200909137 九、發明說明： 【先前技術】 化干機械研磨(”CMP”)製程用於微電子裝置製造中以於 半導體晶圓、場發射顯示器及諸多其他微電子工件上形成 平-表Φ舉例而δ，半導體裝置之製造通常涉及形成各 處理層、選擇性去除或圖案化部分彼等層及於一半導體工 件之表面上沈積其他處理層以形成半導體晶圓。該等處理 r ν./ 層可包括（舉例而言）絕緣層、閘極氧化物層、導電層、及 金屬或玻璃層等。在晶圓製程中之某些步驟中一般期望處 理層之最上部表面係平的（即平坦）以用於隨後層之沈積。 CMP係用於平面化各處理層，其令研磨一經沈積之材料 (例如，導電或絕緣材料)來平面化晶圓，以用於隨後的製 程步驟。 在典型CMP製程中，將一晶圓正面朝下安褒至CMP工 2中之載具上。-力推動該載具及該晶圓向下移向—研磨 塾。該載具及該晶圓均T ^ & 於⑽工具的研磨臺上旋轉的研 摇上方旋轉。在研磨製程期間’通常將研磨 2研磨劑）引入旋轉晶圓及旋轉研磨塾之間。該研磨组 々 質(其與部分晶圓最頂層相互作用 或將其溶解）及一研磨材料（其以物理 J.B u 式去除部分該層）。 根據欲實施的特定研磨製程 同方向或相反方向上旋轉。圓與研磨塾可於相 狀得。*亥载具亦可在研廏喜 研磨墊上振蕩。該製程自晶 、整個 地達成-平坦表面。 移除口忍之材料量且理想 130811.doc 200909137 ⑽研磨墊通常包括兩層或更多層，舉例而言一研磨層 氐(例如子墊)層。多層研磨墊通常藉由層壓兩個或多 個不同材料層而形成。舉例而言，-習用兩層研磨墊包括 :剛性研磨層及-可壓縮較柔軟子塾層兩者以改良經研磨 圓之平i— H及均勾性。可藉由藉助—黏合劑層麈該等研 磨墊層^/成該等層間之結合。在（舉例而言）美國專利第 5,2 5 7,478號中揭示此一多層研磨塾。 傳統上，藉由一壓敏黏合劑（PSA)或熱熔黏合劑（HMA) 將夕個研磨墊層結合在一起。壓敏黏合劑具有相對差之耐 化學性且在研磨期間可能易於被高pH值之研磨劑弱化。黏 δ背|失效可引起在研磨期間各研磨墊層分離（即脫層），導 致研磨墊無法用於研磨。雖然熱熔黏合劑通常具有較好之 耐化學性，但熱熔黏合劑通常具有較低之耐熱性，導致在 較高之研磨溫度下脫層。諸多CMP研磨應用涉及高達7(rc 之温度，因而用於一研磨墊之黏合劑具有一相對高之耐熱 性係重要。 熱熔黏合劑材料通常包括選自由聚烯烴、乙烯_乙酸乙 烯醋、聚醯胺、《、聚亞安s旨及聚氯乙烯構成之群組的 熱塑性或熱固性材料（參見例如美國專利第6,422,92i及 6,905,402號）。 熱熔黏合劑之結合強度可以"T-剝離”強度為表徵（參見例 如美國專利第4,788,798號）。可根據美國測試及材料協會 (ASTM)所陳述之測試（其係AStm D1876 (2001))來執行τ 剝離測試。該測試量測該黏合劑之剥離黏附力。剝離黏附 13081I.doc 200909137 力係以一特定角度及速度自一標準測試面板移除一測試樣 本時每一單位寬度所需之力。介面破裂係一不可逆轉之熵 形成過程，其涉及大量的能量消散。標準τ剝離測試以一 恆定速率增加施加至樣本之力，直至自測試面板上移除樣 本’藉此確定剝離樣本所需之力。 頒予 Wilmington、Delaware2R〇hm & Haas Electronic Materials CMP H〇ldings公司之美國專利7ι〇ΐ 275號（下文 稱作"’275專利”）主張一種利用在一 3〇5 mm/min2研磨速 度下呈現至少大於4〇牛頓（N)力之T-剝離強度之衆多習知 熱熔黏合劑中之任一者之研磨墊（c〇1 6，丨_3行）^雖然 2 7 5專利旦稱.作為該熱溶黏合劑性質之一結果，所揭 示研磨墊係一 ”較先前技術研磨墊更有復原力之研磨墊 (4 12_ 1 3行），但” ’275專利"所提及之熱熔黏合劑係 先前技術所用黏合劑之大體相同類別，並未提供優於先前 技術所用黏合劑之優點，且因此未提供—具有改良之抗脫 層性之研磨墊。舉例而言，美國專利第6,422,921號（下文 稱作92 1專利”）揭示適合使用於該等研磨墊中之大致相 同類別之熱熔黏合劑（比較，921專利，c〇1. 3、22_24行與 275專利，c〇1. 3、33_36行）。雖然該等熱熔黏合劑當根據 ’2乃專利之揭示内容應用至一研磨墊且進行測試時，呈現 甚同於’275專利中所述最小T_剝離強度之平均τ_剝離強 度，但應用此黏合劑之研磨墊在使用期間仍可能脫層，尤 其在高溫研磨應用中。 在研磨期間，存在諸多影響墊脫層之變量。舉例而古， 130811.doc 200909137 打破一黏合劑結合所需之力相依於黏合劑類型、研磨程序 之製程條件及執行研磨程序所處之溫度。具體^， 磨期間施加至研磨晶圓上之麼力及在研磨期間所用之化風 品兩者皆會引起剪切應力及摩擦應力。剪切應力可有宝： 影響熱溶黏合劑之效能’且諸多㈣此黏合劑之研磨塾在 研磨期間均經受剪切變形。τ_剝離測試不必對剪切應力進 行說明，I因此不必始終提供對熱熔黏合劑之結合強度之 準確論斷。 【發明内容】 本發明提供一用於化學機械研磨之研磨墊，其包括： 一研磨層，及（b)—底層，其中該底層與該研磨層大致共同 擴張，及（C) 一熱熔黏合劑，其中該熱熔黏合劑使該研磨層 與邊底層結合在一起，且該熱熔黏合劑包括介於2與工8 Wt.%間之乙烯-乙酸乙烯酯或丙烯酸乙基乙烯基酯（共同稱 作”EVA”）且當該研磨層達到一 40〇c之溫度時該黏合劑大致 抗脫層。 本發明亦提供一種研磨一基板之方法，其包括：（i)提供 一用於化學機械研磨之研磨墊，該研磨墊包括：（a)_研磨 層；（b)—底層，其中該底層與該研磨層大致共同擴張；及 (c) 一熱熔黏合劑，其中該熱熔黏合劑使該研磨層與該底層 結合在一起’該熱熔黏合劑包括介於2與18 wt.%間之EVA 且當該研磨層達到一 40°C之溫度時黏合劑大致抗脫層； (ii)使該基板接觸該研磨墊及一研磨組合物；及（iii)相對於 該基板移動該研磨墊及研磨組合物以使用該研磨墊磨蝕該 130811.doc 200909137 基板表面之至少一部分而研磨該基板。200909137 IX. INSTRUCTIONS: [Prior Art] The Dry Mechanical Grinding ("CMP") process is used in the manufacture of microelectronic devices to form flat-table Φ on semiconductor wafers, field emission displays, and many other microelectronic workpieces. δ, fabrication of a semiconductor device typically involves forming a respective processing layer, selectively removing or patterning portions of the layer, and depositing other processing layers on the surface of a semiconductor workpiece to form a semiconductor wafer. The treatment r ν./ layer may include, for example, an insulating layer, a gate oxide layer, a conductive layer, and a metal or glass layer. It is generally desirable in certain steps in the wafer process that the uppermost surface of the processing layer be flat (i.e., flat) for deposition of subsequent layers. The CMP is used to planarize the various processing layers by polishing a deposited material (e.g., a conductive or insulating material) to planarize the wafer for subsequent processing steps. In a typical CMP process, a wafer is mounted face down on a carrier in CMP 2 . - Force the carrier and the wafer to move downwards - grinding 塾. The carrier and the wafer are both rotated and rotated over the grinding of the (10) tool's grinding table. During the polishing process, the abrasive 2 is typically introduced between the rotating wafer and the rotating abrasive crucible. The abrasive set is enamel (which interacts with or dissolves the topmost layer of the wafer) and an abrasive material (which removes a portion of the layer by physical J.B u). Rotate in the same direction or in the opposite direction depending on the specific grinding process to be implemented. The circle and the abrasive crucible can be obtained in phase. *Hai vehicle can also oscillate on the grinding pad. The process achieves a flat surface from the crystal and the entire surface. The amount of material to be torn is removed and ideally 130811.doc 200909137 (10) The polishing pad typically comprises two or more layers, for example a layer of abrasive layer (e.g., a sub-pad). Multilayer polishing pads are typically formed by laminating two or more layers of different materials. For example, conventional two-layer polishing pads include: a rigid abrasive layer and a compressible softer sub-layer to improve the flatness i-H and uniformity of the ground circle. The polishing mats can be bonded to each other by means of a binder layer. This multilayer abrasive crucible is disclosed in, for example, U.S. Patent No. 5,257,478. Traditionally, a polishing pad has been bonded together by a pressure sensitive adhesive (PSA) or a hot melt adhesive (HMA). Pressure sensitive adhesives have relatively poor chemical resistance and may be susceptible to weakening by high pH abrasives during milling. Viscosity δ back|failure can cause separation of the polishing pads during polishing (ie, delamination), rendering the polishing pads unusable for grinding. Although hot melt adhesives generally have better chemical resistance, hot melt adhesives generally have lower heat resistance, resulting in delamination at higher grinding temperatures. Many CMP grinding applications involve temperatures of up to 7 (rc, so adhesives for a polishing pad have a relatively high heat resistance. Hot melt adhesive materials typically include those selected from the group consisting of polyolefins, ethylene-vinyl acetate, and poly A thermoplastic or thermosetting material of the group consisting of decylamine, "poly", and polyvinyl chloride (see, for example, U.S. Patent Nos. 6,422, 92i and 6,905,402). The bonding strength of the hot-melt adhesive can be "T-stripping "Intensity is a characterization (see, e.g., U.S. Patent No. 4,788,798). The τ peel test can be performed according to the test stated by the American Society for Testing and Materials (ASTM) (which is AStm D1876 (2001)). The test measures the adhesive. Peel adhesion. Stripping adhesion 13081I.doc 200909137 Force is the force required per unit width when removing a test sample from a standard test panel at a specific angle and speed. Interface rupture is an irreversible entropy formation process, It involves a large amount of energy dissipation. The standard τ peel test increases the force applied to the sample at a constant rate until the sample is removed from the test panel. The force required for the sample. Wilmington, Delaware 2R〇hm & Haas Electronic Materials CMP H〇ldings, US Patent 7 〇ΐ 275 (hereinafter referred to as " '275 Patent") claims a use in a 3 〇 A polishing pad of any of the many conventional hot-melt adhesives exhibiting a T-peel strength of at least 4 Newtons (N) force at a grinding speed of 5 mm/min2 (c〇1 6, 丨_3 rows)^ Although the result of the hot-melt adhesive is one of the properties of the hot-melt adhesive, the disclosed polishing pad is a more resilient polishing pad (4 12_ 1 3 rows) than the prior art polishing pad, but "275 The hot melt adhesives referred to in the patents are generally of the same type as the binders used in the prior art, and do not provide advantages over the binders used in the prior art, and thus do not provide a polishing pad having improved delamination resistance. For example, U.S. Patent No. 6,422,921 (hereinafter referred to as the "92 1 patent") discloses a substantially the same type of hot-melt adhesive suitable for use in such polishing pads (Comparative, 921 Patent, c 〇 1. 3, 22_24) Line with 275 patent, c〇1. 3, 33_ 36 lines). Although these hot melt adhesives are applied to a polishing pad and tested according to the disclosure of '2, the average τ_peeling of the minimum T_peel strength described in the '275 patent is presented. Strength, but the abrasive pad using this adhesive may still delaminate during use, especially in high temperature grinding applications. During the grinding process, there are many variables that affect the delamination of the pad. For example, ancient, 130811.doc 200909137 breaking a binder The force required for bonding depends on the type of adhesive, the process conditions of the grinding process, and the temperature at which the grinding process is performed. Specifically, both the force applied to the polished wafer during the grinding and the chemical used during the grinding cause shear stress and frictional stress. Shear stress can be cherished: affecting the effectiveness of hot melt adhesives' and many (d) the abrasive mash of this adhesive undergoes shear deformation during grinding. The τ_peel test does not have to account for shear stress, so it is not necessary to always provide an accurate assertion of the bond strength of the hot melt adhesive. SUMMARY OF THE INVENTION The present invention provides a polishing pad for chemical mechanical polishing, comprising: an abrasive layer, and (b) an underlayer, wherein the underlayer substantially expands together with the abrasive layer, and (C) a hot melt bond And the hot-melt adhesive bonding the abrasive layer to the edge layer, and the hot-melt adhesive comprises ethylene-vinyl acetate or ethyl vinyl acrylate between 2 and 8 Wt.% ( Together referred to as "EVA") and when the abrasive layer reaches a temperature of 40 〇c, the adhesive is substantially resistant to delamination. The present invention also provides a method of polishing a substrate, comprising: (i) providing a polishing pad for chemical mechanical polishing, the polishing pad comprising: (a) an abrasive layer; (b) an underlayer, wherein the underlayer The abrasive layer is substantially coextensive; and (c) a hot melt adhesive, wherein the hot melt adhesive bonds the abrasive layer to the bottom layer. The hot melt adhesive comprises between 2 and 18 wt.%. EVA and the binder is substantially resistant to delamination when the polishing layer reaches a temperature of 40 ° C; (ii) contacting the substrate with the polishing pad and a polishing composition; and (iii) moving the polishing pad relative to the substrate and The composition is ground to abrade the substrate using at least a portion of the surface of the 130811.doc 200909137 substrate using the polishing pad.
本發明進一步提供一種製備一用於一基板之化學機械研 磨之研磨墊之方法’其包括：⑴提供一用於化學機械研磨 之研磨墊’該研磨墊包括：（a)—研磨層；及（b)—底層， 其中該底層與該研磨層大致共同擴張；及（ii)使用一熱溶 黏合劑層壓該研磨層與該底層之至少一者，其中該熱溶黏 合劑使該研磨層與該底層結合在一起，且其中該熱炼黏合 劑包括介於2與18 wt.%間之EVA且當該研磨層達到一4〇t»c 之溫度時該黏合劑大致抗脫層。 【實施方式】 本發明提供一種用於研磨基板之化學_機械研磨墊。該 研磨墊包括：一研磨層、一底層，其中該底層大致與該研 磨層共同擴張；及一熱熔黏合劑。該熱熔黏合劑使該研磨 層與该底層結合在一起。該熱熔黏合劑包括介於^與“ wt/。間之乙烯_乙酸乙烯酯或丙烯酸乙基乙烯基酯（共同稱 作"EVA”）且在該研磨層達到一仰艺之溫度時，能大致抵抗 脫層。 一 該研磨墊之研磨層可係任何合適之研磨層。合意地，該 研磨層與該底層大致共同擴[該研磨塾之研磨層視需要 包括凹槽、通道及/或穿孔。該等特徵結構可促進一研磨 組合物跨研磨層表面之橫向運輸。該等凹槽、通道或穿孔 可為任何適宜型樣且可具有任何適宜之深度及寬度。該研 磨層可具有兩種或以上不同的凹槽型#，例如美國專利第 5,彻，加號中利述之大凹槽與小凹槽之組合。該等凹槽 130811.doc 200909137 可呈線性凹槽、斜凹槽、同心槽、螺旋狀或圓形凹槽或乂 γ交叉型樣之形式，且在連續性上可為連續或不連續。 研磨塾之底層(即子塾)可係任何合適之底層。合意地， 該底層與該研磨層大致共同擴張。 該研磨塾視需要進-步包括—個或多個設置於該研磨層 與底層之間的中間層。視需$，該研磨墊包括三個或更； 個（例如四個或更多個 '六個或更多個、或八個或更多個） 設置於該研磨層與底層之間的層。通常，該研磨墊包括十 個或更少（八個或更少’或六個或更少）的設置於該研磨層 與底層之間的層。 研磨墊之該（或該等）中間層可係任何合適層。合意地， 該(或該等)中間層中之每一者與該研磨層及該底層：致共 同擴張。較佳地使用熱溶黏合劑使該研磨層、底層及該 (或該等）中間層之每一者結合在一起。 該多層研磨墊材料之優點係每一層均可具有不同的物理 或化學性質。舉例而言’在某些應用巾，可能期望每一層 具有相同的化學組合物但具有不同的物理性質，例如，硬 度、密度、孔隙率、壓縮性、剛性、拉伸模量、體積彈性 模量、流變性、蠕變'玻璃化轉變溫度、熔融溫度、黏度 或透明度。在其他應用巾，可能期望研磨墊之各層具有相 似的物理性質但不同的化學性質(例如，+同的化學組合 物）。當然，研磨墊層可既具有不同的化學性質亦具有不 同的物理性質。 研磨墊之各層可係任何合適之層。該研磨墊中之每一層 130811.doc -11 - 200909137 可均為親水、疏水或該兩者之組合。該研磨墊t之每一層 視需要含有粒子，例如倂入該層中之粒子。該等粒子可係 研磨；=)]粒子、聚合物粒子、合成粒子（例如經囊封之粒 子）、有機物粒子、無機物粒子、淨化粒子、水溶性粒子 及其混合物。舉例而言，在美國專利第6,884，156及 7’〇59,936號中說明合適粒子。The present invention further provides a method of preparing a chemical mechanical polishing pad for a substrate comprising: (1) providing a polishing pad for chemical mechanical polishing comprising: (a) an abrasive layer; b) an underlayer, wherein the underlayer is substantially coextensive with the abrasive layer; and (ii) at least one of the abrasive layer and the underlayer is laminated using a hot melt adhesive, wherein the hot melt adhesive causes the abrasive layer to The bottom layer is bonded together, and wherein the heat-curing adhesive comprises between 2 and 18 wt.% EVA and the adhesive is substantially resistant to delamination when the abrasive layer reaches a temperature of 4 〇t»c. [Embodiment] The present invention provides a chemical-mechanical polishing pad for polishing a substrate. The polishing pad comprises: an abrasive layer, a bottom layer, wherein the bottom layer is substantially coextensive with the polishing layer; and a hot melt adhesive. The hot melt adhesive bonds the abrasive layer to the bottom layer. The hot-melt adhesive includes an ethylene-vinyl acetate or ethyl acrylate (co-called "EVA") between "wt/." and when the polishing layer reaches a temperature of a certain temperature, Can resist the delamination. An abrasive layer of the polishing pad can be any suitable abrasive layer. Desirably, the abrasive layer is substantially coextensive with the bottom layer [the abrasive layer of the abrasive layer optionally includes grooves, channels, and/or perforations. These features promote lateral transport of an abrasive composition across the surface of the abrasive layer. The grooves, channels or perforations can be of any suitable type and can have any suitable depth and width. The abrasive layer can have two or more different groove types #, such as the combination of large grooves and small grooves as described in U.S. Patent No. 5, the entire disclosure of which is incorporated herein by reference. The grooves 130811.doc 200909137 may be in the form of linear grooves, oblique grooves, concentric grooves, spiral or circular grooves or γ γ cross patterns, and may be continuous or discontinuous in continuity. The bottom layer of the abrasive crucible (ie, the crucible) can be any suitable underlayer. Desirably, the underlayer and the abrasive layer expand substantially together. The polishing squeezing step further includes one or more intermediate layers disposed between the polishing layer and the underlayer. Optionally, the polishing pad comprises three or more (e.g., four or more 'six or more, or eight or more) layers disposed between the abrasive layer and the bottom layer. Typically, the polishing pad comprises ten or fewer (eight or fewer 'or six or fewer) layers disposed between the abrasive layer and the bottom layer. The (or such) intermediate layer of the polishing pad can be any suitable layer. Desirably, each of the (or the) intermediate layers is coextensive with the abrasive layer and the bottom layer. Preferably, each of the abrasive layer, the primer layer and the (or the intermediate layer) are bonded together using a hot melt adhesive. The advantages of the multilayer polishing pad material are that each layer can have different physical or chemical properties. For example, 'in some applications, it may be desirable for each layer to have the same chemical composition but have different physical properties, such as hardness, density, porosity, compressibility, stiffness, tensile modulus, bulk modulus of elasticity. , rheology, creep 'glass transition temperature, melting temperature, viscosity or transparency. In other applications, it may be desirable for the layers of the polishing pad to have similar physical properties but different chemical properties (e.g., + the same chemical composition). Of course, the polishing pad layer can have both different chemical properties and different physical properties. The layers of the polishing pad can be any suitable layer. Each of the layers of the polishing pad 130811.doc -11 - 200909137 may be hydrophilic, hydrophobic or a combination of the two. Each layer of the polishing pad t optionally contains particles, such as particles that are incorporated into the layer. The particles may be ground; =) particles, polymer particles, synthetic particles (e.g., encapsulated particles), organic particles, inorganic particles, purified particles, water-soluble particles, and mixtures thereof. Suitable particles are described in, for example, U.S. Patent Nos. 6,884,156 and 7'59,936.
該研磨墊之每一層均可具有任何適宜之硬度（例如，3〇_ 5〇蕭氏A或25-80蕭氏D)。同樣地，該等層可具有任何適宜 之密度及/或孔隙率。舉例而言，該等層中之每一者均可 無孔（例如，實體）、近似實體（例如，具有小於之孔 體積）、或多孔，且可具有〇.3克/立方公分或以上（例如 隙 〇.5克/立方公分或以上或〇.7克/立方公分或以上）或甚至〇 9 克/立方公分或更高（例如，1.丨克/立方公分或更高，或達 到該材料理論密度的99%)之密度。就某些應用而言，可能 期望研磨㈣料之—層或多層（例如’研磨層）係硬質、緻 密及/或具有車交低的孔隙帛，而其他（各）層絲質、高孔隙 度及/或具有較低的密度。 該研磨塾之該等層中之每一者均可具有任何合適之厚 度。較佳地，每-層均具有-為研磨塾材料總厚度之至少 10%或以上（例如’ 20。/。或以上’或观或以上）。每一層厚 度部分地取決於研磨塾之總層數。而日 叫丑’ έ亥等研磨墊層中 之兩個或更多個（例如所有）可具有相同 π尽度或該等層可具 有一不同厚度。 步包括一光學端點 該等研磨墊層中之每一者視需要進_ 130811.doc •12- 200909137 偵測埠。合意地’該多層研磨墊中之每一 鈿點偵測埠，且該等光學端點债測痒大致對準。该光= 點偏測埠可係—個或多個縫隙、透明區域或半透明: (例如’如美國專利第5,893,796號中所闡述的窗口）。1研 磨塾與原位CMP製程監視技術聯合使用時，包含該等：隙 或=透明區域（即光學透射區域）較為理想。此項技術中已 知精由分析自工件一表面上反射之光或其他轄射來檢查及 監視研磨製程之技術。㈣而言，在美國專利第 5,196,353 ^ 5,433,651 . 5,609,511 . 5,643,046 . 5,658,183 ^ 5,730,642 > 5,838,447 > 5,893,796 ^ 5,949,927^ 5,964,643 號中描述該等方法。合意地，對正研磨I件之研磨製程進 度所Λ %之檢查或監視能夠決定研磨終點，即，決定何時 結束一特定工件之研磨製程。 該縫隙可具有任何適宜之形狀且可與與疏排通道組合使 用，以最大程度地減小或消除研磨表面上過量的研磨組合 物。光學透射區域可係此項技術中所習知的諸多窗口中之 任何合適窗口。舉例而言，該光學透射區域可包括一插入 該研磨墊之一縫隙中之以玻璃或聚合物為主之插頭或可包 括用於研磨墊剩餘部分中之相同聚合材料。通常，光學透 射區域在介於自190 nm至10,000 nm間（例如自19〇 1^至 3500 nm、自 200 11111至 1000 nm或自 2〇〇 nm至 780 nm)之一 個或多個波長處具有10%或更多（例如2〇%或更多、或3〇0/〇 或更多）之光透射率。 光學透射區域可具有任何合適結構，例如結晶度、密度 I30811.doc 13 200909137 及孔隙率。舉例而言，該光學透射區域可係實體或多孔， 例如多微孔或毫微孔。較佳地，該光學透射區域係實體或 接近實體（例如，具有3%或以下之空隙率）。該光學透射區 域視需要進一步包括選自聚合物粒子、無機物粒子及其組 合中之粒子。光學透射區域視需要含有孔。 该光學透射區域視需要進一步包括一染料，其使研磨墊 之基板材料選擇性地透射一特定波長之光。該染料濾除不 期望的波長的光（例如’背景光），且因此改良偵測之訊雜 比。該光學透射區域可包括任一適宜之染料，或可包括若 干種染料之組合。適宜之染料包括聚次曱基染料、二芳基 及二芳基次甲基染料、二芳基次甲基染料之氮雜類似物、 氮雜（1 8)輪烯染料、天然染料、硝基染料、亞硝基染料、 偶氮染料、蒽醌染料、硫化染料及其類似物。較佳該染料 之透射光譜與用於原位終點偵測之光波長相匹配或重疊。 舉例而言’當用於終點偵測（EPD)系統之光源係HeNe雷射 時’其產生波長為633奈米之可見光，則該染料較佳為紅 色染料’其能夠透射波長為633奈米的光。 該熱熔黏合劑可係任何合適的熱熔黏合劑。該熱熔黏合 劑包括介於2與1 8 wt.%之乙烯-乙酸乙烯酯或丙烯酸乙基乙 烯基酯（共同稱作"EVA")。特定而言，該EVA可以1 8 wt.% 或更少之量存在於熱熔黏合劑中，例如i 6 wt.%或更少、 15 wt.%或更少、12 wt.%或更少、11 wt.%或更少、10 wt_%或更少、8 wt·%或更少、5 wt·%或更少、或3 wt·%或 更少。另一方面，該EVA可以2 wt.%或更多之量存在於熱 1308Il.doc -14· 200909137 溶黏合劑中，例如3 wt·%或更多、5 wt %或更多、8 wt% 更多、10 wt. %或更多、12 wt·%或更多、或15 Wt·%或更 多。舉例而言，該 EVA可以 3-15 wt.%、5-11 wt.%、8-10 wt.%、或12-16 wt·%之量存在於熱熔黏合劑中。 已出乎意料地發現：含有介於2與18 wt.%間之EVA之熱 黏u劑在CMP期間呈現高对化學性及财熱性且因此呈現 南抗脫層性。合意地’當研磨層達到一 4(rc (例如45( ’ 5〇°C，55°C，6(TC，65°C，70°C，75°C，8〇t，85°C，90 C 9 5 C，及1 0 0 C )之溫度時，該熱炫黏合劑層大致呈抗 脫層性。 根據本發明之一熱熔黏合劑之耐熱性可藉由一剪切黏附 力或固持力測試來量測。固持力以升高的溫度且在剪切狀 態下提供一精確的黏合劑強度預測。如本文所用，固持力 係在規定之測試條件下沿_平行於—標準平坦表面之方向 在彼表面上滑動-㈣樣本區域所需之時間。固持力係在Each layer of the polishing pad can have any suitable hardness (e.g., 3 〇 5 〇 Xiao A or 25-80 Xiao D). Likewise, the layers can have any suitable density and/or porosity. For example, each of the layers can be non-porous (eg, solid), approximate entity (eg, having a pore volume less than), or porous, and can have a thickness of 克3 g/cm 3 or more ( For example, a gap of .5 g/cm 3 or more or 〇.7 g/cm 3 or more) or even 〇 9 g/cm 3 or higher (for example, 1. gram / cubic centimeter or higher, or up to Density of 99% of the theoretical density of the material. For some applications, it may be desirable to have a layer or layers of abrasive (four) layers (eg, 'abrasive layers') that are hard, dense, and/or have low porosity, while other layers are silky, highly porous. And / or have a lower density. Each of the layers of the abrasive crucible can have any suitable thickness. Preferably, each layer has - at least 10% or more of the total thickness of the abrasive material (e.g., < 20% or more or more or more). The thickness of each layer depends in part on the total number of layers of the abrasive crucible. Two or more (e.g., all) of the polishing mats may be of the same π degree or the layers may have a different thickness. The step includes an optical endpoint. Each of the polishing pads is in need of _ 130811.doc • 12- 200909137 detection. Desirably, each of the plurality of polishing pads detects flaws, and the optical endpoints are generally aligned. The light = point bias can be one or more slits, transparent regions or translucent: (e.g., the window as set forth in U.S. Patent No. 5,893,796). 1 Research In combination with in-situ CMP process monitoring technology, it is desirable to include such: gap or = transparent region (ie, optical transmission region). Techniques for inspecting and monitoring the grinding process by analyzing light reflected from a surface of a workpiece or other nucleation are known in the art. (d) The methods are described in U.S. Patent Nos. 5,196,353, 5,433,651, 5,609, 5, 5,643,046, 5, 658, 183, 5, 730, 642, 5, 838, 447, 5, 893, 796, 5, 949, 927, 5, 964, 643. Desirably, the inspection or monitoring of the grinding process progress of the grinding of the I piece can determine the end point of the grinding, i.e., the grinding process that determines when a particular workpiece is to be finished. The slit can have any suitable shape and can be used in combination with the evacuation channel to minimize or eliminate excess abrasive composition on the abrasive surface. The optically transmissive area can be any suitable window among the many well known in the art. For example, the optically transmissive region can comprise a glass or polymer based plug inserted into one of the pads of the polishing pad or can comprise the same polymeric material used in the remainder of the polishing pad. Typically, the optically transmissive region has at one or more wavelengths from 190 nm to 10,000 nm (eg, from 19〇1^ to 3500 nm, from 20011111 to 1000 nm, or from 2〇〇nm to 780 nm) Light transmittance of 10% or more (for example, 2% or more, or 3〇0/〇 or more). The optically transmissive region can have any suitable structure, such as crystallinity, density I30811.doc 13 200909137, and porosity. For example, the optically transmissive region can be solid or porous, such as microporous or nanoporous. Preferably, the optically transmissive region is physically or nearly close to the entity (e.g., having a void ratio of 3% or less). The optically transmissive region further includes particles selected from the group consisting of polymer particles, inorganic particles, and combinations thereof, as needed. The optically transmissive area contains pores as needed. The optically transmissive region further includes, if desired, a dye that selectively transmits the substrate material of the polishing pad to a particular wavelength of light. The dye filters out light of undesirable wavelengths (e. g., 'backlight) and thus improves the signal to noise ratio of the detection. The optically transmissive region can comprise any suitable dye or can comprise a combination of several dyes. Suitable dyes include poly-decyl dyes, diaryl and diaryl methine dyes, aza analogs of diaryl methine dyes, aza (18) olefin dyes, natural dyes, nitro Dyes, nitroso dyes, azo dyes, anthraquinone dyes, sulfur dyes and the like. Preferably, the transmission spectrum of the dye matches or overlaps with the wavelength of light used for in situ endpoint detection. For example, 'When the source for the endpoint detection (EPD) system is a HeNe laser, which produces visible light with a wavelength of 633 nm, the dye is preferably a red dye that is capable of transmitting a wavelength of 633 nm. Light. The hot melt adhesive can be any suitable hot melt adhesive. The hot melt adhesive comprises between 2 and 18 wt.% ethylene vinyl acetate or ethyl vinyl acrylate (collectively "EVA"). In particular, the EVA may be present in the hot melt adhesive in an amount of 18 wt.% or less, such as i 6 wt.% or less, 15 wt.% or less, 12 wt.% or less. 11 wt.% or less, 10 wt% or less, 8 wt.% or less, 5 wt.% or less, or 3 wt.% or less. On the other hand, the EVA may be present in the heat 1308Il.doc -14.200909137 solvent in an amount of 2 wt.% or more, such as 3 wt.% or more, 5 wt% or more, 8 wt%. More, 10 wt.% or more, 12 wt.% or more, or 15 Wt·% or more. For example, the EVA can be present in the hot melt adhesive in an amount of 3-15 wt.%, 5-11 wt.%, 8-10 wt.%, or 12-16 wt.%. It has been unexpectedly discovered that a thermal adhesive containing EVA between 2 and 18 wt.% exhibits high chemical and thermal properties during CMP and thus exhibits south delamination resistance. Desirably 'When the abrasive layer reaches a 4 (rc (eg 45 (' 5 ° ° C, 55 ° C, 6 (TC, 65 ° C, 70 ° C, 75 ° C, 8 ° t, 85 ° C, 90 The heat-curing adhesive layer is substantially resistant to delamination at a temperature of C 9 5 C, and 100 ° C. The heat resistance of the hot-melt adhesive according to the present invention can be maintained by a shear adhesion or retention. Force test to measure. The holding force provides an accurate prediction of the strength of the adhesive at elevated temperatures and under shear. As used herein, the holding force is along the _parallel to the standard flat surface under specified test conditions. The direction of sliding on the surface - (d) the time required for the sample area.
一規定負載下在"規定時間量後量測樣本所移動之毫米量 的恒負載蠕變測試。 用於本發明背景中之熱炫黏合劑之相對高之固持力在高 達100。。之研磨溫度下展示黏合劑之耐熱性。舉例而言， 在40°C且在1 kg負載之臃七 | ] 戰之應力下達1小時，該熱熔黏合劑移 動0.2 mm或更少，例如〇 1 c * , 例如0.15 mm或更少、〇1 mm或更少、 0.05 mm或更少、或 一 。在相同溫度及相關應力下24小 時後’該熱溶黏合劑蒋叙Λ ς V> s J移動〇.5 mm或更少，例如0.4 mm或更 少、0.3 mm或更少、〇 9 .. s . 0.2 mm或更少、（μ mm或更少、或〇 130811.doc • 15· 200909137 mm。舉例而言，在60 °C且在1 kg負載之應力下達1個小 時’該熱溶黏合劑移動〇.2 mm或更少，例如〇. 1 5 mm或更 少、0.1 mm或更少、0.05 mm或更少、或〇 mm。在相同溫 度且在相同應力下24小時後，該熱熔黏合劑移動〇.5 mm或 更少，例如0.4 mm或更少、0.3 mm或更少、0.2 mm或更 少、0· 1 mm或更少、或0 mm。舉例而言，在8〇。〇下且在1 kg負載之應力下達1個小時，該熱熔黏合劑移動〇.5 mm或 更少、例如0.4 mm或更少、0.3 mm或更少、0.2 mm或更 少、0 · 1 mm或更少、或0 mm。在相同溫度且在相同應力 下24個小時後，該熱熔黏合劑移動1.0 mm或更少，例如 0.8 mm或更少、0·5 mm或更少、0.3 mm或更少、〇· 1 mm或 更少、或0 mm。舉例而言，在100°C下且在1 kg負載之應 力下達1小時，則該熱熔黏合劑移動〇·5 mm或更少，例如 0.4 mm或更少、0.3 mm或更少、0.2 mm或更少、0_1 mm或 更少、或0 mm。在相同溫度及相同應力24小時後，該熱熔 黏合劑移動1.5 mm或更少、例如，1.2 mm或更少、1 .〇 mm 或更少、0.8 mm或更少、0.5 mm或更少、0.3 mm或更少或 0.1 mm或更少、或〇 mm。 可根據ASTM D123 8 (2004)中所述之測試確定一熱熔黏 合劑之熔體流動指數。熔體流動指數量測熱塑性塑膠以— 指定溫度及負載經由一 口之擠壓速率。其提供一種量測可 用於區別一熔融材料之等級之彼熔融材料之流動的方法。 具體而言，在研磨墊應用之背景中，該熔體流動指數表徵 該黏合劑填充該層上與該黏合劑接觸的表面上可能存在的 130811.doc -16- 200909137 任何草皮層或針孔之速率。 該熱溶黏合劑之’溶體流動指數可係任何合適值。舉例而 言’該熔體流動指數可係400 g/10 min或更少，例如2〇〇 g/10 min或更少、100 g/10 min或更少、75 g/l〇 min或更 少、65 g/10 min或更少、50 g/l〇 min或更少、35 g/l〇 min 或更少、25 g/10 min或更少、15 g/l〇 min或更少、l〇 g/i〇 min或更少或5 g/10 min或更少。另一選擇係或此外，該熔 體流動指數可係4 g/10 min或更多，例如1〇 g/i〇 min或更 多、25 g/10 min或更多、50 g/l〇或更多、75 g/l〇 min或更 多、100 g/10 min或更多、200 g/l〇 min或更多、或 3〇〇 g/10 min或更多。該熱熔黏合劑之熔體流動指數合意地介 於 4 g/10 min與 400 g/l〇 min之間。 可根據ASTM D 1525 (2006)中所述測試來確定一熱熔黏 合劑之Vicat軟化溫度。Vicat軟化溫度係在一規定負載在 一具體負載在一具體加熱速率下1 mm2之平頭針穿透一樣 本至1 mm深度之溫度。Vicat軟化溫度可用於預測當應用 至一研磨塾或當用於一面溫應用中時一黏合劑何時將軟 化。 本發明亦提供一種研磨一基板之方法，其包括：⑴提供 上述用於化學機械研磨之研磨墊；（ii)使該基板接觸該研 磨墊及一研磨組合物；及（iii)相對於該基板移動該研磨墊 及研磨組合物以使用該研磨墊磨蝕該基板表面之至少一部 分而研磨該基板。 特定而言，本發明提供一種研磨一基板之方法，其包 130811.doc -17· 200909137 括：（i)提供—用於化學機械研磨之研磨墊，該研磨墊包 括：（a)—研磨層；（b)—底層’其中該底層與該研磨層2 致共同擴張；及（c)一熱熔黏合劑’其中該熱熔黏合劑使該 研磨層與該底層結合在一起，該熱熔黏合劑包括介於2 = 1 8 wt·%間之EVA且當該研磨層達到一 4〇。〇之溫度時該黏合 劑大致抗脫層；（ii)使該基板接觸該研磨墊及一研磨組合 物；及（iii)相對於該基板移動該研磨墊及研磨組合物以使 用該研磨墊磨蝕該基板表面之至少一部分而研磨該基板。 π亥研磨組合物可為任一適宜之研磨組合物。該研磨組合 物通常包括一水性載體、一 ρΗ值調整劑及視需要一研磨 劑。端視研磨工件的類型而定，研磨組合物視需要可進一 步包含氧化劑、有機酸、錯合劑、1311值緩衝劑、表面活性 劑、腐蝕抑制劑、抗發泡劑及其類似物。 本發明進一步提供一種製備一用於一基板之化學機械研 磨之研磨墊之方法，其包括：⑴提供一用於化學機械研磨 之研磨墊，該研磨墊包括：（a)一研磨層；及（b)一底層， 其中該底層與該研磨層大致共同擴張；及（Η)使用一熱熔 黏合劑層壓該研磨層與該底層之至少一者，其中該熱熔黏 s劑使遠研磨層與該底層結合在一起，且該熱溶黏合劑包 括介於2與1 8 wt.%間之EVA且當該研磨層達到一 4〇〇c之溫 度時黏合劑大致抗脫層。 可藉由任一合適之層壓方法達成層壓。通常，藉由使用 一標準層壓機輥將黏合劑應用至研磨墊層來達成層壓。在 一包括一研磨層及一底層之研磨墊中，舉例而言，熱熔黏 130811.doc 200909137 合劑係應用至該研磨層及該底層中之至少一者，由此使其 接觸在一起。視需要，該熱熔黏合劑施加至該研磨層及該 底層兩者，由此使其接觸在一起。在一於該研磨層與該底 層間設置有一個或多個中間層之研磨墊中，除施加至該研 磨層及/或該底層之外或作為一替代，該熱熔黏合劑亦可 施加至該等中間層之至少一者，由此使該研磨層與該底層 同時或不同時接觸在一起。合意地，該熱熔黏合劑使該等 層中之每一者結合，因此將該熱熔黏合劑應用至互相接觸 之每一對層之至少一者的面上，以便在該對層之間存在黏 合劑。A constant load creep test that measures the amount of millimeters moved by the sample after a specified amount of time under a load. The relatively high holding power of the heat-resistant adhesive used in the background of the present invention is as high as 100. . The heat resistance of the adhesive is exhibited at the grinding temperature. For example, at 40 ° C and under a stress of 1 kg load for 1 hour, the hot melt adhesive moves 0.2 mm or less, such as 〇 1 c * , for example 0.15 mm or less, 〇 1 mm or less, 0.05 mm or less, or one. After 24 hours at the same temperature and the relevant stress, 'the hot-melt adhesive 蒋ΛΛ & V> s J moves 〇. 5 mm or less, such as 0.4 mm or less, 0.3 mm or less, 〇9.. s . 0.2 mm or less, (μ mm or less, or 〇130811.doc • 15· 200909137 mm. For example, at 60 ° C and under 1 kg load stress for 1 hour' the hot melt bonding The agent moves 〇. 2 mm or less, such as 〇. 1 5 mm or less, 0.1 mm or less, 0.05 mm or less, or 〇mm. After 24 hours at the same temperature and under the same stress, the heat The flux adhesive moves 〇5 mm or less, such as 0.4 mm or less, 0.3 mm or less, 0.2 mm or less, 0·1 mm or less, or 0 mm. For example, at 8 〇 Under the armpit and under 1 kg load stress for 1 hour, the hot melt adhesive moves 〇5 mm or less, such as 0.4 mm or less, 0.3 mm or less, 0.2 mm or less, 0 · 1 mm or less, or 0 mm. After 24 hours at the same temperature and under the same stress, the hot melt adhesive moves 1.0 mm or less, such as 0.8 mm or less, 0.5 mm or less, 0.3 mm or less, · 1 mm or less, or 0 mm. For example, at 100 ° C and under 1 kg load stress for 1 hour, the hot melt adhesive moves 〇 5 mm or less, such as 0.4 mm or Less, 0.3 mm or less, 0.2 mm or less, 0_1 mm or less, or 0 mm. After 24 hours at the same temperature and the same stress, the hot melt adhesive moves 1.5 mm or less, for example, 1.2 Mm or less, 1. 〇mm or less, 0.8 mm or less, 0.5 mm or less, 0.3 mm or less or 0.1 mm or less, or 〇mm. According to ASTM D123 8 (2004) The test determines the melt flow index of a hot melt adhesive. The melt flow refers to the measurement of the thermoplastic to - specify the temperature and the rate at which the load is squeezed through the mouth. It provides a measure that can be used to distinguish the grade of a molten material. The method of flowing the molten material. Specifically, in the context of the application of the polishing pad, the melt flow index characterizes the possible filling of the adhesive on the surface of the layer that is in contact with the adhesive 130811.doc -16 - 200909137 The rate of any turf layer or pinhole. The solution of the hot melt adhesive The kinetic index can be any suitable value. For example, the melt flow index can be 400 g/10 min or less, for example 2 〇〇 g/10 min or less, 100 g/10 min or less, 75 g/l〇min or less, 65 g/10 min or less, 50 g/l〇min or less, 35 g/l〇min or less, 25 g/10 min or less, 15 g/ L〇min or less, l〇g/i〇min or less or 5 g/10 min or less. Alternatively or additionally, the melt flow index can be 4 g/10 min or more, for example 1 〇 g/i 〇 min or more, 25 g/10 min or more, 50 g/l 〇 or More, 75 g/l 〇 min or more, 100 g/10 min or more, 200 g/l 〇 min or more, or 3 〇〇 g/10 min or more. The melt flow index of the hot melt adhesive is desirably between 4 g/10 min and 400 g/l 〇 min. The Vicat softening temperature of a hot melt adhesive can be determined according to the test described in ASTM D 1525 (2006). The Vicat softening temperature is the temperature of a 1 mm depth to a specific load at a specific heating rate of 1 mm2. The Vicat softening temperature can be used to predict when a binder will soften when applied to a grinding crucible or when used in a one-temperature application. The present invention also provides a method of polishing a substrate, comprising: (1) providing the above polishing pad for chemical mechanical polishing; (ii) contacting the substrate with the polishing pad and a polishing composition; and (iii) opposing the substrate The polishing pad and the polishing composition are moved to abrade the substrate by abrading at least a portion of the surface of the substrate using the polishing pad. In particular, the present invention provides a method of polishing a substrate, which package 130811.doc -17· 200909137 includes: (i) providing a polishing pad for chemical mechanical polishing, the polishing pad comprising: (a) an abrasive layer (b) - a bottom layer 'where the bottom layer is coextensive with the polishing layer 2; and (c) a hot melt adhesive 'where the hot melt adhesive bonds the abrasive layer to the bottom layer, the hot melt bonding The agent includes an EVA between 2 = 18 wt.% and when the abrasive layer reaches a 4 Torr. The adhesive is substantially resistant to delamination at a temperature of 〇; (ii) contacting the substrate with the polishing pad and a polishing composition; and (iii) moving the polishing pad and the abrasive composition relative to the substrate to abrade using the polishing pad The substrate is polished by at least a portion of the surface of the substrate. The π hai abrasive composition can be any suitable abrasive composition. The abrasive composition typically comprises an aqueous carrier, a pH adjusting agent and, if desired, an abrasive. Depending on the type of abrasive workpiece, the abrasive composition may further comprise an oxidizing agent, an organic acid, a complexing agent, a 1311 value buffer, a surfactant, a corrosion inhibitor, an anti-foaming agent, and the like, as needed. The present invention further provides a method of preparing a polishing pad for chemical mechanical polishing of a substrate, comprising: (1) providing a polishing pad for chemical mechanical polishing, the polishing pad comprising: (a) an abrasive layer; b) a bottom layer, wherein the bottom layer is substantially coextensive with the abrasive layer; and (Η) at least one of the abrasive layer and the bottom layer is laminated using a hot melt adhesive, wherein the hot melt adhesive causes the far abrasive layer In combination with the underlayer, the hot melt adhesive comprises between 2 and 18 wt.% EVA and the binder is substantially resistant to delamination when the abrasive layer reaches a temperature of 4 〇〇c. Lamination can be achieved by any suitable lamination method. Typically, lamination is achieved by applying a bond to the polishing pad using a standard laminator roll. In a polishing pad comprising a polishing layer and a bottom layer, for example, a hot melt adhesive 130811.doc 200909137 is applied to at least one of the abrasive layer and the bottom layer, thereby bringing them together. The hot melt adhesive is applied to both the abrasive layer and the underlayer as needed, thereby bringing them together. In a polishing pad having one or more intermediate layers disposed between the polishing layer and the underlayer, the hot melt adhesive may be applied to or in addition to the polishing layer and/or the underlayer. At least one of the intermediate layers thereby contacting the abrasive layer with the bottom layer at the same time or at different times. Desirably, the hot melt adhesive bonds each of the layers, thereby applying the hot melt adhesive to the face of at least one of each pair of layers in contact with each other so as to be between the pair of layers There is a binder.
可在任一合適層壓溫度及壓力執行層壓。合意地，在一 足以將層加熱至一等於或大於熱熔黏合劑激活溫度之溫度 的溫度下執行層壓。在黏合劑激活溫度或高於該溫度下經 層壓之層即使在相對高之研磨溫度下亦保持固持力且抗脫 層。一以EVA為主之熱熔黏合劑之激活溫度通常介於8〇〇c 與12 0 °C之間，例如介於8 0 °C與110 °C之間、8 0 °C與10 0 °C 之間、80°C 與 90。(：之間、90°C 與 120。(：之間、90°C 與11(TC 之間、90°C 與 l〇〇°C 之間、100°C 與 120°C 之間、100。(：與 ll〇°C之間、或ll〇°C與120°C之間。合意地，在一足以將 層加熱至一介於110°C與120°c (例如112。(：、115°c、或118 °C )之間的一溫度之溫度下執行層壓。 藉由該層實際達到之溫度可能明顯低於一典型層壓裝置 上所設定之層壓溫度。具體而言’藉由該層達成之溫度可 能較所設定之層壓溫度低50°C至70。(：。在層壓裝置上可將 130811.doc • 19· 200909137 該層壓溫度設定至能夠達成合意層溫度之任一合適溫度。 舉例而言，可將該層壓溫度設定至一介於如下範圍之溫 度·· 150 C 至 200 C、例如 15〇°C 至 190°C、1 50°C 至 1 80°C、 150°C 至 17〇°C、150°C 至 160。(：、160°C 至 200°C、16(TC 至 190°C、160°C 至 18〇t：、160°C 至 170°C、170°C 至 20(TC、 17(TC 至 19CTC、170°C 至 180°C、180°C 至 20(TC、180°C 至 190C、或190C至200。〇。通常，將層壓溫度設定至一介 於170C至19CTC範圍之溫度，例如175。(：、180。(：、或185 V。 可以任何適合之速度執行層壓。舉例而言，可以任何合 適之速度使層穿過該層壓機輥且可曝露至該層壓機輥下達 任一合適之駐留時間。合意地，可降低該層壓機輥速度以 增加層之駐留時間，藉此使層之表面溫度更接近於設定於 該層壓裝置上之層壓溫度。 意外地發現：使用一熱熔黏合劑在一足以將該墊表面加 熱至一等於或大於該熱熔黏合劑激活溫度之溫度的溫度下 層壓的研磨塾在高溫研磨應用中呈現改良之抗脫層性。具 體而言，使用一含有介於2與18 wt%間之EVA之熱熔黏合 劑在一介於150 °c至200〇c範圍之溫度下層壓之研磨墊在 CMP期間呈現高耐化學性及耐熱性，且因此抗脫層。具體 而言’當該研磨層達到一 4(TC或更高之溫度例如4〇t、45 C ' 5〇°c > 55〇C > 60°C ' 65〇C ^ 70°C ^ 75〇C ' 80°C ^ 85 C 90 C、95 °c、或100 °C時，該熱熔黏合劑大致抗脫 層0 130811.doc -20· 200909137 實例 以下實例進一步說明本發明，但是，當然不能解釋為以 某方式限制本發明之範疇。 實例1 該實例展示隨EVA含量而變之以EVA為主熱熔黏合劑之 熱穩定性及溶體流動。 確定12種含有改變之EVA量之不同熱熔黏合劑（即黏合劑 1A-1L)之熔點、Vicat軟化點及熔體流動指數。根據ASTM D1238 (2004)確定熔體流動指數以確定各種熱熔黏合劑之 流動。根據ASTM D1525 (2006)確定Vicat軟化點以確定該 熱溶黏合劑之熱穩定性。 表1 :隨EVA含量而變之熱炼黏合劑性質 黏合劑 Wt.% EVA Tm(°C) Vicat軟化溫度 (°C) 熔體流動指數 (g/10 min) 1A (比較例） 0 110 105 20 1B (本發明） 2.5 107 98 5 1C (本發明） 5 104 83 28 1D (本發明） 9 100 80 10 1E (本發明） 12 96 78 2.5 1F (本發明） 15 93 71 43 1G (本發明） 16 89 62 28 1H (本發明） 18 88 60 67 11 (比較例） 25 78 51 800 1J (比較例） 28 72 50 400 130811.doc -21 - 200909137 黏合劑 Wt.% EVA Tm(°C) Vicat軟化溫度 (°C) 熔體流動指數 (g/10 min) 1K (比較例） 32 63 46 43 1L (比較例） 40 47 35 57 該等結果展示：含有介於2與1 8 wt·%範圍間之EVA之 熱熔黏合劑較含有其他量EVA或不含EVA之熱熔黏合劑具 有相對低之熔體流動指數。 實例2Lamination can be performed at any suitable lamination temperature and pressure. Desirably, lamination is performed at a temperature sufficient to heat the layer to a temperature equal to or greater than the activation temperature of the hot melt adhesive. The laminated layer at or above the binder activation temperature maintains holding power and is resistant to delamination even at relatively high grinding temperatures. The activation temperature of an EVA-based hot-melt adhesive is usually between 8〇〇c and 12 0 °C, for example between 80 °C and 110 °C, 80 °C and 10 0 ° Between C, 80 ° C and 90. (: between, 90 ° C and 120. (: between, 90 ° C and 11 (TC, between 90 ° C and l ° ° C, between 100 ° C and 120 ° C, 100. (: between ll 〇 ° C, or between 〇 ° ° C and 120 ° C. Desirably, at a level sufficient to heat the layer to between 110 ° C and 120 ° C (eg 112 ° (:, 115 ° Lamination is performed at a temperature between c, or 118 ° C. The temperature actually achieved by the layer may be significantly lower than the lamination temperature set on a typical laminating device. The temperature reached by this layer may be 50 ° C to 70 lower than the set lamination temperature. (:: 130811.doc • 19· 200909137 can be set on the laminating device to achieve the desired layer temperature. A suitable temperature. For example, the lamination temperature can be set to a temperature ranging from 150 C to 200 C, for example, 15 ° C to 190 ° C, 150 ° C to 180 ° C, 150 ° C to 17 ° ° C, 150 ° C to 160. (:, 160 ° C to 200 ° C, 16 (TC to 190 ° C, 160 ° C to 18 ° t:, 160 ° C to 170 ° C , 170 ° C to 20 (TC, 17 (TC to 19 CTC, 170 ° C to 180 C, 180 ° C to 20 (TC, 180 ° C to 190 C, or 190 C to 200. 〇. Typically, the lamination temperature is set to a temperature in the range of 170 C to 19 CTC, such as 175. (:, 180. (: Or 185 V. Lamination may be performed at any suitable speed. For example, the layer may be passed through the laminator roll at any suitable speed and exposed to the laminator roll for any suitable residence time. The laminator roll speed can be lowered to increase the residence time of the layer, thereby bringing the surface temperature of the layer closer to the lamination temperature set on the laminating apparatus. Surprisingly, it has been found that a hot melt adhesive is used. A polishing crucible laminated at a temperature sufficient to heat the surface of the mat to a temperature equal to or greater than the activation temperature of the hot melt adhesive exhibits improved delamination resistance in high temperature abrasive applications. Specifically, the use of a containing 2 to 18 wt% EVA hot melt adhesive The polishing pad laminated at a temperature ranging from 150 ° C to 200 ° C exhibits high chemical resistance and heat resistance during CMP, and thus is resistant to delamination. For the sake of 'When the abrasive layer reaches a 4 (TC or High temperature such as 4〇t, 45 C ' 5〇°c > 55〇C > 60°C ' 65〇C ^ 70°C ^ 75〇C ' 80°C ^ 85 C 90 C, 95 °c The hot-melt adhesive is substantially resistant to delamination at 100 ° C. The following examples are intended to further illustrate the invention, but are not to be construed as limiting the scope of the invention in any way. EXAMPLE 1 This example demonstrates the thermal stability and solution flow of an EVA-based hot melt adhesive as a function of EVA content. The melting points, Vicat softening point and melt flow index of 12 different hot melt adhesives (i.e., binders 1A-1L) containing varying amounts of EVA were determined. The melt flow index was determined according to ASTM D1238 (2004) to determine the flow of various hot melt adhesives. The Vicat softening point was determined according to ASTM D1525 (2006) to determine the thermal stability of the hot melt adhesive. Table 1: Heat-adhesive adhesive properties as a function of EVA content Wt.% EVA Tm (°C) Vicat softening temperature (°C) Melt flow index (g/10 min) 1A (Comparative Example) 0 110 105 20 1B (Invention) 2.5 107 98 5 1C (Invention) 5 104 83 28 1D (Invention) 9 100 80 10 1E (Invention) 12 96 78 2.5 1F (Invention) 15 93 71 43 1G (Invention) 16 89 62 28 1H (Invention) 18 88 60 67 11 (Comparative Example) 25 78 51 800 1J (Comparative Example) 28 72 50 400 130811.doc -21 - 200909137 Adhesive Wt.% EVA Tm (°C) Vicat softening temperature (°C) Melt flow index (g/10 min) 1K (Comparative) 32 63 46 43 1L (Comparative) 40 47 35 57 These results show: containing between 2 and 18 wt·% The range of EVA hot melt adhesives has a relatively low melt flow index compared to other quantities of EVA or EVA free hot melt adhesives. Example 2
該實例展示在高溫下根據本發明之熱熔黏合劑之固持 力。 確定不同溫度下三種不同黏合劑（即黏合劑2A_2C)之固 持力。黏合劑2A(比較的）係一熱熔黏合劑。黏合劑2B(比 較的）係一壓敏黏合劑。黏合劑2C(發明）係一含有介於2與 18 wt.%間之EVA之以EVA為基礎之熱熔黏合劑。黏合劑⑸ 及2C經兩次測試。 T ^ μ、、.w日π挪/广八从η央 寸長每經層壓樣本均含有一釋放層、一黏合劑層（通 常用以將該墊組件黏附於滾筒上進行研磨）、一子墊、— 將該子墊黏附於該頂墊之黏合劑、及一頂塾。自樣本上移 除釋^襯塾’且將樣本黏附至約1()16 em(4英对）長、tv cm(1英对）寬及〇64_25英七厚之紹板上。允許經層壓 樣本15-30分鐘完全勝著至㈣板上。 每’均包括—直役約〇64 _(〇25英对)之孔洞，以 可將母-板自一吊鈎懸垂於一烤爐中。進一步，將 洞衝壓到每-經層壓樣本中，以便可自該樣本懸垂…之 1308li.d〇c -22- 200909137 重量。在一加熱至不同溫度（約4〇(>c、6〇(>c、8(Γ(：、及100 c)之溫度受控烤爐中執行固持力測試。將包括經層壓樣 本及懸垂站碼在内之紹板放人已加熱之烤爐中。在樣本及 烤爐之溫度穩定後’開啓計時器。在1小時後及在24小時 後，乂錄黏合劑與研磨墊層間之脫層程度。"掉落"表示樣 本70王自研磨塾上脫層，即黏合劑完全自研磨墊層上脫 離。該等結果概括於表2中。This example demonstrates the holding power of a hot melt adhesive according to the present invention at elevated temperatures. Determine the holding power of three different binders (ie, binder 2A_2C) at different temperatures. Adhesive 2A (comparative) is a hot melt adhesive. Adhesive 2B (comparative) is a pressure sensitive adhesive. Adhesive 2C (invention) is an EVA-based hot melt adhesive containing EVA between 2 and 18 wt.%. Adhesives (5) and 2C were tested twice. T ^ μ, , .w, π 移 / 广 八 from the η 阳 inch length each laminated sample contains a release layer, a layer of adhesive (usually used to adhere the pad assembly to the drum for grinding), a a subpad, an adhesive that adheres the subpad to the top pad, and a top pad. The sample was removed from the sample and the sample was adhered to a plate of about 1 () 16 em (4 inches) long, tv cm (1 inch) wide, and 〇 64_25 inches thick. Allow the laminated sample to fully outperform the (four) plate for 15-30 minutes. Each 'includes' holes that are approximately 64 _ (〇 25 inches), so that the mother-board can be suspended from a hook in an oven. Further, the hole is stamped into each of the laminated samples so as to be able to hang from the sample... 1308li.d〇c -22- 200909137 by weight. The holding force test is performed in a temperature controlled oven heated to a different temperature (about 4 Torr (> c, 6 〇 (>, and 100 c). The laminated sample will be included. And the hanging station code is placed in the heated oven. After the temperature of the sample and the oven is stable, the timer is turned on. After 1 hour and after 24 hours, the adhesive is placed between the adhesive and the polishing pad. The degree of delamination. "drop" indicates that the sample 70 king delaminated from the abrasive crucible, that is, the adhesive completely detached from the polishing pad. The results are summarized in Table 2.
表2 :隨時間及溫度而變之黏合劑固持力Table 2: Adhesive retention as a function of time and temperature
該等結果展示：所用黏合劑類型(即壓敏黏合劑或二Γ 黏合劑）及黏合劑之特定化風 ‘、、、… 疋化予組成（即£VA之百分比重）斜 同溫度下黏合劑之固持力 τ + 熔黏合劑展示一較大固持 之熱 持力，即較弱之脫層程度， 高達80°C或10(TC之溫度下。 使在 實例3 130811.doc -23- 200909137 該實例展示層壓溫度對根據本發明之熱炼黏合劑之固持 力之影響。 使用一根據本發明之以EVA為主之熱熔黏合劑在不同層 壓溫度下層壓27個研磨墊（即研磨墊3AA-3BA)。根據實例 2製備層壓墊之樣本，且在70 °C及80 °C下執行固持力測 試。觀察研磨墊1 6個小時（960分鐘），且記錄所觀察到的任 一脫層時間。結果概括於表3中。 表3 :隨層壓溫度而變之熱熔黏合劑之脫層 研磨墊 近似層壓溫度(°C) 烤爐溫度(°C) 脫層時間(min.) 3AA 150 70 >960 (未觀察到脫層） 3AB 165 70 >960 (未觀察到脫層） 3AC 70 80 10 3AD 70 80 10 3AE 70 80 12 3AF 70 80 15 3AG 70 80 8 3AH 120 80 10 3AI 120 80 25 3AJ 120 80 35 3AK 120 80 35 3AL 120 80 20 3AM 150 80 30 3AN 150 80 25 3AO 150 80 20 3AP 150 80 20 3AQ 150 80 30 3AR 165 80 270 3AS 165 80 165 130811.doc -24- 200909137 研磨墊 近似層壓溫度(°C) 烤爐溫度rc) 脫層時間(min.) 3AT 165 80 360 3AU 165 80 260 3AV 165 80 160 3AW 170 80 >960 (未觀察到脫層） 3AX 170 80 >960 (未觀察到脫層） 3AY 170 80 >960 (未觀察到脫層） 3AZ 170 80 >960 (未觀察到脫層） 3BA 170 80 >960 (未觀察到脫層） 該等結果展示：使用根據本發明之一熱熔黏合劑在該熱 熔黏合劑之激活溫度或高於該溫度之一溫度下一經層壓之 研磨墊呈現增加之固持力且在高溫下抗脫層。 實例4 該實例比較使用一根據本發明之一熱熔黏合劑製備的一 研磨墊之性質與使用美國專利6,422,921號所述之熱熔黏合 劑及美國專利7,1 0 1，275號中所述之大體相同類別之熱熔黏 合劑製備的一研磨墊之性質。 ， UAF-420熱炫黏合劑係自New Jersey之Pine Brook黏合劑 膜獲得。使用UAF-420熱熔黏合劑在介於90°C與95°C之層 壓溫度下達1分鐘之駐留時間來層壓四個EPIC™ D1 00墊 ' (Cabot Microelectronics, Aurora, Illinois)(即研磨墊 4A- - 4D)。將層壓機輥壓力設定至8.6 kPa(1.25 psi)且施加至該 墊之實際壓力係550 kPa(80 psi)。在305 mm/min之速度下 確定每一經層壓墊之T-剝離強度。 該等測試參數係根據美國專利第7,1 0 1,275號。具體而 言，'275專利規定該層壓溫度可係自50°C至150°C(col. 5， 130811.doc -25- 200909137 4-5行）且在305 mm/min速度下確定T_剝離強度（參見例如 col 3，4-5行）。275專利揭示聚亞安酯熱熔黏合劑包括於 本”發明'’中（col. 3，33-36行）’且美國專利第6,422,921號 揭示UAF-420係此一聚亞安酯熱熔黏合劑（c〇1. 3，25-27 研磨墊 T·剝離強度(N) 4A(比較例） 48.9 4B(比較例） 58.7 4C(比較例） 58.8 4D(比較例） 59.2 平均(4A-4D) 56.4 該等結果展示：使用先前技術揭示的大體類別熱熔黏合 劑製備的研磨墊展示與隨後在·275專利中所主張研磨墊相 行）。將UAF-420熱熔黏合劑之T_剥離結果概括於表4A中。 表4A :先前技術熱熔黏合劑之T_剝離強度 同之Τ-剝離強度。 使用UAF-420熱熔黏合劑在〗7〇°c層壓溫度下層壓5個額 外的EPIC™ D100墊（即研磨墊4E_4I)。將層壓機輥壓力設 定至8.6 kPa(1.25 psi)且施加至該墊之實際壓力係55〇 kPa(80 psi)。根據實例2製備層壓墊樣本，且在8〇t下執 行固持力賴。觀察該等研磨塾，並記錄所觀察到的任何 脫層之時間。每一脫層均係一完全脫層或"掉落"，即黏合 劑完全自該墊層上脫離。該等結果概括於表4B中。 130811.doc -26 - 200909137 表4B :先前技術熱熔龜合劑之固持力 研磨墊 —- 脫層時間 4E (比較例） 一.—--9 4F (比較例） — 13 4G (比較例） ------ 15 4H (比較例） 16 41 (比較例） 9 平均(4E-4I) 12.4These results show that the type of adhesive used (ie pressure sensitive adhesive or two-way adhesive) and the specific wind of the adhesive ',, ... 疋 予 composition (ie, the percentage weight of £VA) is bonded at the same temperature The holding power of the agent τ + the flux binder exhibits a greater holding heat holding capacity, ie a weaker degree of delamination, up to 80 ° C or 10 (at the temperature of TC.) In Example 3 130811.doc -23- 200909137 This example demonstrates the effect of lamination temperature on the holding power of the heat-curing adhesive according to the present invention. 27 abrasive pads (ie, ground) are laminated at different laminating temperatures using an EVA-based hot melt adhesive according to the present invention. Pad 3AA-3BA). A sample of the laminate pad was prepared according to Example 2, and the holding power test was performed at 70 ° C and 80 ° C. The polishing pad was observed for 16 hours (960 minutes), and the observed ones were recorded. A delamination time. The results are summarized in Table 3. Table 3: Delaminated polishing pad of hot melt adhesive as a function of lamination temperature Approximate lamination temperature (°C) Oven temperature (°C) Delamination time ( Min.) 3AA 150 70 >960 (no delamination observed) 3AB 165 70 >960 (no delamination observed) 3AC 70 80 10 3AD 70 80 10 3AE 70 80 12 3AF 70 80 15 3AG 70 80 8 3AH 120 80 10 3AI 120 80 25 3AJ 120 80 35 3AK 120 80 35 3AL 120 80 20 3AM 150 80 30 3AN 150 80 25 3AO 150 80 20 3AP 150 80 20 3AQ 150 80 30 3AR 165 80 270 3AS 165 80 165 130811.doc -24- 200909137 Abrasive pad approximate lamination temperature (°C) oven temperature rc) delamination time (min.) 3AT 165 80 360 3AU 165 80 260 3AV 165 80 160 3AW 170 80 >960 (no delamination observed) 3AX 170 80 >960 (no delamination observed) 3AY 170 80 >960 (no delamination observed) 3AZ 170 80 > 960 (no delamination observed) 3BA 170 80 > 960 (no delamination observed) These results demonstrate the use of a hot melt adhesive according to the invention at the activation temperature or temperature of the hot melt adhesive The laminated polishing pad at one of the temperatures exhibits increased holding power and resists delamination at elevated temperatures. EXAMPLE 4 This example compares the properties of a polishing pad prepared using a hot melt adhesive according to the present invention to a hot melt adhesive as described in U.S. Patent No. 6,422,921 and the disclosure of U.S. Patent No. 7,110,275. The properties of a polishing pad prepared from substantially the same type of hot melt adhesive. , UAF-420 hot adhesive is obtained from New Jersey's Pine Brook adhesive film. Laminating four EPICTM D1 00 pads' (Cabot Microelectronics, Aurora, Illinois) using a UAF-420 hot melt adhesive at a lamination temperature of 90 ° C and 95 ° C for 1 minute (ie grinding Pad 4A- - 4D). The laminator roll pressure was set to 8.6 kPa (1.25 psi) and the actual pressure applied to the pad was 550 kPa (80 psi). The T-peel strength of each laminated mat was determined at a speed of 305 mm/min. The test parameters are based on U.S. Patent No. 7,10,275. Specifically, the '275 patent specifies that the lamination temperature can be from 50 ° C to 150 ° C (col. 5, 130811.doc -25 - 200909137 4-5 rows) and T_ is determined at a speed of 305 mm/min. Peel strength (see for example col 3, lines 4-5). The '275 patent discloses that polyurethane heat-fusible adhesives are included in the "Invention" (col. 3, 33-36) and U.S. Patent No. 6,422,921 discloses UAF-420 which is a polyurethane heat-fusible bond. Agent (c〇1. 3,25-27 polishing pad T·peel strength (N) 4A (comparative example) 48.9 4B (comparative example) 58.7 4C (comparative example) 58.8 4D (comparative example) 59.2 Average (4A-4D) 56.4 The results show that the polishing pad prepared using the general class of hot melt adhesives disclosed in the prior art exhibits the same results as the polishing pad previously claimed in the '275 patent. The T_peeling result of the UAF-420 hot melt adhesive It is summarized in Table 4A. Table 4A: T_peel strength of prior art hot melt adhesives is the same as the peel strength. 5 additional layers are laminated using a UAF-420 hot melt adhesive at a laminate temperature of 7 ° C. EPICTM D100 pad (ie, polishing pad 4E_4I). The laminator roll pressure was set to 8.6 kPa (1.25 psi) and the actual pressure applied to the pad was 55 kPa (80 psi). A laminate pad sample was prepared according to Example 2. And hold the holding force at 8 〇t. Observe the grinding burrs and record any delamination time observed. A delamination is either a complete delamination or "drop", ie the adhesive is completely detached from the mat. These results are summarized in Table 4B. 130811.doc -26 - 200909137 Table 4B: Prior art heat Retaining force pad for fused tortoise mixture - delamination time 4E (Comparative Example) 1.. - -9 4F (Comparative Example) - 13 4G (Comparative Example) ------ 15 4H (Comparative Example) 16 41 (Comparative example) 9 Average (4E-4I) 12.4
該等結果展示：雖然UAF-420先前技術熱熔黏合劑展示 足以滿足美目專利第7，1G1，275號之申請專利範圍之τ_剝離 強度，但其在高溫下並不呈現與切明背景下所應力之以 EVA為基礎之熱熔黏合劑所呈現的固持力相當之固持力。 特定而言，當研磨墊係使用一根據本發明之以eva為主之 熱熔黏合劑在約17〇。〇下層壓而成且在_8〇。〇之烤爐溫度 下經受固持力測試_，即使在960分鐘後，仍《觀察到脫 層（參見實例3，經層壓研磨墊3AW、3AX、3AY、3AZ、及 3BA)。對照而言，在相同測試條件下僅在一平均HA分鐘 後即觀察到UAF-420黏合劑之完全脫層。 ，該等結果進一步展示：T剝離測試在升高之溫度下且在 :切條件下係黏合劑強度的一不充分指標。雖然祕42〇 先月'』技術熱熔黏合劑呈現足以滿足美國專利第7,⑻，仍號 ^申請專利範圍之T·剝離強度，但該固持力測試結果展示 ::升高之溫度下無法承受剪切力。僅—黏合劑之丁_剝離 又自身無法指示使用彼黏合劑層壓之—研磨塾在高溫研 ‘應用期間會抗脫層。本文所揭示之固持力測試提供在升 130811.dO) -27- 200909137 高之溫度及剪切條件下黏合劑強度之一更準確表示。 【圖式簡單說明j 圖1係EVA之百分含量舆—以為主之熱㈣合劍之溶 點及Vicat軟化溫度之關係的曲線圖。 圖2係-圖解說明藉由對—比較之熱炫黏合劑與一根據 本發明之熱熔黏合劑執行固持力測試而確定之脫層時間圖 表。在約165。。下執行墊層壓’在峨下將黏合劑應用至 epic™ D100^(Cabot Microelectronics, Aurora, Illinois) 且執行固持力測試兩者。 圖3係藉由對根據本發明之一熱熔黏合劑執行固持力測 試所確定之近似層壓溫度與脫層時間之圖表。在肋它下片 熱溶黏合劑應用至Epic™ D100執 100墊且執仃固持力測試。為 之層壓溫度下，即使測試在9叫鐘後停 觀察到脫層。 攻％禾 130811.doc -28-The results show that although the UAF-420 prior art hot-melt adhesive exhibits sufficient τ_peel strength to meet the patent application scope of U.S. Patent No. 7,1G1,275, it does not exhibit and clarify the background at high temperatures. The stress of the EVA-based hot-melt adhesive is equivalent to the holding power. In particular, when the polishing pad is used, an eva-based hot melt adhesive according to the present invention is used at about 17 Torr. Laminated under the armpit and at _8〇. The crucible oven was subjected to a holding test _, even after 960 minutes, delamination was observed (see Example 3, laminated polishing pads 3AW, 3AX, 3AY, 3AZ, and 3BA). In contrast, complete delamination of the UAF-420 adhesive was observed only after an average of HA minutes under the same test conditions. These results further demonstrate that the T-peel test is an inadequate indicator of the strength of the adhesive at elevated temperatures and under: cutting conditions. Although the secret 42 〇 月 ' 'Technical hot-melt adhesive is sufficient to meet the T· peel strength of US Patent No. 7, (8), still claiming the patent range, the retention test results show that: the elevated temperature can not withstand Shear force. Only - the adhesive _ peeling itself can not indicate the use of the adhesive lamination - the grinding 塾 will be resistant to delamination during high temperature application. The retention test disclosed herein provides a more accurate indication of the strength of the adhesive at elevated temperatures of 130811.dO) -27-200909137 and shear conditions. [Simple diagram of the figure j Figure 1 is a graph of the percentage of EVA 舆 - the relationship between the melting point of the main heat and the softening temperature of Vicat. Figure 2 is a diagram illustrating the delamination time chart determined by performing a holding force test on a comparative heat-sensitive adhesive and a hot-melt adhesive according to the present invention. At about 165. . The underlying padding was performed. The adhesive was applied to the epicTM D100^ (Cabot Microelectronics, Aurora, Illinois) under the armpit and both of the holding power tests were performed. Figure 3 is a graph of approximate lamination temperature and delamination time as determined by performing a holding force test on a hot melt adhesive according to the present invention. Under the ribs, the hot-melt adhesive is applied to the EpicTM D100 100 pad and the retention test is performed. For the lamination temperature, delamination was observed even after the test was stopped after 9 minutes. Attack %禾 130811.doc -28-