200827046 九、發明說明· . 【發明所屬之技術領域】 - 本發明係有關於一種以高密相流體去除基板之表面污染物之 '· 方法，尤其是‘關於一種能有效提升基板之殘留物去除效果之以 高密相流體去除基板之表面污染物之方法。 【先前技術】 目前普遍所使用之超臨界流體的物理性質係介於_、济相之 • 間，係如其黏度接近於氣體，密度接近於液體，因密度高，可輸 送較氣體更多的流體；因黏度低，輸送時所須的功率則較液體為 低。又如’擴散係數高於液體10至100倍，亦即質量傳遞阻力遠 較液體為小，因之在質量傳遞上較液體為侠。此外5超臨界流體 更有如氣體幾無表面張力，因此很容易滲入到多孔性组織中。 由於大部分的超g品界流體在常壓下均屬氣態，因此在使用後 只要滅！即會變回氣相，而和其他固、液相的物質分離，呈有容 易回收丹便用之優點，且由於超g品界流體具有低表面張力、低赛 鲁 度、高密度、以及高擴散性的獨特性質，尤其可操控之溶劑般特 性，使其成為有機及水性溶劑之最佳環保替代品。而目前許多氣 體包括二氧化碳、氨(Ammonia)、氦(Helium)、、氬(argon)、4(xen〇n) 或氧化至氮(Nitrous oxide)，或前述氣體之組合均可做為超臨界 • 流體，由於二氧化碳具有無毒、無色、無臭、不燃性、無腐钱性、 . 不需廢水處理、對人體無害、對環境友善及易於達到臨界點（化二 73· 8 bar，TC二31. rc)等製程優點，因而最常被使用。 g前半導體工業在進行離子植入或蝕刻等製裎中，係會運用 5 200827046 尤阻以作為保護基板不需離子植人或·彳之區域，此時，會於遮 瘦70阻層衣面形咸—層不易移除的硬殼，又在侧製程中，會於 則*⑻战—光阻殘留物及働试留物的混合物，此一現 一 一姓之結合力而不容易去除，而習知技術係將基板上 ，以電漿灰化後，相濕錢離液剥離， 但習知技街I右装& 0 p ^ yθ Θ $化學品排放法規限制，及純水與溶劑成本不斷 〜二’νΠΤ^ +完善5而在新-代製程中，在發晨至65、45奈 _ 丨二S、j *於線寬縮小、深寬比加大，再加上晶®具有渠溝或 構時’由於液體表面張力大，不易進入結構内部加以 =兀一二个穷乾無，目前之濕式洗淨製程已經無法滿足次世代產 ^〜冗“文求。疃私界流體有如氣體，幾無表面張力，且使甩後 俨二：壓叶:雯回氣相，而和其他固、液相的物質分離，容易回 囚〜从二氧化碳超臨界流體為清淨劑的製程確可克服 远Id水岭欲的⑺題。因此，習知技術還有以超臨界流體二氧 • ^、胺、溶劑等依-定關泵入壓力容器後，藉由循環泵及循 二長崎之♦㈣雜峻二氧化碳、胺、溶麟續與光阻或光阪 ，4_褐’強蝴其自基板去除之效果，但其超臨界二氧化碳、 2冷劑亚未尤分混合，故有著胺及溶劑不易被帶入基板凹槽内 ‘及溶劑與光阻或殘留物接觸時呈現不均勾之分布，所以去除 破果不佳。 一因此丨氧上地的基板去除效果不佳問題，.、有著化學溶劑 +易被帶人基板凹槽_，及溶劑與級或殘留物接觸時呈現不 岣勻之劣勢。 6 200827046 【發明内容1 鑑於上述f知技狀_，本翻#提供，高密相流體 物接觸B牙呈不均勻，使基板表面殘留物 去除絲衣面殘留物之方法，㈣解㈣知去除基板之表面殘留 物之方法，係贿劑不帶人基板頻内部，導致基板去除殘 L物ίΐ果碑之缺失，同時也克服f知技術之清洗溶劑與殘留 之滑洗效果無法提升之缺200827046 IX. OBJECT DESCRIPTION OF THE INVENTION [Technical Field of the Invention] - The present invention relates to a method for removing surface contaminants of a substrate by a high-density phase fluid, in particular, "About an effect of effectively removing the residue of the substrate A method of removing surface contaminants from a substrate with a high density phase fluid. [Prior Art] The physical properties of supercritical fluids currently used are between _ and MM, such as their viscosity is close to that of gas, density is close to liquid, and because of high density, more fluid can be transported than gas. Because of the low viscosity, the power required for delivery is lower than that of liquid. Another example is that the diffusion coefficient is 10 to 100 times higher than that of the liquid, that is, the mass transfer resistance is much smaller than that of the liquid, so that the mass transfer is more liquid than the liquid. In addition, the 5 supercritical fluid is more like a gas with no surface tension, so it easily penetrates into the porous structure. Since most of the super-g fluids are in a gaseous state under normal pressure, they must be extinguished after use! That will change back to the gas phase, and separate from other solid and liquid substances, which has the advantage of easy recovery, and because of the low surface tension, low Sauror, high density, and high The unique nature of diffusivity, especially the solvent-like properties of handling, make it the best environmentally friendly alternative to organic and aqueous solvents. At present, many gases including carbon dioxide, ammonia (Ammonia), helium (Helium), argon (argon), 4 (xen〇n) or oxidized to nitrogen (Nitrous oxide), or a combination of the foregoing gases can be used as supercritical Fluid, because carbon dioxide is non-toxic, colorless, odorless, non-combustible, non-corrosive, no need for wastewater treatment, harmless to the human body, friendly to the environment and easy to reach the critical point (Chemical 27.3 bar, TC II 31. rc ) and other process advantages, and thus are most commonly used. In the pre-g semiconductor industry, in the process of ion implantation or etching, the system will use 5 200827046 as a protective substrate to protect the substrate without ion implantation or sputum. In this case, it will cover the 70-resistance layer. The salty-layer hard shell that is difficult to remove, in the side process, will be in the *(8) battle--resistance residue and the mixture of the test residue, the combination of the present and the first name is not easy to remove, However, the conventional technology is to remove the phase of the wet liquid from the liquid after the plasma is ashed on the substrate, but the conventional technical street I right-loaded & 0 p ^ yθ Θ $ chemical emission regulations, and pure water and solvent The cost is constant ~ two 'νΠΤ^ + perfect 5 and in the new-generation process, in the morning to 65, 45 na _ 丨 s, j * in line width reduction, aspect ratio increase, plus Crystal ® has Ditch or structure time 'Because of the large surface tension of the liquid, it is not easy to enter the interior of the structure. 兀 One or two poor, the current wet cleaning process can no longer meet the next generation of production ^~ redundant" Wenqiu. Like a gas, there is no surface tension, and the second is: the pressure leaf: Wen back to the gas phase, and other solid and liquid substances Separation, easy to return to prisoner ~ from the carbon dioxide supercritical fluid as a detergent process can indeed overcome the problem of far Id water (7). Therefore, the conventional technology also has supercritical fluids such as dioxane, amine, solvent, etc. After being pumped into the pressure vessel, the effect of removing the substrate from the substrate by the circulation pump and the second Nagasaki ♦ (4) complex carbon dioxide, amine, lysine and photoresist or light saka, 4_ brown 'strong butterfly The supercritical carbon dioxide and the two refrigerants are mixed, so that the amine and the solvent are not easily brought into the groove of the substrate, and the solvent exhibits uneven distribution when it comes into contact with the photoresist or the residue, so the removal of the broken fruit is poor. Therefore, the problem of poor removal of the substrate on the surface of the oxygen, the chemical solvent + easy to be carried by the substrate groove _, and the solvent is inconsistent with the level or residue. 6 200827046 [Invention Content 1 In view of the above-mentioned technique, the method of removing the surface of the substrate is not uniform, and the residue on the surface of the substrate is removed from the surface of the silk surface. (4) Solution (4) Knowing the surface residue of the substrate to be removed Method, bribery without people The inside of the substrate frequency causes the substrate to remove the residual L material, and the lack of fruit monument, and also overcomes the lack of cleaning solvent and residual sliding effect of the known technology.
為達上述目的，本發明係一種以高密相 染物之方法，係包含提供—壓力容器步驟、提供 供-高密相雜麵、進行基板噴 ;^驟K 去除作業步驟、進行即外W 了〜、進域板污染物 … ，丨…丞伋衣茚夕驟及基枳 於安止 驟，係免進行提供一·力宠哭步賢 … ^ iF ^ ^ :… 心刀容器係包含-大體及 一一閉空間，提供—基板步驟 ’. ΐ染物且置於壓力容⑼，再提供-高密相絲步;==有 於—高密相溶液供應裝置並由高密相 == 二且運用—連接於壓力容器之壓力控制器健力2::應劑形 仏力谷^又，妨基柄洗作業，此 7以升降 容器内之喷嘴導入壓力六、，一r 相4夜係經一壓力 基板表面哪,γγ ^力差形錢細化反覆噴洗 液保持與基板接觸=:==去除作業赖，係將高密相溶 至少-部分污料仃動容器之壓力料作業，藉以去除 基板_物。减進行浸潤沖洗基板表面_，用以潔淨 伞發明係一_高密相流體去除基板表面污染物之方法，俤 200827046 ，具備下述數點優於習知作法，並具備如下所述之顯著功效增進。 1.本發明係一輕以咼密相流體去除基板表面污染物之方法， ^ 故較習知去除基板表面殘留物方法，.因將溶劑進行細微化狀態， ‘ 故具有更易均勻分布在基板表面及帶入基板凹槽内部，且又溶劑 I度南由朗更$效的去除光阻或殘留物。 2_本餐明v、一|里以问禮、々目氣體去除基板表面污染物之方法， 故較習知去除基板表面殘留物方法，因將溶劑進行細微化狀態， 鲁故能更易與高密相溶液互溶，而進入基板表面及凹槽内部，藉以 達到去除基板光阻及殘留物之效果。 3.本發明係一種以高密相流體去除基板表面污染物之方法， 霞較奢知*除減衣峨f物方法，隨賴進行細微化狀態， 在最後進行沖洗之過程，更易將基板表面或凹槽内部被高密相流 沖離帶走。 為使對本發明的目的、構造特徵及其功能有進一步的了解， 兹I合招關貫施例及圖式詳細說明如下： _ 【實施方式】 請參閱第1圖及第2圖，本發明係—種以高密相流體去除基 板表面污染物之方法，此以高密相流體去除基板表面污染物之方 法S1，係包含提供-壓力容器（步驟S10)、提供一基板（步驟 娜)、提供一高密相溶液（步驟S30 )、進行基板噴洗(Spray)作業 -(步驟S4G)、進行基板污染物去除作業（步驟S5G)、進行浸潤沖 洗(Rrnse)基板表面（步驟S60)及進行基板取出作業步驟 S70)。 200827046 請再參閱第1圖及第2圖，本發明係一種以高密相流體去除 吞板表面>可染物之方法，此以高密相流體去除基板表面污染物之 方π Si，1糸先進行提供一壓力容态ί、步驟，此壓力容器 係包含一本體11及一上蓋12,且藉由本體11及上蓋12以形成一 密閉空間，再進行提供一基板（步驟S20)，係將此表面具有污染 物之基板20置放於壓力容器10内，再者，提供一高密相溶液（步 驟S30)，此高密相溶液31傜承置於一高密相溶液供應裝置3〇，In order to achieve the above object, the present invention is a method for dyeing a high-density phase, comprising providing a pressure vessel step, providing a high-density phase miscellaneous surface, performing a substrate spray, and performing a K removal operation step, and performing an external W. Into the domain board pollutants ..., 丨 丞汲 丞汲 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 系 系 系 系 系 系 系 系 系 系 系 系 安 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ a closed space, providing - substrate step '. ΐ dye and placed in pressure capacity (9), then provide - high density phase silk step; = = in - high density phase solution supply device and by high density phase == two and use - connected to pressure The pressure controller of the container is 2:: It should be shaped like a force valley. In addition, the handle can be washed by the handle. This 7 introduces the pressure into the nozzle in the lifting container, and a r phase 4 night passes through the surface of a pressure substrate. , γγ ^ force difference shape refinement of the reverse spray liquid to maintain contact with the substrate =: = = removal of the work, the high-density compatibility of at least - part of the dirt to shake the container pressure material operation, thereby removing the substrate_object. The method of reducing the surface of the substrate by immersion is used to remove the surface contamination of the substrate by the high-density phase fluid, 俤200827046, which has the following advantages over the conventional practice, and has the remarkable effect enhancement as described below. . 1. The present invention is a method for removing contaminants on a surface of a substrate by a dense phase fluid, so that it is more conventional to remove the residue on the surface of the substrate, and the solvent is finely divided, so that it is more uniformly distributed on the surface of the substrate. And the inside of the groove of the substrate is introduced, and the solvent is removed to remove the photoresist or residue. 2_This meal shows the method of removing the surface contamination of the substrate by the question and the gas, so it is better to remove the residue on the surface of the substrate. Because the solvent is refined, it is easier and denser. The phase solutions are mutually soluble and enter the surface of the substrate and the inside of the groove, thereby achieving the effect of removing the photoresist and residue of the substrate. 3. The present invention is a method for removing contaminants on a substrate surface by using a high-density phase fluid, and the method of removing the coating material is more expensive than the method of reducing the size of the coating, and the surface of the substrate is more easily replaced by the process of rinsing. The inside of the groove is washed away by the high-density phase flow. In order to further understand the object, structural features and functions of the present invention, the detailed description and the drawings are as follows: _ [Embodiment] Referring to Figures 1 and 2, the present invention is a method for removing contaminants on a surface of a substrate by a high-density phase fluid, wherein the method for removing contaminants on a surface of the substrate by a high-density phase fluid comprises providing a pressure vessel (step S10), providing a substrate (step Na), providing a high density Phase solution (step S30), substrate spray operation (step S4G), substrate contamination removal operation (step S5G), wet rinsing (Rrnse) substrate surface (step S60), and substrate removal operation step S70). 200827046 Please refer to FIG. 1 and FIG. 2 again. The present invention is a method for removing the surface of a swallowing plate by a high-density fluid, which can remove the contaminant on the surface of the substrate by a high-density fluid, π Si, 1 糸 first. The pressure vessel is provided with a body 11 and an upper cover 12, and a sealed space is formed by the body 11 and the upper cover 12, and then a substrate is provided (step S20). The substrate 20 having contaminants is placed in the pressure vessel 10, and further, a high-density phase solution is provided (step S30), and the high-density phase solution 31 is placed in a high-density phase solution supply device 3,
立此南密相溶液31係由高密相溶劑（3〇1¥邮）及反應劑（咖敗时） 形敗，此南密祁溶液31係、為一高密相流體5此高密相溶液訂之 相悲'1糸為超臨界態、亞臨界態或液態，在本實施例中，此高密和 溶液31係為超臨界二氧化碳，並運羯一連接於壓力容器1〇之^ 刀控制器33，進行壓力控制作動藉以加壓壓力容器1〇，當然此^ 力控制器33作壓力控制係還能升壓、持壓、降壓、持壓等之反」 _ ’又’進行基板喷洗作業（步驟S4〇)，係將上述高密相溶 〇1逄過一麼力容器10內之噴嘴34導入壓力容器i0中，並藉由 力m〇興噴嘴34間之壓力差，以形成微細化並反覆噴洗此 •二0衣面人六體而言，係由於壓力容器iq外設有蓄壓槽涊 ♦雨_溶_經過壓力容㈣内之喷嘴34導人壓力容器 T ^藉壓力差形咸微細化反射絲板表面，且由於上述反 學鍵結，來瓦解聚合物及降低污染物與 、、’。口力，運到自基板表面去除殘留物， 改變濃度並喑洗τ 一 一刀么·月匕使合， 茅，⑽錢衣邱’料增加對基絲岭雜去⑹ 、叙'.，貝，每行基被污染物去除作業（步驟S5〇)，係將高密袖 200827046 液31保持與基板2〇接觸，或者係運用喷嘴M喷發高密相溶液31 持續與基板20接觸，藉以增加去除效果，並進行壓力容器1〇之 壓力升降作食，籍以去除基板2〇表面之至少一部分污染物，此對 於壓力容器進行升、降壓操作，係由於升壓時可使超臨界態之溶 液滲入；ό染物内部，降壓使超臨界態之溶液自污染物内部膨脹而 破環>可杂物結構，後來，進行浸潤沖洗基板表面（步驟S6〇)，係 用以潔淨基板·20表面之污染物，最後，係進行基板取出作業步驟 (步驟S70)，係將壓力容器1〇進行洩除壓力並取出基板2〇，進 _完成高密相溶液31去除基板20表面污染物，而上述之壓力容 器：i〇更再包含一與壓力容器10連接之循環幫浦40，以使高密相 溶液31不斷進行循環清洗基板表面，增加對污染物去除效果。 令贫明知一#里以南金"T目疏體7卩者卷板表面 >可举物之万法，上 逆吞板20係為晶圓、半等體巷板、光電元件或平板狀之玻璃、石 英、陶瓷或金屬，且基板之污染物係為光阻外層形成之硬殼，又 此污染物係為光阻、光阻殘留物'蝕刻殘留物、光阻殘留物、敍 刻殘留物、微粒或氧化餘，氧其混合物。 本發明係一種以高密相流體去除基板表面污染物之方法，上 .述高密相溶液31進一步包含一共溶劑（co-solvent)，用以提高高 密相溶劑對反應劑之溶解度，且此共溶劑係為曱醇(alcohols)、 醚(ethers)、嫁基鹵化物（alkyl halides)、燒烴（alkanes)、 烯屬烴（alkenes)、腈類（nitriles)、氨泰化合物（amides)、 芳香族的複合物(aromatic compounds)、矽氧烷(siloxanes)、 丙酮（acetone)、碳酸丙酯（PC03)或其組合者，·而此反應劑係為 10 200827046 胺類（amine)、四級銨鹽（tetraalkyl ammonium bicarbonate)或 四級按碳化物（tetraaIky 1 ammonium carbonate)。 雖然本發明以較佳實施例揭露於上，然其並非用以限定本發 明，任何熟習此項技藝者，在不脫離本發明之精神和範圍内，當 3做些許之更動與潤飾，因此本發明之保護範圍當視後附之申請 範圍所界定者為準。 【圖式簡單說明】The South dense phase solution 31 is formed by a high-density phase solvent (3〇1 ¥ mail) and a reactant (when it is defeated), and the Nanmi 祁 solution 31 is a high-density phase fluid. The sorrow '1 糸 is a supercritical state, a subcritical state or a liquid state. In the present embodiment, the high density and the solution 31 are supercritical carbon dioxide, and the knives controller 33 connected to the pressure vessel 1 , The pressure control operation is performed to pressurize the pressure vessel 1 〇, of course, the pressure controller 33 can also pressurize, hold pressure, depressurize, hold pressure, etc. as a pressure control system. In step S4), the high-density phase-dissolving nozzle 34 in the force container 10 is introduced into the pressure vessel i0, and the pressure difference between the nozzles 34 is increased by force m to form a finer and repeat Spraying this • 20-faced six-body, because of the pressure vessel iq, there is a pressure storage tank 涊 ♦ rain _ dissolved _ through the pressure capacity (four) nozzle 34 lead pressure vessel T ^ by pressure differential salty Micronizing the surface of the reflective silk sheet and, due to the above-mentioned counter-bonding, disintegrating the polymer and reducing contaminants and . Mouth force, transported to the surface of the substrate to remove residue, change the concentration and wash the τ one knife? Moon 匕 合, Mao, (10) Qian Yi Qiu 'material increase on the Kiesling Miscellaneous (6), Syria '., Bay Each row of the substrate is removed by the contaminant (step S5〇), and the high-density sleeve 200827046 liquid 31 is kept in contact with the substrate 2〇, or the high-density phase solution 31 is sprayed by the nozzle M to continuously contact the substrate 20, thereby increasing the removal effect. And performing pressure lifting and lowering of the pressure vessel 1 to remove at least a part of the contaminant on the surface of the substrate 2, wherein the pressure vessel is subjected to the ascending and depressurizing operation, because the supercritical solution can be infiltrated due to the pressure increase; Inside the smear, the anti-pressure causes the solution of the supercritical state to expand from the inside of the contaminant and breaks the ring> the structure of the impurity, and then, the surface of the substrate is immersed and immersed (step S6〇) to clean the surface of the substrate 20 Finally, the substrate removal operation step (step S70) is performed, the pressure vessel 1 is subjected to pressure relief and the substrate 2 is removed, and the high-density phase solution 31 is removed to remove surface contaminants on the substrate 20, and the above pressure is applied. Is: i〇 further comprising re-circulating connection with the pressure vessel 10 of a pump 40, 31 so that the high density phase solution continuously substrate surface wash cycle, increased contaminant removal. Let the poor know one #里南金"T目疏体7卩人卷板面> can be used as a method, the upper reverse plate 20 is a wafer, a semi-equipment board, a photoelectric element or a flat plate Glass, quartz, ceramic or metal, and the contaminant of the substrate is a hard shell formed by the outer layer of the photoresist, and the contaminant is a photoresist, photoresist residue, etching residue, photoresist residue, and engraving Residue, particulate or oxidizing residue, oxygen mixture. The present invention is a method for removing contaminants on a substrate surface by a high-density phase fluid. The high-density phase solution 31 further comprises a co-solvent for increasing the solubility of the high-dense phase solvent to the reactants, and the cosolvent system Alcohols, ethers, alkyl halides, alkanes, alkenes, nitriles, amides, aromatic Aromatic compounds, siloxanes, acetone, propyl carbonate (PC03) or a combination thereof, and the reactant is 10 200827046 amine, quaternary ammonium salt ( Tetraalkyl ammonium bicarbonate) or tetraaIky 1 ammonium carbonate. Although the present invention has been disclosed in its preferred embodiments, it is not intended to limit the invention, and those skilled in the art will be able to make some modifications and refinements without departing from the spirit and scope of the present invention. The scope of protection of the invention is subject to the definition of the scope of the application. [Simple description of the map]
第1圖係本發明㈣密相流體去除基板之表__之壓力容器 示意圖；及 第2圖係本發明㈣密減體去除基板之表時雜之方法流卷 示意圖。 【主要元件符號說明】 S1 步驟sio 步驟S20 少驟S30 步驟S40 步驟S50 步驟S60 步驟S70 10 11 基钣表面污染物之方法 以高密相流體去除 提供一壓力容器 提供一基板 提供一高密相溶液 進行基板喷洗作業 進行基板污染物去除作業 進行浸潤沖洗基板表面 進行I板取出作業 壓力容器 本體 上蓋 12 200827046 20 30 31 32 33 34 40 基板 高密相溶液供應裝置 高密相溶液 蓄壓槽 壓力控制器 喷嘴 循環幫浦BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a pressure vessel of the present invention in the form of a dense phase fluid removing substrate; and Fig. 2 is a flow chart showing the method of the present invention. [Main component symbol description] S1 step sio step S20 less step S30 step S40 step S50 step S60 step S70 10 11 method based on surface contamination to provide a pressure vessel by high-density phase fluid supply to provide a substrate to provide a high-density phase solution for the substrate Spraying operation to carry out substrate contaminant removal operation, infiltrating and rinsing the surface of the substrate for I plate removal operation, pressure vessel body upper cover 12 200827046 20 30 31 32 33 34 40 substrate high density phase solution supply device high density phase solution pressure storage tank pressure controller nozzle circulation Pu
1212