TW202012092A - Solder paste of nano-scale core-shell structure and the preparation method thereof - Google Patents

Abstract

The present invention relates to a solder paste of nano-scale core-shell structure and the preparation method thereof. First, the preparation method of the solder paste of nano-scale core-shell structure uses the DC hydrogen arc plasma evaporation method to produce nano-scale silver copper tin alloy powders, and then applies the displacement reaction method to produce a nano-scale core-shell structure that covers the outer layer of the nano-scale silver copper tin alloy powders. Last, the nano-scale silver copper tin alloy powders of nano-scale core-shell structure are mixed with the auxiliary and then undergo the process of filling and constant temperature storage to produce the solder paste of non-scale core-shell structure. The costs of the manufacturing materials and the preparation method of the present invention are relatively low. The solder paste produced by the present invention has excellent thermal conductivity and stability.

Description

Nano core-shell structure solder paste and preparation method thereof

The invention relates to a solder paste and a preparation method thereof; more specifically, it relates to a nano core-shell structure solder paste and a preparation method thereof.

In recent years, with the development of science and technology, the power and frequency of 3C products have become larger and larger, but it has also been accompanied by greater and greater heat generation, making thermal hazards more and more obvious. In order to reduce the harm of heat to 3C products, the most A common method is to add a fan to increase the heat dissipation speed. However, when the fan is running, it will generate a certain noise and occupy a certain space, making it difficult to miniaturize the 3C product with the fan installed, so some companies will choose not to account for it. Nano solder paste with space and excellent heat dissipation replaces the fan.

At present, the existing nano solder paste is composed of resin, filler, additives and other materials. The filler is made of nano silver powder or nano copper powder with good thermal conductivity. If a large amount of nano silver powder is used as a filler, It has excellent heat dissipation effect, but the cost of the material will also increase greatly; if the relatively cheap nano copper powder is used as a filler, the cost of the material can be well controlled, but the nano copper powder is being processed And it is very easy to oxidize during use, and it leads to poor heat dissipation effect of nano solder paste, but this feature has become an obstacle in the manufacturing process and the use conditions are also more harsh.

In view of this, based on my many years of research and development experience in related fields, I have conducted in-depth discussions on the aforementioned deficiencies and actively sought solutions based on the aforementioned needs. After a long period of hard research and multiple tests, I finally completed the present invention.

The main purpose of the present invention is to reduce the production cost of nano solder paste.

The primary and secondary object of the present invention is to improve the thermal conductivity and stability of nano solder paste.

In order to achieve the above object, the nano core-shell structure solder paste of the present invention is formed by mixing and stirring nano-core alloy powder and additives.

~

。The nano core-shell alloy powder is made of a silver shell coated on the alloy core. The alloy core is composed of copper, silver, tin and trace elements, and the mass ratio of copper: silver: tin: trace elements Between 5~70: 0.1~65: 0.01~98.5:

~

.

The additive is composed of bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylic acid, neodecanoic acid-propylene oxide potassium ester and additives , And bisphenol A diglycidyl ether: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylic acid: neodecanoic acid-potassium propylene oxide: the mass ratio of additives is 8 ~10: 8~10: 2~8: 1~5.

，然後充入高純氬氣，接著開啟循環冷卻水後引燃電極並將電流控制在350A~500A範圍內，之後開啓循環風機將銅銀錫合金蒸氣吹至收集室內的集粉袋，待20~40分鐘後將電極關閉，最後等坩鍋冷卻至常溫後充入高純氬氣至常壓，再取出集粉袋的第一奈米銅銀錫合金粉備用。 B. 酸洗處理：將第一奈米銅銀錫合金粉用濃度為15%~30%稀硫酸洗滌5~15分鐘並使第一奈米銅銀錫合金粉的PH值保持在1~2之間，再來將經過酸洗的第一奈米銅銀錫合金粉用蒸餾水反覆沖洗直到無檢測出銅銀錫離子為止，接續再反覆洗滌第一奈米銅銀錫合金粉至PH值為中性，最後再用離心機甩乾並取得第二奈米銅銀錫合金粉。 C. 奈米核殼製備：利用置換反應法將第二奈米銅銀錫合金粉浸泡在30g/L的氯化亞錫鹽酸敏化液中敏化5~15分鐘後，再用蒸餾水洗滌後取得銅銀錫合金粉液，接著再將銅銀錫合金粉液進行過濾，並在過濾後滴加硝酸銀溶液將銅銀錫合金粉液的PH值調整至4後，再滴加銀氨溶液充分混合反應8~15分鐘，接續再滴加氨水將PH值調整至9並反應25~40分鐘，最後使用離心機進行分離並透過蒸餾水洗滌後得到第一銀包奈米銅銀錫合金粉液，之後將第一銀包奈米銅銀錫合金粉液置於容器中並加入適量蒸餾水，置於70℃恆溫槽中靜置3小時後使用離心機分離第一銀包奈米銅銀錫合金粉液和蒸餾水，再經烤箱烘乾後得到奈米銀核殼包銅銀錫合金粉。 D. 焊膏製備：將上述製備出的奈米銀核殼包銅銀錫合金粉與助劑充分混合攪拌，再進行灌裝、恆溫保存後，即製得奈米核殼結構焊膏。The preparation method of the nano core-shell structure solder paste of the present invention is made through the following steps: A. Nano alloy powder preparation: adopting direct current hydrogen arc plasma evaporation method, placing copper silver tin alloy into the crucible Inside and seal the crucible and evacuate to

, And then filled with high-purity argon gas, then turn on the circulating cooling water, ignite the electrode and control the current in the range of 350A~500A, then turn on the circulation fan to blow the copper, silver, and tin alloy vapor into the powder collection bag in the collection room, wait 20 After ~40 minutes, turn off the electrode, and finally wait for the crucible to cool to room temperature, then fill with high-purity argon gas to room pressure, and then take out the first nanometer copper-silver-tin alloy powder in the powder collection bag. B. Pickling treatment: wash the first nanometer copper-silver-tin alloy powder with 15%~30% diluted sulfuric acid for 5~15 minutes and keep the first nanometer copper-silver-tin alloy powder at a pH of 1~2 In between, the first nano-copper-silver-tin alloy powder after pickling is washed repeatedly with distilled water until no copper-silver-tin ions are detected, and then the first nano-copper-silver-tin alloy powder is repeatedly washed to a pH value Neutral, finally spin dry with a centrifuge and obtain the second nano copper-silver-tin alloy powder. C. Nano core-shell preparation: The second nano-copper-silver-tin alloy powder is immersed in 30g/L stannous chloride hydrochloric acid sensitizing solution for 5~15 minutes by substitution reaction method, and then washed with distilled water Obtain the copper-silver-tin alloy powder, then filter the copper-silver-tin alloy powder, and add silver nitrate solution after the filtration to adjust the pH of the copper-silver-tin alloy powder to 4, and then add the silver ammonia solution Mix the reaction for 8-15 minutes, then add dropwise ammonia to adjust the pH to 9 and react for 25-40 minutes. Finally, use a centrifuge to separate and wash through distilled water to obtain the first silver-coated nano-copper silver-tin alloy powder. Then put the first silver-coated nano-copper-silver-tin alloy powder solution in a container and add an appropriate amount of distilled water, put it in a thermostatic bath at 70℃ for 3 hours, and then use a centrifuge to separate the first silver-coated nano-copper-silver-tin alloy powder. Liquid and distilled water, and then dried in an oven to obtain nano silver core-coated copper silver tin alloy powder. D. Preparation of solder paste: the nano-silver core-coated copper-silver-tin alloy powder prepared above is thoroughly mixed with additives, and after filling and constant temperature storage, the nano-core structure solder paste is prepared.

In summary, the advantages of the nano core-shell structure solder paste and its preparation method of the present invention are as follows: 1. The silver metal core shell can effectively protect the nano alloy powder and prevent its oxidation. 2. The cost of materials used in the manufacturing process of the present invention is relatively low. 3. Use copper, silver, tin alloy to make solder paste, which has excellent thermal conductivity and stability.

It is hoped that the purpose, efficacy, characteristics and structure of this book can be understood in more detail. The preferred embodiments are described below with reference to the drawings.

Please refer to FIG. 1 and FIG. 2 at the same time. FIG. 1 is a schematic diagram of the process of the solder paste of the nano-shell structure of the present invention, and FIG. 2 is a schematic diagram of the equipment for preparing the copper-silver-tin alloy powder of the present invention.

The nano core-shell structure solder paste of the invention is formed by mixing and stirring the nano core-shell alloy powder and the auxiliary agent.

~

，其中，該微量元素為銦、鍺、硒、鈷、鎳其中一種或一種以上。The nano core-shell alloy powder is made of a silver shell coated on the alloy core. The alloy core is composed of copper, silver, tin and trace elements, and the mass ratio of copper: silver: tin: trace elements Between 5~70: 0.1~65: 0.01~98.5:

~

, Wherein the trace element is one or more than one of indium, germanium, selenium, cobalt, and nickel.

The additive is composed of bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylic acid, neodecanoic acid-propylene oxide potassium ester and additives , And bisphenol A diglycidyl ether: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylic acid: neodecanoic acid-propylene oxide potassium ester: the mass ratio of additives is between 8 ~10: 8~10: 2~8: 1~5, where the additive contains ethanol and rosin.

，然後充入高純氬氣，接著開啟循環冷卻水後引燃電極２２３並將電流控制在350A~500A範圍內，之後開啓循環風機２３將銅銀錫合金蒸氣吹至收集室２４內的集粉袋２４１，待20~40分鐘後將電極２２３關閉，最後等坩鍋２２２冷卻至常溫後充入高純氬氣至常壓，再取出集粉袋２４１內的第一奈米銅銀錫合金粉備用，其中，該銅銀錫合金係由銅、銀、錫以及微量元素所組成，且銅：銀：錫：微量元素的質量比例介於5~70：0.1~65：0.01~98.5：

~

，另外該微量元素為銦、鍺、硒、鈷、鎳其中一種或一種以上； B. 酸洗處理１２：首先將第一奈米銅銀錫合金粉用濃度為15%~30%稀硫酸洗滌5~15分鐘並使第一奈米銅銀錫合金粉的PH值保持在1~2之間，再來將經過酸洗的第一奈米銅銀錫合金粉用蒸餾水反覆沖洗直到無檢測出銅銀錫離子為止，接續再反覆洗滌第一奈米銅銀錫合金粉至PH值為中性，最後再用離心機甩乾並取得第二奈米銅銀錫合金粉； C. 奈米核殼製備１３：利用置換反應法將第二奈米銅銀錫合金粉浸泡在30g/L的氯化亞錫鹽酸敏化液中敏化5~15分鐘後，再用蒸餾水洗滌後取得銅銀錫合金粉液，接著再將銅銀錫合金粉液進行過濾，並在過濾後滴加硝酸銀溶液將銅銀錫合金粉液的PH值調整至4後，再滴加銀氨溶液充分混合反應8~15分鐘，接續再滴加氨水將PH值調整至9並反應25~40分鐘，最後使用離心機進行分離並透過蒸餾水洗滌後得到第一銀包奈米銅銀錫合金粉液，之後將第一銀包奈米銅銀錫合金粉液置於容器中並加入適量蒸餾水，置於70℃恆溫槽中靜置3小時後使用離心機分離第一銀包奈米銅銀錫合金粉液和蒸餾水，再經烤箱烘乾後得到奈米銀核殼包銅銀錫合金粉； D. 焊膏製備１４：將上述製備出的奈米銀核殼包銅銀錫合金粉與助劑充分混合攪拌，再進行灌裝、恆溫保存後，即製得奈米核殼結構焊膏，其中，該助劑係由雙酚A二縮水甘油醚、3,4-環氧環己基甲基-3,4-環氧環己烷羧酸、新癸酸-環氧丙烷鉀酯、添加劑所組成，且雙酚A二縮水甘油醚：3,4-環氧環己基甲基-3,4-環氧環己烷羧酸：新癸酸-環氧丙烷鉀酯：添加劑的質量比例介於8~10：8~10：2~8：1~5，另外該添加劑包含有乙醇和松香。The preparation method 1 of the nano core-shell structure solder paste of the present invention is made through the following steps: A. Preparation of the nano alloy powder 11: using the direct current hydrogen arc plasma evaporation method to place the copper silver tin alloy Inside the crucible 222 and seal the crucible 222 and evacuate to

, And then filled with high-purity argon gas, then turn on the circulating cooling water, ignite the electrode 223 and control the current in the range of 350A~500A, then turn on the circulating fan 23 to blow the copper silver tin alloy vapor to the collection powder in the collection chamber 24 Bag 241. After 20~40 minutes, turn off the electrode 223, wait for the crucible 222 to cool to room temperature, fill it with high-purity argon gas to room pressure, and then take out the first nanometer copper-silver-tin alloy powder in the bag 241 Standby, wherein the copper-silver-tin alloy is composed of copper, silver, tin and trace elements, and the mass ratio of copper: silver: tin: trace elements is between 5~70: 0.1~65: 0.01~98.5:

~

In addition, the trace element is one or more than one of indium, germanium, selenium, cobalt and nickel; B. Pickling treatment 12: first wash the first nanometer copper-silver-tin alloy powder with 15%~30% diluted sulfuric acid 5~15 minutes and keep the PH value of the first nano-copper-silver-tin alloy powder between 1~2, then wash the acid-washed first nano-copper-silver-tin alloy powder repeatedly with distilled water until no detection Until the copper, silver, and tin ions, the first nano-copper-silver-tin alloy powder is washed repeatedly until the PH value is neutral, and finally it is spin-dried with a centrifuge and the second nano-copper-silver-tin alloy powder is obtained; Shell preparation 13: The second nano copper-silver-tin alloy powder is immersed in 30g/L stannous chloride hydrochloric acid sensitizing solution for 5-15 minutes, and then washed with distilled water to obtain copper silver tin After the alloy powder solution, the copper silver tin alloy powder solution is filtered, and after the filtration, the silver nitrate solution is added dropwise to adjust the pH value of the copper silver tin alloy powder solution to 4, and then the silver ammonia solution is added dropwise to fully mix and react 8~ After 15 minutes, add another drop of ammonia water to adjust the PH value to 9 and react for 25~40 minutes. Finally, use a centrifuge to separate and wash through distilled water to obtain the first silver-coated nano-copper silver-tin alloy powder. Put the silver-coated nano-copper-silver-tin alloy powder in a container and add an appropriate amount of distilled water. Place it in a thermostatic bath at 70℃ for 3 hours and use a centrifuge to separate the first silver-coated nano-copper-silver-tin alloy powder and distilled water. After drying in the oven, nano silver core-shell copper-silver-tin alloy powder is obtained; D. Preparation of solder paste 14: The nano silver core-shell copper-silver-tin alloy powder prepared above is thoroughly mixed with an auxiliary agent, and then After filling and constant temperature storage, the nano core-shell structure solder paste is prepared, in which the additive is composed of bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-cyclo Oxycyclohexane carboxylic acid, neodecanoic acid-propylene oxide potassium ester, additives, and bisphenol A diglycidyl ether: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane Carboxylic acid: neodecanoic acid-propylene oxide potassium ester: the mass ratio of the additive is between 8-10: 8-10: 2-8: 1-5, and the additive contains ethanol and rosin.

The equipment used in the 11th step of preparing nano-alloy powder includes a circulating gas path 21, a nano-powder production room 22, a circulating fan 23 and a collection room 24. The outlet 221 of the nano-powder production room 22 is placed in the collection room 24 and the outlet 221 sets of powder collection bags 241 placed in the collection chamber 24, the circulation air path 21 is connected to the nano powder production room 22 and the collection room 24, and a circulation fan 23 is provided on the circulation air path 21; in addition, the nano powder production The chamber 22 is also provided with a crucible 222, an electrode 223, a water-cooled cavity 224, a water-cooled copper mold 225, an end of the circulating gas path 21 is provided with a blower tube 211 facing the opening of the crucible 222, and a water-cooled copper mold 225 Placed on the water-cooled cavity 224, the crucible 222 is placed in the water-cooled cavity 224.

In summary, the advantages of the present invention are as follows: 1. The silver metal core shell can effectively protect the nano alloy powder and prevent its oxidation. 2. The cost of materials used in the manufacturing process of the present invention is relatively low. 3. Use copper, silver, tin alloy to make solder paste, which has excellent thermal conductivity and stability.

Therefore, the present invention has excellent progress and practicality in similar products. At the same time, after searching the technical information literature on such structures at home and abroad, it is indeed not found that the same or similar structure exists before the application in this case, so this case It should meet the patent requirements of "Creativity", "Integration to Industry Utilization" and "Progressiveness", and file an application according to law.

However, the above are only the preferred embodiments of the present invention, and those who apply the description of the present invention and other equivalent structural changes of the scope of patent application should be included in the scope of patent application of the present invention.

1: Preparation method of nano core-shell structure solder paste 11: Preparation of nano-alloy powder 12: Pickling treatment 13: Preparation of nano-core shell 14: Preparation of solder paste 21: Circulation gas path 21: Blow pipe 22: Preparation of nano powder Chamber 221: outlet 222: crucible 223: electrode 224: water-cooled cavity 225: copper mold under water cooling 23: circulation fan 24: collection chamber 241: powder collection bag

Figure 1: Schematic diagram of the solder paste of the nano-shell structure of the present invention;

no.

1: Preparation method of nano core-shell structure solder paste

11: Nano alloy powder preparation

12: Pickling treatment

13: Nano core-shell preparation

14: solder paste preparation

Claims (6)

A nano core-shell structure solder paste, which is formed by mixing and stirring nano-core-shell alloy powder and additives; the nano-core-shell alloy powder is formed by coating a silver shell on the outer core of the alloy, the alloy The core system is composed of copper, silver, tin and trace elements, and the mass ratio of copper: silver: tin: trace elements is between 5~70: 0.1~65: 0.01~98.5:

~

The adjuvant is composed of bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylic acid, neodecanoic acid-propylene oxide potassium ester and additives Composition, and bisphenol A diglycidyl ether: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylic acid: neodecanoic acid-propylene oxide potassium ester: the mass ratio of additives 8~10: 8~10: 2~8: 1~5. The nano core-shell structure solder paste according to claim 1, wherein the trace element is one or more than one of indium, germanium, selenium, cobalt, and nickel. The nano core-shell structure solder paste as described in claim 1, wherein the additive contains ethanol and rosin. A preparation method of nano core-shell structure solder paste, the steps are as follows: A. Nano alloy powder preparation: using a direct current hydrogen arc plasma evaporation method, the copper silver tin alloy is placed in a crucible and the crucible is sealed and pumped Vacuum to

, And then filled with high-purity argon gas, then turn on the circulating cooling water, ignite the electrode and control the current in the range of 350A~500A, then turn on the circulation fan to blow the copper, silver, and tin alloy vapor into the powder collection bag in the collection room, wait 20 After ~40 minutes, turn off the electrode, and finally wait for the crucible to cool to normal temperature and fill it with high-purity argon gas to normal pressure, and then take out the first nano-copper-silver alloy powder in the powder collection bag for use; B. Pickling treatment: first Wash the first copper-silver-tin alloy powder with 15%~30% diluted sulfuric acid for 5~15 minutes and keep the PH value of the first copper-silver-tin alloy powder between 1~2. The first nano-copper-silver-tin alloy powder after pickling was washed repeatedly with distilled water until no copper-silver-tin ions were detected, and then the first nano-copper-silver-tin alloy powder was washed repeatedly until the PH value was neutral, and finally used again Spin-dry the centrifuge and obtain the second nano-copper-silver-tin alloy powder; C. Nano core-shell preparation: use the substitution reaction method to soak the second nano-copper-silver-tin alloy powder in 30g/L stannous chloride hydrochloric acid After sensitization in the solution for 5~15 minutes, wash with distilled water to obtain copper-silver-tin alloy powder, then filter the copper-silver-tin alloy powder, and add silver nitrate solution dropwise to filter the copper-silver-tin alloy powder After the PH value of the liquid is adjusted to 4, then add silver ammonia solution to mix and react for 8~15 minutes, then add another drop of ammonia water to adjust the pH value to 9 and react for 25~40 minutes, and finally use a centrifuge to separate and pass through distilled water After washing, the first silver-coated nano-copper-silver-tin alloy powder solution is obtained, and then the first silver-coated nano-copper-silver-tin alloy powder solution is placed in a container and an appropriate amount of distilled water is added, and placed in a thermostatic bath at 70°C for 3 hours. Then use a centrifuge to separate the first silver-coated nano-copper-silver-tin alloy powder liquid and distilled water, and then dry it in the oven to obtain nano-silver core-coated copper-silver-tin alloy powder; D. Preparation of solder paste: the preparation of the above Nano silver core-shell copper-copper silver-tin alloy powder and additives are fully mixed and stirred, and then filled and stored at a constant temperature to prepare the nano core-shell structure solder paste; in the preparation of the nano alloy powder 11, the copper The silver-tin alloy is composed of copper, silver, tin and trace elements, and the mass ratio of copper: silver: tin: trace elements is between 5~70: 0.1~65: 0.01~98.5:

~

; In the preparation of the solder paste, the additive is composed of bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylic acid, neodecanoic acid-epoxy Composed of potassium propane ester and additives, and bisphenol A diglycidyl ether: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylic acid: neodecanoic acid-potassium propylene oxide ester: The mass ratio of additives is between 8-10: 8-10: 2-8: 1-5. The preparation method of the nano core-shell structure solder paste according to claim 4, wherein the trace element is one or more than one of indium, germanium, selenium, cobalt, and nickel. The preparation method of the nano core-shell structure solder paste according to claim 4, wherein the additive contains ethanol and rosin.

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