无氰共沉积电镀Au-Sn凸点的研究
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摘要
发光二级管LED (Light Emitting Diode)作为一种新型的绿色照明光源,与传统的照明灯相比,在功耗、亮度与寿命方面具有无与伦比的优势,必将成为21世纪的发展趋势。倒装芯片技术(Flip-Chip Technology)的使用极大的提高了LEDs的散热能力和出光效率,成为现阶段研究的热点,但同时也对芯片凸点的制作提出了更高的要求。
本论文选择Au-30at.%Sn共晶合金作为芯片的凸点材料,致力于开发一种稳定的无氰Au-Sn镀液来替代传统的氰化物镀液,并通过系列实验确定适用的镀液成分及电镀工艺参数,以实现共沉积法制备Au-30at.%Sn共晶凸点。研究结果表明：
1.开发出一种pH值在6-9内稳定的无氰Au-Sn镀液,该镀液以亚硫酸金钠、硫酸亚锡为主盐,亚硫酸钠、EDTA作为金络合剂,并向镀液中添加了一种锡络合剂。
2.施镀温度对镀层平整性影响较明显：当施镀温度在25～65℃之间变化时,温度过低镀层表面起伏较明显；温度过高,又会降低镀液的稳定性。所以,采用本论文所开发的无氰Au-Sn镀液施镀温度在45～55℃间较合适。
3.峰值电流密度影响镀层锡含量。采用本论文所开发的无氰Au-Sn镀液在低峰值电流密度下得到的镀层锡含量接近50at.%,而在高峰值电流密度下得到的镀层锡含量接近16at.%
4.在T=45℃、J=27.5 mA/cm2时,镀液中其他成分及其浓度保持不变的条件下,[Au(Ⅰ)]／[Na2SO3]摩尔浓度比在1：8～1：20之间时,镀速变化不大,继续改变比率至1：24,镀速有明显的增加。高Au(Ⅰ)浓度未必会带来更高的镀层金含量和更快的镀层生长速度,但却可能降低镀液的稳定性并增大了金的带出的浪费；Na2SO3含量过低,镀液稳定性不好,但过高的Na2SO3含量又会增大镀液的粘滞性。综合考虑,较适宜的Au(Ⅰ)浓度为0.02 mol／L、Na2SO3浓度为0.48 mol／L,对应于[Au(Ⅰ)]／[Na2SO3]=1：24。
As a new type of green lighting source, LED (Light Emitting Diodes) would surely lead the 21st century trends since their unmatched advantages at power consumption, luminance and lifetime compared with traditional lighting sources. The flip-chip technology improved the thermal dissipation and luminescence efficiency of High-power LEDs. However, higher requirements were submitted to the packaging technology.
Au-30at.%Sn eutectic solder was chosen for the bumps, and a stable non-cyanide electroplating solution for Au-Sn alloys must be developed to replace the traditional solutions containing cyanide. Besides, the solution component and the electroplating process parameters were decided for co-electrodepositing Au-30at.%Sn eutectic bumps. The results indicated that:
1. A stable non-cyanide electroplating solution with pH of 6 to 9 for Au-Sn alloys was developed. The solution contained Na3Au(SO3)2 (gold sodium sulfite) as the source of gold and SnSO4 (stannous sulfate) as the source of tin. Na2SO3 and EDTA were added as the complexing agent for gold, and an additional complexing agent for tin.
2. The plating temperature had an obvious effect on the surface planarization of the Au-Sn films. When the temperature was in the range from 25℃to 65℃, the lower the temperature the rougher the films; however, higher temperature would degrade the stability of the solution. The suitable plating temperature for the newly developed solution was 45-55℃.
3. Peak current density affected the tin content of Au-Sn films electroplated from the newly developed solution:Au-Sn films containing 50at.%Sn could be electroplated at low peak current density, while Au-Sn films containing 16at.%Sn electroplated at high peak current density.
4. When [Au (I)]/[Na2SO3] molar ratio varied from 1:8 to 1:20 respectively, the plating rate of the Au-Sn films electroplated under T=45℃, J=27.5 mA/cm2 had no significant change. However, when the ratio varied to 1:24, the plating rate had a sharply increase. High Au (I) concentration in the solution could not result in a higher gold content in the Au-Sn films and higher plating rate, but might degrade the stability of the solution and increase the gold waste. The decreasing of Na2SO3 concentration would degrade the solution stability, while the increasing Na2SO3 concentration would result in a higher viscosity. The suitable concentration for Au (I) and Na2SO3 in solution was 0.02 mol/L and 0.48 mol/L, i.e., the corresponding molar ratio of [Au (I)]/[Na2SO3] was 1:24.
本论文选择Au-30at.%Sn共晶合金作为芯片的凸点材料,致力于开发一种稳定的无氰Au-Sn镀液来替代传统的氰化物镀液,并通过系列实验确定适用的镀液成分及电镀工艺参数,以实现共沉积法制备Au-30at.%Sn共晶凸点。研究结果表明：
1.开发出一种pH值在6-9内稳定的无氰Au-Sn镀液,该镀液以亚硫酸金钠、硫酸亚锡为主盐,亚硫酸钠、EDTA作为金络合剂,并向镀液中添加了一种锡络合剂。
2.施镀温度对镀层平整性影响较明显：当施镀温度在25～65℃之间变化时,温度过低镀层表面起伏较明显；温度过高,又会降低镀液的稳定性。所以,采用本论文所开发的无氰Au-Sn镀液施镀温度在45～55℃间较合适。
3.峰值电流密度影响镀层锡含量。采用本论文所开发的无氰Au-Sn镀液在低峰值电流密度下得到的镀层锡含量接近50at.%,而在高峰值电流密度下得到的镀层锡含量接近16at.%
4.在T=45℃、J=27.5 mA/cm2时,镀液中其他成分及其浓度保持不变的条件下,[Au(Ⅰ)]／[Na2SO3]摩尔浓度比在1：8～1：20之间时,镀速变化不大,继续改变比率至1：24,镀速有明显的增加。高Au(Ⅰ)浓度未必会带来更高的镀层金含量和更快的镀层生长速度,但却可能降低镀液的稳定性并增大了金的带出的浪费；Na2SO3含量过低,镀液稳定性不好,但过高的Na2SO3含量又会增大镀液的粘滞性。综合考虑,较适宜的Au(Ⅰ)浓度为0.02 mol／L、Na2SO3浓度为0.48 mol／L,对应于[Au(Ⅰ)]／[Na2SO3]=1：24。
As a new type of green lighting source, LED (Light Emitting Diodes) would surely lead the 21st century trends since their unmatched advantages at power consumption, luminance and lifetime compared with traditional lighting sources. The flip-chip technology improved the thermal dissipation and luminescence efficiency of High-power LEDs. However, higher requirements were submitted to the packaging technology.
Au-30at.%Sn eutectic solder was chosen for the bumps, and a stable non-cyanide electroplating solution for Au-Sn alloys must be developed to replace the traditional solutions containing cyanide. Besides, the solution component and the electroplating process parameters were decided for co-electrodepositing Au-30at.%Sn eutectic bumps. The results indicated that:
1. A stable non-cyanide electroplating solution with pH of 6 to 9 for Au-Sn alloys was developed. The solution contained Na3Au(SO3)2 (gold sodium sulfite) as the source of gold and SnSO4 (stannous sulfate) as the source of tin. Na2SO3 and EDTA were added as the complexing agent for gold, and an additional complexing agent for tin.
2. The plating temperature had an obvious effect on the surface planarization of the Au-Sn films. When the temperature was in the range from 25℃to 65℃, the lower the temperature the rougher the films; however, higher temperature would degrade the stability of the solution. The suitable plating temperature for the newly developed solution was 45-55℃.
3. Peak current density affected the tin content of Au-Sn films electroplated from the newly developed solution:Au-Sn films containing 50at.%Sn could be electroplated at low peak current density, while Au-Sn films containing 16at.%Sn electroplated at high peak current density.
4. When [Au (I)]/[Na2SO3] molar ratio varied from 1:8 to 1:20 respectively, the plating rate of the Au-Sn films electroplated under T=45℃, J=27.5 mA/cm2 had no significant change. However, when the ratio varied to 1:24, the plating rate had a sharply increase. High Au (I) concentration in the solution could not result in a higher gold content in the Au-Sn films and higher plating rate, but might degrade the stability of the solution and increase the gold waste. The decreasing of Na2SO3 concentration would degrade the solution stability, while the increasing Na2SO3 concentration would result in a higher viscosity. The suitable concentration for Au (I) and Na2SO3 in solution was 0.02 mol/L and 0.48 mol/L, i.e., the corresponding molar ratio of [Au (I)]/[Na2SO3] was 1:24.
引文
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[25]Application of flip-chip-bonders in AuSn solder process to achieve high after bonding accuracy for optoelectronic modules [C]. IEEE/CMPT International electronics manufacturing technology symposium,2001.
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[2]王声学,吴广宁,蒋伟等.LED原理及其照明应用[J].灯与照明,2006,30(4)：32-35.
[3]杨清德,康娅.LED及其工程应用[M].北京：人民邮电出版社,2007：6-15.
[4]武毅.绿色光源-LED[J].灯与照明,2005,30(2)：45-48.
[5]Yanxu Zhu, Chen Xu, Xiaoli Da, et al. Enhanced output of flip-chip light-emitting diodes with a sidewall reflector[J]. Solid-State Electronics,2007,57(5): 674-677.
[6]王占庆,石瑞林.发光二极管(LED)将引发照明领域的革命[J].灯与照明,2005,29(3)：48-51.
[7]K. Takahashi, N. Tadokoro, S. Takeuti. LED array Unit with silicon microreflector [C],7th International Symposium on Micro Machine and Human Science (1994),67-70.
[8]James M. Gee, Jeffrey Y. Tsao, Jerry A. Simmons. Prospects for LED Lighting [C], Proceedings of SPIE Vol.5187(2004),227-233.
[9][日]大谷义彦著,夏晨译.LED照明现状与未来发展[J].中国照明电器,2007(6)：20-24.
[10]方志烈编著.半导体发光材料和器件[M].上海：复旦大学出版社,1992：1-30.
[11]中国LED产业概况.电子工业专用设备[J].2007(总第154)：35-41.
[12]马泽涛.白光高亮度发光二极管(HB-LED)封装技术研究(D).武汉：华中科技大学硕士学位论文,2005.
[13]张国义,陈志忠,杨志坚等.半导体照明光源研究进展[R].海峡两岸第十届照明科技及营销研讨会专题报告文集.2003：139-145.
[14]Jeff Y Tsao. Light Emitting Diodes (LEDs) for General Illumination [R]. Washington, DC:Optoelectronics Industry Development Association (OIDA),2002:7-9.
[15]陈明祥,罗小兵,马泽涛等.大功率白光LED封装设计与研究进展[J].半导体光电,2006,27(6)：6532658.
[16]龙乐.发光二极管封装结构及技术[J].电子与封装,2004,4(4)：24-32.
[17]郭江华,王水弟,张忠会等.倒装芯片凸焊点的UBM[J].半导体技术,2001,26(6)：60-64.
[18]Irving B. brazing and soldering:Facing new challenges [J]. Welding Journal,1998, 71(10):33-37.
[19]Trumble B. Get the lead out:lead-free electronics come of age [J]. JEEE Spectrum, 1998(5):55-60.
[20]刘泽光,陈登权,罗锡明等.金锡钎料性能及应用[J].电子与封装,2004(16)：24-26.
[21]周涛,汤姆鲍勃,马丁奥德等.金锡钎料及其在电子器件封装领域中的应用[J].电子与封装,2005(8)：5-8.
[22]曾华楔,吴仲达.电镀基本原理与实践[M].北京：机械工业出版社,1986.
[23]屠振密,李宁等.实用电镀合金技术[M].北京：国防工业出版社,2007：40-43.
[24]M. Hutter, H. Oppermann, G. Engelmann, et al. Calculation of Shape and Experimental Creation of AuSn Solder Bumps for Flip Chip Applications [C]. Electronic Components and Technology Conference,2002:282-288.
[25]Application of flip-chip-bonders in AuSn solder process to achieve high after bonding accuracy for optoelectronic modules [C]. IEEE/CMPT International electronics manufacturing technology symposium,2001.
[26]Fred C, Hayward. Pulse Plating Process for Deposition of Gold-tin alloy:US 2006/0163080 A1 [P],2006.
[27]邓正平,温青.锡及锡合金可焊性镀层电镀工艺[J].电镀与精饰,2006,28(5)：33-38.
[28]张立茗,方景礼等.实用电镀添加剂[M].北京：化学工业出版社,2007.
[29]方景礼.电镀添加剂理论与应用[M].国防工业出版社.北京：国防工业出版社,2006.
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