A newly developed Cu(Rh) alloy film and its characteristics and applications

Chon-Hsin Lin
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Abstract

A new type of copper (Cu)-rhodium (Rh)-alloy, Cu(Rh), films is developed by co-sputtering copper and rhodium onto silicon (Si) substrates under an argon (Ar) atmosphere. The new films are next annealed at 600 and 670 °C, or alternatively at 100 and 450 °C, for 1 h. Longer annealing to the films, for up to 8 days, is also conducted to explore resistivity variation. The resistivity of the new 300-nm-thick film is 2.19 μΩ cm after annealing at 670 °C for 1 h and drifts to 2.26 and 2.14 μΩ after annealing at 400 and 450 °C, respectively, for 200 h. A 2.7-μm-thick Sn layer is then thermally evaporated atop the new film for stable flip-chip solder joints; their metal and Cu-Sn intermetallic compound (IMC) growth processes vs. various annealing periods are tested. After annealing at 670 °C, the new 300-nm-thick film’s adhesive strength reaches 44.2 ± 0.01 MPa, which is 11 ~ 12-fold that of their pure Cu counterpart. Some key test results of the new film are disclosed herein, including its X-ray diffraction (XRD) patterns, transmission electron microscopy (TEM) images, secondary-ion mass spectrometry (SIMS), time-dependent dielectric-breakdown (TDDB) lifetime curves, and adhesive strength. The new film’s antibacterial efficacy arrives at an antibacterial ratio of approximately 100% against Staphylococcus aureus (S. aureus) BCRC 10451 for the 300-nm-thick film and approximately 99.82% for the 8 nm film, far superior to that of a pure Cu film, which is 0 with the same annealing temperature range. The new film, hence, seems to be a remarkable candidate material for various industrial applications, such as ultra-large-scale integrated circuits (ULSIC), micro-electronic circuits, printed circuits, flip-chip technology, medical care concerning antibacteria, and the like.

Graphical Abstract

A new type of copper (Cu)-rhodium (Rh)-alloy, Cu(Rh), films is developed by co-sputtering copper and rhodium onto silicon (Si) substrates under an argon (Ar) atmosphere and then annealing the new films at 600 and 670 °C, or alternatively at 100 and 450 °C, for 1 h. Longer annealing to the films, for up to 8 days, is also conducted to explore resistivity variation. The resistivity of the new 300-nm-thick film is 2.19 mW cm after annealing at 670 °C for 1 h and drifts to 2.26 and 2.14 mW after annealing at 400 and 450 °C, respectively, for 200 h. A 2.7-μm-thick Sn layer is next thermally evaporated atop the new film for stable flip-chip solder joints; their metal and Cu-Sn intermetallic compound (IMC) growth processes vs. various annealing periods are tested. After annealing at 670 °C, the new 300-nm-thick film’s adhesive strength reaches 44.2 ± 0.01 MPa, which is 11~12-fold that of their pure Cu counterpart. Some key test results of the new film are disclosed herein, including its X-ray diffraction (XRD) patterns, transmission electron microscopy (TEM) images, secondary-ion mass spectrometry (SIMS), time-dependent dielectric-breakdown (TDDB) lifetime curves, and adhesive strength. The new film’s antibacterial efficacy arrives at an antibacterial ratio of approximately 100% against Staphylococcus aureus (S. aureus) BCRC 10451 for the 300-nm-thick film and approximately 99.82% for the 8-nm film, far superior to that of a pure Cu film, which is 0 with the same annealing temperature range. The new film, hence, seems to be a remarkable candidate material for various industrial applications, such as ultra-large-scale integrated circuits (ULSIC), micro-electronic circuits, printed circuits, flip-chip technology, medical care concerning antibacteria, and the like.

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新开发的铜(Rh)合金薄膜及其特性和应用
通过在氩(Ar)气氛下将铜和铑共同溅射到硅(Si)基板上,开发出了一种新型铜(Cu)-铑(Rh)合金(Cu(Rh))薄膜。新薄膜接下来在 600 和 670 ℃ 或 100 和 450 ℃ 下退火 1 小时。在 670 ℃ 退火 1 小时后,新的 300 纳米厚薄膜的电阻率为 2.19 μΩ cm,在 400 ℃ 和 450 ℃ 退火 200 小时后,其电阻率分别降至 2.26 和 2.14 μΩ。在 670 °C 退火后,300 纳米厚的新薄膜的粘合强度达到了 44.2 ± 0.01 MPa,是纯铜薄膜的 11 到 12 倍。本文披露了新薄膜的一些关键测试结果,包括其 X 射线衍射 (XRD) 图样、透射电子显微镜 (TEM) 图像、二次离子质谱 (SIMS)、随时间变化的介电损耗 (TDDB) 寿命曲线和粘合强度。新薄膜的抗菌效果达到:300 nm 厚的薄膜对金黄色葡萄球菌(S. aureus)BCRC 10451 的抗菌率约为 100%,8 nm 薄膜的抗菌率约为 99.82%,远远优于相同退火温度范围内的纯铜薄膜。因此,这种新型薄膜似乎是超大规模集成电路 (ULSIC)、微电子电路、印刷电路、倒装芯片技术、抗菌医疗等各种工业应用的理想候选材料。图解 摘要 在氩(Ar)气氛下,将铜(Cu)和铑(Rh)共同溅射到硅(Si)衬底上,然后在 600 和 670 ℃ 或 100 和 450 ℃ 下退火 1 小时,开发出一种新型铜(Cu)-铑(Rh)合金(Cu(Rh))薄膜。在 670°C 下退火 1 小时后,300 纳米厚的新薄膜的电阻率为 2.19 mW cm,在 400°C 和 450°C 下退火 200 小时后,电阻率分别升至 2.26 mW 和 2.14 mW。接下来,在新薄膜上热蒸发 2.7μm 厚的锡层,以获得稳定的倒装芯片焊点;测试了它们的金属和铜锡金属间化合物 (IMC) 生长过程与不同退火时间的关系。在 670°C 退火后,300 纳米厚的新薄膜的粘合强度达到了 44.2 ± 0.01 兆帕,是纯铜薄膜的 11~12 倍。本文披露了新薄膜的一些关键测试结果,包括其 X 射线衍射 (XRD) 图样、透射电子显微镜 (TEM) 图像、二次离子质谱 (SIMS)、随时间变化的介电损耗 (TDDB) 寿命曲线和粘合强度。新薄膜的抗菌效果达到:300 nm 厚的薄膜对金黄色葡萄球菌 BCRC 10451 的抗菌率约为 100%,8 nm 厚的薄膜对金黄色葡萄球菌 BCRC 10451 的抗菌率约为 99.82%,远远优于相同退火温度范围内的纯铜薄膜。因此,新薄膜似乎是各种工业应用(如超大规模集成电路 (ULSIC)、微电子电路、印刷电路、倒装芯片技术、抗菌医疗等)的理想候选材料。
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