WO2020021800A1 - 導電性ペーストを用いた導電性ピラーの製造方法 - Google Patents

導電性ペーストを用いた導電性ピラーの製造方法 Download PDF

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Publication number
WO2020021800A1
WO2020021800A1 PCT/JP2019/017604 JP2019017604W WO2020021800A1 WO 2020021800 A1 WO2020021800 A1 WO 2020021800A1 JP 2019017604 W JP2019017604 W JP 2019017604W WO 2020021800 A1 WO2020021800 A1 WO 2020021800A1
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Prior art keywords
conductive paste
conductive
pillar
substrate
pillars
Prior art date
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PCT/JP2019/017604
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English (en)
French (fr)
Inventor
亮太 山口
康弘 千手
真 矢田
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Dic株式会社
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Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to KR1020217002282A priority Critical patent/KR20210035187A/ko
Priority to US17/262,067 priority patent/US20210313197A1/en
Publication of WO2020021800A1 publication Critical patent/WO2020021800A1/ja

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    • H01L21/4867—Applying pastes or inks, e.g. screen printing
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Definitions

  • the present invention relates to a method for manufacturing a conductive pillar (Pillar) or a conductive post (Post), which is a flip-chip mounting terminal which is a connection method between a semiconductor chip and a package interposer, in a semiconductor package.
  • the production method of the present invention is characterized by using a conductive paste containing fine metal particles.
  • an electronic circuit is manufactured on a semiconductor chip, and electrodes on the semiconductor chip are connected to electrodes on a semiconductor package.
  • electrodes on a semiconductor chip and electrodes on a semiconductor package have been electrically connected using a bonding wire made of gold or copper.
  • a flip chip method is used as an electrical connection method between a semiconductor chip and a semiconductor package.
  • a gold bump or a solder bump is used as a typical connection method in the flip chip method.
  • the conductive pillar is manufactured on a semiconductor chip, and a tip of the pillar is connected to an electrode of a semiconductor package.
  • the conductive pillar those having a pillar diameter of 70 ⁇ m or less and a pillar height of 50 to 60 ⁇ m are generally used.
  • the conductive pillar can be used for various kinds of metals (such as various metals and alloys such as gold, solder and copper).
  • gold or copper is used as the metal type, it has a lower electric resistance than solder, and can cope with a large current.
  • the conductive pillar can suppress the amount of supplied solder as compared with the solder bump, the pitch of the bump can be reduced, and it is possible to cope with high integration.
  • the conductive pillar can maintain the same cross-sectional area from the electrode on the semiconductor chip to the electrode on the semiconductor package, it has an advantage that it can handle a large current.
  • Patent Literatures 1 and 2 disclose a method in which a plating layer called a seed layer is formed on an electrode pad, and a copper conductive pillar (copper pillar) is manufactured by electrolytic plating.
  • a step of removing the patterned resist layer and seed layer after manufacturing the pillar is required because the seed layer is provided on the entire surface.
  • the step of removing the seed layer by etching causes an undercut of the copper pillar (Patent Document 3). Therefore, there is a problem that it is difficult to produce fine conductive pillars by plating.
  • a method of manufacturing a conductive pillar by a plating technique a method of using electroless plating is also known.
  • a photoresist layer is formed on a semiconductor chip, a photoresist layer is formed in a portion where a conductive pillar is to be formed, a copper pillar is formed using electroless plating in the opening, and a solder plating layer is formed on top of the copper pillar. It is a method of manufacturing.
  • a conductive pillar having a large height / diameter ratio (aspect ratio) by an electroless plating method that is, to manufacture an elongated conductive pillar, it is necessary to grow plating in a deep hole having a small diameter.
  • the plating method requires a large amount of waste liquid to be regenerated or disposed of, and has a large environmental load and requires high cost for equipment maintenance. Therefore, alternative means are desired.
  • a method of manufacturing a pillar by filling a conductive paste in advance in an opening of a patterned resist layer with a squeegee or the like can be considered.
  • the diameter of the conductive pillar is reduced due to the increase in density and definition of the semiconductor mounting, it is difficult to fill the conductive paste deeply into the opening.
  • the conventional electroplating method has a problem that it is difficult to produce fine conductive pillars without being affected by undercut.
  • the electroless plating method has a problem that it is difficult to manufacture pillars having the same shape without voids.
  • An object of the present invention is to provide a method for forming fine conductive pillars by an embedding method using a conductive paste for manufacturing pillars.
  • the present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, after applying a conductive paste containing metal fine particles under reduced pressure, and then releasing the paste to atmospheric pressure, fine and high aspect ratio. It has been found that conductive pillars having a specific ratio can be easily manufactured on a substrate having an electrode portion. The present invention has been found to have a special effect in the production of conductive pillars, which are terminals for flip-chip mounting.
  • the present invention (1) A method for producing a conductive pillar on a substrate having an electrode portion using a conductive paste containing metal fine particles, A first step of applying a conductive paste to a resin surface having an opening pattern formed on a substrate having an electrode portion in an atmosphere having an atmospheric pressure of 10 kPa or less; After applying the conductive paste, return to the standard pressure, a second step of filling the conductive paste in the opening, A third step of removing the conductive paste remaining on the resin surface, A method for producing a conductive pillar having: (2) The method for producing a conductive pillar according to (1), wherein a rubber or metal squeegee is used in the step of applying the conductive paste and the step of removing the conductive paste according to (1). .
  • the present invention is a method for producing a conductive pillar on a substrate having an electrode portion using a conductive paste containing metal fine particles.
  • pillars can be easily manufactured by filling a conductive paste in an opening portion of a patterned resist layer with a squeegee or the like without using a plating technique which is a conventional technique.
  • a plating technique which is a conventional technique.
  • Pillar fabrication using a conductive paste is not subject to limitations such as deterioration of the plating solution or diffusion control of ions, so it is considered that there is a possibility that the problems of the quality and reproducibility of the electroless plating method can be solved.
  • FIG. 4 is a schematic cross-sectional view showing a manufacturing step (first step) of the conductive pillar according to the present invention.
  • FIG. 4 is a schematic cross-sectional view illustrating a manufacturing process of the conductive pillar according to the present invention.
  • 3 is a cross-sectional photograph of a conductive pillar manufactured by the method of the present invention.
  • the metal species that can be used as the metal fine particles is not particularly limited as long as the metal species can chemically bond to a functional group in a protective agent described later.
  • gold, silver, copper, nickel, zinc, aluminum, platinum, palladium, tin, chromium, lead, tungsten, and the like can be used.
  • the metal species may be one kind, a mixture of two or more kinds, or an alloy.
  • the content ratio of the metal fine particles in the conductive paste is not particularly limited. In order to fill the opening, it is necessary to ensure sufficient fluidity, so that it is preferably used in a range of 40% or more and less than 95% by mass.
  • Synthesis of metal fine particles As a method for synthesizing the metal fine particles of the present invention, a chemical reduction method is employed, but any method can be employed as long as the surface of the metal fine particles can be protected by a protective agent and the particle diameter is 1 ⁇ m or less. Can be.
  • a thermal decomposition method and an electrochemical method can be used as the wet method.
  • an in-gas evaporation method or a sputtering method may be employed.
  • the protective agent of the present invention a compound having a functional group having an affinity for metal fine particles and a solvent can be arbitrarily selected.
  • the protective agent used can be used regardless of the molecular weight. By designing a protective agent according to the type of metal used and desired physical properties, high conductivity and dispersion stability can be imparted to the metal fine particles.
  • a protective agent having a carboxy group, a phosphoric acid group, a sulfonic acid group, a heteroaromatic group (for example, an imidazole group) or the like having a somewhat strong adsorption capacity for metal high dispersion stability to fine particles can be obtained.
  • Sex can be added.
  • amino groups eg, dimethylaminoethyl group, dimethylaminopropyl group
  • hydroxy groups hydroxyethyl group, hydroxypropyl group
  • a protective agent having an aromatic group for example, a benzyl group
  • an aromatic group for example, a benzyl group
  • the protective agent for metal fine particles can be freely changed.
  • a low molecular weight protective agent various properties can be exhibited by using two or more compounds in combination.
  • a high molecular weight protective agent various characteristics can be exhibited by changing the number and type of the functional groups in the compound.
  • the protective agent concentration in the conductive paste can be used within the range of 15% by mass or less in the entire paste. More preferably, the concentration is 10% by mass or less. If the concentration of the protective agent is too high, a necking phenomenon between metal particles does not sufficiently occur during sintering, and it becomes difficult to develop high conductivity.
  • solvent The solvent that can be used in the present invention is not particularly limited, and water and / or an organic solvent can be used as the solvent. It is preferable to use a good solvent that does not agglomerate the metal fine particles as the solvent in order to produce a conductive paste having a uniform particle system.
  • the solvent volatilizes during sintering of the conductive paste.
  • a high sintering temperature alters and damages the resin film. Therefore, it is more desirable to use an organic solvent having a boiling point in a temperature range that does not cause damage to the resin film as the solvent.
  • the solvent concentration in the conductive paste is not particularly limited, but is preferably used within a range of 60% by mass or less.
  • the conductive paste for manufacturing a pillar of the present invention can impart a suitable property as the conductive paste of the present invention by adding a solvent that is easy to use as a filling paste to the prepared metal fine particles, or by exchanging a medium. .
  • the conductive paste for manufacturing a pillar according to the present invention includes a binder component such as a resin, an anti-drying agent, a defoaming agent, an adhesion promoter to a substrate, and an Inhibitors, various catalysts for promoting film production, various surfactants such as silicone-based surfactants and fluorine-based surfactants, leveling agents, release accelerators, and the like can be added as assistants.
  • a binder component such as a resin, an anti-drying agent, a defoaming agent, an adhesion promoter to a substrate, and an Inhibitors
  • various catalysts for promoting film production various surfactants such as silicone-based surfactants and fluorine-based surfactants, leveling agents, release accelerators, and the like can be added as assistants.
  • a flux component can be added to the conductive paste of the present invention as long as the effects of the present invention are not impaired. By adding a flux component, it can be used with more reducing power.
  • a flux component a commonly used general flux can be used, and there is no particular limitation.
  • the flux may contain a rosin, an activator, a thixotropic agent and the like which are usually used.
  • the method for manufacturing a conductive pillar according to the present invention includes a first step of applying a conductive paste to a resin surface having an opening pattern formed on a substrate having an electrode portion in an atmosphere at an atmospheric pressure of 10 kPa or less; The method is characterized by comprising a second step of returning the pressure to a standard pressure after the application and filling the opening with a conductive paste, and a third step of removing the conductive paste remaining on the resin surface.
  • 1 and 2 show one embodiment of a method for manufacturing a conductive pillar of the present invention.
  • the method for producing a conductive pillar of the present invention includes a first step of applying a conductive paste to a resin surface having an opening pattern formed on a substrate having an electrode portion in an atmosphere having an atmospheric pressure of 10 kPa or less. And in the present invention, any method can be adopted as long as the conductive paste can be applied to the resin openings in an atmosphere having an atmospheric pressure of 10 kPa or less.
  • a rubber squeegee, a doctor blade, a dispenser, an ink jet, or the like can be employed.
  • FIG. 1 illustrates a method of applying a conductive paste using a rubber squeegee as a reference.
  • the substrate having the electrode portion is a substrate in which the electrode pad 1 is formed on the support 2, and the resin film 3 is formed on a portion other than the electrode pad portion 1 of the substrate (FIG. 1). .
  • the electrode head portion is an opening 4.
  • the atmosphere around the substrate is reduced to an atmospheric pressure of 10 kPa or less. Any method can be adopted as long as the atmospheric pressure around the substrate can be reduced to 10 kPa or less. If the pressure is 10 kPa or less, the incorporation of air bubbles can be prevented even when the pressure is returned to the standard pressure. Atmospheric pressure exceeding 10 kPa is not preferable because air accumulates in the opening and connection failure with the electrode occurs when the substrate and the chip are joined.
  • the squeegee 6 After reducing the atmospheric pressure to 10 kPa or less, the squeegee 6 is moved in the direction of the arrow, that is, parallel to the substrate, and the conductive paste 5 is applied to the resin surface (FIGS. 1 and 2A).
  • the film thickness at the time of coating is not particularly limited, but it is necessary to leave a sufficient amount of the conductive paste for manufacturing the pillar. Therefore, it is preferable to apply with a film thickness of about 1/2 or more of the pillar height (FIG. 2B).
  • the material of the electrode pad is not particularly limited, for example, aluminum, copper, nickel, gold, aluminum / silicon / copper alloy, titanium, titanium nitride, tungsten, polysilicon, tantalum, tantalum nitride, metal silicide, or these. May be used, and various metals may be introduced as an adhesion layer in order to secure adhesion to the conductive paste on the surface of these metals.
  • the material of the support is not particularly limited, and a publicly known material can be used, and any material that can form an electrode pad, a resin layer, a conductive pillar, or the like on the support is not particularly limited. Absent. For example, silicon, glass, ceramic, resin, various metals, and the like can be exemplified.
  • the material of the resin to be used is not particularly limited as long as a cylindrical mold having an opening of 20 to 30 ⁇ m can be manufactured.
  • a photoresist photo-resist
  • polyimide polyimide
  • epoxy epoxy molding compound
  • EMC epoxy molding compound
  • the material of the squeegee is not particularly limited, and a plastic, rubber, or metal squeegee can be used. There is no particular limitation on the thickness and length of the squeegee. As for the pressing pressure at the time of application, it is desirable to use a printing pressure that does not damage the opening pattern of the resin.
  • the method of manufacturing a conductive pillar according to the present invention includes a second step of returning the pressure to a standard pressure after applying the conductive paste and filling the resin opening with the conductive paste. As shown in FIG. 2C, the conductive paste on the resin film having the opening is sucked into the opening, whereby the conductive paste is filled.
  • the standard pressure refers to a state of one atmosphere. According to the above process, the conductive paste can be filled without creating a space up to the electrode pad surface, and the generation of voids can be suppressed. The generation of voids and voids hinders securing of conductivity with the electrode pad, and causes poor bonding.
  • the method for producing a conductive pillar according to the present invention is characterized by including a third step of removing the conductive paste remaining on the resin surface. Any method can be adopted as long as the conductive paste on the resin surface can be removed. A blade or air pressure can be used, or a method of polishing and removing after drying or baking can be adopted.
  • FIG. 1D illustrates a method of removing the conductive paste with a squeegee for reference. The conductive paste remaining on the resin surface hinders peeling of the resin. Further, the remaining conductive paste may cause a short circuit between pillars, which is not preferable.
  • the pillar can be manufactured by heating the conductive paste manufactured by the above method to a temperature at which metal fine particles neck.
  • the sintering method is not particularly limited, but when a metal that is easily oxidized is used as the material, photosintering is performed under a forming gas containing hydrogen, under a nitrogen atmosphere, or in a reducing atmosphere using formic acid or the like. It is preferable to carry out in any of the following.
  • sintering is desirably performed at a temperature of 300 ° C. or less in consideration of the effect on the resin film, and the sintering time is desirably within a range of 1 to 60 minutes.
  • a permanent film can be used as the resin film.
  • a permanent film there is an advantage that the step of removing the resin film can be reduced.
  • the conductive pillar manufactured by the pillar manufacturing method of the present invention can be used for mounting various electronic components and devices including flip-chip mounting.
  • the mixture was returned to room temperature, and a solution of hydrazine hydrate (1.50 g, 30.0 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) diluted with 7 mL of water was slowly dropped using a syringe pump. About 1/4 volume was slowly added dropwise over 2 hours. At this point, the addition was stopped once, and after stirring for 2 hours, it was confirmed that foaming had subsided. Then, the remaining amount was added over 1 hour. The resulting brown solution was heated to 60 ° C. and stirred for another 2 hours to terminate the reduction reaction.
  • aqueous dispersion ⁇ Preparation of aqueous dispersion> Subsequently, the reaction mixture was circulated through a hollow fiber type ultrafiltration membrane module (HIT-1-FUS1582, 145 cm 2 , molecular weight cut off 150,000) manufactured by Daisen Membrane Systems Co., Ltd. And purified by circulating the filtrate from the ultrafiltration module to about 500 mL while adding a 0.1% aqueous solution of hydrazine hydrate. The supply of the 0.1% hydrazine hydrate aqueous solution was stopped, and the mixture was concentrated by ultrafiltration to obtain 2.85 g of an aqueous dispersion of a complex of an organic compound containing a thioether and copper fine particles.
  • HIT-1-FUS1582, 145 cm 2 , molecular weight cut off 150,000 manufactured by Daisen Membrane Systems Co., Ltd.
  • purified by circulating the filtrate from the ultrafiltration module to about 500 mL while adding a 0.1% aque
  • the nonvolatile content in the aqueous dispersion was 16% by mass. From the weight loss by TG-DTA measurement, 3% of an organic substance having a polyethylene oxide structure was present in the obtained copper fine particles.
  • ⁇ Preparation of conductive paste> Each 5 mL of the above aqueous dispersion was sealed in a 50 mL three-necked flask, and while heating to 40 ° C. using a water bath, water was completely removed by flowing nitrogen at a flow rate of 5 ml / min under reduced pressure. Thus, 1.0 g of a dry powder of a copper fine particle composite was obtained. Next, in a glove bag purged with argon gas, ethylene glycol subjected to nitrogen bubbling for 30 minutes is added to the obtained dry powder, and mixed in a mortar for 10 minutes to prepare a conductive paste having a metal fine particle content of 80% by mass. did.
  • the shape of the opening was a columnar shape and the depth was 56 ⁇ m.
  • the diameters of the openings were 100, 50, 40, 30, and 20 ⁇ m. Therefore, the aspect ratios are 0.6, 1.1, 1.4, 1.9, and 2.8, respectively.
  • the coating / embedding process was performed in a glove box (MDB-1KPHYT manufactured by MIWA) using an automatic grind meter (manufactured by HOEI DEVICE).
  • An automatic grind meter equipped with a rubber squeegee for screen printing was installed in a glove box filled with argon gas.
  • a substrate prepared so as to have a width of about 5 cm was placed on a grind gauge portion of an automatic grind meter.
  • the prepared conductive paste was placed on the placed substrate, and the pressure in the glove box was reduced to 3 kPa. Immediately after the pressure reached 3 kPa, the conductive paste was applied to the substrate using an automatic grind meter.
  • the coating speed was about 3 cm / s. After the application was completed, the pressure was immediately returned to the standard pressure using argon gas so that the conductive paste was not dried.
  • ⁇ Sintering process> The sintering step of this example was performed using a hot plate in an argon atmosphere. The obtained substrate was fired at 120 ° C. for 5 minutes, and then sintered at 250 ° C. for 10 minutes. In this example, the resist was not stripped after sintering.
  • Example 2 ⁇ Coating / embedding process> As in Example 1, the coating and embedding steps were performed in a glove box using an automatic grind meter.
  • An automatic grind meter equipped with a rubber squeegee for screen printing was installed in a glove box filled with argon gas.
  • a substrate prepared so as to have a width of about 5 cm was placed on a grind gauge portion of an automatic grind meter.
  • the prepared conductive paste was placed on the placed substrate, and the pressure in the glove box was reduced to 3 kPa. Immediately after the pressure reached 3 kPa, the conductive paste was applied to the substrate using an automatic grind meter.
  • the coating speed was about 3 cm / s. After the application was completed, the pressure was immediately returned to the standard pressure using argon gas so that the conductive paste was not dried.
  • Example 2 As in Example 1, the sintering step of this example was performed using a hot plate in an argon atmosphere. The obtained substrate was fired at 120 ° C. for 5 minutes, and then sintered at 250 ° C. for 10 minutes. In this example, the resist was not stripped after sintering.
  • Example 1 Comparative Example 1 ⁇ Substrate> As the substrate used in this comparative example, the same substrate as that used in Example 1 was used.
  • the shape of the opening was a columnar shape and the depth was 56 ⁇ m.
  • the diameters of the openings were 100, 50, 40, 30, and 20 ⁇ m.
  • the coating and embedding process was performed in a glove box using an automatic grind meter.
  • An automatic grind meter equipped with a rubber squeegee for screen printing was installed in a glove box filled with argon gas so as to have a standard pressure.
  • a substrate prepared so as to have a width of about 5 cm was placed on a grind gauge portion of an automatic grind meter.
  • the prepared conductive paste was placed on the placed substrate, and the conductive paste was immediately applied to the substrate using an automatic grindometer.
  • the coating speed was about 3 cm / s.
  • Example 2 the sintering step of this comparative example was performed using a hot plate in an argon atmosphere. The obtained substrate was fired at 120 ° C. for 5 minutes, and then sintered at 250 ° C. for 10 minutes. In this comparative example, the resist was not stripped after sintering.
  • FIG. 3 shows a state where the conductive paste is filled into the substrate opening obtained after filling the conductive paste into the opening having a diameter of 30 ⁇ m and sintering.
  • FIG. 3A shows the result of Example 1
  • FIG. 3B shows the result of Comparative Example 1.
  • the conductive paste 9 is densely filled up to the upper part of the SUS substrate 8 as the support.
  • the conductive paste is uniformly filled in all the openings shown in the figure.
  • FIG. 3B the conductive paste was observed on the surface of the resist 10, but the conductive paste was not filled up to the interface of the SUS substrate, and the void 11 was observed. Further, in (b), cracks considered to be caused by volume expansion of air due to sintering were observed in the conductive paste.
  • Table 1 shows the filling rates of the conductive paste estimated from the cross-sectional photographs of the samples prepared in each of the examples and comparative examples.
  • the filling ratio indicates a ratio when the volume of the resist opening is 100.

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Abstract

従来方法である電解メッキ法においてはアンダーカットの影響を受けずに微細なピラーを形成することが困難であるという問題があった。また、無電解メッキ法においてはボイドなく同一形状のピラーを形成することが困難であるという問題があった。　本発明者らは、前記諸問題を解決するために鋭意検討を重ねた結果、金属微粒子を含有する導電性ペーストを減圧状態で塗布した後、標準気圧にすることにより、微細かつ高アスペクト比の導電性ピラーを、電極部を有する基板上へ容易に形成可能であることを見出した。本発明は、フリップチップ実装の端子である、金属ピラーの製造に特段の効果を有する。

Description

導電性ペーストを用いた導電性ピラーの製造方法
　本発明は、半導体パッケージ内において、半導体チップとパッケージインターポーザの接続方式であるフリップチップ実装の端子である、導電性ピラー（Ｐｉｌｌａｒ）あるいは導電性ポスト（Ｐｏｓｔ）の製造方法に関する。本発明の製造方法は、金属微粒子を含有する導電性ペーストを使用することを特徴としている。
　半導体装置においては、半導体チップ上に電子回路を製造し、半導体チップ上の電極と半導体パッケージ上の電極とを接続して製造される。従来、半導体チップ上の電極と半導体パッケージ上の電極との間は、金あるいは銅製のボンディングワイヤを用いて電気的に接続されていた。また、半導体チップと半導体パッケージの間の電気的な接続方法としてフリップチップ法が用いられている。フリップチップ法における代表的な接続方法として、金バンプやはんだバンプが用いられている。
　しかしながら、近年のチップの高集積化に伴い、最近は導電性ピラーを用いたフリップチップ実装技術が注目されている。導電性ピラーは、半導体チップ上に製造し、ピラー先端を半導体パッケージの電極と接続する。導電性ピラーとしては、ピラー直径７０μｍ以下、ピラー高さが５０～６０μｍのものが一般に用いられている。
　導電性ピラーには、様々な金属種（金、はんだ、銅などの各種金属や合金等）を用いることができる。金属種に金や銅を用いた場合には、はんだに比べて低電気抵抗であることから、大電流にも対応できる。また、導電性ピラーは、はんだバンプと比較して、はんだ供給量を抑えることができるため、バンプピッチの微細化が可能であり、高集積化にも対応可能である。加えて、導電性ピラーは、半導体チップ上の電極から半導体パッケージ上の電極に至るまで同じ断面積を維持できることからも、大電流に対応可能であるという利点をも有する。
　上記理由により、導電性ピラーの作製は半導体実装において重要であり、導電性ピラーを歩留まり良く、かつ、簡便に製造する方法が望まれている。
　基板上に導電性ピラーを製造する方法として、メッキ技術を利用した方法が知られている。
特許文献１、２によると、シード層と呼ばれるメッキ層を電極パッド上に作製し、電解メッキにより銅製の導電性ピラー（銅ピラー）を製造する方法が開示されている。しかしながら、メッキにより導電性ピラーを製造する場合、全面にシード層を設けるため、ピラー作製後にパターニングされたレジスト層及びシード層を除去する工程が必要となる。シード層をエッチングにより除去する工程は、銅ピラーのアンダーカットを生じさせることとなる（特許文献３）。したがって、メッキ法により微細な導電性ピラーを作製することは困難である、という課題が存在する。
また、メッキ技術により導電性ピラーを製造する方法として、無電解メッキを使用する方法も知られている。半導体チップ上にフォトレジスト層を製造し、導電性ピラーを製造する部分のフォトレジスト層を開口し、開口部分に無電解メッキを用いて銅ピラーを製造し、さらに銅ピラーの頂部にはんだメッキ層を製造する方法である。しかしながら、無電解メッキ方法により導電性ピラーの高さ／直径比（アスペクト比）が大きい、すなわち細長い導電性ピラーを製造するためには、直径が小さく深い穴にメッキを成長させる必要が生じる。この場合、開口部に十分な濃度のメッキ液を送り続けなければならず、導電性ピラーの成長が遅くなり、スループットが悪化する。結果、導電性ピラーの直径が目標より細くなる、形状が不安定になる、析出する金属内部にボイドが生じる、等の問題を生じさせる。これら問題は、品質及び再現性の低下を招くという課題がある（特許文献４）。
　加えて、メッキ法は大量の廃液を再生又は処分する必要があり、環境負荷が大きく設備維持にコストも要することから代替手段が望まれている。
　メッキ法の代替としてスキージ等であらかじめ導電性ペーストをパターニングされたレジスト層の開口部分に充填し、ピラーを製造する方法を考えることができる。しかし、半導体実装の高密度化・高精細化により、導電性ピラーの直径が小さくなった場合、開口部深くまで導電性ペーストを充填することは難しい。
特開２０１１－０２９６３６号公報 特開２０１２－５３２４５９号公報 特開２０１２－０１５３９６号公報 ＷＯ２０１６／０３１９８９号公報
したがって、従来方法である電解メッキ法においてはアンダーカットの影響を受けずに微細な導電性ピラーを製造することが困難であるという問題があった。また、無電解メッキ法においてはボイドなく同一形状のピラーを製造することが困難であるという問題があった。
アンダーカットを防止できるとともに、再現性良く同一形状の導電性ピラーを提供することが求められる。本発明は、ピラー製造用導電性ペーストを用いて、微細な導電性ピラーを埋め込み法により作製する方法を提供することを目的としている。
　本発明者らは、前記諸問題を解決するために鋭意検討を重ねた結果、金属微粒子を含有する導電性ペーストを減圧状態で塗布した後、大気圧状態に開放することにより、微細かつ高アスペクト比の導電性ピラーを電極部を有する基板上に容易に製造可能であることを見出した。
本発明は、フリップチップ実装の端子である、導電性ピラーの製造に特段の効果を有することを見出した。
　すなわち本発明は、
（１）金属微粒子を含有する導電性ペーストを用いて電極部を有する基板上に導電性ピラーを製造する方法であって、
大気圧１０ｋＰａ以下の雰囲気中で、電極部を有する基板上に開口パターンが形成された樹脂表面に導電性ペーストを塗布する第一工程と、
導電性ペーストを塗布した後に標準気圧に戻し、開口部に導電性ペーストを充填させる第二工程と、
樹脂表面に残った前記導電性ペーストを除去する第三工程と、
を有する導電性ピラーの製造方法。
（２）（１）記載の導電性ペーストを塗布する工程及び導電性ペーストを除去する工程に、ゴム製又は金属性スキージを使用することを特徴とする（１）記載の導電性ピラーの製造方法。
（３）（１）記載の導電性ペーストを塗布する工程を、スクリーン印刷により行うことを特徴とする（１）記載の導電性ピラーの製造方法。
（４）（１）記載の電極部を有する基板上に形成された開口パターンの直径が５０μｍ以下であることを特徴とする（１）から（３）のいずれか一記載の導電性ピラーの製造方法
を提供するものである。
　本発明は、金属微粒子を含有する導電性ペーストを用いて電極部を有する基板上に導電性ピラーを製造する方法である。
本発明を用いることにより、従来技術であるメッキ技術を使用することなく、スキージ等であらかじめ導電性ペーストをパターニングされたレジスト層の開口部分に充填させることでピラーを簡便に製造することができる。
導電性ペーストを用いて電極部を有する基板上に直接ピラーを製造することにより、従来方法による課題であったエッチング時のアンダーカットを解決することができ、微細な銅ピラーの製造が可能となる。
導電性ペーストによるピラー作製は、メッキ液の劣化や、イオンの拡散律速などの制限を受けないため、無電解メッキ法の品質や再現性の課題も解決できる可能性があると考えられる。
　本発明を用いることにより、埋め込み法においても半導体実装の高密度化・高集積化に耐えうる微細な導電性ピラーを簡便に作製できる。
本発明に係る導電性ピラーの製造工程（第一工程）を示す断面模式図。 本発明に係る導電性ピラーの製造工程を示す断面模式図。 本発明の方法により作製した導電性ピラーの断面写真。
以下、本発明を詳細に説明する。
＜導電性ペースト＞
　本発明に用いられれる、金属微粒子を含有する導電性ペーストの製造方法について以下詳細に説明する。
（金属微粒子）
金属微粒子として用いることができる金属種は、当該金属種が後述する保護剤中の官能基と化学的に結合できるものであれば特に制限されない。例えば、金、銀、銅、ニッケル、亜鉛、アルミニウム、白金、パラジウム、スズ、クロム、鉛、タングステン等を用いることができる。また、金属種は一種類であっても、二種類以上の混合物、または合金であっても良い。
導電性ペースト中の金属微粒子含有率は、特に制限されるものではないが。開口部分に充填させるには、十分な流動性を確保する必要があることから、４０以上９５質量％濃度未満の範囲で使用することが好ましい。
（金属微粒子の合成）
　本発明の金属微粒子の合成方法としては、化学還元方法を採用したが、金属微粒子表面を保護剤より保護することができ、かつ、粒子径が１μｍ以下であれば、任意の方法を採用することができる。例えば、湿式法として化学還元法のほかに熱分解法、電気化学法を採用することもできる。乾式法としてガス中蒸発法、スパッタ法を採用することもできる。
（保護剤）
　本発明の保護剤は、金属微粒子や溶剤との親和性を有する官能基を有する化合物を任意に選択することができる。また、使用する保護剤は、分子量の大小にかかわらず使用することができる。使用する金属種や所望する物性に応じて保護剤を設計することで高導電性や分散安定性を金属微粒子に付与することが可能である。
　具体的には、金属に対しやや強い吸着能を有するカルボキシ基、リン酸基、スルホン酸基、複素芳香族基（例えばイミダゾール基）等を有する保護剤を使用することにより、微粒子に高い分散安定性を付加することができる。
また、金属に対し中程度の相互作用を示し分散媒の液性によって吸着能が変化するアミノ基（例、ジメチルアミノエチル基、ジメチルアミノプロピル基）、ヒドロキシ基（ヒドロキシエチル基、ヒドロキシプロピル基）、芳香族基（たとえばベンジル基）等を有する保護剤を使用することにより、低温焼結においても低い体積抵抗率を発現する高導電性を付加することができる。
このように種々の目的に応じて金属微粒子用保護剤を選択することで金属微粒子の特性を自在に変更することができる。低分子量の保護剤を用いる場合は、二種以上の化合物を併用することで様々な特性を発現できる。高分子量の保護剤を用いる場合は、化合物中の官能基の数及び種類を変更することで様々な特性を発現できる。
　導電性ペースト中の保護剤濃度は、全ペースト中１５質量％濃度以下の範囲で使用することができる。より、好ましくは１０質量％濃度以下の範囲である。保護剤濃度が高すぎる場合には、焼結時に金属粒子同士のネッキング現象が十分に生じず、高い導電性を発現させることが困難となる。
（溶媒）
　本発明で用いることができる溶媒としては、特に制限されることはなく、水又は／及び有機溶剤を溶媒として用いることが可能である。前記溶媒は、金属微粒子を凝集させない良溶媒を用いることが、均一な粒子系を有する導電性ペーストを製造する上では好ましい。
　溶媒は、導電性ペースト焼結時に揮発することが望ましい。しかし、高い焼結温度は樹脂膜を変質させ、ダメージを与えてしまう。したがって、樹脂膜へのダメージが生じない温度範囲に沸点を有する有機溶剤を溶媒として使用することがより望ましい。
　導電性ペースト中の溶媒濃度は、特に制限されるものではないが、６０質量％濃度以下の範囲で使用することが好ましい。
（導電性ペーストの作製）
　本発明のピラー製造用導電性ペーストは、作製した金属微粒子に充填用のペーストとして使い易い溶媒を加え、あるいは、媒体交換することにより、本発明の導電性ペーストとしての適性を付与することができる。
　本発明のピラー製造用導電性ペーストには、本発明の効果を損なわせない範囲において、必要に応じて、樹脂等のバインダー成分、乾燥防止剤、消泡剤、基板への密着付与剤、酸化防止剤、皮膜製造促進のための各種触媒、シリコーン系界面活性剤、フッ素系界面活性剤の様な各種界面活性剤、レベリング剤、離型促進剤等を助剤として添加できる。
　本発明の導電性ペーストは、本発明の効果を損なわない範囲内でフラックス成分を加えることができる。フラックス成分を加えることにより、一層の還元力を持たせて使用することもできる。フラックスとしては、通常用いられる一般的なフラックスを用いることが可能であり、特に制限するものではない。このフラックス中には、通常用いられるロジン、活性剤、チキソ剤等が含まれていても構わない。
＜導電性ピラーの製造方法＞
以下、図面を参照しながら、本発明に係る導電性ピラーの製造方法の好適な実施形態について詳細に説明する。
本発明の導電性ピラーの製造方法は、大気圧１０ｋＰａ以下の雰囲気中で、電極部を有する基板上に開口パターンが形成された樹脂表面に導電性ペーストを塗布する第一工程と、導電性ペーストを塗布した後に標準気圧に戻し、開口部に導電性ペーストを充填させる第二工程と、樹脂表面に残った前記導電性ペーストを除去する第三工程と、を備えることを特徴としている。図１及び２には、本発明の導電性ピラーの製造方法の一実施形態を示した。
（第一工程）
本発明の導電性ピラーの製造方法は、大気圧１０ｋＰａ以下の雰囲気中で、電極部を有する基板上に開口パターンが形成された樹脂表面に導電性ペーストを塗布する第一工程を有することを特徴とする。
本発明においては、大気圧１０ｋＰａ以下の雰囲気中で、導電性ペーストを樹脂開口部に塗布することができれば、任意の方法を採用することができる。例えば、ゴムスキージ、ドクターブレード、ディスペンサ、インクジェット等を採用することができる。図１では、参考としてゴムスキージにより導電性ペーストを塗布する方法を例示した。
電極部を有する基板とは、支持体２上に電極パッド１が形成されている基板であって、当該基板の電極パッド部分１以外の部分に樹脂膜３を形成したものである（図１）。なお、電極ハッド部分は開口部４となっている。
前記基板に導電性ペーストを塗布する前に、基板周囲の雰囲気を大気圧１０ｋＰａ以下に減圧する。基板周囲の大気圧が１０ｋＰａ以下にできる方法であれば任意の方法を採用することができる。１０ｋＰａ以下であれば標準気圧に戻した際にも、気泡の混入を防止できる。１０ｋＰａを上回る大気圧では、開口部内に空気がたまり、基板とチップを接合した際に電極との接続不良が発生するため、好ましくない。
大気圧を１０ｋＰａ以下にした後、スキージ６を矢印の方向、すなわち基板に対して平行に移動させ、導電性ペースト５を樹脂表面に塗布する（図１、図２（ａ））。塗布する際の膜厚は、とくに制限されるものではないがピラーを製造するのに十分な量の導電性ペーストを残すことが必要である。したがって、おおよそピラー高さの１／２以上の膜厚で塗布することが好ましい（図２（ｂ））。
電極パットの材料について得に制限されるものでなく、例えば、アルミニウム、銅、ニッケル、金、アルミニウム／シリコン／銅合金、チタン、窒化チタン、タングステン、ポリシリコン、タンタル、窒化タンタル、金属シリサイド又はこれらの組み合わせの導電材料を用いても良く、これら金属の表面に導電性ペーストとの密着性を確保するために、密着層として種々の金属を導入することもできる。
支持体の材料としても、特に制限されるものではなく公知公用の物を用いることができ、支持体上に電極パット、樹脂層、導電性ピラー等を形成できるものであれば特に制限させるものではない。例えば、シリコンをはじめ、ガラス、セラミック、樹脂、各種金属等を例示列挙することができる。
開口部４を有する樹脂膜３を作製するためには、公知公用の手法を用いることができる。使用する樹脂の材料は、２０～３０μｍの開口部を有する円柱状の鋳型形状が製造できれば特に制限されるものではない。例えば、フォトレジスト（ｐｈｏｔｏ－ｒｅｓｉｓｔ）、ポリイミド、エポキシ、及びエポキシモールディングコンパウンド（Ｅｐｏｘｙ　Ｍｏｌｄｉｎｇ　Ｃｏｍｐｏｕｎｄ：ＥＭＣ）、各種ドライフィルムを用いることもできる。
スキージについても素材について得に制限されるものではなく、プラスチック、ゴム、金属性のスキージを用いることができる。スキージの厚さ、長さについても特に制限はない。塗布時の押し込み圧力については、樹脂の開口部パターンを破損させない程度の印圧で使用することが望ましい。
（第二工程）
本発明の導電性ピラーの製造方法は、導電性ペーストを塗布した後に標準気圧に戻し、樹脂開口部に導電性ペーストを充填させる第二工程を有することを特徴とする。図２（ｃ）に示すように、開口部を有する樹脂膜上の導電性ペーストが開口部に吸い込まれることにより、導電性ペーストが充填される。
標準気圧とは、１気圧の状態をさす。上記工程により電極パット表面まで空間を生じずに導電性ペーストを充填でき、ボイドの発生を抑制できる。ボイドや空隙の発生は、電極パットとの導電性確保を阻害し、接合不良を生じさせる。
（第三工程）
本発明の導電性ピラーの製造方法は、樹脂表面に残った導電性ペーストを除去する第三工程を有することを特徴とする。樹脂表面の導電性ペーストを除去することができれば、任意の方法を採用することができる。ブレードや空気圧を用いることもできるし、乾燥又は焼成後に研磨除去する方法も採用できる。図１（ｄ）では、参考としてスキージにより導電性ペーストを除去する方法を例示した。
樹脂表面に残留した導電性ペーストは、樹脂の剥離を阻害する。また、残留した導電性ペーストは、ピラー間で短絡を引き起こす可能性があり、好ましくない。
（ピラーの焼結方法）
導電性ペーストに熱硬化性の物を用いる場合、上記方法により作製された導電性ペーストを金属微粒子がネッキングする温度まで加熱し、ピラーを作製することができる。
焼結方法については、特に限定されるものではないが、酸化しやすい金属を材料として用いる場合には、光焼結、水素を含むフォーミングガス下、窒素雰囲気下、又はギ酸等を用いた還元雰囲気下のいずれかで行うことが好ましい。
　焼結工程を経る場合には、樹脂膜への影響を考えると３００℃以下の範囲で焼結することが望ましく、焼結時間は１～６０分間の範囲内が望ましい。
（ピラー製造後の工程について）
本発明に用いる樹脂膜を除去する場合（図２（ｅ））には、公知公用の任意の方法を採用することができる。
本発明のピラー製造方法では、樹脂膜に永久膜を用いることもできる。永久膜を用いる場合には、樹脂膜を剥離する工程を削減することができるという利点がある。
本発明のピラー製造方法により作製した導電性ピラーは、フリップチップ実装をはじめとする種々の電子部品・デバイスの実装に用いることができる。
　以下、実施例をもって本発明を具体的に説明する。ここで「％」は、特に指定がない限り「質量％」である。
（導電性ペーストの作製）
＜金属微粒子の合成＞
　酢酸銅（ＩＩ）一水和物（３．００ｇ、１５．０ｍｍｏｌ）（東京化成工業社製）、エチル３－（３－（メトキシ（ポリエトキシ）エトキシ）－２－ヒドロキシプロピルスルファニル）プロピオナート〔ポリエチレングリコールメチルグリシジルエーテル（ポリエチレングリコール鎖の分子量２０００（炭素数９１））への３－メルカプトプロピオン酸エチルの付加化合物〕（０．４５１ｇ）（ＤＩＣ社製）、およびエチレングリコール（１０ｍＬ）（関東化学社製）からなる混合物に、窒素を５０ｍＬ／分の流量で吹き込みながら加熱し、１２５℃で２時間通気攪拌して脱気した。この混合物を室温に戻し、ヒドラジン水和物（１．５０ｇ、３０．０ｍｍｏｌ）（東京化成工業社製）を水７ｍＬで希釈した溶液を、シリンジポンプを用いてゆっくり滴下した。約１／４量を２時間かけてゆっくり滴下し、ここで一旦滴下を停止し、２時間攪拌して発泡が沈静化するのを確認した後、残量を更に１時間かけて滴下した。得られた褐色の溶液を６０℃に昇温して、さらに２時間攪拌し、還元反応を終結させた。
＜水分散液の調製＞
　つづいて、この反応混合物をダイセン・メンブレン・システムズ社製の中空糸型限外濾過膜モジュール（ＨＩＴ－１－ＦＵＳ１５８２、１４５ｃｍ２、分画分子量１５万）中に循環させ、滲出する濾液と同量の０．１％ヒドラジン水和物水溶液を加えながら、限外濾過モジュールからの濾液が約５００ｍＬとなるまで循環させて精製した。０．１％ヒドラジン水和物水溶液の供給を止め、そのまま限外濾過法により濃縮すると、２．８５ｇのチオエーテルを含む有機化合物と銅微粒子との複合体の水分散液が得られた。　　
得られた銅微粒子を透過型電子顕微鏡（ＴＥＭ）により観察すると、得られた銅微粒子の一次粒子径は２０ｎｍであった。水分散液中の不揮発物含量は１６質量％濃度であった。ＴＧ－ＤＴＡ測定による重量減少より、得られた銅微粒子には３％のポリエチレンオキシド構造を含む有機物が存在していた。
＜導電性ペーストの調製＞
　上記の水分散液５ｍＬをそれぞれ５０ｍＬ三口フラスコに封入し、ウォーターバスを用いて４０℃に加温を行いながら、減圧下、窒素を５ｍｌ／ｍｉｎの流速で流すことで、水を完全に除去し、銅微粒子複合体乾燥粉末１．０ｇを得た。次に得られた乾燥粉末にアルゴンガス置換したグローブバッグ内で、３０分間窒素バブリングしたエチレングリコールを添加し、乳鉢で１０分間混合することで金属微粒子含有率８０質量％濃度の導電性ペーストを作製した。
（実施例１）
＜基板＞
埋め込みに使用した基板は、厚さ５６μｍのドライフィルムレジストを用いてステンレス板（ｔ＝０．５ｍｍ）に、開口部パターンを製造した物を用いた。開口部の形状は、円柱状であり、深さは５６μｍであった。開口部分の直径は、１００、５０、４０、３０、２０μｍであった。したがって、アスペクト比は、それぞれ０．６、１．１、１．４、１．９、及び２．８である。パターンは、Ｈｏｌｅ：Ｓｐａｃｅ＝１：１となるようにデザインした。
＜塗布・埋込工程＞
塗布・埋込工程は、自動グラインドメーター（ＨＯＥＩ　ＤＥＶＩＣＥ社製）を用いて、グローブボックス（ＭＩＷＡ製　ＭＤＢ－１ＫＰＨＹＴ）内にて行った。アルゴンガスで満たしたグローブボックス内に、スクリーン印刷用ゴムスキージを装着した自動グラインドメーターを設置した。自動グラインドメーターのグラインドゲージ部分に、横幅５ｃｍ程度になるように調製した基板を設置した。設置した基板に作製した導電性ペーストをのせ、グローブボックス内を３ｋＰａに減圧した。３ｋＰａの気圧に達した後、ただちに自動グラインドメーターを用いて基板上に導電性ペーストを塗布した。塗布速度は、３ｃｍ／ｓ程度であった。
塗布完了後、導電性ペーストが乾燥しないよう、ただちにアルゴンガスを用いて標準気圧に戻した。
＜除去工程＞
標準気圧に戻した後、再度自動グラインドメーターに設置したゴムスキージを用いて、レジスト表面に残った過剰の導電性ペーストを除去した。
＜焼結工程＞
本実施例の焼結工程は、アルゴン雰囲気下においてホットプレートを用いて行った。得られた基板を、１２０℃で５分間焼成した後、２５０℃で１０分間焼結した。本実施例においては、焼結後のレジスト剥離は行わなかった。
（実施例２）
＜基板＞
埋め込みに使用した基板は、シリコンウェハー（ｔ＝７７５μｍ）に、フォトレジスト（ＳＵ－８）を用いて開口部パターンを製造した物を用いた。開口部の形状は、円柱状であり、深さ（レジスト厚）は、約５０μｍであった。開口部分の直径は、１００、５０、４０、３０、２０μｍであった。したがって、アスペクト比は、それぞれ約０．５、１．０、１．３、１．６、及び２．５である。パターンは、Ｈｏｌｅ：Ｓｐａｃｅ＝１：１となるようにデザインした。
＜塗布・埋込工程＞
実施例１と同様に、塗布・埋込工程は自動グラインドメーターを用いて、グローブボックス内にて行った。アルゴンガスで満たしたグローブボックス内に、スクリーン印刷用ゴムスキージを装着した自動グラインドメーターを設置した。自動グラインドメーターのグラインドゲージ部分に、横幅５ｃｍ程度になるように調製した基板を設置した。設置した基板に作製した導電性ペーストをのせ、グローブボックス内を３ｋＰａに減圧した。３ｋＰａの気圧に達した後、ただちに自動グラインドメーターを用いて基板上に導電性ペーストを塗布した。塗布速度は、３ｃｍ／ｓ程度であった。
塗布完了後、導電性ペーストが乾燥しないよう、ただちにアルゴンガスを用いて標準気圧に戻した。
＜除去工程＞
実施例１と同様に、標準気圧に戻した後、再度自動グラインドメーターに設置したゴムスキージを用いて、レジスト表面に残った過剰の導電性ペーストを除去した。
＜焼結工程＞
実施例１と同様に、本実施例の焼結工程は、アルゴン雰囲気下においてホットプレートを用いて行った。得られた基板を、１２０℃で５分間焼成した後、２５０℃で１０分間焼結した。本実施例においては、焼結後のレジスト剥離は行わなかった。
（比較例１）
＜基板＞
本比較例に用いた基板は、実施例１で用いたものと同様の物を使用した。埋め込みに使用した基板は、厚さ５６μｍのドライフィルムレジストを用いてステンレス板（ｔ＝０．５ｍｍ）に、開口部パターンを製造した物を用いた。開口部の形状は、円柱状であり、深さは５６μｍであった。開口部分の直径は、１００、５０、４０、３０、２０μｍであった。
＜塗布・埋込工程＞
塗布・埋込工程は、自動グラインドメーターを用いて、グローブボックス内にて行った。標準気圧となるようにアルゴンガスで満たしたグローブボックス内に、スクリーン印刷用ゴムスキージを装着した自動グラインドメーターを設置した。自動グラインドメーターのグラインドゲージ部分に、横幅５ｃｍ程度になるように調製した基板を設置した。設置した基板に作製した導電性ペーストをのせ、ただちに自動グラインドメーターを用いて基板上に導電性ペーストを塗布した。塗布速度は、３ｃｍ／ｓ程度であった。
＜除去工程＞
再度自動グラインドメーターに設置したゴムスキージを用いて、レジスト表面に残った過剰の導電性ペーストを除去した。
＜焼結工程＞
実施例１と同様に、本比較例の焼結工程は、アルゴン雰囲気下においてホットプレートを用いて行った。得られた基板を、１２０℃で５分間焼成した後、２５０℃で１０分間焼結した。本比較例においては、焼結後のレジスト剥離は行わなかった。
（評価・観察）
開口部への導電性ペーストの充填状態を評価した。開口部にペーストを充填し、焼結させた基板を１ｃｍ程度の小片に切断し樹脂で包埋した。包埋した試料をカットし断面出しを行った後、光学顕微鏡を用いて観察・評価した。図３には、直径３０μｍの開口部に導電性ペーストを充填し、焼結した後に得られた基板開口部への導電性ペーストの充填状態を示している。図３（ａ）は実施例１、図３（ｂ）は比較例１の結果を示している。
図３（ａ）において、支持体であるＳＵＳ基板８上部まで導電性ペースト９が密に充填していることがわかる。また、図に示したすべての開口部分において均一に導電性ペーストが充填されていることがわかる。一方、図３（ｂ）において、レジスト１０表面に導電性ペーストが観測されたが、ＳＵＳ基板界面まで導電性ペーストが充填されておらず、空隙１１が観測された。また、（ｂ）においては、焼結による空気の体積膨張に起因すると思われるクラックが導電性ペーストに観測された。
・表１
Figure JPOXMLDOC01-appb-I000001
　表１は、各実施例及び比較例において作製した試料の、断面写真より概算した導電性ペーストの充填率をしてしている。充填率は、レジスト開口部分の体積を１００とした場合の割合を示している。電子顕微鏡により確認できるような、粒子間の隙間（１μｍ以下）は、粒子が充填しているものとみなして計算した。
　本発明のピラー製造方法を用いることによって、開口部分の直径が５０μｍ以下の場合において、７０％以上の充填率を確保できることが明らかとなった。本結果は、標準気圧下においてはレベリング剤や溶媒種の最適化を行わなければ作製困難である、導電性ピラーを容易に作製可能であることを示している。
　１　電極パット、２　支持体、３　樹脂（レジスト等）、４　開口部、５　導電性ペースト、６　スキージ、７　導電性ピラー、８　支持体（ＳＵＳ製）、９　銅ペースト、１０　レジスト、１１　空隙。

Claims (4)

  1. 金属微粒子を含有する導電性ペーストを用いて電極部を有する基板上に導電性ピラーを製造する方法であって、
    大気圧１０ｋＰａ以下の雰囲気中で、電極部を有する基板上に開口パターンが形成された樹脂表面に導電性ペーストを塗布する第一工程と、
    導電性ペーストを塗布した後に標準気圧に戻し、開口部に導電性ペーストを充填させる第二工程と、
    樹脂表面に残った前記導電性ペーストを除去する第三工程と、
    を有する導電性ピラーの製造方法。
  2. 請求項１記載の導電性ペーストを塗布する工程及び導電性ペーストを除去する工程に、ゴム製又は金属製スキージを使用することを特徴とする請求項１記載の導電性ピラーの製造方法。
  3. 請求項１記載の導電性ペーストを塗布する工程を、スクリーン印刷により行うことを特徴とする請求項１記載の導電性ピラーの製造方法。
  4. 請求項１記載の電極部を有する基板上に形成された開口パターンの直径が５０μｍ以下であることを特徴とする請求項１から３のいずれか一項記載の導電性ピラーの製造方法。
PCT/JP2019/017604 2018-07-26 2019-04-25 導電性ペーストを用いた導電性ピラーの製造方法 WO2020021800A1 (ja)

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