• Journal of the Microelectronics and Packaging Society
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• v.15 no.4
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• pp.87-92
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• 2008

The interface microstructure of Sn-3.5Ag/Cu joint was modified by electroplating varying amount of Zn on Cu UBM. As the amount of Zn dissolved in Sn-3.5Ag solder increased with the electroplating Zn thickness, Cu-Sn IMCs such as $Cu_6Sn_5$ and $Cu_3Sn$ were replaced by Zn-containing IMCs such as $Cu_5Zn_8$ and $Ag_5Zn_8$, which increased the drop reliability of solder joints significantly. When the amount of Zn dissolved in solder was about 3.8wt%, drop resistance was best due to the effective suppression of Cu-Sn IMC and voids at the interface.

• Korean Journal of Materials Research
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• v.23 no.6
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• pp.304-308
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• 2013

The effect of a sputter deposition sequence of Cu, Zn, and Sn metal layers on the properties of $Cu_2ZnSnS_4$ (CZTS) was systematically studied for solar cell applications. The set of Cu/Sn/Zn/Cu multi metal films was deposited on a Mo/$SiO_2$/Si wafer using dc sputtering. CZTS films were prepared through a sulfurization process of the Cu/Sn/Zn/Cu metal layers at $500^{\circ}C$ in a $H_2S$ gas environment. $H_2S$ (0.1%) gas of 200 standard cubic centimeters per minute was supplied in the cold-wall sulfurization reactor. The metal film prepared by one-cycle deposition of Cu(360 nm)/Sn(400 nm)/Zn(400 nm)/Cu(440 nm) had a relatively rough surface due to a well-developed columnar structure growth. A dense and smooth metal surface was achieved for two- or three-cycle deposition of Cu/Sn/Zn/Cu, in which each metal layer thickness was decreased to 200 nm. Moreover, the three-cycle deposition sample showed the best CZTS kesterite structures after 5 hr sulfurization treatment. The two- and three-cycle Cu/Sn/Zn/Cu samples showed high-efficient photoluminescence (PL) spectra after a 3 hr sulfurization treatment, wheres the one-cycle sample yielded poor PL efficiency. The PL spectra of the three-cycle sample showed a broad peak in the range of 700-1000 nm, peaked at 870 nm (1.425 eV). This result is in good agreement with the reported bandgap energy of CZTS.

• Korean Journal of Materials Research
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• v.23 no.3
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• pp.183-189
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• 2013

$Cu_2ZnSn(S,Se)_4$ material is receiving an increased amount of attention for solar cell applications as an absorber layer because it consists of inexpensive and abundant materials (Zn and Sn) instead of the expensive and rare materials (In and Ga) in $Cu(In,Ga)Se_2$ solar cells. We were able to achieve a cell conversion efficiency to 4.7% by the selenization of a stacked metal precursor with the Cu/(Zn + Sn)/Mo/glass structure. However, the selenization of the metal precursor results in large voids at the absorber/Mo interface because metals diffuse out through the top CZTSe layer. To avoid the voids at the absorber/Mo interface, binary selenide compounds of ZnSe and $SnSe_2$ were employed as a precursor instead of Zn and Sn metals. It was found that the precursor with Cu/$SnSe_2$/ZnSe stack provided a uniform film with larger grains compared to that with $Cu_2Se/SnSe_2$/ZnSe stack. Also, voids were not observed at the $Cu_2ZnSnSe_4$/Mo interface. A severe loss of Sn was observed after a high-temperature annealing process, suggesting that selenization in this case should be performed in a closed system with a uniform temperature in a $SnSe_2$ environment. However, in the experiments, Cu top-layer stack had more of an effect on reducing Sn loss compared to $Cu_2Se$ top-layer stack.

• Proceedings of the Materials Research Society of Korea Conference
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• 2009.05a
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• pp.35.2-35.2
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• 2009

최근 본 연구실에서 무연 솔더를 위한 새로운 Cu-Zn 합금 젖음층을 개발하였다. 전해도금을 통하여 Cu-Zn 합금층을 형성한 뒤 그 위에 Sn-4.0wt% Ag-0.5wt% Cu (SAC 405) 솔더를 리플로 솔더링을 통해 솔더접합부를 형성하였으며 계면에서 생성된 금속간 화합물의 형성 및 성장 거동을 연구하였다. SAC/Cu 시스템의 경우, $150^{\circ}C$에서 시효 처리를 실시하는 동안 솔더와 도금된 Cu 계면에서 $Cu_6Sn_5$ 상과 미세한 공공이 형성된 $Cu_3Sn$ 상이 발견되었다. 반면에 SAC/Cu-Zn 시스템에서는 계면에서 $Cu_6Sn_5$ 상만이 형성되었다. 또한 큰 판상형의 $Ag_3Sn$ 상이 SAC/Cu 시스템에 비해 현저하게 억제되었다. SAC/Cu-Zn 계면에서의 금속간 화합물의 성장 속도가 SAC/Cu 계면에서 형성된 금속간 화합물의 성장 속도보다 느리게 나타났다. Cu-Zn 젖음층의 Zn가 솔더와 Cu-Zn 층 사이에서 Cu와 Sn 원자의 상호 확산을 방해하기 때문이다. 본 연구에서는 Cu와 Cu-Zn 층을 이용한 솔더 접합부의 낙하 충격 신뢰성을 연구하였다. 낙하 충격 시험 시편은 두 개의 인쇄 회로 기판을 SAC 405 솔더볼을 이용하여 리플로를 통해 상호연결 하여 제조되었다. 이 때, 각각의 인쇄 회로 기판의 패드에는 Cu 층과 Cu-Zn층을 전해도금을 통하여 각각 $10{\mu}m$두께의 젖음층을 형성하였다. 낙하 시험 시편을 제조한 뒤, 시효 처리에 대한 낙하 저항 신뢰성의 특성을 연구하기 위해 250, 500 시간동안 시효처리를 한 후 각 조건에서 계면에 형성된 금속간 화합물의 성장 거동을 관찰하였으며, 낙하 충격 시험을 실시하였다. 낙하 시험은 daisy chain으로 연결된 시편의 저항이 100 Ohm 이상 측정되었을 때 중단되도록 하였다. Cu-Zn/SAC/Cu-Zn 시편의 경우 초기 리플로를 하였을 때 불량이 발생하는 평균 낙하 수는 350이며, Cu/SAC/Cu 시편의 평균 낙하수는 200 미만으로 나타났다. Cu/SAC/Cu 시편의 경우, 시효처리 시간이 증가함에 따라 평균 낙하수는 큰 폭으로 감소하였지만, Cu-Zn/SAC/Cu-Zn 시편은 불량이 발생하는 평균 낙하수의 감소폭이 보다 완만하게 나타났다. Cu 층에 Zn를 첨가함으로써 솔더와 젖음층 사이에서 형성된 금속간 화합물의 성장 및 미세 공공의 형성이 억제되었고, 솔더 접합부의 과냉을 감소시킴으로써 큰 판상형의 $Ag_3Sn$ 상의 형성을 억제함으로써 Cu-Zn/SAC/Cu-Zn 솔더 접합부에서 Cu/SAC/Cu 솔더 접합부보다 낙하 충격에 대한 저항성 및 신뢰성이 향상되었다. 이는 무연 솔더에 Zn를 첨가하여 낙하 충격 신뢰성을 향상시킨 것과 동일한 효과를 나타냈음을 확인하였다. 본 연구는 한국 과학 기술 재단의 전자패키지 재료 연구 센터(CEPM)와 지식 경제부의 부품 소재 기술 개발 사업의 지원을 받아 수행되었습니다.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.134-137
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• 2009

Commercially available elemental powders of Cu, Zn, Sn and Se were employed for crystallizing a stannite-type $Cu_2ZnSnSe_4$ compound by means of solid state reaction. $Cu_2ZnSnSe_4$ reaction chemistry was also modeled based on differential-thermal analysis and X-ray powder diffraction results. It was observed that Se tends to react preferably with Cu to form CuSe and $CuSe_2$ phases at low reaction temperature. The formation of $Cu_5Zn_8$ intermetallic phase was found to be the intermediate reaction path for the binary ZnSe formation. A solid state reaction at $320^{\circ}C$ reacted elemental powderst obinary selenides of CuSe, ZnSe and SnSe completely. The crystallization of $Cu_2ZnSnSe_4$ was was detected to begin at $300^{\circ}C$ and its weight fraction increased with an increase of reaction temperature, which most probably formed from the reaction between $Cu_2SnSe_3$ and ZnSe.

• Proceedings of the KWS Conference
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• 2005.11a
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• pp.219-221
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• 2005

Sn-9Zn solder balls were bonded to Cu, ENIG (Electroless Nickel/Immersion Gold) and electrolytic Au/Ni pads, and the effect of aging on their joint reliability was investigated. The interfacial products were different from the general reaction layer formed in a Sn-base solder. The intermetallic compounds formed in the solder/Cu joint were $Cu_{5}Zn_{8}$ and $Cu_{6}Sn_{5}$. After aging treatment, voids formed irregularly at the bottom side of the solder because of Sn diffusion into the $Cu_{5}Zn_{8}$ IMC. In the case of the solder/ENIG joint, $AuZn_{3}$ IMCs were formed at the interface. In the case of the Au/Ni/Cu substrate, an $AuZn_{3}$ IMC layer formed at the interface due to the fast reaction between Au and Zn. In addition, the $AuZn_{3}$ IMC layer became detached from the interface after reflow. When the aging time was extended to 100 h, $Ni_{5}Zn_{21}$ IMC was observed on the Ni substrate.

• Proceedings of the KWS Conference
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• 2005.06a
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• pp.25-27
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• 2005

Sn-9Zn solder balls were bonded to Cu and ENIG (Electroless Nickel/Immersion Gold) pads, and the effect of aging on their joint reliability was investigated. The interfacial products were different from the general reaction layer formed in a Sn-base solder. The intermetallic compounds formed in the solder/Cu joint were $Cu_{5}Zn_{8}$ and $Cu_{6}Sn_{5}$. After aging treatment, voids formed irregularly at the bottom side of the solder because of Sn diffusion into the $Cu_{5}Zn_{8}$ IMC. In the case of the solder/ENIG joint, $AuZn_{3}$ IMCs were formed at the interface. In the case of the Sn-9Zn/ENIG, the shear strength remained nearly constant in spite of aging for 1000 hours at $150^{\circ}C$. On the other hand, in the case of the Sn-9Zn/Cu, the shear strength significantly decreased after aging at $150^{\circ}C$ for 100hours and then remained constant by further prolonged aging. Therefore, the protective plating layer such as ENIG must be used to ensure the mechanical reliability of the Sn-9Zn/Cu joint.

• Journal of Korea Foundry Society
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• v.22 no.2
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• pp.89-96
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• 2002

This study examined the effects of adding Zn to Sn-3.5Ag solder on the microstructure changes and behavior of interface reaction of the solder joint with Cu substrate. The solder/Cu joints were examined with microscope to observe the characteristics of microstructure changes and interfacial reaction layer with aging treatment for up to 120 days at $150^{\circ}C$. Results of the microstructure changes showed that the microstructures were coarsened with aging treatment, while adding 1%Zn suppresses coarsening microstructures. The Sn-3.5Ag/Cu had a fast growth rate of the reaction layer in comparison with the Sn-3.5Ag-1Zn at the aging temperature of $150^{\circ}C$. Through the SEM/EDS analysis of solder joint, it was proved that intermetallic layer was $Cu_6Sn_5$ phase and aged specimens showed that intermetallic layer grew in proportion to $t^{1/2}$, and the precipitate of $Ag_3Sn$ occur to both inner layer and interface of layer and solder. In case of Zn-containing composite solder, $Cu_6Sn_5$ phase formed at the side of substrate and Cu-Zn-Sn phase formed at the other side in double layer. It seems that Cu-Zn-Sn phase formed at solder side did a roll of banrier to suppress the growth of the $Cu_6Sn_5$ layer during the aging treatment.

• Korean Journal of Materials Research
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• v.9 no.7
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• pp.747-752
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• 1999

The interfacial reaction and joint properties of Sn-3.5Ag/Cu and Sn-3.5Ag-1Zn/Cu joint were studied. Modified double lap shear solder joints of Sn-3.5Ag and Sn-3.5Ag- lZn solder were aged for 60days at $100^{\circ}C$ and $150^{\circ}C$ and then loaded to failure in shear. The Sn-3.5Ag/Cu had a fast growth rate of the reaction layer in comparison with the Sn-3.5Ag-lZn at the aging temperature of $150^{\circ}C$ Through the SEM/EDS analysis of solder joint, it was proved that intermatallic layer was $Cu_{6}Sn_5$ phase and aged specimens showed that intermatallic layer grew in proportion to $t_{1/2}$, and the precipitate of $Ag_3Sn$ occur to both inner layer and interface of layer and solder. In case of Zn-containing composite solder, $Cu_{6}Sn_{5}$ phase formed at the side of substrate and $Cu_{5}Zn_{8}$ phase formed at the other side in double layer. The shear strength of the Sn-3.5Ag/Cu joint improved by addition of IZn. The strength of the joint increases with strain rate and decreases with aging temperature

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2331-2334
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• 2014

$Cu_2SnSe_3$ (CTSe) and $Cu_2ZnSnSe_4$ (CZTSe) nanoparticles were synthesized by sonochemical reactions under multibubble sonoluminescence (MBSL) conditions. First, $Cu_2SnSe_3$ nanoparticles were synthesized by the sonochemical method with an 85% yield, using CuCl, $SnCl_2$, and Se. Second, ZnSe was coated on the CTSe nanoparticles by the same method. Then, they were transformed into CZTSe nanoparticles of 5-7 nm diameters by heating them at $500^{\circ}C$ for 1 h. The ratios between Zn and Sn could be controlled from 1 to 3.75 by adjusting the relative concentrations of CTSe and ZnSe. With relatively lower Zn:Sn ratios (0.75-1.26), there are mostly CZTSe nanoparticles but they are believed to include very small amount of CTS and ZnSe particles. The prepared nanoparticles show different band gaps from 1.36 to 1.47 eV depending on the Zn/Sn ratios. In this sonochemical method without using any toxic or high temperature solvents, the specific stoichiometric element Zn/Sn ratios in CZTSe were controllable on demand and their experimental results were always reproducible in separate syntheses. The CZTSe nanoparticles were investigated by using X-ray diffractometer, a UV-Vis spectrophotometer, scanning electron microscope, Raman spectroscopy, and a high resolution-transmission electron microscope.