TWI332017B - Abrasive-free polishing slurry and cmp process - Google Patents

Abrasive-free polishing slurry and cmp process Download PDF

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TWI332017B
TWI332017B TW095148566A TW95148566A TWI332017B TW I332017 B TWI332017 B TW I332017B TW 095148566 A TW095148566 A TW 095148566A TW 95148566 A TW95148566 A TW 95148566A TW I332017 B TWI332017 B TW I332017B
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copper
honing
load
acid
cmp
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TW095148566A
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Chinese (zh)
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TW200732389A (en
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Katsumi Mabuchi
Haruo Akahoshi
Masanobu Habiro
Takafumi Sakurada
Yutaka Nomura
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Hitachi Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/04—Aqueous dispersions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/31051—Planarisation of the insulating layers
    • H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/32115—Planarisation
    • H01L21/3212—Planarisation by chemical mechanical polishing [CMP]

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Description

1332017 Π) 九、發明說明 【發明所屬之技術領域】 本申請案係主張於2005年12月26日所申請之日本 專利申請案第2005-3 7 1 858號的優先權，依據參照其內容 ’摘錄於本申請案中。本發明係關於不含磨蝕劑之硏磨液 及CMP硏磨方法（化學機械硏磨方法），特別係關於在 半導體裝置等之電子電路的配線形成步驟所使用之CMP 硏磨中所使用之硏磨液及CMP硏磨方法。 【先前技術】 • 隨著LSI之高性能化，就LSI製造步驟中之微細加工 技術而言，主要使用所謂鑲嵌（Damascene)法，即於預 先形成溝之絕緣膜上藉電鍍法埋入銅後，藉化學機械硏磨 方法（chemical mechanical polishing，CMP)除去用以形 成配線之溝部以外的過剩之銅而形成配線。 φ —般於CMP所使用之硏磨液，係由氧化劑及固體粒 子所構成，依需要而可添加保護膜形成劑、氧化金屬用溶 , 解劑等。固體粒子係如專利文獻1等所記載般已知有約數 十nm的氧化矽、氧化鋁、氧化锆、氧化鈽等之微粒子。 又，氧化劑係如專利文獻2等所記載般已知有過氧化氫、 硝酸鐵、鐵氰化鉀、過硫酸銨等。 從生產性之提昇觀點而言，尋求以CMP所進行之銅 ' 的硏磨速度之提昇，並提昇習知硏磨速度之方法，以添加 氧化金屬溶解劑爲有效。認爲藉使固體磨蝕劑所削去之金 -5- (2) (2)1332017 屬氧化物的粒子溶解於硏磨液中，因固體磨蝕劑所產生之 削除的效果會增加。亦已知可增加其以外所添加之氧化劑 的濃度。 又，於專利文獻3中係記載著使對水不溶之銅化合物 與可溶之銅化合物形成於銅配線上，於專利文獻4中係記 載著添加胺基酸，於專利文獻5中係記載著含有鐵（III ) 化合物。於專利文獻6中係記載著藉含有鋁、鈦、鉻、鐵 、鈷、鎳、銅、鋅、鍺、銷等之多價金屬，可提昇硏磨速 度。 另外，若提昇硏磨速度，產生金屬配線部之中央如碟 狀般凹陷之碟化現象，使平坦性惡化之問題點仍存在。爲 防止其，一般添加顯示表面保護作用之化合物。此係藉由 於銅表面形成緻密之保護膜，用以抑制氧化劑所造成之銅 的離子化，防止銅於硏磨液中之過剩溶解。一般顯示此作 用之化合物，已知有以苯並三唑（BTA)爲首之螯合劑。 關於此係已記載於專利文獻7中。 一般，若以碟化之降低爲目的而添加（BTA )爲首之 螯合劑，亦於應硏磨之部分爲形成保護皮膜，硏磨速度會 急遽地降低。爲解決此，硏究各種添加劑。例如，有時含 有已記載於專利文獻8之雜多酸及有機高分子者。此雜多 酸係溶解速度快，故可置入有機高分子化合物而抑制溶解 速度’防止碟化之發生。此有機高分子係含有以聚乙烯醇 、聚丙烯醯胺、聚丙烯酸爲首之丙烯酸酯、聚乙烯基乙酸 酯等之聚乙烯基酯類、聚丙烯基胺等。 -6- (3) (3)1332〇17 又，在專利文獻4中係記載著倂用抑制劑與胺基酸之 方法，在專利文獻9中係記載著使用胺基醋酸或醯胺基硫 酸與BTA等保護膜形成劑者，在專利文獻1〇中係記載著 採取具有1個羧基之a-氧酸與保護膜形成劑之均衡的方 法。又，在專利文獻11中係記載著含有與銅形成水不溶 性錯合物之雜環化合物（第1錯化劑）、及與銅形成水難 溶性乃至可溶性錯合物，錯體形成後含有可吸取1個以上 的配位基之雜環化合物（第2錯合劑）者。 (專利文獻1)特開2001-210611號公報 (專利文獻2)特開2001-269859號公報 (專利文獻3)特開2 00 1-110759號公報 (專利文獻4)特開2000-133621號公報 (專利文獻5 )特開平10-163141號公報 (專利文獻6)特開2001-269859號公報 (專利文獻7 )特開平1 1 - 1 9 5 6 2 8號公報 (專利文獻8)特開2002-299292號公報 (專利文獻9)特開平08-083780號公報 (專利文獻10)特開2000-336345號公報 (專利文獻11)特開2003-168660號公報 【發明內容】 (發明之揭示） (發明欲解決之問題） 在CMP中，爲提高生產性係可追求高速化。又，因 (4) 1332017 配線之微細化及多層化係可尋求配線之平坦化。但此兩者 如上述般在於取得平衡之關係，要倂存係極困難。如前述 般，一般，若以碟化之降低爲目的而添加以（BTA )爲首 之螯合劑，亦於應硏磨之部分爲形成保護皮膜，硏磨速度 . 會急遽地降低。爲緩和此，亦硏究調整溶解劑與螯合劑之 * 量而謀求適當化，但很難看出可滿足之條件。爲除去保護 膜，亦認爲可提高硏磨壓力，但今後，若考量多孔型低介 ^ 電率絕緣膜成爲主流，則此方法不適當。亦已有各種硏究 爲使如前述之高速化與平坦化倂存之添加劑、方法。但滿 足性能、成本、隨意地使用之好處等全部的條件者尙未被 ^ 開發出。 本發明之目的在於提供一種抑制碟化，硏磨速度快之 CMP硏磨液。 本發明之另一目的、特徵及優點係從有關本發明之以 下的記載而很明顯可知。 (用以解決問題之手段） 若依本發明，可提供一種CMP硏磨液，係硏磨之際 ，與氧化劑混合所使用，其特徵在於：含有銅防鏽劑、水 «> 溶性高分子、可與銅形成錯合物之pH調整劑及水，其實 質上不含磨蝕劑的CM P硏磨液。又，本發明係可提供一 * 種含有銅之電子電路的化學研磨方法，其特徵爲於含有氧 * 化劑、銅防鏽劑、水溶性高分子、可與銅形成錯合物之 pH調整劑及水，而實質上不含磨蝕劑之CMP硏磨液中， -8 - (5) 1332017 包括：使銅在1 〇 g/cm2以下之荷重下進行化學硏磨之步驟 ，與在超過l〇g/cm2之荷重下進行化學硏磨之步驟。又， 在本說明書中謂「實質上不含磨蝕劑」時的「磨蝕劑」係 謂氧化鋁磨蝕劑（e.g.，褐色氧化鋁磨鈾劑、白色氧化鋁磨 、 蝕劑、單結晶氧化鋁磨蝕劑）、碳化矽磨蝕劑（e.g.，黑色 * 碳化矽磨蝕劑、綠色碳化矽磨蝕劑）、氧化锆氧化鋁磨蝕 劑及超磨蝕劑（e.g.,鑽石、CBN)。 (發明之效果） 若依本發明，可有效地抑制碟化，形成信賴性高之配 . 線。 【實施方式】 (用以實施發明之最佳形態） 若依本發明之較佳實施形態，可達成如下之顯著效果 ，即（1 )埋入配線形成時之碟化或蝕化降低（2 )硏磨之 高速化（3 )可達成CMP後之洗淨的簡單化。若敘述本發 明之代表性實施形態，如以下般。 (實施形態例） (1 )本發明之CMP硏磨液係含有銅防鏽劑、可與銅 形成錯合物之pH調整劑、水溶性化合物及水，使用時可 與氧化劑混合之物。此硏磨劑係實質上不含磨蝕劑，較佳 係若完全形成無磨蝕劑，可解決因以往之CMP硏磨液造 (6) 1332017 成問題之磨蝕劑所削去的粒子造成的蝕化問題。 (2) pH爲2.5以下尤其1.5〜2.5時，取得 與硏磨速度之均衡，可實施效率佳之CMP硏磨。 (3 )本發明之CMP硏磨液的較佳組成，係 、水溶性高分子及氧化劑之含量，於該CMP硏 升中，爲 0.1〜5重量％、0.05〜5重量％、及0.0 PH調整劑之量係爲使該CMP硏磨液之pH調整] 所需之量。 (4 )更佳之硏磨液的組成，係該防鏽劑、 分子及氧化劑之含量，於該 CMP硏磨液每一 0.3〜1重量％、0.1〜2重量％及0.01~5M，該pH調 係爲使該CMP硏磨液之pH調整至1.5〜2.5所需^ (5) 該水溶性高分子係宜選自：具有羧基 、具有楓基之聚合物及含有氮之聚合物之至少一 ，係選自聚丙烯酸、聚丙烯酸鹽、丙烯酸與丙烯 聚物及丙烯酸與丙烯醯胺之共聚物之至少一種。 之水溶性高分子係選自具有颯基之胺化合物聚合 颯基之胺化合物聚合物的鹽之至少一種；含有氮 高分子係選自聚乙烯基吡咯烷酮、聚乙撐基亞胺 醯胺之至少一種。 (6) 較佳之該銅防鏽劑爲含有氮之不飽和 合物。尤其，宜爲喹啉、苯並三唑、苯並咪唑、 吲哚及喹哪啶酸之至少一種。 (7) 該pH調整劑宜爲有機酸、無機酸或其 k碟化抑制 :該防鏽劑 磨液每一 1〜5M，該 g 1 . 5 ~2·5 水溶性高 升中，爲 整劑之量 匕量。 之聚合物 種。尤其 酸之酯共 具有碾基 物及具有 之水溶性 及聚丙烯 雜環式化 吲哚、異 等之混合 -10 - 1332017133 Π 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 技术 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 2005 Extracted from this application. The present invention relates to an abrasive-free honing liquid and a CMP honing method (chemical mechanical honing method), and more particularly to CMP honing used in a wiring forming step of an electronic circuit of a semiconductor device or the like. Grinding and CMP honing methods. [Prior Art] • With the high performance of LSI, the microfabrication technology in the LSI manufacturing process mainly uses the so-called damascene method, that is, after the copper is buried in the insulating film formed in advance by the plating method. The wiring is formed by removing excess copper other than the groove portion for forming wiring by chemical mechanical polishing (CMP). φ The honing liquid used in the CMP is composed of an oxidizing agent and solid particles, and a protective film forming agent or a metal oxide solvent can be added as needed. In the case of the solid particles, as described in Patent Document 1, a fine particle such as cerium oxide, aluminum oxide, zirconium oxide or cerium oxide of about several tens of nm is known. Further, as the oxidizing agent, as described in Patent Document 2, hydrogen peroxide, iron nitrate, potassium ferricyanide, ammonium persulfate or the like is known. From the viewpoint of productivity improvement, it is effective to increase the honing speed of copper by CMP and to increase the speed of conventional honing by adding a metal oxide dissolving agent. It is considered that the gold removed by the solid abrasive -5- (2) (2) 1332017 The particles of the oxide are dissolved in the honing liquid, and the effect of the removal by the solid abrasive increases. It is also known to increase the concentration of the oxidizing agent added thereto. Further, Patent Document 3 describes that a copper compound insoluble in water and a soluble copper compound are formed on a copper wiring, and Patent Document 4 describes the addition of an amino acid, and Patent Document 5 describes that Contains iron (III) compounds. Patent Document 6 describes that the honing speed can be improved by using a polyvalent metal containing aluminum, titanium, chromium, iron, cobalt, nickel, copper, zinc, bismuth, pin, or the like. Further, when the honing speed is increased, a dishing phenomenon in which the center of the metal wiring portion is dished, and the flatness is deteriorated still exists. To prevent this, a compound which exhibits surface protection is generally added. This is because a dense protective film is formed on the surface of the copper to suppress the ionization of copper caused by the oxidant and prevent excessive dissolution of copper in the honing liquid. Compounds which generally exhibit this effect are known as chelating agents including benzotriazole (BTA). This is described in Patent Document 7. In general, if a chelating agent such as (BTA) is added for the purpose of lowering the dishing, and a protective film is formed in the portion to be honed, the honing speed is drastically lowered. In order to solve this, we will study various additives. For example, the heteropoly acid and the organic polymer described in Patent Document 8 may be contained. Since this heteropoly acid has a high dissolution rate, an organic polymer compound can be placed to suppress the dissolution rate, and the occurrence of dishing can be prevented. The organic polymer contains polyvinyl esters such as polyvinyl alcohol, polypropylene decylamine, polyacrylic acid acrylate, polyvinyl acetate, and the like, and a polypropylene-based amine. -6- (3) (3) 1332〇17 Further, Patent Document 4 describes a method of using an inhibitor and an amino acid, and Patent Document 9 describes the use of an aminoacetic acid or a guanamine sulfate. In the case of a protective film forming agent such as BTA, Patent Document 1 describes a method of using a balance of a-oxyacid having one carboxyl group and a protective film forming agent. Further, Patent Document 11 describes a heterocyclic compound (first dissolving agent) containing a water-insoluble complex with copper, and a water-insoluble or soluble complex with copper, and is capable of being absorbed after formation of a complex. One or more ligand heterocyclic compounds (second complexing agent). (Patent Document 1) JP-A-2001-269859 (Patent Document 3) JP-A-2000-133759 (Patent Document 4) JP-A-2000-133621 (Patent Document 5) JP-A-2001-269859 (Patent Document 7) Japanese Patent Publication No. 2001-269859 (Patent Document 7) Japanese Patent Publication No. Hei 1 1 - 1 9 5 6 2 8 (Patent Document 8) Japanese Laid-Open Patent Publication No. Hei. No. 2000-336345 (Patent Document No. JP-A-2003-168660). Problems to be Solved by the Invention In CMP, in order to improve productivity, high speed can be pursued. In addition, (4) 1332017 Wiring and miniaturization of wiring can be sought for flattening of wiring. However, the two are in a balanced relationship as described above, and it is extremely difficult to save the system. As described above, in general, when a chelating agent such as (BTA) is added for the purpose of lowering the dishing, a protective film is formed in a portion to be honed, and the honing speed is drastically lowered. In order to alleviate this, it is also necessary to adjust the amount of the solvent and the chelating agent, and it is difficult to see the conditions that can be satisfied. In order to remove the protective film, it is considered that the honing pressure can be increased. However, in the future, if the porous low dielectric constant insulating film is considered to be the mainstream, this method is not suitable. There have also been various additives and methods for accumulating high speed and flattening as described above. However, all the conditions that satisfy the performance, cost, and the benefits of random use have not been developed. SUMMARY OF THE INVENTION An object of the present invention is to provide a CMP honing fluid which suppresses dishing and has a high honing speed. Other objects, features, and advantages of the invention will be apparent from the description of the invention. (Means for Solving the Problem) According to the present invention, a CMP honing liquid which is used in combination with an oxidizing agent during honing is characterized in that it contains a copper rust inhibitor, water «> a soluble polymer A pH adjuster and water which form a complex with copper, which is substantially free of abrasive CM P honing fluid. Moreover, the present invention provides a chemical polishing method for a copper-containing electronic circuit, which is characterized by pH adjustment of an oxygen-containing agent, a copper rust inhibitor, a water-soluble polymer, and a complex compound with copper. In the CMP honing fluid, which is substantially free of abrasives, -8 - (5) 1332017 includes: a step of chemically honing copper under a load of 1 〇g/cm2 or less, and The step of chemical honing is carried out under the load of 〇g/cm2. In addition, in this specification, "abrasive agent" when it is "substantially free of abrasive" is an alumina abrasive (eg, brown alumina abrasive uranium, white alumina mill, etchant, single crystal alumina abrasion) Agent), cerium carbide abrasive (eg, black* cerium carbide etchant, green cerium carbide etchant), zirconia alumina abrasive and superabrasive (eg, diamond, CBN). (Effects of the Invention) According to the present invention, it is possible to effectively suppress the dishing and form a highly reliable wiring. [Embodiment] (Best Mode for Carrying Out the Invention) According to a preferred embodiment of the present invention, it is possible to achieve the following remarkable effects: (1) reduction in dishing or etching during formation of buried wiring (2) The high speed of honing (3) can achieve simplification of washing after CMP. A representative embodiment of the present invention will be described as follows. (Examples) (1) The CMP honing fluid of the present invention contains a copper rust inhibitor, a pH adjuster which forms a complex with copper, a water-soluble compound, and water, and can be mixed with an oxidizing agent when used. The honing agent is substantially free of abrasives, preferably if it is completely formed of an abrasive-free agent, which can solve the corrosion caused by the particles removed by the conventional CMP honing fluid (6) 1332017. problem. (2) When the pH is 2.5 or less, especially 1.5 to 2.5, a balance with the honing speed is obtained, and CMP honing with high efficiency can be performed. (3) The preferred composition of the CMP honing fluid of the present invention, the content of the water-soluble polymer and the oxidizing agent, is 0.1 to 5% by weight, 0.05 to 5% by weight, and 0.0 PH in the CMP surge. The amount of the agent is the amount required to adjust the pH of the CMP honing fluid. (4) The composition of the better honing liquid is the content of the rust inhibitor, the molecule and the oxidizing agent, and the pH of the CMP honing liquid is 0.3 to 1% by weight, 0.1 to 2% by weight, and 0.01 to 5 M, respectively. In order to adjust the pH of the CMP honing liquid to 1.5 to 2.5, the water-soluble polymer is preferably selected from at least one of a carboxyl group, a polymer having a maple group, and a polymer containing nitrogen. It is at least one selected from the group consisting of polyacrylic acid, polyacrylate, acrylic acid and propylene polymer, and copolymer of acrylic acid and acrylamide. The water-soluble polymer is at least one selected from the group consisting of salts of an amine compound polymer having a mercapto group-containing amine compound-polymerized mercapto group; and the nitrogen-containing polymer is selected from at least polyvinylpyrrolidone and polyethyleneethimide. One. (6) Preferably, the copper rust inhibitor is a nitrogen-containing unsaturated compound. In particular, it is preferably at least one of quinoline, benzotriazole, benzimidazole, anthracene and quinaldine. (7) The pH adjusting agent is preferably an organic acid, a mineral acid or a k-disc inhibition thereof: the rust-preventing agent grinding liquid is 1 to 5 M each, and the g 1 . 5 to 2·5 is water-soluble and high-rise, and is a whole agent. The amount is measured. The polymer species. In particular, acid esters have a mixture of mill bases and water-soluble and polypropylene heterocyclic oximes, heterogeneous mixtures -10 - 1332017

溶液。該銅防鏽劑之濃度（重量％)宜高於水溶性高分子 濃度（重量％)。 (8) 該有機酸或無機酸與銅之錯合物的生成常數之 對數宜爲3以上》 (9) 該水溶性高分子係宜選自：具有羧基之聚合物 、具有楓基之聚合物及含有氮之聚合物之至少一種。 (10 )較佳之CMP硏磨液，其係藉該水溶性高分子 ，宜使在荷重l〇g/cm2以下之荷重旋轉下銅之交換電流密 度（exchange current density)實質上不增加，而在超過 荷重1 Og/cm2之荷重旋轉下銅之交換電流密度會增加。 (11) 較佳之CMP硏磨液，其係在對於應硏磨之銅 的荷重爲〇~1〇 g/cm2之CMP硏磨條件下’交換電流密度 實質上不增加，而在超過l〇g/cm2之荷重下的CMP硏磨條 件下之交換電流密度爲在〇〜1 〇g/cm2之荷重旋轉下的CMP 硏磨中之交換電流密度的2倍以上，其實質上不含磨蝕劑 〇 (12) 在對於應硏磨之銅的荷重爲 〇〜10 g/cm2之 CMP硏磨條件下，係交換電流密度實質上不增加，而在超 過1 Og/cm2之荷重下的CMP硏磨條件下之交換電流密度爲 在〇~10g/cm2之荷重旋轉下的CMP硏磨中之交換電流密度 的5倍以上。 (13) 該水溶性高分子係宜在1〇 g/cm2以下之荷重時 顯示銅之溶解抑制效果’在超過1 〇g/cm2之荷重時顯示銅 之溶解促進效果者。 -11 - (8) (8)1332017 (14)較佳之CMP硏磨液’其係無荷重旋轉下之銅 的交換電流密度爲30μΑ/(：ηι2以下，賦予荷重g/cm2之 荷重旋轉下之銅的交換電流密度爲無荷重旋轉下之時的2 倍以下，賦予荷重150g/cm2之荷重旋轉下之銅的交換電 流密度爲無荷重旋轉下之時的5倍以上，其實質上不含磨 蝕劑。 (1 5 )本發明之化學硏磨方法，係含有氧化劑、銅防 鏽劑、水溶性高分子、可與銅形成錯合物之pH調整劑及 水’其實質上不含磨蝕劑，其特徵在於包括：使銅在10 g/cm2以下之荷重下進行化學硏磨之步驟，與在超過 1 〇g/cm2之荷重下進行化學硏磨之步驟。尤其爲使碟化減 少至最低宜一邊調整荷重一邊進行硏磨。 爲提昇平坦性’其詳細內容係後述，但第一，提昇施 予荷重之部分（荷重旋轉下），亦即銅與墊體接觸之部分 中之銅的溶解速度，同時抑制未施予荷重之部分（無荷重 旋轉下）’亦即銅與墊體未直接接觸之部分中之銅的溶解 速度乃很重要。第二，在低荷重區域，亦即墊體梢與銅接 觸之區域中，銅之溶解速度的荷重依存性低亦成爲重要的 因素。第三，製作完全不含硏磨劑且具有上述第一及第二 之特性的硏磨液。 考量此，爲解決上述課題，本發明之CMP用硏磨液 的組成係至少含有如下者作爲基本構成，即（1 )氧化劑 (過氧化氫等）、（2)使銅溶解同時與銅製作錯合物之 化合物（有機酸及/或無機酸）、（3)在荷重旋轉下及無 -12- (9) 1332017 荷重旋轉下抑制銅之溶解的溶解抑制劑（BTA等 劑）及（4)在荷重旋轉下促進銅之溶解且在無 下抑制銅之溶解的化合物（水溶性高分子）。又， 1)與（2) ~(4)之溶液係分別被調整，且於使月 行混合。 本發明之金屬的氧化劑係有以過氧化氫所代赛 化物、次亞氯酸、過醋酸、重鉻酸化合物、過錳酸 、過硫酸化合物、硝酸鐵、鐵氰化物。此等之中， 解生成物爲無毒之過氧化氫或過硫酸銨所代表之過 。尤宜爲過氧化氫。氧化劑之含量係依所使用之氧 異，例如使用過氧化氫時宜爲〇.5~3M左右，使用 銨時宜爲〇.〇5〜0.2M左右。一般，調整含銅防鏽劑 銅形成錯合物之pH調整劑、水溶性高分子及水之 使用時混合上述溶液與氧化劑。 無機酸係可舉例如磷酸、焦磷酸，有機酸係可 羧酸。羧酸係有單羧酸之蟻酸、醋酸、二羧酸之草 來酸、柄二酸、琥珀酸、氧羧酸之酒石酸、檸檬酸 酸、芳香族羧酸之安息香酸、酞酸等’尤其以氧羧 效。其以外亦以胺基酸、胺基硫酸及其等之鹽、甘 天冬氨酸亦有效。此等之含量係依所調整之PH而 亦即，依此等之酸的添加量而調整PH’故依所使 的種類而添加量相異。所調整之PH宜爲2.5以下 1.5〜2.5之間，最宜爲1.5〜2。此等之酸係可單獨使 可複合而使用，均可得到同樣的效果。此處所使用 .銅防鏽 重旋轉 上述（ 之前進 之過氧 化合物 宜爲分 硫酸鹽 化劑而 過硫酸 、可與 溶液， 舉例如 酸、馬 、蘋果 酸爲有 氨酸、 變化。 用之酸 ，宜爲 用，亦 之酸很 -13- (10) (10)1332017 重要係與銅形成錯合物，尤宜生成常數之對數的値爲3以 上。 可與銅形成錯合物之pH調整劑即無機酸或有機酸的 添加量，係爲使與氧化劑進行混合之前的溶液（水溶性高 分子、銅防鏽劑及水）之pH調整至2.5以下，尤其 L5〜2.5所需的量。依所添加之酸的種類，pH調整必需之 酸的量相異。 發現在本發明中之荷重旋轉下及無荷重旋轉下抑制銅 的溶解之溶解抑制劑，係與銅形成不溶性的錯合物之化合 物、亦即以苯並三唑所代表之三唑、三唑衍生物、喹哪啶 (quinaldine)酸鹽、羥基唾啉（oxine)等之雜環的化合 物外，尙有苯偶因肟、氨茴酸、水楊基醛肟、亞硝基萘酚 、銅鐵靈（cupferron )、鹵醋酸、半胱氨酸等具有如此之 特性。此等之濃度宜爲 0.005!\4〜0.2\4(0.06〜2.4重量％) ，尤宜爲 0·02~0.1Μ(0·25〜1.2重量％ )左右。此等係可 單獨使用，亦可複合而使用，亦可得到相同之效果。 發現使可施加本發明中之荷重的部分（荷重旋轉下） ，亦即銅與墊體接觸之部分中的銅之溶解速度提昇，同時 並可抑制在未施加荷重的部分（無荷重旋轉下），亦即銅 與墊體未直接接觸之部分中的銅之溶解速度之化合物，爲 至少一種選自具有羧基之聚合物、具有碾基之聚合物及含 有氮之聚合物的水溶性高分子。具有羧基之高分子係有聚 丙烯酸及其鹽（鉀鹽、銨鹽）、丙烯酸與丙烯酸酯之共聚 物、丙烯酸與丙烯醯胺之共聚物等，此等係可單獨或複數 -14- (11) (11)1332017 組合而使用。具有颯基之聚合物係可舉例如具有颯基之胺 化合物聚合物及其等之鹽’此等係可單獨或複數組合而使 用。含有氮之聚合物的水溶性高分子可舉例如聚乙烯基吡 咯烷酮 '聚乙撐基亞胺、聚丙烯醯胺等，此等係可單獨或 複數組合而使用。 上述水溶性高分子係任一者均可使用，但尤宜爲離子 性的高分子。此等之濃度宜爲〇.〇5〜10重量％，尤宜爲 0.1〜1重量％’濃度之上限如後述般受共存之銅的防鏽劑 濃度而影響。 在本發明中，重要之點係（3 :銅防鏽劑）與（4 :水 溶性高分子）之濃度均衡。此等之銅防鏽劑及水溶性高分 子的作用係在無荷重旋轉下任一者均可抑制銅的溶解者。 但銅防鏽劑係即使在荷重旋轉下中亦可抑制溶解（抑制效 果係受施加荷重而變小），水溶性高分子係在荷重旋轉下 促進銅之溶解的作用，與抑制銅之溶解的作用，故被調整 至各別之上述濃度範圍以外，（3 )與（4 )之濃度比被控 制成爲用以達成低碟化之必要事項。在本發明中發現（3 )之化合物的濃度（重量％ )必須大於（4)之化合物濃度 (重量％)。即使（3)及（4)之濃度落入上述濃度範圍 ，若於此關係內未控制濃度，亦無法達成低碟化。 在本發明中磨蝕劑宜儘可能地少，即使含有亦宜爲硏 磨液之0.5重量％以下，宜爲0_3重量％以下，最宜完全不 含有者。其理由係爲避免受磨蝕劑造成之蝕化等的阻礙。 又，在本發明之硏磨液5中，前述之主要4成分外，可依 -15- (12) (12)1332017 需要而添加各種之添加劑。例如，有甲醇或乙醇等之水溶 性單體或十二烷基苯磺酸鉀等之界面活性劑。 以下說明有關本發明之原理。但如前述般爲提昇平坦 性’係提昇在施予荷重之部分（荷重旋轉下），亦即銅與 墊體接觸之部分中之銅的溶解速度，同時抑制未施予荷重 之部分（無荷重旋轉下）’亦即銅與墊體未直接接觸之部 分中之銅的溶解速度乃很重要。又，在低荷重區域中，藉 荷重之變動’溶解速度不會極端變化亦成爲很重要的因素 〇 如圖1(a)所示般，於具有基板表面所形成之溝的絕 緣膜1上施予電鍍銅2時’一般對應於配線部之部分顯示 凹陷的形狀3。硏磨之際而使硏磨液5 (硏磨液）從噴嘴 6供給至墊體4與銅膜2之間。在實施CMP之狀態（圖1 (b))中，在凹陷之配線部分中係銅2與墊體4未接觸 ，而在配線部以外的部分中係墊體4與銅2接觸。若與銅 接觸之部分的硏磨速度與未接觸之部分中的硏磨速度相同 ，則硏磨後之形狀係直接保持硏磨前之形狀。另一方面， 接觸之部分的硏磨速度遲於未接觸之硏磨速度時，係如圖 1之（c)所示般，配線部分之凹陷的深度隨硏磨之進行而 變淺。因此，顯示如此之特性的硏磨液可使高速硏磨與低 碟化併存。即使未與墊體接觸之部分的銅的硏磨速度小， 亦與墊體接觸之部分的硏磨速度很慢時，爲減少銅之硏磨 殘留，於硏磨需要時間，於其間會進行未與墊體接觸之部 分的銅之溶出，無法達成低碟化。 -16 - (13) 1332017 又’施加很少之荷重時，在溶解速度急劇增加時，亦 即’在低荷重區域中銅之溶解速度的荷重依存性大時，在 接近硏磨終了之阻隔物出現於表面之階段中，若稍施加荷 . 重’溶解速度會急劇增加，阻隔物金屬係直接使銅之溶解 - 急劇增加。因此（施加荷重處與未施加荷重之部分的溶解 _ 度之差即使很大），很難顯現平坦性。 因此在各種硏磨液中，爲硏究銅之溶解速度的荷重依 φ 存性，考量圖2(a) 、 （b)所示之裝置。在圖中，（a) 顯示裝置之全體構成，（b)爲（a)之A部的擴大圖。銅 之溶解速度係形成交換電流密度而求出。於具有旋轉速度 • 控制機構11之馬達10上安裝具有銅電極13之旋轉電極 . 19的旋轉軸20，押抵於墊體。押抵於墊體之荷重係使用 秤1 4而進行測定，施加於銅電極1 3之荷重係使用連結機 構16而進行調整，而該連結機構16係固定於設置在秤的 下方之座體1 7。 φ 銅之溶解速度係以旋轉之狀態在有無荷重的條件下（ 無荷重旋轉下及荷重旋轉下）使用參考電極15而藉電化 . 學測定系統1 2進行測定。測定係依塔費爾（Tafel )測定 形成交換電流密度而求出。使用塔費爾（Tafel )之關係式 錢 ’亦即在電位域中過電壓（來自浸漬電位之電位差）在 7〇mV〜13 5mV之間電流之對數與電位成爲直線，而使其直 線外插，以與浸漬電位相交之點的電流値作爲交換電流密 度。 交換電流密度之測定係使用於市售之旋轉碟環式電極 -17- (14) 1332017 的白金環電極上電鑛銅呈10〜20μιη厚者（ 鍍銅，但測定係只使用環電極）。測定交 ，在一定時間150g/cm2之荷重旋轉下進 荷重旋轉下及賦予任意之荷重下的荷重旋 別實施分級測定。旋轉速度係以與實硏磨 同之方式形成 2000rpm。電位之掃描速度 較浸漬電位更陽極側掃描電位。 使用本裝置而進行評估，在添加有機 化劑之情形下，發現藉由添加銅防鏽劑， 轉下及荷重旋轉下之任一者之情形，銅之 。但，銅防鏽劑之抑制效果，係在荷重旋 加一起降低。認爲此係因B T A吸附於銅 力量剝離。 又，在本發明中，藉由添加CMP硏 之一即水溶性高分子，可充分降低碟化量 子之作用係當未施加荷重之無荷重旋轉下 與墊體接觸之情形），與防鏽劑同樣地， 之溶解。但荷重旋轉下（相當於銅與墊體 使銅與墊體接觸部分中之銅的溶解速度提 現選自具有羧基之聚合物、具有碾基之聚 聚合物之至少一種的水溶性高分子作爲具 溶性高分子係很有效。如此之水溶性高分 係當無荷重時，可抑制銅的溶解，但銅防 具有可使銅防鏽劑所產生之銅的溶解抑制 碟亦同樣地施予 換電流密度之前 行硏磨後，在無 轉下的條件下分 時之周速度略相 係3 0 m V /分，於 酸或無機酸、氧 即使在無荷重旋 溶解速度亦降低 轉下與荷重之增 上，可以機械之 磨液之構成成分 。此水溶性高分 時（相當於銅未 藉添加可抑制銅 接觸之情形）係 昇已很明確。發 合物及含有氮之 有如此作用之水 子的再一個特徵 鏽劑共存時，亦 效果降低的功能 -18- (15) 1332017 亦已很明確。如此之特性爲何於水溶性高分子 性的高分子中顯現並不很明確。 從此等之特性可知，若過度提高水溶性高 ，會抵消銅之溶解抑制劑的效果，結果係無法 解量，而增大碟化。其另一方面，因此等之特 纏，故若可適當地控制水溶性高分子與銅之溶 濃度均衡，可抑制碟化。 本發明之CMP用硏磨液係可使高的CMP 碟化抑制倂存，並可形成信賴性高的配線。 以下，依實施例詳細說明本發明。對於Ϊ 及比較例1〜6係實施以下之評估。 (實硏磨評估） 使用形成有厚Ιμπι之銅箔的矽基板作爲基 有獨立氣泡之聚胺基甲酸酯樹脂作爲硏磨墊。 固定盤之相對速度設定成3 6m/分》荷重爲 CMP時之硏磨速度係使銅箔之CMP前後的膜 阻値換算而求出。碟化量係於絕緣膜上形成深 ，藉公知之濺鍍法及電鍍法而埋入銅後（圖 CMP，以觸針式段差計從配線金屬部寬ΙΟΟμπι ΙΟΟμιη交互地並排之條改圖案部的表面型狀， 屬部對絕緣部之減少量。 (硏磨評估） 、尤其離子 分子之濃度 降低銅之溶 性複雜地糾 解抑制劑的 硏磨速度與 :施例 1〜1 4 體。使用具 基體與硏磨 3 0 Og/cm2 ° 厚之差從電 0.5 μιη之溝 la )，實施 、絕緣部寬 求出配線金 -19- (16) (16)1332017 在荷重旋轉下及無荷重旋轉下之溶解速度係使用圖2 所示之裝置，使用電化學方法而藉塔費爾（Tafel )測定形 成交換電流密度而求出。旋轉速度爲2000rpm。詳細內容 係敘述解決課題之手段。 (實施例1 ) 使用由作爲銅溶解劑之蘋果酸、作爲氧化劑之2.5Μ 的過氧化氫、作爲防鏽劑（保護膜形成劑）之0.5 wt%苯 並三唑、作爲水溶性高分子之0.2 wt%的聚乙烯基吡咯烷 酮所構成之硏磨液而實施CMP。以成爲特定的pH(pH2.0 )的方式調整銅溶解劑的添加量。如表1所示般，可得到 硏磨速度及碟化均良好的結果。在本硏磨液中之10g/cm2 的荷重旋轉下之銅的交換電流密度爲10.1 μ A/cm2，爲在無 荷重旋轉下之銅的交換電流密度（5.55 μΑ/cm2)的2倍以 下。相對於此，在150g/Cm2的荷重旋轉下之銅的交換電 流密度爲1 95 μΑ/cm2，爲在無荷重下之溶解速度的5倍以 上。 (實施例2) 使用由馬來酸取代用於實施例1之蘋果酸作爲銅溶解 劑、作爲防鏽劑（保護膜形成劑）之0.5 wt%苯並三唑、 作爲水溶性高分子之〇·2 wt%的聚乙烯基吡咯烷酮所構成 之硏磨液而實施CMP。以成爲特定的pH (pH2.0)的方式 調整銅溶解劑的添加量。如表1所示般，可得到硏磨速度 -20- (17) (17)1332017 及碟化均良好的結果。在本硏磨液中之1 Og/cm2的荷重旋 轉下之銅的交換電流密度爲5.91pA/cm2，爲在無荷重旋轉 下之銅的交換電流密度（6.41 μA/cm2 )的2倍以下。相對 於此，在150g/cm2的荷重旋轉下之銅的交換電流密度爲 1 3 8μ A/cm2，爲在無荷重下之溶解速度的5倍以上。 (實施例3 ) 使用由草酸取代用於實施例1之蘋果酸作爲銅溶解劑 、作爲氧化劑之2.5M的過氧化氫、作爲防鏽劑（保護膜 形成劑）之〇.8wt%苯並三唑（BTA )、作爲水溶性高分子 之0.4 wt%的聚丙烯酸所構成之硏磨液而實施CMP。以成 爲特定的pH (p Η 1.8)的方式調整銅溶解劑的添加量。 如表1所示般，可得到硏磨速度及碟化均良好的結果。在 本硏磨液中之1 〇g/cm2的荷重旋轉下之銅的交換電流密度 爲5.23pA/cm2，爲在無荷重旋轉下之銅的交換電流密度（ 4.68μΑ/ί：ιη2 )的2倍以下。相對於此，在150g/cm2的荷重 旋轉下之銅的交換電流密度爲63.2μΑ/οιη2，爲在無荷重下 之溶解速度的5倍以上。 (實施例4 ) 使用由無機酸之磷酸取代用於實施例1之蘋果酸作爲 銅溶解劑、作爲氧化劑之2.5Μ的過氧化氫、作爲防鏽劑 (保護膜形成劑）之〇.7wt%苯並三唑、作爲水溶性高分 子之0.4 wt%的聚丙烯酸所構成之硏磨液而實施CMP。以 -21 - (18) 1332017 成爲特定的pH (p H2.0)的方式調整銅溶解劑的添加量。 如表1所示般，可得到硏磨速度及碟化均良好的結果。在 本硏磨液中之l〇g/cm2的荷重旋轉下之銅的交換電流密度 . 爲4.64 μ A/cm2，爲在無荷重旋轉下之銅的交換電流密度（ - 5.59μΑ/cm2)的2倍以下。相對於此，在150 g/cm2的荷重 . 旋轉下之銅的交換電流密度爲42.7pA/cm2，爲在無荷重下 之溶解速度的5倍以上。 (實施例5 ) 使用由無機酸之焦磷酸取代用於實施例1之蘋果酸作 - 爲銅溶解劑、作爲氧化劑之2.5M的過氧化氫、作爲防鏽 . 劑（保護膜形成劑）之〇.3wt%苯並三唑、作爲水溶性高 分子之〇.2wt%的聚丙燃酸所構成之硏磨液而實施CMP。 以成爲特定的pH ( p H2.3 )的方式調整銅溶解劑的添加量 。如表1所示般，可得到硏磨速度及碟化均良好的結果。 φ 在本硏磨液中之1 〇g/cm2的荷重旋轉下之銅的交換電流密 度爲35·1μΑ/(：πι2，爲在無荷重旋轉下之銅的交換電流密度 (20.7μΑ/<:πι2 )的2倍以下。相對於此，在1 50g/cm2的荷 重旋轉下之銅的交換電流密度爲267pA/cm2，爲在無荷重 下之溶解速度的5倍以上。 (實施例6)Solution. The concentration (% by weight) of the copper rust inhibitor is preferably higher than the water-soluble polymer concentration (% by weight). (8) The logarithm of the formation constant of the organic acid or inorganic acid and copper complex is preferably 3 or more. (9) The water-soluble polymer is preferably selected from the group consisting of a polymer having a carboxyl group and a polymer having a maple group. And at least one of a polymer containing nitrogen. (10) A preferred CMP honing fluid is a water-soluble polymer, and the exchange current density of the copper under a load of less than 1 g/cm 2 is not substantially increased, but The exchange current density of the copper under the load of 1 Og/cm2 is increased. (11) The preferred CMP honing fluid is based on the CMP honing condition of 〇~1〇g/cm2 for the copper to be honed. The exchange current density does not increase substantially, but exceeds 1〇g. The exchange current density under the CMP honing condition under the load of /cm2 is more than twice the exchange current density in the CMP honing under the load rotation of 〇~1 〇g/cm2, which is substantially free of abrasive 〇 (12) Under the CMP honing condition for the copper to be honed to be 〇10 g/cm2, the exchange current density does not increase substantially, and the CMP honing condition under a load exceeding 1 Og/cm2 The exchange current density is more than five times the exchange current density in CMP honing at a load of 〇~10 g/cm2. (13) The water-soluble polymer preferably exhibits a dissolution-suppressing effect of copper when the load is 1 〇 g/cm 2 or less, and exhibits a dissolution-promoting effect of copper when the load exceeds 1 〇g/cm 2 . -11 - (8) (8) 1332017 (14) The preferred CMP honing fluid's exchange current density of copper under no-load rotation is 30μΑ/(:ηι2 or less, giving a load of g/cm2 under load. The exchange current density of copper is less than 2 times that of the case of no load rotation, and the exchange current density of copper under a load of 150 g/cm 2 is 5 times or more when there is no load rotation, which is substantially free of abrasion. (1 5) The chemical honing method of the present invention comprises an oxidizing agent, a copper rust inhibitor, a water-soluble polymer, a pH adjusting agent capable of forming a complex with copper, and water which is substantially free of an abrasive. The invention comprises the steps of: chemically honing copper under a load of 10 g/cm 2 or less, and performing a chemical honing step under a load of more than 1 〇g/cm 2 , especially to minimize dishing. The honing is performed while adjusting the load. The details of the flatness are described later, but first, the portion where the load is applied (under the load rotation), that is, the dissolution rate of copper in the portion where the copper is in contact with the pad body is used. While suppressing the part where the load is not applied (none Under re-spinning), that is, the dissolution rate of copper in the portion where copper is not in direct contact with the pad is important. Second, in the low load region, that is, the region where the pad tip contacts the copper, the dissolution rate of copper The low dependence of the load is also an important factor. Thirdly, a honing liquid which is completely free of the honing agent and has the above first and second characteristics is prepared. In view of the above, the CMP for the present invention is used for solving the above problems. The composition of the grinding liquid contains at least the following basic components: (1) an oxidizing agent (such as hydrogen peroxide) or (2) a compound (organic acid and/or inorganic acid) which dissolves copper and forms a complex with copper; (3) Dissolution inhibitors (BTA, etc.) which inhibit the dissolution of copper under load rotation and without -12- (9) 1332017 load and (4) promote the dissolution of copper under load rotation and inhibit copper in the absence of The dissolved compound (water-soluble polymer). Further, 1) and the solutions of (2) to (4) are respectively adjusted, and the mixture is mixed in a monthly manner. The oxidizing agent for the metal of the present invention is a substitute of hydrogen peroxide, hypochlorous acid, peracetic acid, a dichromic acid compound, permanganic acid, a persulfate compound, iron nitrate or ferricyanide. Among these, the solution product is represented by non-toxic hydrogen peroxide or ammonium persulfate. Especially suitable for hydrogen peroxide. The content of the oxidizing agent depends on the oxygen used. For example, when using hydrogen peroxide, it is preferably about 5 to 3 M, and when ammonium is used, it is preferably about 5 to 0.2 M. In general, the copper-containing rust inhibitor copper is used to form a complex compound of a pH adjuster, a water-soluble polymer, and water. The above solution and an oxidizing agent are mixed. The inorganic acid may, for example, be phosphoric acid, pyrophosphoric acid or an organic acid-based carboxylic acid. The carboxylic acid is a monocarboxylic acid formic acid, acetic acid, dicarboxylic acid, oxalic acid, succinic acid, succinic acid, oxycarboxylic acid, tartaric acid, citric acid, aromatic carboxylic acid, benzoic acid, citric acid, etc. With oxygen carboxyl effect. In addition to this, amino acid, amine sulfuric acid, and the like, and aspartic acid are also effective. The content of these is adjusted according to the pH to be adjusted, i.e., the pH is adjusted according to the amount of acid added, and the amount added varies depending on the type to be used. The adjusted pH should be 2.5 or less and 1.5 to 2.5, and most preferably 1.5 to 2. These acids can be used alone and can be used in combination, and the same effects can be obtained. Used here. Copper rust re-rotation of the above (previously, the peroxy compound is preferably a persulfate agent and persulfate, and can be mixed with a solution, for example, acid, horse, malic acid is a lysine, change. It is suitable for use, and the acid is very -13- (10) (10) 1332017 The important system forms a complex with copper, and it is preferable to form a logarithm of the constant 値 of 3 or more. The pH adjustment of the complex with copper can be formed. The amount of the inorganic acid or the organic acid to be added is adjusted to a pH of 2.5 or less, particularly L5 to 2.5, before the solution with the oxidizing agent (water-soluble polymer, copper rust inhibitor, and water). Depending on the type of acid to be added, the amount of acid necessary for pH adjustment is different. It is found that the dissolution inhibitor which inhibits the dissolution of copper under the load-bearing rotation and the no-load rotation in the present invention forms an insoluble complex with copper. a compound, that is, a compound having a heterocyclic ring such as a triazole, a triazole derivative, a quinaldine acid salt or an oxine represented by benzotriazole, and a benzoin oxime , anthranilic acid, salicyl aldoxime, nitros naphthol, Cupferron, haloacetic acid, cysteine, etc. have such characteristics. The concentration of these should be 0.005!\4~0.2\4 (0.06~2.4% by weight), especially 0.02~0.1 Μ (0·25~1.2% by weight) or so. These may be used singly or in combination, and the same effect can be obtained. It is found that the portion of the load in the present invention can be applied (the load is rotated) That is, the dissolution rate of copper in the portion where the copper is in contact with the pad body is increased, and the dissolution rate of the copper in the portion where the load is not applied (without the load rotation), that is, the portion where the copper is not in direct contact with the pad body, can be suppressed. The compound is at least one selected from the group consisting of a polymer having a carboxyl group, a polymer having a mill base, and a polymer containing nitrogen. The polymer having a carboxyl group is a polyacrylic acid and a salt thereof (potassium salt, ammonium salt) , a copolymer of acrylic acid and acrylate, a copolymer of acrylic acid and acrylamide, etc., which may be used alone or in combination of -14-(11) (11) 1332017. The polymer group having a mercapto group may be exemplified. Such as an amine compound polymer having a mercapto group and The salt of the above may be used singly or in combination. The water-soluble polymer of the polymer containing nitrogen may, for example, be polyvinylpyrrolidone 'polyethyleneimine, polypropylene decylamine or the like. It can be used singly or in combination. Any of the above water-soluble polymers can be used, but it is particularly preferably an ionic polymer. The concentration of these is preferably 〜. 5~10% by weight, particularly preferably 0.1~ The upper limit of the concentration of 1% by weight is affected by the concentration of the rust inhibitor of copper coexisting as described later. In the present invention, the important points are the concentration of (3: copper rust inhibitor) and (4: water soluble polymer). Equilibrium. These copper rust inhibitors and water-soluble polymers act to suppress the dissolution of copper under any load-free rotation. However, the copper rust inhibitor can suppress dissolution even under load rotation (the suppression effect is reduced by the applied load), and the water-soluble polymer promotes the dissolution of copper under load rotation and inhibits the dissolution of copper. Therefore, it is adjusted to be outside the respective concentration ranges, and the concentration ratios of (3) and (4) are controlled to be necessary for achieving low-disc. In the present invention, it is found that the concentration (% by weight) of the compound of (3) must be greater than the concentration (% by weight) of the compound of (4). Even if the concentrations of (3) and (4) fall within the above concentration range, if the concentration is not controlled within this relationship, low dishing cannot be achieved. In the present invention, the abrasive is preferably as small as possible, and even if it is contained, it is preferably 0.5% by weight or less, preferably 0% by weight or less, and most preferably not contained at all. The reason for this is to avoid obstruction by etching or the like caused by the abrasive. Further, in the honing liquid 5 of the present invention, various additives may be added in addition to the above-mentioned main four components in accordance with -15-(12)(12)1332017. For example, there may be a water-soluble monomer such as methanol or ethanol or a surfactant such as potassium dodecylbenzenesulfonate. The principles of the invention are described below. However, as described above, in order to improve the flatness, the portion in which the load is applied (under load rotation), that is, the dissolution rate of copper in the portion where the copper is in contact with the pad body, while suppressing the portion where the load is not applied (no load) Rotating down), that is, the rate of dissolution of copper in the portion of the copper that is not in direct contact with the pad is important. Further, in the low load region, the change in the load weight is not an extremely important factor in the dissolution rate, and as shown in Fig. 1(a), the insulating film 1 having the groove formed on the surface of the substrate is applied. When the copper plating 2 is applied, the portion corresponding to the wiring portion generally shows the shape 3 of the recess. At the time of honing, the honing liquid 5 (honing liquid) is supplied from the nozzle 6 to between the pad body 4 and the copper film 2. In the state where CMP is performed (Fig. 1 (b)), the copper 2 and the pad 4 are not in contact in the wiring portion of the recess, and the pad 4 is in contact with the copper 2 in a portion other than the wiring portion. If the honing speed of the portion in contact with copper is the same as the honing speed in the uncontacted portion, the shape after honing is directly maintained in the shape before honing. On the other hand, when the honing speed of the contact portion is later than the untouched honing speed, as shown in Fig. 1 (c), the depth of the recess of the wiring portion becomes shallow as the honing progresses. Therefore, the honing fluid exhibiting such characteristics can coexist with high speed honing and low disc. Even if the honing speed of the copper which is not in contact with the mat body is small, and the honing speed of the portion which is in contact with the mat body is very slow, in order to reduce the honing residue of the copper, it takes time to perform the honing, and the honing time is not performed therebetween. The dissolution of copper in the portion in contact with the mat body cannot achieve low dishing. -16 - (13) 1332017 In addition, when a small load is applied, when the dissolution rate increases sharply, that is, when the load dependence of the dissolution rate of copper in the low load region is large, the barrier is close to the end of the honing. In the stage of the surface, if a little load is applied, the 'dissolution rate will increase sharply, and the barrier metal will directly dissolve the copper - sharply increase. Therefore, even if the difference between the applied _ degree of the load applied portion and the portion where the load is not applied is large, it is difficult to develop flatness. Therefore, in various honing liquids, in order to investigate the load of copper dissolution rate, the device shown in Fig. 2 (a) and (b) is considered. In the figure, (a) shows the overall configuration of the display device, and (b) is an enlarged view of the portion A of (a). The dissolution rate of copper is determined by forming an exchange current density. The rotating shaft 20 having the rotating electrode 19 of the copper electrode 13 is mounted on the motor 10 having the rotational speed of the control mechanism 11 to be pressed against the pad body. The load applied to the pad body is measured using the scale 14 , and the load applied to the copper electrode 13 is adjusted by the connection mechanism 16 , and the connection mechanism 16 is fixed to the seat body 1 disposed below the scale. 7. The dissolution rate of φ copper is controlled by the reference electrode 15 under the condition of the presence or absence of load (without load rotation and load rotation) in the state of rotation. The measurement system 1 2 performs measurement. The measurement was determined by measuring the exchange current density by Tafel. Using Tafel's relational money', that is, the overvoltage (potential difference from the immersion potential) in the potential domain is between 7 〇mV and 13 5 mV, and the logarithm of the current becomes a straight line, which makes it linearly extrapolated. The current 値 at the point where the immersion potential intersects is used as the exchange current density. The exchange current density was measured using a commercially available rotating disk ring electrode. -17- (14) 1332017 The platinum ring electrode was charged with a thickness of 10 to 20 μm thick (copper plating, but the measurement system only used a ring electrode). The measurement was carried out, and the classification was carried out under a load-rotation of 150 g/cm 2 under a load for a certain period of time under load and rotation and under any load. The rotation speed was 2000 rpm in the same manner as the actual honing. The scanning speed of the potential is more the anode side scanning potential than the immersion potential. Evaluation was carried out using the apparatus, and in the case where an organicizing agent was added, copper was found by adding a copper rust inhibitor, turning down, and rotating under load. However, the inhibitory effect of the copper rust inhibitor is reduced by the rotation of the load. It is considered that this is due to B T A adsorption to copper strength peeling. Further, in the present invention, by adding a water-soluble polymer which is one of CMP defects, the effect of the dishing quantum can be sufficiently reduced to be in contact with the mat body when no load is applied, and the rust preventive agent is used. Again, it dissolves. However, under the load rotation (corresponding to the dissolution rate of copper in the copper and the pad body in the contact portion between the copper and the pad body, the water-soluble polymer selected from the group consisting of a polymer having a carboxyl group and a polymer having a ground group is used as the water-soluble polymer. The soluble polymer system is very effective. Such a water-soluble high-scoring system can suppress the dissolution of copper when there is no load, but the copper prevention has a dissolution inhibiting plate for the copper generated by the copper rust preventive agent. After the honing of the density, the sub-times of the sub-times are slightly offset by 30 m V / min under the condition of no turning, and the dissolution rate of the acid or inorganic acid and oxygen is reduced even under the load-free spinning. It can be added to the composition of the mechanical grinding liquid. This water-soluble high-scoring (corresponding to the case where copper is not added to inhibit copper contact) is very clear. The hair compound and the water containing nitrogen have such a function. When another characteristic rust agent coexists, the function of reducing the effect is also -18-(15) 1332017. It is also clear why such characteristics are manifested in water-soluble polymer polymers. Characteristics It is known that if the water solubility is excessively increased, the effect of the dissolution inhibitor of copper is offset, and as a result, the dissolving amount cannot be solved, and the dishing is increased. On the other hand, it is particularly entangled, so that the water solubility can be appropriately controlled. The concentration of the polymer and copper is equalized, and the dishing can be suppressed. The honing liquid for CMP of the present invention can suppress high CMP disc formation and form a highly reliable wiring. In the present invention, the following evaluations were carried out for Ϊ and Comparative Examples 1 to 6. (Real honing evaluation) A ruthenium substrate formed of a copper foil having a thickness of Ιμπι was used as a ruthenium-based polyurethane resin. The relative speed of the fixed disk is set to 36 m/min. The honing speed when the load is CMP is obtained by converting the film resistance of the copper foil before and after the CMP. The amount of the disk is deep on the insulating film. After the copper is buried by the sputtering method and the plating method (Fig. CMP), the surface shape of the pattern portion is changed from the wiring metal portion width ΙΟΟμπι ΙΟΟμιη by the stylus type step difference, and the portion of the portion is reduced by the insulating portion. Quantity (honor evaluation), especially The concentration of ionic molecules reduces the solubility of copper and complicates the honing rate of the inhibitor complexly with: Example 1~1 4 body. Using the difference between the thickness of the substrate and the honing of 30 Og/cm2 ° from the gap of 0.5 μιη ), implementation and insulation width are determined by wiring gold -19- (16) (16) 1332017 The dissolution rate under load rotation and no load rotation is based on the device shown in Figure 2, using the electrochemical method. The Tafel test was carried out to determine the exchange current density, and the rotation speed was 2000 rpm. The details are described as means for solving the problem. (Example 1) Peroxidation using 2.5 Μ as a copper dissolving agent and 2.5 Μ as an oxidizing agent CMP was carried out by using hydrogen as a honing liquid composed of 0.5 wt% of benzotriazole as a rust preventive (protective film forming agent) and 0.2 wt% of polyvinylpyrrolidone as a water-soluble polymer. The amount of the copper solubilizing agent added was adjusted so as to be a specific pH (pH 2.0). As shown in Table 1, the results of good honing speed and dishing were obtained. The exchange current density of copper under a load of 10 g/cm 2 in the honing liquid was 10.1 μA/cm 2 , which was twice or less the exchange current density (5.55 μΑ/cm 2 ) of copper under no load rotation. On the other hand, the exchange current density of copper under a load of 150 g/cm 2 was 1 95 μΑ/cm 2 , which was more than 5 times the dissolution rate under no load. (Example 2) 0.5 wt% benzotriazole as a copper solvating agent, a rust inhibitor (protective film forming agent), and a water-soluble polymer were used instead of malic acid as the copper dissolving agent. CMP was carried out by using a honing liquid composed of 2 wt% of polyvinylpyrrolidone. The amount of the copper solubilizer added was adjusted so as to be a specific pH (pH 2.0). As shown in Table 1, the results of honing speed -20-(17) (17) 1332017 and good disc formation were obtained. The exchange current density of copper under the rotation of 1 Og/cm2 in the honing liquid was 5.91 pA/cm2, which was twice or less the exchange current density (6.41 μA/cm2) of copper under no load rotation. On the other hand, the exchange current density of copper under a load of 150 g/cm 2 was 138 μA/cm 2 , which was 5 times or more of the dissolution rate under no load. (Example 3) The use of oxalic acid for the substitution of malic acid used in Example 1 as a copper dissolving agent, 2.5 M hydrogen peroxide as an oxidizing agent, and rust inhibitor (protective film forming agent) as a rust inhibitor (8 wt% benzotriene) was used. CMP was carried out by using a ruthenium consisting of azole (BTA) and 0.4 wt% of polyacrylic acid as a water-soluble polymer. The amount of the copper solubilizer added was adjusted to a specific pH (p Η 1.8). As shown in Table 1, the results of good honing speed and dishing were obtained. The exchange current density of copper under the load of 1 〇g/cm 2 in the honing liquid is 5.23 pA/cm 2 , which is the exchange current density ( 4.68 μ Α / ί: ιη 2 ) of copper under no load rotation. Less than the following. On the other hand, the exchange current density of copper under a load of 150 g/cm 2 was 63.2 μΑ / ο η 2 , which was 5 times or more of the dissolution rate under no load. (Example 4) The use of the acid acid of the inorganic acid as the copper dissolving agent, the hydrogen peroxide of 2.5 Å as the oxidizing agent, and the rust inhibitor (protective film forming agent) were used as the rust inhibitor (7 wt%). CMP was carried out by using benzotriazole as a honing liquid composed of 0.4 wt% of polyacrylic acid as a water-soluble polymer. Adjust the amount of copper solvent to be added to -21 - (18) 1332017 to a specific pH (p H2.0). As shown in Table 1, the results of good honing speed and dishing were obtained. The exchange current density of copper under the load of l〇g/cm2 in the honing liquid is 4.64 μA/cm2, which is the exchange current density (- 5.59 μΑ/cm 2 ) of copper under no load rotation. 2 times or less. On the other hand, at a load of 150 g/cm 2 , the exchange current density of copper under rotation was 42.7 pA/cm 2 , which was 5 times or more of the dissolution rate under no load. (Example 5) The malic acid used in Example 1 was replaced with pyrophosphoric acid of the inorganic acid as a copper dissolving agent, 2.5 M hydrogen peroxide as an oxidizing agent, and as a rust preventive agent (protective film forming agent). CMP was carried out by using a honing liquid composed of 3 wt% benzotriazole and 2% by weight of polyacrylic acid as a water-soluble polymer. The amount of the copper solvent to be added is adjusted so as to be a specific pH (p H2.3 ). As shown in Table 1, the results of good honing speed and dishing were obtained. φ The exchange current density of copper under the load of 1 〇g/cm2 in the honing fluid is 35·1 μΑ/(:πι2, which is the exchange current density of copper under no load rotation (20.7 μΑ/< In contrast, the exchange current density of copper under a load of 150 g/cm 2 is 267 pA/cm 2 , which is five times or more the dissolution rate under no load. (Example 6)

使用由作爲銅溶解劑之蘋果酸、作爲氧化劑之2.5M 的過氧化氫、〇·5 wt %嗤哪啶酸取代表示於實施例1之BT A -22- (19) (19)1332017 作爲防鏽劑（保護膜形成劑）、作爲水溶性高分子之0.2 wt %的聚丙烯醯胺所構成之硏磨液而實施CMP。以成爲特 定的pH ( pHl.5 )的方式調整銅溶解劑的添加量。如表1 所示般，可得到硏磨速度及碟化均良好的結果。在本硏磨 液中之1 〇g/cm2的荷重旋轉下之銅的交換電流密度爲 10.5pA/cm2，爲在無荷重旋轉下之銅的交換電流密度（ 8 ·09μΑ/(πη2 )的2倍以下。相對於此，在1 50g/cm2的荷重 旋轉下之銅的交換電流密度爲12MA/Cm2，爲在無荷重下 之溶解速度的5倍以上。 (實施例7) 使用由草酸取代用於實施例1之蘋果酸作爲銅溶解劑 ' 2.5M的過硫酸鉀（K2S2Os)取代表示於實施例1之過 氧化氫作爲氧化劑、作爲防鏽劑（保護膜形成劑）之 0.4wt%苯並三唑（BTA )、作爲水溶性高分子之〇.1 wt%的 聚乙烯基吡咯烷酮所構成之硏磨液而實施CMP。以成爲特 定的pH ( PH2.0 )的方式調整銅溶解劑的添加量。如表i 所示般’可得到硏磨速度及碟化均良好的結果。在本硏磨 液中之lOg/cm2的荷重旋轉下之銅的交換電流密度爲 1 1.8pA/cm2 ’爲在無荷重旋轉下之銅的交換電流密度（ 10·5μΑ/οπη2)的2倍以下。相對於此，在150g/cm2的荷重 旋轉下之銅的交換電流密度爲240 μ A/cm2，爲在無荷重下 之溶解速度的5倍以上。 -23- (20) 1332017 (實施例8) 使用由無機酸之磷酸取代用於實施例1之蘋果酸作爲 銅溶解劑、0.015M的第2硝酸鐵（Fe(N03) 3)取代表 示於實施例1之過氧化氫作爲氧化劑、作爲防鏽劑（保護 膜形成劑）之〇.5wt%水楊基醛肟、作爲水溶性高分子之 0.3 wt %的聚乙撑基亞胺所構成之硏磨液而實施CMP。以 成爲特定的pH (p H2.1)的方式調整銅溶解劑的添加量。 如表1所示般’可得到硏磨速度及碟化均良好的結果。在 本硏磨液中之l〇g/cm2的荷重旋轉下之銅的交換電流密度 爲8.4(^A/cm2，爲在無荷重旋轉下之銅的交換電流密度（ 5.18pA/cm2)的2倍以下。相對於此，在BOg/cm2的荷重 旋轉下之銅的交換電流密度爲50.ΟμΑ/cm2，爲在無荷重下 之溶解速度的5倍以上。 (實施例9 ) φ 使用由無機酸之焦磷酸取代用於實施例1之蘋果酸作 爲銅溶解劑、作爲氧化劑之2 · 5M的過氧化氫、作爲防鏽 劑（保護膜形成劑）之〇.8wt%BTA、作爲水溶性高分子之 0.3wt%的聚丙烯醯胺所構成之硏磨液而實施CMP。以成爲 特定的pH ( p H2.0 )的方式調整銅溶解劑的添加量。如表 1所示般，可得到硏磨速度及碟化均良好的結果。在本硏 磨液中之l〇g/cm2的荷重旋轉下之銅的交換電流密度爲 4.1 8 μΑ/cm2 ’爲在無荷重旋轉下之銅的交換電流密度（ 3.68μΑ/(Μη2)的2倍以下。相對於此，在15〇g/cm2的荷重 -24 - (21) 1332017 旋轉下之銅的交換電流密度爲58.2μΑ/ί：ιη2，爲在無荷重下 之溶解速度的5倍以上。 _ (實施例1 〇 ) - 使用由馬來酸取代用於實施例1之蘋果酸作爲銅溶解 . 劑、作爲氧化劑之2.5M的過氧化氫、作爲防鏽劑（保護 膜形成劑）之 〇.9wt%BTA、作爲水溶性高分子之0.8wt% φ 的聚乙撐基亞胺所構成之硏磨液而實施CMP。以成爲特定 的pH ( p H2.0 )的方式調整銅溶解劑的添加量。如表1所 示般，可得到硏磨速度及碟化均良好的結果。在本硏磨液 • 中之 l〇g/cm2的荷重旋轉下之銅的交換電流密度爲 . 4·18μΑ/(：ιη2，爲在無荷重旋轉下之銅的交換電流密度（ 1·74μΑ/ίίΐη2)的2倍以下。相對於此，在150g/cm2的荷重 旋轉下之銅的交換電流密度爲62.3pA/cm2，爲在無荷重下 之溶解速度的5倍以上。 (實施例1 1 )BT A -22- (19) (19) 1332017, which is represented by the use of malic acid as a copper dissolving agent, 2.5 M hydrogen peroxide as an oxidizing agent, and 〇·5 wt% quinalic acid, is used as an anti-defense method. CMP was carried out by using a rust agent (protective film forming agent) and a honing liquid composed of 0.2 wt% of polyacrylamide as a water-soluble polymer. The amount of the copper solubilizing agent added was adjusted so as to be a specific pH (pH 1.5). As shown in Table 1, the results of good honing speed and dishing were obtained. The exchange current density of copper under the load of 1 〇g/cm2 in the honing liquid is 10.5 pA/cm2, which is the exchange current density of copper under no load rotation (8 · 09 μΑ / (πη2 ) 2 In contrast, the exchange current density of copper under a load of 150 g/cm 2 is 12 MA/cm 2 , which is 5 times or more of the dissolution rate under no load. (Example 7) Use of oxalic acid instead The malic acid of Example 1 was substituted as a copper dissolving agent '2.5 M potassium persulfate (K2S2Os). The hydrogen peroxide represented in Example 1 was used as an oxidizing agent, and 0.4 wt% of benzoic acid as a rust preventive agent (protective film forming agent). CMP is carried out by triazine (BTA) and a turmeric liquid composed of 1 wt% of polyvinylpyrrolidone as a water-soluble polymer. The addition of a copper solvent is adjusted so as to be a specific pH (pH 2.0). The amount of honing speed and dishing is good as shown in Table i. The exchange current density of copper under the load of lOg/cm2 in the honing liquid is 1 1.8pA/cm2 ' The exchange current density (10·5μΑ/οπη2) of copper under no load rotation is less than 2 times. Therefore, the exchange current density of copper under a load of 150 g/cm 2 is 240 μA/cm 2 , which is more than 5 times the dissolution rate under no load. -23- (20) 1332017 (Example 8) The phosphoric acid of the inorganic acid was substituted for the malic acid used in Example 1 as a copper solubilizing agent, and 0.015 M of the second ferric nitrate (Fe(N03) 3 ) was substituted for the hydrogen peroxide of Example 1 as an oxidizing agent as a rust preventive agent ( CMP is carried out by a honing liquid composed of 5 wt% salicylaldoxime and 0.3 wt% of polyethyleneimine as a water-soluble polymer to form a specific pH (p H2). .1) The amount of the copper solubilizer added is adjusted as shown in Table 1. The results of the honing speed and the dishing are good. Under the load of l〇g/cm2 in the honing liquid, The exchange current density of copper is 8.4 (^A/cm2, which is twice or less the exchange current density (5.28 pA/cm2) of copper under no load rotation. In contrast, copper under the load of BOg/cm2 is rotated. The exchange current density is 50.ΟμΑ/cm2, which is more than 5 times the dissolution rate under no load. (Example 9) φ Use of inorganic acid Phosphoric acid is substituted for the malic acid used in Example 1 as a copper solubilizing agent, 2,5 M hydrogen peroxide as an oxidizing agent, rust as a rust preventive agent (protective film forming agent), 8 wt% BTA, 0.3 as a water-soluble polymer CMP was carried out by a honing liquid composed of wt% of polyacrylamide, and the amount of the copper solubilizing agent added was adjusted so as to be a specific pH (p H2.0 ). As shown in Table 1, the results of good honing speed and dishing were obtained. The exchange current density of copper under the load of l〇g/cm2 in the honing liquid is 4.1 8 μΑ/cm 2 ' is the exchange current density of copper under no load rotation ( 3.68 μΑ/(Μη2) 2 In contrast, the exchange current density of copper under a load of 15 〇g/cm 2 -24 - (21) 1332017 is 58.2 μΑ / ί:ιη2, which is more than 5 times the dissolution rate under no load. _ (Example 1 〇) - Substituting malic acid for use in Example 1 as a copper dissolving agent, 2.5 M hydrogen peroxide as an oxidizing agent, and as a rust preventive (protective film forming agent) CMP. 9wt% BTA, a honing liquid composed of 0.8% by weight of a water-soluble polymer of polyethylene oxide imine, and CMP is performed. The copper solvent is adjusted so as to have a specific pH (p H2.0 ). The amount of addition is as shown in Table 1. The results of honing speed and dishing are good. The exchange current density of copper under the load of l〇g/cm2 in the honing fluid is 4. 4 ·18μΑ/(:ιη2, which is twice or less the exchange current density (1·74μΑ/ίίΐη2) of copper under no load rotation. , Exchange current density of copper under a load rotation 150g / cm2 as a sum of 62.3pA / cm2, is at least 5 times the rate of dissolution under the load without (Example 11)

. 使用由作爲銅溶解劑之蘋果酸、作爲氧化劑之2.5M 的過氧化氫、作爲防鏽劑（保護膜形成劑）之〇.4wt%苯 並三唑、作爲水溶性高分子之0.1 wt%的聚乙烯基吡咯烷 酮、作爲添加劑之0.01 wt%的甲醇所構成之硏磨液而實施 CMP。以成爲特定的pH (pH2.0)的方式調整銅溶解劑的 添加量。如表1所示般，可得到硏磨速度及碟化均良好的 結果。在本硏磨液中之10g/cm2的荷重旋轉下之銅的交換 -25- (22) (22)1332017 電流密度爲10.9pA/cm2，爲在無荷重旋轉下之銅的交換電 流密度（9_82pA/cm2 )的 2倍以下。相對於此，在 150g/cm2的荷重旋轉下之銅的交換電流密度爲234pA/cm2 ，爲在無荷重下之溶解速度的5倍以上。 (實施例1 2 ) 使用由作爲銅溶解劑之蘋果酸、作爲氧化劑之2.5M 的過氧化氫、作爲防鏽劑（保護膜形成劑）之0.4 wt%苯 並三唑、作爲水溶性高分子之0.1 wt %的聚乙烯基吡咯烷 酮、作爲添加劑之o.oiwt %的十二烷基苯磺酸鉀所構成之 硏磨液而實施CMP。以成爲特定的ρΗ(ρΗ2·0)的方式調 整銅溶解劑的添加量。如表1所示般，可得到硏磨速度及 碟化均良好的結果。在本硏磨液中之10 g/cm2的荷重旋轉 下之銅的交換電流密度爲3.59pA/cm2，爲在無荷重旋轉下 之銅的交換電流密度（2.09pA/cm2 )的2倍以下。相對於 此，在150g/cm2的荷重旋轉下之銅的交換電流密度爲 201 μA/cm2，爲在無荷重下之溶解速度的5倍以上。 (比較例1 ) 使用不與銅形成錯合物的硝酸作爲銅溶解劑、作爲氧 化劑之2.5M的過氧化氫、作爲防鏽劑（保護膜形成劑） 之0.5wt%苯並三嗤、作爲水溶性高分子之〇.2wt%的聚乙 烯基吡咯烷酮所構成之硏磨液而實施CMP。以成爲特定的 pH (pH2_0)的方式調整銅溶解劑的添加量。與實施例相 -26- (23) (23)1332017 異之部分係銅溶解劑之種類。如表2所示般，硏磨速度良 好，但碟化大，無法滿足規定値。在本硏磨液中之荷重旋 轉下之銅的交換電流密度爲37.4 μΑ/cm2，若稍施加荷重（ lg/cm2)，荷重旋轉下之銅的交換電流密度爲95.5pA/cm2 ，急劇地增加至無荷重旋轉下之銅的交換電流密度的2倍 以上。在150g/cm2的荷重旋轉下之銅的交換電流密度爲 2 74pA/cm2，爲在無荷重下之溶解速度的5倍以上。 (比較例2) 使用不與銅形成錯合物的鹽酸作爲銅溶解劑、作爲氧 化劑之2.5M的過氧化氫、作爲防鏽劑（保護膜形成劑） 之0.5wt%苯並三唑' 作爲水溶性高分子之0.2wt%的聚乙 烯基吡咯烷酮所構成之硏磨液而實施CMP。以成爲特定的 pH ( PH2_0 )的方式調整銅溶解劑的添加量。與實施例相 異之部分係銅溶解劑之種類。如表2所示般，硏磨速度良 好，但碟化大，無法滿足規定値。在本硏磨液中之荷重旋 轉下之銅的交換電流密度爲28.2μΑ/(：ιη2，若稍施加荷重（ lg/cm2)，荷重旋轉下之銅的交換電流密度爲84.5pA/Cm2 ，急劇地增加至無荷重旋轉下之銅的交換電流密度的2倍 以上。在150g/cm2的荷重旋轉下之銅的交換電流密度爲 2 8 8 μΑ/cm2，爲在無荷重下之溶解速度的5倍以上。 (比較例3 )Using 4% by weight of malic acid as a copper dissolving agent, 2.5M hydrogen peroxide as an oxidizing agent, rust inhibitor (protective film forming agent), 4 wt% benzotriazole, 0.1 wt% as a water-soluble polymer CMP was carried out by using a pulverizing liquid composed of polyvinylpyrrolidone and 0.01 wt% of methanol as an additive. The amount of the copper solubilizer added was adjusted so as to be a specific pH (pH 2.0). As shown in Table 1, the results of good honing speed and dishing were obtained. The exchange of copper under the load of 10g/cm2 in the honing liquid -25(22) (22)1332017 The current density is 10.9pA/cm2, which is the exchange current density of copper under no load rotation (9_82pA) /cm2) is less than 2 times. On the other hand, the exchange current density of copper under a load of 150 g/cm 2 was 234 pA/cm 2 , which was 5 times or more of the dissolution rate under no load. (Example 1 2) 0.4 wt% benzotriazole as a water-soluble polymer using malic acid as a copper dissolving agent, 2.5 M hydrogen peroxide as an oxidizing agent, and a rust preventive agent (protective film forming agent) CMP was carried out with 0.1% by weight of polyvinylpyrrolidone and o. oiwt% of potassium dodecylbenzenesulfonate as an additive. The amount of the copper solubilizing agent added is adjusted so as to become a specific ρ Η (ρ Η 2 · 0). As shown in Table 1, the results of good honing speed and dishing were obtained. The exchange current density of copper under a load of 10 g/cm 2 in the honing liquid was 3.59 pA/cm 2 , which was twice or less the exchange current density (2.09 pA/cm 2 ) of copper under no load rotation. In contrast, the exchange current density of copper under a load of 150 g/cm 2 was 201 μA/cm 2 , which was 5 times or more of the dissolution rate under no load. (Comparative Example 1) Nitric acid which does not form a complex with copper is used as a copper dissolving agent, 2.5 M hydrogen peroxide as an oxidizing agent, and 0.5 wt% benzotriazine as a rust preventive agent (protective film forming agent). CMP was carried out by using a honing liquid composed of a water-soluble polymer of 2% by weight of polyvinylpyrrolidone. The amount of the copper solubilizer added was adjusted so as to be a specific pH (pH 2_0). Compared with the examples -26- (23) (23) 1332017 The different parts are copper dissolvers. As shown in Table 2, the honing speed is good, but the disc is large and cannot meet the requirements. The exchange current density of copper under the load rotation in the honing liquid is 37.4 μΑ/cm 2 . If the load is applied slightly ( lg/cm 2 ), the exchange current density of copper under the load rotation is 95.5 pA/cm 2 , which increases sharply. It is more than twice the exchange current density of copper under no load rotation. The exchange current density of copper under a load of 150 g/cm 2 was 2 74 pA/cm 2 , which was 5 times or more of the dissolution rate under no load. (Comparative Example 2) Hydrochloric acid which does not form a complex with copper is used as a copper dissolving agent, 2.5 M hydrogen peroxide as an oxidizing agent, and 0.5 wt% benzotriazole as a rust preventive agent (protective film forming agent) CMP was carried out by using a honing liquid composed of 0.2 wt% of polyvinylpyrrolidone of a water-soluble polymer. The amount of the copper solvent to be added is adjusted so as to be a specific pH (PH2_0). The portion different from the examples is a type of copper dissolving agent. As shown in Table 2, the honing speed is good, but the disc is large and cannot meet the requirements. The exchange current density of copper under the load rotation in the honing liquid is 28.2 μΑ / (: ηη 2 , and if a load ( lg / cm 2 ) is applied slightly, the exchange current density of copper under the load rotation is 84.5 pA / Cm 2 , sharply The ground is increased to more than twice the exchange current density of copper under no-load rotation. The exchange current density of copper under a load of 150 g/cm 2 is 2 8 8 μΑ/cm 2 , which is the dissolution rate under no load. More than double. (Comparative Example 3)

使用由作爲銅溶解劑之蘋果酸、作爲氧化劑之2.5M -27- (24) (24)1332017 的過氧化氫、作爲防鏽劑（保護膜形成劑）之〇· 5 Wt%苯 並三唑、作爲水溶性高分子之 0.2 wt%的聚乙烯基吡咯烷 酮所構成之硏磨液而實施CMP。以成爲特定的ρΗ(ΡΗ2·6 )的方式調整銅溶解劑的添加量。與實施例1相異之點係 在於pH高。因此，硏磨速度慢，無法滿足規定値。又， 若稍施加荷重（lg/cm2 )，荷重旋轉下之銅的交換電流密 度雖小，但成爲無荷重旋轉下之銅的交換電流密度的2倍 以上之値。碟化大，無法滿足規定値。 (比較例4) 使用由作爲銅溶解劑之蘋果酸、作爲氧化劑之2.5Μ 的過氧化氫、作爲防鏽劑（保護膜形成劑）之0.5wt%苯 並三唑、作爲水溶性高分子之 0.2 wt%的聚乙烯基吡咯烷 酮所構成之硏磨液而實施CMP。以成爲特定的PH(pH3.0 )的方式調整銅溶解劑的添加量。與實施例1相異之點係 在於pH高。因此，硏磨速度慢，無法滿足規定値。又， 若稍施加荷重（1 g/cm2 )，荷重旋轉下之銅的交換電流密 度雖小，但成爲無荷重旋轉下之銅的交換電流密度的2倍 以上之値。碟化大，無法滿足規定値。 (比較例5 ) 使用由作爲銅溶解劑之蘋果酸、作爲氧化劑之2.5 M 的過氧化氫、作爲水溶性高分子之0.4 wt%的聚丙輝酸所 構成之硏磨液而實施CMP。以成爲特定的pH(pH2.0)的 -28- (25) (25)1332017 方式調整銅溶解劑的添加量。因不含防鏽劑，與其他之比 較例及實施例比較，無荷重旋轉下之銅的交換電流密度係 明顯很大。在本比較例中係與添加其他之防鏽劑之情形相 異，藉施加荷重（在荷重旋轉下）銅的交換電流密度會減 少。因未添加防鏽劑，硏磨速度係顯示非常大於規定値之 値，但碟化亦大，無法滿足規定値。 (比較例6) 使用由作爲銅溶解劑之蘋果酸、作爲氧化劑之2.5M 的過氧化氫、作爲防鏽劑（保護膜形成劑）之〇.5wt%苯 並三唑所構成之硏磨液而實施CMP。以成爲特定的pH ( PH2.0 )的方式調整銅溶解劑的添加量。與實施例1相異 之點係未添加水溶性高分子。在無荷重旋轉下係BTA可 抑制銅的溶解，故銅之交換電流密度小，但在稍施加荷重 (lg/cm2)之荷重旋轉下BTA容易地從銅脫離，隨著荷重 之施加，銅的交換電流密度會急劇地增加。 在本硏磨液中係如表2所示般，硏磨速度良好，但碟 化大，無法滿足規定値。 (實施例1 3 ) 使用由草酸取代用於實施例1之蘋果酸作爲銅溶解劑 、作爲氧化劑之2.5M的過氧化氫、作爲防鏽劑（保護膜 形成劑）之 〇.2wt%苯並三唑、作爲水溶性高分子之 〇.2wt%的聚丙烯酸所構成之硏磨液而實施CMP。以成爲特 -29- (26) (26)1332017 定的pH (pH 1.8)的方式調整銅溶解劑的添加量。與實施 例3相異之點係水溶性高分子之濃度高於防鏽劑之濃度。 在如此之系統中如表2所示般，藉稍施加荷重（1 g/cm2 ) ，在荷重旋轉下之銅的交換電流密度會急劇地增加。此係 水溶性高分子在荷重旋轉下中具有可促進銅之溶解的效果 ，故若水溶性高分子濃度較防鏽劑之濃度相對地變高，如 此以稍施加荷重，銅之交換電流密度會增加。如此之情形 ，硏磨速度雖良好，但碟化量略變大。 (實施例1 4 ) 使用由磷酸取代用於實施例1之蘋果酸作爲銅溶解劑 、作爲氧化劑之2.5M的過氧化氫、作爲防鏽劑（保護膜 形成劑）之 〇. 7 wt%苯並三唑、作爲水溶性高分子之 〇.7wt%的聚丙烯酸所構成之硏磨液而實施CMP。以成爲特 定的pH ( PH2.0 )的方式調整銅溶解劑的添加量。與實施 例4相異之點係水溶性高分子之濃度與防鏽劑之濃度相同 。在如此之系統中如表2所示般，藉稍施加荷重（1 g/cm2 )，在荷重旋轉下之銅的交換電流密度會急劇地增加。此 係水溶性高分子在荷重旋轉下中具有可促進銅之溶解的效 果，故若水溶性高分子濃度較防鏽劑之濃度相對地變高， 如此以稍施加荷重，銅之交換電流密度會增加。如此之情 形，硏磨速度雖良好，但碟化量略變大。 表1、表2之實施例及比較例的交換電流密度的荷重 依存性、及如圖示其之圖3所示般，在碟化量小之實施例 -30- (27) (27)1332017Using a malic acid as a copper dissolving agent, 2.5M -27-(24) (24) 1332017 hydrogen peroxide as an oxidizing agent, and a rust inhibitor (protective film forming agent) 5·5 Wt% benzotriazole CMP was carried out as a honing liquid composed of 0.2 wt% of polyvinylpyrrolidone of a water-soluble polymer. The amount of the copper solubilizing agent added is adjusted so as to become a specific ρ Η (ΡΗ2·6 ). The point different from Example 1 is that the pH is high. Therefore, the honing speed is slow and the 値 cannot be satisfied. Further, when the load (lg/cm2) is slightly applied, the exchange current density of the copper under the load rotation is small, but it is twice or more the exchange current density of the copper under the loadless rotation. The disc is too big to meet the regulations. (Comparative Example 4) 0.5% by weight of benzotriazole as a sulphur-preventing agent (protective film forming agent), and a water-soluble polymer as a water-soluble polymer CMP was carried out with a honing liquid composed of 0.2 wt% of polyvinylpyrrolidone. The amount of the copper solubilizing agent added was adjusted so as to be a specific pH (pH 3.0). The point different from Example 1 is that the pH is high. Therefore, the honing speed is slow and the 値 cannot be satisfied. Further, when a load (1 g/cm2) is slightly applied, the exchange current density of copper under load rotation is small, but it is twice or more the exchange current density of copper under no load rotation. The disc is too big to meet the regulations. (Comparative Example 5) CMP was carried out using a honing liquid composed of malic acid as a copper dissolving agent, 2.5 M hydrogen peroxide as an oxidizing agent, and 0.4 wt% polypropionic acid as a water-soluble polymer. Adjust the amount of copper solvent to be added in a manner of -28-(25) (25) 1332017 which is a specific pH (pH 2.0). Since the rust-preventing agent is not contained, the exchange current density of copper under no-load rotation is significantly larger than that of the other comparative examples and examples. In this comparative example, unlike the case where other rust inhibitors are added, the exchange current density of copper by the applied load (under the rotation of the load) is reduced. Since the rust preventive agent was not added, the honing speed showed that it was much larger than the specified enthalpy, but the disc was also large and could not meet the specified enthalpy. (Comparative Example 6) A honing liquid composed of malic acid as a copper dissolving agent, 2.5 M hydrogen peroxide as an oxidizing agent, and 55 wt% benzotriazole as a rust preventive agent (protective film forming agent) was used. And implement CMP. The amount of the copper solubilizing agent added was adjusted so as to be a specific pH (pH 2.0). The point different from Example 1 was that no water-soluble polymer was added. BTA can suppress the dissolution of copper under no load rotation, so the exchange current density of copper is small, but BTA is easily detached from copper under the load of a slight load (lg/cm2). With the application of load, copper The exchange current density will increase dramatically. In the honing liquid, as shown in Table 2, the honing speed is good, but the disc is large, and the predetermined enthalpy cannot be satisfied. (Example 1 3) The use of malic acid for the substitution of oxalic acid as a copper dissolving agent, 2.5 M hydrogen peroxide as an oxidizing agent, and rust inhibitor (protective film forming agent) as a rust inhibitor was used. CMP was carried out by using triazole as a honing liquid composed of 2% by weight of polyacrylic acid as a water-soluble polymer. The amount of the copper solubilizer added was adjusted so as to become the pH (pH 1.8) of the special -29-(26) (26) 1332017. The point different from Example 3 is that the concentration of the water-soluble polymer is higher than the concentration of the rust inhibitor. In such a system, as shown in Table 2, by a slight application of a load (1 g/cm2), the exchange current density of copper under load rotation is drastically increased. The water-soluble polymer has an effect of promoting dissolution of copper under load and rotation. Therefore, if the concentration of the water-soluble polymer is relatively higher than the concentration of the rust inhibitor, the exchange current density of copper is increased by slightly applying the load. . In this case, although the honing speed is good, the amount of disc is slightly larger. (Example 1 4) The use of the malic acid used in Example 1 as a copper dissolving agent, 2.5 M hydrogen peroxide as an oxidizing agent, and a rust preventive agent (protective film forming agent) was used. 7 wt% benzene CMP was carried out by using a triazole and a honing liquid composed of 7 wt% of polyacrylic acid as a water-soluble polymer. The amount of the copper solubilizing agent added was adjusted so as to be a specific pH (pH 2.0). The difference from the embodiment 4 is that the concentration of the water-soluble polymer is the same as the concentration of the rust inhibitor. In such a system, as shown in Table 2, by a slight application of a load (1 g/cm2), the exchange current density of copper under load rotation is drastically increased. The water-soluble polymer has an effect of promoting dissolution of copper under load and rotation, so if the concentration of the water-soluble polymer is relatively higher than the concentration of the rust inhibitor, the exchange current density of copper is increased by applying a slight load. . In such a situation, although the speed of honing is good, the amount of disc is slightly larger. The load-exchange density dependence of the examples and the comparative examples of Tables 1 and 2 is as shown in Fig. 3, and the amount of the disk is small as shown in the figure -30-(27) (27) 1332017

中係至1 〇g/cm 2的荷重區域中銅的父換電流密度幾乎無變 化。若超過1 Og/cm2 ’銅的交換電流密度係急劇地增加。 相對於此，碟化量很大之比較例的情形’在荷重爲0中即 使銅的交換電流密度很小時’若稍施加1 g/cm2之重’交 換電流密度會急劇上昇。 -31 - 1332017The parent current exchange density of copper in the load region from medium to 1 〇g/cm 2 is almost unchanged. If the exchange current density exceeds 1 Og/cm2', the amount of copper increases sharply. On the other hand, in the case of the comparative example in which the amount of the electric disk is large, the exchange current density of the copper is slightly increased when the load is 0, even if the exchange current density of copper is small. -31 - 1332017

二撇〕 N 150g/cm2 〇\ 00 ΓΛ <N v〇 νο <N ο <N 〇 ίΝ 〇6 tn m <N v〇 ?； CN ε ο m 緘 戲 CN白 I 〇 〇 ON iri m CN ΙΟ S wS m l〇 o OO 〇 00 00 ••Η — 00 Tj- Ο) Ο Ό\ *〇 ro lg/cm2 Ό 〇〇 ΓΟ (N 00 »η 00 ν〇 廿 — CN 00 Q\ 寸 CN CN v〇 OO 守 ON ίΝ ίΝ OO rn Og/cm2 u-) 寸 VD oo VO — ON ir> 卜 g oo l/~\ 〇 oo Ψ t »〇 oo v〇 cn CN 00 〇\ g oi 碟化 評估 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 硏磨速 度評估 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 ο rsi Ο fN o (N o cn <N 〇 rj ο CNI o 〇 (N ο (Ν o fN 添加劑(濃 m • I • 1 1 1 • 1 1 1 Ε- S 砩验芝 % 11锻s +拼〇 水溶性高分子 (濃度） 補肩 裝s K)區 蜜艺 Si 涯s κι匾 嵌遯 聚丙烯酸 (0.4wt%) M c? k： 1 嵌s 聚丙烯醯胺 (0.2wt%) 聚丙烯醯胺 (0.2wt°/〇) r 涯s M屬 聚乙撐基亞胺 (0.3wt%) 聚丙烯醯胺 (0.35wt%) 聚乙撐基亞胺 (0.8wt°/〇) i篆 ^ % 稍^ 线s κι ffi 酴遯 ί茨 蝴r 缓S Μ匾 踩遯 防鏽劑-保護 膜形成劑-(濃 度） BTA (0.5wt%) BTA(0.5wt%) 1 BTA(0.8wt%) BTA(0.7wt%) BTA(0.3wt%) 經cr ® £ BTA(0.4wt%) 水楊基醛肟 (0.5 wt%) BTA(0.8wt%) BTA(0.9wt%) BTA(0.4wt%) BTA(0.4wt%) 氧化劑(濃度） H2〇2 (2.5M) H2〇2 (2.5M) H202 (2.5M) H202 (2.5M) H202 (2.5M) H202 (2.5M) Κ·2$2〇8 (0.1 Μ) Fe(N03)3 (0.015M) H202 (2.5M) H202 (2.5M) H2〇2 (2.5M) H2〇2 (2.5M) 銅溶解劑- pH調整 劑- 蘋果酸 馬來酸 草酸 磷酸 焦磷酸 蘋果酸| ! 草酸 磷酸 焦磷酸 馬來酸 蘋果酸 蘋果酸 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 _1 實施例7 實施例8 實施例9 習2 Μ 實施例 11 實施例 12 Η-ΚΤΦ/郸 οοοτ-:χ,φ/^οοοζίοοοΓ v , τκιφ/郸 οοοε 〇-m>Msfi«i®s _ΤΚΐ 郸οοοζ : χ ,郸oooyoog : V ,κ-κι^οοοι:〇-w>M^璧 -32- 1332017 (29) 〔CNI5 /—s 150g/cm2 274 288 10.7 5.59 364 274 42.0 a. m 银 Μ 裁 10g/cm2 117.0 3.36 1 1 240 〇 寸 «—Η ο 41.0 lg/cm2 95.5 84.5 2.36 1.73 ΓΟ 40.5 s Og/cm2 37.40 28.20 0.95 0.59 〇 3.82 71.4 2.41 碟化 評估 X X X X X X <3 < 硏磨速 度評估 〇 〇 <3 X 〇 〇 〇 〇 2.00 2.00 2.60 3.00 2.00 2.00 § 2.00 添加劑 (濃度） 1 1 1 1 1 1 1 1 水溶性高分子(濃 m 聚乙烯基姬咯烷酮 (0.2wt%) 聚乙烯基吡咯烷酮 (〇.2vn%) 聚乙烯基吡咯烷酮 (0.2wt%l 聚乙烯基吡咯烷酮1 (0.2wt%) 聚丙烯酸(〇.4wt%) 1 聚丙烯酸(〇.2wt%) 聚丙烯酸(〇.7wt%) 防鏽劑-保護 m /-—ν BTA(0.5wt%) BTA(0.5wt%) BTA(0.5wt°/〇) BTA(0.5wt%) 1 I d 芝 BTA(0.2wt%) BTA(0.7wt°/〇) 氧化劑(濃度） H2〇2 (2.5M) H2〇2 (2.5M) H2〇2 (2.5M) H202 (2.5M) *r\ q X H2〇2 (2.5M) H202 (2.5M) 銅溶解劑- pH調整 劑- 硝酸 鹽酸 蘋果酸 蘋果酸 蘋果酸 蘋果酸 s 磷酸 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 賁施例 13 實施例 14 K-ref^/lii ΟΟΟΓ χ ,φ/郸 ΟΟΟΖ-ΟΟΟΓ v ,叫彡汆/邾 οοοε :〇¥>紘«艘15宙 -33- (30) (30)1332017 在低荷重區域中減少銅之交換電流密度的變化率之組 成’係必須爲（1)具有使銅溶解之作用，且可與銅形成 錯合物之有機酸或無機酸、（2)以BTA、喹哪啶酸酸、 水楊基醛肟爲代表之銅的防鏽劑（保護膜形成劑）、（3 )以聚乙烯基吡咯烷酮、聚丙烯酸、聚丙烯醯胺、聚乙撐 基亞胺爲代表之水溶性高分子。 如比較例1及2所示般，銅之溶解劑如硝酸或鹽酸般 不與銅形成錯合物之酸時（或生成常數之對數很小時）， 硏磨速度即使滿足規定値，碟化量會變大。銅離子與鹽酸 離子之生成常數的對數値爲0.08。在比較例中係未特別顯 示，但硫酸離子（βΐ : 2.36 )亦同樣地碟化大。又，在醋 酸離子（βΐ: 1.83、β2: 3.09)中，係碟化爲略大的△之 評估。較其亦略生成常數之對數値很大，在磷酸（βΐ: 3.2 )或馬來酸（βΐ : 3.90 )中，碟化變小，評估係成爲〇 。若考量此等，至少生成常數之對數値必須爲3以上。又 ，如比較例3及4所示般，即使落入（1 )至（3 )的構成 成分之範圍，銅溶解劑之添加量少，pH大於2.50時，硏 磨速度亦慢於規定値，碟化量亦變大。如比較例6所示般 ，未添加銅防鏽劑時，係硏磨速度變快，但碟化量亦變大 。如實施例13、14所示般，落入（1)至（3)之構成成 分，且pH爲2.0以上，水溶性高分子之濃度亦高於防鏽 劑之濃度的情形，硏磨速度即使滿足，碟化量亦略變大。 若圖示此等之關係。如圖4般，在某比以上之區域中，可 得到高平坦性。 -34- (31) (31)1332017 上述記載係有關於實施例，但本發明不限於此等，而 可在本發明之精神與添附之申請專利範圍的範圍內@行:名_ 種變更及修正係熟悉此技藝者很明白。 【圖式簡單說明】 圖1係使矽基板上所形成之配線溝上的多餘銅層以 CMP除去的步驟圖，（a)表示CMP前，（b)表示CMP 中，（c)表示CMP後。 圖2係在硏磨荷重下之交換電流密度測定裝置的槪念 圖。 圖3係表示在各種CMP硏磨液中之銅的溶解速度的 荷重依存性之圖表。 圖4係表示銅防鏽劑濃度及水溶性高分子濃度與平坦 性之關係的圖表。 【主要元件符號說明】 1 :層間絕緣膜 2 :電鍍銅 3 :凹陷 4 :硏磨墊 5 :硏磨液 I 0 :馬達 II :旋轉控制系 1 2 :電化學測定系統 -35- (32) (32)1332017 1 3 :銅電極 14 :秤 1 5 :參考電極 16 :連結機構 1 7 :座體 1 9 :旋轉電極 20 :旋轉軸N撇] N 150g/cm2 〇\ 00 ΓΛ <N v〇νο <N ο <N 〇ίΝ 〇6 tn m <N v〇?; CN ε ο m CN戏CN白 I 〇〇ON iri m CN ΙΟ S wS ml〇o OO 〇00 00 ••Η — 00 Tj- Ο) Ο Ό\ *〇ro lg/cm2 Ό 〇〇ΓΟ (N 00 »η 00 ν〇廿—CN 00 Q\ inch CN CN v〇OO 守 ON ίΝ ίΝ OO rn Og/cm2 u-) inch VD oo VO — ON ir> 卜g oo l/~\ 〇oo Ψ t »〇oo v〇cn CN 00 〇\ g oi Honing speed evaluation 〇〇〇〇〇〇〇〇〇〇〇〇ο rsi Ο fN o (N o cn <N 〇rj ο CNI o 〇(N ο ( Ν o fN additive (concentrated m • I • 1 1 1 • 1 1 1 Ε- S 砩 芝 %%% 11 s s + 〇 〇 〇 〇 〇 〇 K K ) K K K K K K K K K K K K K匾 遁 polyacrylic acid (0.4wt%) M c? k: 1 embedded s polyacrylamide (0.2wt%) polypropylene decylamine (0.2wt ° / 〇) r s s M is a polyethyleneimine ( 0.3wt%) Polyacrylamide (0.35wt%) Polyethyleneimine (0.8wt°/〇) i篆^ % slightly ^ line s κι f Fi 酴遁 茨 茨 S 遁 遁 遁 rust inhibitor - protective film forming agent - (concentration) BTA (0.5wt%) BTA (0.5wt%) 1 BTA (0.8wt%) BTA (0.7wt%) BTA (0.3 wt%) via cr ® £ BTA (0.4 wt%) Salicylaldoxime (0.5 wt%) BTA (0.8 wt%) BTA (0.9 wt%) BTA (0.4 wt%) BTA (0.4 wt%) Oxidizer (concentration) H2〇2 (2.5M) H2〇2 (2.5M) H202 (2.5M) H202 (2.5M) H202 (2.5M) H202 (2.5M) Κ·2$2〇8 (0.1 Μ) Fe ( N03)3 (0.015M) H202 (2.5M) H202 (2.5M) H2〇2 (2.5M) H2〇2 (2.5M) Copper Solubilizer - pH Adjuster - Malic acid Maleic acid oxalic acid pyrophosphate malic acid Oxalic acid pyrophosphate maleic acid malic acid malic acid Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 _1 Example 7 Example 8 Example 9 Example 2 Example 11 Example 12 Η-ΚΤΦ/郸οοοτ-:χ,φ/^οοοζίοοοΓ v , τκιφ/郸οοοο 〇-m>Msfi«i®s _ΤΚΐ 郸οοοζ : χ ,郸oooyoog : V ,κ-κι^οοοι:〇-w> M^璧-32- 1332017 (29) [CNI5 /-s 150g/cm2 274 288 10.7 5.59 364 274 42.0 a. m Silver Μ Cut 10g/cm2 117.0 3.36 1 1 240 〇 inch «—Η ο 41.0 lg/cm2 95.5 84.5 2.36 1.73 ΓΟ 40.5 s Og/cm2 37.40 28.20 0.95 0.59 〇3.82 71.4 2.41 Disc evaluation XXXXXX <3 < honing speed evaluation 〇〇<3 X 〇〇〇 〇2.00 2.00 2.60 3.00 2.00 2.00 § 2.00 Additive (concentration) 1 1 1 1 1 1 1 1 Water-soluble polymer (concentrated m polyvinylpyrrolidone (0.2wt%) polyvinylpyrrolidone (〇.2vn%) Polyvinylpyrrolidone (0.2wt% l polyvinylpyrrolidone 1 (0.2wt%) polyacrylic acid (〇.4wt%) 1 polyacrylic acid (〇.2wt%) polyacrylic acid (〇.7wt%) rust inhibitor - protection m /--ν BTA (0.5wt%) BTA (0.5wt%) BTA (0.5wt ° / 〇) BTA (0.5wt%) 1 I d Zhi BTA (0.2wt%) BTA (0.7wt ° / 〇) oxidant ( Concentration) H2〇2 (2.5M) H2〇2 (2.5M) H2〇2 (2.5M) H202 (2.5M) *r\ q X H2〇2 (2.5M) H202 (2.5M) Copper Solvent - pH Conditioner - Nitric acid hydrochloric acid Malic acid Malic acid Malic acid Malic acid s Phosphoric acid Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Example 13 Example 14 K-ref^/lii ΟΟΟΓ χ , φ /郸ΟΟΟΖ-ΟΟΟΓ v , 彡/邾οοοε :〇¥>纮«船15宙-33- (30) (30)1332017 The composition of the rate of change of the exchange current density of copper in the low load region is reduced to (1) having copper dissolved An organic or inorganic acid which forms a complex with copper, and (2) a rust inhibitor (protective film forming agent) of copper represented by BTA, quinalidonic acid, salicyl aldoxime, (3) A water-soluble polymer represented by polyvinylpyrrolidone, polyacrylic acid, polypropylene decylamine or polyethyleneimine. As shown in Comparative Examples 1 and 2, when a copper dissolving agent such as nitric acid or hydrochloric acid does not form a complex acid with copper (or the logarithm of the formation constant is small), the honing speed satisfies the prescribed enthalpy Will get bigger. The logarithm of the formation constant of copper ions and hydrochloric acid ions was 0.08. In the comparative example, it was not particularly shown, but the sulfate ion (βΐ: 2.36) was also similarly discsized. Further, in the acetic acid ion (βΐ: 1.83, β2: 3.09), the disc was evaluated as a slightly larger Δ. The logarithm of the constant is slightly larger. In phosphoric acid (βΐ: 3.2) or maleic acid (βΐ: 3.90), the dish becomes smaller and the evaluation system becomes 〇. If you consider this, at least the logarithm of the constant generated must be 3 or more. Further, as shown in Comparative Examples 3 and 4, even if the composition of the components (1) to (3) falls within the range of the constituent components of (1) to (3), the amount of the copper dissolving agent added is small, and when the pH is more than 2.50, the honing speed is slower than the predetermined enthalpy. The amount of disc is also increased. As shown in Comparative Example 6, when the copper rust inhibitor was not added, the honing speed was increased, but the amount of the disk was also increased. As shown in Examples 13 and 14, the constituents of (1) to (3) fall, and the pH is 2.0 or more, and the concentration of the water-soluble polymer is also higher than the concentration of the rust preventive agent, and the honing speed is even Satisfied, the amount of disc is also slightly larger. If such a relationship is shown. As in Fig. 4, high flatness can be obtained in a certain ratio or more. -31- (31) (31) 1332017 The above description is based on the examples, but the invention is not limited thereto, and may be within the scope of the spirit of the invention and the scope of the appended patent application. The revision is familiar to those skilled in the art. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a step of removing excess copper layer on a wiring trench formed on a germanium substrate by CMP, wherein (a) indicates CMP, (b) indicates CMP, and (c) indicates CMP. Figure 2 is a conceptual diagram of the exchange current density measuring device under honing load. Fig. 3 is a graph showing the load dependence of the dissolution rate of copper in various CMP honing liquids. Fig. 4 is a graph showing the relationship between the concentration of the copper rust inhibitor and the concentration of the water-soluble polymer and the flatness. [Main component symbol description] 1 : Interlayer insulating film 2 : Electroplated copper 3 : Depression 4 : Honing pad 5 : Honing fluid I 0 : Motor II : Rotation control system 1 2 : Electrochemical measurement system -35- (32) (32) 1332017 1 3 : Copper electrode 14 : Scale 1 5 : Reference electrode 16 : Connection mechanism 1 7 : Seat 1 9 : Rotating electrode 20 : Rotary axis

-36 --36 -

Claims (1)

13320171332017 十、申請專利範圍 第95 1 48 5 66號專利申請案 中文申請專利範圍修正本 民國99年7月30日修正 1 ·—種CMP硏磨液，係硏磨之際，與氧化劑混合所 使用’其特徵在於含有銅防鏽劑 '水溶性高分子、可與銅 形成錯合物之pH調整劑及水，其中 該水溶性高分子係選自具有羧基之聚合物、具有颯基之聚 合物及含有氮之聚合物之至少一種； 該具有羧基之高分子係選自聚丙烯酸、聚丙烯酸鹽、丙烯 酸與丙烯酸之酯共聚物及丙烯酸與丙烯醯胺之共聚物之至 少一種；具有颯基之水溶性高分子係選自具有颯基之胺化 合物聚合物及具有颯基之胺化合物聚合物的鹽之至少一種 ;含有氮之水溶性高分子係選自聚乙烯基吡咯烷酮、聚乙 撐基亞胺及聚丙烯醯胺之至少一種； 該銅防鏽劑爲含有氮之不飽和雜環式化合物，且該銅防鏽 劑之濃度（重量％)高於水溶性高分子濃度（重量％ ); 該含有氮之不飽和雜環式化合物爲喹啉、苯並三唑、苯並 咪唑、吲哚、異吲哚及喹哪啶酸之至少一種； 而該硏磨液實質上不含磨触劑。 2. 如申請專利範圍第1項之CMP硏磨液，其中不含 磨鈾劑。 3. 如申請專利範圍第1項之CMP硏磨液，其中pH 1332017 爲2.5以下。 4. 如申請專利範圍第1項之CMP硏磨液，其中該防 鏽劑、水溶性高分子及氧化劑之含量，於該CMP硏磨液 每一升中，爲0·1〜5重量％、0.05〜5重量％、及0.01〜5M ，該pH調整劑之量係爲使該CMP硏磨液之pH調整至 1 .5〜2.5所需之量。 5. 如申請專利範圍第1項之CMP硏磨液，其中該防 鏽劑、水溶性高分子及氧化劑之含量，於該CMP硏磨液 每一升中’爲〇·3〜1重量％、0.1〜2重量°/。及0.01〜5M，該 pH調整劑之量係爲使該CMP硏磨液之pH調整至 所需之量。 6. 如申請專利範圍第1項之CMP硏磨液，其中該 pH調整劑爲有機酸、無機酸或其等之混合溶液。 7. 如申請專利範圍第6項之CMP硏磨液’其中該有 機酸或無機酸與銅之錯合物的生成常數之對數爲3以上。 -2-X. Patent Application No. 95 1 48 5 66 Patent Application Revision of Chinese Patent Application Revision of the Republic of China on July 30, 1999. 1 - CMP honing fluid, used in honing, mixed with oxidant The invention is characterized in that it comprises a copper rust inhibitor, a water-soluble polymer, a pH adjuster capable of forming a complex with copper, and a water-soluble polymer selected from the group consisting of a polymer having a carboxyl group and a polymer having a mercapto group. At least one of a polymer containing nitrogen; the polymer having a carboxyl group is selected from the group consisting of polyacrylic acid, polyacrylate, an copolymer of acrylic acid and acrylic acid, and at least one of a copolymer of acrylic acid and acrylamide; The polymer is selected from at least one of an amine compound polymer having a mercapto group and a salt of an amine compound polymer having a mercapto group; and the water-soluble polymer containing nitrogen is selected from the group consisting of polyvinylpyrrolidone and polyethyleneimine. And at least one of polyacrylamide; the copper rust inhibitor is a nitrogen-containing unsaturated heterocyclic compound, and the concentration (% by weight) of the copper rust inhibitor is higher than the water-soluble polymer concentration (weight The nitrogen-containing unsaturated heterocyclic compound is at least one of quinoline, benzotriazole, benzimidazole, indole, isoindole, and quinalic acid; and the honing liquid is substantially not Contains abrasives. 2. For example, the CMP honing fluid of Patent Application No. 1 contains no uranium granules. 3. For the CMP honing fluid according to item 1 of the patent application, the pH 1332017 is 2.5 or less. 4. The CMP honing liquid according to claim 1, wherein the rust inhibitor, the water-soluble polymer and the oxidizing agent are in an amount of from 0.1 to 5% by weight per liter of the CMP honing fluid. 0.05 to 5 wt%, and 0.01 to 5 M, the amount of the pH adjuster is the amount required to adjust the pH of the CMP honing fluid to 1.5 to 2.5. 5. The CMP honing fluid according to claim 1, wherein the content of the rust inhibitor, the water-soluble polymer and the oxidizing agent is 〇·3 to 1% by weight in each liter of the CMP honing fluid. 0.1 to 2 weight ° /. And 0.01 to 5 M, the amount of the pH adjusting agent is adjusted to adjust the pH of the CMP honing liquid to a desired amount. 6. The CMP honing fluid according to claim 1, wherein the pH adjusting agent is a mixed solution of an organic acid, an inorganic acid or the like. 7. The logarithm of the formation constant of the CMP honing solution of the sixth aspect of the patent application, wherein the organic acid or inorganic acid and copper complex is 3 or more. -2-
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