568944 A7568944 A7
B7 發明説明（1 發明之技術領域 本發明提供一種使基材，尤其是包括導電金屬之表面之 拋光或平整化之系統及方法。 發明背景 化學_機械抛光（CMP)為微電子裝置（如半導體晶圓）之基 材表面平整化f &之製程。CMP-般包含將化學反應及機械 研磨拋光組合物或、、漿料〃加於基材表面。拋光組合物一 般係藉由使表面與含浸飽和拋光組合物之拋光墊接觸，加 於基材之表面。當拋光組合物與基材化學反應時，研磨料 會自基材表面移除物質，因而將基材拋光。化學機械拋光 更詳細之說明列於美國專利第4, 671, 851、4, 91〇, 155，及 4, 944, 836 中。 因為平整化表面可使半導體晶圓之效能最佳化，因此選 用之半導體晶圓表面需在不會對底下之結構或型態產生副 作用下’在高速下以高選擇性進行拋光。因此，使移除速 率及選擇性最大化之組合物對於有效的製造微電子裝置相 當重要。 雖然已知有許多CMP組合物及方法可改善移除速率及選 擇性’但該CMP組合物通常使用昂貴且在環境上並不期望之 氧化劑。例如銅之化學-機械拋光過程中使用之氧化劑系敘 述於美國專利第6, 096, 652號中。 因此，目前需要者為可改善移除速率及拋光選擇性，同 時使表面缺陷及下層結構及型態之損害為最小，且不使用 氧化劑之其他拋光系統及方法。本發明係針對提供該拋光 -4-本紙張尺度適用中國國家標準(CMS) A4规格(21〇X 297公釐) 568944 A7 _____ B7 ___ 五、發明説明（5 ) 適用之研磨或非研磨墊。再者，拋光系統可包括拋光墊（研 磨墊或非研磨墊），其中拋光系碎之液體部份懸浮研磨料， 或拋光系統之液體部份中並未懸浮研磨料。適用之研磨墊 敘述於例如美國專利第5, 849, 〇51及5, 849, 〇52號中。適用 之拋光墊包含例如織布及不織布拋光墊。再者，適用之拋 光墊可包括任何不同密度、硬度、厚度、壓著性、壓著之 回彈能力及壓著模數之適用聚合物。適用之聚合物包括例 如聚氯乙缔、聚氟乙烯、尼龍、氟碳化物、聚碳酸酯、聚 酯、聚丙埽酸酯、聚醚、聚乙烯、聚胺基甲酸酯、聚苯乙 婦、聚丙烯、聚二聚氰胺、聚醯胺、聚乙酸乙烯酯、聚丙 晞酸、聚丙烯醯胺、聚楓、其共形成產物及其混合物。當 研磨料全部或部份固定（例如嵌入）在拋光系統之拋光墊之 中或<上時，拋光墊上之該部份可以以任一適當之方式達 拋光系統可包括任-適用之研磨料。研磨料可懸浮在拋 光系統之液態載劑（例如水）中，因此成為㈣系統之液體 邵份<一部份。拋光系統之研磨料可全部或部份固定（例如 嵌入）在拋光墊之中或之上（例如拋光表面）。 拋光系統之研磨料可為任一適用之研磨料。研磨料可經 熱處理及/或化學處理（例如以化學連結之有機官能基研磨） 。適用之研磨料包含例如金屬氧化物。適用之金屬氧化物 包含例如氧化（、氧切、氧化鈥、氧化卸、氧化錐、氧 化鍺' 氧化鎂、及其供形成之產物及其混合物。金屬氧化 物可經發煙(液及熱解）、沉搬、縮合聚合或特性為膠體。 -8 - 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公爱) 568944 A7 B7 五、發明説明（6 ) 例如，金屬氧化物可如美國專利.第5, 230, 833號中所述，或 市售之Akzo - Nobel Bindzil 50/^80 或 Nalco 1050, 2327, 或2 329金屬氧化物顆粒，以及其他購自DuPont, Bayer,B7 Description of the Invention (1) Technical Field of the Invention The present invention provides a system and method for polishing or planarizing a substrate, especially a surface including a conductive metal. BACKGROUND OF THE INVENTION Chemical_mechanical polishing (CMP) is a microelectronic device such as a semiconductor Wafer) process of flattening the substrate surface. CMP generally includes adding chemical reaction and mechanical polishing polishing composition or slurry to the substrate surface. The polishing composition is generally made by bringing the surface and The polishing pad impregnated with the saturated polishing composition comes into contact with the surface of the substrate. When the polishing composition chemically reacts with the substrate, the abrasive will remove material from the surface of the substrate, thus polishing the substrate. Chemical mechanical polishing is more detailed The descriptions are listed in US Patent Nos. 4,671,851, 4,91〇, 155, and 4,944, 836. Because the flattened surface can optimize the performance of the semiconductor wafer, the surface of the selected semiconductor wafer is selected It is necessary to polish at a high speed and with high selectivity without adversely affecting the underlying structure or pattern. Therefore, a composition that maximizes the removal rate and selectivity is effective for manufacturing Electronic devices are important. Although many CMP compositions and methods are known to improve removal rate and selectivity, the CMP composition typically uses expensive and environmentally undesirable oxidants. For example, the chemical-mechanical polishing process of copper The oxidizing agents used in the method are described in US Patent No. 6,096, 652. Therefore, the current need is to improve the removal rate and polishing selectivity, while minimizing surface defects and damage to the underlying structure and type, and Other polishing systems and methods that do not use oxidants. The present invention is aimed at providing the polishing -4- the paper size is applicable to the Chinese National Standard (CMS) A4 specification (21〇X 297 mm) 568944 A7 _____ B7 ___ 5. Description of the invention 5) Applicable abrasive or non-abrasive pads. In addition, the polishing system may include polishing pads (abrasive pads or non-abrasive pads), in which the liquid part of the polishing system is suspended by abrasive material, or the liquid part of the polishing system is not Suspended abrasives. Suitable abrasive pads are described, for example, in U.S. Patent Nos. 5,849, 051 and 5,849, 052. Suitable polishing pads include, for example, woven and non-woven polishing Furthermore, suitable polishing pads may include any suitable polymer of different density, hardness, thickness, crimpability, crimping ability, and modulus of compression. Suitable polymers include, for example, polyvinyl chloride, Polyfluoroethylene, nylon, fluorocarbon, polycarbonate, polyester, polyacrylate, polyether, polyethylene, polyurethane, polystyrene, polypropylene, polymelamine, poly Ammonium, polyvinyl acetate, polypropionic acid, polypropylene ammonium, polymaple, co-formed products and mixtures thereof. When the abrasive is wholly or partially fixed (eg embedded) in the polishing pad of a polishing system or & lt At the time, the part on the polishing pad can be reached in any suitable manner. The polishing system can include any-applicable abrasive. The abrasive can be suspended in a liquid carrier (e.g., water) in the polishing system, thus becoming a liquid portion of the plutonium system. The abrasive of the polishing system can be fixed (eg embedded) in or on the polishing pad (eg polishing surface) in whole or in part. The abrasive of the polishing system can be any suitable abrasive. Abrasives can be heat treated and / or chemically treated (eg, ground with chemically bonded organic functional groups). Suitable abrasives include, for example, metal oxides. Suitable metal oxides include, for example, oxidized (oxygen cut, oxidized, oxidized, oxidized, oxidized cone, germanium oxide 'magnesium oxide, and products and mixtures thereof. Metal oxides can be smoked (liquid and pyrolyzed) ), Shenyang, condensation polymerization, or colloidal properties. -8-This paper size applies Chinese National Standard (CNS) A4 (210 X 297 public love) 568944 A7 B7 5. Description of the invention (6) For example, metal oxides can be As described in U.S. Patent No. 5, 230, 833, or commercially available Akzo-Nobel Bindzil 50 / ^ 80 or Nalco 1050, 2327, or 2 329 metal oxide particles, and others purchased from DuPont, Bayer,
Applied Research, Nissan Chemical, and Clariant之類 似產物。拋光系統之研磨料較好為發煙之金屬氧化物。更 好，研磨料為發煙氧化矽。 研磨料可以以任一適當量存在於拋光系統中。例如，研 磨料可以以約〇· 1-20 wt%之:it存在於抛光系統之液體部份 中。較好，研磨料係以約〇·卜10 wt%之量存在於拋光系統 之液體部份中。更好，研磨料係以約〇·卜1 wt% (例如約 0· 2-0· 8 wt%)之量存在於抱光系統之液體部份中。 抛光系統可視情況包括成膜劑。成膜劑可為任一適用之 成膜劑。適用之成膜劑包含例如任一種化合物或化合物之 混合物’協助在金屬層及/或金屬氧化物層之上形成被動層 (液及溶解抑制層）。適用之成膜劑包含例如寒帶之雜環化 合物。較好，成膜劑包括一種或多種5-6員雜環含氮環。更 好，成膜劑係選自包含1, 2, 3-三唑、1，2, 4-三吐、苯并r 唑、苯并咪唑、苯并噻唑、及其衍生物，例如羥基—、胺基 、亞肢基-、&基_、氣硫基_、硝基_、I尿基_、硫代膽基_ 、或其烷基取代之衍生物。最好，成膜劑為苯并三嗤。 成膜劑可依任一適當之量存在於拋光系統中。較好，成 膜劑在拋光系統之液體部份中之含量為約〇· 005—丨wt%。更 好，成膜劑在拋光系統之液體部份中之含量為約〇 〇1_〇 2 Wt% 0 -9 - 本紙張尺度適用中國國家標準(CMS) A4規格(210 X 297公釐） 568944Similar products are Applied Research, Nissan Chemical, and Clariant. The abrasive of the polishing system is preferably a fuming metal oxide. More preferably, the abrasive is fumed silica. The abrasive can be present in the polishing system in any suitable amount. For example, the abrasive may be present in the liquid portion of the polishing system at about 0.1-20 wt%: it. Preferably, the abrasive is present in the liquid portion of the polishing system in an amount of about 0.1 wt%. More preferably, the abrasive is present in the liquid portion of the light-holding system in an amount of about 0.1 wt% (e.g., about 0.2-20.8 wt%). The polishing system may optionally include a film former. The film-forming agent may be any suitable film-forming agent. Suitable film formers include, for example, any compound or mixture of compounds ' to assist in forming a passive layer (liquid and dissolution inhibiting layer) over the metal layer and / or metal oxide layer. Suitable film-forming agents include, for example, heterocyclic compounds in the cold zone. Preferably, the film-forming agent includes one or more 5-6 membered heterocyclic nitrogen-containing rings. More preferably, the film-forming agent is selected from the group consisting of 1,2,3-triazole, 1,2,4-tritriol, benzorazole, benzimidazole, benzothiazole, and derivatives thereof, such as hydroxy-, Amine, limbyl-, & yl-, thiothio-, nitro-, urethane-, thiocholyl-, or its alkyl-substituted derivatives. Preferably, the film-forming agent is benzotrifluorene. The film forming agent may be present in the polishing system in any suitable amount. Preferably, the content of the film-forming agent in the liquid portion of the polishing system is about 0.005 to 5% by weight. More preferably, the content of the film-forming agent in the liquid portion of the polishing system is about 〇 〇1_〇 2 Wt% 0 -9-This paper size applies the Chinese National Standard (CMS) A4 specification (210 X 297 mm) 568944
拋光系統可具有任何適當之pH。拋光系統之？11較好為約 7一 13。較好，拋光系統之pH為約8-12。更好，拋光系統之 p Η 為約 9 -11， 可使用適當之PH調整劑調整拋光系統之pH。適當之pH調 整劑包含例如酸及鹼。通常，拋光系統包含鹼，如氫氧化 物化合物，例如氫氧化鉀、氫氧化鈉、氫氧化銨、氫氧化 鐘氫氧化鐵、氫氧化躬及氫氧化鋇。pH調整劑可為化合 物之混合物，如氫氧化鉀及氫氧化鋰之混合物。pH調整劑 可為谷易之形式，例如水溶液。可用作pH調整劑之含金屬 氫氧化物溶液之實例為含氩氧化鉀之去離子水或蒸餾水溶 液’其中氫氧化鉀之量約〇·卜〇· 5 wt%(例如約〇. 2-0. 3 wt%) 。較好，pH調整劑為氫氧化鉀。 抛光系統中可存在其他成分（但並非必要）。該其他成分 可為使拋光系統安定，或可改善或提昇拋光系統性能之化 合物。例如，拋光系統中可含緩衝劑。適用之緩衝劑包含 碳酸鹽（例如碳酸鉀）、磷酸鹽及羧酸。較好，拋光系統中 不含氧化劑。 抛光系統之銅對鈕拋光選擇性（亦即CU : Ta移除速率）至 少約1 ·· 1，如至少約2 : 1。拋光系統之銅對四乙氧基矽烷 (TEOS)之拋光選擇性（亦即Cu : ^㈨移除速率〇至少約1 : 2。 本發明亦提供一種將基材拋光或平整化之方法，包括使 至y 部份基材與抛光系統接觸’且抛光一部份基材。抛 光系統可用於拋光任一適用之基材，尤其是一層或多層之 多層基材。較好，拋光系統係用於拋光多層基材，該基材The polishing system may have any suitable pH. Of the polishing systems? 11 is preferably about 7 to 13. Preferably, the pH of the polishing system is about 8-12. Even better, the p Η of the polishing system is about 9 -11, and the pH of the polishing system can be adjusted with a suitable pH adjusting agent. Suitable pH adjusters include, for example, acids and bases. Generally, polishing systems include alkalis, such as hydroxide compounds, such as potassium hydroxide, sodium hydroxide, ammonium hydroxide, iron hydroxide, iron hydroxide, and barium hydroxide. The pH adjusting agent may be a mixture of compounds, such as a mixture of potassium hydroxide and lithium hydroxide. The pH adjusting agent may be in the form of Gu Yi, such as an aqueous solution. An example of a metal hydroxide-containing solution that can be used as a pH adjuster is deionized water or a distilled aqueous solution containing potassium argon oxide, wherein the amount of potassium hydroxide is about 0.005 wt% (e.g., about 0.2- 0. 3 wt%). Preferably, the pH adjusting agent is potassium hydroxide. Other ingredients may be present in the polishing system (but not required). This other component may be a compound that stabilizes the polishing system or may improve or enhance the performance of the polishing system. For example, the polishing system may contain a buffer. Suitable buffering agents include carbonates (such as potassium carbonate), phosphates, and carboxylic acids. Preferably, the polishing system is free of oxidants. The polishing selectivity of the copper button polishing system (ie CU: Ta removal rate) is at least about 1 ·· 1, such as at least about 2: 1. The polishing selectivity of copper to tetraethoxysilane (TEOS) in a polishing system (that is, Cu: ^ ㈨ removal rate is at least about 1: 2: The invention also provides a method for polishing or planarizing a substrate, including Bring a portion of the substrate into contact with the polishing system and polish a portion of the substrate. The polishing system can be used to polish any applicable substrate, especially one or more multilayer substrates. Preferably, the polishing system is used Polished multilayer substrate
裝 訂Binding
kk
• 10- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)• 10- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)