JP2014133920A - Method of producing joint body and oven - Google Patents

Method of producing joint body and oven Download PDF

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Publication number
JP2014133920A
JP2014133920A JP2013002258A JP2013002258A JP2014133920A JP 2014133920 A JP2014133920 A JP 2014133920A JP 2013002258 A JP2013002258 A JP 2013002258A JP 2013002258 A JP2013002258 A JP 2013002258A JP 2014133920 A JP2014133920 A JP 2014133920A
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Japan
Prior art keywords
metal
mixed gas
conductor
heat treatment
partial pressure
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JP2013002258A
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Japanese (ja)
Inventor
Naoki Higuchi
直貴 樋口
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Ibiden Co Ltd
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Ibiden Co Ltd
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Application filed by Ibiden Co Ltd filed Critical Ibiden Co Ltd
Priority to JP2013002258A priority Critical patent/JP2014133920A/en
Priority to PCT/JP2013/082855 priority patent/WO2014109154A1/en
Publication of JP2014133920A publication Critical patent/JP2014133920A/en
Pending legal-status Critical Current

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    • H—ELECTRICITY
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    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
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    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
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Abstract

PROBLEM TO BE SOLVED: To provide a method of producing a joint body which can improve the joining strength of the joint body obtained even when the temperature for heat treatment is relatively low and an oven suitable for the method.SOLUTION: A method of producing a joint body includes a joining step of bringing a metal-made conductor in contact with a joining material containing a joining metal and an organic material and sintering the joining material by a heat treatment. The heat treatment is carried out in a mixed gas comprising at least two gases having different numbers of bonds of O. The mixed gas has a component ratio which meets the conditions (1) and (2) at the temperature for the heat treatment. (1) Producing an oxygen partial pressure equal to or higher than the equilibrium oxygen partial pressure at which carbon and oxygen coexist. (2) Producing an oxygen partial pressure equal to or lower than the equilibrium oxygen partial pressure at which the metal oxide having the smallest standard free energy of formation, among metal oxides of metals constituting the conductor, and the metals constitute the conductor can coexist. An oven capable of supplying the mixed gas is also provided.

Description

本発明は、接合体の製造方法およびオーブンに関する。   The present invention relates to a method for manufacturing a joined body and an oven.

従来、各種スイッチング素子等のパワー半導体素子の接合に代表されるように、大電流が流れ、それによる発熱が懸念される部位を接合するための接合材料として、銀ペーストが多く用いられている。   Conventionally, as represented by bonding of power semiconductor elements such as various switching elements, a silver paste is often used as a bonding material for bonding portions where a large current flows and heat generation is a concern.

例えば、特許文献１には、絶縁基板の導体パターン上に銀微粒子と有機バインダーとを含む銀ペーストを塗布し、この上にパワー半導体素子を載置した後、酸素濃度が１００〜５００ｐｐｍ程度の雰囲気下にて前記銀ペーストを焼結させて接合体を形成する技術が開示されている。   For example, in Patent Document 1, after applying a silver paste containing silver fine particles and an organic binder on a conductor pattern of an insulating substrate and placing a power semiconductor element thereon, an atmosphere having an oxygen concentration of about 100 to 500 ppm is disclosed. A technique for forming a joined body by sintering the silver paste is disclosed below.

特開２００６−３５２０８０号公報JP 2006-352080 A

しかしながら、従来知られる接合体の製造方法は、以下の点で問題がある。すなわち、前記接合材料中には、通常、有機バインダー等の有機物が含まれている。接合材料の熱処理後、焼結による接合体中に有機物の炭化物が残留すると、その部分の金属間結合が妨げられたことにより、接合体の接合強度が低下する。そのため、熱処理時の雰囲気を酸化雰囲気とすることにより有機物の酸化を促し、炭化物の発生を抑制するのが通常である。   However, the conventionally known methods for manufacturing a joined body have the following problems. That is, the bonding material usually contains an organic substance such as an organic binder. After the heat treatment of the bonding material, if organic carbides remain in the sintered bonded body, the bonding strength of the bonded body is lowered due to the intermetallic bond being hindered. Therefore, it is usual to promote the oxidation of organic substances by suppressing the generation of carbides by setting the atmosphere during heat treatment to an oxidizing atmosphere.

しかし、酸化雰囲気中で接合材料の熱処理を行った場合、配線基板の配線パターン等の金属からなる導体表面が酸化され、酸化膜が形成される。導体表面に形成された酸化膜は、接合性を低下させるため、やはり得られる接合体の接合強度が低下する。前記酸化膜の形成を防ぐため熱処理時の雰囲気を還元雰囲気とすると、前記有機物の炭化が促進されてしまい、前記炭化物による接合強度の低下を招く。   However, when the bonding material is heat-treated in an oxidizing atmosphere, the conductor surface made of metal such as the wiring pattern of the wiring board is oxidized, and an oxide film is formed. Since the oxide film formed on the conductor surface lowers the bonding property, the bonding strength of the obtained bonded body also decreases. If the atmosphere during the heat treatment is a reducing atmosphere in order to prevent the formation of the oxide film, the carbonization of the organic matter is promoted, resulting in a decrease in bonding strength due to the carbide.

このように熱処理時の雰囲気を酸化雰囲気、還元雰囲気のいずれを主として調整しても、得られる接合体の接合強度が低下するという問題がある。   As described above, there is a problem that the bonding strength of the obtained bonded body is lowered even if the atmosphere at the time of heat treatment is mainly adjusted to either the oxidizing atmosphere or the reducing atmosphere.

なお、接合材料中の接合用金属を高温にて溶融させて接合を行えば、高い接合強度を有する接合体が得られるとの考え方もある。しかしながら、電子部品の実装等の分野に代表されるように、接合体が必要となる多くの分野では、高温による基材等の劣化を避けるため、できる限り被接合物を高温に曝したくないという事情がある。また、３００℃以下の低温で完全に溶融する接合用金属は、近年使用が控えられているＰｂ程度しかなく、金属の焼結体からなる接合体によって接合強度を向上させるほかないのが実情である。   There is also an idea that a bonded body having high bonding strength can be obtained by performing bonding by melting a bonding metal in a bonding material at a high temperature. However, as represented by the field of electronic component mounting and the like, in many fields where a joined body is required, it is said that the object to be joined should not be exposed to a high temperature as much as possible in order to avoid deterioration of the substrate due to a high temperature. There are circumstances. In addition, the bonding metal that completely melts at a low temperature of 300 ° C. or less is only about Pb, which has been refrained from being used in recent years, and there is no other choice but to improve the bonding strength with a bonded body made of a sintered metal. is there.

本発明は、上述した背景に鑑みてなされたものであり、熱処理時の温度が比較的低くても、得られる接合体の接合強度を向上可能な接合体の製造方法、またこれに適したオーブンを提供しようとして得られたものである。   The present invention has been made in view of the above-described background, and a method for manufacturing a joined body capable of improving the joining strength of the obtained joined body even when the temperature during heat treatment is relatively low, and an oven suitable for the method. It was obtained by trying to provide.

本発明の接合体の製造方法は、金属より形成された導体と、接合用金属と有機物とを含む接合材料とを接触状態とした後、熱処理することにより、前記接合用金属を焼結させる接合工程を有しており、
前記熱処理は、Ｏ（酸素）の結合数が異なる少なくとも２種以上のガスが混合されてなる混合ガス中にて実施され、
前記混合ガスは、前記熱処理時の温度において以下の（１）および（２）の条件を満たす成分比であることを特徴とする（請求項１）。
（１）炭素と酸素とが共存する平衡酸素分圧以上の酸素分圧を生成する
（２）前記導体を形成する金属の金属酸化物のうち、最も標準生成自由エネルギーの小さい金属酸化物と、前記導体を形成する金属とが共存できるような平衡酸素分圧以下の酸素分圧を生成する The method for producing a joined body according to the present invention is a joining method in which a conductor formed from a metal and a joining material containing a joining metal and an organic substance are brought into contact with each other and then heat-treated to sinter the joining metal. Has a process,
The heat treatment is performed in a mixed gas in which at least two kinds of gases having different O (oxygen) bond numbers are mixed,
The mixed gas has a component ratio that satisfies the following conditions (1) and (2) at the temperature during the heat treatment (Claim 1).
(1) Generate an oxygen partial pressure equal to or higher than the equilibrium oxygen partial pressure in which carbon and oxygen coexist. (2) Among the metal oxides of the metal forming the conductor, a metal oxide having the smallest standard free energy of formation; Generates an oxygen partial pressure equal to or lower than the equilibrium oxygen partial pressure so that the metal forming the conductor can coexist.

本発明のオーブンは、金属より形成された導体と、接合用金属と有機物とを含む接合材料とを接触状態とした後、熱処理することにより、前記接合用金属を焼結させる接合工程を有する接合体の製造方法に用いられるオーブンであって、
Ｏ（酸素）の結合数が異なる少なくとも２種以上のガスが混合されてなる混合ガスを供給可能に構成されており、
前記混合ガスは、前記熱処理時の温度において以下の（１）および（２）の条件を満たす成分比であることを特徴とする（請求項１０）。
（１）炭素と酸素とが共存する平衡酸素分圧以上の酸素分圧を生成する
（２）前記導体を形成する金属の金属酸化物のうち、最も標準生成自由エネルギーの小さい金属酸化物と、前記導体を形成する金属とが共存できるような平衡酸素分圧以下の酸素分圧を生成する The oven according to the present invention includes a bonding step in which a conductor formed from a metal and a bonding material containing a bonding metal and an organic substance are brought into contact with each other and then heat-treated to sinter the bonding metal. An oven used in a body manufacturing method,
It is configured to be able to supply a mixed gas in which at least two kinds of gases having different O (oxygen) bond numbers are mixed,
The mixed gas has a component ratio satisfying the following conditions (1) and (2) at the temperature during the heat treatment (claim 10).
(1) Generate an oxygen partial pressure equal to or higher than the equilibrium oxygen partial pressure in which carbon and oxygen coexist. (2) Among the metal oxides of the metal forming the conductor, a metal oxide having the smallest standard free energy of formation; Generates an oxygen partial pressure equal to or lower than the equilibrium oxygen partial pressure so that the metal forming the conductor can coexist.

前記接合体の製造方法は、前記構成を有している。そのため、前記接合体の製造方法は、接合材料の熱処理時に、雰囲気中の酸素分圧が、炭素と酸素とが共存する平衡酸素分圧以上となる。そのため、接合材料中に含まれる有機物の酸化（燃焼）を促すことができ、接合体中の炭化物の残留を抑制することができる。また、前記接合体の製造方法は、接合材料の熱処理時に、雰囲気中の酸素分圧が、導体を形成する金属の金属酸化物のうち、最も標準生成自由エネルギーの小さい金属酸化物と、導体を形成する金属とが共存できるような平衡酸素分圧以下となる。そのため、導体表面の酸化を抑制することができ、接合性を向上させることができる。このように、前記接合体の製造方法は、接合材料の熱処理時の温度が比較的低い温度であっても、接合用金属の焼結時に炭化物および酸化膜を関与させないようにすることができるので、得られる接合体の接合強度を向上させることが可能となる。   The manufacturing method of the joined body has the above configuration. Therefore, in the method for manufacturing the joined body, the oxygen partial pressure in the atmosphere is equal to or higher than the equilibrium oxygen partial pressure in which carbon and oxygen coexist during the heat treatment of the joining material. Therefore, the oxidation (combustion) of the organic substance contained in the bonding material can be promoted, and the residual carbide in the bonded body can be suppressed. Further, in the method for manufacturing the joined body, during the heat treatment of the joining material, the oxygen partial pressure in the atmosphere is a metal oxide having the smallest standard free energy of formation among the metal oxides of the metal forming the conductor, and the conductor. The equilibrium oxygen partial pressure or less is such that the metal to be formed can coexist. Therefore, the oxidation of the conductor surface can be suppressed and the bondability can be improved. As described above, the manufacturing method of the joined body can prevent the carbide and the oxide film from being involved in the sintering of the joining metal even when the temperature during the heat treatment of the joining material is relatively low. Thus, it is possible to improve the bonding strength of the obtained bonded body.

一方、前記オーブンは、前記構成を有している。そのため、前記接合体の製造方法に好適に用いることができる。   On the other hand, the oven has the above configuration. Therefore, it can use suitably for the manufacturing method of the said joined_body | zygote.

以上、本発明によれば、熱処理時の温度が比較的低くても、得られる接合体の接合強度を向上可能な接合体の製造方法、これに適したオーブンを提供することができる。   As mentioned above, according to this invention, even if the temperature at the time of heat processing is comparatively low, the manufacturing method of the joined body which can improve the joining strength of the joined body obtained, and an oven suitable for this can be provided.

実施例にて作製した接合体試料を模式的に示した説明図である。It is explanatory drawing which showed typically the conjugate | zygote sample produced in the Example. 実施例における、熱処理条件が異なる接合体試料の熱処理時の最高温度と接合強度との関係を示した図である。It is the figure which showed the relationship between the highest temperature at the time of the heat processing of the joined body sample from which the heat processing conditions differ in an Example, and joining strength. 実施例にて作製した接合体試料１の断面ＳＥＭ写真である。It is a cross-sectional SEM photograph of the conjugate | zygote sample 1 produced in the Example.

本明細書中、「ｌｏｇ」とは、１０を底とする対数(常用対数)を示す。また、本明細書中、「成分比」は、混合ガスの「成分比」(モル比)を示している。気体のみの関与する成分比であるので、混合ガスの「分圧」と同義である。先ず、本発明の接合体の製造方法の実施形態について説明する。   In this specification, “log” indicates a logarithm with 10 as the base (common logarithm). In the present specification, “component ratio” indicates “component ratio” (molar ratio) of the mixed gas. Since it is a component ratio involving only gas, it is synonymous with “partial pressure” of the mixed gas. First, an embodiment of a method for producing a joined body according to the present invention will be described.

本発明の接合体の製造方法は、金属より形成された導体を接合するための接合体を製造するのに適用される。本発明の接合体の製造方法は、具体的には、例えば、パワーデバイス等の電子部品の実装に用いられる接合体を得るのに好適である。この場合は、熱処理時の温度が比較的低くても、得られる接合体の接合強度を向上させることができるので、実装部品および基板の劣化を抑制しつつ、接合信頼性の高い実装を実施するのに寄与することができる。   The method for producing a joined body of the present invention is applied to produce a joined body for joining conductors formed of metal. Specifically, the method for producing a joined body of the present invention is suitable for obtaining a joined body used for mounting an electronic component such as a power device. In this case, even if the temperature during heat treatment is relatively low, the bonding strength of the obtained bonded body can be improved, so that mounting with high bonding reliability is performed while suppressing deterioration of the mounted components and the substrate. Can contribute.

本発明の接合体の製造方法において、前記接合体は、具体的には、一方の導体と他方の導体との間に介在し、両導体間を接合することができる。接合体は、接合強度向上の観点から、内部に含まれる孔が少ない程好ましいが、孔を完全になくすことは製造コストの上昇等を招くことがある。そのため、接合体は、本発明の趣旨を逸脱しない範囲内で孔を含むことができる。なお、接合体の形状は、特に限定されるものではなく、例えば、層状、フィレット状等の形状を適宜選択することができる。   In the method for producing a joined body of the present invention, the joined body can be interposed between one conductor and the other conductor, and can join the two conductors. From the viewpoint of improving the bonding strength, it is preferable that the bonded body has fewer holes contained therein. However, completely eliminating the holes may cause an increase in manufacturing cost. Therefore, the joined body can include a hole within a range not departing from the gist of the present invention. In addition, the shape of a joined body is not specifically limited, For example, shapes, such as a layer shape and a fillet shape, can be selected suitably.

本発明の接合体の製造方法において、前記導体を形成する金属は、接合面を有することができる。この場合は、接合用金属との接合強度を向上させるのに有利である。導体としては、具体的には、例えば、金属からなる配線パターンを有する配線基板における配線パターン、チップ等の半導体素子が有する電極、リードフレーム等の導体、チップ等の半導体素子に給電するための給電基板等の基板が有する導体などを例示することができる。導体の形状は特に限定されるものではなく、具体的には、例えば、平面状、ピン状（略円柱状等）、略半球状、略球状などの形状とすることができる。   In the method for manufacturing a joined body of the present invention, the metal forming the conductor can have a joined surface. In this case, it is advantageous for improving the bonding strength with the bonding metal. Specific examples of the conductor include, for example, a wiring pattern in a wiring board having a wiring pattern made of metal, an electrode of a semiconductor element such as a chip, a conductor such as a lead frame, and a power supply for supplying power to a semiconductor element such as a chip. The conductor etc. which board | substrates, such as a board | substrate, have can be illustrated. The shape of the conductor is not particularly limited, and specifically, for example, it may be a flat shape, a pin shape (substantially cylindrical shape, etc.), a substantially hemispherical shape, a substantially spherical shape, or the like.

本発明の接合体の製造方法において、前記導体を形成する金属としては、具体的には、例えば、銅、スズ、ニッケルなどを例示することができる。これらのうち、導体を形成する金属としては、銅または銅合金を好適に用いることができる（請求項３）。   In the method for producing a joined body of the present invention, specific examples of the metal forming the conductor include copper, tin, and nickel. Of these, copper or a copper alloy can be suitably used as the metal forming the conductor.

銅または銅合金は高い電気伝導度を有しているので、電気導体として優れる。しかしながら、銅または銅合金であっても、従来のような酸化雰囲気中で焼成を行うと酸素との反応により酸化銅の被膜を形成しやすい。この被膜は接合性を低下させる上、電気抵抗となる。導体を形成する金属として銅または銅合金を用いた場合には、銅または銅合金の優れた電気特性を発揮させやすく、高い接合強度を有し、低電気抵抗の接合体を得やすくなる利点がある。   Since copper or copper alloy has a high electric conductivity, it is excellent as an electric conductor. However, even if copper or a copper alloy is used, it is easy to form a copper oxide film by reaction with oxygen when firing in an oxidizing atmosphere as in the prior art. This film lowers the bondability and also provides electrical resistance. When copper or copper alloy is used as the metal forming the conductor, it is easy to exhibit the excellent electrical characteristics of copper or copper alloy, and has the advantage that it is easy to obtain a bonded body having high bonding strength and low electrical resistance. is there.

本発明の接合体の製造方法において、前記接合材料は、接合用金属と有機物とを含んでいる。接合材料は、例えば、ペースト、溶液などに調製されることができる。接合材料中において、接合用金属は、例えば、粒子状、イオン、錯体、化合物などの状態で存在することができる。なお、接合材料中における接合用金属が例えば錯体状態で含まれている場合は、熱処理により接合用金属を析出させるとともにこれを焼結させる等して接合用金属を焼結体とすることができる。接合材料中には、接合用金属が１種または２種以上含まれていてもよい。   In the method for manufacturing a joined body according to the present invention, the joining material includes a joining metal and an organic substance. The bonding material can be prepared, for example, as a paste or a solution. In the bonding material, the bonding metal can be present in the form of particles, ions, complexes, compounds, and the like. When the bonding metal in the bonding material is contained in a complex state, for example, the bonding metal can be formed into a sintered body by precipitating the bonding metal by heat treatment and sintering it. . In the bonding material, one or more bonding metals may be contained.

本発明の接合体の製造方法において、前記接合用金属は、その標準酸化還元電位が、導体を形成する金属の標準酸化還元電位と同じまたはそれよりも大きいことが好ましい（請求項４）。   In the method for producing a joined body according to the present invention, the joining metal preferably has a standard oxidation-reduction potential equal to or greater than a standard oxidation-reduction potential of the metal forming the conductor (claim 4).

この場合は、粉末状など、比表面積が大きく酸化しやすい接合用金属の粒子表面への酸化膜の形成を防止できるので、強固な結合の接合体を得ることができる。   In this case, it is possible to prevent formation of an oxide film on the particle surface of the bonding metal that has a large specific surface area and is likely to be oxidized, such as powder, so that a bonded body having a strong bond can be obtained.

本発明の接合体の製造方法において、前記接合用金属としては、具体的には、例えば、銅、銀、パラジウム、イリジウム、白金、金などを例示することができる。これらのうち、接合用金属としては、銀を好適に用いることができる（請求項８）。この場合は、２００〜３００℃程度の低温における焼結性が比較的良好であるため、電子部品の実装に好適である。   In the method for producing a joined body of the present invention, specific examples of the joining metal include copper, silver, palladium, iridium, platinum, and gold. Of these, silver can be suitably used as the bonding metal (claim 8). In this case, since the sinterability at a low temperature of about 200 to 300 ° C. is relatively good, it is suitable for mounting electronic components.

一方、本発明の接合体の製造方法において、前記接合材料中の有機物としては、具体的には、例えば、ポリイミド系、アクリル系、エポキシ系樹脂などの有機バインダー、イソプロピルアルコール、テルピネオール、テトラデカン、トルエンなどの有機溶剤、接合用金属の修飾物などを代表的なものとして例示することができる。これらは１種または２種以上含まれていても良い。なお、接合材料中には、他にも、焼結助剤、界面活性剤などの添加剤を１または２以上を含むことができる。   On the other hand, in the method for producing a joined body according to the present invention, as the organic substance in the joining material, specifically, for example, an organic binder such as polyimide, acrylic or epoxy resin, isopropyl alcohol, terpineol, tetradecane, toluene Examples thereof include organic solvents such as those described above, modified metals for bonding, and the like. These may be contained alone or in combination of two or more. In addition, the bonding material may contain one or more additives such as a sintering aid and a surfactant.

本発明の接合体の製造方法において、前記熱処理時の温度は、具体的には、例えば、２００〜３００℃の範囲内とすることができる（請求項２）。なお、前記にいう熱処理時の温度は、熱処理時の最高温度を意味する。   In the method for producing a joined body of the present invention, the temperature during the heat treatment can be specifically set within a range of 200 to 300 ° C., for example (claim 2). In addition, the temperature at the time of the above-mentioned heat treatment means the maximum temperature at the time of heat treatment.

熱処理時の温度が３００℃以下であると、金属により形成された導体および接合用金属の焼結が遅くなるのが通常である。このため、酸化層などが金属の境界に介在すると、金属の焼結に伴って酸化層を構成する酸化物が移動し難いので強固な接合体が得られ難くなる。しかしながら、前記接合体の製造方法においては、金属の境界に酸化層が介在しても、酸化層を取り除くことができるので３００℃以下の低温で熱処理しても強固な接合体を得ることができる。なお、熱処理温度が３００℃を超えると強固な接合体を得ることができることに変わりはない。   When the temperature during the heat treatment is 300 ° C. or lower, the sintering of the conductor formed of the metal and the joining metal is usually slow. For this reason, when an oxide layer or the like is present at the boundary of the metal, the oxide constituting the oxide layer is difficult to move with the sintering of the metal, so that it is difficult to obtain a strong joined body. However, in the manufacturing method of the joined body, even if an oxide layer is present at the metal boundary, the oxidized layer can be removed, so that a strong joined body can be obtained even by heat treatment at a low temperature of 300 ° C. or lower. . Note that when the heat treatment temperature exceeds 300 ° C., a strong bonded body can be obtained.

また、前記接合体を、例えば、電子部品の実装に適用する際に、電子部品、樹脂を用いた配線基板、ソルダーレジストなどを高温に曝すことがなくなるため、各部材の高温による劣化を生じ難く、また、実装順序の自由度を向上させることができる。また、熱処理時の温度の低温化により、各部材の材料選択の自由度も向上させることができる。   Further, when the bonded body is applied to, for example, mounting of an electronic component, the electronic component, a wiring board using a resin, a solder resist, and the like are not exposed to a high temperature, so that each member is hardly deteriorated due to a high temperature. In addition, the degree of freedom in the mounting order can be improved. In addition, the degree of freedom of material selection for each member can be improved by lowering the temperature during the heat treatment.

本発明の接合体の製造方法において、前記熱処理時の温度は、接合強度向上などの観点から、好ましくは２１０℃以上、より好ましくは２１５℃以上、さらに好ましくは２２０℃以上、さらにより好ましくは２２５℃以上とすることができる。前記熱処理時の温度は、被接合物の劣化抑制などの観点から、好ましくは２９０℃以下、より好ましくは２８５℃以下、さらに好ましくは２８０℃以下、さらにより好ましくは２７５℃以下とすることができる。なお、熱処理時間は、前記熱処理時の温度で例えば、０．５〜４時間程度とすることができる。   In the method for producing a bonded body of the present invention, the temperature during the heat treatment is preferably 210 ° C. or higher, more preferably 215 ° C. or higher, further preferably 220 ° C. or higher, and even more preferably 225, from the viewpoint of improving bonding strength. It can be set to at least ° C. The temperature during the heat treatment is preferably 290 ° C. or less, more preferably 285 ° C. or less, further preferably 280 ° C. or less, and even more preferably 275 ° C. or less, from the viewpoint of suppressing deterioration of the bonded object. . In addition, heat processing time can be made into about 0.5 to 4 hours at the temperature at the time of the said heat processing, for example.

本発明の接合体の製造方法において、前記混合ガスは、熱処理時の温度において以下の（１）および（２）の条件を満たす成分比とされている。
（１）炭素（Ｃ）と酸素（Ｏ２）とが共存する平衡酸素分圧以上の酸素分圧を生成する
（２）前記導体を形成する金属の金属酸化物のうち、最も標準生成自由エネルギーの小さい金属酸化物と、前記導体を形成する金属とが共存できるような平衡酸素分圧以下の酸素分圧を生成する In the method for manufacturing a joined body according to the present invention, the mixed gas has a component ratio that satisfies the following conditions (1) and (2) at the temperature during the heat treatment.
(1) Generate an oxygen partial pressure equal to or higher than the equilibrium oxygen partial pressure in which carbon (C) and oxygen (O 2 ) coexist. (2) Among metal oxides of the metal forming the conductor, the most standard free energy of formation Generates an oxygen partial pressure equal to or lower than the equilibrium oxygen partial pressure so that a small metal oxide and the metal forming the conductor can coexist.

本発明の接合体の製造方法において、前記混合ガスが、熱処理時の温度において（１）の条件を満たす成分比となるよう構成することは、接合材料中に含まれる有機物を酸化させるのに十分な酸素分圧を雰囲気内に提供する意義がある。これにより、接合材料の熱処理時に、接合材料中に含まれる有機物を酸化させて（燃焼させて）ＣＯ２とし、接合体中に炭化物が残留しないようにすることができる。一方、前記混合ガスが、熱処理時の温度において（２）の条件を満たす成分比となるよう構成することは、導体を形成する金属を酸化させるのに必要な酸素が雰囲気内に提供されないようにする意義がある。これにより、接合材料の熱処理時に、導体の表面に酸化膜を形成することなく、接合を行うことができる。なお、導体を形成する金属の金属酸化物のうち、導体表面に最も形成されやすい金属酸化物は、最も標準生成自由エネルギーの小さい金属酸化物である。そのため、（２）の条件では、「導体を形成する金属の金属酸化物のうち、最も標準生成自由エネルギーの小さい金属酸化物と、導体を形成する金属とが共存できる」ような平衡酸素分圧以下の酸素分圧を生成する条件を採用している。 In the method for manufacturing a bonded body according to the present invention, it is sufficient that the mixed gas has a component ratio satisfying the condition (1) at the temperature during the heat treatment to oxidize organic substances contained in the bonding material. It is meaningful to provide an oxygen partial pressure in the atmosphere. Thus, during the heat treatment of the bonding material, by oxidizing the organic matter contained in the bonding material (by burning) as CO 2, carbides can be prevented from remaining in the assembly. On the other hand, when the mixed gas has a component ratio that satisfies the condition (2) at the heat treatment temperature, oxygen necessary for oxidizing the metal forming the conductor is not provided in the atmosphere. There is significance to do. Thereby, it is possible to perform bonding without forming an oxide film on the surface of the conductor during heat treatment of the bonding material. Of the metal oxides forming the conductor, the metal oxide that is most easily formed on the conductor surface is the metal oxide having the smallest standard free energy of formation. Therefore, under the condition (2), an equilibrium oxygen partial pressure such that “the metal oxide having the smallest standard free energy of formation and the metal forming the conductor among the metal oxides forming the conductor can coexist” is satisfied. The following conditions for generating oxygen partial pressure are employed.

ここで、前記混合ガスを構成する複数のガスは、それぞれＯ（酸素）の結合数が異なっている。つまり、前記複数のガスは、分子内に含まれうるＯの数がそれぞれ異なっている。混合ガスは、例えば、いずれのガスも分子内にＯを含んでいるが、それぞれのＯの結合数が異なるガスの組み合わせより構成されていても良いし、分子内にＯを含んでいないガスと、分子内にＯを含んでいるガスとの組み合わせより構成することもできる。熱処理時の温度において（１）および（２）の条件を満たす成分比であれば、複数のガスの組み合わせは、特に限定されるものではない。また、複数のガスは、Ｏ２と反応して平衡状態をつくることができる。なお、複数のガスは、熱処理時の温度において気体であればよく、常温においては気体であっても液体であってもよい。 Here, the plurality of gases constituting the mixed gas have different O (oxygen) bond numbers. That is, the plurality of gases have different numbers of Os that can be included in the molecules. The mixed gas includes, for example, any gas containing O in the molecule, but may be composed of a combination of gases having different numbers of O bonds, or a gas not containing O in the molecule. , Or a combination with a gas containing O in the molecule. The combination of the plurality of gases is not particularly limited as long as the component ratio satisfies the conditions (1) and (2) at the heat treatment temperature. A plurality of gases can react with O 2 to create an equilibrium state. The plurality of gases may be gases at the temperature during the heat treatment, and may be gases or liquids at room temperature.

本発明の接合体の製造方法は、混合ガスの成分比を調整することによって混合ガス中の酸素分圧を制御することができるので、酸素ガスを直接用いることなく雰囲気制御がしやすい利点もある。なお、混合ガスの成分比の調整は、混合ガス中におけるガスの体積濃度を調整することなどによって行うことができる。   The method for producing a joined body of the present invention can control the oxygen partial pressure in the mixed gas by adjusting the component ratio of the mixed gas, and thus has an advantage that the atmosphere can be easily controlled without using oxygen gas directly. . The component ratio of the mixed gas can be adjusted by adjusting the volume concentration of the gas in the mixed gas.

本発明の接合体の製造方法において、前記混合ガスは、具体的には、例えば、ＣＯ、ＣＯ２、Ｃ３Ｏ２等、分子内にＣおよびＯを含む物質の組み合わせより構成することができる。より具体的には、前記混合ガスがＣＯとＣＯ２との混合ガスである場合、式１に示すように、ＣＯとＣＯ２との成分比を調整することにより、雰囲気内に所定の酸素分圧を提供することができる。同様に、前記混合ガスがＣ３Ｏ２とＣＯとの混合ガスである場合、式２に示すように、Ｃ３Ｏ２とＣＯとの成分比を調整することにより、雰囲気内に所定の酸素分圧を提供することができる。前記混合ガスがＣ３Ｏ２とＣＯ２との混合ガスである場合、式３に示すように、Ｃ３Ｏ２とＣＯ２との成分比を調整することにより、雰囲気内に所定の酸素分圧を提供することができる。
２ＣＯ＋Ｏ２⇔２ＣＯ２・・・（式１）
２Ｃ３Ｏ２＋Ｏ２⇔６ＣＯ・・・（式２）
２Ｃ３Ｏ２＋４Ｏ２⇔６ＣＯ２・・・（式３） In the method for producing a joined body according to the present invention, the mixed gas can be specifically composed of a combination of substances containing C and O in the molecule, such as CO, CO 2 , and C 3 O 2. . More specifically, when the mixed gas is a mixed gas of CO and CO 2 , as shown in Equation 1, by adjusting the component ratio of CO and CO 2 , a predetermined oxygen content in the atmosphere is obtained. Pressure can be provided. Similarly, when the mixed gas is a mixed gas of C 3 O 2 and CO, by adjusting the component ratio of C 3 O 2 and CO as shown in Equation 2, a predetermined oxygen in the atmosphere is obtained. A partial pressure can be provided. When the mixed gas is a mixed gas of C 3 O 2 and CO 2 , as shown in Equation 3, by adjusting the component ratio of C 3 O 2 and CO 2 , a predetermined oxygen content in the atmosphere Pressure can be provided.
2CO + O 2 ⇔2CO 2 (Formula 1)
2C 3 O 2 + O 2 ⇔6CO (Formula 2)
2C 3 O 2 + 4O 2 ⇔6CO 2 (Formula 3)

本発明の接合体の製造方法において、前記混合ガスは、具体的には、例えば、Ｈ２、Ｈ２Ｏ、Ｈ２Ｏ２等、分子内にＨおよびＯを含む物質とＨ２との組み合わせより形成することができる。より具体的には、前記混合ガスがＨ２とＨ２Ｏとの混合ガスである場合、式４に示すように、Ｈ２とＨ２Ｏとの成分比を調整することにより、雰囲気内に所定の酸素分圧を提供することができる。同様に、前記混合ガスがＨ２とＨ２Ｏ２との混合ガスである場合、式５に示すように、Ｈ２とＨ２Ｏ２との成分比を調整することにより、雰囲気内に所定の酸素分圧を提供することができる。前記混合ガスがＨ２ＯとＨ２Ｏ２との混合ガスである場合、式６に示すように、Ｈ２ＯとＨ２Ｏ２との成分比を調整することにより、雰囲気内に所定の酸素分圧を提供することができる。
４Ｈ２＋Ｏ２⇔２Ｈ２Ｏ・・・（式４）
２Ｈ２＋２Ｏ２⇔２Ｈ２Ｏ２・・・（式５）
２Ｈ２Ｏ＋Ｏ２⇔２Ｈ２Ｏ２・・・（式６） In the method for producing a joined body of the present invention, the mixed gas is specifically a combination of H 2 and a substance containing H and O in the molecule, such as H 2 , H 2 O, H 2 O 2, etc. Can be formed. More specifically, when the mixed gas is a mixed gas of H 2 and H 2 O, by adjusting the component ratio of H 2 and H 2 O as shown in Equation 4, A predetermined oxygen partial pressure can be provided. Similarly, when the mixed gas is a mixed gas of H 2 and H 2 O 2 , as shown in Formula 5, by adjusting the component ratio of H 2 and H 2 O 2 , a predetermined amount is set in the atmosphere. The oxygen partial pressure can be provided. When the mixed gas is a mixed gas of H 2 O and H 2 O 2 , as shown in Equation 6, by adjusting the component ratio of H 2 O and H 2 O 2 , An oxygen partial pressure can be provided.
4H 2 + O 2 ⇔2H 2 O (Formula 4)
2H 2 + 2O 2 ⇔2H 2 O 2 (Formula 5)
2H 2 O + O 2 ⇔2H 2 O 2 (Formula 6)

本発明の接合体の製造方法において、前記混合ガスは、ＣＯ２とＣＯとが混合されてなる、または、Ｈ２とＨ２Ｏとが混合されてなるとよい（請求項５）。 In the method for manufacturing a joined body according to the present invention, the mixed gas may be a mixture of CO 2 and CO, or a mixture of H 2 and H 2 O (Claim 5).

Ｃ３Ｏ２に比べ、ＣＯ２およびＣＯは安定性が高い。また、Ｈ２Ｏ２に比べ、Ｈ２およびＨ２Ｏは安定性が高い。そのため、この場合は、混合ガスの成分比を安定して制御することができ、熱処理時における雰囲気中の酸素分圧を、（１）および（２）の条件を満たす範囲に安定させやすくなる。それ故、この場合は、高い接合強度を有する接合体を得やすくなる利点がある。 CO 2 and CO are more stable than C 3 O 2 . Also, compared to H 2 O 2, H 2 and H 2 O is highly stable. Therefore, in this case, the component ratio of the mixed gas can be stably controlled, and the oxygen partial pressure in the atmosphere during the heat treatment can be easily stabilized within a range satisfying the conditions (1) and (2). Therefore, in this case, there is an advantage that it becomes easy to obtain a bonded body having high bonding strength.

以下に、前記混合ガスがＣＯ２とＣＯとの混合ガスである場合に、混合ガスを構成するガスの成分比を調整することにより、雰囲気中に所定の酸素分圧を提供できる理由について、より具体的に説明する。
前記式１において、ＣＯ２の分圧ＰＣＯ２、ＣＯの分圧ＰＣＯ、Ｏ２の分圧ＰＯ２とすると、式１の平衡定数Ｋｐｃは、以下の式７となる。
Ｋｐｃ＝［ＰＣＯ２］２／（［ＰＣＯ］２・［ＰＯ２］）・・・（式７）
式７を以下のように変形すると、式９が得られる。
ｌｏｇＫｐｃ＝２ｌｏｇ［ＰＣＯ２］−２ｌｏｇ［ＰＣＯ］−ｌｏｇ［ＰＯ２］・・・（式８）
２ｌｏｇ（［ＰＣＯ２］／［ＰＣＯ］）＝ｌｏｇ［ＰＯ２］＋ｌｏｇＫｐｃ・・・（式９）
ｌｏｇＫｐｃは、熱力学の手法により算出することができる固有値である。ｌｏｇＫｐｃが定数であるので、式９より、混合ガスの成分比［ＰＣＯ２］／［ＰＣＯ］を調整することにより、［ＰＯ２］を制御することが可能なことがわかる。 Hereinafter, when the mixed gas is a mixed gas of CO 2 and CO, the reason why the predetermined oxygen partial pressure can be provided in the atmosphere by adjusting the component ratio of the gas constituting the mixed gas is more This will be specifically described.
In Formula 1, the partial pressure P CO2 in the CO 2 partial pressure P CO of CO, when the partial pressure P O2 of O 2, the equilibrium constant K pc of formula 1 is a formula 7 below.
K pc = [P CO2 ] 2 / ([P CO ] 2 · [P O2 ]) (Expression 7)
By transforming Equation 7 as follows, Equation 9 is obtained.
logK pc = 2log [P CO2] -2log [P CO] -log [P O2] ··· ( Equation 8)
2 log ([P CO2 ] / [P CO ]) = log [P O2 ] + log K pc (Equation 9)
logK pc is an eigenvalue that can be calculated by a thermodynamic technique. Since logK pc is a constant, it can be seen from Equation 9 that [P O2 ] can be controlled by adjusting the component ratio [P CO2 ] / [P CO ] of the mixed gas.

次に、前記混合ガスがＨ２とＨ２Ｏとの混合ガスである場合に、混合ガスを構成するガスの成分比を調整することにより、雰囲気中に所定の酸素分圧を提供できる理由について、より具体的に説明する。
前記式４において、Ｈ２の分圧ＰＨ２、Ｈ２Ｏの分圧ＰＨ２Ｏ、Ｏ２の分圧ＰＯ２とすると、式４の平衡定数Ｋｐｈは、以下の式１０となる。
Ｋｐｈ＝［ＰＨ２Ｏ］２／（［ＰＨ２］２・［ＰＯ２］）・・・（式１０）
式１０を以下のように変形すると、式１２が得られる。
ｌｏｇＫｐｈ＝２ｌｏｇ［ＰＨ２Ｏ］−２ｌｏｇ［ＰＨ２］−ｌｏｇ［ＰＯ２］・・・（式１１）
２ｌｏｇ（［ＰＨ２Ｏ］／［ＰＨ２］）＝ｌｏｇ［ＰＯ２］＋ｌｏｇＫｐｈ・・・（式１２）
ｌｏｇＫｐｈは、熱力学の手法により算出することができる固有値である。ｌｏｇＫｐｈが定数であるので、式１２より、混合ガスの成分比［ＰＨ２Ｏ］／［ＰＨ２］を調整することにより、［ＰＯ２］を制御することが可能なことがわかる。前記混合ガスがその他のガスの組み合わせよりなる場合も同様である。 Next, when the mixed gas is a mixed gas of H 2 and H 2 O, the reason why a predetermined oxygen partial pressure can be provided in the atmosphere by adjusting the component ratio of the gas constituting the mixed gas This will be described more specifically.
In Formula 4, partial pressure P H2, H 2 O partial pressure P H2 O of H 2, when the partial pressure P O2 of O 2, the equilibrium constant K ph of Formula 4 is a formula 10 below.
K ph = [P H2O ] 2 / ([P H2 ] 2 · [P O2 ]) (Formula 10)
By transforming Equation 10 as follows, Equation 12 is obtained.
logK ph = 2log [P H2O ] −2 log [P H2 ] −log [P O2 ] (Equation 11)
2 log ([P H2O ] / [P H2 ]) = log [P O2 ] + log K ph (12)
logK ph is an eigenvalue that can be calculated by a thermodynamic technique. Since log K ph is a constant, it can be seen from Equation 12 that [P O2 ] can be controlled by adjusting the component ratio [P H2O ] / [P H2 ] of the mixed gas. The same applies when the mixed gas is a combination of other gases.

本発明の接合体の製造方法において、前記混合ガスとしては、とりわけ、ＣＯ２とＣＯとの混合ガスを用いることができる。Ｈ２Ｏ、Ｈ２Ｏ２は、沸点が高く、常温で液体である。これに対し、ＣＯ２とＣＯは、常温で気体である。そのため、この場合は、混合ガスが供給管内あるいはオーブン内の温度の低い部分で凝集することがなく、均一な混合ガスを調整しやすい。また、ＣＯ２、ＣＯは、光などで分解し難く、比較的安定な分子である。そのため、この場合は、混合ガスの成分比を精度よく調整するのに有利である。 In the method for manufacturing a joined body according to the present invention, as the mixed gas, a mixed gas of CO 2 and CO can be used. H 2 O and H 2 O 2 have a high boiling point and are liquid at room temperature. In contrast, CO 2 and CO are gases at room temperature. Therefore, in this case, the mixed gas does not aggregate at a low temperature in the supply pipe or the oven, and it is easy to adjust the uniform mixed gas. CO 2 and CO are relatively stable molecules that are not easily decomposed by light or the like. Therefore, this case is advantageous for accurately adjusting the component ratio of the mixed gas.

本発明の接合体の製造方法において、前記混合ガスは、ＣＯ２とＣＯとが混合されてなり、この混合ガスにおけるＣＯ濃度は、体積比で０．３ｐｐｂ〜１０ｐｐｍの範囲内とすることができる（請求項９）。 In the method for manufacturing a joined body according to the present invention, the mixed gas is a mixture of CO 2 and CO, and the CO concentration in the mixed gas can be within a range of 0.3 ppb to 10 ppm by volume ratio. (Claim 9).

この場合は、ＣＯ２とＣＯとが混合されてなる混合ガスが、熱処理時の温度において（１）および（２）の条件を満たす酸素分圧を生成しやすくなる。そのため、この場合は、熱処理時の温度が比較的低くても、得られる接合体の接合強度を向上させることができるという効果を確実なものとすることができる。 In this case, the mixed gas formed by mixing CO 2 and CO easily generates an oxygen partial pressure that satisfies the conditions (1) and (2) at the temperature during the heat treatment. Therefore, in this case, even if the temperature at the time of heat treatment is relatively low, the effect that the bonding strength of the obtained bonded body can be improved can be ensured.

前記ＣＯ濃度は、ＣＯが鉄などの金属と反応してカルボニルを形成し濃度が変化しやすいなどの観点から、好ましくは０．３ｐｐｂ以上、より好ましくは１ｐｐｂ以上、さらに好ましくは１０ｐｐｂ以上とすることができる。前記ＣＯ濃度は、熱処理の過程で最高温度に到達するまでに低い温度で導体などを酸化させないなどの観点から、好ましくは１０ｐｐｍ以下、より好ましくは３ｐｐｍ以下、さらに好ましくは１ｐｐｍ以下とすることができる。   The CO concentration is preferably 0.3 ppb or more, more preferably 1 ppb or more, and even more preferably 10 ppb or more, from the viewpoint that CO reacts with a metal such as iron to form carbonyl to easily change the concentration. Can do. The CO concentration is preferably 10 ppm or less, more preferably 3 ppm or less, and even more preferably 1 ppm or less from the viewpoint of not oxidizing the conductor or the like at a low temperature before reaching the maximum temperature in the heat treatment process. .

さらに、前記混合ガスは、ＣＯ２が主成分であることが好ましい。前記反応はＣＯ２とＣＯとの比率によって前記反応の進行が決定されるが、その他のガスが前記混合ガスに多量に含まれているとＣＯ２とＣＯとの比率によって進行する反応の速度が遅くなるので、ＣＯ２が主成分であることが好ましい。混合ガス全体に対する望ましいＣＯ２の成分比は９０ｍｏｌ％以上、好ましくは９９ｍｏｌ％以上、さらに好ましくは９９．９ｍｏｌ％以上とすることができる。いずれの場合も、混合ガス中のＣＯ２の残部にＣＯが含まれている。 Further, it is preferable that the mixed gas contains CO 2 as a main component. The progress of the reaction is determined by the ratio of CO 2 and CO. However, when other gas is contained in a large amount in the mixed gas, the rate of the reaction proceeding by the ratio of CO 2 and CO is increased. since slower, it is preferred that CO 2 is the main component. A desirable component ratio of CO 2 with respect to the entire mixed gas can be 90 mol% or more, preferably 99 mol% or more, and more preferably 99.9 mol% or more. In any case, CO is contained in the balance of CO 2 in the mixed gas.

本発明の接合体の製造方法は、例えば、前記接合材料として、接合用金属と有機物とを含むペーストを準備し、導体の表面とペーストとを接触状態とした後、前記混合ガス中にて熱処理することにより、ペースト中の接合用金属を焼結させる第１接合手順を含むことができる（請求項６）。   In the method for producing a joined body of the present invention, for example, a paste containing a joining metal and an organic substance is prepared as the joining material, and the conductor surface and the paste are brought into contact with each other, and then heat treatment is performed in the mixed gas. By doing, the 1st joining procedure which sinters the metal for joining in paste can be included (Claim 6).

この場合は、比較的短い接合時間で高い接合強度を有する接合体が得やすくなるので、生産性の向上に有利である。なお、第１接合手順では、接合材料として、より具体的には、接合用金属の粒子と有機物とを含むペーストを好適に用いることができる。   In this case, since it becomes easy to obtain a joined body having high joining strength in a relatively short joining time, it is advantageous in improving productivity. In the first bonding procedure, more specifically, a paste containing bonding metal particles and an organic substance can be suitably used as the bonding material.

また、本発明の接合体の製造方法は、前記接合材料として、接合用金属と有機物とを含む溶液を準備し、導体の表面と溶液とを接触状態とした後、前記混合ガス中にて熱処理し、溶液から接合用金属を析出させるとともにこの析出した接合用金属を焼結させる第２接合手順を含むことができる（請求項７）。   In the method for producing a joined body of the present invention, a solution containing a joining metal and an organic substance is prepared as the joining material, the conductor surface is brought into contact with the solution, and then heat treatment is performed in the mixed gas. And a second joining procedure for depositing the joining metal from the solution and sintering the deposited joining metal (claim 7).

この場合も、より高い接合強度を有する接合体が得やすくなる。なお、第２接合手順では、接合材料として、より具体的には、接合用金属の錯体溶液を好適に用いることができる。   Also in this case, it becomes easy to obtain a bonded body having higher bonding strength. In the second bonding procedure, more specifically, a bonding metal complex solution can be suitably used as the bonding material.

また、本発明の接合体の製造方法は、前記第１接合手順と第２接合手順とを有する第３接合手順を含むことも可能である。より具体的には、前記接合材料として、接合用金属と有機物とを含むペーストを準備する。次いで、接合すべき一方の導体の表面と前記ペーストとを接触状態とした後、前記混合ガス中にて熱処理することにより、ペースト中の接合用金属を焼結させる第１接合手順を行い、多孔質の接合用金属の焼結体からなる多孔質焼結体を形成する。次いで、接合すべき他方の導体と前記多孔質焼結体の表面とを接触させるとともに、多孔質焼結体の孔内に前記溶液を浸透させることにより、前記他方の導体表面と前記溶液とを接触状態とする。なお、多孔質焼結体の表面と接合すべき他方の導体とは、接合強度を向上させやすくなる観点から、加圧した状態で接触させることができる。次いで、これを前記混合ガス中にて熱処理し、溶液から接合用金属を析出させるとともにこの析出した接合用金属を焼結させる。前記接合体の製造方法は、このような第３接合手順を含むことができる。   Moreover, the manufacturing method of the conjugate | zygote of this invention can also include the 3rd joining procedure which has the said 1st joining procedure and a 2nd joining procedure. More specifically, a paste containing a bonding metal and an organic substance is prepared as the bonding material. Next, after bringing the surface of one of the conductors to be bonded into contact with the paste, a first bonding procedure is performed in which the bonding metal in the paste is sintered by heat treatment in the mixed gas. A porous sintered body made of a sintered body of a high quality joining metal is formed. Next, the other conductor surface to be joined and the surface of the porous sintered body are brought into contact with each other, and the solution is infiltrated into the pores of the porous sintered body, thereby bringing the other conductor surface and the solution into contact with each other. Keep in contact. The surface of the porous sintered body and the other conductor to be joined can be brought into contact in a pressurized state from the viewpoint of easily improving the joining strength. Subsequently, this is heat-processed in the said mixed gas, and the joining metal is precipitated from a solution, and this deposited joining metal is sintered. The manufacturing method of the joined body may include such a third joining procedure.

この場合は、多孔質焼結体の孔内、および多孔質焼結体の表面と第１導体との界面において接合用金属が析出するとともに、析出した接合用金属を焼結させる。そのため、この場合は、より一層高い接合強度を有する接合体を得やすくなる。また、孔の少ない接合体が得られるので、孔に起因する破壊等が生じ難く、接合信頼性の高い接合体を製造するのに寄与することができる。なお、多孔質焼結体の孔内への溶液の浸透と前記混合ガス中での熱処理は、繰り返し行うことが可能である。   In this case, the bonding metal is deposited in the pores of the porous sintered body and at the interface between the surface of the porous sintered body and the first conductor, and the deposited bonding metal is sintered. Therefore, in this case, it becomes easy to obtain a bonded body having a higher bonding strength. In addition, since a joined body with few holes is obtained, it is difficult to cause breakage or the like due to the holes, and it is possible to contribute to manufacturing a joined body with high joining reliability. The solution penetration into the pores of the porous sintered body and the heat treatment in the mixed gas can be repeated.

本発明の接合体の製造方法は、前記熱処理を行う前に、導体表面に存在する酸化膜を予め除去する工程を有していてもよい。この場合には、接合材料の熱処理時に、導体の表面に酸化膜がなく、かつ、雰囲気中の酸素によって新たに酸化膜が形成されることもない。そのため、この場合は、高い接合強度を有する接合体を得やすくなる利点がある。なお、導体の酸化膜の除去は、特に限定されることなく、各種の方法を用いて行うことができる。前記方法としては、例えば、塩酸、硝酸等の酸性溶液や、これらの蒸気等を用いて酸化膜を除去する方法などを例示することができる。   The method for producing a joined body of the present invention may include a step of removing in advance an oxide film present on the conductor surface before performing the heat treatment. In this case, there is no oxide film on the surface of the conductor during heat treatment of the bonding material, and no new oxide film is formed by oxygen in the atmosphere. Therefore, in this case, there is an advantage that it becomes easy to obtain a bonded body having high bonding strength. The removal of the oxide film of the conductor is not particularly limited and can be performed using various methods. Examples of the method include an acidic solution such as hydrochloric acid and nitric acid, a method of removing an oxide film using these vapors, and the like.

次に、本発明のオーブンの実施形態について説明する。なお、前記オーブンの構成については、前記接合体の製造方法の説明を適宜準用することができる。   Next, an embodiment of the oven of the present invention will be described. In addition, about the structure of the said oven, description of the manufacturing method of the said conjugate | zygote can be applied mutatis mutandis.

本発明のオーブンは、上述した特定の混合ガスを熱処理時の雰囲気中に供給可能に構成することができる。前記混合ガスの生成は、具体的には、例えば、各ガス源からのガスをマスフローコントローラー、ニードルバルブ等の流量調節手段により調節し、混合機にて混合することなどによって実施することができる。また、前記混合は、混合ガスの成分比を安定化させるなどのために、１回または複数回実施することが可能である。複数回に分けて実施した場合は、混合ガスの成分比の差が大きい場合に段階的に希釈することができる。   The oven of the present invention can be configured so that the above-described specific mixed gas can be supplied into the atmosphere during the heat treatment. Specifically, the generation of the mixed gas can be performed, for example, by adjusting the gas from each gas source by a flow rate adjusting means such as a mass flow controller or a needle valve, and mixing with a mixer. Further, the mixing can be performed once or a plurality of times in order to stabilize the component ratio of the mixed gas. In the case where the process is divided into a plurality of times, dilution can be performed in stages when the difference in the component ratio of the mixed gas is large.

以下、実施例の接合体の製造方法およびオーブンについて説明する。   Hereinafter, the manufacturing method and oven of the joined body of an Example are demonstrated.

＜金属より形成された導体＞
シリコン（厚み７２５μｍ）の表面に、スパッタリング法を用いてＴｉスパッタ層（厚み０．１μｍ）、Ｃｕスパッタ層（厚み０．１μｍ）を順に形成した後、さらに電解めっき法を用いてＣｕめっき層（厚み５μｍ）を形成することにより、試験チップを作製した。また、Ｃｕよりなるピン型導体（直径０．４５ｍｍ）を準備した。本例では、前記試験チップが有するＣｕめっき層、前記Ｃｕよりなるピン型導体を、導体として用いる。 <Conductor made of metal>
After a Ti sputter layer (thickness 0.1 μm) and a Cu sputter layer (thickness 0.1 μm) are formed in this order on the surface of silicon (thickness 725 μm) by sputtering, a Cu plating layer ( A test chip was produced by forming a thickness of 5 μm. Further, a pin type conductor (diameter 0.45 mm) made of Cu was prepared. In this example, the Cu plating layer of the test chip and the pin-type conductor made of Cu are used as the conductor.

＜接合材料＞
５０％体積累積径ｄ５０が１μｍのＡｇ粉末と５０％体積累積径ｄ５０が０．１μｍのＡｇ粉末とを質量比１：１の割合で混合することにより、大きなＡｇ粒子の隙間に小さなＡｇ粒子の詰まった混合Ａｇ粉末を作製した。そして、この混合Ａｇ粉末をターピネオールに懸濁させることにより、Ａｇペーストを調製した。また、カルボン酸銀をイソプロピルアルコール（ＩＰＡ）に溶解することにより、Ａｇ錯体溶液を調製した。本例では、前記Ａｇペーストと前記Ａｇ錯体溶液を接合材料として用いる。 <Bonding material>
By mixing an Ag powder having a 50% volume cumulative diameter d 50 of 1 μm and an Ag powder having a 50% volume cumulative diameter d 50 of 0.1 μm in a mass ratio of 1: 1, a small Ag particle is formed in a gap between large Ag particles. A mixed Ag powder packed with particles was prepared. Then, an Ag paste was prepared by suspending the mixed Ag powder in terpineol. Further, an Ag complex solution was prepared by dissolving silver carboxylate in isopropyl alcohol (IPA). In this example, the Ag paste and the Ag complex solution are used as bonding materials.

＜オーブン＞
熱処理を実施するための熱処理空間に、熱処理時の雰囲気ガスとして、ＣＯ２とＣＯとが混合されてなる混合ガスを供給可能に構成したオーブンＡを準備した。オーブンＡは、具体的には、ＣＯ２ボンベから供給されるＣＯ２の流量とＣＯボンベから供給されるＣＯの流量とをマスフローコントローラーにより所定の流量比となるように調節し、混合機にて混合することにより、後述する表１および表２に示す混合ガスを生成し、当該混合ガスを、熱処理空間に供給可能に構成されている。また、比較のため、熱処理を実施するための熱処理空間に、熱処理時の雰囲気ガスとして、Ｎ２ボンベからＮ２ガスを供給可能に構成したオーブンＢも併せて準備した。 <Oven>
An oven A configured to supply a mixed gas formed by mixing CO 2 and CO as an atmosphere gas at the time of heat treatment was prepared in a heat treatment space for performing heat treatment. Specifically, the oven A adjusts the flow rate of CO 2 supplied from the CO 2 cylinder and the flow rate of CO supplied from the CO cylinder so that the flow rate becomes a predetermined flow ratio by a mass flow controller. By mixing, the mixed gas shown in Table 1 and Table 2 described later is generated, and the mixed gas can be supplied to the heat treatment space. For comparison, an oven B configured to be able to supply N 2 gas from an N 2 cylinder as an atmosphere gas during heat treatment was also prepared in the heat treatment space for performing heat treatment.

＜接合工程＞
本例では、前記準備した導体と前記準備した接合材料とを接触状態とした後、前記準備したオーブンＡ、オーブンＢを用いて所定の雰囲気ガス中にて熱処理し、Ａｇを焼結させる接合工程を経ることにより、各接合体試料を作製した。以下に詳細に説明する。 <Joint process>
In this example, after the prepared conductor and the prepared bonding material are brought into contact with each other, a heat treatment is performed in a predetermined atmosphere gas using the prepared oven A and oven B, and Ag is sintered. Each joined body sample was produced by passing through. This will be described in detail below.

（試料１の作製）
前記試験チップが有するＣｕめっき層の表面に、スクリーン印刷法により前記Ａｇペーストを厚み５０μｍにて塗布した。これにより、試験チップが有するＣｕめっき層と、Ａｇペーストとを接触状態とした。次いで、これをオーブンＡの熱処理空間に配置し、ＣＯ２とＣＯとが混合されてなる混合ガス中にて熱処理を行った。この際、熱処理は、５０℃にて５分間、１００℃にて５分間、１５０℃にて５分間、２００℃にて３０分間順に加熱するという加熱条件にて行った。したがって、試料１の作製における熱処理時の温度は、最高温度の２００℃ということになる。また、ＣＯ２とＣＯとが混合されてなる混合ガスにおけるＣＯ濃度は体積比で５０ｐｐｂとした。この混合ガスは、熱処理時の温度である２００℃において、上述した（１）条件における炭素（Ｃ）と酸素（Ｏ２）とが共存する平衡酸素分圧以上の酸素分圧を生成する成分比、上述した（２）条件に相当するＣｕＯ２とＣｕとが共存できるような平衡酸素分圧以下の酸素分圧を生成する成分比となっている。その理由は以下の通りである。 (Preparation of sample 1)
The Ag paste was applied to the surface of the Cu plating layer of the test chip with a thickness of 50 μm by screen printing. Thereby, Cu plating layer which a test chip has, and Ag paste were made into a contact state. Next, this was placed in the heat treatment space of the oven A, and heat treatment was performed in a mixed gas in which CO 2 and CO were mixed. At this time, the heat treatment was performed under heating conditions of heating at 50 ° C. for 5 minutes, 100 ° C. for 5 minutes, 150 ° C. for 5 minutes, and 200 ° C. for 30 minutes in this order. Therefore, the temperature at the time of heat treatment in the production of Sample 1 is the maximum temperature of 200 ° C. The CO concentration in the mixed gas formed by mixing CO 2 and CO was 50 ppb by volume ratio. This mixed gas has a component ratio that generates an oxygen partial pressure that is equal to or higher than the equilibrium oxygen partial pressure in which carbon (C) and oxygen (O 2 ) coexist in the condition (1) described above at 200 ° C., which is the temperature during heat treatment. The component ratio is such that an oxygen partial pressure equal to or lower than the equilibrium oxygen partial pressure is generated so that CuO 2 and Cu corresponding to the condition (2) described above can coexist. The reason is as follows.

すなわち、熱処理時の温度が２００℃の場合、Ｃの酸化（Ｃの燃焼）反応は、主に式１３によって生じる。したがって、この場合は、式１３の反応を考慮すればよいことになる。
Ｃ＋Ｏ２⇔ＣＯ２・・・（式１３） That is, when the temperature at the time of heat treatment is 200 ° C., the oxidation reaction of C (combustion of C) is mainly caused by Equation 13. Therefore, in this case, the reaction of Formula 13 should be considered.
C + O 2 ⇔CO 2 (Formula 13)

式１３の反応において、上述した（１）条件における炭素（Ｃ）と酸素（Ｏ２）とが共存する平衡酸素分圧Ｐ（１）は、−４３．６１[常用対数値]となる。 In the reaction of Formula 13, the equilibrium oxygen partial pressure P (1) in which carbon (C) and oxygen (O 2 ) coexist in the condition (1) described above is −43.61 [common logarithmic value].

また、熱処理時の温度が２００℃の場合、導体を形成するＣｕの酸化物である酸化銅のうち、最も標準生成自由エネルギーの小さい酸化銅は、ＣｕＯ２であり、Ｃｕの酸化反応は、主に式１４によって生じる。したがって、この場合は、式１４の反応を考慮すればよいことになる。
２Ｃｕ＋Ｏ２⇔２ＣｕＯ２・・・（式１４） Further, when the temperature during the heat treatment is 200 ° C., the copper oxide having the smallest standard free energy of formation is CuO 2 among the copper oxides that are Cu oxides forming the conductor, and the oxidation reaction of Cu is mainly performed. Resulting from Equation 14. Therefore, in this case, the reaction of Formula 14 should be considered.
2Cu + O 2 Ｃｕ2CuO 2 (Formula 14)

式１４の反応において、上述した（２）条件に相当するＣｕＯ２とＣｕとが共存する平衡酸素分圧Ｐ（２）は、−２９．７７[常用対数値]となる。 In the reaction of Formula 14, the equilibrium oxygen partial pressure P (2) in which CuO 2 and Cu corresponding to the condition (2) described above coexist is −29.77 [common logarithm].

そうすると、熱処理時の温度を２００℃とし、導体を形成する金属としてＣｕを用いる場合、混合ガスは、前記熱処理時の温度において、前記平衡酸素分圧Ｐ（１）以上、前記平衡酸素分圧Ｐ（２）以下の範囲内の酸素分圧ＰＯ２を生成する成分比であればよいことになる。本例では、混合ガスは、ＣＯ２とＣＯとが混合されている。そのため、上述したように、混合ガスの成分比［ＰＣＯ２］／［ＰＣＯ］を調整し、前記範囲内の酸素分圧ＰＯ２を生成させるようにすればよいといえる。本例では、ＣＯ２とＣＯとの混合ガス中におけるＣＯの体積濃度を調整することにより、前記混合ガスの成分比の調整を行うことにした。 Then, when the temperature at the time of the heat treatment is 200 ° C. and Cu is used as the metal forming the conductor, the mixed gas is equal to or higher than the equilibrium oxygen partial pressure P (1) at the temperature at the time of the heat treatment. (2) Any component ratio that generates an oxygen partial pressure P02 within the following range may be used. In this example, the mixed gas is a mixture of CO 2 and CO. Therefore, as described above, it can be said that the component ratio [P CO2 ] / [P CO ] of the mixed gas is adjusted to generate the oxygen partial pressure P O2 within the above range. In this example, the component ratio of the mixed gas is adjusted by adjusting the volume concentration of CO in the mixed gas of CO 2 and CO.

具体的には、熱処理時の温度が２００℃の場合、（１）条件における平衡酸素分圧Ｐ（１）を生成する成分比［ＰＣＯ］／［ＰＣＯ２］は、１２．２９×１０−６である。ＣＯの比率は圧倒的に小さいので、この成分比を与えるＣＯ濃度は、体積比で１２ｐｐｍと考えてよい。一方、（２）条件における平衡酸素分圧Ｐ（２）を生成する成分比［ＰＣＯ］／［ＰＣＯ２］は、１．４７×１０−１２である。ＣＯの比率は圧倒的に小さいので、この成分比を与えるＣＯ濃度は、体積比で１．４ｐｐｔと考えてよい。このことから、熱処理時の温度が２００℃の場合、混合ガス中のＣＯ濃度を、体積比で１．４ｐｐｔ〜１２ｐｐｍの範囲内とすれば、混合ガスが、前記平衡酸素分圧Ｐ（１）以上、前記平衡酸素分圧Ｐ（２）以下の範囲内の酸素分圧ＰＯ２を生成可能となる。
なお、ここではＣＯ２に対してＣＯの成分比が圧倒的に小さいので、「濃度」の概念で取り扱い易いよう「［ＰＣＯ２］／［ＰＣＯ］」に変えて「［ＰＣＯ］／［ＰＣＯ２］」で記載してある。「［ＰＣＯ］／［ＰＣＯ２］」は「［ＰＣＯ２］／［ＰＣＯ］」の逆数である。 Specifically, when the temperature during the heat treatment is 200 ° C., the component ratio [P CO ] / [P CO2 ] that generates the equilibrium oxygen partial pressure P (1) under the condition (1) is 12.29 × 10 − 6 . Since the ratio of CO is overwhelmingly small, the CO concentration that gives this component ratio may be considered to be 12 ppm by volume. On the other hand, the component ratio [P CO ] / [P CO2 ] for generating the equilibrium oxygen partial pressure P (2) under the condition (2) is 1.47 × 10 −12 . Since the ratio of CO is overwhelmingly small, the CO concentration that gives this component ratio may be considered to be 1.4 ppt in volume ratio. From this, when the temperature at the time of heat treatment is 200 ° C., if the CO concentration in the mixed gas is within the range of 1.4 ppt to 12 ppm by volume ratio, the mixed gas will have the equilibrium oxygen partial pressure P (1) As described above, it is possible to generate the oxygen partial pressure P02 within the range of the equilibrium oxygen partial pressure P (2) or less.
Here, since the component ratio of CO is overwhelmingly small with respect to CO 2 , it is changed to “[P CO2 ] / [P CO ]” so that it is easy to handle with the concept of “concentration”, and “[P CO ] / [ P CO2 ] ”. “[P CO ] / [P CO2 ]” is the reciprocal of “[P CO2 ] / [P CO ]]”.

以上の理由により、本例では、ＣＯ濃度が体積比で５０ｐｐｂである前記混合ガスを準備した。なお、前記と異なる混合ガス成分を用いる場合や熱処理時の温度が異なる場合などは、前記と同様の考え方によって（１）および（２）の条件を満たす成分比の混合ガスを準備すればよい。   For the above reason, in this example, the mixed gas having a CO concentration of 50 ppb by volume ratio was prepared. In addition, when using a mixed gas component different from the above or when the temperature during the heat treatment is different, a mixed gas having a component ratio that satisfies the conditions (1) and (2) may be prepared based on the same concept as described above.

前記混合ガス中での熱処理により、Ａｇペースト中のＡｇ粒子を焼結させ、試験チップのＣｕめっき層の表面に多孔質のＡｇの焼結体からなる多孔質焼結体を形成した。   By heat treatment in the mixed gas, Ag particles in the Ag paste were sintered, and a porous sintered body made of a porous Ag sintered body was formed on the surface of the Cu plating layer of the test chip.

次いで、これを一旦オーブンＡから取り出した。次いで、多孔質焼結体の表面に、圧力１ｋｇ／ｍｍ２にて前記ピン型導体のピン先端部を押し付け状態としたまま、多孔質焼結体の孔内にＡｇ錯体溶液を浸透させることにより、ピン型導体とＡｇ錯体溶液とを接触状態とした。次いで、再びこれをオーブンＡの熱処理空間に配置し、前記と同じ混合ガス中、前記と同じ加熱条件にて熱処理を行った。そして、この熱処理により、多孔質焼結体の孔内、および多孔質焼結体の表面とピン型導体との界面において、Ａｇ錯体溶液からＡｇを析出させるとともに、析出したＡｇを焼結させ、多孔質焼結体の表面にピン型導体を接合した。その後、前記と同じＡｇ錯体溶液の浸透と熱処理を２回繰り返した。これにより、試料１の接合体を得た。 Subsequently, this was once taken out from the oven A. Next, the Ag complex solution is infiltrated into the pores of the porous sintered body while the pin tip portion of the pin-type conductor is pressed against the surface of the porous sintered body at a pressure of 1 kg / mm 2 . The pin-type conductor and the Ag complex solution were brought into contact with each other. Next, this was again placed in the heat treatment space of the oven A, and heat treatment was performed in the same mixed gas as described above under the same heating conditions as described above. Then, by this heat treatment, Ag is precipitated from the Ag complex solution in the pores of the porous sintered body and at the interface between the surface of the porous sintered body and the pin-type conductor, and the precipitated Ag is sintered, A pin-type conductor was joined to the surface of the porous sintered body. Thereafter, the same Ag complex solution infiltration and heat treatment were repeated twice. Thereby, a joined body of Sample 1 was obtained.

なお、図１に示すように、試料１の接合体１０は、接合すべき一方の導体１１としてのＣｕめっき層と、接合すべき他方の導体１２としてのピン型導体との間を接合する層状の接合層である。また、接合体１０は、Ａｇからなる多孔質焼結体１０１と、多孔質焼結体１０１の孔内および表面に存在するＡｇからなる緻密質焼結部１０２とを有している。なお、図１中、１３はＣｕスパッタ層、１４はＴｉスパッタ層、１５はシリコンである。   As shown in FIG. 1, the joined body 10 of the sample 1 is a layered structure that joins between a Cu plating layer as one conductor 11 to be joined and a pin-type conductor as the other conductor 12 to be joined. This is a bonding layer. Moreover, the joined body 10 includes a porous sintered body 101 made of Ag, and a dense sintered portion 102 made of Ag existing in the pores and on the surface of the porous sintered body 101. In FIG. 1, 13 is a Cu sputter layer, 14 is a Ti sputter layer, and 15 is silicon.

（試料２〜１０の作製）
試料１の作製において、熱処理条件を、表１および表２に示すように変更した以外は同様にして、試料２〜１０の接合体を得た。なお、試料９および試料１０の作製時には、前記オーブンＢを用いた。 (Preparation of samples 2 to 10)
In the production of Sample 1, bonded bodies of Samples 2 to 10 were obtained in the same manner except that the heat treatment conditions were changed as shown in Tables 1 and 2. Note that the oven B was used when the samples 9 and 10 were manufactured.

＜接合強度＞
得られた各接合体について、接合強度を以下のようにして測定した。すなわち、接合体試料が上下に動かないように固定した後に、接合していないもう一方のピン型導体の先端部分を上下可動のロードセルと直結させたピンセットでつまみ、５０ｍｍ／ｍｉｎの速度でロードセルを上昇させ、接合部が破壊される際の最大強度を記録した。記録した最大強度を接合面積で割り、これを単位面積あたりの接合強度とした。図２に、接合体試料の熱処理時の最高温度と接合強度との関係を示す。また、図３（ａ）、（ｂ）に、代表例として、接合体試料１の断面ＳＥＭ写真を示す。 <Joint strength>
About each obtained joined body, joint strength was measured as follows. That is, after fixing the joined body sample so that it does not move up and down, the tip of the other unconnected pin type conductor is pinched with tweezers directly connected to the vertically movable load cell, and the load cell is moved at a speed of 50 mm / min. Raised and recorded the maximum strength at which the joint was destroyed. The recorded maximum strength was divided by the bonding area, which was defined as the bonding strength per unit area. FIG. 2 shows the relationship between the maximum temperature during the heat treatment of the bonded body sample and the bonding strength. In addition, FIGS. 3A and 3B show cross-sectional SEM photographs of the joined body sample 1 as a representative example.

以上の結果から次のことがわかる。試料９、試料１０の接合体は、Ｎ２雰囲気中にて熱処理を行う接合工程を経て作製されている。そのため、熱処理時の最高温度が比較的低温では、他に比較して接合強度が低いことがわかる。これは、熱処理時に接合材料中に含まれていた有機物が十分に酸化されず、接合層中に炭化物として残留しやすかったためである。なお、十分な酸化雰囲気中にて熱処理を行った場合には、導体表面に容易に酸化膜が形成され、接合性が低下し、高い接合強度が得られ難いので、今回試験を実施していない。 From the above results, the following can be understood. The joined bodies of Sample 9 and Sample 10 are manufactured through a joining process in which heat treatment is performed in an N 2 atmosphere. Therefore, it can be seen that when the maximum temperature during heat treatment is relatively low, the bonding strength is lower than others. This is because the organic matter contained in the bonding material during the heat treatment was not sufficiently oxidized and easily remained as a carbide in the bonding layer. In addition, when heat treatment is performed in a sufficiently oxidizing atmosphere, an oxide film is easily formed on the conductor surface, the bondability is lowered, and it is difficult to obtain a high bonding strength. .

これらに対し、試料１〜８の接合体の作製方法では、Ｏの結合数が異なるＣＯ２とＣＯとが混合されてなる混合ガス中にて接合工程における熱処理を行っている。そして、試料１〜８の接合体の作製に用いた混合ガスは、各熱処理時の温度において、前記（１）条件における炭素（Ｃ）と酸素（Ｏ２）とが共存する平衡酸素分圧Ｐ（１）以上、前記（２）条件に相当するＣｕＯ２とＣｕとが共存する平衡酸素分圧Ｐ（２）以下の条件を満たす酸素分圧を生成する成分比とされている。 On the other hand, in the manufacturing method of the joined body of Samples 1 to 8, heat treatment in the joining process is performed in a mixed gas in which CO 2 and CO having different numbers of O bonds are mixed. And the mixed gas used for the manufacture of the joined bodies of Samples 1 to 8 is an equilibrium oxygen partial pressure P in which carbon (C) and oxygen (O 2 ) coexist in the condition (1) above at the temperature during each heat treatment. (1) above, there is a the (2) the equilibrium oxygen partial CuO 2 and the Cu coexist corresponding to the condition pressure P (2) component ratio to produce the following condition is satisfied oxygen partial pressure.

そのため、試料１〜８の接合体の作製方法によれば、接合材料中に含まれる有機物の酸化（燃焼）を促すことができ、接合体中の炭化物の残留を抑制することができる。また、導体表面の酸化を抑制することができるので、接合性を向上させることができる。このように、試料１〜８の接合体の作製方法は、前記接合時に炭化物および酸化膜を関与させないようにすることができるので、熱処理時の温度を低温化しても、得られる接合体の接合強度を向上させることができた。とりわけ、今回の結果から、熱処理時の温度を２５０℃程度まで下げた場合でも、半田接合とほぼ同等の高い接合強度を有する接合体が得られることが確認された。   Therefore, according to the method for manufacturing the joined body of Samples 1 to 8, oxidation (combustion) of organic substances contained in the joining material can be promoted, and residual carbides in the joined body can be suppressed. Moreover, since the oxidation of the conductor surface can be suppressed, the bondability can be improved. As described above, since the method for manufacturing the joined body of Samples 1 to 8 can prevent the carbide and oxide film from being involved during the joining, the joining of the obtained joined body even when the temperature during the heat treatment is lowered. The strength could be improved. In particular, it was confirmed from this result that even when the temperature during the heat treatment was lowered to about 250 ° C., a bonded body having a high bonding strength almost equal to that of solder bonding was obtained.

以上、実施例について説明したが、本発明は、前記実施例により限定されるものではなく、本発明の趣旨を損なわない範囲内で種々の変形を行うことができる。   As mentioned above, although the Example was described, this invention is not limited by the said Example, A various deformation | transformation can be performed within the range which does not impair the meaning of this invention.

１０ 接合体
１０１ 多孔質焼結体
１０２ 緻密質焼結部
１１、１２ 導体 DESCRIPTION OF SYMBOLS 10 Joining body 101 Porous sintered body 102 Dense sintered part 11, 12 Conductor

Claims (10)

金属より形成された導体と、接合用金属と有機物とを含む接合材料とを接触状態とした後、熱処理することにより、前記接合用金属を焼結させる接合工程を有しており、
前記熱処理は、Ｏ（酸素）の結合数が異なる少なくとも２種以上のガスが混合されてなる混合ガス中にて実施され、
前記混合ガスは、前記熱処理時の温度において以下の（１）および（２）の条件を満たす成分比であることを特徴とする接合体の製造方法。
（１）炭素と酸素とが共存する平衡酸素分圧以上の酸素分圧を生成する
（２）前記導体を形成する金属の金属酸化物のうち、最も標準生成自由エネルギーの小さい金属酸化物と、前記導体を形成する金属とが共存できるような平衡酸素分圧以下の酸素分圧を生成する A bonding step of sintering the bonding metal by bringing the conductor formed of metal and the bonding material including the bonding metal and the organic material into contact and then heat-treating the conductive material;
The heat treatment is performed in a mixed gas in which at least two kinds of gases having different O (oxygen) bond numbers are mixed,
The mixed gas has a component ratio that satisfies the following conditions (1) and (2) at the temperature at the time of the heat treatment.
(1) Generate an oxygen partial pressure equal to or higher than the equilibrium oxygen partial pressure in which carbon and oxygen coexist. (2) Among the metal oxides of the metal forming the conductor, a metal oxide having the smallest standard free energy of formation; Generates an oxygen partial pressure equal to or lower than the equilibrium oxygen partial pressure so that the metal forming the conductor can coexist. 請求項１に記載の接合体の製造方法において、
前記熱処理時の温度は、２００〜３００℃の範囲内であることを特徴とする接合体の製造方法。 In the manufacturing method of the joined object according to claim 1,
The temperature during the heat treatment is in the range of 200 to 300 ° C. 請求項１または２に記載の接合体の製造方法において、
前記導体を形成する金属は、銅または銅合金であることを特徴とする接合体の製造方法。 In the manufacturing method of the joined object according to claim 1 or 2,
The metal forming the conductor is copper or a copper alloy. 請求項１〜３のいずれか１項に記載の接合体の製造方法において、
前記接合用金属は、その標準酸化還元電位が、前記導体を形成する金属の標準酸化還元電位と同じまたはそれよりも大きいことを特徴とする接合体の製造方法。 In the manufacturing method of the joined object given in any 1 paragraph of Claims 1-3,
The joining metal has a standard oxidation-reduction potential equal to or greater than a standard oxidation-reduction potential of a metal forming the conductor. 請求項１〜４のいずれか１項に記載の接合体の製造方法において、
前記混合ガスは、ＣＯ２とＣＯとが混合されてなる、または、Ｈ２とＨ２Ｏとが混合されてなることを特徴とする接合体の製造方法。 In the manufacturing method of the joined object given in any 1 paragraph of Claims 1-4,
The method of manufacturing a joined body, wherein the mixed gas is a mixture of CO 2 and CO, or a mixture of H 2 and H 2 O. 請求項１〜５のいずれか１項に記載の接合体の製造方法において、
前記接合材料として、前記接合用金属と前記有機物とを含むペーストを準備し、
前記導体の表面と前記ペーストとを接触状態とした後、前記混合ガス中にて熱処理することにより、前記ペースト中の接合用金属を焼結させる第１接合手順を含むことを特徴とする接合体の製造方法。 In the manufacturing method of the joined object given in any 1 paragraph of Claims 1-5,
As the bonding material, preparing a paste containing the bonding metal and the organic matter,
A joined body comprising a first joining step of sintering the joining metal in the paste by bringing the surface of the conductor into contact with the paste and then heat-treating in the mixed gas. Manufacturing method. 請求項１〜５のいずれか１項に記載の接合体の製造方法において、
前記接合材料として、前記接合用金属と前記有機物とを含む溶液を準備し、
前記導体の表面と前記溶液とを接触状態とした後、前記混合ガス中にて熱処理し、前記溶液から前記接合用金属を析出させるとともに該析出した接合用金属を焼結させる第２接合手順を含むことを特徴とする接合体の製造方法。 In the manufacturing method of the joined object given in any 1 paragraph of Claims 1-5,
As the bonding material, preparing a solution containing the bonding metal and the organic matter,
After bringing the surface of the conductor into contact with the solution, heat treatment is performed in the mixed gas to precipitate the joining metal from the solution and to sinter the deposited joining metal. The manufacturing method of the joined body characterized by including. 請求項１〜７のいずれか１項に記載の接合体の製造方法において、
前記接合用金属は、銀であることを特徴とする接合体の製造方法。 In the manufacturing method of the joined object given in any 1 paragraph of Claims 1-7,
The method for manufacturing a joined body, wherein the joining metal is silver. 請求項１〜８のいずれか１項に記載の接合体の製造方法において、
前記混合ガスは、ＣＯ２とＣＯとが混合されてなり、
前記混合ガスにおける前記ＣＯ濃度は、体積比で０．３ｐｐｂ〜１０ｐｐｍの範囲内にあることを特徴とする接合体の製造方法。 In the manufacturing method of the joined object given in any 1 paragraph of Claims 1-8,
The mixed gas is a mixture of CO 2 and CO,
The method for producing a joined body, wherein the CO concentration in the mixed gas is in a range of 0.3 ppb to 10 ppm by volume ratio. 金属より形成された導体と、接合用金属と有機物とを含む接合材料とを接触状態とした後、熱処理することにより、前記接合用金属を焼結させる接合工程を有する接合体の製造方法に用いられるオーブンであって、
Ｏ（酸素）の結合数が異なる少なくとも２種以上のガスが混合されてなる混合ガスを供給可能に構成されており、
前記混合ガスは、前記熱処理時の温度において以下の（１）および（２）の条件を満たす成分比であることを特徴とするオーブン。
（１）炭素と酸素とが共存する平衡酸素分圧以上の酸素分圧を生成する
（２）前記導体を形成する金属の金属酸化物のうち、最も標準生成自由エネルギーの小さい金属酸化物と、前記導体を形成する金属とが共存できるような平衡酸素分圧以下の酸素分圧を生成する Used in a method of manufacturing a joined body having a joining step of sintering the joining metal by heat-treating a conductor formed of a metal and a joining material containing a joining metal and an organic substance after being brought into contact with each other. An oven,
It is configured to be able to supply a mixed gas in which at least two kinds of gases having different O (oxygen) bond numbers are mixed,
The oven characterized in that the mixed gas has a component ratio that satisfies the following conditions (1) and (2) at the temperature during the heat treatment.
(1) Generate an oxygen partial pressure equal to or higher than the equilibrium oxygen partial pressure in which carbon and oxygen coexist. (2) Among the metal oxides of the metal forming the conductor, a metal oxide having the smallest standard free energy of formation; Generates an oxygen partial pressure equal to or lower than the equilibrium oxygen partial pressure so that the metal forming the conductor can coexist.
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