200405453 玖、發明說明： I明所屬之技術領域 本發明係有關於適用於半導體裝置之配線形成製程的 硏磨液及使用該硏磨液之硏磨方法。 先前技術 近年來，隨著半導體積體電路（LSI)之高集積化、高性 能化而開發新的微細加工技術。化學機械硏磨（以下稱爲 CMP)法也爲其中之一種，其係爲在製造LSI之製程，特 別在多層配線形成製程之層間絕緣層的平坦化、金屬插塞 (plug)之形成、與埋入配線之形成等頻繁的利用之技術。 此種技術係例如開示於美國專利4,944,836號發明說明 書。 近年來，爲使LSI成爲高性能化，對於配線材料係嘗 試使用銅合金。但，對於銅合金之微細加工係很困難使用 習知之鋁合金配線的形成所頻繁採用之乾溶蝕（dry etching) 法。於是，主要採用所謂之鑲嵌法（damascene)，係在預先 形成溝之絕緣層上，以堆積銅合金薄膜加以埋入，其次以 CMP去除溝以外之銅合金薄層加以形成埋入配線。此項技 術係開示於例如日本專利特開平2-278822號公報。 金屬之CMP的一般方法係在圓形之硏磨台（platen)上 貼附硏磨墊（pad)，使硏磨墊表面以金屬用之硏磨液加以浸 濕，將基板之形成金屬層的面向硏磨墊按壓，從其背面以 加所定之壓力（硏磨壓力或硏磨載重）的狀態使硏磨台旋 轉，藉由硏磨液與金屬層之凸部的機械性摩擦使凸部之金 11849pif.doc/008 5 200405453 屬層加以去除。 CMP所用之硏磨液一般係由氧化劑及硏磨粒所構成， 按照需要可更再添加氧化金屬溶解劑、金屬防蝕劑等。首 先，由氧化使金屬層表面加以氧化，使其氧化層以固體硏 磨粒加以削除爲其基本機構(mechanism)。凹部之金屬表面 的氧化層係不大會接觸於硏磨墊，由於固體硏磨粒之削除 效果未能到達此處之關係，因此藉由CMP之進行，同時 去除凸部之金屬層，以使基板表面平坦化。此項詳細說明 係開示於電子化學學會雜誌（Journal of Electromechanical Society)之第138卷11號（1991年出版）的3460〜3464頁。 提高CMP之硏磨速度的方法係以使硏磨液之pH設定 成爲低値，在此添加氧化金屬溶解劑是有效的。其可解釋 爲因爲由固體硏磨粒所削除之金屬氧化物的粒子會溶解於 硏磨液，所以會增進固體硏磨粒之削除效果。但，凹部之 金屬層表面的氧化層也會被溶解（溶蝕）以使金屬層表面露 出時，然後再由氧化劑使金屬層表面氧化。如此重複進行 凹部之金屬層的溶蝕，而恐怕就會影響平坦化的效果（碟 狀凹陷）。爲了維持硏磨速度及平坦化特性，而希望使用 不會進行溶蝕之高pH領域的硏磨液，藉由添加劑使金屬 表面加以改質，以得到硏磨速度及平坦化特性。 藉由此種pH之控制與添加添加劑，可以得到在使CMP 之硏磨速度提昇之同時，也可減低因CMP所造成之金屬 表面的損傷（damage)的效果。 另一方面’在配線材料之銅或銅合金等的下層，作爲 11849pif.doc/008 6 200405453 防止銅之擴散至層間絕緣層中的阻障（barrier)層是由多旦 (tantalum、Ta)、氮化鉬（tantalum nitride)、鉬合金或宜他 钽化合物、鎢（tungsten，W)、氮化鎢（tungsten nitride)、鶴 合金或其他鎢化合物等的導體層所形成。因此，在銅I或銅I 合金之埋入配線部分以外，係有必要以CMP去除露出白勺 阻障層。 但，此等之阻障導體層，由於其硬度係比銅或銅合金 高，因此配合銅或銅合金用之硏磨材料並無法取得充分的 CMP速度。而且，在利用CMP去除阻障導體層之期間， 銅或銅合金等會被溶蝕，進而在表面產生腐蝕或碟狀凹 陷，於是就會產生配線厚度低降的問題。 發明內容 因此本發明係提供一種硏磨液，可一面保持低的溶鈾 速度，一面能使硏磨速度充分提昇，以抑制金屬表面之腐 蝕與碟狀凹陷的發生，可以形成可靠性高的金屬層之埋入 圖案。又，本發明提供一種硏磨方法，係可形成此種金屬 層之埋入圖案，具有良好的生產性，作業性、良率。 本發明之（1)係關於一種包含氧化劑、水、pH調整劑、 及促進化學硏磨之環狀有機化合物的硏磨液，其特徵在 於，此硏磨液之pH爲5〜10，又上述環狀有機化合物係含 具有咪唑骨架之化合物。 又本發明之（2)係關於上述（1)所述之硏磨液，上述環狀 有機化合物係選自具有咪唑骨架之化合物、具有吡唑 (phrazole)之化合物，具有噻哩(thizaole)骨架之化合物及具 11849pif.doc/008 7 200405453 有三哩（triazole)骨架之化合物所組之族群之至少一種化合 物。 本發明之（3)係關於在上述（1)或（2)所述之硏磨液，上 述具有咪1^骨架之化合物係選自下述一般式⑴200405453 发明 Description of the invention: Technical field to which the present invention belongs The present invention relates to a honing liquid suitable for a semiconductor device wiring forming process and a honing method using the same. Prior art In recent years, new microfabrication technologies have been developed as semiconductor integrated circuits (LSIs) have become more integrated and more powerful. The chemical mechanical honing (hereinafter referred to as CMP) method is also one of them, which is a process of manufacturing an LSI, especially a planarization of an interlayer insulating layer in a multilayer wiring formation process, a formation of a metal plug, and Frequently used technology such as formation of buried wiring. Such technology is disclosed, for example, in U.S. Patent No. 4,944,836. In recent years, in order to improve the performance of LSIs, copper alloys have been tried for wiring materials. However, it is difficult for micro-processing of copper alloys to use the dry etching method frequently used in the formation of conventional aluminum alloy wiring. Therefore, the so-called damascene method is mainly used to deposit a copper alloy thin film on an insulating layer in which trenches are formed in advance, and then CMP removes copper alloy thin layers other than the trenches to form buried wiring. This technology is disclosed in, for example, Japanese Patent Laid-Open No. 2-278822. The general method of metal CMP is to attach a honing pad to a circular platen, so that the surface of the honing pad is wet with a honing liquid for metal, and the substrate is formed into a metal layer. Press against the honing pad, and rotate the honing table under a predetermined pressure (honing pressure or honing load) from the back of the honing pad. The mechanical friction between the honing liquid and the convex part of the metal layer makes the convex part Gold 11849pif.doc / 008 5 200405453 was removed. The honing fluid used in CMP is generally composed of an oxidizing agent and honing particles, and a metal oxide dissolving agent, a metal anticorrosive agent, etc. may be further added as required. First, the surface of the metal layer is oxidized by oxidation, and its oxide layer is shaved off with solid 硏 abrasive grains as its basic mechanism. The oxide layer on the metal surface of the concave part is not likely to contact the honing pad. Because the removal effect of the solid honing particles cannot reach the relationship here, the CMP process is performed while the metal layer of the convex part is removed to make the substrate The surface is flat. This detailed description is published on pages 3460 to 3464 of the Journal of Electromechanical Society, Vol. 138, No. 11 (published in 1991). The method of increasing the honing speed of CMP is to set the pH of the honing liquid to a low honing rate, and it is effective to add a metal oxide dissolving agent here. It can be explained that since the particles of metal oxides removed by the solid honing particles are dissolved in the honing liquid, the removal effect of the solid honing particles is enhanced. However, when the oxide layer on the surface of the metal layer in the recess is also dissolved (dissolved) to expose the surface of the metal layer, the surface of the metal layer is oxidized by the oxidizing agent. Repeating the dissolution of the metal layer of the recessed portion in this manner may affect the effect of planarization (disc-shaped depression). In order to maintain the honing speed and planarization characteristics, it is desirable to use a honing fluid in a high pH range that does not dissolve, and modify the metal surface with additives to obtain the honing speed and planarization characteristics. With such pH control and addition of additives, it is possible to increase the honing speed of CMP while reducing the damage on the metal surface caused by CMP. On the other hand, in the lower layer of copper or copper alloy, such as wiring materials, the barrier layer that prevents copper from diffusing into the interlayer insulation layer is 11849pif.doc / 008 6 200405453. Tantalum, Ta, It is formed of a conductor layer such as molybdenum nitride, molybdenum alloy, or other tantalum compound, tungsten (tungsten, W), tungsten nitride, crane alloy, or other tungsten compound. Therefore, it is necessary to remove the exposed barrier layer by CMP in addition to the buried wiring portion of copper I or copper I alloy. However, since these barrier conductor layers have higher hardness than copper or copper alloys, it is not possible to obtain sufficient CMP speeds by using a honing material for copper or copper alloys. In addition, during the removal of the barrier conductor layer by CMP, copper or copper alloys will be eroded, and corrosion or dish-like depressions will occur on the surface, which will cause a problem of a decrease in the thickness of the wiring. SUMMARY OF THE INVENTION Accordingly, the present invention is to provide a honing fluid which can maintain a low uranium dissolution rate and at the same time can fully improve the honing rate to suppress the corrosion of metal surfaces and the occurrence of dish-like depressions, and can form highly reliable metals Embedded pattern of layers. In addition, the present invention provides a honing method, which can form an embedded pattern of such a metal layer, and has good productivity, workability, and yield. (1) The present invention relates to a honing liquid containing an oxidizing agent, water, a pH adjusting agent, and a cyclic organic compound that promotes chemical honing, characterized in that the pH of the honing liquid is 5 to 10, as described above. The cyclic organic compound is a compound containing an imidazole skeleton. Also, (2) of the present invention is the honing liquid according to the above (1), wherein the cyclic organic compound is selected from a compound having an imidazole skeleton, a compound having a phrazole, and a thizaole skeleton. At least one compound of the group consisting of a compound having 11849pif.doc / 008 7 200405453 and a compound having a triazole skeleton. (3) of the present invention relates to the honing liquid as described in (1) or (2) above, and the compound having a mi 1 skeleton is selected from the following general formula:
RiRi
r2 ⑴ (式⑴中，Ri、R2及R3係各以獨立表示氫原子、胺基 (amino)、還有從q至C12之烷基(alkyl)。）所表示之化合 物及疏基苯並咪哗（mercaptobenzoimidazole)所組之族群之 至少一種。 本發明之（4)係關於在上述（1)〜(3)中任一所述之硏磨 液，上述具有咪唑骨架之化合物係選自咪唑、2-甲基咪唑 (2-methylimidazole)、2-乙基咪P-ethylimizazole)、2-異 丙基咪唑（2-isopropylimidazole)、2-丙基咪唑（2-propylimizazole)、2-異丁 基咪哩（2_isobutylimidazole)、2-丁 基咪唑（2-butylimidazole) 、 4-甲基咪唑（4- methylimidazole)、4-乙基咪 _(4-ethylimidazole)、2，4-二 甲基咪 Π 坐（2，4-dimethylimidazole)、2-乙基-4-甲基咪哗（2-ethyl-4-methylimidazole)、2-胺基咪口坐（2-aminoimidazole) 8 11849pif.doc/008 200405453 及疏基苯並咪唑（mercapto-benzoimidazole)所組之族群之至 少一種。 又本發明之（5)係關於上述（2)所述之硏磨液，具有批_ (pyrazole)骨架之化合物係爲3，5-二甲基D比哗（3，5-dimethylpyrazole)、3-甲基-5- D比口坐啉酮（3-methyl_5- pyrazolone) 、 3-胺基-5-甲基 D比口坐（3-amino-5- methylpyrazole)、3-胺基-5-經基 〇比 口坐（3-amino-5-hydroxypyrazole)等 ° 又本發明之（6)係關於上述（2)所述之硏磨液，具有噻_ 骨架化合物係爲2-胺基噻Π坐（2-aminothiazole)、4，5-二甲 基噻唑（4，5-dimethylthiazole)、2-胺基-2-噻唑啉（2-amino-2-thiazoline)、2，4·二甲基噻哩（2，4-dimethylthiazole)、2-胺基-4-甲基噻哩（2-amino-4-methylthiazole)等。 又本發明之（7)係關於上述（1)所述之硏磨液，具有三唑 骨架之化合物係爲1，2, 4-三唑（1，2, 4-triazole)、3-胺基-1，2, 4-三Π坐（3-amino-l，2，4-triazole)、4-胺基-1，2，4-二哩（4-amino-1，2，4-triazole))、1，2，4-三哩並[1，5-a]喃 D定（1，2, 4-triazolo[l，5-a] pyrimidine)等。 又本發明之（8)係關於上述（1)〜(7)中之任一所述之硏磨 液係更再包含水溶性聚合物(polymer)。 又本發明之（9)係關於上述（8)所述之硏磨液，其水溶性 聚合物係選自多糖類，多聚羥酸(poly carboxylic acid)、多 聚羥酸酯、多聚羥酸塩、聚丙烯酸胺(polyacrylamide)及乙 烯基系聚合物(vinyl polymer)等所組的族群之至少一種。 9 11849pif.doc/008 200405453 又本發明之（10)係關於上述（1)〜(9)之任一項所述之硏 磨液’其氧化劑係選自過氧化氣（hydrogen peroxide)、硝 酸（nitric acid)、局确酸鉀（patassium periodate)、次氯酸 (hypochlorous acid)、過硫酸塩（persulfate)及臭氧（ozone)所 所組之族群之至少一種。 又本發明之（11)係關於上述（1)〜(10)中之任一項所述之 硏磨液，其pH調整劑係選自有機酸、有機酸之酯、有機 酸之銨塩及硫酸等所組之族群之至少一種。 又本發明之（12)係關於上述（1)〜(11)中之任一項所述之 硏磨液，更再包含硏磨粒。 又本發明之（13)係關於上述（1)〜(12)中之任一項所述之 硏磨液，被硏磨物係爲金屬層，該金屬層係選自銅、銅合 金、銅之氧化物、銅合金之氧化物、鉅及其化合物、鈦 (titan，Ti)及其化合物、鎢及其化合物等所組之族群之至少 —'種。 又本發明之（14)係關於一種硏磨方法，係使上述（1)〜(13) 任一項硏磨液一面供給於硏磨台之硏磨布上，一面使基底 之被硏磨面在按壓於硏磨布上之狀態，利用硏磨布與基體 的相對移動，以硏磨被硏磨面。 又本發明之（15)係關於一種硏磨方法，係使上述（1)〜 中之任一項所述之硏磨液一面供給於硏磨台之硏磨布上’ 一面對由兩種以上的金屬層所組成堆疊層，進行連續研1 磨。 又本發明之（16)係關於上述（15)所述之硏磨方法’對金 11849pif.doc/008 10 200405453 屬層之堆疊層的組合，先硏磨之層係選自從銅、銅合金、 銅之氧化物所組之族群之至少一種，上述層之次一層係選 自鉅及其化合物、鈦及其化合物、鎢及其化合物所組之族 群之至少一種。 又本發明之（17)係關於一種硏磨方法係包含第一硏磨 製程與第二硏磨製程。第一硏磨製程包括對具有凹凸表面 的層間絕緣層、沿著層間絕緣層上覆蓋之阻障導體層、及 在已覆蓋有阻障導體層之層間絕緣層的凹陷處塡入金屬層 之基板，進行硏磨直到位於凸部的阻障導體層裸露出來。 此外’第二硏磨製程包括至少對阻障導體層與凹陷處的金 屬層進行硏磨，並使得凸部的層間絕緣層裸露出來。在第 一硏磨製程及第二硏磨製程之至少一方製程，使用上述 (1)〜(13)中的任一項所述之硏磨液進行硏磨。 爲讓本發明之上述原理和其他目的、特徵和優點能更 明福易懂，下文特舉一較佳實施例，並配合所附圖式，作 詳細說明如下： 以下，加以詳細說明本發明。 本發明之硏磨液，其主要構成成分係包含氧化劑、水、 ΡΗ調整劑、及促進化學硏磨的環狀有機化合物。 在本發明之硏磨液的pH，從CMP之硏磨速度要大， 以有效果的抑制溶蝕速度之觀點，必需爲5〜10。但是，促 進化學硏磨之環狀有機化合物在包含後述之具有咪唑骨架 的化合物之場合除外，此種場合係並非必需爲5〜10。硏磨 11849pif.doc/〇〇8 11 200405453 液之pH係特別以在6〜9之範圍爲宜。pH低於5時金屬之 溶蝕量有增大之傾向，pH超過10時，硏磨速度有極端減 少之傾向。pH係可由酸之添加量加以調整。又也可藉由 添加氨（ammonia)、氫氧化鈉（sodium hydroxide)、氬氧化 四甲基鏡（tetramethyl ammonium hydroxide TMAH)等之鹼 性成分加以調整。 在本發明之促進化學硏磨的環狀有機化合物（以下，也 稱環狀有機化合物）仍可舉具有咪唑骨架之化合物、具有 吡唑骨架之化合物、具有噻唑骨架之化合物、具有三唑骨 架之化合物，由上述化合物所組之族群以一種單獨、或以 二種以上混合加以使用。環狀有機化合物係以含具有咪唑 骨架之化合物爲較好，更好係具有咪唑骨架之化合物。 環狀有機物係至少在所使用之pH領域內，具體而言 係在上述pH5〜10之硏磨液中，以具有促進被硏磨面之化 學作用爲宜。尙且如上所述，在環狀有機化合包含具有咪 唑骨架之化合物的場合，硏磨液pH係並非特別加以限定。 環狀有機化合物係以鹼性之環狀有機化合物爲宜。 對於具有咪唑骨架之化合物係無特別的限制，舉例來 說可以是上述一般式（I)所表示之化合物及锍基苯並咪唑 等，並可由此等化合物中選擇之一種以上加以使用。尙且， 式⑴中，Ri、R2及R3係以各獨立表示氫原子、胺基、還 有從6至C12之烷基。具體的係可例示咪唑、2-甲基咪唑、 2-乙基咪唑、2-異丙基咪唑、2-丙基咪唑、2-異丁基咪唑、 2_丁基咪唑、4-甲基咪唑、4-乙基咪唑、2, ‘二甲基咪唑、 11849pif.doc/008 12 200405453 2-乙基-4-甲基咪唑、2-胺基咪哩及锍基苯並咪唑等。此等 化合物係可以一種單獨，或組合兩種以上加以使用。 對於具有吡唑骨架之化合物係可例示3，5-二甲基吡 口坐、3-甲基-5-D比哩琳嗣、3-胺基-5-甲基D比哩、3-胺基-5-經 基D比哩等。此等化合物係可以單獨或組合兩種以上加以使 用。 對於具有噻唑骨架之化合物係可例示2-胺基噻唑、4, 5-二甲基噻唑、2-胺基-2-噻唑啉、2, 4-二甲基噻唑、2-胺基-4-甲基噻唑等。此等化合物係可以單獨或組合兩種以上加 以使用。 對於具有三唑骨架之化合物係可例示1，2, 4-三唑、3-胺基-1，2,4-三唑、4-胺基-1，2, 4-三唑、1，2, 4-三唑並[1，5-a] 嘧啶等。此等化合物係可以單獨或以組合兩種以上加以使 用。 在本發明之促進化學硏磨的環狀有機化合物之摻合量 係對硏磨液之總量以0.001〜10重量％爲較好，以0.01〜8 重量％爲更好，以〇·〇2〜5重量％爲特好。此摻合量在0.001 重量％未滿時，有硏磨速度低降之傾向，超過1〇重量％時 金屬之溶蝕量有增大的傾向。 在本發明之氧化劑，例如是過氧化氫（η2〇2)、硝酸、 高碘酸鉀、次氯酸、過硫酸塩及臭氧水等，其中以過氧化 氫爲特好。此等化合物係以一種單獨，或兩種以上混合加 以使用。在硏磨之適用對象的基體爲含積體電路用元件之 矽基板的場合，由於鹼金屬、鹼土類金屬、鹵化物等之污 11849pif.doc/008 13 200405453 染係爲不所期望的關係，因此以不含不捍發成分之氧化劑 爲宜。但，臭氧水係因組成會隨時間變化激烈的關係，因 此以過氧化氫爲最適合。但，在基體爲不含半導體元件之 玻璃基板等的埸合，使用含不揮發成分之氧化劑也沒有關 係。 氧化劑之摻合量係對硏磨液之總量以0.1〜50重量％爲 較好，以0.2〜25重量％爲更好，在0.3〜15重量％爲特好。 摻合量在未滿〇.1重量％時，金屬之氧化不充分CMP速度 有降低的傾向，在超過50重量％時，在被硏磨面有發生粗 糙之傾向。 在本發明之pH調整劑，只要爲水溶性的就可以，而 沒有特別的限制，舉例來說，包括甲酸(methanoic acid)、 乙酸（acetic acid)、丙酸（propionic acid)、丁酸（butanoic acid)、戊酸（pentoic acid)、2-甲基丁酸（2-ethyl-butanoic acid)，n-己酸（n-hexanoicacid)3，3-二甲基丁酸（3，3-dimethyl-butanoic acid)、2-乙基丁酸（2-ethyl-butanoic acid)、4-甲基戊酸（4-methyl pentanoic acid)、n-庚酸（n-heptanoic acid)、2-甲基己酸（2-methyl-hexanoic acid)、n-辛酸（n-octanoic acid)、2-乙基己酸（2-ethyl-heaxnoic acid)、 安息香酸（benzoic acid)、乙醇酸（glycolic acid)、柳酸 (salicylic acid)、甘油酸（glyceric acid)、草酸（oxalic acid)、 丙二酸（malonic acid)、琥珀酸（succinic acid)、戊二酸 (glutaric acid)、肥酸（adipic acid)、庚二酸(pimelic acid)、 馬來酸（maleic acid)、苯二甲酸（phtalic acid)、蘋果酸（malic 14 11849pif.doc/008 200405453 acid)、酒石酸（tartaric acid)、檸檬酸（lemon acid)等之有機 酸、此等有機酸之酯類及此等有機酸之銨塩等。又可舉塩 酸、硫酸、硝酸等之無機酸，此等無機酸之銨塩類、例如 過硫酸銨（ammoniun persulfate)、硝酸銨（ammonium nitrate)、氯化錢（ammonium chloride)等、鉻酸（chromic acid) 等。 此等氧化劑之中，特別對金屬層加以CMP硏磨具有效 果者，係以甲酸、丙二酸、蘋果酸、酒石酸、檸檬酸、琥 珀酸、戊二酸、肥酸等之有機酸、有機酸之酯、有機酸之 銨塩及硫酸爲適宜。此等PH調整劑係可以單獨一種’或 混合兩種以上加以使用。 在本發明之pH調整劑的摻合量’對硏磨液之總量’ 係以0.001〜10重量％爲較好，以〇.01〜8重量％爲更好，以 0.02〜5重量％爲特好。此摻合量在〇·〇〇1重量％未滿時硏 磨速度有極端減少之傾向，超過10重量％時’硏磨速度在 飽和之傾向。 本發明之硏磨液係可含水溶性聚合物。對於水溶性聚 合物，並無特別限制，舉例來說，包括藻酸(alginic acid)、 果膠酸（pectic acid)、羧甲基纖維素（carboxymdhy1 cellulose)、明膠（gelatin)、卡多醋（curdlan)及支鍵殿粉 (pullulan)等之多糖類；聚天冬氨酸（P〇ly asParaginic acid)、 聚谷氨酸（poly glutamic acid)、聚賴热酸(poly lysine)、聚 蘋果酸（poly malic acid)、聚甲基丙烯酸(P〇ly methacrylic aicd)、聚甲基丙烯酸銨塩（poly ammonium methacrylate)、 11849pif.doc/008 15 200405453 聚甲基丙烯酸鈉塩（Poly natrium methacrylate)、聚酰胺基 酸(poly amido acid)、聚馬來酸(P〇ly maleic acid)、聚衣康 酸（poly itaconic acid)、聚富馬酸（P〇ly fumaric acid)、聚（p- 苯乙烯羧酸）(p〇iy(p-styrene carboxylic acid)、聚丙烯酸 (poly acrylic acid)、聚丙烯酰胺(P〇iy acrylamide)、聚胺基 丙烯酰胺（poly amino acrylamide)、聚丙烯酸銨塩（poly ammonium acrylate)、聚丙細酸納塩（poly natrium acrylate)、聚酰胺基酸(P〇ly amido acid)、聚酰胺基酸銨塩 (poly ammonium amidate)、及聚乙酸酸（poly glyoxialic acid) 等之聚羧酸、聚羧酸酯、聚羧酸塩及聚羧酸衍生物；聚乙 烯醇（poly vinyl alcohol)、聚乙烯 D比略院酮（p〇ly vinyl pyrrolidone)及聚丙烯醒（poly acrolein)等之乙烯基系聚合 物；此上述化合物之酯類、銨塩等。但’在所適用之基體 爲半導體電路用砂基板等的場合，由於鹼金屬、鹼土類金 屬、鹵化物等之污染係爲不所期望的關係，因此係以酸或 其銨塩爲宜。在基體爲玻璃基板等之場合並不在其限。其 中，係以選自多糖類、聚羧酸、聚羧酸酯、聚羥酸塩、聚 丙烯酰胺及乙烯基系聚合物所組的族群之至少一種爲宜， 具體係以果膠酸、明膠、聚蘋果酸、聚甲基丙烯酸、聚丙 烯酸、聚丙烯酰胺、聚乙烯醇及聚乙烯吡咯烷嗣、此等之 酯類及此等之銨塩爲宜。 摻合水溶性聚合物之場合的摻合量係對硏磨液總量以 10%重量以下爲較好，以5重量％以下爲更好，以1重量 %以下爲特好。此摻合量超過10重量％時硏磨速度有降低 11849pif.doc/008 16 200405453 之傾向。 水溶性聚合物之重量平均分子量係以在500以上爲較 好，以1，50〇以上爲更好，以5,000以上爲特好。重量平 均分子量之上限雖係無特別加以規定’從溶解性之觀點係 以500萬以下爲宜。重量平均分子量未滿500時有無法顯 現高硏磨速度之傾向。在本發明’係以使用重量平均分子 量爲500以上之至少一種水溶性聚合物爲宜。 本發明之硏磨液係可添加硏磨粒。對於硏磨粒係可例 如是氧化砂（silica)、氧化銘（alumina)、氧化锆（zirconia)、 二氧化鈽（ceria)、二氧化鈦（titania)、氧化鍺（germania)、 碳化矽（silicon carbide)等之無機物硏磨粒、聚苯乙烯(poly styrene)、聚丙烯基(P〇ly acryl)、乙烯基氯(vinyl chloride) 等之有機硏磨粒。在硏磨液中之分散安定性良好，由CMP 所發生之硏磨傷（scratch)的發生數少者，係以平均粒徑爲 100nm以下之膠態氧化矽，膠態氧化鋁爲宜。 添加硏磨粒之場合的摻合量係對硏磨液全重量以10重 量％以下爲較好，以5重量％以下爲更好。此摻合量超過1〇 重量％時由CMP之硏磨速度係變成飽和，即使加到此摻合 量以上時也不會發現硏磨速度增加。 在本發明之硏磨液，除上述材料以外，係也可含有陰 離子（anion)系、陽離子（cation)系、非離子丨!^!^!!)系之界 面活性劑（interfacial active agent)、維多利亞純藍（victoria pure blue)等之染料、駄菁綠(phthalocyanine green)等之顔 料等之著色劑。尙且，水之摻合量係可爲剩餘部分，只要 11849pif.doc/008 17 200405453 含有即可並無特別限制。 適用本發明之硏磨液進行硏磨者係例如是金屬胃胃方々 該金屬層係包括銅、銅合金、銅之氧化物、銅合金之氧化 物（以下，稱爲銅及其化合物。）、鉅、氮化迫、Μ合金、 其他之鉅化合物（以下，稱爲鉅及其化合物。 鈦、鈦合金、其他之鈦化合物(以下，稱爲鈦及其;化合^勿）、 鎢、氮化鎢、鎢合金、其他鎢化合物（以下，稱胃 化合物。）等。可由公知之濺鍍法、電鍍法加以成M。比匕 等金屬層係以一種或組合兩種上加以硏磨。 金屬層係也可以—^種以上之上述金屬加以組合的纟隹胃 層。適用本發明之堆疊層，在所硏磨之金屬層的堆疊層中， 先行硏磨之第一層係選自上述銅及其化合物選擇，該層之 其次硏磨之第二層係從上述钽及其化合物、鈦及其化合 物、鎢及其化合物選擇之加以組合的堆疊層。 藉由使用本發明之硏磨液，可以連續硏磨上述之兩種 以上的金屬層之堆疊層。 本發明之第一硏磨方法，係一面使上述本發明之硏磨 液供給於硏磨台上之硏磨布上，一面使基體之被硏磨面按 壓於硏磨布之狀態’將硏磨布與基體以相對移動加以硏磨 被硏磨面爲特徵的硏磨方法。 對於硏磨裝置’係例如可使用具有硏磨台與保持架 (holder)之一般硏磨裝置。其中，硏磨台，係可貼附硏磨 墊（硏磨布），接連於迴轉數可變更之馬達。保持架，係可 保持被硏磨之基體。對於硏磨布，係可使用一般的無紡織 11849pif.doc/008 18 200405453 物（unwover fabric)、泡沬聚胺基甲酸酯（foamed polyurethane)、多孔質氟樹脂（fluororesin)等，在此並無特 別限制。硏磨條件雖無限制，硏磨台之迴轉速度係以不使 基板飛出之2000rpm以下的低迴轉爲宜。具有被硏磨面之 基體的按壓於硏磨布之壓力（硏磨壓力），係以1〜lOOkPa爲 宜，爲滿足CMP速度之被硏磨面內均一性及圖案之平坦 性，係以5〜50kPa爲更好。在硏磨期間，係使硏磨液以泵 浦等連續供給於硏磨布。此供給量雖無限制，係以使硏磨 布之表面經常由硏磨液覆蓋爲宜。硏磨終了後之基體，係 在流水中加以良好淸洗後，用旋轉乾燥等使附著於基體上 之水滴掉落，再行乾燥爲宜。 硏磨布與基體的相對移動方法，除了使硏磨台旋轉以 外，也可使保持架旋轉或搖動。又，使硏磨台以行星旋轉 之方式，例如使帶狀之硏磨墊在長度方向之一方向以直線 狀移動的硏磨方法等。尙且，保持架係以固定、旋轉、搖 動之任一狀態均可。此等硏磨方法，只要可使硏磨墊與基 體可以相對移動即可’而可由被硏磨面或硏磨裝置加以適 宜選擇。 又，本發明之第二硏磨方法，係一面使本發明之硏磨 液供給於硏磨台之硏磨布上，一面使二種以上之金屬層的 堆暨層以連續的加以硏磨者。例如，在金屬層之疊積層的 組口，先fj硏磨之層係從上述銅及其化合物所選擇之至少 一種，與先行硏磨之層所堆疊的層即次層，係選自上述鉅 及其化合物、鈦及其合物、鎢及其化合物之至少一種。 11849pif.doc/008 19 200405453 本發明係例如在半導體裝置之配線層的形成中，可適 於金屬配線用之導電性物質層、防止上述導電性物質向層 間絕緣層擴散的阻障導體層（以上，稱爲阻障層）、及層間 絕緣層等之化學機械硏磨（CMP)。上述先行硏磨的層係相 當於導電性物質層、該層之次層係相當於阻障層。 即本發明之第三硏磨方法係包含第一硏磨製程與第二 硏磨製程。其中，第一硏磨製程係硏磨具有層間絕緣層、 阻障層及金屬層之基板的金屬層以使下述凸部的阻障層加 以露出’並且，層間絕緣層係表面由凹部及凸部所構成’ 阻障層係沿上述層間絕緣層表面加以覆蓋，金屬層係充塡 上述凹部以覆蓋阻障層。第二硏磨製程係在該第一硏磨製 程後’至少硏磨阻障層及凹部之金屬層以使凸部之層間絕 緣層加以露出。在第一硏磨製程及第二硏磨製程之至少一 方製程，使用本發明之硏磨液加以硏磨爲其特微。 以下，沿半導體裝置之配線形成，加以說明本發明之 硏磨方法的實施樣態之一例。 首先，在矽基板上加以疊積二氧化矽等之層間絕緣層。 其次，藉由光阻層形成、蝕刻等之習知手段，在層間絕緣 層表面形成所定圖案之凹部（基板露出部）做爲由凸部及凹 部所構成之層間絕緣層。在此層間絕緣層上，沿表面之凸 凹使钽等藉由蒸鑛或CVD等方式成膜而覆蓋層間絕緣層 以做爲阻障層。更且，以充塡上述凹部方式加以覆蓋阻障 層的導電性物質層（以下，稱爲金屬層），係使銅等藉由蒸 鍍、電鍍或CVD等方式形成以得到金屬層之堆疊層。層 11849pif.doc/008 20 200405453 間絕緣層、阻障層及金屬層之形成厚度係各以0·01〜2·〇β m、1〜lOOnm、0.01 〜0.25 // m 程度爲宜。 (第一硏磨製程）其次，使此半導體基板固定於硏磨裝 置，以表面之金屬層爲被硏磨面，一面供給本發明之硏磨 液一面加以硏磨。藉此，層間絕緣層凸部之阻障層露出於 基板表面，在層間絕緣層凹部殘留上述金屬層以得到所期 望的導體圖案。 (第二硏磨製程）再其次，以上述導體圖案之至少上述 露出的阻障層及凹部的金屬層作爲被硏磨面，一面供給本 發明之硏磨液一面加以硏磨。以致凸部之阻障層下的層間 絕緣層全部露出，並在凹部殘留下成爲配線層之上述金屬 層，在凸部與凹部之境界露出阻障層的斷面而得到所期望 的圖案的時候停止硏磨。尙且，在硏磨終了時爲確保更良 好的平坦性，更可以進行過硏磨（例如，在第二硏磨製程 以得到所期望之圖案的時間爲100秒之場合，在此100秒 之硏磨加上追加50秒之硏磨者稱爲過硏磨50%)而可硏磨 至含凸部之層間絕緣層之一部分的深度。 在此第一硏磨製程及第二硏磨製程之至少一方，藉由 使用本發明之硏磨液加以硏磨，一面可保持低溶蝕速度， 一面能充分提昇硏磨速度，可抑制被硏磨面之腐蝕與碟狀 凹陷之發生。在第一硏磨製程及第二硏磨製程，也可如上 述以連續使用本發明之硏磨液加以硏磨。此種場合，在第 一硏磨製程與第二硏磨製程之間，雖並不需要特別進行被 硏磨面之淸洗製程或乾燥製程等，在更換硏磨台或硏磨 11849pif.doc/008 21 200405453 布，或變更加工載重時等也可加以停止。$第〜硏磨製程 及第二硏磨製程所使用之本發明的硏磨液雖然可使用同: 組成或相異組成者，如爲同一組成時，由於從第〜硏磨製 程至第二硏磨製程可以連續不停止進行硏磨，因此有良好 的生產性。 在以此種方法所形成之金屬配線上’再形成層間絕緣 層、阻障層及第二層的配線金屬層，並對其加以硏磨而在 所有半導體基板全面形成作爲平滑面的第二層金屬配線。 此種製程藉由重複設定數次時，可製造具有所期望配線層 數的半導體裝置。 π (實施例） 以下，更藉由實施例以說明本發明。本發明並非由實 施例加以限制。 (實施例1〜138及比較例1〜6 ;硏磨速度） [硏磨液製作方法] 對硏磨液總量，使第1表〜第6表所示促進化學硏磨之 環狀有機化合物以0.1重量％，平均粒徑50nm之膠態氧化 矽以〇·5重量％，30%之過氧化氫以30重量％及剩餘部分 以水加以混合後，添加琥珀酸或氨調整pH爲6、7或8加 以製作。 [硏磨條件] 銅基體：堆積厚度1500nm之銅金屬的矽基板 鎢基體：堆積厚度600nm之鎢化合物(氮化鎢）的矽基 板 11849pif.doc/008 22 200405453 硏磨台上之硏磨墊：泡沬聚胺基甲酸酯樹脂（洛德公司 製型號IC1000) 基體與硏磨台之相對速度：20m/分 硏磨壓力：30kPa [硏磨成品評價項目] 硏磨速度：使各層之硏磨前後的層厚差從電阻値加以 換算而求得之。 在第1表〜第3表係表示對基體之CMP硏磨速度的結 果，在第4表〜第6表係表示對鎢基體之CMP硏磨速度的 結果。 11849pif.doc/008 23 200405453 第1表 實施例 環狀有機化合物 pH 銅硏磨速度(nm/min) 1 咪唑 6 283 2 咪唑 7 211 3 咪唑 8 185 4 2-甲基咪唑 6 269 5 2-甲基咪唑 7 203 6 2-甲基咪唑 8 168 7 2-乙基咪唑 6 268 8 2-乙基咪唑 7 199 9 2-乙基咪唑 8 159 10 2-異丙基咪唑 6 271 11 2-異丙基咪唑 7 195 12 2-異丙基咪唑 8 160 13 2-丙基咪唑 6 254 14 2-丙基咪唑 7 185 15 2-丙基咪唑 8 151 16 2-丁基咪唑 6 234 17 2-丁基咪唑 7 171 18 2-丁基咪唑 8 136 19 4-甲基咪唑 6 267 20 4-甲基咪唑 7 201 21 4-甲基咪唑 8 169 22 2, 4-二甲基咪唑 6 274 23 2, 4-二甲基咪唑 7 189 24 2, 4-二甲基咪唑 8 157 25 2-乙基-4-甲基咪唑 6 257 26 2-乙基-4-甲基咪唑 7 171 27 2-乙基-4-甲基咪唑 8 143 28 3, 5-二甲基吡唑 6 275 29 3, 5-二甲基吡唑 7 188 30 3, 5-二甲基吡唑 8 155 24 11849pif.doc/008 200405453 第2表 實施例 環狀有機化合物 pH 銅硏磨速度（nm/min) 31 3-甲基-5-吡唑啉酮 6 265 32 3-甲基-5-吡唑啉酮 7 179 33 3-甲基-5-吡唑啉酮 8 151 34 3-胺基-5-甲基吡唑 6 193 35 3-胺基-5-甲基吡唑 7 185 36 3-胺基-5-甲基吡唑 8 162 37 3-胺基-5-羥基吡唑 6 191 38 3-胺基-5-羥基吡唑 7 181 39 3-胺基-5-羥基吡唑 8 159 40 3-胺基-5-甲基吡唑 6 190 41 3-胺基-5-甲基吡唑 7 181 42 3-胺基-5-甲基吡唑 8 158 43 2-胺基噻唑 6 281 44 2-胺基噻唑 7 205 45 2-胺基噻唑 8 183 46 4, 5-二甲基噻唑 6 193 47 4, 5-二甲基噻唑 7 178 48 4, 5-二甲基噻唑 8 159 49 2-胺基-2-噻唑啉 6 175 50 2-胺基-2-噻唑啉 7 143 51 2-胺基-2-噻唑啉 8 139 52 2, 4-二甲基噻唑 6 191 53 2, 4-二甲基噻唑 7 174 54 2, 4-二甲基噻唑 8 156 55 2-胺基-4-甲基噻唑 6 201 56 2-胺基-4-甲基噻唑 7 189 57 2-胺基-4-甲基噻唑 8 169 58 1，2, 4-三唑 6 173 59 1，2, 4-三唑 7 139 60 1，2, 4-三唑 8 121 25 11849pif.doc/008 200405453 第3表 環狀有機化合物 pH 銅硏磨速度（nm/min) 實施例61 3-胺基-1，2, 4-三唑 6 156 實施例62 3-胺基-1，2, 4-三唑 7 132 實施例63 3-胺基-1，2, 4-三唑 8 119 實施例64 4-胺基-1，2, 4-三唑 6 163 實施例65 4-胺基-1，2, 4-三唑 7 138 實施例66 4-胺基-1，2, 4-三唑 8 124 實施例67 1，2, 4-三唑並 [1，5-a]嘧啶 6 176 實施例68 1，2, 4-三唑並 [1，5-a]嘧啶 7 149 實施例69 1，2, 4-三唑並 [1，5-a]嘧啶 8 129 比較例1 Μ j\\\ 6 25 比較例2 Μ y\\\ 7 17 比較例3 Μ 8 5 26 11849pif.doc/008 200405453 第4表 實施例 環狀有機化合物 pH 氮化鎢硏磨速度（nm/min) 70 咪唑 6 236 71 咪唑 7 199 72 咪唑 8 147 73 2-甲基咪唑 6 215 74 2-甲基咪唑 7 167 75 2-甲基咪唑 8 121 76 2-乙基咪唑 6 211 77 2-乙基咪唑 7 161 78 2-乙基咪唑 8 142 79 2-異丙基咪唑 6 214 80 2-異丙基咪唑 7 165 81 2-異丙基咪唑 8 141 82 2-丙基咪唑 6 201 83 2-丙基咪唑 7 143 84 2-丙基咪唑 8 126 85 2-丁基咪唑 6 192 86 2-丁基咪唑 7 134 87 2-丁基咪唑 8 109 88 4-甲基咪唑 6 213 89 4-甲基咪唑 7 161 90 4-甲基咪唑 8 139 91 2, 4-二甲基咪唑 6 201 92 2, 4-二甲基咪唑 7 139 93 2, 4-二甲基咪唑 8 121 94 2-乙基-4-甲基咪唑 6 189 95 2-乙基-4-甲基咪唑 7 131 96 2-乙基-4-甲基咪唑 8 118 97 3, 5-二甲基吡唑 6 227 98 3, 5-二甲基吡唑 7 147 99 3, 5-二甲基吡唑 8 105 100 3-甲基-5-吡唑啉酮 6 217 11849pif.doc/008 27 200405453 第5表 實施例 環狀有機化合物 pH 氮化鎢硏磨速度（nm/min) 101 3-甲基-5-吡唑啉酮 7 127 102 3-甲基-5-吡唑啉酮 8 103 103 3-胺基-5-甲基吡唑 6 144 104 3-胺基-5-甲基吡唑 7 134 105 3-胺基-5-甲基吡唑 8 115 106 3-胺基-5-羥基吡唑 6 140 107 3-胺基-5-羥基吡唑 7 133 108 3-胺基-5-羥基吡唑 8 107 109 3-胺基-5-甲基吡唑 6 141 110 3-胺基-5-甲基吡唑 7 133 111 3-胺基-5-甲基吡唑 8 110 112 2-胺基噻唑 6 233 113 2-胺基噻唑 7 154 114 2-胺基噻唑 8 133 115 4, 5-二甲基噻唑 6 143 116 4, 5-二甲基噻唑 7 127 117 4, 5-二甲基噻唑 8 113 118 2-胺基-2-噻唑啉 6 125 119 2-胺基-2-噻唑啉 7 103 120 2-胺基-2-噻唑啉 8 93 121 2, 4-二甲基噻唑 6 143 122 2, 4-二甲基噻唑 7 126 123 2, 4-二甲基噻唑 8 104 124 2-胺基-4-甲基噻唑 6 150 125 2-胺基-4-甲基噻唑 7 136 126 2-胺基-4-甲基噻唑 8 117 127 1，2, 4-三唑 6 123 128 1，2, 4-三唑 7 98 129 1，2, 4-三唑 8 76 130 3-胺基-1，2, 4-三唑 6 106 28 11849pif.doc/008 200405453 第6表 環狀有機化合物 pH 氮化鎢硏磨速度（nm/min) 窗_31 3-胺基-1，2, 4-三唑 7 89 勣_32 3-胺基-1，2, 4-三唑 8 83 勣_ 133 4-胺基-1，2, 4-三唑 6 113 勣_34 4-胺基-1，2, 4-三唑 7 91 135 4-胺基-1，2, 4-三唑 8 78 勣娜36 1，2, 4-三唑並 [1，5-a]嘧啶 6 126 勣_ 137 1，2, 4-三唑並 [1，5-a]嘧啶 7 99 實施例138 1，2, 4-三唑並 [1，5-a]嘧啶 8 79 比較例4 Μ j \ \\ 6 30 比較例5 Μ j \ \\ 7 21 比較例6 iffi j\\\ 8 13 實施例1〜69之銅的硏磨速度係均在100nm/min以上， 與比較例1〜3比較時有所改善。 氮化鎢之硏磨速度，在實施例70〜117、121〜126係均 在100nm/min以上，在實施例118〜120、127〜138係均在 75nm/min以上，與30nm/min以下之比較例4〜6比較時有 所改善。 (實施例139 :碟狀凹陷） 29 11849pif.doc/008 200405453 對硏磨液總量，使促進化學硏磨之環狀有機化合物白勺 咪唑以0.1重量％、平均粒徑50nm之膠態氧化矽以〇·5重 量％、水溶性聚合物以0.2重量％，30%過氧化氫以30重 量％，剩餘部分以水加以混合後，添加琥珀酸調整pH爲6 加以製作。 製備在二氧化矽中形成有深度0.5〜100//m之溝、以習 知之方法形成有厚度50nm做爲阻障層的氮化鎢層、在# 上層形成有之銅層的矽基板。在此基板表面之全 面以上述硏磨液進行硏磨至二氧化矽之凸部露出。硏磨曰寺 間係2分，得到約500nm/min以上之硏磨速度。其次，使 用觸針式段差儀求出從配線金屬層部寬l〇〇#m、絕緣餍 部寬100//m以交替排列之條紋(stripe)狀圖案部的表面形 狀對絕緣層部之配線金屬層部的膜減量（碟狀凹陷量）胃 75nm，係爲可充分實用之値。 (實施例140) 阻障層以厚度50nm之氮化鉅層替代氮化鎢層以外’ 係與實施例139以同樣方法使用矽基板，在基板表面之全 面，以上述實施例139所製作之硏磨液進行硏磨至二氧化 之凸部露出。硏磨時間係2分，得到約500nm/min以上之 硏磨速度。 其次，與實施例139同樣求對絕緣層之配線金屬部的 層減量爲65nm，係爲可充分實用之値。 本發明之硏磨液係可以充分提升硏磨速度，並抑制金 屬表面之腐蝕與碟狀凹陷的發生’而能夠形成可靠度高的 11849pif.doc/008 30 200405453 金屬層之埋入圖案。 又，本發明之方法係可以充分提升硏磨速度，並抑制 金屬表面之腐蝕與碟狀凹陷，能以良好的生產性、作業性、 良率進行可靠性高的金屬層的埋入圖案之形成。 雖然本發明已以一較佳實施例揭露如上，然其並非用 以限定本發明，任何熟習此技藝者，在不脫離本發明之精 神和範圍內，當可作些許之更動與潤飾，因此本發明之保 護範圍當視後附之申請專利範圍所界定者爲準。 gl式之簡單說明 j \\\ ffl式之標示說明: 钲 j \ w 11849pif.doc/008 31r2 ⑴ (In the formula ，, Ri, R2, and R3 each independently represent a hydrogen atom, an amino group, and an alkyl group from q to C12.) and a benzyl benzimidate At least one of the groups of mercaptobenzoimidazole. (4) The present invention relates to the honing liquid according to any one of (1) to (3), wherein the compound having an imidazole skeleton is selected from the group consisting of imidazole, 2-methylimidazole, and 2 -Ethylimidazole (P-ethylimizazole), 2-isopropylimidazole (2-isopropylimidazole), 2-propylimizazole (2-propylimizazole), 2-isobutylimidazole (2-isobutylimidazole), 2-butylimidazole (2 -butylimidazole), 4-methylimidazole, 4-ethylimidazole, 2,4-dimethylimidazole, 2-ethyl- Groups of 2-ethyl-4-methylimidazole, 2-aminoimidazole 8 11849pif.doc / 008 200405453 and mercapto-benzoimidazole At least one of them. (5) The present invention relates to the honing fluid described in (2) above, and the compound having a pyrazole skeleton is 3,5-dimethylpyrazole (3,5-dimethylpyrazole), 3 -Methyl-5-D than 3-methyl-5-pyrazolone, 3-amino-5-methylD than 3-amino-5-methylpyrazole, 3-amino-5- The 3-amino-5-hydroxypyrazole is equivalent to the amino group, and the (6) of the present invention relates to the honing liquid described in the above (2), and the compound having a thio skeleton is 2-aminothio 2-aminothiazole, 4,5-dimethylthiazole, 2-amino-2-thiazoline, 2,4 · dimethylthiazole 2,4-dimethylthiazole, 2-amino-4-methylthiazole, etc. (7) The present invention relates to the honing liquid described in (1) above, and the compound having a triazole skeleton is 1,2,4-triazole (1,2,4-triazole), 3-amino group 1,2,4-triazole (3-amino-1,2,4-triazole), 4-amino-1,2,4-triazole (4-amino-1,2,4-triazole) ), 1,2,4-triazolo [1,5-a] pyrimidine (1,2,4-triazolo [l, 5-a] pyrimidine) and the like. (8) The present invention relates to the honing liquid system according to any one of (1) to (7), further comprising a water-soluble polymer. (9) The present invention relates to the honing liquid according to the above (8), wherein the water-soluble polymer is selected from the group consisting of polysaccharides, poly carboxylic acid, polyhydroxy acid ester, and polyhydroxy acid. At least one of the group consisting of acid sulfonium, polyacrylamide, and vinyl polymer. 9 11849pif.doc / 008 200405453 and (10) of the present invention relates to the honing fluid according to any one of (1) to (9) above, and its oxidant is selected from the group consisting of hydrogen peroxide and nitric acid ( nitric acid), potassium periodate, hypochlorous acid, persulfate, and ozone. (11) The present invention relates to the honing liquid according to any one of the above (1) to (10), wherein the pH adjusting agent is selected from the group consisting of organic acids, esters of organic acids, ammonium salts of organic acids, and At least one of the groups of sulfuric acid. (12) The present invention relates to the honing fluid according to any one of the above (1) to (11), and further comprises honing grains. Also, (13) of the present invention is the honing fluid according to any one of (1) to (12), and the object to be honed is a metal layer, and the metal layer is selected from copper, copper alloy, copper At least one of the groups of oxides, copper alloy oxides, giants and their compounds, titanium (Ti) and its compounds, tungsten and its compounds. Another aspect of the present invention (14) relates to a honing method, in which the honing liquid of any one of the above (1) to (13) is supplied to a honing cloth on a honing table while the honing surface of the substrate is made In the state of being pressed on the honing cloth, the relative movement of the honing cloth and the substrate is used to honing the honing surface. Another aspect of the present invention (15) relates to a honing method in which the honing liquid described in any one of the above (1) to 1 is supplied to a honing cloth of a honing table. The stacked layers composed of the above metal layers are subjected to continuous grinding. Also, (16) of the present invention relates to the honing method described in (15) above. The combination of stacked layers of metal layers 11849pif.doc / 008 10 200405453, the first honing layer is selected from copper, copper alloy, At least one of the groups of copper oxides, and the next layer is at least one selected from the group of giants and their compounds, titanium and its compounds, and tungsten and its compounds. Another aspect (17) of the present invention relates to a honing method including a first honing process and a second honing process. The first honing process includes an interlayer insulating layer having a concave-convex surface, a barrier conductor layer covered along the interlayer insulation layer, and a substrate in which a metal layer is inserted into a recess of the interlayer insulation layer covered with the barrier conductor layer. , Honing until the barrier conductor layer at the convex portion is exposed. In addition, the second honing process includes honing at least the barrier conductor layer and the metal layer in the depression, and exposing the interlayer insulating layer of the convex portion. In at least one of the first honing process and the second honing process, the honing liquid described in any one of (1) to (13) is used for honing. In order to make the above principles and other objects, features, and advantages of the present invention more comprehensible, a preferred embodiment is described below in detail with the accompanying drawings as follows: The present invention is described in detail below. The honing fluid of the present invention is mainly composed of an oxidizing agent, water, a pH adjusting agent, and a cyclic organic compound that promotes chemical honing. The pH of the honing liquid of the present invention must be 5 to 10 from the viewpoint that the honing speed of the CMP is large, and that the corrosion rate is effectively suppressed. However, the cyclic organic compound that promotes chemical honing is excluded from the case where a compound having an imidazole skeleton described later is included, and in this case, it is not necessarily 5 to 10. Honing 11849pif.doc / 〇〇8 11 200405453 The pH of the liquid is particularly preferably in the range of 6 to 9. When the pH is lower than 5, the amount of corrosion of the metal tends to increase, and when the pH exceeds 10, the honing rate tends to decrease extremely. The pH is adjusted by the amount of acid added. It can also be adjusted by adding alkaline components such as ammonia, sodium hydroxide, and tetramethyl ammonium hydroxide TMAH. The cyclic organic compound (hereinafter, also referred to as a cyclic organic compound) that promotes chemical honing in the present invention may still be a compound having an imidazole skeleton, a compound having a pyrazole skeleton, a compound having a thiazole skeleton, or a compound having a triazole skeleton. The compound is a group consisting of the aforementioned compounds and used alone or in combination of two or more. The cyclic organic compound is preferably a compound having an imidazole skeleton, and more preferably a compound having an imidazole skeleton. The cyclic organic substance is preferably at least in the pH range used, and specifically in the above-mentioned honing liquid having a pH of 5 to 10, and preferably has a chemical action to promote the honing surface. In addition, as described above, when the cyclic organic compound contains a compound having an imidazole skeleton, the pH of the honing liquid is not particularly limited. The cyclic organic compound is preferably a basic cyclic organic compound. The compound having an imidazole skeleton is not particularly limited, and examples thereof include the compound represented by the general formula (I), fluorenylbenzimidazole, and the like, and one or more compounds selected from these compounds can be used. In addition, in formula (I), Ri, R2, and R3 each independently represent a hydrogen atom, an amine group, and an alkyl group of 6 to C12. Specific examples include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-propylimidazole, 2-isobutylimidazole, 2-butylimidazole, 4-methylimidazole , 4-ethylimidazole, 2, 'dimethylimidazole, 11849pif.doc / 008 12 200405453 2-ethyl-4-methylimidazole, 2-aminoimidazole, and fluorenylbenzimidazole. These compounds may be used alone or in combination of two or more. Examples of the compound having a pyrazole skeleton include 3,5-dimethylpyridine, 3-methyl-5-D bilimimidine, 3-amino-5-methyl Dbiline, and 3-amine. Base-5- via base D, etc. These compounds may be used alone or in combination of two or more. Examples of the compound system having a thiazole skeleton include 2-aminothiazole, 4,5-dimethylthiazole, 2-amino-2-thiazoline, 2,4-dimethylthiazole, and 2-amino-4- Methyl thiazole and the like. These compounds may be used alone or in combination of two or more. Examples of the compound system having a triazole skeleton include 1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, and 1,2 , 4-triazolo [1,5-a] pyrimidine and the like. These compounds may be used alone or in combination of two or more. The blending amount of the cyclic organic compound for promoting chemical honing in the present invention is preferably 0.001 to 10% by weight, more preferably 0.01 to 8% by weight, and 0.02 to the total amount of the honing liquid. ~ 5% by weight is particularly good. When the blending amount is less than 0.001% by weight, the honing rate tends to decrease, and when it exceeds 10% by weight, the amount of metal corrosion tends to increase. Examples of the oxidizing agent of the present invention include hydrogen peroxide (η202), nitric acid, potassium periodate, hypochlorous acid, thallium persulfate, and ozone water. Among them, hydrogen peroxide is particularly preferred. These compounds are used singly or in combination of two or more. When the substrate to which honing is applied is a silicon substrate containing integrated circuit elements, due to contamination by alkali metals, alkaline earth metals, halides, etc. 11849pif.doc / 008 13 200405453 Dyeing system is an undesired relationship, Therefore, it is advisable not to contain oxidants that do not defend the ingredients. However, since the composition of ozone water systems changes drastically over time, hydrogen peroxide is most suitable. However, in the case where the substrate is a glass substrate containing no semiconductor element, it does not matter if an oxidizing agent containing a nonvolatile component is used. The blending amount of the oxidizing agent is preferably 0.1 to 50% by weight, more preferably 0.2 to 25% by weight, and particularly preferably 0.3 to 15% by weight based on the total amount of the honing liquid. When the blending amount is less than 0.1% by weight, the oxidization speed of the metal is insufficient, and when it exceeds 50% by weight, the roughened surface tends to be rough. The pH adjusting agent in the present invention may be water-soluble, and is not particularly limited. For example, it includes formic acid (acetic acid), acetic acid (propionic acid), butanoic acid (butanoic) acid), pentoic acid, 2-ethyl-butanoic acid, n-hexanoicacid 3,3-dimethylbutanoic acid (3,3-dimethyl- butanoic acid), 2-ethyl-butanoic acid, 4-methyl pentanoic acid, n-heptanoic acid, 2-methylhexanoic acid (2-methyl-hexanoic acid), n-octanoic acid, 2-ethyl-heaxnoic acid, benzoic acid, glycolic acid, salicylic acid (salicylic acid), glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid Acid (pimelic acid), maleic acid (phtalic acid), malic acid (malic 14 11849pif.doc / 008 200405453 acid), tartaric acid (ta organic acids such as rtaric acid), lemon acid, etc., esters of these organic acids, and ammonium phosphonium of these organic acids. Other examples include inorganic acids such as osmic acid, sulfuric acid, nitric acid, and the like, such as ammonium persulfate, ammonium nitrate, ammonium chloride, and chromic acid. acid) and so on. Among these oxidants, those having a CMP honing effect on the metal layer in particular are organic acids and organic acids such as formic acid, malonic acid, malic acid, tartaric acid, citric acid, succinic acid, glutaric acid, and ferric acid. Esters, ammonium sulfonium organic acids and sulfuric acid are suitable. These pH adjusting agents may be used singly or in combination of two or more kinds. In the present invention, the blending amount of the pH adjusting agent to the total amount of the honing liquid is preferably 0.001 to 10% by weight, more preferably 0.01 to 8% by weight, and 0.02 to 5% by weight. great. When the blending amount is less than 0.001% by weight, the honing rate tends to decrease extremely, and when it exceeds 10% by weight, the 'honing rate tends to be saturated. The honing liquid system of the present invention may contain a water-soluble polymer. The water-soluble polymer is not particularly limited, and includes, for example, alginic acid, pectic acid, carboxymdhy1 cellulose, gelatin, and cardoacetate ( polysaccharides such as curdlan and pullulan; polyasparaginic acid, poly glutamic acid, poly lysine, polymalic acid (Poly malic acid), polymethacrylic aicd, poly ammonium methacrylate, 11849pif.doc / 008 15 200405453 poly natrium methacrylate, poly Poly amido acid, poly maleic acid, poly itaconic acid, poly fumaric acid, poly (p-styrenecarboxylic acid) Acid) (p〇iy (p-styrene carboxylic acid), poly acrylic acid, polyacrylamide (Poly acrylamide), poly amino acrylamide, poly ammonium acrylate (poly ammonium acrylate), poly natriu m acrylate), polyamic acid (Poly amido acid), poly ammonium amidate (poly ammonium amidate), and poly glyoxialic acid (poly carboxylic acid, polycarboxylic acid ester, polycarboxylic acid) Acid fluorene and polycarboxylic acid derivatives; vinyl polymers such as polyvinyl alcohol, poly vinyl pyrrolidone, and poly acrolein; the above Esters of compounds, ammonium sulfonium, etc. However, when the applicable substrate is a sand substrate for semiconductor circuits, etc., since the pollution of alkali metals, alkaline earth metals, halides, etc. is an undesirable relationship, it is based on An acid or its ammonium sulfonium is suitable. When the substrate is a glass substrate, it is not limited thereto. Among them, it is selected from the group consisting of polysaccharides, polycarboxylic acids, polycarboxylic acid esters, polyacrylic acid, polyacrylamide, and vinyl. It is preferably at least one of the groups of the polymer group, and specifically includes pectinic acid, gelatin, polymalic acid, polymethacrylic acid, polyacrylic acid, polyacrylamide, polyvinyl alcohol, and polyvinylpyrrolidine, and the like. Ester and ammonium phosphonium are suitable. When the water-soluble polymer is blended, the blending amount is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 1% by weight or less based on the total amount of the honing liquid. When this blending amount exceeds 10% by weight, the honing speed tends to decrease 11849pif.doc / 008 16 200405453. The weight average molecular weight of the water-soluble polymer is preferably 500 or more, more preferably 1,500 or more, and particularly preferably 5,000 or more. Although the upper limit of the weight average molecular weight is not particularly specified, it is preferably 5 million or less from the viewpoint of solubility. When the weight average molecular weight is less than 500, there is a tendency that a high honing speed cannot be exhibited. In the present invention, it is preferable to use at least one water-soluble polymer having a weight average molecular weight of 500 or more. The honing liquid of the present invention may be added with honing particles. The honing grain system may be, for example, silica, alumina, zirconia, ceria, titania, germania, silicon carbide And other inorganic abrasive grains, polystyrene (poly styrene), polypropylene (Poly acryl), vinyl chloride (vinyl chloride) and other organic abrasive grains. The dispersion stability in the honing fluid is good, and those with a small number of scratches caused by CMP are colloidal silica with an average particle diameter of 100 nm or less, and colloidal alumina is preferred. When honing particles are added, the blending amount is preferably 10% by weight or less based on the total weight of the honing liquid, and more preferably 5% by weight or less. When the blending amount exceeds 10% by weight, the honing speed of the CMP becomes saturated, and even when the blending amount is more than this, no increase in the honing speed is found. In the honing fluid of the present invention, in addition to the above materials, the system may also contain anion (cation), cation (non-ionic), non-ionic (!! ^! ^ !!), interfacial active agent, Dyestuffs such as Victoria pure blue and pigments such as phthalocyanine green. Moreover, the blending amount of water may be the remainder, as long as it is contained in 11849pif.doc / 008 17 200405453, there is no particular limitation. The honing system to which the honing fluid of the present invention is applied is, for example, a metal stomach and stomach. The metal layer system includes copper, a copper alloy, an oxide of copper, and an oxide of copper alloy (hereinafter referred to as copper and its compounds), Giant, nitrided, M alloy, other giant compounds (hereinafter, referred to as giant and its compounds. Titanium, titanium alloy, other titanium compounds (hereinafter, referred to as titanium and its compounds), tungsten, nitride Tungsten, tungsten alloys, other tungsten compounds (hereinafter referred to as stomach compounds), etc. can be formed into M by a known sputtering method or electroplating method. Metal layers such as metal knives are honed in one or a combination of two. Metal layers It can also be a stomach layer combined with more than one of the above metals. For the stacking layer to which the present invention is applied, among the stacking layers of the metal layer to be honing, the first layer to be honing is selected from the above-mentioned copper and The compound is selected, and the second honing second layer is a stacked layer selected from the above-mentioned tantalum and its compound, titanium and its compound, tungsten and its compound. By using the honing liquid of the present invention, Continuous honing The first honing method of the present invention is to supply the honing liquid of the present invention to a honing cloth on a honing table while pressing the honing surface of the substrate on the honing cloth. The state of the honing cloth is a honing method characterized in that the honing cloth and the base are honed with relative movement. The honing device is, for example, a general type having a honing table and a holder. Honing device. Among them, the honing table can be attached with a honing pad (honing cloth), which is connected to a motor that can change the number of revolutions. The holder can hold the honing substrate. For honing cloth, General non-woven 11849pif.doc / 008 18 200405453 (unwover fabric), foamed polyurethane, porous fluororesin, etc. can be used, and there is no particular limitation here. Honing Although the conditions are not limited, the rotation speed of the honing table is preferably a low rotation below 2000 rpm that does not allow the substrate to fly out. The pressure of the substrate with the honing surface against the honing cloth (honing pressure) is based on 1 ~ 100kPa is appropriate, in order to meet the CMP speed The uniformity in the honing surface and the flatness of the pattern are more preferably 5 ~ 50kPa. During honing, the honing liquid is continuously supplied to the honing cloth by a pump or the like. Although the supply amount is unlimited It is advisable that the surface of the honing cloth is often covered with honing liquid. After the honing is finished, the substrate is washed well in running water, and the water droplets attached to the substrate are dropped by spin drying, etc. The method of relative movement of the honing cloth and the substrate, in addition to rotating the honing table, can also rotate or shake the holder. In addition, the honing table is rotated in a planetary manner, such as a band-shaped hoe A honing method in which the polishing pad moves linearly in one of the longitudinal directions, etc. Furthermore, the holder may be fixed, rotated, or shaken. These honing methods can be selected as long as the honing pad and the substrate can be relatively moved ', and can be appropriately selected by the honing surface or the honing device. In addition, the second honing method of the present invention is one in which the honing liquid of the present invention is supplied to the honing cloth of the honing table, and the stack and layers of two or more metal layers are continuously honed. . For example, in the stacking layer of the metal layer, the fj honing layer is at least one selected from the above copper and its compounds, and the layer stacked with the previous honing layer, that is, the second layer, is selected from the giant And at least one of its compounds, titanium and its compounds, tungsten and its compounds. 11849pif.doc / 008 19 200405453 The present invention relates to the formation of a wiring layer of a semiconductor device, for example, a conductive material layer suitable for metal wiring, and a barrier conductor layer (above, which prevents the conductive material from diffusing into the interlayer insulation layer) , Called barrier layer), and chemical mechanical honing (CMP) of interlayer insulation layers. The previously-honed layer system is equivalent to the conductive material layer, and the secondary layer of this layer corresponds to the barrier layer. That is, the third honing method of the present invention includes a first honing process and a second honing process. Among them, the first honing process is honing a metal layer of a substrate having an interlayer insulating layer, a barrier layer, and a metal layer to expose the barrier layer of the convex portion described below, and the surface of the interlayer insulating layer is composed of the concave portion and the convex portion. The barrier layer is formed along the surface of the interlayer insulating layer, and the metal layer fills the recess to cover the barrier layer. After the second honing process, at least the barrier layer and the metal layer of the concave portion are honed to expose the interlayer insulating layer of the convex portion. In at least one of the first honing process and the second honing process, the honing liquid of the present invention is used for honing. An example of an embodiment of the honing method of the present invention will be described below along the wiring of a semiconductor device. First, an interlayer insulating layer such as silicon dioxide is laminated on a silicon substrate. Next, a recessed portion (substrate exposed portion) having a predetermined pattern is formed on the surface of the interlayer insulating layer by a conventional means such as photoresist layer formation, etching, etc., as an interlayer insulating layer composed of the protruding portions and the recessed portions. On this interlayer insulating layer, the protrusions and depressions along the surface make tantalum or the like be formed by vapor deposition or CVD to cover the interlayer insulating layer as a barrier layer. Furthermore, a conductive material layer (hereinafter, referred to as a metal layer) that covers the barrier layer by filling the recessed portion is formed by stacking copper or the like by evaporation, plating, or CVD to obtain a stacked layer of the metal layer. . Layer 11849pif.doc / 008 20 200405453 The formation thickness of the insulating layer, the barrier layer and the metal layer is preferably about 0.01 ~ 2.〇β m, 1 ~ 100nm, 0.01 ~ 0.25 // m. (First honing process) Next, the semiconductor substrate is fixed to a honing device, and the surface metal layer is used as a honing surface, and the honing liquid of the present invention is supplied while honing. Thereby, the barrier layer of the convex portion of the interlayer insulating layer is exposed on the substrate surface, and the above-mentioned metal layer remains in the concave portion of the interlayer insulating layer to obtain a desired conductor pattern. (Second Honing Process) Secondly, at least the exposed barrier layer and the metal layer of the recessed portion of the conductor pattern are used as the honing surface, and the honing liquid of the present invention is supplied for honing. When the interlayer insulation layer under the barrier layer of the convex portion is completely exposed, and the above-mentioned metal layer of the wiring layer is left behind in the concave portion, when the cross section of the barrier layer is exposed at the boundary between the convex portion and the concave portion to obtain a desired pattern Stop honing. Furthermore, in order to ensure better flatness at the end of honing, honing may be performed (for example, when the second honing process takes 100 seconds to obtain the desired pattern, here is 100 seconds Honing plus an additional 50 seconds of honing is called over honing 50%) and can be honed to the depth of a part of the interlayer insulating layer containing the convex portion. Here, at least one of the first honing process and the second honing process, by using the honing liquid of the present invention for honing, can maintain a low dissolution rate on the one hand, and can fully increase the honing rate on the other hand, and can be honed. Corrosion of the surface and the occurrence of dish-like depressions. In the first honing process and the second honing process, the honing liquid of the present invention may be continuously honed as described above. In this case, although the honing process or the drying process does not need to be performed between the first honing process and the second honing process, the honing table or honing is replaced 11849pif.doc / 008 21 200405453 It can also be stopped when changing the processing load. Although the honing liquid of the present invention used in the first honing process and the second honing process can be used with the same composition or different compositions, if the same composition is used, since the first honing process to the second honing process The grinding process can continue honing without stopping, so it has good productivity. An interlayer insulating layer, a barrier layer, and a second layer of the wiring metal layer are further formed on the metal wiring formed in this way, and are polished to form a second layer as a smooth surface on all semiconductor substrates. Metal wiring. When this process is repeated several times, a semiconductor device having a desired number of wiring layers can be manufactured. π (Examples) Hereinafter, the present invention will be described with reference to examples. The invention is not limited by the examples. (Examples 1 to 138 and Comparative Examples 1 to 6; Honing speed) [Honing liquid preparation method] For the total amount of honing liquid, the cyclic organic compounds that promote chemical honing are shown in Tables 1 to 6 After adding 0.1% by weight of colloidal silica with an average particle size of 50nm to 0.5% by weight, 30% of hydrogen peroxide at 30% by weight and the remainder with water, add succinic acid or ammonia to adjust the pH to 6, 7 or 8 to make. [Honing conditions] Copper substrate: silicon substrate with copper metal deposited in a thickness of 1500 nm tungsten substrate: silicon substrate with tungsten compound (tungsten nitride) deposited in a thickness of 600 nm 11849pif.doc / 008 22 200405453 Honing pad on a honing table: Polyurethane foam resin (model IC1000 manufactured by Rohde & Co.) Relative speed of substrate and honing table: 20m / min Honing pressure: 30kPa [Honing product evaluation item] Honing speed: Honing of each layer The difference between the layer thicknesses before and after is calculated from the resistance 値. Tables 1 to 3 show the results of the CMP honing rate on the substrate, and Tables 4 to 6 show the results of the CMP honing rate on the tungsten substrate. 11849pif.doc / 008 23 200405453 Table 1 Example Cyclic Organic Compounds pH Copper Honing Speed (nm / min) 1 Imidazole 6 283 2 Imidazole 7 211 3 Imidazole 8 185 4 2-methylimidazole 6 269 5 2-methyl Imidazole 7 203 6 2-methylimidazole 8 168 7 2-ethylimidazole 6 268 8 2-ethylimidazole 7 199 9 2-ethylimidazole 8 159 10 2-isopropylimidazole 6 271 11 2-isopropyl Imidazole 7 195 12 2-isopropylimidazole 8 160 13 2-propylimidazole 6 254 14 2-propylimidazole 7 185 15 2-propylimidazole 8 151 16 2-butylimidazole 6 234 17 2-butyl Imidazole 7 171 18 2-butylimidazole 8 136 19 4-methylimidazole 6 267 20 4-methylimidazole 7 201 21 4-methylimidazole 8 169 22 2, 4-dimethylimidazole 6 274 23 2, 4 -Dimethylimidazole 7 189 24 2, 4-dimethylimidazole 8 157 25 2-ethyl-4-methylimidazole 6 257 26 2-ethyl-4-methylimidazole 7 171 27 2-ethyl- 4-methylimidazole 8 143 28 3, 5-dimethylpyrazole 6 275 29 3, 5-dimethylpyrazole 7 188 30 3, 5-dimethylpyrazole 8 155 24 11849pif.doc / 008 200405453 Table 2 Example Cyclic Organic Compound pH Copper Honing Speed (nm / min) 31 3-methyl-5- Pyrazinone 6 265 32 3-methyl-5-pyrazolone 7 179 33 3-methyl-5-pyrazolone 8 151 34 3-amino-5-methylpyrazole 6 193 35 3 -Amino-5-methylpyrazole 7 185 36 3-amino-5-methylpyrazole 8 162 37 3-amino-5-hydroxypyrazole 6 191 38 3-amino-5-hydroxypyrazole 7 181 39 3-amino-5-hydroxypyrazole 8 159 40 3-amino-5-methylpyrazole 6 190 41 3-amino-5-methylpyrazole 7 181 42 3-amino-5 -Methylpyrazole 8 158 43 2-aminothiazole 6 281 44 2-aminothiazole 7 205 45 2-aminothiazole 8 183 46 4, 5-dimethylthiazole 6 193 47 4, 5-dimethyl Thiazole 7 178 48 4, 5-Dimethylthiazole 8 159 49 2-Amino-2-thiazoline 6 175 50 2-Amino-2-thiazoline 7 143 51 2-Amino-2-thiazoline 8 139 52 2, 4-dimethylthiazole 6 191 53 2, 4-dimethylthiazole 7 174 54 2, 4-dimethylthiazole 8 156 55 2-amino-4-methylthiazole 6 201 56 2-amine Methyl-4-methylthiazole 7 189 57 2-Amino-4-methylthiazole 8 169 58 1,2,4-triazole 6 173 59 1,2,4-triazole 7 139 60 1,2,4 -Triazole 8 121 25 11849pif.doc / 008 200405453 Table 3 Cyclic organic compounds pH copper honing Degree (nm / min) Example 61 3-Amino-1,2,4-triazole 6 156 Example 62 3-Amino-1,2,4-triazole 7 132 Example 63 3-Amino- 1,2,4-triazole 8 119 Example 64 4-amino-1,2,4-triazole 6 163 Example 65 4-amino-1,2,4-triazole 7 138 Example 66 4 -Amine-1,2,4-triazol 8 124 Example 67 1,2,4-triazolo [1,5-a] pyrimidine 6 176 Example 68 1,2,4-triazolo [1 , 5-a] pyrimidine 7 149 Example 69 1,2,4-triazolo [1,5-a] pyrimidine 8 129 Comparative Example 1 Μ j \\\ 6 25 Comparative Example 2 Μ y \\\ 7 17 Comparative Example 3 Μ 8 5 26 11849pif.doc / 008 200405453 Table 4 Example Cyclic Organic Compound pH Tungsten Nitride Honing Speed (nm / min) 70 Imidazole 6 236 71 Imidazole 7 199 72 Imidazole 8 147 73 2-methyl Imidazole 6 215 74 2-methylimidazole 7 167 75 2-methylimidazole 8 121 76 2-ethylimidazole 6 211 77 2-ethylimidazole 7 161 78 2-ethylimidazole 8 142 79 2-isopropyl Imidazole 6 214 80 2-isopropylimidazole 7 165 81 2-isopropylimidazole 8 141 82 2-propylimidazole 6 201 83 2-propylimidazole 7 143 84 2-propylimidazole 8 126 85 2-butyl Imidazole 6 192 86 2-butylimidazole 7 134 87 2-butylimidazole 8 109 88 4-methylimidazole 6 213 89 4-methylimidazole 7 161 90 4-methylimidazole 8 139 91 2, 4-dimethylimidazole 6 201 92 2, 4-dimethylimidazole 7 139 93 2, 4-dimethylimidazole 8 121 94 2-ethyl-4-methylimidazole 6 189 95 2-ethyl-4-methylimidazole 7 131 96 2-ethyl-4-methylimidazole 8 118 97 3, 5-dimethylpyrazole 6 227 98 3, 5-dimethylpyrazole 7 147 99 3, 5-dimethylpyrazole 8 105 100 3 -Methyl-5-pyrazolinone 6 217 11849pif.doc / 008 27 200405453 Table 5 Example Cyclic organic compound pH Tungsten nitride honing rate (nm / min) 101 3-methyl-5-pyrazole 7-127 102 3-methyl-5-pyrazolone 8 103 103 3-amino-5-methylpyrazole 6 144 104 3-amino-5-methylpyrazole 7 134 105 3-amine Methyl-5-methylpyrazole 8 115 106 3-amino-5-hydroxypyrazole 6 140 107 3-amino-5-hydroxypyrazole 7 133 108 3-amino-5-hydroxypyrazole 8 107 109 3-amino-5-methylpyrazole 6 141 110 3-amino-5-methylpyrazole 7 133 111 3-amino-5-methylpyrazole 8 110 112 2-aminothiazole 6 233 113 2-aminothiazole 7 154 114 2- Thiathiazole 8 133 115 4, 5-dimethylthiazole 6 143 116 4, 5-dimethylthiazole 7 127 117 4, 5-dimethylthiazole 8 113 118 2-amino-2-thiazoline 6 125 119 2-amino-2-thiazoline 7 103 120 2-amino-2-thiazoline 8 93 121 2, 4-dimethylthiazole 6 143 122 2, 4-dimethylthiazole 7 126 123 2, 4- Dimethylthiazole 8 104 124 2-Amino-4-methylthiazole 6 150 125 2-Amino-4-methylthiazole 7 136 126 2-Amino-4-methylthiazole 8 117 127 1,2, 4-triazole 6 123 128 1,2,4-triazole 7 98 129 1,2,4-triazole 8 76 130 3-amino-1,2,4-triazole 6 106 28 11849pif.doc / 008 200405453 Table 6 Ring organic compound pH Tungsten nitride honing rate (nm / min) Window_31 3-amino-1,2,4-triazole 7 89 Product_32 3-amino-1,2, 4-triazole 8 83 product_133 4-amino-1,2,4-triazole 6 113 product_34 4-amino-1,2,4-triazole 7 91 135 4-amino-1, 2, 4-triazol 8 78 Jenna 36 1,2,4-triazolo [1,5-a] pyrimidine 6 126 _ 137 1,2,4-triazolo [1,5-a] pyrimidine 7 99 Example 138 1,2,4-triazolo [1,5-a] pyrimidine 8 79 Comparative Example 4 Μ j \ \\ 6 30 Comparison 5 Μ j \ \\ 7 21 Comparative Example 6 iffi j \\\ 8 13 Example 1~69 WH polishing rate of the copper-based embodiment were 100nm / min or more, when compared with Comparative Examples 1~3 improved. The honing speed of tungsten nitride is 100 nm / min or more in Examples 70 to 117, 121 to 126, and 75 nm / min or more in Examples 118 to 120, 127 to 138, and 30 nm / min or less. Comparative Examples 4 to 6 improved when compared. (Example 139: dish-shaped depressions) 29 11849pif.doc / 008 200405453 A colloidal silica having an average particle size of 50 nm and an average particle diameter of 50 nm of the cyclic organic compound that promotes chemical honing with 0.1% by weight of the honing liquid. 0.5% by weight, 0.2% by weight of a water-soluble polymer, 30% by weight of 30% hydrogen peroxide, and the remainder were mixed with water, and then succinic acid was added to adjust the pH to 6 to prepare the product. A silicon substrate having a trench having a depth of 0.5 to 100 // m in silicon dioxide, a tungsten nitride layer having a thickness of 50 nm as a barrier layer, and a copper layer formed on a # layer was prepared by a conventional method. The entire surface of the substrate was honed with the honing liquid described above until the convex portions of the silicon dioxide were exposed. The Honma Temple was 2 minutes, and the honing speed was about 500 nm / min or more. Next, a stylus-type step meter was used to obtain the wiring of the insulating layer portion from the surface shape of the stripe pattern portion arranged alternately from the width of the wiring metal layer portion 100 #m and the width of the insulating portion 100 // m. The thickness of the metal layer (disc-shaped depression) in the stomach is 75nm, which is sufficient for practical use. (Example 140) The barrier layer was replaced by a nitrided giant layer with a thickness of 50 nm instead of the tungsten nitride layer. 'A silicon substrate was used in the same manner as in Example 139, and the entire surface of the substrate was prepared in the same manner as in Example 139. The polishing liquid is honed until the protruding portions of the dioxide are exposed. The honing time was 2 minutes, and a honing speed of about 500 nm / min or more was obtained. Next, in the same manner as in Example 139, the layer reduction of the wiring metal portion of the insulating layer was 65 nm, which is a practically sufficient amount. The honing liquid system of the present invention can sufficiently improve the honing speed and suppress the occurrence of corrosion on the metal surface and the occurrence of dish-like depressions, and can form a highly reliable 11849pif.doc / 008 30 200405453 embedded pattern of a metal layer. In addition, the method of the present invention can sufficiently improve the honing speed, suppress the corrosion of the metal surface and the dish-like depression, and can form a highly reliable embedded pattern of the metal layer with good productivity, workability and yield. . Although the present invention has been disclosed as above with a preferred embodiment, it is not intended to limit the present invention. Any person skilled in the art can make some changes and retouch without departing from the spirit and scope of the present invention. The scope of protection of the invention shall be determined by the scope of the attached patent application. A simple explanation of the gl formula j \\\ ffl formula: 钲 j \ w 11849pif.doc / 008 31