturing the layered electronic component. The method may include providing a substrate and forming the stack. The stack may include depositing a first EAP layer material, depositing an EAP composite layer composition, and further depositing a second EAP layer material.

According to various embodiments, the layered electronic component may be a flexible actuator with haptic feedback. According to various embodiments, the layered electronic device may be a flexible thin film haptic feedback actuator.

Brief description of the drawings

• - 1A und 1 B zeigen als Beispiel schematische Darstellungen eines Querschnitts eines geschichteten elektronischen Bauelements 100 gemäß verschiedenen Ausführungsformen;
• - 2A und 2B zeigen schematische Darstellungen von geschichteten elektronischen Bauelementen 200 und 230, als Beispiel, gemäß verschiedenen Ausführungsformen;
• - 3 zeigt eine schematische Darstellung eines beispielhaften Verfahrens 300 zur Herstellung eines geschichteten elektronischen Bauelements 100 gemäß verschiedenen Ausführungsformen;
• - 4 zeigt eine rasterelektronenmikroskopische (REM) Aufnahme des Querschnitts der EAP / ZrO₂:EAP / EAP-Schichten, als Beispiel, gemäß verschiedenen Ausführungsformen;
• - 5A und 5B zeigen die Röntgenbeugungsspektren (XRD) zum Vergleich der (A) EAP / ZrO₂-Schichten und der EAP / ZrO₂: EAP / EAP-Schichten und (B) der EAP / TiO₂-Schichten und der EAP / TiO₂: EAP / EAP-Schichten, als Beispiel, gemäß verschiedenen Ausführungsformen;
• - 6A bis 6C zeigen die elektrische Durchbruchverteilung und das ferroelektrische Hysteresediagramm der EAP / ZrO₂: EAP / EAP-Schichten im Vergleich zu den EAP / ZrO₂-Schichten, als Beispiel, gemäß verschiedenen Ausführungsformen;
• - 7A bis 7C zeigen die Verteilung des elektrischen Durchbruchs und die ferroelektrische Hysteresekurve der EAP / TiO₂: EAP / EAP-Schichten im Vergleich zu den EAP / TiO₂-Schichten, als Beispiel, gemäß verschiedenen Ausführungsformen; und
• - 8 zeigt ein Diagramm, das die Ausgangskraft der EAP / ZrO₂: EAP / EAP-Schichten, der EAP / TiO₂: EAP / EAP-Schichten und der reinen EAP / EAP / EAP-Schichten gemäß verschiedenen Ausführungsformen beispielhaft vergleicht.

The invention will be better understood with reference to the detailed description when considered in conjunction with the non-limiting examples and accompanying drawings, in which:

• - 1A and 1 B show, as an example, schematic representations of a cross section of a layered electronic component 100 according to various embodiments;
• - 2A and 2 B show schematic representations of layered electronic components 200 and 230, by way of example, according to various embodiments;
• - 3 shows a schematic representation of an exemplary method 300 for producing a layered electronic component 100 according to various embodiments;
• - 4 shows a scanning electron microscope (SEM) image of the cross section of the EAP/ZrO ₂ :EAP/EAP layers, as an example, according to various embodiments;
• - 5A and 5B show the X-ray diffraction spectra (XRD) for comparing the (A) EAP / ZrO ₂ layers and the EAP / ZrO ₂ : EAP / EAP layers and (B) the EAP / TiO ₂ layers and the EAP / TiO ₂ : EAP / EAP layers, by way of example, according to various embodiments;
• - 6A until 6C show the electrical breakdown distribution and ferroelectric hysteresis diagram of the EAP/ZrO ₂ :EAP/EAP layers compared to the EAP/ZrO ₂ layers, as an example, according to various embodiments;
• - 7A until 7C show the electrical breakdown distribution and ferroelectric hysteresis curve of the EAP/TiO ₂ :EAP/EAP layers compared to the EAP/TiO ₂ layers, as an example, according to various embodiments; and
• - 8th shows a diagram that compares, by way of example, the output force of the EAP / ZrO ₂ : EAP / EAP layers, the EAP / TiO ₂ : EAP / EAP layers and the pure EAP / EAP / EAP layers according to various embodiments.

Detailed description

The following detailed description refers to the accompanying drawings, which show, by way of illustration, specific details and embodiments in which the disclosure may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to utilize the disclosure. Other embodiments may be employed, and structural and logical changes may be made, without departing from the scope of the disclosure. The various embodiments are not necessarily mutually exclusive, as some embodiments may be combined with one or more other embodiments to form new embodiments.

Features described in connection with one embodiment may apply correspondingly to the same or similar features in the other embodiments. Features described in connection with one embodiment may apply correspondingly to the other embodiments, even if they are not expressly described in those other embodiments. In addition, additions and/or combinations and/or alternatives as described for a feature in connection with one embodiment may apply correspondingly to the same or similar feature in the other embodiments.

The disclosure illustratively described herein may be conveniently carried out in the absence of one or more elements or limitations not specifically disclosed herein. For example, the terms “comprising,” “including,” “including,” etc. are intended to be broadly construed and not limited. Accordingly, the word “comprise” or variations such as “comprises” or “comprising” are to be understood to imply the inclusion of a particular integer or group of integers, but not the exclusion of any other integer or group of integers. Furthermore, the terms and expressions used herein have been used for purposes of description rather than limitation, and the use of such terms and expressions is not intended to exclude equivalents of the features shown and described or portions thereof, but rather acknowledges that various modifications may occur within the scope of the disclosure is possible. It should therefore be understood that although the present disclosure has been specifically disclosed through example embodiments and optional features, modifications and variations to the disclosure embodied herein may be made by those skilled in the art.

In connection with various embodiments, the articles "a," "an," and "the" used in reference to a feature or element include a reference to one or more of the features or elements. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items.

The reference symbols in parentheses in the claims serve to better understand the disclosure and have no limiting effect on the scope of the claims.

As used herein and in various embodiments, the “J” may mean delamination, e.g. For example, “A/B” can mean that components A and B exist in separate layers, such as B. a main surface of layer A opposite a main surface of layer B, the layers A and B lie on top of each other, the layers A and B overlap each other directly or indirectly with further layers in between. As used herein and according to various embodiments, the ":" may mean that the components of a layer represent a mixture or mixture, e.g. B. “A : B” can mean that A and B are mixed or blended in a common layer.

According to various embodiments, the term "layered" as used herein may refer to an arrangement of layers or sheets stacked one on top of the other. The term “layered” may include two or more layers arranged in a multi-stack structure. For example, the term "layered" may refer to an assembly that includes a first electroactive polymer layer (EAP), an electroactive composite layer stacked on the first EAP layer, and a second EAP layer stacked on the electroactive composite layer is, includes. Accordingly, the term “layered electronic device” may refer to an electronic device that can be formed by the arrangement of layers. As used herein and in accordance with various embodiments, the terms "top" and "bottom" are used to mean various those sides, and may further denote a position or stacking direction with respect to the substrate or the bottom, for example the substrate being closer to the bottom than the electroactive layers which may be “on top” of the substrate.

According to various embodiments, the term "particles" as used herein may refer to individual parts, which may be composed of ceramic or metallic materials. For example, ceramic particles can be inorganic and additionally heat-resistant and consist of both metallic and non-metallic compounds. Metallic particles can consist of metallic elements. The ceramic particles and the metallic particles may have one or more dielectric, ferroelectric, or piezoelectric properties, according to various embodiments. Within the scope of the disclosure, some embodiments and examples may use ceramic particles. However, it is conceivable that the embodiments and examples according to the disclosure also use metal particles instead of (or in addition to) ceramic particles.

The 1A shows a schematic representation of a cross section of a layered electronic component 100 as an example. The inset shows an enlarged view of a portion of the electroactive composite layer 130 according to various embodiments. The layered electronic component 100 may include a substrate 110 and a stack 170. The stack 170 may include a first EAP layer 120, an electroactive composite layer 130, and a second EAP layer 140. The electroactive composite layer 130 may be disposed between the first and second EAP layers 120, 140 and may have a thickness along a first direction 1D. The first direction 1D can run perpendicular to the substrate 110 according to various embodiments. The electroactive composite layer 130 may be aligned parallel to the substrate 110. The electroactive composite layer 130 may be embedded between the first and second EAP layers 120, 140. The layered electronic component 100 may further include a first electrode 180 and a second electrode 190 as well as the stack 170 arranged between the first electrode 180 and the second electrode 190. The stack 170 can, for example, be embedded between the first and second electrodes 180, 190. The first EAP layer 120 can be in contact with the first electrode 180 and the second EAP layer 140 can be in contact with the second electrode 190. Within the scope of the present disclosure and in accordance with various embodiments, the layered electronic device 100 may be an electromechanical device, e.g. B. an actuator with haptic feedback. As another example, the layered electronic component 100 may be a flexible actuator with haptic feedback.

According to various embodiments, substrate 110 may include any substrate suitable for use in actuators. For example, the substrate 110 may be a flexible substrate and/or a transparent substrate. As another example, the substrate 110 may be a polymeric substrate, for example polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), which may be flexible and/or transparent.

The first and second EAP layers 120, 140 may each contain an EAP material. A significant portion of the first and second EAP layers 120, 140 may be free of particles 160 (e.g., ceramic particles).

According to various embodiments, the term "electroactive polymer" or its abbreviation EAP, as used herein, may refer to a polymer that can undergo a shape change in response to an applied electric field, wherein the polymer can additionally emit an electrical signal upon mechanical stimulation . The electrical signal can be detected via electrodes connected to the EAP. The EAP may be a type of electroactive material. Within the scope of the present disclosure and in accordance with various embodiments, the EAP is a polymer that undergoes a shape change in response to an applied electric field. Examples of EAPs may include: dielectric EAP (dEAP), piezoelectric active polymer (piezoEAP). Examples of piezoelectric EAPs are poly(vinylidene fluoride), abbreviated (PVDF), and its copolymers, namely: ferroelectric EAPs (ferroEAPs) such as poly (vinylidene fluoride - trifluoroethylene - chlorotrifluoroethylene), abbreviated as P(VDF - TrFE - CTFE), poly (vinylidene fluoride - Trifluoroethylene - Chlorofluoroethylene), abbreviated as P(VDF - TrFE - CFE), Poly(vinylidene fluoride - trifluoroethylene - hexafluoropropylene), abbreviated as P(VDF - TrFE - HFP), and Poly[(vinylidene fluoride - co - trifluoroethylene], abbreviated as P(VDF - TrFE), Poly[(vinylidene fluoride - co - hexafluoropropylene], abbreviated as P(VDF - HFP), Poly[(vinylidene fluoride - co - chlorotrifluoroethylene], abbreviated as P(VDF - CTFE). Examples of dielectric EAPs are : Acrylic elastomers, silicone elastomers, fluoroelastomers, polyurethane, natural/synthetic rubbers.

According to various embodiments, the term “EAP material” as used herein may refer to a material that contains EAPs as defined above. For example, an EAP material may include an EAP composition that contains at least one EAP. According to various embodiments, the term EAP material may include or be an EAP.

According to various embodiments, as used herein, the term "substantial portion thereof" with respect to a layer may mean that a large portion of the layer is a material, e.g. B. the EAP, includes or essentially consists of it. In other words, the layer must contain no or only small amounts of a contaminant, e.g. B. contain inorganic particles such as ceramic particles. The term “significant share” can e.g. B. mean that the proportion of EAP in the layer accounts for more than 95% or more than 98% of the thickness of the layer or that the layer is free of particles.

According to various embodiments, the term "particulate-free" as used herein may refer to the EAP material, e.g. B. an EAP composition containing an EAP that may contain no particles (e.g., ceramic particles) or trace or minute amounts of particles (e.g., ceramic particles). For example, minute amounts of the particles (e.g., ceramic particles) may inadvertently enter the EAP material of the adjacent EAP layers (e.g., first and second EAP layers) due to the diffusion of the particles (e.g. Ceramic particles) from the electroactive composite layer (e.g. during the formation of the layered electronic component). The term particle-free (e.g., ceramic particles) may refer to an EAP material that contains 96 to 100 vol% of the EAP (e.g., ≤ 5 vol% of the particles, e.g., ceramic particles) . The term free of particles (e.g. ceramic particles) may, for example, refer to an EAP material that contains 98 to 100% by volume of the EAP (e.g. ≤ 2% by volume of the particles, e.g . Ceramic particles). As used herein and in accordance with various embodiments, the term “free of particulates (e.g., ceramic particles)” may refer to the EAP material containing ≤2% by volume of particulates (e.g., ceramic particles). In other words, the EAP material of the first and second EAP layers 120, 140 may contain at least 98% by volume of the EAP.

According to various embodiments, the EAP material of the first and second EAP layers 120, 140 may comprise an EAP composition that includes an electroactive material, e.g. B. an EAP. As another example, the EAP material may include FerroEAPs such as PVDF - TrFE, P(VDF - TrFE - CTFE), P(VDF - TrFE - CFE). According to a preferred embodiment, the EAP material of the first and second EAP layers 120, 140 may be P(VDF - TrFE - CTFE).

In the 1A the inset shows an enlarged view of an exemplary schematic representation of the electroactive composite layer 130 according to various embodiments. The electroactive composite layer 130 may contain a polymer matrix 150 and particles 160 (e.g., ceramic particles). For example, the electroactive composite layer 130 may contain particles 160 (e.g., ceramic particles) dispersed in the polymer matrix 150. Another example is that the polymer matrix 150 may be a mass in which the particles 160 (e.g. ceramic particles) are embedded. The particles 160 (e.g., ceramic particles) may contain particles with a high dielectric constant (e.g., higher than the dielectric constant of silicon dioxide, e.g., >3.9) to increase the permittivity and polarizability of the electroactive composite layer 130 increase. The particles 160 can be, for example, ceramic particles, which can also include dielectric ceramic nanoparticles.

While those in the 1A and 1B Particles 160 (e.g., ceramic particles) shown have different dimensions, the particles 160 may have a regular size and/or shape in some embodiments. For example, each particle 160 (e.g., ceramic particles) may be substantially identical and have a narrow size distribution.

According to various embodiments, the polymer matrix 150 may be a matrix containing an electroactive material, for example an EAP. As another example, the polymer matrix may contain 150 ferroEAPs, for example PVDF - TrFE, P(VDF - TrFE - CTFE), P(VDF - TrFE - CFE). According to a preferred embodiment, the polymer matrix 150 may contain the P(VDF-TrFE-CTFE) EAP. The first (120) and second (140) EAP layers and the polymer matrix (150) of the electroactive composite layer (130) may contain the same EAP material as a major component, according to various embodiments. The same EAP material can be, for example, the P(VDF - TrFE - CTFE) EAP.

According to various embodiments, the particles 160 (e.g., ceramic particles) may be on a nanometer range (e.g., scale) of dimensions. The size, e.g. B. the diameter of the particles 160 (e.g. ceramic particles) can e.g. B. Dimensions in the range from 2 nm to 300 nm. For example, the size (e.g. diameter) of the particles 160 (e.g. ceramic particles) can be in the range from 2 nm to 200 nm. Within the scope of the present disclosure, the particles 160 (e.g., ceramic particles) may be nanoparticles 160 (e.g., ceramic nanoparticles) having a size (e.g. Diameter) in the range from 2 nm to 100 nm.

According to various embodiments, the particles 160 may include or be ceramic particles. The ceramic particles 160 may contain a metal oxide. The metal oxide may include particles containing a metal cation and an oxide anion. The metal oxide may have a high dielectric constant and may be a piezoelectric metal oxide. Therefore, the particles 160 can generate an electrical current in response to mechanical stress. Examples of metal oxides are zirconium dioxide, abbreviated (ZrO ₂ ), titanium dioxide, abbreviated (TiO ₂ ), barium titanate, abbreviated (BaTiO ₃ ), barium strontium titanate, abbreviated ((Ba Sr)TiO ₃ ), magnesium titanium oxide, abbreviated as (MgTiO ₃ ), calcium copper titanate, abbreviated as (CaCu _a Ti ₄ O ₁₂ ), lead magnesium niobate lead titanate, abbreviated as (Pb(Mg _1/3 Nb _2/3 )O ₃ ), lead zirconate titanate , abbreviated as (Pb(Zr,Ti)O ₃ ). According to various embodiments, the ceramic particles 160 can consist of ZrO ₂ or TiO ₂ .

According to various embodiments, the weight ratio of the particles 160 (e.g. ceramic particles) to the polymer matrix 150 of the electroactive composite layer 130 can be between 2% by volume and 70% by volume. For example, the weight ratio of the ceramic particles 160 to the polymer matrix 150 can be between 2% by volume and 60% by volume or between 2% by volume and 50% by volume.

According to various embodiments, the particles 160 (e.g., ceramic particles) in the electroactive composite layer 130 may be randomly dispersed in the polymer matrix 150, for example, in a second direction 2D, which may be perpendicular to the first direction 1D. The second direction 2D can z. B. run parallel to the substrate 110. For example, the particles 160 (e.g., ceramic particles) in the polymer matrix 150 may be arranged in a non-uniform or irregular manner along the second direction 2D within the polymer matrix 150 of the electroactive composite layer 130. As another example, each particle 160 (e.g., ceramic particles) within the polymer matrix 150 may be disposed in different planes along the thickness of the electroactive composite layer 130 (e.g., along the first direction 1D, perpendicular to the substrate 110). To illustrate, a first particle 160 could not be aligned with a second particle 160 within the polymer matrix 150. In other words, the particles 160 may not be distributed in a regular arrangement in the polymer matrix 150. According to various embodiments, the particles 160 may include or be ceramic particles 160.

The 1B shows an exemplary schematic representation of a cross section of the layered electronic component 100. The insets (a) and (b) show enlarged views of areas of the electroactive composite layer 130 according to various embodiments. According to various embodiments, the concentration of the particles 160 (e.g., ceramic particles) in the electroactive composite layer 130 in a first range may vary from the concentration of the particles 160 (e.g., ceramic particles) in the electroactive composite layer 130 in a second range within the Polymer matrix 150 differ. The first and second regions may be located along the second direction 2D (e.g., parallel to the substrate 110). The first and second regions may include a thickness along the first direction 1D of the electroactive composite layer 130 and may be remote from the substrate 110. In the 1 B Inset (a) shows an enlarged view of the schematic representation of an exemplary first region in the electroactive composite layer 130. Inset (b) shows an enlarged view of the schematic representation of an exemplary second region in the electroactive composite layer 130. The first region (e.g. Inset (a)) may contain a larger number of particles 160 (e.g., ceramic particles) dispersed in the polymer matrix 150 than the second region (e.g., inset (b)). In other words: The concentration of the particles 160 (e.g. ceramic particles) in the first region of the electroactive composite layer 130 can be higher than the concentration of the particles 160 (e.g. ceramic particles) in the second region (e.g. inset (b )) within the polymer matrix 150. In other words, the concentration of the particles 160 (e.g. ceramic particles) in the second region may be lower than that in the first region within the polymer matrix 150 of the electroactive composite layer 130. For example, the difference between the concentration of particles 160 (e.g. ceramic particles) between the first and second regions are less than 20%, less than 10% or less than 5%. Alternatively, the concentration of the particles 160 (e.g., ceramic particles) within the polymer matrix 150 of the electroactive composite layer 130 may be substantially uniform, according to various embodiments. For example, the concentration of particles 160 (e.g., ceramic particles) may be the same in the first and second regions.

According to various embodiments, the thickness of the electroactive composite layer 130 may be less than 10 μm, less than 5 μm, or less than 2 μm. Thus, the size (e.g., diameter) of the particles 160 (e.g., ceramic particles in the range of 2 nm to 100 nm) may be less than half, less than 10%, less than 5%, or include or be less than 1% of the thickness of the electroactive composite layer 130.

According to various embodiments, the thickness of the stack 170 may be less than 300 μm, less than 200 μm, or less than 100 μm. For example, the thickness of the stack 170 may be between 2 µm and 100 µm or between 2 µm and 50 µm. Thus, the thickness of the layered electronic component 100 as a whole may have a thickness suitable for electromechanical applications, e.g. B. for electromechanical thin film applications (e.g. for use in flexible haptic thin film actuators). According to various embodiments, the thickness of the layered electronic device 100 may be less than 800 μm or less than 500 μm and may include the substrate 110, the stack 170, and the first and second electrodes 180, 190.

The 2A shows a schematic representation of a layered electronic component 200, as an example, according to an embodiment. The layered electronic device 200 may include a substrate 210 and a plurality of the stacks 220 arranged as an array. The substrate 210 may be a common substrate 210 for each stack 170 of the plurality of stacks 220. The majority of stacks 220 may contain a single stack 170. For example, the single stack 170 may include the first and second EAP layers 120, 140 and the electroactive composite layer 130 lying between the first and second EAP layers 120, 140. Individual stacks 170 from the plurality of stacks 220 may be arranged side by side in a direction parallel to a major surface of the common substrate 210, thus forming the array. For example, each stack 170 of the plurality of stacks 220 may be arranged side by side and in a regular array along a plane that is parallel to the major surface of the common substrate 210. Another example is that each stack 170 of the plurality of stacks 220 may be in contact with one another (e.g., parallel to the surface of the plurality of stacks 220). For example, the first 120 and second 140 EAP layers and the electroactive composite layer 130 of a first stack 170 of the plurality of stacks 220 may be in contact with the second stack 170 of the plurality of stacks 220. The layered electronic device 200 may further include electrodes, and the plurality of stacks 220 may be disposed between the electrodes.

The 2 B shows a schematic representation of a layered electronic component 230, as an example, according to another embodiment. The layered electronic device 230 may include a substrate 240 and a plurality of the stacks 250 arranged as a superstack. For example, substrate 240 may be a common substrate 240 for the majority of stacks 250. The majority of stacks 250 may include a single stack 170. The single stack 170 may include, for example, the first and second EAP layers 120, 140 and the electroactive composite layer 130. Individual stacks 170 of the plurality of stacks 250 may be arranged in a multi-story arrangement (e.g., superstacks). For example, each stack 170 of the plurality of stacks 250 may be stacked in a direction perpendicular to the main surface of the common substrate 240 and stacked one above the other in a regular arrangement. To illustrate, a second stack may be placed on top of a first stack and a third stack on top of the second stack such that the plurality of stacks 250 form a multi-story structure. As another example, each stack 170 of the plurality of stacks 250 may be in contact with each other (e.g., in the direction perpendicular to the major surface of the common substrate 240). For example, the second EAP layer 140 of a first stack 170 of the plurality of stacks 250 may be in contact with the first EAP layer 120 of a second stack 170 of the plurality of stacks 250. Alternatively, a single EAP layer, for example between two individual stacks 170 of the superstack 250, the second EAP layer 140 of the first stack 170 of the plurality of stacks 250 and the first EAP layer 120 of the second stack 170 of the plurality of stacks 250 ( that are in contact with each other). The layered electronic device 230 may further include electrodes, and the plurality of stacks 250 may be disposed between the electrodes (in the 2 B not shown).

The ones in the 2A and 2 B Arrangements shown are merely examples, and other embodiments are also conceivable (e.g., a layered electronic device that includes both the array of stacks 220 and superstack 250). Thus, there may be flexibility in fabricating various complex actuator designs according to the layered electronic device 100 of the present disclosure.

The detailed description of the manufacturing process is provided in connection with the 3 shown, which shows a schematic representation of an exemplary method 300 for producing a layered electronic component 100 according to various embodiments. The method 300 may include a step of providing the substrate 110 and the first electrode 180.

Step 310 includes applying a first EAP layer material 120. The first EAP layer material 120 may be applied to the underlying substrate 110 or the underlying electrode, e.g. B. the first electrode 180 (e.g. in a component) are deposited. According to various embodiments, the material of the first EAP layer 120 may include an EAP composition that contains an EAP. The material of the first EAP layer 120 can be coated, for example, with the help of squeegees, coating using a bar coating machine, roller coating with a rod coating acting from below, screen printing, slot die coating, spin coating, roller-to-roll coating (R2R) or another coating technique applied, e.g. B. be coated. The 3 shows an example of the rod coating with the rod 160. The first EAP layer 120 may further be patterned or unpatterned according to various embodiments.

Step 310 may further include a post-processing step in which the material of the first EAP layer 120 is dried to remove the solvent and/or annealed. Annealing can strengthen the crystalline structure and further enhance the ferroelectric properties of FerroEAPs. To facilitate the post-processing step, vacuum and/or heat may be applied.

Step 320 includes depositing an electroactive composite layer 130 composition. The composition of the electroactive composite layer 130 may contain the particles 160 (e.g., ceramic particles) dispersed in the polymer matrix 150 and may be deposited on the first EAP layer 120. The composition of the electroactive composite layer 130 can be applied using conventional coating methods as described above in step 310, e.g. B. coated. The composition of the electroactive composite layer 130 can also, for example, B. can be applied using a polymer thin-film transfer technique. This technique may include fabricating the electroactive composite layer 130 as a thin film multiup on a reusable temporary glass support and later transferring the electroactive composite layer 130 to a layer of choice, such as the underlying first EAP layer 120.

According to various embodiments, the composition of the electroactive composite layer 130 including the polymer matrix 150 and the particles 160 (e.g., ceramic particles) may be a solution. For example, the polymer matrix 150 and the particles 160 (e.g., ceramic particles) may be suspended in the solution. The solution may contain a solvent that can be selected to dissolve the EAP of the polymer matrix 150 and disperse the particles 160 (e.g., ceramic particles) and prevent them from agglomerating. Additionally, the selected solvent may prevent the underlying layer (e.g., first EAP layer 120) from dissolving and/or destroying the crystallinity achieved by a prior annealing process in step 310. Solvents for dissolving PVDF and its co- and terpolymers include, but are not limited to, methyl ethyl ketone, abbreviated (MEK), acetone, methyl isobutyl ketone and cyclohexanone.

In the example of step 320 from the 3 The Meyer rod coating can be chosen for the deposition of the electroactive composite layer 130 composition due to its fast speed and ease of use. However, other suitable coating processes can also be used, e.g. B. Squeegee coating, spray coating, screen printing and others. The bar squeegee 160 may be the same or different than that used in step 310. The electroactive composite layer 130 may further be patterned or unpatterned according to various embodiments.

Step 320 may further include a post-processing step in which the composition of the electroactive composite layer 130 is dried to remove the solvent and/or annealed, as described in step 310 above.

Step 330 includes depositing a second EAP layer material 140, which may be deposited on the underlying layer, such as the electroactive composite layer 130. According to various embodiments, the material of the second EAP layer 140 may include an EAP composition having an EAP. The material of the second EAP layer 140 can be applied using suitable coating methods, e.g. B. coated, or applied using the polymer thin film transfer process, as described in steps 310 and 320, respectively. Step 330 may further include a post-processing step in which the material of the second EAP layer 140 is dried to remove the solvent and/or annealed, as described in step 310 above. The second EAP layer 120 may further be patterned or unpatterned according to various embodiments.

Step 340 includes treating the stack 170 including the first and second EAP layers 120, 140 and the electroactive layers composite layer 130. The treatment may include any conventional heat treatment and/or stretching treatment to improve the polymer crystallinity and hence the dielectric properties of the layered electronic device 100. For example, step 340 may include heat treatment at 110°C for 120 minutes.

The step 350 of 3 shows the layered electronic device 100 manufactured according to various embodiments. Step 350 may include attaching a second electrode 190 to the underlying layer, e.g. B. the second EAP layer 140. The second electrode 190 can be deposited using any suitable layer coating technique, e.g. B. by sputtering, vapor deposition or using techniques as described above in step 310. The first electrode 180 can also be deposited using one of these techniques, in a similar manner to the second electrode. The first and second electrodes 180, 190 may be deposited independently of one another and may each be patterned or unpatterned. According to various embodiments, the layered electronic device may include the substrate 110, the first and second EAP layers 120, 140, the electroactive composite layer 130, and the first and second electrodes 180, 190.

According to various embodiments, the method 300 may further include forming an encapsulation. For example, a protective insulating layer may be applied to the top electrode (e.g., second electrode 190) to protect it, e.g. B. to electrically isolate the layered electronic component 100 from a user touching the component.

Examples

In the following examples, the particles 160 are referred to as ceramic particles 160. However, it is conceivable that the particles 160 also include or can be metallic particles.

The 4 shows a scanning electron microscope (SEM) image of the cross section of the exemplary EAP / ZrO ₂ : EAP / EAP layers (e.g. stack 170 in the 1A , including the first 120 and second 140 EAP layers and the electroactive composite layer 130 lying between the first 120 and second 140 EAP layers). The first 120 and second 140 EAP layers and the electroactive composite layer 130 may contain the EAP P(VDF - TrFE - CTFE). The concentration of the ceramic particles 160, ZrO ₂ , may be at a weight ratio of 50 vol%, and the scale bar represents 1 micrometer. As in the 4 As can be seen, the electroactive composite layer 130 is clearly distinguishable from the first 120 and second 140 EAP layers and shows relatively sharp boundaries.

The 5 until 8th show comparative examples of the EAP/ZrO ₂ or EAP/TiO ₂ layers compared to the EAP/ZrO ₂ : EAP/EAP or EAP/TiO ₂ : EAP/EAP layers (e.g. stack 170). The EAP/ZrO ₂ or EAP/TiO ₂ layers can be an EAP layer, e.g. B. the first EAP layer 120, and the electroactive composite layer 130 include. In the electroactive composite layer 130 of the EAP/ZrO ₂ or the EAP/TiO ₂ layers, the weight ratio of the ceramic particles 160 to the polymer matrix 150 can be between 10 and 50 vol.%. On the other hand, the EAP/ _ZrO2 :EAP/EAP or the EAP/ _TiO2 :EAP/EAP layers may contain the electroactive composite layer 130 sandwiched between two EAP layers, e.g. B. the first and second EAP layers 120, 140 (e.g. stack 170 in 1A) , is arranged. In the electroactive composite layer 130 of the EAP/ZrO ₂ :EAP/EAP or the EAP/TiO ₂ :EAP/EAP layers, the weight ratio of the ceramic particles 160 to the polymer matrix 150 can be 50% by volume. The first and second EAP layers 120, 140 and the electroactive composite layer 130 may each contain EAP, P(VDF - TrFE - CTFE). In the following examples, the solvent MEK was used for the manufacturing process (e.g. Process 300 in 3 ).

The 5 shows exemplary X-ray diffraction spectra (XRD) of the: (A) EAP/ZrO ₂ layers and the EAP/ZrO ₂ : EAP/EAP layers, and (B) EAP/TiO ₂ layers and the EAP/TiO ₂ : EAP/EAP -Layers. Like in the 5A and 5B shown, the peak intensity of the EAP/ _ZrO2 :EAP/EAP or the EAP/ _TiO2 :EAP/EAP layers remains at 18.3° regardless of the type of ceramic particles 160 used. In the 5A When using the ZrO ₂ ceramic particle 160 (marked by an arrow), the peak intensity can lie between that of the EAP / ZrO ₂ layers, which have a weight ratio of 40 vol.-% (marked with 510) to 50 vol.-% (marked with 520) from ZrO ₂ to the polymer matrix 150. In the 5B The peak intensity using the TiO ₂ ceramic particle 160 (indicated by an arrow) may be between that of the EAP/TiO ₂ layers with a weight ratio of 30 vol% (indicated as 530) to 40 vol%. From the 5A and 5B It can be seen that the EAP / ZrO ₂ : EAP / EAP and the EAP / TiO ₂ : EAP / EAP layers have a higher crystallinity compared to the EAP ZrO ₂ and EAP / TiO ₂ layers because the first and second EAP layers 120, 140, which are free of ceramic particles 160, the formation of polymer crystallites in the electroactive composite layer 130 during drying The preparation and tempering process (e.g. post-processing step 320) must not be hindered.

The 6A until 6C show an example of the distribution of electrical failures and the ferroelectric hysteresis curve of the EAP / ZrO ₂ : EAP / EAP layers in comparison to the EAP / ZrO ₂ layers. The 6 shows the (A) Weibull distribution of the electrical failures and the (B) polarization curve of the EAP / ZrO ₂ and the EAP / ZrO ₂ : EAP / EAP layers at 75 V/µm. The 6C shows the corresponding table of the electrical dielectric strength E _B , the (dielectric) loss factor DF and the polarization P of the EAP / ZrO ₂ and EAP / ZrO ₂ :EAP / EAP layers, obtained from the diagrams of 6A and 6B . From the 6A until 6C It can be seen that the EAP / ZrO ₂ : EAP / EAP layers have a significantly higher dielectric strength E _B of 113.3 MV/m compared to the EAP / ZrO ₂ layers at different ZrO ₂ concentrations. For example, the electrical dielectric strength E _B of the EAP/ZrO ₂ :EAP/EAP layers can be 143.1% of the EAP/ZrO ₂ layers with a ZrO ₂ weight ratio of 40 vol.%. In relation to 6B The polarization P of the EAP/ _ZrO2 :EAP/EAP layers can be similar to that of the EAP/ _ZrO2 layers with a weight ratio of 40 vol% and have a slimmer hysteresis loop, suggesting lower dielectric loss. In addition, the EAP / ZrO ₂ : EAP / EAP layers have a lower loss factor DF than the EAP / ZrO ₂ layers with a ZrO ₂ weight ratio of 30 vol.%. In other words, the EAP/ZrO ₂ :EAP/EAP layers have an increased dielectric strength E _B and polarization P compared to the EAP/ZrO ₂ layers with a ZrO ₂ weight ratio of 40 vol.% a lower loss factor DF and dielectric losses (shown by arrows in 6C displayed).

The 7A until 7C show an example of the distribution of electrical failures and the ferroelectric hysteresis curve of the EAP / TiO ₂ : EAP / EAP layers in comparison to the EAP / TiO ₂ layers. The 7 shows the (A) Weibull distribution of the electrical failures and the (B) polarization curve of the EAP / TiO ₂ layers and the EAP / TiO ₂ : EAP / EAP layers at 75 V/µm. The 7C shows the corresponding table of the electrical dielectric strength E _B , the loss factor DF and the polarization P of the EAP / TiO ₂ and EAP / TiO ₂ : EAP / EAP layers, which are taken from the diagrams of 7A and 7B were received. From the 7A until 7C It can be seen that the EAP / TiO ₂ : EAP / EAP layers have a significantly higher electrical dielectric strength E _B of 103.8 MV/m than the EAP / TiO ₂ layers at different TiO ₂ concentrations. For example, the electrical dielectric strength E _B of the EAP/TiO ₂ :EAP/EAP layers can be 200% of the EAP/TiO ₂ layers with a TiO ₂ weight ratio of 20 vol.%. In relation to 7B The polarization P of the EAP/ _TiO2 :EAP/EAP layers may be similar to that of the EAP/ _TiO2 layers with a weight ratio of 20 vol% and have a slimmer hysteresis loop, suggesting lower dielectric loss. In addition, the EAP/TiO ₂ :EAP/EAP layers have a lower loss factor DF than the EAP/TiO ₂ layers with a TiO ₂ weight ratio of 20% by volume. In other words, the EAP/TiO ₂ :EAP/EAP layers have an increased dielectric strength E _B and polarization P compared to the EAP/TiO ₂ layers with a TiO ₂ weight ratio of 20 vol.% a lower loss factor DF and dielectric loss (shown by arrows in 7C displayed).

The 8th shows a diagram in which the initial force of the EAP / ZrO ₂ : EAP / EAP, the EAP / TiO ₂ : EAP / EAP layers and the pure EAP / EAP / EAP layers are compared as an example. The pure EAP/EAP/EAP layers may contain EAP layers (e.g. without the electroactive composite layer 130), e.g. B. three EAP layers stacked on top of each other. It is shown that the initial force of the EAP/ _ZrO2 :EAP/EAP and the EAP/ _TiO2 :EAP/EAP layers can be higher than that of the pure EAP/EAP/EAP layers with increasing electric field strengths. For example, to generate an output force of 1 mN, the electric field strength required by the EAP / ZrO ₂ : EAP / EAP and the EAP / TiO ₂ : EAP / EAP layers can be 10 MV/m, compared to the pure EAP / EAP / EAP layers that require a significantly higher electric field strength of 25 MV/m. Another example: For a given electric field strength of 10 MV/m, the EAP / ZrO ₂ : EAP / EAP and the EAP / TiO ₂ : EAP / EAP layers can produce a significantly higher output force, in particular an output force that is 9. 3 times and 8.5 times higher, respectively, than the initial force generated by the pure EAP / EAP / EAP layers.

• - Erhöhte Durchschlagsfestigkeit, Permittivität und Polarisierbarkeit im Vergleich zu den reinen EAP-Schichten;
• - Abschwächung der starken Verschlechterung der elektrischen Durchschlagsfestigkeit und des dielektrischen Verlusts;
• - Hoher Widerstand gegen elektrischen Durchschlag in elektronischen geschichteten Bauelementen aufgrund der Einbeziehung der beiden EAP-Schichten, die die elektroaktive Verbundschicht sandwichartig umgeben;
• - Verbesserte Betätigungsleistung bei hoher zulässiger angelegter Spannung / elektrischem Feld ohne vorzeitigen elektrischen Durchbruch;
• - Hohe Kompatibilität mit Standard-Schichtbeschichtungsverfahren, z. B. Rakel, Stabbeschichtung bzw. Walzenbeschichtung mit von unten wirkender Stabrakel (rod coating), Stangenbeschichtung bzw. Beschichtung mittels einer Rakelstreichmaschine (bar coating), der Siebdruck, Schlitzdüsenbeschichtung, Schleuderbeschichtung, R2R-Beschichtung und andere;
• - Die Strukturierung von Bereichen mit hoher und niedriger Dielektrizitätskonstante ist durch die räumliche Steuerung der Partikeldichte und damit die Steuerung des Grades der Dielektrizitätskonstante des geschichteten elektronischen Bauelements möglich;
• - Flexibilität bei der Herstellung verschiedener haptischer Aktuator-Designs (z. B. komplexes Array oder mehrfach gestapelte Strukturen) und Up-Scaling;

The layered electronic component 100, which can be manufactured by the method 300 according to various embodiments, has the following advantages:

• - Increased dielectric strength, permittivity and polarizability compared to pure EAP layers;
• - Mitigation of the severe deterioration in electrical dielectric strength and dielectric loss;
• - High resistance to electrical breakdown in electronic layered devices due to the inclusion of the two EAP layers sandwiching the electroactive composite layer;
• - Improved actuation performance at high allowable applied voltage/electric field without premature electrical breakdown;
• - High compatibility with standard layer coating processes, e.g. B. squeegee, rod coating or roller coating with rod coating acting from below, rod coating or coating using a squeegee coating machine (bar coating), screen printing, slot die coating, spin coating, R2R coating and others;
• - The structuring of areas with high and low dielectric constant is possible by spatially controlling the particle density and thus controlling the degree of dielectric constant of the layered electronic component;
• - Flexibility in manufacturing different haptic actuator designs (e.g. complex array or multi-stacked structures) and up-scaling;

The present disclosure also advantageously presents a simple, cost- and time-efficient manufacturing method for layered electronic devices 100, particularly for flexible thin-film piezoelectric, such as ferroelectric, polymer actuators for haptic feedback applications. The layered electronic component 100 can provide higher actuation amplitudes while maintaining a permissible drive voltage, according to various embodiments. The layered electronic device 100 can also be used in actuators with patterned or non-patterned electrodes and/or active layers, as well as in designs with multiple active layers.

Several examples of the disclosure relate to the layered electronic device containing particles such as ceramic particles. The present disclosure also provides embodiments (e.g., a layered electronic device) that include metallic particles, e.g. B. metallic particles.

While the disclosure has been particularly shown and described with reference to specific embodiments, it should be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. to deviate. The scope of the invention is therefore indicated by the appended claims and all changes which come within the scope of meaning and equivalence of the claims are therefore intended to be embraced.

Claims (15)

Layered electronic component (100), comprising: a stack (170) having a first (120) and a second (140) electroactive polymer layer (EAP), each comprising an EAP material, wherein the stack (170) comprises an electroactive composite layer (130) disposed between the first (120) and second (140) EAP layers and having a thickness along a first direction (1D), wherein each of the first (120) and second (140) EAP layers or a substantial portion thereof is free of particles (160), and wherein the electroactive composite layer (130) comprises a polymer matrix (150) containing particles (160). Layered electronic component (100). Claim 1 , wherein each of the EAP materials of the first (120) and second (140) EAP layers comprises at least 98% by volume of an EAP. Layered electronic component (100). Claim 1 or Claim 2 , wherein the weight ratio of the particles (160) to the polymer matrix (150) in the electroactive composite layer (130) is between 2% by volume and 50% by volume. Layered electronic component (100) according to one of the Claims 1 until 3 , wherein the particles (160) in the electroactive composite layer (130) have dimensions in the range from 2 nm to 100 nm. Layered electronic component (100) according to one of the Claims 1 until 4 , wherein the particles (160) in the electroactive composite layer (130) comprise a metal oxide. Layered electronic component (100) according to one of the Claims 1 until 5 , wherein the particles (160) in the electroactive composite layer (130) are randomly dispersed in the polymer matrix (150) in a second direction perpendicular to the first direction. Layered electronic component (100) according to one of the Claims 1 until 6 , wherein a concentration of particles (160) in the electroactive composite layer (130) in a first region is higher than the concentration of particles in a second region within the polymer matrix (150), and wherein the first region and the second region lie along the second direction (2D). Layered electronic component (100) according to one of the Claims 1 until 7 , wherein the polymer matrix (150) in the electroactive composite layer (130) comprises a polymer selected from a group consisting of poly(vinylidene fluoride) (PVDF), poly[(vinylidene fluoride - co - trifluoroethylene] (PVDF - TrFE), poly (vinylidene fluoride - trifluoroethylene - chlorotrifluoroethylene) P(VDF - TrFE - CTFE), poly(vinylidene fluoride - trifluoroethylene - chlorofluoroethylene) P(VDF - TrFE - CFE). Layered electronic component (100) according to one of the Claims 1 until 8th , the thickness of the stack (170) being in the range from 5 µm to 20 µm. Layered electronic component (200), which has a plurality of stacks (220) according to one of the Claims 1 until 9 which share a common substrate (210) and are arranged side by side in a direction parallel to a main surface of the substrate (110). Layered electronic component (230), which has a plurality of stacks (250) according to one of the Claims 1 until 10 which share a common substrate (240) and are stacked in a direction perpendicular to the main surface of the substrate (110). Method (300) for producing the layered electronic component (100) according to one of Claims 1 until 11 , comprising: providing the substrate (110); Forming the stack (170) by: depositing a first EAP layer material (120); depositing an electroactive composite layer composition (130); and depositing a second EAP layer material (140). Procedure (300). Claim 12 , further comprising: heating the stack (170). Procedure (300). Claim 12 or Claim 13 , further comprising: providing a first electrode (180) on the substrate (110), and providing a second electrode (190) on the stack (170). Flexible haptic feedback actuator manufactured by method (300) of Claim 14 .

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