JP2018103189A - Heat bonding material and manufacturing method of electric and electronic equipment - Google Patents
Heat bonding material and manufacturing method of electric and electronic equipment Download PDFInfo
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- JP2018103189A JP2018103189A JP2016248767A JP2016248767A JP2018103189A JP 2018103189 A JP2018103189 A JP 2018103189A JP 2016248767 A JP2016248767 A JP 2016248767A JP 2016248767 A JP2016248767 A JP 2016248767A JP 2018103189 A JP2018103189 A JP 2018103189A
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Abstract
Description
本発明は、金属部材、電子部品部材、半導体部材、及びセラミックス部材から選択される同種部材間、又は異種部材間を加熱接合させるペーストの代替材料となる加熱接合材及び電気電子機器の製造方法に関する。 The present invention relates to a method for manufacturing a heating bonding material and an electric / electronic device as an alternative material for a paste that heat-bonds the same type of members selected from metal members, electronic component members, semiconductor members, and ceramic members, or between different types of members. .
電気電子機器の実装工程において、各部品の接合は一般的にはんだ付けによって行われる。はんだ材料として、以前は鉛を含むはんだ（例えば、錫−鉛（Ｓｎ−Ｐｂ）系はんだ）が広く用いられてきた。しかしながら、近年、電気電子機器業界では、比較的環境負荷低い材料、鉛を含まないはんだ（鉛フリーはんだ）が求められている。 In the mounting process of electrical and electronic equipment, each component is generally joined by soldering. As a solder material, solder containing lead (for example, tin-lead (Sn—Pb) solder) has been widely used. However, in recent years, in the electrical and electronic equipment industry, a material having a relatively low environmental load and a solder containing no lead (lead-free solder) have been demanded.
そこで、近時では金属微粒子を含むペースト（ 以下、金属ペーストという）がある（例えば、特許文献１参照）。 金属ペーストは、金属微粒子に、保存時や製造工程中の金属微粒子同士の凝縮を防止する有機分散剤と、接合時に有機分散剤と反応して有機分散剤を除去する分散補助物質とを添加し、これに溶剤等を混合させてペースト状にしたものである。金属微粒子は、少なくとも粒径が１ｎｍ〜５００ｎｍ程度の極めて微細な粒子を含むものであり、表面は活性状態である。 Therefore, recently, there is a paste containing metal fine particles (hereinafter referred to as a metal paste) (see, for example, Patent Document 1). In the metal paste, an organic dispersant that prevents condensation between metal fine particles during storage or during the manufacturing process and a dispersion auxiliary material that reacts with the organic dispersant during bonding to remove the organic dispersant are added to the metal fine particles. These are mixed with a solvent or the like to make a paste. The metal fine particles include at least extremely fine particles having a particle diameter of about 1 nm to 500 nm, and the surface is in an active state.
金属ペーストを用いて半導体素子と基板とを接合するには、半導体素子および／または基板の接合面に金属ペーストをディスペンサー、またはスクリーン印刷により塗布し、１５０℃〜３００℃で所定時間（１分〜１時間程度）加熱する。これにより、有機分散剤と分散補助材とが反応して有機分散剤が除去され、同時に溶剤も揮発して除去される。有機分散剤や溶剤が除去されると、活性状態にある金属微粒子同士が互いに結合し、その金属成分の単体膜となる。 In order to bond the semiconductor element and the substrate using the metal paste, the metal paste is applied to the bonding surface of the semiconductor element and / or the substrate by a dispenser or screen printing, and a predetermined time (from 1 minute to 150 ° C. to 300 ° C.). Heat for about 1 hour). As a result, the organic dispersant and the dispersion aid react to remove the organic dispersant, and at the same time, the solvent is volatilized and removed. When the organic dispersant and the solvent are removed, the metal fine particles in the active state are bonded to each other to form a single film of the metal component.
金属ペーストをディスペンサーやスクリーン印刷を用いて、接合面に塗布する場合、溶剤等の量を調節して、金属ペーストの粘度をある程度低くする必要がある。しかしながら、粘度を下げると、金属ペーストを接合面に塗布する際に、金属ペーストが飛散して半導体素子や基板の接合面以外の部分に付着して半導体素子や基板が汚染されてしまうという問題があった。また、金属ペーストを接合面に塗布するための専用の装置が必要だという問題があった。 When applying a metal paste to a joint surface using a dispenser or screen printing, it is necessary to adjust the quantity of a solvent etc. and to make the viscosity of a metal paste low to some extent. However, when the viscosity is lowered, there is a problem that when the metal paste is applied to the bonding surface, the metal paste scatters and adheres to a portion other than the bonding surface of the semiconductor element or the substrate and the semiconductor element or the substrate is contaminated. there were. In addition, there is a problem that a dedicated device for applying the metal paste to the joint surface is necessary.
そこで、２５℃で液状の、アルコール類を主成分とする有機化合物分散媒に金属微粒子が分散された、常温でペースト状でなく高粘度の加熱接合材が提案されている（特許文献２、参照）。この加熱接合材は、常温で高粘度であるため、シート形状、扁平状細片、鱗片状細片等の形状を維持することが可能になり、接合面へパターニングし、そのままの形状で他の被接合体と接触させた状態で加熱焼結できる。 In view of this, there has been proposed a heat-bonding material that is liquid at 25 ° C. and in which metal fine particles are dispersed in an organic compound dispersion medium containing alcohols as a main component and that is not pasty at room temperature and has a high viscosity (see Patent Document 2). ). Since this heat-bonding material has a high viscosity at room temperature, it becomes possible to maintain the shape of a sheet, flat strips, scale strips, etc. Heat sintering can be performed in a state of being in contact with the object to be joined.
しかしながら、上記特許文献２に記載の加熱接合材は、金属微粒子の質量分が高く、また、接合体として成形する際には取り扱い性等の点からある程度の厚みが必要であるため、焼結時の溶媒の蒸発による抜けが悪く、焼結後に接合体内に溶媒が残ったり、またはボイドが多く残ったりするおそれがあった。焼結後の接合体内に溶媒が残ったり、またはボイドが多く残ったりした場合、接合強度が低くなるという問題があった。 However, the heat-bonded material described in Patent Document 2 has a high mass of metal fine particles, and when it is molded as a bonded body, a certain amount of thickness is required from the viewpoint of handleability and the like. There was a possibility that the solvent could not escape due to evaporation of the solvent, and the solvent could remain in the joined body after sintering or a lot of voids might remain. When a solvent remains or a lot of voids remain in the bonded body after sintering, there is a problem that the bonding strength is lowered.
そこで、本発明は、取り扱い性がよく、焼結時の溶媒の抜けがよい加熱接合材及び電気電子機器の製造方法を提供することを課題とする。 Then, this invention makes it a subject to provide the manufacturing method of the heat-joining material and electrical / electronic equipment with a good handleability and the detachment | desorption of the solvent at the time of sintering.
以上の課題を解決するため、本発明に係る加熱接合材は、金属のバルク材から形成される金属層と、前記金属層の両面に積層して設けられた金属接合層とを有し、前記金属接合層は、高分子分散剤（Ｄ）に被覆され、金属単体、合金及び金属化合物からなる群から選択される少なくとも１種からなる金属微粒子（Ｐ）を有機溶媒（Ｓ）に分散させた分散溶液をフィルム状に成形してなることを特徴とする。 In order to solve the above problems, a heat bonding material according to the present invention has a metal layer formed from a metal bulk material, and a metal bonding layer provided on both surfaces of the metal layer, The metal bonding layer was coated with the polymer dispersant (D), and metal fine particles (P) consisting of at least one selected from the group consisting of simple metals, alloys and metal compounds were dispersed in the organic solvent (S). The dispersion solution is formed into a film shape.
また、上記加熱接合材は、前記金属微粒子（Ｐ）が、銅、銀、金、白金、パラジウムからなる群から選択される少なくとも１種からなることが好ましい。 In the heat bonding material, the metal fine particles (P) are preferably made of at least one selected from the group consisting of copper, silver, gold, platinum, and palladium.
また、上記加熱接合材は、前記高分子分散剤（Ｄ）が、分子中に少なくとも１つのカルボニル基を有する化合物、又は分子中に少なくとも１つの窒素原子を有する化合物であることが好ましい。 In the heat bonding material, the polymer dispersant (D) is preferably a compound having at least one carbonyl group in the molecule or a compound having at least one nitrogen atom in the molecule.
また、上記加熱接合材は、前記金属層を構成する前記バルク材の金属元素含有量が９９質量％以上であることが好ましい。 Moreover, it is preferable that the said heat joining material is 99 mass% or more of metal element content of the said bulk material which comprises the said metal layer.
また、上記加熱接合材は、前記金属層を構成する前記バルク材が、前記金属微粒子（Ｐ）と同種の金属単体または合金であることが好ましい。 Moreover, as for the said heat joining material, it is preferable that the said bulk material which comprises the said metal layer is a metal single-piece | unit or alloy of the same kind as the said metal microparticle (P).
また、上記加熱接合材は、前記金属層を構成する前記バルク材が、前記金属微粒子（Ｐ）と異なる種類の金属単体または合金であってもよい。 Moreover, as for the said heat joining material, the said bulk material which comprises the said metal layer may be a metal single-piece | unit or alloy of a different kind from the said metal fine particle (P).
また、上記加熱接合材は、前記高分子分散剤（Ｄ）が、ポリビニルピロリドン、ポリエチレンイミン、ポリアクリル酸、カルボキシメチルセルロース、ポリアクリルアミド、ポリビニルアルコール、ポリエチレングリコール、ポリエチレンオキシド、デンプン、及びゼラチンからなる群から選択される少なくとも１種であることが好ましい。 In the heat bonding material, the polymer dispersant (D) is made of polyvinylpyrrolidone, polyethyleneimine, polyacrylic acid, carboxymethylcellulose, polyacrylamide, polyvinyl alcohol, polyethylene glycol, polyethylene oxide, starch, and gelatin. It is preferable that it is at least 1 type selected from.
また、上記加熱接合材は、一方の前記金属接合層に含まれる前記金属微粒子（Ｐ）は、他方の前記金属接合層に含まれる前記金属微粒子（Ｐ）と同種の金属単体、合金または金属化合物からなることが好ましい。 Further, in the heating bonding material, the metal fine particles (P) contained in one of the metal bonding layers is the same kind of simple metal, alloy or metal compound as the metal fine particles (P) contained in the other metal bonding layer. Preferably it consists of.
また、上記加熱接合材は、一方の前記金属接合層に含まれる前記金属微粒子（Ｐ）は、他方の前記金属接合層に含まれる前記金属微粒子（Ｐ）と異なる種類の金属単体、合金または金属化合物からなっていてもよい。 Further, in the heat bonding material, the metal fine particles (P) contained in one of the metal bonding layers is different from the metal fine particles (P) contained in the other metal bonding layer of a single metal, alloy or metal of a different type. It may consist of a compound.
また、上記加熱接合材は、前記金属接合層の厚みがそれぞれ０．１５ｍｍ〜０．２２５ｍｍであることが好ましい。 Moreover, it is preferable that the thickness of the said metal joining layer is 0.15 mm-0.225 mm, respectively.
また、上記加熱接合材は、前記金属層の厚みが０．０５ｍｍ〜０．２ｍｍであることが好ましい。 Moreover, it is preferable that the thickness of the said metal layer is 0.05 mm-0.2 mm.
また、以上の課題を解決するため、本発明に係る電気電子機器の製造方法は、一の部品の接合面に、請求項１から１１に記載の加熱接合材を載せた後、該加熱接合材上に更に接続する他の部品の接合面を配置し、加熱処理により金属微粒子（Ｐ）を焼結して、前記一の部品と前記他の部品とを接合し、電気電子機器を製造することを特徴とする。 Moreover, in order to solve the above subject, the manufacturing method of the electrical / electronic device which concerns on this invention is, after mounting the heating joining material of Claim 1 to 11 on the joint surface of one component, this heating joining material A bonding surface of another component to be further connected is disposed on the surface, and the metal fine particles (P) are sintered by heat treatment, and the one component and the other component are bonded to manufacture an electric / electronic device. It is characterized by.
また、上記電気電子機器の製造方法は、大気雰囲気中又は不活性ガス雰囲気中で、有機溶媒（Ｓ）の沸点よりも４０〜５０℃低い温度範囲で行うことが好ましい。 Moreover, it is preferable to perform the manufacturing method of the said electrical / electronic device in a temperature range 40-50 degreeC lower than the boiling point of an organic solvent (S) in air | atmosphere atmosphere or inert gas atmosphere.
本発明によれば、取り扱い性がよく、焼結時の溶媒の抜けがよい加熱接合材及び電気電子機器の製造方法を提供することができる。 According to the present invention, it is possible to provide a method for manufacturing a heat-bonding material and an electric / electronic device that are easy to handle and have good solvent removal during sintering.
以下、本発明の実施の形態に係る加熱接合材１を図面に基づいて説明する。図１は一実施形態に係る加熱接合材１を示す断面図である。 Hereinafter, the heating bonding material 1 which concerns on embodiment of this invention is demonstrated based on drawing. FIG. 1 is a cross-sectional view showing a heat bonding material 1 according to an embodiment.
図１に示すように、本発明の一実施形態に係る加熱接合材１は、金属のバルク材から形成される金属層２を有しており、金属層２の両面には、金属接合層３が積層されている。金属接合層３は、高分子分散剤（Ｄ）に被覆され、金属単体、合金及び金属化合物からなる群から選択される少なくとも１種からなる金属微粒子（Ｐ）を有機溶媒（Ｓ）に分散させた分散溶液をフィルム状に成形してなる。 As shown in FIG. 1, a heat bonding material 1 according to an embodiment of the present invention has a metal layer 2 formed from a metal bulk material, and a metal bonding layer 3 is formed on both surfaces of the metal layer 2. Are stacked. The metal bonding layer 3 is coated with a polymer dispersant (D), and metal fine particles (P) made of at least one selected from the group consisting of simple metals, alloys and metal compounds are dispersed in an organic solvent (S). The dispersion solution is formed into a film.
なお、加熱接合材１は、金属接合層３を保護するための離型フィルムが、金属接合層３の表面に設けられていてもよい。離型フィルムとしては、公知のものを使用することができる。 In the heating bonding material 1, a release film for protecting the metal bonding layer 3 may be provided on the surface of the metal bonding layer 3. A well-known thing can be used as a release film.
加熱接合材１は、電子部品等の接合面にあわせて予め所定の大きさや形状に切断されていてもよい。 The heat bonding material 1 may be cut into a predetermined size or shape in advance in accordance with a bonding surface of an electronic component or the like.
以下、本実施形態の加熱接合材１の各構成要素について詳細に説明する。 Hereinafter, each component of the heat bonding material 1 of the present embodiment will be described in detail.
（１）金属層２
金属層２は、金属のバルク材から形成される。バルク材は、接合材料としての導電性を確保する観点から、金属元素含有量が９９質量％以上であることが好ましい。また、バルク材は、一の金属単体で構成されてもよいし、複数の金属からなる合金金で構成されてもよい。金属元素としては、特に限定されるものではないが、金属単体の場合は、例えば、銅、銀、金、白金、およびパラジウムからなる群から選択されることが好ましい。合金の場合は、例えば、銅、銀、金、白金、およびパラジウムの中から選択される少なくとも２種以上から構成されることが好ましい。また、バルク材は、後述の金属微粒子（Ｐ）と同種の金属単体または合金であってもよいし、異なる種類の金属単体または合金であってもよい。
(1) Metal layer 2
The metal layer 2 is formed from a metal bulk material. The bulk material preferably has a metal element content of 99% by mass or more from the viewpoint of ensuring conductivity as a bonding material. The bulk material may be composed of a single metal or an alloy gold composed of a plurality of metals. Although it does not specifically limit as a metal element, In the case of a metal single-piece | unit, it is preferable to be selected from the group which consists of copper, silver, gold | metal | money, platinum, and palladium, for example. In the case of an alloy, it is preferably composed of at least two or more selected from, for example, copper, silver, gold, platinum, and palladium. Further, the bulk material may be a single metal or an alloy of the same type as the metal fine particles (P) described later, or may be a different type of single metal or alloy.
金属層２は、上述のバルク材をシート状あるいはフィルム状に形成したものであれば、形状や製法は限定されるものではないが、箔が好ましく、銅箔、銅合金箔が特に好ましい。その他、金属メッシュ、金属多孔質体なども用いることができる。 The shape and manufacturing method of the metal layer 2 are not limited as long as the above-described bulk material is formed in a sheet shape or a film shape, but a foil is preferable, and a copper foil and a copper alloy foil are particularly preferable. In addition, a metal mesh, a metal porous body, etc. can also be used.
金属層２の厚みは、特に限定するものではないが０．０５ｍｍ〜０．２ｍｍであることが好ましい。金属層２の厚みが０．０５ｍｍ未満であると、加熱接合材１としての取り扱い性や接合部材としての剛性などの観点から、金属接合層３の厚みを大きくする必要があり、焼結時の有機溶媒（Ｓ）の抜けが悪くなり、有機溶媒（Ｓ）の残存やボイドが発生するおそれがある。金属層２の厚みが０．２ｍｍ超であると、線膨張係数の差に起因して金属接合層３と金属層２を加熱する際に発生する応力が大きくなり、加熱接合材１が割れやすくなるおそれがある。また、金属層２を厚くすることで金属接合層３の厚みを薄くする必要があり、接合強度が低下する原因になると考えられる。 The thickness of the metal layer 2 is not particularly limited, but is preferably 0.05 mm to 0.2 mm. If the thickness of the metal layer 2 is less than 0.05 mm, it is necessary to increase the thickness of the metal bonding layer 3 from the viewpoint of the handling property as the heat bonding material 1 and the rigidity as the bonding member. There is a possibility that the organic solvent (S) may be lost and the organic solvent (S) may remain or voids may be generated. When the thickness of the metal layer 2 is more than 0.2 mm, the stress generated when the metal bonding layer 3 and the metal layer 2 are heated due to the difference in linear expansion coefficient is increased, and the heat bonding material 1 is easily cracked. There is a risk. Moreover, it is necessary to reduce the thickness of the metal bonding layer 3 by increasing the thickness of the metal layer 2, which is considered to cause a decrease in bonding strength.
（２）金属接合層３
金属接合層３は、高分子分散剤（Ｄ）に被覆され、金属単体、合金及び金属化合物からなる群から選択される少なくとも１種からなる金属微粒子（Ｐ）を有機溶媒（Ｓ）に分散させた分散溶液をフィルム状に成形してなる。
(2) Metal bonding layer 3
The metal bonding layer 3 is coated with a polymer dispersant (D), and metal fine particles (P) made of at least one selected from the group consisting of simple metals, alloys and metal compounds are dispersed in an organic solvent (S). The dispersion solution is formed into a film.
（２−１）高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）
金属微粒子（Ｐ）は、特に限定されるものではないが、銅、銀、金、白金、およびパラジウムからなる金属元素群から選ばれる１種の微粒子、前記金属元素群から選ばれる２種以上を混合した微粒子、前記金属元素群から選ばれる２種以上の元素の合金からなる微粒子、前記金属元素群から選ばれる１種の微粒子または前記金属元素群から選ばれる２種以上を混合した微粒子と前記金属元素群から選ばれる２種以上の元素の合金からなる微粒子とを混合した微粒子、これらの酸化物、または、これらの水酸化物等を用いることができる。
(2-1) Fine metal particles (P) coated with a polymer dispersant (D)
The metal fine particles (P) are not particularly limited, but include one kind of fine particles selected from a metal element group consisting of copper, silver, gold, platinum, and palladium, and two or more kinds selected from the metal element group. Mixed fine particles, fine particles made of an alloy of two or more elements selected from the metal element group, one kind of fine particles selected from the metal element group, or fine particles obtained by mixing two or more kinds selected from the metal element group; Fine particles obtained by mixing fine particles made of an alloy of two or more elements selected from a metal element group, oxides thereof, hydroxides thereof, or the like can be used.
金属層２の一方側の面に設けられる金属接合層３に含まれる前記金属微粒子（Ｐ）は、金属層２の他方側の面に設けられる金属接合層３に含まれる前記金属微粒子（Ｐ）と同種の金属単体、合金または金属化合物からなっていてもよいし、異なる種類の金属単体、合金または金属化合物からなっていてもよい。 The metal fine particles (P) contained in the metal bonding layer 3 provided on one surface of the metal layer 2 are the metal fine particles (P) contained in the metal bonding layer 3 provided on the other surface of the metal layer 2. And the same kind of simple metal, alloy or metal compound, or different kinds of simple metal, alloy or metal compound.
金属微粒子（Ｐ）は、加熱処理前の平均一次粒径が５〜５００ｎｍであることが好ましく、１０〜５０ｎｍであることがさらに好ましい。上記金属微粒子（Ｐ）の平均一次粒子径が、５〜５００ｎｍである場合には、加熱接合材１を加熱処理して、金属微粒子（Ｐ）の焼結を行う過程（焼結過程）で、有機溶媒（Ｓ）の加水分解反応において、金属微粒子（Ｐ）が触媒として作用し、加水分解反応の進行速度を向上させ、金属微粒子（Ｐ）の焼結を促進させる効果が期待できる。 The metal fine particles (P) preferably have an average primary particle size before heat treatment of 5 to 500 nm, and more preferably 10 to 50 nm. When the average primary particle diameter of the metal fine particles (P) is 5 to 500 nm, the heat bonding material 1 is subjected to heat treatment and the metal fine particles (P) are sintered (sintering process). In the hydrolysis reaction of the organic solvent (S), the metal fine particles (P) act as a catalyst, and the effect of improving the progress rate of the hydrolysis reaction and promoting the sintering of the metal fine particles (P) can be expected.
金属微粒子（Ｐ）の平均一次粒子径が、５ｎｍ未満である場合には、金属微粒子（Ｐ）が酸化され易くなる他、凝集し易くなり、均一に分散され難く、粘度の保存安定性に劣るおそれがある。一方、金属微粒子（Ｐ）の平均一次粒子径が、５００ｎｍを超える場合には、加熱接合材１を加熱処理して、金属微粒子（Ｐ）の焼結を行う過程（焼結過程）で、焼結温度を上げなければならず、緻密性の高い均質な焼結膜を形成することができないおそれがある。 When the average primary particle diameter of the metal fine particles (P) is less than 5 nm, the metal fine particles (P) are likely to be oxidized, easily aggregated, difficult to be uniformly dispersed, and inferior in storage stability of viscosity. There is a fear. On the other hand, when the average primary particle diameter of the metal fine particles (P) exceeds 500 nm, the heat bonding material 1 is subjected to heat treatment to sinter the metal fine particles (P) (sintering process). There is a possibility that the sintering temperature must be increased and a dense sintered film with high density cannot be formed.
ここで「平均一次粒子径」とは、走査型電子顕微鏡（ＳＥＭ）を使用して、観察可能な任意に選択した粒子の一次粒径をそれぞれ測定し、特定の粒径分布範囲にある粒子を対象として、それぞれの一次粒径の測定値の平均を算出する。 Here, the “average primary particle size” means that the primary particle size of arbitrarily selected particles that can be observed is measured using a scanning electron microscope (SEM), and particles in a specific particle size distribution range are measured. As an object, the average of the measured values of the respective primary particle diameters is calculated.
具体的には、走査型電子顕微鏡（ＳＥＭ）を使用して、観察可能な任意に選択した８０個の金属微粒子（Ｐ）の一次粒径を測定したものである。測定した金属微粒子（Ｐ）全体（８０個）のうち、一次粒径が小さい方から順に数えて、金属微粒子（Ｐ）全体（８０個）の５％に相当する金属微粒子（Ｐ）（４個）と、一次粒径が大きい方から順に数えて、金属微粒子（Ｐ）全体（８０個）の５％に相当する金属微粒子（Ｐ）（４個）とを除き、残り金属微粒子（Ｐ）全体（８０個）の９０％に相当する金属微粒子（Ｐ）（７２個）を対象とし、７２個の金属微粒子（Ｐ）の一次粒径の測定値の平均を算出し、金属微粒子（Ｐ）の平均一次粒径とする。 Specifically, the primary particle diameter of 80 arbitrarily selected fine metal particles (P) that can be observed is measured using a scanning electron microscope (SEM). Among the measured metal fine particles (P) (80 particles), the metal fine particles (P) (4 particles) corresponding to 5% of the whole metal fine particles (P) (80 particles) counted in order from the smallest primary particle size. ) And the remaining fine metal particles (P) except for the fine metal particles (P) (4) corresponding to 5% of the total fine metal particles (P) (80 particles), counting from the larger primary particle size. For the metal fine particles (P) (72 particles) corresponding to 90% of (80 particles), the average of the measured primary particle diameters of the 72 metal particles (P) was calculated, and the metal fine particles (P) The average primary particle size is used.
（２−２）高分子分散剤（Ｄ）
本発明で用いる高分子分散剤（Ｄ）は、金属微粒子（Ｐ）の原料となる金属の表面を被覆して、金属微粒子（Ｐ）を形成することができるものであれば、特に限定されるものではない。
(2-2) Polymer dispersant (D)
The polymer dispersant (D) used in the present invention is particularly limited as long as it can coat the surface of the metal used as the raw material of the metal fine particles (P) to form the metal fine particles (P). It is not a thing.
ここで「被覆」とは、金属微粒子（Ｐ）の原料となる金属の表面の少なくとも一部を覆うものであってもよいし、金属微粒子（Ｐ）の原料となる金属の表面の全体を覆うものであってもよい。 Here, the “coating” may cover at least part of the surface of the metal that is the raw material of the metal fine particles (P), or covers the entire surface of the metal that is the raw material of the metal fine particles (P). It may be a thing.
本発明で用いる高分子分散剤（Ｄ）の数平均分子量は、特に限定されないが、３，０００〜５，０００であることが好ましい。 The number average molecular weight of the polymer dispersant (D) used in the present invention is not particularly limited, but is preferably 3,000 to 5,000.
上記高分子分散剤（Ｄ）の数平均分子量が、上記範囲未満である場合には、金属微粒子（Ｐ）の原料となる金属の表面を好適に被覆させることができず、金属微粒子（Ｐ）の粒径がナノサイズよりも大きくなるおそれがあり、サイズ効果による焼結性の向上を期待できなくなる。 When the number average molecular weight of the polymer dispersant (D) is less than the above range, the surface of the metal used as the raw material of the metal fine particles (P) cannot be suitably coated, and the metal fine particles (P) There is a possibility that the particle size of the material becomes larger than the nano size, and improvement in sinterability due to the size effect cannot be expected.
一方、上記高分子分散剤（Ｄ）の数平均分子量が、上記範囲を超える場合には、加熱処理により金属微粒子（Ｐ）の焼結を行う過程（焼結過程）で、焼結膜内に高分子分散剤（Ｄ）が残留し、電気抵抗を高める原因となるおそれがある。 On the other hand, when the number average molecular weight of the polymer dispersant (D) exceeds the above range, a high level in the sintered film is obtained in the process of sintering the metal fine particles (P) by heat treatment (sintering process). The molecular dispersant (D) remains and may cause an increase in electrical resistance.
本発明で用いる高分子分散剤（Ｄ）は、金属微粒子（Ｐ）の原料となる金属の表面を好適に被覆させる観点から、分子中に少なくとも１つのカルボニル基を有する化合物、又は分子中に少なくとも１つの窒素原子を有する化合物であることが好ましい。 The polymer dispersant (D) used in the present invention is a compound having at least one carbonyl group in the molecule, or at least in the molecule, from the viewpoint of suitably coating the surface of the metal used as the raw material of the metal fine particles (P). A compound having one nitrogen atom is preferable.
本発明で用いる高分子分散剤（Ｄ）としては、金属微粒子（Ｐ）の原料となる金属の表面を好適に被覆させることができるものであれば、特に限定されないが、例えば、ポリビニルピロリドン、ポリエチレンイミン、ポリアクリル酸、カルボキシメチルセルロース、ポリアクリルアミド、ポリビニルアルコール、ポリエチレングリコール、ポリエチレンオキシド、デンプン、およびゼラチン等が挙げられ、これらの中から選択される１種又は２種以上であることが好ましい。 The polymer dispersant (D) used in the present invention is not particularly limited as long as it can suitably coat the surface of the metal used as the raw material of the metal fine particles (P). For example, polyvinyl pyrrolidone, polyethylene Examples include imine, polyacrylic acid, carboxymethylcellulose, polyacrylamide, polyvinyl alcohol, polyethylene glycol, polyethylene oxide, starch, and gelatin, and one or more selected from these are preferable.
本発明で用いる、高分子分散剤（Ｄ）と高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）との重量比（Ｄ／Ｐ）は、特に限定されないが、０．２〜０．５の範囲にあることが好ましい。 The weight ratio (D / P) of the polymer dispersant (D) and the metal fine particles (P) coated with the polymer dispersant (D) used in the present invention is not particularly limited, but is 0.2 to 0. Preferably it is in the range of .5.
上記高分子分散剤（Ｄ）と金属微粒子（Ｐ）との重量比（Ｄ／Ｐ）が、上記範囲未満である場合には、高分子分散剤（Ｄ）の割合が少な過ぎ、金属微粒子（Ｐ）の原料となる金属の表面を好適に被覆させることができず、金属微粒子（Ｐ）の粒径がナノサイズよりも大きくなるおそれがあり、サイズ効果による焼結性の向上を期待できなくなる。 When the weight ratio (D / P) between the polymer dispersant (D) and the metal fine particles (P) is less than the above range, the proportion of the polymer dispersant (D) is too small, and the metal fine particles ( The surface of the metal used as the raw material of P) cannot be suitably coated, and the particle size of the metal fine particles (P) may be larger than the nano size, so that improvement in sinterability due to the size effect cannot be expected. .
一方、上記高分子分散剤（Ｄ）の含有量が、上記範囲を超える場合には、高分子分散剤（Ｄ）の割合が多過ぎ、加熱処理により金属微粒子（Ｐ）の焼結を行う過程（焼結過程）で、焼結膜内に高分子分散剤（Ｄ）が残留し、電気抵抗を高める原因となるおそれがある。 On the other hand, when the content of the polymer dispersant (D) exceeds the above range, the ratio of the polymer dispersant (D) is too large, and the metal fine particles (P) are sintered by heat treatment. In the (sintering process), the polymer dispersant (D) remains in the sintered film, which may increase the electrical resistance.
本発明において、平均一次粒子径が５〜５００ｎｍの範囲にある、高分子分散剤（Ｄ）で被覆された表面を有する金属微粒子（Ｐ）を製造する方法は、特に限定されないが、液相還元法（電解法又は無電解法）を用いて製造することができる。 In the present invention, the method for producing the metal fine particles (P) having a surface coated with the polymer dispersant (D) having an average primary particle diameter in the range of 5 to 500 nm is not particularly limited, but is liquid phase reduction. It can be produced using a method (electrolytic method or electroless method).
電解法による液相還元法では、例えば、金属イオンを含む水溶液および高分子分散剤（Ｄ）を含む混合溶液を電解槽に入れ、電極（陽極：アノード、陰極：カソード）を配置し、アノードとカソード間で通電させることによってカソード付近に、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）が電析し、回収される。 In the liquid phase reduction method by electrolysis, for example, a mixed solution containing an aqueous solution containing metal ions and a polymer dispersant (D) is placed in an electrolytic cell, electrodes (anode: anode, cathode: cathode) are arranged, and the anode and By energizing between the cathodes, the metal fine particles (P) coated with the polymer dispersant (D) are electrodeposited and collected in the vicinity of the cathodes.
これに対して、無電解法による液相還元法では、例えば、還元剤を含む水溶液に、高分子分散剤（Ｄ）を添加して、攪拌溶解させ、金属イオンを含む水溶液を滴下し、金属微粒子の混合溶液を調製する。 On the other hand, in the liquid phase reduction method by the electroless method, for example, the polymer dispersant (D) is added to an aqueous solution containing a reducing agent, dissolved by stirring, and an aqueous solution containing metal ions is dropped. A mixed solution of fine particles is prepared.
なお、金属微粒子の混合溶液は、金属イオンを含む水溶液に、高分子分散剤（Ｄ）を添加して、攪拌溶解させ、還元剤を含む水溶液を加えて調製されてもよい。 The mixed solution of metal fine particles may be prepared by adding the polymer dispersant (D) to an aqueous solution containing metal ions, stirring and dissolving, and adding an aqueous solution containing a reducing agent.
ここで用いる還元剤としては、例えば、水素化ホウ素ナトリウム、ヒドラジン、ジメチルアミノボラン、およびトリメチルアミノボラン等が挙げられる。 Examples of the reducing agent used here include sodium borohydride, hydrazine, dimethylaminoborane, and trimethylaminoborane.
また、ここで用いる金属イオンを形成する金属塩としては、例えば、塩化物、硝酸塩、亜硝酸塩、硫酸塩、アンモニウム塩、および酢酸塩等の金属塩が挙げられる。 Moreover, as a metal salt which forms the metal ion used here, metal salts, such as a chloride, nitrate, nitrite, a sulfate, an ammonium salt, and acetate, are mentioned, for example.
次に、上記のように調製した金属微粒子の混合溶液に、凝集促進剤などの添加剤を添加し、攪拌し静置した後、沈殿した固形分を含む混合溶液を遠心分離機に供給することによって、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）が分離・回収される。 Next, an additive such as an aggregation accelerator is added to the mixed solution of metal fine particles prepared as described above, and the mixture is stirred and allowed to stand, and then the mixed solution containing the precipitated solid content is supplied to the centrifuge. Thus, the metal fine particles (P) coated with the polymer dispersant (D) are separated and recovered.
ここで用いる凝集促進剤としては、ハロゲン系炭化水素が好ましく用いられ、例えば、塩化メチル、塩化メチレン、クロロホルム、および四塩化炭素等の炭素原子数１の塩素系化合物；塩化エチル、１,１−ジクロルエタン、１,２−ジクロルエタン、１,１−ジクロルエチレン、１,２−ジクロルエチレン、トリクロルエチレン、四塩化アセチレン、およびエチレンクロロヒドリン等の炭素原子数２の塩素系化合物；１,２−ジクロルプロパン、および塩化アリル、等の炭素原子数３の塩素系化合物；クロロプレン等の炭素原子数４の塩素系化合物；クロルベンゼン、塩化ベンジル、ｏ−ジクロルベンゼン、ｍ−ジクロルベンゼン、ｐ−ジクロルベンゼン、α−クロルナフタリン、およびβ−クロルナフタリン等の芳香族系塩素系化合物；ブロモホルム、およびブロムベンゾール等の臭素系化合物；等が挙げられる。 As the aggregation accelerator used here, halogen-based hydrocarbons are preferably used. For example, chlorine-based compounds having 1 carbon atom such as methyl chloride, methylene chloride, chloroform, and carbon tetrachloride; ethyl chloride, 1,1- Chlorine compounds having 2 carbon atoms such as dichloroethane, 1,2-dichloroethane, 1,1-dichloroethylene, 1,2-dichloroethylene, trichloroethylene, acetylene tetrachloride, and ethylene chlorohydrin; 1,2 -Chlorine compounds having 3 carbon atoms such as dichloropropane and allyl chloride; Chlorine compounds having 4 carbon atoms such as chloroprene; chlorobenzene, benzyl chloride, o-dichlorobenzene, m-dichlorobenzene, aromatic chlorinated compounds such as p-dichlorobenzene, α-chloronaphthalene, and β-chloronaphthalene; Arm, and bromine compounds such as bromine benzol; and the like.
（２−３）有機溶媒（Ｓ）
本発明で用いる有機溶媒は、特に限定されないが、二価アルコール及び／又は三価アルコールからなる有機溶媒（Ｓ）であることが好ましい。上記二価アルコール及び／又は三価アルコールからなる有機溶媒（Ｓ）を用いることで、加熱処理により金属微粒子（Ｐ）の焼結を行う過程（焼結過程）で、有機溶媒（Ｓ）が、ガス成分と水分子（Ｈ2Ｏ）とに好適に分解される。
(2-3) Organic solvent (S)
Although the organic solvent used by this invention is not specifically limited, It is preferable that it is the organic solvent (S) which consists of a dihydric alcohol and / or a trihydric alcohol. By using the organic solvent (S) composed of the above dihydric alcohol and / or trihydric alcohol, the organic solvent (S) is a process (sintering process) in which the metal fine particles (P) are sintered by heat treatment. It is suitably decomposed into gas components and water molecules (H 2 O).
二価アルコールとしては、例えば、エチレングリコール、ジエチレングリコール、１，２−プロパンジオール、１，３−プロパンジオール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール、２−ブテン−１，４−ジオール、１，２−ペンタンジオール、１，５−ペンタンジオール、１，２−ヘキサンジオール、および１，６−ヘキサンジオール等が挙げられ、これらの中から選択される少なくとも１種であることが好ましい。 Examples of the dihydric alcohol include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2- Butene-1,4-diol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol and the like, and at least one selected from these Preferably it is a seed.
また、三価アルコールとしては、例えば、グリセロール、１，２，４−ブタントリオール、および１，２，６−ヘキサントリオール等が挙げられ、これらの中から選択される少なくとも１種であることが好ましい。 Examples of the trihydric alcohol include glycerol, 1,2,4-butanetriol, and 1,2,6-hexanetriol, and are preferably at least one selected from these. .
高分子分散剤（Ｄ）に被覆され、金属単体、合金及び金属化合物からなる群から選択される少なくとも１種からなる金属微粒子（Ｐ）を有機溶媒（Ｓ）に分散させた分散溶液は、高分子分散剤（Ｄ）に被覆された金属微粒子（Ｐ）を５０〜９０重量％、有機溶媒（Ｓ）を１０〜５０重量％含有することが好ましい。すなわち、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）と有機溶媒（Ｓ）との重量比（（Ｄ＋Ｐ）／Ｓ）は、特に限定されないが、５０／５０〜９０／１０の範囲にあることが好ましい。 A dispersion solution in which metal fine particles (P) made of at least one selected from the group consisting of a metal simple substance, an alloy and a metal compound are dispersed in an organic solvent (S) and coated with a polymer dispersant (D) It is preferable to contain 50 to 90% by weight of the metal fine particles (P) coated with the molecular dispersant (D) and 10 to 50% by weight of the organic solvent (S). That is, the weight ratio ((D + P) / S) of the metal fine particles (P) coated with the polymer dispersant (D) and the organic solvent (S) is not particularly limited, but is 50/50 to 90/10. It is preferable to be in the range.
高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）と有機溶媒（Ｓ）との重量比（（Ｄ＋Ｐ）／Ｓ）が、上記範囲未満である場合には、有機溶媒（Ｓ）の割合が多過ぎ、金属微粒子（Ｐ）の分散溶液をフィルム化するのに適した粘度よりも低く、液だれし易いおそれがある他に、加熱処理による金属微粒子（Ｐ）の焼結を行う過程（焼結過程）で、有機溶媒（Ｓ）が、ガス成分と水分子（Ｈ2Ｏ）とに好適に分解されないおそれがある。 When the weight ratio ((D + P) / S) of the metal fine particles (P) coated with the polymer dispersant (D) and the organic solvent (S) is less than the above range, the organic solvent (S) The ratio is too high, the viscosity is lower than the viscosity suitable for forming a dispersion of metal fine particles (P), and there is a risk of dripping, and the process of sintering the metal fine particles (P) by heat treatment In the (sintering process), the organic solvent (S) may not be suitably decomposed into gas components and water molecules (H 2 O).
一方、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）と有機溶媒（Ｓ）との重量比（（Ｄ＋Ｐ）／Ｓ）が、上記範囲を超える場合には、有機溶媒（Ｓ）の割合が少な過ぎ、金属微粒子（Ｐ）の分散溶液をフィルム化するのに適した粘度よりも高く、塗布する方法が制限されるおそれがある他に、加熱処理による焼結を行う過程（焼結過程）で、焼結膜を形成する加熱温度（焼結温度）に達する前に有機溶媒（Ｓ）が枯渇してしまう（気化してしまう）おそれがある。 On the other hand, when the weight ratio ((D + P) / S) of the metal fine particles (P) coated with the polymer dispersant (D) and the organic solvent (S) exceeds the above range, the organic solvent (S) The ratio is too low and the viscosity is higher than the viscosity suitable for forming a dispersion of metal fine particles (P), which may limit the application method. There is a risk that the organic solvent (S) may be depleted (vaporized) before reaching the heating temperature (sintering temperature) at which the sintered film is formed.
本発明で用いる、二価アルコール及び／又は三価アルコールからなる有機溶媒（Ｓ）は、緻密性の高い均質な焼結膜を形成する観点から、加熱処理による焼結を行う際に焼結膜を形成する加熱温度（焼結温度）よりも高い沸点を有するものが好ましく用いられる。 The organic solvent (S) composed of a dihydric alcohol and / or a trihydric alcohol used in the present invention forms a sintered film during sintering by heat treatment from the viewpoint of forming a dense sintered film with high density. Those having a boiling point higher than the heating temperature (sintering temperature) are preferably used.
二価アルコール及び／又は三価アルコールからなる有機溶媒（Ｓ）は、沸点が、焼結膜を形成する加熱温度（焼結温度）よりも４０〜５０℃高く、２５０℃以上の範囲にあるものが、さらに好ましく用いられる。 The organic solvent (S) composed of a dihydric alcohol and / or a trihydric alcohol has a boiling point that is 40 to 50 ° C. higher than the heating temperature (sintering temperature) for forming the sintered film and in the range of 250 ° C. or higher. More preferably.
上記有機溶媒（Ｓ）の沸点が、上記範囲未満である場合には、加熱処理による焼結を行う過程（焼結過程）で、焼結膜を形成する加熱温度（焼結温度）に達する前に有機溶媒（Ｓ）が気化して枯渇してしまうおそれがある。 When the boiling point of the organic solvent (S) is less than the above range, before reaching the heating temperature (sintering temperature) for forming the sintered film in the process of sintering by heat treatment (sintering process) There is a possibility that the organic solvent (S) is vaporized and exhausted.
本発明において、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）を、二価アルコール及び／又は三価アルコールからなる有機溶媒（Ｓ）に添加し、３本ロールミル、遠心混練、および超音波発生機（超音波ホモジナイザー）などの分散機を用いて分散処理を行うことで、均一分散させる。 In the present invention, the metal fine particles (P) coated with the polymer dispersant (D) are added to an organic solvent (S) composed of a dihydric alcohol and / or a trihydric alcohol, a three-roll mill, centrifugal kneading, and Dispersion is performed using a dispersing machine such as an ultrasonic generator (ultrasonic homogenizer) to uniformly disperse.
高分子分散剤（Ｄ）に被覆され、金属単体、合金及び金属化合物からなる群から選択される少なくとも１種からなる金属微粒子（Ｐ）を有機溶媒（Ｓ）に分散させた分散溶液には、本発明の効果を損なわない範囲で、必要に応じて消泡剤、分散剤、可塑剤、界面活性剤、増粘剤など公知の添加物を加えることができる。 In a dispersion solution in which metal fine particles (P) consisting of at least one selected from the group consisting of a metal simple substance, an alloy and a metal compound are dispersed in an organic solvent (S) and coated with a polymer dispersant (D), As long as the effects of the present invention are not impaired, known additives such as an antifoaming agent, a dispersing agent, a plasticizer, a surfactant, and a thickener can be added as necessary.
高分子分散剤（Ｄ）に被覆された金属微粒子（Ｐ）の含有量は、高分子分散剤（Ｄ）に被覆され、金属単体、合金及び金属化合物からなる群から選択される少なくとも１種からなる金属微粒子（Ｐ）を有機溶媒（Ｓ）に分散させた分散溶液の全量１００重量％に対して、５０〜９０重量％であることが好ましい。 The content of the metal fine particles (P) coated with the polymer dispersant (D) is coated with the polymer dispersant (D) and is at least one selected from the group consisting of simple metals, alloys and metal compounds. It is preferable that it is 50 to 90 weight% with respect to 100 weight% of the whole quantity of the dispersion solution which disperse | distributed the metal microparticles (P) which become the organic solvent (S).
上記金属微粒子（Ｐ）の含有量が、上記範囲にある場合には、金属微粒子（Ｐ）の分散溶液をフィルム化するのに適した粘度が得られ、加熱処理による焼結を行う過程（焼結過程）で、有機溶媒（Ｓ）の加水分解反応において、金属微粒子（Ｐ）が触媒として作用し、加水分解反応の進行速度を向上させ、金属微粒子（Ｐ）の焼結を促進させる効果が期待できる。 When the content of the metal fine particles (P) is within the above range, a viscosity suitable for forming a dispersion of the metal fine particles (P) into a film can be obtained, and a process of sintering by sintering (calcination). In the hydrolysis process of the organic solvent (S), the metal fine particles (P) act as a catalyst to improve the progress rate of the hydrolysis reaction and promote the sintering of the metal fine particles (P). I can expect.
上記金属微粒子（Ｐ）の含有量が、上記範囲未満である場合には、金属微粒子（Ｐ）の分散溶液をフィルム化するのに適した粘度よりも低く、液だれし易いおそれがある他に、加熱処理による焼結を行う過程（焼結過程）で、金属微粒子（Ｐ）が触媒として作用する効果が期待できないおそれがある。 When the content of the metal fine particles (P) is less than the above range, the viscosity is lower than the viscosity suitable for forming a dispersion of the metal fine particles (P) into a film, and the liquid may be easily drained. In the process of sintering by heat treatment (sintering process), the effect of the metal fine particles (P) acting as a catalyst may not be expected.
一方、上記金属微粒子（Ｐ）の含有量が、上記範囲を超える場合には、金属微粒子（Ｐ）の分散溶液をフィルム化するのに適した粘度よりも高く、加熱処理による焼結を行う過程（焼結過程）で、焼結膜を形成する加熱温度（焼結温度）に達する前に有機溶媒（Ｓ）が枯渇してしまう（気化してしまう）おそれがある。 On the other hand, when the content of the metal fine particles (P) exceeds the above range, the viscosity is higher than that suitable for forming a dispersion of the metal fine particles (P) into a film, and the sintering is performed by heat treatment. In the (sintering process), the organic solvent (S) may be depleted (vaporized) before reaching the heating temperature (sintering temperature) for forming the sintered film.
次に、本実施形態の加熱接合材１の製造方法について説明する。 Next, the manufacturing method of the heat bonding material 1 of this embodiment is demonstrated.
まず、上述の金属微粒子（Ｐ）の分散溶液をフィルム化する。フィルム化の方法は限定されるものではないが、例えば、分散溶液を乾燥後の膜厚が所定の厚さとなるように離型フィルム上に塗布し、加熱処理などにより乾燥させる方法が挙げられる。乾燥条件は、使用する有機溶媒（Ｓ）にもよるが、望ましくは１００〜２００℃の温度で１５〜３０分間である。このとき、金属接合層３中の金属微粒子（Ｐ）の割合が８０〜９５重量％となるように、離型フィルム上に塗布された分散溶液を乾燥させることが好ましく、金属微粒子（Ｐ）の割合が８５重量％程度であることがさらに好ましい。 First, the dispersion solution of the above-mentioned metal fine particles (P) is formed into a film. The method for forming the film is not limited, and examples thereof include a method in which the dispersion solution is applied onto a release film so that the film thickness after drying becomes a predetermined thickness, and dried by heat treatment or the like. The drying conditions depend on the organic solvent (S) to be used, but are desirably 15 to 30 minutes at a temperature of 100 to 200 ° C. At this time, it is preferable to dry the dispersion solution coated on the release film so that the ratio of the metal fine particles (P) in the metal bonding layer 3 is 80 to 95% by weight. More preferably, the proportion is about 85% by weight.
金属微粒子（Ｐ）の分散溶液を塗布する方法は、特に限定されないが、例えば、スキージ法、スクリーン印刷、マスク印刷、インクジェット印刷、ディスペンサー印刷、スプレーコート、バーコート、ナイフコート、およびスピンコート等が挙げられる。なお、分散溶液の粘度が高い場合は、分散溶液を離型フィルム上に載せた後、プレス機でプレスしてもよいし、ローラー等で圧延してもよい。このようにして、金属層２の一方側の面に設けられる金属接合層３と、金属層２の他方側の面に設けられる金属接合層３とを作製する。 The method for applying the metal fine particle (P) dispersion solution is not particularly limited, and examples thereof include squeegee method, screen printing, mask printing, ink jet printing, dispenser printing, spray coating, bar coating, knife coating, and spin coating. Can be mentioned. In addition, when the viscosity of a dispersion solution is high, after mounting a dispersion solution on a release film, you may press with a press machine and may roll with a roller etc. In this way, the metal bonding layer 3 provided on one surface of the metal layer 2 and the metal bonding layer 3 provided on the other surface of the metal layer 2 are produced.
金属接合層３は、厚みが０．１５ｍｍ〜０．２２５ｍｍであることが好ましい。金属接合層３の厚みが０．１５ｍｍ未満であると、金属接合層３を均一に製膜するのが困難になり、均質な焼結膜が得られず接合強度が低下するおそれがある。金属接合層３の厚みが０．２２５ｍｍを超えると、焼結時の有機溶媒（Ｓ）の抜けが悪くなり、有機溶媒（Ｓ）の残存やボイドが発生するおそれがあり、有機溶媒（Ｓ）の残存やボイドが発生した場合、接合強度が低下する。 The metal bonding layer 3 preferably has a thickness of 0.15 mm to 0.225 mm. If the thickness of the metal bonding layer 3 is less than 0.15 mm, it is difficult to form the metal bonding layer 3 uniformly, and a homogeneous sintered film cannot be obtained, and the bonding strength may be reduced. If the thickness of the metal bonding layer 3 exceeds 0.225 mm, the organic solvent (S) may not be removed easily during sintering, and the organic solvent (S) may remain or void. When residual or voids are generated, the bonding strength decreases.
加熱接合用材料の厚みは、１．０ｍｍ以下であることが好ましく、通常は０．５ｍｍ程度である。全体として、この厚みになるように、金属層２や金属接合層３の厚みや、金属接合層３の厚みを適宜設計するとよい。また、金属接合層３は全体として所望の厚みになればよく、分散溶液をシート化したものを複数積層してもよい。 The thickness of the heat bonding material is preferably 1.0 mm or less, and is usually about 0.5 mm. As a whole, the thickness of the metal layer 2 and the metal bonding layer 3 and the thickness of the metal bonding layer 3 may be appropriately designed so as to have this thickness. Moreover, the metal joining layer 3 should just become desired thickness as a whole, and you may laminate | stack the thing which made the dispersion solution the sheet | seat.
その後、金属層２の両面にそれぞれ金属接合層３をローラーで圧着するなどして貼合することにより、本実施形態に係る加熱接合材１が得られる。 Then, the heat bonding | jointing material 1 which concerns on this embodiment is obtained by sticking the metal joining layer 3 on both surfaces of the metal layer 2, respectively by crimping with a roller.
次に、本実施形態の加熱接合材１の使用方法について説明する。 Next, the usage method of the heat bonding material 1 of this embodiment is demonstrated.
本実施形態の加熱接合材１は電気電子機器を製造する際に用いることができる。具体的には、電気電子機器の一の部品の接合面に本実施形態の加熱接合材１を載せた後、該加熱接合材１上に更に接続する他の部品の接合面を載置し、加熱処理により焼結して、一の部品と他の部品とを接合し、電気電子機器を製造する。本実施形態の加熱接合材１は、金属微粒子（Ｐ）が焼結されることにより、電気電子機器において部品間の導電接続部材を構成することになる。 The heat-bonding material 1 of this embodiment can be used when manufacturing an electrical / electronic device. Specifically, after placing the heating bonding material 1 of the present embodiment on the bonding surface of one component of the electrical and electronic equipment, the bonding surface of another component to be further connected is placed on the heating bonding material 1, Sintering is performed by heat treatment, and one part and another part are joined to produce an electric / electronic device. The heat bonding material 1 according to the present embodiment constitutes a conductive connecting member between components in an electric / electronic device by sintering the metal fine particles (P).
電気電子機器の部品としては、半導体素子、回路基板の電極端子、及び導電性基板などが挙げられる。基板の種類は、特に限定されないが、例えば、ガラス基板、セラミック基板、銅基板、およびポリイミド基板等が挙げられる。 Examples of components of electrical and electronic equipment include semiconductor elements, circuit board electrode terminals, and conductive substrates. Although the kind of board | substrate is not specifically limited, For example, a glass substrate, a ceramic substrate, a copper substrate, a polyimide substrate, etc. are mentioned.
導電接続部材としては、半導体素子と導電性基板間を接合するための導電性ダイボンド部等が挙げられるがこれらに限定されない。 Examples of the conductive connection member include, but are not limited to, a conductive die bond portion for joining the semiconductor element and the conductive substrate.
導電性ダイボンド部は、通常、加熱接合材１を電子部品における回路基板の接合面に載せ、当該加熱接合材１上に更に接続する他方の電極端子の接合面を積層配置した後、加熱処理又は加圧処理により上記一の接合面と上記他の接合面とを焼結して形成される。 The conductive die-bonding portion is usually formed by placing the heat bonding material 1 on the bonding surface of the circuit board in the electronic component and laminating the bonding surface of the other electrode terminal further connected on the heat bonding material 1, It is formed by sintering the one joining surface and the other joining surface by pressure treatment.
焼結時の加熱処理は加圧下で行ってもよい。加圧下の加熱処理は、両電極端子間、又は電極端子と基板間の加圧により加熱接合材１と両電極端子接合面、又は電極端子と導電性基板間との接合を確実にするか、又は加熱接合材１に適切な変形を生じさせて電極端子接合面との確実な接合を行うことができるとともに、加熱接合材１と電極端子接合面との接合面積が大きくなり、接合信頼性を一層向上することができる。 The heat treatment during sintering may be performed under pressure. The heat treatment under pressure is to ensure the bonding between the heat bonding material 1 and both electrode terminal bonding surfaces, or between the electrode terminals and the conductive substrate by pressing between the electrode terminals or between the electrode terminal and the substrate, Alternatively, the heating bonding material 1 can be appropriately deformed to perform reliable bonding with the electrode terminal bonding surface, and the bonding area between the heating bonding material 1 and the electrode terminal bonding surface is increased, thereby improving the bonding reliability. This can be further improved.
また、半導体素子と加熱接合材１を加圧型ヒートツ−ル等を用いて加圧下で焼結を行うと、接合部での焼結性が向上してより良好な接合部が得られる。上記両電極端子間、又は電極端子と基板間の加圧は、０．５〜１５ＭＰａが好ましい。 Further, when the semiconductor element and the heat bonding material 1 are sintered under pressure using a pressure type heat tool or the like, the sinterability at the bonding portion is improved and a better bonding portion is obtained. The pressure between the electrode terminals or between the electrode terminal and the substrate is preferably 0.5 to 15 MPa.
また、焼結は、大気雰囲気中又は不活性ガス雰囲気中で行うことが好ましい。焼結膜を形成する加熱温度（焼結温度）は、緻密性の高い均質な焼結膜を形成する観点から、２００〜２７０℃の温度範囲にあり、有機溶媒（Ｓ）の沸点よりも４０〜５０℃低い温度範囲であることが好ましい。 Further, the sintering is preferably performed in an air atmosphere or an inert gas atmosphere. The heating temperature (sintering temperature) for forming the sintered film is in the temperature range of 200 to 270 ° C. from the viewpoint of forming a dense sintered film with high density, and is 40 to 50 higher than the boiling point of the organic solvent (S). It is preferable that the temperature range be lower.
上記焼結膜を形成する加熱温度（焼結温度）が、２００℃未満である場合には、焼結温度が低過ぎ、金属微粒子（Ｐ）の分散溶液の焼結を好ましく進行させることができず、緻密性の高い均質な焼結膜が形成されず、電気抵抗が増大し導電性に劣る、焼結導電体しか得られないおそれがある。 When the heating temperature (sintering temperature) for forming the sintered film is less than 200 ° C., the sintering temperature is too low, and the sintering of the dispersion solution of the metal fine particles (P) cannot be preferably progressed. There is a possibility that a dense sintered film with high density will not be formed, and only a sintered conductor having an increased electrical resistance and poor conductivity will be obtained.
次に、本発明の実施例について説明するが、本発明はこれら実施例に限定されるものではない。
本実施例及び比較例において行った試験方法は、以下のとおりである。
Next, examples of the present invention will be described, but the present invention is not limited to these examples.
The test methods performed in the examples and comparative examples are as follows.
（１）金属微粒子（Ｐ）の評価（平均一次粒子径）
走査型電子顕微鏡（ＳＥＭ）を使用して、観察可能な任意に選択した８０個の金属微粒子（Ｐ）の一次粒径を測定した。
測定した金属微粒子（Ｐ）全体（８０個）のうち、一次粒径が小さい方から順に数えて、金属微粒子（Ｐ）全体（８０個）の５％に相当する金属微粒子（Ｐ）（４個）と、一次粒径が大きい方から順に数えて、金属微粒子（Ｐ）全体（８０個）の５％に相当する金属微粒子（Ｐ）（４個）とを除き、残り金属微粒子（Ｐ）全体（８０個）の９０％に相当する金属微粒子（Ｐ）（７２個）を対象とし、７２個の金属微粒子（Ｐ）の一次粒径の測定値の平均を算出し、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）の平均一次粒子径とした。
(1) Evaluation of metal fine particles (P) (average primary particle diameter)
Using a scanning electron microscope (SEM), the primary particle size of 80 arbitrarily selected observable metal fine particles (P) was measured.
Among the measured metal fine particles (P) (80 particles), the metal fine particles (P) (4 particles) corresponding to 5% of the whole metal fine particles (P) (80 particles) counted in order from the smallest primary particle size. ) And the remaining fine metal particles (P) except for the fine metal particles (P) (4) corresponding to 5% of the total fine metal particles (P) (80 particles), counting from the larger primary particle size. The average of the measured values of the primary particle diameter of 72 metal fine particles (P) is calculated for the fine metal particles (P) (72) corresponding to 90% of (80), and the polymer dispersant (D The average primary particle diameter of the metal fine particles (P) coated with
（２）焼結膜の評価
（２−１）ボイドの含有率（％）
金属接合層３の金属微粒子（Ｐ）の焼結工程において得られた、ガラス基板上に形成された焼結膜を、走査型電子顕微鏡（ＳＥＭ）を用い、５００倍率で観察した。
焼結膜に発生した空隙の大きさを、画像処理ソフトで２値化し、所定の単位面積当たり５０％以上の空隙を有する部分をボイドとし、焼結膜に発生したボイドの含有率（％）を算出した。
(2) Evaluation of sintered film (2-1) Void content (%)
The sintered film formed on the glass substrate obtained in the sintering process of the metal fine particles (P) of the metal bonding layer 3 was observed at a magnification of 500 using a scanning electron microscope (SEM).
The size of the voids generated in the sintered film is binarized using image processing software, and the void content generated in the sintered film is calculated (%) with voids of 50% or more per predetermined unit area as voids. did.
（２−２）接合部の評価（ダイシェア強度）
金属接合層３をガラス基板（基板サイズ；１５ｍｍ×１５ｍｍ）の接合面に載置後、金属接合層３上にシリコンチップの接合面を積層配置した。続いて、窒素ガス雰囲気中、２５０℃の温度で５分間、無加圧下で、加熱処理による焼結を行い、ガラス基板とシリコンチップとを接合させ、室温まで炉冷し、ダイシェア強度測定用のサンプルを作製した。
上記作製したサンプルに対して、ダイシェア強度測定機（テイジ・ジャパン株式会社製、製品名；万能型ボンドテスター、型式；シリーズ４０００）を用い、米国ＭＩＬ‐ＳＴＤ‐８８３に準拠し、２５℃の条件下で、ガラス基板とシリコンチップとの接合部のダイシェア強度（剥離強度）を測定した。
(2-2) Joint evaluation (die shear strength)
After the metal bonding layer 3 was placed on the bonding surface of a glass substrate (substrate size: 15 mm × 15 mm), the bonding surface of the silicon chip was laminated on the metal bonding layer 3. Subsequently, sintering is performed by heat treatment in a nitrogen gas atmosphere at a temperature of 250 ° C. for 5 minutes under no pressure, the glass substrate and the silicon chip are bonded, furnace cooled to room temperature, and used for die shear strength measurement. A sample was made.
Using the die shear strength measuring device (manufactured by Tage Japan Co., Ltd., product name; universal bond tester, model; series 4000) for the above prepared sample, in accordance with US MIL-STD-883, at 25 ° C. Below, the die shear strength (peeling strength) of the junction part of a glass substrate and a silicon chip was measured.
（実施例１）
（金属微粒子（Ｐ）の分離・回収工程）
金属微粒子（Ｐ）の原料として酢酸第二銅（（ＣＨ3ＣＯＯ）2Ｃｕ・１Ｈ2Ｏ）０．２ｇを蒸留水１０ｍｌに溶解させ、酢酸第二銅水溶液１０ｍｌを調製した。
一方、金属イオン還元剤として水素化ホウ素ナトリウム（ＮａＢＨ4）を、濃度が５．０ｍoｌ/ｌとなるように蒸留水に混合し、水素化ホウ素ナトリウム水溶液１００ｍｌを調製した。
Example 1
(Metal fine particle (P) separation and recovery process)
As a raw material for the metal fine particles (P), 0.2 g of cupric acetate ((CH 3 COO) 2 Cu · 1H 2 O) was dissolved in 10 ml of distilled water to prepare 10 ml of an aqueous cupric acetate solution.
On the other hand, sodium borohydride (NaBH 4 ) as a metal ion reducing agent was mixed with distilled water to a concentration of 5.0 mol / l to prepare 100 ml of an aqueous sodium borohydride solution.
次に、上記調製した水素化ホウ素ナトリウム水溶液１００ｍｌに、高分子分散剤（Ｄ）としてポリビニルピロリドン（ＰＶＰ、数平均分子量；約３，５００）０．１ｇ（金属微粒子（Ｐ）の全量に対して０．５重量％）を添加して攪拌溶解させ、続いて、窒素ガス雰囲気中で、上記調製した酢酸第二銅水溶液１０ｍｌを滴下し、金属微粒子の混合溶液を調製した。 Next, 100 g of the aqueous sodium borohydride solution prepared above was added to 0.1 g of polyvinyl pyrrolidone (PVP, number average molecular weight; approximately 3,500) as the polymer dispersant (D) (based on the total amount of metal fine particles (P)). 0.5 wt%) was added and dissolved by stirring, and then 10 ml of the prepared cupric acetate aqueous solution was added dropwise in a nitrogen gas atmosphere to prepare a mixed solution of metal fine particles.
次に、上記調製した金属微粒子の混合溶液に、凝集促進剤としてクロロホルム（ＣＨＣｌ3）５ｍｌを添加して数分間攪拌し、更に数分間静置した後、沈殿した固形分を含む混合溶液を遠心分離機に供給し、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）を分離、回収した。 Next, 5 ml of chloroform (CHCl 3 ) as an aggregation accelerator is added to the prepared mixed solution of fine metal particles, stirred for several minutes, allowed to stand for several minutes, and then the mixed solution containing the precipitated solid is centrifuged. The metal fine particles (P) coated with the polymer dispersant (D) were separated and recovered by supplying to the separator.
ここで、上記分離・回収した金属微粒子（Ｐ）の一部を採取し、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）の一次粒径を測定し、平均一次粒子径を算出したところ１２ｎｍであった。 Here, a part of the separated and collected metal fine particles (P) is collected, the primary particle diameter of the metal fine particles (P) coated with the polymer dispersant (D) is measured, and the average primary particle diameter is calculated. As a result, it was 12 nm.
（金属微粒子（Ｐ）の分散溶液を得る工程）
上記金属微粒子（Ｐ）の分離・回収工程で回収された、金属微粒子（Ｐ）５５重量％（金属微粒子の分散溶液の全量に対する含有量）、を、三価アルコールからなる有機溶媒（Ｓ）としてグリセロール（示性式；Ｃ3Ｈ5（ＯＨ）3，沸点；２９０℃）４５重量％（金属微粒子の分散溶液の全量対する含有量）に添加して、超音波発生機（超音波ホモジナイザー）による分散処理を３０分間行い、金属微粒子の分散溶液を得た。
(Step of obtaining a dispersion of metal fine particles (P))
55 wt% of the metal fine particles (P) collected in the metal fine particle (P) separation / recovery step (content with respect to the total amount of the dispersion of metal fine particles) is used as the organic solvent (S) made of trihydric alcohol. Add to 45% by weight of glycerol (chemical formula: C 3 H 5 (OH) 3 , boiling point: 290 ° C.) (content with respect to the total amount of the dispersion solution of metal fine particles), and with an ultrasonic generator (ultrasonic homogenizer) Dispersion treatment was performed for 30 minutes to obtain a dispersion solution of metal fine particles.
（加熱接合材１の作製・焼結工程）
上記得られた金属微粒子（Ｐ）の分散溶液を、載置台の上に、離型フィルム（５０μｍのポリエチレンテレフタレートフィルム）、その上に、スキージ法で０．１５ｍｍ塗布し（塗布サイズ；１０ｍｍ×１０ｍｍ）を形成し、８０℃、６０秒間乾燥させ、フィルム化し金属接合層３を形成した。このとき、乾燥後の金属接合層３における金属接合層３の割合は、８５重量％であった。この金属接合層３を２枚作製した。同サイズの銅箔（型番：ＧＴＳ−ＳＴＤ、厚み０．２ｍｍ）を片方の金属接合層３に配置し、その上にもう片方の金属接合層３を配置し実施例１に係る加熱接合材１を得た。この加熱接合材１をガラス基板（基板サイズ；１５ｍｍ×１５ｍｍ）上に配置し、その加熱接合材１上にシリコンチップの接合面を積層配置した。
(Preparation / sintering process of heat bonding material 1)
The obtained dispersion solution of fine metal particles (P) is applied on a mounting table by a release film (50 μm polyethylene terephthalate film), and then applied by 0.15 mm by a squeegee method (application size: 10 mm × 10 mm). ) And dried at 80 ° C. for 60 seconds to form a film and form the metal bonding layer 3. At this time, the ratio of the metal bonding layer 3 in the dried metal bonding layer 3 was 85% by weight. Two metal bonding layers 3 were produced. A copper foil of the same size (model number: GTS-STD, thickness 0.2 mm) is disposed on one metal bonding layer 3, and the other metal bonding layer 3 is disposed thereon. Got. This heat bonding material 1 was placed on a glass substrate (substrate size: 15 mm × 15 mm), and a silicon chip bonding surface was laminated on the heat bonding material 1.
上述の積層体を窒素ガス雰囲気中、２５０℃の温度で５分間、５ＭＰａ圧下で加熱加圧処理し、金属接合層３の焼結を行い、室温まで炉冷し、ガラス基板上に焼結膜が形成された焼結導電体の実装サンプルを得た。 The above-mentioned laminate is heated and pressurized at a temperature of 250 ° C. for 5 minutes under a 5 MPa pressure in a nitrogen gas atmosphere, the metal bonding layer 3 is sintered, cooled to room temperature, and a sintered film is formed on the glass substrate. A mounting sample of the formed sintered conductor was obtained.
作成した実装サンプルについて、断面加工を行い、ＳＥＭでボイドの観察をして評価した結果、ボイド率は８％だった。また、ダイシェア試験により接合強度を測定した結果、接合強度は３６ＭＰａであった。 The created mounting sample was subjected to cross-section processing and was evaluated by observing voids with an SEM. As a result, the void ratio was 8%. Moreover, as a result of measuring joint strength by the die shear test, joint strength was 36 MPa.
（実施例２）
実施例１と同様の方法で上記得られた金属微粒子（Ｐ）の分散溶液を、載置台の上に、離型フィルム（５０μｍのポリエチレンテレフタレートフィルム）、その上に、スキージ法で０．２２５ｍｍ塗布し（塗布サイズ；１０ｍｍ×１０ｍｍ）を形成し、８０℃、６０秒間乾燥させ、フィルム化し金属接合層３を形成した。このとき、乾燥後の金属接合層３における金属接合層３の割合は、８５重量％であった。この金属接合層３を２枚作製した。同サイズの銅箔（型番：ＧＴＳ−ＳＴＤ、厚み０．２ｍｍ）を片方の金属接合層３に配置し、その上にもう片方の金属接合層３を配置し、実施例２に係る加熱接合材１を得た。この加熱接合材１をガラス基板（基板サイズ；１５ｍｍ×１５ｍｍ）上に配置し、その加熱接合材１上にシリコンチップの接合面を積層配置した。
(Example 2)
The dispersion solution of metal fine particles (P) obtained in the same manner as in Example 1 was applied to a release film (50 μm polyethylene terephthalate film) on a mounting table, and 0.225 mm by squeegee method. (Coating size; 10 mm × 10 mm) was formed, dried at 80 ° C. for 60 seconds, and formed into a film to form the metal bonding layer 3. At this time, the ratio of the metal bonding layer 3 in the dried metal bonding layer 3 was 85% by weight. Two metal bonding layers 3 were produced. A copper foil of the same size (model number: GTS-STD, thickness 0.2 mm) is disposed on one metal bonding layer 3, and the other metal bonding layer 3 is disposed thereon. 1 was obtained. This heat bonding material 1 was placed on a glass substrate (substrate size: 15 mm × 15 mm), and a silicon chip bonding surface was laminated on the heat bonding material 1.
上述の積層体を窒素ガス雰囲気中、２５０℃の温度で５分間、５ＭＰａ圧下で加熱加圧処理し、金属接合層３の焼結を行い、室温まで炉冷し、ガラス基板上に焼結膜が形成された焼結導電体の実装サンプルを得た。 The above-mentioned laminate is heated and pressurized at a temperature of 250 ° C. for 5 minutes under a 5 MPa pressure in a nitrogen gas atmosphere, the metal bonding layer 3 is sintered, cooled to room temperature, and a sintered film is formed on the glass substrate. A mounting sample of the formed sintered conductor was obtained.
作成した実装サンプルについて、断面加工を行い、ＳＥＭでボイドの観察をして評価した結果、ボイド率は２０％だった。また、ダイシェア試験により接合強度を測定した結果、接合強度は２２ＭＰａであった。 The fabricated mounting sample was subjected to cross-section processing and was evaluated by observing voids with an SEM. As a result, the void ratio was 20%. Moreover, as a result of measuring joint strength by the die shear test, joint strength was 22 MPa.
（比較例１）
実施例１と同様の方法で金属微粒子（Ｐ）を得て同様の方法で金属微粒子（Ｐ）の分散溶液を得た。この分散溶液をスキージ法でガラス基板（基板サイズ；１５ｍｍ×１５ｍｍ）上に０．５ｍｍ厚となるように塗布し、その上にシリコンチップの接合面を積層配置した。
(Comparative Example 1)
Metal fine particles (P) were obtained by the same method as in Example 1, and a dispersion of metal fine particles (P) was obtained by the same method. This dispersion solution was applied on a glass substrate (substrate size: 15 mm × 15 mm) by a squeegee method so as to have a thickness of 0.5 mm, and a silicon chip bonding surface was laminated thereon.
上述の積層体を窒素ガス雰囲気中、２５０℃の温度で５分間、５ＭＰａ圧下で加熱加圧処理し、金属接合層３の焼結を行い、室温まで炉冷し、ガラス基板上に焼結膜が形成された焼結導電体の実装サンプルを得た。 The above-mentioned laminate is heated and pressurized at a temperature of 250 ° C. for 5 minutes under a 5 MPa pressure in a nitrogen gas atmosphere, the metal bonding layer 3 is sintered, cooled to room temperature, and a sintered film is formed on the glass substrate. A mounting sample of the formed sintered conductor was obtained.
作成した実装サンプルについて、断面加工を行い、ＳＥＭでボイドの観察をして評価した結果、ボイド率は４７％だった。また、ダイシェア試験により接合強度を測定し、接合強度は１０ＭＰａであった。 The created mounting sample was subjected to cross-section processing and was evaluated by observing voids with an SEM. As a result, the void ratio was 47%. Further, the bonding strength was measured by a die shear test, and the bonding strength was 10 MPa.
１：加熱接合材
２：金属層
３：金属接合層
1: Heat bonding material 2: Metal layer 3: Metal bonding layer
Claims (13)
前記金属層の両面に積層して設けられた金属接合層とを有し、
前記金属接合層は、高分子分散剤（Ｄ）に被覆され、金属単体、合金及び金属化合物からなる群から選択される少なくとも１種からなる金属微粒子（Ｐ）を有機溶媒（Ｓ）に分散させた分散溶液をフィルム状に成形してなることを特徴とする加熱接合材。 A metal layer formed from a metal bulk material;
A metal bonding layer provided on both surfaces of the metal layer,
The metal bonding layer is coated with a polymer dispersant (D), and metal fine particles (P) selected from the group consisting of simple metals, alloys and metal compounds are dispersed in an organic solvent (S). A heat-bonding material obtained by forming the dispersion solution into a film.
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| WO2021187362A1 (en) * | 2020-03-19 | 2021-09-23 | 三井金属鉱業株式会社 | Bonding sheet and bonded structure |
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