201006548 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種介電層薄膜之製作方法，特別是應 ‘ 用於提升超臨界流體氧化力的方法。 【先前技術】 由於超臨界流體兼具有氣態與液態的特性，使其具備 有氣體之低黏度、高擴散性、液體的流體密度及優異的流 ❹ 動性。此外，由於具高壓縮性，使得超臨界流體亦具有大 範圍的溶劑特性。也因此，超臨界流體已廣泛的應用於各 種產業中’例如製藥、層析、萃取、土壤及廢水污染整治 、化學反應程序的應用及結晶與吸附之溶劑使用等應用。 由於超臨界二氧化碳本身性質較為穩定，通常應用於 粉體製作及物件表面之清潔；此外，於溫度高於水之臨界 溫度的環境下，水分子中之氫鍵將消失，使得水分子成為 非極性分子，藉此，有機物及氧氣可於超臨界水中混合形 ❹ 成一均勻相’而透過所添加之氧氣可有效對該有機物進行 氧化分解，因此超臨界水於廢水處理之應用中極具潛力。 如上所述，一般超臨界流體性質較為穩定，氧化力較 * 為不足，無法對有機物進行氧化分解；而超臨界水本身之 氧化力亦相當有限，因此必須額外將氧氣添加入該超臨界 水中，以透過該氧氣之氧化活性對該廢水中之有機物進行 氧化分解，因而造成製程上之不便利性。基於上述原因， 有必要進一步提升超臨界流體之氡化力。 【發明内容】 201006548 本發明之主要目的係提供一種提升超臨界流體氧化 力的方法’係·-料絲對—超臨界流體進行照射， 以透過紫外光使該超臨界流體之分子鍵結斷裂進而生成 高氧化活性之自由基，並使得本發明具有提升超臨界流體 氧化力之功效。201006548 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a method of fabricating a dielectric layer film, and more particularly to a method for improving the oxidizing power of a supercritical fluid. [Prior Art] Since the supercritical fluid has both gaseous and liquid characteristics, it has a low viscosity of gas, a high diffusibility, a fluid density of a liquid, and excellent flow turbulence. In addition, due to its high compressibility, supercritical fluids also have a wide range of solvent characteristics. Therefore, supercritical fluids have been widely used in various industries such as pharmaceuticals, chromatography, extraction, soil and wastewater pollution remediation, application of chemical reaction procedures, and use of solvents for crystallization and adsorption. Since the supercritical carbon dioxide itself is relatively stable, it is usually applied to the production of powders and the cleaning of the surface of objects. In addition, in the environment where the temperature is higher than the critical temperature of water, the hydrogen bonds in the water molecules will disappear, making the water molecules non-polar. Molecules, whereby organic matter and oxygen can be mixed into supercritical water to form a homogeneous phase, and the added oxygen can effectively oxidize the organic matter, so supercritical water has great potential in wastewater treatment applications. As mentioned above, the general supercritical fluid is relatively stable in nature, and the oxidizing power is insufficient to be oxidatively decomposed. Therefore, the oxidizing power of the supercritical water itself is quite limited, so oxygen must be additionally added to the supercritical water. The organic matter in the wastewater is oxidatively decomposed by the oxidation activity of the oxygen, thereby causing process inconvenience. For the above reasons, it is necessary to further enhance the deuteration force of the supercritical fluid. SUMMARY OF THE INVENTION 201006548 The main object of the present invention is to provide a method for improving the oxidizing power of a supercritical fluid by irradiating a supercritical fluid with ultraviolet light to break the molecular bond of the supercritical fluid. The high oxidation active free radicals are generated and the invention has the effect of increasing the oxidative power of the supercritical fluid.
根據本發明之提升超臨界流體氧化力的方法，係包含 :將-超臨界流體通人—腔體中’且該超臨界流體係為含 氧化合物；及彻-紫外細照射該超臨界流體，以透過 該紫外光_提供之能量，使該超臨職體之分子鍵結斷 裂’進而產生自由基。藉此，可藉由該高活性之 升該超臨界流體之氧化力。 【實施方式】 為讓本發明之上述及其他目的、特徵及優點能更明顯 易懂，下文特舉本發明之較佳實施例，並配合所附圖 作詳細說明如下： ❹ 請參照第1圖所示，本發明較佳實施例之提升超臨界 流體氧化力的方法係先將一超臨界流體通入一腔體中，且 該超臨界流體係為含氧化合物。更詳言之，由於二氧化碳 聽氣便宜且容易取得，因此，該含氧化合物係可選擇以 二氧化碳（co2)或氧氣（〇2)等物f ;該腔體較佳係選 擇為一可密閉空間，以便控制該腔體内之環境條件， 溫度、壓力或濕度等環境條件。 請再參照第1 ®所示，本發明之提升超臨界流體氧化 力的方法接著利用一紫外光源（uvlight)照射該超臨界流 201006548 體，使該超臨界流體之分子鍵結斷裂，進而產生自由基。 更詳s之，本實施例係透過功率為35〇冒至12〇〇w之紫外 光源照射該超臨界二氧化碳或超臨界氧丨至3小時以提供 旎量，使該超臨界二氧化碳或超臨界氧中之分子鍵結斷裂 ’進而形成具有高氧化活性之自由基，例如使超臨界二氧 化碳之碳氧雙鍵斷裂，或者使超臨界氧之氧氧雙鍵斷裂， 而產生氧自由基，如此便可透過該自由基之產生，而有效 的提高該超臨界流體之氧化力。當然，亦可於該紫外光源 照射前，於該超臨界流體中添加一助劑，該助劑為液、氣 或固態皆可均勻混合於該超臨界流體中，且該助劑係為含 氧化合物（例如：二氧化碳或氧），以使該紫外光源所提供 之能量可同時使該助劑中之鍵結斷裂，進一步增加自由基 之產量，而增進本發明提升超臨界流體氧化力之效果。 此外，本實施例係透過觀察半導體經各種不同狀態下 之超臨界流體處理後之電性變化，而進一步驗證本發明確 實具有提升超臨界流體氧化力之功效。 請參照第2圖所示，其係為一電子元件刮面圖，該電 子元件係由基板1、閘極2、閘極介電層3、源極4、没極 5及半導體元件6所組成，其中該半導體元件6係為氧化 鋅（ZnO)，由於該半導體元件6於成膜時通常並未完全氧 化，具有缺陷，而表現出較差之電性。若利用照光後之超 臨界流體對該半導體元件6之表面進行處理，而使得該半 導體元件6電性表現提升，便可推知本發明處理後之超臨 界流體的氧化力確實被明顯提升，使得該照光後之超臨界 201006548 流體可氧化修補該半導體元件6之缺陷，而提升該半導體 元件6之電性表現。其中，下述實施例之分析中，超臨界 • 流體對該半導體元件6表面之處理時間選擇為1小時，且 - 處理溫度選擇為150。(：。 第3及4圖係為汲極電壓（VD)對汲極電流（iD)之 相對變化圖。其中’對照組係為未經處理之半導體元件6 所表現出來之電性結果；第A組係經超臨界二氧化碳處理 ❹ 後之半導體元件6所表現之電性結果，且該超臨界二氧化 碳之壓力為30〇〇psi ;第B組係經超臨界二氧化碳處理後 之半導體元件6所表現之電性結果，該超臨界二氧化碳經 功率為350W之紫外光照射、小時，且壓力係為3〇〇〇psi 。由第3圖結果可得知，經超臨界二氧化碳處理後之半導 體兀•件6之電性表現並未有明顯差異。而由第4圖結果可 得知，於相同汲極電壓Vd下，第B組之汲極電流1〇具有 更為明顯之增加，結果皆可看出第B組之電性表現有明顯 ❹ 之改善’如上所述’可推知超臨界二氧化碳經本發明照光 處理後，超臨界二氡化碳之氧化力可有效提升。 第5圖為鋅（Zn)之束缚能（咖沿呢energy)對強度 (in—)之相對變化圖，1 6圖為氧⑻之束缚能（ Duuhng_gy) _度之_變化圖，以了解半導體元件 ‘ 6中之鋅及氧之數量變化。由第5圖可得知，第A組僅使 信號向右略微偏移，且線下面積並無明顯改變；而第B组 則使信號大幅向右偏移，表示辞能量提升，亦即辞價數增 加，受到氧化；由第6圖可得知，第A組僅使信號向右略 201006548 微偏移，且線下面積並無明顯改變；而第B組則使信號大 幅向右偏移，表示氧能量提升，而線下面積亦大幅增加， . 即表示氧之數量大幅增加，表示第B組之半導體元件ό内 ' 《含氧量大幅提昇，可推知超臨界流體經本發明照光處理 後，超臨界二氧化碳之氧化力可有效提升，使得該第Β組 之半導體元件6内之含氧量大幅提昇。 請參照第7及8圖所示，其為光激螢光（ ❹ P 〇t〇luminescence，PL)分析結果圖’由結果可得知，對照 組及第A組之發光強度並無明顯差異，而第B組與對照組 ，組相較之下，第B組之半導體元件6的發光強度大 幅增加，可得知該半導體元件6之缺陷已被修補改善，進 而推知經本發明照光處理後之超臨界流體之氧化力提升， 可有效氧化修補該半導體元件6之缺陷。 帛9及1〇圖係汲極電壓（Vd)對汲極電流⑹之 對變化圖H第c組係為經超臨界氧處理後之半導 〇 6所表現之電性結果，且該超臨界氧之M力係為 〇Psi’第D組為經超臨界氧處理後之半導體元件6所表 =之電性結果，該超臨界氧經功率為35GW之紫外光照射 時’且壓力係為100〇Psi。由第9及10圖結果可得知 =相同汲極電壓Vd下，第c組之祕電流Μ有提升 明2第D組相較之下’第D組之》及極電流匕提升幅度 .〃第C組之數百倍以上，可推知超臨界氧經本發明照 "理後，超臨界氧之氧化力可有效提升。 第11圖係鋅（Zn)之束缚能（binding energy)對強 9 201006548 度（intensity)之相對變化圖。第12圖係氧（〇)之束缚 能對強度之相對變化圖，以了解半導體元件6中之辞及氣 . t數量變化。由第11圖可得知，第C組僅使信號向右略 ‘ 微偏移·’而第D組則使信號大幅向右偏移，表示鋅能量提 升，亦即鋅價數增加，受到氧化。由第12圖可得知，第c 組僅使信號向右略微偏移；而第〇組使信號右移幅度大於 第C組’表示氧能量提升，可推知超臨界流體經本發明照 ❹ 歧理後’超臨界氧之氡化力可有效提升’使得該第D組 之半導體元件6氧化程度提昇。 請參照第13圖所示，其係光激螢光（ Ph—聰inesc嶋，PL)分析結果圖由結果可得知第^ 組之半導體元件6之發光強度明顯較第c組增加許多，可 ，知該半導體元件6之缺陷已錄補改善，進而推知超臨 ’氧紐紫外光照射後之氧化力較未經照射之超臨界氧高， 因，，本發明照光處理後之超臨界流體之氧化力確實有明 ❹ 升’可有效氧化修補該半導體元件6之缺陷。 :上述分析可得知，不論是以二氧化碳或氧做為超臨 =&紫外光騎後之超臨界流體的氧化力均有大幅 .^ ’因此本發财實可有效提升超臨錢體之氧化力； 卜，亦可推㈣超臨界流財若添加由含合物所組 装之助谢’該紫外光源同理亦可使該助綱鍵並產生自由 。’而進-步提升本㈣騎臨界⑽氧化力提升之效果 所述本發明係利用紫外光源照射一超臨界流體 201006548 ，且該超臨界流體係為含氧化合物，以透過該紫外光源所 提供之能量使該含氧化合物斷鍵，形成自由基，進而提升 該超臨界流體之氧化力；再者，該超臨界流體中係可另包 含一助劑，且該助劑係為含氧化合物，以使該紫外光源所 提供之能量可同時使該超臨界流體及助劑斷鍵，而產生自 由基，進而提升該超臨界流體之氧化力。 雖然本發明已利用上述較佳實施例揭示，然其並非用 以限定本發明’任何熟習此技藝者在不脫離本發明之精神 和範圍之内’相對上述實施例進行各種更動與修改仍屬本 發明所保護之技術範疇，因此本發明之保護範圍當視後附 之申清專利範圍所界定者為準。 ❹ —11 — 201006548 【圖式簡單說明】 第1圖：本發明之提升超臨界流體氧化力之方法的流程 ， 圖。 - 第2圖：電性分析中電子元件的剖面圖。 第3圖：對照組及第A組之沒極電壓（VD)對汲極電 流（ID)之相對變化圖。 第4圖：對照組及第b組之汲極電壓（VD)對汲極電 ❹ 流（b)之相對變化圖。 第5圖：辞之束缚能（binding energy)對強度（intensity )之相對變化圖（對照組、第A及B組）。 第6圖：氧之束缚能（binding energy)對強度（intensity )之相對變化圖（對照組、第A及B組）。 第7圖··對照組及第B組之光激螢光（PL)分析結果 圖。 第8圖：第A及B組之光激螢光（PL)分析結果圖。 Q 第9圖··對照組及第C組之汲極電壓（VD)對汲極電 流（Id)之相對變化圖。 第10圖：對照組及第D組之汲極電壓（VD)對汲極電 流（ID)之相對變化圖。 第11圖：鋅之束缚能（binding energy )對強度（intensity ‘ ）之相對變化圖（對照組、第C及D組）。 第12圖：氧之束缚能（binding energy )對強度（intensity )之相對變化圖（對照組、第C及D組）。 第13圖：對照紕、第c及D組之光激螢光（PL)分析 —12 — 201006548 結果圖。 【主要元件符號說明】 1 基板 2 閘極. 3 閘極介電層 4 源極 5 汲極 6 半導體元件The method for improving the oxidizing power of a supercritical fluid according to the present invention comprises: passing a supercritical fluid into a cavity - and the supercritical fluid system is an oxygen-containing compound; and thoroughly irradiating the supercritical fluid with a thorough-ultraviolet light, By absorbing the energy provided by the ultraviolet light, the molecular bonds of the super-professional body are broken, thereby generating free radicals. Thereby, the oxidizing power of the supercritical fluid can be raised by the high activity. BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features, and advantages of the present invention will become more <RTIgt; As shown in the preferred embodiment of the present invention, the method for increasing the oxidizing power of a supercritical fluid is to first pass a supercritical fluid into a cavity, and the supercritical fluid system is an oxygen-containing compound. More specifically, since the carbon dioxide gas is cheap and easy to obtain, the oxygen compound may be selected from carbon dioxide (co2) or oxygen (〇2); the cavity is preferably selected as a confinable space. In order to control the environmental conditions in the chamber, environmental conditions such as temperature, pressure or humidity. Referring to FIG. 1 again, the method for improving the oxidizing power of the supercritical fluid of the present invention is followed by irradiating the supercritical fluid 201006548 with an ultraviolet light source (uvlight) to break the molecular bond of the supercritical fluid, thereby generating freedom. base. More specifically, in the present embodiment, the supercritical carbon dioxide or supercritical oxygen is irradiated by an ultraviolet light source having a power of 35 Torr to 12 〇〇w to provide a volume of the supercritical carbon dioxide or supercritical oxygen. In the molecular bond cleavage', a free radical having a high oxidizing activity is formed, for example, a carbon-oxygen double bond of supercritical carbon dioxide is broken, or an oxygen-oxygen double bond of a supercritical oxygen is broken to generate an oxygen radical, so that The oxidizing power of the supercritical fluid is effectively increased by the generation of the radical. Of course, before the irradiation of the ultraviolet light source, an auxiliary agent may be added to the supercritical fluid, and the auxiliary agent may be uniformly mixed in the supercritical fluid in liquid, gas or solid state, and the auxiliary agent is an oxygen compound. (for example: carbon dioxide or oxygen), so that the energy provided by the ultraviolet light source can simultaneously break the bond in the auxiliary agent, further increasing the yield of the free radical, and improving the effect of the invention for improving the oxidizing power of the supercritical fluid. In addition, this embodiment further demonstrates that the present invention has the effect of improving the oxidizing power of the supercritical fluid by observing the electrical change of the semiconductor after treatment with the supercritical fluid in various states. Please refer to FIG. 2 , which is an electronic component scraping diagram composed of a substrate 1 , a gate 2 , a gate dielectric layer 3 , a source 4 , a gate 5 and a semiconductor component 6 . The semiconductor element 6 is zinc oxide (ZnO), and since the semiconductor element 6 is usually not completely oxidized at the time of film formation, it has defects and exhibits poor electrical properties. If the surface of the semiconductor device 6 is treated by the supercritical fluid after illumination, and the electrical performance of the semiconductor device 6 is improved, it can be inferred that the oxidizing power of the supercritical fluid after the treatment of the present invention is significantly improved, so that the Supercritical 201006548 after exposure The fluid oxidatively repairs the defects of the semiconductor component 6 to enhance the electrical performance of the semiconductor component 6. Here, in the analysis of the following examples, the treatment time of the supercritical fluid to the surface of the semiconductor element 6 was selected to be 1 hour, and - the treatment temperature was selected to be 150. (: Figures 3 and 4 are plots of the relative variation of the drain voltage (VD) versus the drain current (iD). The 'control group is the electrical result of the untreated semiconductor component 6; Group A is the electrical result of semiconductor element 6 after supercritical carbon dioxide treatment, and the pressure of the supercritical carbon dioxide is 30 psi; Group B is represented by semiconductor component 6 after supercritical carbon dioxide treatment. As a result of electrical conductivity, the supercritical carbon dioxide is irradiated with ultraviolet light at a power of 350 W for hours, and the pressure is 3 psi. From the results of Fig. 3, the semiconductor device after supercritical carbon dioxide treatment is known. The electrical performance of 6 is not significantly different. From the results of Fig. 4, it can be seen that under the same buckling voltage Vd, the buckling current of group B has a more significant increase, and the results can be seen. The electrical performance of Group B has a significant improvement in ' 'as described above'. It can be inferred that after the illuminating treatment of supercritical carbon dioxide by the present invention, the oxidizing power of supercritical carbon dioxide can be effectively improved. Fig. 5 is a zinc (Zn) Binding energy For the relative change of intensity (in-), Figure 16 shows the change of oxygen (8) binding energy (Duuhng_gy) _ degree to understand the change in the amount of zinc and oxygen in the semiconductor device '6. It is known that Group A only slightly shifts the signal to the right, and the area under the line does not change significantly; while Group B shifts the signal to the right, indicating that the energy is increased, that is, the number of words is increased, and Oxidation; as can be seen from Fig. 6, the group A only slightly shifts the signal to the right of 201006548, and the area under the line does not change significantly; while the group B shifts the signal to the right, indicating the increase of oxygen energy. The area under the line has also increased significantly, which means that the amount of oxygen has increased significantly, indicating that the semiconductor component of Group B has a large increase in oxygen content. It can be inferred that supercritical fluid is supercritical carbon dioxide after being treated by the present invention. The oxidizing power can be effectively increased, so that the oxygen content in the semiconductor element 6 of the second group is greatly increased. Please refer to Figs. 7 and 8 for the analysis of 激P 〇t〇luminescence (PL). The results are shown in the results, the control group and the group A There is no significant difference in the luminescence intensity, and the luminescence intensity of the semiconductor element 6 of the group B is greatly increased in the group B and the control group, and it is known that the defect of the semiconductor element 6 has been repaired and improved. It is inferred that the oxidizing power of the supercritical fluid after the illuminating treatment of the present invention can effectively oxidize and repair the defects of the semiconductor element 6. The 汲9 and 1 〇 diagrams are the relationship between the threshold voltage of the drain current (Vd) and the drain current (6). Group c is the electrical result of semi-conducting 〇6 after supercritical oxygen treatment, and the M-force of the supercritical oxygen is 〇Psi'. Group D is the semiconductor component 6 after supercritical oxygen treatment. Table = electrical results, the supercritical oxygen was irradiated with ultraviolet light of 35 GW' and the pressure system was 100 〇 Psi. From the results of the 9th and 10th graphs, it can be seen that under the same bungee voltage Vd, the secret current of the c-group is improved by the second group D and the "group D" and the polar current 匕 increase range. More than several hundred times of the group C, it can be inferred that the supercritical oxygen can be effectively improved by the invention. Figure 11 is a plot of the relative change in zinc (Zn) binding energy versus strong 9 201006548 intensity. Fig. 12 is a graph showing the relative change in the binding force of oxygen (〇) to the intensity to understand the change in the number of words in the semiconductor element 6. It can be seen from Fig. 11 that the group C only makes the signal slightly 'micro-offset' to the right and the group D shifts the signal to the right, indicating that the zinc energy is increased, that is, the zinc valence is increased and is oxidized. . It can be seen from Fig. 12 that the group c only slightly shifts the signal to the right; and the third group makes the signal shift to the right larger than the group C, indicating that the oxygen energy is increased, and it can be inferred that the supercritical fluid is ambiguous by the present invention. After the 'supercritical oxygen enthalpy can be effectively improved', the degree of oxidation of the semiconductor component 6 of the group D is increased. Please refer to Fig. 13 for the results of the analysis of the photoluminescence (Ph-Cong inesc, PL). It can be seen from the results that the luminescence intensity of the semiconductor component 6 of the group is significantly higher than that of the c-group. It is known that the defects of the semiconductor component 6 have been recorded and improved, and it is inferred that the oxidizing power after the irradiation of the ultraviolet light is higher than that of the unsuperposed supercritical oxygen, because the supercritical fluid after the light treatment of the present invention The oxidizing power does have a significant increase in the defects of the semiconductor element 6 which can be effectively oxidized. : The above analysis shows that the oxidizing power of the supercritical fluid after riding the carbon dioxide or oxygen as the super-advertising =& ultraviolet light has a large amount. ^ 'So the money can effectively improve the super-money Oxidizing power; Bu, can also push (4) Supercritical fluids if added by the inclusion of the compound to help the 'the ultraviolet light source can also make the auxiliary key and free. The process of the present invention utilizes an ultraviolet light source to illuminate a supercritical fluid 201006548, and the supercritical fluid system is an oxygen-containing compound for transmission through the ultraviolet light source. The energy causes the oxygenate to break bonds to form a radical, thereby increasing the oxidizing power of the supercritical fluid; further, the supercritical fluid may further comprise an auxiliary agent, and the auxiliary agent is an oxygen compound, so that The energy provided by the ultraviolet light source simultaneously breaks the supercritical fluid and the auxiliary agent to generate free radicals, thereby increasing the oxidizing power of the supercritical fluid. The present invention has been disclosed in the above-described preferred embodiments, and is not intended to limit the invention. It is intended that the present invention may be practiced without departing from the spirit and scope of the invention. The technical scope of the invention is protected, and therefore the scope of the invention is defined by the scope of the appended claims. ❹—11 — 201006548 [Simplified illustration] Fig. 1: Flow chart of the method for improving the oxidizing power of supercritical fluid of the present invention. - Figure 2: Sectional view of the electronic components in the electrical analysis. Figure 3: Relative change in the dipole current (ID) of the control group and Group A. Figure 4: Relative change of the buckling voltage (VD) of the control group and the b group to the 汲 电 ( flow (b). Figure 5: Diagram of the relative change in binding energy versus intensity (control group, groups A and B). Figure 6: Relative change in oxygen binding energy (intensity) (control group, groups A and B). Fig. 7 is a graph showing the results of light fluorescence (PL) analysis of the control group and the group B. Figure 8: Photograph of the results of the optical fluorescence (PL) analysis of Groups A and B. Q Fig. 9 is a graph showing the relative change in the buckling current (Id) of the buckling voltage (VD) of the control group and the C group. Figure 10: Relative change in the threshold voltage (VD) of the control group and Group D for the buckling current (ID). Figure 11: Relative energy change of binding energy (intensity ‘ ) of zinc (control group, groups C and D). Figure 12: Relative change in oxygen binding energy (intensity) (control group, groups C and D). Figure 13: Photoluminescence (PL) analysis of control 纰, groups c and D —12 — 201006548 Results. [Main component symbol description] 1 substrate 2 gate. 3 gate dielectric layer 4 source 5 drain 6 semiconductor device
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