WO2022040987A1 - 一种薄膜电容器的制备方法以及薄膜电容器 - Google Patents

一种薄膜电容器的制备方法以及薄膜电容器 Download PDF

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Publication number
WO2022040987A1
WO2022040987A1 PCT/CN2020/111447 CN2020111447W WO2022040987A1 WO 2022040987 A1 WO2022040987 A1 WO 2022040987A1 CN 2020111447 W CN2020111447 W CN 2020111447W WO 2022040987 A1 WO2022040987 A1 WO 2022040987A1
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Prior art keywords
layer
thin film
substrate
sacrificial layer
film
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PCT/CN2020/111447
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English (en)
French (fr)
Inventor
贾婷婷
胡芳
方伟
丁振
于淑会
孙蓉
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/33—Thin- or thick-film capacitors (thin- or thick-film circuits; capacitors without a potential-jump or surface barrier specially adapted for integrated circuits, details thereof, multistep manufacturing processes therefor)

Definitions

  • the present application relates to the field of preparation of electronic components, in particular to a preparation method of a film capacitor and a film capacitor.
  • the current market capacitors include ceramic capacitors, aluminum electrolytic capacitors, tantalum electrolytic capacitors and film capacitors.
  • film capacitors often use plastic films such as polyethylene, polypropylene, polystyrene or polycarbonate as the dielectric layer, which have many excellent characteristics.
  • plastic films such as polyethylene, polypropylene, polystyrene or polycarbonate as the dielectric layer, which have many excellent characteristics.
  • Film capacitors with high dielectric constant inorganic materials as dielectric layers have the advantages of high withstand voltage, long life, stable temperature characteristics, and low loss. wiring part, thereby realizing lower impedance and wider frequency band.
  • the main technical problem to be solved by the present application is to provide a method for preparing a film capacitor and a film capacitor, which can prepare a film capacitor with excellent properties such as high withstand voltage, long life, stable temperature characteristics, and low loss.
  • a first aspect of the present application provides a method for preparing a thin film capacitor, the method comprising: providing a substrate; forming a sacrificial layer, a dielectric thin film layer, and a first electrode layer in sequence on the substrate and capacitor base layer; wherein, the material of the substrate and the dielectric thin film layer are the same; remove the substrate and the sacrificial layer; on the side of the dielectric thin film layer away from the first electrode layer A second electrode layer is formed to obtain a thin film capacitor structure; the thin film capacitor structure is packaged by using 3D printing technology.
  • the use of 3D printing technology to encapsulate the thin film capacitor structure includes:
  • a bottom module for placing the thin film capacitor structure is prepared by 3D printing technology, wherein the bottom module has a groove for placing the capacitor structure according to the size of the capacitor; the thin film capacitor structure is placed in the groove In the middle; using in-situ 3D printing technology, the top module is printed in-situ on the basis of the bottom module to complete the integrated packaging of the thin-film capacitor structure.
  • the method before the in-situ printing of the top module on the basis of the bottom module, the method further includes: respectively preparing metal pins and/or metal leads on the first electrode layer and the second electrode layer.
  • the encapsulation layer of the top module corresponds to the encapsulation layer of the bottom module and has the same surface area, and the encapsulation layer The layer is larger than the capacitor structure size, so that when the film capacitor structure is packaged by 3D printing technology, the top module and the bottom module are seamlessly connected in situ, so that the top module and the bottom module form a seamless integrated package
  • the module, the thin film capacitor structure, the metal pins and the packaging module form a unified whole.
  • the bottom module and the top module of the 3D printing module are designed according to the film capacitor structure, the 3D packaging bottom module is printed on the periphery of the film capacitor structure, and the 3D printing process is used in-situ after embedding the film capacitor structure. Seamlessly build 3D package top modules.
  • forming a sacrificial layer, a dielectric film layer, a first electrode layer and a capacitor base layer on the substrate in sequence includes: coating a first colloid on the substrate and placing it in the air heating to form a first precursor film; heating the first precursor film in oxygen to form the sacrificial layer; coating a second colloid on the sacrificial layer and heating in air to form a second precursor film; heating the second precursor film in oxygen to form the dielectric film layer; forming a first electrode layer and a capacitor base layer on the dielectric film layer.
  • the coating of the first colloid on the substrate and heating in the air to form a first precursor film includes: spin-coating the first colloid on the substrate, placing the first colloid on the substrate The air is heated to a first preset temperature, and the first preset temperature is maintained for a first preset time, so that the first colloid forms the first precursor film.
  • the heating of the first precursor film in oxygen to form the sacrificial layer includes: placing the first precursor film in a heating furnace in an oxygen atmosphere, and setting the oxygen flow rate as the first Presetting the flow rate of oxygen, heating to a second preset temperature, and maintaining the second preset temperature for a second preset time, so that the first precursor thin film forms the sacrificial layer.
  • the step of coating a second colloid on the sacrificial layer and heating it in air to form a second precursor film includes: spin-coating the second colloid on the sacrificial layer, and placing it on the sacrificial layer. The air is heated to a third preset temperature, and the third preset temperature is maintained for a third preset time, so that the second colloid forms the second precursor film.
  • the heating of the second precursor film in oxygen to form the dielectric film layer includes: placing the first precursor film in a heating furnace in an oxygen atmosphere, and setting the oxygen flow rate to The second preset oxygen flow rate is heated to a fourth preset temperature, and the fourth preset temperature is maintained for a fourth preset time, so that the second precursor film forms the dielectric film thin layer.
  • the forming the first electrode layer and the capacitor base layer on the dielectric film layer includes: forming a first electrode layer on the dielectric film layer by ion sputtering; gluing the capacitor base layer on the first electrode layer.
  • the first colloid is prepared by the following method: adding aluminum nitrate and strontium nitrate into nitric acid, and stirring to obtain a first solution; dissolving citric acid in water to obtain a second solution, and the amount of the citric acid greater than the sum of metal ions in the first solution; mixing the first solution and the second solution, heating and stirring to make the metal ions complex with the citric acid, and evaporating water to obtain the first solution colloid.
  • the second colloid is prepared by the following method: mixing strontium acetate and glacial acetic acid, stirring to obtain a third solution, adding glacial acetic acid containing PVP to the third solution and stirring to obtain a fourth solution; Adding ethylene glycol methyl ether to tetrabutyl acid, stirring to obtain the fifth solution, adding acetylacetone to the fifth solution, stirring to obtain the sixth solution; mixing the fourth solution and the sixth solution, After stirring, ethylene glycol was added to the mixed solution, heated and stirred, cooled and filtered to obtain a second colloid.
  • forming a sacrificial layer, a dielectric thin film layer, a first electrode layer and a capacitor base layer on the substrate in sequence includes: burning a first target with a pulsed laser to deposit on the substrate A sacrificial layer; a second target is burned with a pulsed laser to deposit a dielectric thin film layer on the sacrificial layer; a first electrode layer and a capacitor base layer are formed on the dielectric thin film layer.
  • the using a pulsed laser to burn the first target to deposit a sacrificial layer on the substrate includes: placing the substrate and the strontium aluminate target in a reaction chamber of a pulsed laser deposition system; In the oxygen environment, the strontium aluminate target is burned by a pulsed laser to deposit strontium aluminate plasma on the substrate to form the sacrificial layer.
  • the using a pulsed laser to burn the second target to deposit a dielectric thin film layer on the sacrificial layer includes: placing the strontium titanate substrate on which the sacrificial layer is prepared and the strontium titanate target material. in the reaction chamber of the pulsed laser deposition system; in the oxygen environment, the strontium titanate target is burned with a pulsed laser to deposit strontium titanate plasma on the substrate to form the dielectric thin film layer.
  • the sacrificial layer is made of a hydrolyzable material; the removing the substrate and the sacrificial layer includes: including the substrate, the sacrificial layer, a dielectric film layer, and a first electrode layer And the material of the capacitor base layer is put into water to hydrolyze the sacrificial layer, so that the substrate is peeled off.
  • a second aspect of the present application provides a thin film capacitor prepared by the method for preparing a thin film capacitor provided in the first aspect.
  • the present application forms a sacrificial layer, a dielectric thin film layer, a first electrode layer and a capacitor base layer on the substrate in sequence, and then removes the sacrificial layer and the substrate, and then removes the sacrificial layer and the substrate.
  • a second electrode layer is formed on the side of the electric thin film layer away from the first electrode layer to prepare a thin film capacitor.
  • the prepared film capacitor has the characteristics of high withstand voltage, long life, stable temperature characteristics and low loss.
  • the application also encapsulates the film capacitor structure through 3D printing technology, and does not use liquid adhesive in the whole process, which avoids the adverse effects on the capacitor structure due to high temperature curing or chemical corrosion in the traditional packaging process.
  • FIG. 1 is a schematic block diagram of a flow chart of an embodiment of a method for preparing a film capacitor of the present application
  • FIG. 2 is a schematic flow diagram of steps S12 to S14 of the present application.
  • 3 is a schematic block diagram of the flow of an embodiment of the 3D printing package of the present application.
  • FIG. 4 is a schematic flow diagram of an embodiment of the 3D printing package of the present application.
  • FIG. 5 is a schematic structural diagram of an embodiment of the bottom module of the present application.
  • FIG. 6 is a schematic diagram of a capacitor module prepared by a method for preparing a film capacitor in the present application
  • FIG. 7 is a schematic flow diagram of another embodiment of the method for preparing a film capacitor of the present application.
  • FIG. 8 is a schematic flow diagram of steps S22 to S26 of the present application.
  • FIG. 9 is a schematic structural diagram of another embodiment of the bottom module of the present application.
  • FIG. 10 is a schematic structural diagram of another embodiment of the bottom module of the present application.
  • FIG. 11 is a schematic flowchart of another embodiment of steps S24 to S26 of the present application.
  • Fig. 12 is the XRD diffraction pattern of the film capacitor of the present application.
  • Fig. 13 is the surface topography diagram of the STO dielectric thin film layer of the present application.
  • Fig. 14 is the surface topography diagram of the SAO sacrificial layer of the present application.
  • Fig. 15 is the surface topography diagram of the STO substrate of the present application.
  • Figure 16a is a graph of the energy storage density of STO films with different thicknesses under a positive electric field
  • Fig. 16b is a graph showing the variation of the relative permittivity ⁇ r of the film capacitor of the present application with the frequency f;
  • Figure 16c is a J-E curve diagram of the current-electric field of the film capacitor of the present application.
  • FIG. 16d is a graph showing the variation of the capacitance C and the loss factor tan ⁇ of the film capacitor with the frequency f.
  • first and second in this application are only used for descriptive purposes, and should not be construed as indicating or implying relative importance or implicitly indicating the number of technical features shown. Thus, a feature delimited with “first”, “second” may expressly or implicitly include at least one of that feature.
  • the terms “comprising” and “having”, and any conjugations thereof, are intended to cover non-exclusive inclusion. For example, a process, method, system, product or device comprising a series of steps or units is not limited to the listed steps or units, but optionally also includes unlisted steps or units, or optionally also includes For other steps or units inherent to these processes, methods, products or devices.
  • the core of the preparation method of the thin film capacitor of the present application is to introduce a sacrificial layer, so that the preparation step of the electrode of the thin film capacitor is followed by the preparation step of the dielectric thin film layer, so that the electrode layer is not subjected to the high temperature environment during the preparation of the dielectric thin film layer, and is free from High temperature oxidation, thereby improving the electrical performance of the capacitor, reducing losses, and extending the life of the capacitor.
  • FIG. 1 is a schematic flow diagram of an embodiment of a method for preparing a film capacitor of the present application
  • FIG. 2 is a schematic flow diagram of steps S12 to S14 of the present application.
  • the preparation method of this embodiment includes the following steps:
  • the substrate 01 is used as the growth substrate layer of the sacrificial layer 02 and the dielectric thin film layer 03 in step S12, and the substrate 01 of the same material or different material as the dielectric thin film layer 03 can be selected according to actual requirements, which is not limited here.
  • a sacrificial layer 02 is formed on the substrate 01, and then a dielectric film layer 03 is formed on the side of the sacrificial layer 02 away from the substrate 01, and then a second layer is formed on the side of the dielectric film layer 03 away from the sacrificial layer 02.
  • An electrode layer 04, and finally a capacitor base layer 05 is formed on the side of the first electrode layer 04 away from the dielectric film layer 03.
  • the sacrificial layer 02 is prepared from a hydrolyzable substance, for example, the sacrificial layer 02 may be a strontium aluminate thin film layer.
  • the first electrode layer 04 is copper or other metals with good electrical conductivity.
  • the formation method of the sacrificial layer 02 includes, but is not limited to, a sol-gel method, a vapor deposition method, and a pulsed laser deposition method.
  • the preparation method of the dielectric thin film layer 03 includes, but is not limited to, a sol-gel method, a vapor deposition method, and a pulsed laser deposition method.
  • the preparation method of the first electrode layer 04 includes, but is not limited to, an electrodeposition method, an ion sputtering method, and the like.
  • the material of the substrate 01 and the dielectric thin film layer 03 is the same.
  • the dielectric film layer 03 of the present application can be prepared from a single crystal material or a polycrystalline material.
  • the substrate 01 is made of the same material as the dielectric thin film layer 03. Materials, using the homoepitaxial growth of the dielectric thin film layer 03, the high quality dielectric thin film layer 03 can be obtained.
  • the steps of preparing the sacrificial layer 02 and the dielectric thin film layer 03 by a sol-gel method are as follows a1-d1:
  • the first precursor film is heated in oxygen to form the sacrificial layer 02 .
  • the second precursor film is heated in oxygen to form the dielectric film layer 03 .
  • the first colloid when preparing the sacrificial layer 02, spin-coat the first colloid on the substrate 01, place it in the air and heat it to a first preset temperature, and maintain the first preset temperature for a first preset time, so that the first The colloid forms a first precursor film, and then the first precursor film is placed in a heating furnace in an oxygen atmosphere, the oxygen flow rate is set to a first preset oxygen flow rate, heated to a second preset temperature, and maintained for a second preset time.
  • the second preset temperature enables the first precursor thin film to form the sacrificial layer 02 .
  • the dielectric thin film layer 03 When preparing the dielectric thin film layer 03, spin-coat the second colloid on the sacrificial layer 02, place it in the air and heat it to a third preset temperature, and maintain the third preset temperature for a third preset time, so that the first The two colloids form a second precursor film, and then the first precursor film is placed in a heating furnace in an oxygen atmosphere, the oxygen flow rate is set to the second preset oxygen flow rate, heated to a fourth preset temperature, and heated to a fourth preset time The fourth preset temperature is maintained, so that the second precursor thin film forms the dielectric thin film layer 03 .
  • the first colloid and the second colloid are the precursor colloids of the sacrificial layer 02 and the dielectric thin film layer 03, respectively.
  • the preparation steps of the first colloid are as follows a2-d2:
  • the preparation steps of the second colloid are as follows a3-d3:
  • the sacrificial layer 02 and the dielectric thin film layer 03 can also be prepared by using a pulsed laser deposition method, and the steps are as follows a4-b4 :
  • the first target can be a strontium aluminate target
  • the second target can be a strontium titanate target.
  • the substrate 01 and the strontium aluminate target are placed In the reaction chamber of the pulsed laser deposition system, in the oxygen environment, the strontium aluminate target is burned by the pulsed laser to deposit the strontium aluminate plasma on the substrate to form the sacrificial layer 02; in the preparation of the dielectric thin film layer 03
  • the strontium titanate substrate prepared with the sacrificial layer 02 and the strontium titanate target are placed in the reaction chamber of the pulsed laser deposition system, in the oxygen environment, the strontium titanate target is burned by the pulsed laser, so that the sacrificial strontium titanate Strontium titanate plasma is deposited on layer 02 to form dielectric thin film layer 03 .
  • Using the pulsed laser method to deposit the sacrificial layer 02 and the dielectric thin film layer 03 has high efficiency, and can prepare the sacrificial layer 02 and the dielectric thin film layer 03 with uniform thickness.
  • the capacitor base layer 05 is glued on the side of the first electrode layer 04 away from the dielectric film layer 03 by adhesive.
  • the materials prepared in step S12 including the substrate 01, the sacrificial layer 02, the dielectric film layer 03, the first electrode layer 04 and the capacitor base layer 05, can be put into water , the sacrificial layer 02 is hydrolyzed to make the substrate 01 fall off, and the material including the dielectric thin film layer 03 , the first electrode layer 04 and the capacitor base layer 05 is obtained.
  • Step S13 obtains the material including the dielectric thin film layer 03, the first electrode layer 04 and the capacitor base layer 05, and forms the second electrode layer 06 on the side of the dielectric thin film layer 03 away from the first electrode layer 04 to obtain the thin film capacitor structure 10 .
  • the preparation method of the second electrode layer 06 can be prepared by electrodeposition, magnetron sputtering, ion sputtering or the like.
  • a copper layer is deposited on the side of the dielectric thin film layer 03 away from the first electrode layer 04 by ion sputtering, and the copper layer is used as the second electrode layer 06 .
  • the thin film capacitor structure 10 obtained in step S14 may be encapsulated by epoxy resin, polyurethane, silicone resin, or the like.
  • 3D printing technology is to install printing materials such as liquid or powder in the 3D printer.
  • the printing materials are solidified and stacked layer by layer, and finally the blueprint on the computer is turned into a three-dimensional object.
  • the 3D printing technology is used to package the film capacitor structure 10 , and the structure diagram of the package module can be precisely designed according to the size and shape of the film capacitor structure 10 in advance, so that the package module can be adapted to the size and shape of the film capacitor structure 10 , and then print the package.
  • the film capacitor structure 10 is packaged in an integrated manner to obtain a highly integrated film capacitor, which can effectively simplify the packaging process and avoid errors in the bonding process.
  • FIG. 3 is a schematic block diagram of the flow of an embodiment of the 3D printing packaging of the present application
  • FIG. 4 is a schematic diagram of the 3D printing packaging of the present application.
  • the present embodiment uses the 3D printing technology to package the thin film capacitor structure 10 and specifically includes steps S151 to S153:
  • FIG. 5 is a schematic structural diagram of a bottom module according to an embodiment of the present application.
  • the bottom module 200 is provided with a groove 201 , and the groove 201 is adapted to the size design of the thin film capacitor structure 10 .
  • the metal pins 1001 can be prepared on the first electrode layer 04 and the second electrode layer 06 before or after the thin film capacitor structure 10 is placed in the groove 201, and after the thin film capacitor structure 10 is placed in the groove 201, the metal leads The pins 1001 can extend beyond the packaging layer of the bottom module 200 (ie, the surface around the groove 201 that is connected to the top module during packaging), so that after the film capacitor structure 10 is packaged, the metal pins 1001 can be exposed in the package. outside the material.
  • This step prints the top module to form the capacitor module 1000 shown in FIG. 6 .
  • the first electrode layer 04 and the second electrode layer 06 in this embodiment are both prepared after the dielectric thin film layer 03 is prepared, and are not subjected to a high temperature environment, so as to avoid oxidation of the first electrode layer 04 and the second electrode layer 06 in the high temperature environment , effectively improve the performance of the capacitor, is conducive to prolonging the life of the capacitor, the process is simple, easy to implement.
  • Capacitor module 1000 as shown in Figure 6 is obtained by encapsulating capacitors by 3D printing technology. Capacitor module 1000 has no assembly traces and has excellent sealing performance. Using 3D printing technology to encapsulate can effectively simplify the device preparation process, and reduce the reliability of the device due to complex processes such as metal interconnection. sexual influence.
  • the inner and outer shapes and structures of the bottom module 200 and the top module are precisely designed according to the shape and structure of the thin film capacitor structure 10 before 3D printing the package.
  • the encapsulation layer of the top module corresponds to the encapsulation layer of the bottom module 200 and has the same surface area, and the encapsulation layer is larger than the size of the capacitor structure, so that when the film capacitor structure 10 is encapsulated by 3D printing technology, the top module and the bottom module 200 are covered with a thin film
  • the peripheral area of the capacitor structure 10 can be seamlessly connected in situ, so that the top module and the bottom module 200 form a seamless integrated package module, and the film capacitor structure 10, the metal pins 1001 and the package module form a unified whole.
  • FIG. 7 is a schematic flowchart of another embodiment of the method for manufacturing a film capacitor of the present application
  • FIG. 8 is a schematic flowchart of steps S22 to S26 of the present application, and the method for manufacturing a thin film capacitor in this embodiment is The steps include:
  • the substrate 01 is used as the growth substrate layer of the sacrificial layer 02 and the dielectric thin film layer 03 in step S21, and the substrate 01 of the same material or different material as the dielectric thin film layer 03 can be selected according to actual needs, which is not limited here.
  • a sacrificial layer 02 is formed on the substrate 01, and then a dielectric film layer 03 is formed on the side of the sacrificial layer 02 away from the substrate 01, and then a second layer is formed on the side of the dielectric film layer 03 away from the sacrificial layer 02.
  • An electrode layer 04, and finally a capacitor base layer 05 is formed on the side of the first electrode layer 04 away from the dielectric film layer 03.
  • the sacrificial layer 02 is prepared from a hydrolyzable substance.
  • the materials prepared in step S12 including the substrate 01, the sacrificial layer 02, the dielectric film layer 03, the first electrode layer 04 and the capacitor base layer 05, can be put into water , the sacrificial layer 02 is hydrolyzed to make the substrate 01 fall off, and the material including the dielectric thin film layer 03 , the first electrode layer 04 and the capacitor base layer 05 is obtained.
  • FIG. 9 is a schematic structural diagram of another embodiment of the bottom module of the present application.
  • the bottom module 200 is provided with a groove 201.
  • the side wall of the groove 200 is provided with at least one through hole 202, and one end of the through hole 202 is open.
  • the opening at the other end is disposed in the same direction as the opening of the groove 200 , forming a curved through hole 202 .
  • the first electrode layer 04 is exposed through the through hole 202
  • the second electrode layer 06 is deposited by ion sputtering on the exposed side of the dielectric film layer 03
  • the metal lead 07 is deposited in the through hole 202, so that the metal One end of the lead 07 is connected to the first electrode layer 04, and the first electrode layer 04 can be connected to the metal pin 1001 through the metal lead 07 during packaging.
  • the bottom module can also be as shown in FIG. 10 .
  • the bottom module 200 includes a groove 201 , and the sidewall of the groove 201 is provided with at least one first through hole 203 and at least one second through hole 204 .
  • FIG. 11 is a schematic flow diagram of another embodiment of steps S24-S26.
  • steps S24-S26 materials including the dielectric film layer 03, the first electrode layer 04 and the capacitor base layer 05 are placed in the bottom module 200 , the capacitor base layer 05 contacts the bottom of the groove 201 , the side of the dielectric film layer 03 away from the first electrode layer 04 is exposed, and the first electrode layer 04 is exposed through the through hole 203 .
  • step S25 the second electrode layer 06 is deposited on the exposed side of the dielectric thin film layer 03 by ion sputtering to form the thin film capacitor structure 10. After the 3D printing technology is used for encapsulation in step S26, the second electrode layer 06 is passed through the second pass.
  • the hole 204 is exposed, the first electrode layer 04 is exposed through the first through hole 203, the metal pins 1001 are prepared in the first through hole 203 and the second through hole 204, respectively, and the first electrode layer 04 and the second electrode layer 06 are respectively Connect with the metal pins 1001 to obtain the packaged film capacitor module 1000 .
  • the bottom module 200 mentioned in the above embodiments is a schematic illustration, and those skilled in the art can design the size and shape of the bottom module and the top module of the package module according to actual needs, and are not limited to those shown in the above embodiments. way out.
  • the present application also provides a specific example of a method for preparing a film capacitor, and the preparation steps are as follows:
  • An STO (SrTiO 3 , strontium titanate) substrate is provided.
  • the SAO (Sr 2 Al 6 O 3 , strontium aluminate) sacrificial layer and the STO dielectric thin film layer are sequentially prepared by sol-gel method or pulsed laser deposition method.
  • the preparation of the SAO sacrificial layer and the STO dielectric film layer by the sol-gel method specifically includes the following steps:
  • e1 Weigh aluminum nitrate, strontium nitrate and molar ratio of 3:1, add to nitric acid, add an appropriate amount of water, and stir at room temperature for 30 minutes;
  • h1 Coat the SAO precursor sol obtained in step g1 on the STO substrate, spin at 3000-6000r/min for 10-60s, place it in the air, heat it to 160°C on a heating table, and keep it for 30min to obtain SAO precursor film;
  • step i1 Place the SAO precursor film obtained in step h1 in a heating furnace in an oxygen atmosphere with an oxygen flow rate of 1 L/min, raise the temperature to 1000° C. at a rate of 5-100° C./min, and hold for 120 min to obtain a SAO sacrificial layer.
  • h2 Coat the STO precursor sol obtained in step g2 on the side of the SAO sacrificial layer obtained from S4 far away from the STO substrate, spin at 3000-6000r/min for 10-60s, and place it in the air on a heating table The temperature is raised from 200°C to 300°C, then raised to 450°C, then cooled to 300°C, and finally lowered to 200°C, and kept for 5-10min each to obtain the STO precursor film;
  • step i2 Place the STO precursor film obtained in step h2 in a heating furnace in an oxygen atmosphere, the oxygen flow rate is 1L/min, the temperature is raised to 450-500°C at a rate of 5-100°C/min, and the STO dielectric film is obtained by holding for 120min Floor.
  • the preparation of the SAO sacrificial layer and the STO dielectric thin film layer by the pulsed laser deposition method specifically includes steps e3 to g3:
  • f3 Fill the reaction chamber with oxygen to maintain the oxygen pressure at 50mTorr, set the energy of the laser to 250mJ and the frequency to 9.9Hz, set the substrate temperature to 600°C, make the laser emit laser light, and the number of dots is 18,000 times. Sintered on the strontium aluminate target, so that the strontium aluminate plasma is deposited on the strontium titanate substrate to form the SAO sacrificial layer.
  • g3 Adjust the oxygen in the reaction chamber to keep the oxygen pressure at 50mTorr, set the energy of the laser to 200mJ and the frequency to 9.9Hz, set the substrate temperature to 650°C, make the laser emit laser, the number of dots is 18000 times, and the cautery is at On the strontium titanate target, the strontium titanate plasma is deposited on the SAO sacrificial layer to form the STO dielectric thin film layer.
  • a first copper electrode layer is deposited on the side of the STO dielectric thin film layer obtained in step (2) away from the SAO sacrificial layer by ion sputtering.
  • the organic substrate PET is glued on the side of the first copper electrode layer away from the STO dielectric film layer, so that the PET substrate and the Cu electrode are fully contacted.
  • the materials including the STO substrate, the SAO sacrificial layer, the STO dielectric film layer, the first copper electrode layer, and the PET substrate are immersed in water, so that the SAO sacrificial layer is hydrolyzed and the STO substrate falls off, thereby removing the SAO sacrificial layer and STO substrate to obtain the thin film capacitor structure 10 .
  • the film capacitor structure 10 is placed in the groove 201 of the 3D printed mold 200, so that the PET substrate contacts the bottom of the groove 201, the side of the STO dielectric film layer away from the first copper electrode layer is exposed, and the first electrode The layers are exposed through the vias 202 of the mold 200 .
  • a second copper electrode layer is deposited on the exposed side of the STO dielectric film layer by ion sputtering, and a copper wire is deposited in the through hole 202 at the same time, so that one end of the copper wire is connected to the first copper electrode layer.
  • a high dielectric constant film capacitor module with excellent airtight performance is prepared.
  • This module can be used as a single component or as an embedded capacitive component in combination with a large-scale integrated circuit, etc., and can be applied in a variety of devices.
  • FIG. 12 is the XRD diffraction pattern of the thin film capacitor of the present application, which shows that SAO thin film, SRO (SrRuO3) thin film and single crystal STO thin film are prepared.
  • FIG. 13 is the surface topography diagram of the STO dielectric film layer of the application
  • FIG. 14 is the surface topography diagram of the SAO sacrificial layer of the application
  • FIG. 15 is the surface topography diagram of the STO lining layer of the application Bottom surface topography.
  • the surface roughness value Ra of the STO dielectric film layer is 520pm
  • the surface roughness value Ra of the SAO sacrificial layer is 316pm
  • the surface roughness value Ra of the STO substrate is 138pm, indicating that the prepared film is extremely smooth and meets the requirements of device applications. .
  • Figure 16a shows the energy storage density of STO films with different thicknesses under a positive electric field
  • Figure 16b shows the variation curve of the relative permittivity ⁇ r of film capacitors with frequency f. It can be seen that the relative permittivity of film capacitors is about the same as that of current commercial capacitors. 2 times that of the film.
  • Figure 16c is the JE curve of the current-electric field of the film capacitor. It can be seen that the breakdown field strength of the film capacitor is about 6MV/cm2, which is about 1000 times that of the current industrial film.
  • the capacitance C of the film capacitor and the change curve of the loss factor tan ⁇ with the frequency f, the film capacitor prepared by this method has a lower dielectric loss.
  • the film capacitor prepared in this embodiment has high withstand voltage, long life, stable temperature characteristics, low loss, and the preparation process is simple and easy to implement, and can be prepared in large quantities.

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Abstract

本申请公开了一种薄膜电容器的制备方法以及薄膜电容器，其中，该制备方法包括：提供一衬底；在所述衬底上依次形成牺牲层、介电薄膜层、第一电极层和电容器基底层；去除所述衬底和所述牺牲层；在所述介电薄膜层远离所述第一电极层的一侧形成第二电极层，以得到薄膜电容结构；采用3D打印技术对所述薄膜电容进行封装。通过上述方法可以制备得到耐压高、寿命长、温度特性稳定、损耗低的薄膜电容器，可用于各种相关电子设备及大规模集成电路等。

Description

一种薄膜电容器的制备方法以及薄膜电容器 【技术领域】
本申请涉及电子元器件的制备领域，特别是涉及一种薄膜电容器的制备方法以及薄膜电容器。
【背景技术】
随着科技发展，5G时代到来，电子信息产业发展使得电子器件发展越来越趋于小型化、高容量、耐击穿。
目前市面的电容器有陶瓷电容器、铝电解质电容器、钽电解质电容器以及薄膜电容器等。其中，薄膜电容器常以聚乙酯，聚丙烯，聚苯乙烯或聚碳酸酯等塑料薄膜等作为介质层，具有很多优良的特性，相较于陶瓷电容器、铝电解质电容器、钽电解质电容器而言，以具有高介电常数无机材料作为电介质层的薄膜电容器具有耐压高、寿命长、温度特性稳定、损耗低等优势，同时可用作中间基板的叠层电容器能够有效地消除引起电感增大的布线部分，由此实现较低阻抗和较宽频带。
【发明内容】
本申请主要解决的技术问题是提供一种薄膜电容器的制备方法以及薄膜电容器，能够制备具有耐压高、寿命长、温度特性稳定、损耗低等优异性能的薄膜电容器。
为解决上述技术问题，本申请第一方面提供了一种薄膜电容器的制备方法，该方法包括：提供一衬底；在所述衬底上依次形成牺牲层、介电薄膜层、第一电极层和电容器基底层；其中，所述衬底和所述介电薄膜层的材料相同；去除所述衬底和所述牺牲层；在所述介电薄膜层远离所述第一电极层的一侧形成第二电极层，以得到薄膜电容结构；采用3D打印技术对所述薄膜电容结构进行封装。
可选地，所述采用3D打印技术对所述薄膜电容结构进行封装，包括：
采用3D打印技术制备用于放置所述薄膜电容结构的底部模块，其 中，所述底部模块具有根据电容器尺寸所需用于放置电容结构的凹槽；将所述薄膜电容结构置入所述凹槽中；采用原位3D打印技术，在所述底部模块的基础上原位打印顶部模块，完成对所述薄膜电容结构的一体化封装。
可选地，所述在所述底部模块的基础上原位打印顶部模块之前，还包括：分别在所述第一电极层和所述第二电极层制备金属引脚和/或金属引线。
可选地，所述采用3D打印技术对所述薄膜电容结构进行封装的过程中不使用额外的粘结剂，无需高温固化；所述采用3D打印技术对所述薄膜电容结构进行封装之前，包括：根据所述薄膜电容结构的形状与结构精密设计所述底部模块和顶部模块的内外形状与结构；所述顶部模块的封装层与所述底部模块的封装层对应且表面积相等，且所述封装层大于电容器结构尺寸，以在利用3D打印技术对所述薄膜电容结构进行封装时，所述顶部模块和底部模块原位无缝衔接，使得所述顶部模块和底部模块组成无缝一体化的封装模块，所述薄膜电容结构、金属引脚和封装模块形成统一整体。
本申请提供的3D打印封装方法，根据薄膜电容结构设计3D打印模块的底部模块和顶部模块，在所述薄膜电容结构的外围打印3D封装底部模块，在嵌入薄膜电容结构后采用3D打印工艺原位无缝构建3D封装顶部模块。
可选地，所述在所述衬底上依次形成牺牲层、介电薄膜层、第一电极层和电容器基底层，包括：在所述衬底上涂覆第一胶体，并置于空气中加热，以形成第一前驱薄膜；将所述第一前驱薄膜置于氧气中加热，以形成所述牺牲层；在所述牺牲层上涂覆第二胶体，并置于空气中加热，以形成第二前驱薄膜；将所述第二前驱薄膜置于氧气中加热，以形成所述介电薄膜层；在所述介电薄膜层上形成第一电极层和电容器基底层。
可选地，所述在所述衬底上涂覆第一胶体，并置于空气中加热，以形成第一前驱薄膜，包括：在所述衬底上旋涂所述第一胶体，置于空气中加热到第一预设温度，并在第一预设时间内保持所述第一预设温度， 以使所述第一胶体形成所述第一前驱薄膜。
可选地，所述将所述第一前驱薄膜置于氧气中加热，以形成所述牺牲层，包括：将所述第一前驱薄膜置于氧气气氛的加热炉中，设置氧气流量为第一预设氧气流量，加热到第二预设温度，并在第二预设时间内保持所述第二预设温度，以使所述第一前驱薄膜形成所述牺牲层。
可选地，所述在所述牺牲层上涂覆第二胶体，并置于空气中加热，以形成第二前驱薄膜，包括：在所述牺牲层上旋涂所述第二胶体，置于空气中加热到第三预设温度，并在第三预设时间内保持所述第三预设温度，以使所述第二胶体形成所述第二前驱薄膜。
可选地，所述将所述第二前驱薄膜置于氧气中加热，以形成所述介电薄膜层，包括：将所述第一前驱薄膜置于氧气气氛的加热炉中，设置氧气流量为第二预设氧气流量，加热到第四预设温度，并在第四预设时间内保持所述第四预设温度，以使所述第二前驱薄膜形成所述介电膜薄层。
可选地，所述在所述介电薄膜层上形成第一电极层和电容器基底层，包括：采用离子溅射法在所述介电薄膜层上形成第一电极层；将电容器基底层胶合在所述第一电极层上。
可选地，所述第一胶体采用以下方法制作得到：将硝酸铝、硝酸锶加入硝酸，并搅拌，得到第一溶液；将柠檬酸溶于水，得到第二溶液，所述柠檬酸的用量大于所述第一溶液中金属离子总和；将所述第一溶液和所述第二溶液混合，并加热搅拌使得所述金属离子与所述柠檬酸络合，并蒸发水分，得到所述第一胶体。
可选地，所述第二胶体采用以下方法制作得到：混合醋酸锶和冰乙酸，搅拌，得到第三溶液，将含有PVP的冰醋酸加入到第三溶液并搅拌，得到第四溶液；将钛酸四丁酯加入乙二醇甲醚，搅拌，得到第五溶液，在所述第五溶液中加入乙酰丙酮，搅拌，得到第六溶液；将所述第四溶液和所述第六溶液混合，搅拌后向混合溶液中加入乙二醇，加热搅拌，冷却后过滤，得到第二胶体。
可选地，所述在所述衬底上依次形成牺牲层、介电薄膜层、第一电 极层和电容器基底层，包括：利用脉冲激光烧灼第一靶材，以在所述衬底上沉积牺牲层；利用脉冲激光烧灼第二靶材，以在所述牺牲层上沉积介电薄膜层；在所述介电薄膜层上形成第一电极层和电容器基底层。
可选地，所述利用脉冲激光烧灼第一靶材，以在所述衬底上沉积牺牲层，包括：将所述衬底和铝酸锶靶材置于脉冲激光沉积系统的反应室；在氧气的环境下，利用脉冲激光灼烧铝酸锶靶材，以在所述衬底上沉积铝酸锶等离子体，形成所述牺牲层。
可选地，所述利用脉冲激光烧灼第二靶材，以在所述牺牲层上沉积介电薄膜层，包括：将制备有所述牺牲层的钛酸锶衬底和钛酸锶靶材置于脉冲激光沉积系统的反应室；在氧气的环境下，利用脉冲激光灼烧所述钛酸锶靶材，以在所述衬底上沉积钛酸锶等离子体，形成所述介电薄膜层。
可选地，所述牺牲层由可水解的材料制成；所述去除所述衬底和所述牺牲层，包括：将包括所述衬底、牺牲层、介电薄膜层、第一电极层和电容器基底层的材料放入水中，以水解所述牺牲层，使得所述衬底脱落。
为解决上述技术问题，本申请第二方面提供了一种薄膜电容器，该薄膜电容器由上述第一方面提供的薄膜电容器的制备方法制备而成。
本申请的有益效果是：区别于现有技术的情况，本申请在衬底上依次形成牺牲层、介电薄膜层、第一电极层和电容器基底层，再去除牺牲层和衬底，在介电薄膜层远离第一电极层的一侧形成第二电极层，制备得到薄膜电容。通过在制备完成介电薄膜层后，制备第一电极层和第二电极层，使得第一电极层和第二电极层不经受制备介电薄膜层时的高温环境，从而避免电极层的高温氧化，制备而成的薄膜电容器具有耐压高、寿命长、温度特性稳定、损耗低等特点。本申请还通过3D打印技术对薄膜电容器结构进行封装，全程不使用液态粘结剂，避免了传统封装工艺中由于高温固化或化学腐蚀等对电容器结构产生的不利影响。
【附图说明】
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例描 述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。其中：
图1是本申请薄膜电容器的制备方法一实施例的流程示意框图；
图2是本申请步骤S12～S14的流程示意简图；
图3是本申请3D打印封装一实施例的流程示意框图；
图4是本申请3D打印封装一实施例的流程示意简图；
图5是本申请底部模块一实施例的结构示意图
图6是本申请通过薄膜电容器的制备方法制备得到的电容器模块示意图；
图7是本申请薄膜电容器的制备方法另一实施例的流程示意框图；
图8是本申请步骤S22～S26的流程示意简图；
图9是是本申请底部模块另一实施例的结构示意图；
图10是本申请底部模块还一实施例的结构示意图；
图11是本申请步骤S24～S26另一实施例的流程示意图；
图12是本申请薄膜电容器的XRD衍射图；
图13是本申请STO介电薄膜层的表面形貌图；
图14是本申请SAO牺牲层的表面形貌图；
图15是本申请STO衬底的表面形貌图；
图16a是不同厚度STO薄膜在正电场下的储能密度图；
图16b是本申请薄膜电容器相对介电常数εr随频率f的变化曲线图；
图16c是本申请薄膜电容器电流-电场的J-E曲线图；
图16d为薄膜电容器的电容C以及损耗因子tanδ随频率f的变化曲线图。
【具体实施方式】
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅是本申请的一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术 人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
本申请中的术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。此外，术语“包括”和“具有”以及他们任何形变，意图在于覆盖不排他的包含。例如包含了一系列步骤或单元的过程、方法、系统、产品或设备没有限定于已列出的步骤或单元，而是可选地还包括没有列出的步骤或单元，或可选地还包括对于这些过程、方法、产品或设备固有的其它步骤或单元。
在本文中提及“实施例”意味着，结合实施例描述的特定特征、结构或特性可以包含在本申请的至少一个实施例中。在说明书中的各个位置出现该短语不一定均是指相同的实施例，也不是与其它实施例互斥的独立的或备选的实施例。本领域技术人员显式地和隐式地理解是，本文所描述的实施例可以与其他实施例结合。
本申请薄膜电容器的制备方法的核心在于，引入牺牲层，使得薄膜电容器的电极的制备步骤后于介电薄膜层的制备步骤，使得电极层不经受制备介电薄膜层时的高温环境，免于高温氧化，从而提高电容器的电学性能，降低损耗，延长电容器的使用寿命。
参阅图1和图2，图1为本申请薄膜电容器的制备方法一实施例的流程示意框图，图2为本申请步骤S12～S14的流程示意简图，本实施例的制备方法包括以下步骤：
S11，提供一衬底。
衬底01作为步骤S12牺牲层02和介电薄膜层03的生长衬底层，可按照实际需求选取与介电薄膜层03相同材料或不同材料的衬底01，在此不作限定。
S12，在衬底上依次形成牺牲层、介电薄膜层、第一电极层和电容器基底层。
此步骤首先在衬底01上形成牺牲层02，再在牺牲层02上远离衬底 01的一侧形成介电薄膜层03，然后在介电薄膜层03上远离牺牲层02的一侧形成第一电极层04，最后在第一电极层04上远离介电薄膜层03的一侧制备电容器基底层05。
其中，牺牲层02由可水解物质制备而成，例如牺牲层02可以是铝酸锶薄膜层。可选地，第一电极层04为铜或其他导电性能良好的金属。
其中，牺牲层02的生成方式包括但不限于溶胶凝胶法、气相沉积法、脉冲激光沉积法。介电薄膜层03的制备方法包括但不限于溶胶凝胶法、气相沉积法、脉冲激光沉积法。第一电极层04的制备方法包括但不限于电沉积法、离子溅射法等。
可选地，衬底01与介电薄膜层03的材料相同。具体而言，本申请的介电膜薄层03可选用单晶材料或多晶材料制备，其中，选用单晶材料制备介电薄膜层03时，衬底01选用与介电薄膜层03相同的材料，利用同质外延生长介电薄膜层03，可以得到高质量的介电薄膜层03。
可选地，利用溶胶凝胶法制备牺牲层02和介电薄膜层03的步骤如a1～d1：
a1.在衬底01上涂覆第一胶体，并置于空气中加热，以形成第一前驱薄膜。
b1.将第一前驱薄膜置于氧气中加热，以形成牺牲层02。
c1.在牺牲层上涂覆第二胶体，并置于空气中加热，以形成第二前驱薄膜。
d1.将第二前驱薄膜置于氧气中加热，以形成介电薄膜层03。
具体在制备牺牲层02时，在衬底01上旋涂第一胶体，置于空气中加热到第一预设温度，并在第一预设时间内保持第一预设温度，以使第一胶体形成第一前驱薄膜，再将第一前驱薄膜置于氧气气氛的加热炉中，设置氧气流量为第一预设氧气流量，加热到第二预设温度，并在第二预设时间内保持第二预设温度，以使第一前驱薄膜形成牺牲层02。在制备介电薄膜层03时，在牺牲层02上旋涂第二胶体，置于空气中加热到第三预设温度，并在第三预设时间内保持第三预设温度，以使第二胶体形成第二前驱薄膜，再将第一前驱薄膜置于氧气气氛的加热炉中，设 置氧气流量为第二预设氧气流量，加热到第四预设温度，并在第四预设时间内保持第四预设温度，以使第二前驱薄膜形成介电膜薄层03。
其中，第一胶体和第二胶体分别为牺牲层02和介电薄膜层03的前驱胶体。可选地，制备铝酸锶牺牲层时，第一胶体的制备步骤如a2～d2：
a2.将硝酸铝、硝酸锶加入硝酸，并搅拌，得到第一溶液；
b2.将柠檬酸溶于水，得到第二溶液，其中，柠檬酸的用量大于第一溶液中金属离子总和；
c2.将第一溶液和第二溶液混合，并加热搅拌使得金属离子与柠檬酸络合，并蒸发水分，得到第一胶体。
可选地，制备钛酸锶单晶介电薄膜层时，第二胶体的制备步骤如a3～d3：
a3.混合醋酸锶和冰乙酸，搅拌，得到第三溶液，将含有PVP(聚乙烯吡咯烷酮)的冰醋酸加入到第三溶液并搅拌，得到第四溶液；
b3.将钛酸四丁酯加入乙二醇甲醚，搅拌，得到第五溶液，在第五溶液中加入乙酰丙酮，搅拌，得到第六溶液；
c3.将第四溶液和第六溶液混合，搅拌后向混合溶液中加入乙二醇，加热搅拌，冷却后过滤，得到第二胶体。
以上仅是制备铝酸锶牺牲层和钛酸锶介电薄膜层所需的第一胶体和第二胶体制备方法的示意性说明，本领域技术人员可按照实际需求进行第一胶体和第二胶体的配置，此处不做限定。
除了利用上述的溶胶凝胶法制备牺牲层02和介电薄膜层03外，在另外的实施例中，还能利用脉冲激光沉积法制备牺牲层02和介电薄膜层03，步骤如a4～b4：
a4.利用脉冲激光烧灼第一靶材，以在衬底01上沉积牺牲层02；
b4.利用脉冲激光烧灼第二靶材，以在牺牲层02上沉积介电薄膜层03。
其中，第一靶材可以是铝酸锶靶材，第二靶材可以是钛酸锶靶材，在制备牺牲层02和介电薄膜层03时，将衬底01和铝酸锶靶材置于脉冲激光沉积系统的反应室，在氧气的环境下，利用脉冲激光灼烧铝酸锶 靶材，以在衬底上沉积铝酸锶等离子体，形成牺牲层02；在制备介电薄膜层03时，将制备有牺牲层02的钛酸锶衬底和钛酸锶靶材置于脉冲激光沉积系统的反应室，在氧气的环境下，利用脉冲激光灼烧钛酸锶靶材，以在牺牲层02上沉积钛酸锶等离子体，形成介电薄膜层03。
利用脉冲激光法沉积牺牲层02和介电薄膜层03的效率高，能够制备得到厚度均匀的牺牲层02和介电薄膜层03。
可选地，电容器基底层05通过粘合剂胶合在第一电极层04远离介电薄膜层03的一侧。
S13，去除衬底和牺牲层。
具体地，去除衬底01和牺牲层02可通过将步骤S12制备得到的，包括衬底01、牺牲层02、介电薄膜层03、第一电极层04和电容器基底层05的材料放入水中，水解牺牲层02，使得衬底01脱落，得到包括介电薄膜层03、第一电极层04和电容器基底层05的材料。
S14，在介电薄膜层远离第一电极层的一侧形成第二电极层，以得到薄膜电容结构。
步骤S13得到包括介电薄膜层03、第一电极层04和电容器基底层05的材料，在介电薄膜层03远离第一电极层04的一侧形成第二电极层06，得到薄膜电容结构10。第二电极层06的制备方式可以是电沉积、磁控溅射、离子溅射等方式制备而成。
可选地，以金属铜为靶材，利用离子溅射法在介电薄膜层03远离第一电极层04的一侧沉积铜层，以铜层作为第二电极层06。
S15，采用3D打印技术对薄膜电容结构进行封装。
步骤S14中获得的薄膜电容结构10可以利用环氧树脂、聚氨酯、有机硅树脂等进行封装。
3D打印技术是在3D打印机内装有液体或粉末等打印材料，打印时将打印材料逐层固化和逐层叠加，最终把计算机上的蓝图变成立体实物。
本实施例利用3D打印技术封装薄膜电容结构10，可以预先依照薄膜电容结构10的尺寸、形状等精密设计封装模块的结构图，以使封装 模块适应于薄膜电容结构10的尺寸形状，再打印封装模块，对薄膜电容结构10进行一体化封装，能够得到高度一体化的薄膜电容器，能够有效简化封装工艺，并能避免键合过程中的误差。
可选地，利用3D打印技术对薄膜电容结构10结构进行封装，请参阅图3和图4，图3为本申请3D打印封装一实施例的流程示意框图，图4为本申请3D打印封装一实施例的流程示意简图。本实施例利用3D打印技术对薄膜电容结构10进行封装具体包括步骤S151～S153：
S151，采用3D打印技术制备用于放置薄膜电容结构的底部模块，其中，底部模块具有适应于薄膜电容结构的尺寸的凹槽。
请参阅图5，图5为本申请底部模块一实施例的结构示意图，底部模块200设有一凹槽201，凹槽201适应于薄膜电容结构10的尺寸设计。
S152，将薄膜电容结构置入凹槽中。
其中，可在将薄膜电容结构10置入凹槽201之前或之后，在第一电极层04和第二电极层06制备金属引脚1001，薄膜电容结构10被置入凹槽201后，金属引脚1001可延伸出底部模块200的封装层(即凹槽201四周的、在封装时与顶部模块连接的表面)之外，使得在薄膜电容结构10封装完毕后，金属引脚1001可裸露在封装材料之外。
S153，采用原位3D打印技术，在底部模块的基础上原位打印顶部模块，完成对薄膜电容结构的一体化封装。
本步骤打印顶部模块，以形成图6所示的电容器模块1000。本实施例的第一电极层04和第二电极层06均在介电薄膜层03制备完成之后进行制备，不经受高温环境，以免高温环境使得第一电极层04和第二电极层06发生氧化，有效提高电容器的性能，有利于延长电容器的寿命，工艺简单，易于实现。通过3D打印技术进行电容器封装得到如图6所示的电容器模块1000，电容器模块1000无组装痕迹，密封性能优异，利用3D打印技术封装可以有效简化器件制备工艺，降低金属互联等复杂工艺对器件可靠性的影响。
可选地，在3D打印封装之前，根据薄膜电容结构10的形状与结构精密设计底部模块200和顶部模块(未示出)的内外形状与结构。其中， 顶部模块的封装层与底部模块200的封装层对应且表面积相等，且封装层大于电容器结构尺寸，以在利用3D打印技术对薄膜电容结构10进行封装时，顶部模块和底部模块200覆盖薄膜电容结构10的外围区域，且能够原位无缝衔接，使得顶部模块和底部模块200组成无缝一体化的封装模块，薄膜电容结构10、金属引脚1001和封装模块形成统一整体。
请参阅图7和图8，图7为本申请薄膜电容器的制备方法另一实施例的流程示意框图，图8为本申请步骤S22～S26的流程示意简图，本实施例薄膜电容器的制备方法的步骤包括：
S21，提供一衬底。
衬底01作为步骤S21牺牲层02和介电薄膜层03的生长衬底层，可按照实际需求选取与介电薄膜层03相同材料或不同材料的衬底01，在此不作限定。
S22，在衬底上依次形成牺牲层、介电薄膜层、第一电极层和电容器基底层。
此步骤首先在衬底01上形成牺牲层02，再在牺牲层02上远离衬底01的一侧形成介电薄膜层03，然后在介电薄膜层03上远离牺牲层02的一侧形成第一电极层04，最后在第一电极层04上远离介电薄膜层03的一侧制备电容器基底层05。
其中，牺牲层02由可水解物质制备而成。
S23，去除衬底和牺牲层。
具体地，去除衬底01和牺牲层02可通过将步骤S12制备得到的，包括衬底01、牺牲层02、介电薄膜层03、第一电极层04和电容器基底层05的材料放入水中，水解牺牲层02，使得衬底01脱落，得到包括介电薄膜层03、第一电极层04和电容器基底层05的材料。
S24，将包括介电薄膜层、第一电极层和电容器基底层的材料容置入底部模块中。
S25，在介电薄膜层远离第一电极层的一侧形成第二电极层。
请参阅图9，图9为本申请底部模块另一实施例的结构示意图，底部模块200设有一凹槽201，凹槽200的侧壁上设有至少一通孔202， 通孔202的一端开口设置于凹槽200侧壁的内侧，另一端开口与凹槽200开口的朝向一致设置，形成弯曲通孔202。将包括介电薄膜层03、第一电极层04和电容器基底层05的材料置入底部模块200时，电容器基底层05接触凹槽201底部，介电薄膜层03远离第一电极层04的一侧裸露，第一电极层04通过通孔202裸露，在介电薄膜层03裸露的一侧利用离子溅射法沉积第二电极层06，同时在通孔202中沉积金属引线07，以使金属引线07的一端连接第一电极层04，封装时第一电极层04便可通过金属引线07连接金属引脚1001。
S26，采用3D打印技术，在底部模块的基础上制作完整封装装置，以对所述薄膜电容结构进行封装。
在另外的实施例中，底部模块还可以是图10所示的那样，底部模块200包括凹槽201，凹槽201的侧壁设置至少一第一通孔203以及至少一第二通孔204。
请参阅图11，图11所示为步骤S24～S26另一实施例的流程示意简图，步骤S24将包括介电薄膜层03、第一电极层04和电容器基底层05的材料置入底部模块200，电容器基底层05接触凹槽201底部，介电薄膜层03远离第一电极层04的一侧裸露，第一电极层04通过通孔203裸露。步骤S25在介电薄膜层03裸露的一侧利用离子溅射法沉积第二电极层06，形成薄膜电容结构10，在步骤S26采用3D打印技术进行封装后，第二电极层06通过第二通孔204裸露，第一电极层04通过第一通孔203裸露，分别在第一通孔203和第二通孔204中制备金属引脚1001，将第一电极层04和第二电极层06分别与金属引脚1001连接，得到封装后的薄膜电容模块1000。
以上各实施例所提及的底部模块200均为示意性的说明，本领域技术人员可按实际需求设计封装模块的底部模块和顶部模块的的尺寸和形状，而不限于上述各实施例所示出的方式。
基于上述实施方式，本申请还提供一薄膜电容器的制备方法的具体实施例，制备步骤如下：
(1)提供STO(SrTiO 3，钛酸锶)衬底。
(2)利用溶胶凝胶法或脉冲激光沉积法依次制备SAO(Sr 2Al 6O 3，铝酸锶)牺牲层和STO介电薄膜层。
其中，利用溶胶凝胶法制备SAO牺牲层和STO介电薄膜层具体包括以下步骤：
1)制备SAO牺牲层，具体包括步骤e1～i1：
e1：将硝酸铝、硝酸锶、按摩尔比3:1称重，加入硝酸中、适量加水，常温搅拌30分钟；
f1：将柠檬酸溶于水中，其中，柠檬酸的用量为金属离子总和的1.2～1.3倍，制成柠檬酸溶液；
g1：将金属离子的硝酸盐混合溶液倒入柠檬酸溶液中，在90℃下搅拌使金属离子与柠檬酸络合完全，并使水分蒸发.继续搅拌直至溶液变成粘性淡黄色的溶胶，并最终转变成粘滞不动的稠状凝胶，得到SAO前驱体溶胶；
h1：将步骤g1中得到的SAO前驱体溶胶涂覆到STO衬底上，以3000-6000r/min旋涂10-60s后，置于空气中，在加热台上加热至160℃，保温30min得到SAO前驱薄膜；
i1：将步骤h1中得到的SAO前驱薄膜置于氧气气氛的加热炉中，氧气流量为1L/min，以5-100℃/min的速度升温至1000℃，保温120min得到SAO牺牲层。
2)制备STO介电薄膜层，具体包括步骤e2～i2：
e2：制备锶源：混合醋酸锶和冰乙酸，70～90℃搅拌0.5～2h，缓慢降温至40～60℃，加入添加PVP的冰醋酸，搅拌20～60min，其中，醋酸锶：PVP＝1mol：3～8g，醋酸锶：乙酸总量＝1mol：1.5～2.5L；
f2：制备钛源：钛酸四丁酯溶解于乙二醇甲醚，40～60℃搅拌10～60min，加入乙酰丙酮，40～60℃搅拌0.5～2h钛酸四丁酯：乙二醇甲醚：乙酰丙酮＝1mol：2～3L：0.08～0.12L；
g2：将钛源缓慢加入锶源中，40～60℃，搅拌5～30min，加入乙二醇，保持40～60℃，搅拌2～4h，冷却至室温，前驱液过滤，得到STO前驱体溶胶。其中，锶源：乙二醇＝1mol：0.1～0.3L。
h2：将步骤g2中得到的STO前驱体溶胶覆到S4得到的SAO牺牲层远离STO衬底的一侧，以3000-6000r/min旋涂10-60s后，置于空气中，在加热台上由200℃升温至300℃，再升至450℃再降温至300℃，最后降温200℃，各保温5-10min得到STO前驱薄膜；
i2：将步骤h2中得到的STO前驱薄膜置于氧气气氛的加热炉中，氧气流量为1L/min，以5-100℃/min的速度升温至450-500℃，保温120min得到STO介电薄膜层。
利用脉冲激光沉积法制备SAO牺牲层和STO介电薄膜层具体包括步骤e3～g3：
e3：将STO衬底，铝酸锶靶材，钛酸锶靶材放入脉冲激光沉积系统的反应室中，对反应室进行抽真空；
f3：向反应室中充入氧气，使氧压维持在50mTorr，设定激光器的能量为250mJ和频率为9.9Hz，设定衬底温度为600℃，使激光器射出激光，打点数为18000次，烧灼在铝酸锶靶材上，使得铝酸锶等离子体沉积在钛酸锶衬底上，形成SAO牺牲层。
g3：调节反应室中氧气，使氧压维持在50mTorr，设定激光器的能量为200mJ和频率为9.9Hz，设定衬底温度为650℃，使激光器射出激光，打点数为18000次，烧灼在钛酸锶靶材上，使得钛酸锶等离子体沉积在SAO牺牲层上，形成STO介电薄膜层。
(3)采用离子溅射法在步骤(2)得到的STO介电薄膜层远离SAO牺牲层的一侧沉积第一铜电极层。
(4)将有机基底PET胶合在第一铜电极层远离STO介电薄膜层的一侧，使得使PET基底与Cu电极充分接触。
(5)将包括STO衬底、SAO牺牲层、STO介电薄膜层、第一铜电极层、PET基底的材料浸泡在水中，使得SAO牺牲层水解，STO衬底脱落，从而去除SAO牺牲层和STO衬底，得到薄膜电容结构10。
(6)将薄膜电容结构10置于3D打印的模具200的凹槽201中，使得PET基底接触凹槽201的底部，STO介电薄膜层远离第一铜电极层的一侧裸露，第一电极层通过模具200的通孔202裸露。
(7)采用离子溅射法在STO介电薄膜层裸露的一侧沉积第二铜电极层，同时在通孔202中沉积铜导线，以使铜导线的一端连接第一铜电极层。
(8)利用3D打印技术进行封装。
具体封装流程可参阅上述各实施例的封装步骤，此处不再进行赘述。
通过上述步骤(1)～(8)制备得到密闭性能优异的高介电常数薄膜电容器模块，此模块可以作为单一元件或作为埋入式电容元件置于与大规模集成电路结合等，可被应用于多种器件场合。
请参阅图12，图12为本申请薄膜电容的XRD衍射图，表明制备获得了SAO薄膜、SRO(SrRuO3)薄膜以及单晶的STO薄膜。
请一并参阅图13、图14和图15，图13为本申请STO介电薄膜层的表面形貌图，图14为本申请SAO牺牲层的表面形貌图，图15为本申请STO衬底的表面形貌图。STO介电薄膜层的表面粗糙度值Ra为520pm，SAO牺牲层的表面粗糙度值Ra为316pm，STO衬底的表面粗糙度值Ra为138pm，说明制备的薄膜极为平整，满足器件应用的要求。
请一并参阅图16a、16b、16c和16d，为薄膜电容器的电学性能测试结果。图16a为不同厚度STO薄膜在正电场下的储能密度图，图16b为薄膜电容器相对介电常数εr随频率f的变化曲线，可以看出，薄膜电容器的相对介电常数约为目前商用电容器薄膜的2倍，图16c为薄膜电容器电流-电场的J-E曲线图，可以看出薄膜电容器的击穿场强约为6MV/cm2抗击穿能力强，约为目前工业化薄膜的1000倍，图16d为薄膜电容器的电容C以及损耗因子tanδ随频率f的变化曲线图，此方法制备出的薄膜电容器具有较低的介电损耗。
本实施例的制备的薄膜电容器耐压高、寿命长、温度特性稳定、损耗低，而且制备工艺简单易于实现，能够大量制备。
以上所述仅为本申请的实施方式，并非因此限制本申请的专利范围，凡是利用本申请说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本申请的 专利保护范围内。

Claims (14)

  1. 一种薄膜电容器的制备方法，其特征在于，所述方法包括：
    1)提供一衬底；
    2)在所述衬底上依次形成牺牲层、介电薄膜层、第一电极层和电容器基底层；
    3)去除所述衬底和所述牺牲层；
    4)在所述介电薄膜层远离所述第一电极层的一侧形成第二电极层，以得到薄膜电容结构；
    5)采用3D打印技术对所述薄膜电容结构进行封装。
  2. 根据权利要求1所述的方法，其特征在于，
    所述采用3D打印技术对所述薄膜电容结构进行封装，包括：
    1)采用3D打印技术制备用于放置所述薄膜电容结构的底部模块，其中，所述底部模块具有适应于所述薄膜电容结构的尺寸的凹槽；
    2)将所述薄膜电容结构置入所述凹槽中；
    3)采用原位3D打印技术，在所述底部模块的基础上原位打印顶部模块，完成对所述薄膜电容结构的一体化封装。
  3. 根据权利要求2所述的方法，其特征在于，
    所述在所述底部模块的基础上原位打印顶部模块之前，还包括：
    分别在所述第一电极层和所述第二电极层制备金属引脚和/或金属引线。
  4. 根据权利要求3所述的方法，其特征在于，
    所述采用3D打印技术对所述薄膜电容结构进行封装的过程中不使用额外的粘结剂，无需高温固化；
    所述采用3D打印技术对所述薄膜电容结构进行封装之前，包括：
    根据所述薄膜电容结构的形状与结构精密设计所述底部模块和顶部模块的内外形状与结构；
    所述顶部模块的封装层与所述底部模块的封装层对应且表面积相等，且所述封装层大于电容器结构尺寸，以在利用3D打印技术对所述薄膜电容结构进行封装时，所述顶部模块和底部模块原位无缝衔接，使 得所述顶部模块和底部模块组成无缝一体化的封装模块，所述薄膜电容结构、金属引脚和封装模块形成统一整体。
  5. 根据权利要求1所述的方法，其特征在于，
    所述在所述衬底上依次形成牺牲层、介电薄膜层、第一电极层和电容器基底层，包括：
    在所述衬底上涂覆第一胶体，并置于空气中加热，以形成第一前驱薄膜；
    将所述第一前驱薄膜置于氧气中加热，以形成所述牺牲层；
    在所述牺牲层上涂覆第二胶体，并置于空气中加热，以形成第二前驱薄膜；
    将所述第二前驱薄膜置于氧气中加热，以形成所述介电薄膜层；
    在所述介电薄膜层上形成所述第一电极层和所述电容器基底层。
  6. 根据权利要求5所述的方法，其特征在于，
    所述在所述衬底上涂覆第一胶体，并置于空气中加热，以形成第一前驱薄膜，包括：
    在所述衬底上旋涂所述第一胶体，置于空气中加热到第一预设温度，并在第一预设时间内保持所述第一预设温度，以使所述第一胶体形成所述第一前驱薄膜；
    所述将所述第一前驱薄膜置于氧气中加热，以形成所述牺牲层，包括：
    将所述第一前驱薄膜置于氧气气氛的加热炉中，设置氧气流量为第一预设氧气流量，加热到第二预设温度，并在第二预设时间内保持所述第二预设温度，以使所述第一前驱薄膜形成所述牺牲层；
    所述在所述牺牲层上涂覆第二胶体，并置于空气中加热，以形成第二前驱薄膜，包括：
    在所述牺牲层上旋涂所述第二胶体，置于空气中加热到第三预设温度，并在第三预设时间内保持所述第三预设温度，以使所述第二胶体形成所述第二前驱薄膜；
    所述将所述第二前驱薄膜置于氧气中加热，以形成所述介电薄膜 层，包括：
    将所述第一前驱薄膜置于氧气气氛的加热炉中，设置氧气流量为第二预设氧气流量，加热到第四预设温度，并在第四预设时间内保持所述第四预设温度，以使所述第二前驱薄膜形成所述介电膜薄层。
  7. 根据权利要求5所述的方法，其特征在于，
    所述在所述介电薄膜层上形成所述第一电极层和所述电容器基底层，包括：
    采用离子溅射法在所述介电薄膜层上形成所述第一电极层；
    将所述电容器基底层胶合在所述第一电极层上。
  8. 根据权利要求5所述的方法，其特征在于，
    所述第一胶体采用以下方法制作得到：
    将硝酸铝、硝酸锶加入硝酸，并搅拌，得到第一溶液；
    将柠檬酸溶于水，得到第二溶液，所述柠檬酸的用量大于所述第一溶液中金属离子总和；
    将所述第一溶液和所述第二溶液混合，并加热搅拌使得所述金属离子与所述柠檬酸络合，并蒸发水分，得到所述第一胶体。
  9. 根据权利要求5所述的方法，其特征在于，
    所述第二胶体采用以下方法制作得到：
    混合醋酸锶和冰乙酸，搅拌，得到第三溶液，将含有PVP的冰醋酸加入到第三溶液并搅拌，得到第四溶液；
    将钛酸四丁酯加入乙二醇甲醚，搅拌，得到第五溶液，在所述第五溶液中加入乙酰丙酮，搅拌，得到第六溶液；
    将所述第四溶液和所述第六溶液混合，搅拌后向混合溶液中加入乙二醇，加热搅拌，冷却后过滤，得到第二胶体。
  10. 根据权利要求1所述的方法，其特征在于，
    所述在所述衬底上依次形成牺牲层、介电薄膜层、第一电极层和电容器基底层，包括：
    利用脉冲激光烧灼第一靶材，以在所述衬底上沉积所述牺牲层；
    利用脉冲激光烧灼第二靶材，以在所述牺牲层上沉积所述介电薄膜 层；
    在所述介电薄膜层上形成所述第一电极层和所述电容器基底层。
  11. 根据权利要求10所述的方法，其特征在于，
    所述利用脉冲激光烧灼第一靶材，以在所述衬底上沉积牺牲层，包括：
    将所述衬底和铝酸锶靶材置于脉冲激光沉积系统的反应室；
    在氧气的环境下，利用脉冲激光灼烧铝酸锶靶材，以在所述衬底上沉积铝酸锶等离子体，形成所述牺牲层。
  12. 根据权利要求10所述的方法，其特征在于，
    所述利用脉冲激光烧灼第二靶材，以在所述牺牲层上沉积介电薄膜层，包括：
    将制备有所述牺牲层的钛酸锶衬底和钛酸锶靶材置于脉冲激光沉积系统的反应室；
    在氧气的环境下，利用脉冲激光灼烧所述钛酸锶靶材，以在所述牺牲层上沉积钛酸锶等离子体，形成所述介电薄膜层。
  13. 根据权利要求1所述的方法，其特征在于，
    所述牺牲层由可水解的材料制成；
    所述去除所述衬底和所述牺牲层，包括：
    将包括所述衬底、牺牲层、介电薄膜层、第一电极层和电容器基底层的材料放入水中，以水解所述牺牲层，使得所述衬底脱落。
  14. 一种薄膜电容器，其特征在于，
    所述薄膜电容器利用如权利要求1～13任一项所述方法制备而成。
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