200534955 玖、發明說明： 【發明所屬之技術領域】 本發明提出用於在玻璃、半導體、電介質/金屬複合物、 磁性大容量存儲媒介物及積體電路等項目上產生光滑、超 平表面之拋光墊。更確切而言，本發明提出適用於使某些 拋光墊載體黏著到拋光裝置以延長墊在發生脫層前之壽命 之黏著劑材料。 【先前技術】 化學機械拋光（CMP)作為平面化技術廣泛用於製造VLSI 積體電路。在1C處理中其具有使多種材料平面化之潛力， 但最廣泛用於使半導體晶圓上的金屬化層及中間級電介質 平面化，且用於使淺渠溝隔離所用的基材平面化。 一例如，在淺渠溝隔離（STI)中，必須使大面積場氧化膜拋 光，以產生平面狀初始晶圓。用常規蝕刻方法跨晶圓之完 全直徑取得可接受平面化在很大程度上尚未成功。但，利 用習知CMP，在用機械抛光輪及化學餘刻劑漿料使晶圓拋 光日守’不需要的氧化物質用高度平面性除去。 類似在多級金屬化方法中，多級結構中的各級促成不規 則形貌。在製程進行時，平 技術水平1C製程中受到支持 共同目的，且由用插入ψ ，平面化中間級介電層現在在很多200534955 发明 Description of the invention: [Technical field to which the invention belongs] The present invention proposes polishing for producing smooth, ultra-flat surfaces on glass, semiconductors, dielectric / metal composites, magnetic mass storage media, and integrated circuits, etc. pad. More precisely, the present invention proposes an adhesive material suitable for adhering certain polishing pad carriers to a polishing device to extend the life of the pad before delamination occurs. [Previous Technology] Chemical mechanical polishing (CMP) is widely used as a planarization technology to manufacture VLSI integrated circuits. It has the potential to planarize a variety of materials in 1C processing, but it is most widely used to planarize metallization layers and intermediate-level dielectrics on semiconductor wafers and to planarize substrates used for shallow trench isolation. For example, in shallow trench isolation (STI), a large area field oxide film must be polished to produce a planar initial wafer. Achieving acceptable planarization across the full diameter of the wafer using conventional etch methods has largely not been successful. However, the conventional CMP is used to remove unwanted oxides on the wafer using a mechanical polishing wheel and a chemical finish slurry. The oxides are removed with a high degree of planarity. Similar to the multi-level metallization method, the levels in the multi-level structure contribute to the irregular topography. As the process progresses, flat technology level 1C processes are supported by the common purpose, and by inserting ψ, the planarized intermediate dielectric layer is now in a lot of
CMP亦可用於使氧化層拋光，如 ’然後用CMP除去過量金屬。 ’如 Si02、Ta2〇4 w2〇5，或使 92663.doc 200534955 氮化物層抛光，如Si3N4、TaN、TiN。 但’習知抛光墊材料有多種缺點。各種材料（如，聚胺基 曱酸酯、聚碳酸酯、耐綸、聚脲、毛氈或聚酯）具有不良内 在抛光能力’且因此其純態不用作拋光墊。在某些例中， 機械或化學結構可能使此等材料變形，由此使它們用於拋 光。對防止晶圓不平拋光重要的另一考慮為使拋光墊附著 到拋光台台板所用背膜之選擇及耐久性。背膜使晶圓在拋 光期間置於墊上，並補償晶圓或背板中的厚度變化。另一 考慮為用於使拋光墊黏著到台板的黏著劑。 可以認為，化學機械拋光中所用的漿料導致拋光墊自拋 光台之台板脫層。隨之的問題可為，在脫層早期階段產生 不良品質晶圓的晶圓不理想平面化，乃至在脫層的拋光墊 飛離移動拋光台時晶圓和拋光設備完全毁壞。脫層被認為 在用於使拋光墊固定到拋光台台板的黏著劑由漿料化學侵 蝕時發生。這又導致在黏著劑/台板界面的黏著劑可能由於 黏著劑溶解而破壞。由於脫層顯著增加製造積體電路的總 成本，所以製造的足夠鬲品質半導體晶圓數減少。 減少由脫層導致製造損耗的一種方法為使用強力使拋光 墊偶合到台板之黏著劑。此方法以這樣一種觀點為基礎， 如果拋光墊牢固偶合到台板，則拋光漿料不太容易達到在 台板和塾之間導致脫層的入口。但，利用此方法的一個問 題為極難改變拋光墊。一般需要特殊設備幫助此等墊剝離 台板。在台板表面上通常保留殘餘黏著劑，必須用有機溶 劑才能使黏著劑清離台板。此等額外除去和清洗步驟增加 92663.doc 200534955 製造積體電路的總時間和成本。 因此，需要一種改良的CMP拋光墊，該拋光墊能夠提供 咼度平面狀晶圓表面，且在CMp期間具有改良的耐久性， 同時不經歷以上提到的問題。 【發明内容】 為解決以上討論的缺陷問題，在一具體實施例中，本發 明提供一種用於使半導體晶圓拋光之化學機械拋光墊。拋 光墊包括熱塑性背膜及偶合到熱塑性背膜之感壓黏著劑。 感壓黏著劑經佈置，以使拋光墊偶合到拋光台板，並提供 月匕夠經暴路於具有約4或更高pH之拋光漿料媒介物至少約4 天實負上防止化學機械拋光墊自拋光台板脫層之界面。 在另一具體實施例中，本發明提供製造化學機械拋光墊 之方法。该方法包括，提供熱塑性拋光發泡體，並使熱塑 性背膜層合到熱塑性拋光發泡體。該方法進一步包括使感 壓黏著劑偶合到熱塑性背膜。感壓黏著劑經佈置，以使化 子機械拋光墊偶合到拋光台板，並提供上述界面。本發明 另具體貫施例為用於使半導體晶圓拋光的由上述方法製 ^之化學機械抛光塾。 别述已概括本發明的較佳及選擇性特徵，所以，熟諳此 藝者可杈佳理解以下本發明之詳細說明。以後描述形成本 發明申請專利範圍主題的本發明之額外特徵。熟諳此藝者 應瞭解’可报容易用所揭示的概念和明確具體實施例作基 礎’為疋成本發明相同目的以此基礎設計或改進其他結 構。熟請此藝者亦應認識到，此等相當結構不應脫離本發 92663.doc 200534955 明之範圍。 【實施方式】 與習知墊和黏著劑組合比較，本發明揭示經較長工作日士 間提供優良拋光品質之拋光墊背膜和黏著劑材料之組合： 特別發現，黏著劑和塑膠背膜的某些組合提供令人驚气地 優良抗酸性及在衆料媒介物中建立的氧化條件，同時在水 平（台板）平面保持極佳剪切強度及在垂直平面（垂直於△板 的低㈣強度。特別發現，—種雙側感壓黏著劑（PSA)i供 出乎意料地優良抗脫層性，該感壓黏著劑包括具有以聚梦 氧為基礎的黏著劑之台板側黏著劑及具有以㈣酸系㈣ 為基礎黏著劑之背膜側黏著劑。可以認為，以聚㈣為基 礎的黏著劑對CMP漿料化學侵姓之耐性給予抗脫層性。另 外，有較少漿料進入台板/黏著劑界面，因此，僅台板/黏著 劑界面之周邊與漿料接觸。 在㈣應用中使用聚石夕氧黏著劑與自黏著劑的聚石夕氧化 合㈣入石夕晶圓且不可逆轉污染晶圓的傳統觀點相反。特 別是長期認為，聚石夕氧貌的不穩定單體性組分與石夕晶圓表 面，應’因此有害改變晶圓的半導特性。本發明避免此等 問題，因為：以石夕為基礎的黏著劑僅在台板側上；低量襞 料進入台板/黏著劑界面；且以石夕為基礎的黏著劑對⑽聚 料化學侵蝕具有内在耐性。 按照本發明意圖，黏著劑定義為任何能夠使拋光墊材料 (特別為背膜）由化學或避 4 ^械作用或二者黏著到拋光台板且 m溶劑、壓力、熱、冷或其他方法活化之材 92663.doc 200534955 料。感壓黏著劑指在室溫僅由短暫施加的壓力黏著到表面 之黏著劑類型。 圖1顯示本發明一具體實施例，一種用於使半導體晶圓拋 光之化學機械拋光墊1〇〇。拋光塾1〇〇包括熱塑性背膜及 偶合到熱塑性背膜105之感壓黏著劑110。感壓黏著劑11〇經 佈置，以使化學機械拋光墊100偶合到拋光台板115。 感壓黏者劑11 0亦經佈置’以提供能夠經暴露於具有約4 或更高pH之拋光漿料媒介物125至少約4天實質上防止化學 機械拋光墊100自拋光台板115脫層之界面120。更佳經暴露 於拋光漿料媒介物125至少14天防止脫層。實質防止脫層由 漿料進入130進入小於約2毫米之界面120顯示，如以下試驗 部分中所進一步例示。 拋光墊100之較佳具體實施例包括感壓黏著劑110，該感 壓黏著劑為雙側，在可偶合到台板11 5的第一側13 5上具有 以t砍乳為基礎的黏者劑’而在可偶合到熱塑性背膜1 Q $的 第二側140上具有以丙烯酸系材料為基礎之黏著劑。理想僅 在弟一側13 5上具有以聚石夕氧為基礎的黏著劑，因為拋光台 板115—般具有高表面能量。熱塑性背膜1〇5一般由以足夠 強度使拋光墊100偶合到拋光台板115的不黏著到以聚石夕氧 為基礎之黏者劑之低表面能1材料組成，如，高穷产聚乙 稀。 感壓黏著劑110最佳具有低單體性聚矽氧含量，因為這使 污染欲拋光半導體晶圓的可能性最低。雖然本發明之範圍 不受理論限制，但可推斷，可能的任何污染源係自感壓黏 92663.doc 200534955 :劑110第-側135上的以聚矽氧為基礎之黏著劑。以聚矽 氧為基礎的黏著劑之單體性聚矽氧含量理想低得足以在拋 光期間限於第一側135。 了通過習知製造方法使感壓黏4劑110之單體性聚石夕氧 ^量降低到滿意水平。製成的帶結構中單體性聚梦氧之含 :可由熟諳此藝者熟悉的一些習知萃取步驟測定。例如， 單體性聚碎氧可自感壓黏著劑110或第-側135上的以聚石夕 =為基礎之黏著劑經乙醇萃取，然後在氮氣氣氛下再乾 知。然後在氮氣中乾燥萃取物之殘餘物，且由紅外光譜檢 測(例如)在804釐米-1之聚石夕氧吸收峰分析聚石夕氧含量。例 如丄在較佳具體實施财，自以聚⑪氧為基礎黏著劑的乙 醇萃取物之經乾燥樣品在804釐米^具有對應小於約100吸 收單位/克之聚矽氧含量。萃取物更佳在804釐米-1具有每克 樣重里小於約5 〇且更佳小於約2 0之吸收單位。 在拋光墊100的其他較佳具體實施例中，感壓黏著劑11〇 進一步包括（例如）包含聚酯且位於感壓黏著劑第一和二級 側135 I40間之載膜145。載膜145亦可包括具有足夠高表 月匕1以使以來石夕氧和丙浠酸系材料為基礎的黏著劑黏著 到載膜強於黏著到台板或熱塑性背膜之其他聚合物材料。 此等材料之實例為耐綸、高密度聚乙烯（HDpE)及非塑化聚 氯乙烯（HDPE)。 在拋光墊100的其他具體實施例中，熱塑性背膜1〇5為高 密度聚乙烯（即，密度大於約0.96克/立方釐米），更佳為經 縮合高密度聚乙烯。適合用作背膜1〇5之高密度聚乙烯之實 92663.doc -10- 200534955 例為產品DGDA-2490及DGDA-2480(道化學公司（D〇wCMP can also be used to polish the oxide layer, such as' and then use CMP to remove excess metal. ’Such as Si02, Ta2 04 w205, or polishing 92663.doc 200534955 nitride layer, such as Si3N4, TaN, TiN. However, the conventional polishing pad material has various disadvantages. Various materials (e.g. polyurethane, polycarbonate, nylon, polyurea, felt or polyester) have poor intrinsic polishing capabilities ' and therefore are not used in their pure state as polishing pads. In some cases, mechanical or chemical structures may deform these materials, thereby making them useful for polishing. Another consideration that is important to prevent wafer polishing is the choice and durability of the backing film used to attach the polishing pad to the polishing platen. The backing film places the wafer on the pad during polishing and compensates for thickness variations in the wafer or backplane. Another consideration is the adhesive used to adhere the polishing pad to the platen. It can be considered that the slurry used in chemical mechanical polishing causes the polishing pad to delaminate from the platen of the polishing table. A subsequent problem may be that wafers that produce poor quality wafers in the early stages of delamination are not ideally planarized, or the wafers and polishing equipment are completely destroyed when the delaminated polishing pads fly off the mobile polishing table. Delamination is believed to occur when the adhesive used to secure the polishing pad to the polishing platen is chemically attacked by the slurry. This in turn may cause the adhesive at the adhesive / platen interface to break due to the dissolution of the adhesive. Since delamination significantly increases the total cost of manufacturing integrated circuits, the number of semiconductor wafers of sufficient quality to be manufactured is reduced. One way to reduce manufacturing losses due to delamination is to use a strong adhesive that couples the polishing pad to the platen. This method is based on the idea that if the polishing pad is firmly coupled to the platen, the polishing slurry is less likely to reach the entrance that causes delamination between the platen and the concrete. However, one problem with this method is that it is extremely difficult to change the polishing pad. Special equipment is usually needed to help these pads strip the platen. Residual adhesive is usually left on the surface of the platen, and an organic solvent must be used to remove the adhesive from the platen. These additional removal and cleaning steps increase the total time and cost of manufacturing integrated circuits. Therefore, there is a need for an improved CMP polishing pad that is capable of providing a flat wafer surface with a degree of flatness and has improved durability during CMP without experiencing the problems mentioned above. SUMMARY OF THE INVENTION In order to solve the problems discussed above, in a specific embodiment, the present invention provides a chemical mechanical polishing pad for polishing a semiconductor wafer. The polishing pad includes a thermoplastic backing film and a pressure sensitive adhesive coupled to the thermoplastic backing film. The pressure-sensitive adhesive is arranged so that the polishing pad is coupled to the polishing platen and provides a sufficient temperature to prevent chemical mechanical polishing by polishing the polishing slurry medium having a pH of about 4 or higher for at least about 4 days Interface for pad delamination from polished platens. In another embodiment, the present invention provides a method for manufacturing a chemical mechanical polishing pad. The method includes providing a thermoplastic polishing foam and laminating a thermoplastic backing film to the thermoplastic polishing foam. The method further includes coupling a pressure sensitive adhesive to the thermoplastic backing film. The pressure-sensitive adhesive is arranged to couple the mechanical polishing pad to the polishing platen and provide the interface described above. Another embodiment of the present invention is a chemical mechanical polishing pad manufactured by the above method for polishing a semiconductor wafer. The detailed description has summarized the preferred and optional features of the present invention, so those skilled in the art can better understand the following detailed description of the present invention. Additional features of the invention that form the subject of the patentable scope of the invention are described hereinafter. Those skilled in the art should understand that 'the reported concept can be easily used as the basis for clear specific embodiments' to design or improve other structures based on the same purpose of the invention. Those who are familiar with this art should also realize that these equivalent structures should not depart from the scope of this publication 92663.doc 200534955. [Embodiment] Compared with the combination of conventional pads and adhesives, the present invention discloses a combination of a polishing pad backing film and an adhesive material that provides excellent polishing quality over a long working day: It is particularly found that an adhesive and a plastic backing film These combinations provide surprisingly good acid resistance and the oxidative conditions established in the crowd media, while maintaining excellent shear strength in the horizontal (platen) plane and low toe strength in the vertical plane (vertical to the delta plate) In particular, it was found that a double-sided pressure-sensitive adhesive (PSA) i provides unexpectedly excellent delamination resistance. The pressure-sensitive adhesive includes a platen-side adhesive with a polyoxymethylene-based adhesive and a Adhesive based on rhenium-based rhenium-based adhesive. It can be considered that polyfluorene-based adhesives provide resistance to chemical resistance to CMP slurry delamination. In addition, there is less penetration of slurry Platen / adhesive interface, therefore, only the perimeter of the platen / adhesive interface is in contact with the slurry. In the application of polysilicon oxygen adhesive and self-adhesive polylithium oxide, it is mixed into Shixi wafer. Irreversible pollution The traditional view of wafers is contrary. In particular, it has been long believed that the unstable monomeric components of polysilicon oxygen appearance and the surface of Shixi wafers should 'hence harmfully change the semiconducting characteristics of the wafers. The present invention avoids such problems Because: Shi Xi-based adhesive is only on the platen side; low amount of concrete enters the platen / adhesive interface; and Shi Xi-based adhesive has inherent resistance to chemical attack on the aggregate. For the purpose of the present invention, an adhesive is defined as any material that can make the polishing pad material (especially the back film) adhere to the polishing platen chemically or mechanically, or both, and be activated by solvents, pressure, heat, cold, or other methods. 92663.doc 200534955. Pressure-sensitive adhesive refers to the type of adhesive that adheres to the surface by only a brief applied pressure at room temperature. Figure 1 shows a specific embodiment of the present invention, a chemical machinery for polishing semiconductor wafers The polishing pad 100. The polishing pad 100 includes a thermoplastic back film and a pressure sensitive adhesive 110 coupled to the thermoplastic back film 105. The pressure sensitive adhesive 11 is arranged so that the chemical mechanical polishing pad 100 is coupled to the polishing table. 115. The pressure sensitive adhesive agent 110 is also arranged to provide a medium capable of being exposed to a polishing slurry medium having a pH of about 4 or higher 125 for at least about 4 days to substantially prevent the chemical mechanical polishing pad 100 from polishing the platen 115 Delaminated interface 120. It is better to prevent delamination by exposure to polishing slurry medium 125 for at least 14 days. Substantial prevention of delamination from slurry entering 130 into interface 120 less than about 2 mm is shown, as further described in the experimental section below For example, a preferred embodiment of the polishing pad 100 includes a pressure-sensitive adhesive 110, which is double-sided, and has a t-cut milk-based adhesive on the first side 13 5 which can be coupled to the platen 115. Adhesive 'has an acrylic-based adhesive on the second side 140 that can be coupled to the thermoplastic backing film 1 Q $. Ideally, only polysilicon oxygen-based on the younger side 13 5 Adhesive, because polishing platen 115-generally has a high surface energy. The thermoplastic backing film 105 generally consists of a low surface energy 1 material that couples the polishing pad 100 to the polishing platen 115 with sufficient strength to a non-adhesive to a polylithic oxygen-based adhesive, such as a high-yield polymer. Bronze. The pressure-sensitive adhesive 110 preferably has a low monomeric polysiloxane content because it minimizes the possibility of contamination of a semiconductor wafer to be polished. Although the scope of the present invention is not limited by theory, it can be inferred that any possible source of contamination is a pressure-sensitive adhesive 92663.doc 200534955: Polysiloxane based adhesive on the first-side 135 of Agent 110. The polysiloxane content of the polysiloxane-based adhesive is ideally low enough to be limited to the first side 135 during polishing. The conventional manufacturing method is used to reduce the amount of monomeric polylithic oxygen of the pressure-sensitive adhesive 110 to a satisfactory level. The content of monomeric poly dream oxygen in the prepared belt structure can be determined by some conventional extraction steps familiar to those skilled in the art. For example, the monomeric polyoxygen can be extracted from the pressure-sensitive adhesive 110 or the polylithium-based adhesive on the -side 135 by ethanol, and then dried in a nitrogen atmosphere. The residue of the extract is then dried in nitrogen, and the polyoxygen content is analyzed by infrared spectrum detection (for example) of the polyoxygen absorption peak at 804 cm-1. For example, in the preferred embodiment, a dried sample of an ethanol extract based on polyoxyethylene-based adhesive has a polysiloxane content of less than about 100 absorption units / gram at 804 cm ^. The extract more preferably has an absorption unit of less than about 50 and more preferably less than about 20 per gram sample weight at 804 cm-1. In other preferred embodiments of the polishing pad 100, the pressure-sensitive adhesive 110 further includes, for example, a carrier film 145 containing polyester and located between the first and second sides 135-40 of the pressure-sensitive adhesive. The carrier film 145 may also include other polymer materials having a sufficiently high surface adhesion force based on the adhesives based on the conventional oxygen and propionate-based materials to the carrier film to be stronger than the carrier plate or the thermoplastic backing film. Examples of these materials are nylon, high-density polyethylene (HDpE), and non-plasticized polyvinyl chloride (HDPE). In other specific embodiments of the polishing pad 100, the thermoplastic backing film 105 is a high-density polyethylene (i.e., a density greater than about 0.96 g / cm3), and more preferably a condensed high-density polyethylene. Examples of high-density polyethylene suitable for use as backing film 105663.doc -10- 200534955 Examples are products DGDA-2490 and DGDA-2480 (Dow Chemical Corporation (Dow)
Chemical Corp))、產品 Paxon BA7718及Escorene HD7845(埃 克森公司（Exxon Corp·))。用於背膜105的其他適合材料包 括經縮合低密度聚乙烯（LDPE)、線性低密度聚乙烯 (LLDPE)、聚丙烯（PP)、乙基乙烯基乙酸酯聚烯烴共聚物 (EVAO)、熱塑性彈性體（TPE)、熱塑性橡膠（TpR)、聚碳酸 酯（PC)、聚醯胺6,6、己二酸-1，6-己二胺聚合物（pA6)及熱塑 性聚胺基甲酸酯（TPU)。背膜105較佳於約5和約5〇密耳厚度 之間。 界面120表佳在平行於台板150旋轉平面之平面具有高剪 切強度。例如’在平行於拋光台板15〇平面之平面，界面12() 在至溫（〜72 F )於1000克具有等於至少約1〇〇〇〇小時之剪切 強度或在158°F於500克具有約i 0000小時之剪切強度。 同時，為有利於替換拋光墊，界面12〇理想在垂直於拋光 平面155之平面具有中間剝落強度。例如，界面12〇在室溫 (〜72 F )72小時停留時間後具有約i和約2〇〇盎司/英寸 (oz/inch)間之剝落強度，更佳在約1〇和約15〇盎司/英寸之 間，更佳在約10和約50盘司/英寸之間。剝落強度較佳在拋 光漿料媒介物125(例如，包含在pH4的至高1〇體積％H2〇2) 中歷至少約24小時保持實質不變。 拋光墊的其他具體實施例進一步包括偶合到熱塑性背膜 105之熱塑性拋光發泡體160。在某些具體實施例中，熱塑 性拋光發泡體160可包括經交聯聚烯烴，如聚乙烯、聚丙烯 及其組合。在某些較佳具體實施例中，拋光體丨6〇由經交聯 92663.doc 11 200534955 同聚物或共聚物之閉孔發泡體組成。含聚乙烯（PE)的閉孔 交聯同聚物發泡體之實例包括：VolaraTM* VolextraTM，自 沃泰克公司（乂〇以1〇(1^\^^11。6，1^八）；八11?1&以1^，自1乂8塑 膠供應公司（JMS Plastics Supply，Inc.)(Nepture，NJ);或 Senflex T-CellTM(Rogers Corp·，Rogers，CT)。含聚乙烯和乙 烯乙酸乙烯酯（EVA)的閉孔交聯共聚物發泡體之實例包 括：VolaraTM*VolextraTM(自沃泰克公司）；Senflex EVA™ (自Rogers公司）；及J-fomaTM(自JMS塑膠供應公司）。 在其他較佳具體實施例中，熱塑性拋光發泡體16〇之閉孔 發泡體由交聯乙烯乙酸乙烯酯共聚物及低密度聚乙稀共聚 物（即，較佳於約0·1和約0.3克/立方釐米之間）之摻合物組 成。在其他有利具體實施例中，摻合物具有約1 ··9和約9: i 間之乙烯乙酸乙烯酯：聚乙烯重量比。在某些較佳具體實施 例中，摻合物包含約5至約45重量％範圍之EVA，較佳約6 至約25重量。/❶，更佳約12至約24重量％。可以認為，此等摻 合物有盈於理想製造具有小尺寸之凹面胞室，如以下進一 步討論。在更佳具體實施例中，摻合物具有約〇 6:9 4和約 1·8··8_2間之乙烯乙酸乙烯酯··聚乙烯重量比。在更佳具體實 施例中，摻合物具有約〇·6:9·4和約12.8 8間之乙烯乙酸乙 細醋··聚乙稀重量比。 在其他有盈具體實施例中，熱塑性拋光發泡體16〇之特徵 :為具有至少約85重量％之二甲苯不溶性物質。檢測二甲 苯不/合性物負之方法為熟諳此藝者所熟悉。此等方法可包 J汝在一甲笨中於120°C蒸煮摻合物24小時，隨後乾 92663.doc -12- 200534955 燥，並比較殘餘不溶性物質與預蒸煮物質之重量。 熱塑性拋光發泡體160可進一步包括至高約25重量％之 無機填料。無機填料可由熟諳此藝者熟悉的任何第I族、第 Π族或過渡金屬組成，以給予發泡體基材理想半透明、顏色 或潤滑特性。例如，無機填料可選自由滑石、氧化鈦、矽 酸鈣、碳酸鈣、矽酸鎂及鋅鹽所組成之群組。在某些較佳 具體實施例中，熱塑性拋光發泡體16〇由約17重量％滑石組 成。在其他具體實施例中，填料包括熟諳此藝者所熟悉的 石夕石（約20至約25重量％)、氧化鋅（約丨重量％)、硬脂酸⑻ 重量。/。）及其它添加劑及顏料（至高約2%)。其他習知填料亦 在本發明之範圍内，如美國專利第6,419,556號、第6,〇99,954 號、第6,425,816號及第M25,803號所揭示，此等專利係以 引用之方式併入本文中。 在其他較佳具體實施例中，拋光體160包括具有具填料顆 粒之基材之V熱性聚合物。在基材内結合包含第II族鹽之填 料顆粒。例如，第„族鹽可為與相容陰離子(較佳；氧根； =合的任何在週期表第„族中包括的元素之陽離子形式，較 佳為鎂（n)。與習知拋光墊比較，由於此等拋光體⑽具有 較高熱導率，在拋光製程中固有的摩擦和放熱化學事件產 生的熱量之耗散改良。此外，可關擇性混人—定類型、 量、形狀及大小的填料顆粒在抛光期間控制熱處理。、 在本發明的某些具體實施例中，第„族鹽包括含硫酸根、 ，脂酸根或碳酸根之一之陰離子。在某些較佳具體實施例 ，第II知鹽包括氧根陰離子，如氧化鎖或氧化每。在其他 92663.doc 200534955 較佳體實施例中，第π族鹽包括 ^ ^ &氧虱根之陰離子，例如， 虱氧化鎂。在其中陰離子為氫4 、 卜 勹虱虱化根之具體實施例中，可 認為，氫氧根放熱分解成氧根 和水在熱處理中擔當有利角 色，並改良CMP製程期間的濕潤性。 在某些較佳具體實施例中，導埶取 _丨 v…、艰合物具有大於約1瓦米- K-之熱導率，較佳大於約$瓦来-〗〗 足木 κ ，最佳大於約15瓦 米 κ-至約20瓦米f。除具有高熱導率夕卜，為避免對位 於欲拋光半導體晶圓上的電晶體或其他電元件之有宝作 用，如短路，抛光體16〇亦較佳為電中性或不導電。例口如， 導熱性聚合物應在25 t：具有大於約lxl〇u歐姆釐米^之體 積電阻’較佳在25。。具有大於約5χ1〇15歐姆釐米-3之體積電 阻。此外’在某些較佳具體實施例中，導熱性聚合物在約2 至約12之pH範圍穩定。在本文中，穩定指併入拋光裝置時 導熱性聚合物在CMP漿料中不顯示可見分解跡象，在使用 期間既不磨損也不破碎。此外，導熱性聚合物不經歷壓鉻 (chromic)效應。因此，與CMp有關的壓力負荷實質上不影 響聚合物之導熱性。例如，此等壓力負荷可在約〇.丨磅/平方 英寸至約50磅/平方英寸之範圍内，較佳約〇·5至約1〇磅/平 方英寸，更佳約1磅/平方英寸至約8磅/平方英寸。 上述基材可為任何在CMP應用所用拋光墊中使用且與完 全併入填料顆粒相容之聚合物。例如，在某些較佳具體實 施例中，基材可由聚胺基甲酸酯、聚烯烴或聚乙烯基酯組 成。基材的選擇性具體實施例包括聚脲、聚碳酸酯、脂族 聚酮、聚砜、芳族聚酮、6,6耐綸、6，12耐綸或聚醯胺。在 92663.doc -14- 200534955 其他具體實施例中，基材為 ^ y 、至性橡膠或可熔融處理的梭 膠。但，基材由閉孔聚丙烯、 ,^ 邱承乙烯、經交聯聚乙烯、乙 坏乙酉夂乙稀醋或聚乙酸乙嫌 s 1 乙Μ組成之具體實施例亦在本發 明之範圍内。 甘个知 對第一近似，對於特定填料顆粒組合物、尺寸和形狀， 熱導率與所存在的填料之量成比例增力 佳具體實施例中，填料㈣i ^在某些較 十顆拉包括至少約2 0重量％之導埶性Chemical Corp.), Paxon BA7718 and Escorene HD7845 (Exxon Corp.). Other suitable materials for the backsheet 105 include condensed low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene (PP), ethyl vinyl acetate polyolefin copolymer (EVAO), Thermoplastic elastomer (TPE), thermoplastic rubber (TpR), polycarbonate (PC), polyamide 6,6, adipic acid-1,6-hexanediamine polymer (pA6), and thermoplastic polyurethane Ester (TPU). The back film 105 is preferably between about 5 and about 50 mils thick. The interface 120 has a high shear strength in a plane parallel to the plane of rotation of the platen 150. For example, 'on a plane parallel to the 15 ° plane of the polishing platen, the interface 12 () has a shear strength equal to at least about 10,000 hours at 1000 gram (~ 72 F) or 500 at 158 ° F Grams have a shear strength of about 10,000 hours. At the same time, in order to facilitate the replacement of the polishing pad, the interface 120 preferably has an intermediate peeling strength in a plane perpendicular to the polishing plane 155. For example, interface 120 has a peel strength between about i and about 200 ounces per inch (oz / inch) after a 72-hour residence time at room temperature (~ 72 F), more preferably between about 10 and about 150 ounces Per inch, more preferably between about 10 and about 50 pans per inch. The peel strength is preferably kept substantially constant for at least about 24 hours in the polishing slurry vehicle 125 (e.g., contained up to 10% by volume H202 at pH 4). Other specific embodiments of the polishing pad further include a thermoplastic polishing foam 160 coupled to the thermoplastic backing film 105. In certain embodiments, the thermoplastic polishing foam 160 may include a cross-linked polyolefin, such as polyethylene, polypropylene, and combinations thereof. In certain preferred embodiments, the polishing body 60 is composed of a closed-cell foamed body of a cross-linked 92663.doc 11 200534955 homopolymer or copolymer. Examples of polyethylene (PE) -containing closed-cell cross-linked homopolymer foams include: VolaraTM * VolextraTM, from Voltec Corporation (10 to 10 (1 ^ \ ^^ 11.6, 1 ^ 8); 8 1 1 & 1 ^, from 1 乂 8 Plastic Supply Company (JMS Plastics Supply, Inc.) (Nepture, NJ); or Senflex T-CellTM (Rogers Corp., Rogers, CT). Contains polyethylene and ethylene Examples of the closed-cell crosslinked copolymer foam of vinyl acetate (EVA) include: VolaraTM * VolextraTM (from Voltec Corporation); Senflex EVA ™ (from Rogers Corporation); and J-fomaTM (from JMS Plastics Supply Corporation) In other preferred embodiments, the closed-cell foam of the thermoplastic polishing foam 160 is composed of a crosslinked ethylene vinyl acetate copolymer and a low density polyethylene copolymer (ie, preferably less than about 0.1 And about 0.3 grams per cubic centimeter) of the blend composition. In other advantageous embodiments, the blend has an ethylene vinyl acetate: polyethylene weight ratio between about 1. · 9 and about 9: i. In certain preferred embodiments, the blend comprises EVA in the range of about 5 to about 45% by weight, preferably about 6 to about 25% by weight. It is preferably about 12 to about 24% by weight. It is believed that these blends are advantageous for making concave cells with small dimensions, as discussed further below. In a more specific embodiment, the blends have about 0.6 : 9 4 and about 1 · 8 ·· 8_2 weight ratio of ethylene vinyl acetate · polyethylene. In a more preferred embodiment, the blend has a ratio between about 0.6: 9 · 4 and about 12.8 Ethylene acetate acetic acid ·· polyethylene weight ratio. In other specific embodiments, the thermoplastic polishing foam 16 is characterized by having xylene insoluble matter of at least about 85% by weight. The xylene is not detected / The method of negative compounding is familiar to those skilled in the art. These methods can be used to cook the blend at 120 ° C for 24 hours in a paraffin, and then dry 92663.doc -12- 200534955 dry and compare The weight of the residual insoluble material and the pre-cooked material. The thermoplastic polishing foam 160 may further include up to about 25% by weight of an inorganic filler. The inorganic filler may be composed of any Group I, Group Ⅱ, or transition metal familiar to those skilled in the art, To give the foam substrate ideal translucency and color Or lubricating properties. For example, the inorganic filler can be selected from the group consisting of talc, titanium oxide, calcium silicate, calcium carbonate, magnesium silicate, and zinc salts. In certain preferred embodiments, the thermoplastic polishing foam 160 is composed of about 17% by weight of talc. In other specific embodiments, the filler includes stone xisite (about 20 to about 25% by weight), zinc oxide (about 丨% by weight), stearin, which is familiar to those skilled in the art. Acid weight. /. ) And other additives and pigments (up to about 2%). Other conventional fillers are also within the scope of the present invention, as disclosed in U.S. Patent Nos. 6,419,556, 6,099,954, 6,425,816, and M25,803, which are incorporated herein by reference. . In other preferred embodiments, the polishing body 160 includes a V-thermopolymer having a substrate with filler particles. Filler particles comprising a Group II salt are incorporated in the substrate. For example, the salt of group „may be a cationic form of a compatible anion (preferred; oxygen radicals) with any of the elements included in group„ of the periodic table, preferably magnesium (n). With conventional polishing pads In comparison, due to the higher thermal conductivity of these polished bodies, the friction and heat dissipation generated by exothermic chemical events inherent in the polishing process are improved. In addition, it can be selectively mixed—type, amount, shape, and size The filler particles are controlled for heat treatment during polishing. In some embodiments of the present invention, the group salt includes an anion containing one of sulfate group, fatty acid group or carbonate group. In some preferred embodiments, Group II salts include oxygen anions, such as oxidative locks or oxidants. In other preferred embodiments of 92663.doc 200534955, the group π salts include anions of oxygen lice root, for example, lice magnesium oxide. In a specific embodiment in which the anion is hydrogen 4 and the roots of lice, it is believed that the exothermic decomposition of hydroxide to oxygen and water play a beneficial role in heat treatment and improve the wettability during the CMP process. Some more In a specific embodiment, the lead __v ..., the hard compound has a thermal conductivity of greater than about 1 watt meter-K-, preferably greater than about $ watts-〖〗 Full wood κ, most preferably greater than about 15 watts M κ- to about 20 watts m. In addition to having a high thermal conductivity, in order to avoid the valuable role of transistors or other electrical components on the semiconductor wafer to be polished, such as a short circuit, the polishing body 16 is also better It is electrically neutral or non-conductive. For example, the thermally conductive polymer should be at 25 t: having a volume resistance greater than about 1 × 10u ohm cm ^, preferably at 25. having a volume resistance greater than about 5 × 10 15 ohm cm-3 In addition, in certain preferred embodiments, the thermally conductive polymer is stable at a pH range of about 2 to about 12. In this context, stable refers to the thermally conductive polymer in the CMP slurry when incorporated into a polishing device There are no visible signs of decomposition, neither wear nor break during use. In addition, the thermally conductive polymer does not experience the chromium effect. Therefore, the pressure load associated with CMP does not substantially affect the thermal conductivity of the polymer. For example, these pressure loads can range from about 0.1 pounds per square inch to about 5 Within the range of 0 psi, preferably from about 0.5 to about 10 psi, more preferably from about 1 psi to about 8 psi. The substrates described above can be used in any CMP application Polymers used in polishing pads that are compatible with fully incorporated filler particles. For example, in certain preferred embodiments, the substrate may consist of polyurethane, polyolefin, or polyvinyl ester. Substrate Selective specific examples include polyurea, polycarbonate, aliphatic polyketone, polysulfone, aromatic polyketone, 6,6 nylon, 6,12 nylon, or polyamide. In 92663.doc -14- 200534955 In other specific embodiments, the substrate is ^ y, virgin rubber, or melt-processable shuttle rubber. However, the substrate is made of closed-cell polypropylene, ^ Qiu Cheng ethylene, cross-linked polyethylene, diethyl ether Specific examples of the composition of acetic acid or polyacetic acid s 1 and MH are also within the scope of the present invention. For the first approximation, for a specific filler particle composition, size and shape, the thermal conductivity is proportional to the amount of filler present. In a specific embodiment, the filler ㈣i ^ Conductivity of at least about 20% by weight
聚合物，更佳約40至約70重量％ …J 里。填枓顆粒之大小和形肤 亦影響導熱性聚合物之導熱性之程度。例如，在某此 具體實施例中，填料顆粒具有球形形狀。在其他㈣具體 實施例中，填料顆粒具有在約 一 在、力50裢未至約1微米範圍之平均 直徑，更佳約5微米至約丨微米。在苹 你示雙百盃具體實施例中， 填料顆粒實質上遍及基材混入 竹匕入以在基材中提供均勻顆粒 分佈。 熱塑性拋光發泡體160由黏著劑162偶合到熱塑性背膜 ⑻，如詩使背膜⑻偶合到抛光台板ιΐ5之感壓黏著劑 110。或者’熱塑性拋光發泡體16〇藉由熱熔接或藉由使熔 融背膜105擠壓塗覆於熱塑性發泡體16〇之片上而偶合。偶 合亦可用化學接合方法取得。在某些有益具體實施财， 熱塑性拋光發泡體160具有由凹面胞室17〇和塗覆凹面胞室 170之内表面180之拋光劑175組成之表面。 在某些具體實施例，熱塑性拋光發泡體16〇具有在整個發 泡體内形成的胞室16 5。在某些較佳具體實施例中，胞室i 6 5 實質上為球形。在其他較佳具體實施例中，胞室i65之大小 92663.doc -15- 200534955 應使在切削基材時，在基材表面的開放凹面胞室1 7 0具有於 約100微米和600微米間之平均大小。凹面胞室165之平均大 小在約100至約350微米之範圍内，較佳約1〇〇至約25〇微 米，更佳約115至約200微米。胞室165大小可用美國材料實 驗學會（West Conshohocken，ΡΑ)研究和頒佈的標準規程測 定，例如，ASTMD3 576，此規程係以引用之方式併入本文 中。在某些較佳具體實施例中，在胞室165之形狀實質為球 形時，胞室大小約等於平均胞室直徑。在包含EVA共聚物 之具體實施例中，例如，如以引用之方式併入本文的派瑞 茲（Perez)等人，j· Appl. Polymer Sci，vol. 68，1998 pp 1237-1244所揭示，胞室直徑為共聚物摻合物之eva含量之 函數。如派瑞茲等人所揭示，體積密度和胞室密度呈相反 關係。因此，在其他具體實施例中，凹面胞室1 70在基材表 面之密度在2.5和約1〇〇個胞室/毫米2之間，更佳在約6〇和約 100個胞室/毫米2之間。例如，胞室密度可自視覺檢查基材 表面之顯微像測定。 拋光劑175可包括由在拋光體表面上二級反應劑接枝產 生的一或多種陶瓷性化合物或一或多種有機聚合物，如頒 予遙S·奥本（Yaw S· Obeng)和愛德華M.約克利（Edward M. Yokley)的美國專利申請案第〇9/994,407號’’ 一種改變及保 持拋光墊之表面性能之方法及其特定應用”（A Method of Altering and Preserving the Surface Properties of A Polishing Pad and Specific Applications Therefor)所揭示， 此專利係以引用之方式併入本文中。陶瓷拋光劑175可包括 92663.doc •16- 200534955 在用含氧有機金屬化合物作為二級反應劑產生經接枝表面 時產生的無機金屬氧化物。例如，在某些具體實施例中， 拋光劑175為無定形石夕石或氧化鈦。在此具體實施例中，二 級電漿混合物包括鈦。其他實例包括含過渡金屬（如，㈣ 鈕)之二級電槳混合物。但，能夠生成揮發性有機金屬化合 物（如，包含一或多個氧原子的金屬醋）且能夠接枝到聚合物 表面的任何金屬元素適用。 口 亦可詩作為有機金屬性二級電漿混合物之金屬部分。 在此等具體實施例中，有機金屬反應劑之有機部分可為 係u由乳切和氧化鈦所組成之料（如，二氧化石夕 :::氧化鈦)、四乙氧基錢聚合物和烧氧基鈦聚合物之群 仁可用很多其他二級反應劑產生陶竟椒光劑⑺。 電漿反應劑可包括臭氧、烧氧基石夕院、水、氨、醇、：物 氧化氫。例如，在較佳具體實施例中，二級電聚 1可包括’鈦酿’燒氧基组，包括其中燒氧部分具有 1::原子之炫氧基組;溶於水的乙酸链溶 油精的烷醇錳；乙酸铉· 7t 广、观 踐m .甘 乙丙啊鐘；醇紹，·燒氧基紹酸 ^ 呂〜、中烷氧部分具有卜5個碳原子之烷氧美夢. =基錯酸鹽；乙酸鎂;及乙酿_。亦涵蓋用：級 的其他具體實施例’例如’規氧基錢和臭氧、 基㈣和氨、鈦1旨和水、㈣和醇或鈦S旨和臭氧。 或者’在财機化合物作為二級„反應劑時:抛光劑 92663.doc < 17- 200534955 1 75可包括有機聚合物。此等二級反應劑之實例包括··烯丙 醇，烯丙胺，其中烧基包含1_8個碳原子之烯丙基烧胺；烯 丙其中烧基包含個碳原子之二級胺；其中烧基包含 1-8個碳原子之烷基肼；丙烯酸；甲基丙烯酸；含丨_8個碳原 子之丙烯酸酯；含1-8個碳原子之甲基丙烯酸酯；或乙烯基 吡啶及乙烯基酯，例如，乙酸乙烯酯。在某些較佳具體實 施例中，拋光劑1 75選自由聚醇和聚胺組成之聚合物之群 組。 在較佳環境（拋光裝置180)中，拋光墊1〇〇描繪於圖1中。 裝置1 80包括機械驅動的載頭1 85和載環1 90，以固定半導體 曰曰圓195。載頭185可對拋光台板115放置，以對拋光台板115 給予拋光力。 圖2A-2C顯示根據本發明另一具體實施例的選擇性步驟 之橫截面視圖，一種製造化學機械拋光墊2〇〇之方法。如圖 2A中所示’该方法包括提供熱塑性抛光發泡體2〇5。如圖2B 中所示，該方法亦包括使熱塑性背膜21〇層合到熱塑性拋光 發泡體205。層合由化學接合用習知黏著劑取得，如熟諳此 藝者所熟悉的環氧材料或其他材料或感壓黏著劑，如雙側 材料，兩側均為以丙浠酸系材料為基礎的黏著劑。在其他 較佳具體實施例中，層合由使熔融的背膜材料擠壓塗覆於 舍泡體上取得’而在另外的其他具體實施例中，背膜21 〇係 熱熔接到熱塑性拋光發泡體205上。 該方法進一步包括使感壓黏著劑215偶合到熱塑性背膜 210(圖2C)。如上提到，感壓黏著劑215經佈置，以使化學 92663.doc -18- 200534955 機械拋光墊200偶合到拋光台板220，並提供能夠經暴露於 具有約4或更高pH之拋光漿料媒介物至少約4天實質上防止 拋光墊200自拋光台板220脫層之界面225。 感壓黏著劑21 5較佳包括雙側帶，該雙側帶具有包含以聚 石夕氧為基礎黏著劑之第一側23 0及包含夾於載膜240間的以 丙烯酸系材料為基礎黏著劑之第二側235。以丙烯酸系材料 為基礎之黏著劑係偶合到熱塑性背膜21 〇，而以聚矽氧為基 礎之黏著劑經佈置，以偶合到拋光台板220。 本發明之另一具體實施例（由上述方法製造的用於拋光 半導體晶圓之化學機械拋光墊）顯示於圖2C中。可將任何上 述拋光體205、背膜210及感壓黏著劑21 5之具體實施例用於 製造化學機械拋光墊2〇〇之方法。 例如，提供熱塑性拋光發泡體2〇5包括暴露拋光發泡體 205内的胞室245，以形成包含凹面胞室255之表面25〇，並 用拋光劑260塗覆凹面胞室之内表面。拋光發泡體2〇5内的 封閉胞室245之大小影響最終在表面25〇上形成的凹面胞室 255之大小。有數種因素影響封閉胞室245之大小。可控制 乙烯乙酸乙烯酯共聚物和聚乙烯的相對量，以最佳調節在 毛心製私中產生的胞室之大小。此外，所用發泡方法種類 可產生不同胞室大小。凹面胞室255較佳具有約1〇〇微米和 約600微米間之平均大小及至少約4·5個胞室/毫米2之胞室 么度，更佳具有約100微米和約200微米間之大小及至少約 60個胞室/毫米2之胞室密度。 可用熟諳此藝者所熟悉的任何f知發泡方法提供抛光發 92663.doc -19- 200534955 泡體205。發泡方法可包括（例如）在摻合機中摻合含拋光發 泡體205之聚合物。發泡方法亦可包括用照射或化學方法取 得交聯使聚合物在拋光發泡體205中交聯（XL)。發泡方法可 進一步包括較佳在壓力下形成發泡體2〇5和發泡劑之混合 物，並通過習知模擠壓混合物，以形成封閉胞室發泡體之 片。 使胞室245暴露成含凹面胞室255之表面可由熟諳此藝者 所熟悉的任何習知方法取得。例如，暴露可藉由在平面狀 表面上固定抛光發泡體205 '且自拋光發泡體2〇5之表面切 割薄層（即’約1200微米和約2000微米之間）而取得。在某些 較佳具體實施例中，切削或切割可用切削裝置進行，如由 非月-克非爾（Feken-Kirfel)(Aachen，Germany)提供者。 用拋光劑260塗覆内表面用以引用之方式併入本文的美 國專利申請案第09/994,407號所揭示之接枝步驟取得。因 此’在某些具體實施例中，塗覆包括使凹面胞室内表面2 5 5 暴路於引發電漿反應劑（第一電漿反應劑），以在其上產生經 改質之表面α塗覆可進一步包括使經改質表面暴露於二級 電漿反應劑（第二電漿反應劑），以在經改質表面上產生經接 枝的表面，經接枝表面包括拋光劑26〇。可將美國專利申請 案第09/994,407號中描述的任何一級和二級反應劑或步驟 用於接枝製程，以在拋光發泡體205之凹面胞室245之内表 面上塗覆拋光劑260。 現已描述本發明，可以相信，藉由參考以下試驗，本發 明將變得更加顯而易見。應瞭解，試驗僅用於說明目的， 92663.doc -20- 200534955 且不應解釋為限制本發明。例如，雖然以下所述試驗可在 實驗室裝置中進行，但熟諳此藝者可將具體數字、尺寸和 量調節到完全規模工廠裝置所用的適合值。 試驗 檢驗數種市售PSAs，以檢定在不同類型媒介物中漿料進 入動力學及剝落強度。自3M公司（St. Paul，MN)的產品9731 為雙側PS A，該PS A在聚醋載膜一側具有聚矽氧黏著劑，在 另一側具有丙浠酸系黏著劑。檢驗數種其他3M產品： 9425(丙烯酸酯聚合物和聚氯乙烯之混合物）、701DL、 943 0、9495LSE及NPE-201。另外檢驗自黏著劑研究公司 (Adhesive Research Inc.)(Glenrock，PA)的產品 DEV8906、 DEV 8 0492 8及EL8917。亦檢驗自埃沃瑞-丹尼森公司（Avery Dennison Inc.)(Painesville，OH)的產品 FT 8300，一 種處於 聚酯載膜上的丙烯酸系黏著劑。 試驗1 對不同PSAs和背膜之組合研究具有不同pHs之溶液進 入。使PSAs和背膜相互偶合，並使墊黏著到工業台頂拋光 機之拋光台板。將此裝配用在4至10範圍pH的連續流工業緩 衝液（Fisher Scientific，Pittsburgh，PA)淹沒，以模擬化學機 械拋光期間的漿流。測量流體侵入的引導邊緣移動的距 離，由此測定溶液進入PAS和背膜間界面之進入。為便於測 量，用由聚碳酸酯或高密度聚乙烯組成的透明熱塑膠片模 擬拋光墊之背膜。 圖3A-3I中顯示進入（單位，毫米）作為浸泡時間平方根之 92663.doc -21 - 200534955 函數之典型結果。進入數據作為時間平方根之函數緣製， 以查看是否進入受擴散限制。直線顯示擴散限制機制。產 品9731比其他PSAs具有實質較慢進入速率。例如，在4 溶液中，在（80分）1/2(約4.4天）後進入小於2毫米，且在中性 和鹼性pHs具有甚至更慢進入速率（約14天）。 試驗2 研究氧化溶液對不同黏著劑背膜之剝落強度之影響。在 1-10%私〇2存在與不存在下於調節到約pH 4之溶液中浸泡 〇至約24小時後，試驗夾在不銹鋼板和鋁片間的不同As。 剝落強度用90。試驗角用AR_1000型黏著/釋放檢驗儀 (Cheminstrument，Mentor，〇H)檢測。數據分析用製造商提 供的EZ STATS分析軟體進行。 典型結果顯示於圖4中，用單位盘司/英寸表示。自此等 研究的結果顯示，與其他黏著劑比較，產品973丨之剝落強 度對游離基和氏〇2所產生氧化種類導致的變化更有耐性。 與其他黏著劑不同，產品9731之剝落強度達至少24小時之 停留時間理想保持不變，且處於易於良好使用的中間值。 雖然已詳細描述本發明，但熟諳此藝者應懂得，可在不 脫離本發明範圍下做出各種變化、代替及變更。 【圖式簡單說明】 為更完全瞭解本發明，參考以上說明應結合以下附圖， 其中： 圖1顯示本發明之拋光墊橫截面； 圖2A-C顯示根據本發明原理製造拋光墊之方法之選擇性 92663.doc -22- 200534955 步驟之橫截面視圖； 圖3 A至31顯示本發明之感壓黏著劑及其它黏著劑之進入 試驗之典型數據；及 圖4顯示本發明之感壓黏著劑及其它黏著劑之剝落強度 試驗之典型數據。 【圖式代表符號說明】 100 化學機械拋光墊 105 熱塑性背膜 110 感壓黏著劑 115 拋光台板 120 界面 125 拋光漿料媒介物 130 漿料進入 135 第一側 140 第二側 145 載膜 150 台板 155 抛光平面 160 熱塑性拋光發泡體 162 黏著劑 165 胞室 170 凹面胞室 175 拋光劑 180 内表面 92663.doc -23- 200534955 185 載頭 190 載環 195 半導體晶圓 200 化學機械拋光墊 205 熱塑性拋光發泡體 207 未發現 210 熱塑性背膜 215 感壓黏著劑 220 拋光台板 225 界面 230 第一側 235 第二側 240 載膜 245 胞室 250 表面 255 凹面胞室 260 - 拋光劑 92663.doc -24-Polymer, more preferably about 40 to about 70% by weight ... The size and shape of the filler particles also affect the degree of thermal conductivity of the thermally conductive polymer. For example, in one such embodiment, the filler particles have a spherical shape. In other embodiments, the filler particles have an average diameter in the range of about 50 μm to about 1 μm, and more preferably about 5 μm to about 1 μm. In the two-hundred cup embodiment, filler particles are incorporated throughout the substrate to provide a uniform particle distribution in the substrate. The thermoplastic polishing foam 160 is coupled to the thermoplastic backing film 由 by an adhesive 162, such as the pressure sensitive adhesive 110 which couples the backing film ⑻ to the polishing platen 5. Alternatively, the ' thermoplastic polished foam 160 is coupled by heat welding or by extruding the molten backing film 105 onto a sheet of the thermoplastic foam 160. Couplings can also be obtained by chemical joining methods. In some beneficial implementations, the thermoplastic polishing foam 160 has a surface composed of a concave cell 170 and a polishing agent 175 that coats the inner surface 180 of the concave cell 170. In certain embodiments, the thermoplastic polishing foam 160 has cells 165 formed throughout the foam. In certain preferred embodiments, the cell i 6 5 is substantially spherical. In other preferred embodiments, the size of the cell i65 is 92663.doc -15- 200534955. When cutting the substrate, the open concave cell 1 70 on the surface of the substrate should be between about 100 microns and 600 microns. The average size. The average size of the concave cell 165 is in the range of about 100 to about 350 microns, preferably about 100 to about 250 microns, and more preferably about 115 to about 200 microns. Cell size 165 can be determined using standard protocols developed and published by the American Society for Materials Testing (West Conshohocken, PA), for example, ASTM D3 576, which is incorporated herein by reference. In certain preferred embodiments, when the shape of the cell 165 is substantially spherical, the cell size is approximately equal to the average cell diameter. In a specific embodiment comprising an EVA copolymer, for example, as disclosed by Perez et al., J. Appl. Polymer Sci, vol. 68, 1998 pp 1237-1244, which is incorporated herein by reference, Cell diameter is a function of the eva content of the copolymer blend. As revealed by Paritz et al., Bulk density and cell density are inversely related. Therefore, in other specific embodiments, the density of the concave cells 1 70 on the substrate surface is between 2.5 and about 100 cells / mm 2, and more preferably between about 60 and about 100 cells / mm. Between 2. For example, cell density can be determined from a microscopic image of the surface of a substrate by visual inspection. The polishing agent 175 may include one or more ceramic compounds or one or more organic polymers produced by grafting a secondary reactant on the surface of the polishing body, such as awarded to Yaw S. Obeng and Edward M. A Method of Altering and Preserving the Surface Properties of A, U.S. Patent Application No. 09 / 994,407 by Edward M. Yokley Polishing Pad and Specific Applications Therefor), this patent is incorporated herein by reference. Ceramic polishing agent 175 may include 92663.doc • 16- 200534955 in the use of oxygen-containing organometallic compounds as secondary reactants An inorganic metal oxide generated on the surface of a branch. For example, in certain embodiments, the polishing agent 175 is amorphous stone or titanium oxide. In this embodiment, the secondary plasma mixture includes titanium. Other examples Includes secondary electric paddle mixtures containing transition metals (eg, krypton). However, it is capable of generating volatile organometallic compounds (eg, containing one or more oxygen species) Metal vinegar) and any metal element that can be grafted onto the polymer surface is suitable. Oral can also be used as the metal part of the organometallic secondary plasma mixture. In these specific embodiments, the organic part of the organometallic reactant It can be a material consisting of milk cut and titanium oxide (eg, SiO2 ::: titanium oxide), a group of tetraethoxy polymers, and titanium oxide polymers. Many other secondary grades are available. The reactant produces Tao Jingjiao brightener 电. Plasma reactants may include ozone, oxy-fired stone Xiyuan, water, ammonia, alcohol, hydrogen peroxide. For example, in a preferred embodiment, the secondary electropolymerization 1 May include 'titanium-brewed' oxy-oxygen groups, including oxy-oxy groups in which the oxy-oxygen moiety has 1 :: atoms; manganese alkoxides of acetic acid chain-soluble olein soluble in water; osmium acetate · 7t Glycolyl alcohol; Alcohol, succinic acid ^ Lu ~, alkoxy sweet dreams with 5 carbon atoms in the alkoxy moiety. = Glyoxylate; Magnesium acetate; and Ethanol. Covered with: Other specific examples of the stage 'e.g., oxidant and ozone, hydrazone and ammonia, titanium and water And (iv) an alcohol or titanium and ozone purpose or S 'in the earnings as two organic compounds "reaction solvent: Polishing agent 92663.doc < 17- 200534955 1 75 may include an organic polymer. Examples of such secondary reactants include allyl alcohol, allylamine, in which the allyl group contains 1 to 8 carbon atoms; allyl, wherein the allyl group contains a secondary carbon atom; Alkyl hydrazines containing 1-8 carbon atoms; acrylic acid; methacrylic acid; acrylates containing __ 8 carbon atoms; methacrylates containing 1-8 carbon atoms; or vinylpyridine and vinyl esters , For example, vinyl acetate. In certain preferred embodiments, the polishing agent 175 is selected from the group of polymers consisting of a polyol and a polyamine. In a preferred environment (polishing device 180), the polishing pad 100 is depicted in FIG. The device 1 80 includes a mechanically-driven carrier head 1 85 and a carrier ring 1 90 to hold a semiconductor, namely a circle 195. The carrier 185 may be placed on the polishing platen 115 to give a polishing force to the polishing platen 115. Figures 2A-2C show cross-sectional views of selective steps according to another embodiment of the present invention, a method of manufacturing a chemical mechanical polishing pad 2000. As shown in Figure 2A ', the method includes providing a thermoplastic polished foam body 205. As shown in FIG. 2B, the method also includes laminating a thermoplastic backing film 21 to a thermoplastic polishing foam 205. Lamination is obtained with conventional adhesives used in chemical bonding, such as epoxy materials or other materials familiar to the artist or pressure-sensitive adhesives, such as double-sided materials, both sides of which are based on propionic acid-based materials. Adhesive. In other preferred embodiments, the lamination is obtained by extruding the molten back film material onto the foam body, and in still other specific embodiments, the back film 2 0 is thermally fused to the thermoplastic polishing hair. On the body 205. The method further includes coupling a pressure sensitive adhesive 215 to the thermoplastic backing film 210 (FIG. 2C). As mentioned above, the pressure sensitive adhesive 215 is arranged to couple the chemical 92663.doc -18- 200534955 mechanical polishing pad 200 to the polishing platen 220 and provide a polishing slurry capable of being exposed to a pH of about 4 or higher The medium substantially prevents the polishing pad 200 from delaminating the interface 225 from the polishing platen 220 for at least about 4 days. The pressure-sensitive adhesive 21 5 preferably includes a double-sided tape having a first side 23 0 containing a polylithium-based oxygen-based adhesive and an acrylic-based material including a sandwich between the carrier film 240.剂 的 第二 侧 235. An acrylic-based adhesive is coupled to the thermoplastic backing film 21, and a polysiloxane-based adhesive is arranged to be coupled to the polishing platen 220. Another specific embodiment of the present invention (a chemical mechanical polishing pad for polishing a semiconductor wafer manufactured by the above method) is shown in FIG. 2C. Any of the above-mentioned specific embodiments of the polishing body 205, the back film 210, and the pressure-sensitive adhesive 215 can be used in a method for manufacturing a chemical mechanical polishing pad 200. For example, providing the thermoplastic polishing foam body 205 includes exposing the cells 245 inside the polishing foam body 205 to form a surface 250 including a concave cell 255, and coating the inner surface of the concave cell with a polishing agent 260. The size of the closed cell 245 in the polished foam body 205 affects the size of the concave cell 255 that is finally formed on the surface 25. Several factors affect the size of the closed cell 245. The relative amounts of ethylene-vinyl acetate copolymer and polyethylene can be controlled to optimally adjust the size of the cells produced in wool cores. In addition, the type of foaming method used can produce different cell sizes. The concave cell 255 preferably has an average size between about 100 microns and about 600 microns and a cell size of at least about 4.5 cells / mm2, more preferably between about 100 microns and about 200 microns. Size and cell density of at least about 60 cells / mm2. The polished body 92663.doc -19- 200534955 foam 205 can be provided by any foaming method familiar to those skilled in the art. The foaming method may include, for example, blending a polymer containing polishing foam 205 in a blender. The foaming method may also include cross-linking (XL) of the polymer in the polished foam 205 by obtaining crosslinking by irradiation or chemical methods. The foaming method may further include forming a mixture of the foam body 205 and the foaming agent preferably under pressure, and extruding the mixture through a conventional die to form a sheet of closed cell foam body. The surface of the cell 245 exposed to include a concave cell 255 can be obtained by any conventional method familiar to those skilled in the art. For example, exposure can be obtained by fixing the polishing foam 205 'on a planar surface and cutting a thin layer (i.e.,' between about 1200 microns and about 2000 microns) from the surface of the polishing foam 205. In certain preferred embodiments, cutting or cutting can be performed with a cutting device, such as provided by a Feken-Kirfel (Aachen, Germany) provider. The inner surface is coated with a polishing agent 260 for reference by the grafting procedure disclosed in U.S. Patent Application No. 09 / 994,407, which is incorporated herein by reference. Therefore, in some embodiments, the coating includes causing the surface of the concave cell to be exposed to a plasma reactant (first plasma reactant) to generate a modified surface alpha coating thereon. The coating may further include exposing the modified surface to a secondary plasma reactant (second plasma reactant) to produce a grafted surface on the modified surface, the grafted surface including a polishing agent 26. Any of the primary and secondary reagents or steps described in U.S. Patent Application No. 09 / 994,407 can be used in the grafting process to coat the polishing agent 260 on the inner surface of the concave cell 245 of the polishing foam 205. Having described the invention, it is believed that the invention will become more apparent by reference to the following tests. It should be understood that the tests are for illustrative purposes only, 92663.doc -20-200534955 and should not be construed as limiting the invention. For example, although the tests described below can be performed in a laboratory installation, those skilled in the art can adjust specific numbers, sizes, and quantities to suitable values for full-scale factory installations. Testing Several commercially available PSAs were tested to verify the kinetics of the slurry ingress and peeling strength in different types of media. The product 9731 from 3M Company (St. Paul, MN) is a double-sided PS A. The PS A has a polysiloxane adhesive on one side of the polyacetate carrier film and a propionic acid-based adhesive on the other side. Inspected several other 3M products: 9425 (mixture of acrylic polymer and polyvinyl chloride), 701DL, 943 0, 9495LSE, and NPE-201. In addition, products DEV8906, DEV 8 0492 8 and EL8917 from Adhesive Research Inc. (Glenrock, PA) were examined. Also tested was FT 8300, a product of Avery Dennison Inc. (Painesville, OH), an acrylic adhesive on a polyester carrier film. Experiment 1 The study of the combination of different PSAs and backing films with different pHs was performed. The PSAs and the back film were coupled to each other and the pad was adhered to the polishing platen of an industrial bench top polishing machine. This assembly was flooded with a continuous flow industrial buffer (Fisher Scientific, Pittsburgh, PA) in the pH range of 4 to 10 to simulate a slurry flow during chemical mechanical polishing. The distance at which the leading edge of the fluid invades was measured was measured to determine the entry of the solution into the interface between the PAS and the dorsal membrane. To facilitate measurement, the backing film of the polishing pad was simulated with a transparent thermoplastic sheet composed of polycarbonate or high-density polyethylene. Figures 3A-3I show the typical results of the entry (unit, mm) as a function of the square root of the soaking time 92663.doc -21-200534955. Enter the data as a function of the square root of time to see if the entry is restricted by diffusion. The straight line shows the diffusion limiting mechanism. Product 9731 has a substantially slower entry rate than other PSAs. For example, in a 4 solution, it enters less than 2 mm after (80 minutes) 1/2 (about 4.4 days), and has even slower entry rates (about 14 days) at neutral and alkaline pHs. Experiment 2 investigated the effect of the oxidizing solution on the peel strength of the back film with different adhesives. After immersing in a solution adjusted to about pH 4 in the presence and absence of 1-10% O2 for 0 to about 24 hours, the different As sandwiched between the stainless steel plate and the aluminum sheet were tested. Use 90 for peeling strength. The test angle was detected with an AR-1000 adhesion / release tester (Cheminstrument, Mentor, OH). Data analysis was performed using EZ STATS analysis software provided by the manufacturer. Typical results are shown in Figure 4, expressed in units of pans / inch. The results of these studies have shown that, compared with other adhesives, the peeling strength of the product 973 丨 is more resistant to changes caused by free radicals and oxidative species produced by θ2. Unlike other adhesives, the product 9731 has a peel strength of at least 24 hours and a dwell time ideally unchanged and at an intermediate value that is easy to use. Although the present invention has been described in detail, those skilled in the art will understand that various changes, substitutions and alterations can be made without departing from the scope of the invention. [Brief description of the drawings] For a more complete understanding of the present invention, the following description should be combined with reference to the above description, wherein: FIG. 1 shows a cross-section of a polishing pad of the present invention; Selective 92663.doc -22- 200534955 cross-sectional view of steps; Figures 3 A to 31 show typical data for entry tests of pressure sensitive adhesives and other adhesives of the invention; and Figure 4 shows pressure sensitive adhesives of the invention Typical data for peel strength tests of other adhesives. [Illustration of the representative symbols of the figure] 100 chemical mechanical polishing pad 105 thermoplastic back film 110 pressure-sensitive adhesive 115 polishing platen 120 interface 125 polishing slurry medium 130 slurry entering 135 first side 140 second side 145 carrier film 150 units Plate 155 Polishing plane 160 Thermoplastic polishing foam 162 Adhesive 165 Cell 170 Concave cell 175 Polish 180 Internal surface 92663.doc -23- 200534955 185 Carrier 190 Carrier ring 195 Semiconductor wafer 200 Chemical mechanical polishing pad 205 Thermoplastic Polishing foam 207 No 210 found Thermoplastic back film 215 Pressure-sensitive adhesive 220 Polishing platen 225 Interface 230 First side 235 Second side 240 Carrier film 245 Cell 250 Surface 255 Concave cell 260-Polishing agent 92663.doc- twenty four-