| 摘要註: |
(1)目前最有可能成為下一世代的半導體微影技術是利用13.5奈米光源的極紫外光微影技術。本實驗使用的13.5奈米 (91.84eV)同步輻射光源照射光阻成像成分的光酸產生劑樣品，針對光酸產生劑因光游離-解離反應所釋出的陽離子釋氣進行定性與定量的研究。本實驗使用的光源是來自國家同步輻射研究中心的BL08A1BM-LSGM光束線，並以四極質譜儀測量陽離子的釋氣訊號。實驗測量分兩個部份，一為比較各光酸產生劑樣品，F+的相對釋氣量，二為掃描各光酸產生劑樣品在範圍10-200u的全質譜，以比較光酸產生劑之間，相對總離子的釋氣量。實驗共使用18種光酸產生劑，其中N-Hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butane sulfonate屬於含C4F9SO3氟化物的共價鍵非離子性光酸產生劑，而其餘的17種光酸產生劑皆為離子性光酸產生劑，陰離子團可分為為C4F9SO3-或CF3SO3-，而陽離子團的中心可分為硫離子與碘離子兩種。 光酸產生劑經13.5奈米光的照射，F+離子為主要的釋氣離子。大部分的光酸產生劑所釋氣出的F+離子，佔整體釋氣量的65-95%。除了少數例外，本研究發現F+釋氣量正比於各光酸產生劑的F原子吸收比例。光酸產生劑的結構中，若陰離子為C4F9SO3-的光酸產生劑會釋放出F+、CF+、CF2+、CF3+、C2F4+、C2F5+以及C3F5+的含氟離子，而陰離子含CF3SO3-的光酸產生劑只會釋放出F+、CF+、CF2+以及CF3+，若光酸產生劑的陽離子含R(C6H5)2S+、R2I+，經13.5nm光源的照射會各自產生少量的(C6H5)2S+、I+。本實驗發現有C11H9+以及C12H8+的釋氣離子，推測R(C6H5)2S+的光酸產生劑同時發生了聚合反應與釋氣反應。(2)本實驗使用Al2O3、SiO2、Alumina-modified SiO2 (AlSiO)為模板，以化學氣相澱積法熱解碳源氣體CH4合成碳材。碳材/模板複合物以6%或12%HF水溶液進行酸蝕反應去除模板。實驗所製成的碳材/模板複合物與碳材樣品以X光粉末繞射儀進行進行樣品的結構定性分析，比表面積與孔徑分析儀測量產物的比表面積、比體積與孔洞粒徑分布，重量法計算碳材產率以及熱重分析儀則鑑定產物的熱穩定度及碳材產率。 樣品碳材的重量分析結果顯示，碳材成長會因AlSiO模板的孔洞堵塞而遲滯，而以SiO2及Al2O3為模板合成的碳材則無此現象。以AlSiO、SiO2以及Al2O3模板製成碳材的X-Ray (002)繞射峰分別位於25.3°、25.7°與25.7°，小於石墨的26.3° (002) 繞射峰。因此，由CH4 CVD法所合成的碳材材料，其碳層間距較石墨大，碳材的碳層較不平整或較呈曲面。以AlSiO為模板合成的碳材，其比表面積最大可達1300m2/g，孔洞的比體積約在2.5cm3/g，孔徑大小分佈範圍則類似於原始模板4.0nm。當反應時間提高，澱積的碳材反而會造成封口效應而不利於高比表面積與高比孔洞體積的中孔碳材生成。SiO2與Al2O3模板所製作的碳材孔徑具有雙峰分佈，因此推測此二模板所製成的碳材不具孔洞的獨特性。熱重分析的結果顯示，利用AlSiO反應5小時所製成的碳材燃燒溫度較低，推測是較不穩定的碳材燃燒所致。高反應時間所製成的碳材於800℃後仍有燃燒，推測是封口的碳材燃燒後，孔洞內的碳材開始燃燒所造成。 (1)Extreme ultraviolet (EUV) lithography at 13.5-nm is the most likely candidate of the next-generation lithography. This work studies dissociative photoionization (ionic outgassing) of the photoacid generator (PAG), which is one important composition of chemically amplified photoresist, upon irradiation at 13.5-nm (91.84eV). The 13.5-nm light soure was provided by BL08A1BM-LSGM beamline of National Synchrotron Radiation Research Center (NSRRC). This work used quadrupole mass spectrometer (QMS) to detect outgassed ions from the dissociative photoionization process. The ionic outgassing study includes two parts: one is to determine the relative proportion of F+ outgassing, and another is to identify ion species outgassed in the10-200u range in order to derive the relative total ion yield. The measurement of ionic outgassing includes eighteen commercially available PAG, seventeen ionic-type and a molecular-type. The PAG samples contain either triarylsulfonium or diaryliodonium salts, and have C4F9SO3- or CF3SO3- as anion. F+ outgassing is dominant. For each PAG measured, the extent of F+ outgassing amounts to 65-95% of it is overall outgassed ions. The extent of F+ outgassing is proportional to the ratio of F atomic photoabsorption over the molecular photoabsorption. For these PAG containing C4F9SO3-, outgassed ions include F+, CF+, CF2+, CF3+, C2F4+, C2F5+and C3F5+; and for those PAG containing CF3SO3-, outgassed ions are F+, CF+, CF2+and CF3+ . The molecular type PAG (N-Hydroxy-5-norbornene- 2,3-dicarboximide perfluoro-1-butane sulfonate) emits the most extent of hydrocarbon ions and F+. PAG containing R(C6H5)2S+ or R2I+ salts will give off (C6H5)2S+ or I+. C11H9+ and C12H8+ which outgassed from R(C6H5)2S+ provides evidence of concurrent outgassing and polymerization of PAG.(2) This work used Al2O3, SiO2 and Alumina-modified SiO2 (AlSiO) as templates, and utilized the CH4 chemical vapor deposition (CVD) method to synthesize mesoporous carbon. The template of the synthesized carbon/template composite was removed by 6% or 12% HF solution. The carbon/template composites and resulting porous carbon materials were characterized by means of power X-ray diffraction, surface area and porosity analyzer, and thermogravimetric analyzer (TGA). A yield analysis shows the loss of template porosity will limit the carbon growth when using AlSiO as template, while no such limitation is observed when using SiO2 or Al2O3. The XRD (002) diffraction peak of porous carbons synthesized via AlSiO, SiO2 and Al2O3 are at 25.3°, 25.7° and 25.7°, respectively, which is at a smaller scattering angle than that of graphite (26.3°). The porous carbons grown by the CH4 CVD method, should be less structural than graphite. The physical absorption- desorption result of porous carbon synthesized using the AlSiO template suggests that the mesoporous carbon can achieve the highest surface area 1300 m2/g, pore volume 2.5cm3/g, and pore size 4.0nm. By increasing the reaction time, further grown carbon may seal the mesopore entrance and result in decreasing porosity. Carbon materials synthesized by Al2O3 or SiO2 have no specificity on the pore-size distribution, which spreads over the range of 2-40nm. The result of the TGA analysis indicates that the maximum combustion rate is identical for all after-etched carbon materials of this work and is at ~765℃. The mesoporous carbon grown on AlSiO with a reaction time of 5hrs shows a substantial combustion reaction that occurs below 756℃, which should be ascribed to carbons with extensive porosity and disorderness. Similar mesoporous carbons with an equivalent reaction time of 20 and 28 hours show a second peak of combustion at 871℃, which should be ascribed to additional combustion process of encapsulated then re-opened carbon surfaces. |