• Applied Science and Convergence Technology
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• v.23 no.6
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• pp.345-350
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• 2014

The surface oxidation mechanism of lead-free solder alloys has been investigated with multiple reflow using X-ray photoelectron spectroscopy. It was found that the solder surface of Sn-Ag-Cu-In solder alloy is surrounded by a thin $InO_x$ layer after reflow process; this coating protects the metallic surface from thermal oxidation. Based on this result, we have performed a wetting balance test at various temperatures. The Sn-Ag-Cu-In solder alloy shows characteristics of both thermal oxidation and wetting balance better than those of Sn-Ag-Cu solder alloy. Therefore, Sn-Ag-Cu-In solder alloy is a good candidate to solve the two problems of easy oxidation and low wettability, which are the most critical problems of Pb-free solders.

• Journal of the Korean Society for Heat Treatment
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• v.23 no.5
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• pp.233-238
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• 2010

The phase transformations and the shape memory effect in In-rich Pb alloys and In rich-Sn alloys have been studied by means of X-ray diffractometry supplemented by metallographic observations. The alloys containing 12~15 at.%Pb transform from the ${\alpha}_2$ (fct) phase to the ${\alpha}_1$ (fct) phase by way of an intermediate phase (m phase) on cooling. The results of X-ray diffraction show that the metastable intermediate phase is observed both on cooling and heating, and has a face-centered orthorhombic (fco) structure. It is concluded that the ${\alpha}_1{\rightleftarrows}{\alpha}_2$ transformation is expressed by the ${\alpha}_1{\rightleftarrows}m{\rightleftarrows}{\alpha}_2$ transformation both on usual cooling and heating with the rate more than $8{\times}10^{-3}$ K/s. The $m{\rightleftarrows}{\alpha}_2$ transformation takes place with a mechanism involving macroscopic shear and are of diffusionless (martensitic) type. The temperature hysteresis in the two transformations is 10~13 K between the heating and cooling transformations. The alloys containing 0~11 at.%Sn are -phase solid solutions with a face centered tetragonal structure (c/a > 1) at room temperature, the axial ratio increasing continuously with tin content. The In-(11~15) at.%Sn alloys are mixtures of ${\alpha}$ and ${\beta}$ phases, the ${\beta}$ phase having a f. c. tetragonal structure (c/a < 1). The alloys containing more than 15 at.%Sn are ${\beta}$-phase solid solutions. The In-(12.9~15.0) at.%Sn alloys show a shape memory effect only when quenched to the temperature of liquid nitrogen, although their effect becomes weak and finally disappears after keeping at room temperature for a long time. The ${\beta}{\rightarrow}{\alpha}^{\prime}$ phase transformation is of the diffusionless (martensitic) type, and takes place between 330 K at 12.9 at.%Sn and 150 K at 14.5 at.%Sn. The hysteresis of transformation temperatures on heating and cooling is considerably large (29~40 K), depending on the composition. Both In-Pb and In-Sn alloys showed distinct the shape memory effects.

• Journal of the Microelectronics and Packaging Society
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• v.8 no.3
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• pp.37-42
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• 2001

The concerns of the toxicity and health hazard of lead in solders have demanded the research to find suitable lead-free solder alloys. It was discussed that effect of the intermetallic formation and structure on the reliability of solder joints. In this study, lead-free solder alloys with compositions of Sn/3.5Ag/0.75Cu, Sn/2.0Ag/0.5Cu/2.0Bi were applied to the 48 $\mu$BGA packages. Also, the lead-free solder alloys compared with eutectic Sn/37Pb solder using shear test under various aging temperature. Common $\mu$BGA with solder components was aged at $130^{\circ}C$, $150^{\circ}C$ and $170^{\circ}C$. And the each temperature applied to 300, 600 and 900 hours. The thickness of the intermetallics was measured for each condition and the activation energy for their growth was computed. The fracture surfaces were analyzed using SEM (Scanning Electron Microscope) with EDS (Energy Dispersive Spectroscopy). These results for reliability of lead-free interconnections are discussed.

• Proceedings of the KWS Conference
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• 2009.11a
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• pp.72-72
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• 2009

전자부품의 내부접속 및 파워반도체의 다이본딩과 같은 1차실장에는 고온환경에서의 사용과 2차실장에서의 재용융방지를 위해 높은 액상선온도 및 고상선온도를 필요로 하여, Pb-5wt%Sn, Pb-2.5wt%Ag로 대표되는 납성분 85%이상의 고온솔더가 널리 사용되고 있다. 생태계와 인체에 대한 납의 유해성이 보고된 이래, 무연솔더에 대한 연구가 활발히 진행되어 왔으나, Sn-Ag-Cu계로 대표되는 Sn계 합금으로 대체 중인 중온용 솔더와는 달리, 고온용 솔더에 대해서는 대체합금에 대한 연구가 미흡한 실정이다. 대체재의 부재로 인해 기존의 납을 다량함유한 솔더로 1차실장이 지속됨으로서, 2차실장의 무연화에도 불구하고 전자부품 및 기기의 재활용에 큰 어려움을 겪고 있다. 지금까지 고온용 무연솔더로서는 융점에 근거해 Au-(Sn, Ge, Si)계, Bi-Ag계, Zn-(Al, Sn)계의 극히 제한된 합금계만이 보고되어 왔다. Au계 솔더는 현재 플럭스를 사용하지 않는 광학, 디스플레이 분야 등 고부가가치 공정에 사용되고 있으나, 합금가격이 매우 비싸며 가공성이 나빠 대체재료로서는 적합하지 않다. Bi-Ag계 솔더 또한 취성합금으로 와이어 및 박판으로 가공하는데 어려움이 크며, 솔더로서 중요한 특성중 하나인 전기전도도 및 열전도도가 나쁜 편이다. 이에 비해, Zn계 합금은 비교적 낮은 합금가격, 적절한 가공성과 뛰어난 인장강도, 우수한 전기전도도 및 열전도도를 지녀, 고온용솔더 대체재료의 유력한 후보로 생각된다.이전 연구에서, 필자의 연구그룹은 Zn-Sn계 합금을 고온용 무연솔더로서 제안한 바 있다. Zn-Sn계 합금은 충분히 높은 융점과 함께, 금속간화합물이 없는 미세조직, 우수한 기계적 특성, 높은 전기전도도 및 열전도도 등의 장점을 나타내었다. 본 연구에서는 기초합금특성상 고온솔더로서 다양한 장점을 지닌 Zn-30wt%Sn합금을 고온용 솔더의 대표적인 적용의 하나인 다이본딩에 적용하여, 접합부의 강도 및 미세조직, 열피로 신뢰성에 대해 분석을 함으로서 실제 공정에의 적용가능성에 대해 검토하였다. Zn-30wt%Sn을 이용해 Au/TiN(Titanium nitride) 코팅한 Si다이를 AlN-DBC(aluminum nitride-direct bonded copper)기판에 접합한 결과, 양측에 완전히 젖은 기공이 없는 양호한 다이접합부를 얻었으며, 솔더내부에는 금속간화합물을 형성하지 않았다. Si다이와의 계면에는 TiN만이 존재하였으며, Cu와의 계면에는 Cu로부터 $Cu_5Zn_8,\;CuZn_5$의 반응층을 형성하였다. 온도사이클시험을 통한 열피로특성평가에서, Zn-30wt%Sn를 이용한 다이접합부는 1500사이클 지점에서 Cu와 Cu-Zn금속간화합물의 사이에서 피로균열이 형성되며, 접합강도가 크게 감소하였다. 열피로특성 향상을 위해 Cu표면에 TiN코팅을 하여 Zn-30wt%Sn 솔더로 다이접합한 결과, Si다이와 기판 양측에 TiN만으로 구성된 계면을 형성하였으며, TEM관찰을 통해 Zn-30wt%Sn과 극히 미세한 접합계면이 형성하고 있음을 확인하였다. Zn-wt%30Sn솔더와 TiN층의 병용으로 2000사이클까지 미세조직의 변화 및 강도저하가 없는 극히 안정된 고신뢰성의 다이접합부를 얻을 수가 있었다.

• Journal of Welding and Joining
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• v.24 no.6
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• pp.21-27
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• 2006

This study was focused on the evaluation of the thermo-mechanical board-level reliability of Pb-bearing and Pb-free surface mount assemblies. The composition of Pb-bearing solder was a typical Sn-37Pb and that of Pb-free solder used in this study was a representative Sn-3.0Ag-0.5Cu in mass %. Thermal shock test was chosen for the reliability evaluation of the solder joints. Typical $Cu_6Sn_5$ intermetallic compound (IMC) layer was formed between both solders and Cu lead frame at the as-reflowed state, while a layer of $Cu_3Sn$ was additionally formed between the $Cu_6Sn_5$ and Cu lead frame during the thermal shock testing. Thickness of the IMC layers increased with increasing thermal shock cycles, and this is very similar result with that of isothermal aging study of solder joints. Shear test of the multi layer ceramic capacitor(MLCC) joints was also performed to investigate the degradation of mechanical bonding strength of solder joints during the thermal shock testing. Failure mode of the joints after shear testing revealed that the degradation was mainly due to the excessive growth of the IMC layers during the thermal shock testing.

• Proceedings of the KIEE Conference
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• 1991.07a
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• pp.194-197
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• 1991

In this study, $(Pb_{0.99}La_{0.01})[(Sb_{1/2}Sn_{1/2})_{0.10}Ti_{0.25}Zr_{0.65}]O_3$, added $MnO_2$ (0-0.30[mol%]) ceramics were fabricated by the mixed oxide method. The sintering temperature and time were $1250[^{\circ}C]$, 2[hr], respectively. In the $(Pb_{0.99}La_{0.01})[(Sb_{1/2}Sn_{1/2})_{0.10}Ti_{0.25}Zr_{0.65}]O_3$ added $MnO_2$ (0.24[mol%]) specimens, relative dielectric constant and dielectric loss were minimum values 3.52, 0.003, respectively, and Curie temperature were highest values $256[^{\circ}C]$. Pyroelectric coefficient and voltage responsivity of the $(Pb_{0.99}La_{0.01})[(Sb_{1/2}Sn_{1/2})_{0.10}Ti_{0.25}Zr_{0.65}]O_3$, and added $MnO_2$ (0.24[mol%]) specimen were good values, $6.73{\times}10^{-8}[C/cm^2K],\;125[v/W]$, respectively. Figure of merit of pyroelectric current, voltage and detectivity of the specimen, $(Pb_{0.99}La_{0.01})[(Sb_{1/2}Sn_{1/2})_{0.10}Ti_{0.25}Zr_{0.65}]O_3$ added $MnO_2$ (0.24[mol%]) were good values $2.714{\times}10^{-8}[Ccm/J],\;7.706{\times}10^{-11}[Ccm/J],\;2.640{\times}10^{-8}[Ccm/J]$, respectively. Voltage responsivity of the $(Pb_{0.99}La_{0.01})[(Sb_{1/2}Sn_{1/2})_{0.10}Ti_{0.25}Zr_{0.65}]O_3$ added $MnO_2$ (0.24[mol%]) specimens were decreased with increasing the chopper frequency.

• Proceedings of the Materials Research Society of Korea Conference
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• 2003.03a
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• pp.68-68
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• 2003

최근의 전자부품은 고밀도 고집적화 됨에 따라 여러 가지 문제점들이 발생되고 있다. 그 중 부품이 실장되는 부분에 사용되는 솔더나 전기적 회로를 구성하는 패턴간에 금속 이온 마이그레이션(Metallic Ion Migration)이 발생하여 전기적 단락(Short)를 유발함으로써 전자제품의 치명적 고장을 유발한다. 본 연구는 이온 마이그레이션 현상을 물방울시험(Water Drop Test)을 통하여 재현함으로써 발생 메카니즘을 확인하여 발생원인을 직접적으로 관찰하고, 각 종 패턴의 거리 및 전압에 따른 발생속도의 차이를 조사하기 위하여 수행되었다. 이러한 실험을 위하여 콤 패턴(Comb Pattern)의 FR-4 재질 인쇄회로기판(PCB : Printed Circuit Board)을 사용하였으며, 사용된 전극재질로는 Cu, SnPb, Au를 사용하였고, 패턴간 거리는 0.5, 1.0, 2.0mm의 3가지 종류로 구분하였다. 또한 패턴간에 인간 된 전압은 6.5V, 15V를 인가한 후 마이그레이션이 발생되는 시간을 측정하였다. 이러한 실험으로부터 다음과 같은 결론을 얻었다. (1) 6.5V의 인가전압에서는 Cu 패턴이 대체적으로 가장 빠르게 마이그레이션이 발생하였으며, 다음으로 Au가 발생하였고, Cu와 SnPb의 발생시간은 대체적으로 근사한 값을 나타내었다. 이것은 비슷한 평형전위를 갖는 재료는 마이그레이션 발생시간이 유사하게 나타나며, 높은 (+)전위를 갖을수록 발생시간이 지연됨을 알 수 있다. (2) 15V를 인가하였을 때 패턴간격이 0.5mm인 경우 Cu, Au, SnPb의 순으로 나타났으며, 1.0mm는 SnPb, Cu, Au, 2.0mm인 경우는 SnPb, Au, Cu의 순으로 마이그레이션이 발생하였다. 인가전압이 높은 경우 초기 발생에는 큰 차이가 없지만 수지상이 발생 후 성장하는데 많은 영향을 미치는 것으로 보인다. 이것은 초기 수지상의 형성에 큰 영향을 미치는 것은 재료의 평형전위에 의한 값이 좌우하지만, 수지상이 일정길이 이상 형성된 이후에는 성장속도가 평형전위에 따른 값과는 다소 다르게 나타남을 알 수 있다.

• Transactions of the Korean Society of Automotive Engineers
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• v.21 no.3
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• pp.134-141
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• 2013

Reflow soldering process is essential in electronic package. Reflow process for a long time results from the decrease of reliability because IMC is formed excessively. Solder alloys of Sn-37Pb and Sn-Ag with different kinds of Cu contents (0, 0.5 and 1 wt.%) as compared with Ni and Cu plate joints are investigated according to varying reflow time. The interfaces of solder joints are observed to analyze IMC (intermetallic compound) growth rate by scanning electron microscope (SEM). Shear test is also performed by using SP (Share-Punch) tester. The test results are compared with the solder joints of two different plates (Ni and Cu plate). $Cu_6Sn_5$ IMCs are formed on Cu plate interfaces after reflows in all samples. Ni3Sn4 and $(Cu,Ni)_6Sn_5$ IMCs are also formed on Ni plate interfaces. The IMC layer forms are affected by reflow time and contents of solder alloy. These results show that mechanical strength of solder joints strongly depends on thickness and shape of IMC.

• Resources Recycling
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• v.14 no.5 s.67
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• pp.24-31
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• 2005

In order to recover valuable metals from fine-grained electronic waste, bioleaching of Cu, Zn, Al, Co, Ni, Fe, Sn and Pb were carried out using Aspergillus niger as a leaching microorganism in a shaking flask. Aspergillus niger was able to grow in the presence of electronic scrap. The formation of organic acids(citric and oxalic acid) from Aspergillus niger caused the mobilization of metals from waste electronic scrap. In a preliminary study, in order to obtain the data on the leaching of Cu, Zn, Al, Fe, Co and Ni from electronic scrap, chemical leaching using organic acid(Citric acid and Oxalic acid) was accomplished. At the electronic scrap concentration of 50 g/L, Aspergillus niger were able to leach more than 95% of the available Cu, Co. But Al, Zn, Pb and Sn were leached about 15-35%. Ni and Fe were detected in the leachate less than 10%.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 1993.11a
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• pp.10-13
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• 1993

ln this study, x PSN - y PT - z PZ ceramics doped with w MnO$_2$were fabricated by the mixed oxide method at 1250[$^{\circ}C$] for 2[hr] and then the dielectric and pyroelectric properties were investigated. In the 0.05 PSN - 0.4 PT - 0.55 PZ specimen with 0.5[wt.%] MnO$_2$, the pyroelectric coefficient was 6.6${\times}$10$\^$-8/[C/cm$^2$$.$$^{\circ}C$], respectibly.