TW202014260A - Production method for copper particles, bonding paste, semiconductor device, and electrical and electronic components - Google Patents

Abstract

Provided is a production method for copper particles having: a step for mixing a copper compound, an amine compound, and a reducing compound in an organic solvent and obtaining a copper particle dispersion; and a cleaning step for subjecting the copper particle dispersion obtained in the aforementioned step to solvent cleaning and separating copper particles from the copper particle dispersion by a solid-liquid separation process, wherein the cleaning step is carried out in a closed system.

Description

銅粒子之製造方法、接合用膏及半導體裝置以及電氣‧電子零件Copper particle manufacturing method, bonding paste, semiconductor device, and electrical and electronic parts

本發明係關於一種銅粒子之製造方法、接合用膏及使用該接合用膏所製造之半導體裝置以及電氣・電子零件。The present invention relates to a method for manufacturing copper particles, a bonding paste, and a semiconductor device and electrical/electronic parts manufactured using the bonding paste.

伴隨半導體製品之大容量、高速處理化及微細配線化，如何處理半導體製品作動中產生之熱受到關注。尤其要求進行自半導體製品散熱之所謂熱管理。因此，通常採用於半導體製品安裝熱散播器、散熱器等散熱構件之方法等。又，業界期望於半導體製品接著散熱構件之材料本身之導熱率更高。 又，為了使熱管理更有效率，視半導體製品之形態不同，採用於半導體元件本身或接著有半導體元件之引線框架之晶片座部接著熱散播器的方法、以及藉由使晶片座部於封裝表面露出而使其具有作為散熱板之功能的方法(例如參照專利文獻1)等。Along with the large-capacity, high-speed processing and fine wiring of semiconductor products, attention has been paid to how to deal with the heat generated in the operation of semiconductor products. In particular, the so-called thermal management of heat dissipation from semiconductor products is required. Therefore, the method of mounting heat dissipation members such as heat spreaders and heat sinks on semiconductor products is generally used. In addition, the industry expects that the thermal conductivity of the material of the semiconductor product and the heat dissipation member itself will be higher. In addition, in order to make the thermal management more efficient, depending on the form of the semiconductor product, a method of attaching the heat spreader to the wafer seat of the semiconductor element itself or the lead frame followed by the semiconductor element, and by making the wafer seat in the package A method of exposing the surface to function as a heat sink (see Patent Document 1, for example).

又，進而亦存在將半導體元件接著於具有熱通孔等散熱機構之有機基板等之情形。於該情形時，亦要求接著半導體元件之材料具有高導熱性。又，近年來，得益於白色發光LED(Light Emitting Diode，發光二極體)之高亮度化，亦開始廣泛應用於全彩液晶畫面之背光照明、吸頂燈、筒燈等照明裝置。然，因發光元件之高輸出化帶來高電流輸入，而有將發光元件與基板接著之接著劑因熱及光等變色，或產生電阻值之經時變化之虞。尤其是完全依賴接著劑之接著力將發光元件與基板接合之方法有於電子零件之焊接時會因接合材料在焊料熔融溫度下失去接著力而引起剝離之虞，擔憂導致不發光。又，白色發光LED之高性能化會導致發光元件晶片之發熱量增大，伴隨於此，對於LED之構造及其使用之構件亦要求散熱性之提昇。Furthermore, there are cases where semiconductor elements are bonded to organic substrates having heat dissipation mechanisms such as thermal vias. In this case, the material of the semiconductor element is required to have high thermal conductivity. In addition, in recent years, thanks to the high brightness of white light-emitting LEDs (Light Emitting Diodes), they have also been widely used in lighting devices such as backlighting, ceiling lamps, and downlights for full-color LCD screens. However, the higher output of the light-emitting element results in a higher current input, and the adhesive that connects the light-emitting element and the substrate may change color due to heat, light, or the like, or the resistance value may change with time. In particular, the method of bonding the light-emitting element and the substrate completely depending on the adhesive force of the adhesive may cause peeling due to the loss of the adhesive force of the bonding material at the melting temperature of the solder during the soldering of the electronic parts, which may cause non-luminescence. In addition, the higher performance of white light-emitting LEDs will increase the heat generation of the light-emitting element chips. Along with this, the structure of LEDs and the components used therefor also require improved heat dissipation.

尤其，近年來，盛行開發使用電力損耗較少之如碳化矽(SiC)、氮化鉀等寬帶隙半導體之功率半導體裝置，從而使元件本身之耐熱性較高，可實現大電流下250℃以上之高溫動作。然而，為了發揮該特性，必須使動作發熱有效地散熱，謀求除導電性及傳熱性優異以外，長期高溫耐熱性亦優異之接合材料。In particular, in recent years, the development of power semiconductor devices using wide-bandgap semiconductors such as silicon carbide (SiC), potassium nitride, etc., which have low power losses, has led to a higher heat resistance of the device itself, which can achieve a temperature of 250°C or higher at high current. High temperature action. However, in order to exhibit this characteristic, it is necessary to effectively dissipate heat generated during operation, and in addition to having excellent electrical conductivity and heat transfer properties, a bonding material having excellent long-term high-temperature heat resistance is also desired.

如此，要求用於半導體裝置及電氣・電子零件之各構件之接著之材料(晶粒接合膏及散熱構件接著用材料等)具有較高之導熱性。又，該等材料同時亦必須耐受製品之基板搭載時之回焊處理，進而要求大面積之接著之情形亦較多，需要亦兼具用以降低因構成構件間之熱膨脹係數不同導致之翹曲等之產生率的低應力性。In this way, materials used for bonding of various members of semiconductor devices and electrical/electronic parts (die bonding paste and materials for bonding heat dissipation members, etc.) are required to have high thermal conductivity. In addition, these materials must also withstand the reflow process when the substrate of the product is mounted, and then require a large area to be adhered to in many cases. It is also necessary to reduce the warpage caused by the different thermal expansion coefficients of the constituent members Low stress of the rate of occurrence of flexures.

此處，通常為了獲得具有高導熱性之接著劑，需要以銀粉、銅粉等金屬填料及氮化鋁、氮化硼等陶瓷系填料等作為填充劑，並以高含有率分散於有機系黏合劑中(例如參照專利文獻2)。Here, in order to obtain an adhesive with high thermal conductivity, it is necessary to use metal fillers such as silver powder and copper powder, ceramic fillers such as aluminum nitride and boron nitride as fillers, and disperse the organic binder at a high content rate In the agent (for example, refer to Patent Document 2).

然而，最近，作為能夠滿足此種要求之接合方法之候補，較塊體銀可於更低溫度之條件下接合的利用銀奈米粒子之接合方法受到關注(例如參照專利文獻3)。 然，雖然銀粒子導電性優異，但考慮到其較高之價格及耐遷移性，正研究其他之代替金屬。於是，目前，與銀粒子相比價格更低且具有遷移耐性之銅粒子受到了關注。 [先前技術文獻] [專利文獻]However, recently, as a candidate for a bonding method that can meet such requirements, a bonding method using silver nanoparticles that can bond at a lower temperature than bulk silver has attracted attention (see, for example, Patent Document 3). Of course, although silver particles have excellent conductivity, in consideration of their higher price and migration resistance, other alternative metals are being studied. Therefore, at present, copper particles, which are cheaper than silver particles and have migration resistance, have attracted attention. [Prior Technical Literature] [Patent Literature]

[專利文獻1]日本專利特開2006-086273號公報 [專利文獻2]日本專利特開2005-113059號公報 [專利文獻3]日本專利特開2011-240406號公報[Patent Document 1] Japanese Patent Laid-Open No. 2006-086273 [Patent Document 2] Japanese Patent Laid-Open No. 2005-113059 [Patent Document 3] Japanese Patent Laid-Open No. 2011-240406

[發明所欲解決之問題][Problems to be solved by the invention]

然而，利用銅奈米粒子之接合為表現出導電性需要300℃之高溫，進而，其粒徑較小，容易氧化，出於該等原因，存在其操作及處理耗費工時之情形。進而，就去除表面氧化膜之觀點而言，銅粒子之燒結需要在還原氣氛中進行燒結。However, the bonding using copper nanoparticles requires a high temperature of 300° C. to exhibit electrical conductivity, and furthermore, the particle size is small, and it is easy to oxidize. For these reasons, there are cases where its operation and processing are time-consuming. Furthermore, from the viewpoint of removing the surface oxide film, the sintering of copper particles needs to be sintered in a reducing atmosphere.

又，雖然著重進行研究開發之配線用銅奈米粒子可實現相對較低溫度之燒結，但用於接合用之情形時，於接合層內部與填角部，燒結速度及燒結度會產生差，難以獲得可靠性較高之接合體。In addition, although copper nanoparticles for wiring that focus on research and development can achieve relatively low-temperature sintering, when used for bonding, the sintering speed and the degree of sintering will be poor inside the bonding layer and the corner fillet. It is difficult to obtain a bonded body with high reliability.

本發明係鑒於此種實情完成者，提供一種即便並非還原氣氛亦可實現低溫燒結，接合層內部與填角部之燒結速度及燒結度均勻且接合特性良好之銅粒子之製造方法、包含藉由該製造方法所獲得之銅粒子之接合用膏以及藉由使用該接合用膏從而可靠性優異之半導體裝置及電氣・電子零件。 [解決問題之技術手段]The present invention has been completed in view of this fact, and provides a method for manufacturing copper particles that can achieve low-temperature sintering even in a non-reducing atmosphere, have uniform sintering speed and degree of sintering inside the bonding layer and the fillet portion, and have good bonding characteristics, including by The bonding paste for copper particles obtained by this manufacturing method and the semiconductor device and electrical/electronic parts excellent in reliability by using this bonding paste. [Technical means to solve the problem]

本發明者等人為了解決上述問題而進行了銳意研究，結果發現藉由下述揭示可解決該問題。The inventors of the present invention conducted intensive research in order to solve the above problems, and found that the problems can be solved by the following disclosure.

即，本案發明係關於以下內容。 [1]一種銅粒子之製造方法，其包括以下步驟：將銅化合物、胺化合物、及還原性化合物於有機溶劑中混合，獲得銅粒子分散液；及洗淨步驟，其係對上述步驟所得之銅粒子分散液進行溶劑洗淨，將銅粒子自上述銅粒子分散液中固液分離；且 於密閉系統中實施上述洗淨步驟。 [2]如上述[1]所記載之銅粒子之製造方法，其中於上述洗淨步驟中，連續地進行溶劑置換及洗淨。 [3]如上述[1]或[2]所記載之銅粒子之製造方法，其中於上述洗淨步驟中，將含有1～50質量%之上述銅粒子之上述銅粒子分散液以流量5～1500 kg/hr・m² 、壓力0.03～1.0 MPa供給至過濾膜。 [4]如上述[1]至[3]中任一項記載之銅粒子之製造方法，其中上述銅粒子之平均粒徑為1～1000 nm。 [5]一種接合用膏，其包含藉由如上述[1]至[4]中任一項記載之製造方法所獲得之銅粒子。 [6]一種半導體裝置，其係使用如上述[5]所記載之接合用膏接合而成。 [7]一種電氣・電子零件，其係使用如上述[5]所記載之接合用膏接合而成。 [發明之效果]That is, the present invention relates to the following. [1] A method for producing copper particles, comprising the steps of: mixing a copper compound, an amine compound, and a reducing compound in an organic solvent to obtain a copper particle dispersion liquid; and a washing step, which is obtained by the above steps The copper particle dispersion liquid is washed with a solvent, and the copper particles are solid-liquid separated from the copper particle dispersion liquid; and the above washing step is performed in a closed system. [2] The method for producing copper particles as described in [1] above, wherein in the washing step, solvent replacement and washing are continuously performed. [3] The method for producing copper particles according to the above [1] or [2], wherein in the washing step, the copper particle dispersion liquid containing 1 to 50% by mass of the copper particles is flowed at a flow rate of 5 to 1500 kg/hr·m ² and pressure 0.03～1.0 MPa are supplied to the filter membrane. [4] The method for producing copper particles according to any one of the above [1] to [3], wherein the average particle diameter of the copper particles is 1 to 1000 nm. [5] A bonding paste comprising copper particles obtained by the production method described in any one of [1] to [4] above. [6] A semiconductor device formed by bonding using the bonding paste as described in [5] above. [7] An electrical/electronic component formed by joining using the bonding paste as described in [5] above. [Effect of invention]

根據本發明，可提供即便並非還原氣氛亦可實現低溫燒結，接合層內部與填角部之燒結速度及燒結度均勻且接合特性良好之銅粒子之製造方法、包含藉由該製造方法所獲得之銅粒子之接合用膏以及藉由使用該接合用膏從而可靠性優異之半導體裝置及電氣・電子零件。According to the present invention, it is possible to provide a method for producing copper particles that can achieve low-temperature sintering even in a non-reducing atmosphere, have uniform sintering speed and degree of sintering in the inside of the bonding layer and the corner fillet, and have good bonding characteristics, including those obtained by the manufacturing method A bonding paste for copper particles and a semiconductor device and electrical/electronic parts with excellent reliability by using the bonding paste.

＜銅粒子之製造方法＞ 本發明之銅粒子之製造方法包括以下步驟：將銅化合物、胺化合物、及還原性化合物於有機溶劑中混合，獲得銅粒子分散液；及洗淨步驟，其係對上述步驟所得之銅粒子分散液進行溶劑洗淨，將銅粒子自上述銅粒子分散液中固液分離；且於密閉系統中實施上述洗淨步驟。 於本發明之銅粒子之製造方法中，藉由於密閉系統中實施上述洗淨步驟，可獲得銅粒子表面之氧化得到控制，接合特性良好之銅粒子。<Manufacturing method of copper particles> The method for producing copper particles of the present invention includes the following steps: mixing a copper compound, an amine compound, and a reducing compound in an organic solvent to obtain a copper particle dispersion; and a washing step, which is to disperse the copper particles obtained in the above steps The liquid is washed with a solvent, and the copper particles are solid-liquid separated from the copper particle dispersion liquid; and the above washing step is performed in a closed system. In the method for producing copper particles of the present invention, by performing the above-mentioned washing step in a closed system, it is possible to obtain copper particles with controlled oxidation of the surface of the copper particles and excellent bonding characteristics.

以下，參照一實施形態對本發明進行詳細說明。Hereinafter, the present invention will be described in detail with reference to an embodiment.

[獲得銅粒子分散液之步驟] 於本步驟中，將作為原料之銅化合物、胺化合物、及還原性化合物於有機溶劑中混合，獲得銅粒子分散液。 (銅化合物) 本實施形態中使用之銅化合物只要包含銅原子則並無特別限定。作為銅化合物，例如可列舉羧酸銅、氧化銅、氫氧化銅、氮化銅等。就反應時之均勻性之觀點而言，銅化合物可為羧酸銅。該等可單獨使用亦可併用2種以上。[Procedure for obtaining copper particle dispersion] In this step, the copper compound, the amine compound, and the reducing compound as raw materials are mixed in an organic solvent to obtain a copper particle dispersion liquid. (Copper compound) The copper compound used in this embodiment is not particularly limited as long as it contains copper atoms. Examples of the copper compound include copper carboxylate, copper oxide, copper hydroxide, and copper nitride. From the viewpoint of uniformity during the reaction, the copper compound may be copper carboxylate. These can be used alone or in combination of two or more.

作為羧酸銅，可列舉：甲酸銅(I)、乙酸銅(I)、丙酸銅(I)、丁酸銅(I)、戊酸銅(I)、己酸銅(I)、辛酸銅(I)、癸酸銅(I)、甲酸銅(II)、乙酸銅(II)、丙酸銅(II)、丁酸銅(II)、戊酸銅(II)、己酸銅(II)、辛酸銅(II)、癸酸銅(II)、檸檬酸銅(II)等羧酸銅無水物或水合物。就生產性及獲得容易性之觀點而言，羧酸銅可為乙酸銅(II)一水合物。又，該等可單獨使用亦可併用2種以上。Examples of the copper carboxylate include copper formate (I), copper acetate (I), copper propionate (I), copper butyrate (I), copper valerate (I), copper caproate (I), and copper octoate (I), copper(I) caprate, copper(II) formate, copper(II) acetate, copper(II) propionate, copper(II) butyrate, copper(II) valerate, copper(II) caproate , Copper (II) octoate, copper (II) caprate, copper (II) citrate and other copper carboxylate anhydrates or hydrates. From the viewpoints of productivity and availability, the copper carboxylate may be copper (II) acetate monohydrate. Moreover, these may be used individually or in combination of 2 or more types.

又，羧酸銅可使用市售者，亦可使用藉由合成而獲得者。In addition, the copper carboxylate may be a commercially available product or a compound obtained through synthesis.

羧酸銅之合成可藉由公知之方法進行，例如可藉由將氫氧化銅(II)與羧酸化合物進行混合、加熱而獲得。The synthesis of copper carboxylate can be carried out by a known method, for example, it can be obtained by mixing and heating copper (II) hydroxide and a carboxylic acid compound.

作為氧化銅，可列舉氧化銅(II)、氧化銅(I)，就生產性之觀點而言，可為氧化銅(I)。又，作為氫氧化銅，可列舉氫氧化銅(II)、氫氧化銅(I)。 該等可單獨使用亦可併用2種以上。Examples of the copper oxide include copper oxide (II) and copper oxide (I). From the viewpoint of productivity, copper oxide (I) may be used. Moreover, as copper hydroxide, copper (II) hydroxide and copper (I) hydroxide are mentioned. These can be used alone or in combination of two or more.

(胺化合物) 本實施形態中使用之胺化合物只要為與銅化合物形成錯合物者，則並無特別限定，就燒結性之觀點而言，可為包含選自烷基胺、胺基醇、烷氧基胺及羧酸胺鹽之至少1種化合物，亦可為羧酸胺鹽。 上述胺化合物係於加熱銅化合物與胺化合物之錯合物而使銅化合物分解時作為銅化合物之分解反應之反應介質發揮功能者。進而，上述胺化合物具有附著於藉由使銅化合物熱分解所獲得之銅粒子之表面從而控制氧化之功能。(Amine compound) The amine compound used in this embodiment is not particularly limited as long as it forms a complex with a copper compound, and from the viewpoint of sinterability, it may be selected from alkylamines, amino alcohols, and alkoxyamines. At least one compound of carboxylic acid amine salt may be carboxylic acid amine salt. The above amine compound functions as a reaction medium for the decomposition reaction of the copper compound when the copper compound and the amine compound are heated to decompose the copper compound. Furthermore, the amine compound has a function of adhering to the surface of copper particles obtained by thermally decomposing the copper compound to control oxidation.

因此，本實施形態中使用之胺化合物可根據與銅化合物之錯合物之熱分解之條件、對待製造之銅粒子期待之特性等自公知之胺化合物適當選擇使用。Therefore, the amine compound used in this embodiment can be appropriately selected from known amine compounds according to the conditions of thermal decomposition of the complex with the copper compound, the expected characteristics of the copper particles to be produced, and the like.

此處，烷基胺只要為具有烷基等脂肪族烴基作為與胺基鍵結之基之胺化合物即可，其構造並無特別限制，例如可列舉具有1個胺基之烷基單胺、具有2個胺基之烷基二胺等。再者，上述烷基亦可進而具有取代基。Here, the alkylamine may be an amine compound having an aliphatic hydrocarbon group such as an alkyl group as a group bonded to the amine group, and its structure is not particularly limited. For example, an alkyl monoamine having one amine group, Alkyl diamine with 2 amine groups, etc. In addition, the alkyl group may further have a substituent.

具體而言，作為烷基單胺，可列舉：二丙基胺、丁基胺、二丁基胺、己基胺、環己基胺、庚基胺、辛基胺、壬基胺、癸基胺、3-胺基丙基三乙氧基矽烷、十二烷基胺、油基胺等，作為烷基二胺，可列舉：乙二胺、N,N-二甲基乙二胺、N,N'-二甲基乙二胺、N,N-二乙基乙二胺、N,N'-二乙基乙二胺、1,3-丙二胺、2,2-二甲基-1,3-丙二胺、N,N-二甲基-1,3-二胺基丙烷、N,N'-二甲基-1,3-二胺基丙烷、N,N-二乙基-1,3-二胺基丙烷、1,4-二胺基丁烷、1,5-二胺基-2-甲基戊烷、1,6-二胺基己烷、N,N'-二甲基-1,6-二胺基己烷、1,7-二胺基庚烷、1,8-二胺基辛烷等。 再者，為了與上述羧酸銅反應而有效率地形成羧酸銅-胺錯合物，烷基單胺可為一級胺(R¹ NH₂ )或二級胺(R² R³ NH)等烷基單胺。 再者，烷基胺不包含以下說明之胺基醇及烷氧基胺。Specifically, examples of the alkyl monoamine include dipropylamine, butylamine, dibutylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, and decylamine. 3-Aminopropyltriethoxysilane, dodecylamine, oleylamine, etc. Examples of the alkyldiamine include ethylenediamine, N,N-dimethylethylenediamine, N,N '-Dimethylethylenediamine, N,N-diethylethylenediamine, N,N'-diethylethylenediamine, 1,3-propanediamine, 2,2-dimethyl-1, 3-propanediamine, N,N-dimethyl-1,3-diaminopropane, N,N'-dimethyl-1,3-diaminopropane, N,N-diethyl-1 ,3-diaminopropane, 1,4-diaminobutane, 1,5-diamino-2-methylpentane, 1,6-diaminohexane, N,N'-dimethyl 1,6-Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, etc. Furthermore, in order to efficiently react with the copper carboxylate to form a copper carboxylate-amine complex, the alkyl monoamine may be a primary amine (R ¹ NH ₂ ) or a secondary amine (R ² R ³ NH), etc. Alkyl monoamine. In addition, the alkylamine does not include the amino alcohol and alkoxyamine described below.

又，作為胺基醇，只要為具有羥基作為官能基之胺化合物，其結構並無特別限制，例如可列舉具有1個胺基之烷醇單胺等。具體而言，可列舉胺基乙醇、庚胺醇(Heptaminol)、異丙腎上腺素(Isoetharine)、丙醇胺、神經鞘胺醇、1-胺基-2-丙醇、2-胺基二丁醇、2-二乙基胺基乙醇、3-二乙基胺基-1,2-丙二醇、3-二甲基胺基-1,2-丙二醇、3-甲基胺基-1,2-丙二醇、3-胺基-1,2-丙二醇等。In addition, the amino alcohol is not particularly limited as long as it is an amine compound having a hydroxyl group as a functional group, and examples thereof include an alkanol monoamine having one amino group. Specific examples include aminoethanol, heptaminol (Heptaminol), isoproterenol (Isoetharine), propanolamine, sphingosine, 1-amino-2-propanol, 2-aminodibutyl Alcohol, 2-diethylaminoethanol, 3-diethylamino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, 3-methylamino-1,2- Propylene glycol, 3-amino-1,2-propanediol, etc.

又，作為烷氧基胺，只要為具有烷氧基作為取代基之胺化合物即可，其構造並無特別限制，例如可列舉具有1個胺基之烷氧基單胺、具有2個胺基之烷氧基二胺等。具體而言，作為烷氧基單胺，可列舉甲氧基乙基胺、2-乙氧基乙基胺、3-丁氧基丙基胺等，作為烷氧基二胺，可列舉N-甲氧基-1,3-丙二胺、N-甲氧基-1,4-丁二胺等。考慮到對還原生成之銅之配位力，烷氧基胺可為一級胺(R¹ ONH₂ )或二級胺(R² (R³ O)NH)等烷氧基單胺。In addition, as the alkoxyamine, as long as it is an amine compound having an alkoxy group as a substituent, the structure is not particularly limited, and examples thereof include an alkoxy monoamine having one amine group and two amine groups. The alkoxy diamine and so on. Specifically, examples of the alkoxy monoamine include methoxyethylamine, 2-ethoxyethylamine, and 3-butoxypropylamine, and examples of the alkoxydiamine include N- Methoxy-1,3-propanediamine, N-methoxy-1,4-butanediamine, etc. In consideration of the coordination power with respect to the copper formed by reduction, the alkoxyamine may be a primary amine (R ¹ ONH ₂ ) or a secondary amine (R ² (R ³ O)NH) and other alkoxy monoamines.

此處，上述烷基胺及烷氧基胺中記載之一級胺之取代基R¹ 表示烷基，可為碳數4～18之烷基。又，二級胺之取代基R² 及R³ 表示烷基，可均為碳數4～18之烷基。取代基R² 及R³ 可相同亦可不同。進而，該等烷基亦可具有矽烷基、縮水甘油基等取代基。Here, the substituent R ¹ of the primary amine described in the alkylamine and alkoxyamine represents an alkyl group, and may be an alkyl group having 4 to 18 carbon atoms. In addition, the substituents R ² and R ^{3 of the} secondary amine represent an alkyl group, and both of them may be a C 4-18 alkyl group. The substituents R ² and R ³ may be the same or different. Furthermore, these alkyl groups may have substituents such as silane groups and glycidyl groups.

羧酸胺鹽可自羧酸化合物與胺化合物獲得，可使用市售者，亦可使用預先藉由合成所得者。羧酸胺鹽亦可於銅粒子之製造步驟中在反應容器內分別分開投入羧酸化合物與胺化合物而原地(in-situ)生成。The carboxylic acid amine salt can be obtained from a carboxylic acid compound and an amine compound, and a commercially available one can be used, or one obtained in advance by synthesis can be used. The carboxylic acid amine salt can also be produced in-situ by separately putting the carboxylic acid compound and the amine compound into the reaction vessel in the copper particle production step.

羧酸胺鹽係藉由將羧酸化合物與胺化合物以官能基等量之方式調配於有機溶劑中，並於室溫(25℃)至100℃左右之相對溫和之溫度條件下進行混合而生成。羧酸胺鹽可藉由蒸餾法或再結晶法等自包含生成物之上述反應液提取。Carboxylic acid amine salt is produced by mixing the carboxylic acid compound and the amine compound in an organic solvent in an equal amount of functional groups, and mixing under relatively mild temperature conditions of room temperature (25°C) to about 100°C . The carboxylic acid amine salt can be extracted from the above reaction solution containing the product by distillation or recrystallization.

構成羧酸胺鹽之羧酸化合物只要為具有羧基之化合物則並無特別限定，例如可列舉單羧酸、二羧酸、芳香族羧酸、羥酸等。該等可單獨使用亦可併用2種以上。就使接合層內部與填角部之燒結速度之差變小之觀點而言，上述羧酸化合物可為單羧酸、二羧酸。The carboxylic acid compound constituting the carboxylic acid amine salt is not particularly limited as long as it has a carboxyl group, and examples thereof include monocarboxylic acids, dicarboxylic acids, aromatic carboxylic acids, and hydroxy acids. These can be used alone or in combination of two or more. The carboxylic acid compound may be a monocarboxylic acid or a dicarboxylic acid from the viewpoint of reducing the difference in the sintering rate between the inside of the bonding layer and the fillet.

構成羧酸胺鹽之羧酸化合物就使接合層內部與填角部之燒結速度之差變小之觀點而言，熱分解溫度可為200℃以下，可為190℃以下，亦可為180℃以下。The carboxylic acid compound constituting the carboxylic acid amine salt has a thermal decomposition temperature of 200°C or less, 190°C or less, or 180°C from the viewpoint of reducing the difference in the sintering rate between the inside of the bonding layer and the fillet portion the following.

又，構成羧酸胺鹽之羧酸化合物中，關於在較熱分解溫度更低溫之區域具有沸點之化合物，沸點可為280℃以下，可為260℃以下，亦可為240℃以下。若羧酸化合物之沸點處於該範圍，則接合層內部與填角部之燒結速度之差變小。In addition, among the carboxylic acid compounds constituting the carboxylic acid amine salt, the compound having a boiling point in a region lower than the thermal decomposition temperature may have a boiling point of 280°C or lower, 260°C or lower, or 240°C or lower. If the boiling point of the carboxylic acid compound is within this range, the difference in the sintering rate between the inside of the bonding layer and the fillet portion becomes small.

構成羧酸胺鹽之羧酸化合物中，作為單羧酸，可列舉：甲酸、乙酸、丙酸、丁酸、戊酸、己酸、辛酸(caprylic acid)、辛酸(octylic acid)、壬酸、癸酸、油酸、硬脂酸、異硬脂酸等。該等可單獨使用亦可併用2種以上。單羧酸就使接合層內部與填角部之燒結速度之差變小之觀點而言，可為甲酸、乙酸、丙酸、丁酸、戊酸、己酸、辛酸(caprylic acid)、辛酸(octylic acid)、壬酸、癸酸，亦可為戊酸、己酸、辛酸(caprylic acid)、壬酸、辛酸(octylic acid)。Among the carboxylic acid compounds constituting the carboxylic acid amine salt, examples of the monocarboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, caprylic acid, octylic acid, nonanoic acid, Capric acid, oleic acid, stearic acid, isostearic acid, etc. These can be used alone or in combination of two or more. The monocarboxylic acid may be formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, caprylic acid, octanoic acid from the viewpoint of reducing the difference between the sintering speed of the inside of the bonding layer and the corner fillet. octylic acid, nonanoic acid, capric acid, valeric acid, caproic acid, caprylic acid, nonanoic acid, octylic acid.

構成羧酸胺鹽之羧酸化合物中，作為二羧酸，可列舉：草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、二甘醇酸等。該等可單獨使用亦可併用2種以上。就使接合層內部與填角部之燒結速度之差變小之觀點而言，可為草酸、丙二酸、琥珀酸、戊二酸、己二酸、二甘醇酸，亦可為草酸、丙二酸、琥珀酸、二甘醇酸。Among the carboxylic acid compounds constituting the carboxylic acid amine salt, examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Acid, diethylene glycol acid, etc. These can be used alone or in combination of two or more. From the viewpoint of reducing the difference in the sintering speed between the inside of the bonding layer and the fillet, it may be oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, diglycolic acid, or oxalic acid, Malonic acid, succinic acid, diethylene glycol acid.

構成羧酸胺鹽之羧酸化合物中，作為芳香族羧酸，可列舉苯甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、水楊酸、五倍子酸等。該等可單獨使用亦可併用2種以上。芳香族羧酸就使接合層內部與填角部之燒結速度之差變小之觀點而言，亦可為苯甲酸。Among the carboxylic acid compounds constituting the carboxylic acid amine salt, examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, and gallic acid. These can be used alone or in combination of two or more. The aromatic carboxylic acid may be benzoic acid from the viewpoint of reducing the difference in the sintering rate between the inside of the bonding layer and the corner fillet.

構成羧酸胺鹽之羧酸化合物中，作為羥酸，可列舉：乙醇酸、乳酸、羥基丙二酸、蘋果酸、甘油酸、羥基丁酸、酒石酸、檸檬酸、異檸檬酸等。該等可單獨使用亦可併用2種以上。上述羧酸化合物就使接合層內部與填角部之燒結速度之差變小之觀點而言，可為乙醇酸、乳酸、蘋果酸。Among the carboxylic acid compounds constituting the carboxylic acid amine salt, examples of the hydroxy acid include glycolic acid, lactic acid, hydroxymalonic acid, malic acid, glyceric acid, hydroxybutyric acid, tartaric acid, citric acid, and isocitric acid. These can be used alone or in combination of two or more. The carboxylic acid compound may be glycolic acid, lactic acid, or malic acid from the viewpoint of reducing the difference in the sintering speed between the inside of the bonding layer and the fillet.

作為構成羧酸胺鹽之胺化合物，只要為具有羧基之化合物則並無特別限定，例如可列舉烷基單胺、烷基二胺、烷醇胺等。該等可單獨使用亦可併用2種以上。上述胺化合物就燒結性之觀點而言，可為烷基單胺、烷醇胺。The amine compound constituting the carboxylic acid amine salt is not particularly limited as long as it has a carboxyl group, and examples thereof include alkyl monoamines, alkyl diamines, and alkanolamines. These can be used alone or in combination of two or more. From the viewpoint of sinterability, the amine compound may be an alkyl monoamine or an alkanolamine.

構成羧酸胺鹽之胺化合物中，作為烷基單胺，可列舉：甲基胺、乙基胺、丙基胺、丁基胺、己基胺、辛基胺、癸基胺、十二烷基胺等。該等可單獨使用亦可併用2種以上。上述烷基單胺就燒結性之觀點而言，可為己基胺、辛基胺、癸基胺。Among the amine compounds constituting the carboxylic acid amine salt, examples of the alkyl monoamine include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, and dodecyl Amines. These can be used alone or in combination of two or more. From the viewpoint of sinterability, the alkyl monoamine may be hexylamine, octylamine, or decylamine.

構成羧酸胺鹽之胺化合物中，作為烷基二胺，可列舉：1,1-甲二胺、1,2-乙二胺、1,3-丙二胺、1,4-丁二胺、1,6-己二胺、1,8-辛二胺等。該等可單獨使用亦可併用2種以上。上述烷基二胺就燒結性之觀點而言，可為1,4-丁二胺、1,6-己二胺。Among the amine compounds constituting the carboxylic acid amine salt, examples of the alkyl diamine include 1,1-methylenediamine, 1,2-ethylenediamine, 1,3-propanediamine, and 1,4-butanediamine. , 1,6-hexanediamine, 1,8-octanediamine, etc. These can be used alone or in combination of two or more. From the viewpoint of sinterability, the alkyl diamine may be 1,4-butanediamine or 1,6-hexanediamine.

構成羧酸胺鹽之胺化合物中，作為烷醇胺，可列舉：單乙醇胺、單丙醇胺、單丁醇胺、2-(2-胺基乙基胺基)乙醇、2-(2-胺基乙氧基)乙醇、1-胺基-2-丙醇、2-胺基-1-丙醇、3-胺基-1,2-丙二醇等。該等可單獨使用亦可併用2種以上。上述烷醇胺類就燒結性之觀點而言，可為單乙醇胺、單丙醇胺、單丁醇胺、1-胺基-2-丙醇、2-胺基-1-丙醇。Among the amine compounds constituting the carboxylic acid amine salt, examples of the alkanolamine include monoethanolamine, monopropanolamine, monobutanolamine, 2-(2-aminoethylamino)ethanol, and 2-(2- Aminoethoxy) ethanol, 1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1,2-propanediol and the like. These can be used alone or in combination of two or more. From the viewpoint of sinterability, the alkanolamines may be monoethanolamine, monopropanolamine, monobutanolamine, 1-amino-2-propanol, and 2-amino-1-propanol.

上述胺基化合物之沸點可為70℃以上280℃以下，可為100℃以上260℃以下，亦可為120℃以上240℃以下。若胺基化合物之沸點為上述範圍，則所得之銅粒子表現出良好之燒結性。 又，若胺基化合物之沸點為70℃以上，則所得之接合用膏會控制加熱步驟中胺基化合物之揮發，因此得以保持反應系統中之均勻性。若胺基化合物之沸點為280℃以下，則胺基化合物於接合用膏之燒結時容易被去除，因此表現出低溫燒結性。 進而，胺基化合物之沸點為加熱步驟中之加熱溫度以上，亦可為使用時之燒結溫度以下。The boiling point of the amine compound may be 70°C or higher and 280°C or lower, 100°C or higher and 260°C or lower, or 120°C or higher and 240°C or lower. If the boiling point of the amine compound is within the above range, the obtained copper particles exhibit good sinterability. In addition, if the boiling point of the amine-based compound is 70° C. or higher, the resulting bonding paste will control the volatilization of the amine-based compound during the heating step, so that the uniformity in the reaction system can be maintained. If the boiling point of the amine-based compound is 280° C. or lower, the amine-based compound is easily removed during the sintering of the bonding paste, so it exhibits low-temperature sinterability. Furthermore, the boiling point of the amine compound is higher than the heating temperature in the heating step, and may be lower than the sintering temperature during use.

(還原性化合物) 本實施形態中使用之還原性化合物只要為將銅化合物還原，具有使金屬銅游離之還原力者即可，並無特別限定。進而，還原性化合物之沸點可為70℃以上，亦可為加熱步驟中之加熱溫度以上。進而，還原性化合物亦可為溶解於包含碳、氫及氧之下述有機溶劑中之化合物。(Reducing compound) The reducing compound used in the present embodiment is not particularly limited as long as it reduces the copper compound and has a reducing power to free metallic copper. Furthermore, the boiling point of the reducing compound may be 70°C or higher, or may be higher than the heating temperature in the heating step. Furthermore, the reducing compound may be a compound dissolved in the following organic solvent containing carbon, hydrogen, and oxygen.

作為此種還原性化合物，典型而言可列舉肼衍生物。作為肼衍生物，例如可列舉：肼一水合物、甲基肼、乙基肼、正丙基肼、異丙基肼、正丁基肼、異丁基肼、第二丁基肼、第三丁基肼、正戊基肼、異戊基肼、新戊基肼、第三戊基肼、正己基肼、異己基肼、正庚基肼、正辛基肼、正壬基肼、正癸基肼、正十一烷基肼、正十二烷基肼、環己基肼、苯基肼、4-甲基苯基肼、苄基肼、2-苯基乙基肼、2-肼基乙醇、乙醯肼等。該等可單獨使用亦可併用2種以上。Examples of such reducing compounds include hydrazine derivatives. Examples of hydrazine derivatives include hydrazine monohydrate, methylhydrazine, ethylhydrazine, n-propylhydrazine, isopropylhydrazine, n-butylhydrazine, isobutylhydrazine, second butylhydrazine, and third Butylhydrazine, n-amylhydrazine, isoamylhydrazine, neopentylhydrazine, third amylhydrazine, n-hexylhydrazine, isohexylhydrazine, n-heptylhydrazine, n-octylhydrazine, n-nonylhydrazine, n-decyl Hydrazine, n-undecylhydrazine, n-dodecylhydrazine, cyclohexylhydrazine, phenylhydrazine, 4-methylphenylhydrazine, benzylhydrazine, 2-phenylethylhydrazine, 2-hydrazinoethanol , Acetohydrazine, etc. These can be used alone or in combination of two or more.

本實施形態之銅粒子之製造方法亦可進而包含下述化合物。 (碳數1～12之羧酸) 碳數1～12之羧酸係用以控制所得之銅粒子之粒徑。羧酸只要具有羧基則並無特別限定。例如可列舉：甲酸、乙酸、丙酸、丁酸、戊酸、己酸、辛酸(caprylic acid)、辛酸(octylic acid)、壬酸、癸酸、油酸、硬脂酸、異硬脂酸等單羧酸；草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、二甘醇酸等二羧酸；苯甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、水楊酸、五倍子酸等芳香族羧酸；乙醇酸、乳酸、羥基丙二酸、蘋果酸、甘油酸、羥基丁酸、酒石酸、檸檬酸、異檸檬酸等羥酸等。就粒徑控制之容易性之觀點而言，可為甲酸、乙酸、丙酸、丁酸、戊酸、己酸、辛酸(caprylic acid)、辛酸(octylic acid)、壬酸、癸酸、油酸、硬脂酸、異硬脂酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、二甘醇酸，就燒結性之觀點而言，可為甲酸、乙酸、丙酸、丁酸、戊酸、己酸、辛酸(caprylic acid)、辛酸(octylic acid)、草酸、丙二酸、琥珀酸，亦可為己酸、辛酸(caprylic acid)、辛酸(octylic acid)、草酸、丙二酸。The method for producing copper particles of this embodiment may further include the following compounds. (Carbon number 1-12 carboxylic acid) The carboxylic acid having 1 to 12 carbon atoms is used to control the particle size of the obtained copper particles. The carboxylic acid is not particularly limited as long as it has a carboxyl group. For example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, octylic acid, nonanoic acid, capric acid, oleic acid, stearic acid, isostearic acid, etc. Monocarboxylic acids; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, diglycolic acid and other dicarboxylic acids; benzoic acid, ortho Phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid and other aromatic carboxylic acids; glycolic acid, lactic acid, hydroxymalonic acid, malic acid, glyceric acid, hydroxybutyric acid, tartaric acid, citric acid , Hydroxy acids such as isocitrate, etc. From the viewpoint of ease of particle size control, it can be formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, caprylic acid, octylic acid, nonanoic acid, capric acid, oleic acid , Stearic acid, isostearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, diglycolic acid, sintered From a sexual point of view, it can be formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, caprylic acid, octylic acid, oxalic acid, malonic acid, succinic acid, or hexanoic acid , Caprylic acid, octylic acid, oxalic acid, malonic acid.

(有機溶劑) 本實施形態中使用之有機溶劑只要為可用作不阻礙由混合上述各原料獲得之混合物生成之錯合物等之性質的反應溶劑者，則可無特別限定地使用。有機溶劑亦可為對上述還原性化合物表現出相溶性之醇。(Organic solvents) The organic solvent used in the present embodiment can be used without particular limitation as long as it can be used as a reaction solvent that does not hinder properties such as complex compounds formed by mixing the above-mentioned raw materials. The organic solvent may be an alcohol that exhibits compatibility with the reducing compound.

又，利用還原性化合物進行之銅離子之還原反應為放熱反應。因此，有機溶劑可為於還原反應中不揮發之有機溶劑。含有此種有機溶劑之接合膏可穩定地控制銅化合物-胺錯合物之分解引起之銅離子之生成、及所生成之銅離子之還原引起之金屬銅之析出。藉此，所生成之銅粒子之粒徑穩定。因此，有機溶劑之沸點可為70℃以上。進而，有機溶劑可包含碳、氫及氧。In addition, the reduction reaction of the copper ion by the reducing compound is an exothermic reaction. Therefore, the organic solvent may be an organic solvent that is not volatile in the reduction reaction. The bonding paste containing such an organic solvent can stably control the generation of copper ions caused by the decomposition of the copper compound-amine complex and the precipitation of metallic copper caused by the reduction of the generated copper ions. By this, the particle size of the generated copper particles is stabilized. Therefore, the boiling point of the organic solvent may be above 70°C. Furthermore, the organic solvent may contain carbon, hydrogen, and oxygen.

作為用作有機溶劑之上述醇，可列舉：1-丙醇、2-丙醇、丁醇、戊醇、己醇、庚醇、辛醇、乙二醇、1,3-丙二醇、1,2-丙二醇、丁基卡必醇、丁基卡必醇乙酸酯、乙基卡必醇、乙基卡必醇乙酸酯、二乙二醇二***、丁基溶纖劑等。該等可單獨使用亦可併用2種以上。Examples of the above alcohol used as an organic solvent include 1-propanol, 2-propanol, butanol, pentanol, hexanol, heptanol, octanol, ethylene glycol, 1,3-propanediol, 1,2 -Propylene glycol, butyl carbitol, butyl carbitol acetate, ethyl carbitol, ethyl carbitol acetate, diethylene glycol diethyl ether, butyl cellosolve, etc. These can be used alone or in combination of two or more.

(混合物之形成) 關於本實施形態之銅粒子之製造方法，首先於反應容器中收容有機溶劑，於該有機溶劑中將上述說明之原料化合物即銅化合物、胺化合物、及還原性化合物進行混合。該等化合物之混合順序並無特別限定，可以任何順序混合上述化合物。(Formation of mixture) Regarding the method for producing copper particles of this embodiment, first, an organic solvent is contained in a reaction vessel, and the copper compound, the amine compound, and the reducing compound, which are the raw material compounds described above, are mixed in the organic solvent. The mixing order of these compounds is not particularly limited, and the above compounds may be mixed in any order.

再者，於有效率地形成銅化合物與胺化合物之錯合物之情形時，可先將銅化合物與胺化合物混合，預先於0～110℃下混合5～30分鐘左右，進而，添加還原性化合物並進行混合。In addition, when the complex compound of the copper compound and the amine compound is efficiently formed, the copper compound and the amine compound can be mixed first, and the mixture is pre-mixed at 0 to 110°C for about 5 to 30 minutes. Compound and mix.

於上述混合時，各化合物之使用量可為相對於銅化合物1 mol，胺化合物0.1～10 mol、還原性化合物0.5～5 mol，亦可為胺化合物1～10 mol、還原性化合物1～3 mol。此時，有機溶劑只要為可使各成分充分反應之量即可，例如可使用50～2000 mL左右。In the above mixing, the amount of each compound used may be 0.1 to 10 mol of the amine compound, 0.5 to 5 mol of the reducing compound, 1 to 10 mol of the amine compound, and 1 to 3 of the reducing compound relative to 1 mol of the copper compound. mol. In this case, the organic solvent should just be an amount which can fully react each component, for example, about 50-2000 mL can be used.

(混合物之加熱) 關於本實施形態之銅粒子之製造方法，其次，將上述混合所得之混合物充分地加熱，使銅化合物之還原反應進行。藉由該加熱，可消除未反應之銅化合物，使金屬銅析出、成長，從而可形成銅粒子。(Heating of the mixture) Regarding the method for producing copper particles of the present embodiment, next, the mixture obtained by the above mixing is sufficiently heated to allow the reduction reaction of the copper compound to proceed. By this heating, unreacted copper compounds can be eliminated, and metallic copper can be precipitated and grown, thereby forming copper particles.

此時，胺化合物具有附著於銅粒子之表面，控制成長從而防止粒子粗大化的作用。At this time, the amine compound has a function of attaching to the surface of the copper particles, controlling growth, and preventing the particles from coarsening.

上述混合物之加熱溫度為可將銅化合物熱分解及還原而生成銅粒子之溫度即可。上述加熱溫度可為70～150℃下，亦可為80～120℃。又，加熱溫度亦可低於原料化合物及有機溶劑之沸點。若加熱溫度處於上述範圍內，則可有效率地生成銅粒子。進而，藉由除使用胺化合物以外還併用羧酸，從而控制該等揮發成分之揮發。The heating temperature of the above mixture may be a temperature at which the copper compound can be thermally decomposed and reduced to produce copper particles. The heating temperature may be 70 to 150°C or 80 to 120°C. In addition, the heating temperature may be lower than the boiling point of the raw material compound and the organic solvent. If the heating temperature is within the above range, copper particles can be efficiently produced. Furthermore, by using a carboxylic acid together with an amine compound, the volatilization of these volatile components is controlled.

藉由將加熱溫度設為70℃以上，使銅化合物之熱分解進行。藉由將加熱溫度設為150℃以下，控制胺化合物之揮發，因此得以保持反應系統中之均勻性。By setting the heating temperature to 70° C. or higher, the thermal decomposition of the copper compound proceeds. By setting the heating temperature to 150° C. or lower, the volatilization of the amine compound is controlled, so that the uniformity in the reaction system can be maintained.

如此，可獲得銅粒子分散液。再者，本實施形態之接合膏之製造方法亦可於所得之銅粒子分散液中加入下述洗淨溶劑，將該銅粒子分散液中含有之銅粒子之濃度調整為1～50質量%。In this way, a copper particle dispersion liquid can be obtained. In addition, in the method for manufacturing the bonding paste of this embodiment, the following cleaning solvent may be added to the obtained copper particle dispersion liquid, and the concentration of the copper particles contained in the copper particle dispersion liquid may be adjusted to 1 to 50% by mass.

[洗淨步驟] 於本步驟中，於密閉系統中對上述步驟所得之銅粒子分散液進行溶劑洗淨，將銅粒子自上述銅粒子分散液中固液分離。 銀微粒子之製造時通常使用之藉由離心分離等進行之分離作業無法連續地進行溶劑置換，於大氣中進行與洗淨溶劑之攪拌作業。根據本發明者等人之見解，所合成之銅粒子之粒子表面容易被氧化，尤其擔憂於大氣中與洗淨溶劑攪拌時，混入至銅粒子分散液之氧與合成之銅粒子接觸會導致銅粒子表面之氧化進展。與此相對，於本步驟中，藉由於密閉系統中對銅粒子分散液進行溶劑洗淨，可降低銅粒子之表面氧化。[Washing steps] In this step, the copper particle dispersion liquid obtained in the above step is solvent-washed in a closed system, and the copper particles are solid-liquid separated from the copper particle dispersion liquid. The separation operation by centrifugal separation or the like, which is generally used in the production of silver fine particles, cannot continuously replace the solvent, and the stirring operation with the cleaning solvent is performed in the atmosphere. According to the findings of the present inventors and others, the surface of the synthesized copper particles is easily oxidized, and it is particularly worried that the oxygen mixed into the copper particle dispersion and the synthesized copper particles may cause copper when stirred with the cleaning solvent in the atmosphere The oxidation of the particle surface progresses. On the other hand, in this step, by performing solvent cleaning on the copper particle dispersion liquid in a closed system, the surface oxidation of the copper particles can be reduced.

又，本洗淨步驟亦可為連續之溶劑置換及洗淨方法。由本實施形態之銅粒子之製造方法所得之銅粒子藉由連續地進行處理，降低銅粒子之表面氧化。 具體之溶劑置換洗淨方法為：將含有1～50質量%之銅粒子之上述銅粒子分散液不進行再成漿(reslurry)而以流量5～1500 kg/hr・m² 、壓力0.03～1.0 MPa之條件供給至過濾膜，進而，以上述條件連續地對該過濾膜供給洗淨溶劑。藉由本實施形態之銅粒子之製造方法所得之銅粒子係以此種方式對銅粒子分散液以流量5～1500 kg/hr・m² 供給洗淨溶劑，以0.03～1.0 MPa進行加壓，於密閉系統中進行銅粒子分散液與洗淨用劑之置換，藉此於不存在氧之狀態下洗淨銅粒子，因此可降低該銅粒子之表面氧化。 又，就此種觀點而言，上述流量可為10～1000 kg/hr・m² ，可為15～500 kg/hr・m² ，亦可為20～200 kg/hr・m² 。上述壓力可為0.1～0.8 MPa，亦可為0.2～0.6 MPa。 再者，上述溶劑置換及洗淨亦可於進行下述減壓乾燥、離心分離等後再實施。In addition, this washing step can also be a continuous solvent replacement and washing method. The copper particles obtained by the method for producing copper particles of this embodiment are continuously processed to reduce the surface oxidation of the copper particles. A specific solvent replacement cleaning method is to disperse the above copper particle dispersion containing 1 to 50% by mass of copper particles without reslurry at a flow rate of 5 to 1500 kg/hr·m ² and a pressure of 0.03 to 1.0 The filter membrane is supplied under the condition of MPa, and further, the cleaning solvent is continuously supplied to the filter membrane under the above conditions. The copper particles obtained by the method for producing copper particles of this embodiment are supplied with a cleaning solvent at a flow rate of 5 to 1500 kg/hr·m ² to the copper particle dispersion liquid in this way, and pressurized at 0.03 to 1.0 MPa. The replacement of the copper particle dispersion liquid and the cleaning agent is performed in a closed system, whereby the copper particles are washed in the absence of oxygen, so the surface oxidation of the copper particles can be reduced. From this viewpoint, the flow rate may be 10 to 1000 kg/hr·m ² , 15 to 500 kg/hr·m ² , or 20 to 200 kg/hr·m ² . The above pressure may be 0.1 to 0.8 MPa or 0.2 to 0.6 MPa. In addition, the above-mentioned solvent replacement and washing may be carried out after performing the following reduced-pressure drying, centrifugal separation, and the like.

洗淨溶劑只要為不對所生成之銅粒子之保護基造成損傷者，則可無特別限定地使用。具體而言，可列舉水；乙醇、甲醇等醇類；二乙二醇等醇類；及其他溶劑等。洗淨溶劑可供給濾室容積3～7倍之量。The cleaning solvent can be used without particular limitation as long as it does not damage the protective group of the generated copper particles. Specific examples include water; alcohols such as ethanol and methanol; alcohols such as diethylene glycol; and other solvents. The cleaning solvent can be supplied to the volume of the filter chamber 3-7 times.

溶劑置換裝置只要可密閉地進行溶劑洗淨則並無特別限定，例如可為旋轉型膜分離裝置，具體而言可列舉水平濾板式過濾機(三菱化工機(股)製造)。 藉由對過濾分離之固形物進行例如減壓乾燥、離心分離等，可獲得銅粒子。The solvent replacement device is not particularly limited as long as the solvent can be cleaned in a sealed manner. For example, it may be a rotary membrane separation device, and specifically, a horizontal filter plate filter (manufactured by Mitsubishi Chemical Machinery Co., Ltd.) may be mentioned. Copper particles can be obtained by performing, for example, reduced-pressure drying and centrifugal separation on the solid matter separated by filtration.

(銅粒子之形狀、尺寸) 推測藉由本實施形態之銅粒子之製造方法所獲得之銅粒子係銅化合物於胺化合物中被還原性化合物還原，溶出之銅原子凝聚，經過核形成、核成長，而形成由胺化合物被覆之銅粒子。因此，藉由適當選擇使用之銅化合物、胺化合物、還原性化合物之種類、反應溫度，可使銅原子之供給速度、或胺化合物之吸附能力變化，從而可獲得任意形狀及尺寸之銅粒子。(Shape and size of copper particles) It is speculated that the copper particles obtained by the method for producing copper particles of the present embodiment are copper compounds which are reduced by a reducing compound in an amine compound, and the eluted copper atoms are aggregated to form a copper coated with an amine compound through nucleation and growth particle. Therefore, by appropriately selecting the type of copper compound, amine compound, and reducing compound used, and the reaction temperature, the supply rate of copper atoms or the adsorption capacity of the amine compound can be changed to obtain copper particles of any shape and size.

藉由本實施形態之銅粒子之製造方法所獲得之銅粒子可實現未達300℃之低溫焙燒。使用其之接合用膏之接合層內部與填角部之燒結速度及燒結度不存在差，可獲得接合可靠性較高之接合層。The copper particles obtained by the method for producing copper particles of this embodiment can achieve low-temperature firing up to 300°C. There is no difference in the sintering speed and sintering degree between the inside of the bonding layer using the bonding paste and the fillet, and a bonding layer with high bonding reliability can be obtained.

上述銅粒子之平均粒徑就接合層之緻密性之觀點而言，可為1～1000 nm，可為20～800 nm，亦可為30～500 nm。 再者，上述銅粒子之平均粒徑係作為基於掃描電子顯微鏡(例如日本電子(股)製造，商品名：JSM-7600F；SEM)之觀察圖像所任意選擇之10個銅粒子(n＝10)之平均值算出。再者，平均值為算術平均值，於該算出時亦可使用10個以上銅粒子。The average particle diameter of the copper particles may be 1 to 1000 nm, 20 to 800 nm, or 30 to 500 nm from the viewpoint of the compactness of the bonding layer. In addition, the average particle diameter of the above copper particles is 10 copper particles (n=10) arbitrarily selected as an observation image based on a scanning electron microscope (for example, manufactured by JEOL Ltd., trade name: JSM-7600F; SEM) ) The average value is calculated. In addition, the average value is an arithmetic average value, and 10 or more copper particles can also be used for this calculation.

＜接合用膏＞ 本實施形態之接合用膏包含藉由上述銅粒子之製造方法所獲得之銅粒子。本實施形態之接合用膏可實現無加壓之接合，接著性優異。又，本實施形態之接合用膏之接合層內部與填角部之燒結速度及燒結度均勻，接合特性良好。 因此，本實施形態之接合用膏可用作元件接著用晶粒接合膏或散熱構件接著用材料。<Paste for joining> The bonding paste of this embodiment includes the copper particles obtained by the method for producing copper particles described above. The bonding paste of this embodiment can realize bonding without pressure, and is excellent in adhesiveness. In addition, the sintering speed and sintering degree of the bonding layer inside the bonding layer and the fillet portion of this embodiment are uniform, and the bonding characteristics are good. Therefore, the bonding paste of this embodiment can be used as a die bonding paste for element bonding or as a material for bonding heat dissipation members.

本實施形態之接合用膏亦可併用2種以上之平均粒徑不同之銅粒子。例如，相對於第一銅粒子之平均粒徑，具有較該第一銅粒子更大平均粒徑之第二銅粒子之平均粒徑可為2～10倍左右。又，相對於第一銅粒子之調配量，第二銅粒子之調配量可為1.5～10倍左右。In the bonding paste of this embodiment, two or more types of copper particles having different average particle diameters may be used in combination. For example, the average particle size of the second copper particles having a larger average particle size than the first copper particles may be about 2 to 10 times the average particle size of the first copper particles. In addition, the amount of the second copper particles may be about 1.5 to 10 times the amount of the first copper particles.

本實施形態之接合用膏除包含上述銅粒子以外，亦可包含粒徑大於上述銅粒子之大粒徑銅粒子、熱硬化性樹脂、有機溶劑、及其他添加劑。藉此，可緩和銅粒子之燒結收縮之影響，形成可靠性更高之接合層。In addition to the copper particles, the bonding paste of the present embodiment may include large-diameter copper particles having a larger particle size than the copper particles, a thermosetting resin, an organic solvent, and other additives. By this, the influence of the sintering shrinkage of the copper particles can be relaxed, and a more reliable bonding layer can be formed.

(大粒徑銅粒子) 大粒徑銅粒子之平均粒徑可大於1 μm且為30 μm以下，亦可為2～20 μm。又，形狀並無特別限定，可使用球狀、板型、薄片狀、鱗片狀、樹枝狀、棒狀、線狀等。 再者，上述大粒徑銅粒子之平均粒徑可使用雷射繞射散射式粒度分佈測定裝置等進行測定。(Large particle size copper particles) The average particle size of the large-diameter copper particles may be greater than 1 μm and less than 30 μm, or may be 2-20 μm. In addition, the shape is not particularly limited, and a spherical shape, a plate shape, a flake shape, a scale shape, a dendritic shape, a rod shape, a linear shape, or the like can be used. In addition, the average particle diameter of the above-mentioned large-diameter copper particles can be measured using a laser diffraction scattering type particle size distribution measuring device or the like.

上述大粒徑銅粒子可使用經滑材、防銹劑處理者。作為此種處理，典型者為利用羧酸化合物進行之處理。作為羧酸化合物，例如可列舉：甲酸、乙酸、丙酸、丁酸、戊酸、己酸、辛酸(caprylic acid)、辛酸(octylic acid)、壬酸、癸酸、棕櫚酸、油酸、硬脂酸、異硬脂酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、二甘醇酸、苯甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、水楊酸、五倍子酸、乙醇酸、乳酸、羥基丙二酸、蘋果酸、甘油酸、羥基丁酸、酒石酸、檸檬酸、異檸檬酸等。羧酸化合物就與銅粒子之燒結性之觀點而言，可為甲酸、乙酸、丙酸、丁酸、戊酸、己酸、辛酸(caprylic acid)、辛酸(octylic acid)、壬酸、癸酸、棕櫚酸、油酸、硬脂酸、異硬脂酸、草酸、丙二酸、琥珀酸、戊二酸。又，羧酸化合物就銅粒子之分散性及耐氧化性之觀點而言，可為己酸、辛酸(caprylic acid)、辛酸(octylic acid)、壬酸、癸酸、丙二酸、琥珀酸、戊二酸。The above-mentioned large-diameter copper particles can be treated with a sliding material or a rust inhibitor. As such treatment, a treatment using a carboxylic acid compound is typical. Examples of the carboxylic acid compound include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, octylic acid, nonanoic acid, capric acid, palmitic acid, oleic acid, and hard acid. Fatty acid, isostearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, diglycolic acid, benzoic acid, ortho Phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, glycolic acid, lactic acid, hydroxymalonic acid, malic acid, glyceric acid, hydroxybutyric acid, tartaric acid, citric acid, isocitric acid, etc. . The carboxylic acid compound can be formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, octylic acid, nonanoic acid, capric acid from the viewpoint of sinterability with copper particles , Palmitic acid, oleic acid, stearic acid, isostearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid. In addition, the carboxylic acid compound can be hexanoic acid, caprylic acid, octylic acid, nonanoic acid, capric acid, malonic acid, succinic acid, from the viewpoint of the dispersibility and oxidation resistance of copper particles. Glutaric acid.

(熱硬化性樹脂) 熱硬化性樹脂只要為一般用於接著劑用途之熱硬化性樹脂，則可無特別限定地使用。熱硬化性樹脂可為液狀樹脂，亦可為於室溫(25℃)下為液狀之樹脂。作為上述熱硬化性樹脂，例如可列舉：氰酸酯樹脂、環氧樹脂、自由基聚合性丙烯酸系樹脂、馬來醯亞胺樹脂等。該等可單獨使用亦可併用2種以上。 藉由使本實施形態之接合用膏包含熱硬化性樹脂，可製成具有適當黏度之接著材料(膏)。又，若本實施形態之接合用膏包含熱硬化性樹脂，則藉由其硬化時之反應熱而使接合用膏之溫度上升，促進銅粒子之燒結性。(Thermosetting resin) The thermosetting resin can be used without particular limitation as long as it is a thermosetting resin generally used for adhesives. The thermosetting resin may be a liquid resin or a liquid resin at room temperature (25°C). Examples of the thermosetting resin include cyanate resin, epoxy resin, radical polymerizable acrylic resin, and maleimide resin. These can be used alone or in combination of two or more. By including the thermosetting resin in the bonding paste of this embodiment, an adhesive material (paste) having an appropriate viscosity can be produced. In addition, if the bonding paste of the present embodiment contains a thermosetting resin, the temperature of the bonding paste is increased by the reaction heat at the time of curing, and the sinterability of the copper particles is promoted.

氰酸酯樹脂為於分子內具有-NCO基之化合物，為藉由加熱使-NCO基反應，藉此形成三維網狀結構而硬化之樹脂。具體例示，可列舉：1,3-二氰酸酯基苯、1,4-二氰酸酯基苯、1,3,5-三氰酸酯基苯、1,3-二氰酸酯基萘、1,4-二氰酸酯基萘、1,6-二氰酸酯基萘、1,8-二氰酸酯基萘、2,6-二氰酸酯基萘、2,7-二氰酸酯基萘、1,3,6-三氰酸酯基萘、4,4'-二氰酸酯基聯苯、雙(4-氰酸酯基苯基)甲烷、雙(3,5-二甲基-4-氰酸酯基苯基)甲烷、2,2-雙(4-氰酸酯基苯基)丙烷、2,2-雙(3,5-二溴-4-氰酸酯基苯基)丙烷、雙(4-氰酸酯基苯基)醚、雙(4-氰酸酯基苯基)硫醚、雙(4-氰酸酯基苯基)碸、亞磷酸三(4-氰酸酯基苯基)酯、磷酸三(4-氰酸酯基苯基)酯、及藉由酚醛清漆樹脂與鹵化氰之反應所得之氰酸酯類等。氰酸酯樹脂亦可使用藉由使上述多官能氰酸酯樹脂之氰酸酯基三聚化而形成之具有三𠯤環之預聚物。該預聚物可藉由以例如無機酸、路易斯酸等酸、醇鈉、三級胺類等鹼、碳酸鈉等鹽類作為觸媒，使上述多官能氰酸酯樹脂單體聚合而獲得。The cyanate resin is a compound having a -NCO group in the molecule, and is a resin hardened by reacting the -NCO group by heating, thereby forming a three-dimensional network structure. Specific examples include: 1,3-dicyanate-based benzene, 1,4-dicyanate-based benzene, 1,3,5-tricyanate-based benzene, and 1,3-dicyanate-based Naphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7- Dicyanate-based naphthalene, 1,3,6-tricyanate-based naphthalene, 4,4'-dicyanate-based biphenyl, bis(4-cyanate-based phenyl)methane, bis(3, 5-dimethyl-4-cyanoylphenyl) methane, 2,2-bis(4-cyanoylphenyl)propane, 2,2-bis(3,5-dibromo-4-cyano Ester-based phenyl) propane, bis(4-cyanate-based phenyl) ether, bis(4-cyanate-based phenyl) sulfide, bis(4-cyanate-based phenyl) sulfite, phosphorous acid Tris (4-cyanate phenyl) ester, tris (4-cyanate phenyl) phosphate, cyanate esters obtained by the reaction of novolak resin and cyanogen halide, and the like. As the cyanate ester resin, a prepolymer having a triple ring formed by trimerizing the cyanate group of the above multifunctional cyanate ester resin can also be used. This prepolymer can be obtained by polymerizing the above-mentioned polyfunctional cyanate resin monomer by using, for example, acids such as inorganic acids and Lewis acids, alkalis such as sodium alkoxides and tertiary amines, and salts such as sodium carbonate as catalysts.

作為氰酸酯樹脂之硬化促進劑，可使用一般公知者。例如可列舉：辛酸鋅、辛酸錫、環烷酸鈷、環烷酸鋅、乙醯丙酮鐵等有機金屬錯合物；氯化鋁、氯化錫、氯化鋅等金屬鹽；三乙基胺、二甲基苄基胺等胺類，但並不限定於該等。該等硬化促進劑可使用1種或混合2種以上使用。As the curing accelerator of the cyanate resin, generally known ones can be used. For example, organic metal complexes such as zinc octoate, tin octoate, cobalt naphthenate, zinc naphthenate, and iron acetone; metal salts such as aluminum chloride, tin chloride, and zinc chloride; triethylamine , Dimethyl benzylamine and other amines, but not limited to these. These hardening accelerators can be used alone or in combination of two or more.

環氧樹脂為於分子內具有1個以上縮水甘油基之化合物，且係藉由加熱使縮水甘油基反應，藉此形成三維網狀結構而硬化之樹脂。縮水甘油基亦可於1分子內包含2個以上。其原因在於：僅具有1個縮水甘油基之化合物即便進行反應亦無法表現出充分之硬化物特性。於1分子內包含2個以上縮水甘油基之化合物可使具有2個以上羥基之化合物環氧化而獲得。作為此種化合物，可列舉：使雙酚A、雙酚F、聯苯酚等雙酚化合物或該等之衍生物；氫化雙酚A、氫化雙酚F、氫化聯苯酚、環己二醇、環己烷二甲醇、環己烷二乙醇等具有脂環結構之二醇或該等之衍生物；丁二醇、己二醇、辛二醇、壬二醇、癸二醇等脂肪族二醇或該等之衍生物等環氧化而成之2官能者；使具有三羥基苯基甲烷骨架、胺基苯酚骨架之化合物等環氧化而成之3官能者；使苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、苯酚芳烷基樹脂、聯苯芳烷基樹脂、萘酚芳烷基樹脂等環氧化而成之多官能者等；但並不限定於該等。又，為了使接合用膏於室溫(25℃)下為膏狀，上述環氧樹脂可為單獨成分或以混合物之形式於室溫(25℃)下為液狀者。亦可如通常般使用反應性稀釋劑。作為反應性稀釋劑，可列舉苯基縮水甘油醚、甲苯酚基縮水甘油醚等單官能之芳香族縮水甘油醚類、脂肪族縮水甘油醚類等。The epoxy resin is a compound having one or more glycidyl groups in the molecule, and is a resin that hardens by reacting the glycidyl group by heating to form a three-dimensional network structure. The glycidyl group may contain two or more in one molecule. The reason for this is that a compound having only one glycidyl group cannot exhibit sufficient cured product characteristics even if it reacts. A compound containing two or more glycidyl groups in one molecule can be obtained by epoxidizing a compound having two or more hydroxyl groups. Examples of such compounds include bisphenol compounds such as bisphenol A, bisphenol F, and biphenol, or derivatives thereof; hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated biphenol, cyclohexanediol, cyclic Diols with alicyclic structure such as hexanedimethanol and cyclohexanediethanol or derivatives thereof; aliphatic diols such as butanediol, hexanediol, octanediol, nonanediol and decanediol or Epoxidized 2-functional ones of these derivatives; 3-functional epoxidized compounds with trihydroxyphenylmethane skeleton, aminophenol skeleton etc.; phenol novolak resin, cresol novolak Polyfunctional ones formed by epoxidation of resins, phenol aralkyl resins, biphenyl aralkyl resins, naphthol aralkyl resins, etc.; but not limited to these. In addition, in order to make the bonding paste paste-like at room temperature (25°C), the epoxy resin may be a single component or a mixture at room temperature (25°C) in the form of a liquid. A reactive diluent can also be used as usual. Examples of the reactive diluent include monofunctional aromatic glycidyl ethers such as phenyl glycidyl ether and cresyl glycidyl ether, and aliphatic glycidyl ethers.

此時，為了使環氧樹脂硬化而使用硬化劑，作為環氧樹脂之硬化劑，例如可列舉：脂肪族胺、芳香族胺、雙氰胺、二醯肼化合物、酸酐、酚樹脂等。作為二醯肼化合物，可列舉：己二酸二醯肼、十二酸二醯肼、間苯二甲酸二醯肼、對羥基苯甲酸二醯肼等羧酸二醯肼等，作為酸酐，可列舉鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、內亞甲基四氫鄰苯二甲酸酐、十二烯基琥珀酸酐、馬來酸酐與聚丁二烯之反應物、馬來酸酐與苯乙烯之共聚物等。In this case, a hardener is used to harden the epoxy resin. Examples of the hardener for the epoxy resin include aliphatic amines, aromatic amines, dicyandiamide, dihydrazine compounds, acid anhydrides, and phenol resins. Examples of the dihydrazide compound include adipic acid dihydrazide, dodecanoic acid dihydrazide, isophthalic acid dihydrazide, p-hydroxybenzoic acid dihydrazide, etc. As the acid anhydride, may be List phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, internal methylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, maleic anhydride and polybutadiene Reactant, copolymer of maleic anhydride and styrene, etc.

進而，為了促進硬化，可調配硬化促進劑，作為環氧樹脂之硬化促進劑，可列舉：咪唑類、三苯基膦或四苯基膦及其等之鹽類、二氮雜雙環十一烯等胺系化合物及其鹽類等。硬化促進劑可為2-甲基咪唑、2-乙基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、2-苯基-4,5-二羥基甲基咪唑、2-C₁₁ H₂₃ -咪唑、2-甲基咪唑與2,4-二胺基-6-乙烯基三𠯤之加成物等咪唑化合物。硬化促進劑亦可為熔點180℃以上之咪唑化合物。Furthermore, in order to promote hardening, a hardening accelerator may be formulated. As the hardening accelerator of epoxy resin, imidazoles, triphenylphosphine, tetraphenylphosphine and salts thereof, diazabicycloundecene, etc. may be mentioned. Such as amine compounds and their salts. Hardening accelerator can be 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole , 2-phenyl-4,5-dihydroxymethylimidazole, 2-C ₁₁ H ₂₃ -imidazole, adducts of 2-methylimidazole and 2,4-diamino-6-vinyl triamine, etc. Imidazole compounds. The hardening accelerator may also be an imidazole compound with a melting point of 180°C or higher.

自由基聚合性之丙烯酸樹脂係於分子內具有(甲基)丙烯醯基之化合物，且係藉由使(甲基)丙烯醯基反應而形成三維網狀結構從而硬化之樹脂。(甲基)丙烯醯基亦可於分子內包含1個以上。The radically polymerizable acrylic resin is a compound having a (meth)acryloyl group in the molecule, and is a resin hardened by reacting the (meth)acryloyl group to form a three-dimensional network structure. The (meth)acryloyl group may contain one or more in the molecule.

此處，作為丙烯酸系樹脂，例如可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、1,2-環己二醇單(甲基)丙烯酸酯、1,3-環己二醇單(甲基)丙烯酸酯、1,4-環己二醇單(甲基)丙烯酸酯、1,2-環己烷二甲醇單(甲基)丙烯酸酯、1,3-環己烷二甲醇單(甲基)丙烯酸酯、1,4-環己烷二甲醇單(甲基)丙烯酸酯、1,2-環己烷二乙醇單(甲基)丙烯酸酯、1,3-環己烷二乙醇單(甲基)丙烯酸酯、1,4-環己烷二乙醇單(甲基)丙烯酸酯、甘油單(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、三羥甲基丙烷單(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、季戊四醇單(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、新戊二醇單(甲基)丙烯酸酯等具有羥基之(甲基)丙烯酸酯及使該等具有羥基之(甲基)丙烯酸酯與二羧酸或其衍生物反應所獲得之具有羧基之(甲基)丙烯酸酯等。作為此處可使用之二羧酸，例如可列舉草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、馬來酸、富馬酸、鄰苯二甲酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸及該等之衍生物等。Here, examples of the acrylic resin include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth)acrylic acid. 2-hydroxybutyl ester, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,2-cyclohexanediol mono(meth)acrylate, 1,3-cyclohexyl Glycol mono(meth)acrylate, 1,4-cyclohexanediol mono(meth)acrylate, 1,2-cyclohexanedimethanol mono(meth)acrylate, 1,3-cyclohexane Dimethanol mono(meth)acrylate, 1,4-cyclohexane dimethanol mono(meth)acrylate, 1,2-cyclohexanediethanol mono(meth)acrylate, 1,3-cyclohexane Alkyl diethanol mono (meth) acrylate, 1,4-cyclohexane diethanol mono (meth) acrylate, glycerol mono (meth) acrylate, glycerol di (meth) acrylate, trimethylol Propane mono(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, new Phenylene glycol mono(meth)acrylates and other (meth)acrylates with hydroxyl groups and the (meth)acrylates with carboxyl groups obtained by reacting these (meth)acrylates with hydroxyl groups with dicarboxylic acids or their derivatives Base) acrylate, etc. Examples of the dicarboxylic acid that can be used here include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, Fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and their derivatives, etc.

又，尤其作為丙烯酸系樹脂，可列舉分子量為100～10000之聚醚、聚酯、聚碳酸酯、聚(甲基)丙烯酸酯且具有(甲基)丙烯醯基之化合物、具有羥基之(甲基)丙烯酸酯、具有羥基之(甲基)丙烯醯胺等。In addition, as the acrylic resin, polyethers having a molecular weight of 100 to 10,000, polyesters, polycarbonates, poly(meth)acrylates, compounds having a (meth)acryloyl group, and hydroxyl groups containing (meth) Group) acrylate, (meth)acrylamide with hydroxyl group, etc.

馬來醯亞胺樹脂為於1分子內包含1個以上馬來醯亞胺基之化合物，且係藉由加熱使馬來醯亞胺基反應藉此形成三維網狀結構而硬化之樹脂。例如可列舉：N,N'-(4,4'-二苯基甲烷)雙馬來醯亞胺、雙(3-乙基-5-甲基-4-馬來醯亞胺苯基)甲烷、2,2-雙[4-(4-馬來醯亞胺苯氧基)苯基]丙烷等雙馬來醯亞胺樹脂。馬來醯亞胺樹脂為藉由二聚酸二胺與馬來酸酐之反應所獲得之化合物、藉由馬來醯亞胺乙酸、馬來醯亞胺己酸等馬來醯亞胺化胺基酸與多元醇之反應所獲得之化合物。馬來醯亞胺化胺基酸係藉由使馬來酸酐與胺基乙酸或胺基己酸反應而獲得。作為多元醇，可為聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇、聚(甲基)丙烯酸酯多元醇，亦可為不包含芳香族環者。The maleimide resin is a compound containing more than one maleimide group in one molecule, and is a resin hardened by reacting the maleimide group by heating to form a three-dimensional network structure. For example, N,N'-(4,4'-diphenylmethane) bismaleimide, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane , 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane and other bismaleimide resins. Maleimide resin is a compound obtained by the reaction of a dimer acid diamine and maleic anhydride, and a maleimide imidized amino group such as maleimide acetic acid, maleimide caproic acid, etc. A compound obtained by the reaction of an acid and a polyol. Maleimide imidized amino acid is obtained by reacting maleic anhydride with aminoacetic acid or aminohexanoic acid. The polyol may be polyether polyol, polyester polyol, polycarbonate polyol, poly(meth)acrylate polyol, or may not contain an aromatic ring.

此處，於調配熱硬化性樹脂之情形時，將上述銅粒子及大粒徑銅粒子之總量設為100質量份時，調配1～20質量份。若熱硬化性樹脂為1質量份以上，則可充分獲得熱硬化性樹脂帶來之接著效果，若熱硬化性樹脂為20質量份以下，則可於不使銅成分之比率降低之情況下充分確保高導熱性，從而可提昇散熱性。又，不使有機成分過多，抑制光及熱造成之劣化，其結果，可提高發光裝置之壽命。藉由設為此種調配範圍，可利用熱硬化性樹脂之接著性能，減少銅粒子及/或大粒徑銅粒子彼此之接觸，且可容易地保持接著層整體之機械強度。Here, when the thermosetting resin is prepared, when the total amount of the copper particles and the large-diameter copper particles is 100 parts by mass, 1 to 20 parts by mass is prepared. If the thermosetting resin is 1 part by mass or more, the adhesive effect by the thermosetting resin can be sufficiently obtained, and if the thermosetting resin is 20 parts by mass or less, it is sufficient without reducing the ratio of the copper component Ensure high thermal conductivity, which can improve heat dissipation. In addition, the organic components are not excessive, and deterioration due to light and heat is suppressed. As a result, the lifespan of the light emitting device can be increased. By setting it as such a formulation range, the adhesive properties of the thermosetting resin can be utilized to reduce contact between copper particles and/or large-diameter copper particles, and the mechanical strength of the entire adhesive layer can be easily maintained.

(有機溶劑) 有機溶劑只要為作為還原劑發揮功能之溶劑即可，可使用公知之溶劑。 作為上述有機溶劑，可為醇，可列舉例如脂肪族多元醇。作為脂肪族多元醇，例如可列舉：乙二醇、二乙二醇、丙二醇、二丙二醇、1,4-丁二醇、甘油、聚乙二醇等醇類等。該等有機溶劑可單獨使用亦可併用2種以上。(Organic solvents) The organic solvent should just be a solvent which functions as a reducing agent, and a well-known solvent can be used. The organic solvent may be an alcohol, and examples thereof include aliphatic polyhydric alcohols. Examples of the aliphatic polyhydric alcohol include alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, glycerin, and polyethylene glycol. These organic solvents may be used alone or in combination of two or more.

醇藉由膏硬化(燒結)時之熱處理而成為高溫，使還原力增大。銅粒子中部分存在之氧化銅及金屬基板上之氧化金屬(例如氧化銅)被醇還原，成為純金屬。其結果，接合用膏更緻密且導電性較高，形成與基板之密接性較高之硬化膜。又，藉由夾於半導體元件與金屬基板之間，於膏硬化時之熱處理中(沸點以上之膏硬化溫度)一部分醇成為回流狀態，從而更有效率地還原氧化金屬。The alcohol becomes high temperature by heat treatment when the paste is hardened (sintered), which increases the reducing power. The copper oxide partially present in the copper particles and the metal oxide on the metal substrate (such as copper oxide) are reduced by the alcohol to become a pure metal. As a result, the bonding paste is denser and has higher conductivity, and a cured film with higher adhesion to the substrate is formed. In addition, by sandwiching between the semiconductor element and the metal substrate, part of the alcohol in the heat treatment during paste curing (the paste curing temperature above the boiling point) becomes a reflow state, thereby reducing the metal oxide more efficiently.

有機溶劑之沸點具體而言可為100～300℃，亦可為150～290℃。若沸點為100℃以上，則即便在常溫下揮發性亦不會過高，可控制因分散介質之揮發導致還原能力降低，獲得穩定之接著強度。又，若沸點為300℃以下，則容易產生硬化膜(導電膜)之燒結，可形成緻密性優異之膜。又，可控制有機溶劑不揮發而殘留於膜中。The boiling point of the organic solvent may specifically be 100 to 300°C or 150 to 290°C. If the boiling point is above 100°C, the volatility will not be too high even at normal temperature, and the reduction of the reducing ability due to the volatilization of the dispersion medium can be controlled to obtain a stable adhesive strength. In addition, if the boiling point is 300°C or lower, sintering of the cured film (conductive film) is likely to occur, and a film with excellent compactness can be formed. In addition, the organic solvent can be controlled to remain in the film without volatilization.

於調配有機溶劑之情形時，將上述銅粒子及大粒徑銅粒子之總量設為100質量份時，其調配量可為7～20質量份。若為7質量份以上，則黏度不會變得過高，可提昇作業性，若為20質量份以下，則控制黏度降低，控制膏中之銅下沈，從而可提高可靠性。In the case of blending organic solvents, when the total amount of the copper particles and large-diameter copper particles is 100 parts by mass, the blending amount may be 7-20 parts by mass. If it is more than 7 parts by mass, the viscosity will not become too high, and the workability will be improved. If it is less than 20 parts by mass, the viscosity will be reduced, and the copper in the paste will be controlled to sink, thereby improving reliability.

本實施形態之接合用膏中除以上各成分以外，可視需要調配此種組合物中通常調配之硬化促進劑、橡膠、聚矽氧等低應力化劑、偶合劑、消泡劑、界面活性劑、著色劑(顏料、染料)、各種聚合抑制劑、抗氧化劑、溶劑、及其他各種添加劑。該等各添加劑均可使用1種，亦可混合使用2種以上。In addition to the above components, the bonding paste of this embodiment can be formulated with a hardening accelerator, rubber, polysiloxane, and other low-stressing agents, coupling agents, defoaming agents, and surfactants that are usually formulated in such a composition as needed. , Colorants (pigments, dyes), various polymerization inhibitors, antioxidants, solvents, and other various additives. One of these additives can be used alone, or two or more of them can be used in combination.

本實施形態之接合用膏可藉由以下方式製備：將上述銅粒子、及視需要調配之大粒徑銅粒子、熱硬化性樹脂、有機溶劑、偶合劑等添加劑等充分混合後，進而藉由分散機、捏合機、三輥研磨機等進行混練處理，繼而進行脫泡。The bonding paste of the present embodiment can be prepared by thoroughly mixing the above copper particles, copper particles with large particle size, thermosetting resin, organic solvent, coupling agent, etc., if necessary, and then by The disperser, kneader, three-roll mill, etc. are subjected to kneading treatment, followed by defoaming.

本實施形態之接合用膏之黏度例如可為20～300 Pa・s，亦可為40～200 Pa・s。 又，本實施形態之接合用膏之接合強度可為25 MPa以上，亦可為30 MPa以上。 再者，上述黏度及接合強度可藉由實施例記載之方法進行測定。The viscosity of the bonding paste of this embodiment may be, for example, 20 to 300 Pa·s or 40 to 200 Pa·s. In addition, the bonding strength of the bonding paste of this embodiment may be 25 MPa or more or 30 MPa or more. In addition, the above-mentioned viscosity and bonding strength can be measured by the method described in the Examples.

以此種方式獲得之本實施形態之接合用膏之導熱性較高，散熱性優異。因此，若用作元件或散熱構件於基板等之接合材料，則可改善裝置內部之熱向外部之散出性，使製品特性穩定。The bonding paste of this embodiment obtained in this way has high thermal conductivity and excellent heat dissipation. Therefore, if it is used as a bonding material for an element or a heat dissipation member to a substrate, the heat dissipation inside the device to the outside can be improved, and the product characteristics can be stabilized.

＜半導體裝置及電氣・電子零件＞ 本實施形態之半導體裝置及電氣・電子零件係使用上述接合用膏接合而成，因此可靠性優異。<Semiconductor devices and electrical/electronic parts> The semiconductor device and electrical/electronic parts of the present embodiment are formed using the above-mentioned bonding paste, and therefore have excellent reliability.

本實施形態之半導體裝置係使用上述接合用膏將半導體元件接著於作為元件支持構件之基板上而成者。即，此處接合用膏係用作晶粒接合膏，經由此膏將半導體元件與基板接著固定。The semiconductor device of the present embodiment is obtained by bonding the semiconductor element on the substrate as the element support member using the bonding paste. That is, here, the bonding paste is used as a die bonding paste, and the semiconductor element and the substrate are subsequently fixed via this paste.

此處，半導體元件只要為公知之半導體元件即可，例如可列舉電晶體、二極體等。進而，作為該半導體元件，可列舉LED等發光元件。又，發光元件之種類並無特別限制，例如可列舉藉由MOBVC法等於基板上形成InN、AlN、GaN、InGaN、AlGaN、InGaAlN等氮化物半導體作為發光層者。 又，作為元件支持構件，可列舉以銅、銅鍍銅、PPF(預鍍引線框架)、玻璃環氧樹脂、陶瓷等材料所形成之支持構件。Here, the semiconductor element may be a well-known semiconductor element, and examples thereof include transistors and diodes. Furthermore, as the semiconductor element, a light-emitting element such as an LED can be mentioned. In addition, the type of light-emitting element is not particularly limited. For example, a nitride semiconductor such as InN, AlN, GaN, InGaN, AlGaN, and InGaAlN formed on the substrate by the MOBVC method can be cited as a light-emitting layer. In addition, as the element support member, a support member formed of copper, copper-plated copper, PPF (pre-plated lead frame), glass epoxy resin, ceramic, or the like can be cited.

本實施形態之接合用膏亦可接合未經金屬鍍覆處理之基材。以此種方式所得之半導體裝置對於安裝後之溫度循環之連接可靠性與先前相比飛躍性提昇。又，電阻值充分小，經時變化較少，因此具有即便進行長時間驅動，輸出之經時性減少亦較少而實現長壽命之優點。The bonding paste of this embodiment can also bond substrates that have not been subjected to metal plating. The connection reliability of the semiconductor device obtained in this way with respect to the temperature cycle after installation is dramatically improved compared with the previous one. In addition, the resistance value is sufficiently small and there is little change over time. Therefore, even if it is driven for a long period of time, there is an advantage that the output time is less reduced and a long life is achieved.

又，本實施形態之電氣・電子零件係使用上述接合用膏於發熱構件接著散熱構件而成者。即，此處接合用膏用作散熱構件接著用材料，經由該接合用膏將散熱構件與發熱構件接著固定。In addition, the electrical and electronic parts of the present embodiment are obtained by using the above-mentioned bonding paste on a heat generating member followed by a heat dissipating member. That is, here, the bonding paste is used as a material for adhering the heat dissipation member, and the heat dissipation member and the heat generating member are subsequently fixed via the bonding paste.

作為發熱構件，可為上述半導體元件或具有該半導體元件之構件，亦可為其以外之發熱構件。作為半導體元件以外之發熱構件，可列舉光拾取器、功率電晶體等。又，作為散熱構件，可列舉散熱器、熱散播器等。The heat-generating member may be the above-mentioned semiconductor element or a member having the semiconductor element, or may be another heat-generating member. Examples of heat generating members other than semiconductor elements include optical pickups and power transistors. Moreover, as a heat radiation member, a heat sink, a heat spreader, etc. are mentioned.

如此，藉由使用上述接合用膏於發熱構件接著散熱構件，可將發熱構件所產生之熱自散熱構件高效率地散出至外部，抑制發熱構件之溫度上升。再者，發熱構件與散熱構件可經由接合用膏直接接著，亦可於其間夾著其他導熱率較高之構件而間接地接著。 [實施例]In this way, by using the above-mentioned bonding paste for the heat generating member and the heat dissipating member, the heat generated by the heat generating member can be efficiently radiated from the heat dissipating member to the outside, and the temperature rise of the heat generating member can be suppressed. Furthermore, the heat-generating member and the heat-radiating member may be directly bonded via the bonding paste, or may be indirectly bonded between other members with higher thermal conductivity. [Example]

其次，藉由實施例對本發明具體進行說明，但本發明並不受該等例任何限定。Next, the present invention will be specifically described by examples, but the present invention is not limited by these examples.

(羧酸胺鹽之製備) [製備例1] 將壬酸(東京化成工業(股)製造，商品名：壬酸)40 mmol、己基胺(東京化成工業(股)製造，商品名：己基胺)40 mmol放入至50 mL之樣品瓶中，於鋁塊式加熱攪拌機中攪拌、混合，使其發熱至60℃。繼而，於60℃下攪拌、混合15分鐘，冷卻至室溫(25℃)，藉此獲得壬酸己胺鹽(產量10.3 g，產率99.2%)。(Preparation of carboxylic acid amine salt) [Preparation Example 1] Put 40 mmol of nonanoic acid (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: nonanoic acid) and 40 mmol of hexylamine (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: hexylamine) into a 50 mL sample bottle. Stir and mix in an aluminum block-type heating mixer to heat it to 60°C. Then, it was stirred and mixed at 60°C for 15 minutes, and cooled to room temperature (25°C), thereby obtaining hexylamine nonanoate (yield 10.3 g, yield 99.2%).

(銅粒子之製造) [合成例1] 於具備氮氣導入管、熱電偶、戴氏冷凝器、滴液漏斗之2000 mL之四口可分離式燒瓶中，放入作為銅化合物之乙酸銅(II)一水合物(東京化成工業(股)製造，商品名：乙酸銅(II)一水合物)4 mol、作為胺化合物之製備例1所得之壬酸己胺鹽40 mmol、及作為有機溶劑之丁基溶纖劑(東京化成工業(股)製造)600 mL，於90℃下混合5分鐘，製得銅前驅物溶液。將該銅前驅物溶液冷卻至室溫(25℃)後，將在1-丙醇500 mL中溶解肼一水合物(Fuji Film Wako Pure Chemical(股)製造，商品名：肼一水合物)3 mol作為還原性化合物而成之溶液滴加至銅前驅物溶液中，攪拌30分鐘。再次升溫至90℃，加熱攪拌2小時後，冷卻至室溫(25℃)，藉此獲得含有2質量%之銅粒子之銅粒子分散液。(Manufacture of copper particles) [Synthesis Example 1] In a 2000 mL four-necked separable flask equipped with a nitrogen introduction tube, thermocouple, Dairy condenser, and dropping funnel, put copper(II) acetate monohydrate (Tokyo Chemical Industry Co., Ltd.) as a copper compound Manufacturing, trade name: copper (II) acetate monohydrate) 4 mol, 40 mmol of hexylnonanoate salt obtained in Preparation Example 1 as an amine compound, and butyl cellosolve (manufactured by Tokyo Chemical Industry Co., Ltd.) as an organic solvent ) 600 mL, mixed at 90°C for 5 minutes to prepare a copper precursor solution. After cooling the copper precursor solution to room temperature (25°C), hydrazine monohydrate (manufactured by Fuji Film Wako Pure Chemical Co., Ltd., trade name: hydrazine monohydrate) was dissolved in 500 mL of 1-propanol. 3 A solution of mol as a reducing compound was added dropwise to the copper precursor solution and stirred for 30 minutes. The temperature was raised to 90°C again, heated and stirred for 2 hours, and then cooled to room temperature (25°C), thereby obtaining a copper particle dispersion liquid containing 2% by mass of copper particles.

將上述銅粒子分散液以流量20 kg/hr・m² 、壓力0.1 MPa供給至密閉之DyF152/s(商品名，水平濾板式過濾機，三菱化工機(股)製造)之過濾膜，進而，連續地供給乙醇1000 mL，獲得以乙醇進行溶劑置換所得之銅粒子濃縮液。於DyF152/s中，對經乙醇溶劑置換所得之銅粒子濃縮液進而連續地供給二乙二醇(東京化成工業(股)製造)1000 mL，以二乙二醇進行溶劑置換後，進行離心分離(4000 rpm)，獲得平均粒徑50 nm之銅粒子濃縮液。 再者，關於所得之銅粒子之平均粒徑，對所得之銅粒子濃縮液進行離心分離(4000 rpm(1分鐘))，獲得固體物，對該離心分離所得之固體物進行減壓乾燥，作為基於掃描電子顯微鏡(日本電子(股)製造，商品名：JSM-7600F；SEM)之觀察圖像所任意選擇之10個銅粒子(n＝10)之平均值算出。The above copper particle dispersion liquid was supplied to a closed DyF152/s (trade name, horizontal filter plate filter, manufactured by Mitsubishi Chemical Machinery Co., Ltd.) filter membrane at a flow rate of 20 kg/hr·m ² and a pressure of 0.1 MPa, and further, 1000 mL of ethanol was continuously supplied to obtain a copper particle concentrate obtained by solvent replacement with ethanol. In DyF152/s, 1000 mL of diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) was continuously supplied to the copper particle concentrate obtained by ethanol solvent replacement, and after solvent replacement with diethylene glycol, centrifugal separation was performed. (4000 rpm), a copper particle concentrate with an average particle size of 50 nm was obtained. Furthermore, regarding the average particle diameter of the obtained copper particles, the obtained copper particle concentrate was subjected to centrifugal separation (4000 rpm (1 minute)) to obtain a solid substance, and the solid substance obtained by the centrifugal separation was dried under reduced pressure as The average value of 10 copper particles (n=10) selected arbitrarily based on the observation image of a scanning electron microscope (manufactured by JEOL Ltd., trade name: JSM-7600F; SEM) was calculated.

(實施例1) 以合成例1中所得之銅粒子成為100質量份，作為有機溶劑之二乙二醇(東京化成工業(股)製造)成為15質量份之方式進行製備，用輥進行混練，獲得接合用膏。對於所得之接合用膏，以下述方法進行評價。將其結果一併示於表1。(Example 1) The copper particles obtained in Synthesis Example 1 were prepared so that 100 parts by mass and diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) as an organic solvent would be 15 parts by mass, and kneaded with a roller to obtain a bonding paste. The obtained bonding paste was evaluated by the following method. The results are shown in Table 1.

＜接合用膏之評價方法＞ [黏度] 使用E型黏度計(東機產業(股)製造，製品名：VISCOMETER-TV22，應用錐板型轉子：3°×R17.65)，測定25℃、5 rpm下之值。<Evaluation method of bonding paste> [Viscosity] Using an E-type viscometer (manufactured by Toki Industries Co., Ltd., product name: VISCOMETER-TV22, application cone-plate rotor: 3°×R17.65), the value at 25°C and 5 rpm was measured.

[適用期] 測定將接合用膏放置於25℃之恆溫槽內時之黏度增加至初始黏度之0.7倍以上時之天數。[valid period] The number of days when the viscosity of the bonding paste placed in a thermostatic bath at 25°C increased to more than 0.7 times the initial viscosity was measured.

[電阻] 藉由網版印刷法於玻璃基板(厚度1 mm)以厚度成為25 μm之方式塗佈接合用膏，於200℃下硬化60分鐘。使用Loresta GP(商品名，MITSUBISHI CHEMICAL ANALYTECH(股)製造)，利用四探針法對所得之燒結膜測定電阻。[resistance] A glass substrate (thickness 1 mm) was coated with a bonding paste so as to have a thickness of 25 μm by screen printing, and cured at 200° C. for 60 minutes. Using Loresta GP (trade name, manufactured by MITSUBISHI CHEMICAL ANALYTECH Co., Ltd.), the resistance of the obtained sintered film was measured by a four-probe method.

＜半導體裝置之評價方法＞ [接合強度] 使用接合用膏，將於2 mm×2 mm之接合面設置有金蒸鍍層之矽晶片安裝於無垢之銅框架及PPF(鍍有Ni-Pd/Au之銅框架)，在氮氣(3%氫氣)氛圍下，於200℃下硬化60分鐘。於硬化後及吸濕處理(85℃，相對濕度85%，72小時)後，對各者使用DAGE 4000Plus(製品名，Nordson(股)製造)，測定室溫(25℃)下之晶片剪切強度。<Evaluation method of semiconductor device> [Joining strength] Using a bonding paste, the silicon wafer with a gold vapor deposition layer on the 2 mm × 2 mm bonding surface is mounted on a scale-free copper frame and PPF (Ni-Pd/Au-coated copper frame) in nitrogen (3% hydrogen ) Hardened at 200°C for 60 minutes in an atmosphere. After curing and after hygroscopic treatment (85°C, 85% relative humidity, 72 hours), DAGE 4000Plus (product name, manufactured by Nordson Corporation) was used for each, and the wafer shear at room temperature (25°C) was measured strength.

[耐冷熱衝擊性] 使用接合用膏，將於2 mm×2 mm之接合面設置有金蒸鍍層之矽晶片安裝於無垢之銅框架及PPF，在氮氣(3%氫氣)氛圍下，於200℃下硬化60分鐘。將其使用KYOCERA(股)製造之環氧樹脂密封材(商品名：KE-G3000D)於下述條件下成形為封裝，對該封裝以85℃、相對濕度85%、168小時之條件進行吸濕處理後，進行IR(Infrared Radiation，紅外線)回焊處理(260℃，10秒)及冷熱循環處理(將自-55℃升溫至150℃，再冷卻至-55℃之操作設為1次循環，進行1000次循環)，於各處理後，以超音波顯微鏡(Hitachi Power Solutions(股)製造，商品名：FineSAT)觀察各封裝內部裂痕之產生數量。 再者，表1中表示5個樣品產生裂痕之樣品數。[Cold and thermal shock resistance] Using a paste for bonding, the silicon wafer with a gold vapor deposition layer on the bonding surface of 2 mm × 2 mm was mounted on a scale-free copper frame and PPF, and cured at 200°C for 60 minutes under a nitrogen (3% hydrogen) atmosphere. It was molded into a package using epoxy resin sealing material (trade name: KE-G3000D) manufactured by KYOCERA under the following conditions, and the package was subjected to moisture absorption under the conditions of 85°C, relative humidity of 85%, and 168 hours. After the treatment, IR (Infrared Radiation, Infrared) reflow treatment (260°C, 10 seconds) and hot and cold circulation treatment (heating from -55°C to 150°C and then cooling to -55°C are set as 1 cycle. After 1000 cycles), after each treatment, the number of cracks in each package was observed with an ultrasonic microscope (manufactured by Hitachi Power Solutions Co., Ltd., trade name: FineSAT). In addition, Table 1 shows the number of samples with cracks in 5 samples.

(成形條件) 封裝：80pQFP(14 mm×20 mm×2 mm厚度) 晶片：背面鍍金矽晶片 引線框架：PPF及銅 密封材之成形：175℃、2分鐘 後熟化：175℃、8小時(Forming conditions) Package: 80pQFP (14 mm×20 mm×2 mm thickness) Wafer: back side gold-plated silicon wafer Lead frame: PPF and copper Sealing material forming: 175℃, 2 minutes After curing: 175℃, 8 hours

[表1]

[Table 1]

根據以上結果，包含藉由於密閉系統進行洗淨步驟之本發明之銅粒子之製造方法所獲得之銅粒子的接合用膏於塗膜狀態、接合狀態下均獲得較高之燒結性。 又，可知包含藉由本發明之銅粒子之製造方法所獲得之銅粒子的接合用膏獲得較高之接合可靠性。因此，藉由使用該接合用膏，可獲得可靠性優異之半導體裝置及電氣電子機器。Based on the above results, the bonding paste including the copper particles obtained by the method for producing copper particles of the present invention by performing a cleaning step in a closed system obtains high sinterability in both the coating film state and the bonding state. In addition, it can be seen that the bonding paste including the copper particles obtained by the method for producing copper particles of the present invention has high bonding reliability. Therefore, by using this bonding paste, a semiconductor device and an electrical and electronic device with excellent reliability can be obtained.

Claims (7)

一種銅粒子之製造方法，其包括以下步驟：將銅化合物、胺化合物、及還原性化合物於有機溶劑中混合，獲得銅粒子分散液；及洗淨步驟，其係對上述步驟所得之銅粒子分散液進行溶劑洗淨，將銅粒子自上述銅粒子分散液中固液分離；且 於密閉系統中實施上述洗淨步驟。A method for manufacturing copper particles, comprising the steps of: mixing a copper compound, an amine compound, and a reducing compound in an organic solvent to obtain a copper particle dispersion liquid; and a washing step, which is to disperse the copper particles obtained in the above steps The liquid is washed with a solvent, and the copper particles are solid-liquid separated from the copper particle dispersion liquid; and Carry out the above washing steps in a closed system. 如請求項1之銅粒子之製造方法，其中於上述洗淨步驟中，連續地進行溶劑置換及洗淨。The method for producing copper particles according to claim 1, wherein in the washing step, solvent replacement and washing are continuously performed. 如請求項1或2之銅粒子之製造方法，其中於上述洗淨步驟中，將含有1～50質量%之上述銅粒子之上述銅粒子分散液以流量5～1500 kg/hr・m² 、壓力0.03～1.0 MPa供給至過濾膜。The method for producing copper particles according to claim 1 or 2, wherein in the washing step, the copper particle dispersion liquid containing 1 to 50% by mass of the copper particles is flowed at a flow rate of 5 to 1500 kg/hr·m ² , A pressure of 0.03 to 1.0 MPa is supplied to the filter membrane. 如請求項1至3中任一項之銅粒子之製造方法，其中上述銅粒子之平均粒徑為1～1000 nm。The method for producing copper particles according to any one of claims 1 to 3, wherein the average particle diameter of the copper particles is 1 to 1000 nm. 一種接合用膏，其包含藉由如請求項1至4中任一項之製造方法所獲得之銅粒子。A bonding paste comprising copper particles obtained by the manufacturing method according to any one of claims 1 to 4. 一種半導體裝置，其係使用如請求項5之接合用膏接合而成。A semiconductor device formed by bonding using the bonding paste according to claim 5. 一種電氣・電子零件，其係使用如請求項5之接合用膏接合而成。An electrical/electronic part, which is formed by using the bonding paste as described in claim 5.