JP7708426B2 - Method for manufacturing a solid oxide fuel cell - Google Patents
Method for manufacturing a solid oxide fuel cellInfo
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- JP7708426B2 JP7708426B2 JP2022066258A JP2022066258A JP7708426B2 JP 7708426 B2 JP7708426 B2 JP 7708426B2 JP 2022066258 A JP2022066258 A JP 2022066258A JP 2022066258 A JP2022066258 A JP 2022066258A JP 7708426 B2 JP7708426 B2 JP 7708426B2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0094—Composites in the form of layered products, e.g. coatings
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Description
本発明は、多孔性シリコンを用いた応力弛緩構造を有する薄膜型固体酸化物燃料電池及びその製造方法に関する。 The present invention relates to a thin-film solid oxide fuel cell having a stress relaxation structure using porous silicon and a method for manufacturing the same.
固体酸化物燃料電池（Ｓｏｌｉｄ Ｏｘｉｄｅ Ｆｕｅｌ Ｃｅｌｌ：ＳＯＦＣ）は化学エネルギーを電気エネルギーに変換する高効率のエネルギー変換装置の一種で、電解質として固体酸化物膜を用いる燃料電池である。 A solid oxide fuel cell (SOFC) is a type of highly efficient energy conversion device that converts chemical energy into electrical energy, and is a fuel cell that uses a solid oxide membrane as an electrolyte.
ＳＯＦＣの電解質膜に用いられる電解質としてはＹＳＺ（Ｙｔｔｒｉａ Ｓｔａｂｉｌｉｚｅｄ Ｚｉｒｃｏｎｉａ）が主に用いられ、Ｍｉｃｒｏ－ｅｌｅｃｔｒｏ－ｍｅｃｈａｎｉｃａｌ Ｓｙｓｔｅｍ（ＭＥＭＳ）工程を介して製造する薄膜型（Ｔｈｉｎｆｉｌｍ）ＳＯＦＣはシリコン基板にＦｒｅｅ Ｓｔａｎｄｉｎｇ方式で電解質膜と電極を形成する後面エッチングのメンブレン構造を有する（例えば、特許文献１参照）。 YSZ (Yttrium Stabilized Zirconia) is the main electrolyte used in the electrolyte membrane of SOFCs, and thin-film SOFCs manufactured through a micro-electro-mechanical system (MEMS) process have a membrane structure that is rear-etched, with the electrolyte membrane and electrodes formed on a silicon substrate using a free standing method (see, for example, Patent Document 1).
即ち、シリコン基板上に電解質薄膜を形成した後、後面エッチングを介して電解質薄膜の下部を露出した後に、電解質薄膜の上下に電極を形成することで電解質の両面に反応気体が到達できるようにする。 That is, after forming a thin electrolyte film on a silicon substrate, the bottom of the thin electrolyte film is exposed through rear etching, and electrodes are then formed above and below the thin electrolyte film, allowing reactive gases to reach both sides of the electrolyte.
このように、ＭＥＭＳ基盤の薄膜型ＳＯＦＣはメンブレンと電極を薄膜で形成することで電解質内のイオン伝導によるオーミック損失を最小化し、低温での動作性能を向上させる長所があるが、動作時に縁の付近に応力が集中し、この付近に位置するセルが損傷する短所がある（例えば、特許文献２参照）。 As such, MEMS-based thin-film SOFCs have the advantage of minimizing ohmic loss due to ionic conduction in the electrolyte by forming the membrane and electrodes as thin films, improving operating performance at low temperatures. However, they have the disadvantage that stress is concentrated near the edges during operation, damaging cells located in this vicinity (see, for example, Patent Document 2).
本発明は上記に鑑みてなされたものであり、メンブレン縁の応力弛緩構造を有する薄膜型固体酸化物燃料電池を提供することを一つの目的とする。 The present invention has been made in consideration of the above, and one of its objectives is to provide a thin-film solid oxide fuel cell with a stress relaxation structure at the membrane edge.
さらに、メンブレン縁の応力弛緩構造を有する薄膜型固体酸化物燃料電池の製造方法を提供することをもう一つの目的とする。 Another object of the present invention is to provide a method for manufacturing a thin-film solid oxide fuel cell having a stress relaxation structure at the membrane edge.
本発明の解決課題は以上で言及されたものに限定されず、言及されていない他の解決課題は下記の記載から当該技術分野における通常の知識を有した者に明確に理解できるであろう。 The problems solved by the present invention are not limited to those mentioned above, and other problems not mentioned will be clearly understood by a person having ordinary skill in the art from the following description.
本発明の少なくとも一つの実施例においては、シリコン基板と、前記シリコン基板の第１面に形成された電解質膜と、前記電解質膜の第１面の少なくとも一部に形成された第１電極と、前記シリコン基板の前記第１面の反対面である第２面から前記電解質膜の前記第１面の反対面である第２面の前記第１電極に対向する一部が露出するように形成されたリセス部と、少なくとも前記電解質膜の露出した前記第２面に形成された第２電極とを備え、前記シリコン基板は少なくとも前記リセス部の縁の付近に多孔性で形成された多孔質部を含む、固体酸化物燃料電池を提供する。 In at least one embodiment of the present invention, a solid oxide fuel cell is provided, comprising: a silicon substrate; an electrolyte membrane formed on a first surface of the silicon substrate; a first electrode formed on at least a portion of the first surface of the electrolyte membrane; a recessed portion formed so that a portion of the second surface of the electrolyte membrane, which is the opposite surface of the first surface of the silicon substrate, facing the first electrode, is exposed from a second surface of the electrolyte membrane, which is the opposite surface of the first surface of the silicon substrate; and a second electrode formed on at least the exposed second surface of the electrolyte membrane, the silicon substrate including a porous portion formed with porosity at least near the edge of the recessed portion.
本発明の少なくとも一つの実施例においては、シリコン基板の第１面及び前記第１面の反対面である第２面にそれぞれ誘電体膜を蒸着する工程と、前記第２面に蒸着した誘電体膜を所定のパターンによって除去する工程と、前記第１面に蒸着した前記誘電体膜の第１面に電解質膜を形成する工程と、前記第２面の前記誘電体膜が除去された部分をエッチングし、前記第１面に蒸着した前記誘電体膜が露出するようにリセス部を形成する工程と、前記リセス部を介して露出した前記第１面に蒸着した前記誘電体膜及び前記第２面に残っている前記誘電体膜を除去する工程と、前記シリコン基板の少なくとも前記リセス部の縁の付近を多孔性で形成する工程と、前記電解質膜の第１面の少なくとも一部に第１電極を形成する工程と、前記リセス部を介して露出した前記第１面に蒸着した前記誘電体膜を除去することで露出した前記電解質膜の前記第１面の反対面である第２面に第２電極を形成する工程とを備える、固体酸化物燃料電池の製造方法を提供する。 In at least one embodiment of the present invention, a method for manufacturing a solid oxide fuel cell is provided, which includes the steps of depositing a dielectric film on a first surface of a silicon substrate and a second surface opposite to the first surface, removing the dielectric film deposited on the second surface according to a predetermined pattern, forming an electrolyte film on the first surface of the dielectric film deposited on the first surface, etching the portion of the second surface from which the dielectric film has been removed to form a recess so that the dielectric film deposited on the first surface is exposed, removing the dielectric film deposited on the first surface exposed through the recess and the dielectric film remaining on the second surface, forming at least the vicinity of the edge of the recess of the silicon substrate porous, forming a first electrode on at least a portion of the first surface of the electrolyte film, and forming a second electrode on the second surface opposite to the first surface of the electrolyte film exposed by removing the dielectric film deposited on the first surface exposed through the recess.
本発明の少なくとも一つの実施例においては、多孔性シリコン基板と、前記多孔性シリコン基板の第１面に形成された電解質膜と、前記電解質膜の第１面の少なくとも一部に形成された第１電極と、前記多孔性シリコン基板の前記第１面の反対面である第２面から前記電解質膜の前記第１面の反対面である第２面の前記第１電極に対向する一部が露出するように形成されたリセス部と、少なくとも前記電解質膜の露出した前記第２面に形成された第２電極とを備える、固体酸化物燃料電池を提供する。 In at least one embodiment of the present invention, a solid oxide fuel cell is provided, comprising: a porous silicon substrate; an electrolyte membrane formed on a first surface of the porous silicon substrate; a first electrode formed on at least a portion of the first surface of the electrolyte membrane; a recess formed such that a portion of the second surface of the electrolyte membrane, which is the opposite surface of the first surface of the porous silicon substrate, facing the first electrode, is exposed from a second surface, which is the opposite surface of the porous silicon substrate to the first surface; and a second electrode formed on at least the exposed second surface of the electrolyte membrane.
本発明の少なくとも一つの実施例においては、単結晶シリコン基板の第１面及び前記第１面の反対面である第２面にそれぞれ誘電体膜を蒸着する工程と、前記第２面に蒸着した誘電体膜を所定のパターンによって除去する工程と、前記第１面に蒸着した前記誘電体膜の第１面に電解質膜を形成する工程と、前記第２面の前記誘電体膜が除去された部分をエッチングし、前記第１面に蒸着した前記誘電体膜が露出するようにリセス部を形成する工程と、前記リセス部を介して露出した前記第１面に蒸着した前記誘電体膜及び前記第２面に残っている前記誘電体膜を除去する工程と、前記シリコン基板を多孔性で形成する工程と、前記電解質膜の第１面の少なくとも一部に第１電極を形成する工程と、前記リセス部を介して露出した前記第１面に蒸着した前記誘電体膜を除去することで露出した前記電解質膜の前記第１面の反対面である第２面に第２電極を形成する工程とを備える、固体酸化物燃料電池の製造方法を提供する。 In at least one embodiment of the present invention, a method for manufacturing a solid oxide fuel cell is provided, which includes the steps of depositing a dielectric film on a first surface of a single crystal silicon substrate and a second surface opposite to the first surface, removing the dielectric film deposited on the second surface according to a predetermined pattern, forming an electrolyte film on the first surface of the dielectric film deposited on the first surface, etching the portion of the second surface from which the dielectric film has been removed to form a recess so that the dielectric film deposited on the first surface is exposed, removing the dielectric film deposited on the first surface exposed through the recess and the dielectric film remaining on the second surface, forming the silicon substrate porous, forming a first electrode on at least a portion of the first surface of the electrolyte film, and forming a second electrode on the second surface opposite to the first surface of the electrolyte film exposed by removing the dielectric film deposited on the first surface exposed through the recess.
本明細書でそれぞれの実施例は互いに独立的に記載されている場合であっても、それぞれの実施例は相互組合せが可能であり、組合せによる実施例も本発明の権利範囲に含まれる。 Even if the embodiments are described independently of one another in this specification, they may be combined with one another, and combined embodiments are also included within the scope of the present invention.
上述した要約は単に説明のためのものであり、如何なる形でも限定を意図するものではない。上述した説明様態、実施例、及び特徴に加え、追加の様態、実施例、及び特徴が図面及び詳細な説明を参照することで明確になるはずである。 The foregoing summary is illustrative only and is not intended to be in any way limiting. In addition to the illustrative aspects, embodiments, and features described above, additional aspects, embodiments, and features will become apparent upon review of the drawings and detailed description.
本発明の少なくとも一つの実施例によれば、メンブレン縁の応力弛緩構造を有する薄膜型固体酸化物燃料電池を提供できるという効果を奏する。 At least one embodiment of the present invention has the effect of providing a thin-film solid oxide fuel cell having a stress relaxation structure at the membrane edge.
さらに、本発明の少なくとも一つの実施例によれば、メンブレン縁の応力弛緩構造を有する薄膜型固体酸化物燃料電池の製造方法を提供できるという効果を奏する。 Furthermore, at least one embodiment of the present invention has the effect of providing a method for manufacturing a thin-film solid oxide fuel cell having a stress relaxation structure at the membrane edge.
本発明の効果は以上で言及されたものなどに限定されず、言及されていない他の効果は下記の記載から当該技術分野における通常の知識を有した者に明確に理解できるはずである。 The effects of the present invention are not limited to those mentioned above, and other effects not mentioned will be clearly understood by those with ordinary skill in the art from the description below.
以下、添付図面を参照し、本発明の少なくとも一つの実施例に係る多孔性シリコンを用いた応力弛緩構造を有する薄膜型固体酸化物燃料電池及びその製造方法について詳しく説明する。 The thin-film solid oxide fuel cell having a stress relaxation structure using porous silicon according to at least one embodiment of the present invention and the manufacturing method thereof will be described in detail below with reference to the attached drawings.
図１は、本発明の少なくとも一つの実施例に係る薄膜型固体酸化物燃料電池１００の側断面図である。 Figure 1 is a cross-sectional side view of a thin-film solid oxide fuel cell 100 according to at least one embodiment of the present invention.
図1に示すように、本発明の少なくとも一つの実施例に係る薄膜型固体酸化物燃料電池１００は、シリコン基板１１０、シリコン基板１１０の第１面（図1に示す例では上面）に形成された電解質膜１２０、電解質膜１２０の第１面の少なくとも一部に形成された第１電極１３０、シリコン基板１１０の第１面の反対面である第２面（図1に示す例では下面）から電解質膜１２０の第１面の反対面である第２面の第１電極１３０に対向する一部が露出するように形成されたリセス部１４０、及び少なくともリセス部１４０を介して露出した電解質膜１２０の第２面に形成された第２電極１５０で構成される。 As shown in FIG. 1, a thin-film solid oxide fuel cell 100 according to at least one embodiment of the present invention is composed of a silicon substrate 110, an electrolyte membrane 120 formed on a first surface (upper surface in the example shown in FIG. 1) of the silicon substrate 110, a first electrode 130 formed on at least a part of the first surface of the electrolyte membrane 120, a recessed portion 140 formed so that a part of the second surface (the opposite surface of the first surface of the electrolyte membrane 120, facing the first electrode 130) is exposed from a second surface (the lower surface in the example shown in FIG. 1) that is the opposite surface of the first surface of the silicon substrate 110, and a second electrode 150 formed on the second surface of the electrolyte membrane 120 exposed at least through the recessed portion 140.
本発明の少なくとも一つの実施例に係る薄膜型固体酸化物燃料電池１００はＭＥＭＳ基盤の薄膜型ＳＯＦＣで、メンブレンと電極を薄膜で形成することで電解質内のイオン伝導によるオーミック損失を最小化し、低温での動作性能を向上させる構造を有する。 The thin-film solid oxide fuel cell 100 according to at least one embodiment of the present invention is a MEMS-based thin-film SOFC, and has a structure in which the membrane and electrodes are formed as thin films to minimize ohmic losses due to ionic conduction in the electrolyte and improve operating performance at low temperatures.
動作時にメンブレンの縁の付近（メンブレンにおいてリセス部１４０の縁の付近）に応力が数中止、この付近に位置するセルが損傷する短所を解決するため、本発明の少なくとも一つの実施例に係る薄膜型固体酸化物燃料電池１００はシリコン基板１１０の少なくともリセス部１４０の縁の付近に多孔性で形成された多孔質部１６０を含む。 To solve the problem of stress occurring near the edge of the membrane (near the edge of the recessed portion 140 in the membrane) during operation, which can damage cells located in this vicinity, the thin-film solid oxide fuel cell 100 according to at least one embodiment of the present invention includes a porous portion 160 formed of porosity at least near the edge of the recessed portion 140 of the silicon substrate 110.
このように、シリコン基板１１０の少なくともリセス部１４０の縁の付近に多孔性で形成された多孔質部１６０を形成することで、メンブレンの縁の付近（メンブレンにおいてリセス部１４０の縁の付近）に集中する応力を分散させることができる。 In this way, by forming a porous portion 160 formed with porosity at least near the edge of the recessed portion 140 of the silicon substrate 110, it is possible to disperse stress that is concentrated near the edge of the membrane (near the edge of the recessed portion 140 in the membrane).
図1ではシリコン基板１１０のリセス部１４０の縁の付近に多孔性で形成された多孔質部１６０を形成してメンブレンの縁の付近（メンブレンにおいてリセス部１４０の縁の付近）に集中する応力を分散させる例を示しているが、シリコン基板１１０全体を多孔性にしてメンブレンの縁の付近（メンブレンにおいてリセス部１４０の縁の付近）に集中する応力を分散させることも可能である。 Figure 1 shows an example in which a porous portion 160 formed with porosity is formed near the edge of the recessed portion 140 in the silicon substrate 110 to disperse stress concentrated near the edge of the membrane (near the edge of the recessed portion 140 in the membrane), but it is also possible to make the entire silicon substrate 110 porous to disperse stress concentrated near the edge of the membrane (near the edge of the recessed portion 140 in the membrane).
このために、本発明の少なくとも一つの実施例において、薄膜型固体酸化物燃料電池１００は、多孔性シリコン基板１１０、多孔性シリコン基板１１０の第１面に形成された電解質膜１２０、電解質膜１２０の第１面の少なくとも一部に形成された第１電極１３０、多孔性シリコン基板１１０の第２面から電解質膜１２０の第２面の第１電極１３０に対向する一部が露出するように形成されたリセス部１４０、及び少なくともリセス部１４０を介して露出した電解質膜１２０の第２面に形成された第２電極１５０で構成される。 To this end, in at least one embodiment of the present invention, the thin-film solid oxide fuel cell 100 is composed of a porous silicon substrate 110, an electrolyte membrane 120 formed on a first surface of the porous silicon substrate 110, a first electrode 130 formed on at least a portion of the first surface of the electrolyte membrane 120, a recessed portion 140 formed so that a portion of the second surface of the electrolyte membrane 120 facing the first electrode 130 is exposed from the second surface of the porous silicon substrate 110, and a second electrode 150 formed on the second surface of the electrolyte membrane 120 exposed at least through the recessed portion 140.
本発明の少なくとも一つの実施例において、電解質膜１２０はＭＥＭＳ工程を用いたイオン伝導性セラミック電解質膜で形成することができ、第１電極１３０及び第２電極１５０は多孔性白金材質を用いて形成することができる。 In at least one embodiment of the present invention, the electrolyte membrane 120 may be formed of an ion-conductive ceramic electrolyte membrane using a MEMS process, and the first electrode 130 and the second electrode 150 may be formed using a porous platinum material.
本発明の少なくとも一つの実施例において、電解質膜１２０はイットリア安定化ジルコニア（ＹＳＺ）のような個体酸素イオン伝導体またはイットリウムドープドＢａＺｒＯ３（ＢＹＺ）のようなプロトン伝導体で形成することができる。 In at least one embodiment of the present invention, electrolyte membrane 120 may be formed of a solid oxygen ion conductor such as yttria stabilized zirconia (YSZ) or a proton conductor such as yttrium doped BaZrO 3 (BYZ).
図２Ａないし図２Ｇは、本発明の少なくとも一つの実施例に係る薄膜型固体酸化物燃料電池１００の製造工程を説明するための概略図である。 Figures 2A to 2G are schematic diagrams illustrating the manufacturing process of a thin-film solid oxide fuel cell 100 according to at least one embodiment of the present invention.
図２Ａに示すように、両面をポリシングしたシリコン基板１１０の第１面（図２Ａに示す例では上面）及び第１面の反対面である第２面（図２Ａに示す例では下面）にそれぞれ誘電体膜１１１及び誘電体膜１１２を蒸着する。ここで、誘電体膜１１１及び誘電体膜１１２にはＳｉＮを用いることができる。 As shown in FIG. 2A, a dielectric film 111 and a dielectric film 112 are deposited on a first surface (the upper surface in the example shown in FIG. 2A) of a silicon substrate 110 that has been polished on both sides, and on a second surface (the lower surface in the example shown in FIG. 2A) that is the opposite surface of the first surface. Here, SiN can be used for the dielectric film 111 and the dielectric film 112.
その後、図２Ｂに示すように、第２面に蒸着した誘電体膜１１２を所定のパターンによって除去する。即ち、第２面に蒸着した誘電体膜に所定のパターンを有するマスクを用いてフォトリソグラフィーを介してＳｉＮ誘電体膜１１２にパターニングをした後に適切なエッチャントを用いたエッチングを介してパターに沿って誘電体膜１１２を除去する。 Then, as shown in FIG. 2B, the dielectric film 112 deposited on the second surface is removed according to a predetermined pattern. That is, the SiN dielectric film 112 is patterned through photolithography using a mask having a predetermined pattern on the dielectric film deposited on the second surface, and then the dielectric film 112 is removed along the pattern through etching using an appropriate etchant.
その後、図２Ｃに示すように、第１面に蒸着した誘電体膜１１１の第１面に電解質膜１２０を形成する。第２面に蒸着した誘電体膜１１２を所定のパターンによって除去する工程と第１面に蒸着した誘電体膜１１１の第１面に電解質膜１２０を形成する工程は順番を逆にしても良い。 Then, as shown in FIG. 2C, an electrolyte membrane 120 is formed on the first surface of the dielectric film 111 deposited on the first surface. The order of the process of removing the dielectric film 112 deposited on the second surface according to a predetermined pattern and the process of forming the electrolyte membrane 120 on the first surface of the dielectric film 111 deposited on the first surface may be reversed.
その後、図２Ｄに示すように、第２面の誘電体膜１１２が除去された部分をエッチングし、第１面に蒸着した誘電体膜１１１が露出するようにリセス部１４０を形成する。このとき、下部からシリコン基板１１０をエッチングするためにＫＯＨ溶液を用いたウェットエッチングを行うことができる。 Then, as shown in FIG. 2D, the portion of the second surface from which the dielectric film 112 has been removed is etched to form a recess 140 so that the dielectric film 111 deposited on the first surface is exposed. At this time, wet etching using a KOH solution can be performed to etch the silicon substrate 110 from the bottom.
その後、図２Ｅに示すように、リセス部１４０を介して露出した第１面に蒸着した誘電体膜１１１及び第２面に残っている誘電体膜１１２を除去する。 Then, as shown in FIG. 2E, the dielectric film 111 deposited on the first surface exposed through the recessed portion 140 and the dielectric film 112 remaining on the second surface are removed.
その後、図２Ｆに示すように、シリコン基板１１０の少なくともリセス部１４０の縁の付近を多孔性で形成する。このとき、例えば単結晶シリコンを所定の濃度のフッ酸溶液に浸した後に陽極処理して多孔性シリコンを形成する方法を用いることができる。 Then, as shown in FIG. 2F, at least the area near the edge of the recessed portion 140 of the silicon substrate 110 is made porous. At this time, for example, a method of forming porous silicon can be used in which single crystal silicon is immersed in a hydrofluoric acid solution of a predetermined concentration and then anodized.
その後、図２Ｇに示すように、電解質膜１２０の第１面の少なくとも一部に第１電極１３０を形成し、リセス部１４０を介して露出した第１面に蒸着した誘電体膜１１１を除去することで露出した電解質膜１２０の第２面に第２電極１５０を形成する。 Then, as shown in FIG. 2G, a first electrode 130 is formed on at least a portion of the first surface of the electrolyte membrane 120, and the dielectric film 111 deposited on the first surface exposed through the recessed portion 140 is removed to form a second electrode 150 on the exposed second surface of the electrolyte membrane 120.
このように製造した薄膜型固体酸化物燃料電池１００はＭＥＭＳ基盤の薄膜型ＳＯＦＣで、メンブレンと電極を薄膜で形成することで電解質内のイオン伝導によるオーミック損失を最小化し、低温での動作性能を向上させることが可能である。 The thin-film solid oxide fuel cell 100 manufactured in this way is a MEMS-based thin-film SOFC, and by forming the membrane and electrodes from thin films, it is possible to minimize ohmic losses due to ionic conduction in the electrolyte and improve operating performance at low temperatures.
動作時にメンブレンの縁の付近（メンブレンにおいてリセス部１４０の縁の付近）に応力が集中し、この付近に位置するセルが損傷するのを防ぐために、シリコン基板１１０の少なくともリセス部１４０の縁の付近に多孔性で形成された多孔質部１６０を形成することで、メンブレンの縁の付近（メンブレンにおいてリセス部１４０の縁の付近）に集中する応力を分散させることができる。 To prevent stress from concentrating near the edge of the membrane (near the edge of the recessed portion 140 in the membrane) during operation and damaging the cells located in this vicinity, a porous portion 160 is formed at least near the edge of the recessed portion 140 of the silicon substrate 110, thereby dispersing the stress concentrating near the edge of the membrane (near the edge of the recessed portion 140 in the membrane).
本発明の少なくとも一つの実施例において、電解質膜１２０はＭＥＭＳ工程を用いてイオン伝導性セラミック電解質膜として形成することができ、第１電極１３０及び第２電極１５０は多孔性白金材質を用いて形成することができる。 In at least one embodiment of the present invention, the electrolyte membrane 120 may be formed as an ion-conductive ceramic electrolyte membrane using a MEMS process, and the first electrode 130 and the second electrode 150 may be formed using a porous platinum material.
本発明の少なくとも一つの実施例において、電解質膜１２０はイットリア安定化ジルコニア（ＹＳＺ）のような個体酸素イオン伝導体またはイットリウムドープドＢａＺｒＯ３（ＢＹＺ）のようなプロトン伝導体で形成することができる。 In at least one embodiment of the present invention, electrolyte membrane 120 may be formed of a solid oxygen ion conductor such as yttria stabilized zirconia (YSZ) or a proton conductor such as yttrium doped BaZrO 3 (BYZ).
図２Ａないし図２Ｇではシリコン基板１１０のリセス部１４０の縁の付近に多孔性で形成された多孔質部１６０を形成してメンブレンの縁の付近（メンブレンにおいてリセス部１４０の縁の付近）に集中する応力を分散させる例を示しているが、シリコン基板１１０の全体を多孔性にしてメンブレンの縁の付近（メンブレンにおいてリセス部１４０の縁の付近）に集中する応力を分散させることも可能である。 2A to 2G show an example in which a porous portion 160 formed with porosity is formed near the edge of the recessed portion 140 of the silicon substrate 110 to disperse stress concentrated near the edge of the membrane (near the edge of the recessed portion 140 in the membrane), but it is also possible to make the entire silicon substrate 110 porous to disperse stress concentrated near the edge of the membrane (near the edge of the recessed portion 140 in the membrane).
例えば、両面をポリシングした単結晶シリコン基板１１０の第１面及び第２面にそれぞれ誘電体膜１１１及び誘電体膜１１２を蒸着する。ここで、誘電体膜１１１及び誘電体膜１１２にはＳｉＮを用いることができる。 For example, dielectric films 111 and 112 are deposited on the first and second surfaces of a single crystal silicon substrate 110 that has been polished on both sides. Here, SiN can be used for the dielectric films 111 and 112.
その後、第２面に蒸着した誘電体膜１１２を所定のパターンによって除去する。即ち、第２面に蒸着した誘電体膜に所定のパターンを有するマスクを用いてフォトリソグラフィーを介してＳｉＮ誘電体膜１１２にパターニングをした後に適切なエッチャントを用いたエッチングを介してパターンに沿って誘電体膜１１２を除去する。 Then, the dielectric film 112 deposited on the second surface is removed according to a predetermined pattern. That is, the SiN dielectric film 112 is patterned through photolithography using a mask having a predetermined pattern on the dielectric film deposited on the second surface, and then the dielectric film 112 is removed along the pattern through etching using an appropriate etchant.
その後、第１面に蒸着した誘電体膜１１１の第１面に電解質膜１２０を形成する。第２面に蒸着した誘電体膜１１２を所定のパターンによって除去する工程と第１面に蒸着した誘電体膜１１１の第１面に電解質膜１２０を形成する工程は順番を逆にしても良い。 Then, the electrolyte membrane 120 is formed on the first surface of the dielectric film 111 deposited on the first surface. The order of the process of removing the dielectric film 112 deposited on the second surface using a predetermined pattern and the process of forming the electrolyte membrane 120 on the first surface of the dielectric film 111 deposited on the first surface may be reversed.
その後、第２面の誘電体膜１１２が除去された部分をエッチングし、第１面に蒸着した誘電体膜１１１が露出するようにリセス部１４０を形成する。このとき、下部からシリコン基板１１０をエッチングするためにＫＯＨ溶液を用いたウェットエッチングを行うことができる。 Then, the portion of the second surface from which the dielectric film 112 has been removed is etched to form a recess 140 so that the dielectric film 111 deposited on the first surface is exposed. At this time, wet etching using a KOH solution can be performed to etch the silicon substrate 110 from below.
その後、リセス部１４０を介して露出した第１面に蒸着した誘電体膜１１１及び第２面に残っている誘電体膜１１２を除去する。 Then, the dielectric film 111 deposited on the first surface exposed through the recessed portion 140 and the dielectric film 112 remaining on the second surface are removed.
その後、シリコン基板１１０を多孔性で形成する。このとき、例えば単結晶シリコンを所定の濃度のフッ酸溶液に浸した後に陽極処理して多孔性シリコンを形成する方法を用いることができる。 Then, the silicon substrate 110 is made porous. For example, a method can be used in which single crystal silicon is immersed in a hydrofluoric acid solution of a predetermined concentration and then anodized to form porous silicon.
その後、電解質膜１２０の第１面の少なくとも一部に第１電極１３０を形成し、リセス部１４０を介して露出した第１面に蒸着した誘電体膜１１１を除去することで露出した電解質膜１２０の第２面に第２電極１５０を形成する。 Then, a first electrode 130 is formed on at least a portion of the first surface of the electrolyte membrane 120, and a second electrode 150 is formed on the exposed second surface of the electrolyte membrane 120 by removing the dielectric film 111 deposited on the first surface exposed through the recessed portion 140.
このように製造した薄膜型固体酸化物燃料電池１００はＭＥＭＳ基盤の薄膜型ＳＯＦＣで、メンブレンと電極を薄膜で形成することで電解質内のイオン伝導によるオーミック損失を最小化し、低温での動作性能を向上させることが可能である。 The thin-film solid oxide fuel cell 100 manufactured in this way is a MEMS-based thin-film SOFC, and by forming the membrane and electrodes from thin films, it is possible to minimize ohmic losses due to ionic conduction in the electrolyte and improve operating performance at low temperatures.
動作時にメンブレンの縁の付近（メンブレンにおいてリセス部１４０の縁の付近）に応力が集中し、この付近に位置するセルが損傷するのを防ぐために、シリコン基板１１０を多孔性で形成することで、メンブレンの縁の付近（メンブレンにおいてリセス部１４０の縁の付近）に集中する応力を分散させることができる。 To prevent stress from concentrating near the edge of the membrane (near the edge of the recessed portion 140 in the membrane) during operation and damaging the cells located in this vicinity, the silicon substrate 110 is made porous, which disperses the stress that is concentrated near the edge of the membrane (near the edge of the recessed portion 140 in the membrane).
本発明の少なくとも一つの実施例において、電解質膜１２０はＭＥＭＳ工程を用いてイオン伝導性セラミック電解質膜として形成することができ、第１電極１３０及び第２電極１５０は多孔性白金材質を用いて形成することができる。 In at least one embodiment of the present invention, the electrolyte membrane 120 may be formed as an ion-conductive ceramic electrolyte membrane using a MEMS process, and the first electrode 130 and the second electrode 150 may be formed using a porous platinum material.
本発明の少なくとも一つの実施例において、電解質膜１２０はイットリア安定化ジルコニア（ＹＳＺ）のような個体酸素イオン伝導体またはイットリウムドープドＢａＺｒＯ３（ＢＹＺ）のようなプロトン伝導体で形成することができる。 In at least one embodiment of the present invention, electrolyte membrane 120 may be formed of a solid oxygen ion conductor such as yttria stabilized zirconia (YSZ) or a proton conductor such as yttrium doped BaZrO 3 (BYZ).
以上のように、本発明の少なくとも一つの実施例によれば、多孔性シリコンを用いたメンブレン縁の応力弛緩構造を有する薄膜型固体酸化物燃料電池を提供することができる。 As described above, according to at least one embodiment of the present invention, it is possible to provide a thin-film solid oxide fuel cell having a membrane edge stress relaxation structure using porous silicon.
さらに、本発明の少なくとも一つの実施例によれば、多孔性シリコンを用いたメンブレン縁の応力弛緩構造を有する薄膜型固体酸化物燃料電池の製造方法を提供することができる。 Furthermore, according to at least one embodiment of the present invention, a method for manufacturing a thin-film solid oxide fuel cell having a membrane edge stress relaxation structure using porous silicon can be provided.
以上、本発明を実施の形態を用いて説明したが、本発明の技術的範囲は上記実施の形態に記載の範囲には限定されない。上記実施の形態に、多様な変更又は改良を加えることが可能であることが当業者に明らかである。そのような変更又は改良を加えた形態も本発明の技術的範囲に含まれ得ることが、特許請求の範囲の記載から明らかである。 The present invention has been described above using an embodiment, but the technical scope of the present invention is not limited to the scope described in the above embodiment. It is clear to those skilled in the art that various modifications and improvements can be made to the above embodiment. It is clear from the claims that forms with such modifications or improvements can also be included in the technical scope of the present invention.
１００：固体酸化物燃料電池
１１０：シリコン基板
１１１、１１２：誘電体膜
１２０：電解質膜
１３０：第１電極
１４０：リセス部
１５０：第２電極
１６０：多孔質部
100: Solid oxide fuel cell 110: Silicon substrate 111, 112: Dielectric film 120: Electrolyte film 130: First electrode 140: Recessed portion 150: Second electrode 160: Porous portion
Claims (2)
前記第２面に蒸着した誘電体膜を所定のパターンによって除去する工程と、
前記第１面に蒸着した前記誘電体膜の第１面に電解質膜を形成する工程と、
前記第２面の前記誘電体膜が除去された部分をエッチングし、前記第１面に蒸着した前記誘電体膜が露出するようにリセス部を形成する工程と、
前記リセス部を介して露出した前記第１面に蒸着した前記誘電体膜及び前記第２面に残っている前記誘電体膜を除去する工程と、
前記シリコン基板の少なくとも前記リセス部の縁の付近を多孔性で形成する工程と、
前記電解質膜の第１面の少なくとも一部に第１電極を形成する工程と、
前記リセス部を介して露出した前記第１面に蒸着した前記誘電体膜を除去することで露出した前記電解質膜の前記第１面の反対面である第２面に第２電極を形成する工程と
を備える、
固体酸化物燃料電池の製造方法。 depositing a dielectric film on a first surface of the silicon substrate and a second surface opposite the first surface;
removing the dielectric film deposited on the second surface according to a predetermined pattern;
forming an electrolyte film on the first surface of the dielectric film deposited on the first surface;
etching the portion of the second surface from which the dielectric film has been removed to form a recess so that the dielectric film deposited on the first surface is exposed;
removing the dielectric film deposited on the first surface exposed through the recess and the dielectric film remaining on the second surface;
forming a porous portion of the silicon substrate at least near an edge of the recess;
forming a first electrode on at least a portion of a first surface of the electrolyte membrane;
and forming a second electrode on a second surface of the electrolyte membrane, the second surface being the opposite surface to the first surface of the electrolyte membrane exposed by removing the dielectric film deposited on the first surface exposed through the recessed portion.
A method for manufacturing a solid oxide fuel cell.
前記第２面に蒸着した誘電体膜を所定のパターンによって除去する工程と、
前記第１面に蒸着した前記誘電体膜の第１面に電解質膜を形成する工程と、
前記第２面の前記誘電体膜が除去された部分をエッチングし、前記第１面に蒸着した前記誘電体膜が露出するようにリセス部を形成する工程と、
前記リセス部を介して露出した前記第１面に蒸着した前記誘電体膜及び前記第２面に残っている前記誘電体膜を除去する工程と、
前記シリコン基板を多孔性で形成する工程と、
前記電解質膜の第１面の少なくとも一部に第１電極を形成する工程と、
前記リセス部を介して露出した前記第１面に蒸着した前記誘電体膜を除去することで露出した前記電解質膜の前記第１面の反対面である第２面に第２電極を形成する工程と
を備える、
固体酸化物燃料電池の製造方法。 depositing a dielectric film on a first surface of the single crystal silicon substrate and on a second surface opposite to the first surface;
removing the dielectric film deposited on the second surface according to a predetermined pattern;
forming an electrolyte film on the first surface of the dielectric film deposited on the first surface;
etching the portion of the second surface from which the dielectric film has been removed to form a recess so that the dielectric film deposited on the first surface is exposed;
removing the dielectric film deposited on the first surface exposed through the recess and the dielectric film remaining on the second surface;
forming the silicon substrate porous;
forming a first electrode on at least a portion of a first surface of the electrolyte membrane;
and forming a second electrode on a second surface of the electrolyte membrane, the second surface being the opposite surface to the first surface of the electrolyte membrane exposed by removing the dielectric film deposited on the first surface exposed through the recessed portion.
A method for manufacturing a solid oxide fuel cell.
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| JP2003059496A (en) | 2001-08-13 | 2003-02-28 | Nissan Motor Co Ltd | Solid oxide fuel cell and manufacturing method thereof |
| US20040072039A1 (en) | 2002-07-01 | 2004-04-15 | The Regents Of The University Of California | MEMS-based fuel cells with integrated catalytic fuel processor and method thereof |
| JP2007103092A (en) | 2005-09-30 | 2007-04-19 | Dainippon Printing Co Ltd | Solid oxide fuel cell |
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