200946614 六、發明說明 【發明所屬之技術領域】 本發明係提供一種塗佈組成物’其係在半導體元件之 製造及MEMS之製造中的半導體基板之加工步驟中’用 以製作保護膜，而該有機膜係可使用於用以保護晶圓及晶 片搬送時之裝置。 〇 【先前技術】 半導體元件係具有：於晶圓經過各種之加工、層合而 製作晶片之步驟；進一步切割所製作之晶片’固定於導 線，進行裝封之組裝步驟。此等之步驟係有：連續而進行 之情形與不同的位置進行之情形。於不同之位置進行步驟 之情形，係必須搬送晶圓及晶片，但於此搬送中恐損傷裝 置（晶圓、晶片）。爲防止此裝置（晶圓、晶片）損傷’ 已提出一種使聚乙烯醇、聚乙烯基吡咯烷酮等之水溶性樹 Q 脂溶解於水之水溶液進行塗佈、乾燥，形成被膜而保護之 方法（參照專利文獻1 )。 另外，與LSI及1C晶片之半導體元件製造步驟同樣 地，加工矽晶圓所製造之MEMS裝置係必須加工矽晶圓 表背雙面。製作晶圓面之一者（晶圓表面）作爲裝置面 時，裝置面係以金屬、氧化膜、氮化膜等爲數百nm乃至 數十μιη之段差所形成。但，與裝置相反之矽面（晶圓背 面）係藉異方性蝕刻等，對矽實施數十乃至數百μιη之加 工（主要爲矽之孔洞、或空洞形狀）。進行此加工時，一 -5- 200946614 般係使用KOH (氫氧化鉀）水等之鹼水溶液’利用蝕刻 速度對矽之各結晶面的差異，製作孔洞形狀。 但，近年，隨著MEMS裝置的輕薄短小化’重新以 SF6 (六氟化硫）及C4F8 (八氟環丁烷）等之電紫蝕刻砍 而製作孔洞形狀的Bosch法正盛行起來。 在此Bosch法中係於蝕刻裝置內搬送晶圓’實施蝕 刻，取出晶圓。此時，裝置面變成下面’故若裝置面抵到 搬送手臂等，於裝置部分引起損傷，成爲不良品，故良率 0 降低。因此，暫時地保護此裝置面，使用後可簡單地除去 之保護膜被期望著。尤其，於此蝕刻裝置內每一保護膜置 入晶圓之情形，亦有時裝置內成爲高溫，故對保護膜亦宜 期望耐熱性。有關溫度係依存於蝕刻裝置及蝕刻條件者之 標準係認爲約30乃至150°C之使用環境，故於保護膜係 必須爲即使於如此之常溫至高溫均可使用之耐熱性。 對其他之加工實施晶圓背面時，亦必須使晶圓背面 (裝置面）朝下而於裝置間搬送，但同樣地恐損傷裝置 Q 面。因此，爲充分保護此裝置面，必須爲可充分覆蓋段差 之膜厚，必須形成Ιμπι以上之膜厚。宜必須爲3μηι以上 之膜厚。 進一步，保護膜進行目的之加工步驟後，必須除去。 有關此除去係必須未對裝置造成損傷地進行除去，故宜儘 可能地存在許多之除去方法。其除去方法係有：由有機溶 劑、水所構成之藥液進行的濕式除去之方法；以氧電漿等 進行之乾式蝕刻的方法。繼而，依據裝置係從氧電漿對於 -6 - 200946614 裝置的氧化之影響，乾式蝕刻除去不宜，而宜爲濕式除去 之情形。進行其濕式除去之情形，係從對裝置之降低損 傷，宜只以有機溶劑或只以水進行除去之方法，宜可藉由 裝置之種類而選擇。 可以如此之水及有機溶劑除去保護膜之樹脂，可想到 水溶性樹脂。但，使水溶性樹脂溶解於水乃至以水爲主體 之溶劑而使用時，存在以下之問題。 〇 在半導體之最前端領域係用以埋入銅配線所形成之絕 緣膜的孔洞製作步驟，在孔洞形成後之洗淨，係水會對孔 洞底的銅配線造成損傷之影響已爲人所知。具體上係藉由 水之pH而水硏磨銅表面，在前步驟後端的銅配線形成步 驟中係已控制pH之水被使用於洗淨。因此，於裝置面保 護藉由旋塗法而形成含有水之樹脂水溶液時，必須藉由旋 塗後之烘烤而乾燥除去殘留於膜內之水，但此時裝置面被 曝露於暫時被加熱之水，故擔心對銅表面之損傷。 〇 進一步，用以形成保護膜的塗佈器係從對裝置之投 資、營運成本等之成本問題並非設有專用之塗佈器，宜可 使用塗佈其他之光阻等之樹脂溶液的塗佈器。假如，於同 一塗佈器內使用溶劑爲水之保護膜用之樹脂溶液時，一般 之光阻係不溶於水，故有於塗佈槽內形成殘物而殘存之光 阻成分或與溶劑成分混合之光阻的聚合物進行析出之問 題。或，想到於排水管內所析出之聚合物會成爲堵塞之原 因。 又，於各裝置內以機械手臂等自動搬送時，係保護膜 -7- 200946614 要求厚度之均一性。若不爲無凹凸之平滑膜，恐晶圓不設 置於特定位置或於搬送中晶圓落下等之虞。 進一步，在矽蝕刻裝置中，晶圓係以靜電吸盤所產生 之吸附固定，但於實際之蝕刻時，係於晶圓與靜電吸盤之 間流入氨氣，使晶圓表面之熱逸出。此時，接觸於靜電吸 盤之晶圓表面不平滑時，氮氣之流出量變大，蝕刻裝置內 之晶圓無法牢固地以靜電吸盤固定。晶圓無法充分固定 時，於蝕刻中晶圓會移動，產生無法進行精度佳之蝕刻的 @ 問題。因此，一般係設定氨洩漏量之上限値，若超過此 値，蝕刻裝置之安全裝置會作用，成爲不能蝕刻步驟之機 構。因此，要求氨之洩露量成爲設定値以下之保護膜的平 坦化性。 專利文獻1 :特開平9- 1 0698 1號（專利申請範圍） 【發明內容】 發明之揭示 © 發明欲解決之課題 因此，半導體元件之製造及MEMS製造時之搬送用 保護膜、尤其矽之鈾刻時的裝置面之保護膜係要求滿足如 下之特性。 亦即，可簡單地形成平滑的膜，使用後容易除去膜。 尤其，使用後，可氧電漿蝕刻、或以水、有機溶劑進行的 濕式除去。爲充分保護裝置面’可形成1 Mm以上之膜 厚。保護膜可承受蝕刻處理之耐熱性約爲150 °C。烘烤時 -8 - 200946614 不對裝置造成損傷。保護膜塗佈用之塗佈器可與光阻等之 樹脂溶液共有。 用以解決課題之手段 本發明人等係經專心硏究之結果，發現藉由使用將水 溶性樹脂溶解於有機溶液之溶液組成物而可達成上述課 題，終完成本發明。 Ο 亦即，本發明係有關以下記載之半導體元件保護膜用 塗佈組成物的發明，其係含有有機溶劑、與溶解於此之水 溶性樹脂。 又，在以下之說明中，於適用本發明之塗佈組成物的 半導體元件保護膜，係除一般之半導體元件保護膜外，應 可理解爲尤其亦相當MEMS製造時之搬送用保護膜等。 因此，記載於本案申請專利範圍之塗佈組成物係相當於其 等半導體元件之保護膜用塗佈組成物。 © 水溶性樹脂其特徵在於：爲選自由聚乙烯醇、聚乙烯 基吡咯烷酮、及水溶性纖維素衍生物所構成之群者，較佳 係聚乙烯基吡咯烷酮。上述水溶性樹脂係就重量平均分子 量可使用例如1000乃至1000萬，又，1萬乃至500萬， 又，3萬乃至300萬之範圍者。 進一步，就溶解水溶性樹脂之溶劑係可使用有機溶 劑。溶解之有機溶劑具體上可舉例如甲醇、乙醇、丙醇、 異丙醇、丁醇、環己醇等之低級醇、乙二醇、二乙二醇、 丙二醇、三乙二醇、1，4-丁二醇等之甘醇、丙二醇單甲基 -9- 200946614 醚、丙二醇單乙基醚、二乙二醇單甲基醚、三乙二醇單甲 基醚、二乙二醇二甲基醚等之甘醇醚等之含有羥基（ -OH)的有機溶劑。 又’可舉例如二甲基甲醯胺、二甲基乙醯胺、N_甲基 吡咯烷酮、N -乙烯基吡咯烷酮等之具有醯胺鍵（ -CO-N<)的醯胺系溶劑。進一步，亦可使用乳酸甲酯、 乳酸乙酯、乳酸丁酯等之乳酸酯、二甲基亞楓、氯仿、二 氯甲烷等。 又，此等之有機溶劑係亦可混合而使用。又，於有機 溶劑中係可含有吸水程度之水，但較佳係愈沒有愈佳。爲 形成膜厚Ιμιη以上之塗佈膜，係使用高分子量之水溶性 樹脂，或必須提高水溶性樹脂之濃度，故宜爲上述之良溶 劑。依需要，於溶解有聚乙烯基吡咯烷酮之溶液中，爲使 溶液之塗佈性良好，亦可添加界面活性劑等之塗佈性改良 劑。 有關塗佈組成物之溶液中的水溶性樹脂之濃度係只要 爲水溶性樹脂溶解於有機溶劑之範圍即可，無特別限定， 但可依保護膜之膜厚或所使用之水溶性樹脂的分子量而決 定。例如，爲保護具段差之晶圓的裝置面必須平滑地被 覆，故宜爲Ιμπι以上之膜厚。爲形成膜厚，關係到水溶 性樹脂之分子量，但必須某一定値以上之水溶性樹脂的濃 度。其情形，水溶性樹脂之濃度宜於塗佈組成物中含有 1〜50質量％的濃度，更宜含有5〜40質量％的濃度，尤宜 含有5〜25質量％的濃度。若小於1質量％，很難形成1 μ™ 200946614 以上之水溶性樹脂的保護膜，若超過50質量％，水溶性 樹脂之溶解性差，很難製作水溶性樹脂之塗佈組成物的溶 液。又，若成爲高濃度，易成爲膜之平滑性亦差之傾向。 發明之效果 本發明之聚乙烯基吡咯烷酮樹脂溶液係可容易形成 1 μ m以上之膜。 〇 又，藉由使溶劑爲有機溶劑，可形成平滑的膜。然 而，形成水溶液時，係於所形成之膜的表面產生很大的凹 凸，無法形成平滑的膜。 在矽蝕刻裝置之搬送試驗，從有機溶劑所得到之膜顯 示良好的結果，然而，從水溶液所得到之膜係產生不佳情 形。此事係從水溶液所得到之膜在矽蝕刻裝置之自動搬送 的情形不佳，恐晶圓不設置於特定的位置，或於搬送中晶 圓會掉落。 Ο 進一步，使用有機溶劑，可避免水造成裝置表面的損 傷、塗佈器內之光阻聚合物析出問題。 又，即使在溫度150 °C中亦無膜溶融，可在150 °C以 上之使用環境下使用。 進一步，晶圓搬送及加工後，可容易地除去此聚乙烯 基吡咯烷酮膜。亦即，亦可溶解於水而除去，亦可溶解於 有機溶劑而除去。亦可以硫酸/過氧化氫水進行除去。 又，以上述液體所產生之除去方法以外，亦可以氧等 之電漿等的氣體所產生的蝕刻或灰化進行除去。 -11 - 200946614 【實施方式】 實施例 以下舉出實施例而說明本發明，但本發明係不限定於 此等之例。 〈保護膜用之樹脂溶液的準備〉 (1) 聚乙烯基毗咯烷酮（BASF公司製品，商品名 Luvitec，K9 0，重量平均分子量120萬乃至200萬）溶解 於二甲基乙醯胺（以下DM AC )，得到聚乙烯基吡咯烷酮 20質量％之DMAC溶液。稱此DMAC溶液爲A液。 (2) 聚乙烯基吡咯烷酮（BASF公司製品，商品名 Luvitec，K90)溶解於N-甲基吡咯烷酮（以下NMP )， 得到聚乙烯基吡咯烷酮20質量％之NMP溶液。稱此NMP 溶液爲B液。 (3) 聚乙烯基吡咯烷酮（BASF公司製品，商品名 Luvitec，K90 )溶解於乳酸乙酯（以下EL )，得到聚乙 烯基吡咯烷酮13.3質量％之EL溶液。稱此EL溶液爲c 液。200946614 VI. Description of the Invention [Technical Field] The present invention provides a coating composition 'which is used to fabricate a protective film in a process of manufacturing a semiconductor device and a semiconductor substrate in the fabrication of MEMS, and The organic film can be used for devices for protecting wafers and wafers.先前 [Prior Art] The semiconductor element has a step of forming a wafer by various processing and lamination of the wafer, and a step of assembling the wafer to be further diced to the wire and performing sealing. These steps are those that take place continuously and at different locations. In the case where the steps are performed at different positions, it is necessary to transport the wafer and the wafer, but the device (wafer, wafer) is damaged during the transfer. In order to prevent damage to the device (wafer, wafer), a method of coating and drying an aqueous solution of a water-soluble tree Q fat such as polyvinyl alcohol or polyvinylpyrrolidone in water to form a film has been proposed (see Patent Document 1). Further, similarly to the semiconductor element manufacturing steps of the LSI and the 1C chip, the MEMS device manufactured by processing the germanium wafer must be processed on both sides of the wafer. When one of the wafer faces (wafer surface) is used as the device surface, the device surface is formed by a step of a few hundred nm or even tens of μm of a metal, an oxide film, a nitride film, or the like. However, the opposite side of the device (the back side of the wafer) is subjected to anisotropic etching or the like, and is processed for tens or even hundreds of μm (mainly a hole or a void shape). In the case of this processing, a hole shape is formed by using an alkali aqueous solution of KOH (potassium hydroxide) water or the like by a difference in etching speed with respect to each crystal plane of the crucible, as in the case of -5-200946614. However, in recent years, the Bosch method of making a hole shape by the electro-violet etching of SF6 (sulfur hexafluoride) and C4F8 (octafluorocyclobutane) has become popular as the MEMS device has become lighter and shorter. In this Bosch method, the wafer is transferred in an etching apparatus to perform etching, and the wafer is taken out. At this time, the device surface becomes the lower side. Therefore, if the device surface is brought to the transfer arm or the like, the device portion is damaged and becomes a defective product, so that the yield 0 is lowered. Therefore, the protective film is temporarily protected, and a protective film which can be easily removed after use is expected. In particular, in the case where each of the protective films in the etching apparatus is placed on the wafer, and sometimes the inside of the apparatus becomes a high temperature, heat resistance is also desired for the protective film. The standard for which the temperature depends on the etching apparatus and the etching conditions is considered to be about 30 to 150 ° C. Therefore, the protective film must have heat resistance which can be used even at such a normal temperature to a high temperature. When the wafer back surface is applied to other processes, the wafer back surface (device surface) must be moved downward between the devices, but the device Q surface is damaged in the same manner. Therefore, in order to sufficiently protect the surface of the device, it is necessary to sufficiently cover the film thickness of the step, and it is necessary to form a film thickness of Ιμπι or more. It is preferable to have a film thickness of 3 μηι or more. Further, after the protective film is subjected to the intended processing step, it must be removed. It is necessary that the removal system must be removed without causing damage to the apparatus, so that many removal methods are possible as much as possible. The removal method includes a method of wet removal by a chemical solution composed of an organic solvent or water, and a dry etching method using an oxygen plasma or the like. Then, depending on the effect of the device from the oxidation of the oxygen plasma to the device of -6 - 200946614, the dry etching is not suitable, and the wet removal is preferred. The wet removal is carried out by reducing the damage to the apparatus, preferably by removing the organic solvent or only water, preferably by the type of the apparatus. A resin which can remove the protective film by such water and an organic solvent is conceivable as a water-soluble resin. However, when the water-soluble resin is dissolved in water or a solvent mainly composed of water, the following problems occur.最In the forefront of semiconductors, the hole fabrication step for embedding the insulating film formed by the copper wiring is known to be cleaned after the hole is formed, and the effect of water on the copper wiring at the bottom of the hole is known. . Specifically, the copper surface is water honed by the pH of the water, and the pH-controlled water is used for washing in the copper wiring forming step at the rear end of the previous step. Therefore, when the water-repellent resin aqueous solution is formed by spin coating on the device surface protection, it is necessary to dry and remove the water remaining in the film by baking after spin coating, but at this time, the device surface is exposed to be temporarily heated. The water is worried about the damage to the copper surface. Further, the applicator for forming a protective film is not provided with a dedicated applicator from the cost of investment in the device, operating cost, etc., and coating of a resin solution coated with other photoresist or the like may be used. Device. If a resin solution for a protective film of water is used in the same applicator, the general photoresist is insoluble in water, so that a photoresist component or a solvent component remains in the coating tank. The problem of precipitation of the mixed photoresist is carried out. Or, it is thought that the polymer precipitated in the drain pipe may become a cause of clogging. In addition, when the robot is automatically transported by a robot or the like in each device, the uniformity of the thickness is required for the protective film -7-200946614. If it is not a smooth film without bumps, it is feared that the wafer is not placed at a specific position or the wafer is dropped during transport. Further, in the tantalum etching apparatus, the wafer is adsorbed and fixed by the electrostatic chuck, but in actual etching, ammonia gas flows between the wafer and the electrostatic chuck to cause heat to escape from the surface of the wafer. At this time, when the surface of the wafer that is in contact with the electrostatic chuck is not smooth, the amount of outflow of nitrogen becomes large, and the wafer in the etching apparatus cannot be firmly fixed by the electrostatic chuck. When the wafer is not sufficiently fixed, the wafer moves during etching, causing a problem that the etching cannot be performed with high precision. Therefore, the upper limit of the amount of ammonia leakage is generally set. If it exceeds this, the safety device of the etching apparatus acts and becomes a mechanism in which the etching step cannot be performed. Therefore, the leakage amount of ammonia is required to be the flatness of the protective film set below 値. Patent Document 1: Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei. No. Hei. The protective film of the device surface at the time of engraving is required to satisfy the following characteristics. That is, a smooth film can be easily formed, and the film can be easily removed after use. In particular, after use, it can be etched by an oxygen plasma or wetly removed with water or an organic solvent. In order to fully protect the device surface, a film thickness of 1 Mm or more can be formed. The heat resistance of the protective film to withstand etching is about 150 °C. When baking -8 - 200946614 No damage to the unit. The applicator for coating a protective film can be shared with a resin solution such as a photoresist. Means for Solving the Problems As a result of intensive investigation, the inventors of the present invention have found that the above problems can be attained by using a solution composition in which a water-soluble resin is dissolved in an organic solution, and the present invention has been completed. In other words, the present invention relates to a coating composition for a semiconductor element protective film described below, which comprises an organic solvent and a water-soluble resin dissolved therein. In the following description, the semiconductor element protective film to which the coating composition of the present invention is applied is not particularly limited to a general semiconductor element protective film, and is particularly suitable for a protective film for transport at the time of MEMS production. Therefore, the coating composition described in the patent application of the present invention corresponds to a coating composition for a protective film of a semiconductor element. The water-soluble resin is characterized in that it is selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, and water-soluble cellulose derivatives, and is preferably polyvinylpyrrolidone. The above water-soluble resin may be used in a weight average molecular weight of, for example, 1,000 to 10,000,000, 10,000 to 5,000,000, and 30,000 to 3,000,000. Further, an organic solvent can be used as the solvent for dissolving the water-soluble resin. Specific examples of the organic solvent to be dissolved include lower alcohols such as methanol, ethanol, propanol, isopropanol, butanol, and cyclohexanol, ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, and 1,4. - Glycol, such as butanediol, propylene glycol monomethyl-9- 200946614 ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol dimethyl An organic solvent containing a hydroxyl group (-OH) such as a glycol ether such as ether. Further, for example, a guanamine-based solvent having a guanamine bond (-CO-N<) such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone or N-vinylpyrrolidone can be mentioned. Further, a lactate such as methyl lactate, ethyl lactate or butyl lactate, dimethyl sulfoxide, chloroform or methylene chloride can also be used. Further, these organic solvents may be used in combination. Further, it is possible to contain water having a degree of water absorption in an organic solvent, but it is preferably less. In order to form a coating film having a film thickness of Ιμη or more, a high molecular weight water-soluble resin is used, or the concentration of the water-soluble resin must be increased, so it is preferable to use the above-mentioned good solvent. In the solution in which polyvinylpyrrolidone is dissolved, a coating property improver such as a surfactant may be added in order to improve the coating property of the solution. The concentration of the water-soluble resin in the solution of the coating composition is not particularly limited as long as the water-soluble resin is dissolved in the organic solvent, but may be depending on the film thickness of the protective film or the molecular weight of the water-soluble resin used. And decided. For example, in order to protect the device surface of the wafer having a stepped surface, it is preferable to cover the film thickness of Ιμπι or more. In order to form a film thickness, it is related to the molecular weight of the water-soluble resin, but it is necessary to have a concentration of a water-soluble resin of a certain thickness or more. In this case, the concentration of the water-soluble resin is preferably from 1 to 50% by mass in the coating composition, more preferably from 5 to 40% by mass, particularly preferably from 5 to 25% by mass. When it is less than 1% by mass, it is difficult to form a protective film of a water-soluble resin of 1 μTM 200946614 or more. When the amount is more than 50% by mass, the solubility of the water-soluble resin is poor, and it is difficult to prepare a solution of the coating composition of the water-soluble resin. Further, when the concentration is high, the smoothness of the film tends to be poor. EFFECT OF THE INVENTION The polyvinylpyrrolidone resin solution of the present invention can easily form a film of 1 μm or more. Further, by making the solvent an organic solvent, a smooth film can be formed. However, when an aqueous solution is formed, a large unevenness is formed on the surface of the formed film, and a smooth film cannot be formed. In the transfer test of the ruthenium etching apparatus, the film obtained from the organic solvent showed good results, however, the film system obtained from the aqueous solution produced a poor condition. In this case, the film obtained from the aqueous solution is not automatically transported by the ruthenium etching apparatus, and the wafer is not placed at a specific position, or the wafer is dropped during transportation. Ο Further, the use of an organic solvent avoids water damage to the surface of the device and the precipitation of photoresist in the applicator. Further, even if the film is not melted at a temperature of 150 ° C, it can be used in an environment of 150 ° C or higher. Further, after the wafer is transferred and processed, the polyvinylpyrrolidone film can be easily removed. That is, it may be dissolved in water to be removed, or may be dissolved in an organic solvent to be removed. It can also be removed by sulfuric acid/hydrogen peroxide water. Further, in addition to the method of removing the liquid, it may be removed by etching or ashing of a gas such as plasma such as oxygen. 1-1 - 200946614 EXAMPLES Hereinafter, the present invention will be described by way of Examples, but the present invention is not limited thereto. <Preparation of Resin Solution for Protective Film> (1) Polyvinylpyrrolidone (product of BASF Corporation, trade name Luvitec, K9 0, weight average molecular weight of 1.2 million or even 2 million) is dissolved in dimethylacetamide ( The following DM AC ) gave a 20% by mass solution of polyvinylpyrrolidone in DMAC. This DMAC solution is referred to as liquid A. (2) Polyvinylpyrrolidone (product of BASF Corporation, trade name Luvitec, K90) was dissolved in N-methylpyrrolidone (hereinafter NMP) to obtain a 20 mass% NMP solution of polyvinylpyrrolidone. This NMP solution is referred to as liquid B. (3) Polyvinylpyrrolidone (product of BASF Corporation, trade name Luvitec, K90) was dissolved in ethyl lactate (hereinafter EL) to obtain an EL solution of 13.3% by mass of polyvinylpyrrolidone. This EL solution is referred to as c liquid.
(4) 聚乙烯基耻咯烷酮（BASF公司製品，商品名 Luvitec，K90 )溶解於乳酸乙酯（以下EL )，得到聚乙 烯基吡咯烷嗣1 1 .1質量％之EL溶液。稱此EL溶液爲D 液。 (5) 聚乙烯基吡咯烷酮（BASF公司製品，商品名 Luvitec，K30，重量平均分子量4萬 5000乃至 5萬 200946614 5000 )溶解於乙醇，得到聚乙烯基吡咯烷酮2〇質量％之 乙醇溶液。稱此乙醇溶液爲E液。 (6) 聚乙烯基吡咯烷酮（BASF公司製品，商品名 Luvitec ’ K30 )溶解於異丙醇（以下IPA)，得到聚乙烯 基吡咯烷酮20質量％之IPA溶液。稱此IPA溶液爲F 液。 (7) 聚乙烯基吡咯烷酮（BASF公司製品，商品名 φ Luvitec，K3 0)溶解於丙二醇單甲基醚（以下PGME ), 得到聚乙烯基吡咯烷酮20質量％之PGME溶液。稱此 PGME溶液爲G液。 (8) 聚乙烯基吡咯烷酮（BASF公司製品，商品名 Luvitec，K3 0)溶解於乳酸乙酯（以下EL)，得到聚乙 烯基吡咯烷酮20質量％之EL溶液。稱此EL溶液爲η 液。 (9) 聚乙烯基吡咯烷酮（BASF公司製品，商品名 〇 Luvitec，K90 )溶解於純水，得到聚乙烯基吡咯烷酮2〇 質量％之水溶液。稱此溶液爲I液。 (10) 聚乙烯基吡咯烷酮（BASF公司製品，商品名 Luvitec，K90)溶解於純水，得到聚乙烯基吡咯烷酮U.7 質量％之水溶液。稱此溶液爲J液。 (11) 聚乙烯基吡咯烷酮（BASF公司製品，商品名 Luvitec，K30 )溶解於純水，得到聚乙烯基吡咯烷酮20 質量％之水溶液。稱此溶液爲K液。 (12) 聚乙烯基吡咯烷酮（BASF公司製品，商品名 -13- 200946614(4) Polyvinylpyrrolidone (product of BASF Co., Ltd., trade name: Luvitec, K90) was dissolved in ethyl lactate (hereinafter EL) to obtain a 11.1 mass% EL solution of polyvinylpyrrolidinium. This EL solution is referred to as D solution. (5) Polyvinylpyrrolidone (product of BASF Corporation, trade name Luvitec, K30, weight average molecular weight 40,000 or even 50,000, 200946614 5000) was dissolved in ethanol to obtain a polyvinylpyrrolidone 2% by mass ethanol solution. This ethanol solution is referred to as E solution. (6) Polyvinylpyrrolidone (product of BASF Corporation, trade name Luvitec 'K30) was dissolved in isopropyl alcohol (hereinafter IPA) to obtain a 20% by mass solution of polyvinylpyrrolidone in IPA. This IPA solution is referred to as F liquid. (7) Polyvinylpyrrolidone (product of BASF Corporation, trade name φ Luvitec, K30) was dissolved in propylene glycol monomethyl ether (hereinafter PGME) to obtain a PGME solution of polyvinylpyrrolidone 20% by mass. This PGME solution is referred to as G solution. (8) Polyvinylpyrrolidone (product of BASF Co., Ltd., trade name: Luvitec, K30) was dissolved in ethyl lactate (hereinafter EL) to obtain an EL solution of 20% by mass of polyvinylpyrrolidone. This EL solution is referred to as η solution. (9) Polyvinylpyrrolidone (product of BASF Corporation, trade name 〇 Luvitec, K90) was dissolved in pure water to obtain an aqueous solution of polyvinylpyrrolidone (2% by mass). This solution is referred to as liquid I. (10) Polyvinylpyrrolidone (product of BASF Corporation, trade name Luvitec, K90) was dissolved in pure water to obtain an aqueous solution of polyvinylpyrrolidone of U. 7 mass%. This solution is referred to as J liquid. (11) Polyvinylpyrrolidone (product of BASF Corporation, trade name Luvitec, K30) was dissolved in pure water to obtain an aqueous solution of 20% by mass of polyvinylpyrrolidone. This solution is referred to as K solution. (12) Polyvinylpyrrolidone (BASF product, trade name -13- 200946614
Luvitec，K30 )溶解於純水：乙醇=50 : 50之質量比的混 合液，得到聚乙烯基吡咯烷酮20質量％之溶液。稱此溶 液爲L液。 〈保護膜之形成〉 以記載於下述之條件，以旋塗法製作保護膜。 將A液滴下於4英吋矽晶圓，以2000rpm旋轉晶圓 60秒後，以150°C燒成60秒，得到膜厚約6.3μιη之聚乙 烯基吡咯烷酮膜。 將Β液滴下於4英吋矽晶圓，以2000rpm旋轉晶圓 60秒後’以150 °C燒成60秒，得到膜厚約8.Ιμιη之聚乙 烯基吡咯烷酮膜。 將C液滴下於4英吋矽晶圓，以2000rpm旋轉晶圓 6 0秒後’以1 5 0 °C燒成6 0秒，得到膜厚約8 · 8 μ m之聚乙 烯基吡咯烷酮膜。 將D液滴下於4英吋矽晶圓，以2〇〇〇rpm旋轉晶圓 6 0秒後’以1 5 0 °C燒成6 0秒，得到膜厚約5.2 μ m之聚乙 烯基吡咯烷酮膜。 將E液滴下於4英吋矽晶圓，以15〇〇rpm旋轉晶圓 60秒後’以150°C燒成60秒，得到膜厚約5 4μιη之聚乙 烯基吡咯烷酮膜。 將F液滴下於4英吋矽晶圓，以丨5〇〇rpm旋轉晶圓 60秒後，以150°C燒成60秒，得到膜厚約5 9μιιη之聚乙 烯基吡咯烷酮膜。 200946614 將G液滴下於4英吋矽晶圓，以15〇〇rpjn旋轉晶圓 60秒後，以l5〇C燒成60秒，得到膜厚約3 6μιη之聚乙 烯基吡咯烷酮膜。 將Η液滴下於4英吋矽晶圓’以2〇〇〇rpin旋轉晶圓 60秒後’以150°C燒成60秒’得到膜厚約2 8fim之聚乙 烯基吡咯烷酮膜。 將Ϊ液滴下於4英吋矽晶圓，以2〇〇〇rpin旋轉晶圓 〇 60秒後’以150°C燒成60秒，得到膜厚約8·Ομπΐ之聚乙 烯基吡咯烷酮膜。 將I液滴下於4英吋矽晶圓，以5〇〇〇rpm旋轉晶圓 60秒後’以150°C燒成60秒，得到膜厚約5 1μπ1之聚乙 烯基吡略烷酮膜。 將J液滴下於4英吋矽晶圓’以2〇〇〇rpm旋轉晶圓 60秒後’以150°C燒成60秒’得到膜厚約5 〇μιη之聚乙 烯基吡咯烷酮膜。 © 將尺液滴下於4英吋矽晶圓，以150〇rpm旋轉晶圓 6 0秒後，以1 5 0 °C燒成6 0秒，得到膜厚約丨9 μπι之聚乙 烯基吡咯烷酮膜。 將L液滴下於4英吋矽晶圓，以150〇rpm旋轉晶圓 60秒後，以150°C燒成60秒，得到膜厚約4 4μιη之聚乙 烯基吡咯烷酮膜。 又’於4英吋砂晶圓係使用約6：25μιη之厚者。 〈保護膜之平滑性試驗〉 -15- 200946614 膜厚及膜之平面平坦化性係以Veeco公司製觸針式表 面形狀測定器（DekTak6M )測定。 此等之結果表示於表1中。 (表1 ) 讎旨 溶液 旋轉數 (rpm) 膜厚 (μιη) 膜之平面 平坦化性 K=90 A(DMAC 20 質量 ％) 2000 6.3 平滑、 無凹凸 Κ=90 Β(ΝΜΡ 20 質量％) 2000 8.1 平滑、 無凹凸 Κ=90 C(EL 13.3 質量0/〇) 2000 8.8 平滑、 無凹凸 實 施 Κ=90 D(EL 11.1 ΜΑ%) 2000 5.2 平滑、 無凹凸 例 Κ=30 E(乙醇20質量％) 1500 5.4 平滑、 無凹凸 Κ=30 F(IPA 20 質量％) 1500 5.9 平滑、 無凹凸 Κ=30 G(PGME 20 質量 ％) 1500 3.6 平滑、 無凹凸 Κ=30 H〇EL 20 質量0/〇) 1500 2.8 平滑、 無凹凸 Κ=90 1(水20質量％) 2000 8.0 0.2ym 之 凹凸觀察 比 Κ=90 1(水20質量％) 5000 5.1 (λ2μηι 之 凹凸觀察 較 例 Κ=90 J(水16.7質量％) 2000 5.0 0.2μιη 之 凹凸觀察 Κ=30 K(水20質量0/〇) 1500 1.9 凹凸觀察 Κ=30 L(水溶液*、20質量％) 1500 4.4 凹凸觀察 *水溶液=水：乙醇=5 0 : 5 0質量比 -16- 200946614 如表1所示，從使用有機溶劑作爲溶劑之溶液及使用 水之溶液所得到之膜進行比較後，從有機溶劑溶液得到之 聚乙烯基吡咯烷酮膜的表面係平滑且無凹凸，但從水溶劑 溶液得到之聚乙烯基吡咯烷酮膜觀察到0.2 μπι之凹凸乃至 凹凸。因此，可確認出從有機溶劑溶液得到之聚乙烯基吡 咯烷酮膜的表面優越性。 © 〈矽蝕刻裝置的搬送試驗〉 以住友精密工業（股）公司之矽蝕刻裝置MUC-21進 行搬送試驗。試樣係使用Α液、G液' Η液，於4英吋矽 晶圓形成聚乙烯基吡咯烷酮膜，使聚乙烯基吡咯烷酮膜側 朝下側，進行朝矽蝕刻裝置MUC-21之搬送、氦洩漏及蝕 刻試驗。氨洩漏量之判斷係以住友精密工業之標準設定値 的20Pa/分鐘以下進行判斷，少於20Pa/分鐘之情形爲良 好。氦之洩露量爲超過2 0Pa/分鐘之比較例的情形，安全 © 裝置會作用，無法進行蝕刻試驗。氦之洩露量爲未達 2 0Pa/分鐘之實施例係無問題，可進行飩刻試驗。 其結果表不於表2中。 [表2] 樹脂 溶液 洩露量 判定 實施例 K=90 A(DMAC 20 質量 ％) 11.6 Pa/分鐘 良 Κ=30 Ε(乙醇20質量％) 15.0 Pa/分鐘 良 Κ=30 F(IPA 20 質量 ％) 11.3 Pa/分鐘 良 Κ=30 G(PGME 20 質量％) 4.4 Pa/分鐘 良 Κ=30 H(EL 20 質量％) 3.4 Pa/分鐘 良 比較例 Κ=30 K(水20質量％) 28.8 Pa/分鐘 不良 Κ=30 L(水溶液、20質量％) 36.0Pa/分鐘 不良 -17- 200946614 〈光阻溶液與聚乙烯基吡咯烷酮溶液之混合試驗〉 以下述說明光阻溶液與聚乙烯基吡咯烷酮溶液之混合 試驗之方法進行。光阻溶液係使用東京應化工業（股）公 司製之THMR-iP 3000，置入於玻璃容器中5mL。 再使聚乙烯基吡咯烷酮（BASF公司製品，商品名 Luvitec，K30)溶解於二甲基乙醯胺（以下DMAC ) ’得 到聚乙烯基吡咯烷酮20質量％之 DMAC溶液。稱此 DMAC溶液爲Μ液。 _ 將Μ液（DMAC溶液）、11液（£1^溶液）、Κ液 (水溶液）分別置入裝有各5mL THMR-iP 3000之玻璃容 器中，確認出攪拌後之狀態。將此等之結果表示於表3 中。 如表3所示般，聚乙烯基吡咯烷酮有機溶劑溶液與光 阻溶液之混合中係有色透明且可溶解，但，聚乙烯基吡咯 烷酮水溶液與光阻溶液之混合中可觀察到析出物。 〇 [表3] 樹脂 溶液 結果 實施例 Κ = 30 M(DMAC 20 質量 ％) 溶解 Κ = 30 H(EL 20 質量 ％) 溶解 ~ 比較例 Κ = 30 K(水 20質量％) 有析出~~ 〈耐熱性評估〉 以前述保護膜的形成所記載之條件於4英吋矽晶圓準 備從A液得到之聚乙烯基吡咯烷酮膜（膜厚6.3μηι)，觀 -18- 200946614 察於加熱板上之變化。於加熱至150 °C之加熱板上放置已 被覆上述膜之晶圓，分別觀察經過5分鐘經過後、10分 鐘經過後、及20分鐘經過後。確認出膜厚、形狀均無變 化，於耐熱性無問題。 同樣地準備從C及D液得到之聚乙烯基吡咯烷酮 膜，於加熱至150°C之加熱板上放置上述膜，分別觀察經 過5分鐘經過後、10分鐘經過後、及20分鐘經過後。確 D 認出膜厚、形狀均無變化，於耐熱性無問題。 從此等之結果，聚乙烯基吡咯烷酮膜係即使在15(TC 之環境下亦可充分地使用來作爲保護膜。 〈溶解性評估〉 以前述保護膜的形成所記載之條件於4英吋矽晶圓準 備從A液得到之聚乙烯基吡咯烷酮膜（膜厚6·3μΐη)，對 純水之浸漬進行溶解試驗。結果，在室溫下浸漬3分鐘， 〇 繼而’進行純水清洗，乾燥後，在目視上可除去聚乙烯基 吡咯烷酮膜。 同樣地，準備從Α液得到之聚乙烯基吡咯烷酮膜 (膜厚6·3μπι)，對DM AC之浸漬進行溶解試驗。結果， 在室溫下浸漬3分鐘，繼而，進行純水清洗，乾燥後，在 目視上可除去聚乙烯基吡咯烷酮膜。 產業上之利用可能性 若依本發明，可藉由使用將水溶性樹脂溶解於有機溶 -19- 200946614 劑之溶液組成物而可使平滑的保護膜形成於晶圓上，晶圓 搬送及加工時，晶圓上之元件受損傷之擔心會消失。又， 保護膜係可容易地以水或有機溶劑除去，於晶圓上亦無任 何痕跡殘留’故在其後之步驟中，對晶圓上之元件的使用 不造成阻礙。 ❿Luvitec, K30) was dissolved in a mixture of pure water: ethanol = 50:50 by mass to obtain a 20% by mass solution of polyvinylpyrrolidone. This solution is referred to as L solution. <Formation of Protective Film> A protective film was produced by a spin coating method under the conditions described below. A was dropped on a 4 inch wafer, and the wafer was rotated at 2000 rpm for 60 seconds, and then fired at 150 ° C for 60 seconds to obtain a polyvinylpyrrolidone film having a film thickness of about 6.3 μm. The crucible was dropped on a 4 inch wafer, and the wafer was rotated at 2000 rpm for 60 seconds, and then fired at 150 ° C for 60 seconds to obtain a polyvinylpyrrolidone film having a film thickness of about 8. Ι μηη. C was dropped on a 4 inch wafer, and the wafer was rotated at 2000 rpm for 60 seconds, and then fired at 150 ° C for 60 seconds to obtain a polyvinylpyrrolidone film having a film thickness of about 8 · 8 μm. D was dropped on a 4 inch wafer, and the wafer was rotated at 2 rpm for 60 seconds, and then fired at 150 ° C for 60 seconds to obtain a polyvinylpyrrolidone having a film thickness of about 5.2 μm. membrane. E was dropped on a 4 inch wafer, and the wafer was rotated at 15 rpm for 60 seconds, and then fired at 150 ° C for 60 seconds to obtain a polyvinylpyrrolidone film having a film thickness of about 5 4 μm. F was dropped on a 4 inch wafer, and the wafer was rotated at 5 rpm for 60 seconds, and then fired at 150 ° C for 60 seconds to obtain a polyvinylpyrrolidone film having a film thickness of about 5 μm. 200946614 G was dropped on a 4 inch wafer, and the wafer was rotated at 15 〇〇rpjn for 60 seconds, and then fired at 15 ° C for 60 seconds to obtain a polyvinylpyrrolidone film having a film thickness of about 3 μm. The crucible was dropped on a 4 inch wafer, and the wafer was rotated by 2 rpin for 60 seconds and then fired at 150 ° C for 60 seconds to obtain a polyvinylpyrrolidone film having a film thickness of about 28 μm. The crucible was dropped on a 4 inch wafer, and the wafer was rotated by 2 rpin for 60 seconds, and then fired at 150 ° C for 60 seconds to obtain a polyvinylpyrrolidone film having a film thickness of about 8 μm. I was dropped on a 4 inch wafer, and the wafer was rotated at 5 rpm for 60 seconds, and then fired at 150 ° C for 60 seconds to obtain a polyvinylpyrrolidone film having a film thickness of about 5 1 μπ. J was dropped on a 4 inch wafer "rotating the wafer at 2 rpm for 60 seconds" and then fired at 150 ° C for 60 seconds to obtain a polyvinylpyrrolidone film having a film thickness of about 5 Å. © Drop the ruler on a 4 inch wafer, rotate the wafer at 150 rpm for 60 seconds, and then fire at 150 °C for 60 seconds to obtain a polyvinylpyrrolidone film with a film thickness of about 9 μm. . L was dropped on a 4 inch wafer, and the wafer was rotated at 150 rpm for 60 seconds, and then fired at 150 ° C for 60 seconds to obtain a polyvinylpyrrolidone film having a film thickness of about 4 4 μm. Also, the thickness of the 6-inch sand wafer system is about 6:25 μm. <Smoothness Test of Protective Film> -15- 200946614 The film thickness and the planar flatness of the film were measured by a stylus type surface measuring device (DekTak6M) manufactured by Veeco Corporation. The results of these are shown in Table 1. (Table 1) Number of rotations of the solution (rpm) Film thickness (μιη) Planar flatness of the film K = 90 A (DMAC 20% by mass) 2000 6.3 Smooth, no ridges = 90 Β (ΝΜΡ 20% by mass) 2000 8.1 Smooth, no bumps Κ = 90 C (EL 13.3 mass 0 / 〇) 2000 8.8 Smooth, no bump implementation Κ = 90 D (EL 11.1 ΜΑ%) 2000 5.2 Smooth, no bumps Κ = 30 E (ethanol 20% by mass ) 1500 5.4 Smooth, no bumps Κ = 30 F (IPA 20% by mass) 1500 5.9 Smooth, no bumps Κ = 30 G (PGME 20% by mass) 1500 3.6 Smooth, no bumps Κ = 30 H〇EL 20 Mass 0/〇 ) 1500 2.8 Smooth, no blemish Κ = 90 1 (water 20% by mass) 2000 8.0 0.2ym Concavity observation ratio Κ = 90 1 (water 20% by mass) 5000 5.1 (λ2μηι bump observation example = 90 J (water 16.7 mass%) 2000 5.0 0.2μιη Concavity and convexity observation Κ = 30 K (water 20 mass 0 / 〇) 1500 1.9 Concavity observation Κ = 30 L (aqueous solution *, 20% by mass) 1500 4.4 Concavity observation * Aqueous solution = water: Ethanol = 5 0 : 50 mass ratio - 16- 200946614 As shown in Table 1, a solution using an organic solvent as a solvent and a solution using water After the obtained film was compared, the surface of the polyvinylpyrrolidone film obtained from the organic solvent solution was smooth and free from irregularities, but 0.2 μm of unevenness or unevenness was observed in the polyvinylpyrrolidone film obtained from the aqueous solvent solution. The surface superiority of the polyvinylpyrrolidone film obtained from the organic solvent solution was confirmed. © <Transfer test of the 矽 etching apparatus> The transfer test was carried out by the Mickey MU etching apparatus MUC-21 of Sumitomo Precision Industries Co., Ltd. The sputum and the G liquid' sputum were formed into a polyvinylpyrrolidone film on a 4 inch wafer, and the polyvinylpyrrolidone film was turned to the lower side, and the mashing apparatus MUC-21 was transported, leaked, and etched. The judgment of the ammonia leakage amount is judged by the Sumitomo Precision Industry standard setting of 20 Pa/min or less, and the case of less than 20 Pa/min is good. In the case of the comparative example in which the leakage amount is more than 20 Pa/min, safety is safe. © The device will work and the etching test will not be possible. The example in which the leakage amount is less than 20 Pa/min is no problem and the engraving test can be performed. The results are shown in Table 2. [Table 2] Resin solution leakage amount determination Example K = 90 A (DMAC 20% by mass) 11.6 Pa/min Liang = 30 Ε (ethanol 20% by mass) 15.0 Pa/min Liangzhu =30 F (IPA 20% by mass) 11.3 Pa/min liang = 30 G (PGME 20% by mass) 4.4 Pa/min Liang Κ = 30 H (EL 20% by mass) 3.4 Pa/min. Comparative example Κ = 30 K (20% by mass of water) 28.8 Pa/min defective Κ = 30 L (aqueous solution, 20% by mass) 36.0 Pa/min defective -17- 200946614 <mixing test of photoresist solution and polyvinylpyrrolidone solution> The photoresist is described below The method of mixing the solution with the polyvinylpyrrolidone solution is carried out. The photoresist solution was THMR-iP 3000 manufactured by Tokyo Ohka Kogyo Co., Ltd., and placed in a glass vessel at 5 mL. Further, polyvinylpyrrolidone (product of BASF Corporation, trade name Luvitec, K30) was dissolved in dimethylacetamide (DMAC below) to obtain a DMAC solution of polyvinylpyrrolidone 20% by mass. This DMAC solution is referred to as mash. _ The mash (DMAC solution), the 11 liquid (£1^ solution), and the mash (aqueous solution) were placed in a glass container containing each 5 mL THMR-iP 3000, and the state after the stirring was confirmed. The results of these are shown in Table 3. As shown in Table 3, the mixture of the polyvinylpyrrolidone organic solvent solution and the photoresist solution was colored transparent and soluble, but precipitates were observed in the mixture of the polyvinylpyrrolidone aqueous solution and the photoresist solution. 〇 [Table 3] Resin solution Results Example Κ = 30 M (DMAC 20% by mass) Dissolved Κ = 30 H (EL 20% by mass) Dissolution ~ Comparative Example Κ = 30 K (water 20% by mass) Precipitated ~~ 〈 Evaluation of heat resistance> A polyvinylpyrrolidone film (film thickness: 6.3 μηι) obtained from the liquid A was prepared on a 4-inch wafer under the conditions described for the formation of the protective film, and it was observed on a hot plate at -18-200946614. Variety. The wafer on which the film was coated was placed on a hot plate heated to 150 ° C, and observed after 5 minutes passed, 10 minutes passed, and after 20 minutes passed. It was confirmed that the film thickness and shape did not change, and there was no problem in heat resistance. Similarly, a polyvinylpyrrolidone film obtained from the liquids C and D was prepared, and the film was placed on a hot plate heated to 150 ° C, and observed after 5 minutes passed, 10 minutes passed, and 20 minutes passed. It is confirmed that D does not change in film thickness and shape, and there is no problem in heat resistance. As a result of the above, the polyvinylpyrrolidone film can be sufficiently used as a protective film even in an environment of 15 (TC). <Solubility Evaluation> The conditions described in the formation of the protective film are 4 inches. The polyvinylpyrrolidone film (film thickness: 6.3 μm) obtained from the liquid A was prepared and subjected to a dissolution test on the impregnation of pure water. As a result, it was immersed for 3 minutes at room temperature, and then washed with pure water and dried. The polyvinylpyrrolidone film was visually removed. Similarly, a polyvinylpyrrolidone film (film thickness: 6.3 μm) obtained from the mash was prepared, and a immersion test was performed on the immersion of DM AC. As a result, it was immersed at room temperature. In a minute, and then, it is washed with pure water, and after drying, the polyvinylpyrrolidone film can be visually removed. Industrial Applicability According to the present invention, the water-soluble resin can be dissolved in the organic solution by using -19-200946614 A smooth protective film can be formed on the wafer by the solution composition of the agent, and the fear of damage to components on the wafer disappears during wafer transfer and processing. To remove water or an organic solvent, on a wafer nor any remaining traces' of it in the subsequent step, the elements of the wafer does not cause obstruction. ❿
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