200829367 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種用於化學機械研磨之研磨墊及一種製 造研磨墊之方法。 【先前技射ί】 化學機械研磨（CMP)係一種用於以研磨墊平坦化基板表 面之方法。CMP—般用於研磨透鏡、鏡面、液晶顯示器基 板、石夕晶圓及矽晶圓上氧化及/或金屬層。 以石夕晶圓為例，首先將單晶矽錠切成片。通常將晶圓磨 平使其平坦以便隨後進行化學蝕刻。在蝕刻過程後需要研 磨過程。在研磨過程期間，研磨墊與研磨漿一起與晶圓表 之夕原子發生化學反應而形成比下層碎軟的反應表 面此外，連績擦去反應表面，從而使新鮮矽暴露於研磨 漿及研磨墊。 習知研磨墊包含具有用於研磨基板之表面之基底材料。 該表面包含織品及後入織品中之彈性體。在研磨過程中， $ 口口之纖維與彈性體_起發揮載運研磨漿及自晶圓移除反 ^面之功能。不織布常詩基底材料中。習知不織布使 之情況下形成^ =具有小於1Gem之長度）在無編織 含複合不^ 成織品之方式，不織布通常包 、 針扎不織布、熔喷不織布、 網積層不織布、濕式布 f補不織布、 布。然而，短纖維應經由疏棉編不織布及水扎不織 造針札不織布時亦需要針扎過程°。：二程:成’且在製 荨過程導致纖維不均 113535.doc 200829367 勻分佈，且在不織布中易觀測到纖維聚集。此外，由於此 等過程亦發生纖維斷裂。此外，在將彈性體嵌入織品後， 由於纖維不均勻分佈所致之彈性體的不均勻分佈影響由纖 維及彈性體組成之單元尺寸、硬度、均一性、彈性體密度 及厚度，且研磨漿不能平滑流動且研磨漿中之研磨顆粒不 能均勻擴散。研磨時常觀測到起球。除此之外，研磨期間 所形成之殘餘物傾向於留在研磨墊之表面上且其難以移 • 除；由此，殘餘物刮擦且損壞待研磨之基板。 【發明内容】 本發明之一目的係提供一種研磨墊，其包含具有一基底 材料，該基底材料具有一表面，用以研磨一基板，其中該 表面包含不織布及彈性體。不織布係由長纖維製成，且該 彈性體嵌入該不織布中。 本發月之另目的係&供一種研磨基板之方法。該方法 包含使用上文提及之研磨墊研磨基板表面之步驟。 • 本發明之另一目的係提供-種製造上文所述之研磨塾之 方法。該方法包含下列步驟：（a)提供基底材料，其包含由 長纖維製成t不織布；（b)用彈性體溶液浸潰基底材料表 面；及（C)使浸潰於基底材料表面中之彈性體固化。 【實施方式】 本發明提供包含一研磨墊，其包含具有一基底材料，該 基底材料具有-表面，用以研磨一基板，其中該表面包含 不織布及彈性體。不織布係由長纖維製成，且該彈性體喪 入該不織布中。 113535.doc 200829367 . 如本文所用之「不織布」係指除紙及經編織、針織、蔡 織、縫編併人黏合紗線或長絲或藉由濕磨黏結之產品（經 額外針缝或未經额外針縫）外，藉由摩擦及/或凝聚及/或黏 著而黏結之定向或隨意定向纖維之經製造薄片、網或塾。 纖維可為天然或人造來源。其可為切段或連續長絲或經原 位形成。根據形成網之方法，不織布常包含複合不織布、 針刺不織布、熔噴不織布、纺黏不織布、網積層不織布、 • 濕、式布層不織布、縫編不織布及水刺不織布。與編織品相 比’不織布具有更佳材料性質。 在本發明之-較佳實施例中，不織布係以改良批次均一 性之卷軸方式使用。 如本文所用之術語「纖維」係指單纖維或複合纖維，較 佳為複合纖維。根據待研磨之基板來選擇纖維。基底材料 表面之纖維為研磨提供突起以及提供支架以便將彈性體安 置於由支架界定之空間中。熟習此領域者可選擇適合種類 籲（纖維且根據本說明書之揭示内容使彈性體聚合物與纖維 配合。長纖維較佳係由至少一種選自由下列各物組成之群 之材料製成：聚醯胺、對苯二甲醯胺、聚酯、聚甲基丙烯 酸甲醋、聚對苯二甲酸乙二醋、聚丙烯腈及其混合 如此領域所定義之術語「長纖維」係指長度超過i〇 em 之纖維。長纖維之形狀係延伸的且長度在理論上無限制。 長纖維易扭曲以改良強度及應力。 在本發明之一較佳實施例中，纖維係海島型纖維。如本 - 文所用之術語「海島型纖維」（亦稱為「海島型複合纖 113535.doc 200829367 、准」）係指包含海洋組份及島嶼組份之纖維。舉例而言， =島型纖維藉由以海島型方式複合紡絲或摻㈣ = 製造。在本發明之一較佳實施例中，將海島型纖: 错由降低重量來降低海洋組份之比例進行處理。降低海洋 組份重量^方法為熟習此領域者所熟知，諸如使用氫氧化 鈉或甲苯之方法。較佳將降低海洋組份後之長纖維分成 〇·05至0·0001 丹尼爾（Denier)。200829367 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a polishing pad for chemical mechanical polishing and a method of manufacturing the polishing pad. [Previous technique] Chemical mechanical polishing (CMP) is a method for planarizing a surface of a substrate with a polishing pad. CMP is commonly used to polish lenses, mirrors, liquid crystal display substrates, etched wafers, and oxide and/or metal layers on germanium wafers. Taking Shixi wafer as an example, the single crystal germanium ingot is first cut into pieces. The wafer is typically flattened to be flat for subsequent chemical etching. A grinding process is required after the etching process. During the grinding process, the polishing pad and the polishing slurry chemically react with the atoms of the wafer surface to form a reaction surface that is softer than the lower layer. In addition, the reaction surface is wiped off, thereby exposing the fresh crucible to the slurry and the polishing pad. . Conventional polishing pads comprise a substrate material having a surface for polishing a substrate. The surface comprises a fabric and an elastomer that is placed into the fabric. During the grinding process, the fiber and elastomer of the mouth function to carry the slurry and remove the reverse surface from the wafer. Non-woven in the poetry base material. Conventional non-woven fabrics make it possible to form a fabric having a length of less than 1 Gem. Non-woven fabrics are usually wrapped, needle-punched non-woven fabrics, melt-blown non-woven fabrics, net-laid non-woven fabrics, wet fabrics, non-woven fabrics. , cloth. However, the short fiber should be woven through the cotton weave and the water is not woven into the needle. : Two-way: □ and the fiber unevenness caused by the process of making 113 113535.doc 200829367 is evenly distributed, and fiber aggregation is easily observed in the non-woven fabric. In addition, fiber breakage also occurs due to these processes. In addition, after the elastomer is embedded in the fabric, the uneven distribution of the elastomer due to the uneven distribution of the fibers affects the unit size, hardness, uniformity, elastomer density and thickness composed of the fibers and the elastomer, and the slurry cannot be The smooth flow and the abrasive particles in the slurry do not spread uniformly. Pilling is often observed during grinding. In addition to this, the residue formed during the grinding tends to remain on the surface of the polishing pad and it is difficult to remove; thus, the residue scrapes and damages the substrate to be polished. SUMMARY OF THE INVENTION One object of the present invention is to provide a polishing pad comprising a substrate material having a surface for polishing a substrate, wherein the surface comprises a nonwoven fabric and an elastomer. The nonwoven fabric is made of long fibers, and the elastic body is embedded in the nonwoven fabric. Another purpose of this month is to provide a method of polishing a substrate. The method comprises the step of grinding the surface of the substrate using the polishing pad mentioned above. Another object of the present invention is to provide a method of making the abrasive crucible described above. The method comprises the steps of: (a) providing a substrate material comprising t-woven fabric made of long fibers; (b) impregnating the surface of the substrate material with an elastomer solution; and (C) elastically impregnating the surface of the substrate material Body solidification. [Embodiment] The present invention provides a polishing pad comprising a substrate material having a surface for polishing a substrate, wherein the surface comprises a nonwoven fabric and an elastomer. The nonwoven fabric is made of long fibers, and the elastic body is immersed in the nonwoven fabric. 113535.doc 200829367 . As used herein, "non-woven fabric" means a product that is woven and woven, knitted, woven, stitched and woven into a yarn or filament or bonded by wet grinding (with additional stitching or not) Sheets, webs or crepe are produced by oriented or randomly oriented fibers bonded by friction and/or coacervation and/or adhesion, in addition to additional stitching. The fibers can be of natural or artificial origin. It can be formed as a staple or continuous filament or in situ. According to the method of forming a net, the non-woven fabric often includes a composite non-woven fabric, a needle-punched nonwoven fabric, a melt-blown nonwoven fabric, a spunbonded nonwoven fabric, a mesh laminate non-woven fabric, a wet fabric, a non-woven fabric, a non-woven fabric, and a spunlace nonwoven fabric. Compared to woven fabrics, 'non-woven fabrics have better material properties. In the preferred embodiment of the invention, the nonwoven fabric is used in a reel format that improves batch uniformity. The term "fiber" as used herein refers to a single fiber or a composite fiber, preferably a composite fiber. The fibers are selected according to the substrate to be polished. The fibers on the surface of the substrate material provide protrusions for the grinding and provide a support for placing the elastomer in the space defined by the stent. Those skilled in the art will be able to select suitable types of fibers (fibers and blend the elastomeric polymer with the fibers in accordance with the disclosure of the present specification. The long fibers are preferably made of at least one material selected from the group consisting of: polyfluorene Amine, terephthalamide, polyester, polymethyl methacrylate, polyethylene terephthalate, polyacrylonitrile, and mixtures thereof. The term "long fiber" as defined in the art refers to a length exceeding i〇 The fiber of em. The shape of the long fiber is extended and the length is theoretically unlimited. The long fiber is easily twisted to improve strength and stress. In a preferred embodiment of the invention, the fiber is an island-in-the-sea fiber. The term "island-type fiber" (also known as "island-type composite fiber 113535.doc 200829367, standard") refers to fibers containing marine components and island components. For example, = island fibers by island Type of composite spinning or doping (IV) = manufacturing. In a preferred embodiment of the invention, the island-type fiber is treated by reducing the weight to reduce the proportion of the marine component. It is well known to those skilled in the art, such as the method of using sodium hydroxide or toluene. It is preferred to divide the long fibers after the reduction of the marine component into 〇·05 to 0·0001 Denier.
在本發明之-較佳實施例中，不織布包含網狀框架。如 本文所用之術語「網狀框架」係指經設計以改良本發明之 不織布強度之薄的且經增強之材料。網狀框架之材料較佳 為水醯胺、聚酯或聚烯烴。網狀框架較佳由長纖維製成。 纖、准可經編織或不經編織而形成網狀框架。為使長纖維形 成本發明之不織布，網狀框架包含網目，且網狀框架之纖 維與不織布之長纖維彼此纏繞。網狀框架較佳具有〇 〇1至 1.0 mm之厚度。網狀框架具有1〇至2〇() g/m2之單位面積重 里。此外’網狀框架具有10至150網目。 如本文所用之術語「彈性體」（亦稱為「彈性聚合物」） 係指展現類橡膠品質之聚合物類型。在研磨時，彈性體充 S優良緩衝劑以避免刮擦待研磨之基板表面。在本發明之 一較佳實施例中’彈性體為發泡樹脂。如本文所用之術語 發泡樹脂”係指含有熱塑性樹脂及熱分解發泡劑之材 料。彈性體較佳係選自由下列各物組成之群之至少一者： 聚胺醋、聚酸胺、聚碳酸酯、聚胺基腈、聚甲基丙烯酸 醋、環氧樹脂、酚系樹脂、聚甲基丙烯酸甲酯、聚胺基 113535.doc 200829367 酯、乙烯苯聚合物、丙烯酸系樹脂及聚胺酯。In a preferred embodiment of the invention, the nonwoven fabric comprises a mesh frame. The term "mesh frame" as used herein refers to a thin and reinforced material designed to improve the nonwoven strength of the present invention. The material of the mesh frame is preferably salicylamine, polyester or polyolefin. The mesh frame is preferably made of long fibers. The fiber frame can be woven or unwoven to form a mesh frame. In order to make the long fiber shape non-woven fabric of the invention, the mesh frame comprises a mesh, and the fibers of the mesh frame and the long fibers of the non-woven fabric are entangled with each other. The mesh frame preferably has a thickness of from 〇1 to 1.0 mm. The mesh frame has a weight per unit area of 1 〇 to 2 〇 () g/m2. In addition, the mesh frame has 10 to 150 mesh. The term "elastomer" (also referred to as "elastic polymer") as used herein refers to a type of polymer that exhibits rubber-like qualities. At the time of grinding, the elastomer is filled with an excellent buffer to avoid scratching the surface of the substrate to be polished. In a preferred embodiment of the invention, the elastomer is a foamed resin. The term "foamed resin" as used herein refers to a material comprising a thermoplastic resin and a thermally decomposable blowing agent. The elastomer is preferably selected from at least one of the group consisting of: polyamine vinegar, polyamine, poly Carbonate, polyamine nitrile, polymethacrylic acid vinegar, epoxy resin, phenolic resin, polymethyl methacrylate, polyamine 113535.doc 200829367 ester, vinyl benzene polymer, acrylic resin and polyurethane.
本發明之研磨墊可避免由短纖維製成之習知研磨墊之缺 點。因為長纖維能夠在不使用盤帶過程或針札過程的情況 下形成不織布，所以繼而避免由於此等過程所致之纖維不 均勻分佈、纖維聚集及纖維斷頭。由此，本發明之彈性體 均勻礙入不織布中。此外，由纖維及彈性體組成之單元尺 寸、硬度、均一性、彈性體密度、厚度、壓縮比及壓縮後 回復率均得到改良。研磨漿可平滑流動且研磨顆粒亦可均 勻擴散。本發明之研磨墊不損壞待研磨之基板表面且起球 顯著減少。此外，應用本發明之研磨墊時研磨效率令人滿 意0 本發明亦提供一種研磨基板之方法。該方法包含使用如 上文提及之研磨墊研磨基板表面之步驟。 本發明進一步提供一種製造如上文提及之研磨墊之方 法。該方法包含下列步驟：（a)提供基底材料，其包含由長 纖維製成之不織布；（b)用彈性體溶液浸潰基底材料表面； 及（C)使浸潰於基底材料表面中之彈性體固化。 在該方法之步驟（b)中’用彈性體溶液浸潰基底材料之 方式係用彈性體溶液浸透不織布之方法。浸潰條件為熟習 此領域者所熟知。用於彈性體溶液中之適合溶劑包括二甲 基甲醯胺（歷）。彈性體溶液視情況包含諸如清潔劑之添 加劑。彈性體溶液中彈性體之濃度較佳在2 Wt%至60 wt% 之範圍内。 步驟（b)較佳進一 步包含用彈性體溶液浸潰整個基底材 113535.doc 200829367 料。 在該方法之步驟（c)中，使浸潰於基底材料中之彈性體固 化之方式係使不織布中之彈性體固化。在本發明之一實施 例中’將基底材料放人目化溶液巾以進行固化。固化溶液 車^佳包含水中〇至4〇 wt%之二甲基甲醯胺。固化條件為熟 1此領域者所熟知。固化較佳在室溫及壓力下進行。The polishing pad of the present invention avoids the disadvantages of conventional polishing pads made of staple fibers. Since the long fibers can form a non-woven fabric without using the tape process or the needle-drawing process, uneven distribution of fibers, fiber aggregation, and fiber breakage due to such processes are avoided. Thereby, the elastomer of the present invention uniformly interferes with the nonwoven fabric. In addition, the unit size, hardness, uniformity, elastomer density, thickness, compression ratio, and recovery after compression of the fibers and elastomers are improved. The slurry can flow smoothly and the abrasive particles can spread evenly. The polishing pad of the present invention does not damage the surface of the substrate to be polished and the pilling is significantly reduced. Further, the polishing efficiency is satisfactory when the polishing pad of the present invention is applied. The present invention also provides a method of polishing a substrate. The method comprises the step of grinding the surface of the substrate using a polishing pad as mentioned above. The invention further provides a method of making a polishing pad as mentioned above. The method comprises the steps of: (a) providing a substrate material comprising a nonwoven fabric made of long fibers; (b) impregnating the surface of the substrate material with an elastomer solution; and (C) elastically impregnating the surface of the substrate material Body solidification. In the step (b) of the method, the method of impregnating the base material with the elastomer solution is a method of impregnating the nonwoven fabric with the elastomer solution. The impregnation conditions are well known to those skilled in the art. Suitable solvents for use in the elastomer solution include dimethylformamide (calendar). The elastomer solution optionally contains additives such as detergents. The concentration of the elastomer in the elastomer solution is preferably in the range of 2 Wt% to 60 wt%. Preferably, step (b) comprises impregnating the entire substrate with an elastomer solution 113535.doc 200829367. In step (c) of the method, the elastomer impregnated in the substrate material is cured in such a manner that the elastomer in the nonwoven fabric is cured. In one embodiment of the invention, the substrate material is placed in a solution to effect curing. The curing solution is preferably composed of hydrazine in water to 4% by weight of dimethylformamide. Curing conditions are cooked as is well known in the art. Curing is preferably carried out at room temperature and pressure.
在本發明之一較佳實施例中，製造研磨墊之方法進一步 包3在步驟（c)後洗滌基底材料之步驟（cl)。洗滌之目的係 自研磨墊移除殘餘物。在本發明之一實施例中，用水洗滌 且視;兄使用擠壓輪。洗滌條件為熟習此領域者所熟知。 # k在5G至9GC之水中洗務基底材料j接著使其經歷擠壓 製造研磨墊之方法進一步 之步驟（c2)。乾燥之目的 燥條件為熟習此領域者所 乾餘為空氣乾燥’且乾燥 在本發明之一更佳實施例中， 包含在步驟（cl)後乾燥基底材料 係自步驟（cl)移除過量溶劑。乾 熟知。在本發明之一實施例中， 溫度在loot：至16(TC之範圍内。 衣=研磨墊之方法較佳進—步包含機械研磨基底材料表 面及彈I*生體之步驟(c3)。舉例而言，機械研磨可使用噴砂 來元成。機械研磨之彳‘ /也& 傷之條件為热習此領域者所熟知。更佳在 機械研磨後纖維暴露於基底材料表面。 在本發月之較佳實施例中，重複步驟（b)及（c)數次。 每次使用之彈性體種類可不同或相同。 以下貝例僅為達成說明之目的且不意欲限制本發明之範 113535.doc •11- 200829367 * 嘴。 實例：In a preferred embodiment of the invention, the method of making a polishing pad further comprises the step (cl) of washing the substrate material after step (c). The purpose of the washing is to remove the residue from the polishing pad. In one embodiment of the invention, the water is washed and viewed; the brother uses a squeeze wheel. Washing conditions are well known to those skilled in the art. #k The substrate material j is washed in water of 5G to 9GC and then subjected to a further step (c2) of extrusion of the method for producing the polishing pad. Drying conditions are dry conditions for those skilled in the art to dry and dry in a preferred embodiment of the invention, including drying the substrate material after step (cl) to remove excess solvent from step (cl) . Well known. In one embodiment of the invention, the temperature is in the range of loot: to 16 (TC). The method of dressing = polishing pad preferably comprises the step of mechanically grinding the surface of the substrate material and the step of bombing the I* body (c3). For example, mechanical grinding can be performed using sand blasting. The conditions of mechanical grinding are also well known to those skilled in the art. It is better to expose the fibers to the surface of the substrate after mechanical grinding. In the preferred embodiment of the month, steps (b) and (c) are repeated several times. The type of elastomer used each time may be different or the same. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention 113535 .doc •11- 200829367 * Mouth. Example:
羞扁#存：將聚對苯二曱酸乙二酯碎片在260°C至300°C 下熔融紡絲且在室溫下淬火。接著使碎片經歷砑光機以獲 得具有10至150網目且具有0.7 mm之厚度及150 g/m2之重量 的基底材料。 锷欢#裘：切開織品以獲得網狀物。將數片網狀物安置 φ 好且接著用70丹尼爾之耐綸6(Nylon 6)紗線編織以獲得具 有0.15 mm之厚度及35 g/m2之重量的30網目薄片。接著將 薄片針刺（每平方公尺700次）以獲得具有475 g/m2之重量的 網狀框架。 浸滂：將基底材料浸潰於具有700至850 Cps之黏度的彈 性體溶液中。彈性體溶液包含50 wt%之聚胺酷、49 wt%之 二甲基甲醯胺及1 wt%之清潔劑。 思Vfc :在浸潰後，將基底材料放入包含水中25\¥丨％之二 • 甲基甲醯胺之固化溶液中以使浸潰於纖維中之彈性體成 型。 遂瀠：藉由擠壓輪移除殘餘物及過量固化溶液。接著將 基底材料在80°C之水中洗滌且接著使其經歷擠壓輪數次。 乾# :在洗滌後，接著將基底材料在140°C下乾燥。 研蘑：在乾燥後，使基底材料經歷使用#150及#400砂紙 在1200及1300 rpm下之機械研磨，且獲得具有平坦表面之 1.28 mm產品。 • 獪定：檢定本發明之具有長纖維之研磨墊（長纖維）及具 113535.doc -12- 200829367 β 有短纖維之習知研磨墊（短纖維）且結果顯示於表1中。與習 知研磨墊相比，本發明之研磨墊之壓縮比及壓縮後回復率 均得到改良。 表1 : 厚度(mm) 壓縮比(％) 壓縮後回復率(％) 長纖維 1.40 19.63 92.34 短纖維 1.35 15.99 89.67 上述實施例僅為說明本發明之原理及其功效，而非限制 本發明。本發明所屬技術領域中具通常知識者對上述實施 例所做之修改及變化仍不違背本發明之精神。本發明之權 利範圍應如後述之申請專利範圍所列。Shy flat #存: The polyethylene terephthalate fragments were melt spun at 260 ° C to 300 ° C and quenched at room temperature. The chips were then subjected to a calender to obtain a substrate material having 10 to 150 meshes and having a thickness of 0.7 mm and a weight of 150 g/m2.锷欢#裘: Cut the fabric to obtain a mesh. A number of webs were placed φ and then woven with 70 denier Nylon 6 yarns to obtain a 30 mesh sheet having a thickness of 0.15 mm and a weight of 35 g/m2. The sheet was then needled (700 times per square meter) to obtain a mesh frame having a weight of 475 g/m2. Dipping: The substrate material is immersed in an elastomer solution having a viscosity of 700 to 850 Cps. The elastomer solution contained 50 wt% of polyamine, 49 wt% of dimethylformamide and 1 wt% of detergent. Vfc: After impregnation, the base material is placed in a solidified solution containing 2% methylformamide in water to form an elastomer impregnated into the fiber.遂潆: The residue and excess curing solution are removed by a squeeze wheel. The substrate material was then washed in water at 80 ° C and then subjected to a squeeze wheel several times. Dry #: After washing, the base material was then dried at 140 °C. Mushrooms: After drying, the substrate material was subjected to mechanical grinding at 1200 and 1300 rpm using #150 and #400 sandpaper, and a 1.28 mm product having a flat surface was obtained. • Determination: A conventional polishing pad (long fiber) having a long fiber of the present invention and a conventional polishing pad (short fiber) having a short fiber of 113535.doc -12-200829367 β were examined and the results are shown in Table 1. The compression ratio of the polishing pad of the present invention and the recovery rate after compression are improved as compared with the conventional polishing pad. Table 1: Thickness (mm) Compression ratio (%) Recovery rate after compression (%) Long fiber 1.40 19.63 92.34 Short fiber 1.35 15.99 89.67 The above examples are merely illustrative of the principles of the invention and its effects, and are not intended to limit the invention. Modifications and variations of the embodiments described above will be apparent to those skilled in the art without departing from the scope of the invention. The scope of the invention should be as set forth in the appended claims.
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