本研究主要探討釕合金薄膜作為積體電路內連線系統中擴散阻障層/銅晶種層之應用與分析。各種釕合金薄膜(15奈米厚之釕-氮、釕-鉭、釕-鉭-氮與5奈米厚之釕-碳)為利用雙槍磁控濺鍍法製備，並以純釕薄膜作為對照組；吾人首先檢測各釕合金薄膜之材料特性，以拉賽福背向式散射儀分析合金薄膜中之各元素組成比例，以低掠角X光繞射儀及四點探針量測薄膜初鍍及經過不同溫度、30分鐘退火處理後之相結構與片電阻值變化，並得到該薄膜之電阻率；吾人再將各釕合金薄膜沉積於矽或二氧化矽/矽之基板上並覆蓋上銅薄膜製成銅/阻障層/基板疊層結構，將疊層試片進行400至900 oC真空退火處理後，來觀察各擴散阻障層之對銅阻障能力，先以低掠角X光繞射儀及四點探針量測疊層試片之微結構與片電阻值變化，再以歐傑電子能譜儀與二次離子質譜儀分析試片中各元素訊號的縱深分佈與各摻雜原子(氮、鉭及碳等)之熱穩定性，而後以穿透式電子顯微鏡觀察試片的相結構與界面性質變化；另外並以無銅薄膜覆蓋之阻障層直接進行電鍍銅測試，以觀察釕合金薄膜同時作為銅晶種層之效用，並以掃描式電子顯微鏡與原子力顯微鏡來觀察直接電鍍所得之銅薄膜的表面形態與表面粗糙度；最後，再以量測銅原子在阻障層中之擴散活化能，藉以定量的表示阻障層薄膜對銅阻障能力之優劣。
實驗結果顯示，15奈米厚之釕-鉭-氮與5奈米厚之釕-碳薄膜具有最優異之對銅阻障能力，最高可阻擋銅原子在疊層試片經過700 oC、30分鐘退火處理後仍不會擴散進入下層結構，而15奈米厚之釕-鉭、釕-氮與純釕薄膜則依序可阻擋銅原子在疊層試片經過600、500及400 oC退火處理後之擴散。各薄膜對銅阻障能力之優劣主要為受薄膜之微結構所影響；純釕薄膜具有高度結晶性結構，而將鉭或氮摻雜進入釕薄膜後，釕-鉭與釕-鉭-氮薄膜之相結構轉變為奈米微晶或非晶質結構，將可減少銅原子透過阻障層薄膜晶界擴散之機會；而厚度較薄之釕-碳薄膜雖具結晶性之結構，但由於小原子半徑之C元素添加使得釕-碳薄膜具有與非晶質釕-鉭-氮薄膜相同之阻障能力。另外，隨著薄膜結晶性的減低將伴隨著提高薄膜之電阻率，而若將銅/阻障層雙層結構製備於矽或二氧化矽/矽基板上，則無明顯阻障層表現之差異。
各釕合金薄膜作為銅晶種層之測試結果顯示，銅薄膜皆可在所有本研究中之各釕合金薄膜上直接電鍍生成，且所生成之銅薄膜皆具有(111)之優選方向，將有利於提高其抗電致遷移能力；各電鍍銅薄膜之表面粗糙度略有差異，其可能原因為阻障層薄膜之微結構與電阻率差異，或電鍍槽中之化學添加物所造成。
對於以定量方式來評估阻障層薄膜對銅阻障能力之表現上，吾人以四點探針與X光繞射圖譜兩分析方法來測試試片在不同退火溫度下之失效時間，並配合擴散與阿瑞尼氏方程式來得到銅原子在阻障層中之擴散係數與擴散活化能；其結果顯示銅原子在釕-碳薄膜中擴散所需活化能為1.11 eV，而銅原子在純釕膜薄中擴散只需活化能0.54 eV，映證本研究中之釕-碳薄膜之對銅阻障能力確實較純釕薄膜優異。
本研究的結果顯示，在阻障層厚度、對銅阻障能力與可直接電鍍銅等性質表現之考量上，5奈米厚之釕-碳薄膜為最具有可取代現有之銅晶種層/氮化鉭/鉭三層結構之優勢。

In this study, the characteristics of Ru alloy thin films and their applications as the diffusion barrier/Cu-seed layer for interconnect in integrated circiuts are explored. The 15 nm Ru-N, Ru-Ta and Ru-Ta-N and 5 nm Ru-C thin films used in this study were prepared by reactive co-sputtering. For the comparison, pure Ru films were prepared under the same deposition condition. Material characteristics of the Ru alloy thin films were examined by Rutherford backscattering spectrometry (RBS) for the elemental composition. Microstructural evaluation and sheet resistance variation of the Ru alloy films before and after annealing at different temperatures for 30 min were explored by glanzing incident angle X-ray diffraction (GIAXRD) and four point probe. To evaluate the barrier perfomance of Ru alloy films against Cu diffusion, the barrier films on Si or SiO2/Si substrates were covered by Cu films and the Cu/barrier/substrate film stacks were subsequently annealed at 400-900 oC in vacuum. The elemental depth profiles of the film stacks and the thermal stability of the added element in the barrier films were examined by Auger electron spectroscopy (AES) and second ion mass spectrometer (SIMS). Transmission electron microscopy (TEM) was used to further explore the microstructure of the films and the interfaces between Cu, barrier and substrate. Surface morphology and the root-mean-square roughness of direct electrochemical plating Cu films on barrier layers were examined by scanning electron microscopy (SEM) and atomic force microscopy (AFM), respectively. Finally, the activation energy of Cu diffusion in barrier layer was measured to estimate the barrier performacne quantitatively.
The experimental results reveal that the 15 nm Ru-Ta-N and 5 nm Ru-C films have the best barrier performacne against Cu diffusion. The two barriers can prevent the diffusion of Cu into underlayers when the Cu/barrier/substrate samples were annealed at 700 oC for 30 min. The 15 nm Ru-Ta, Ru-N and Ru films can prevent the diffusion of Cu after annealing the samples at 600, 500 and 400 oC for 30 min, respectively. The performance of the barrier films should be related to their microstructure. The Ru film is highly crystalline. By adding the Ta or N into the Ru matrix, the crystal structures of Ru-Ta and Ru-Ta-N are changed to nanocrystalline or amouphous, which would prevent the diffusion of Cu through the grain boundaries. Although the 5 nm Ru-C film is also crystalline, the C atoms with small atomic radius shall effectively stuff on the grain boundaries of Ru-C grains and make the 5 nm Ru-C film has the same barrier performance with 15 nm amorphous Ru-Ta-N film. In addition, the resistivity values of Ru-C and Ru-Ta-N are 119 and 570.0 μΩ-cm, respectively, which promises both as conductive barrier layers.
For the direct electrochemical plating of Cu on Ru alloy films, all Ru alloy films examined in this study can be successfully used as Cu-seed layer and the electroplated Cu films have (111) preferred orientation. The surface roughnesses of the Cu films on various Ru alloy films were different, probably due to difference of the microstructure and the resistivity of Ru alloy films, or the chemical additives in electrochemical bath.
To quantitatively estimate the diffusivity of Cu in the Ru alloy barriers, the onset of the Cu-Si formation as a function of annealing temperatures in the Cu/barrier/Si samples is detected by sheet resistance variation and XRD analysis and as an indication of Cu diffusion through the barrier. By fitting the dependence of diffusivities on temperatures, the activation energy for Cu diffusion in Ru-C film is 1.11 eV, which is substantially higher than that in Ru film (0.54 eV), which confirms the superior diffusion barrier performace of Ru-C film.
In summary, the 5 nm Ru-C film will be a highly promising diffusion barrier/Cu-seed layer for Cu metallization to scale down the interconnection dimensions and simplify the fabrication processes.

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