A gold-tin alloy nanoparticle and a method for preparing the same

Abstract

The application discloses gold-tin alloy nanoparticles and a preparation method thereof, and belongs to the technical field of electronic device packaging. The gold-tin alloy nanoparticles are prepared from raw materials including metal elements Au and Sn; wherein the molar ratio of Au and Sn is 1:x, and 0.1<=x<=10. The gold-tin alloy nanoparticles further enhance the micro-bump packaging effect through component regulation, and have excellent phase change capability in the ball mounting process, so that the conductive performance of the irradiation melting solidification into micro-bumps is more excellent.

Description

Technical Field

[0001] This invention belongs to the field of electronic device packaging technology, and in particular relates to a gold-tin alloy nanoparticle and its preparation method. Background Technology

[0002] For advanced deposition processes such as additive manufacturing, cold spraying, thermal spraying, and laser cladding, the preparation technology of metal microsphere deposition raw materials aims to obtain metal powders with high sphericity, high fluidity, narrow particle size distribution, high purity, and dense and uniform internal structure to meet the requirements of powder uniformity, powder feeding continuity, and high-quality deposition layer. The current mainstream preparation methods include gas atomization, plasma rotating electrode atomization, and plasma spheroidization: gas atomization is the most widely used, plasma rotating electrode atomization can produce high-quality powders with smooth surfaces and no satellite spheres, but the cost is high; plasma spheroidization can transform irregular powders into dense spherical powders, which is particularly suitable for refractory metals and reactive metals. The main challenge in this field is to improve the yield of the target particle size range and achieve the controllable preparation of refractory and alloy microspheres (Li Shaoqiang, Sun Jianhao, Lai Yunjin, et al. Research progress on metal spherical powder preparation technology [J]. Foundry Technology, 2025, 46(7):626-644.).

[0003] Therefore, this invention focuses on the preparation of raw materials by directional deposition of micron-sized metal microsphere arrays, with the aim of providing a method for preparing gold-tin alloy nanoparticles. This method can prepare highly dispersed gold-tin alloy nanoparticles at the nanoscale, avoiding equipment blockage during the packaging process and ensuring the continuity and reliability of the packaging. Summary of the Invention

[0004] This invention provides a low-cost, high-efficiency method for preparing gold-tin alloy nanoparticles for high-performance device packaging materials. This method is simple, quick, highly selective, and easy to mass-produce.

[0005] The objective of this invention is achieved through the following technical solution: This invention provides gold-tin alloy nanoparticles, wherein the molar ratio of Au to Sn is 1:x, 0.1≤x≤10; and the average particle size is 16.1nm~20.6nm.

[0006] The present invention also provides a method for preparing the above-mentioned gold-tin alloy nanoparticles, comprising the following steps: 1) Dissolve the soluble gold salt in the solution, stir and heat after complete dissolution to obtain the gold salt solution; 2) Add the reducing agent to the gold salt solution, continue stirring and heating until the color changes, and obtain a gold nanoparticle solution; 3) After adding soluble tin salt and capping agent to the gold nanoparticle solution, a reducing agent is added to obtain a gold-tin alloy nanoparticle solution.

[0007] Optionally, in step 1), the soluble gold salt is one or more of HAuCl4·3H2O, NaAuCl4·2H2O, and KAuCl4·H2O.

[0008] Optionally, in step 1), the solution is H2O or (CH3)3SiO.

[0009] Optionally, in step 1), the stirring speed is 100~10000 r / min.

[0010] Optionally, in step 1), the heating temperature is 90~200℃.

[0011] Optionally, in step 2), the reducing agent is one or more of C6H8O7, C6H8O, and C4H6O4S.

[0012] Optionally, in step 2), the average particle size of the gold nanoparticles is 16.1 nm to 20.6 nm.

[0013] Optionally, in step 3), the soluble tin salt is one or more of SnCl4·5H2O, SnCl2·2H2O, Sn(CH3COO)2, SnSO4, and Sn(SO4)2.

[0014] Optionally, in step 3), the capping agent is (C6H9NO). n One or more of C6H8O7.

[0015] Optionally, in step 3), the reducing agent is one or more of NaBH4 and KBH4.

[0016] The beneficial effects of this invention are as follows: (1) The present invention uses a chemical reduction method to prepare gold-tin alloy nanoparticles, which can save equipment costs compared with traditional methods.

[0017] (2) The present invention can prepare highly dispersed gold-tin alloy nanoparticles at the nanoscale. By changing the ratio of gold and tin precursors, gold-tin alloy nanoparticles with different proportions can be prepared, which is beneficial to the control of packaging costs.

[0018] (3) The preparation process of the present invention is simple, highly operable, short in time, low in energy consumption, and easy to achieve mass production. Attached Figure Description

[0019] Figure 1 These are TEM images and particle size distribution diagrams of the gold-tin alloy nanoparticles obtained in Example 1.

[0020] Figure 2These are gold-tin alloy nanoparticles obtained in Example 1, where (a) is a HAADF image, and (b), (c), and (d) are EDS elemental surface scans.

[0021] Figure 3 This is the XRD pattern of the gold-tin alloy nanoparticles obtained in Example 1.

[0022] Figure 4 These are TEM images and particle size distribution diagrams of the gold-tin alloy nanoparticles obtained in Example 2.

[0023] Figure 5 These are gold-tin alloy nanoparticles obtained in Example 2, where (a) is a HAADF image, and (b), (c), and (d) are EDS elemental surface scans.

[0024] Figure 6 This is the XRD pattern of the gold-tin alloy nanoparticles obtained in Example 2.

[0025] Figure 7 These are TEM images and particle size distribution diagrams of the gold-tin alloy nanoparticles obtained in Example 3.

[0026] Figure 8 These are gold-tin alloy nanoparticles obtained in Example 3, where (a) is a HAADF image, and (b), (c), and (d) are EDS elemental surface scans.

[0027] Figure 9 This is the XRD pattern of the gold-tin alloy nanoparticles obtained in Example 3. Detailed Implementation

[0028] To make the objectives and methods of this invention clearer, the invention will be further described in detail below with reference to the embodiments. The examples described herein are for illustrative purposes only and are not intended to limit the invention.

[0029] Example 1 Step (1): Dissolve 39.78 mg of NaAuCl4·3H2O in a round-bottom flask containing 100 ml of ultrapure water (18.2 MΩ) and a stir bar using ultrasonication. Secure the condenser to the neck of the round-bottom flask, circulate boiling water to the condenser, and ensure all components are securely mounted on the ring support. Place the round-bottom flask in an oil bath set to 120°C and 100 r / min and begin stirring to obtain the gold salt solution.

[0030] Step (2): When NaAuCl4 boils and the reaction vessel is clearly under reflux, quickly add 600 μL of 100 mM C6H8O7 solution. After heating and stirring for 8 minutes, remove the reaction vessel from the oil bath to obtain a red gold nanoparticle solution.

[0031] Step (3): Pour 12 mL of the gold nanoparticle solution synthesized in steps (1) and (2), 150 μL of 10 wt.% C6H9NO solution, and 0.47 mg of SnCl4·5H2O solution into a glass bottle equipped with a magnetic stirrer, and stir at 100 r / min for two minutes. After stirring, place the glass bottle in a 60°C water bath and heat for 20 minutes. Then, add 100 μL of 1 M NaBH4 solution dropwise, and continue heating in a 60°C water bath for 30 minutes to finally obtain the gold-tin alloy nanoparticle solution.

[0032] The gold-tin alloy nanoparticles obtained in Example 1 were observed using a transmission electron microscope, and TEM, HAADF and EDS images were obtained. The particle size of the gold-tin alloy nanoparticles was also statistically analyzed. The gold-tin alloy nanoparticles obtained in Example 1 were tested using an X-ray diffractometer.

[0033] Figure 1 TEM images and particle size distribution diagrams of the gold-tin alloy nanoparticles obtained in Example 1 are shown.

[0034] Depend on Figure 1 It can be seen that the average particle size of the gold-tin alloy nanoparticles obtained in Example 1 is 16.1 nm.

[0035] Figure 2 The gold-tin alloy nanoparticles obtained in Example 1 are shown, where (a) is a HAADF image and (b), (c), and (d) are EDS elemental surface scans.

[0036] Depend on Figure 2 It can be seen that the gold and tin are evenly distributed in the product prepared in Example 1, indicating that gold-tin alloy nanoparticles were successfully prepared.

[0037] Figure 3 The XRD pattern of the gold-tin alloy nanoparticles obtained in Example 1 is shown.

[0038] Depend on Figure 3 As can be seen, the product prepared in Example 1, when compared with the AnSn card, shows that the characteristic diffraction peaks of the two correspond, further indicating that gold-tin alloy nanoparticles were successfully prepared.

[0039] Example 2 Step (1): Dissolve 39.78 mg of HAuCl4·3H2O in a round-bottom flask containing 100 ml of ultrapure water (18.2 MΩ) and a stir bar using ultrasonication. Secure the condenser to the neck of the round-bottom flask, circulate boiling water to the condenser, and ensure all components are securely mounted on the ring support. Place the round-bottom flask in an oil bath set to 200℃ and 1000 r / min and begin stirring to obtain the gold salt solution.

[0040] Step (2): When the gold salt solution boils and the reaction vessel is clearly under reflux, quickly add 400 μL of 100 mM C6H8O7 solution. After heating and stirring for 8 minutes, remove the reaction vessel from the oil bath to obtain a red gold nanoparticle solution.

[0041] Step (3): Add 12 mL of the gold nanoparticle solution synthesized in steps (1) and (2), and 1 mL of 10 wt.% (C6H9NO) n The solution and 45 mg SnCl4·5H2O solution were poured into a glass bottle equipped with a magnetic stirrer and stirred at 800 rpm for two minutes. After stirring, the glass bottle was placed in a 60°C water bath and heated for 20 minutes. Subsequently, 600 μL of 1M NaBH4 solution was added dropwise, and the mixture was heated in a 60°C water bath for another 30 minutes to finally obtain a gold-tin alloy nanoparticle solution.

[0042] The gold-tin alloy nanoparticles obtained in Example 2 were observed using a transmission electron microscope, and TEM, HAADF and EDS images were obtained. The particle size of the gold-tin alloy nanoparticles was also statistically analyzed. The gold-tin alloy nanoparticles obtained in Example 2 were tested using an X-ray diffractometer.

[0043] Figure 4 TEM images and particle size distribution diagrams of the gold-tin alloy nanoparticles obtained in Example 2 are shown.

[0044] Depend on Figure 4 It can be seen that the average particle size of the gold-tin alloy nanoparticles obtained in Example 2 is 19.35 nm.

[0045] Figure 5 The gold-tin alloy nanoparticles obtained in Example 2 are shown, where (a) is a HAADF image, and (b), (c), and (d) are EDS elemental surface scans.

[0046] Depend on Figure 5 It can be seen that the gold and tin are evenly distributed in the product prepared in Example 2, indicating that gold-tin alloy nanoparticles were successfully prepared.

[0047] Figure 6 The XRD pattern of the gold-tin alloy nanoparticles obtained in Example 2 is shown.

[0048] Depend on Figure 6 As can be seen, the product prepared in Example 2, when compared with the AnSn card, shows that the characteristic diffraction peaks of the two correspond, further indicating that gold-tin alloy nanoparticles were successfully prepared.

[0049] Example 3 Step (1): Dissolve 39.78 mg of HAuCl4·3H2O in a round-bottom flask containing 100 ml of ultrapure water (18.2 MΩ) and a stir bar using ultrasound. Secure the condenser to the neck of the round-bottom flask, circulate boiling water to the condenser, and ensure all components are securely mounted on the ring support. Place the round-bottom flask in an oil bath set to 200℃ and 2000 r / min and begin stirring to obtain the gold salt solution.

[0050] Step (2): When the gold salt solution boils and the reaction vessel is clearly under reflux, quickly add 400 μL of 100 mM C6H8O7 solution. After heating and stirring for 8 minutes, remove the reaction vessel from the oil bath to obtain a red gold nanoparticle solution.

[0051] Step (3): Add 12 mL of the gold nanoparticle solution synthesized in steps (1) and (2) and 530 μL of 10 wt.% (C6H9NO) n The solution and 47.9 mg SnCl4·5H2O solution were poured into a glass bottle equipped with a magnetic stirrer and stirred at 1500 rpm for two minutes. After stirring, the glass bottle was placed in a 60°C water bath and heated for 20 minutes. Subsequently, 2 mL of 1 M NaBH4 solution was added dropwise, and the mixture was heated in a 60°C water bath for another 30 minutes to finally obtain a solution of gold-tin alloy nanoparticles.

[0052] The gold-tin alloy nanoparticles obtained in Example 3 were observed using a transmission electron microscope, and TEM, HAADF and EDS images were obtained. The particle size of the gold-tin alloy nanoparticles was also statistically analyzed. The gold-tin alloy nanoparticles obtained in Example 3 were tested using an X-ray diffractometer.

[0053] Figure 7 TEM images and particle size distribution diagrams of the gold-tin alloy nanoparticles obtained in Example 3 are shown.

[0054] Depend on Figure 7 It can be seen that the average particle size of the gold-tin alloy nanoparticles obtained in Example 3 is 20.54 nm.

[0055] Figure 8 The gold-tin alloy nanoparticles obtained in Example 3 are shown, where (a) is a HAADF image, and (b), (c), and (d) are EDS elemental surface scans.

[0056] Depend on Figure 8 It can be seen that the gold and tin are evenly distributed in the product prepared in Example 3, indicating that gold-tin alloy nanoparticles were successfully prepared.

[0057] Figure 9 The XRD pattern of the gold-tin alloy nanoparticles obtained in Example 3 is shown.

[0058] Depend on Figure 9 As can be seen, the product prepared in Example 3, when compared with the AnSn card, shows that the characteristic diffraction peaks of the two correspond, further indicating that gold-tin alloy nanoparticles were successfully prepared.

Claims

1. A gold-tin alloy nanoparticle, characterized in that, The molar ratio of Au to Sn is 1:x, 0.1≤x≤10; the average particle size is 16.1nm~20.6nm.

2. A method for preparing gold-tin alloy nanoparticles as described in claim 1, characterized in that, Includes the following steps: 1) Dissolve the soluble gold salt in a solvent, stir and heat after complete dissolution to obtain a gold salt solution; 2) Add the reducing agent to the gold salt solution, continue stirring and heating until the color changes, and obtain a gold nanoparticle solution; 3) After adding soluble tin salt and capping agent to the gold nanoparticle solution, a reducing agent is added to obtain a gold-tin alloy nanoparticle solution.

3. The preparation method according to claim 2, characterized in that, In step 1), the soluble gold salt is one or more of HAuCl4·3H2O, NaAuCl4·2H2O, and KAuCl4·H2O.

4. The preparation method according to claim 2, characterized in that, In step 1), the solvent is H2O or (CH3)3SiO.

5. The preparation method according to claim 2, characterized in that, In step 1), the stirring speed is 100~2000 r / min; the heating temperature is 90~200℃.

6. The preparation method according to claim 2, characterized in that, In step 2), the reducing agent is one or more of C6H8O7, C6H8O, and C4H6O4S.

7. The preparation method according to claim 2, characterized in that, In step 2), the average particle size of the gold nanoparticles is 16.1 nm to 20.6 nm.

8. The preparation method according to claim 2, characterized in that, In step 3), the soluble tin salt is one or more of SnCl4·5H2O, SnCl2·2H2O, Sn(CH3COO)2, SnSO4, and Sn(SO4)2.

9. The preparation method according to claim 2, characterized in that, In step 3), the capping agent is (C6H9NO). n One or more of C6H8O7.

10. The preparation method according to claim 2, characterized in that, In step 3), the reducing agent is one or more of NaBH4 and KBH4.

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