TWI407607B - Piezoelectric element and method for making the same - Google Patents
Piezoelectric element and method for making the same Download PDFInfo
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本發明涉及一種壓電元件及其製備方法。 The present invention relates to a piezoelectric element and a method of fabricating the same.
壓電元件為將壓力轉換為電訊號的元件，其包括一壓電材料層以及位於該壓電材料層兩側的電極層。當在該壓電元件表面施加一壓力時，可在該兩電極層檢測到相對應的電訊號輸出。該壓電材料層由具有壓電效應的材料製成，先前技術中較為常用的壓電材料為壓電陶瓷，如鈦酸鋇、鈦酸鉛及鎬鈦酸鉛等，以及壓電聚合物，如聚偏氟乙烯等。 The piezoelectric element is an element that converts pressure into an electrical signal, and includes a layer of piezoelectric material and an electrode layer on both sides of the layer of piezoelectric material. When a pressure is applied to the surface of the piezoelectric element, a corresponding electrical signal output can be detected at the two electrode layers. The piezoelectric material layer is made of a material having a piezoelectric effect. The piezoelectric materials commonly used in the prior art are piezoelectric ceramics such as barium titanate, lead titanate and lead bismuth titanate, and piezoelectric polymers. Such as polyvinylidene fluoride and the like.
聚丙烯腈(polyacrylonitrile,PAN)係由單體丙烯腈經自由基聚合反應而得到。聚丙烯腈係製造合成纖維的主要原料，可以用於製造腈綸及碳纖維等材料，主要用於紡織及化工領域(請參見W.WATT & W.JOHNSON，Mechanism of oxidisation of polyacrylonitrile fibres，Nature ，257,210-212(1975))。然而，目前尚未見到有採用聚丙烯腈用作壓電元件的報道。 Polyacrylonitrile (PAN) is obtained by radical polymerization of monomeric acrylonitrile. Polyacrylonitrile is the main raw material for the manufacture of synthetic fibers. It can be used in the manufacture of materials such as acrylic and carbon fiber. It is mainly used in the textile and chemical industries (see W. WATT & W. JOHNSON, Mechanism of oxidisation of polyacrylonitrile fibres, Nature, 257, 210- 212 (1975)). However, there have been no reports of the use of polyacrylonitrile as a piezoelectric element.
有鑒於此，提供一種新型的壓電元件及其製備方法實為必要 。 In view of this, it is necessary to provide a novel piezoelectric element and a preparation method thereof. .
一種壓電元件，其包括：一聚合物層，該聚合物層的材料包括熱解聚丙烯腈；一第一金屬層設置於該聚合物層一表面；以及一第二金屬層設置於該聚合物層另一表面，該第一金屬層與第二金屬層具有不同的功函數。 A piezoelectric element comprising: a polymer layer, the material of the polymer layer comprising pyrolyzed polyacrylonitrile; a first metal layer disposed on a surface of the polymer layer; and a second metal layer disposed on the polymer The other surface of the object layer, the first metal layer and the second metal layer have different work functions.
一種壓電元件的製備方法，其包括：提供一聚丙烯腈原料，將該聚丙烯腈原料在220℃至350℃加熱，使該聚丙烯腈原料受熱分解為熱解聚丙烯腈；將該熱解聚丙烯腈與一黏結劑及一揮發性溶劑混合形成一漿料；將該漿料塗覆於一第一金屬層表面，形成一聚合物層；乾燥該聚合物層；以及將一第二金屬層覆蓋於該聚合物層表面並相互壓合。 A method for preparing a piezoelectric element, comprising: providing a polyacrylonitrile raw material, heating the polyacrylonitrile raw material at 220 ° C to 350 ° C to thermally decompose the polyacrylonitrile raw material into pyrolyzed polyacrylonitrile; Dissolving polyacrylonitrile with a binder and a volatile solvent to form a slurry; applying the slurry to a surface of a first metal layer to form a polymer layer; drying the polymer layer; and placing a second A metal layer covers the surface of the polymer layer and is pressed against each other.
一種壓電元件的製備方法，其包括：提供一聚丙烯腈原料，將該聚丙烯腈原料在220℃至350℃條件下加熱，使該聚丙烯腈原料受熱分解為熱解聚丙烯腈；將該熱解聚丙烯腈與一黏結劑及一揮發性溶劑混合形成一漿料；提供一絕緣基板，在該絕緣基板表面形成一第一金屬；將所述漿料塗附於該第一金屬層表面，形成一聚合物層；以及在該聚合物層表面形成一第二金屬層。 A method for preparing a piezoelectric element, comprising: providing a polyacrylonitrile raw material, heating the polyacrylonitrile raw material at 220 ° C to 350 ° C to thermally decompose the polyacrylonitrile raw material into pyrolyzed polyacrylonitrile; The pyrolyzed polyacrylonitrile is mixed with a binder and a volatile solvent to form a slurry; an insulating substrate is provided, a first metal is formed on the surface of the insulating substrate; and the slurry is coated on the first metal layer a surface forming a polymer layer; and forming a second metal layer on the surface of the polymer layer.
相較於先前技術，本方法以聚丙烯腈為原料，製備得到了具有壓電效應的壓電元件，拓寬了聚丙烯腈的應用領域。該壓電元件通過具有不同功函數的金屬與該熱解聚丙烯腈相互層叠，當受到一壓力作用時，由於該熱解聚丙烯腈與不同功函 數的金屬具有不同的肖特基接觸(Schottky contacts)，從而產生電勢差。 Compared with the prior art, the method uses polyacrylonitrile as a raw material to prepare a piezoelectric element having a piezoelectric effect, and broadens the application field of polyacrylonitrile. The piezoelectric element is laminated to the pyrolyzed polyacrylonitrile by a metal having different work functions, and when subjected to a pressure, due to the pyrolysis of polyacrylonitrile and different work functions The number of metals has different Schottky contacts, resulting in a potential difference.
100‧‧‧壓電元件 100‧‧‧Piezoelectric components
110‧‧‧第一金屬層 110‧‧‧First metal layer
120‧‧‧聚合物層 120‧‧‧ polymer layer
130‧‧‧第二金屬層 130‧‧‧Second metal layer
圖1係本發明實施例一種壓電元件的結構示意圖。 1 is a schematic view showing the structure of a piezoelectric element according to an embodiment of the present invention.
圖2係本發明第一實施例一種壓電元件的製備方法的流程圖。 Fig. 2 is a flow chart showing a method of manufacturing a piezoelectric element according to a first embodiment of the present invention.
圖3係本發明第二實施例一種壓電元件的製備方法的流程圖。 Fig. 3 is a flow chart showing a method of manufacturing a piezoelectric element according to a second embodiment of the present invention.
圖4係圖1中壓電元件測試時的連接關係示意圖。 FIG. 4 is a schematic diagram showing the connection relationship of the piezoelectric element in FIG. 1 during testing.
圖5係圖1中壓電元件的測試曲線。 Figure 5 is a test curve of the piezoelectric element of Figure 1.
以下將結合附圖詳細說明本發明實施例壓電元件100及其製備方法。 Hereinafter, a piezoelectric element 100 and a method of manufacturing the same according to embodiments of the present invention will be described in detail with reference to the accompanying drawings.
請參閱圖1，本發明實施例提供一種壓電元件100，其包括一聚合物層120、一第一金屬層110以及一第二金屬層130。該聚合物層120具有兩個相對的表面，該第一金屬層110及第二金屬層130分別設置在所述聚合物層120兩個相對的表面，形成三層貼合層叠設置結構，該聚合物層120設置在該第一金屬層110與該第二金屬層130之間。 Referring to FIG. 1 , an embodiment of the present invention provides a piezoelectric element 100 including a polymer layer 120 , a first metal layer 110 , and a second metal layer 130 . The polymer layer 120 has two opposite surfaces. The first metal layer 110 and the second metal layer 130 are respectively disposed on two opposite surfaces of the polymer layer 120 to form a three-layer laminated laminated structure. The object layer 120 is disposed between the first metal layer 110 and the second metal layer 130.
該聚合物層120的主要材料為熱解聚丙烯腈(pyrolytic polyacrylonitrile,PPAN)。該熱解聚丙烯腈為將聚丙烯腈在350℃以下加熱一定時間得到。由於加熱的作用，該聚 丙烯腈中的分子鏈產生環化作用，形成聚並吡啶單元()。 The main material of the polymer layer 120 is pyrolytic polyacrylonitrile (PPAN). The pyrolyzed polyacrylonitrile is obtained by heating polyacrylonitrile at 350 ° C or lower for a certain period of time. Due to the action of heating, the molecular chain in the polyacrylonitrile is cyclized to form a polypyridyl unit ( ).
進一步地，該聚合物層120還可包含少量黏結劑，使該聚合物層120更好的與金屬層相結合並成型。該熱解聚丙烯腈占聚合物層120總質量的90%以上，優選為95%以上。本實施例中，該聚合物層120包括占總重量比97%的熱解聚丙烯腈，以及占總重量比3%的黏結劑。本實施例中，該黏結劑為PAN。該聚合物層120的厚度為1微米~500微米，優選為100微米~200微米。本實施例中，該聚合物層120的厚度約為150微米。 Further, the polymer layer 120 may further contain a small amount of a binder, so that the polymer layer 120 is better combined with the metal layer and molded. The pyrolyzed polyacrylonitrile accounts for 90% or more, preferably 95% or more of the total mass of the polymer layer 120. In this embodiment, the polymer layer 120 comprises 97% by weight of pyrolyzed polyacrylonitrile, and 3% by weight of the total binder. In this embodiment, the binder is PAN. The polymer layer 120 has a thickness of from 1 micrometer to 500 micrometers, preferably from 100 micrometers to 200 micrometers. In this embodiment, the polymer layer 120 has a thickness of about 150 microns.
該第一金屬層110的金屬的功函數與該第二金屬層130的金屬的功函數不相等。優選地，該第一金屬層110的金屬的功函數與該第二金屬層130的金屬的功函數差別較大，優選相差0.5eV以上。具有不同功函數的第一金屬層110與第二金屬層130與該聚合物層120相互層叠，當受到一壓力作用時，該熱解聚丙烯腈內部產生電荷分離，由於該熱解聚丙烯腈與不同功函數的金屬具有不同的肖特基接觸(Schottky contacts)，從而產生電勢差及電流。該第一金屬層110與第二金屬層130的金屬的功函數差別越大，則產生的電勢差越大。 The work function of the metal of the first metal layer 110 is not equal to the work function of the metal of the second metal layer 130. Preferably, the work function of the metal of the first metal layer 110 is different from the work function of the metal of the second metal layer 130, and preferably differs by more than 0.5 eV. The first metal layer 110 and the second metal layer 130 having different work functions are laminated on each other, and when subjected to a pressure, the pyrolysis of the polyacrylonitrile generates charge separation due to the pyrolysis of the polyacrylonitrile. Metals with different work functions have different Schottky contacts, resulting in a potential difference and current. The greater the difference in the work function of the metal of the first metal layer 110 and the second metal layer 130, the greater the potential difference generated.
具體地，該第一金屬層110與第二金屬層130的材料可以為鋁/銅(Al/Cu)，鋁/鎳(Al/Ni)、鋁/金(Al/Au)、鋅/金 (Zn/Au)的組合。本實施例中，該第一金屬層110的材料為Al(功函數4.28eV)，該第二金屬層130的材料為Au(功函數5.1eV)。該第一金屬層110及第二金屬層130可以均為金屬箔片或金屬薄膜，或分別為金屬箔片及金屬薄膜。該金屬箔片可與該聚合物層120相壓合，該金屬薄膜可通過電鍍或沈積等方法直接形成於該聚合物層120的表面。該金屬箔片的厚度優選為1毫米~200微米。該金屬薄膜的厚度優選為200微米~1微米。本實施例中，該第一金屬層110及第二金屬層130均為厚度約為0.5毫米的金屬箔片。 Specifically, the material of the first metal layer 110 and the second metal layer 130 may be aluminum/copper (Al/Cu), aluminum/nickel (Al/Ni), aluminum/gold (Al/Au), zinc/gold. A combination of (Zn/Au). In this embodiment, the material of the first metal layer 110 is Al (work function 4.28 eV), and the material of the second metal layer 130 is Au (work function 5.1 eV). The first metal layer 110 and the second metal layer 130 may each be a metal foil or a metal thin film, or a metal foil and a metal thin film, respectively. The metal foil may be pressed against the polymer layer 120, and the metal film may be directly formed on the surface of the polymer layer 120 by plating or deposition. The thickness of the metal foil is preferably from 1 mm to 200 μm. The thickness of the metal thin film is preferably from 200 μm to 1 μm. In this embodiment, the first metal layer 110 and the second metal layer 130 are each a metal foil having a thickness of about 0.5 mm.
請參閱圖2，本發明第一實施例提供一種壓電元件100的製備方法，其包括以下步驟：S10：提供一聚丙烯腈原料，並將該聚丙烯腈原料在220℃至350℃加熱1小時至10小時，使該聚丙烯腈原料受熱分解為熱解聚丙烯腈。 Referring to FIG. 2, a first embodiment of the present invention provides a method for preparing a piezoelectric element 100, which includes the following steps: S10: providing a polyacrylonitrile raw material, and heating the polyacrylonitrile raw material at 220 ° C to 350 ° C. The polyacrylonitrile starting material is thermally decomposed into pyrolyzed polyacrylonitrile from hour to 10 hours.
由於加熱的作用，該聚丙烯腈中的分子鏈產生環化作用，形成聚並吡啶單元()。 Due to the action of heating, the molecular chain in the polyacrylonitrile is cyclized to form a polypyridyl unit ( ).
優選地，該溫度為300℃，加熱時間為5小時。本實施例中，該聚丙烯腈為粉末狀，加熱後的熱解聚丙烯腈仍為粉末狀。 Preferably, the temperature is 300 ° C and the heating time is 5 hours. In this embodiment, the polyacrylonitrile is in the form of a powder, and the pyrolyzed polyacrylonitrile after heating is still in a powder form.
S11：將該熱解聚丙烯腈與一黏結劑及一揮發性溶劑混合形成一漿料。該熱解聚丙烯腈與該黏結劑以質量比為90：10至 99：1的比例混合，優選為97：3。該揮發性溶劑使該漿料具有一定的流動性，易於塗膜。該揮發性溶劑可以為乙醇、甲醇或丙酮等有機溶劑。本實施例中，將9.7克熱解聚丙烯腈與0.3克丙烯腈，並加入10毫升二甲基甲醯胺(Dimethylformamide，DMF)，在研鉢中充分混合均勻。 S11: mixing the pyrogenic polyacrylonitrile with a binder and a volatile solvent to form a slurry. The pyrolysis polyacrylonitrile and the binder are in a mass ratio of 90:10 to A ratio of 99:1 is mixed, preferably 97:3. The volatile solvent imparts a certain fluidity to the slurry and is easy to coat. The volatile solvent may be an organic solvent such as ethanol, methanol or acetone. In this example, 9.7 g of pyrogenic polyacrylonitrile and 0.3 g of acrylonitrile were added, and 10 ml of Dimethylformamide (DMF) was added and thoroughly mixed in a mortar.
S12：將該漿料塗覆於一第一金屬層110表面，形成一聚合物層120。該聚合物層120的厚度優選為500微米~10微米。本實施例中，具體採用一刮刀將所述漿料塗覆於一鋁箔表面，所形成的聚合物層120的厚度約為150微米。 S12: Applying the slurry to the surface of a first metal layer 110 to form a polymer layer 120. The thickness of the polymer layer 120 is preferably from 500 micrometers to 10 micrometers. In this embodiment, the slurry is applied to the surface of an aluminum foil by a doctor blade, and the polymer layer 120 is formed to have a thickness of about 150 μm.
S13：乾燥該聚合物層120，以去除所述溶劑。具體地，可將該第一金屬層110連同該聚合物層120放置於一烘箱中加熱乾燥。該烘箱的溫度可以為40℃~100℃，乾燥時間可以為2~10小時。本實施例中，乾燥溫度為60℃，乾燥時間為6小時。 S13: The polymer layer 120 is dried to remove the solvent. Specifically, the first metal layer 110 and the polymer layer 120 may be placed in an oven and dried by heating. The oven can have a temperature of 40 ° C to 100 ° C and a drying time of 2 to 10 hours. In this example, the drying temperature was 60 ° C and the drying time was 6 hours.
S14：將一第二金屬層130覆蓋於該聚合物層120表面並相互壓合。本實施例中，該第二金屬層130為一金箔。 S14: covering a surface of the polymer layer 120 with a second metal layer 130 and pressing each other. In this embodiment, the second metal layer 130 is a gold foil.
具體地，可將該第二金屬層130覆蓋在該聚合物層120表面後通過一軋輥，使第一金屬層110、聚合物層120以及第二金屬層130緊密貼合。 Specifically, the second metal layer 130 may be covered on the surface of the polymer layer 120 and passed through a roll to make the first metal layer 110, the polymer layer 120 and the second metal layer 130 closely adhere.
可以理解，所述壓電元件100並不限於採用上述方法製備，請參閱圖3，本發明第二實施例提供一種壓電元件100的製備方法，其包括以下步驟： It is to be understood that the piezoelectric element 100 is not limited to being prepared by the above method. Referring to FIG. 3, a second embodiment of the present invention provides a method for fabricating the piezoelectric element 100, which includes the following steps:
S20：提供一聚丙烯腈原料，並將該聚丙烯腈原料在220℃至 350℃加熱1小時至10小時，使該聚丙烯腈原料受熱分解為熱解聚丙烯腈。 S20: providing a polyacrylonitrile raw material, and the polyacrylonitrile raw material is at 220 ° C to The polyacrylonitrile starting material is thermally decomposed into pyrolyzed polyacrylonitrile by heating at 350 ° C for 1 hour to 10 hours.
S21：將該熱解聚丙烯腈與一黏結劑及一揮發性溶劑混合形成一漿料。 S21: mixing the pyrolytic polyacrylonitrile with a binder and a volatile solvent to form a slurry.
該步驟S20及S21與第一實施例的步驟S10及S11相同。 This step S20 and S21 is the same as steps S10 and S11 of the first embodiment.
S22：提供一絕緣基板，在該絕緣基板表面形成一第一金屬層110。該第一金屬層110可通過電鍍、沈積、蒸鍍或濺射等方式形成在該絕緣基板表面。通過上述方法形成的第一金屬層110可以具有較薄的厚度。本實施例中採用濺射方法在一矽基底表面形成一100微米厚的鋁膜作為該第一金屬層110。 S22: providing an insulating substrate, and forming a first metal layer 110 on the surface of the insulating substrate. The first metal layer 110 may be formed on the surface of the insulating substrate by plating, deposition, evaporation, sputtering, or the like. The first metal layer 110 formed by the above method may have a relatively thin thickness. In the present embodiment, a 100 μm-thick aluminum film is formed as a first metal layer 110 on the surface of a substrate by a sputtering method.
S23：將所述漿料塗附於該第一金屬層110表面，形成一聚合物層120。該漿料可通過與上述第一實施例S12相同的方法塗附於該第一金屬層110表面。 S23: coating the slurry on the surface of the first metal layer 110 to form a polymer layer 120. This paste can be applied to the surface of the first metal layer 110 by the same method as the above-described first embodiment S12.
S24：在該聚合物層120表面形成一第二金屬層130。該第二金屬層130可通過與所述步驟S22相同的方法形成。本實施例中採用濺射方法在該聚合物層120的表面形成一100微米厚的金膜作為該第二金屬層130。 S24: forming a second metal layer 130 on the surface of the polymer layer 120. The second metal layer 130 can be formed by the same method as the above step S22. In the present embodiment, a 100 μm thick gold film is formed on the surface of the polymer layer 120 as the second metal layer 130 by a sputtering method.
請參閱圖4，將通過第一實施例的方法形成的壓電元件100接入一回路中測試該壓電元件100的壓電效應，其中，該回路的負載電阻R為4.0×106歐姆(Ω)，該壓電元件100的大小為20×20毫米。請參閱圖5，當該壓電元件100表面受到的壓力隨時間逐漸增大時，可測得該負載電阻R兩端的電壓值不斷 增大，具體數據如表1所示。該壓力持續一段時間後，該電壓值極為緩慢的下降，並可持續達數小時以上。當壓力增大或減小時，該電壓隨壓力的變化而迅速變化。當受到壓力分別為4千牛及60千牛時，該壓電元件100的輸出功率為0.3奈瓦(nW)及3nw。 Referring to FIG. 4, the piezoelectric element 100 formed by the method of the first embodiment is connected to a circuit to test the piezoelectric effect of the piezoelectric element 100, wherein the load resistance R of the circuit is 4.0×10 6 ohms ( Ω), the piezoelectric element 100 has a size of 20 × 20 mm. Referring to FIG. 5, when the pressure applied to the surface of the piezoelectric element 100 gradually increases with time, the voltage value across the load resistor R can be continuously increased. The specific data is shown in Table 1. After the pressure continues for a period of time, the voltage value drops very slowly and can last for more than a few hours. As the pressure increases or decreases, the voltage changes rapidly as the pressure changes. When the pressure is 4 kN and 60 kN, respectively, the piezoelectric element 100 has an output of 0.3 naW (nW) and 3 nw.
該壓電元件100通過具有不同功函數的金屬與該熱解聚丙烯腈相互層叠，當受到一壓力作用時，該熱解聚丙烯腈內部產生電荷分離，由於該熱解聚丙烯腈與不同功函數的金屬具有不同的肖特基接觸(Schottky contacts)，從而產生電勢差及電流。該壓電元件100基於與先前技術不同的壓電原理，具有較為簡單的結構及製備方法，可應用於傳感器等壓力-電轉換領域。 The piezoelectric element 100 is laminated on the pyrolyzed polyacrylonitrile by a metal having different work functions, and when subjected to a pressure, the pyrolysis of the polyacrylonitrile generates charge separation due to the pyrolysis of the polyacrylonitrile and the different work. The metal of the function has different Schottky contacts, resulting in a potential difference and current. The piezoelectric element 100 has a relatively simple structure and a preparation method based on a piezoelectric principle different from the prior art, and can be applied to a pressure-electric conversion field such as a sensor.
綜上所述，本發明確已符合發明專利之要件，遂依法提出專利申請。惟，以上所述者僅為本發明之較佳實施例，自不能 以此限制本案之申請專利範圍。舉凡習知本案技藝之人士援依本發明之精神所作之等效修飾或變化，皆應涵蓋於以下申請專利範圍內。 In summary, the present invention has indeed met the requirements of the invention patent, and has filed a patent application according to law. However, the above is only a preferred embodiment of the present invention, and it cannot This limits the scope of the patent application in this case. Equivalent modifications or variations made by those skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims.
100‧‧‧壓電元件 100‧‧‧Piezoelectric components
110‧‧‧第一金屬層 110‧‧‧First metal layer
120‧‧‧聚合物層 120‧‧‧ polymer layer
130‧‧‧第二金屬層 130‧‧‧Second metal layer
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3940637A (en) * | 1973-10-15 | 1976-02-24 | Toray Industries, Inc. | Polymeric piezoelectric key actuated device |
| TWI270982B (en) * | 2004-03-24 | 2007-01-11 | Rohm & Haas | Memory devices based on electric field programmable films |
| US20080287313A1 (en) * | 2003-01-07 | 2008-11-20 | Ngk Insulators, Ltd. | Reactive chips and methods for detecting bindings of target substances utilizing the chips |
| US20090301875A1 (en) * | 2006-01-23 | 2009-12-10 | Hitachi Chemical Co., Ltd. | Ionic polymer devices and methods of fabricating the same |
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- 2010-01-22 TW TW99101721A patent/TWI407607B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3940637A (en) * | 1973-10-15 | 1976-02-24 | Toray Industries, Inc. | Polymeric piezoelectric key actuated device |
| US20080287313A1 (en) * | 2003-01-07 | 2008-11-20 | Ngk Insulators, Ltd. | Reactive chips and methods for detecting bindings of target substances utilizing the chips |
| TWI270982B (en) * | 2004-03-24 | 2007-01-11 | Rohm & Haas | Memory devices based on electric field programmable films |
| US20090301875A1 (en) * | 2006-01-23 | 2009-12-10 | Hitachi Chemical Co., Ltd. | Ionic polymer devices and methods of fabricating the same |
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