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研究生:林佐安
研究生(外文):Tso-An Lin
論文名稱:多孔隙二氧化矽/銅之電性量測
論文名稱(外文):Porous SiO2/Cu Electric Measurement
指導教授:葉鳳生
指導教授(外文):Fon-Shan Huang
學位類別:碩士
校院名稱:國立清華大學
系所名稱:電子工程研究所
學門:工程學門
學類:電資工程學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:49
中文關鍵詞:多孔二氧化矽NH3電漿處理低介電常數表面改質
外文關鍵詞:Porous SiO2NH3 plasma treatmentlow dielectric constantsurface modification
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本篇論文分三個研究主題:第一個研究主題為藉由調變配置porous SiO2 之先驅溶液時的水解溫度及膠化反應時滴入先驅溶液之鹼催化劑NH4OH的體積;研究降低porous SiO2 之介電常數值的條件。第二個主題為使用NH3電漿處理來對porous SiO2的表面作改質,以加強porous SiO2 阻擋銅離子擴散的能力。最後我們研究Cu/ porous SiO2 damascene結構經過化學機械研磨後如果在介電層上有銅的殘留時,NH3電漿處理對其漏電流的影響。在這篇論文中,我們使用FTIR、C-V和I-V量測曲線來嘹解有關porous SiO2薄膜的親水改質斥水、介電常數值、漏電流機制…等等現象。
我們調變porous SiO2薄膜的水解溫度從50℃到80℃以及將膠化反應中滴入3ml先驅溶液的鹼催化劑NH4OH之體積從0.2調變至0.3ml時,porous SiO2 薄膜的介電常數會從2.2增加到3.4。發現porous SiO2 薄膜最好的沉積參數為水解溫度為50℃、鹼催化劑體積為0.2ml,其薄膜之介電常數為2.2。更進一步地,使用NH3電漿處理和remote NH3電漿處理來對PEoxide/porous SiO2的表面作改質,以加強PEoxide/porous SiO2阻擋銅離子擴散的能力。從C-V曲線的數據中得知,15分鐘的NH3電漿處理可以讓Cu/PEoxide/porous SiO2的熱穩定溫度增加到450℃。但是也從漏電流的量測中可知Cu與PEoxide/porous SiO2界面卻被NH3電漿破壞的很嚴重。不過如果是使用remote NH3電漿處理卻可以降低介面被破壞的程度。最後,從我們量測Cu/ porous SiO2 damascene結構的漏電流顯示NH3電漿處理也可以應用在CMP cleaning的製程中,而且在此porous SiO2 薄膜中的漏電流機制為Frenkel —Pool emission 。

The purpose of the thesis is to find the condition that can lower the dielectric constant of porous SiO2, by changing the reflux temperature and the volume of catalyst NH4OH, to use NH3 plasma treatment as the porous SiO2 film surface modification to enhance the Cu diffusion resistance, and to investigate
the effect of NH3 plasma treatment after CMP process on Cu/ porous SiO2 damascene structure. We use FTIR, C-V, and I-V measurements to understand the phenomenon of hydrophobic surface, dielectric constant, and leakage current mechanism.
The porous SiO2 film were refluxed at temperature varying from 50℃to 80℃and added catalyst NH4OH changing from 0.2ml to 0.3ml/3ml precursor. The value of the film increase from 2.2 to 3.4. We find the best deposition condition of the porous SiO2 film is 50℃ for the reflux temperature, 0.2ml for the volume of the catalyst NH4OH. Dielectric constant of this film is 2.2. Meanwhile, the NH3 plasma and remote NH3 plasma treatment were applied to modify the surface of deposited PEoxide/porous SiO2,in order to enhance Cu diffusion resistance. From C-V data, this 15min. NH3 plasma treatment can increase the thermal stable temperature of Cu/PEoxide
/porous SiO2 up to 450℃. But the damage on the interface was observed in leakage current measurements. But the remote NH3 plasma can reduce this interface damage. Finally, NH3 plasma is a good after CMP cleaning process. It is shown on our leakage current measurements onCu/porous SiO2 damascene structure. Frenkel —Pool emission was the leakage mechanism in this porous SiO2 film.

第一章 緒論....................................................1
第二章 多孔二氧化矽之沈積、改質及漏電流機制....................4
2-1 多孔二氧化矽的沈積機制.....................................4
2-1-1 水解反應...........................................4
2-1-2 聚合反應...........................................5
2-2 多孔二氧化矽置換機制.......................................6
2-2-1 HMDS和TMCS置換效應................................6
2-3 多孔二氧化矽的漏電流機制..................................7
2-3-1 Frenkel-Poole emission 機制........................7
第三章 儀器與量測原理..........................................8
3-1 AGCVD系統..................................................8
3-2 四點探針..................................................10
3-3 α-step...................................................12
3-4 電壓特性分析..............................................12
3-5 電流─電壓特性分析........................................12
第四章 實驗與量測.............................................14
4-1 試樣之準備................................................14
4-1-1多孔二氧化矽膠質溶液-膠體(so-gel)之詳細製程步驟.....
...................................................14
4-1-2 樣品分類...........................................18
4-1-3 介電常數(K值)量測................................18
4-1-4 Cu/Porous SiO2/Si 經由NH3電漿處理之電容樣品作........
...................................................20
4-2 量測......................................................26
4-2-1 厚度...............................................26
4-2-2 電容─電壓特性分析.................................26
4-2-3 四點探針-片電阻之量測..............................26
4-2-4 電流-電壓特性分析..................................27
4-2-5 高頻電容-電壓曲線量測..............................27
第五章 結果與討論.............................................28
5-1 多孔二氧化矽薄膜..........................................28
5-1-1 介電常數改善結果...................................28
5-1-2 親水性改質斥水性結果...............................29
5-2 NH3 Plasma 處理對多孔二氧化矽之影響.......................30
5-2-1 電容的熱穩定性與介電常數之變化.....................30
5-2-2 電容的I-V特性量測..................................31
5-3 Group C 的I-V特性量測以及NH3電漿處理對銅導線漏電流的影響.33
5-3-1 Group C 的I-V特性量測結果..........................33
第六章 結論...................................................48
參考文獻......................................................49
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