本論文所研究的重點是有關於微電子構裝中銲接點界面微結構變化所衍生之銲接點可靠度之問題。在環保概念抬頭、金屬化層之電致遷移問題(electromigration)日趨嚴重的今天，銲錫與金屬化層接合体(joint assembly)中(無鉛銲錫/金屬化層)是一典型的代表，而在一些加速時效(thermal aging)實驗後之機性測試，如剪切應力(shear stress)、拉力試驗(pull-off)、冷熱循環測試(thermal cycling)中，均顯示銲錫/金屬化層之界面斷裂(interfacial fracture)佔整体破壞比例中的大部分。究其原因，實因銲錫/金屬化層界面微結構變化所致，其中介金屬(intermetallic compound)的形成更影響其斷裂機制。
在本論文前半段之研究中，係以熱浸漬(hot dipping)的方法製作無鉛銲錫/金屬化層接合体，經熱時效試驗後，經由界面處表面形貌(interfacial morphology)的研究對介金屬化層作一系列的研究。發現其成長之機制是屬擴散控制(diffusion-controlled)，且其擴散係數(diffusivity)之活化能可藉由阿倫尼亞斯(Arrhenius)定律求得，而其介金屬層的厚度亦可經由數值分析的方法求得。至於銅及錫之元素濃度分布則可藉誤差函數(error function)做各區段的最適化，並經由Matano plane的訂定將原始之銲錫金屬化層界面求出。

論文之第二部份係以一些理論的模式將介金屬層之形成與成長作特性化(characterizatic)描述，經化簡後，以Gosele之理論代入，證明本研究中之銲錫/金屬化層組合界面處之兩種介金屬層均會成長。除此之外，再以Shatynski之模式驗證兩種金屬化層的厚度，是故本實驗所用的銲錫/金屬化層之接合体的衍進可與理論推導相配合。

第三部份則嘗試以統計的半定量量測結果來界定反應層各個相的界面，以電子微探儀中"相分析"(phase analysis)的軟體做輔助工具，代之以理論的推導後得到誤差小於5 %的精確結果，可有效地解決長久以來由於相變化(phase transformation)所形成之相界不明的問題。

第四部份中闡述了一種將介金屬化層厚度作精確量測的方法，經統計之分佈驗證其厚度之分佈是呈常態分配(normal distribution)，可藉由單次的二維面積量測取代一維的多次量測，而得到其真正的均值(mean)，與傳統之多次一維量測比較，發覺其量測誤差呈指數型降低(exponential decay)，根據這些指數函數的參數可以訂定一套更精確且省時的量測技術。

最後係以錫-銀及錫-銀-鋅兩種無鉛銲錫與鉑-銀/氧化鋁及銅/氧化鋁兩種作接合体，發覺其成長之動力學(kinetics)有別於前段(Sn/IMCs/Cu block joint assembly)之擴散控制之機制，經與實驗數據作最適化，發覺介金屬成長機制對錫-銀/鉑-銀/氧化鋁及錫-銀/銅/氧化鋁為晶界擴散控制(grain-boundary-diffusion controlled)，而錫-銀-鋅/鉑-銀/氧化鋁及錫-銀-鋅/銅/氧化鋁則分別為非平面化擴散機制(nonplanar diffusion-controlled)及平面化擴散機制(planar diffusion-controlled).

The development of the microstructure at the solder/metallization on solder/substrate interface significantly affects the mechanical properties of the joint assembly, and the degradation of the mechanical properties of the solder joint is caused by the formation of the intermetallic compound (IMC) during both the soldering and aging processes. Investigation concerning the growth kinetics, thermodynamics, and phase transformation related to the IMC, therefore, dominate the critical evaluation of the solder joint reliability in the microelectronic packaging.
In the first phase of this research, a joint assembly of lead-free solder/intermetallic layers/copper was prepared by hot-dipped solder coated on a copper substrate and then by thermal aging at 100, 125, 150, and 170℃ for 50, 100, 200, and 600 hours, respectively. Results of interfacial morphologies and concentration profiles on the solder/copper joint were presented. OM and SEM were used to measure the thickness of intermetallic layers and then to illucidate the development of microstructure at the joint assembly. The phases of intermetallic compound were identified to be Cu3Sn and Cu6Sn5 by both X-ray mapping in EPMA, and X-ray diffraction. The intermetallic layers, subtracted from the initial thickness formed by hot dipping, showed a linear dependence of square root of aging time at various aging temperature. The diffusion coefficients of intermetallic compounds are estimated by Arrhenius equation, and the pre-exponential terms of Cu3Sn layer and Cu6Sn5 layer are 7.10×10-7 cm2/sec and 6.1×10-3 cm2/sec, respectively. The associated activation energies of Cu3Sn layer and Cu6Sn5 layer are 57.03 KJ/mol and 83.76 KJ/mol, respectively. A model of diffusion-controlled mechanism is used to fit the concentration profiles of the joint assembly, and exhibits a fairly good quantitative agreement with the measured data. The initial thickness formed as soldering is also taken into account to evaluate the apparent thickness by introducing a term of correcting aging time.

The phase transformation of the joint assembly was compared to the phase diagram of binary alloy, Cu - Sn, and it showed an agreement with the resultant intermetallic phases formed between the pure tin and pure copper. Two theoretical models proposed by Gosele and Shatynski were developed and then employed to characterize the assembly. The Gosele's model was used to predict whether the intermetallic layers grew or shrank during aging, while the Shatynski's model was employed to estimate the related reactive thicknesses and hence the ratios of the interdiffusivities in the joint assembly. After a series of calculations, the Gosele's model predicted that Cu6Sn5 and Cu3Sn intermetallic layers became thicker. Evaluation of intermetallic interdiffusivities was also proven to approach theoretical ones from the Shatynski's model.

In addition, X-ray color mappings by electron probe microanalyzer (EPMA) of copper and tin were also applied to study the concentration variations near the interfaces in the joint assembly. According to the intensities of Cu and Sn, collected by color mapping, a developed software was employed to construct series of statistical graphs, and the detailed concentration profiles at the interfaces of the assembly were investigated from these graphs. Two important results are derived. The first is that analysis of interfacial concentration profile exhibits the phases of Cu3Sn-rich, Cu6Sn5-rich and tin-rich, which match with boundaries of solder/Cu6Sn5, Cu6Sn5/ Cu3Sn and Cu3Sn/copper, respectively. The second is that the semi-quantitative measurement with a peak-fitting model employed suffices to evaluate the interfacial concentration profiles with a statistical variation less than 5 mol %.

A MLC/Sn-Ag-Zn/Pt-Ag metallization joint assembly aged at 150 ℃ was then prepared and investigated with electron microscope. Both secondary electron image (SEI) and backscattered electron image (BEI) were employed to observe the intermetallic layers, Ag3Sn, which were formed between solder and metallization with an irregular shape. The thickness profile of intermetallic layer showed a typical normal distribution by the employment of Person's goodness-of-fit. The mean of intermetallic thickness was obtained by transformation from one-dimensional linear length measurement to two-dimensional area measurement with an image processor. A criterion of which deviation of average thickness from the mean is less than 0.5% was established as the reference to estimate the relative error of other measurements with different measuring times. With the increasing measuring times, both the relative error to mean for average thickness and relative deviation to the standard deviation of the criterion were decreased with an exponential decay function. In addition, a quantitative measurement method to reduce the measuring error was demonstrated by the exponential function.

Finally, the kinetics of the IMC growth was investigated with the joint assemblies of Sn-Ag-1Zn/Pt-Ag, Sn-Ag/PtAg, Sn-Ag-1Zn/Cu, or Sn-Ag/Cu experienced thermal aging at 1500C. The morphologies of these joint assemblies were investigated by electron microscope. Related kinetics models were derived to cope with the microstructure development of the intermetallic compound (IMC) growth. After modified fitting with the derived model, the measured IMC thicknesses exhibited good regression with theoretically modeled curves. The derived kinetics for various joint assemblies were nonplanar-diffusion-controlled for Sn-Ag-1Zn/Pt-Ag, grain boundary diffusion controlled for Sn-Ag/PtAg, planar-diffusion-controlled for Sn-Ag-1Zn/Cu, and grain boundary diffusion controlled for both Sn-Ag/Pt-Ag and Sn-Ag/Cu, respectively. The obtained interdiffusivity of IMC for the joint assemblies of Sn-Ag-1Zn/Pt-Ag and Sn-Ag-1Zn/Cu were 2.76’10-12 cm2/sec for DAg3Sn and 1.12’10-12 cm2/sec for DCu6Sn5, respectively. Correlations of the derived model in various joint assembly with the morphological evolution in the microstructure investigation of the interfaces are discussed. Particularly the time dependence of IMC growth thickness is probed and compared with those in literature. In addition, a detailed precision measurement of IMC thickness is proposed.

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