1296287 九、發明說明： 發明所屬之技術領域 、本發明係關於-種移除多孔性材料中不純物的方法， 尤其有關-種利用超臨界流體從具有奈米孔洞的多孔 料移除不純物的方法。 # 先前技術 如何有效且環保的達到元件表面潔淨、新材料純化以 提升產品良率及可靠度已成為各高科技產業未來製程需求 急待克服的間題。過去清洗製程使用的清潔方法，包括使 用具酸驗性、強氧化性溶液與有機溶劑等，雖然頗有成效 且已订之有年，但也相對衍生負面問題’例如須使用大量 純水和化學_ ’如此*但極易導致產品與環境污毕、、主 :後仍須費時的加以乾燥。然而’當元件具有深溝或高： 寬比結構（hlgh aspect ratio)、或是元件為多孔隙組成 1P_S media)時’傳統的酸驗清洗程序由於液體的表面張 、過大’無法有效且迅速的清洗此類元件的細部結構或是 、凡件的不米級孔隙。亦即無法達成全面性的潔淨程 度’不論是在製程階段或是清洗階段皆有程度不等之污毕 =水氣殘留1且元件經傳統㈣、有機溶劑清洗程序 須搭配乾燥階段’在乾燥的過程中，清洗溶劑的表 過大會造成元件圖案倒塌（pattern c〇iiapse)、破 結構導致特性劣化。此外，《乾燥時間相對較 0燥效果亦不理想，嚴重影響後續製程之搭配銜接， 1296287 因此傳統液態溶劑清洗方式無法符合未來具有複雜結構或 是多孔性新穎材料之有效洗淨需求。 超臨界流體的物理性質介於氣、液相之間。超臨界流 體兼具有如氣體般的低黏度（輸送時所須的功率則較液體 為低）、高擴散係數（擴散係數高於液體1〇至1〇〇倍，亦即 質量傳遞阻力遠較液體為小，在質量傳遞上較液體為快）、 低表面張力（容易滲入到多孔性組織中），有如液體般的高 密度（可輸送較氣體更多的超臨界流體；可增加流體在反應 器内的停滞時間，故可使用連續式的操作）。除物理性質外， 超臨界流體的化學性質亦與其在氣、液態時有所不同，例 如二氧化碳在氣體狀態下不具萃取能力，但當進入超臨界 狀態後，二氧化碳轉變為親有機性，因而具有溶解有機物 的能力’此溶解能力隨溫度及壓力調整而改變。使用後的 超臨界流體只需減壓即會返回氣相，而和其他固、液相的 物質分離，因此容易回收再使用，此為超臨界流體的優點 之一。在眾多流體中又以二氧化碳之應用最受歡迎與重視， 因其臨界條件溫和、臨界點易達到，臨界溫度3 i 2〇C接近 室溫、臨界壓力約72 · 8 atm。同時不具毒性、不具燃燒性， 性質穩定，來源可由石化燃料燃燒副產物中回收且價格不 南’對於高科技產業的相關應用而言將具有其發展優勢與 潛力。 己知利用超臨界流體進行多孔性低介電常數薄膜（1〇w dielectric constant film，i〇w k)中不純物之移除的相關專利 有3件。US63 06754利用超臨界流體清洗多孔性低介電常 1296287 數薄膜被蝕刻後孔隙中的雜質以及光阻殘餘物，超臨界流 體為乙烯或是二氧化碳並添加醇、酮或其混合物當作修飾 劑’操作壓力為70 - 200 atm、操作溫度為35 — 100〇c。 US6669785利用超臨界流體清洗移除多孔性低介電常數材 料之氧化物（oxide)，光阻或蝕刻殘餘物及環境污染物；超 臨界流體為C〇2，包含第一清洗流體與第二清洗流體，操 作密度為0.150 g/cc — 1·1 g/cc，操作溫度為〇 — 8〇〇c，共 溶劑種類為胺（嗎佛啉（morpholine)，苯胺（aniHne)或二丁胺 (dibutylamine)、或是 C1 — C4 醇，添加比例為 〇 丨 一 4〇% w/w; 0·1 - 5% w/w界面活性劑。US2004018452利用超臨界流體 添加鈍化劑（passivating agent)清洗多孔介電材料表面蝕刻 之後殘餘物以減低材料劣化’超臨界流體為C〇2、鈍化劑 為酸或是氟化物。分析上述專利技術内容後，發現目前利 用超臨界流體清洗多孔性低介電常數薄膜材料之流體種類 主要仍為二氧化碳，但都需伴隨添加不同性質、比例的修 飾劑達到污染物移除的目的。被移除的污染物種類大多數 為光阻、光阻殘餘物、鈦刻殘餘物等有機物質，目前尚無 專利發表特定水氣去除或是同時利用同一種修飾劑針對製 程中水氣、有機污染物等不純物進行清洗與表面特性改 質。然而，對於多孔性低介電常數薄膜材料而言，經過蝕 刻之後極易造成薄膜材料劣化、水氣吸附殘留孔隙導致介 電常數值上升，因此水氣與有機污染物共同存在的問題^ 不容忽視並急待解決。若是無法同時去除有機污染物與水 氣達成元件表面活化與改質，如此對於多孔性材料之清洗 1296287 與製程整合開發應用潛力將受限。 超臨界流體移除奈米 $無發現有利用 碳管中不純物之先前技藝。 發明内容 本發明的主要目的為袒彳 太乎m的夕, .、、、楗仪一種利用超臨界流體從具有 不未孔洞的多孔性材料移除 … 十移除包括水氣的不純物的方法。 本毛明的另一目的為提供一 磁其较w 種利用超臨界流體從奈米 故管移除不純物的方法。 *為達成上述本發明目的，本發明利用超臨界C〇2盘一 =、種類修飾劑之添加，於適當之溫度、厂 "操；條 =進行多孔性材料中水氣、有機污染物之清洗移除。超 /、成為相當良好的攜帶流體(carrier)，可將額外添加的修飾 劑均句分散後進人多孔性材料之奈米級孔洞，在不破壞材 :原有之特性與結構的前提之下，進-步將水氣與有機污 染物等雜質自孔洞中帶出，超臨界流體經解壓至常壓後， 不純物與修飾劑即可與流體分離，無殘留等問題產生。本 技術的優點為清洗後幾乎無清洗廢液產生、省水省能、減 廢、所需清洗時間短、效率高、無二次污染、亦為環境友 善處理方法之一。本發明並針對清洗後之元件表面特性進 订评估與驗證，發現清洗後的多孔性材料更能顯現出其 性。 … 1296287 實施方式 ，發明提供-種從具有奈米孔洞的多孔性材料移除包 括水礼的*純物的方法，包含將—超臨界流體與—多孔性 材料接觸’其中該多孔性材料具有奈米孔洞或渠，及位於 該奈米孔洞或渠内的包括水氣在内的不純物，於是位於該 不米孔洞或渠内的包括水氣在内的不純物為該超臨界流體 所攜帶出，而與該多孔性材料分離。 較佳的，該超臨界流體包含-惰性氣體及-選自醇或 酮的修飾劑。更佳的’該惰性氣體為二氧化碳。更佳的， 該修飾劑包含甲醇、乙醇m、賴或它們的混 合0 較佳的’該接觸係於一處理槽内進行，及該超臨界流 體被連續的流經該處理槽。更佳的，本發明方法進一步包 含停止該超臨界流體的流動，通過降壓使該超臨界流體轉 變成氣體，及從該處理槽内移出該多孔性材料。 車父佳的’該多孔性材料包含奈米碳管。 較佳的，該超臨界流體具有一介於4〇至8〇〇c的溫度、 一介於lOOOpsi至50〇〇psi的壓力，及一介於〇 5至^體 積％的修飾劑，以該超臨界流體的體積為基準。 較佳的’該接觸持續1分鐘至6〇分鐘。 以下，將參考圖1的流程圖來說明本發明的一較佳具 體實施例。 ’、 液態二氧化碳經加溫加壓達到設定超臨界流體後以一 固定流量輸送至經恆溫控制之試片處理槽，在超臨界二氧 1296287 化碳流體進入該處理槽之前將修飾劑以一定體積比（固定 流量）添加至超臨界二氧化碳流體。所產生的被修飾的超臨 界二氧化碳流體連續的被導入該試片處理槽，到達一預定 壓力後，從該試片處理槽排出相同流量的廢流。一段時間 後，停止被修飾的超臨界二氧化碳流體的進流及廢流的排 出。試片處理槽經降溫、解壓後，取出試片完成清洗動作。 清洗後的試片被進行相關特性分析與驗證工作。 本發明將藉由下列實施例被進一步瞭解，該等實施例 僅作為說明之，而非用於限制本發明範圍。 實施例一 本實施例中以二極奈米碳管（CNT)場發射器為清洗對 象。於一玻璃基板上先形成銀電極，再於銀電極上塗佈含 有奈米碳管的一漿料，經高溫（4〇〇〜5〇〇。〇燒結後，製作成 -極CNT場發射器。本實施例所使用之奈米碳管係由工研 院電子所所提供。將剛製備好的二極CNT場發射器先經泡 水處理，再進行水氣移除的實驗。 一極CNT場發射器的製程中並不需泡水，但是在製程 中圖案化的過程將接觸濕式溶劑（例如酸、鹼等溶液），此 夺亦將導人酸、驗、水氣等污染，造成元件電性缺陷。本 實驗泡水的目的只為了簡單模擬二極CNT場發射器經濕製 i後其電性缺陷之現象是否可藉由超臨界流體清洗方式予 以活化改善。泡水時間為—天以i，直到元件電性反應行 為降低或完全消失。泡水後的試片再直接放到1〇3。〇左右 1296287 的 oven 烘乾 1〇〜2〇 min 依圖 1所示的方法、仓y 万去進伃清洗實驗，實驗條件··試片處 理槽内的壓力3000 psi，、w P ▲度為50°C。超臨界二氧化碳添 加7體積％正丙醇作為佟 F馬修飾劑。清洗時間為5分鐘。 、超臨界CQ2處理前/後之二極CNT場發射器的電性表 見被示於圖2圖2中x轴為操作電場，y軸為cnt場發 射器之電机密度。操作電場要越小越省電，電流密度的曲 線要越陡㈣越有利於元件的控制。圖2的結果顯示經清洗 後之二極CNT場發射器的場發射效率明顯增高。 本案發明人亦曾進行類似實施例一的實驗，但改變正 丙醇的體積％為3%及5%，實驗結果發現有相同於實施例 一的清洗效果。 本發明已被描述於上，熟悉本技術的人士仍可作出未 脫離下列申請專利範圍的多種變化及修飾。 圖式簡單說明 圖1是本發明的較佳具體實施例的流程示意圖。 圖2顯示超臨界C02處理前（菱形點）/後（方形點）之二 極CNT場發射器的電性表現，其中X軸為操作電場，y軸 為CNT場發射器之電流密度（J)。1296287 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for removing impurities in a porous material, and more particularly to a method for removing impurities from a porous material having nanopores using a supercritical fluid. # 前技术 How to effectively and environmentally improve the surface of components and purify new materials to improve product yield and reliability has become an urgent need to overcome the future process requirements of various high-tech industries. The cleaning methods used in the past cleaning process, including the use of acid-testing, strong oxidizing solutions and organic solvents, although quite effective and have been booked for a number of years, are also relatively negative problems - for example, the use of large amounts of pure water and chemistry _ 'So* but it is very easy to cause the product and the environment to be filthy, and the main: it still takes time to dry. However, 'when the component has a deep groove or high: hlgh aspect ratio, or the component is a porous composition 1P_S media), the 'traditional acid cleaning procedure cannot be effectively and quickly cleaned due to the surface of the liquid being too large. The detailed structure of such components is not the non-meter-level pores of the pieces. That is to say, it is impossible to achieve a comprehensive degree of cleanliness. Whether it is in the process stage or in the cleaning stage, there are varying degrees of contamination = water residue 1 and components are traditional (4), organic solvent cleaning procedures must be combined with the drying stage 'drying' During the process, the surface of the cleaning solvent is too large, causing the pattern to collapse (pattern c〇iiapse), and the broken structure causes deterioration in characteristics. In addition, the drying time is relatively unsatisfactory, which seriously affects the matching of subsequent processes. 1296287 Therefore, the traditional liquid solvent cleaning method cannot meet the effective cleaning requirements of future complex structures or porous materials. The physical properties of supercritical fluids are between gas and liquid phases. The supercritical fluid has a low viscosity like gas (the power required for transportation is lower than that of liquid) and a high diffusion coefficient (the diffusion coefficient is higher than 1〇 to 1〇〇 of the liquid, that is, the mass transfer resistance is much longer than the liquid. Small, faster than liquid in mass transfer), low surface tension (easy to penetrate into porous tissue), high density like liquid (can transport more supercritical fluid than gas; can increase fluid in reactor The stagnation time inside, so continuous operation can be used). In addition to physical properties, the chemical properties of supercritical fluids are also different from those in gas and liquid. For example, carbon dioxide does not have the ability to extract in a gaseous state, but when it enters a supercritical state, carbon dioxide is converted to an organophilic property and thus has a solubility. The ability of organic matter 'this solubility changes with temperature and pressure adjustment. The supercritical fluid after use is returned to the gas phase only under reduced pressure, and is separated from other solid and liquid substances, so it is easy to recycle and reuse, which is one of the advantages of the supercritical fluid. Among the many fluids, the application of carbon dioxide is the most popular and important, because its critical conditions are mild and the critical point is easy to reach. The critical temperature is 3 i 2〇C close to room temperature and the critical pressure is about 72 · 8 atm. At the same time, it is non-toxic, non-flammable, stable in nature, and its source can be recovered from fossil fuel combustion by-products and its price is not good. It will have its development advantages and potential for high-tech industry related applications. It is known that there are three patents relating to the removal of impurities in a porous low dielectric constant film (i〇w k) using a supercritical fluid. US63 06754 uses a supercritical fluid to clean impurities and photoresist residues in porous pores after etching a porous low dielectric 1296287 film. The supercritical fluid is ethylene or carbon dioxide and is added with alcohol, ketone or a mixture thereof as a modifier. The operating pressure is 70 - 200 atm and the operating temperature is 35 - 100 〇c. US6669785 uses supercritical fluid cleaning to remove oxides, photoresists or etching residues and environmental contaminants of porous low dielectric constant materials; supercritical fluid is C〇2, including first cleaning fluid and second cleaning Fluid, operating density is 0.150 g / cc - 1 · 1 g / cc, operating temperature is 〇 - 8 〇〇 c, cosolvent type is amine (morpholine, aniline (aniHne) or dibutylamine (dibutylamine) ) or C1 - C4 alcohol, the addition ratio is 〇丨4〇% w/w; 0·1 - 5% w/w surfactant. US2004018452 uses supercritical fluid to add a passivating agent to clean porous media. The residue of the surface of the electric material is etched to reduce the deterioration of the material. The supercritical fluid is C〇2, the passivating agent is acid or fluoride. After analyzing the above patented technology, it is found that the porous low dielectric constant film is cleaned by supercritical fluid. The type of fluid of the material is still mainly carbon dioxide, but it needs to be added with different properties and proportions of modifiers to achieve the purpose of pollutant removal. Most of the pollutants removed are photoresists, photoresist residues, Organic substances such as titanium engraved residues have not been patented for specific water vapor removal or at the same time using the same modifier to clean and modify the surface properties of impurities such as water vapor and organic pollutants in the process. However, for low porosity In the dielectric constant film material, after etching, it is easy to cause deterioration of the film material, and the residual pores of water vapor adsorption cause the dielectric constant value to rise. Therefore, the problem of water vapor and organic pollutants together cannot be ignored and urgently needs to be solved. It is impossible to remove organic pollutants and moisture at the same time to achieve surface activation and modification of the components, so the potential for cleaning and cleaning of porous materials 1296287 and process integration will be limited. Supercritical fluid removal of nanometers has not been found in the use of carbon tubes. Prior art of the invention. SUMMARY OF THE INVENTION The main object of the present invention is to 袒彳太m, 、, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The method of impureness. Another purpose of Ben Maoming is to provide a magnetic one that uses supercritical fluids from nanometers. Method for removing impurities. * In order to achieve the above object of the present invention, the present invention utilizes a supercritical C〇2 disk== addition of a type modifier, at a suitable temperature, a factory" Cleaning and removal of gas and organic pollutants. Ultra/, becoming a fairly good carrier, can be added to the nano-scale pores of the porous material after dispersing the additional modifiers, without destroying the material: Under the premise of characteristics and structure, impurities such as water vapor and organic pollutants are taken out from the pores. After the supercritical fluid is decompressed to normal pressure, the impurities and the modifier can be separated from the fluid without residue. And so on. The advantage of this technology is that there is almost no cleaning waste liquid after cleaning, water saving, energy saving, waste reduction, short cleaning time, high efficiency, no secondary pollution, and one of environmentally friendly treatment methods. The present invention also evaluates and verifies the surface characteristics of the component after cleaning, and finds that the porous material after cleaning is more capable of exhibiting its properties. 1296287 Embodiments, the invention provides a method for removing a *pure material including a water ritual from a porous material having nanopores, comprising: contacting a supercritical fluid with a porous material, wherein the porous material has a naphthalene a mound hole or a canal, and an impurity including moisture in the hole or channel of the nanometer, so that impurities including moisture in the hole or the canal are carried by the supercritical fluid, and Separated from the porous material. Preferably, the supercritical fluid comprises an inert gas and a modifier selected from the group consisting of alcohols or ketones. More preferably, the inert gas is carbon dioxide. More preferably, the modifier comprises methanol, ethanol, m or a mixture thereof. Preferably, the contact is carried out in a treatment tank, and the supercritical fluid is continuously passed through the treatment tank. More preferably, the method of the present invention further comprises stopping the flow of the supercritical fluid, converting the supercritical fluid into a gas by depressurization, and removing the porous material from the treatment tank. The car's porous material contains a carbon nanotube. Preferably, the supercritical fluid has a temperature of between 4 Torr and 8 〇〇c, a pressure of from 1000 psi to 50 psi, and a modifier of between 5% and 5% by volume of the supercritical fluid. The volume is based on the benchmark. Preferably, the contact lasts from 1 minute to 6 minutes. Hereinafter, a preferred embodiment of the present invention will be described with reference to the flowchart of Fig. 1. ', liquid carbon dioxide is heated and pressurized to reach the set supercritical fluid and then delivered to the thermostatically controlled test strip processing tank at a fixed flow rate. The supercritical dioxygen 1296287 carbonized fluid enters the treatment tank before the modifier is in a certain volume. The ratio (fixed flow) is added to the supercritical carbon dioxide fluid. The resulting modified supercritical carbon dioxide fluid is continuously introduced into the test strip processing tank, and after reaching a predetermined pressure, the waste stream of the same flow rate is discharged from the test strip processing tank. After a period of time, the inflow of the modified supercritical carbon dioxide fluid and the discharge of the waste stream are stopped. After the test piece processing tank is cooled and decompressed, the test piece is taken out to complete the cleaning operation. The cleaned test piece was subjected to relevant characteristic analysis and verification work. The invention is further described by the following examples, which are intended to be illustrative only and not to limit the scope of the invention. Embodiment 1 In this embodiment, a two-pole carbon nanotube (CNT) field emitter is used as a cleaning object. A silver electrode is first formed on a glass substrate, and a slurry containing a carbon nanotube is coated on the silver electrode, and is subjected to a high temperature (4 〇〇 to 5 〇〇. After sintering, a CNT field emitter is fabricated. The carbon nanotubes used in this embodiment are provided by the Institute of Electronics of the Institute of Technology. The newly prepared two-pole CNT field emitter is treated by soaking water and then subjected to water gas removal experiments. The process of the field emitter does not require water soaking, but the process of patterning in the process will be exposed to wet solvents (such as acid, alkali, etc.), which will also lead to acid, test, moisture and other pollution, resulting in pollution The electrical defect of the component. The purpose of the water soaking in this experiment is only to simply simulate whether the phenomenon of electrical defects of the two-pole CNT field emitter after wet i can be activated by supercritical fluid cleaning. The soaking time is - Days i, until the component's electrical reaction behavior is reduced or completely disappeared. The test piece after soaking water is placed directly to 1〇3. The left and right 1296287 of the oven is dried 1〇~2〇min according to the method shown in Figure 1,仓 y 10,000 go to the cleaning experiment, experimental conditions · test strip processing tank The pressure is 3000 psi, and the w P ▲ degree is 50 ° C. Supercritical carbon dioxide is added with 7 vol% n-propanol as the 佟F horse modifier. The cleaning time is 5 minutes. The supercritical CQ2 treatment before/after the bipolar CNT The electric field of the field emitter is shown in Figure 2, where the x-axis is the operating electric field and the y-axis is the motor density of the cnt field emitter. The smaller the operating electric field is, the more power is saved, and the curve of the current density is steeper. (4) The more favorable the control of the components. The results of Fig. 2 show that the field emission efficiency of the cleaned bipolar CNT field emitter is significantly increased. The inventors also conducted experiments similar to the first example, but changed the volume of n-propanol. The % is 3% and 5%, and the results of the experiment are found to have the same cleaning effect as in the first embodiment. The present invention has been described above, and those skilled in the art can still make various changes and modifications without departing from the scope of the following claims. Brief Description of the Drawings Figure 1 is a schematic flow diagram of a preferred embodiment of the present invention. Figure 2 shows the electrical performance of a two-pole CNT field emitter before (diamond point)/back (square point) of supercritical CO 2 treatment, where X The axis is the operating electric field and the y axis is CN Current density of the T field emitter (J).