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(1) 薄膜材料經13.5 nm光照射之釋氣定性與定量研究(2) 有機溶...

國立高雄大學應用化學系碩士班

(1) 薄膜材料經13.5 nm光照射之釋氣定性與定量研究(2) 有機溶劑在70-150 eV能量範圍的絕對光游離 = (1) Qualitative and quantitative study on outgassing from thin-film materials upon irradiation at 13.5 nm(2) Absolute photoionization of organic solvents in the 70-150 eV range

紀錄類型:	書目-語言資料,印刷品 : 單行本
並列題名:	(1) Qualitative and quantitative study on outgassing from thin-film materials upon irradiation at 13.5 nm(2) Absolute photoionization of organic solvents in the 70-150 eV range
作者:	邵峙樺,
其他團體作者:	國立高雄大學
出版地:	[高雄市]
出版者:	撰者;
出版年:	2011[民100]
面頁冊數:	127面圖，表格 : 30公分;
標題:	光游離截面積
標題:	photoresist
電子資源:	http://handle.ncl.edu.tw/11296/ndltd/64041650243189978296
摘要註:	(1)13.5 nm的極紫外光(EUV, extreme ultraviolet)被視為後16 nm積體電路製造技術節點微影製程之首選光源。光阻或底層材料經13.5 nm光照射後產生之釋氣會汙染曝光機台的光學元件，此汙染現象為在EUV微影製程所獨有的新議題。本研究使用四級桿質譜(QMS)法以及壓力上升法進行釋氣之定性及定量研究。本實驗使用的13.5 nm 極紫外光光源來自於國家同步輻射中心的BL08A-LSGM 光束線。中性釋氣量之量測的樣品為不同厚度之EUV模型光阻和PMMA (Poly-methylmethacrylate)，以及由二家公司所提供之薄膜材料。本研究中性釋氣與SEMATECH以及I-Institute的報告標竿評準相符，顯示本研究在台灣完成了具有國際水準的釋氣測量系統設備。本實驗也證實了樣品釋氣量與厚度無關，而是與EUV光吸收截面積係數以及材料的分子結構有關。　　本實驗針對9個含矽以及2個含鈦的新穎底層材料進行離子釋氣定性研究。此兩種材料在EUV光照射下，會使得矽/鈦醇的濃度增高，而觀測到持續增強的H3O+脫附訊號。本實驗在含鈦化合物中除了H3O+外，也發現O+及OH+離子釋氣在經13.5 nm光照射下訊號亦持續增強；本研究因此提出，此持續增強離子釋氣現象乃矽鈦類底層材料表面鍵結經EUV光照射後被破壞後所引起的後續反應現象。 (2)　　本研究利用四極桿質譜儀(QMS)量測有機溶劑在光源能量範圍為70-150 eV的光游離斷片分支比及絕對光游離截面積。本研究所使用樣品為半導體產業常見之九種有機溶劑，光源為來自於國家同步輻射研究中心的BL08A-LSGM 光束線。為量測光游離截面積的絕對值，本研究利用鈍氣以及氮氣之混合氣體對於QMS作校正。本研究與美國國家標準技術研究院(NIST)於70 eV的電子衝擊斷片分支結果比較結果顯示，除了質量較小的斷片分支比以外，絕大部分主要的斷片物質分支比差異皆小於±40%之內。本研究以有機溶劑斷片分支比成果為基礎，結合熱力學計算並歸納出在70-150 eV的氣體光游離反應機制：(1)芳香族分子如本研究之苯及甲苯，母離子為主要之光游離產物。(2) 除(1)所列之外，有機溶劑的主要光解離游離之反應途徑皆為直接的斷鍵反應，且斷鍵分支比分布依照解離游離的反應熱大小順序排列。(3)重排光游離解離反應為反應熱吸熱較小的反應，但並非為主要之游離解離之途徑。(4) 分子鍵結的斷鍵趨勢為C-O > C-C > C-H。本研究在所有溶劑光游離斷片質譜圖中發現，隨著光源能量的增強，在質量較高的斷片物質的分支比會明顯得變小，而在質量較小的斷片物質分支比會變大。本研究以QMS法所計算出之光游離截面積絕對值以及量子產率結果顯示，量子產率比一般理論量子產率小約100%。此為本研究之初步結果，此技術仍需後續繼續研究，以達到絕對光游離截面積的絕對值測量。 (1) Extreme ultraviolet (EUV) light at 13.5 nm is regarded as the most likely excitation source for microlithography processing beyond the 16 nm technology node of IC manufacturing. Outgassing from photoresists or underlayer materials upon the EUV exposure can lead to contamination of optics, which is a new issue to microlithographic applications. This work uses quadrupole mass spectrometer (QMS) and pressure rise methods to characterize and quantitatively measure outgassing. The light source of this work is from the BL08A-LSGM beamline of NSRRC. Samples investigated include EUV model resists and PMMA (poly-methylmethacrylate) in various thickness and some confidential samples provided by two companies. Our quantitative results on outgassing are benchmarked and agree well to those reported by SEMATECH and I-institute. The benchmarking tests demonstrate that we have established an EUV outgassing evaluation system in Taiwan, which meets international standards. In addition to facility, we show that the amount of outgassing is thickness independent but EUV absorption and material structure dependent.This work investigates ionic outgassing from novel materials of nine silicon-containing and two titanium-containing compounds. When undergone EUV irradiation, H3O+ (m/z = 19) from the silicon-containing compounds keep on increasing. The same H3O+ phenomenon are also observed for O+ and OH+ outgassing from the Ti-containing compounds are also observed. Possible mechanisms of EUV photoinduced surface bond breakage leading to H3O+ outgassing are proposed. (2) This work uses quadrupole mass spectrometer (QMS) to determine branching ratios and absolute photoionization cross sections in the 70-150 eV energy range for organic solvents. The samples are nine organic samples commonly used in semiconductor manufacturing. The light source is from BL08A-LSGM beamline at National Synchrotron Radiation Research Center. In order to measure absolute photoionization cross section, we calibrate QMS with a mixture of N2¬ and noble gases to obtain QMS detection sensitivity. We compare our results to those of NIST which was derived by electron impact ionization at 70 eV. Major branching ratio between both works show similar results with a difference within ±40%. This work combines the branching ratio results and thermal chemical calculation, and proposes EUV photochemical mechanisms of photoionization in 70-150 eV energy range: (1) Aromatic compounds like benzene and toluene, the production of their parent ion is the major channel. (2) Besides (1), the major reaction pathways of the solvents are direct dissociative photoionization. The order of branching ratios depends on the order of reaction endothermicity. (3) Molecular rearrangement prior dissociative photoionization is never the major channel, even if its endothermicity is relatively less. (4) The trend of bond dissociation is: C-O > C-C > C-H. In ion mass spectrum of all solvents, this work finds that the branching ratio of high mass species is getting smaller with higher energies. The results of photoionization cross section and quantum yield show that the quantum yields contain about 100% uncertainty lower than typical quantum yield. This work is primary, and more studied are needed to achieve quantitative measurements.

(1) 薄膜材料經13.5 nm光照射之釋氣定性與定量研究(2) 有機溶劑在70-150 eV能量範圍的絕對光游離 = (1) Qualitative and quantitative study on outgassing from thin-film materials upon irradiation at 13.5 nm(2) Absolute photoionization of organic solvents in the 70-150 eV range
邵, 峙樺

(1) 薄膜材料經13.5 nm光照射之釋氣定性與定量研究(2) 有機溶劑在70-150 eV能量範圍的絕對光游離 = (1) Qualitative and quantitative study on outgassing from thin-film materials upon irradiation at 13.5 nm(2) Absolute photoionization of organic solvents in the 70-150 eV range / 邵峙樺撰 - [高雄市] : 撰者, 2011[民100]. - 127面 ; 圖，表格 ; 30公分.
參考書目：(1)面59-60；(2)面43-45.
光游離截面積photoresist

(1) 薄膜材料經13.5 nm光照射之釋氣定性與定量研究(2) 有機溶劑在70-150 eV能量範圍的絕對光游離 = (1) Qualitative and quantitative study on outgassing from thin-film materials upon irradiation at 13.5 nm(2) Absolute photoionization of organic solvents in the 70-150 eV range
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330 $a (1)13.5 nm的極紫外光(EUV, extreme ultraviolet)被視為後16 nm積體電路製造技術節點微影製程之首選光源。光阻或底層材料經13.5 nm光照射後產生之釋氣會汙染曝光機台的光學元件，此汙染現象為在EUV微影製程所獨有的新議題。本研究使用四級桿質譜(QMS)法以及壓力上升法進行釋氣之定性及定量研究。本實驗使用的13.5 nm 極紫外光光源來自於國家同步輻射中心的BL08A-LSGM 光束線。中性釋氣量之量測的樣品為不同厚度之EUV模型光阻和PMMA (Poly-methylmethacrylate)，以及由二家公司所提供之薄膜材料。本研究中性釋氣與SEMATECH以及I-Institute的報告標竿評準相符，顯示本研究在台灣完成了具有國際水準的釋氣測量系統設備。本實驗也證實了樣品釋氣量與厚度無關，而是與EUV光吸收截面積係數以及材料的分子結構有關。　　本實驗針對9個含矽以及2個含鈦的新穎底層材料進行離子釋氣定性研究。此兩種材料在EUV光照射下，會使得矽/鈦醇的濃度增高，而觀測到持續增強的H3O+脫附訊號。本實驗在含鈦化合物中除了H3O+外，也發現O+及OH+離子釋氣在經13.5 nm光照射下訊號亦持續增強；本研究因此提出，此持續增強離子釋氣現象乃矽鈦類底層材料表面鍵結經EUV光照射後被破壞後所引起的後續反應現象。 (2)　　本研究利用四極桿質譜儀(QMS)量測有機溶劑在光源能量範圍為70-150 eV的光游離斷片分支比及絕對光游離截面積。本研究所使用樣品為半導體產業常見之九種有機溶劑，光源為來自於國家同步輻射研究中心的BL08A-LSGM 光束線。為量測光游離截面積的絕對值，本研究利用鈍氣以及氮氣之混合氣體對於QMS作校正。本研究與美國國家標準技術研究院(NIST)於70 eV的電子衝擊斷片分支結果比較結果顯示，除了質量較小的斷片分支比以外，絕大部分主要的斷片物質分支比差異皆小於±40%之內。本研究以有機溶劑斷片分支比成果為基礎，結合熱力學計算並歸納出在70-150 eV的氣體光游離反應機制：(1)芳香族分子如本研究之苯及甲苯，母離子為主要之光游離產物。(2) 除(1)所列之外，有機溶劑的主要光解離游離之反應途徑皆為直接的斷鍵反應，且斷鍵分支比分布依照解離游離的反應熱大小順序排列。(3)重排光游離解離反應為反應熱吸熱較小的反應，但並非為主要之游離解離之途徑。(4) 分子鍵結的斷鍵趨勢為C-O > C-C > C-H。本研究在所有溶劑光游離斷片質譜圖中發現，隨著光源能量的增強，在質量較高的斷片物質的分支比會明顯得變小，而在質量較小的斷片物質分支比會變大。本研究以QMS法所計算出之光游離截面積絕對值以及量子產率結果顯示，量子產率比一般理論量子產率小約100%。此為本研究之初步結果，此技術仍需後續繼續研究，以達到絕對光游離截面積的絕對值測量。 (1) Extreme ultraviolet (EUV) light at 13.5 nm is regarded as the most likely excitation source for microlithography processing beyond the 16 nm technology node of IC manufacturing. Outgassing from photoresists or underlayer materials upon the EUV exposure can lead to contamination of optics, which is a new issue to microlithographic applications. This work uses quadrupole mass spectrometer (QMS) and pressure rise methods to characterize and quantitatively measure outgassing. The light source of this work is from the BL08A-LSGM beamline of NSRRC. Samples investigated include EUV model resists and PMMA (poly-methylmethacrylate) in various thickness and some confidential samples provided by two companies. Our quantitative results on outgassing are benchmarked and agree well to those reported by SEMATECH and I-institute. The benchmarking tests demonstrate that we have established an EUV outgassing evaluation system in Taiwan, which meets international standards. In addition to facility, we show that the amount of outgassing is thickness independent but EUV absorption and material structure dependent.This work investigates ionic outgassing from novel materials of nine silicon-containing and two titanium-containing compounds. When undergone EUV irradiation, H3O+ (m/z = 19) from the silicon-containing compounds keep on increasing. The same H3O+ phenomenon are also observed for O+ and OH+ outgassing from the Ti-containing compounds are also observed. Possible mechanisms of EUV photoinduced surface bond breakage leading to H3O+ outgassing are proposed. (2) This work uses quadrupole mass spectrometer (QMS) to determine branching ratios and absolute photoionization cross sections in the 70-150 eV energy range for organic solvents. The samples are nine organic samples commonly used in semiconductor manufacturing. The light source is from BL08A-LSGM beamline at National Synchrotron Radiation Research Center. In order to measure absolute photoionization cross section, we calibrate QMS with a mixture of N2¬ and noble gases to obtain QMS detection sensitivity. We compare our results to those of NIST which was derived by electron impact ionization at 70 eV. Major branching ratio between both works show similar results with a difference within ±40%. This work combines the branching ratio results and thermal chemical calculation, and proposes EUV photochemical mechanisms of photoionization in 70-150 eV energy range: (1) Aromatic compounds like benzene and toluene, the production of their parent ion is the major channel. (2) Besides (1), the major reaction pathways of the solvents are direct dissociative photoionization. The order of branching ratios depends on the order of reaction endothermicity. (3) Molecular rearrangement prior dissociative photoionization is never the major channel, even if its endothermicity is relatively less. (4) The trend of bond dissociation is: C-O > C-C > C-H. In ion mass spectrum of all solvents, this work finds that the branching ratio of high mass species is getting smaller with higher energies. The results of photoionization cross section and quantum yield show that the quantum yields contain about 100% uncertainty lower than typical quantum yield. This work is primary, and more studied are needed to achieve quantitative measurements.
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