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TW200818299A - Semiconductor device polishing method - Google Patents

Semiconductor device polishing method Download PDF

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Publication number
TW200818299A
TW200818299A TW96130135A TW96130135A TW200818299A TW 200818299 A TW200818299 A TW 200818299A TW 96130135 A TW96130135 A TW 96130135A TW 96130135 A TW96130135 A TW 96130135A TW 200818299 A TW200818299 A TW 200818299A
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Taiwan
Prior art keywords
honing
group
liquid
film
barrier metal
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TW96130135A
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Chinese (zh)
Inventor
Takamitsu Tomiga
Katsuhiro Yamashita
Tomoo Kato
Kenji Takenouchi
Tetsuya Kamimura
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Fujifilm Corp
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Publication of TW200818299A publication Critical patent/TW200818299A/en

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  • Mechanical Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

A semiconductor device polishing method, comprising continuously polishing, with one polishing liquid, a barrier metal film formed over a surface of a substrate having a concavity or a surface of an interlayer insulating film formed on the substrate, and a copper or copper alloy conducting film formed on a surface of the barrier metal film so as to fill the concavity, wherein the polishing liquid comprises: an amino acid; an oxidant; polishing particles; and a barrier metal film polishing rate adjusting agent represented by the following Formula (I): Formula (I) R1-CH2-SO3H wherein in the Formula (I), R1 represents H, CH3 or NH2.

Description

.200818299 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種半導體裝置的製造，特別是有關 於半導體裝置的配線製程之平坦化所使用之硏磨方法。 特別是有關於一種應用所謂1階段硏磨之硏磨方法， 在銅平坦化CMP技術，以高硏磨速度、且使用同一硏磨液 來連續地硏磨導體膜及阻障金層障。 【先前技術】 ® 近年來，在以半導體積體電路（以下，簡稱「LSI」）爲 代表之半導體裝置的開發，爲了小型化、高速化，要求藉 由配線的微細化及積層化來高密度化、高積體化。此目的 之技術係使用化學機械硏磨（Chemical Mechanical Polishing、以下簡稱「CMP」）等各種的技術。 CMP之通常的方法係將硏磨墊貼在圓形的硏磨轉盤 (壓板）上，使用硏磨液浸漬硏磨墊表面，並將基板（晶圓） 的表面往硏磨墊壓住，在從其背面施加規定壓力（硏磨壓 ^ 力）之狀態下，使硏磨轉盤及基板雙方旋轉，藉由產生的機 械性摩擦來使基板的表平坦化。 CMP所使用之金屬用硏磨溶液通常係含有硏磨粒子 (例如，氧化鋁、二氧化矽）及氧化劑（例如，過氧化氫、過 硫酸）之物，認爲係藉由氧化劑來將金屬表面氧化，並藉由 硏磨粒子除去其氧化皮膜來進行硏磨。 但是，使用含有此種固體硏磨粒子之金屬用硏磨溶液 來進行CMP時，會有產生硏磨傷（刮傷、硏磨面整面被硏 200818299 磨至必要以上的現象（硏磨變形）、硏磨金屬面非平面狀、 只有中央被硏磨較深而產生碟狀凹陷之現象（凹狀扭曲硏 磨；dishing)、以及金屬配線間的絕緣體被硏磨至必要以上 且複數個配線金屬面表面形成碟狀凹部之現象（侵蝕）等情 爲了解決此種先前的固體硏磨粒子之問題點，例如有 揭示（例如，參照專利文獻1) 一種金屬用硏磨溶液、及硏磨 方法，該金屬用硏磨溶液係由過氧化氫/蘋果酸/苯并三唑/ • 聚丙烯酸銨及水所構成的金屬用硏磨溶液作爲未含有硏磨 粒子之金屬用硏磨溶液。依照同文獻所記載之硏磨方法 時，能夠得到選擇性地將半導體基體之凸部的金屬膜化學 機械硏磨（CMP)，且在凹部殘留有金屬膜之需要的導體圖 案，但是因爲藉由與機械性遠比含有先前的固體硏磨粒子 柔軟的硏磨墊摩擦來進行CMP，會有難以得到充分的硏磨 速度之問題點。 又，有揭示（例如，參照專利文獻2)—種化學機械硏磨 ^ 用水系分散體，含有有機化合物用以抑制硏磨墊的劣化。 但是，即便藉由該硏磨用水系分散體，亦有因配線部金屬 被過剩地硏磨而產生碟上凹陷之凹狀扭曲硏磨現象之可能 近年來，爲了提高生產力，LSI製造時的晶圓直徑逐 漸大型化，目前直徑2 0 0毫米以上被廣泛使用，亦已開始 製造3 00毫米以上之大尺寸。隨著如此的晶圓大型化，晶 圓中心部與周邊部變爲容易產生硏磨速度差異，達成硏磨 200818299 的均勻性變爲重要。· 對此，已知有一種利用化學溶解作用之方法（例如，參 照專利文獻3 )，係一種未具有機械性硏磨手段之化學硏磨 方法，用以硏磨對銅及銅合金。但是只藉由化學溶解作用 之化學硏磨方法，與能夠選擇性地化學機械性硏磨凸部的 金屬膜之CMP比較時，存在有凹部的削入、亦即因產生凹 狀扭曲硏磨等而使其平面性成爲重大課題。 又，銅配線使用時，爲了防止銅離子往絕緣材料擴散 • 之目的，通常可在配線部與絕緣層之間設置稱爲阻障層之 防止擴散層。該阻障層係由1層或2層以上所構成的金屬 膜（阻障金屬膜）所構成，該金屬膜含有選自TaN、TaSiN、 Ta、TiN、Ti、Ru、Nb、W、WN、Co、Zr、ZrN、及 CuTa 等的合金等之1種。但是，因爲此等阻障層材料本身具有 導電性，爲了防止漏電等錯誤產生，必須完全除去絕緣層 上的阻障層材料，該除去加工能夠藉由與金屬配線材的表 體硏磨同樣的方法來達成（該方法亦有稱爲「.阻障CMP」之 籲情形.)。 目前，係使用2階段製程，先使用對導體膜的硏磨速 度比對阻障金屬膜的硏磨速度高之金屬用硏磨液，以阻障 金屬膜作爲停止層來硏磨導體膜，接著，使用不同的金屬 用硏磨液，來進行硏磨導體膜及阻障金屬膜。又，爲了配 合上述情形，因爲對各自金屬用硏磨液之最適當的製程消 耗構件不同，係使用複數硏磨墊來進行硏磨。 但是，使用上述複數硏磨墊時，必須有配合此等各自 200818299 之製程消耗構件，會有花費成本、且製造製程變爲複雜導 致總加工時間延遲等之許多問題點。因此，爲了解決此等 問題，認爲必須使用一種硏磨墊來進行硏磨。但是使用一 種硏磨墊且複數種硏磨液來硏磨晶圓時，由於金屬用硏磨 液的交換或準備、進而硏磨墊的洗淨需要時間’可舉出需 要花費很多時間及勞力等問題點。 因此，對具有絕緣膜（層間絕緣膜）、障阻障金屬膜及 導體膜之基板，考慮使用同一金屬用硏磨液連續地硏磨導 體膜及阻障金屬膜之硏磨製程（以下，稱爲1階段製程）。 若能夠實現一階段製程時，隨著降低金屬用硏磨液的 交換頻率，能夠使硏磨時間迅速化，能夠提升半導體裝置 製造生產線的生產效率，而且不必複數台的硏磨裝置，並 且亦能夠期待實現裝置的小型化等許多實用的優點。又， 現行的硏磨方法因爲硏磨後的廢液係混合有2種類漿體之 狀態，所以難以處理，相對地，因爲1階段製程時漿體係 1種類，廢液的處理變爲簡便，亦能夠有助於降低環境負 荷。 爲了實現1階段製程，必須在可能的程度組合在導體 膜、阻障金屬膜、絕緣膜之硏磨速度比（以下，簡稱「選擇 比」）。 而且，成爲實現1階段製程之障礙，係連續硏磨導體 膜及阻障金屬膜時未存在有使硏磨停止的層（所謂停止 層）。結果，會有產生刮傷、配線部及絕緣膜凸部平坦性變 差等問題。 : 200818299 如此，關於在CMP實現〗階段製程，目前尙未能夠提 供有效的技術。 [專利文獻1 ]特開2 〇 0 1 - 1 2 7 0 1 9號公報 [專利文獻2]特開2001-279231號公報 [專利文獻3]特開昭49-122432號公報 【發明內容】 [解決課題之手段] 鑒於上述先前的問題點，本發明係以達成以下的目的 # 作爲課題。 亦即，本發明的目的係提供一種半導體裝置之硏磨方 法，其特徵係能夠連續地以同一硏磨液進行硏磨具有絕緣 膜、導體膜及阻障金屬膜之基板，硏磨後之被硏磨面的平 坦性良好、且能夠降低產生刮傷。 [解決課題之手段] 本發明者專心硏討在1階段製程所使用的硏磨液之問 題點，結果發現藉由使用在含有氧化劑、胺基酸及硏磨粒 ^ 子之溶液系添加特定的阻障金屬膜硏磨速度調整劑而成的 硏磨液，能夠以同一硏磨液進行硏磨導體膜及阻障金屬 膜，同時絕緣膜能夠作爲停止層之功能，而完成了本發明。 亦即，解決前述課題之手段如下。 < 1 > 一種半導體裝置之硏磨方法，其特徵係連續地以一種 硏磨液進行硏磨阻障金屬膜及導體膜；該阻障金屬膜係一 面地形成在具有凹部之基板或形成於該基板上之層間絕緣 膜的表面；而該導體膜係由銅或銅合金所構成，形成於該 200818299 阻障金屬膜的表面用以將前述凹部塡埋；上述硏磨液係含 有下述通式（I)所示之阻障金屬膜硏磨速度調整劑、胺基 酸、氧化劑及硏磨粒子， R1 — CH2— S03H 通式（I) (通式（I)中，R1係表示Η、CH3、或NH2)。 <2>如<1>之硏磨方法，其中前述硏磨速度調整劑與前述 月女基酸之旲耳比爲（硏磨速度g周整劑）··（胺基酸）= 3: 1〜8: •卜 <3>如<1>或<2>之硏磨方法，其中前述胺基酸係下述通式 (II)所示之化合物， 、 R3 R5BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the manufacture of a semiconductor device, and more particularly to a honing method for planarizing a wiring process of a semiconductor device. In particular, there is a honing method using a so-called one-stage honing method in which a copper planarization CMP technique is used to continuously honing a conductor film and a barrier gold barrier at a high honing speed and using the same honing liquid. [Prior Art] In recent years, in the development of semiconductor devices such as semiconductor integrated circuits (hereinafter referred to as "LSI"), in order to reduce the size and speed, it is required to have a high density by wiring miniaturization and lamination. Chemicalization and high integration. A technique for this purpose is to use various techniques such as Chemical Mechanical Polishing (hereinafter referred to as "CMP"). The usual method of CMP is to attach a honing pad to a circular honing turntable (pressing plate), impregnate the surface of the honing pad with a honing liquid, and press the surface of the substrate (wafer) against the honing pad. In a state where a predetermined pressure (honing pressure) is applied to the back surface, both the honing turntable and the substrate are rotated, and the surface of the substrate is flattened by mechanical friction generated. The metal honing solution used in CMP usually contains honing particles (for example, alumina, cerium oxide) and an oxidizing agent (for example, hydrogen peroxide, persulfuric acid), and is considered to be a metal surface by an oxidizing agent. Oxidation, and honing by removing the oxide film by honing the particles. However, when CMP is performed using a honing solution containing a metal containing such solid honing particles, there is a problem of scratching (scratching, honing of the entire surface of the honing surface by 200818299 and grinding to more than necessary (honing deformation) The honing of the metal surface is non-planar, and only the center is honed deep to produce dishing depressions (concave twisting; dishing), and the insulators in the metal wiring are honed to more than necessary and a plurality of wiring metals The phenomenon of forming a dish-shaped recess on the surface of the surface (erosion), etc., in order to solve the problem of such a conventional solid honing particle, for example, it is disclosed (for example, refer to Patent Document 1) a metal honing solution, and a honing method, The metal honing solution is a honing solution for a metal composed of hydrogen peroxide/malic acid/benzotriazole/•polyacrylic acid ammonium and water as a honing solution for a metal not containing honing particles. In the honing method described above, it is possible to obtain a conductor pattern which is required to selectively chemically honing (CMP) the metal film of the convex portion of the semiconductor substrate and leaving a metal film in the concave portion, but Since CMP is performed by friction with a honing pad which is mechanically farther than the solid honing particles, it is difficult to obtain a sufficient honing speed. Further, it is disclosed (for example, refer to Patent Document 2) - Chemical mechanical honing ^ Water-based dispersion containing an organic compound to suppress deterioration of the honing pad. However, even if the water-based dispersion is honed by the honing, the metal in the wiring portion is excessively honed. In the recent years, in order to improve productivity, the wafer diameter during LSI manufacturing has gradually increased in size. Currently, the diameter of 200 mm or more is widely used, and more than 300 mm has been manufactured. With such a large-scale wafer, the center portion of the wafer and the peripheral portion become easy to produce a difference in honing speed, and it becomes important to achieve the uniformity of 200818299. · For this, a chemical dissolution is known. The method of action (for example, refer to Patent Document 3) is a chemical honing method which does not have a mechanical honing means for honing copper and copper alloys, but only borrows The chemical honing method for chemical dissolution is compared with the CMP of a metal film capable of selectively chemically honing the convex portion, and the concave portion is cut, that is, the concave portion is honed or etched to make the plane In order to prevent copper ions from diffusing into the insulating material during the use of the copper wiring, a diffusion preventing layer called a barrier layer is usually provided between the wiring portion and the insulating layer. It is composed of a metal film (barrier metal film) composed of one or two or more layers containing TaN, TaSiN, Ta, TiN, Ti, Ru, Nb, W, WN, Co, Zr, ZrN. One type of alloy such as CuTa, etc. However, since these barrier layer materials themselves have electrical conductivity, in order to prevent errors such as electric leakage, it is necessary to completely remove the barrier layer material on the insulating layer, and the removal processing can be performed by It is achieved in the same way as the surface of the metal wiring material. This method is also called ". CMP". At present, a two-stage process is used, in which a honing liquid for a conductor film is honed at a higher speed than a honing speed of a barrier metal film, and a conductor film is etched with a barrier metal film as a stopper layer, and then Use different metal honing fluids to honing the conductor film and the barrier metal film. Further, in order to cope with the above, since the most appropriate process consumption members for the respective metal honing liquids are different, a plurality of honing pads are used for honing. However, when the above-mentioned plurality of honing pads are used, there must be a problem in that the cost of the manufacturing process of the respective processes of 200818299 is complicated, and the manufacturing process becomes complicated, resulting in a delay in the total processing time. Therefore, in order to solve these problems, it is considered that an honing pad must be used for honing. However, when using a honing pad and a plurality of honing liquids to honing the wafer, it takes time and labor for the exchange or preparation of the metal honing liquid and the cleaning of the honing pad. Problems. Therefore, for a substrate having an insulating film (interlayer insulating film), a barrier metal film, and a conductor film, a honing process in which a conductor film and a barrier metal film are continuously honed using the same metal honing liquid is considered (hereinafter, For the 1-stage process). When the one-stage process can be realized, the frequency of exchange of the honing liquid for metal can be reduced, the honing time can be made faster, the production efficiency of the semiconductor device manufacturing line can be improved, and a plurality of honing devices are not required, and Many practical advantages such as miniaturization of the device are expected. Moreover, the current honing method is difficult to handle because the pulverized waste liquid is mixed with two types of slurry, and the treatment of the waste liquid is relatively simple because of the type of the slurry system in the one-stage process. Can help reduce environmental load. In order to realize the one-stage process, it is necessary to combine the honing speed ratio (hereinafter, referred to as "selection ratio") of the conductor film, the barrier metal film, and the insulating film to the extent possible. Further, as a hindrance to the one-stage process, there is no layer (so-called stop layer) for stopping the honing when the conductor film and the barrier metal film are continuously honed. As a result, there is a problem that scratches occur, and the flatness of the wiring portion and the convex portion of the insulating film is deteriorated. : 200818299 As such, there is currently no effective technology available for the CMP implementation phase. [Patent Document 1] JP-A-2001-279231 [Patent Document 3] JP-A-49-122432 (Summary of the Invention) [ Means for Solving the Problem In view of the above-mentioned prior problems, the present invention has attained the following object # as a problem. That is, an object of the present invention is to provide a honing method for a semiconductor device, characterized in that the substrate having the insulating film, the conductor film and the barrier metal film can be honed continuously with the same honing liquid, and the honing is The honing surface is excellent in flatness and can reduce scratches. [Means for Solving the Problem] The present inventors focused on the problem of the honing liquid used in the one-stage process, and as a result, found that a specific solution was added by using a solution containing an oxidizing agent, an amino acid, and a honing agent. The honing liquid obtained by blocking the metal film honing speed adjusting agent can honing the conductor film and the barrier metal film with the same honing liquid, and the insulating film can function as a stopping layer, and the present invention has been completed. That is, the means for solving the above problems are as follows. < 1 > A honing method for a semiconductor device, characterized in that a barrier metal film and a conductor film are continuously honed with a honing liquid; the barrier metal film is formed on one side of a substrate having a concave portion or formed a surface of the interlayer insulating film on the substrate; and the conductor film is made of copper or a copper alloy, and is formed on the surface of the barrier film of the 200818299 to bury the recess; the honing liquid system has the following Barrier metal film honing speed modifier, amino acid, oxidizing agent and honing particles represented by the formula (I), R1 - CH2 - S03H Formula (I) (In the formula (I), R1 represents Η , CH3, or NH2). <2> The honing method according to <1>, wherein the ratio of the honing speed adjusting agent to the aforesaid oxane acid is (honing speed g-leveling agent) · (amino acid) = 3 The honing method of <1> or <2>, wherein the aforementioned amino acid is a compound represented by the following formula (II), R3 R5

Hooe-R—e-N 通式（11)Hooe-R-e-N general formula (11)

R4 VR4 V

[通式（π)中，R2係表示單鍵、伸烷基、或伸芳基，R3及R4 Φ 係各自獨立地表不氫原子、鹵素原子、羧基、烷基、環院 基、烯基、炔基或芳基，R5及R6係各自獨立地表示氫原子、 鹵素原子、殘基、院基、或醯基。其中R2係單鍵時，r5 及R6之至少其中一個不爲氫原子]。 &lt;4&gt;如&lt;1&gt;至&lt;3&gt;中任〜項之硏磨方法，其中前述氧化劑係 過氧化氫液體。. &lt;5&gt;如&lt;1&gt;至&lt;4&gt;中任一項之硏磨方法，其中前述硏磨液的 pH爲5〜8。 .200818299 &lt; 6 &gt;如&lt; 1 &gt;至&lt; 5 &gt;中任一項之硏磨方法，其中前述硏磨粒子 係二氧化矽粒子。 [發明之效果] 依照本發明，能夠提供一種半導體裝置之硏磨方法，能 夠連續地以同一硏磨液進行硏磨具有導體膜及阻障金屬膜 之基板，硏磨後之被硏磨面的平坦性良好、且能夠降低產 生刮傷。 【實施方式】 本發明係一種半導體裝置之硏磨方法，其特徵係連續 地以一種硏磨液進行硏磨阻障金屬膜及導體膜；該阻障金 屬膜係一面地形成在具有凹部之基板或形成於該基板上之 層間絕緣膜的表面；而該導體膜係由銅或銅合金所構成， 形成於該阻障金屬膜的表面用以將前述凹部塡埋；上述硏 磨液係含有下述通式（I)所示之阻障金屬膜硏磨速度調整 劑、胺基酸、氧化劑及硏磨粒子， R1 — CH2— S03H 通式（I) 通式（I)中，R1係表示H、CH3、或NH2。 首先，說明在本發明的硏磨方法適合使用之硏磨液’ 接著說明本發明的硏磨方法，但是未限定於此等。 [硏磨液] 本發明之硏磨液含有成分（1)下述通式（0所示之阻障金 屬膜硏磨速度調整劑、成分（2)胺基酸、成分（3)氧化劑、及 成分（4)硏磨粒子， 200818299 R1 - CH2— S03H 通式（I) 通式（I)中，R1係表示H、CH3、或NH2。 在本發明之硏磨液，其特徵係含有前述成分（1)〜（4) 作爲必要成分。通常含有水而構成。在本發明之硏磨液亦 可按照需要更含有其他的成分。較佳之其他成分可舉出作 爲鈍態膜形成劑添加之化合物（雜環化合物等）、界面活性 劑及/或親水性聚合物、酸、鹼、緩衝劑等添加劑。 • 前述硏磨液所含有之上述各成分（必要成分及任意成 分）可單獨使用1種，亦可並用2種以上。 又，在本發明，「硏磨液」係指不只是使用於硏磨時 之硏磨液，亦包含硏磨液之濃縮液。濃縮液係指使用於硏 磨時以水或水溶液等稀釋而使用於硏磨之，稀釋倍率通常 爲1〜20體積倍。 · 以下，說明各構成成分。 &lt;成分（1):硏磨速度調整劑&gt; 本發明之硏磨液含有下述通式（I)所示之阻障金屬膜 硏磨速度調整劑。藉由在本發明的硏磨液含有下述通式（I) 所示之化合物，不只是能夠提升對Ta等阻障金屬膜（一面 地形成在具有凹部之基板或形成於詨基板上之層間絕緣膜 的表面）之硏磨速度，且能夠使導體膜與阻障金屬膜之選擇 比（導體膜/阻障金屬膜）最適化， R1 — CH2 — S03H -通式（I) 200818299 通式（I)中，R1係表示Η、CH3、或NH2。 硏磨速度調整劑可舉出例如通式（1)所示之甲基磺 酸、乙基磺酸、胺基甲磺酸等。其中’從減小導體膜與阻 障金屬膜的硏磨速度選擇比（導體膜/阻障金屬膜）之觀點’ 以胺基甲磺酸爲特佳。 通式（I)所示之化合物的合成方法’沒有特別限制，能 夠藉由眾所周知的方法。又，通式（1)所示之化合物亦可使 用市售品。 Φ 阻障金屬膜與導體膜的硏磨速度選擇比（以下，簡稱 「選擇比」），未添加本發明之成分（1)時，（導體膜/阻障金 屬膜）=4 0 0〜5 0 0左右。相對地，每1升硏磨液在〇 . 〇 3 〇莫 耳〜〇. 5 0 8莫耳的範圍添加本發明之硏磨速度調整劑時，選 擇比成爲1 〇〜1 〇 〇。又，進行使硏磨速度調整劑的濃度最 適化時，能夠成爲更佳態樣。藉由每1升硏磨液在0.127 莫耳〜0.2 5 4莫耳的範圍添加本發明之硏磨速度調整劑 時，選擇比成爲1 〇〜20。更佳之態樣係每1升硏磨液在 ® 0.1 2 7莫耳〜0.2 5 4莫耳的範圍添加本發明之硏磨速度調整 劑，且在硏磨液添加下述通式（II)所示之化合物作爲成分 (2)之胺基酸時，選擇比成爲10〜18。 &lt;成分(2):胺基酸&gt; 本發明之硏磨液含有胺基酸來顯示促進氧化、調整 p Η、及作爲緩衝劑之作用。以下詳述胺基酸。 胺基酸以選自以下群組之物爲更佳。 甘胺酸、L-丙胺酸、/3 -丙胺酸、L-2-胺基丁酸、L- 200818299 戊胺酸、L-纈胺酸、L-白胺酸、L-正白胺酸、L_異白胺酸、 L·別白胺酸、L-苯基丙胺酸、脯胺酸、肌胺酸、L-鳥胺 酸、L-離胺酸、牛胺酸、l·絲胺酸、L-蘇胺酸、L-別蘇胺 酸、L-高絲胺酸、L-酪胺酸、3,5_二碘-L-酪胺酸、θ -(3,4-二羥基苯基）-L_丙胺酸、L•甲狀腺素、4·羥基-^脯胺酸、 L-半胱胺酸、L-甲硫胺酸、L_乙硫胺酸、L-半毛硫胺酸、 L-胱硫醚、L-胱胺酸、L·磺基丙胺酸、天冬胺酸、l-麩 胺酸、S-(羧基甲基半胱胺酸、4-胺基丁酸、L-天冬醯 ® 胺酸、L -麩醯胺酸、氮絲胺酸、L -精胺酸、L _刀豆胺酸、 L-瓜胺酸、5 -羥基-L-離胺酸、肌酸、L-犬尿素、L-組胺酸、 1 -甲基· L -組胺酸、3 -甲基_ L -組胺酸、麥角硫醇、L -色胺酸、 放線菌素C1、蜂毒明肽（apmin)、高血壓蛋白寧、高血壓蛋 白寧II、抗木瓜酶等。 又，在本發明，前述胺基酸中，以使用下述通式（11) 所示之化合物爲特佳。藉由在本發.明之硏磨液添加下述通 式（II)所示之化合物及前述通式⑴所示之化合物，能夠將 ^ 導體膜與阻障金屬膜的選擇比（導體膜/阻障金屬膜）最適 化。以下說明通式（II)所示之化合物。 f /R5 HOOC-R2-G~N 通式（II) R4 R6 R係表不卓鍵、伸院基、或伸芳基。 R3及R4係各自獨立地表示氫原子、鹵素原子、羧基、 院基、環院基、烯基.、炔基或芳基。 -14- 200818299 R5及R6係各自獨立地表示氫原子、鹵素原子、羧基、 烷基、或醯基。 其中R2係單鍵時，R5及R6之至少其中一個不爲氫原 子。 在通式（Π)，R2之伸烷基可以是直鏈狀、分枝狀、及 環狀中任一者，較佳係碳數1〜8，可舉出例如亞甲基、伸 乙基。伸烷基之可以具有的取代基，可舉出羥基、鹵素原 子等。 • 在通式（II)，R3及R4之伸烷基以碳數1〜8爲佳，可 舉出例如甲基、丙基等。 在通式（Π)，R3及R4之環烷基以碳數5〜15爲佳，可 舉出例如環戊基、環己基、環辛基。 在通式（II)，R3及R4之烯基以碳數2〜9爲佳，可舉 出例如乙烯基、丙烯基、烯丙基。 在通式（Π)，R3及R4之炔基以碳數2〜9爲佳，可舉 出例如乙炔基、丙炔基、丁炔基。 • 在通式（II)，R3及R4之芳基以碳數6〜15爲佳，可舉 出例如苯基。 在此等基之伸烷基鏈中，亦可具有氧原子、硫原子等 雜原子。 在通式（II)，R3及R4之各基可以具有的取代基，可舉 出羥基、鹵素原子、芳香環（較佳是碳數3〜15)、羧基、胺 基等。 在通式（II)，R5及R6之烷基以碳數1〜8爲佳，可舉 200818299 出例如甲基、乙基等。 醯基以碳數2〜9爲佳，可舉出例如甲基碳基。 在通式（Π)，R5及R6之各基可以具有的取代基，可舉 出羥基、胺基、鹵素原子。 在通式（II)，較佳是R5及R6之至少其中一個不爲氫 原子。 又，在通式（II)，以R2爲單鍵、R3及R5爲氫原子爲 特佳。此時，R4係表示氫原子、鹵素原子、羧基、烷基、 ^ 環烷基、烯基、炔基或芳基，以氫原子、烷基爲特佳。R6 係表示氫原子、鹵素原子、羧基、烷基、或醯基，以烷基 爲特佳。R3之烷基可以具有的取代基，以羥基、羧基或胺 基爲佳。R5之烷基可以具有的取代基，以羥基、或胺基爲 佳。 以下顯不通式（II)所示化合物之具體例，未限定於此 等。 m f /R5 響 HOOG~~R2—G—N、 通式（ιι) R4 R6 16- 200818299 [表1][In the formula (π), R2 represents a single bond, an alkylene group, or an extended aryl group, and R3 and R4 Φ each independently represent a hydrogen atom, a halogen atom, a carboxyl group, an alkyl group, a ring-based group, an alkenyl group, An alkynyl group or an aryl group, each of R5 and R6 independently represents a hydrogen atom, a halogen atom, a residue, a deutero group, or a fluorenyl group. When R2 is a single bond, at least one of r5 and R6 is not a hydrogen atom]. The method of honing according to any one of <1> to <3> wherein the oxidizing agent is a hydrogen peroxide liquid. The honing method according to any one of <1> to <4>, wherein the honing liquid has a pH of 5 to 8. The method of honing according to any one of <1>, wherein the honing particles are cerium oxide particles. [Effects of the Invention] According to the present invention, it is possible to provide a honing method for a semiconductor device, which can continuously honing a substrate having a conductor film and a barrier metal film with the same honing liquid, and honing the surface to be honed The flatness is good and the scratch can be reduced. [Embodiment] The present invention is a honing method for a semiconductor device, characterized in that a barrier metal film and a conductor film are continuously honed with a honing liquid; the barrier metal film is formed on one side of a substrate having a concave portion Or a surface of the interlayer insulating film formed on the substrate; and the conductor film is made of copper or a copper alloy, and is formed on a surface of the barrier metal film for burying the recess; the honing liquid system is contained The barrier metal film honing speed modifier, amino acid, oxidizing agent and honing particles represented by the general formula (I), R1 - CH2 - S03H Formula (I) In the formula (I), R1 represents H , CH3, or NH2. First, the honing liquid suitable for use in the honing method of the present invention will be described. Next, the honing method of the present invention will be described, but it is not limited thereto. [Mulching liquid] The honing liquid of the present invention contains the component (1) a barrier metal film honing speed adjusting agent represented by the following formula (0), a component (2) amino acid, a component (3) oxidizing agent, and Component (4) honing particles, 200818299 R1 - CH2 - S03H Formula (I) In the formula (I), R1 represents H, CH3 or NH2. The honing fluid of the present invention is characterized by containing the aforementioned components. (1) to (4) are essential components and usually contain water. The honing liquid of the present invention may further contain other components as needed. Preferred examples of the other components include compounds added as a passive film forming agent. Additives such as (heterocyclic compound, etc.), surfactant, and/or hydrophilic polymer, acid, alkali, buffer, etc. • The above components (essential components and optional components) contained in the honing fluid may be used alone. In the present invention, the term "honing fluid" means not only the honing liquid used in honing but also the concentrated liquid of the honing liquid. The concentrated liquid is used for honing. When it is diluted with water or an aqueous solution, it is used for honing, and the dilution ratio is usually 1 to 20 times the volume. The following is a description of each component. <Component (1): honing speed adjusting agent&gt; The honing liquid of the present invention contains a barrier metal film represented by the following formula (I). The tempering agent of the present invention contains a compound represented by the following formula (I), and it is possible to enhance not only a barrier metal film such as Ta but also a substrate formed on a concave portion or formed on the substrate The honing speed of the surface of the interlayer insulating film on the substrate, and the selection ratio of the conductor film to the barrier metal film (conductor film/barrier metal film) can be optimized, R1 - CH2 - S03H - general formula (I In the formula (I), R1 represents hydrazine, CH3, or NH2. The honing speed adjusting agent may, for example, be a methanesulfonic acid, an ethylsulfonic acid or an amine methylsulfonate represented by the general formula (1). Acid or the like. Among them, 'from the viewpoint of reducing the honing speed selection ratio (conductor film/barrier metal film) of the conductor film and the barrier metal film, it is particularly preferable to use an aminomethanesulfonic acid. The formula (I) is shown. The method for synthesizing the compound 'is not particularly limited and can be carried out by a well-known method. Further, it is represented by the formula (1) Commercially available products can also be used. Φ The ratio of honing speed of the barrier metal film to the conductor film (hereinafter referred to as "selection ratio"), when the component (1) of the present invention is not added, (conductor film / barrier metal) Membrane)=4 0 0~5 0 0. Relatively, every 1 liter of honing liquid is in the range of 〇. 〇3 〇莫耳~〇. 5 0 8 moles when adding the honing speed modifier of the present invention, The selection ratio becomes 1 〇~1 〇〇. Further, when the concentration of the honing speed adjusting agent is optimized, it can be a better aspect. By using 1 liter of honing liquid at 0.127 mm to 0.25 4 m When the honing speed adjusting agent of the present invention is added in the range, the selection ratio becomes 1 〇 20-20. In a better aspect, the honing speed adjusting agent of the present invention is added per liter of the honing liquid in the range of 0.1 0.17 mol to 0.25 4 mol, and the following formula (II) is added to the honing fluid. When the compound is shown as the amino acid of the component (2), the selection ratio is 10 to 18. &lt;Component (2): Amino acid&gt; The honing liquid of the present invention contains an amino acid to exhibit an effect of promoting oxidation, adjusting p Η, and acting as a buffer. The amino acid is detailed below. The amino acid is more preferably selected from the group consisting of the following. Glycine, L-alanine, /3-alanine, L-2-aminobutyric acid, L-200818299 glutamic acid, L-proline, L-leucine, L-positive, L-isoleucine, L. leucine, L-phenylalanine, valine, sarcosine, L-ornithine, L-lysine, uric acid, l-serine , L-threonine, L-beuric acid, L-homoserine, L-tyrosine, 3,5-diiodo-L-tyrosine, θ-(3,4-dihydroxyphenyl )-L_alanine, L•thyroxine, 4·hydroxy-^proline, L-cysteine, L-methionine, L-ethylthioacetate, L-half-methionine, L-cystathionine, L-cystine, L. sulfoalanine, aspartic acid, l-glutamic acid, S-(carboxymethylcysteine, 4-aminobutyric acid, L- Aspartame® Aminic acid, L-glutamic acid, Azlactone, L-arginine, L-cutosin, L-citrulline, 5-hydroxy-L-lysine, Creatine , L-canine urea, L-histamine, 1-methyl·L-histidine, 3-methyl-L-histidine, ergothiol, L-tryptophan, actinomycin C1 Bee venom peptide (apmin), hypertension protein, hypertension protein II, anti-papaya enzyme, etc. In the present invention, the amino acid represented by the following formula (11) is particularly preferred. The compound represented by the following formula (II) is added to the honing liquid of the present invention. The compound represented by the above formula (1) can optimize the selection ratio (conductor film/barrier metal film) of the conductor film and the barrier metal film. The compound represented by the formula (II) will be described below. f /R5 HOOC -R2-G~N General formula (II) R4 R6 R series represents a bond, a stretching group, or an aryl group. R3 and R4 each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a yard, and a ring. a group, an alkenyl group, an alkynyl group or an aryl group. -14- 200818299 R5 and R6 each independently represent a hydrogen atom, a halogen atom, a carboxyl group, an alkyl group, or a fluorenyl group. In the case where R2 is a single bond, R5 and R6 are At least one of them is not a hydrogen atom. In the formula (Π), the alkyl group of R2 may be any of a linear chain, a branched chain, and a cyclic group, and preferably has a carbon number of 1 to 8, and may be exemplified. For example, a methylene group and an ethyl group may be mentioned. Examples of the substituent which the alkyl group may have include a hydroxyl group, a halogen atom, etc. • In the formula (II), R3 and R4 are alkyl groups. The number of carbon atoms is preferably from 1 to 8, and examples thereof include a methyl group and a propyl group. The cycloalkyl group of R3 and R4 is preferably a carbon number of 5 to 15, and examples thereof include a cyclopentyl group. In the formula (II), the alkenyl group of R3 and R4 is preferably a carbon number of 2 to 9, and examples thereof include a vinyl group, a propenyl group, and an allyl group. The alkynyl group of R3 and R4 is preferably a carbon number of 2 to 9, and examples thereof include an ethynyl group, a propynyl group and a butynyl group. • In the formula (II), the aryl group of R3 and R4 has a carbon number of 6 to 15 Preferably, for example, a phenyl group is mentioned. The alkyl chain of these groups may have a hetero atom such as an oxygen atom or a sulfur atom. The substituent which the respective groups of the formula (II) and R3 and R4 may have include a hydroxyl group, a halogen atom, an aromatic ring (preferably having a carbon number of 3 to 15), a carboxyl group, an amine group and the like. The alkyl group of the formula (II), R5 and R6 is preferably a carbon number of 1 to 8, and examples thereof include, for example, a methyl group and an ethyl group. The mercapto group is preferably a carbon number of 2 to 9, and examples thereof include a methyl carbon group. The substituent which the respective groups of R5 and R6 may have in the general formula (Π) may, for example, be a hydroxyl group, an amine group or a halogen atom. In the formula (II), preferably at least one of R5 and R6 is not a hydrogen atom. Further, in the formula (II), it is particularly preferable that R2 is a single bond and R3 and R5 are a hydrogen atom. In this case, R4 represents a hydrogen atom, a halogen atom, a carboxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group or an aryl group, and is particularly preferably a hydrogen atom or an alkyl group. R6 represents a hydrogen atom, a halogen atom, a carboxyl group, an alkyl group or a mercapto group, and is particularly preferably an alkyl group. The alkyl group of R3 may have a substituent, preferably a hydroxyl group, a carboxyl group or an amine group. The substituent which the alkyl group of R5 may have is preferably a hydroxyl group or an amine group. Specific examples of the compound represented by the formula (II) are not limited thereto. m f /R5 ring HOOG~~R2—G—N, general formula (ιι) R4 R6 16- 200818299 [Table 1]

R2 R3 R4 R5 R6 A-l - -Η -Η -H -ch3 A-2 • -Η -Η -H -CH2OH A-3 - -Η -Η -CH2OH -CH2OH A-4 - -Η -Η -H -CH2CH2OH A-5 -Η -Η -CH2CH2OH -CH2CH2OH A-6 一 -Η -ch3 -H -CH2OH A-7 - -Η -ch3 -CH2CH2OH -ch2ch2oh A-8 麵 -Η -ch2oh -H -ch2oh A-9 -Η -ch2(ch3)2 -CH2OH -ch2oh A· 10 - -Η -Ph -H -(CH2CH20)2-H A-ll - -Η H -CH2CH2OH -ch2ch2oh A-12 • -Η -CH2SCH3 -CH2CH2OH -ch2ch2oh A-13 -Η -H -H -COCH2NH2 A-14 丨 -Η -CH2OH -H -COCH2NH2 A-15 篇 -Η -H -H -COCH3 A-16 -ch2- -Η -H -CH2CH2OH -ch2ch2oh A-17 -ch2- -Η -H -H -ch2oh A-18 -ch2- -Η -H -H -COCH2NH2 A-19 -CH2CH2- -Η -H -H -H A-20 一 -Η -ch3 -H -ch2ch2oh A-21 爾 -Η -ch3 -H -ch2oh A-22 釋 -Η -CH2CH3 _H -CH2CH20H A-23 两 -Η -ch3 -H -CH2OH A-24 • -Η -ch3 -H -COCH2NH2 A-25 • -Η -CH2(CH3)2 -H -CH2CH20H A-26 -Η 苯基 -H -CH2CH20H A-27 -Η -H -H -(CH2)3OH 200818299 通式（II)所示之化合物的合成方法沒有特別限制’能 夠藉由眾所周知的方法合成。又，通式（II)所示之化合物亦 可使用市售品。 爲了使導體膜與阻障金屬膜的選擇比（導體膜/阻障金 屬膜）最適化，本發明之胺基酸之含有比與前述硏磨速度調 整劑之莫耳比，係硏磨速度調整劑：胺基酸=3 : 1〜8 : 1 爲佳，以4 : 1〜5 ·· 1爲更佳。 &lt;成分（3):氧化劑&gt; Φ 在本發明之硏磨液含有氧化劑（能夠氧化硏磨對象之 化合物）。 氧化劑可舉出例如過氧化氫、過氧化物、硝酸鹽、碘 酸鹽、過碘酸鹽、次氯酸鹽、亞氯酸鹽、氯酸鹽、過氯酸 鹽、過硫酸鹽、重鉻酸鹽、過錳酸鹽、臭氧水、及銀（II) 鹽、鐵（III)鹽。鐵（III)鹽除了使用例如硝酸鐵（III)、氯化 鐵（in)、硫酸鐵（III)、溴化鐵（III)等無機鐵（III)鹽以外， 以使用鐵（III)的有機錯鹽爲佳。 ® 前述氧化劑之中，以過氧化氫、過硫酸鹽、和鐵（III) 的伸乙二胺-^&gt;1’，：^’-四乙酸、1，3-二胺基丙烷-1^，1^少，，]^，-四乙酸、及伸乙二胺二琥珀酸（SS體）的錯合物爲最佳。 相對於硏磨液，氧化劑的添加量以在〇 · 〇 〇 3〜8莫耳/ 升的範圍爲佳，以在0 · 0 3〜6莫耳/升的範圍爲更佳，以在 〇 . 1〜1 · 5莫耳/升的範圍爲特佳。亦即，從金屬充分氧化且 確保高CMP速度而言，氧化劑的添加量以〇.〇〇3莫耳/升以 上爲佳，從防止硏磨面粗糙而言，以8莫耳/升以下爲佳。 -1 8 - 200818299 在使用硏磨液進行硏磨時’氧化劑以混合含有氧化劑 以外的其他成分之組成物而使用爲佳。混合氧化劑之時期 以即將使用硏磨液之前1小時以內爲佳，以5分鐘以內爲 更佳，以在硏磨裝置之即將供給硏磨液處設置混合器，在 即將供給至被硏磨面之前5秒內進行混合爲特佳。 &lt;成分（4):硏磨粒子&gt; 本發明之硏磨液含有硏磨粒子。 硏磨粒子可以是二氧化砂、氧化銘、鈽氧、二氧化欽、 φ 氧化锆、鍺、碳化矽等無機物粒子、聚苯乙烯、聚丙烯酸、 聚氯乙烯等有機粒子中任一者。其中以選自二氧化矽、氧 化鋁、鈽氧、二氧化鈦、氧化锆及鍺中之至少1種粒子爲 佳，因爲在硏磨液中的分散安定性良好、CMP所產生硏磨 傷（刮傷）的產生次數少，以二氧化矽粒子（沈降二氧化矽、 霧狀二氧化矽、膠體二氧化矽、合成二氧化矽）爲佳。因爲 對含銅金屬之硏磨速度高，二氧化矽粒子以膠體二氧化矽 或霧狀二氧化矽爲佳，以膠體二氧化矽爲更佳。 ® 又，在本發明之硏磨液所含有的硏磨粒子，較佳是藉 由動態光散射法所求得的體積平均粒徑係在2 5〜7 0奈米 範圍的粒子。 前述粒子的體積平均粒徑係藉由動態光散射法求 得。具體上能夠藉由採用動態光散射法之粒度分布測定裝 置（堀場製作所公司製、LB- 5 0 0)來測定。 前述膠體二氧化矽能夠藉由已被熟悉的製法得到。金 屬氧化物的濕式製法係例如以金屬烷氧化物作爲起始物 -19- 200818299 質，藉由使其加水分解之方法而得到膠體二氧化砂’具體 上能夠在混合醇而成的驗水溶液中以某一規定速度滴加正 砂酸甲酯來使其產生加水分解經由粒成長時期及藉由淬熄 劑停止粒成長的時期來製造。此外’亦可使用銘或纟太等的 烷氧化物來製造膠體粒子。此時’通常加水分解速度比使 用二氧化矽烷氧化物更快’能夠順地製造超微細粒子。 又，金屬氧化物的乾式製法能夠藉由將金屬的氯化物 導入氫氧火焰中，藉由使該已脫氯化的金屬氧化能夠得霧 • 狀粒子。而且，將欲含有在目標物質之金屬或合金粉碎成 粉體，投入含有自燃性氣體之氧火焰中，藉由金屬的氧化 熱使其產生連續反應，來得到微細的氧化物粒子之方法亦 已實用化。藉由此等燃燒法所製造的粒子’因爲曝露在高 溫後急冷卻，所以粒子非晶化，又，與濕式粒子比較時’ 因爲在內部之羥基等雜質少，其特徵係通常固體密度高' 且表面的羥基密度亦低。 相對於使用時之硏磨液，硏磨粒子的添加量以在 馨 0.0 0 0 1〜5質量％的範圍爲佳，以在0 . 1〜2.0質量％的範圍 爲更佳。爲了得到提高硏磨速度、及降低在晶圓面內之硏 磨速度的不均之充分效果，以0.000 1質量％以上爲佳’因 爲使用CMP之硏磨速度飽和，以5質量％以下爲佳。 &lt;硏磨液的pH&gt; 在本發明之硏磨液的pH爲2以上，以pH爲2〜10 的範圍爲佳，以pH爲5〜8的範圍爲更佳。藉由在此範圍’ 本發明之硏磨液能夠發揮特別優良的效果。本發明之硏磨 -20- 200818299 液在硏磨時，可以是未含水之形態，亦可以是藉由水或水 溶液稀釋。又，藉由水或水溶液稀釋時，本發明之P Η係表 示使用水或水溶液稀釋後的値。 本發明之硏磨液的pH能夠考慮對硏磨面的吸附性或 反應性、硏磨金屬的溶解性、被硏磨面的電化學性質、化 合物官能基的解離狀態、作爲液體之安定性等而設定。 pH係例如添加後述的鹼劑，並藉由添加成分（2)以外 的酸、緩衝劑等來進行調整。 • &lt;其他成分&gt; -雜環化合物- 本發明之硏磨液以含有用以在硏磨對象的金屬表面 形成鈍態膜之雜環化合物爲佳。 [雜環化合物]係指具有含有雜原子之化合物。 具有雜環之化合物所含有雜原子之數目沒有限定，以 2個以上爲佳，以含有4個以上之雜原子爲更佳。特別是 使用含有3個以上氮原子之雜環化合物爲佳，使用含有4 個以上葱j原子之雑環化合物時，能夠發揮本發明的顯著效 果，乃是較佳。 又’雜環可以是單環亦可以是具有稠環之多環。單環 日寸之貝數以5〜7爲佳’以5爲特佳。具有稠環時之環數以 2或3爲佳。 此等雜環具體上可舉出以下之物。 吡咯環、噻吩環、呋喃環、吡喃環、噻吡喃環、咪唑 環、吡唑環、噻唑環、異噻唑環、曙唑環、異噚哩環、啦 200818299 D定環、啦阱環、嘧啶環、嗒阱環、吡咯啶環、吡唑啶環、 咪哩D定環、異噚唑啶環、異噻唑啶環、哌啶環、哌阱環、 味啉環、噻味啉環、色滿環、噻色滿環、異色滿環、異噻 色滿環、吲哚滿環、異吲哚滿環、4-氮茚（pyrindine)、吲 哚哄環、吲哚環、吲唑環、嘌呤環、喹啉啶（quinolidine)、 異喹啉環、喹啉環、萘啶環、酞阱環、喹曙啉環、喹唑啉 環、啐啉環、喋啶環、吖啶環、咱啶環、啡啉環、咔唑環、 咔'咐、啡哄環、葱任D定（a n t h y r i d i n e)、噻二D坐環、噚二D坐、 • 三哄環、三唑環、四唑環、苯并咪唑環、苯并噚唑環、苯 并噻唑環、苯并N -氧化噚二唑環、萘并咪唑環、苯并三唑 環、四氮雜茚環。 能夠導入本發明所使用的雜環化合物之取代基可舉 出例如以下之物。 雜環能夠具有之取代基，可舉出例如鹵素原子、烷基 (可以是直鏈狀、分枝或環狀的烷基，亦可以是如雙環烷基 之多環烷基，亦可含有活性次甲基）、烯基、炔基、芳基、 ^ 胺基、雜環基等。而且，亦可以是複數個取代基之中2個 以上互相結合而形成環，例如亦可形成芳香環、脂肪族烴 環、雜環等。 在本發明，特別適合使用之雜環化合物的具體例可舉 出例如以下之物，但是未限定於此等。 亦即，1，2,3,4-四唑、5-胺基-1,2,3,4-四唑、5-甲基 -1，2，3，4 -四唑、1，2，3 -三唑、4 -胺基-1，2，3 -三唑、4，5 -二胺 基-1，2,3-三唑、1，2,4-三唑、3 -胺基-1，2,4-三唑、3,5-二胺 -22- 200818299 基-1，2，4 -三唑、苯并三唑。 本發明所使用之雜環化合物可單獨使用 種以上。又，本發明所使用之雜環化合物除 用方法來合成以外，亦可用市售品。 本發明所使用之雜環化合物的添加量之 於硏磨時之1升硏磨液（亦即，使用水或水溶 釋後的硏磨液）中，以 〇 · 〇 〇 〇 1〜1 · 〇莫耳的 0.0005〜0.5莫耳的範圍爲較佳，以〇.〇 005〜 Φ 圍爲更佳。 -界面活性劑及/或親水性聚合物- 本發明所使用的硏磨液以含有界面活 聚合物爲佳。 界面活性劑及親水性聚合物任一者都 磨面的接觸角之作用，且具有促進均勻的硏 夠使用之界面活性劑或親水性聚合物，以選 物爲佳。 # 陰離子界面活性劑可舉出羧酸鹽、磺 鹽、磷酸酯鹽，陽離子界面活性劑可舉出月旨 肪族4級銨鹽、氯化苄烷銨、氯化苄乙氧每 咪唑鑰鹽，兩性界面活性劑可舉出羧基甜菜 酸鹽、咪唑鑰甜菜鹼、卵磷脂、氧化烷基胺 活性劑可舉出醚型、酯醚型、酯型、含氮型 出氟系界面活性劑等。 而且，親水性聚合物可舉出聚乙二醇_ ’亦可並用2 了能夠依照常 總量，在使用 液稀釋時係稀 範圍爲佳，以 〇 . 〇 5莫耳的範 性劑或親水性 具有降低被硏 磨之作用。能 自以下群組之 酸鹽、硫酸酯 肪族胺鹽、脂 :、吡啶鑰鹽、 :鹼型、胺基羧 :，非離子界面 :，又，亦可舉 ，聚甘醇類、聚 -23- 200818299 乙烯醇、聚乙烯基吡咯啶酮、海藻酸等多糖類、聚甲基丙 烯酸等含羧酸之聚合物等。 上述之物，因爲不會產生鹼金屬、鹼土類金屬、鹵化 物等所造成的污物，以酸或其銨鹽爲佳。上述例示化合物 之中，以環己醇、聚丙烯酸銨鹽、聚乙烯醇、琥珀醯胺、 聚乙烯基吡咯啶酮、聚乙二醇、聚氧乙烯聚氧丙烯類嵌段 聚合物爲更佳。 此等界面活性劑或親水性聚合物的重量平均分子量 φ 以500〜100000爲佳，以2000〜50000爲特佳。 界面活性劑及/或親水性聚合物的添加量之總量’在使 用於硏磨時之1升硏磨液中，以0.001〜10克爲佳，以〇.〇1 〜5克爲更佳，以0.1〜3克爲特佳。 -鉗合劑、鹼、緩衝劑- 在本發明，以更添加鉗合劑、鹼、及緩衝劑爲佳。以 下說明本發明能夠使用之鉗合劑、鹼、及緩衝劑。 (鉗合劑） φ 在本發明之硏磨液，爲了防止混入的多價金屬離子等 之不良影響，以按照必要含有鉗合劑（亦即硬水軟化劑）爲 佳。 鉗合劑係鈣或鎂的防沈澱劑之泛用硬水軟化劑或其 類似化合物，可舉出例如氰基三乙酸、二伸乙三胺五乙酸、 伸乙二胺四乙酸、N，N，N-三亞甲基磺酸、伸乙二胺 -N，N，N’-N’-四亞甲基磺酸、反式環己二胺四乙酸、L2-二 胺基丙烷四乙酸、乙二醇醚二胺四乙酸、伸乙二胺鄰羥基 苯基乙酸、伸乙二胺二琥珀酸（SS體）、Ν_(2·羧酸酯乙基）-L- -24- 200818299 天冬胺酸、A -丙胺酸二乙酸、2 -膦酸基丁院_ i 酸、1-經基亞乙基-1，1-二磺酸、N，N，-雙（2-經基： 二胺-N，N’-二乙酸、1，2-二羥基苯-4,6·二磺酸等&lt; 鉗合劑亦可按照必要並用2種以上。 紺合劑的添加量係若是能夠封鎖混入之多 子等金屬離子之充分量時即可，例如，在使用於 1升硏磨液中，能夠以0 · 0 〇 〇 3莫耳〜〇 . 〇 7莫耳的 法添加。 # (鹼劑、緩衝劑） 又，在本發明之硏磨液，爲了調整ρ Η，可涛 且從抑制pH的變動而言，可以含有緩衝劑。 鹼劑及緩衝劑能夠使用氫氧化銨及氫氧化 有機氫氧化銨、如二甲醇胺、三乙醇胺、三異丙 烷醇胺類等的非金屬鹼劑、氫氧化鈉、氫氧化鉀 鋰等鹼金屬氫氧化物、碳酸鹽、磷酸鹽、硼酸鹽 鹽、羥基苯甲酸鹽、甘胺醯鹽、N，N-二甲基甘胺 ® 胺酸鹽、正白胺酸鹽、鳥嘌呤鹽、3,4-三羥苯基？ 丙胺酸鹽、胺基丁酸鹽、2-胺基-2-甲基-1，3-丙傷 纈胺酸鹽、脯胺酸鹽、三羥基胺基甲烷鹽、離胺 鹼劑及緩衝劑的具體例，可舉出氨、氫氧伯 化鉀、氫氧化鋰、碳酸鈉、碳酸鉀、重碳酸鈉、I 磷酸三鈉、磷酸三鉀、磷酸二鈉、磷酸二鉀、硼 酸鉀、四硼鈉（硼砂）、四硼酸鉀、鄰羥基苯甲酸鈉 鄰羥基苯甲酸鉀、5-磺酸基-2-羥基苯甲酸鈉（5-¾ ，2,4-三羧 斧基）伸乙 t 價金屬離 硏磨時之 範圍之方 〖加鹼劑， 四甲銨等 醇胺等的 、氫氧化 、四硼酸 醯鹽、白 ί胺酸鹽、 [二醇鹽、 酸鹽等。 :鈉、氫氧 I碳酸鉀、 丨酸鈉、硼 (柳酸鈉）、 I酸基柳酸 -25- 200818299 鈉）、5-磺酸基-2-羥基苯甲酸鉀（5_磺酸基柳酸鉀）、氫氧化 銨等。 牛寸佳之驗劑有氫氧化鏡、氫氧化鉀、氫氧化鋰及氫氧 化四甲銨。 鹼及緩衝劑的添加量，若能夠維持pH在較佳範圍時 之重即可’在使用於硏磨時之1升硏磨液中，以0.0001莫 耳〜1 · 〇莫耳的範圍爲佳，以〇 · 〇 〇 3莫耳〜〇 · 5莫耳的範圍 爲更佳。 ® 在本發明，從液體的流動性或硏磨性能的安定性等而 言，硏磨液的比重以0.8〜1 . 5的範圍爲佳，以在0 · 9 5〜1 . 3 5 的範圍爲特佳。 [硏磨方法] 本發明的硏磨方法其特徵係以導體膜側的面作爲被 硏磨面來硏磨阻障金屬膜及導體膜之硏磨方法；該阻障金 屬膜係一面地形成在具有凹部之基板或形成於該基板上之 層間絕緣膜的表面；而該導體膜係由銅及/或銅合金所構 ^ 成’形成於該阻障金屬膜的表面用以將前述凹部塡埋；前 述硏磨液連續地以一種硏磨液進行硏磨。 亦即，本發明的硏磨方法係能夠使用1種類的硏磨 液，進行化學機械硏磨在絕緣膜的前述凹部以外的表面製 膜而成之凸狀突出的導體膜後，繼續使用同一硏磨液連續 地硏磨導體膜的殘膜及阻障金屬膜之化學機械硏磨方法’ 此種硏磨液，係使用本發明之硏磨液。 在本發明的硏磨方法所使用之硏磨液，可以是濃縮 -26- 200818299 液’在使用時添加水來而稀釋作爲使用液之情況；或是各 成分係後述之水溶液形態而將該等混合，必要時添加水稀 釋而使用之情況；或是調製成使用液的情況。本發明之硏 磨液沒有特別限制，在本發明可應用上述任一種態樣。 本發明的硏磨方法，係將硏磨液供給至硏磨轉盤上之 硏磨墊，使其與被硏磨面接觸並使被硏磨面與硏磨墊相對 運動（相對地移動）來進行硏磨之硏磨方法。 硏磨裝置能夠使用具有保持器與硏磨轉盤之通常的 • 硏磨裝置，該保持器係用以保持具有被硏磨面之半導體基 板等；而該硏磨轉盤（安裝有能夠改變旋轉數之馬達等）係 貼有硏磨墊。 、 硏磨墊能夠使用通常的不織布、發泡聚胺基甲酸酯、 多孔質氟樹脂等，沒有特別限制。又，硏磨用的硏磨墊亦 可使用無發泡結構之硏磨墊。前者係將使用如塑膠板之硬 質的合成樹脂塊狀材使用於硏磨墊。後者係進而具有獨立 發泡體（乾式發泡系）、連續發泡體（濕式發泡系）、及2層複 ^ 合體（積層系）之三種，以2層複合體（積層系）爲特佳。發泡 可以均句亦可以不均句。 而且，硏磨墊亦可以是含有使用於硏磨之粒子（例 如’铈氧、二氧化矽、氧化鋁、樹脂等）。 又，硏磨墊之各自的硬度有軟質之物及硬質之物，任 一種都可以，積層系以在各自的層使用不同硬度之物爲 佳。材質以不織布、人工皮革、聚醯胺、聚胺基甲酸酯、 聚酯、聚碳酸酯等爲佳。又，亦可對與硏磨面接觸的面， -27 - 200818299 施加格子槽、孔穴/同心槽/螺旋狀槽等加工。 硏磨條件沒有限制，硏磨轉盤的線速度以1公尺/秒以 上爲佳。 將具有被硏磨面（被硏磨膜）之半導體基板往硏磨墊壓 住時之壓力（加壓壓力），以20kPa以下爲佳，藉由在13kPa 以下的低壓條件下，因爲能夠在維持高硏磨速度狀態，提 升硏磨速度的晶圓面內均勻性及圖案的平坦性，乃是更佳。 又，加壓壓力大於20kPa時，會有平坦性變差之情形。 • 又，加壓壓力的下限沒有特別限制，以2kPa以上爲 佳，以3.5kPa以上爲更佳。 在硏磨期間，使用泵等連續地將硏磨液供給至硏磨 墊。該供給量沒有特別限制，以經常以硏磨液覆硏磨墊的 表面爲佳。硏磨結束後的半導體基板係在流水中充分地洗 淨後，使用旋轉乾燥機等將水滴從半導體基板上拂落後使 其乾燥。 在本發明的硏磨方法，稀釋硏磨液之水溶液係與下述 ®的水溶液相同。 水溶液係使用預先含有氧化劑、酸、添加劑、界面活 性劑中至少1種以上之水’來使在水溶液中所含有的成分 與被稀釋硏磨液的成分之合計成分，成爲使用硏磨液進行 硏磨時之成分。以水溶液稀釋硏磨液而使用時，能夠將不 容易溶解的成分，以水溶液的形式調配，且能夠調製更濃 縮而成的硏磨液。 在濃縮過的硏磨液添加水或水溶液來稀釋的方法，有 -28- 200818299 使供給濃縮過的硏磨液之配管與供給水或水溶液之配管在 途中合流並混合，然後將被混合稀釋的硏磨液供給至硏磨 墊之方法。混合通常可採用使在施加壓力狀態通常狹窄的 通路之液體之間產生衝撞混合之方法；在配管中裝塡玻璃 管等塡充物，來使液體的流動重複地產生分流分離、合流 之方法；及在配管中設置使用動力旋轉之葉片之方法等。 硏磨液的供給速度以10〜1 000毫升/分鐘的範圍爲 佳，爲了滿足硏磨速度的晶圓面內均勻性及圖案的平坦 ♦ 性，以1 7 0〜8 0 0毫升/分鐘的範圍爲更佳。 使用水或水溶液等稀釋濃縮過的硏磨液，來硏磨之方 法，可舉出獨立地設置供給硏磨液的配管及供給水或水溶 液的配管，各自將規定量的液體供給至硏磨墊，並使硏磨 墊與被硏磨面邊藉由相對運動混合、邊硏磨之方法。又， 亦能夠應用在1個容器加入規定量之濃縮過的硏磨液與水 或水溶液，將該混合過的硏磨液混合後供給至硏磨墊，來 進行硏磨之方法。 ® 在本發明’亦可將硏磨液所應含有的成分，分開成爲 至少2個構成成分，在使用此等時，添加水或水溶液來加 以稀釋而供給至硏磨轉盤上的硏磨墊，並使其與被硏磨面 藉由使被硏磨面與硏磨墊相對運動來硏磨之方法 例如，將氧化劑作爲1個構成成分（A )，將添加劑、 界面活性劑及水作爲1個構成成分（B)，在使用此等時使用 水或水溶液來稀釋構成成分（A)及構成成分（B)而使用。 又’將溶解度較低的添加劑分成2個構成成分（c )及 -29 - .200818299 (D) ’將氧化劑、添加劑及界面活性劑作爲i個構成成分 (C)，將酸、添加劑、界面活性劑及水作爲1個構成成分， 在使用此等時添加水或水溶液來稀釋構成成分（c)及構成 成分（D)而使用。 該例子的情況，必須有3個配管用以各自供給構成成 分（C) '構成成分（D)及水或水溶液，稀釋混合有將3個配 管結合於供給至硏磨墊之1個配管，而在該配管內混合之 方法，此時，亦可結合2個配管後，結合其他的1個配管。 例如，有將含有不容易溶解的添加劑之構成成分與其 他的構成成分混合，然後使混合路徑增長確保溶解時間 後，進而結合水或水溶液的配管之方法。 其他的混合方法，可舉出如上述之直接將3個配管各 自引導至硏磨墊，然後藉由硏磨墊與被硏磨面之相對運動 來混合之方法；及在1個容器混合3個構成成分，然後將 稀釋過的硏磨液供給至硏磨墊之方法。在上述之硏磨方 法，亦可使含有氧化劑之1個構成成分在40 °C以下，使其 他的構成成分從室溫加溫至1 〇〇 °C的範圍，且在添加1個 構成成分及其他的構成成分或水或水溶液、稀釋而使用 時，混合後爲40 °C以下。因爲溫度高時溶解度變高，能夠 提高硏磨液之溶解度低的原料之溶解度’乃是較佳。 將未含有氧化劑之其他成分從室溫加溫至1 〇〇°c的範 圍來使其溶解而成的原料，因爲溫度下降時會從溶液中析 出，使用溫度已下降之該成分時’必須預先加溫來使析出 物溶解。這能夠採用輸送已加溫溶解的構成成分液體之手 -30- 200818299 段，及採用預先攪拌含有析出物的液體，然後送液並加溫 配管來使其溶解之手段。加溫過的成分若將含有氧化劑之 1個構成成分的溫度提高至40 °c以上時，因爲氧化劑有分 解的可能性，因此，必須使加溫過的構成成分與冷卻該加 溫過的構成成分之含有氧化劑之1個構成成分混合後的情 況，爲4 0 °C以下。 又，在本發明，亦可如上述將硏磨液的成分，分開成 2個以上而供給至硏磨面。此時，以分開成含有氧化劑之 • 成分、及含有酸的成分爲佳。又，亦可使硏磨液爲濃縮液， 將稀釋水另外供給至硏磨面。 硏磨液的供給方法，能夠區別爲如上述將硏磨液的成 分，分開成2個以上而供給至硏磨面之情況；及使硏磨液 爲濃縮液，將稀釋水另外供給至硏磨面之情況。但是，任 一種硏磨液的供給方法，在本發明都能夠使用1種類的硏 磨液，進行化學機械硏磨在絕緣膜的凸部上製膜而成導體 膜後，繼續使用同一硏磨液連續地硏磨導體膜的殘膜及阻 • 障金屬膜。 藉由本發明的硏磨方法之硏磨對象，係具有在阻障金 屬膜及導體膜之基板；該阻障金屬膜係一面地形成在具有 凹部之層間絕緣膜的表面；而該導體膜係由銅及/或銅合金 所構成，形成於該阻障金屬膜的表面用以將前述凹部塡 埋；該基板係半導體基板，以具有由銅金屬及/或銅合金所 構成的配線之L S I爲佳，以配線係銅合金爲特佳。 而且，在銅合金之中，以含有銀之銅合金爲佳。在銅 -31- 200818299 合金中所含有的銀含量以40質量％以下爲佳，以1 〇質量％ 以下爲較佳，以1質量％以下爲更佳’在0.0 0 0 0 1〜0.1質 量％的範圍之銅合金能夠發揮最優良的效果。 在本發明，硏磨對象之半導體基板例如DRAM裝置 時，半間距以〇. 1 5微米以下爲佳，以ο · 1 〇微米以下爲較佳’ 以0.0 8微米以下爲更佳。另一方面，Μ P U系裝置時’以 0.12微米以下爲佳，以0.09微米以下爲較佳，具有0.07 微米以下的配線之LSI爲更佳。對於此等LSI，藉由使用 ® 本發明之硏磨液，能夠發揮特別優良的效果。 (基板） 本發明所使用的基板之例子，可舉出8英吋、1 2英吋 半導體用晶圓製程、或是微機械製程所使用之物。其種類 包含半導體用矽晶圓或S 01晶圓、亦包含半導體雷射等所 使用之化合物半導體的藍寶石基板等。此外，亦可使用於 在高分子的薄膜基板上形成配線圖案、或平坦化之用途。 本發明之硏磨液進行CMP之對象晶圓，以直徑200 φ 毫米以上爲佳，以3 0 0毫米以上爲特佳。3 0 0毫米以上時 能夠顯著地發揮本發明的效果。 (層間絕緣膜） 本發明的硏磨方法，不只是將基板上的配線平坦化， 亦能夠使用於將多層配線基板平坦化。此時，能夠將形成 在層間絕緣膜上的配線平坦化。本發明之層間絕緣膜係指 形成在前述基板（矽晶圓）上且與後述的阻障金屬膜之間用 以使各層間絕緣之膜。 -32 - 200818299 本發明之層間絕緣膜係若是形成在前述基板上時沒 有特別限定，從有效地達成本發明的效果而言，以二氧化 矽系被膜或有機系被膜爲佳。其中，以二氧化矽系被膜爲 佳。二氧化矽被膜可舉出摻雜碳而成之二氧化矽系被膜、 氟化矽玻璃、矽酸氫鹽類、甲基矽酸鹽類等，以摻雜碳而 成之二氧化矽系被膜爲佳。 在摻雜碳而成之二氧化矽系被膜之碳含量，從降低有 效介電常數的觀點、及從維持絕緣膜本身的機械強度而 _ 言，以2 0質量％〜6 0質量％爲佳，以2 5質量％〜3 5質量％ 爲特佳。 有機系被目吴可舉出聚釀亞胺、聚對二甲苯（pa rylene)、 Teflon(註冊商標）等，以聚醯亞胺爲佳。 又，從能夠有效地達成本發明的效果而言，層間絕緣 膜以具有介電常數爲2.6以下的特性之物爲佳，以2.4〜2 · 5 爲更佳。 本發明之層間絕緣膜以前述較佳例子之組合爲更佳。 垂 又’本發明之層間絕緣膜的厚度能夠按照在多層配線 的上部及下部、或世代間（結點）而適當地調整。 又’形成本發明之層間絕緣膜的厚度方法，可舉出美 國專利（US)第6，440,866號、同第6,410,463號、同第 6,5 96,6 54號等各說明書所記載之方法。 (阻障金屬膜） 阻障金屬膜係指在半導體基板上，設置在由銅及/或銅 合金所構成的導體膜（配線）與層間絕緣膜之間，用以防止 -33- .200818299 銅擴散之膜（層）。 阻障金屬膜的材料以低電阻之金屬材料爲佳，具體I 以含有選自組或鉅化合物、鈦或鈦化合物、鎢或鎢化合物' 及鐫之至少1種爲佳，以含有TiN、TiW、Ta、TaN ' W、 WN、Ru爲更佳，其中以含有Ta、TaN爲特佳。 阻障金屬膜之厚度以5〜30奈米左右爲佳。 如上述，藉由本發明的硏磨方法硏磨半導體裝置，能 夠以同一硏磨液連續地硏磨具有絕緣膜、導體膜、及阻障 Φ 金層障之基板，硏磨後之被硏磨面的平坦性良好、且能夠 減少產生刮傷。 [實施例] 以下，藉由實施例來具體地說明本發明。本發明未限 定於此等實施例。 &lt;硏磨液的調整&gt; (實施例1) 0.01質量％ 0.03 175莫耳/升 0.13莫耳/升 0.13莫耳/升 1.5質量％ 6.5 1000毫升 •雜環化合物：苯并三唑 •成分（1):胺基甲磺酸 •成分（2): A-16· · ·下述結構式 •成分（3):過氧化氫 •成分（4):硏磨粒子（PL-3、扶桑化學公司製 膠體二氧化矽、體積平均粒徑·· 35奈米） • pH(使用氨水及硫酸調整） •添加純水之總量 -34- ,200818299R2 R3 R4 R5 R6 Al - -Η -Η -H -ch3 A-2 • -Η -Η -H -CH2OH A-3 - -Η -Η -CH2OH -CH2OH A-4 - -Η -Η -H - CH2CH2OH A-5 -Η -Η -CH2CH2OH -CH2CH2OH A-6 -Η -ch3 -H -CH2OH A-7 - -Η -ch3 -CH2CH2OH -ch2ch2oh A-8 Face-Η -ch2oh -H -ch2oh A- 9 -Η -ch2(ch3)2 -CH2OH -ch2oh A· 10 - -Η -Ph -H -(CH2CH20)2-H A-ll - -Η H -CH2CH2OH -ch2ch2oh A-12 • -Η -CH2SCH3 - CH2CH2OH -ch2ch2oh A-13 -Η -H -H -COCH2NH2 A-14 丨-Η -CH2OH -H -COCH2NH2 A-15 -Η -H -H -COCH3 A-16 -ch2- -Η -H -CH2CH2OH -ch2ch2oh A-17 -ch2- -Η -H -H -ch2oh A-18 -ch2- -Η -H -H -COCH2NH2 A-19 -CH2CH2- -Η -H -H -H A-20 -Η -ch3 -H -ch2ch2oh A-21 -Η -ch3 -H -ch2oh A-22 Release -Η -CH2CH3 _H -CH2CH20H A-23 Two-Η -ch3 -H -CH2OH A-24 • -Η -ch3 - H -COCH2NH2 A-25 • -Η -CH2(CH3)2 -H -CH2CH20H A-26 -Η Phenyl-H -CH2CH20H A-27 -Η -H -H -(CH2)3OH 200818299 Formula (II) The method of synthesizing the compound shown is not particularly limited 'can be synthesized by a well-known method. Further, a commercially available product can also be used as the compound represented by the formula (II). In order to optimize the selection ratio of the conductor film to the barrier metal film (conductor film/barrier metal film), the ratio of the content of the amino acid of the present invention to the molar ratio of the aforementioned honing speed adjusting agent is the honing speed adjustment. Agent: Amino acid = 3: 1~8: 1 is better, and 4: 1~5 ··1 is more preferable. &lt;Component (3): Oxidizer&gt; Φ The honing liquid of the present invention contains an oxidizing agent (a compound capable of oxidizing a honing target). Examples of the oxidizing agent include hydrogen peroxide, peroxide, nitrate, iodate, periodate, hypochlorite, chlorite, chlorate, perchlorate, persulfate, and heavy chrome. Acid salt, permanganate, ozone water, and silver (II) salt, iron (III) salt. The iron (III) salt is organic using iron (III) in addition to inorganic iron (III) salts such as iron (III) nitrate, iron chloride (in), iron (III) sulfate, and iron (III) bromide. The wrong salt is better. ® Among the above oxidizing agents, ethylenediamine-^&gt;1',:^'-tetraacetic acid, 1,3-diaminopropane-1^ with hydrogen peroxide, persulfate, and iron (III) The complex of 1^ less,,]^,-tetraacetic acid, and ethylenediamine disuccinic acid (SS body) is preferred. The amount of the oxidizing agent added is preferably in the range of 〜· 〇〇3 to 8 mol/liter with respect to the honing liquid, and is preferably in the range of 0·0 3 to 6 m/liter, in the 〇. The range of 1 to 1 · 5 m / liter is particularly good. That is, from the case where the metal is sufficiently oxidized and the high CMP speed is ensured, the amount of the oxidizing agent added is preferably 〇.3 mol/liter or more, and from the viewpoint of preventing the roughness of the honing surface, it is 8 mol/liter or less. good. -1 8 - 200818299 When honing with a honing liquid The oxidizing agent is preferably used by mixing a composition containing a component other than the oxidizing agent. The period of mixing the oxidizing agent is preferably within 1 hour immediately before the use of the honing liquid, and preferably within 5 minutes, to provide a mixer at the supply of the honing liquid immediately before the honing device, just before being supplied to the honed surface Mixing in 5 seconds is especially good. &lt;Component (4): Honing particles&gt; The honing liquid of the present invention contains honing particles. The honing particles may be any of inorganic particles such as silica sand, oxidized quartz, cerium oxide, dioxins, φ zirconia, cerium, and cerium carbide, and organic particles such as polystyrene, polyacrylic acid, and polyvinyl chloride. Among them, at least one selected from the group consisting of cerium oxide, aluminum oxide, cerium oxide, titanium oxide, zirconium oxide and cerium is preferred because of good dispersion stability in the honing liquid and burrs (scratches) caused by CMP The number of occurrences is small, and cerium oxide particles (precipitated cerium oxide, hazy cerium oxide, colloidal cerium oxide, or synthetic cerium oxide) are preferred. Since the honing speed of the copper-containing metal is high, the cerium oxide particles are preferably colloidal cerium oxide or hazy cerium oxide, and colloidal cerium oxide is more preferable. Further, the honing particles contained in the honing liquid of the present invention are preferably particles having a volume average particle diameter of from 2 5 to 70 nm as determined by dynamic light scattering. The volume average particle diameter of the above particles is determined by dynamic light scattering. Specifically, it can be measured by a particle size distribution measuring apparatus (manufactured by Horiba, Ltd., LB-500) using a dynamic light scattering method. The aforementioned colloidal cerium oxide can be obtained by a conventionally known method. The wet process for metal oxides is, for example, a metal alkoxide as a starting material -19-200818299, and a colloidal silica sand is obtained by a method of hydrolyzing it. Methyl orthosilicate is added dropwise at a predetermined rate to cause hydrolysis to occur by a period of grain growth and a period in which grain growth is stopped by a quenching agent. In addition, it is also possible to use alkoxides such as Ming or 纟 too to make colloidal particles. At this time, 'normally, the rate of hydrolysis is faster than that of using cerium oxide oxide', and ultrafine particles can be produced smoothly. Further, the dry process of the metal oxide can obtain the mist-like particles by introducing the metal chloride into the oxyhydrogen flame and oxidizing the dechlorinated metal. Further, a method in which a metal or an alloy to be contained in a target substance is pulverized into a powder, an oxygen flame containing a pyrophoric gas is introduced, and a continuous reaction is generated by the heat of oxidation of the metal to obtain fine oxide particles has been used. Practical. The particles produced by the above-described combustion method are amorphized because they are rapidly cooled after being exposed to a high temperature, and when compared with wet particles, 'because there are few impurities such as hydroxyl groups in the interior, the characteristics are usually high solid density. ' And the surface hydroxyl density is also low. The amount of the honing particles to be added is preferably in the range of 0.00 0 1 to 5 mass%, more preferably in the range of 0.1 to 2.0 mass%, relative to the honing liquid at the time of use. In order to obtain a sufficient effect of increasing the honing speed and reducing the unevenness of the honing speed in the wafer surface, it is preferably 0.0001% by mass or more. "Because the honing speed of CMP is saturated, it is preferably 5% by mass or less. . &lt;pH of honing liquid&gt; The pH of the honing liquid of the present invention is 2 or more, preferably in the range of pH 2 to 10, and more preferably in the range of pH 5 to 8. By this range, the honing liquid of the present invention can exert a particularly excellent effect. The honing -20-200818299 of the present invention may be in the form of no water when honed, or may be diluted by water or an aqueous solution. Further, when diluted with water or an aqueous solution, the P oxime of the present invention means hydrazine diluted with water or an aqueous solution. The pH of the honing liquid of the present invention can take into account the adsorption or reactivity to the honing surface, the solubility of the honing metal, the electrochemical property of the honed surface, the dissociation state of the compound functional group, the stability as a liquid, and the like. And set. The pH is added, for example, to an alkali agent to be described later, and is adjusted by adding an acid other than the component (2), a buffer, or the like. &lt;Other Components&gt; - Heterocyclic Compound - The honing liquid of the present invention preferably contains a heterocyclic compound for forming a passive film on the surface of the metal to be honed. [Heterocyclic compound] means a compound having a hetero atom. The number of the hetero atoms contained in the compound having a hetero ring is not limited, and it is preferably two or more, and more preferably four or more hetero atoms. In particular, a heterocyclic compound containing three or more nitrogen atoms is preferably used, and when an anthracene compound containing four or more onion j atoms is used, the remarkable effect of the present invention can be exhibited, which is preferable. Further, the heterocyclic ring may be a single ring or a polycyclic ring having a condensed ring. The number of single-rings is 5 to 7, which is better than 5. The number of rings having a fused ring is preferably 2 or 3. Specific examples of such heterocyclic rings include the following. Pyrrole ring, thiophene ring, furan ring, pyran ring, thipy ring, imidazole ring, pyrazole ring, thiazole ring, isothiazole ring, indazole ring, isoindole ring, 200818299 D ring, trap ring , pyrimidine ring, hydrazine trap ring, pyrrolidine ring, pyrazolidine ring, hydrazide D ring, isoxazolidine ring, isothiazolidine ring, piperidine ring, piperazine ring, porphyrin ring, thiaxoline ring , color full ring, thiae full ring, heterochromatic full ring, isothialan full ring, indane ring, isoindole ring, 4-azine (pyrindine), anthracene ring, anthracene ring, carbazole Ring, anthracene ring, quinolidine, isoquinoline ring, quinoline ring, naphthyridine ring, hydrazine ring, quinoxaline ring, quinazoline ring, porphyrin ring, acridine ring, acridine ring , acridine ring, phenanthroline ring, carbazole ring, 咔'咐, 哄 哄 ring, onion D. (anthyridine), thiadiazole D ring, 噚二D sit, • triterpene ring, triazole ring, four An azole ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a benzo N-oxo-oxadiazole ring, a naphthoimidazole ring, a benzotriazole ring, and a tetraazaindole ring. The substituent which can introduce the heterocyclic compound used in the present invention may, for example, be the following. The substituent which the heterocyclic ring can have, for example, a halogen atom, an alkyl group (which may be a linear, branched or cyclic alkyl group, a polycyclic alkyl group such as a bicycloalkyl group, or an active group) A methine group, an alkenyl group, an alkynyl group, an aryl group, an amine group, a heterocyclic group, and the like. Further, two or more of a plurality of substituents may be bonded to each other to form a ring, and for example, an aromatic ring, an aliphatic hydrocarbon ring, a hetero ring or the like may be formed. Specific examples of the heterocyclic compound which is particularly preferably used in the present invention include, for example, the following, but are not limited thereto. That is, 1,2,3,4-tetrazole, 5-amino-1,2,3,4-tetrazole, 5-methyl-1,2,3,4-tetrazole, 1,2, 3-triazole, 4-amino-1,2,3-triazole, 4,5-diamino-1,2,3-triazole, 1,2,4-triazole, 3-amino- 1,2,4-triazole, 3,5-diamine-22- 200818299 keto-1,2,4-triazole, benzotriazole. The heterocyclic compound used in the present invention may be used alone or in combination of two or more. Further, in addition to the method of synthesizing the heterocyclic compound used in the present invention, a commercially available product may be used. The amount of the heterocyclic compound used in the present invention is 1 liter of the honing liquid (that is, the honing liquid after water or water is dissolved) in the honing, and 〇·〇〇〇1 to 1 · 〇 Mohr's range of 0.0005~0.5 m is better, preferably 〇.〇005~ Φ. - Surfactant and/or hydrophilic polymer - The honing fluid used in the present invention preferably contains an interfacial living polymer. Any of the surfactant and the hydrophilic polymer have a contact angle of the surface to be polished, and a surfactant or a hydrophilic polymer which promotes uniform use is preferred. # Anionic surfactants include carboxylates, sulfonates, and phosphate salts. Examples of cationic surfactants include aliphatic 4-grade ammonium salts, benzalkonium chloride, and benzyloxyethyl persimazole. Examples of the amphoteric surfactant include a carboxylated betainate, an imidazolium betaine, a lecithin, and an alkylamine active agent, and examples thereof include an ether type, an ester ether type, an ester type, and a nitrogen-containing fluorine-containing surfactant. . Further, the hydrophilic polymer may be exemplified by polyethylene glycol _', which may be used in combination with a constant amount, and may be used in a dilute range when diluted with a liquid, and may be a standard or hydrophilic substance. Sex has the effect of reducing the temper. Acidic acid, sulfated aliphatic amine salt, lipid: pyridine key salt, base type, amino carboxy group: nonionic interface:, and, also, polyglycols, poly- 23- 200818299 Polyvinyl alcohol, polyvinylpyrrolidone, alginic acid and other polysaccharides, carboxylic acid-containing polymers such as polymethacrylic acid. In the above, since an alkali metal, an alkaline earth metal, a halogenated substance or the like is not generated, an acid or an ammonium salt thereof is preferred. Among the above exemplified compounds, cyclohexanol, ammonium polyacrylate, polyvinyl alcohol, succinimide, polyvinylpyrrolidone, polyethylene glycol, polyoxyethylene polyoxypropylene block polymer is more preferable. . The weight average molecular weight φ of these surfactants or hydrophilic polymers is preferably from 500 to 100,000, particularly preferably from 2,000 to 50,000. The total amount of the surfactant and/or the hydrophilic polymer added is preferably 0.001 to 10 g in 1 liter of the honing liquid used for honing, and more preferably 〇1 to 5 g. It is especially good at 0.1~3g. - Clamping agent, base, buffering agent - In the present invention, it is preferred to further add a chelating agent, a base, and a buffering agent. The tongs, bases, and buffers which can be used in the present invention are explained below. (Clamping agent) φ The honing liquid of the present invention preferably contains a chelating agent (i.e., a hard water softening agent) as necessary in order to prevent adverse effects such as the incorporation of polyvalent metal ions. The chelating agent is a general hard water softening agent or the like of a calcium or magnesium anti-precipitating agent, and examples thereof include cyanotriacetic acid, diethylenetriamine pentaacetic acid, ethylenediaminetetraacetic acid, N, N, N. -trimethanesulfonic acid, ethylenediamine-N,N,N'-N'-tetramethylenesulfonic acid, transcyclohexanediaminetetraacetic acid, L2-diaminopropanetetraacetic acid, ethylene glycol Ether diamine tetraacetic acid, ethylenediamine o-hydroxyphenylacetic acid, ethylenediamine disuccinic acid (SS body), Ν_(2·carboxylate ethyl)-L--24-200818299 aspartic acid, A-alanine diacetic acid, 2-phosphonic acid butyl acid _ i acid, 1-transethylidene-1,1-disulfonic acid, N,N,-bis(2-radio:diamine-N N'-diacetic acid, 1,2-dihydroxybenzene-4,6-disulfonic acid, etc. &lt; The chelating agent may be used in combination of two or more kinds as necessary. The amount of the chelating agent added is such that it can block the incorporation of many substances, etc. A sufficient amount of the metal ion may be used, for example, in a 1 liter honing liquid, and it can be added in a manner of 0. 0 〇〇 3 摩尔 〇 〇 7 摩尔. # (alkali agent, buffer) Moreover, in the honing fluid of the present invention, in order to adjust ρ Η, Further, a buffer may be contained in order to suppress fluctuations in pH. As the alkali agent and the buffering agent, non-metal such as ammonium hydroxide or organic ammonium hydroxide, such as dimethanolamine, triethanolamine or triisopropanolamine can be used. Alkali metal hydroxide, carbonate, phosphate, borate, hydroxybenzoate, glycidinium salt, N,N-dimethylglycolamine amine, such as alkali agent, sodium hydroxide or lithium hydroxide Acid salt, orthotylamine, guanine salt, 3,4-trihydroxyphenyl alanine, aminobutyrate, 2-amino-2-methyl-1,3-propanolamine Specific examples of the acid salt, the guanamine salt, the trihydroxy amino methane salt, the amine base agent, and the buffer agent include ammonia, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate. , I trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium hydroxybenzoate, potassium hydroxybenzoate, 5-sulfonate-2- Sodium hydroxybenzoate (5-3⁄4, 2,4-tricarboxymethyl) is a range of the range of the valence metal from the honing of the sulphur metal. Adding an alkali agent, an amine such as tetramethylammonium or the like Hydroxide, barium tetraborate, leucine, [diol salt, acid salt, etc.: sodium, hydrogen oxy-potassium carbonate, sodium citrate, boron (sodium citrate), acid oleic acid-25 - 200818299 Sodium), potassium 5-sulfonate-2-hydroxybenzoate (potassium 5-sulfonate), ammonium hydroxide, and the like. The test of Niu Jingjia has a hydrogen hydroxide mirror, potassium hydroxide, lithium hydroxide and tetramethylammonium hydroxide. The amount of alkali and buffer added can be as long as the pH can be maintained in the preferred range. In the case of 1 liter of honing liquid used for honing, the range of 0.0001 mol to 1 · 〇 Mo is preferred. , to 〇· 〇〇 3 Moer ~ 〇 · 5 Moel range is better. In the present invention, the specific gravity of the honing liquid is preferably in the range of 0.8 to 1.5 in terms of the fluidity of the liquid or the stability of the honing performance, and is in the range of 0·9 5 to 1. 3 5 . It is especially good. [Horing method] The honing method of the present invention is characterized in that the surface of the conductor film side is used as a honing surface to honing the barrier metal film and the conductor film; the barrier metal film is formed on one side at a time a substrate having a recess or a surface of an interlayer insulating film formed on the substrate; and the conductor film is formed of a copper and/or a copper alloy formed on a surface of the barrier metal film to bury the recess The aforementioned honing fluid is continuously honed with a honing fluid. In other words, the honing method of the present invention can continue to use the same crucible after chemically mechanically honing a conductive film which is formed by projecting a film formed on the surface other than the concave portion of the insulating film by using one type of honing liquid. The grinding machine continuously hones the residual film of the conductor film and the chemical mechanical honing method of the barrier metal film. The honing liquid of the present invention uses the honing liquid of the present invention. The honing liquid used in the honing method of the present invention may be a case where the concentrated -26-200818299 liquid is diluted with water at the time of use as a use liquid, or each component is an aqueous solution form described later. Mixing, if necessary, adding water to dilute and use; or when preparing to use a liquid. The mash liquid of the present invention is not particularly limited, and any of the above aspects can be applied to the present invention. The honing method of the present invention is to supply the honing liquid to the honing pad on the honing turntable so as to be in contact with the honed surface and to be relatively moved (relatively moved) by the honing surface and the honing pad. Honing and honing method. The honing device can use a conventional honing device having a holder for holding a semiconductor substrate having a honed surface, and the like, and the honing wheel (which is capable of changing the number of rotations) The motor, etc.) is attached with a honing pad. The honing pad can be a general non-woven fabric, a foamed polyurethane, a porous fluororesin or the like, and is not particularly limited. Further, the honing pad for honing can also be used as a honing pad without a foaming structure. The former uses a hard synthetic resin block such as a plastic sheet for the honing pad. The latter further has three types of independent foam (dry foaming), continuous foam (wet foaming), and two-layer composite (layered), and a two-layer composite (layered) Very good. Foaming can be a uniform sentence or an uneven sentence. Further, the honing pad may also contain particles for use in honing (e.g., 'oxygen, cerium oxide, aluminum oxide, resin, etc.). Further, the hardness of each of the honing pads may be either a soft material or a hard material, and any one of them may be laminated with a different hardness in each layer. The material is preferably non-woven fabric, artificial leather, polyamide, polyurethane, polyester, polycarbonate, or the like. In addition, it is also possible to apply a lattice groove, a hole/concentric groove/spiral groove to the surface in contact with the honing surface, -27 - 200818299. The honing condition is not limited, and the linear speed of the honing turntable is preferably 1 m/sec or more. The pressure (pressurization pressure) when the semiconductor substrate having the honed surface (the honed film) is pressed against the honing pad is preferably 20 kPa or less, and can be maintained under a low pressure condition of 13 kPa or less. It is better to have a high honing speed state and to improve the in-plane uniformity of the honing speed and the flatness of the pattern. Further, when the pressurizing pressure is more than 20 kPa, the flatness may be deteriorated. Further, the lower limit of the pressurizing pressure is not particularly limited, and is preferably 2 kPa or more, and more preferably 3.5 kPa or more. During the honing, the honing liquid is continuously supplied to the honing pad using a pump or the like. The amount of supply is not particularly limited, and it is preferable to cover the surface of the pad with a honing liquid. After the semiconductor substrate after completion of the honing is sufficiently washed in running water, the water droplets are dried from the semiconductor substrate by a spin dryer or the like to be dried. In the honing method of the present invention, the aqueous solution of the diluted honing liquid is the same as the aqueous solution of the following ®. In the aqueous solution, the total amount of the component contained in the aqueous solution and the component of the diluted honing fluid is adjusted by using at least one or more of the oxidizing agent, the acid, the additive, and the surfactant, and the honing liquid is used. The ingredients of the grinding time. When the honing liquid is diluted with an aqueous solution and used, a component which is not easily dissolved can be prepared in the form of an aqueous solution, and a more concentrated honing liquid can be prepared. The method of adding water or an aqueous solution to the concentrated honing liquid to dilute the method, -28-200818299, the piping for supplying the concentrated honing liquid and the piping for supplying water or the aqueous solution are combined and mixed on the way, and then mixed and diluted. A method of supplying honing fluid to a honing pad. The mixing generally employs a method of causing collision mixing between liquids in a path in which a pressure state is generally narrowed; a filling such as a glass tube is installed in the piping to repeatedly generate a flow separation and a combined flow of the liquid; And a method of providing a blade that uses power to rotate in a pipe. The supply rate of the honing liquid is preferably in the range of 10 to 1 000 ml/min. In order to satisfy the in-plane uniformity of the honing speed and the flatness of the pattern, the temperature is 190 to 800 ml/min. The range is better. A method of honing a concentrated honing liquid by using water or an aqueous solution or the like, and separately providing a pipe for supplying the honing fluid and a pipe for supplying water or an aqueous solution, and supplying a predetermined amount of liquid to the honing pad And the method of mixing and honing the honing pad with the honed surface by relative motion. Further, it is also possible to apply a method in which a predetermined amount of the concentrated honing liquid and water or an aqueous solution are added to one container, and the mixed honing liquid is mixed and supplied to the honing pad to perform honing. In the present invention, the components to be contained in the honing liquid may be separated into at least two constituent components, and when used, water or an aqueous solution may be added and diluted to be supplied to the honing pad on the honing turntable. And honing the surface to be honed by the relative movement of the honed surface and the honing pad, for example, using an oxidizing agent as one constituent component (A), and using an additive, a surfactant, and water as one The component (B) is used by diluting the component (A) and the component (B) with water or an aqueous solution when using these. In addition, the additive with lower solubility is divided into two components (c) and -29 - .200818299 (D) 'The oxidizing agent, the additive and the surfactant are used as the constituent components (C), and the acid, the additive and the interface are active. The agent and water are used as one constituent component, and when using these, water or an aqueous solution is added to dilute the component (c) and the component (D). In the case of this example, three pipes are required to supply the component (C) 'constituting component (D) and water or an aqueous solution, respectively, and the three pipes are combined and supplied to one pipe supplied to the honing pad. In the method of mixing in the pipe, in this case, two pipes may be combined and one pipe may be combined. For example, there is a method in which a component containing an additive which is not easily dissolved is mixed with other constituent components, and then the mixing path is increased to ensure a dissolution time, and then a pipe of water or an aqueous solution is combined. For other mixing methods, the three pipes are directly guided to the honing pad as described above, and then mixed by the relative movement of the honing pad and the honed surface; and three containers are mixed in one container. A method of constituting the component and then supplying the diluted honing liquid to the honing pad. In the above honing method, one of the constituent components containing the oxidizing agent may be at 40 ° C or lower, and the other constituent components may be heated from room temperature to 1 〇〇 ° C, and one constituent component may be added. When other components, water or an aqueous solution are used for dilution, the mixture is 40 ° C or lower after mixing. Since the solubility is high when the temperature is high, it is preferable to increase the solubility of the raw material having a low solubility of the honing liquid. A raw material obtained by heating another component which does not contain an oxidizing agent from a room temperature to a range of 1 〇〇 ° C to be dissolved from the solution when the temperature is lowered, and when the temperature is lowered, the component must be Warming is performed to dissolve the precipitate. This can be carried out by hand-delivering the component liquid -30-200818299 which has been heated and dissolved, and by dissolving the liquid containing the precipitate in advance, and then supplying the liquid and heating the pipe to dissolve it. When the temperature of the component containing the oxidizing agent is increased to 40 ° C or more, the oxidizing agent may be decomposed. Therefore, it is necessary to cool the constituent component and cool the heated composition. In the case where one component of the component containing the oxidizing agent is mixed, it is 40 ° C or lower. Further, in the present invention, the components of the honing liquid may be separated into two or more and supplied to the honing surface as described above. In this case, it is preferred to separate into a component containing an oxidizing agent and a component containing an acid. Further, the honing liquid may be a concentrated liquid, and the diluted water may be additionally supplied to the honing surface. The method of supplying the honing liquid can be distinguished as the case where the components of the honing liquid are separated into two or more and supplied to the honing surface as described above; and the honing liquid is a concentrated liquid, and the diluted water is additionally supplied to the honing The situation. However, in any of the methods for supplying a honing liquid, in the present invention, it is possible to use one type of honing liquid, chemical mechanical honing to form a film on the convex portion of the insulating film, and continue to use the same honing liquid continuously. The residual film of the conductor film and the barrier metal film are ground. The object of honing by the honing method of the present invention has a substrate on the barrier metal film and the conductor film; the barrier metal film is formed on one surface of the surface of the interlayer insulating film having a recess; and the conductor film is a copper and/or a copper alloy formed on the surface of the barrier metal film for burying the recess; the substrate is a semiconductor substrate, preferably an LSI having a wiring made of copper metal and/or a copper alloy. It is especially good for wiring copper alloy. Further, among the copper alloys, a copper alloy containing silver is preferred. The content of silver contained in the copper-31-200818299 alloy is preferably 40% by mass or less, preferably 1% by mass or less, more preferably 1% by mass or less, and more preferably 0.001% by mass to 0.1% by mass. The range of copper alloys can achieve the best results. In the present invention, in the case of a semiconductor substrate to be honed, for example, a DRAM device, the half pitch is preferably 1.25 μm or less, more preferably ο · 1 〇 μm or less, and more preferably 0.0 8 μm or less. On the other hand, in the case of the Μ P U system, it is preferable to use 0.12 μm or less, preferably 0.09 μm or less, and more preferably LSI having a wiring of 0.07 μm or less. With these LSIs, particularly excellent effects can be exhibited by using the honing liquid of the present invention. (Substrate) Examples of the substrate used in the present invention include an 8-inch, 12-inch semiconductor wafer process or a micro-machine process. The type includes a semiconductor wafer or a S 01 wafer, and a sapphire substrate including a compound semiconductor used for a semiconductor laser or the like. Further, it can also be used for forming a wiring pattern or flattening on a polymer film substrate. The target wafer for performing CMP in the honing liquid of the present invention is preferably 200 φ mm or more in diameter and more preferably 300 mm or more. When the temperature is 300 mm or more, the effects of the present invention can be remarkably exhibited. (Interlayer insulating film) The honing method of the present invention can be used not only to planarize the wiring on the substrate, but also to planarize the multilayer wiring substrate. At this time, the wiring formed on the interlayer insulating film can be flattened. The interlayer insulating film of the present invention is a film formed on the substrate (germanium wafer) and insulated from the barrier metal film to be described later to insulate the layers. -32 - 200818299 The interlayer insulating film of the present invention is not particularly limited as long as it is formed on the substrate, and it is preferable to use a cerium oxide-based film or an organic film in order to effectively achieve the effects of the present invention. Among them, a ruthenium dioxide-based film is preferred. The cerium oxide coating film is a cerium oxide-based coating film obtained by doping carbon, a cerium oxide-based coating film, a cerium fluoride glass, a hydrogen hydride salt, a methyl silicate, or the like, and a carbon dioxide-based cerium oxide coating film. It is better. The carbon content of the cerium oxide-based coating film formed by doping carbon is preferably from 20% by mass to 60% by mass from the viewpoint of lowering the effective dielectric constant and maintaining the mechanical strength of the insulating film itself. It is particularly good at 25% by mass to 35% by mass. The organic system is exemplified by polyiimine, parylene, Teflon (registered trademark), and the like, and polyimide is preferred. Further, from the viewpoint of effectively achieving the effects of the present invention, the interlayer insulating film is preferably one having a dielectric constant of 2.6 or less, more preferably 2.4 to 2.5. The interlayer insulating film of the present invention is more preferably a combination of the above preferred examples. The thickness of the interlayer insulating film of the present invention can be appropriately adjusted in accordance with the upper and lower portions of the multilayer wiring or between generations (nodes). Further, the method of forming the thickness of the interlayer insulating film of the present invention is exemplified by the methods described in each of the specifications of U.S. Patent No. 6,440,866, the same as No. 6,410,463, and No. 6,5,96,6,54. (Barrier Metal Film) The barrier metal film is provided on a semiconductor substrate between a conductor film (wiring) composed of copper and/or a copper alloy and an interlayer insulating film to prevent -33-.200818299 copper Diffused film (layer). The material of the barrier metal film is preferably a low-resistance metal material, and specifically, at least one selected from the group consisting of a group or a giant compound, a titanium or a titanium compound, a tungsten or a tungsten compound, and a tantalum, preferably contains TiN and TiW. Ta, TaN 'W, WN, Ru are more preferable, and it is particularly preferable to contain Ta and TaN. The thickness of the barrier metal film is preferably about 5 to 30 nm. As described above, by honing the semiconductor device by the honing method of the present invention, the substrate having the insulating film, the conductor film, and the barrier Φ gold barrier can be continuously honed with the same honing liquid, and the honed surface is honed The flatness is good and scratching can be reduced. [Examples] Hereinafter, the present invention will be specifically described by way of examples. The invention is not limited to the examples. &lt;Adjustment of honing liquid&gt; (Example 1) 0.01% by mass 0.03 175 mol/liter 0.13 mol/liter 0.13 mol/liter 1.5 mass% 6.5 1000 ml•heterocyclic compound: benzotriazole•ingredient (1): Aminomethanesulfonic acid • Component (2): A-16· · · The following structural formula • Component (3): Hydrogen peroxide • Component (4): Honing particles (PL-3, Fuso Chemical Company made colloidal cerium oxide, volume average particle size · · 35 nm) • pH (adjusted with ammonia and sulfuric acid) • Total amount of pure water added -34- , 200818299

hoog-ch 厂 e~NHoog-ch factory e~N

pH2CH2OH A— 1 6pH2CH2OH A-1 6

CH2CH2OH 以各成分成爲上述濃度的方式調製水溶液，然後使用 高速均化器攪拌使均勻分散，而得實施例1的硏磨液。使 用該硏磨液進行下述硏磨試驗並評價。 &lt;硏磨條件&gt; 硏磨裝置係使用LAPMASTER公司製「LGP-612」，以 下述條件進行硏磨。具體上係邊將前述硏磨液的漿體供給 至硏磨裝置的硏磨轉盤的硏磨墊上，邊在將硏磨基板壓住 硏磨墊的狀態，使硏磨轉盤與基板相對地移動來硏磨金屬 膜。 •固定台旋轉數： 64rpm •轉盤頭旋轉數： 65rpm •硏磨壓力 13kPa •硏磨墊：Rohm and Haas 公司製品名 IC-1 400 (K-grv) + (A2 1) •漿體供給速度： 200毫升/分鐘 基板係使用的8英吋晶圓，係藉由光微影步驟及反應性 離子蝕刻步驟將矽氧化膜（絕緣膜）圖案化，來形成寬度 0.09〜100微米、深度600奈米之配線用槽及連接孔（凹 部），而且藉由濺鍍法形成厚度爲20奈米之Ta膜（阻障金 屬膜），隨後藉由濺鍍法形成5 0奈米的銅膜後，藉由鍍敷 法形成合計厚度1 000奈米的銅膜（導體膜）而成。 -35- 200818299 (實施例2〜6、比較例1) 在實施例1，除了使用表2所示之組成以外，與實施例 1同樣地進行硏磨試驗並評價。 [.評價項目] (硏磨速度） -銅及Ta膜- 從電阻値換算求得導體膜及阻障金屬膜之銅及Ta膜之 在CMP前後的膜厚度差。測定膜厚度差係使用國際電氣 • ALPHA股份公司製VR-200來進行。具體上係藉由硏磨速 度（奈米/分鐘）= [(硏磨前之銅及Ta膜的厚度）-(硏磨後之銅 及Ta膜的厚度）]/硏磨時間來測定。 -絕緣膜- 從電阻値換算求得絕緣膜之矽氧化膜在CMP前後的膜 厚度差。測定膜厚度差係使用FILMETRICS股份公司製F20 來進行。具體上係藉由硏磨速度（奈米/分鐘）= [(硏磨前之絕 緣膜厚度）-(硏磨後之絕緣膜厚度）]/硏磨時間來測定。 β (選擇比） 求取從各種膜的硏磨速度計算得的選擇比。在此選擇比 係表示各材料之硏磨速度的比。此等比越小時，表示能夠 均勻地硏磨不同的膜。 (銅膜及Ta膜之有無刮傷） . 目視觀察硏磨後之各基板的外觀。評價基準係〇：無刮 傷，△:觀察到數條刮傷，X :觀察到數條明顯成爲問題的 刮傷。 -36- 200818299 (凹狀扭曲硏磨評價） 將圖案晶圓硏磨至非配線部分的銅完全被硏磨爲止，並 繼續進行硏磨相當於該時間之30%的時間’使用觸針式段 差測量機器名Deketak321si(KLA-TENCOR公司製）測定線 與間隙部分（線1 0 0微米、間隙1⑽微米）之凹狀扭曲硏磨。 -37 - 200818299CH2CH2OH The aqueous solution was prepared so that the respective components became the above-mentioned concentrations, and then uniformly dispersed by stirring with a high-speed homogenizer to obtain the honing liquid of Example 1. The honing test was carried out using the honing liquid and evaluated. &lt;Horse Conditioning&gt; The honing apparatus was honed by the following conditions using "LGP-612" manufactured by LAPMASTER. Specifically, the slurry of the honing liquid is supplied to the honing pad of the honing wheel of the honing device, and the honing plate is moved relative to the substrate while the honing plate is pressed against the honing pad. Honing the metal film. • Fixed table rotation number: 64 rpm • Rotary head rotation number: 65 rpm • Honing pressure 13 kPa • Honing pad: Rohm and Haas Company name IC-1 400 (K-grv) + (A2 1) • Slurry supply speed: The 8-inch wafer used in the 200 ml/min substrate is patterned by a photolithography step and a reactive ion etching step to form a width of 0.09 to 100 μm and a depth of 600 nm. a wiring groove and a connection hole (recessed portion), and a Ta film (barrier metal film) having a thickness of 20 nm is formed by sputtering, and then a 50 nm copper film is formed by sputtering. A copper film (conductor film) having a total thickness of 1,000 nm was formed by a plating method. -35-200818299 (Examples 2 to 6 and Comparative Example 1) A honing test was carried out in the same manner as in Example 1 except that the composition shown in Table 2 was used. [Evaluation item] (honing speed) - Copper and Ta film - The difference in film thickness between the copper film and the Ta film of the conductor film and the barrier metal film before and after CMP was obtained from the resistance 値 conversion. The difference in film thickness was measured using VR-200 manufactured by International Electric Co., Ltd., ALPHA Corporation. Specifically, it is determined by honing speed (nano/min) = [(thickness of copper and Ta film before honing) - (thickness of copper and Ta film after honing)] / honing time. - Insulating film - The film thickness difference of the tantalum oxide film of the insulating film before and after CMP was obtained from the resistance 値 conversion. The film thickness difference was measured using F20 manufactured by FILMETRICS AG. Specifically, it is determined by honing speed (nano/min) = [(insulating film thickness before honing) - (thickness of insulating film after honing)] / honing time. β (selection ratio) The selection ratio calculated from the honing speed of various films was obtained. The selection ratio here indicates the ratio of the honing speed of each material. The smaller the ratio, the more the different films can be honed uniformly. (There was no scratch on the copper film and the Ta film). The appearance of each substrate after honing was visually observed. The evaluation criteria were: no scratches, △: several scratches were observed, and X: several scratches which were clearly problematic were observed. -36- 200818299 (Concave twisted honing evaluation) The copper honed to the non-wiring part of the pattern wafer is completely honed and continues to be honed for 30% of the time 'Using the stylus type step The measurement machine name Deketak 321si (manufactured by KLA-TENCOR Co., Ltd.) was used to measure the concave twist honing of the line and the gap portion (line 10 μm, gap 1 (10) μm). -37 - 200818299

評價 凹狀扭 曲硏磨 [奈米] ο 00 jn 00 g 〇 有無刮傷 〇 〇 〇 〇 〇 〇 〇 U 〇 〇 〇 〇 〇 〇 〇 選擇比 Cu/Si02 ν〇 m r-H 209 392 Cu/Ta g f—t ο 〇〇 〇 &lt;N 〇\ m 硏磨速度[奈米/分鐘] Si02 CN m r—Η 寸 (N ON m 04 β 408 417 丨457 j 462 612 256 392 硏磨液(漿體)組成 成分(4): 硏磨用粒子 PL^3 PL-3 PL-3 PL-3 PL-3 PL-3 PL-3 成分(3) z 氧化劑 過氧化氫 過氧化氫 過氧化氫 過氧化氫 過氧化氫 過氧化氫 過氧化氫 成分(2” 有機酸 A-16 ____1 A-16 A-16 I A-16 甘胺酸 A-16 A-16 成分⑴ 的濃度 [莫耳/升] 0.03175 0.0635 0.127 0.254 1- 0.254 0.254 ! 成分⑴： 硏磨速度比 調整劑 / 胺基甲磺酸 胺基甲磺酸 , 1 胺基甲磺酸 胺基甲磺酸 胺基甲磺酸 乙基磺酸 1 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 比較例1Evaluation of concave twist honing [nano] ο 00 jn 00 g 〇With or without scratch 〇〇〇〇〇〇〇U 〇〇〇〇〇〇〇Selection ratio Cu/Si02 ν〇m rH 209 392 Cu/Ta gf— t ο 〇〇〇&lt;N 〇\ m honing speed [nano/min] Si02 CN mr-Η inch (N ON m 04 β 408 417 丨457 j 462 612 256 392 honing fluid (slurry) composition (4): honing particles PL^3 PL-3 PL-3 PL-3 PL-3 PL-3 PL-3 components (3) z oxidant hydrogen peroxide hydrogen peroxide hydrogen peroxide hydrogen peroxide hydrogen peroxide Hydrogen peroxide hydrogen peroxide component (2" Organic acid A-16 ____1 A-16 A-16 I A-16 Glycine A-16 A-16 Concentration of component (1) [mole / liter] 0.03175 0.0635 0.127 0.254 1 - 0.254 0.254 ! Ingredient (1): Honing speed ratio adjuster / Amino methanesulfonate methanesulfonic acid, 1 Amino methanesulfonyl methanesulfonate methanesulfonate methanesulfonic acid 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1

.200818299 如表2所示，使用實施例的硏磨液時，與比較例比較， 在確保對Cu —定的硏磨速度之同時，能夠選擇性地變化 Ta的硏磨速度。又，得知能夠得到平坦性良好、且不會產 生刮傷的硏磨面。 詳細地，清楚明白在實施例1至5，藉由增加胺基甲 磺酸的添加量，Ta的硏磨速度增加，能夠效率良好地硏磨 T a 〇 又，藉由添加硏磨速度調整劑，能夠改善Cu/Ta、及 ® Cu/Si02的選擇比，凹狀扭曲硏磨亦顯示實用上無問題的 値。 而且，在實施例6，得知藉由添加乙基磺酸代替胺基 甲磺酸，Cu與Ta的選擇比、Cu與Si02的選擇比、及凹狀 扭曲硏磨係與添加胺基甲磺酸時相同程度，能夠以同一硏 磨液連續地硏磨。 &lt;實施例7&gt; 在矽晶圓表面，藉由光微影步驟及反應性離子飩刻步 ® 驟將矽氧化膜圖案化，來形成寬度0.09〜100微米、深度 600奈米之配線用槽及連接孔，而且藉由濺鍍法形成厚度 爲2 0奈米之Ta膜，隨後藉由濺鍍法形成50奈米的銅膜 後，使用將藉由鍍敷法形成有合計厚度1 〇 〇 〇奈米的銅膜之 圖案晶圓切成6 0 X 6 0毫米之物，使用實施例3的硏磨液進 行硏磨該圖案晶圓的表面1 2 0秒鐘。結果，位於比T a膜更 上方的C u膜被除去’隨後，係使用同一硏磨液將露出的 Ta膜硏磨而成之狀態。 -39- 200818299 使用光學顯微鏡觀察硏磨後之矽晶圓表面時，確認配 線用槽以外的矽氧化膜及配線槽的Cu膜露出，且Ta膜完 全被除去。從該結果，清楚知道藉由使用該硏磨液，能夠 連續地硏磨導體膜及阻障金屬膜。 【圖式簡單說明】 〇 【元件符號說明】 Μ 〇 j\ \\.200818299 As shown in Table 2, when the honing liquid of the example was used, the honing speed of Ta was selectively changed while ensuring the honing speed for Cu as compared with the comparative example. Further, it was found that a honing surface which is excellent in flatness and which does not cause scratches can be obtained. In detail, it is clear that in Examples 1 to 5, by increasing the addition amount of the aminomethanesulfonic acid, the honing speed of Ta is increased, and the T a 〇 can be efficiently honed by adding the honing speed adjusting agent. It is possible to improve the selection ratio of Cu/Ta and ® Cu/Si02, and the concave distortion honing also shows that there is no problem in practical use. Further, in Example 6, it was found that the substitution ratio of Cu to Ta, the selection ratio of Cu to SiO 2 , and the concave twist honing system and the addition of the amine methyl sulfonate were added by adding ethyl sulfonic acid instead of the amino methanesulfonic acid. The same degree of acid can be continuously honed with the same honing liquid. &lt;Example 7&gt; A tantalum oxide film was patterned on the surface of a tantalum wafer by a photolithography step and a reactive ion etching step to form a wiring groove having a width of 0.09 to 100 μm and a depth of 600 nm. And a connection hole, and a Ta film having a thickness of 20 nm is formed by sputtering, and then a 50 nm copper film is formed by sputtering, and a total thickness of 1 形成 is formed by plating. The pattern wafer of the copper film of 〇 nanometer was cut into 60×60 mm, and the surface of the patterned wafer was honed using the honing liquid of Example 3 for 120 seconds. As a result, the Cu film located above the T a film was removed. Subsequently, the exposed Ta film was honed using the same honing liquid. -39- 200818299 When observing the surface of the wafer after honing with an optical microscope, it was confirmed that the tantalum oxide film other than the wiring groove and the Cu film of the wiring groove were exposed, and the Ta film was completely removed. From this result, it is clear that the conductor film and the barrier metal film can be continuously honed by using the honing liquid. [Simple description of the diagram] 〇 [Description of component symbols] Μ 〇 j\ \\

-40 --40 -

Claims (1)

200818299 十、申請專利範圍： i . 一種半導體裝置之硏磨方法，其特徵係連續地以一種硏 磨液進行硏磨阻障金屬膜及導體膜；該阻障金屬膜係一 面地形成在具有凹部之基板或形成於該基板上之層間絕 緣膜的表面；而該導體膜係由銅或銅合金所構成，形成 於該阻障金屬膜的表面用以將該凹部塡埋；該硏磨液係 含有下述通式（I)所示之阻障金屬膜硏磨速度調整劑、胺 基酸、氧化劑及硏磨粒子， R1 - CH2- SO3H 通式（I) (通式（I)中，R1係表示h、ch3、或nh2)。 2 .如申請專利範圍第1項之硏磨方法，其中該硏磨速度調 整劑與該胺基酸之莫耳比爲（硏磨速度調整劑）：（胺基 酉変）= 3: 1〜8: 1 ° 3 ·如申請專利範圍第1或2項之硏磨方法，其中該胺基酸 係下述通式（Π)所示之化合物，200818299 X. Patent application scope: i. A honing method for a semiconductor device, characterized in that a barrier metal film and a conductor film are continuously honed with a honing liquid; the barrier metal film is formed on one side with a concave portion a substrate or a surface of the interlayer insulating film formed on the substrate; and the conductor film is made of copper or a copper alloy, and is formed on a surface of the barrier metal film for burying the recess; the honing liquid system The barrier metal film honing speed modifier, amino acid, oxidizing agent and honing particles represented by the following formula (I), R1 - CH2-SO3H (I) (in the formula (I), R1 It means h, ch3, or nh2). 2. The honing method according to claim 1, wherein the molar ratio of the honing speed adjusting agent to the amino acid is (honing speed adjusting agent): (amine hydrazine) = 3: 1~ 8: 1 ° 3 · The honing method according to claim 1 or 2, wherein the amino acid is a compound represented by the following formula (Π), 通式（II) Ψ3 R5 HOOG-R2—G-N R4 R6 [通式（Π)中，R2係表示單鍵、伸烷基、或伸芳基，R3及 R4係各自獨立地表示氫原子、鹵素原子、羧基、烷基、 環烷基、烯基、炔基或芳基，R5及R6係各自獨立地表示 氫原子、鹵素原子、羧基、烷基、或醯基，其中R2爲單 鍵時，R5及R6之至少其中一個不爲氫原子]。 -41 - 200818299 4. 如申請專利範圍第1或2項之硏磨方法，其中該氧化劑 係過氧化氫液體。 5. 如申請專利範圍第1或2項之硏磨方法，其中該硏磨液 的p Η爲5〜8。 6. 如申請專利範圍第1或2項之硏磨方法，其中該硏磨粒 子係二氧化矽粒子。General formula (II) Ψ3 R5 HOOG-R2-GN R4 R6 [In the formula (R), R2 represents a single bond, an alkylene group, or an extended aryl group, and R3 and R4 each independently represent a hydrogen atom or a halogen atom. Or a carboxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group or an aryl group, and R5 and R6 each independently represent a hydrogen atom, a halogen atom, a carboxyl group, an alkyl group or a fluorenyl group, wherein R2 is a single bond, R5 And at least one of R6 is not a hydrogen atom]. -41 - 200818299 4. The honing method of claim 1 or 2, wherein the oxidizing agent is a hydrogen peroxide liquid. 5. The honing method according to claim 1 or 2, wherein the honing liquid has a p Η of 5 to 8. 6. The honing method of claim 1 or 2, wherein the honing particles are cerium oxide particles. -42 - 200818299 七、指定代表圖： (一） 本案指定代表圖為：無。 (二) 本代表圖之元件符號簡單說明： 〇 /V \Λ 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式·· R1 — CH2 - S03H 通式（I)-42 - 200818299 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 〇 /V \Λ VIII. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention. · R1 — CH2 - S03H General formula (I)
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