JP2004063131A - Chemical reaction apparatus, fuel cell system and manufacturing method for them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chemical reaction apparatus whose film quality, pattern precision and electric connection of a thin film heater and heater wiring used for a microreactor, are secured well simply, to provide a manufacturing method therefor, and to provide a fuel cell system which uses the chemical reaction apparatus having such a simple and highly reliable construction as a fuel supply apparatus or the like . <P>SOLUTION: The chemical reaction apparatus is made in such a way that an yttrium thin film layer 51<SB>X</SB>, a titanium-tungsten thin film layer 52<SB>X</SB>and a gold thin film layer 53<SB>X</SB>are laminated in this order as shown in the figure on the thin film heater 40 which is disposed corresponding a forming area of a reaction flow channel 20, wiring electrodes which have a prescribed pattern are formed by etching the titanium-tungsten thin film layer 52<SB>X</SB>and the gold thin film layer 53<SB>X</SB>continuously using single photoresist wherein the yttrium thin film layer 51<SB>X</SB>acts as an etching barrier, and an insulating protector film 60 is formed by treating the exposed yttrium thin film layer 51<SB>X</SB>in an area outside the pattern of the wiring electrodes using thermal oxidation. <P>COPYRIGHT: (C)2004,JPO

Description

【００６４】
表１に示すように、上記各条件を設定してヘリコンドライエッチングを行った場合、チタン−タングステン薄膜層５２ｘのエッチングレートは、概ね３３ｎｍ／ｍｉｎ（３３０Å／ｍｉｎ）程度、薄膜ヒータ４０（Ｔａ−Ｓｉ−Ｏ−Ｎ系の化合物薄膜）のエッチングレートは、概ね５２．５ｎｍ／ｍｉｎ（５２５Å／ｍｉｎ）程度、フォトレジストのエッチングレートは、概ね１３１．１ｎｍ／ｍｉｎ（１３１１Å／ｍｉｎ）程度が観測されたのに対して、イットリウム薄膜層５１ｘのエッチングレートは、概ね０．３ｎｍ／ｍｉｎ（３Å／ｍｉｎ）程度と顕著に小さく、ほとんどエッチングされないことが確認された。
【００６５】
そこで、本実施形態では、このようなイットリウム薄膜層５１ｘと他の薄膜材料とのエッチングレートの顕著な差異を利用して、チタン−タングステン薄膜層５２ｘのエッチング工程において、チタン−タングステン薄膜層５２ｘの下層のイットリウム薄膜層５１ｘをエッチングバリヤ（エッチング停止層）として用いるとともに、上記フォトレジスト７０をそのままマスクとして用い、上記条件を設定したヘリコンドライエッチングを、エッチング時間を厳密に制御することなく、下層のイットリウム薄膜層５１ｘが露出する状態までエッチング処理を継続することにより、チタン−タングステン薄膜層５２ｘを良好にエッチングすることができる。
【００６６】
すなわち、所定の膜厚を有するチタン−タングステン薄膜層を良好にエッチングするためのエッチング時間（ジャストエッチング時間）は、下層にエッチングバリヤが形成されていない場合には、例えば、チタン−タングステン薄膜層の膜厚が２００ｎｍの場合、上記表１のエッチングレート（約３３ｎｍ／ｍｉｎ）から概ね６分となるが、本実施形態に示したような製造方法によれば、６分以上の充分長い時間を設定した場合であっても、イットリウム薄膜層５１ｘにより、下層の薄膜ヒータ４０がエッチングダメージを受けることはない。
【００６７】
次いで、図５（ｂ）に示すように、フォトレジスト７０を剥離することにより、薄膜ヒータ４０（イットリウム薄膜層５１ｘ）上の所定の領域に、配線電極５０の上層の電極層（第２の電極層）を構成する積層構造が得られる。
その後、上記中間電極層５２及び上部電極層５３からなる積層電極の形成領域以外の領域にイットリウム薄膜層５１ｘが露出した主基板１０を、大気中、もしくは、酸素雰囲気中でホットプレート（図示を省略）上に載置して概ね４００℃程度に加熱することにより、図５（ｃ）に示すように、上記露出したイットリウム薄膜層５１ｘのみを熱酸化させる。ここで、熱酸化処理工程において設定される温度（４００℃程度）では、上部電極層５３を構成する金は、酸化反応や膜質の劣化を生じることがなく、また、中間電極層５２を構成するチタン−タングステンは、上層に形成された上部電極層５２の金により酸化反応が阻止される。したがって、配線電極５０の形成領域以外の領域に形成されたイットリウム薄膜層５１ｘのみが酸化イットリウム（Ｙ_２Ｏ_３）からなる絶縁性の保護膜６０に変化して、少なくとも薄膜ヒータ４０を被覆保護する。
【００６８】
また、このとき、熱酸化処理工程において中間電極層５２及び上部電極層５３の下層にあって、露出していないイットリウム薄膜層５１ｘは、酸化されずにイットリウム本来の導電性をそのまま保持するので、配線電極５０の下層の電極層（第１の電極層）を構成することになり、薄膜ヒータ４０の所定の領域に、下層電極層５１、中間電極層５２及び上部電極層５３からなる積層構造を有する配線電極５０が形成される。
【００６９】
したがって、本実施形態に係る化学反応装置の製造方法によれば、化学反応装置を構成する主基板の特定の面に、薄膜ヒータや配線電極等を積層形成する際、薄膜ヒータ上にエッチングバリヤとなる導電層（イットリウム薄膜層）を形成した後、上層の導電層（金薄膜層、チタン−タングステン薄膜層）をエッチングして配線電極をパターニング形成することにより、単一のフォトレジストを用いた異なる条件でのエッチング処理を行う場合であっても、厳密にエッチング時間を制御することなく、薄膜ヒータへのエッチングダメージを抑制することができるとともに、配線電極のパターン精度や電気的特性の劣化を抑制することができる。
【００７０】
また、配線電極のパターニング形成後、熱酸化処理を行うことにより、上記配線電極のエッチング工程においてエッチングバリヤとなり、かつ、配線電極の形成領域以外の領域に露出した導電層（イットリウム薄膜層）を簡易に絶縁性の保護膜（酸化イットリウム）に変化させることができるので、薄膜ヒータを良好に被覆保護することができるとともに、配線電極部分においては、導電層（イットリウム薄膜層）が酸化されることなく良導体としての特性をそのまま保持させることができるので、該保護膜から露出し、電気的特性が良好な配線電極を形成することができる。
【００７１】
なお、上述した実施形態に示した製造方法においては、エッチングバリヤ（又は、下部電極層）としてイットリウム薄膜層を形成し、中間電極層としてチタン−タングステン薄膜層、上部電極層として金薄膜層を積層形成した場合を示したが、本発明はこれに限定されるものではない。すなわち、エッチングバリヤは、中間電極層及び上部電極層を特定のエッチング方法によりパターニング形成する際に、エッチングレートが顕著に小さく、かつ、酸化処理等により簡易に絶縁性化する導電性材料であればよく、また、上部電極層は、エッチングバリヤとなる導電層に対して酸化処理もしくは不純物導入処理を行う際に、本来の膜質や導電性を良好に保持しつつ、下層の中間電極層の膜質や導電性をも保持することができる導電性材料であれば、他の材料を適用するものであってもよいことはいうまでもない。
【００７２】
また、上述した実施形態においては、上部電極層及び中間電極層のパターニング形成後、フォトレジストを除去した後、エッチングバリヤを熱酸化処理する場合（図５（ａ）〜（ｃ）参照）について示したが、本発明はこの製造手順に限定されるものではなく、例えば、図６に示すように、上部電極層５３及び中間電極層５２のパターニング形成後、フォトレジスト７０を除去することなく、エッチングバリヤとなったイットリウム薄膜層５１ｘを熱酸化処理して絶縁性の保護膜６０を形成するようにしてもよい。これによれば、上部電極層５３を構成する金及びフォトレジスト７０の双方により、中間電極層５２を構成するチタン−タングステンの酸化反応や膜質の劣化がより確実に阻止される。
【００７３】
さらに、上述した実施形態においては、主基板１０の他面側に反応流路２０の平面形状（形成領域）に対応する単一の矩形形状を有する薄膜ヒータ４０を設け、該薄膜ヒータ４０上の両端部に配線電極５０を積層形成した構成であって、配線電極５０の上層を保護膜６０から露出させた化学反応装置及びその製造方法を示したが、本発明は、これに限定されるものではなく、薄膜ヒータ４０の平面形状や配線電極５０の形成位置は、反応流路２０の平面形状や化学反応装置外部との電気的な導通を行う位置等に応じて、適宜設定されるものであってもよいことはいうまでもない。したがって、薄膜ヒータが、上記反応流路の平面形状に対応する領域にのみ形成された構成（すなわち、図７に示すように、蛇行形状を有する反応流路２０の形成領域に対応して、薄膜ヒータ４１を蛇行形状に形成した構成）を有し、また、該平面形状の長手方向の両端部に配線電極５０が形成された構成を有するものであっても、本発明に係る化学反応装置の構成及び製造方法を良好に適用することができる。
【００７４】
＜電源システムへの適用例＞
次に、本発明に係る化学反応装置（マイクロリアクタ）を、燃料改質型の燃料電池を備えた電源システムに適用した場合の具体例について説明する。
図８は、本発明に係る化学反応装置を適用可能な電源システム（燃料電池システム）の要部構成、及び、該電源システムより駆動されるデバイスを示すブロック図である。なお、ここでは、燃料改質方式を採用した固体高分子型の燃料電池を適用した電源システムについて説明する。
【００７５】
図８に示すように、本発明に係る化学反応装置が適用される電源システム３００は、概略、所定の発電用燃料に基づいて電力を発生する発電モジュール１００と、該発電モジュール１００に対して着脱可能に構成され、所定の発電用燃料が封入された燃料パック２００と、から構成されている。
発電モジュール１００は、大別して、燃料改質方式の固体高分子型燃料電池の構成を有する発電部（燃料電池本体）１１０と、燃料パック２００の燃料封入部２１０に貯蔵、封入された発電用燃料（例えば、水素を含む液体燃料、液化燃料及び気体燃料や水）の発電部１１０への供給量を制御する燃料制御部１２０と、発電部１１０への空気（酸素）の供給量を制御する空気制御部１３０と、燃料制御部１２０により供給された発電用燃料を改質して、発電用燃料に含有される水素をガス化して発電部１１０に供給する燃料改質部１４０と、発電部１１０及び燃料改質部１４０を必要に応じて加熱するための温度制御部１５０と、発電部１１０により生成された電力の一部若しくは全部を充電するコンデンサを有する充電部１６０と、発電モジュール１００内の発電動作、充電動作、後述する動作制御部１８０により充電部１６０の蓄電状態を検知する動作等のための必要な電力を出力する副電源部１７０と、発電モジュール１００内の駆動動作を演算処理する動作制御部１８０と、を有して構成されている。
【００７６】
燃料制御部１２０は、燃料封入部２１０から毛細管現象等の原理を利用した物理的手段により送出された発電用燃料を、動作制御部１８０からの指令信号にしたがって、燃料改質部１４０に所定量供給するように構成されている。
空気制御部１３０は、燃料電池システム３００の外部から空気（大気）を取込み、発電部１１０に酸素ガス（Ｏ_２）又は空気を供給するように構成されている。
【００７７】
燃料改質部１４０は、燃料パック２００内のアルコール（ＡＬＣＯＨＯＬ）及び水（Ｈ_２Ｏ）から構成される発電用燃料を、燃料制御部１２０を介して取り込み、水素（Ｈ_２）と副生成物の二酸化炭素（ＣＯ_２）、さらに、微量の一酸化炭素（ＣＯ）を生成する水蒸気改質反応部１４０ａと、次に示す一酸化炭素改質部と、を有して構成されている。一酸化炭素改質部は、水蒸気改質反応部１４０ａから供給された一酸化炭素（ＣＯ）を燃料制御部１２０及び／又は発電部１１０から供給された水（Ｈ_２Ｏ）と反応させ、二酸化炭素（ＣＯ_２）及び水素（Ｈ_２）を生成する水性シフト反応部１４０ｂと、水性シフト反応部１４０ｂにおける反応で残留した一酸化炭素（ＣＯ）を酸素（Ｏ）と反応させて、二酸化炭素（ＣＯ_２）を生成する選択酸化反応部１４０ｃのうち、少なくとも一方を備えた構成を有している。
【００７８】
温度制御部１５０は、動作制御部１８０からの指令信号により、上記燃料改質部１４０（水蒸気改質反応部１４０ａ、水性シフト反応部１４０ｂ、選択酸化反応部１４０ｃ）の各反応部に設けられた薄膜ヒータに電力を供給することにより加熱制御するように構成されている。また、発電部１１０にも薄膜ヒータが設けられている場合にあっては、同様に、所定の電力が供給されるように構成されている。ここで、燃料改質部１４０及び発電部１１０に設けられる薄膜ヒータは、上述した実施形態に示した薄膜ヒータ４０に相当し、例えば、金属酸化膜又は金属窒化膜等の所定の発熱特性を有する抵抗体材料からなる薄膜層により形成されている。
【００７９】
発電部１１０は、燃料改質部１４０から供給された水素（Ｈ_２）、及び、空気制御部１３０から供給された酸素ガス（Ｏ_２）に基づいて、所定の電力を発生（発電）するように構成され、また、充電部１６０は、発電部１１０で発電された電力を充電するように構成され、これらの発電部１１０及び充電部１６０の少なくとも一方により、電源システム３００より駆動されるデバイスＤＶＣの負荷ＬＤに電力を供給するように構成されている。
副電源部１７０は、動作制御部１８０からの指令信号に応じて、充電部１６０で蓄電された電力に基づいて、燃料制御部１２０、温度制御部１５０及び動作制御部１８０に所定の動作電力を供給するとともに、必要に応じて発電部１１０にも動作電力を供給するように構成されている。
【００８０】
動作制御部１８０は、充電部１６０で蓄電されたチャージ（充電電位）を検知するために常時駆動し、該チャージが所定値まで低下したことを検知すると、燃料制御部１２０、温度制御部１５０、必要に応じて発電部１１０に動作電力を供給するように指令信号を副電源部１７０に出力する。また、必要量の燃料を燃料改質部１４０に供給するように燃料制御部１２０に対して指令信号を出力するとともに、燃料改質部１４０の反応炉（本発明に係る化学反応装置の反応流路に相当）を所定の時間、必要温度に加熱するように温度制御部１５０に対して指令信号を出力する。
【００８１】
そして、発電モジュール１００と着脱自在に構成された燃料パック２００は、発電用燃料が封入された燃料封入部２１０と、発電部１１０により生成された副生成物（主に、水（Ｈ_２Ｏ））を回収する副生成物回収部２２０と、を有して構成されている。
発電モジュール１００及び燃料パック２００で構成された燃料電池システム３００は、デバイスＤＶＣの負荷ＬＤに対して所定の駆動電力を供給することにより、コントローラＣＮＴの制御にしたがってデバイスＤＶＣを正常に駆動させることができる。
【００８２】
ここで、発電部１１０は、周知の固体高分子型の燃料電池本体の構成を有し、概略、白金や白金・ルテニウム等の触媒微粒子が付着した炭素電極からなる燃料極（カソード）と、白金等の触媒微粒子が付着した炭素電極からなる空気極（アノード）と、該燃料極と空気極の間に介装されたフィルム状のイオン導電膜（交換膜）と、を有して構成されている。
【００８３】
そして、このような構成を有する発電部１１０における発電原理は、燃料極に燃料改質部１４０を介して抽出された水素ガス（Ｈ_２）が供給されることにより、次の化学反応式（１）に示すように、上記触媒により電子（ｅ⁻）が分離した水素イオン（プロトン；Ｈ^＋）が発生し、イオン導電膜を介して空気極側に通過するとともに、燃料極を構成する炭素電極により電子（ｅ⁻）が取り出されて負荷（上述した電源システムにおいては、デバイスＤＶＣの負荷ＬＤ及び充電部１６０）に供給される。
３Ｈ_２　→　６Ｈ^＋＋６ｅ⁻　　　　　　　　・・・（１）
【００８４】
一方、空気極に空気制御部１３０を介して大気中の酸素ガス（Ｏ_２）が供給されることにより、次の化学反応式（２）に示すように、上記触媒により負荷を経由した電子（ｅ⁻）とイオン導電膜を通過した水素イオン（Ｈ^＋）と空気中の酸素ガス（Ｏ_２）が反応して水（Ｈ_２Ｏ）が生成される。
６Ｈ^＋＋（３／２）Ｏ_２＋６ｅ⁻　→　３Ｈ_２Ｏ　　　　　・・・（２）
このような一連の電気化学反応（化学反応式（１）、（２））は、概ね室温〜８０℃の比較的低温の環境下で進行し、電力以外の副生成物は、基本的に水（Ｈ_２Ｏ）のみとなる。なお、上述したような電気化学反応により負荷に供給される電力（電圧・電流）は、上記化学反応式（１）、（２）に示したように、発電部１１０の燃料極に供給される水素ガス（Ｈ_２）の量に依存する。
【００８５】
したがって、燃料制御部１２０は、発電部１１０において、所定の電力を生成、出力するために必要な量の水素ガス（Ｈ_２）となる分の燃料（メタノール）や水等を取り込んで、燃料改質部１４０により水素ガスに改質して、発電部１１０の燃料極に供給する制御を行う。なお、空気制御部１３０は、発電部１１０の空気極に供給する酸素ガス（Ｏ_２）の量を制御する機能を有しているが、発電部１１０における単位時間あたりの酸素の最大消費量に相当する空気を供給可能であれば、発電部１１０の空気極に供給する酸素ガスの量を制御することなく、発電部１１０の駆動時に常時酸素ガスを供給するものであってもよい。また、空気制御部１３０の他の構成としては、発電部１１０における電気化学反応の進行状態を、燃料制御部１２０において調整される水素ガスの供給量のみで制御し、空気制御部１３０の代わりに通気孔を設け、発電部１１０における電気化学反応に用いられる上記最大消費量以上の空気（大気）が通気孔を介して供給されるようにしたものであってもよい。
【００８６】
次いで、本電源システムに適用される燃料改質部１４０の構成及び動作について詳しく説明する。
図９は、本発明に係る化学反応装置の構成を適用した燃料改質部の具体例を示す概略構成図である。
上述したように、燃料改質部１４０は、主に、燃料制御部１２０により所定の供給量で供給される発電用燃料に対して、所定の吸熱触媒反応（水蒸気改質反応）を利用して発電用燃料に含まれる水素成分を抽出して上記発電部１１０に供給する機能を有するものであって、燃料改質部１４０を構成する各反応部において、上述した実施形態（図１、図７参照）に示した薄膜ヒータを備えたマイクロリアクタ（化学反応装置）の構成を良好に適用することができる。
【００８７】
燃料改質部１４０（水蒸気改質反応部１４０ａ）においては、具体的には、メタノール等の水素を含む液体燃料（アルコール類）から、吸熱触媒反応である水蒸気改質反応を利用して、水素ガス（Ｈ_２）を生成する化学反応が行われる。ここで、現在、研究開発が行われている燃料改質方式の燃料電池に適用されている発電用燃料としては、上記発電部１１０により、比較的高いエネルギー変換効率で電力を生成することができる燃料であって、例えば、メタノール、エタノール、ブタノール等のアルコール系の液体燃料や、ジメチルエーテル、イソブタン、天然ガス（ＣＮＧ）等の液化ガス等の常温常圧で気化される炭化水素からなる液化燃料、あるいは、水素ガス等の気体燃料等の流体物質を良好に適用することができる。
【００８８】
すなわち、燃料改質部１４０（水蒸気改質反応部１４０ａ）における水素ガスの生成に利用される吸熱触媒反応の例としては、液体燃料の一例としてメタノールを適用した場合、次の化学反応式（３）に示すような水蒸気改質反応が生じ、また、常温常圧で気体となる液化燃料の一例としてジメチルエーテルを適用した場合には、次の化学反応式（４）に示すような水蒸気改質反応が生じる。
ＣＨ_３ＯＨ＋Ｈ_２Ｏ　→　３Ｈ_２＋ＣＯ_２　　　　　　　　　・・・（３）
ＣＨ_３ＯＣＨ_３＋３Ｈ_２Ｏ　→　６Ｈ_２＋２ＣＯ_２　　　　　・・・（４）
【００８９】
なお、いずれの水蒸気改質反応においても、概ね３００℃の熱条件の下で当該反応が良好に進行する。また、この改質反応により生成される水素以外の微量の生成物（主に、ＣＯ_２）は、大気中に排出される。したがって、上述した実施形態に示したような化学反応装置（図１、図７参照）を燃料改質部１４０（水蒸気改質反応部１４０ａ）に適用し、反応流路（反応炉）の形成領域に対応して設けられた薄膜ヒータに、配線電極を介してヒータ電源から所定の電力を供給して発熱させることにより、反応流路（触媒層）に対して、上記各化学反応式（３）、（４）に示した吸熱を伴う水蒸気改質反応の進行に寄与する所定の熱量を供給することができ、水素ガスを良好に生成することができる。
【００９０】
ここで、燃料改質部１４０に適用される具体的な構成例は、例えば、図９（ａ）に示すように、シリコン等の微小基板（上述した主基板１０に相当する）１４１の一面側（図の上面側）に、半導体デバイス製造技術等の微細加工技術を用いて、所定の断面形状及び平面形状を有して溝状に設けられた燃料吐出部１４２ａ、水吐出部１４２ｂ、燃料気化部１４３ａ、水気化部１４３ｂ、混合部１４３ｃ、改質反応流路１４４、水素ガス排気部１４５からなる流路（各構成が上述した反応流路２０に相当する）と、例えば、上記改質反応流路１４４の形成領域を含む所定の領域に、微小基板１４１の他面側（図の下面側）に設けられた矩形状の薄膜ヒータ（上述した実施形態における薄膜ヒータ４０に相当する）１４６と、薄膜ヒータの両端部に所定のパターン形状を有して積層形成された配線電極（上述した実施形態における配線電極５０に相当する；図示を省略、図１参照）と、微小基板１４１上に上記流路の開放端を閉止するように接合された微小基板（上述した実施形態における閉止基板３０に相当する；図示の都合上、二点鎖線で表示）１４７と、を備えて構成されている。
【００９１】
燃料吐出部１４２ａ及び水吐出部１４２ｂは、上述したような水蒸気改質反応における原料物質となる発電用燃料（アルコール系液体燃料等）及び水を、例えば、所定の単位量ごとに液状粒として流路内に吐出する流体吐出機構を有している。したがって、燃料吐出部１４２ａ及び水吐出部１４２ｂにおける発電用燃料又は水の吐出量に基づいて、例えば、上記化学反応式（３）式に示した水蒸気改質反応の進行状態が制御されることになるため（詳しくは、薄膜ヒータ１４６から供給される熱エネルギーも密接に関連する）、燃料吐出部１４２ａ及び水吐出部１４２ｂは、燃料供給量の調整を行う燃料制御部としての機能を有している。
【００９２】
燃料気化部１４３ａ及び水気化部１４３ｂは、例えば、それぞれ発電用燃料及び水の沸点等の揮発（気化）条件に応じて加熱されるヒータを備え、燃料吐出部１４２ａ及び水吐出部１４２ｂから液状粒として吐出された発電用燃料又は水を、加熱処理あるいは減圧処理等することにより気化し、混合部１４３ｃにおいて、燃料ガスと水蒸気の混合ガスを生成する。ここで、燃料気化部１４３ａ及び水気化部１４３ｂとして、加熱処理を行う機構を採用する場合には、上述した改質反応流路１４４と同様に、燃料気化部１４３ａ及び水気化部１４３ｂを構成する流路の形成領域を含む所定の領域に薄膜ヒータを設けた構成を適用するものであってもよい。
【００９３】
改質反応流路１４４は、上記混合部１４３ｃにおいて生成された混合ガスが導入され、改質反応流路１４４の内壁面に付着形成された銅−亜鉛（Ｃｕ−Ｚｎ）系の触媒層（図示を省略）に対して、該改質反応流路１４４の形成領域に対応する領域に設けられた薄膜ヒータ１４６から所定の熱量が供給されることにより、上記化学反応式（３）、（４）に示した水蒸気改質反応を生じさせて、水素ガス（Ｈ_２）を生成する。
水素ガス排気部１４５は、改質反応流路１４４において生成された水素ガスを排出して、上述した発電部１１０を構成する燃料電池の燃料極に供給する。これにより、発電部１１０において、上記化学反応式（１）及び（２）に基づく一連の電気化学反応が生じて、所定の電力が生成される。
【００９４】
そして、上述したように、このような構成を有する燃料改質部１４０の微小基板１４１に形成された流路の形成領域に対応して、上述した実施形態に示した場合と同様に、微細加工技術を用いて微小基板１４１の他面側（図の下面側）に薄膜ヒータ１４６及び配線電極を積層形成することができ、少なくとも薄膜ヒータ１４６の形成領域に、上述した実施形態に示した製造方法に基づいて保護膜（図示を省略、図１又は図７参照）を被覆形成することにより、配線電極を露出しつつ、微小基板１４１及び薄膜ヒータ１４６を被覆保護することができる。
【００９５】
これにより、燃料改質部１４０全体又は一部を微小空間に集積化して、他の周辺部材への接合や複数の燃料改質部１４０の積層化等を良好に実現しつつ、構成相互の電気的な接続を良好に確保することができるので、燃料改質部１４０を含む発電モジュール１００の省スペース化や小型化を図ることができるとともに、薄膜ヒータから放出される熱量を良好に上記流路に供給して、熱伝導効率の高い電源システムを実現することができる。したがって、例えば、日本工業規格（ＪＩＳ）に則った汎用の一次電池や種々の二次電池等と略同一の外形形状及び外形寸法を有するように小型化することができ、既存の一次電池や二次電池市場において互換可能なポータブル電源を実現することができる。
【００９６】
なお、本適用例に示した電源システム（発電部）は、上述した実施形態に示したようなマイクロリアクタ（化学反応装置）を適用した燃料改質部により生成される所定の流体物質（水素ガス等）を発電用燃料として用いて、発電を行うことができるものであれば、燃料電池に限定されるものではない。したがって、化学反応装置（燃料改質部）により生成された流体物質の燃焼反応に伴う熱エネルギーによるもの（温度差発電）や、燃焼反応等に伴う圧力エネルギーを用いて発電器を回転させて電力を発生する力学的なエネルギー変換作用等によるもの（ガス燃焼タービンやロータリーエンジン、スターリングエンジン等の内燃、外燃機関発電）、また、発電用燃料ＦＬの流体エネルギーや熱エネルギーを電磁誘導の原理等を利用して電力に変換するもの（電磁流体力学発電、熱音響効果発電等）等、種々の形態を有する発電装置に適用することができる。
【００９７】
また、図９（ａ）に示した構成においては、上記化学反応式（３）において、発電用燃料としてメタノール等と水を、別個の吐出部１４２ａ、１４２ｂ及び供給経路を介して供給、気化し、混合部１４３ｃにおいて混合する構成を備えた燃料改質部を示したが、予めメタノール等に水が混合された発電用燃料を直接燃料改質部に供給して、水素ガスを生成する水蒸気改質反応を生じさせるものであってもよい。このような場合にあっては、例えば、図９（ｂ）に示すように、微小基板１４１の一面側に、単一の燃料吐出部１４２ｃ及び燃料気化部１４３ｄと、上述した改質反応流路１４４、水素ガス排気部１４５からなる単一の流路を備えた構成を適用することができる。
【００９８】
また、上述した電源システムに示した燃料改質部１４０においては、上記化学反応式（３）や（４）での反応以外に極微量の一酸化炭素（ＣＯ）が生成される恐れがあるため、図８に示したように、生成された一酸化炭素を無害化するような反応部（水性シフト反応部１４０ｂ、選択酸化反応部１４０ｃ）を設けてもよい。
すなわち、発電モジュール１００の燃料改質部１４０は、上述したように、燃料パック２００内のアルコール及び水から構成される燃料を燃料制御部１２０から供給され、水素（Ｈ_２）と副生成物の二酸化炭素（ＣＯ_２）、さらに、微量の一酸化炭素（ＣＯ）を生成する水蒸気改質反応部１４０ａに加えて、水蒸気改質反応部１４０ａから供給された一酸化炭素（ＣＯ）を燃料制御部１２０及び／又は発電部１１０から供給された水（Ｈ_２Ｏ）と反応させ、二酸化炭素（ＣＯ_２）及び水素（Ｈ_２）を生成する水性シフト反応部１４０ｂ、及び、水性シフト反応部１４０ｂにおける反応で残留した（反応しきれなかった）一酸化炭素（ＣＯ）を酸素（Ｏ）と反応させて二酸化炭素（ＣＯ_２）を生成する選択酸化反応部１４０ｃのうちの少なくとも一方からなる一酸化炭素燃料改質部を備えた構成を有し、燃料パック２００に封入された燃料を、改質して得られる水素（Ｈ_２）を発電部１１０に供給するとともに、微量に生じる一酸化炭素（ＣＯ）を無毒化するように構成したものであってもよい。以下に示す例では、一酸化炭素燃料改質部が水性シフト反応部１４０ｂ及び選択酸化反応部１４０ｃの両方を有する構成を示す。
【００９９】
以下、燃料改質部１４０の各構成と図９に示した構成との関係について説明する。
燃料改質部１４０の水蒸気改質反応部１４０ａは、図９（ａ）に示す構造と概略同一であり、燃料気化部１４３ａ及び水気化部１４３ｂは、薄膜ヒータ１４６と同様に、例えば、金属酸化膜又は金属窒化膜等からなる薄膜層を備えている。ここで、温度制御部１５０により制御された電力を、配線電極を介して供給することにより上記薄膜層（薄膜ヒータ）が所定温度に加熱され、メタノール（ＣＨ_３ＯＨ）及び水（Ｈ_２Ｏ）を気化させる。
【０１００】
そして、水蒸気改質反応過程においては、上記気化したメタノール（ＣＨ_３ＯＨ）及び水（Ｈ_２Ｏ）に対して、薄膜ヒータ１４６で概ね３００℃の温度条件の雰囲気を設定することにより、４９．４ｋＪ／ｍｏｌ程度の熱エネルギーを吸熱して、上述した化学反応式（３）に示すように、水素（Ｈ_２）と微量の二酸化炭素（ＣＯ_２）が生成される。この二酸化炭素（ＣＯ_２）は、発電モジュール１００の外側に選択的に排出される。なお、この水蒸気改質反応においては、水素（Ｈ_２）と二酸化炭素（ＣＯ_２）以外に副生成物として微量の一酸化炭素（ＣＯ）が生成される場合がある。
【０１０１】
ここで、水蒸気改質反応過程において、副生成物として生成される一酸化炭素（ＣＯ）を除去するために、水蒸気改質反応部１４０ａの後段に水性シフト反応部１４０ｂ及び選択酸化反応部１４０ｃを付設して、水性シフト反応及び選択酸化反応からなる各過程を介して、一酸化炭素（ＣＯ）を二酸化炭素（ＣＯ_２）及び水素（Ｈ_２）に変換して、有害物質の排出を抑止するように構成する。
具体的には、水性シフト反応部１４０ｂは、図９（ａ）に示す構造と概略同一であるが、燃料吐出部１４２ａの代わりに、水蒸気改質反応部１４０ａで改質後に残存する一酸化炭素（ＣＯ）を微量に含む水素ガス（Ｈ_２）を吐出する吐出部が設けられ、かつ、薄膜ヒータ１４６と同様に、例えば、金属酸化膜又は金属窒化膜等の発熱抵抗体からなる薄膜層を備えている。
【０１０２】
水性シフト反応部１４０ｂにおける水性シフト反応過程では、一酸化炭素（ＣＯ）に対して水（水蒸気；Ｈ_２Ｏ）を反応させることにより４０．２ｋＪ／ｍｏｌ程度の熱エネルギーを発熱して、次の化学反応式（５）に示すように、二酸化炭素（ＣＯ_２）と水素（Ｈ_２）が生成される。このとき発生される二酸化炭素（ＣＯ_２）は、発電モジュール１００の外側に選択的に排出される。
ＣＯ＋Ｈ_２Ｏ　→ＣＯ_２＋Ｈ_２　　　　　　　・・・（５）
【０１０３】
水性シフト反応部１４０ｂの後段に付設された選択酸化反応部１４０ｃは、水性シフト反応部１４０ｂで未反応の一酸化炭素（ＣＯ）を二酸化炭素（ＣＯ_２）に改質するものであり、概略図９（ａ）から燃料気化部１４３ａ、水気化部１４３ｂを省略し、燃料吐出部１４２ａ、水吐出部１４２ｂの代わりに、それぞれ水性シフト反応部１４０ｂからの気体を吐出する吐出部と、発電モジュール１００の外側から取り込んだ空気あるいは酸素（Ｏ）を吐出する吐出部と、が設けられ、かつ、薄膜ヒータ１４６と同様に、例えば、金属酸化膜又は金属窒化膜等の発熱抵抗体からなる薄膜層を備えている。
【０１０４】
選択酸化反応過程において、水性シフト反応により二酸化炭素（ＣＯ_２）と水素（Ｈ_２）に変換されなかった一酸化炭素（ＣＯ）に対して酸素（Ｏ_２）を反応させることにより２８３．５ｋＪ／ｍｏｌ程度の熱エネルギーを発熱して、次の化学反応式（６）に示すように、二酸化炭素（ＣＯ_２）が生成される。
ＣＯ＋（１／２）Ｏ_２　→ＣＯ_２　　　　　　・・・（６）
なお、選択酸化反応部１４０ｃは、水蒸気改質反応部１４０ａと水性シフト反応部１４０ｂとの間に設けてもよい。
上記一連の改質反応により生成される水素（Ｈ_２）以外の微量の生成物（主に、二酸化炭素（ＣＯ_２））は、発電モジュール１００に設けられた排出孔を介して、外部に排出される。
【０１０５】
次いで、上述した電源システムに適用される発電モジュール１００及び燃料パック２００の形状、並びに、電源システム全体の具体構成例について、図面を参照して説明する。
図１０（ａ）〜図１０（ｄ）及び図１０（ｅ）〜図１０（ｈ）は、それぞれ上述した電源システムに適用される一実施例の燃料パック及びホルダー部（発電モジュール）を上方向、前方向、横方向、後方向から見た外形形状を示す概略構成図である。ここでは、説明の都合上、後述する電源システムの具体構成例（図１１）を適宜参照するものとする。なお、図１１は、上述した電源システム全体の具体構成例を示す要部構成図である。
【０１０６】
図１０（ａ）〜図１０（ｄ）及び図１０（ｅ）〜図１０（ｈ）に示すように、本実施例に係る電源システムは、発電用燃料が所定の条件で封入された燃料パック２００と、該燃料パック２００が装着自在及び取り外し自在に構成された発電モジュール１００を収納したホルダー部４００と、を備えて構成されている。
ここで、燃料パック２００は、図１０（ａ）〜図１０（ｄ）に示すように、例えば、発電用燃料ＦＬを封入する透明の分解性高分子ケースであって、未使用の場合には、バクテリア等の分解要因から保護するパッケージＰＫでケースの周囲全体が被覆されており、燃料パック２００の装着時には、パッケージＰＫを剥離する構成になっている。
また、燃料パック２００は透明なケースで構成されるとともに、図１０（ａ）に示すように、その側面の適当な位置に指標（目盛り）２０３を設けた構成を有しており、これにより、燃料パック２００内に残存する発電用燃料ＦＬの量（残量）を視覚的に確認することができるようになっている。
【０１０７】
ホルダー部４００は、図１０（ｅ）〜図１０（ｈ）に示すように、大別して、上述した適用例と同等の構成を有する発電モジュール１００が収納され、正極端子ＥＬ（＋）が設けられた発電機能部４０１と、負極端子ＥＬ（−）が設けられた対向部４０２と、発電機能部４０１と対向部４０２を連結するとともに、発電機能部４０１と負極端子ＥＬ（−）を電気的に接続する連結部４０３と、を有して構成されている。ここで、発電機能部４０１、対向部４０２及び連結部４０３により囲まれた貫通した空間ＳＰが、上記燃料パック２００を結合した際の収納位置となる（図１０（ｅ）、（ｇ）参照）。
【０１０８】
また、ホルダー部４００は、燃料パック２００が空間ＳＰに装着、収納された状態で、燃料パック２００の底部２０２が接触する対向部４０２の当接部分の周囲にバネ材等の弾性を有し、中央に孔を有する凸部４０４と、該凸部４０４の孔及び発電モジュール１００の副生成物供給経路１０４（図１１参照）を連結する副生成物回収経路４０５と、を備えている。なお、ホルダー部４００の連結部４０３には、図１０（ｅ）に示すように、図１０（ａ）に示した燃料パック２００の指標２０３に代えて、又は、指標２０３と併設するように、指標４０６が刻まれた構成を適用するものであってもよい。これにより、ホルダー部４００に燃料パック２００を結合した際に、発電用燃料ＦＬの残量を視覚により簡易かつ正確に確認することができる。なお、この場合、連結部４０３は、不透明である方が指標４０６を視認しやすい。
【０１０９】
そして、このような構成を有する発電モジュール１００（発電機能部４０１）は、より具体的には、図１１に示すように、概略、円柱形状の円周側面に沿って延在する発電部１１０と、円柱状の発電モジュール１００内部に、各々深さ及び幅がそれぞれ５００μｍ以下の燃料流路及び流路内の空間を所定温度に設定する個別の薄膜ヒータ（図示を省略）が形成された水蒸気改質反応部（水蒸気改質反応炉）１４０ａ、水性シフト反応部（水性シフト反応炉）１４０ｂ及び選択酸化反応部（選択酸化反応炉）１４０ｃと、発電機能部４０１の内部にマイクロチップ化されて収納された動作制御部１８０と、発電モジュール１００の円柱側面から上記発電部１１０の空気極まで貫通し、外部の空気を取り入れる複数の通気孔（スリット）１３０ａと、上記空気極側において生成される副生成物（水等）を液化（凝縮）して分離回収する分離回収部１０２と、回収した副生成物の一部を水蒸気改質反応部１４０ａに供給する副生成物供給経路１０４と、円柱上面から上記発電部１１０の燃料極まで貫通し、少なくとも、発電部１１０の燃料極側や水蒸気改質反応部１４０ａ、水性シフト反応部１４０ｂ、選択酸化反応部１４０ｃにおいて生成される、非回収物質である副生成物（二酸化炭素等）を発電機能部４０１の外部に排出する排出孔１０６と、図示を省略した副電源部１７０と、を備えて構成されている。
【０１１０】
水蒸気改質反応部１４０ａ及び水性シフト反応部１４０ｂは、反応に必要な水として、発電部１１０で生成され、副生成物供給経路１０４を介して供給される水、及び、燃料パック２００内の発電用燃料ＦＬに含まれる水の少なくとも一方を利用する。
また、燃料パック２００は、発電部１１０に供給される発電用燃料ＦＬが充填、封入される燃料封入部２１０（図８参照）と、上記分離回収部１０２により回収された副生成物（水）を固定的に保持する副生成物回収部２２０（図８参照）と、発電モジュール１００との結合部分に設けられ、発電用燃料ＦＬの漏出を防止する燃料供給弁２０１ａと、回収保持された副生成物（回収物）の漏出を防止する副生成物取込弁２０４（図１０（ａ）参照）と、を有して構成されている。
【０１１１】
このような構成を有する電源システムにおいて、パッケージＰＫを剥がした燃料パック２００をホルダー部４００の空間ＳＰ１に装着、収納すると、図１１に示すように、燃料送出経路となる燃料送出管４０６が燃料パック２００の燃料送出口２０１に係合して、燃料送出口２０１内に形成され、例えば、バネ等の弾性機構によりで閉止方向に姿勢が強制されている燃料供給弁２０１ａを押し下げて、燃料パック２００の漏出防止機能が解除される。これにより、燃料パック２００の燃料封入部２１０に封入された発電用燃料ＦＬが、毛細管２０１ｂ内及び燃料送出管４０６内での表面張力により自動的に吸い上げ搬送されて発電モジュール１００に供給される。なお、燃料パック２００をホルダー部４０３から取り外すと、燃料供給弁２０１ａがバネ等の弾性機構の復元力で元の閉止状態に戻り、内部に封入された発電用燃料ＦＬが漏れないようになる。
【０１１２】
そして、上述したような発電モジュール１００における発電動作により、電力とともに生成される副生成物のうち、水（Ｈ_２Ｏ）は、連結部４０３に設けられた副生成物回収経路４０５、対向部４０２に設けられた凸部４０４の孔及び燃料パック２００の底部２０２に設けられた回収孔（副生成物取込弁２０４）を介して、燃料パック２００内の副生成物回収部２２０に回収、保持される。したがって、燃料パック２００の内部には、上記燃料封入部２１０及び副生成物回収部２２０が、例えば、隔壁膜等を介して相互に隔絶して設けられ、かつ、双方の容量変化に応じて、上記隔壁膜等が相対的に変形又は移動等するように構成されている。
【０１１３】
これにより、図８に示したように、発電モジュール１００に供給された発電用燃料ＦＬから燃料改質部１４０において、水素ガスが生成され、発電部１１０において、所定の電力が生成されて充電部１６０に供給、充電（蓄電）されるとともに、充電部１６０に蓄電されたチャージにより充電される副電源部１７０により、常時燃料制御部１２０、温度制御部１５０及び動作制御部１８０に動作電力が供給される。また、本実施例に係る電源システムに所定のデバイスＤＶＣが接続されることにより、充電部１６０あるいは発電部１１０から出力された電力の一部が、発電機能部４０１に設けられた正極端子ＥＬ（＋）及び対向部４０２に設けられた負極端子ＥＬ（−）を介して、デバイスＤＶＣに内蔵されたコントローラＣＮＴ及び負荷ＬＤに駆動電力として供給される。
【０１１４】
ここで、電源システムは、図１０（ｇ）に示すように、燃料パック２００が空間ＳＰに収納され、ホルダー部４００に結合された状態（二点鎖線で示した燃料パック２００を含む全体構成）において、例えば、日本国内において市販されている汎用の化学電池（一次電池又は二次電池）と略同等の外形形状及び寸法を有するように構成することができる。また、このとき、燃料パック２００が空間ＳＰに正常に収納された状態で、燃料パック２００の燃料送出口２０１が、発電機能部４０１側の燃料送出経路（燃料送出管４０６）に良好に係合するとともに、燃料パック２００がホルダー部４００から不用意に脱落することを防止するために、燃料パック２００底部２０２が対向部４０２により適当な圧力で押圧されるように構成されていることが望ましい。
【０１１５】
したがって、本実施例に係る電源システムを、汎用の化学電池と同様に簡易に取り扱うことができ、汎用の化学電池と同一又は同等の外形形状（ここでは、円柱形状）及び寸法を有するように構成するとともに、同一又は同等の電気的特性を有する電力を供給するように発電状態を制御することにより、汎用の化学電池と極めて互換性の高い電源システムを実現することができ、既存の携帯機器等のデバイスの電源として、良好に適用することができる。
なお、上述した電源システムの適用例及び具体構成例は、本発明に係る化学反応装置（マイクロリアクタ）を燃料改質部に適用した電源システムのごく一例を示したものにすぎず、本発明に係る化学反応装置の適用はこの形態に限定されるものではないことはいうまでもない。
【０１１６】
【発明の効果】
以上説明したように、本発明に係る化学反応装置及びその製造方法によれば、微小空間に形成された反応流路内で、所定の化学反応を生じることにより所望の物質を生成するマイクロリアクタにおいて、反応流路に所定の熱量を供給して上記化学反応を促進又は制御する薄膜ヒータと、該薄膜ヒータに電力を供給して所定の熱量を発生させるための積層構造を有する配線電極と、少なくともヒータ配線形成領域以外の薄膜ヒータ上に被覆形成され、該薄膜ヒータをエッチングダメージから保護する保護膜と、を備え、該保護膜が、上記配線電極の最下層となる電極層と同層に形成される導電性材料により一体的に形成されるとともに、少なくとも上記配線電極の上層となる電極層をパターニング形成する際に高いエッチング耐性を示し、かつ、上記パターニングの後、熱酸化処理することにより形成された絶縁性の薄膜により構成されているので、上記保護膜となる導電層の上層に積層構造を有する配線電極を形成する際に、異なる条件で各種エッチング処理を行った場合であっても、厳密にエッチング条件を設定することなく、薄膜ヒータの膜質へのエッチングダメージを抑制しつつ、配線電極のパターン精度や電気的特性の劣化を抑制することができる。
【０１１７】
また、上記配線電極のパターニング後、熱酸化処理により上記エッチングバリヤとなった導電層を簡易に絶縁性の保護膜に変化させることができるとともに、配線電極部分においては、酸化されることなく良導体としての特性をそのまま保持するので、薄膜ヒータを良好に被覆保護することができるとともに、該保護膜から露出し、電気的特性が良好な配線電極を実現することができる。
【０１１８】
したがって、配線電極のパターニング工程において、エッチング条件やプロセス制御、パターン精度等の制約を緩和して、簡易な製造方法及び製造装置により、良好な膜質やパターン精度、電気的接続を実現することができるマイクロリアクタを提供することができるので、このようなマイクロリアクタを燃料改質部等に適用した電源システムの製造コストを抑制しつつ、信頼性を向上させることができる。また、マイクロリアクタの特定の面に対して、他の周辺部材を接合する場合や、複数のマイクロリアクタ相互を積層形成する場合等に、上下方向（積層方向）で電気的な接続を行うことができるので、電源システムの設計自由度を向上させて、装置規模の小型化や所望の外形形状への適用を図ることができる。
【図面の簡単な説明】
【図１】本発明に係る化学反応装置の一実施形態を示す概略構成図である。
【図２】本実施形態に係る化学反応装置の積層構造を示す要部断面図である。
【図３】本発明に係る化学反応装置の全体の製造方法を示す製造プロセス図である。
【図４】本実施形態に係る化学反応装置に適用される配線電極部の具体的な製造方法の一例を示す製造プロセス図（その１）である。
【図５】本実施形態に係る化学反応装置に適用される配線電極部の具体的な製造方法の一例を示す製造プロセス図（その２）である。
【図６】本実施形態に係る化学反応装置に適用される配線電極部の具体的な製造方法の他の例を示す製造プロセス図である。
【図７】本発明に係る化学反応装置の他の実施形態を示す概略構成図である。
【図８】本発明に係る化学反応装置の適用が可能な電源システム（燃料電池システム）の要部構成、及び、該電源システムより駆動されるデバイスを示すブロック図である。
【図９】本発明に係る化学反応装置の構成を適用した燃料改質部の具体例を示す概略構成図である。
【図１０】上述した電源システムに適用される一実施例の燃料パック及びホルダー部（発電モジュール）の外形形状を示す概略構成図である。
【図１１】上述した電源システム全体の具体構成例を示す要部構成図である。
【図１２】従来技術における化学反応装置（マイクロリアクタの反応流路部）の概略構成を示す図である。
【図１３】従来技術における化学反応装置（マイクロリアクタ）に適用される薄膜ヒータ及び配線電極を示す要部断面図である。
【図１４】従来技術における化学反応装置に適用されるヒータ配線の製造方法の一例を示す製造プロセス図（その１）である。
【図１５】従来技術における化学反応装置に適用されるヒータ配線の製造方法の一例を示す製造プロセス図（その２）である。
【符号の説明】
１０　　　　　主基板
２０　　　　　反応流路
３０　　　　　閉止基板
４０　　　　　薄膜ヒータ
５０　　　　　配線電極
５１　　　　　下部電極層
５２　　　　　中間電極層
５３　　　　　上部電極層
６０　　　　　保護膜[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a chemical reaction device, a fuel cell system, and a method of manufacturing the same, and more particularly, to a chemical reaction device capable of generating a desired fluid substance such as hydrogen gas by a catalytic reaction in a reaction channel formed in a micro-substrate, and The present invention relates to a fuel cell system provided with the chemical reaction device, and a method for manufacturing the same.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, in the field of chemical reaction engineering, a chemical reaction device (“catalyst reaction”) that generates a desired fluid substance through a chemical reaction (catalytic reaction) of a fluidized mixed substance by a catalyst provided in a reaction channel (channel). Flow channel reactors "or" channel reactors "are known.
[0003]
In recent years, in the technical field of such a chemical reaction apparatus, by applying a so-called micromachine manufacturing technique including a micromachining technique (microtechnology) accumulated in a field of manufacturing semiconductor devices such as integrated circuits, for example, Research and development of microreactors (also called "microchannel reactors") in which various functional elements such as millimeter-order or micron-order mixers, reaction channels, and analyzers are integrated in a minute space on a single silicon chip It is being actively conducted.
[0004]
Here, a reaction channel portion, which is a main configuration in the microreactor, will be briefly described with reference to FIG.
As schematically shown in FIGS. 12A, 12B, and 12C, the reaction channel portion of the microreactor is formed on one surface side of a small main substrate 10p made of silicon or the like by using a photoetching technique or the like. After forming a reaction channel (microchannel) 20p composed of a groove having a width and depth on the order of microns, a predetermined catalyst 21p is attached to the inner wall surface (side wall surface or bottom surface, etc.) of the reaction channel 20p. A closed substrate 30p made of glass or the like is joined to one surface of the main substrate 10p so as to close an open portion (open end of the groove) of the reaction channel 20p.
[0005]
In particular, when a chemical reaction (catalytic reaction) in the microreactor involves an endothermic reaction under a specific thermal condition, a specific amount of heat is supplied to the reaction channel 20p (specifically, the catalyst 21p) during the chemical reaction. As shown in FIGS. 12B and 12C, for example, the planar shape (formation) of the reaction channel 20p is formed on the other surface of the main substrate 10p (the surface opposite to the joint surface with the closed substrate 30p). The thin-film heater 40p formed of a heating resistor or the like patterned in a meandering shape corresponding to the (area) and an upper layer of the thin-film heater 40p, for example, formed along both ends of the planar shape of the thin-film heater 40p. The configuration including the heater wiring 50p is applied. Here, in the drawing, PAD is an electrode pad for electrically connecting to a heater power supply (not shown), and is provided at a predetermined position such as an end of the heater wiring 50p.
[0006]
In FIGS. 12A and 12C, the reaction channel 20p and the thin-film heater 40p are hatched in order to make the shapes clear. Further, FIG. 12 shows a configuration in which the introduction part 20a and the discharge part 20b of the fluid substance to the reaction flow path 20p are provided on the side of the microreactor (chemical reaction device), but the main substrate 10p or the closed substrate 30p On the other hand, a configuration in which the introduction unit 20a and the discharge unit 20b are provided in a vertical direction (that is, a direction perpendicular to the paper surface in FIGS. 12A and 12C) may be employed.
[0007]
In a microreactor having such a schematic configuration, for example, a fluid substance (mixed gas) obtained by vaporizing a raw material substance consisting of methanol and water is introduced from the introduction section 20a side of the reaction flow path 20p, and a heater power supply (not shown) is provided. By applying a predetermined voltage to the thin-film heater 40p and heating it, and supplying thermal energy so that the reaction channel 20p has a predetermined temperature, the heat absorbing catalyst by the catalyst 21p attached and formed in the reaction channel 20p A reaction occurs, and hydrogen gas and a small amount of carbon dioxide are generated (methanol steam reforming reaction), and are discharged from the discharge portion 20b of the reaction channel 20p. The technology of generating hydrogen gas from the above-mentioned steam-based reforming reaction from an alcohol-based material such as methanol is a fuel reforming type fuel cell which has been actively researched and developed for practical use in recent years. This technology is also applied to the fuel (hydrogen) supply device in the system.
[0008]
In particular, a microreactor is characterized in that the following various advantages can be obtained by miniaturizing the configuration of the reaction channel.
(1) Since the reaction volume in the reaction channel is reduced, the ratio of the surface area between the reaction channel and the heater to the volume of the reaction channel (surface area / volume ratio) is increased, and the heat conduction characteristics during the catalytic reaction are improved. Thus, there is an advantage that the reaction efficiency of the chemical reaction as described above is improved.
[0009]
(2) Also, since the diameter (the size of the cross-sectional shape) of the reaction channel becomes small, the diffusion and mixing time of the reaction molecules constituting the mixed substance becomes short, and the progress rate of the catalytic reaction in the reaction channel (reaction speed) There is an advantage that is improved.
(3) Furthermore, since the microreactor itself is small, it can be scaled up stepwise according to the results of verification in small experimental reactors (applicable when manufacturing large furnaces (increase in scale of equipment and fluid materials). This is advantageous in that complicated reaction engineering studies associated with the improvement of the production capability of methane are unnecessary.
In addition, a specific configuration example of the microreactor will be described in detail in an embodiment of the invention described later.
[0010]
By the way, in the field of micromachine manufacturing technology and semiconductor device manufacturing technology, as a thin film heater that emits desired thermal energy, for example, a resistance layer having a predetermined heat generation characteristic such as a metal oxide film or a metal nitride film is used. Further, as the wiring, for example, a metal layer having excellent conductivity such as gold is used. Here, in a microreactor as shown in FIG. 12, when a metal oxide film or a metal nitride film is applied to a thin film heater and a material having excellent conductivity such as gold is applied to a heater wiring, an oxide or a nitride is used. Since the bonding property of gold or the like to the resistive material of the system is extremely low, there is a problem that delamination or poor electrical connection occurs due to external stress or thermal influence.
[0011]
Therefore, in order to solve such a problem, conventionally, for example, a high melting point metal such as tungsten is included between a thin film heater made of a metal oxide film or a metal nitride film and a heater wiring made of gold or the like. By interposing a buffer layer made of an alloy, good bonding properties and electrical connection to both are ensured. That is, as shown in FIG. 13, for example, the heater wiring 50p has a laminated structure composed of two different conductive layers, an upper layer is provided with a gold layer 52p as the heater wiring, and a lower layer is formed of titanium-tungsten as the buffer layer. The layer 51p was provided. In FIG. 13, reference numeral 60p denotes an insulating protective film formed on one surface of the main substrate 10p including the thin film heater 40p and the heater wiring 50p. In addition, the same components as those in FIG. 12 are denoted by the same reference numerals.
[0012]
Here, an example of a method for manufacturing a microreactor to which a heater wiring having such a laminated structure is applied will be briefly described with reference to FIGS.
First, as shown in FIG. 14A, the other surface side of the main substrate 10p such as silicon having an oxide film formed on the surface (the upper surface side in FIGS. 14 and 15; the lower surface side in FIG. 12B) ), A resistor layer made of a resistor material such as a metal oxide or a metal nitride is formed by a sputtering method or the like, and etched using a photoresist (not shown) to correspond to the planar shape of the reaction channel. A thin film heater 40p having a predetermined shape (for example, a rectangular shape) is formed.
Next, a titanium-tungsten (WTi) layer 51px and a gold (Au) layer 52px are sequentially formed on the entire surface of the main substrate 10p including the thin film heater 40p by sputtering or vapor deposition.
[0013]
Next, as shown in FIG. 14B, a region on the gold layer 52px corresponding to the planar shape of the heater wiring 50 (a predetermined region along an end of the thin film heater 40p in FIG. 12). The photoresist 70p is formed by patterning, and the uppermost gold layer 52px is wet-etched using a predetermined etching solution (Au etchant) using the photoresist 70p as an etching mask. As a result, as shown in FIG. 14C, the exposed gold layer 52px where the photoresist 70p is not formed is removed by etching, and only the gold layer immediately below the photoresist 70p remains and the upper electrode of the heater wiring 50 is removed. The layer 52p is formed.
[0014]
Next, as shown in FIG. 14C, the titanium-tungsten layer 51px is wet-etched with a predetermined etchant (WTi etchant) using the photoresist 70p used for etching the gold layer 51px as an etching mask. Do. As a result, as shown in FIG. 15A, the exposed titanium-tungsten layer 51px where the photoresist 70p is not formed is removed by etching, and only the titanium-tungsten layer immediately below the photoresist 70p remains and the heater wiring is removed. The lower electrode layer 51p of 50 is formed.
[0015]
Thereafter, as shown in FIG. 15B, by removing the resist 70p, a heater wiring 50p having a laminated structure including a lower electrode layer 51p made of titanium-tungsten and an upper electrode layer 52p made of gold is obtained. . Then, an oxide-based or nitride-based insulating protective film 60 is formed over the entire area on the other surface side of the main substrate 10p including the heater wiring layer 50p and the thin-film heater 40p, so that the plane shown in FIG. A microreactor having the structure and the cross-sectional structure shown in FIG. 13 is obtained.
[0016]
[Problems to be solved by the invention]
However, the method of manufacturing a microreactor (particularly, a thin film heater and a heater wiring) according to the related art as described above has the following problems.
That is, in the prior art, in order to prevent delamination between the heater wiring layer and the thin-film heater and to ensure good electrical connection, a laminated structure made of different materials for the heater wiring (a two-layer structure in FIG. 13). Therefore, as described above, when the electrode layer is etched and patterned (see FIGS. 14B to 14A), the material constituting each electrode layer (in FIG. 13, , Gold and titanium-tungsten), it is necessary to perform the etching process in a plurality of times under the etching conditions corresponding to the conditions.
[0017]
At this time, if a manufacturing process of sequentially etching a plurality of electrode layers using a single photoresist is employed in order to accurately pattern the shape of the electrode layer, damage to the photoresist due to the etching process (resist of the resist) Sufficient resistance (etching resistance) is required for film quality deterioration and peeling, pattern accuracy deterioration, and the like, and there is a problem that material selection, handling, etching conditions, and the like of a resist material are restricted.
[0018]
Further, in the case where a manufacturing process of forming an individual photoresist for each etching process of each electrode layer is adopted in order to solve the problem of the deterioration of the photoresist as described above, the upper surface of the patterned upper electrode layer is formed. In addition, a new photoresist for etching the lower electrode layer has to be formed with extremely high positional accuracy, which requires a high-precision manufacturing apparatus and complicated and complicated manufacturing steps. I was
[0019]
Further, even when a plurality of electrode layers are sequentially etched using a single photoresist having sufficient etching resistance, when the wet etching method is applied, the etching time can be accurately controlled. It is difficult, and there is a problem that over-etching in which the side surface portion of the electrode layer is excessively etched occurs, resulting in deterioration of pattern accuracy and deterioration of electrical characteristics. In addition, even when a dry etching method is applied as another etching method, it is necessary to accurately control the etching time, and the electrode layer to be etched may be unevenly etched due to poor control, or the electrode layer may not be etched. There has been a problem that the thin film heater (resistor layer) formed in the lower layer is also etched, and the film quality is damaged.
[0020]
In view of the above-mentioned problems, the present invention provides a chemical reaction device and a method of manufacturing the same, which can easily secure the film quality, pattern accuracy, and electrical connection of a thin film heater and a heater wiring used in a microreactor with a simple configuration. It is a second object to provide a fuel cell system in which a chemical reaction device having such a simple and highly reliable configuration is applied to a fuel supply device or the like.
[0021]
[Means for Solving the Problems]
The chemical reaction device according to claim 1, further comprising a reaction channel formed at least continuously, wherein a chemical reaction that generates a chemical reaction that converts a first fluid substance into a second fluid substance in the reaction channel. In the apparatus, at least, a temperature adjustment layer formed to correspond to a region including the reaction channel and supplying a predetermined amount of heat to the reaction channel, and a lamination formed on a first region on the temperature adjustment layer. A first electrode layer, at least an insulating layer on the temperature adjustment layer and formed in a second region other than the first region, and a stacked layer formed on the first electrode layer; A second electrode layer that supplies power for generating the predetermined amount of heat in the temperature adjustment layer via the first electrode layer; and wherein the insulating layer includes a first electrode layer and a second electrode layer. It must be made of an insulating material obtained by oxidizing the same layer of conductive material. It is a symptom.
[0022]
The chemical reaction device according to claim 2 is the chemical reaction device according to claim 1, wherein the insulating layer is made of a material having high resistance to an etching process when patterning and forming the second electrode layer. It is characterized by:
The chemical reaction device according to claim 3 is the chemical reaction device according to claim 1, wherein the second electrode layer is made of a material having high resistance to an oxidation treatment when forming the insulating layer. It is characterized by.
The chemical reaction device according to claim 4 is the chemical reaction device according to any one of claims 1 to 3, wherein the second electrode layer has a stacked structure including a plurality of conductive layers. And
[0023]
The chemical reaction device according to claim 5 is the chemical reaction device according to claim 4, wherein the temperature adjustment layer is a heating resistor made of a metal oxide film or a metal nitride film, and the second electrode layer is at least The conductive layer constituting the upper layer of the second electrode layer has non-adhesiveness to the temperature adjustment layer.
The chemical reaction device according to claim 6 is the chemical reaction device according to claim 5, wherein the temperature adjustment layer is made of a material containing each element of tantalum, silicon, oxygen, and nitrogen at a predetermined composition ratio. And
[0024]
The chemical reaction device according to claim 7, wherein the conductive layer forming the upper layer of the second electrode layer is gold and an alloy containing gold, in the chemical reaction device according to any one of claims 4 to 6. And the conductive layer constituting the lower surface of the second electrode layer is made of tungsten, molybdenum, tantalum, an alloy containing tungsten, an alloy containing molybdenum, and an alloy containing tantalum. Characterized by being made of a material selected from the group consisting of:
The chemical reaction device according to claim 8 is the chemical reaction device according to any one of claims 1 to 7, wherein the first electrode layer contains yttrium, an alloy containing yttrium, aluminum, and aluminum. The insulating layer is made of a material selected from alloys, and the insulating layer is made of a material selected from yttrium oxide and aluminum oxide.
[0025]
According to a ninth aspect of the present invention, in the chemical reaction device according to any one of the first to eighth aspects, the reaction channel has a groove having a predetermined channel shape on one surface side of the first substrate. Then, one surface of the second substrate is joined to one surface of the first substrate, and the open end of the groove is closed.
The chemical reaction device according to claim 10 is the chemical reaction device according to claim 9, wherein the temperature adjustment layer, the first electrode layer, the second electrode layer, and the insulating layer are other than the first substrate. It is characterized in that it is formed on the surface side.
[0026]
The chemical reaction device according to claim 11, wherein the temperature adjustment layer, the first electrode layer, the second electrode layer, and the insulating layer are other than the second substrate. It is characterized in that it is formed on the surface side.
The chemical reaction device according to claim 12 is the chemical reaction device according to any one of claims 9 to 11, wherein at least the first substrate and the second substrate are each formed of a minute substrate, The reaction channel is formed to have a micronized channel shape on the order of microns.
[0027]
The chemical reaction device according to claim 13 is the chemical reaction device according to any one of claims 1 to 12, wherein the chemical reaction device has a plurality of reaction regions in which the reaction channels are individually formed, It is characterized in that different chemical reactions are generated for each of the reaction regions.
The chemical reaction device according to claim 14 is the chemical reaction device according to any one of claims 1 to 13, wherein the chemical reaction device is provided with a predetermined catalyst layer in at least a part of the reaction channel, Generating the second fluid substance from the first fluid substance by causing the chemical reaction accompanied by endothermic or heat generation based on a predetermined amount of heat supplied to the catalyst layer from the temperature adjustment layer. Features.
[0028]
The chemical reaction device according to claim 15, wherein in the chemical reaction device according to any one of claims 1 to 14, the first fluid substance is a mixed gas containing an alcohol-based gaseous fuel and oxygen. The second fluid substance is a hydrogen gas, and the chemical reaction device generates a steam reforming reaction in the reaction channel based on at least the amount of heat supplied from the temperature adjustment layer, so that the first Wherein the second fluid substance is generated from the fluid substance.
[0029]
17. The chemical reaction device according to claim 16, wherein the first fluid substance is an alcohol-based liquid fuel or water, and the second fluid substance is the second fluid substance. Is a fuel gas or water vapor in which the first fluid substance is vaporized, wherein the chemical reaction device generates a vaporization reaction in the reaction flow path based on at least the amount of heat supplied from the temperature adjustment layer. Thus, the second fluid substance is generated from the first fluid substance.
[0030]
The chemical reaction device according to claim 17, wherein in the chemical reaction device according to any one of claims 1 to 14, the first fluid substance is a mixed gas containing carbon monoxide gas and oxygen; Is a hydrogen gas and a carbon dioxide gas, and the chemical reaction device generates an aqueous shift reaction and a selective oxidation reaction in the reaction channel based on at least the amount of heat supplied from the temperature adjustment layer. Thereby, the second fluid substance is generated from the first fluid substance.
[0031]
The method for manufacturing a chemical reaction device according to claim 18, further comprising a reaction channel formed at least continuously, and performing a chemical reaction for converting a first fluid substance into a second fluid substance in the reaction channel. In the resulting method of manufacturing a chemical reaction device, a step of forming a temperature adjustment layer for supplying a predetermined amount of heat to the reaction channel, corresponding to at least the region including the reaction channel, and at least on the temperature adjustment layer, Forming a first conductive layer made of a conductive material to be insulated by an oxidation treatment; and forming a second conductive film made of a conductive material having a high resistance to the oxidation treatment on the first conductive layer. Forming a layer, and forming a third conductive layer made of a conductive material having high resistance to oxidation treatment and non-adhesiveness to the temperature adjustment layer on the second conductive layer. Forming, and the third conductive layer And the second conductive layer are continuously etched using a single etching resist to form an electrode layer having a predetermined pattern, and the first conductive layer in a region other than the pattern of the electrode layer is formed. The method further comprises: exposing; and oxidizing the exposed first conductive layer to form an insulating layer between the electrode layers.
[0032]
The method for manufacturing a chemical reaction device according to claim 19 is the method for manufacturing a chemical reaction device according to claim 18, wherein the temperature adjustment layer is a heating resistor made of a metal oxide film or a metal nitride film. Is formed of a material selected from tungsten, molybdenum, tantalum, an alloy containing tungsten, an alloy containing molybdenum, and an alloy containing tantalum, and the third conductive layer is made of gold, And a material selected from gold-containing alloys.
According to a twentieth aspect of the present invention, in the method of the nineteenth aspect, the temperature adjustment layer contains each element of tantalum, silicon, oxygen, and nitrogen at a predetermined composition ratio. It is characterized by being made of a material.
[0033]
The method for manufacturing a chemical reaction device according to claim 21 is the method for manufacturing a chemical reaction device according to any one of claims 18 to 20, wherein the first conductive layer includes yttrium, an alloy containing yttrium, aluminum, And a material selected from alloys containing aluminum.
According to a twenty-second aspect, in the method for manufacturing a chemical reaction device according to any one of the eighteenth to twenty-first aspects, the step of etching the third conductive layer and the second conductive layer includes a helicon etching method. Is used.
[0034]
24. The fuel cell system according to claim 23, wherein at least a reaction channel formed continuously and a region including the reaction channel are formed so as to correspond to an area including the reaction channel, and a temperature control for supplying a predetermined amount of heat to the reaction channel. A layer, a first electrode layer stacked on a first region on the temperature adjustment layer, and a layer formed on a second region other than the first region on the temperature adjustment layer, An insulating layer made of an insulating material obtained by oxidizing a conductive material of the same layer integrally with the first electrode layer; and an insulating layer formed on the first electrode layer, and via the first electrode layer, A second electrode layer for supplying electric power for generating the predetermined amount of heat in the temperature adjustment layer, wherein at least the heat amount supplied from the temperature adjustment layer is used to generate steam in the reaction flow path. By causing a reforming reaction, alcohol-based gaseous fuel and acid It is characterized chemically reactor a mixed gas comprising converting the hydrogen gas, by comprising a fuel cell which generates power by reacting the generated hydrogen and oxygen by the chemical reactor.
[0035]
In other words, the chemical reaction device and the method of manufacturing the same according to the present invention provide a method in which a fine closed substrate (second substrate) is provided on a fine main substrate (first substrate) provided with a groove having a predetermined flow path shape. For example, a chemical reaction that generates a hydrogen gas (a second fluid substance) from a mixed gas (a first fluid substance) of an alcohol-based gaseous fuel and oxygen occurs in a reaction channel formed by joining. A microreactor (chemical reaction device), which supplies a predetermined amount of heat to a reaction channel to promote or control the chemical reaction, and a predetermined amount of heat by supplying electric power to the thin film heater. Film (first and second electrode layers) having a layered structure for generating the film, and a protective film formed on at least the thin film heater other than the heater wiring forming region to protect the thin film heater from etching damage An insulating layer), wherein the protective film is formed in the same layer with the same conductive material as the lowermost electrode layer (first electrode layer) of the wiring electrode, and at least the wiring electrode It has high etching resistance when patterning (etching) the upper electrode layer (second electrode layer), and is composed of an insulating thin film formed by thermal oxidation after the above patterning. Have been.
[0036]
Here, the thin film heater is constituted by a heating resistor having a predetermined heating characteristic such as a metal oxide film or a metal nitride film, and an electrode layer (first electrode layer) serving as a lowermost layer of the wiring electrode is For example, the electrode layer (second electrode layer) which is made of a conductive material which has high etching resistance such as yttrium or aluminum and is made insulating by thermal oxidation treatment, and which is an upper layer of the wiring electrode is made of, for example, a high melting point material such as tungsten. An electrode structure in which each conductive layer made of a conductive material containing a metal and a conductive material excellent in electric conductivity such as gold is stacked can be used.
[0037]
The chemical reaction device having such a configuration includes a first conductive layer serving as the first electrode layer and a second conductive layer on a temperature adjustment layer provided corresponding to a reaction channel formation region. A second and a third conductive layer to be an electrode layer are sequentially laminated, and the third and the second conductive layer are formed as a single photoresist (etching resist) by using the first conductive layer as an etching barrier (etching stop layer). ) To form a wiring electrode (second electrode layer) having a predetermined pattern, and to expose the first conductive layer in a region other than the wiring electrode pattern region. One conductive layer can be formed by a series of manufacturing processes in which an insulating protective film is formed by thermal oxidation treatment.
[0038]
According to this, a conductive layer serving as an etching barrier is provided on the thin film heater when a thin film heater, a wiring electrode, and the like are stacked on a specific surface of the microreactor, and thus has a stacked structure on the conductive layer. Even if various etching processes are performed under different conditions to form the wiring electrodes, the pattern accuracy of the wiring electrodes can be reduced while suppressing the etching damage to the film quality of the thin film heater without strictly setting the etching conditions. And deterioration of electrical characteristics can be suppressed.
In addition, after patterning of the wiring electrode, the conductive layer that has become the etching barrier by thermal oxidation can be easily changed to an insulating protective film, and the wiring electrode portion is not oxidized and serves as a good conductor. Since the characteristics are maintained as they are, the thin-film heater can be covered and protected well, and a wiring electrode exposed from the protective film and having good electric characteristics can be realized.
[0039]
Therefore, in the patterning step of the wiring electrode, restrictions on the etching conditions, process control, pattern accuracy, and the like are relaxed, and good film quality, pattern accuracy, and electrical connection can be realized by a simple manufacturing method and a simple manufacturing apparatus. Since a microreactor can be provided, the reliability can be improved while suppressing the manufacturing cost of a power supply system in which such a microreactor is applied to a fuel reformer or the like. Further, when other peripheral members are joined to a specific surface of the microreactor, or when a plurality of microreactors are stacked, electrical connection can be made in the vertical direction (stacking direction). In addition, it is possible to improve the degree of freedom in designing the power supply system, reduce the size of the device, and apply the device to a desired external shape.
[0040]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of a chemical reaction device, a fuel cell system, and a method of manufacturing the same according to the present invention will be described with reference to the drawings.
<Structure of chemical reactor>
First, an embodiment showing a configuration of a chemical reaction device according to the present invention will be described with reference to the drawings.
FIG. 1 is a schematic configuration diagram showing one embodiment of a chemical reaction device according to the present invention, and FIG. 2 is a cross-sectional view of a main part showing a laminated structure of the chemical reaction device according to this embodiment. In FIG. 1, in order to clarify the configuration of the chemical reaction apparatus, the flow path shape of the reaction flow path and the planar shape of the thin film heater are hatched for convenience.
[0041]
As shown in FIG. 1, the chemical reaction device (microreactor) according to the present embodiment is roughly divided into a main substrate (first substrate) 10 composed of a small substrate and a predetermined groove-shaped portion on one surface side of the main substrate 10. Formed on the inner surface of the reaction flow channel 20 (for example, the side wall surface or the bottom surface of the reaction flow channel 20). Catalyst layer 21, a closed substrate (second substrate) 30 composed of a small substrate joined to one surface side of the main substrate 10 (the open end side of the groove of the reaction channel 20), and the other surface of the main substrate 10 On the side (the surface opposite to the side joined to the closed substrate 30), a region including the shape region (planar shape) of the reaction channel 20 is formed of a single heating resistor or the like formed in a single rectangular shape. A thin film heater (temperature adjustment layer) 40 and a predetermined shape The wiring electrode (first electrode layer, second electrode) 50 formed in the thinning and the region (second region) where the thin film heater 40 is formed except for at least the region (first region) where the wiring electrode 50 is formed. And an insulating protective film (insulating layer) 60 for covering and protecting the region.
[0042]
Here, as shown in FIGS. 1 (a) and 1 (b), the reaction channel 20 has an arbitrary groove-shaped cross-sectional shape and a planar shape (here, meandering) on one surface side of a main substrate 10 made of silicon or the like. And a groove formed on the inner wall surface (in this case, the bottom surface) with, for example, a copper-zinc (Cu-Zn) -based catalyst layer 21 attached thereto. By joining and closing the closing substrate 30 made of glass or the like, a flow path (reaction flow path 20) having a continuous pattern and blocked from the outside is formed. That is, a flow path having an opening only at the inlet 20a and the outlet 20b of the predetermined fluid substance is formed.
[0043]
In FIG. 1, the main substrate 10 and the closed substrate 30 that constitute the reaction channel of the chemical reaction apparatus are provided with a fluid substance introduction part 20a and a discharge part 20b to the reaction channel 20 on the side. However, the present invention is not limited to this, and the present invention is described in a direction perpendicular to the main substrate 10 or the closed substrate 30 (that is, in FIG. 1A and FIG. It may have a configuration in which the introduction section 20a and the discharge section 20b are provided.
[0044]
The thin-film heater 40 includes, for example, as shown in FIGS. 1B and 1C, a reaction channel 20 formed on the other surface of the main substrate 10 and at least on one surface of the main substrate 10. Is formed of a thin film layer of a resistor (heating resistor) having a predetermined planar shape (here, a single rectangular shape) and having predetermined heat generation characteristics. Here, as the thin film heater 40, a heating resistor made of a metal oxide, a metal nitride, or the like can be used. For example, tantalum (Ta), tungsten-titanium (WTi), or an oxide of tungsten (W) can be used. (-O), nitride (-N) and the like can be favorably applied. Specifically, a Ta-Si-ON-based compound including tantalum (Ta), silicon (Si), oxygen (O), and nitrogen (N) can be favorably applied. For example, a thin film having a thickness of 100 nm (1000 °) to 300 nm (3000 °) is provided.
[0045]
The wiring electrode 50 includes, for example, a lower electrode layer (first electrode layer) 51 made of a different conductive material in a predetermined region on the thin film heater 40 as shown in FIG. It has a stacked electrode structure including an intermediate electrode layer (a conductive layer forming the lower surface of the second electrode layer) 52 and an upper electrode layer (a conductive layer forming an upper layer of the second electrode layer) 53. . Here, each of the electrode layers 51 to 53 constituting the wiring electrode 50 is at least a conductive material having a predetermined low resistance characteristic, and can supply electric energy to the thin film heater 40 with high electric conduction efficiency. Anything that can be applied can be applied.
[0046]
In particular, the lower electrode layer 51 is laminated at least in a predetermined region on the thin-film heater 40, and peels off the resistive material constituting the thin-film heater 40 and an intermediate electrode layer 52 described later, and deteriorates electrical characteristics. A conductive material that hardly occurs and has high bonding or adhesion properties is applied. In addition, as described later, since the conductive material forming the lower electrode layer 51 is also used at least as a material for forming the insulating protective film 60 formed on the thin film heater 40, a thermal oxidation process or an impurity introduction process is performed. It is necessary that the material be a material that easily changes into an insulating thin film by a predetermined processing step such as the above. Furthermore, in the method for manufacturing a chemical reaction device described later, when at least the intermediate electrode layer 52 is patterned by a specific etching process, the material must have a significantly lower etching rate than the material constituting the intermediate electrode layer 52. Need. Specifically, yttrium (Y), aluminum (Al), or an alloy material containing these metal materials can be favorably applied. In the present embodiment, for example, 5 nm (50 °) to 100 nm ( An yttrium film having a thickness of 1000 ° is provided.
[0047]
For the intermediate electrode layer 52, a conductive material having good bonding or adhesion to the lower electrode layer 51 and an upper electrode layer 53 described later is applied. Specifically, refractory metal materials such as tungsten (W), molybdenum (Mo), and tantalum (Ta), or any of these refractory metal materials selected from titanium (Ti), aluminum, silicon, etc. In this embodiment, a titanium-tungsten film having a thickness of, for example, 200 nm (2000 °) is provided.
[0048]
Further, for the upper electrode layer 53, a conductive material having good bonding or adhesion to the intermediate electrode layer 52 is applied. Specifically, gold (Au), copper (Cu), or a metal compound (alloy) containing an arbitrary material can be favorably applied to these metals. In the present embodiment, for example, 700 nm ( A gold film having a thickness of 7000 °) is provided.
[0049]
The protective film 60 is formed at least on the thin film heater 40 in a region other than the region where the lower electrode layer 51 is formed, and is made of an insulating material that is unlikely to peel off from the resistive material constituting the thin film heater 40. It is configured. In particular, in the present invention, the protective film 60 is formed by making the same conductive material as that of the lower electrode layer 51 insulative by oxidation treatment or impurity introduction treatment. Therefore, the material for forming the protective film 60 is laminated (formed) in the same manufacturing process as the lower electrode layer 51, and only the region where the protective film 60 is formed is oxidized to be insulated, and the other regions are insulated. In addition, the lowermost layer of the wiring electrode 50 is formed while maintaining the function as an original conductive material without being made insulating. Specifically, an oxide of yttrium (Y) or aluminum (Al), or an oxide of an alloy material containing these metal materials can be favorably applied. In this embodiment, the lower electrode layer Similarly to 51, for example, yttrium oxide (Y) having a thickness of 50 nm (500 °) to 100 nm (1000 °) is used. ₂ O ₃ ) Provide a film.
[0050]
Therefore, according to the chemical reaction device having such a wiring electrode, on a specific surface (in the present embodiment, on the other surface side of the main substrate 10 on which the thin film heater 40, the wiring electrode 50, and the like are stacked), good results are obtained. It is possible to realize a microreactor in which the main substrate 10 and the thin film heater 40 are well covered and protected by the insulating protective film 60 while exposing the wiring electrode 50 having a high conductivity. In the case where other peripheral members are joined, or when a plurality of microreactors are laminated, electrical connection (conduction) can be performed in the vertical direction, and space saving and miniaturization of the device scale can be achieved. The design flexibility of the microreactor can be improved.
[0051]
In the present embodiment (FIG. 1), the reaction channel 20 is configured by joining one surface side of the closed substrate 30 so as to close the open end of the groove provided on one surface side of the main substrate 10. In addition, the configuration of the chemical reaction device (microreactor) in which the thin film heater 40, the wiring electrode 50, and the protective film 60 are sequentially formed on the other surface side of the main substrate 10 has been described, but the present invention is not limited to this. Instead, for example, it may have a configuration in which the thin film heater 40, the wiring electrode 50, and the protective film 60 are laminated on the other surface side of the closed substrate 30. In short, if the thin film heater 40, the wiring electrode 50, and the protective film 60 are formed so that a predetermined amount of heat can be supplied to the reaction channel 20 formed in the main substrate 10, Thus, the configuration of the chemical reaction device according to the present invention can be favorably applied.
[0052]
<Method of manufacturing chemical reaction device>
Next, a method for manufacturing the chemical reaction device having the above-described configuration will be described with reference to the drawings.
FIG. 3 is a manufacturing process diagram showing the entire manufacturing method of the chemical reaction device according to the present invention. FIGS. 4 and 5 show specific examples of the wiring electrode portion applied to the chemical reaction device according to the present embodiment. It is a manufacturing process figure showing an example of a manufacturing method. FIG. 6 is a manufacturing process diagram showing another example of a specific method for manufacturing a wiring electrode portion applied to the chemical reaction device according to the present embodiment.
[0053]
The method of manufacturing the chemical reaction device according to the present embodiment is roughly divided into a first conductive layer serving as a lower electrode layer 51 on a thin film heater (temperature adjusting layer) 40 provided corresponding to a reaction channel formation region. A layer, a second conductive layer serving as the intermediate electrode layer 52, and a third conductive layer serving as the upper electrode layer 53 are sequentially laminated, and a single layer formed corresponding to the pattern shape of the wiring electrode is formed. A step of continuously etching the third and second conductive layers by using an etching resist and using the first conductive layer as an etching barrier (etching stop layer); Forming an insulating protective film by subjecting the conductive layer to a thermal oxidation treatment.
[0054]
More specifically, first, as shown in FIG. 3A, a predetermined groove shape serving as a reaction channel 20 is formed on one surface side of a main substrate 10 made of a silicon substrate or the like by using a photoetching technique or the like. After the groove 20x having the cross-sectional shape and the planar shape of FIG. 1 is formed by etching, copper-zinc (Cu) is formed on the inner wall surface (side wall surface or bottom surface; bottom surface in this embodiment) of the groove portion by chemical vapor deposition (CVD) or the like. -Zn) -based catalyst layer 21 is formed to an arbitrary thickness (for example, 1 μm to 100 μm). Here, the cross-sectional shape of the groove 20x constituting the reaction channel 20 is a size that allows the catalyst layer 21 to be satisfactorily formed on the inner wall surface. Since the effective cross-sectional area in which the fluid substance flows and moves decreases, the size is set so as to allow for the decrease.
[0055]
Next, as shown in FIG. 3B, one surface of the closed substrate 30 made of a glass substrate or the like is joined to one surface of the main substrate 10 so as to close the open end of the groove 20x. Thereby, while having a continuous pattern (flow path shape), the catalyst layer 21 is provided on the inner wall surface, and the reaction flow path 20 blocked from the outside is formed.
Next, as shown in FIGS. 3C and 4A, the heat formed on the entire other surface side of the main substrate 10 (the upper surface in FIGS. 3C and 4A). On the oxide film 11, a heating resistor layer 40x made of a metal oxide, a metal nitride, or the like to be the thin film heater 40 is formed.
[0056]
Here, the heating resistor layer 40x is formed of, for example, oxygen gas (O ₂ ) And nitrogen (N ₂ A) by sputtering using a stripe target of tantalum (Ta) and silicon (Si) in an atmosphere of an argon gas (Ar) mixed with a gas, the composition is composed of each element of tantalum-silicon-oxygen-nitrogen. The Ta-Si-ON-based thin film is formed in a thickness of 100 nm (1000 °) to 300 nm (3000 °).
[0057]
Next, a resist film (not shown) is formed in a predetermined region on the heating resistor layer 40x using a photolithography technique, a reactive ion etching (RIE) method, or the like, and is not covered with the resist film. By etching the heating resistor layer 40x, as shown in FIGS. 1 and 2, a thin film heater having a plane shape (here, a single rectangular shape) corresponding to the flow path shape of the reaction flow path 20 Form 40.
[0058]
Next, as shown in FIG. 4A, an yttrium thin film layer (first conductive layer) 51x to be the lower electrode layer 51 is formed over the entire area on the other surface side of the main substrate 10 including the thin film heater 40 by a sputtering method or the like. Is formed to a thickness of, for example, 5 nm (50 °) to 100 nm (1000 °), and a titanium-tungsten thin film layer (second conductive layer) 52x serving as the intermediate electrode layer 52 is formed thereon, for example, to a thickness of 200 nm (2000 °). ), And a gold thin film layer (third conductive layer) 53x to be the upper electrode layer 51 is sequentially formed to a thickness of, for example, 700 nm (7000 °) by using a vapor deposition method, a plating method, or the like. Form.
[0059]
Next, as shown in FIG. 4B, a photoresist 70 having a pattern shape of the wiring electrode 50 is formed at a predetermined position on the gold thin film layer 53x by using a photolithography technique. Is used as a mask, wet etching using a gold etching solution (Au etchant) is performed to etch the gold thin film layer 53x that is not covered with the photoresist 70, and as shown in FIG. The upper electrode layer 53 constituting 50 is patterned and the lower titanium-tungsten thin film layer 52x is exposed.
[0060]
Next, as shown in FIG. 4C, dry etching is performed on the titanium-tungsten thin film layer 52x exposed in the above-described etching step using a photoresist 70 used in the above-mentioned etching step as a mask using a helicon etching apparatus. By doing so, the titanium-tungsten thin film layer 52x not covered with the photoresist 70 is etched to pattern and form the intermediate electrode layer 52 constituting the wiring electrode 50, as shown in FIG. The yttrium thin film layer 51x is exposed.
[0061]
Here, the helicon etching apparatus is a high-density plasma etcher that performs etching using both a physical force (sputter) by ions and a chemical force (chemical reaction) by radicals (active species). It is. The helicon etching method has a feature that the etching resolution is higher than other etching methods.
[0062]
Hereinafter, the effect of applying such a helicon etching method will be specifically verified.
In the present embodiment, a helicon etching device L-210H-W (product name) manufactured by Anelva Co., Ltd. is used as an etching device used in the etching process shown in FIGS. 4C and 5A. As the etching conditions for the titanium-tungsten thin film layer 52x, an etching gas CF is used. ₄ Dry etching was performed under the conditions of a gas flow rate of 25 sccm, an etching source power supply of 250 W, a bias power supply of 150 W, and an etching process pressure of 0.5 Pa.
Here, the helicon dry etching is performed on the thin film heater 40, the yttrium thin film layer 51x, the titanium-tungsten thin film layer 52x, and the photoresist 70 shown in FIG. Table 1 shows the performance (etching rate).
[0063]
[Table 1]

[0064]
As shown in Table 1, when helicon dry etching is performed under the above-described conditions, the etching rate of the titanium-tungsten thin film layer 52x is approximately 33 nm / min (330 ° / min), and the thin film heater 40 (Ta− The etching rate of the Si-ON-based compound thin film) is about 52.5 nm / min (525 ° / min), and the etching rate of the photoresist is about 131.1 nm / min (1311 ° / min). On the other hand, the etching rate of the yttrium thin film layer 51x was remarkably small at about 0.3 nm / min (3 ° / min), and it was confirmed that almost no etching was performed.
[0065]
Therefore, in the present embodiment, by utilizing such a remarkable difference in the etching rate between the yttrium thin film layer 51x and the other thin film materials, the titanium-tungsten thin film layer 52x is etched in the etching step of the titanium-tungsten thin film layer 52x. Using the lower yttrium thin film layer 51x as an etching barrier (etching stop layer), using the photoresist 70 as a mask as it is, and performing helicon dry etching with the above conditions set, without strictly controlling the etching time, By continuing the etching process until the yttrium thin film layer 51x is exposed, the titanium-tungsten thin film layer 52x can be favorably etched.
[0066]
That is, the etching time (just etching time) for satisfactorily etching the titanium-tungsten thin film layer having a predetermined film thickness is, for example, when the etching barrier is not formed under the titanium-tungsten thin film layer. When the film thickness is 200 nm, the etching rate is about 6 minutes from the etching rate (about 33 nm / min) in Table 1, but according to the manufacturing method described in the present embodiment, a sufficiently long time of 6 minutes or more is set. Even in this case, the yttrium thin film layer 51x does not damage the lower thin film heater 40 by etching.
[0067]
Next, as shown in FIG. 5B, the photoresist 70 is peeled off, so that a predetermined region on the thin-film heater 40 (the yttrium thin-film layer 51x) is provided in an upper electrode layer (second electrode) on the wiring electrode 50. Layer) is obtained.
Thereafter, the main substrate 10 in which the yttrium thin film layer 51x is exposed in a region other than the region where the stacked electrode including the intermediate electrode layer 52 and the upper electrode layer 53 is formed is placed on a hot plate (not shown) in the air or an oxygen atmosphere. 5) By heating the substrate on the substrate and heating it to approximately 400 ° C., only the exposed yttrium thin film layer 51x is thermally oxidized as shown in FIG. 5C. Here, at the temperature set in the thermal oxidation process (about 400 ° C.), the gold constituting the upper electrode layer 53 does not cause an oxidation reaction or deterioration of film quality, and forms the intermediate electrode layer 52. The oxidation reaction of titanium-tungsten is prevented by the gold of the upper electrode layer 52 formed on the upper layer. Therefore, only the yttrium thin film layer 51x formed in a region other than the region where the wiring electrode 50 is formed is made of yttrium oxide (Y ₂ O ₃ ) To cover and protect at least the thin-film heater 40.
[0068]
Further, at this time, the yttrium thin film layer 51x which is under the intermediate electrode layer 52 and the upper electrode layer 53 and is not exposed in the thermal oxidation treatment step is not oxidized and maintains the original conductivity of yttrium. The lower electrode layer (first electrode layer) of the wiring electrode 50 is formed, and a laminated structure including a lower electrode layer 51, an intermediate electrode layer 52, and an upper electrode layer 53 is formed in a predetermined region of the thin film heater 40. Is formed.
[0069]
Therefore, according to the method for manufacturing a chemical reaction device according to the present embodiment, when a thin film heater, a wiring electrode, and the like are laminated on a specific surface of a main substrate constituting the chemical reaction device, an etching barrier is formed on the thin film heater. After forming a conductive layer (yttrium thin film layer), the upper conductive layer (gold thin film layer, titanium-tungsten thin film layer) is etched to form a wiring electrode, thereby forming a different pattern using a single photoresist. Even if the etching process is performed under the conditions, it is possible to suppress the etching damage to the thin film heater without strictly controlling the etching time and to suppress the deterioration of the pattern accuracy and the electrical characteristics of the wiring electrode. can do.
[0070]
In addition, by performing a thermal oxidation treatment after the patterning of the wiring electrode, the conductive layer (yttrium thin film layer) which serves as an etching barrier in the above-described wiring electrode etching step and is exposed in a region other than the wiring electrode formation region can be simplified. Since the protective film can be changed to an insulating protective film (yttrium oxide), the thin film heater can be covered and protected well, and the conductive layer (yttrium thin film layer) is not oxidized in the wiring electrode portion. Since the characteristics as a good conductor can be maintained as it is, a wiring electrode exposed from the protective film and having good electric characteristics can be formed.
[0071]
In the manufacturing method shown in the above-described embodiment, an yttrium thin film layer is formed as an etching barrier (or lower electrode layer), a titanium-tungsten thin film layer is stacked as an intermediate electrode layer, and a gold thin film layer is stacked as an upper electrode layer. Although the case of forming is shown, the present invention is not limited to this. That is, the etching barrier is a conductive material that has a remarkably low etching rate when patterning and forming the intermediate electrode layer and the upper electrode layer by a specific etching method, and that easily becomes insulative by oxidation treatment or the like. In addition, the upper electrode layer, when performing oxidation treatment or impurity introduction treatment on the conductive layer serving as an etching barrier, while maintaining the original film quality and conductivity well, the film quality of the lower intermediate electrode layer and the like. Needless to say, any other material may be used as long as it is a conductive material that can maintain conductivity.
[0072]
Further, in the above-described embodiment, the case where the etching barrier is thermally oxidized after the photoresist is removed after the pattern formation of the upper electrode layer and the intermediate electrode layer (see FIGS. 5A to 5C). However, the present invention is not limited to this manufacturing procedure. For example, as shown in FIG. 6, after forming the patterning of the upper electrode layer 53 and the intermediate electrode layer 52, the etching is performed without removing the photoresist 70. The yttrium thin film layer 51x serving as a barrier may be thermally oxidized to form the insulating protective film 60. According to this, the oxidation reaction of titanium-tungsten constituting the intermediate electrode layer 52 and the deterioration of the film quality are more reliably prevented by both the gold constituting the upper electrode layer 53 and the photoresist 70.
[0073]
Further, in the above-described embodiment, the thin film heater 40 having a single rectangular shape corresponding to the planar shape (formation region) of the reaction channel 20 is provided on the other surface side of the main substrate 10. Although a chemical reaction device and a method of manufacturing the same in which the wiring electrodes 50 are laminated and formed at both ends and the upper layer of the wiring electrodes 50 are exposed from the protective film 60 have been described, the present invention is not limited to this. Rather, the planar shape of the thin-film heater 40 and the formation position of the wiring electrode 50 are appropriately set according to the planar shape of the reaction channel 20 and the position where electrical conduction with the outside of the chemical reaction device is performed. It goes without saying that it may be present. Therefore, a configuration in which the thin film heater is formed only in the region corresponding to the planar shape of the reaction channel (that is, as shown in FIG. 7, the thin film heater corresponds to the formation region of the reaction channel 20 having a meandering shape) Even if the heater 41 has a configuration in which the heater 41 is formed in a meandering shape and the wiring electrodes 50 are formed at both ends in the longitudinal direction of the planar shape, the chemical reaction device according to the present invention can be used. The configuration and the manufacturing method can be applied favorably.
[0074]
<Example of application to power supply system>
Next, a specific example will be described in which the chemical reaction device (microreactor) according to the present invention is applied to a power supply system including a fuel reforming type fuel cell.
FIG. 8 is a block diagram showing a main configuration of a power supply system (fuel cell system) to which the chemical reaction device according to the present invention can be applied, and devices driven by the power supply system. Here, a power supply system to which a polymer electrolyte fuel cell employing a fuel reforming method is applied will be described.
[0075]
As shown in FIG. 8, a power supply system 300 to which the chemical reaction device according to the present invention is applied generally includes a power generation module 100 that generates electric power based on a predetermined fuel for power generation, and a power generation module 100 that is attached to and detached from the power generation module 100. And a fuel pack 200 in which a predetermined fuel for power generation is sealed.
The power generation module 100 is roughly divided into a power generation unit (fuel cell main body) 110 having a configuration of a polymer fuel cell of a fuel reforming type, and a power generation fuel stored and sealed in a fuel filling unit 210 of a fuel pack 200. A fuel control unit 120 that controls a supply amount of liquid fuel (for example, liquid fuel containing hydrogen, a liquefied fuel, a gaseous fuel, or water) to the power generation unit 110, and an air that controls a supply amount of air (oxygen) to the power generation unit 110 A control unit 130, a fuel reforming unit 140 that reforms the power generation fuel supplied by the fuel control unit 120, gasifies hydrogen contained in the power generation fuel, and supplies the gas to the power generation unit 110; A temperature control unit 150 for heating the fuel reforming unit 140 as necessary; a charging unit 160 having a capacitor for charging a part or all of the electric power generated by the power generation unit 110; A sub power supply unit 170 that outputs necessary power for a power generation operation and a charging operation in the module 100, an operation of detecting a state of charge of the charging unit 160 by an operation control unit 180 described below, and a driving operation in the power generation module 100. And an operation control unit 180 that performs arithmetic processing on
[0076]
The fuel control unit 120 sends a predetermined amount of the fuel for power generation sent from the fuel filling unit 210 by physical means using a principle such as a capillary phenomenon to the fuel reforming unit 140 in accordance with a command signal from the operation control unit 180. It is configured to supply.
The air control unit 130 takes in air (atmosphere) from the outside of the fuel cell system 300 and supplies oxygen gas (O 2) to the power generation unit 110. ₂ ) Or to supply air.
[0077]
The fuel reforming unit 140 is configured to supply alcohol (ALCOHOOL) and water (H ₂ O), the fuel for power generation is taken in through the fuel control unit 120, and hydrogen (H ₂ ) And by-product carbon dioxide (CO ₂ ) And a steam reforming reaction section 140a for generating a trace amount of carbon monoxide (CO), and a carbon monoxide reforming section shown below. The carbon monoxide reforming unit converts the carbon monoxide (CO) supplied from the steam reforming reaction unit 140a into water (H) supplied from the fuel control unit 120 and / or the power generation unit 110. ₂ O) and react with carbon dioxide (CO ₂ ) And hydrogen (H ₂ ) Is generated, and carbon monoxide (CO) remaining in the reaction in the aqueous shift reaction unit 140b is reacted with oxygen (O) to produce carbon dioxide (CO). ₂ ) Is configured to include at least one of the selective oxidation reaction units 140c that generate).
[0078]
The temperature control unit 150 is provided in each reaction unit of the fuel reforming unit 140 (the steam reforming reaction unit 140a, the water shift reaction unit 140b, and the selective oxidation reaction unit 140c) according to a command signal from the operation control unit 180. Heating is controlled by supplying electric power to the thin film heater. When the power generation unit 110 is also provided with a thin film heater, the power generation unit 110 is similarly configured to be supplied with predetermined power. Here, the thin film heater provided in the fuel reforming unit 140 and the power generation unit 110 corresponds to the thin film heater 40 described in the above-described embodiment, and has a predetermined heat generation characteristic such as a metal oxide film or a metal nitride film. It is formed of a thin film layer made of a resistor material.
[0079]
The power generation unit 110 uses the hydrogen (H ₂ ) And oxygen gas (O 2) supplied from the air control unit 130. ₂ ) Is configured to generate (generate) predetermined power, and the charging unit 160 is configured to charge the power generated by the power generation unit 110, and the power generation unit 110 and the charging unit 160 is configured to supply power to the load LD of the device DVC driven by the power supply system 300.
The sub power supply unit 170 supplies a predetermined operation power to the fuel control unit 120, the temperature control unit 150, and the operation control unit 180 based on the electric power stored in the charging unit 160 in response to a command signal from the operation control unit 180. It is configured to supply the operating power to the power generation unit 110 as necessary.
[0080]
The operation control unit 180 is constantly driven to detect the charge (charge potential) stored in the charging unit 160, and when detecting that the charge has decreased to a predetermined value, the fuel control unit 120, the temperature control unit 150, It outputs a command signal to sub-power supply unit 170 to supply operating power to power generation unit 110 as necessary. In addition, a command signal is output to the fuel control unit 120 so as to supply a required amount of fuel to the fuel reforming unit 140, and a reaction furnace of the fuel reforming unit 140 (reaction flow of the chemical reaction device according to the present invention) is used. (Corresponding to a road) for a predetermined time to a required temperature.
[0081]
The fuel pack 200 detachably attached to the power generation module 100 includes a fuel filling section 210 in which fuel for power generation is filled, and a by-product (mainly, water (H ₂ O)) for recovering the by-products.
The fuel cell system 300 composed of the power generation module 100 and the fuel pack 200 supplies the predetermined drive power to the load LD of the device DVC, and can normally drive the device DVC under the control of the controller CNT. it can.
[0082]
Here, the power generation unit 110 has a configuration of a well-known polymer electrolyte fuel cell main body, and roughly includes a fuel electrode (cathode) composed of a carbon electrode to which catalyst fine particles such as platinum or platinum / ruthenium are attached, and a platinum electrode. And the like, and an air electrode (anode) formed of a carbon electrode to which catalyst fine particles such as the above are adhered, and a film-like ion conductive film (exchange membrane) interposed between the fuel electrode and the air electrode. I have.
[0083]
The power generation principle of the power generation unit 110 having such a configuration is based on the hydrogen gas (H ₂ ) Is supplied, and as shown in the following chemical reaction formula (1), electrons (e) are ⁻ ) Separated hydrogen ion (proton; H ⁺ ) Is generated and passes through the ionic conductive film to the air electrode side, and electrons (e) are generated by the carbon electrode constituting the fuel electrode. ⁻ ) Is taken out and supplied to the load (in the power supply system described above, the load LD of the device DVC and the charging unit 160).
3H ₂ → 6H ⁺ + 6e ⁻ ... (1)
[0084]
On the other hand, oxygen gas (O 2) in the air is supplied to the air electrode via the air control unit 130. ₂ ) Is supplied, and as shown in the following chemical reaction formula (2), the electrons (e ⁻ ) And hydrogen ions (H ⁺ ) And oxygen gas (O ₂ ) Reacts with water (H ₂ O) is generated.
6H ⁺ + (3/2) O ₂ + 6e ⁻ → 3H ₂ O ... (2)
Such a series of electrochemical reactions (chemical reaction formulas (1) and (2)) generally proceed in a relatively low temperature environment of room temperature to 80 ° C, and by-products other than electric power are basically water. (H ₂ O) only. The power (voltage / current) supplied to the load by the above-described electrochemical reaction is supplied to the fuel electrode of the power generation unit 110 as shown in the chemical reaction formulas (1) and (2). Hydrogen gas (H ₂ ) Depends on the quantity.
[0085]
Therefore, the fuel control unit 120 controls the power generation unit 110 to generate hydrogen gas (H ₂ ), The fuel (methanol), water and the like are taken in, the fuel is reformed into hydrogen gas by the fuel reforming section 140, and the hydrogen gas is supplied to the fuel electrode of the power generation section 110. The air control unit 130 supplies oxygen gas (O 2) to the air electrode of the power generation unit 110. ₂ ) Has a function of controlling the amount of oxygen gas supplied to the air electrode of the power generation unit 110 if the air corresponding to the maximum consumption of oxygen per unit time in the power generation unit 110 can be supplied. The oxygen gas may be constantly supplied when the power generation unit 110 is driven without controlling the amount. Further, as another configuration of the air control unit 130, the progress of the electrochemical reaction in the power generation unit 110 is controlled only by the supply amount of hydrogen gas adjusted in the fuel control unit 120, and instead of the air control unit 130, An air hole may be provided so that air (atmosphere) that is used for the electrochemical reaction in the power generation unit 110 or more than the maximum consumption amount is supplied through the air hole.
[0086]
Next, the configuration and operation of the fuel reforming unit 140 applied to the power supply system will be described in detail.
FIG. 9 is a schematic configuration diagram showing a specific example of a fuel reforming section to which the configuration of the chemical reaction device according to the present invention is applied.
As described above, the fuel reforming section 140 mainly utilizes a predetermined endothermic catalytic reaction (steam reforming reaction) for the power generation fuel supplied at a predetermined supply amount by the fuel control section 120. It has a function of extracting a hydrogen component contained in the fuel for power generation and supplying the hydrogen component to the power generation unit 110, and in each reaction unit constituting the fuel reforming unit 140, the above-described embodiment (FIGS. 1 and 7) ) Can be satisfactorily applied.
[0087]
Specifically, in the fuel reforming section 140 (steam reforming reaction section 140a), a liquid fuel (alcohols) containing hydrogen such as methanol is converted into hydrogen using a steam reforming reaction which is an endothermic catalytic reaction. Gas (H ₂ ) Is performed. Here, as the power generation fuel applied to the fuel reforming type fuel cell which is currently being researched and developed, the power generation unit 110 can generate power with relatively high energy conversion efficiency. A fuel, for example, a liquefied fuel composed of a hydrocarbon vaporized at normal temperature and normal pressure, such as an alcohol-based liquid fuel such as methanol, ethanol, and butanol; a liquefied gas such as dimethyl ether, isobutane, and natural gas (CNG); Alternatively, a fluid substance such as a gaseous fuel such as hydrogen gas can be favorably applied.
[0088]
That is, as an example of the endothermic catalytic reaction used to generate hydrogen gas in the fuel reforming section 140 (steam reforming reaction section 140a), when methanol is used as an example of a liquid fuel, the following chemical reaction formula (3) In the case where dimethyl ether is used as an example of a liquefied fuel that becomes a gas at normal temperature and pressure, a steam reforming reaction as shown in the following chemical reaction formula (4) occurs. Occurs.
CH ₃ OH + H ₂ O → 3H ₂ + CO ₂ ... (3)
CH ₃ OCH ₃ + 3H ₂ O → 6H ₂ + 2CO ₂ ... (4)
[0089]
In any steam reforming reaction, the reaction proceeds favorably under a heat condition of about 300 ° C. In addition, a small amount of products other than hydrogen produced by this reforming reaction (mainly CO 2 ₂ ) Are released into the atmosphere. Therefore, the chemical reaction apparatus (see FIGS. 1 and 7) as shown in the above-described embodiment is applied to the fuel reforming section 140 (steam reforming reaction section 140a), and the reaction channel (reaction furnace) formation region is formed. By supplying a predetermined power from a heater power supply via a wiring electrode to a thin-film heater provided in correspondence with the above, and generating heat, the above-mentioned chemical reaction formula (3) is applied to the reaction channel (catalyst layer). And (4) can be supplied with a predetermined amount of heat that contributes to the progress of the steam reforming reaction accompanied by endotherm, and hydrogen gas can be favorably generated.
[0090]
Here, a specific configuration example applied to the fuel reforming section 140 is, for example, as shown in FIG. 9A, one surface side of a micro substrate (corresponding to the main substrate 10) 141 of silicon or the like. On the upper surface side of the figure, using a microfabrication technique such as a semiconductor device manufacturing technique, a fuel discharge section 142a, a water discharge section 142b, and a fuel vaporization section having a predetermined sectional shape and a planar shape and provided in a groove shape. A flow path (each of which corresponds to the above-described reaction flow path 20) including a section 143a, a water vaporization section 143b, a mixing section 143c, a reforming reaction flow path 144, and a hydrogen gas exhaust section 145; A rectangular thin-film heater (corresponding to the thin-film heater 40 in the above-described embodiment) 146 provided on the other surface side (the lower surface side in the drawing) of the micro substrate 141 in a predetermined region including the region where the flow channel 144 is formed. At both ends of the thin film heater An open end of the flow path on the micro-substrate 141 and a wiring electrode (corresponding to the wiring electrode 50 in the above-described embodiment; not shown, see FIG. 1) laminated and formed with a fixed pattern shape are closed. 147 (corresponding to the closed substrate 30 in the above-described embodiment; indicated by a two-dot chain line for the sake of illustration).
[0091]
The fuel discharge part 142a and the water discharge part 142b allow the power generation fuel (alcohol-based liquid fuel or the like) and water, which are the raw materials in the steam reforming reaction as described above, to flow, for example, as liquid particles in predetermined unit amounts. It has a fluid discharge mechanism for discharging into the road. Therefore, for example, the progress state of the steam reforming reaction represented by the chemical reaction formula (3) is controlled based on the discharge amount of the power generation fuel or water in the fuel discharge unit 142a and the water discharge unit 142b. Therefore (specifically, the thermal energy supplied from the thin-film heater 146 is also closely related), the fuel discharge unit 142a and the water discharge unit 142b have a function as a fuel control unit that adjusts the fuel supply amount. I have.
[0092]
The fuel vaporization unit 143a and the water vaporization unit 143b include, for example, heaters that are heated according to the volatilization (vaporization) conditions such as the power generation fuel and the boiling point of water. The power-generating fuel or water discharged as a gas is vaporized by a heating process or a decompression process, and a mixed gas of fuel gas and steam is generated in the mixing unit 143c. Here, when a mechanism for performing a heat treatment is adopted as the fuel vaporization unit 143a and the water vaporization unit 143b, the fuel vaporization unit 143a and the water vaporization unit 143b are configured similarly to the reforming reaction channel 144 described above. A configuration in which a thin film heater is provided in a predetermined area including a flow path forming area may be applied.
[0093]
The mixed gas generated in the mixing section 143 c is introduced into the reforming reaction channel 144, and a copper-zinc (Cu—Zn) -based catalyst layer (shown in the drawing) attached to the inner wall surface of the reforming reaction channel 144. Is omitted), a predetermined amount of heat is supplied from the thin film heater 146 provided in a region corresponding to the formation region of the reforming reaction channel 144, whereby the above chemical reaction formulas (3) and (4) are obtained. The steam reforming reaction shown in FIG. ₂ ).
The hydrogen gas exhaust unit 145 discharges the hydrogen gas generated in the reforming reaction channel 144 and supplies the hydrogen gas to the fuel electrode of the fuel cell constituting the power generation unit 110 described above. Thereby, a series of electrochemical reactions based on the chemical reaction formulas (1) and (2) occur in the power generation unit 110, and predetermined power is generated.
[0094]
Then, as described above, the fine processing is performed in the same manner as in the above-described embodiment, corresponding to the formation region of the flow path formed in the micro-substrate 141 of the fuel reformer 140 having such a configuration. The thin film heater 146 and the wiring electrode can be laminated on the other surface side (the lower surface side in the drawing) of the micro substrate 141 by using the technique, and the manufacturing method described in the above-described embodiment is provided at least in the formation region of the thin film heater 146. By covering and forming a protective film (not shown, see FIG. 1 or FIG. 7) based on the above, it is possible to cover and protect the micro substrate 141 and the thin film heater 146 while exposing the wiring electrodes.
[0095]
As a result, the whole or a part of the fuel reforming unit 140 is integrated in the minute space, and the connection to the other peripheral members and the stacking of the plurality of fuel reforming units 140 can be satisfactorily realized. Good connection can be ensured, so that the power generation module 100 including the fuel reforming section 140 can be saved in space and downsized, and the amount of heat released from the thin film heater can be satisfactorily reduced in the flow path. And a power supply system with high heat conduction efficiency can be realized. Therefore, for example, it is possible to reduce the size to have substantially the same external shape and external dimensions as a general-purpose primary battery or various secondary batteries conforming to the Japanese Industrial Standards (JIS), and to use an existing primary battery or secondary battery. A portable power supply compatible in the secondary battery market can be realized.
[0096]
The power supply system (power generation unit) shown in this application example is a predetermined fluid substance (hydrogen gas or the like) generated by the fuel reforming unit to which the microreactor (chemical reaction device) as shown in the above-described embodiment is applied. The fuel cell is not limited to a fuel cell as long as power generation can be performed using ()) as a fuel for power generation. Therefore, the electric power is generated by rotating the generator using the thermal energy generated by the combustion reaction of the fluid substance generated by the chemical reaction device (fuel reforming unit) (temperature difference power generation) or the pressure energy generated by the combustion reaction. (Such as internal combustion of gas combustion turbines, rotary engines, Stirling engines, etc., and external combustion engine power generation), and the principle of electromagnetic induction, such as fluid energy and heat energy of power generation fuel FL. The present invention can be applied to power generation devices having various forms, such as a device that converts electric power into electric power (magnetohydrodynamic power generation, thermoacoustic power generation, etc.).
[0097]
Further, in the configuration shown in FIG. 9A, in the chemical reaction formula (3), methanol and the like and water as power generation fuel are supplied and vaporized through separate discharge units 142a and 142b and a supply path. Although the fuel reforming section having a configuration in which mixing is performed in the mixing section 143c is shown, the steam reforming section that directly supplies the fuel for power generation in which water is mixed with methanol or the like directly to the fuel reforming section to generate hydrogen gas is used. It may be one that causes a quality reaction. In such a case, for example, as shown in FIG. 9B, a single fuel discharge section 142c and a fuel vaporization section 143d and 144, a configuration having a single flow path composed of the hydrogen gas exhaust unit 145 can be applied.
[0098]
Further, in the fuel reforming unit 140 shown in the above-described power supply system, a trace amount of carbon monoxide (CO) may be generated in addition to the reactions in the chemical reaction formulas (3) and (4). As shown in FIG. 8, a reaction section (aqueous shift reaction section 140b, selective oxidation reaction section 140c) for detoxifying generated carbon monoxide may be provided.
That is, as described above, the fuel reforming unit 140 of the power generation module 100 is supplied with the fuel composed of alcohol and water in the fuel pack 200 from the fuel control unit 120 and supplies the fuel (hydrogen (H) ₂ ) And by-product carbon dioxide (CO ₂ In addition, in addition to the steam reforming reaction section 140a that generates a trace amount of carbon monoxide (CO), the carbon monoxide (CO) supplied from the steam reforming reaction section 140a is used for the fuel control section 120 and / or power generation. Water (H ₂ O) and react with carbon dioxide (CO ₂ ) And hydrogen (H ₂ ) Is generated, and carbon monoxide (CO) remaining (not completely reacted) in the reaction in the aqueous shift reaction unit 140b is reacted with oxygen (O) to produce carbon dioxide (CO). ₂ ) Is provided with a carbon monoxide fuel reforming section composed of at least one of the selective oxidation reaction sections 140c, and hydrogen (H) obtained by reforming the fuel sealed in the fuel pack 200 is obtained. ₂ ) May be supplied to the power generation unit 110 and a small amount of carbon monoxide (CO) generated may be detoxified. In the example shown below, a configuration is shown in which the carbon monoxide fuel reforming unit has both the aqueous shift reaction unit 140b and the selective oxidation reaction unit 140c.
[0099]
Hereinafter, the relationship between each configuration of the fuel reforming unit 140 and the configuration illustrated in FIG. 9 will be described.
The steam reforming reaction section 140a of the fuel reforming section 140 is substantially the same as the structure shown in FIG. 9A, and the fuel vaporizing section 143a and the water vaporizing section 143b are formed, for example, of metal oxide, similarly to the thin film heater 146. A thin film layer made of a film or a metal nitride film is provided. Here, the thin film layer (thin film heater) is heated to a predetermined temperature by supplying the electric power controlled by the temperature control unit 150 through the wiring electrode, and methanol (CH) ₃ OH) and water (H ₂ O) is vaporized.
[0100]
Then, in the steam reforming reaction process, the vaporized methanol (CH ₃ OH) and water (H ₂ O), the thin film heater 146 sets an atmosphere under a temperature condition of about 300 ° C., thereby absorbing heat energy of about 49.4 kJ / mol, and as shown in the above chemical reaction formula (3). , Hydrogen (H ₂ ) And traces of carbon dioxide (CO ₂ ) Is generated. This carbon dioxide (CO ₂ ) Are selectively discharged to the outside of the power generation module 100. In this steam reforming reaction, hydrogen (H ₂ ) And carbon dioxide (CO ₂ ), A small amount of carbon monoxide (CO) may be generated as a by-product.
[0101]
Here, in order to remove carbon monoxide (CO) generated as a by-product in the steam reforming reaction process, an aqueous shift reaction unit 140b and a selective oxidation reaction unit 140c are provided downstream of the steam reforming reaction unit 140a. In addition, carbon monoxide (CO) is converted to carbon dioxide (CO 2) through respective processes including an aqueous shift reaction and a selective oxidation reaction. ₂ ) And hydrogen (H ₂ ) To suppress emission of harmful substances.
Specifically, the aqueous shift reaction section 140b is substantially the same as the structure shown in FIG. 9A, but the carbon monoxide remaining after reforming in the steam reforming reaction section 140a is replaced with the fuel discharge section 142a. Hydrogen gas (H) containing a trace amount of (CO) ₂ And a thin film layer made of a heating resistor such as a metal oxide film or a metal nitride film, similarly to the thin film heater 146.
[0102]
In the aqueous shift reaction process in the aqueous shift reaction section 140b, carbon monoxide (CO) is converted to water (steam; H). ₂ O) to generate heat energy of about 40.2 kJ / mol, and as shown in the following chemical reaction formula (5), carbon dioxide (CO) ₂ ) And hydrogen (H ₂ ) Is generated. The carbon dioxide generated at this time (CO ₂ ) Are selectively discharged to the outside of the power generation module 100.
CO + H ₂ O → CO ₂ + H ₂ ... (5)
[0103]
The selective oxidation reaction section 140c provided at the subsequent stage of the aqueous shift reaction section 140b converts carbon monoxide (CO) not reacted in the aqueous shift reaction section 140b into carbon dioxide (CO2). ₂ 9), the fuel vaporization unit 143a and the water vaporization unit 143b are omitted from the schematic diagram of FIG. 9 (a), and instead of the fuel discharge unit 142a and the water discharge unit 142b, the water shift reaction unit 140b is used. A discharge unit for discharging gas and a discharge unit for discharging air or oxygen (O) taken in from the outside of the power generation module 100 are provided, and, like the thin film heater 146, for example, a metal oxide film or a metal nitride film. A thin film layer made of a heating resistor such as a film is provided.
[0104]
In the selective oxidation reaction process, carbon dioxide (CO 2 ₂ ) And hydrogen (H ₂ ) To carbon monoxide (CO) not converted to oxygen (O ₂ ) To generate heat energy of about 283.5 kJ / mol, and as shown in the following chemical reaction formula (6), carbon dioxide (CO 2) ₂ ) Is generated.
CO + (1/2) O ₂ → CO ₂ ... (6)
The selective oxidation reaction section 140c may be provided between the steam reforming reaction section 140a and the aqueous shift reaction section 140b.
Hydrogen (H ₂ ) And other minor products (mainly carbon dioxide (CO ₂ )) Is discharged to the outside through a discharge hole provided in the power generation module 100.
[0105]
Next, the shapes of the power generation module 100 and the fuel pack 200 applied to the above-described power supply system, and a specific configuration example of the entire power supply system will be described with reference to the drawings.
FIGS. 10 (a) to 10 (d) and FIGS. 10 (e) to 10 (h) show a fuel pack and a holder (power generation module) of one embodiment applied to the above-described power supply system, respectively. FIG. 3 is a schematic configuration diagram showing an external shape viewed from a front direction, a lateral direction, and a rear direction. Here, for convenience of explanation, a specific configuration example (FIG. 11) of the power supply system to be described later will be appropriately referred to. FIG. 11 is a main configuration diagram showing a specific configuration example of the entire power supply system described above.
[0106]
As shown in FIGS. 10 (a) to 10 (d) and FIGS. 10 (e) to 10 (h), the power supply system according to the present embodiment has a fuel pack in which fuel for power generation is sealed under predetermined conditions. The fuel pack 200 includes a holder 400 that houses the power generation module 100 that is configured to be attachable and detachable.
Here, as shown in FIGS. 10A to 10D, the fuel pack 200 is, for example, a transparent decomposable polymer case for enclosing the fuel FL for power generation. The entire periphery of the case is covered with a package PK that protects against decomposition factors such as bacteria, and the package PK is peeled when the fuel pack 200 is mounted.
Further, the fuel pack 200 is formed of a transparent case, and has a configuration in which an index (scale) 203 is provided at an appropriate position on a side surface thereof, as shown in FIG. The amount (remaining amount) of the power generation fuel FL remaining in the fuel pack 200 can be visually confirmed.
[0107]
As shown in FIGS. 10 (e) to 10 (h), the holder unit 400 roughly stores the power generation module 100 having the same configuration as that of the above-described application example, and is provided with the positive electrode terminal EL (+). The power generating function unit 401, the facing unit 402 provided with the negative electrode terminal EL (-), the power generating function unit 401 and the facing unit 402 are connected, and the power generating function unit 401 and the negative terminal EL (-) are electrically connected. And a connecting portion 403 for connection. Here, the penetrated space SP surrounded by the power generation function unit 401, the facing unit 402, and the connecting unit 403 is a storage position when the fuel pack 200 is connected (see FIGS. 10E and 10G). .
[0108]
Further, the holder portion 400 has elasticity such as a spring material around a contact portion of the facing portion 402 with which the bottom portion 202 of the fuel pack 200 contacts with the fuel pack 200 mounted and stored in the space SP, A projection 404 having a hole at the center and a by-product recovery path 405 connecting the hole of the projection 404 and the by-product supply path 104 (see FIG. 11) of the power generation module 100 are provided. As shown in FIG. 10 (e), the connecting portion 403 of the holder 400 may be provided instead of the index 203 of the fuel pack 200 shown in FIG. A configuration in which the index 406 is engraved may be applied. Thus, when the fuel pack 200 is coupled to the holder section 400, the remaining amount of the power generation fuel FL can be visually and simply and accurately confirmed. In this case, when the connecting portion 403 is opaque, the indicator 406 is more easily visually recognized.
[0109]
The power generation module 100 (power generation function unit 401) having such a configuration is, more specifically, as shown in FIG. 11, a power generation unit 110 extending substantially along a circumferential surface of a columnar shape. A water vapor reformer in which a fuel flow channel having a depth and a width of 500 μm or less and an individual thin film heater (not shown) for setting a space in the flow channel to a predetermined temperature is formed inside the cylindrical power generation module 100. Quality reaction section (steam reforming reaction furnace) 140a, aqueous shift reaction section (aqueous shift reaction furnace) 140b, selective oxidation reaction section (selective oxidation reaction furnace) 140c, and housed in microchip form inside power generation function section 401 And a plurality of ventilation holes (slits) 130a that penetrate from the cylindrical side surface of the power generation module 100 to the air electrode of the power generation unit 110 and take in external air. The separation and recovery unit 102 that liquefies (condenses) by-products (water and the like) generated on the air electrode side and separates and recovers them, and supplies a part of the recovered by-products to the steam reforming reaction unit 140a. The by-product supply path 104 penetrates from the upper surface of the cylinder to the fuel electrode of the power generation unit 110, and at least the fuel electrode side of the power generation unit 110, the steam reforming reaction unit 140a, the aqueous shift reaction unit 140b, and the selective oxidation reaction unit 140c. , A discharge hole 106 for discharging a by-product (such as carbon dioxide) as a non-recovered substance to the outside of the power generation function unit 401, and a sub-power supply unit 170 (not shown). .
[0110]
The steam reforming reaction section 140a and the aqueous shift reaction section 140b generate water required for the reaction by the power generation section 110 and supplied through the by-product supply path 104, and the power generation in the fuel pack 200. At least one of the water contained in the fuel for use FL is used.
Further, the fuel pack 200 includes a fuel filling part 210 (see FIG. 8) in which the power generation fuel FL supplied to the power generation part 110 is filled and filled, and a by-product (water) collected by the separation and collection part 102. And a fuel supply valve 201a provided at a portion connected to the power generation module 100 to prevent the fuel FL for power generation from leaking. And a by-product intake valve 204 (see FIG. 10A) for preventing leakage of the product (recovered material).
[0111]
In the power supply system having such a configuration, when the fuel pack 200 from which the package PK has been peeled is mounted and stored in the space SP1 of the holder unit 400, the fuel delivery pipe 406 serving as a fuel delivery path is connected to the fuel pack 200 as shown in FIG. The fuel supply valve 201a is engaged with the fuel delivery port 201 of the fuel pack 200, and the fuel supply valve 201a, which is formed in the fuel delivery port 201 and whose posture is forced in the closing direction by an elastic mechanism such as a spring, is pushed down, and the fuel pack 200 The leak prevention function is released. As a result, the fuel FL for power generation sealed in the fuel sealing portion 210 of the fuel pack 200 is automatically drawn up and conveyed by the surface tension in the capillary tube 201b and the fuel delivery tube 406 and supplied to the power generation module 100. When the fuel pack 200 is removed from the holder 403, the fuel supply valve 201a returns to the original closed state by the restoring force of an elastic mechanism such as a spring, so that the fuel FL for power generation sealed inside does not leak.
[0112]
Then, of the by-products generated together with the power by the power generation operation in the power generation module 100 as described above, water (H ₂ O) is a by-product recovery path 405 provided in the connecting portion 403, a hole of the convex portion 404 provided in the facing portion 402, and a recovery hole (by-product intake valve) provided in the bottom 202 of the fuel pack 200. 204), is collected and held by the by-product collection unit 220 in the fuel pack 200. Therefore, inside the fuel pack 200, the fuel filling section 210 and the by-product collecting section 220 are provided, for example, separated from each other via a partition wall film or the like, and according to a change in both capacities, The partition wall film or the like is configured to relatively deform or move.
[0113]
As a result, as shown in FIG. 8, hydrogen gas is generated in the fuel reforming unit 140 from the fuel FL for power generation supplied to the power generation module 100, and predetermined power is generated in the power generation unit 110 to charge the charging unit. Operating power is constantly supplied to the fuel control unit 120, the temperature control unit 150, and the operation control unit 180 by the sub-power supply unit 170 which is supplied and charged (stored) in the charging unit 160 and charged by the charge stored in the charging unit 160. Is done. In addition, by connecting a predetermined device DVC to the power supply system according to the present embodiment, part of the power output from the charging unit 160 or the power generation unit 110 is converted to a positive electrode terminal EL ( The power is supplied as drive power to the controller CNT and the load LD incorporated in the device DVC via (+) and the negative electrode terminal EL (−) provided in the facing unit 402.
[0114]
Here, as shown in FIG. 10 (g), the power supply system is in a state in which the fuel pack 200 is housed in the space SP and is coupled to the holder unit 400 (overall configuration including the fuel pack 200 indicated by a two-dot chain line). For example, it can be configured to have an outer shape and dimensions substantially equivalent to general-purpose chemical batteries (primary batteries or secondary batteries) marketed in Japan. At this time, with the fuel pack 200 normally stored in the space SP, the fuel outlet 201 of the fuel pack 200 satisfactorily engages with the fuel delivery path (fuel delivery pipe 406) on the power generation function unit 401 side. In addition, in order to prevent the fuel pack 200 from being accidentally dropped from the holder section 400, it is preferable that the bottom section 202 of the fuel pack 200 is pressed by the facing section 402 with an appropriate pressure.
[0115]
Therefore, the power supply system according to the present embodiment can be easily handled similarly to a general-purpose chemical battery, and is configured to have the same or equivalent outer shape (here, a cylindrical shape) and dimensions as a general-purpose chemical battery. In addition, by controlling the power generation state so as to supply power having the same or equivalent electrical characteristics, it is possible to realize a power supply system that is extremely compatible with general-purpose chemical batteries, and can be used with existing portable devices and the like. As a power source for the device.
The application examples and specific configuration examples of the power supply system described above are merely examples of the power supply system in which the chemical reaction device (microreactor) according to the present invention is applied to the fuel reforming section, and the present invention relates to the present invention. It goes without saying that the application of the chemical reaction device is not limited to this mode.
[0116]
【The invention's effect】
As described above, according to the chemical reaction device and the method of manufacturing the same according to the present invention, in a microreactor that generates a desired substance by generating a predetermined chemical reaction in a reaction channel formed in a minute space, A thin film heater for supplying a predetermined amount of heat to the reaction channel to promote or control the chemical reaction, a wiring electrode having a laminated structure for supplying power to the thin film heater to generate a predetermined amount of heat, and at least a heater A protective film that is formed on the thin film heater other than the wiring forming region and protects the thin film heater from etching damage, wherein the protective film is formed in the same layer as the lowermost electrode layer of the wiring electrode. Integrally formed of a conductive material having a high etching resistance when patterning at least an electrode layer to be an upper layer of the wiring electrode, and After the above-mentioned patterning, since it is constituted by an insulating thin film formed by a thermal oxidation treatment, when forming a wiring electrode having a laminated structure on a conductive layer to be the above-mentioned protective film, under different conditions. Even if various etching processes are performed, it is possible to suppress deterioration of pattern accuracy and electrical characteristics of wiring electrodes while suppressing etching damage to the film quality of a thin film heater without strictly setting etching conditions. Can be.
[0117]
In addition, after patterning the wiring electrode, the conductive layer that has become the etching barrier by thermal oxidation can be easily changed to an insulating protective film, and the wiring electrode portion is not oxidized as a good conductor. Is maintained as it is, so that the thin-film heater can be covered and protected well, and a wiring electrode exposed from the protective film and having good electric characteristics can be realized.
[0118]
Therefore, in the patterning step of the wiring electrode, restrictions on the etching conditions, process control, pattern accuracy, and the like are relaxed, and good film quality, pattern accuracy, and electrical connection can be realized by a simple manufacturing method and a simple manufacturing apparatus. Since a microreactor can be provided, the reliability can be improved while suppressing the manufacturing cost of a power supply system in which such a microreactor is applied to a fuel reformer or the like. Further, when other peripheral members are joined to a specific surface of the microreactor, or when a plurality of microreactors are stacked, electrical connection can be made in the vertical direction (stacking direction). In addition, it is possible to improve the degree of freedom in designing the power supply system, reduce the size of the device, and apply the device to a desired external shape.
[Brief description of the drawings]
FIG. 1 is a schematic configuration diagram showing one embodiment of a chemical reaction device according to the present invention.
FIG. 2 is a cross-sectional view of a main part showing a laminated structure of the chemical reaction device according to the embodiment.
FIG. 3 is a manufacturing process diagram showing the entire manufacturing method of the chemical reaction device according to the present invention.
FIG. 4 is a manufacturing process diagram (part 1) illustrating an example of a specific manufacturing method of a wiring electrode portion applied to the chemical reaction device according to the embodiment.
FIG. 5 is a manufacturing process diagram (part 2) illustrating an example of a specific manufacturing method of a wiring electrode portion applied to the chemical reaction device according to the embodiment.
FIG. 6 is a manufacturing process diagram showing another example of a specific method for manufacturing a wiring electrode portion applied to the chemical reaction device according to the present embodiment.
FIG. 7 is a schematic configuration diagram showing another embodiment of the chemical reaction device according to the present invention.
FIG. 8 is a block diagram showing a main configuration of a power supply system (fuel cell system) to which the chemical reaction device according to the present invention can be applied, and devices driven by the power supply system.
FIG. 9 is a schematic configuration diagram showing a specific example of a fuel reforming section to which the configuration of the chemical reaction device according to the present invention is applied.
FIG. 10 is a schematic configuration diagram showing an outer shape of a fuel pack and a holder unit (power generation module) according to an embodiment applied to the power supply system described above.
FIG. 11 is a main part configuration diagram showing a specific configuration example of the entire power supply system described above.
FIG. 12 is a diagram showing a schematic configuration of a chemical reaction device (reaction flow channel part of a microreactor) in a conventional technique.
FIG. 13 is a cross-sectional view of a main part showing a thin-film heater and a wiring electrode applied to a chemical reaction device (microreactor) in a conventional technique.
FIG. 14 is a manufacturing process diagram (part 1) illustrating an example of a method for manufacturing a heater wiring applied to a chemical reaction apparatus according to the related art.
FIG. 15 is a manufacturing process diagram (part 2) illustrating an example of a method for manufacturing a heater wiring applied to a chemical reaction device according to the related art.
[Explanation of symbols]
10 Main board
20 Reaction channel
30 Closed board
40 Thin film heater
50 wiring electrodes
51 Lower electrode layer
52 Intermediate electrode layer
53 Upper electrode layer
60 Protective film

Claims (23)

In a chemical reaction device having a reaction channel formed at least continuously, and generating a chemical reaction for converting a first fluid substance into a second fluid substance in the reaction channel,
At least, a temperature adjustment layer formed corresponding to a region including the reaction channel and supplying a predetermined amount of heat to the reaction channel,
A first electrode layer laminated on a first region on the temperature adjustment layer;
At least an insulating layer formed on the temperature adjustment layer and stacked in a second region other than the first region;
A second electrode layer that is formed on the first electrode layer and that supplies power for generating the predetermined amount of heat in the temperature adjustment layer via the first electrode layer;
With
The chemical reaction device according to claim 1, wherein the insulating layer is made of an insulating material obtained by oxidizing a conductive material in the same layer as the first electrode layer. 2. The chemical reaction device according to claim 1, wherein the insulating layer is made of a material having high resistance to an etching process when patterning the second electrode layer. 3. 2. The chemical reaction device according to claim 1, wherein the second electrode layer is made of a material having high resistance to an oxidizing process when forming the insulating layer. 3. 4. The chemical reaction device according to claim 1, wherein the second electrode layer has a laminated structure including a plurality of conductive layers. 5. The temperature adjustment layer is a heating resistor made of a metal oxide film or a metal nitride film,
The chemical reaction device according to claim 4, wherein the second electrode layer has at least a conductive layer constituting an upper layer of the second electrode layer non-adhesive to the temperature adjustment layer. The chemical reaction apparatus according to claim 5, wherein the temperature adjustment layer is made of a material containing each element of tantalum, silicon, oxygen, and nitrogen at a predetermined composition ratio. The conductive layer constituting the upper layer of the second electrode layer is made of a material selected from gold and an alloy containing gold,
The conductive layer constituting the lower surface of the second electrode layer is made of a material selected from tungsten, molybdenum, tantalum, an alloy containing tungsten, an alloy containing molybdenum, and an alloy containing tantalum. The chemical reaction device according to any one of claims 4 to 6, wherein The first electrode layer is made of a material selected from yttrium, an alloy containing yttrium, aluminum, and an alloy containing aluminum,
The chemical reaction device according to any one of claims 1 to 7, wherein the insulating layer is made of a material selected from yttrium oxide and aluminum oxide. In the reaction channel, a groove having a predetermined channel shape is formed on one surface of a first substrate, and one surface of a second substrate is joined to one surface of the first substrate to open the groove. The chemical reaction device according to any one of claims 1 to 8, wherein the end is closed. The chemical reaction device according to claim 9, wherein the temperature adjustment layer, the first electrode layer, the second electrode layer, and the insulating layer are formed on the other surface of the first substrate. . The chemical reaction device according to claim 9, wherein the temperature adjustment layer, the first electrode layer, the second electrode layer, and the insulating layer are formed on the other surface of the second substrate. . The chemical reaction device is characterized in that at least the first substrate and the second substrate are formed of minute substrates, and the reaction channel is formed to have a micronized channel shape. The chemical reaction device according to any one of claims 9 to 11, wherein 2. The chemical reaction apparatus according to claim 1, wherein the reaction channel has a plurality of reaction regions in which the reaction channels are individually formed, and each of the reaction regions generates a different chemical reaction. 13. The chemical reaction device according to any one of claims to 12. In the chemical reaction device, a predetermined catalyst layer is provided in at least a part of the reaction channel, and based on a predetermined amount of heat supplied from the temperature adjustment layer to the catalyst layer, the chemical reaction involving heat absorption or heat generation. 14. The chemical reaction device according to claim 1, wherein the second fluid material is generated from the first fluid material by causing a reaction. The first fluid substance is a mixed gas containing an alcohol-based gaseous fuel and oxygen, and the second fluid substance is a hydrogen gas,
The chemical reaction device generates the second fluid material from the first fluid material by causing a steam reforming reaction in the reaction channel based on at least the amount of heat supplied from the temperature adjustment layer. The chemical reaction device according to any one of claims 1 to 14, wherein: The first fluid substance is an alcohol-based liquid fuel or water, and the second fluid substance is a fuel gas or water vapor of the first fluid substance,
The chemical reaction device generates the second fluid material from the first fluid material by causing a vaporization reaction in the reaction channel based on at least the amount of heat supplied from the temperature adjustment layer. The chemical reaction device according to claim 1, wherein: The first fluid material is a mixed gas containing carbon monoxide gas and oxygen, and the second fluid material is hydrogen gas and carbon dioxide gas,
The chemical reaction device is configured to generate an aqueous shift reaction and a selective oxidation reaction in the reaction channel based on at least the amount of heat supplied from the temperature adjustment layer, so that the second fluid is removed from the first fluid substance. The chemical reaction device according to any one of claims 1 to 14, wherein the chemical reaction device generates a substance. A method for manufacturing a chemical reaction device having a reaction channel formed at least continuously and generating a chemical reaction for converting a first fluid substance into a second fluid substance in the reaction channel,
Forming a temperature adjustment layer that supplies a predetermined amount of heat to the reaction channel, corresponding to at least the region including the reaction channel;
A step of forming a first conductive layer made of a conductive material to be insulated by an oxidation treatment, at least on the temperature adjustment layer;
Forming a second conductive layer made of a conductive material having high resistance to oxidation treatment on the first conductive layer;
Forming, on the second conductive layer, a third conductive layer made of a conductive material having high resistance to oxidation treatment and having non-adhesiveness to the temperature adjustment layer;
The third conductive layer and the second conductive layer are continuously etched using a single etching resist to form an electrode layer having a predetermined pattern, and the electrode layer in a region other than the pattern of the electrode layer. Exposing the first conductive layer;
Oxidizing the exposed first conductive layer to form an insulating layer between the electrode layers;
A method for producing a chemical reaction device, comprising: The temperature adjustment layer is a heating resistor made of a metal oxide film or a metal nitride film,
The second conductive layer is made of a material selected from tungsten, molybdenum, tantalum, an alloy containing tungsten, an alloy containing molybdenum, and an alloy containing tantalum,
19. The method according to claim 18, wherein the third conductive layer is made of a material selected from gold and an alloy containing gold. 20. The method according to claim 19, wherein the temperature adjustment layer is made of a material containing each element of tantalum, silicon, oxygen, and nitrogen at a predetermined composition ratio. 21. The method according to claim 18, wherein the first conductive layer is made of a material selected from yttrium, an alloy containing yttrium, aluminum, and an alloy containing aluminum. Manufacturing method of chemical reaction equipment. 22. The method according to claim 18, wherein the step of etching the third conductive layer and the second conductive layer uses a helicon etching method. At least, a reaction channel formed continuously, a temperature adjustment layer formed to correspond to a region including the reaction channel, and supplying a predetermined amount of heat to the reaction channel, and a temperature adjustment layer on the temperature adjustment layer. A first electrode layer laminated on the first region, and a first electrode layer laminated on the temperature adjustment layer in a second region other than the first region, and integrally formed with the first electrode layer; An insulating layer made of an insulating material obtained by oxidizing a conductive material of a layer, and an insulating layer formed on the first electrode layer, and the predetermined amount of heat is applied to the temperature adjustment layer via the first electrode layer. A second electrode layer for supplying electric power for generation of the alcohol-based liquid, by generating a steam reforming reaction in the reaction channel based on at least the amount of heat supplied from the temperature adjustment layer. Gas mixture containing gaseous fuel and oxygen into hydrogen gas And Manabu reactor,
A fuel cell that generates power by reacting hydrogen and oxygen generated by the chemical reaction device,
A fuel cell system comprising:

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