磁控濺鍍系統鍍製鋯鈦鎳金屬玻璃薄膜之性質及阻障層應用

Characteristics and Barrier Appllication of Magnetron Sputtered Zr-Ti-Ni Thin Film Metallic Glass

陳筑萱(Chu-Shuan Chen)

指導教授 ： 薛承輝

國立臺灣大學/工學院/材料科學與工程學研究所/碩士(2013年)

https://doi.org/10.6342/NTU.2013.02177

摘要

本實驗以單靶射頻磁控濺鍍方式，在Si（100）及AISI 420 不鏽鋼基材上鍍製1 μm 厚之Zr46Ti26Ni28 金屬玻璃薄膜。未經熱處理之Zr46Ti26Ni28 薄膜呈現非晶質特性，且具有高的玻璃轉換溫度及結晶溫度。其薄膜硬度為6.2 GPa，在玻璃轉換溫度範圍退火，可使硬度提升至11.1 GPa，在結晶溫度範圍退火則可使硬度提升至13.4 GPa。Zr46Ti26Ni28 金屬玻璃薄膜在經過400 °C 退火後具有優異的附著強度及抗刮能力。根據電子顯微鏡結果，推測良好的機械性能來自於退火過程中形成的奈米晶粒。由於上述獨特性質，鋯-鈦-鎳金屬玻璃薄膜在製造高強度微小零件及保護性塗層之應用面具有潛力。

本實驗另將Zr46Ti26Ni28 金屬玻璃薄膜作為銅矽間擴散阻障層，並探討濺鍍阻障層時通入氮氣之效果。電性結果顯示濺鍍時通入氮氣、於450 °C 退火一小時之參數下，可有效提升阻障層性能。在XRD 結果中，僅觀察到銅層結晶面趨向完整、缺陷減少之趨勢，不見銅矽化合物生成。電子顯微鏡結果顯示，即使退火溫度提升至500°C，阻障層也沒有受到銅矽穿透導致破壞之現象。根據本實驗結果，可預期鋯-鈦-鎳（氮）金屬玻璃薄膜具有獨特之阻障潛力。

關鍵字

金屬玻璃薄膜 ； 磁控濺鍍系統 ； 機械性質 ； 附著性 ； 擴散阻障層

並列摘要

In this study 1μm-thick Zr46Ti26Ni28 thin film metallic glass was fabricated by radio frequency magnetron single target sputtering on Si (100) and AISI 420 stainless steel substrates. The as-deposited film was found to be fully amorphous with high glass transition and crystallization temperatures. Its hardness progressively increased from 6.2 GPa to as high as 11.1 GPa when subjected to annealing near the glass-transition temperature. It was also of good adhesive strength and scratch resistance after the annealing treatment at 400 °C. Transmission electron microscopy results revealed annealing-induced nanocrystals that accounted for such superior mechanical properties. With the above unique properties, Zr-Ti-Ni thin film metallic glass has the potential for the fabrication of high strength micro parts and protective coating.

The Zr46Ti26Ni28 thin film metallic glass was also applied as a diffusion barrier between copper and silicon. The effect of purging nitrogen during deposition on its barrier performance was also investigated. Resistivity measurements showed that the performance of nitrogen-purged barrier was significantly improved after annealing at 450 °C for 1 hour. No observable Cu-Si compounds could be found under XRD, and only the copper layer became less defective. Electron microscopy results showed no sign of breakdown after annealed at 500 °C, although the barrier was penetrated by both copper and silicon. According to the above results, it is suggested that the (Zr-Ti-Ni)N thin film metallic glass could stand annealing temperature and duration beyond experimental values, possessing high potential of barrier applications.

並列關鍵字

Thin film metallic glass ； magnetron sputtering system ； mechanicalproperties ； adhesion ； diffusion barrier

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