TW202033779A - Particles for joining material and production method thereof, joining paste and preparation method thereof, and production method of joined body - Google Patents

Particles for joining material and production method thereof, joining paste and preparation method thereof, and production method of joined body Download PDF

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TW202033779A
TW202033779A TW108135975A TW108135975A TW202033779A TW 202033779 A TW202033779 A TW 202033779A TW 108135975 A TW108135975 A TW 108135975A TW 108135975 A TW108135975 A TW 108135975A TW 202033779 A TW202033779 A TW 202033779A
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bonding
particles
ions
bonding material
copper
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TW108135975A
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TWI819113B (en
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山口朋彦
乙川光平
樋上晃裕
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日商三菱綜合材料股份有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/062—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts
    • B22F7/064—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts using an intermediate powder layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables

Abstract

These particles for a joining material are produced by forming an organic protective film on the surface of copper nanoparticles, have a BET specific surface area in a range of 3.5 m2/g to 8 m2/g and a BET diameter in a range of 80 nm to 200 nm, and include the organic protective film in a range of 0.5% to 2.0% by mass with respect to the particles for the joining material. When the particles for the joining material are analyzed using a time-of-flight secondary ion mass spectrometry (TOF-SIMS) method, the amounts of detected C3H3O3- ions and C3H4O2- ions are respectively in a range of 0.05 times to 0.2 times the amount of detected Cu+ ions, and the amount of detected C5 or higher ions is in a range of less than 0.005 times the amount of detected Cu+ ions.

Description

接合材料用粒子及其製造方法、接合用糊料及其調製方法以及接合體之製造方法Particles for bonding materials and methods for producing them, pastes for bonding and methods for preparing them, and methods for manufacturing bonded bodies

本發明關於在銅奈米粒子表面上形成有有機保護膜之接合材料用粒子及其製造方法，該接合材料係作為電子零件之組裝或安裝時的接合用糊料之原料使用。又，關於該接合材料用粒子之接合用糊料及其調製方法。再者，關於使用該接合用糊料的接合體之製造方法。還有，本國際申請案主張以2018年10月4日申請的日本發明專利申請案第2018-188905號(特願2018-188905)及2018年12月27日申請日本發明專利申請案第2018-245662號(特願2018-245662)為基礎之優先權，在本國際申請案中援用特願2018-188905及特願2018-245662之全部內容。The present invention relates to particles for bonding materials having an organic protective film formed on the surface of copper nanoparticles and a method for manufacturing the bonding materials. The bonding material is used as a raw material for bonding paste during assembly or mounting of electronic parts. In addition, it relates to the bonding paste of the particles for bonding material and the preparation method thereof. Furthermore, it is about the manufacturing method of the bonded body using this bonding paste. In addition, this international application claims the Japanese invention patent application No. 2018-188905 (Special Application 2018-188905) filed on October 4, 2018 and the Japanese invention patent application No. 2018- on December 27, 2018. Priority based on No. 245662 (Special Application 2018-245662), the entire contents of Special Application 2018-188905 and Special Application 2018-245662 are used in this international application.

於電子零件之組裝或安裝時，當接合2個以上的零件時，一般使用接合材。作為如此的接合材，已知在溶劑中分散有金屬粒子之糊料狀接合材。使用接合材接合零件時，可在一個零件之表面上塗佈接合材，使塗佈面接觸另一個零件，於此狀態下加熱而接合。When assembling or installing electronic parts, when joining two or more parts, joining materials are generally used. As such a bonding material, a paste-like bonding material in which metal particles are dispersed in a solvent is known. When using a bonding material to join parts, the bonding material can be coated on the surface of one part so that the coated surface touches the other part, and in this state, it is heated and joined.

於供如此用途之原料金屬粒子，一般要求高熱傳導率或高耐熱性。因此，大多使用金、銀等之金屬粒子，其中大多使用比金便宜的銀。然而，使用銀粒子時，在所形成的接合部或配線部中有容易發生遷移之問題。For raw metal particles for such purposes, high thermal conductivity or high heat resistance is generally required. Therefore, metal particles such as gold and silver are mostly used, and most of them use silver which is cheaper than gold. However, when silver particles are used, there is a problem that migration easily occurs in the formed junction or wiring.

關於上述遷移之抑制，使用銅材料係比銀材料更有效。特別地，銅奈米粒子係比塊狀銅在更比較低溫下燒結，所得之接合層係在熱傳導性與高耐熱性之方面優異。又，成本比銀材料便宜，但另一方面因銅奈米粒子之比表面積大，有銅奈米粒子表面容易氧化之問題。Regarding the suppression of the above migration, the use of copper materials is more effective than silver materials. In particular, copper nanoparticles are sintered at a lower temperature than bulk copper, and the resulting bonding layer is superior in terms of thermal conductivity and high heat resistance. In addition, the cost is lower than that of silver materials, but on the other hand, because the specific surface area of copper nanoparticles is large, there is a problem that the surface of copper nanoparticles is easily oxidized.

作為防止銅奈米粒子之氧化的方法，有揭示以聚矽氧油在銅奈米粒子之製作時被覆於周圍之方法(例如參照專利文獻1(請求項1))，或在銅的微細粉末之製作時添加蘋果酸、檸檬酸、酒石酸等之添加劑而抑制氧化之方法(例如參照專利文獻2(請求項1、請求項3))，或製作在粒子表面上具有檸檬酸的銅奈米粒子之方法(例如參照專利文獻3(請求項1))。於專利文獻3之方法中，相對於銅之重量，檸檬酸之量為15wt%以上40wt%以下。 [先前技術文獻] [專利文獻]As a method of preventing the oxidation of copper nanoparticles, there are disclosed methods of coating the surroundings with polysiloxane oil during the production of copper nanoparticles (for example, refer to Patent Document 1 (claim 1)), or in the case of copper fine powder A method to suppress oxidation by adding additives such as malic acid, citric acid, and tartaric acid during production (for example, refer to Patent Document 2 (claim 1, claim 3)), or produce copper nanoparticles with citric acid on the particle surface (For example, refer to Patent Document 3 (claim 1)). In the method of Patent Document 3, the amount of citric acid relative to the weight of copper is 15 wt% or more and 40 wt% or less. [Prior Technical Literature] [Patent Literature]

專利文獻1：日本特開2005-060779號公報 專利文獻2：日本特開2007-258123號公報 專利文獻3：日本發明專利第5227828號公報Patent Document 1: Japanese Patent Application Publication No. 2005-060779 Patent Document 2: Japanese Patent Application Publication No. 2007-258123 Patent Document 3: Japanese Invention Patent No. 5227828

[發明所欲解決的問題][The problem to be solved by the invention]

專利文獻1所揭示之以聚矽氧油所被覆的銅奈米粒子，係在抗氧化性之點上非常優異，但由於在熱處理後未揮發盡的聚矽氧油會殘留在接合層中，有因燒結不良而導致接合強度或熱傳導率大幅降低之問題。The copper nanoparticle coated with silicone oil disclosed in Patent Document 1 is very excellent in terms of oxidation resistance. However, since the silicone oil that has not evaporated after heat treatment remains in the bonding layer, There is a problem that the bonding strength or thermal conductivity is greatly reduced due to poor sintering.

於專利文獻2所揭示之方法中，於所製作之銅粉末中添加能抑制後續的氧化之添加劑，以球磨機等使其吸附。然而，於此手法中由於難以均勻地塗佈，故難以完全地防止銅奈米粒子之氧化。In the method disclosed in Patent Document 2, an additive capable of inhibiting subsequent oxidation is added to the produced copper powder, and then adsorbed by a ball mill or the like. However, in this method, it is difficult to apply uniformly, so it is difficult to completely prevent the oxidation of copper nanoparticles.

於專利文獻3所揭示之方法中，藉由製作在表面上具有檸檬酸的銅奈米粒子，而抑制氧化。然而，相對於前述銅之質量，該檸檬酸量係15wt%以上40wt%以下之非常多，在接合體形成時，有因表面保護膜之脫離而發生的氣體係在接合膜等的接合地方變成空隙之問題。基於以上，要求：具有已賦予抗氧化性的表面保護膜，且在該保護膜脫離之際所發生的氣體成分為非常少，低溫燒結性優異的接合材料用之銅奈米粒子。In the method disclosed in Patent Document 3, oxidation is suppressed by producing copper nanoparticles having citric acid on the surface. However, relative to the mass of the aforementioned copper, the amount of citric acid is very much from 15wt% to 40wt%. When the bonded body is formed, the gas system caused by the detachment of the surface protective film may become at the bonding place such as the bonding film. The problem of gaps. Based on the above, there is a demand for copper nano particles for bonding materials that have a surface protective film that has been imparted with oxidation resistance, have very few gas components that are generated when the protective film is detached, and have excellent low-temperature sintering properties.

又，於專利文獻3所揭示之方法中，混合分別經調整至pH10以上且未達pH12之範圍的第1水溶液與第2水溶液，製造銅奈米粒子。然後，於該鹼性溶液中銅離子係變成氫氧化銅(II)，該氫氧化銅(II)容易沈澱，有目標粒子之產率降低之問題。基於以上，要求以高產率製造具有已賦予抗氧化性的表面保護膜，且低溫燒結性優異的接合材料用之銅奈米粒子的方法。In addition, in the method disclosed in Patent Document 3, a first aqueous solution and a second aqueous solution adjusted to a pH of 10 or more and a range of less than pH 12 are mixed to produce copper nanoparticles. Then, the copper ions in the alkaline solution become copper (II) hydroxide, the copper (II) hydroxide is easy to precipitate, and there is a problem that the yield of target particles decreases. Based on the above, there is a demand for a high-yield method for producing copper nanoparticles for bonding materials that have surface protection films that have been imparted with oxidation resistance and are excellent in low-temperature sintering properties.

本發明之第1目的在於提供一種接合材料用粒子，其係保管中的抗氧化性優異，接合時的低溫燒結性優異，在保護膜脫離之際所發生的氣體成分少，提高接合時的接合強度。本發明之第2目的在於提供一種以高產率製造接合材料用粒子之方法，該接合材料用粒子係保管中的抗氧化性優異，接合時的低溫燒結性優異，且接合時的接合強度高。本發明之第3目的在於提供一種包含如此的接合材料用粒子之接合用糊料及一種其調製方法。本發明之第4目的在於提供一種使用如此的接合用糊料之接合體之製造方法。 [解決問題的手段]The first object of the present invention is to provide particles for bonding materials that have excellent oxidation resistance during storage, excellent low-temperature sintering properties during bonding, and less gas components generated when the protective film is detached, thereby improving bonding during bonding strength. The second object of the present invention is to provide a method for producing bonding material particles with high yield, which has excellent oxidation resistance during storage, excellent low-temperature sintering properties during bonding, and high bonding strength during bonding. The third object of the present invention is to provide a bonding paste containing such bonding material particles and a method of preparing the bonding paste. The fourth object of the present invention is to provide a method of manufacturing a bonded body using such bonding paste. [Means to solve the problem]

本發明之第1觀點係一種接合材料用粒子，其係在銅奈米粒子表面上形成有有機保護膜之接合材料用粒子，其特徵為：前述接合材料用粒子係BET比表面積在3.5m2 /g以上8m2 /g以下之範圍，由前述比表面積所換算的BET徑在80nm以上200nm以下之範圍，相對於前述接合材料用粒子100質量%，前述有機保護膜係以0.5質量%以上2.0質量%以下之範圍含有，使用飛行時間型二次離子質量分析法(TOF-SIMS(Time-of-Flight Secondary ion Mass Spectrometry))分析前述接合材料用粒子時，相對於Cu+ 離子的檢出量，C3 H3 O3 - 離子與C3 H4 O2 - 離子各自的檢出量在0.05倍以上0.2倍以下之範圍，相對於Cu+ 離子的檢出量，C5 以上之離子的檢出量在未達0.005倍之範圍。The first aspect of the present invention is a particle for bonding material, which is a particle for bonding material having an organic protective film formed on the surface of copper nanoparticle, and is characterized in that the BET specific surface area of the particle for bonding material is 3.5 m 2 /g or more and 8m 2 /g or less, the BET diameter converted from the aforementioned specific surface area is within the range of 80nm or more and 200nm or less, relative to 100% by mass of the bonding material particles, the organic protective film is 0.5% by mass or more and 2.0 Contained in the range of mass% or less, when using TOF-SIMS (Time-of-Flight Secondary ion Mass Spectrometry) to analyze the aforementioned bonding material particles, relative to the detected amount of Cu + ions , C 3 H 3 O 3 - ions and C 3 H 4 O 2 - ions detectable amounts of each more than 0.05 times and 0.2 times or less of the range, relative to the amount of Cu ions is detected, the C 5 + ions over the specimen The output is in the range of less than 0.005 times.

本發明之第2觀點係以第1觀點為基礎之發明，為一種接合材料用粒子，於惰性氣體環境下以300℃之溫度加熱30分鐘時，前述有機保護膜係分解50質量%以上，分解的氣體係二氧化碳氣體、氮氣、丙酮的蒸發氣體及水蒸氣。The second aspect of the present invention is an invention based on the first aspect. It is a particle for bonding material. When heated at a temperature of 300°C for 30 minutes in an inert gas environment, the aforementioned organic protective film decomposes by more than 50% by mass. The gas system is carbon dioxide gas, nitrogen, acetone evaporation gas and water vapor.

本發明之第3觀點係一種接合用糊料，其包含揮發性溶劑與第1或第2觀點之接合材料用粒子。The third aspect of the present invention is a bonding paste containing a volatile solvent and the bonding material particles of the first or second aspect.

本發明之第4觀點係一種製造接合材料用粒子之方法，其係在室溫的檸檬酸銅的水分散液中添加pH調整劑而將pH調整至pH3以上且未達pH7，於惰性氣體環境下在該經pH調整之檸檬酸銅的水分散液中添加混合肼化合物，於惰性氣體環境下將此混合液加熱至60℃以上80℃以下之溫度，藉由保持1.5小時以上2.5小時以下，還原前述檸檬酸銅而生成銅奈米粒子，在此銅奈米粒子之表面上形成有機保護膜。The fourth aspect of the present invention is a method of manufacturing particles for bonding materials, which is to add a pH adjuster to an aqueous dispersion of copper citrate at room temperature to adjust the pH to pH 3 or higher and not pH 7 in an inert gas environment Next, add a hydrazine compound to the pH-adjusted aqueous dispersion of copper citrate, heat the mixture to a temperature above 60°C and below 80°C under an inert gas environment, and maintain it for 1.5 hours to 2.5 hours. The aforementioned copper citrate is reduced to produce copper nanoparticles, and an organic protective film is formed on the surface of the copper nanoparticles.

本發明之第5觀點係一種調製接合用糊料之方法，其係混合揮發性溶劑與以第1或第2觀點之接合材料用粒子或以第4觀點之方法所製造的接合材料用粒子。The fifth aspect of the present invention is a method of preparing a bonding paste by mixing a volatile solvent with the bonding material particles according to the first or second aspect or the bonding material particles produced according to the fourth aspect.

本發明之第6觀點係一種接合體之製造方法，其包含：將第3觀點之接合用糊料或以第5觀點之方法所調製的接合用糊料塗佈於基板或電子零件之表面而形成塗佈層之步驟；隔著前述塗佈層疊合前述基板與前述電子零件之步驟；與，藉由將前述經疊合的前述基板與前述電子零件，一邊施加30MPa以下之壓力，一邊在惰性環境下，以200℃以上300℃以下之溫度加熱而燒結前述塗佈層，而形成接合層，藉由此接合層接合前述基板與前述電子零件之步驟。 [發明的效果]The sixth aspect of the present invention is a method of manufacturing a bonded body, comprising: applying the bonding paste of the third aspect or the bonding paste prepared by the method of the fifth aspect to the surface of a substrate or an electronic component. The step of forming a coating layer; the step of laminating the substrate and the electronic component via the coating; and, by applying a pressure of 30MPa or less to the laminated substrate and the electronic component while being inert In an environment, the coating layer is sintered by heating at a temperature above 200°C and below 300°C to form a bonding layer, and the bonding layer is used to bond the substrate and the electronic component. [Effects of the invention]

本發明之第1觀點之接合材料用粒子，由於母體粒子的銅奈米粒子係被有機保護膜所被覆，故保管中的抗氧化性優異。由於接合材料用粒子之BET比表面積在3.5m2 /g以上8m2 /g以下之範圍，由比表面積所換算的BET徑在80nm以上200nm以下之範圍，故接合材料用粒子之反應面積大，接合時之加熱所致的反應性高，藉此可使接合材料用粒子在比較低溫下燒結。又，有機保護膜相對於接合材料用粒子100質量%之比例，由於在比專利文獻3記載的15質量%以上40質量%以下之比例更極少的0.5質量%以上2.0質量%以下之範圍，故在燒成時有機保護膜分解的氣體量少，起因於分解氣體所造成的接合膜等之接合地方的空隙之數係減少，可提高接合強度。The bonding material particles of the first aspect of the present invention have excellent oxidation resistance during storage because the copper nanoparticles of the matrix particles are covered with an organic protective film. Since the BET specific surface area of the bonding material particles is in the range of 3.5 m 2 /g or more and 8 m 2 /g or less, and the BET diameter converted from the specific surface area is in the range of 80 nm or more and 200 nm or less, the reaction area of the bonding material particles is large. The high reactivity due to heating at the time allows the particles for the bonding material to be sintered at a relatively low temperature. In addition, the ratio of the organic protective film to 100% by mass of the bonding material particles is within the range of 0.5% by mass to 2.0% by mass, which is extremely small compared to the ratio of 15% by mass to 40% by mass as described in Patent Document 3. During firing, the amount of gas that decomposes the organic protective film is small, and the number of voids in the bonding area of the bonding film and the like caused by the decomposed gas is reduced, and the bonding strength can be improved.

又，使用飛行時間型二次離子質量分析法(TOF-SIMS)分析接合材料用粒子時，由於相對於Cu+ 離子的檢出量，C3 H3 O3 - 離子與C3 H4 O2 - 離子各自的檢出量在0.05倍以上0.2倍以下之範圍，故在保護銅奈米粒子上，有機保護膜之量不是過與不足。因此，有機保護膜係使銅奈米粒子之表面不氧化，防止接合材料用粒子彼此之凝聚。又，由於相對於Cu+ 離子的檢出量，C5 以上之離子的檢出量在未達0.005倍之範圍，故不損害接合材料用粒子之燒結性，不使燒結溫度成為高溫。Furthermore, if using the time-of-flight secondary ion mass spectrometry (TOF-SIMS) analysis of the particles with a bonding material, since with respect to the detection of the amount of Cu + ions, C 3 H 3 O 3 - ions and C 3 H 4 O 2 -The detection amount of each ion is in the range of 0.05 times or more and 0.2 times or less. Therefore, the amount of organic protective film is not excessive or insufficient for protecting copper nanoparticles. Therefore, the organic protective film prevents the surface of the copper nanoparticle from being oxidized, and prevents aggregation of the particles for the bonding material. In addition, since the detection amount of C 5 or more ions relative to the detection amount of Cu + ions is less than 0.005 times, the sinterability of the bonding material particles is not impaired, and the sintering temperature does not become high.

本發明之第2觀點的接合材料用粒子，由於在惰性氣體環境下以300℃之溫度加熱30分鐘時，有機保護膜係分解50質量%以上，故接合膜內的有機保護膜之殘渣少，不使上述接合強度降低。又，由於有機保護膜之分解的氣體為二氧化碳氣體、氮氣、丙酮的蒸發氣體及水蒸氣，故具有接合材料用粒子被比較低溫下容易脫離的構成之有機保護膜所被覆之特點。According to the second aspect of the present invention, the bonding material particles are heated at a temperature of 300°C for 30 minutes in an inert gas environment, and the organic protective film is decomposed by 50% by mass or more, so there is little residue of the organic protective film in the bonding film. The above-mentioned joint strength is not reduced. In addition, since the decomposed gases of the organic protective film are carbon dioxide gas, nitrogen, acetone vaporized gas, and water vapor, the bonding material particles are coated with an organic protective film that is easily detached at a relatively low temperature.

本發明之第3觀點的接合用糊料，由於包含上述接合材料用粒子與揮發性溶劑，故此糊料係具有可低溫燒結接合體，在接合部或配線部中不發生接合材料成分的遷移之特點。The bonding paste of the third aspect of the present invention contains the above-mentioned bonding material particles and a volatile solvent. Therefore, the paste has a low-temperature sinterable bonding body and does not cause migration of bonding material components in the bonding part or the wiring part. Features.

於本發明之第4觀點的接合材料用粒子之製造方法中，在pH3以上且未達pH7的酸性液中添加混合作為還原劑的肼化合物，而在液中生成銅奈米粒子時，由檸檬酸銅所生成的檸檬酸係快速地被覆銅奈米粒子表面，抑制銅奈米粒子之溶解。因此將檸檬酸銅還原時，銅離子不易變成氫氧化銅(II)且不易作為氫氧化銅(II)沈澱，可以高產率製造目標的粒子。In the method for producing particles for bonding materials according to the fourth aspect of the present invention, a hydrazine compound as a reducing agent is added and mixed in an acidic liquid with a pH of 3 or higher and less than pH 7, and when copper nanoparticles are produced in the liquid, lemon The citric acid produced by the acid copper quickly coats the surface of the copper nanoparticle and inhibits the dissolution of the copper nanoparticle. Therefore, when the copper citrate is reduced, the copper ions are not easily changed into copper (II) hydroxide and are not easily precipitated as copper (II) hydroxide, and the target particles can be produced at a high yield.

又，由於所製造之母體粒子的銅奈米粒子係被有機保護膜所被覆，故保管中的抗氧化性優異。另外，由於所製造之母體粒子為銅奈米粒子，故接合材料用粒子之反應面積大，接合時之加熱所致的反應性高，因此可使接合材料用粒子在比較低溫下燒結。In addition, since the copper nanoparticles of the produced matrix particles are covered with an organic protective film, they have excellent oxidation resistance during storage. In addition, since the produced matrix particles are copper nanoparticles, the particles for the bonding material have a large reaction area and the reactivity due to heating during bonding is high. Therefore, the particles for the bonding material can be sintered at a relatively low temperature.

再者，所製造之接合材料用粒子係在燒成時有機保護膜分解的氣體量少，起因於分解氣體所造成的接合膜中的空隙之數係減少，可提高接合強度。Furthermore, the produced particles for bonding material have a small amount of gas that decomposes the organic protective film during firing, and the number of voids in the bonding film caused by the decomposed gas is reduced, and the bonding strength can be improved.

於本發明之第5觀點的接合用糊料之調製方法中，由於混合上述接合材料用粒子與揮發性溶劑而製造糊料，故所製造的糊料係具有可低溫燒結接合體，在接合部或配線部中不發生接合材料成分的遷移之特點。In the method for preparing a bonding paste according to the fifth aspect of the present invention, since the above-mentioned bonding material particles and a volatile solvent are mixed to produce the paste, the produced paste has a low-temperature sinterable joint body, and the bonding part Or the characteristic that the bonding material component does not migrate in the wiring part.

於本發明之第6觀點的接合體之製造方法中，使用包含上述接合材料用粒子的接合用糊料，隔著塗佈層將基板與電子零件，一邊施加30MPa以下之壓力，一邊在惰性環境下，以200℃以上300℃以下之溫度加熱。藉由此方法，在200℃以上300℃以下之比較低溫下，對於基板與電子零件，不造成機械損傷及熱損傷，可以高的生產性製造接合強度高之接合體。In the method for manufacturing a bonded body according to the sixth aspect of the present invention, the bonding paste containing the particles for bonding material is used, and the substrate and electronic parts are interposed through the coating layer, while applying a pressure of 30 MPa or less in an inert environment Next, heat at a temperature above 200°C and below 300°C. With this method, at a relatively low temperature of 200°C or more and 300°C or less, there is no mechanical or thermal damage to the substrate and electronic parts, and a bonded body with high bonding strength can be manufactured with high productivity.

實施發明的形態Implementation of the invention

接著，以圖式為基礎，說明用於實施本發明之實施形態。Next, an embodiment for implementing the present invention will be described based on the drawings.

[接合材料用粒子] 如圖1所示，於此實施形態之接合材料用粒子10中，母體粒子11包含銅奈米粒子，此母體粒子11之表面係被有機保護膜12所被覆。[Particles for bonding materials] As shown in FIG. 1, in the bonding material particle 10 of this embodiment, the matrix particle 11 includes copper nanoparticle, and the surface of the matrix particle 11 is covered with an organic protective film 12.

接合材料用粒子10係其BET比表面積之範圍為3.5m2 /g以上8m2 /g以下，由比表面積所換算的BET徑在80nm以上200nm以下之範圍。較佳的BET比表面積在4.0m2 /g以上8.0m2 /g以下之範圍，較佳的BET徑在80nm以上170nm以下之範圍。若BET比表面積未達3.5m2 /g或BET徑超過200nm，則接合材料用粒子之反應面積不變大，接合時之加熱所致的反應性低，因此無法在比較低溫下燒結。又，若BET比表面積超過8m2 /g或BET徑未達80nm，則在製作糊料時，於特定的組成中有增黏之不良狀況。接合材料用粒子之形狀係不限於球狀，也可為針狀、扁平的板狀。由於母體粉末的銅奈米粒子之熔點為1085℃，故在塗佈接合用糊料及回流後的接合膜等之接合地方之耐熱性優異。The bonding material particles 10 have a BET specific surface area ranging from 3.5 m 2 /g to 8 m 2 /g, and the BET diameter converted from the specific surface area is within a range of 80 nm to 200 nm. The preferred BET specific surface area 8.0m 2 / g or less of the range, preferred range of BET diameter of less than 80nm 170nm in 4.0m 2 / g or more. If the BET specific surface area is less than 3.5 m 2 /g or the BET diameter exceeds 200 nm, the reaction area of the bonding material particles does not increase, and the reactivity due to heating during bonding is low, and therefore, sintering at a relatively low temperature cannot be performed. In addition, if the BET specific surface area exceeds 8 m 2 /g or the BET diameter is less than 80 nm, there is a problem of thickening in a specific composition when the paste is made. The shape of the particles for the bonding material is not limited to a spherical shape, and may be a needle shape or a flat plate shape. Since the melting point of the copper nanoparticle of the matrix powder is 1085°C, it has excellent heat resistance in the bonding area such as the application of bonding paste and the bonding film after reflow.

有機保護膜12係來自檸檬酸之膜，被覆母體粒子11的銅奈米粒子之表面，達成防止於製造後到成為接合用糊料為止之保管中的銅奈米粒子之氧化的任務。此有機保護膜12係相對於接合材料用粒子100質量%而言為0.5質量%以上2.0質量%以下，較佳為以0.8質量%以上1.8質量%以下之範圍含有。有機保護膜12之被覆量或含量未達0.5質量%時，成為有機保護膜不完全地被覆於銅奈米粒子之狀態，由於銅奈米粒子之一部分係成為氧化物，故在接合時不進行接合材料用粒子之燒結。又，若有機保護膜12之被覆量或含量超過2.0質量%，則在接合時起因於因有機保護膜之脫離而發生的氣體，在接合膜等之接合地方發生空隙，接合強度下降。The organic protective film 12 is a citric acid-derived film that covers the surface of the copper nanoparticle of the matrix particle 11, and achieves the task of preventing oxidation of the copper nanoparticle in storage until it becomes the bonding paste. This organic protective film 12 is 0.5 mass% or more and 2.0 mass% or less with respect to 100 mass% of particles for bonding materials, and it is preferable to contain it in the range of 0.8 mass% or more and 1.8 mass% or less. When the coating amount or content of the organic protective film 12 is less than 0.5% by mass, the organic protective film will be incompletely covered with the copper nanoparticles. Since part of the copper nanoparticles is oxide, the bonding is not performed Sintering of particles for bonding materials. In addition, if the coating amount or content of the organic protective film 12 exceeds 2.0% by mass, the gas generated due to the separation of the organic protective film during bonding will generate voids in the bonding area such as the bonding film, and the bonding strength will decrease.

本實施形態之接合材料用粒子，由於有機保護膜係以0.5質量%以上2.0質量%以下之比例被覆母體粒子的銅奈米粒子，故在氮氣、氬氣等惰性氣體環境下，以300℃之溫度加熱30分鐘時，有機保護膜係分解50質量%以上。又，由於是來自檸檬酸的有機保護膜，故在分解時發生二氧化碳氣體、氮氣、丙酮的蒸發氣體及水蒸氣。The particles for the bonding material of this embodiment are copper nanoparticles coated with the matrix particles at a ratio of 0.5% by mass to 2.0% by mass in an organic protective film. Therefore, in an inert gas atmosphere such as nitrogen and argon, the temperature is When the temperature is heated for 30 minutes, the organic protective film is decomposed by more than 50% by mass. In addition, since it is an organic protective film derived from citric acid, carbon dioxide gas, nitrogen gas, acetone evaporation gas, and water vapor are generated during decomposition.

此接合材料用粒子10係使用飛行時間型二次離子質量分析法(TOF-SIMS)進行分析時，相對於Cu+ 離子的檢出量，C3 H3 O3 - 離子與C3 H4 O2 - 離子各自的檢出量在0.05倍以上0.2倍以下之範圍，相對於Cu+ 離子的檢出量，C5 以上之離子的檢出量在未達0.005倍之範圍。When this particle bonding material 10 lines were analyzed using time-of-flight secondary ion mass spectrometry (TOF-SIMS), with respect to the detected amount of Cu + ions, C 3 H 3 O 3 - ions and C 3 H 4 O The detection amount of each 2 - ion is in the range of 0.05 times or more and 0.2 times or less, and the detection amount of ions above C 5 is less than 0.005 times relative to the detection amount of Cu + ions.

於飛行時間型二次離子質量分析法中，相對於所檢測的Cu+ 離子，C3 H3 O3 - 離子與C3 H4 O2 - 離子、C5 以上之離子係來自被覆銅奈米粒子之表面的有機保護膜。因此，相對於Cu+ 離子的檢出量，若C3 H3 O3 - 離子與C3 H4 O2 - 離子各自的檢出量未達0.05倍，則被覆銅奈米粒子之表面的有機保護膜之量係變過少，銅奈米粒子之表面變成活性，容易使銅奈米粒子氧化，而且銅奈米粒子變容易凝聚，在成為接合用糊料時，糊料之黏度上升，塗佈性降低。另一方面，相對於Cu+ 離子的檢出量，若C3 H3 O3 - 離子與C3 H4 O2 - 離子各自的檢出量超過0.2倍，則由於在形成接合體時產生氣隙(空洞)，故接合強度容易降低。又，被覆銅奈米粒子之表面的有機保護膜之量係變過多，接合材料用粒子的燒結性降低，有必須將用於燒結接合材料用粒子的加熱溫度設為高溫。為了更進一步提高接合材料用粒子之保管中的抗氧化性，且更進一步提高接合時的低溫燒結性，相對於Cu+ 離子的檢出量，C3 H3 O3 - 離子與C3 H4 O2 - 離子各自的檢出量較佳在0.08倍以上0.16倍以下之範圍，相對於Cu+ 離子的檢出量，C5 以上之離子的檢出量較佳在未達0.003倍之範圍。又，於飛行時間型二次離子質量分析法中，相對於所檢測的Cu+ 離子，若C5 以上之離子的檢出量為0.005倍以上，則還原反應不充分，不適合作為接合材所用的粒子。In the time-of-flight secondary ion mass analysis method, relative to the detected Cu + ions, C 3 H 3 O 3 - ions and C 3 H 4 O 2 - ions, and ions above C 5 are derived from the coated copper nanometer Organic protective film on the surface of particles. Therefore, relative to the detected amount of Cu + ions, if the detected amounts of C 3 H 3 O 3 - ions and C 3 H 4 O 2 - ions are less than 0.05 times, the organic surface of the coated copper nanoparticles When the amount of protective film becomes too small, the surface of the copper nanoparticle becomes active, and it is easy to oxidize the copper nanoparticle, and the copper nanoparticle becomes easy to agglomerate. When it becomes the bonding paste, the viscosity of the paste increases. Sexual decrease. On the other hand, with respect to the detected amount of Cu + ions, if the detected amounts of C 3 H 3 O 3 - ions and C 3 H 4 O 2 - ions each exceed 0.2 times, gas is generated during the formation of the joined body. Since there are gaps (voids), the bonding strength is likely to decrease. In addition, the amount of the organic protective film covering the surface of the copper nanoparticle becomes too large, and the sinterability of the bonding material particles is reduced, and the heating temperature for sintering the bonding material particles must be high. To further increase the bonding material keeping the particles in oxidation resistance, and further improve the low-temperature sintering property during joining, with respect to Cu + ions detectable amount, C 3 H 3 O 3 - C 3 H 4 ions The detected amount of each of O 2 - ions is preferably in the range of 0.08 times or more and 0.16 times or less, and the detected amount of ions above C 5 is preferably in the range of less than 0.003 times relative to the detected amount of Cu + ions. In addition, in the time-of-flight secondary ion mass analysis method, if the detected amount of C 5 or more ions is 0.005 times or more relative to the detected Cu + ions, the reduction reaction is insufficient and it is not suitable as a bonding material. particle.

[接合材料用粒子之製造方法] 本實施形態之接合材料用粒子，係在檸檬酸銅的水分散液中添加pH調整劑而將pH調整至pH3以上且未達pH7，於惰性氣體環境下在該經pH調整之檸檬酸銅的水分散液中，添加混合能還原銅離子之1.0倍當量分以上1.2倍當量分以下的肼化合物作為還原劑，於惰性氣體環境下將此混合液加熱至60℃以上80℃以下之溫度，藉由保持1.5小時以上2.5小時以下，還原上述檸檬酸銅而生成銅奈米粒子，在此銅奈米粒子之表面上形成有機保護膜而製作。[Method for manufacturing particles for bonding material] The particles for the bonding material of this embodiment are prepared by adding a pH adjuster to an aqueous dispersion of copper citrate to adjust the pH to pH 3 or higher and below pH 7, and the pH-adjusted copper citrate is used in an inert gas environment. In the aqueous dispersion, add a hydrazine compound capable of reducing copper ions from 1.0 times equivalent to 1.2 times equivalent as a reducing agent, and heat the mixed solution to a temperature above 60°C and below 80°C under an inert gas environment. It is produced by keeping the copper citrate for 1.5 hours or more and 2.5 hours or less to reduce the copper citrate to produce copper nanoparticle, and form an organic protective film on the surface of the copper nanoparticle.

檸檬酸銅的水分散液，係以在如蒸餾水、離子交換水的純水中使粉末狀的檸檬酸銅成為25質量%以上40質量%以下之濃度的方式添加，使用攪拌葉片攪拌，使其均勻地分散而調製。作為pH調整劑，可舉出檸檬酸三銨、檸檬酸氫銨、檸檬酸等。其中，從容易溫和地調整pH來看，較佳為檸檬酸三銨。pH調整劑的pH調整係成為pH3以上且未達pH7，未達pH3時，從檸檬酸銅溶出銅離子係慢，反應難以快速地進行，難以得到目標之粒子。又，pH7以上時，以肼化合物將檸檬酸銅還原時，所溶出的銅離子容易變成氫氧化銅(II)且容易沈澱，無法以高產率製造接合材料用粒子。又，由於肼之還原力變強，反應變容易進行，故難以得到目標之粒子。較佳的pH為4以上6以下。The aqueous dispersion of copper citrate is added in such a way that the powdered copper citrate becomes a concentration of 25% by mass to 40% by mass in pure water such as distilled water and ion-exchanged water, and is stirred with a stirring blade to make it Evenly dispersed and prepared. As a pH adjuster, triammonium citrate, ammonium hydrogen citrate, citric acid, etc. are mentioned. Among them, triammonium citrate is preferred from the viewpoint of easy pH adjustment. The pH adjustment system of the pH adjuster is pH 3 or more and less than pH 7, and when the pH is less than 3, the elution of copper ions from copper citrate is slow, the reaction is difficult to proceed quickly, and it is difficult to obtain target particles. In addition, when the pH is 7 or higher, when copper citrate is reduced with a hydrazine compound, the eluted copper ions are likely to become copper (II) hydroxide and precipitate easily, and it is impossible to produce bonding material particles with high yield. In addition, since the reducing power of hydrazine becomes stronger, the reaction becomes easier to proceed, so it is difficult to obtain the target particles. The preferred pH is 4 or more and 6 or less.

肼化合物所致的檸檬酸銅之還原係在惰性氣體環境下進行。此係為了防止液中溶出的銅之氧化。作為惰性氣體，可舉出氮氣、氬氣等。肼化合物係在酸性下將檸檬酸銅還原時，於還原反應後不發生殘渣，具有安全性比較高及操作容易等之有利點。作為該肼化合物，可舉出肼-水合物、無水肼、鹽酸肼、硫酸肼等。其中，由於希望沒有能變成硫或氯的雜質之成分，故較佳為肼-水合物。The reduction of copper citrate caused by hydrazine compounds is carried out in an inert gas environment. This is to prevent the oxidation of copper dissolved in the liquid. As the inert gas, nitrogen, argon, etc. can be cited. When the hydrazine compound reduces copper citrate under acidic conditions, there is no residue after the reduction reaction, and it has the advantages of high safety and easy operation. Examples of the hydrazine compound include hydrazine monohydrate, anhydrous hydrazine, hydrazine hydrochloride, and hydrazine sulfate. Among them, since it is desired that there is no component that can turn into sulfur or chlorine impurities, hydrazine-hydrate is preferred.

一般而言，在未達pH7的酸性液中生成的銅係會溶解。然而於本實施形態中，在未達pH7的酸性液中添加混合作為還原劑的肼化合物，若在液中生成銅奈米粒子，則來自由檸檬酸銅所生成的檸檬酸離子之成分係快速地被覆銅奈米粒子表面，抑制銅奈米粒子之溶解。未達pH7的酸性液在溫度50℃以上70℃以下者，係還原反應容易進行而較宜。Generally speaking, the copper system generated in the acidic liquid below pH 7 dissolves. However, in this embodiment, a hydrazine compound as a reducing agent is added and mixed in an acidic liquid below pH 7, and if copper nanoparticles are produced in the liquid, the components derived from the citrate ion produced by copper citrate are fast The ground coats the surface of copper nanoparticles to inhibit the dissolution of copper nanoparticles. For acidic liquids with a pH of less than 7 at a temperature of 50°C or more and 70°C or less, the reduction reaction is easier to proceed and is more suitable.

將於惰性氣體環境下混合有肼化合物之混合液加熱至60℃以上80℃以下之溫度，保持1.5小時以上2.5小時以下者，係為了將檸檬酸銅還原而生成銅奈米粒子，於此銅奈米粒子之表面上形成0.5質量%以上2.0質量%以下之範圍的來自檸檬酸銅的有機保護膜及被覆。於惰性氣體環境下加熱保持者，係為了防止銅奈米粒子之氧化。起始原料的檸檬酸銅通常包含35質量%左右的銅成分。於包含此程度的銅成分之檸檬酸銅中添加作為還原劑的肼化合物，升溫加熱到上述溫度範圍，藉由保持指定的時間，而進行檸檬酸銅之還原，成為銅成分為98質量%以上99.5質量%以下的粒子。此粒子的銅成分以外之成分量的0.5質量%以上2.0質量%係成為有機保護膜。若加熱溫度未達60℃、保持時間未達1.5小時，則檸檬酸銅不完全地還原，不變成銅成分為98質量%以上的粒子，有機保護膜之被覆量或形成量超過2.0質量%。因此，如上述，起因於在接合時因有機保護膜之脫離所發生的氣體，在接合膜等之接合地方發生空隙，接合強度下降。又，若加熱溫度超過80℃且保持時間超過2.5小時，則銅成分超過99.5質量%，有機保護膜被覆量或形成量變成未達0.5質量%。因此，如上述，有機保護膜係成為不完全地被覆銅奈米粒子之狀態，銅奈米粒子之一部分變成氧化物，故在接合時不進行接合材料用粒子之燒結。較佳的加熱溫度為65℃以上75℃以下，較佳的保持時間為2小時以上2.5小時以下。The mixed solution mixed with the hydrazine compound in an inert gas environment is heated to a temperature above 60°C and below 80°C, and kept for 1.5 hours to 2.5 hours, in order to reduce copper citrate to produce copper nanoparticles, where copper On the surface of the nanoparticle, an organic protective film and coating derived from copper citrate are formed in the range of 0.5% by mass to 2.0% by mass. The heating and holding in an inert gas environment is to prevent the oxidation of copper nanoparticles. The copper citrate as a starting material usually contains a copper component of about 35% by mass. Add a hydrazine compound as a reducing agent to copper citrate containing this level of copper, heat it up to the above temperature range, and keep it for a specified time to reduce the copper citrate to a copper content of 98% by mass or more 99.5 mass% or less of particles. 0.5% by mass or more of 2.0% by mass of the components other than the copper component of this particle becomes an organic protective film. If the heating temperature is less than 60°C and the holding time is less than 1.5 hours, the copper citrate is not completely reduced and does not become particles with a copper content of 98% by mass or more, and the amount of coating or formation of the organic protective film exceeds 2.0% by mass. Therefore, as described above, due to the gas generated due to the separation of the organic protective film during bonding, voids are generated in the bonding place such as the bonding film, and the bonding strength is reduced. In addition, if the heating temperature exceeds 80° C. and the holding time exceeds 2.5 hours, the copper content exceeds 99.5% by mass, and the amount of coating or formation of the organic protective film becomes less than 0.5% by mass. Therefore, as described above, the organic protective film is in a state of incompletely covering the copper nanoparticle, and part of the copper nanoparticle becomes an oxide. Therefore, the bonding material particles are not sintered during bonding. The preferred heating temperature is 65°C or more and 75°C or less, and the preferred holding time is 2 hours or more and 2.5 hours or less.

將由已還原檸檬酸銅之液所生成的粒子，在惰性氣體環境下從該液中，例如使用離心分離機，進行固液分離，藉由冷凍乾燥法、減壓乾燥法進行乾燥，而得到目標粒子之在上述銅奈米粒子表面上形成有有機保護膜之接合材料用粒子。此接合材料用粒子，由於銅奈米粒子表面被有機保護膜所被覆，故在作為接合用糊料使用之前，即使在大氣中保管，也能防止粒子之氧化。The particles produced from the reduced copper citrate liquid are separated from the liquid in an inert gas environment, for example, using a centrifugal separator, and then dried by freeze-drying and reduced-pressure drying to obtain the target The particles are particles for bonding materials in which an organic protective film is formed on the surface of the copper nanoparticle. Since the surface of the copper nanoparticle is covered with an organic protective film, the bonding material particles can prevent oxidation of the particles even if they are stored in the air before being used as a bonding paste.

[接合用糊料] 說明包含上述接合材料用粒子與揮發性溶劑之接合用糊料。作為揮發性溶劑，可舉出醇系溶劑、二醇系溶劑、乙酸酯系溶劑、烴系溶劑及胺系溶劑。作為醇系溶劑之具體例，可舉出α-萜品醇、異丙醇。作為二醇系溶劑之具體例，可舉出乙二醇、二乙二醇、聚乙二醇。作為乙酸酯系溶劑之具體例，可舉出乙酸丁酯卡必醇酯。作為烴系溶劑之具體例，可舉出癸烷、十二烷、十四烷。作為胺系溶劑之具體例，可舉出己胺、辛胺、十二胺。[Paste for bonding] A bonding paste containing the above-mentioned bonding material particles and a volatile solvent will be described. Examples of volatile solvents include alcohol-based solvents, glycol-based solvents, acetate-based solvents, hydrocarbon-based solvents, and amine-based solvents. As specific examples of alcohol-based solvents, α-terpineol and isopropanol can be given. As specific examples of glycol-based solvents, ethylene glycol, diethylene glycol, and polyethylene glycol can be given. As a specific example of the acetate-based solvent, butyl carbitol acetate may be mentioned. Specific examples of hydrocarbon solvents include decane, dodecane, and tetradecane. Specific examples of amine solvents include hexylamine, octylamine, and dodecylamine.

相對於接合用糊料之全體量，接合用糊料中的接合材料用粒子之含量較佳為50質量%以上，特佳在70質量%以上95質量%以下之範圍。若接合材料用粒子之含量在上述之範圍，則接合用糊料之黏度不過度變低，可將接合用糊料安定地塗佈於構件之表面。又，藉由燒成接合用糊料，可得到密度高、空隙的發生量少之燒結體(接合層)。另外，接合用糊料亦可進一步包含抗氧化劑、黏度調整劑等之添加劑。相對於接合用糊料100質量%，此等的添加劑之含量較佳在1質量%以上5質量%以下之範圍。The content of the bonding material particles in the bonding paste is preferably 50% by mass or more, and particularly preferably in the range of 70% by mass to 95% by mass relative to the total amount of the bonding paste. If the content of the bonding material particles is within the above range, the viscosity of the bonding paste does not become too low, and the bonding paste can be stably applied to the surface of the member. In addition, by firing the bonding paste, a sintered body (bonding layer) having a high density and a small amount of voids can be obtained. In addition, the bonding paste may further contain additives such as antioxidants and viscosity modifiers. The content of these additives is preferably in the range of 1% by mass to 5% by mass relative to 100% by mass of the bonding paste.

[接合用糊料之調製方法] 接合用糊料例如可藉由使用混煉裝置，將混合揮發性溶劑與接合材料用粒子而得之混合物予以混煉而製造。作為混煉裝置，可舉出三輥磨機。[Preparation method of bonding paste] The bonding paste can be manufactured by kneading a mixture obtained by mixing a volatile solvent and particles for bonding material, for example, using a kneading device. As a kneading device, a three-roll mill can be mentioned.

[接合體之製造方法] 本實施形態之接合體係經過以下步驟而製造：將上述接合用糊料塗佈於基板或電子零件之表面而形成塗佈層之步驟；隔著該塗佈層疊合上述基板與上述電子零件之步驟；與，藉由將該經疊合的上述基板與上述電子零件，一邊施加30MPa以下之壓力，一邊在惰性環境下，以200℃以上300℃以下之溫度加熱而燒結上述塗佈層，而形成接合層，藉由此接合層接合上述基板與上述電子零件之步驟。[Method of manufacturing junction body] The bonding system of this embodiment is manufactured through the following steps: a step of applying the bonding paste to the surface of a substrate or electronic part to form a coating layer; a step of laminating the substrate and the electronic part via the coating ; And, by applying a pressure of 30 MPa or less while applying a pressure of 30 MPa or less while applying a pressure of less than 30 MPa, the coating layer is sintered by heating at a temperature of 200° C. or more and 300° C. or less in an inert environment to form The bonding layer is a step of bonding the substrate and the electronic component through the bonding layer.

作為上述基板，並沒有特別的限定，但例如可舉出無氧銅板、銅鉬板、高散熱絕緣基板(例如，DBC(直接銅黏結，Direct Copper Bond))、LED(發光二極體，Light Emitting Diode)封裝等之半導體元件搭載用基材等。又，作為上述電子零件，可舉出IGBT(Insulated Gate Bipolar Transistor，絕緣閘雙極電晶體)、二極體、肖特基屏障二極體、MOS-FET(Metal Oxide Semiconductor Field Effect Transistor，金屬氧化物半導體場效電晶體)、閘流體、邏輯、感測器、類比積體電路、LED、半導體雷射、發送器等之半導體元件。塗佈方法係沒有特別的限定，但例如可舉出旋轉塗佈法、金屬遮罩法、噴塗法、分配器塗佈法、刀塗法、狹縫塗佈法、噴墨塗佈法、網版印刷法、平版印刷法、模塗法等。The above-mentioned substrate is not particularly limited, but for example, an oxygen-free copper plate, a copper molybdenum plate, a high heat dissipation insulating substrate (for example, DBC (Direct Copper Bond)), LED (Light Emitting Diode, Light Emitting Diode) package and other semiconductor element mounting substrates. Moreover, as the above-mentioned electronic components, IGBT (Insulated Gate Bipolar Transistor), diodes, Schottky barrier diodes, MOS-FET (Metal Oxide Semiconductor Field Effect Transistor, metal oxide Semiconductor field effect transistors), thyristors, logic, sensors, analog integrated circuits, LEDs, semiconductor lasers, transmitters and other semiconductor components. The coating method is not particularly limited, but for example, spin coating method, metal mask method, spray coating method, dispenser coating method, knife coating method, slit coating method, inkjet coating method, mesh Plate printing method, offset printing method, die coating method, etc.

形成塗佈層後，隔著塗佈層疊合基板與電子零件。塗佈層之厚度較佳為均勻。將經疊合的基板與電子零件，一邊施加30MPa以下之壓力，一邊在惰性環境下，以200℃以上300℃以下之溫度加熱。若所施加的壓力超過30MPa，則有對於基板或電子零件造成機械損傷之虞。所施加的壓力較佳為5MPa以上30MPa以下。若壓力未達5MPa，則塗佈層中的銅奈米粒子變不易燒結，有無法形成接合層之虞。又，從環境沒有因煙火而著火之虞，防止接合體的氧化之觀點來看，指定氮氣、氬氣等之惰性環境。又，加熱溫度未達200℃時，塗佈層中的銅奈米粒子變不易燒結，有無法形成接合層之虞。另外，若超過300℃，則有對於基板或電子零件造成熱損傷之虞。較佳的加熱溫度為230℃以上300℃以下。After the coating layer is formed, the substrate and the electronic component are laminated via coating. The thickness of the coating layer is preferably uniform. The laminated substrate and electronic parts are heated at a temperature of 200°C or more and 300°C in an inert environment while applying a pressure of 30MPa or less. If the applied pressure exceeds 30 MPa, it may cause mechanical damage to the substrate or electronic parts. The applied pressure is preferably 5 MPa or more and 30 MPa or less. If the pressure is less than 5 MPa, the copper nanoparticles in the coating layer will not be easily sintered, and the bonding layer may not be formed. In addition, from the viewpoint of preventing the oxidation of the joined body, an inert environment such as nitrogen, argon, etc. is specified from the point of view that the environment is not likely to catch fire due to fireworks. In addition, when the heating temperature is less than 200°C, the copper nanoparticles in the coating layer become difficult to sinter, and the bonding layer may not be formed. In addition, if it exceeds 300°C, it may cause thermal damage to the substrate or electronic components. The preferred heating temperature is 230°C or more and 300°C or less.

藉由將如此疊合的基板與電子零件，一邊加壓，一邊在惰性環境下，以200℃以上300℃以下之溫度加熱，而燒結塗佈層中的銅奈米粒子，製造本實施形態之接合體。 [實施例]By heating the laminated substrate and electronic parts at a temperature of 200°C or more and 300°C or less in an inert environment while pressurizing, the copper nanoparticles in the coating layer are sintered to produce the embodiment of this embodiment. Junction body. [Example]

接著，詳細說明本發明之實施例與比較例。Next, examples and comparative examples of the present invention will be described in detail.

＜實施例1＞ 首先，將作為起始原料之市售的檸檬酸銅・2.5水合物(和光純藥公司製)加入室溫的離子交換水中，使用攪拌葉片攪拌，調製濃度30質量%之檸檬酸銅的水分散液。其次，於此檸檬酸銅的水分散液中加入作為pH調整劑的檸檬酸銨水溶液，將上述水分散液的pH調整至3。接著，使經pH調整之液成為50℃之溫度，於氮氣環境下，在經pH調整之液中一次添加能還原銅離子之1.2倍當量分的肼-水合物水溶液(2倍稀釋)當作還原劑，使用攪拌葉片均勻地混合。再者，為了合成目標之接合材料用粒子，將上述水分散液與上述還原劑之混合液在氮氣環境下升溫到最高溫度之70℃為止，在70℃保持2小時。使用離心分離機，固液分離在經加熱保持的液中所生成的粒子。以減壓乾燥法乾燥所回收的粒子，製造實施例1之接合材料用粒子。圖2中顯示將此實施例1之接合材料用粒子的集合體放大至30,000倍而拍攝的顯微鏡照相圖。由圖2可知，實施例1之接合材料用粒子的集合體係由百奈米左右之粒子所構成者。下述表1中顯示實施例1及以下所述之實施例2～11以及比較例1～9的接合材料用粒子之製造條件。<Example 1> First, commercially available copper citrate 2.5 hydrate (manufactured by Wako Pure Chemical Industries, Ltd.) as a starting material is added to ion-exchange water at room temperature, and stirred with a stirring blade to prepare a water dispersion of copper citrate with a concentration of 30% by mass. liquid. Next, an aqueous ammonium citrate solution as a pH adjuster was added to this aqueous dispersion of copper citrate, and the pH of the aqueous dispersion was adjusted to 3. Then, the pH-adjusted liquid was brought to a temperature of 50°C, and under a nitrogen environment, a 1.2-fold equivalent of hydrazine-hydrate aqueous solution (diluted by 2 times) that reduced copper ions was added to the pH-adjusted liquid at a time. The reducing agent is mixed evenly with a stirring blade. Furthermore, in order to synthesize the target bonding material particles, the mixture of the aqueous dispersion and the reducing agent was heated to the maximum temperature of 70°C in a nitrogen atmosphere, and kept at 70°C for 2 hours. Using a centrifugal separator, the particles generated in the heated and held liquid are separated into solid and liquid. The recovered particles were dried by a reduced-pressure drying method to produce the particles for bonding material of Example 1. Fig. 2 shows a micrograph taken by magnifying the aggregate of particles for the bonding material of Example 1 to 30,000 times. It can be seen from FIG. 2 that the assembly system of particles for the bonding material of Example 1 is composed of particles of about one hundred nanometers. The following Table 1 shows the production conditions of the bonding material particles of Example 1 and the following Examples 2 to 11 and Comparative Examples 1 to 9.

Figure 02_image001
Figure 02_image001

＜實施例2～11、比較例1～3及比較例6～9＞ 於實施例2～8中，實施例1之起始原料及還原劑係不變，如上述表1所示，變更實施例1所示之檸檬酸銅的水分散液之pH，變更還原劑的氧化還原電位E，變更或維持在合成接合材料用粒子時的最高溫度與其保持時間。其以外係與實施例1同樣地，製造實施例2～8、比較例1～3及比較例6～9之接合材料用粒子。於實施例9～11中，使用無水肼作為還原劑，還原劑的氧化還原電位E為-0.6V，合成時的最高溫度為70℃，其保持時間為2.0小時。<Examples 2 to 11, Comparative Examples 1 to 3, and Comparative Examples 6 to 9> In Examples 2-8, the starting materials and reducing agent of Example 1 were unchanged. As shown in Table 1, the pH of the aqueous dispersion of copper citrate shown in Example 1 was changed, and the reducing agent's The oxidation-reduction potential E is changed or maintained at the highest temperature and its retention time when the particles for the bonding material are synthesized. Otherwise, in the same manner as in Example 1, the bonding material particles of Examples 2 to 8, Comparative Examples 1 to 3, and Comparative Examples 6 to 9 were produced. In Examples 9-11, anhydrous hydrazine was used as the reducing agent, the redox potential E of the reducing agent was -0.6V, the highest temperature during synthesis was 70°C, and the retention time was 2.0 hours.

可知以肼-水合物為首的肼系還原劑係在酸性範圍與鹼性範圍中發生不同的反應。又，於實施例2～11、比較例1～3及比較例6～9中，因使反應液中的pH變化而在還原力造成差異。表1中顯示各條件下的氧化還原電位E(V)。 (酸性範圍) N2 H5 + = N2 + 5H+ + 4e- (鹼性範圍) N2 H4 + 4OH- = N2 + 4H2 O + 4e- 氧化還原電位E：-0.23  -0.975pHIt can be seen that hydrazine-based reducing agents including hydrazine-hydrate react differently in the acidic range and the alkaline range. In addition, in Examples 2 to 11, Comparative Examples 1 to 3, and Comparative Examples 6 to 9, there was a difference in reducing power due to the change in pH in the reaction liquid. Table 1 shows the oxidation-reduction potential E (V) under each condition. (Acid range) N 2 H 5 + = N 2 + 5H + + 4e - ( basic range) N 2 H 4 + 4OH - = N 2 + 4H 2 O + 4e - oxidation-reduction potential E: -0.23 -0.975pH

＜比較例4＞ 將實施例1之還原劑的肼-水合物變更為甲酸銨，變更此還原劑之氧化還原電位E(E：0.3V)。實施例1之合成時的最高溫度與其保持時間係不變，變更檸檬酸銅的水分散液之pH值，其以外係與實施例1同樣地，製造比較例4之接合材料用粒子。<Comparative Example 4> The hydrazine-hydrate of the reducing agent of Example 1 was changed to ammonium formate, and the redox potential E (E: 0.3V) of this reducing agent was changed. The maximum temperature during the synthesis of Example 1 and its retention time were unchanged, and the pH value of the aqueous dispersion of copper citrate was changed, except that it was the same as Example 1, and the bonding material particles of Comparative Example 4 were produced.

＜比較例5＞ 將實施例1之還原劑的肼-水合物變更為甲酸，變更此還原劑之氧化還原電位E(E：-0.2V)。實施例1之檸檬酸銅的水分散液之pH值、合成時的最高溫度及其保持時間係不變更，其以外係與實施例1同樣地，製造比較例5之接合材料用粒子。<Comparative Example 5> The hydrazine-hydrate of the reducing agent of Example 1 was changed to formic acid, and the redox potential E (E: -0.2V) of this reducing agent was changed. The pH value, the maximum temperature during synthesis, and the retention time of the aqueous dispersion of copper citrate of Example 1 were not changed, except that the particles for the bonding material of Comparative Example 5 were produced in the same manner as in Example 1.

＜比較評價試驗與結果＞ 分別算出或測定實施例1～11及比較例1～9中製造接合材料用粒子時的粒子各自之製造產率、實施例1～11及比較例1～9所得之20種類的接合材料用粒子之母體粒子組成、BET比表面積及BET徑、關聯有機保護膜的飛行時間型二次離子質量分析法(TOF-SIMS)測定之相對於Cu+ 離子的檢出量而言C3 H3 O3 - 離子與C3 H4 O2 - 離子各自的檢出量、C5 以上之離子的檢出量。以下之表2中顯示此等之結果。<Comparative evaluation test and results> Calculate or measure the production yields of the particles in the production of bonding material particles in Examples 1 to 11 and Comparative Examples 1 to 9, respectively, and those obtained in Examples 1 to 11 and Comparative Examples 1 to 9 The matrix particle composition, BET specific surface area and BET diameter of the 20 types of particles for bonding materials, and the time-of-flight secondary ion mass analysis (TOF-SIMS) related to the organic protective film are measured relative to the detected amount of Cu + ions Introduction C 3 H 3 O 3 - ions and C 3 H 4 O 2 - ions detectable amount of each of the detection of the amount of C 5 or more ions. These results are shown in Table 2 below.

Figure 02_image003
Figure 02_image003

又，分別算出或測定有機保護膜相對於接合材料用粒子之質量比例、氮氣環境下的有機保護膜之分解量比例及在燒成接合材料用粒子時所發生的氣體成分。以下之表3中顯示此等之結果。對於因還原不充分而無法算出製造產率之粒子(比較例1、比較例4～6、比較例9)，不測定BET比表面積、BET徑、有機保護膜之特性。In addition, the mass ratio of the organic protective film to the particles for the bonding material, the ratio of the amount of decomposition of the organic protective film in a nitrogen atmosphere, and the gas component generated when the particles for the bonding material are fired are respectively calculated or measured. These results are shown in Table 3 below. For particles whose production yield cannot be calculated due to insufficient reduction (Comparative Example 1, Comparative Examples 4-6, and Comparative Example 9), the BET specific surface area, BET diameter, and characteristics of the organic protective film were not measured.

Figure 02_image005
Figure 02_image005

(1)粒子之製造產率 粒子之製造產率係將檸檬酸銅所含有的銅量當作理論量時，求出乾燥後的回收粉末量之比率當作製造產率。(1) Manufacturing yield of particles The production yield of particles is based on the ratio of the amount of recovered powder after drying when the amount of copper contained in copper citrate is taken as the theoretical amount, and the production yield is obtained.

(2)粒子之BET比表面積 粒子之比表面積係使用QUANTACHROME AUTOSORB-1(QUANTACHROME儀器製)作為測定裝置，從N2 氣體對於經冷卻的接合材料用粒子之吸附量求出。(2) BET specific surface area of particles The specific surface area of particles is determined from the amount of adsorption of N 2 gas to the cooled particles for bonding material using QUANTACHROME AUTOSORB-1 (manufactured by QUANTACHROME instrument) as a measuring device.

(3)粒子之BET徑 粒子之BET徑係在測定上述比表面積(BET法)後，將此面積在全部稱為球的前提之下計算，表示銅奈米粒子為真球時的理論直徑。(3) BET diameter of particles The BET diameter of the particles is calculated after measuring the above-mentioned specific surface area (BET method), and this area is calculated on the premise that all the particles are called spheres, and represents the theoretical diameter when the copper nanoparticle is a true sphere.

(4)飛行時間型二次離子質量分析法之測定 相對於Cu+ 離子而言C3 H3 O3 - 離子與C3 H4 O2 - 離子、C5 以上之離子的各檢測，係使用飛行時間型二次離子質量分析法(TOF-SIMS)，如以下地測定。將銅粉埋沒在In箔表面者當作測定用試料。測定裝置係使用ULVAC PHI公司製nanoTOFII。於測定範圍為100μm平方之範圍、一次離子為Bi3 ++ (30kV)、測定時間為5分鐘之條件下測定，得到TOF-SIMS圖譜。從所得之TOF-SIMS圖譜，求出Cu+ 離子、C3 H3 O3 - 離子、C3 H4 O2 - 離子、C5 以上之離子的檢出量，將C3 H3 O3 - 離子與C3 H4 O2 - 離子、C5 以上之離子的檢出量分別除以Cu+ 離子的檢出量，算出相對於Cu+ 離子而言C3 H3 O3 - 離子與C3 H4 O2 - 離子、C5 以上之離子的檢出量。(4) Measurement of time-of-flight secondary ion mass analysis method Compared with Cu + ions, the detection of C 3 H 3 O 3 - ions, C 3 H 4 O 2 - ions, and ions above C 5 are used Time-of-flight secondary ion mass analysis (TOF-SIMS) is measured as follows. The copper powder buried in the surface of the In foil was used as the measurement sample. The measurement device used nanoTOFII manufactured by ULVAC PHI. The measurement range is 100μm square, the primary ion is Bi 3 ++ (30kV), and the measurement time is 5 minutes to obtain the TOF-SIMS spectrum. From the resultant TOF-SIMS spectrum of the obtained Cu + ions, C 3 H 3 O 3 - ions, C 3 H 4 O 2 - ion, a detectable amount of C 5 or more ions, the C 3 H 3 O 3 - Divide the detected amounts of ions and C 3 H 4 O 2 - ions and C 5 or more ions by the detected amounts of Cu + ions to calculate C 3 H 3 O 3 - ions and C 3 relative to Cu + ions The detection amount of H 4 O 2 - ions and ions above C 5 .

(5)接合材料用粒子中的有機保護膜之質量比例 接合材料用粒子中的有機保護膜之質量比例，係量取接合材料用粒子，於氮氣環境下以300之溫度加熱30分鐘後，放置冷卻到室溫為止，測定金屬粒子凝聚體之質量。藉由下述之式算出。 接合材料用粒子中的有機保護膜之質量比例(質量%)=(A－B)/A×100 惟，A為加熱前的接合材料用粒子之質量，B為加熱後的接合材料用粒子之質量。(5) Mass ratio of organic protective film in particles for bonding material The mass ratio of the organic protective film in the bonding material particles is measured by measuring the bonding material particles, heating them at a temperature of 300 for 30 minutes in a nitrogen atmosphere, and then cooling them to room temperature to measure the mass of the metal particle aggregates. Calculate by the following formula. The mass ratio of the organic protective film in the bonding material particles (mass%)=(A－B)/A×100 However, A is the mass of the particles for the bonding material before heating, and B is the mass of the particles for the bonding material after heating.

(6)氮氣環境下的有機保護膜之分解量比例 有機保護膜之分解量比例，係以與算出有機保護膜之質量比例的方法相同之方法，在氮氣環境下將接合材料用粒子以500℃之溫度加熱30分鐘，求出300℃條件下的減少量相對於500℃條件下的減少量之比例當作分解量比例。(6) Decomposition ratio of organic protective film in nitrogen environment The decomposition ratio of the organic protective film is the same as the method for calculating the mass ratio of the organic protective film. The bonding material particles are heated at 500°C for 30 minutes in a nitrogen atmosphere to obtain the reduction at 300°C. The ratio of the amount to the amount of decrease under 500°C is regarded as the ratio of the amount of decomposition.

(7)接合材料用粒子之燒成時發生的氣體成分 接合材料用粒子之燒成時發生的氣體成分，係使用熱分解氣相層析法，鑑定從室溫到300℃為止發生的氣體成分。(7) Gas components generated during firing of particles for bonding materials The gas components generated during the firing of the bonding material particles were identified using thermal decomposition gas chromatography to identify the gas components generated from room temperature to 300°C.

(8)接合體之製造條件、接合條件及接合強度 藉由混合實施例1～11及比較例2、3、7、8所得之15種類的接合材料用粒子與作為揮發性溶劑的乙二醇(EG)，而調製接合用糊料。具體而言，以乙二醇85質量%與接合材料用粒子15質量%之比例，將溶劑與粒子置入聚丙烯製容器中，以混煉機(THINKY製，脫泡練太郎)進行混煉。於混煉：1,000rpm×60秒及脫泡：1,000rpm×60秒之條件下預備混煉，更使用三輥(EXACT製，80E)，將間隙(Gap)寬度分別設定在第1次：50μm、第2次：10μm、第3次：5μm，正式地混煉。藉此，調製接合用糊料。(8) Manufacturing conditions, joining conditions and joining strength of the joined body The 15 types of particles for bonding materials obtained in Examples 1 to 11 and Comparative Examples 2, 3, 7, and 8, and ethylene glycol (EG) as a volatile solvent were mixed to prepare bonding pastes. Specifically, the solvent and particles are placed in a polypropylene container at a ratio of 85% by mass of ethylene glycol to 15% by mass of particles for bonding material, and kneaded with a kneader (manufactured by THINKY, defoaming Nentaro) . Pre-mixing under the conditions of mixing: 1,000 rpm×60 seconds and defoaming: 1,000 rpm×60 seconds, using three rolls (manufactured by EXACT, 80E), and setting the gap (Gap) width at the first time: 50μm , The second time: 10μm, the third time: 5μm, formally knead. In this way, the bonding paste is prepared.

將接合用糊料，使用設於金屬遮罩印刷機的金屬遮罩版(2.5mm、50μmt)，印刷在無氧銅板(0.8mmt)上，於室溫30分鐘的預備乾燥後，搭載Si虛設元件。燒成條件係使用加壓接合裝置(AYUMI工業製，RB-50)，於氮氣環境下，將接合溫度設定在200℃、230℃、250℃、300℃之4水準。又，接合荷重係在接合溫度為300℃時設定在10MPa，在接合溫度為230℃及250℃時設定在20MPa，在接合溫度為200℃時設定在30MPa。升溫速度為30℃/分鐘，接合保持時間係在接合溫度為230℃、250℃及300℃時設定在15分鐘，在接合溫度為200℃時設定在30分鐘。The bonding paste was printed on an oxygen-free copper plate (0.8mmt) using a metal mask plate (2.5mm, 50μmt) set in a metal mask printer, and after preliminary drying at room temperature for 30 minutes, the Si dummy was mounted element. The firing conditions used a pressure bonding device (manufactured by AYUMI Industries, RB-50) and set the bonding temperature to 4 levels of 200°C, 230°C, 250°C, and 300°C in a nitrogen atmosphere. The bonding load was set at 10 MPa when the bonding temperature was 300°C, 20 MPa when the bonding temperatures were 230°C and 250°C, and 30 MPa when the bonding temperature was 200°C. The heating rate was 30°C/min, and the bonding holding time was set to 15 minutes when the bonding temperature was 230°C, 250°C, and 300°C, and was set to 30 minutes when the bonding temperature was 200°C.

於上述接合條件下製造接合體。所得之接合體係使用接合測試機(ORIENTEC製，Tensilon RTF-1310)，評價接合強度，將得到15MPa以上的強度之接合體評價為良好。以下之表4～表6中顯示此等之結果。The joined body is manufactured under the above joining conditions. The resulting bonding system was evaluated with a bonding tester (manufactured by ORIENTEC, Tensilon RTF-1310), and the bonded body obtained a strength of 15 MPa or more was evaluated as good. The results are shown in Table 4 to Table 6 below.

Figure 02_image007
Figure 02_image007

Figure 02_image009
Figure 02_image009

Figure 02_image011
Figure 02_image011

如由表1～表3及表6可明知，於比較例1中，由於在pH2的強酸性下添加混合還原劑，故雖將合成液在70℃加熱2小時，但檸檬酸銅之還原係未完成，成為有機保護膜之質量比例亦多之結果，無法製造目標之粒子。As can be seen from Table 1 to Table 3 and Table 6, in Comparative Example 1, since the mixed reducing agent was added under the strong acidity of pH 2, although the synthetic solution was heated at 70°C for 2 hours, the reduction system of copper citrate Unfinished, as a result of the mass ratio of the organic protective film, the target particles cannot be produced.

於比較例2中，由於在pH8的鹼性下添加混合還原劑，故在液中銅離子變成氫氧化銅(II)，粒子之製造產率為90%之不高。又，在液中發生粒成長，所得之接合材料用粒子的BET比表面積為1.9m2 /g之小，而且BET徑為353nm之大，有機保護膜之質量比例亦為0.4質量%之低。另外，於飛行時間型二次離子質量分析中，相對於Cu+ 離子的檢出量，C3 H3 O3 - 離子與C3 H4 O2 - 離子各自的檢出量為0.21倍與0.48倍之大。據此，低溫燒結性差，接合強度亦為4MPa及8MPa之低。In Comparative Example 2, since the mixed reducing agent was added under the alkalinity of pH 8, the copper ions in the liquid became copper (II) hydroxide, and the production yield of particles was not high at 90%. In addition, particle growth occurred in the liquid, and the BET specific surface area of the resulting bonding material particles was as small as 1.9 m 2 /g, and the BET diameter was as large as 353 nm, and the mass ratio of the organic protective film was also as low as 0.4% by mass. In addition, in the time-of-flight type secondary ion mass analysis, relative to the detected amount of Cu + ions, the detected amounts of C 3 H 3 O 3 - ions and C 3 H 4 O 2 - ions are 0.21 times and 0.48. Times bigger. Accordingly, the low-temperature sinterability is poor, and the bonding strength is also as low as 4 MPa and 8 MPa.

於比較例3中，由於在pH10的鹼性下添加混合還原劑，故在液中銅離子變成氫氧化銅(II)，粒子之製造產率為80%之不高。又，在液中發生粒成長，所得之接合材料用粒子的BET比表面積為1.8m2 /g之小，而且BET徑為373nm之大，有機保護膜之質量比例亦為0.3質量%之低。另外，於飛行時間型二次離子質量分析中，相對於Cu+ 離子的檢出量，C3 H3 O3 - 離子與C3 H4 O2 - 離子各自的檢出量為0.30倍與0.50倍之大。還有，相對於Cu+ 離子的檢出量，C5 以上之離子的檢出量為0.010倍之大。據此，低溫燒結性差，接合強度亦為4MPa及8MPa之低。In Comparative Example 3, since the mixed reducing agent was added under the alkalinity of pH 10, the copper ions in the liquid became copper (II) hydroxide, and the production yield of particles was not high at 80%. In addition, particle growth occurred in the liquid, and the BET specific surface area of the resulting bonding material particles was as small as 1.8 m 2 /g, and the BET diameter was as large as 373 nm, and the mass ratio of the organic protective film was also as low as 0.3% by mass. In addition, in the time-of-flight type secondary ion mass analysis, relative to the detected amount of Cu + ions, the detected amounts of C 3 H 3 O 3 - ions and C 3 H 4 O 2 - ions are 0.30 times and 0.50. Times bigger. In addition, the detected amount of ions above C 5 is 0.010 times greater than the detected amount of Cu + ions. Accordingly, the low-temperature sinterability is poor, and the bonding strength is also as low as 4 MPa and 8 MPa.

於比較例4及5中，由於使用甲酸銨及甲酸作為還原劑，故檸檬酸銅之還原不進行，無法製造目標之粒子。In Comparative Examples 4 and 5, since ammonium formate and formic acid were used as reducing agents, the reduction of copper citrate did not proceed, and the target particles could not be produced.

於比較例6中，由於將合成液在70℃僅加熱1小時，故檸檬酸銅之還原係未完成，無法製造目標之粒子。In Comparative Example 6, since the synthesis solution was heated at 70°C for only 1 hour, the reduction system of copper citrate was not completed, and the target particles could not be produced.

於比較例7中，由於將合成液在70℃長時間加熱3小時，故檸檬酸銅之還原係過度進行，在液中發生粒成長，所得之接合材料用粒子的BET比表面積為2.5m2 /g之小，而且BET徑為268nm之大，有機保護膜之質量比例亦為0.4質量%之低。於飛行時間型二次離子質量分析中，相對於Cu+ 離子的檢出量，C3 H3 O3 - 離子的檢出量為0.04倍之小。據此，低溫燒結性差，接合強度亦為10MPa之低。In Comparative Example 7, since the synthesis solution was heated at 70°C for a long time for 3 hours, the reduction system of copper citrate proceeded excessively, and grain growth occurred in the solution. The BET specific surface area of the resulting bonding material particles was 2.5 m 2 /g is small, and the BET diameter is as large as 268nm, and the mass ratio of the organic protective film is also as low as 0.4% by mass. In the time-of-flight secondary ion mass analysis, the detected amount of C 3 H 3 O 3 - ions is 0.04 times less than the detected amount of Cu + ions. Accordingly, the low-temperature sinterability is poor, and the bonding strength is also as low as 10 MPa.

於比較例8中，由於將合成液在85℃之高溫加熱1.5小時，故檸檬酸銅之還原係過度進行，在液中發生粒成長，所得之接合材料用粒子的比表面積為2.9m2 /g之小，而且BET徑為231nm之大。於飛行時間型二次離子質量分析中，相對於Cu+ 離子的檢出量，C3 H3 O3 - 離子與C3 H4 O2 - 離子各自的檢出量為0.03倍與0.04倍之小。據此，低溫燒結性差，接合強度亦為12MPa之低。In Comparative Example 8, since the synthesis solution was heated at a high temperature of 85°C for 1.5 hours, the reduction system of copper citrate was excessively advanced, and particle growth occurred in the solution. The specific surface area of the resulting bonding material particles was 2.9m 2 / g is small, and the BET diameter is as large as 231 nm. In secondary ion mass spectrometry time of flight with respect to the detection of the amount of Cu + ions, C 3 H 3 O 3 - ions and C 3 H 4 O 2 - ions detectable amount of each of 0.03 times and 0.04 times the small. Accordingly, the low-temperature sinterability is poor, and the bonding strength is also as low as 12 MPa.

於比較例9中，由於將合成液在55℃之低溫加熱2.5小時，故檸檬酸銅之還原係未完成，無法製造目標之粒子。In Comparative Example 9, since the synthesis solution was heated at a low temperature of 55°C for 2.5 hours, the reduction system of copper citrate was not completed, and the target particles could not be produced.

相對於其，如由表1～表6可明知，於實施例1～11中，由於在pH3以上且未達pH7之酸性下添加混合還原劑，使用肼-水合物及無水肼作為還原劑，將合成液之加熱時的最高溫度設為60℃以上80℃以下，將其保持時間設為1.5小時以上2.5小時以下，故接合材料用粒子之製造產率為90%以上97%以下之高，BET比表面積為3.5m2 /g以上7.5m2 /g以下之大。BET徑為89nm以上192nm之小。又，有機保護膜之質量比例為0.5質量%以上2.0質量%以下，完全地被覆母體粒子的銅奈米粒子。另外，於飛行時間型二次離子質量分析中，相對於Cu+ 離子的檢出量，C3 H3 O3 - 離子與C3 H4 O2 - 離子各自的檢出量在0.05倍以上0.2倍以下之範圍，相對於Cu+ 離子的檢出量，C5 以上之離子的檢出量未達0.005倍。還有，有機保護膜之分解量比例係以75質量%以上88質量%以下之高比例分解，有機保護膜之殘渣少。又，接合材料用粒子之燒成時的發生氣體成分為N2 、H2 O、CO2 、C3 H6 O。根據此等，作為接合溫度在200℃以上300℃以下之範圍且15MPa以上52MPa以下之接合體，得到良好的接合強度。 [產業上的利用可能性]In contrast, as can be seen from Tables 1 to 6, in Examples 1 to 11, since the mixed reducing agent was added at pH 3 or higher and below pH 7, hydrazine-hydrate and anhydrous hydrazine were used as reducing agents. The maximum temperature during heating of the synthetic solution is set to 60°C or more and 80°C or less, and the holding time is set to 1.5 hours or more and 2.5 hours or less, so the production yield of particles for bonding materials is as high as 90% or more and 97% or less. BET specific surface area of 3.5m 2 / g or more large 7.5m 2 / g or less of. The BET diameter is from 89 nm to 192 nm. In addition, the organic protective film has a mass ratio of 0.5% by mass to 2.0% by mass, and completely covers the copper nanoparticle of the matrix particles. Further, in the secondary ion mass spectrometry time of flight with respect to the detection of the amount of Cu + ions, C 3 H 3 O 3 - ions and C 3 H 4 O 2 - ions detectable amounts of each more than 0.05 times 0.2 In the range below times, the detected amount of ions above C 5 is less than 0.005 times the amount of Cu + ions detected. In addition, the decomposition rate of the organic protective film is decomposed at a high ratio of 75% by mass to 88% by mass, and the residue of the organic protective film is small. In addition, the gas components generated during the firing of the bonding material particles are N 2 , H 2 O, CO 2 , and C 3 H 6 O. According to these, a good bonding strength can be obtained as a bonded body having a bonding temperature in the range of 200°C or more and 300°C or less and 15 MPa or more and 52 MPa or less. [Industrial use possibility]

本發明之接合材料用粒子係可利用作為細間距用無鉛的接合用粒子，以該接合用粒子作為原料而得之接合用糊料係可適用於微細的電子零件之安裝。The particles for the bonding material of the present invention can be used as lead-free bonding particles for fine pitch, and the bonding paste obtained from the bonding particles as a raw material can be applied to the mounting of fine electronic parts.

10:接合材料用粒子 11:母體粒子(銅奈米粒子) 12:有機保護膜10: Particles for bonding materials 11: Matrix particles (copper nanoparticles) 12: Organic protective film

[圖1]係示意地表示本發明實施形態之接合材料用粒子的剖面構造之圖。 [圖2]係以顯微鏡拍攝實施例1之接合材料用粒子的集合體之照相圖。Fig. 1 is a diagram schematically showing a cross-sectional structure of a particle for bonding material according to an embodiment of the present invention. [Fig. 2] A photograph of the aggregate of particles for bonding material of Example 1 taken with a microscope.

10:接合材料用粒子 10: Particles for bonding materials

11:母體粒子(銅奈米粒子) 11: Matrix particles (copper nanoparticles)

12:有機保護膜 12: Organic protective film

Claims (6)

一種接合材料用粒子，其係在銅奈米粒子表面上形成有有機保護膜之接合材料用粒子，其特徵為： 前述接合材料用粒子係BET比表面積在3.5m2 /g以上8m2 /g以下之範圍，由前述比表面積所換算的BET徑在80nm以上200nm以下之範圍， 相對於前述接合材料用粒子100質量%，前述有機保護膜係以0.5質量%以上2.0質量%以下之範圍含有， 使用飛行時間型二次離子質量分析法(TOF-SIMS)分析前述接合材料用粒子時，相對於Cu+ 離子的檢出量，C3 H3 O3 - 離子與C3 H4 O2 - 離子各自的檢出量在0.05倍以上0.2倍以下之範圍，相對於Cu+ 離子的檢出量，C5 以上之離子的檢出量在未達0.005倍之範圍。A particle for bonding material, which is a particle for bonding material with an organic protective film formed on the surface of copper nanoparticle, characterized in that: the BET specific surface area of the particle for bonding material is 3.5m 2 /g or more and 8m 2 /g In the following range, the BET diameter converted from the aforementioned specific surface area is within the range of 80 nm or more and 200 nm or less, and the organic protective film is contained in the range of 0.5% by mass to 2.0% by mass relative to 100% by mass of the particles for bonding material, analysis using time of flight secondary ion mass spectrometry (TOF-SIMS) when the bonding material particle, with respect to Cu + ions detectable amount, C 3 H 3 O 3 - ions and C 3 H 4 O 2 - ions The detection amount of each is in the range of 0.05 times or more and 0.2 times or less, and the detection amount of ions above C 5 is less than 0.005 times the detection amount of Cu + ions. 如請求項1之接合材料用粒子，其中於惰性氣體環境下以300℃之溫度加熱30分鐘時，前述有機保護膜係分解50質量%以上，分解的氣體係二氧化碳氣體、氮氣、丙酮的蒸發氣體及水蒸氣。Such as the particles for bonding material of claim 1, wherein when heated at a temperature of 300°C for 30 minutes in an inert gas environment, the aforementioned organic protective film decomposes by more than 50% by mass, and the decomposed gas system is carbon dioxide gas, nitrogen gas, and acetone evaporation gas And water vapor. 一種接合用糊料，其包含揮發性溶劑與如請求項1或2之接合材料用粒子。A bonding paste comprising a volatile solvent and particles for bonding material as claimed in claim 1 or 2. 一種製造接合材料用粒子之方法，其係在室溫的檸檬酸銅的水分散液中添加pH調整劑而將pH調整至pH3以上且未達pH7，於惰性氣體環境下在該經pH調整之檸檬酸銅的水分散液中添加混合肼化合物，於惰性氣體環境下將此混合液加熱至60℃以上80℃以下之溫度，且保持1.5小時以上2.5小時以下，藉此還原前述檸檬酸銅而生成銅奈米粒子，在此銅奈米粒子之表面上形成有機保護膜。A method of manufacturing particles for bonding materials, which is to add a pH adjuster to an aqueous dispersion of copper citrate at room temperature to adjust the pH to pH 3 or higher and below pH 7, and the pH adjusted under an inert gas environment A hydrazine compound is added to the aqueous dispersion of copper citrate, and the mixed solution is heated to a temperature above 60°C and below 80°C under an inert gas environment, and maintained for 1.5 hours to 2.5 hours, thereby reducing the aforementioned copper citrate. The copper nanoparticle is generated, and an organic protective film is formed on the surface of the copper nanoparticle. 一種調製接合用糊料之方法，其係混合揮發性溶劑與如請求項1或2之接合材料用粒子或以如請求項4之方法所製造的接合材料用粒子。A method of preparing a bonding paste by mixing a volatile solvent with the bonding material particles according to claim 1 or 2 or the bonding material particles manufactured by the method according to claim 4. 一種接合體之製造方法，其包含：將如請求項3之接合用糊料或以如請求項5之方法所調製的接合用糊料塗佈於基板或電子零件之表面而形成塗佈層之步驟；隔著前述塗佈層疊合前述基板與前述電子零件之步驟；與，藉由將前述經疊合的前述基板與前述電子零件，一邊施加30MPa以下之壓力，一邊在惰性環境下，以200℃以上300℃以下之溫度加熱而燒結前述塗佈層，而形成接合層，藉由此接合層接合前述基板與前述電子零件之步驟。A method of manufacturing a bonded body, comprising: coating the bonding paste of claim 3 or the bonding paste prepared by the method of claim 5 on the surface of a substrate or electronic part to form a coating layer Step; the step of laminating the substrate and the electronic component via the coating; and, by applying a pressure of 30 MPa or less to the substrate and the electronic component that have been laminated, under an inert environment at 200 The step of sintering the coating layer at a temperature higher than or equal to 300°C to form a bonding layer, and bonding the substrate and the electronic component through the bonding layer.
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