Preparation and Characterization of Electroplated Cu/Graphene Composite

Xin Wang, Qian Wang, Jian Cai, Changmin Song, Yang Hu, Yang Zhao, Yu Pei
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Abstract

Cu and unoxidized graphene composite films were prepared by electroplating under room temperature. Graphene was added to the electrolyte of Cu to form composite materials to improve the performance of Cu for interconnection. Composite electrolyte containing high concentration of graphene (up to 0.5 g/L) was prepared by adding CTAB as surfactant. And ultrasound was also used to increase dispersion degree and reduce graphene agglomeration in electrolyte. Average coefficient of thermal expansion (CTE) of the composite films determined by thermo-mechanical analysis (TMA) shows a decrease from 17.3 ppm/K to 14.2 ppm/K from 260 K to 320 K, which reduce CTE by 18 % compared with Cu. CTE of the composite materials can be reduced to 10 ppm/K at 243 K, which is only 60 % of CTE of Cu. The thermal conductivity of the composite materials measured by phase sensitive transient thermo-reflectance (PSTTR) technique shows an improvement from 385 W/m.K to 468 W/m.K. CTE and thermal conductivity of the composite materials both decrease with the increase of current density. And they also both increase with the increase of graphene concentration. The composite materials also show good mechanical properties. The average hardness is 2.5 GPa, which is about 2 times of Cu. And the average elastic modulus is 145 GPa, which is 38 % higher than that of Cu. The resistivity of the composite materials is basically equivalent to that of pure Cu. Result of the experiment proved that the composite materials have better performance under low temperature conditions. The improvement of material properties makes composite materials have good application prospects for 3D interconnection in the near future.
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电镀铜/石墨烯复合材料的制备与表征
采用室温电镀法制备了Cu和未氧化石墨烯复合薄膜。将石墨烯加入到Cu的电解液中形成复合材料,提高Cu的互连性能。以CTAB为表面活性剂,制备了含高浓度石墨烯(高达0.5 g/L)的复合电解质。超声波也可以提高石墨烯在电解液中的分散程度,减少石墨烯的团聚。热力学分析(TMA)测定的复合膜的平均热膨胀系数(CTE)在260 ~ 320 K时从17.3 ppm/K降至14.2 ppm/K,与Cu相比降低了18%。在243 K时,复合材料的CTE可降至10 ppm/K,仅为Cu的60%。采用相敏瞬态热反射(pstr)技术测量复合材料的导热系数比385 W/m有所提高。K至468 W/m.K。复合材料的CTE和导热系数均随电流密度的增大而减小。它们都随着石墨烯浓度的增加而增加。复合材料也表现出良好的力学性能。平均硬度为2.5 GPa,约为Cu的2倍。平均弹性模量为145 GPa,比Cu的弹性模量高38%。复合材料的电阻率基本相当于纯铜的电阻率。实验结果表明,该复合材料在低温条件下具有较好的性能。材料性能的提高使得复合材料在不久的将来具有良好的三维互联应用前景。
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