TW201002805A

TW201002805A - Slurry for metal polishing and polishing method thereof

Info

Publication number: TW201002805A
Application number: TW98109990A
Authority: TW
Inventors: Hisataka Minami; Masato Fukasawa; Jin Amanokura
Original assignee: Hitachi Chemical Co Ltd
Priority date: 2008-03-28
Filing date: 2009-03-26
Publication date: 2010-01-16
Also published as: JPWO2009119485A1; WO2009119485A1

Abstract

Slurry for metal polishing with a pH value from 1 to 5 including water, an oxidizing agent, an anti-corrosive reagent and a dissolution reagent for oxidized metal is provided. The anti-corrosive reagent contains at least one of tolyltriazole and diphenylguanidine. The polishing method of the invention is a polishing method for a substrate and includes the following steps. Under a condition that the surface of the substrate which needs to be polished is pressed to a polishing pad of a polishing platen, the slurry for metal polishing is supplied to above-mentioned surface and the polishing pad, and the polishing platen and the substrate are moved oppositely so as to perform the polishing process.

Description

201002805 六、發明說明：【發明所屬之技術領域】本發明主要是關於一種半導體裝置的配線形成步驟中的金屬用研磨液以及使用此研磨液的研磨方法。【先前技術】近年來’隨著半導體積體電路（Large Scale[Technical Field] The present invention relates to a polishing liquid for a metal in a wiring forming step of a semiconductor device and a polishing method using the polishing liquid. [Prior Art] In recent years' with semiconductor integrated circuits (Large Scale

Integration ’ LSI)的高積體化以及高性能化，正在開發新穎的微細加工技術》化學機械研磨（Chemical Mechanical Polishing，CMP)法亦是其中之一，此方法是在[幻製造步驟、尤其是多層配線形成步驟中的層間絕緣膜的平坦化、金屬插塞（plug)形成、形成埋設配線時頻繁利用的技術（例如參照美國專利第4944836號說明書）。'、 …Μ- Μ π丨王月b化，試利用銅合金斗。然而’銅合金難以使用先前鋁合金配線的 /、韻利用的乾式敍刻（dry etching)法來進 7採^下的㈣金屬賴法（d__e 在預先於其中一面側具有由槽部（凹部）與隆起二差部的絕緣膜上堆積銅合金薄膜而在壓盤（顯（細Π))上軸如下··在圓形的研磨貼附研磨布’利用金屬用研磨液 201002805 ^潰研磨布表面，將基體（基板）的形成有金屬膜的面按聖於研磨布上，於自基板背面施加特定壓力（研磨壓力或研磨負荷）的狀態下使研磨壓盤旋轉，藉由金屬用研磨液與金屬_狄部的機械摩擦來除去金制的隆起部。對含有銅或銅合金的金屬膜進行CMP時所使用的金屬用研磨液通常含有氧化劑以及固體紙粒（細) (以下稱作「祕」）。—般認為使用此金制研磨液的研广磨的基本機制（―）如下：首先藉由氧化劑將金、 4膜表面氧化而形成金屬氧化層，再藉由雜將化層磨去。 $ 此處，位於絕緣膜的槽部中的金屬表面的金屬氧化声紐起部上的金屬氧化層相比，不太與研磨布接觸，故^ . 較到雜的磨去作用，因此隨著CMP的進行而隆起部上的金屬氧化層被除去，基體表面變平坦（例如參照電化學學會雜誌' (Journal ofElectr〇_Chemicals〇cie以），第⑶ 卷11號（1991年發行），346〇〜3464頁）。 j 另一方面，關於提高CMP的研磨速度的方法，於金屬用研^液中添加氧化金屬溶解劑被視為有效方法。研磨速度提南的主要原因雖然不明確，但可解釋其原因在於·· 由砥粒所磨去的金屬氧化物的顆粒溶解 -(以下稱作、刻」），雜的磨去效果增強研磨液中然而，於藉由添加氧化金屬溶解劑來提高CMP的研磨速度之情形時’有時埋設在槽部中的金屬層（金屬配線）表面的金屬氧化層亦被姓刻，而使金屬膜表面露出。此時， 5 201002805 所路出的金屬膜表面由於氧化劑而進一步受到氧化若此情況反覆’則對埋設在槽部中的金屬層亦進行蝕刻。因此，埋设在槽部中的金屬層表面中央部分於研磨之後會產生如盤般窪陷的現象（以下稱作「凹陷（dishing)」），被研磨膜的平坦化效果受損。、為了防止此種情況發生，而在金屬用研磨液中進—步添加防蝕劑（例如參照曰本專利特開平〇8_8378〇號公報）。防蝕劑在金屬膜表面上形成保護膜，而防止金屬氧化層洛解於金屬用研磨液中。業界期望此保護膜具有如下特性·可利用砥粒容易地磨去，並且不會降低CMp的研磨速度。圖1是表示CMP的研磨步驟的一例的剖面示意圖。於圖1 (a)的基板100中，在由銅或銅合金等所構成的金屬層30的下方，配置有在其中一面14侧具有由槽部u 與隆起部12決定的階差部13的層間絕緣膜1〇，且於金屬層30與層間絕緣膜1〇之間配置有用以防止銅成分擴散至層間絕緣膜10中的阻障層2〇。層間絕緣膜1〇例如可使用二氧化矽膜。阻障層20例如可使用钽、钽合金、氮化鈕、其他钽化合物等的導體膜。為了使基板100的表面變平坦，除了埋設銅或銅合金等的配線部分（槽部n)以外，必須利用CMP將位於層間絕緣膜1〇的隆起部12上方的阻障層20去除。然而，該些阻障層20中所使用的導體膜的硬度高於銅或銅合金等的配線部分，因此含有銅或銅合金等的研磨 201002805, 所用的研磨材料的研磨液大多情況下無法獲得充分的 CMP研磨速度。若欲使用含有此種研磨材料的金屬用研磨液對金屬層30進行研磨後亦連續地研磨阻障層2〇，則會導致配線部分產生凹陷。Integration ' LSI ' is highly integrated and high-performance, and is developing a new micro-machining technology. Chemical Mechanical Polishing (CMP) is one of them. This method is in [Fantasy manufacturing steps, especially The technique of flattening the interlayer insulating film in the multilayer wiring forming step, forming a metal plug, and frequently using the buried wiring (for example, refer to the specification of U.S. Patent No. 4944836). ', ...Μ- Μ π丨王月 b, try to use copper alloy bucket. However, the 'copper alloy is difficult to use the dry etching method of the previous aluminum alloy wiring, and the (four) metal ray method (d__e) has a groove portion (concave portion) on one side in advance. A copper alloy film is deposited on the insulating film of the bulging portion and the upper plate is pressed on the platen (bright). The polishing cloth is attached to the circular polishing. The surface of the abrasive cloth is rubbed with a metal polishing liquid 201002805. The surface of the substrate (substrate) on which the metal film is formed is placed on the polishing cloth, and the polishing platen is rotated in a state where a specific pressure (grinding pressure or polishing load) is applied from the back surface of the substrate, and the polishing liquid for metal is used. The mechanical friction of the metal portion is used to remove the raised portion of the gold. The polishing liquid for metal used for CMP of a metal film containing copper or a copper alloy usually contains an oxidizing agent and solid paper particles (fine) (hereinafter referred to as "secret" The basic mechanism (-) of the grinding machine using this gold-based polishing liquid is as follows: first, the surface of the gold film and the film are oxidized by an oxidizing agent to form a metal oxide layer, and then the layer is ground by the impurity layer. . $ Here, the metal oxide layer on the metal oxide surface of the metal surface in the groove portion of the insulating film is less in contact with the polishing cloth, so that the grinding effect is more complicated, so The CMP is performed and the metal oxide layer on the ridge portion is removed, and the surface of the substrate is flattened (for example, refer to the Journal of Electrochemical Society (Journal of Electron 〇 Chemicals 〇cie), Vol. 3 (Issued 1991), 346 〇 ~3464 pages). On the other hand, regarding the method of increasing the polishing rate of CMP, adding a metal oxide dissolving agent to the metalworking solution is considered to be an effective method. Although the main reason for the polishing rate is not clear, Explain that the reason is that the particles of the metal oxide that are ground by the granules are dissolved - (hereinafter referred to as "etched"), and the effect of the miscellaneous grinding is enhanced in the polishing liquid. However, it is improved by adding a metal oxide dissolving agent. In the case of the polishing rate of CMP, the metal oxide layer on the surface of the metal layer (metal wiring) sometimes embedded in the groove portion is also engraved by the surname, and the surface of the metal film is exposed. At this time, the metal film of 5 201002805 table The surface is further oxidized by the oxidizing agent. If this is the case, the metal layer buried in the groove portion is also etched. Therefore, the central portion of the surface of the metal layer buried in the groove portion is disc-like after polishing. The phenomenon (hereinafter referred to as "dishing") is impaired by the flattening effect of the polishing film. In order to prevent this from happening, an anti-corrosion agent is further added to the polishing liquid for metal (for example, refer to the patent) Japanese Laid-Open Patent Publication No. 8-8378-A. The corrosion inhibitor forms a protective film on the surface of the metal film to prevent the metal oxide layer from being dissolved in the polishing liquid for metal. It is expected that the protective film has the following characteristics. Go and do not reduce the grinding speed of CMp. FIG. 1 is a schematic cross-sectional view showing an example of a polishing step of CMP. In the substrate 100 of FIG. 1(a), a step portion 13 having a groove portion u and a raised portion 12 on the one surface 14 side is disposed below the metal layer 30 made of copper or a copper alloy or the like. The interlayer insulating film 1 〇 is disposed between the metal layer 30 and the interlayer insulating film 1 以 to prevent the copper component from diffusing into the interlayer insulating film 10 . As the interlayer insulating film 1 , for example, a hafnium oxide film can be used. As the barrier layer 20, for example, a conductor film of ruthenium, iridium alloy, nitride button, or other ruthenium compound can be used. In order to flatten the surface of the substrate 100, in addition to the wiring portion (groove portion n) such as copper or a copper alloy, the barrier layer 20 located above the bump portion 12 of the interlayer insulating film 1 is removed by CMP. However, since the hardness of the conductor film used in the barrier layer 20 is higher than that of a wiring portion such as copper or a copper alloy, the polishing liquid containing the copper or copper alloy or the like is not available in many cases. Full CMP grinding speed. If the metal layer 30 is to be polished by using a polishing liquid for a metal containing such an abrasive, the barrier layer 2 is continuously polished, and a recess is formed in the wiring portion.

因此’關於銅或銅合金等的金属鑲嵌配線形成、鶴 (tungsten)等的插塞配線形成等金屬埋設形成，研究了如下方法（二階段研磨法）：分如圖1(b)及圖i(c)所示的第1步驟與如圖1 (d)所示的第2步驟兩個階段，來對基板100進行研磨。於第1步驟中，對金屬層30進行研磨直至金屬層30稍許殘留之程度為止（圖1 (b))，或者進行研磨直至阻障層20露出為止（圖i (c))。於第2步驟中，進行研磨直到至少位於隆起部l2上方的阻障層2〇全部消失為止（圖1 (d))。又，於第2步驟中，視需要有時亦進一步對層間絕緣膜10進行研磨。要有時古對於上述第1步驟中所使用的金屬用研磨液，為了提 ^ LSI等的生產性或良率，而謀求一種可對金屬層進行高 '研磨且可獲得優異平坦性的金屬用研磨液。 _ π』个丨利则双鯽佘金荨的配線部分的凹陷而形 2靠性高的LSI配線，提倡—種使用如下CMp用金屬液的方法：此CMP用金屬用研磨液含有過硫酸錢至酸（quinaldie aeid)作為氧化劑，並且呈中性而本專利特開綱1·59號公報）。然但研磨逮研磨液，則雖財坦性非常優異， 7 201002805 另-方面，為了抑制銅或銅合金等的配線部分於研磨過程中的腐钱、並且對配線部分進行高速研磨，已知―種，用，下金屬用研磨㈣方法：此金相研磨液含有添加 1相對於金屬用研磨液總量為大於等於1〇重量百分比的作為雜的二氧化⑦、作為防糊的苯并三 (=贈ia牆，BTA)、作為氧化金餘解躺有機酸以及作為减_過氧化氫，且呈酸性或中性（例如參 :專：特開2购麵號公報)。然而，於使用該些金用研磨液之情料，雜:轉部分的研 $ 侵⑽r。贿）等平坦性惡化_痕（_灿= 剝洛等缺陷而言，尚有改善的餘地。次相對於此，為了提高平坦性或減少缺陷，而提倡使用不含雜、且含有水溶性聚合物作為氧化金種整劑的金屬用研磨液的方法（例如史 I :解調 ·2-222782號公報）。』如…日本專利特開然而，對於上述日本專利特開2〇〇2·222782 =載的金屬用研磨液而言，上述金屬埋設形成時== 屬層、阻障層以及層間絕緣膜的基板的研並$ 分’尚有改善的餘地。亚不充再者，例如於上述金屬埋設形成時，表面凹凸 :研磨初期的研磨速度與形成有配線的晶圓（圖宰 ^研磨速度相對應，但隨著進行研磨而表面凹 =趨於平坦化’其研磨速度近似於無配線晶圓= 曰曰圓( — ))的研磨速度。因此，對於上屬:二 201002805 磨液j為了使金屬埋設形成時的基板的研磨速度優異，而要求毯覆式晶圓以及圖案晶圓的研磨速度優異。【發明内容】因此，本發明之目的在於提供一種可獲得優異的毯覆式晶圓的研磨速度且可獲得優異的圖案晶圓的研磨速度的金屬用研磨液、以及使用此研磨液的研磨方法。為了解決上述課題，本發明的發明者等人潛心研究，結果發現了以下見解’從而完成了本發明。即，通常於酸性的金屬用研磨液林含雜之情形或雜的添加量較少之情形（例如相對於金屬騎磨液總量，雜的添加量未滿1.0重量百分比）時，機械研磨作用並未充分發揮。於使=此種金難研磨液之情料，毯覆式晶圓以及圖案晶 3麽：要是藉由研磨布與如下錯合物層的接觸所引起來物，上賴合物層是被研磨金屬（例如銅上的。/、金翻研磨液成分反應而生成於被研磨金屬表面目I舍111研磨料疏水性，故若錯合物層為親水性， St在布與錯合物層間的金屬用研磨液難以被到抑制，；磨迷;ΐ降，研磨布與錯合物層的接觸受會滞留金屬用研磨液，金屬㈣磨液進入至 &沭，二θ ^物層之間，由此研磨速度進一步下降。如上 ^ ;不含砥粒之情形或砥粒的添加量較少之情形時， 9 201002805 已判明無法充分提高研磨速度。因此’本發明者考慮到，藉水性來提高研騎與錯合物層錯合物層的疏速度。例如，有時會在金屬率，從而提尚研磨水溶性聚合物，作為了摇a 液中添加具有親水性的減少金屬用研磨液而考慮到而，若減少水溶性聚合物的添加量^ 口法。然速度會下降’平坦性亦大幅度地以卜另 =通常亦考慮到增加疏水性高的防二：其錯合物層為疏水性的方法1而，若增加防 2的研磨速度，但大多情況下毯覆式晶圓=磨= 下降。因此，本發明者等人基於該些見解而潛心研究，結果發現，藉由使用特定的防蝕劑可解決上述問題。即，本發明的金屬用研磨液是含有水、氧化劑、氧化金屬溶解劑、防蝕劑以及氧化金屬溶解調整劑的研磨液，並且研磨液的pH值在1〜5的範圍内，防钱劑包含甲苯三唾（tolyltriazole)以及二苯胍（diphenylguanidine)中的至少一方。於本發明的金屬用研磨液中，防蝕劑包含甲笨三唑以及二苯胍中的至少一方，故可將金屬用研磨液成分的疏水性保持得較高。因此，被研磨金屬與金屬用研磨液成分反應而形成的錯合物層的疏水性提高，研磨布與錯合物層的 201002805 接觸變良好。如上所述’藉由使研磨布與錯合物層的接觸良好’可利用本發明的金屬用研磨液獲得優異的毯覆式晶圓的研磨速度、並且獲得優異的圖案晶圓的研磨速度。 . 氧化金屬溶解調整劑較好的是包含具有陰離子性基團的水溶性聚合物。此時，可獲得更優異的毯覆式晶圓以及圖案晶圓的研磨速度。又’具有陰離子性基團的水溶性聚合物較好的是包含選自甲基丙烯酸（methacrylic acid )、丁烯酸（crotonic acid)、2-甲基丁烯酸以及3_曱基丁烯酸所組成的族群中的至少一種不飽和羧酸化合物與丙烯酸的共聚物或其鹽，上述共聚物的共聚合比（丙烯酸/不飽和竣酸化合物）為 (99.5/0.5)〜（80/20)。此時，可獲得更優異的毯覆式晶圓以及圖案晶圓的研磨速度。氧化劑較好的是包含選自過氧化氫、過硫酸銨、硝酸、過碘酸鹽、次氯酸以及臭氧水（〇z〇ne water) 的族群中的至少一種。、成 " 氧化金屬溶解劑較好的是包含選自無機酸、有機酸、胺基乙酸（aminoacetic acid )、胺基磺酸（amid〇sulfuHc 肊记）以及該等酸之鹽所組成的族群中的至少一種。防蝕劑較好的是更包含選自含氮雜環化合物、含氮雜 - 環化合物的鹽、硫醇（mercaptan)、葡萄糖（gluc〇se)以及纖維素（cellulose)所組成的族群中的至少一種。本發明的金制研磨液亦可含有相對於研磨液 i於等於1.G重量百分比的研餘子。較好的是研磨粒子 11 201002805 包含選ί二氧化石夕、氧化銘、二氧㈣、二氧化欽、，鍅以及氧化錯所虹成的族群中的至少一種。乳化麻’二的是本發明的金屬用研磨液用於基板的研土 #具有形成有隆起部及槽部的面的層間纟 =::=的面而設置的阻障層、二= 2 又，本發明的金屬用研磨液在包括第1步驟以及第驟中’較好的是用於上述至少第1步驟中，上述第1步驟自金屬層側對基板崎 3=^的至少_部分露出，上述第2步騎==Therefore, the following methods (two-stage polishing method) have been studied for the formation of metal damascene wiring such as copper or copper alloy, and the formation of plug wiring such as cranes, etc., as shown in Fig. 1(b) and Fig. The substrate 100 is polished by the first step shown in (c) and the second step shown in FIG. 1(d). In the first step, the metal layer 30 is polished until the metal layer 30 is slightly left (Fig. 1 (b)), or polished until the barrier layer 20 is exposed (Fig. i(c)). In the second step, the polishing is performed until at least the barrier layer 2 which is located above the ridge portion l2 disappears (Fig. 1 (d)). Further, in the second step, the interlayer insulating film 10 may be further polished as occasion demands. In order to improve the productivity or yield of the LSI or the like, the polishing liquid for metal used in the first step is required to be used for a metal which can be highly polished and obtain excellent flatness. Slurry. _ π 丨丨则则则则配线配线配线配线配线配线配线配线配线配线配线配线配线配线 LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI LSI (quinaldie aeid) is an oxidizing agent and is neutral and is disclosed in Japanese Patent Laid-Open Publication No. Hei. However, the grinding liquid is very good, and it is very good. 7 201002805 In addition, in order to suppress the corrosion of the wiring part of copper or copper alloy in the grinding process, and to perform high-speed grinding of the wiring part, it is known that ― Grinding method for the use of the lower metal (IV): the metallographic slurry contains the addition of 1 as a total amount of the polishing liquid for the metal of 1% by weight or more as a heterogeneous oxidized 7 as an anti-paste benzotriene ( = ia wall, BTA), organic acid as oxidized gold, and as oxidized hydrogen peroxide, and it is acidic or neutral (for example, see: special: special open 2). However, in the case of using the gold-based slurry, the miscellaneous portion of the rotating portion is invaded (10)r. There is still room for improvement in terms of flatness such as bribery. A method of using a polishing liquid for a metal as a gold oxide seeding agent (for example, I: Demodulation, No. 2-222782). The Japanese Patent Laid-Open No. 2,222,782 = for the metal-based polishing liquid, there is room for improvement in the formation of the substrate of the == layer, the barrier layer, and the interlayer insulating film when the metal is buried. When the metal is buried, the surface unevenness: the polishing speed at the initial stage of polishing corresponds to the wafer on which the wiring is formed (corresponding to the polishing speed of the wafer, but the surface is concave = tends to be flattened as the polishing is performed), and the polishing speed is similar to that of no wiring. The polishing rate of the wafer = 曰曰 round ( — )). Therefore, for the superior: 2 201002805 The grinding liquid j is required to make the polishing speed of the substrate when the metal is buried, and the blanket wafer and the pattern wafer are required. Excellent grinding speed SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a polishing liquid for a metal which can obtain an excellent polishing rate of a blanket wafer and which can obtain an excellent polishing speed of a pattern wafer, and a polishing liquid using the same. In order to solve the above problems, the inventors of the present invention have intensively studied and found the following findings to complete the present invention. That is, the acidic metal slurry is usually mixed with impurities or impurities. In less cases (for example, the amount of impurities added is less than 1.0% by weight relative to the total amount of metal riding fluid), the mechanical grinding action is not fully exerted. Wafer and pattern crystal 3: If the object is caused by the contact of the polishing cloth with the following complex layer, the upper lysate layer is a metal to be polished (for example, on copper). On the surface of the metal to be polished, the abrasive material is hydrophobic, so if the complex layer is hydrophilic, the polishing liquid for the metal between the cloth and the complex layer is difficult to be suppressed. The contact between the polishing cloth and the complex layer is affected by the retention of the metal polishing liquid, and the metal (4) grinding liquid enters between the & 沭, two θ ^ layer, whereby the polishing rate is further lowered. In the case of bismuth-containing granules or when the amount of cerium particles added is small, 9 201002805 has been found to be unable to sufficiently increase the grinding speed. Therefore, the inventors considered that the water-based layer can improve the layer of the compounding layer of the riding and the complex layer. For example, sometimes at the metal rate, it is recommended to grind the water-soluble polymer, and it is considered as a hydrophilic liquid for reducing the metal slurry in the shake liquid, and if the water-soluble polymer is reduced, Adding amount ^ mouth method. However, the speed will decrease. 'Flatness is also greatly improved. In addition, it is generally considered to increase the hydrophobicity of the anti-two: the complex layer is hydrophobic. The grinding speed, but in most cases the blanket wafer = mill = drop. Therefore, the present inventors conducted intensive studies based on these findings, and as a result, found that the above problems can be solved by using a specific corrosion inhibitor. That is, the polishing liquid for metal of the present invention is a polishing liquid containing water, an oxidizing agent, a metal oxide dissolving agent, an anticorrosive agent, and a metal oxide dissolution adjusting agent, and the pH of the polishing liquid is in the range of 1 to 5, and the anti-money agent contains At least one of tolyltriazole and diphenylguanidine. In the polishing liquid for metal of the present invention, since the corrosion inhibitor contains at least one of benzotriazole and diphenyl hydrazine, the hydrophobicity of the polishing liquid component for metal can be kept high. Therefore, the hydrophobicity of the complex layer formed by the reaction of the ground metal with the polishing liquid component of the metal is improved, and the contact between the polishing cloth and the compound layer of 201002805 becomes good. As described above, 'the contact between the polishing cloth and the complex layer is good'. The polishing liquid for the metal of the present invention can be used to obtain an excellent polishing rate of the blanket crystal, and an excellent polishing speed of the pattern wafer can be obtained. The oxidized metal dissolution modifier preferably contains a water-soluble polymer having an anionic group. At this time, a more excellent blanket wafer and a polishing speed of the pattern wafer can be obtained. Further, the water-soluble polymer having an anionic group preferably comprises a selected from the group consisting of methacrylic acid, crotonic acid, 2-methylbutenoic acid, and 3-mercaptobutenoic acid. a copolymer of at least one unsaturated carboxylic acid compound and acrylic acid or a salt thereof in the group of the composition, wherein the copolymerization ratio (acrylic acid/unsaturated citric acid compound) of the copolymer is (99.5/0.5) to (80/20) . At this time, a more excellent blanket wafer and a polishing speed of the pattern wafer can be obtained. The oxidizing agent preferably contains at least one selected from the group consisting of hydrogen peroxide, ammonium persulfate, nitric acid, periodate, hypochlorous acid, and ozone water. The oxidized metal dissolving agent preferably comprises a group selected from the group consisting of inorganic acids, organic acids, aminoacetic acid, amino sulfonic acid (amid sulfu Hc )), and salts of such acids. At least one of them. Preferably, the corrosion inhibitor further comprises at least one selected from the group consisting of a nitrogen-containing heterocyclic compound, a nitrogen-containing heterocyclic compound salt, a mercaptan, glucose (gluc〇se), and cellulose (cellulose). One. The gold polishing liquid of the present invention may further contain a researcher having a weight percentage of 1.G with respect to the polishing liquid i. Preferably, the abrasive particles 11 201002805 comprise at least one of the group selected from the group consisting of sulphur dioxide, oxidized, dioxane, dioxins, oximes, and oxidized. In the case of the emulsified mash, the polishing liquid for metal of the present invention is used for the grounding of the substrate. The barrier layer having the surface of the layer 纟=::= having the surface of the ridge portion and the groove portion is formed, and the second layer is 2; In the first step and the second step, the polishing liquid for metal of the present invention is preferably used in at least the first step, and the first step is exposed from the metal layer side to at least a portion of the substrate. , step 2 above, ride ==

电缘膜的至阻障屬以及金屬層進行研磨，使隆起部的層間絕緣膜的至少一部分露出。曰J 阻障層較好的是包含選自紐、氮化麵、紐合金、里他组化合物、鈦 '氮化鈦、欽合金、其他鈦化合物令化鎢、鶴合金、其他鎢化合物、釕、氮化釕、釕合金以^ 其他釕化合物所組成的族群中的至少—種。機聚較好的是㈣賴、麵無航合膜或有又，本發明的研磨方法是基板的研磨方法，並且其於將基板的需研磨的面按壓於研磨壓盤的研磨布上的狀熊下，一方面將上述本發明的金屬用研磨液供給於上述面= 研磨布之間，一方面使研磨布與基板相對移動，而對基^ 12 201002805. 進行研磨。於本發_研磨料巾，时肖與錯合物層的接觸良好二二案::圓的研磨賴研磨速度，並且可獲得優異的圖 ::ί:?==:== 進灯研磨，或者對金屬層與阻障層的至少一部分進行研磨。又，本發明的研磨方法較好的是使用上述本發明的金屬用研磨絲進行包括第！步_ 中:至少第i步驟’上述第丨步驟自金屬層側對= 研磨’使位於隆起部上方的阻障層的至少一部分露 ^第2步驟對位於隆起部上方的阻障層以及金屬層進行研磨，使隆起部的層間絕緣膜的至少一部分露出。The barrier film and the metal layer of the electric film are polished to expose at least a portion of the interlayer insulating film of the bump. The barrier layer of 曰J is preferably selected from the group consisting of nucleus, nitrided surface, neodymium alloy, lithothermic compound, titanium titanium nitride, alloy, other titanium compounds, tungsten, crane alloy, other tungsten compounds, lanthanum At least one of the group consisting of cerium nitride and cerium alloy with other cerium compounds. Preferably, the polishing method of the present invention is a method of polishing a substrate, and the method of polishing the surface of the substrate to be pressed against the polishing cloth of the polishing platen. Under the bear, on the one hand, the above-mentioned metal polishing liquid of the present invention is supplied between the above-mentioned surface = polishing cloth, and on the other hand, the polishing cloth and the substrate are relatively moved, and the polishing is performed on the substrate 12 201002805. In the hair _ abrasive towel, the contact between the shawl and the complex layer is good. The second case: the round grinding and polishing speed, and the excellent picture can be obtained:: ί:?==:== Or grinding at least a portion of the metal layer and the barrier layer. Further, the polishing method of the present invention is preferably carried out using the above-described polishing wire for metal of the present invention. Step _ medium: at least the i-th step 'the above-mentioned second step from the metal layer side pair = grinding' causes at least a portion of the barrier layer above the ridge portion to be exposed. The second step is to block the barrier layer and the metal layer above the ridge portion. Polishing is performed to expose at least a part of the interlayer insulating film of the ridge portion.

U 於本發明的研磨方法中，較好的是阻障層包含選自 ^化组、组合金、其他组化合物、鈦、氮化鈦、欽合 “、八他鈦化合物、鎢、氮化鎢、鎢合金、其他鎢化合物、 =少=釘、訂合金以及其他釘化合物所組成的族群中的於本發明的研磨方法中’較好的是層間絕緣膜為石夕系被膜、有機無機混合膜或有機聚合物膜。 [發明之效果] 13 201002805 根據本發明，可提供一種可獲得研磨速度且亦可獲得優異的圖^的毯覆式曰曰_ 研磨液、以及使用此研磨液研磨速度的金屬用為讓本發明之上述特徵和舉實施例，並配合所附圓式作mr下顯易懂，下文特【實施方式】的最：二:一參照圖式—方面詳細說明用以實施發明 3 明圖式中’對相同或等效部分標註相同的比率。圖式的尺寸比率並不限於圖示本實施形態的金屬用研磨漭r 水、氧化劑、氧化金屬溶_ 研磨液）是含有調整劑的研舰。以下，金屬溶解明。跣CMP研磨液的各成分加以說 :::磨後的凹陷的方〜二磨於⑽重量百分比’更好的是大於等面而令=笨^4==對金屬層的研磨速度優異的方小於i於^目對於㈣液總重量較好的是 ^等於3.0 h百分比，更好的是小於等於2 q重^ 又，關於二苯胍的添加量，就可更有效率地抑制研磨 14U In the polishing method of the present invention, it is preferred that the barrier layer comprises a group selected from the group consisting of a combination of gold, other groups of compounds, titanium, titanium nitride, accommodating, octahedron, tungsten, tungsten nitride. In the polishing method of the present invention in the group consisting of tungsten alloy, other tungsten compound, = less nail, alloy, and other nail compounds, it is preferable that the interlayer insulating film is a stone coating film or an organic-inorganic hybrid film. Or an organic polymer film. [Effects of the Invention] 13 201002805 According to the present invention, it is possible to provide a blanket type 研磨_grinding liquid which can obtain a polishing speed and which can also obtain an excellent image, and a polishing rate using the polishing liquid. The metal is used to make the above-mentioned features and embodiments of the present invention, and it is easy to understand with the accompanying circular form, and the following is a detailed description of the second embodiment of the present invention. 3 In the drawings, 'the same ratios are used for the same or equivalent parts. The dimensional ratio of the drawings is not limited to the metal polishing 漭r water, oxidizing agent, or oxidized metal solution _ polishing liquid in the present embodiment. The whole agent of the research ship. Below, the metal dissolves. The components of the 跣CMP slurry are said to be::: the square of the dent after grinding ~ two mills in (10) weight percent 'better is greater than the equal surface and make = stupid ^ 4==The polishing rate of the metal layer is less than i. The total weight of the liquid is preferably equal to 3.0 h percentage, more preferably less than or equal to 2 q weight ^ and, regarding the addition of diphenyl hydrazine Quantity, it can inhibit grinding 14 more effectively

201002805, 4 ，百77比’更好的是大於等於G.G2重量百分比说CMP對金屬層的研磨速度優異的方面而女，二本胍的添加量相對於研磨液總重量較 ^ Μ重量百錢，更好岐持等於0.5«百分比。另外亦可为別於上述細内—併添加甲苯三销二苯脈來防蝕劑。又二防_亦可更包含甲苯三嗤及二苯胍以外的化合物。甲苯二唑及二苯胍以外的化合物較好的是選自含氮化合物及其鹽、猶、葡躲以及纖較所組成的族群中的至少一種。含氮化合物例如可列舉：具有咪唑（imidaz〇le)骨架、三口坐（triazole )骨架、哺咬（pyrimidine )骨架、胍（即肪通狀）骨·嚷0坐（thiazole)骨架或η比β坐（pyraz〇ie)骨架的化合物。含氮化合物更好的是雜環化合物，較理想的是選自以下群組中的含氮雜環化合物。即，含氮雜環化合物可列舉：苯并咪峻-2-硫醇（benzoimidazole-2-thiol)、三嗓二硫醇（triazine dithiol)、三嗪三硫醇、2-[2-(苯并噻唑基)]硫代丙酸（2-[2-(benzothiazolyl)]thiopropionic acid)、2-[2-(苯并噻唑基)]硫代丁酸、2-M基苯并噻唑、1，2,3-三唑、1，2,4-三口坐、3-胺基-1H-1，2,4-三嗤（3-amino-lH-l,2,4-triazole)、苯并三0坐、1-經基苯并三。坐（1-hydroxybenzotriazole)、1-二羥丙基苯并三唑、2,3-二羧丙基苯并三唑 (2,3-dicarboxypropylbenzotriazole)、4-經基苯并三唾、4- 15 201002805 敌基-1H-苯并三吐、4-叛基-1H-苯并三η坐甲醋 (4-carboxy-lH- benzotriazole methylester)、4-叛基-1H-苯并三唑丁酯、4-羧基-1H-苯并三唑辛酯、5-己基苯并三唑、 [1,2,3-苯并三唑基-1_甲基][1，2,4-三唑基-1-甲基][2_乙基己基]胺、萘驗三°坐（naphthotriazole)、雙[(1-苯并三β坐基）甲基]膦酸（bis[(l-benzotriazolyl)methyl]phosphonicacid)等唑等。該些化合物可單獨使用一種，或者混合使用兩種或兩種以上。關於甲本二0坐及一本脈以外的化合物的添加量，就可抑制研磨後的凹陷的方面而言’相對於研磨液總重量較好的是大於等於0.01重量百分比，更好的是大於等於〇1重量:分比。又，就CMP對金屬層的研磨速度提高的方面而σ，甲本二β坐及一本胍以外的化合物的添加量相對於研磨液總重量較好的是小於等於3.〇重量百分比，更好的是小於等於2.0重量百分比。又，於CMP研磨液中，較好的是含有具有陰離子性基團的水溶性聚合物（陰離子性高分子化合物）或1睡作 $氧化金屬溶解調整劑。上述陰離子性基團較好的是^自猶基、紐基、魏基以及雖祕所組成的族群中的至夕種g此基，更好的是確酸基、叛酸基、碟酸基，進而較好的料酸基、紐基。陰離子性高分子化合物中可 ^該些陰離子性基财的單獨—種或者兩種或兩種以上0 上述水溶性聚合物例如可列舉：聚丙稀酸、不飽和叛 16 201002805 酸化合物與丙烯酸的共聚物及其鹽。共聚物的鹽可列舉：銨鹽、鹼金屬鹽、鹼土金屬鹽、齒化物。但是，於所應用的基板為半導體積體電路用矽基板等之情形時’就可抑制鹼金屬、鹼土金屬、鹵化物等所引起的汚染的方面而言，較理想的是上述共聚物或其銨鹽。、又，就進一步提高被研磨金屬與研磨液成分反應而形成的錯合物層的疏水性、使研磨布與錯合物層的接觸更為良好的方面而言，水溶性聚合物較好的是包含選自甲基丙稀酸、丁烯酸、2-甲基丁烯酸以及3·甲基丁烯酸所組成的族群中的至少一種不飽和鲮酸化合物（疏水性丙烯酸）與丙烯酸的共聚物或其鹽。〃關於共聚物的共聚合比（丙浠酸/不飽和羧酸化合物）’就研磨後的平坦性變良好、CMp對毯覆式晶圓以及圖案晶圓的研磨速度進一步提高的方面而言，較好的是丙烯酸相對於不飽和羧酸化合物的共聚合比大於等於 U0/20)，更好的是大於等於（82/18)，進而較好的是大 ( ;等於（85/15 )。又’就錯合物層的疏水性增大、CMP對，案晶圓的研磨速度進—步提高的方面而言，較好的是丙烯酸相對於不飽和羧酸化合物的共聚合比小於等於 (99.5/0.5)，更好的是小於等於（撕），進而較好的是小 • 於等於（98/2)。又，氧化金屬溶解調整劑即便包含兩種或兩種以上的所3陰離子性基團各不相同的陰離子性高分子化合物亦可吏用陰離子性南分子化合物可列舉：聚苯乙稀續酸 17 201002805 (polystyrene sulphonic acid )、聚丙稀 Μ 胺曱基丙續酸 (polyacrylamide methylpropanesulphonic acid )、聚蘋果酸 (polymalic acid)、聚叛酸、聚丙稀酸、聚曱基丙稀酸、聚衣康酸（polyitaconic acid )、聚順丁烯二酸（polymaleic acid )、聚反丁稀二酸（polyfumaric acid )'聚天冬胺酸 (polyasparaginic acid)、聚穀胺酸（polyglutamic acid)、聚離胺酸（polylysine)、聚填酸（polyphosphoric acid)、偏磷酸（metaphosphoricacid)及其鹽等。鹽可列舉：銨鹽、鹼金屬鹽、鹼土金屬鹽、齒化物等。但是，於所應用的基板為半導體積體電路用矽基板等之情形時，就可抑制鹼金屬、鹼土金屬、鹵化物等所引起的汚染的方面而言較理想的是上述酸（例如聚羧酸、聚丙烯酸）或其銨鹽。於CMP研磨液令，氧化金屬溶解調整劑的合計添加量就CMP 屬層的研磨速度提高的方面而言，於 = Ϊ是大於等於〇_〇1重量百分比，更好的等重篁百分比。又，就可抑制研磨後的凹陷 =5重量總重量較好的是小比。重百刀比，更好的是小於等於2.0重量百分分步=屬溶解，的重量平均等於500,更好的是大於:、方面而&，較好的是大於於琴就藉由大於等 201002805 -/ Vf 〆》度的方面而s，乳化金屬溶解調整劑的重量平均分子量較好的是小於等於500,000 ’更好的是小於等於300,000。氧化金屬溶解調整劑的重量平均分子量可藉由凝膠滲透層析法（Gel Permeation Chromatography)使用標準聚苯乙烯的校準曲線（calibration curve )來測定。 . CMP研磨液中所使用的氧化金屬溶解劑較好的是水溶性的氧化金屬溶解劑。水溶性的氧化金屬溶解劑例如較 f_ 好的是：丙二酸（malonic acid)、檸檬酸（citric acid)、蘋 ' 果酸、乙醇酸（gb^icacid)、榖胺酸、醛糖酸（glyc〇nic acid )、草酸（oxaiic acid )、酒石酸（tartaric add )、吡咬曱酸（picolinic acid )、於驗酸（nic〇tinic acjd )、爲桃酸 (mandelic add)、乙酸、甲酸、乳酸〇actic acid)、鄰笨二甲酸（phthalic acid)、反丁烯二酸、順丁烯二酸等有機酸，硫酸、硝酸、磷酸、鹽酸等無機酸，胺基乙酸、胺基嶒酸及其鹽。該些水溶性的氧化金屬溶解劑對於包含選自銅、銅合金、銅的氧化物以及銅合金的氧化物所組成的族 f中的至少一種作為需研磨的金屬的積層膜（金屬層）而言較為合適。水溶性的氧化金屬溶解劑之中，就維持實用性的毯覆式晶圓以及圖案晶圓的研磨速度、並且可有效地抑制姓刻速度的方面而言，更好的是韻果酸、酒石酸檬酸、罐酸、硫酸。丁關於氧化金屬溶解獅添加量，就毯覆式晶圓以及圖案晶f的研磨速度進一步提高的方面而言，相對於研磨液總重量較好的是大於等於〇〇〇5重量百分比，更好的是大 201002805 於等於0.01重量百分比。就提高平坦性、抑制缺陷產生的方面而a ’乳化金屬溶解劑的添加量較好的是小於等於1〇重量百分比，更好的是小於等於1重量百分比。關於CMP研磨液的pH值，就CMP對毯覆式晶圓以及圖案晶圓的研磨速度優異、並且可有效地抑制蝕刻速度的方面而言，此pH值在1〜5的範圍内，較好的是2〜4 的範圍内，更好的是2.5〜4的範圍内。 CMP研磨液的pH值可藉由酸或鹼成分的添加量來調整。酸成分可列舉上述氧化金屬溶解劑。鹼成分可列舉：氨、氫氧化鉀、氫氧化鈉、氫氧化四甲基銨 (Tetramethylammonium hydroxide，TMAH)等，該些驗成分可單獨使用一種或者組合使用兩種或兩種以上。 CMP研磨液的PH值可使用PH計（pH meter)(例如電二學儀器公司製造’型號rPHL_4〇」）來測定。更具體，二，pH值是作為如下值來測定的：使用標準緩衝液（鄰苯二甲酸鹽PH緩衝液PH值：4.01 (25。〇,中性碟酸鹽 PH緩衝液PH值：6.86 (25X：))進行兩點校正之後，二 $放入至研磨液中，經過2分贼2分鐘以上而穩定後 CMP研磨液中亦可含有研磨粒子（以下稱作「紙 it Γ較好的是包含二氧糾、氧触、二氧化飾、氧化。_、，化锆、氧化鍺等，其中更好的是氧化鋁、二 =石。二氧化矽較好的是矽酸膠（colloidalsilic _立可單獨㈣—種或者混合使用兩種或兩種以上。° — 20 201002805 ^\jy / jpif 關於雜的添加量，就提高平坦性、抑制缺陷產生的 =面而。相對於研磨液總重量較好的是小於等於1〇重罝百分比，更好的是小於等於〇 5重量百分比。關於絲的-:綠子的_ (—摊徑），就平坦性 j的方面而言’較好的是小於等於綱nm，更好的是小二於15〇 nm，進而較好的是小於等於1〇〇肺。紙粒的一次粒子的一次粒徑較好的是大於等於5 nm。201002805, 4, Hundred and 77 is better than G.G2 by weight. The CMP is excellent in the polishing rate of the metal layer. The amount of the two bismuth is relative to the total weight of the polishing liquid. Money, better hold is equal to 0.5« percentage. In addition, it may be different from the above-mentioned fines - and add toluene three-pin dibenzophenone to prevent corrosion. Further, it is also possible to further contain a compound other than toluene triterpenes and diphenyl hydrazine. The compound other than toluenediazole and diphenylguanidine is preferably at least one selected from the group consisting of a nitride-containing compound and a salt thereof, a juvenile, a scutellaria, and a fiber. Examples of the nitrogen-containing compound include an imidaz〇le skeleton, a triazole skeleton, a pyrimidine skeleton, a ruthenium (ie, a fat-like) bone, a thiazole skeleton, or an η ratio β. Sit (pyraz〇ie) a compound of the skeleton. More preferably, the nitrogen-containing compound is a heterocyclic compound, and more preferably a nitrogen-containing heterocyclic compound selected from the group consisting of the following. That is, the nitrogen-containing heterocyclic compound may, for example, be benzoimidazole-2-thiol, triazine dithiol, triazine trithiol, 2-[2-(benzene 2-[2-(benzothiazolyl)]thiopropionic acid), 2-[2-(benzothiazolyl)]thiobutyric acid, 2-M-benzobenzothiazole, 1, 2,3-triazole, 1,2,4-trisole, 3-amino-1H-1,2,4-triazole (3-amino-lH-l, 2,4-triazole), benzotriene 0 sitting, 1-aminobenzotriene. 1-hydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-pyridylbenzotriazole, 4- 15 201002805 Dihydrocarbyl-1H-benzotriazole, 4-carboxy-lH-benzotriazole methylester, 4-reactive-1H-benzotriazolidine, 4-carboxy-1H-benzotriazol octyl ester, 5-hexylbenzotriazole, [1,2,3-benzotriazolyl-1_methyl][1,2,4-triazolyl- 1-methyl][2-ethylhexyl]amine, naphthotriazole, bis[(1-benzotriazolyl)methyl] Phosphonic acid) and the like. These compounds may be used alone or in combination of two or more. With respect to the addition amount of the compound other than the one sitting and one pulse, the amount of the depression after the grinding can be suppressed from being preferably 0.01% by weight or more, more preferably greater than the total weight of the polishing liquid. Equal to 〇1 weight: fraction. Further, in terms of the improvement of the polishing rate of the metal layer by CMP, the amount of the compound other than the total weight of the polishing liquid is preferably equal to or less than 3. Preferably, it is 2.0% by weight or less. Further, in the CMP polishing liquid, a water-soluble polymer (anionic polymer compound) having an anionic group or a oxidizing metal dissolution adjusting agent is preferably contained. The above anionic group is preferably an anthracene group, a neotyl group, a thiol group, and a group of the genus of the genus, and more preferably an acid group, a tick acid group, or a disc acid group. Further, it is preferably an acid group or a Newtyl group. In the anionic polymer compound, the anionic group may be used alone or in two or more kinds. The above water-soluble polymer may, for example, be a copolymer of polyacrylic acid or unsaturated rebel 16 201002805 acid compound and acrylic acid. And its salt. The salt of the copolymer may, for example, be an ammonium salt, an alkali metal salt, an alkaline earth metal salt or a tooth compound. However, when the substrate to be applied is a tantalum substrate for a semiconductor integrated circuit or the like, it is preferable to suppress the contamination caused by an alkali metal, an alkaline earth metal, a halide or the like, and the copolymer or the copolymer thereof Ammonium salt. Further, in order to further improve the hydrophobicity of the complex layer formed by the reaction between the polishing metal and the polishing liquid component, and to improve the contact between the polishing cloth and the complex layer, the water-soluble polymer is preferred. Is at least one unsaturated citric acid compound (hydrophobic acrylic acid) and acrylic acid comprising a group selected from the group consisting of methyl acrylic acid, crotonic acid, 2-methyl crotonic acid, and 3 - methyl crotonic acid. Copolymer or a salt thereof. 〃 The copolymerization ratio (propionate/unsaturated carboxylic acid compound) of the copolymer is improved in the flatness after polishing, and the CMp is further improved in the polishing rate of the blanket wafer and the pattern wafer. It is preferred that the copolymerization ratio of acrylic acid to the unsaturated carboxylic acid compound is greater than or equal to U0/20), more preferably equal to or greater than (82/18), and further preferably large (equal to (85/15). Further, in terms of the increase in the hydrophobicity of the complex layer, the CMP pair, and the improvement of the polishing rate of the wafer, it is preferred that the copolymerization ratio of the acrylic acid to the unsaturated carboxylic acid compound is less than or equal to ( 99.5/0.5), more preferably less than or equal to (tear), and further preferably less than (98/2). Further, the oxidized metal dissolution modifier contains two or more of the anionic The anionic polymer compound having different groups may also be used as an anionic south molecule compound: polystyrene sulfonate 17 201002805 (polystyrene sulphonic acid), polyacrylamide methylpropanesulphonic acid (polyacrylamide methylpropanesulphonic acid) ), Polymalic acid, polyphenolic acid, polyacrylic acid, polyacrylic acid, polyitaconic acid, polymaleic acid, polyfumaric acid Acid ) 'polyasparaginic acid, polyglutamic acid, polylysine, polyphosphoric acid, metaphosphoric acid and its salts. In the case where the substrate to be applied is a tantalum substrate for a semiconductor integrated circuit, etc., it is possible to suppress an alkali metal, an alkaline earth metal, a halide, etc., in the case of a substrate, or the like. The above-mentioned acid (for example, polycarboxylic acid, polyacrylic acid) or an ammonium salt thereof is preferable in terms of the contamination caused. In the CMP polishing liquid, the total addition amount of the oxidation metal dissolution adjusting agent increases the polishing rate of the CMP layer. In terms of, = is greater than or equal to 〇〇重量 1 weight percent, a better equal weight percentage. In addition, it can suppress the depression after grinding = 5 weight total weight is preferably a small ratio. ratio, Preferably, it is less than or equal to 2.0 weight percent step = is dissolved, the weight average is equal to 500, more preferably greater than:, aspect and &, preferably greater than the piano by greater than etc. 201002805 - / Vf 〆 In terms of degree, the weight average molecular weight of the emulsified metal dissolution modifier is preferably 500,000 or less, and more preferably 300,000 or less. The weight average molecular weight of the metal oxide dissolution modifier can be determined by gel permeation chromatography (Gel Permeation Chromatography) using a calibration curve of standard polystyrene. The metal oxide dissolving agent used in the CMP polishing liquid is preferably a water-soluble metal oxide dissolving agent. The water-soluble metal oxide dissolving agent is, for example, better than f_: malonic acid, citric acid, citric acid, glycolic acid (gb^icacid), proline, aldonic acid ( Glycidnic acid ), oxaiic acid, tartaric add, picolinic acid, nic〇tinic acjd, mandelic add, acetic acid, formic acid, lactic acid 〇actic acid), organic acids such as phthalic acid, fumaric acid, maleic acid, inorganic acids such as sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, aminoacetic acid, amino decanoic acid and salt. The water-soluble metal oxide dissolving agent is at least one of a group f consisting of an oxide selected from the group consisting of copper, a copper alloy, an oxide of copper, and an oxide of a copper alloy as a laminated film (metal layer) of a metal to be polished. The words are more appropriate. Among the water-soluble metal oxide dissolving agents, vermic acid and tartaric acid are more preferable in terms of maintaining the practical polishing speed of the blanket wafer and the pattern wafer, and effectively suppressing the speed of the surname. Citric acid, can acid, sulfuric acid. Regarding the amount of oxidized metal dissolved lion, the polishing speed of the blanket wafer and the pattern crystal f is further improved, and the total weight of the polishing liquid is preferably 5% by weight or more, more preferably The big 201002805 is equal to 0.01 weight percent. The amount of the a 'emulsified metal dissolving agent added is preferably 1% by weight or less, more preferably 1% by weight or less, in terms of improving flatness and suppressing the occurrence of defects. Regarding the pH value of the CMP polishing liquid, the pH is in the range of 1 to 5 in terms of the excellent polishing rate of the CMP to the blanket wafer and the pattern wafer, and the etching rate can be effectively suppressed. The range is 2 to 4, and the better is within the range of 2.5 to 4. The pH of the CMP slurry can be adjusted by the addition amount of the acid or alkali component. The acid component is exemplified by the above metal oxide dissolving agent. Examples of the alkali component include ammonia, potassium hydroxide, sodium hydroxide, and tetramethylammonium hydroxide (TMAH). These test components may be used alone or in combination of two or more. The pH of the CMP slurry can be measured using a pH meter (e.g., Model RPHL_4® manufactured by Seiko Instruments Inc.). More specifically, second, the pH is determined as follows: standard buffer (phthalate pH buffer pH: 4.01 (25. 〇, neutral dish pH buffer pH: 6.86) (25X:)) After the two-point calibration is performed, the second amount is placed in the polishing liquid, and after 2 minutes or more of the thief for 2 minutes or more, the CMP polishing liquid may also contain abrasive particles (hereinafter referred to as "paper". It is composed of dioxobic, oxygen, oxidized, oxidized, _, zirconium oxide, cerium oxide, etc., among which alumina and bismuth are preferred. cerium oxide is preferably colic acid (colloidalsilic _ Li can be used alone or in combination of two or more types. ° — 20 201002805 ^\jy / jpif Regarding the amount of addition, the flatness is improved and the surface of the defect is suppressed. Preferably, it is less than or equal to 1% by weight, more preferably less than or equal to 〇5 by weight. Regarding the silk-: green _ (--a diameter), in terms of flatness j, 'better It is less than or equal to the outline nm, and more preferably the second is at 15 〇 nm, and more preferably less than or equal to 1 〇. Lung. Primary particle diameter of primary particles is preferably greater than or equal paper particles 5 nm.

於雜凝聚之情形時，二次粒子的粒徑（二次粒徑） ^坦性，南的方面而言較好的是小於等於· nm，更好 ’進而較好的是小於等於100励。就砥粒對錯合物層的機械除絲力 =及圖案晶圓的研磨速度進—步提高的方面5 ii 的粒徑（二次_)較好的是大於等於l〇nm。徑可穿透式電子顯微鏡（例 J限=立製作所製造’商品名「84700」))來測定。可❹錢射散射絲度料儀（例如研磨液中的金屬氧化劑可列舉：過氧化氮水蓉2 硫酸錢、石肖酸、過蛾酸鹽、次氯酸以及臭氧使ί二別好的是過氧化氫。該些金屬氧化劑可單獨為包人^/合使用兩種或兩㈣上。於需研磨的基體屬、:土⑽路用70件的祕板之情科，就可抑制驗金等所引起的汚染的方面而言’較理想的是使 21 201002805 發成分的氧化劑。但是，因臭氧水的組成隨時為不故取適合的是過氧化氫。於應用對象的基板非揮===;板等之情形時’即™ 幸曰ΓΓ氧化劑的添加量’就CMP對毯覆式晶圓以及圖進―步提高的方面而言，相對於研磨液『重=子的是！重量百分比〜40重量百分比更好的是重置百》比〜3G重量百分比。上述氧化劑進=算氧化劑的添加量是根據水溶液中的氧化劑換水ίΖΓ射㈣㈣水㈣合蚊蒸财、離子交明。接著，就本發明的研磨方法的較佳實施形態加以說將αΪΙΓϊ的具有#研磨_基板的研磨方法，是於下的面按壓於書盤的研磨布上的狀態盘研MP研舰供給於基板的需研磨的面 =基:，二=^ 障層 ί :ί:層3°側(需研磨的面)進行二=)研有ΐ?需要亦除去阻障層2°，上述層間絕緣膜，、有形成有由相互鄰接的隆起部（凸部與槽部（凹 22 201002805 部）11決定的階差部13的面14，上述阻障層2〇是沿著此層間絕緣膜10的面14而設置的，上述金屬層3〇是以覆蓋此阻障層20的方式而設置的。另外，基板的構成並不限定於此，亦可僅具備金屬層30以及阻障層2〇中的一方。進而，本實施形態的研磨方法較好的是於包括第j步驟以及第2步驟的研磨步驟中的至少第丨步驟中使用上述 CMP研磨液，上述第1步驟自金屬層3〇侧對基板1⑻進行研磨而獲得基板2〇〇後，進—步對金屬層3〇進行研磨，而獲得使位於隆起部12上方的阻障層2()的至少一部分露出的基板300 (^⑻、圖1(c))，上述第2步驟對位於隆起部i2上方的阻障層2G以及金屬層％進行研磨，使隆=的層間絕緣膜1G的至少—部分板 400 (圖 1 (d))。 t τ土 :縣置例何㈣如下的料研錄置··具備安裝有轉速可變的馬達等且可貼附研磨布的壓盤、以板100的固持器（holder)。 ’、等土普通的不織布、發泡聚験3布並無特別限制’可使用磨條件並絲別、多孔質氟樹脂等。研小於等於2GG a，較好的是將壓盤的旋轉速度設定為輕細_刚不會飛出。 kPa〜1GG 圖^日^研磨布的研磨壓力較好的是4 句性以及圖案的整個基板表面的研磨速度均 w —生優異的觀點而言，更好的县6 a。車父好的是於研磨榮地供給於研磨布。盆徂仏旦翊間中使用泵等將研磨液連續 ^ Ό里並無限制，較好的是研磨布表 23 201002805 面:直被研磨液所覆蓋。研磨結束後的基板較好水中充分清洗後，使用旋轉乾騎（__『）於半導體基板上的水滴撣落後加以乾燥。、、寸者作為CMP研磨液的研磨對象的被研磨金屬構成金㈣30的導電性物質、或構成阻障層Μ = ，至少-方。導電性物質較好的是選自銅、銅合金、= 二化物、銅合金的氧化物以及其他銅化合物所組成的族= 種。又，阻障層20只要是由防止導電性物質擴 ^ =絕緣膜10中的材料所構成的層則並無限制，較好的疋〇 3選自组、1化!旦，合金、其他组化合物，化鈦鈦合金、其他鈦化合物、鶴、氮化鶴鶴合金、 j鶴化合物、釕、氮化合金以及其他釕化合物所組成的族群中的至少一種。層間絕緣膜Η)具代表性的是使用⑽2，較好的是盘 ^的Si〇2相比可降低元件之間或配線之間的寄生電容的絕緣膜。例如，較好的是選自SiOF、含Si-H的Si〇2等 2被膜’含碳的Si〇2 (Si〇c)、含甲基的吨等有機無 =合膜以及氟樹脂系聚合物、聚醯亞胺系聚合物、聚芳 Γ勝Ϊ合物或聚對二甲笨（Parylene)系聚合物等有機聚合 :膜中的至少-種。該些物質藉由經多孔（P_s)化可 '步降低層間絕緣膜1〇的介電常數。因此，層間絕緣膜較好的是根據所需強度來適宜選擇經多孔化的物質。再者近年來為了抑制研磨後的平坦性下降或研磨劃 '艮的產生，而存在減小研磨壓力（例如2psi±；?l3 7kpa) 24 201002805 觸面藉I、、、而’若研磨壓力小’則研磨布與被研磨膜的接研麼故存在圖案晶圓的研磨速度慢於毯覆式晶圓的步驟題。若圖案晶圓的研磨速度小’則存在研磨 ‘、—、時間變長、產量（throughput)下降的問題。起的πΐΓ述’圖案晶圓與毯覆式晶圓的研磨速度差所引 ===::情形時容易產生。如先前所述，磨之产开，：研磨，力（例如5㈣4.4 kPa)進行研由於研隸力高而研磨速度提高，因此抑制了圖案日日圓的研磨速度下降。 =圖案晶_研磨速度與毯覆式晶圓的研磨速度相 ^二小（研磨速度之差大）之情形時，於上述金屬埋設 =成時’研磨初期的研磨速度慢，隨著研磨進行而研又變陕。因此’有時難以辨別研磨終點，導致過了研磨終 =依然進行研磨。此時’例如會產生配線部分的厚度與層曰絕緣膜10-併變薄的侵姓或凹陷，而產生配線電阻的辦加或圖案欲度之差異等所引起的電阻不均。In the case of heteroaggregation, the particle diameter (secondary particle diameter) of the secondary particles is sturdy, and in the south, it is preferably less than or equal to nm, more preferably 'and more preferably less than or equal to 100 Å. The particle diameter (secondary _) of the mechanical entanglement force of the ruthenium-particle-aligned layer = and the polishing rate of the pattern wafer is preferably greater than or equal to 10 〇 nm. The diameter was measured by a transmission electron microscope (manufactured by Lisho Co., Ltd., trade name "84700"). It can be used to scatter the filature meter (for example, the metal oxidant in the slurry can be exemplified by: Nitrous oxide sulphate 2 sulphuric acid, sulphuric acid, molybdate, hypochlorous acid and ozone. Hydrogen peroxide. These metal oxidants can be used alone or in combination with two or two (4). In the case of the substrate to be ground, the soil (10) road uses 70 pieces of the secret board to suppress the gold test. In terms of the pollution caused by it, it is preferable to make the oxidant of the composition of 21 201002805. However, since the composition of the ozone water is suitable for hydrogen peroxide at any time, the substrate of the application object is non-volatile == =; in the case of a board, etc., that is, the amount of oxidant added by the TM is the percentage of the CMP to the blanket wafer and the step-by-step improvement of the slurry. ~40% by weight is better to reset the percentage of ~3G by weight. The above oxidant is added = the amount of oxidant added is changed according to the oxidant in the aqueous solution. ΖΓ ΖΓ ( 四四四四四四四四四四四四四四四四四。。。。。。。。。。。。。。。。 The preferred method of the grinding method of the present invention In the embodiment, the polishing method of the #研磨_substrate having the #研磨_substrate is a state in which the lower surface is pressed against the polishing cloth of the book tray, and the surface to be polished supplied by the MP researcher to the substrate is replaced by the base: ^ Barrier layer ί : ί: Layer 3° side (surface to be grounded) is subjected to two =) grinding? It is necessary to remove the barrier layer by 2°, and the above interlayer insulating film is formed with ridges adjacent to each other ( The surface 14 of the step portion 13 determined by the convex portion and the groove portion (the recess 22 201002805 portion) 11 is provided along the surface 14 of the interlayer insulating film 10, and the metal layer 3 is The structure of the barrier layer 20 is provided. The configuration of the substrate is not limited thereto, and only one of the metal layer 30 and the barrier layer 2 may be provided. Further, the polishing method of the embodiment is preferred. The CMP polishing liquid is used in at least the second step of the polishing step including the jth step and the second step, and the first step is performed by polishing the substrate 1 (8) from the side of the metal layer 3 to obtain the substrate 2, Stepping on the metal layer 3〇 to obtain a position above the ridge 12 The substrate 300 (^(8), FIG. 1(c)) in which at least a part of the barrier layer 2 is exposed, and the second step of polishing the barrier layer 2G and the metal layer % located above the ridge i2 to make the ridge= At least part of the plate 400 of the interlayer insulating film 1G (Fig. 1 (d)). t τ soil: county setting example (4) The following materials are recorded. ·The motor is mounted with a variable speed motor and can be attached to the polishing cloth. The platen is a holder of the plate 100. 'The ordinary non-woven fabric of the same soil, and the expanded poly3 fabric are not particularly limited. 'The grinding conditions can be used, and the fiber, the porous fluororesin, etc. can be used. 2GG a, it is better to set the rotation speed of the platen to a lighter size _ just not flying out. kPa~1GG Fig. ^日^ The polishing pressure of the polishing cloth is better than the four-sentence and the polishing rate of the entire substrate surface of the pattern is good. It is good for the car father to supply the abrasive cloth to the grinding. There is no limit to the use of a pump or the like in the basin. There is no restriction on the polishing cloth. It is better to polish the cloth table 23 201002805. The surface is covered directly by the polishing liquid. After the polishing, the substrate is preferably sufficiently washed in water, and then dried by using a spin dry ride (__") on the semiconductor substrate. The material to be polished as the polishing target of the CMP polishing liquid constitutes a conductive material of gold (four) 30 or constitutes a barrier layer , = at least square. The conductive material is preferably a group selected from the group consisting of copper, a copper alloy, a = compound, an oxide of a copper alloy, and other copper compounds. Further, the barrier layer 20 is not limited as long as it is formed of a material which prevents the conductive material from expanding into the insulating film 10. The preferred layer 3 is selected from the group consisting of a group, a compound, an alloy, and other groups. At least one of a compound, a titanium-titanium alloy, another titanium compound, a crane, a nitrided crane product, a j-heavy compound, a ruthenium, a nitrided alloy, and other ruthenium compounds. The interlayer insulating film Η) is typically an insulating film using (10) 2, preferably a Si 〇 2 of a disk, which can reduce parasitic capacitance between elements or between wirings. For example, it is preferably a film selected from the group consisting of SiOF, Si-H containing Si〇2, carbon-containing Si〇2 (Si〇c), methyl-containing ton, and the like, and fluororesin polymerization. Organic polymerization such as a polyimine-based polymer, a polyarylene complex or a Parylene polymer: at least one of the films. These materials can reduce the dielectric constant of the interlayer insulating film 1 藉 by the porous (P_s). Therefore, it is preferred that the interlayer insulating film is appropriately selected from the porous material depending on the desired strength. In addition, in recent years, in order to suppress the decrease in flatness after polishing or the occurrence of polishing strokes, there is a reduction in the polishing pressure (for example, 2 psi ±; 13 7 kpa) 24 201002805, the contact surface is I, , and 'if the grinding pressure is small 'The grinding cloth and the film to be polished have the problem that the polishing speed of the pattern wafer is slower than that of the blanket wafer. If the polishing rate of the pattern wafer is small, there is a problem that the polishing is performed, and the time is long and the throughput is lowered. The difference in the polishing speed between the pattern wafer and the blanket wafer is hereinafter referred to as ===:: it is easy to occur. As described earlier, grinding, grinding, and force (for example, 5 (four) 4.4 kPa) are carried out. Since the grinding speed is high and the polishing speed is increased, the polishing rate of the pattern sun circle is suppressed from decreasing. = Pattern crystal _ When the polishing rate is smaller than the polishing rate of the blanket wafer (the difference between the polishing rates is large), the polishing rate at the initial stage of polishing is slow at the time of the metal embedding = formation, and the polishing proceeds. Research has changed to Shaanxi. Therefore, it is sometimes difficult to discern the end of the grinding, resulting in the end of the grinding = still grinding. At this time, for example, the thickness of the wiring portion and the insult or the depression of the thickness of the layered insulating film 10 are reduced, and unevenness in resistance due to the difference in wiring resistance or the difference in pattern is caused.

另一方面，於本實施形態中，因研磨液具有如上所述的特有組成，故即便於研磨壓力小之情形時，亦可獲得優異的毯覆式晶B1的研磨速度，並且可獲得優異的圖案晶的研磨速度’此外亦可減小圖案晶_毯覆式晶圓的^ 速度差。藉此’即便於基板表面上有局部的圖案存在量案密度）差的情形時，亦不易產生局部的研磨量的差異θ 從而可提高基板整個面的平坦性（全域（global)平垣性' ’。另外，圖案晶圓與毯覆式晶圓的研磨速度之差例如可根據 25 201002805 圖案晶圓的研磨速度相對於毯覆式晶圓的研磨速度的相對比來進行評價，此相對比越接近100%越好。實施例以下’藉由實施例來說明本發明。但是，本發明並不限於該些實施例。 x (研磨液的製作方法）對於實施例1〜實施例9以及比較例i〜比較例6中使用的研磨液，以達到表1所示的各調配量的方式來調配氧化金屬溶解劑（蘋果酸）、防蝕劑、氧化金屬溶解調整劑、紙粒以及純水，製備中間液。於實施例1〜實施例7以及比較例！〜比較例5中，於此中間液80.0重量份中添加過氧化氫水（特級試劑，3〇，量百分比的水溶液）20.0重量份（以過氧化氫水濃度換鼻為6重量百分比）作為金屬氧化劑，將所得混合液作為研磨液。於實施例8、實施例9以及比較例6中，於此中間液50.0重量份中添加過氧化氫水（特級試劑，重量百分比的水溶液）則重量份（以過氧化氫水濃度換算為 I5重量百分比）作為金屬氧化劑，將所得混合液作為研磨液。另外，表1中所示的值表示相對於中間液總量的調配量。使用該些研磨液，於下述研磨條件下對被研磨基板進行研磨。又’如後述’使被研磨金屬片含浸於該些研磨液中，對金屬表面上生成的錯合物層與純水的接觸角進行測定，而評價錯合物層的疏魏。進而，對該些研磨液依據 26 201002805 下述條件進行pH值測定。另外，研磨液的pH值是藉由氨的添加量來調整的。將研磨液的pH值的測定結果示^表1 中。 (pH值測定）On the other hand, in the present embodiment, since the polishing liquid has the specific composition as described above, even when the polishing pressure is small, the polishing rate of the excellent blanket crystal B1 can be obtained, and excellent polishing can be obtained. The polishing rate of the pattern crystals can also reduce the difference in the speed of the pattern crystals. By the fact that even if there is a difference in the density of the partial pattern on the surface of the substrate, it is difficult to produce a difference θ in the local polishing amount, thereby improving the flatness of the entire surface of the substrate (global flatness ' ' In addition, the difference between the polishing speeds of the pattern wafer and the blanket wafer can be evaluated, for example, according to the relative ratio of the polishing speed of the pattern wafer to the polishing speed of the blanket wafer, and the closer the ratio is. The present invention will be described by way of examples. However, the present invention is not limited to the examples. x (Manufacturing method of polishing liquid) For Examples 1 to 9 and Comparative Example i ~ The polishing liquid used in Comparative Example 6 was prepared by dissolving a metal oxide dissolving agent (malic acid), an anticorrosive agent, a metal oxide dissolving agent, paper particles, and pure water so as to achieve the respective amounts shown in Table 1. In Examples 1 to 7 and Comparative Examples! to Comparative Example 5, hydrogen peroxide water (special grade reagent, 3 Torr, aqueous solution) was added to 80.0 parts by weight of the intermediate liquid. 0.0 parts by weight (6 wt% of nasal hydrogen peroxide concentration) was used as a metal oxidant, and the obtained mixed liquid was used as a polishing liquid. In Example 8, Example 9 and Comparative Example 6, 50.0 parts by weight of the intermediate liquid was used. Hydrogen peroxide water (special grade reagent, aqueous solution by weight) was added as a metal oxidant in parts by weight (in terms of hydrogen peroxide water concentration, I5 weight percent), and the obtained mixed liquid was used as a polishing liquid. The value indicates the amount of the mixture with respect to the total amount of the intermediate liquid. The polishing liquid is used to polish the substrate to be polished under the following polishing conditions, and the metal to be polished is impregnated into the polishing liquid as will be described later. The contact angle of the complex layer formed on the metal surface with the pure water was measured, and the dispersion of the complex layer was evaluated. Further, the polishing liquid was subjected to pH measurement according to the following conditions of 26 201002805. The pH of the liquid is adjusted by the amount of ammonia added. The measurement results of the pH of the slurry are shown in Table 1. (pH measurement)

測定溫度：25±5°C pH值測定裝置：使用電氣化學計器公司製造的型號「PHL-40」來測定。 [表1] 防侧氧化金1溶解調整« 蘋果酸砥粗 pH值重量百分比重量百分比重量百分比重量百分比 — 實施例1 A 0.15 E0.8 0.2 10.1 3.8 實施例2 A 0.06 B0.12 E0.8 0.2 10.1 3.8 實施例3 B0.12 C0.08 E0.8 0.2 10.1 3.8 實施例4 Β0·06 C0.08 Ε0·8 0.2 10.1 3.8 實施例5 Β0.06 C0.08 F0.8 0.2 10.1 3.8 實施例6 Β0.06 C0.08 G0.8 0.2 10.1 3.8 實施例7 Β0.06 C0.08 Η 0.8 0.2 10.1 3.8 實施例8 A 0.2 Ε1·2 0.3 J0.5 3.6 實施例9 A 0.15 B0.05 Ε1.2 0.3 J0.5 3.6 比較例1 B0.07 D0.3 Ε0.8 0.2 10.1 3.8 比較例2 B0.38 D0.1 Ε0.8 0.2 10.1 3.7 比較例3 ΒΘ.38 D0.3 £0.8 0.2 10.1 3.7 比敉例4 Β0Λ3 Ε0·8 0.2 10.1 3.8 比較例5 B0J8 Ε0.8 0.2 10.1 3.7 比敉例6 D0.25 Ε1·2 0.3 J0.5 3.6 27 201002805 上述表1中’各記號表示下述物質 (防餘劑） A:曱苯三唑（東京化成工業公司製造）， B : 1，2,3·苯并三唾（東京化成工業公司製造 C: I,3-二苯胍（東京化成工業公司製造） D: I,2,4-三唑（和光純藥工業公司製造） (氧化金屬溶解調整劑） E.聚丙刘ϊ酸（重量平均分子量.20萬）咸酸 F:丙烯酸-曱基丙烯酸共聚物（（丙烯酸/甲基芮.’ (8〇/2〇)，熏量平均分子量：20萬）酉知 G :丙烯酸- 曱基丙烯酸共聚物（（丙烯酸/甲基丙烯久 =(90/10)，重量平均分子量：2〇萬） Η :丙烯酸-甲基丙烯酸共聚物（（丙烯酸/甲基丙烯酸） =(95/5)，重量平均分子量：2〇萬） (紙粒） I .二次粒彳空為35 nm的石夕酸膠 J .二次粒徑為45 nm的石夕酸膠 (基板） (1) 表面形成有膜厚為1以瓜的金屬層（銅膜）的矽基板（BTW) (2) 形成有深度為400 nm的槽的積層基板（矽基板 /層間絕緣膜（二氧化石夕膜，膜厚為300 nm)) /阻障層（组膜’膜厚為50 nm) /金屬層（銅，膜厚為900 nm)的附圖案基板（PTW) 28 201002805 另外上述基板（2)是以如下方式而製作的。首先，於矽基板上利用化學氣相沈積（Chemical Vapor Deposition，CVD)法形成厚度為3⑻nm的二氧化石夕膜。於此二氧化矽膜上，藉由光微影法以配線密度達到1〇〜 90%的方式形成配線寬度為〇 25㈣〜剛㈣、深度為 4〇〇 nm的槽部（與金屬配線相對應），從而形成此槽=與鄰接於槽部的隆起部交替排列而成的階差部。接著，利用厂公知的濺鍍法，沿著層間絕緣膜表面的階差部的形狀而形成作為阻障層的厚度為5〇 nm的氮化组膜，繼而利用法形成900 nm的銅膜作為金屬層，並利用眾所周知的熱處理來埋設至二氧化矽膜上的所有槽部中。、對上述基板（1)、基板（2)分別使用所製作的研磨夜來實施上述第1研磨步驟。於研磨步驟中，一方面將研磨液供給於研磨壓盤的研磨布，一方面於將研磨布按壓於金屬層的狀態下使研磨壓盤與基板相對移動，由此對金屬層進行研磨。以下表示第1研磨步驟中的研磨條件。 V (CMP研磨條件）研磨裝置：Mirra ( APPLIED MATERIALS公司製造）研磨液流量：200 mL/min 研磨布：具有獨立氣泡的發泡聚胺基甲酸酯樹脂 (Rodale公司製造，型號「IC1000」））研磨壓力：13.7kPa 基板與研磨壓盤的相對速度：80m/mm 研磨壓盤的旋轉速度：90rpm 29 201002805 (CMP後的清洗）於CMP處理之後，使用聚乙浠醇（p〇iyVinyi aic〇h〇i， PVA)毛刷、超音波水進行清洗後’利用旋轉乾燥器（spin dryer)來進行乾燥。 (研磨品評價項目） CMP研磨速度：關於實施例1〜實施例9以及比較例 1〜比較例6 ’根據金屬層的電阻值的變化量進行換算而求出基板（PTW以及BTW)的CMP研磨前後的臈厚差，並根據此膜厚差及研磨時間來算出研磨速度。凹陷量：於PTW的研磨中，作為第1研磨步驟，以在基板整個表面上恰好露出層間絕緣膜（二氧化矽）上的阻障層（钽）的時間+30秒來進行研磨。利用觸針式輪廓儀，根據配線金屬（寬度為100 em)、阻障層（寬度為 100 em)交替排列的條紋狀圖案部（凹陷評價部）的表面形狀’計算出配線金屬相對於阻障層的膜減少量。研磨摩擦力（摩擦比）：將使Mirra的研磨壓盤驅動的馬達的動作電流值輸出為類比訊號（電壓（V))，利用基恩斯（Keyence)公司製造的型號「NR-250」進行讀取，將此值的平均值設為摩擦力，對PTW與BTW中所得的摩擦力進行相對比較，獲得研磨摩擦比。 (錯合物層的接觸角評價）Measurement temperature: 25 ± 5 ° C pH measuring device: It was measured using the model "PHL-40" manufactured by Electrochemical Meter Co., Ltd. [Table 1] Anti-lateral oxidation gold 1 dissolution adjustment « Malic acid mash crude pH weight percent weight percent weight percent weight percent - Example 1 A 0.15 E0.8 0.2 10.1 3.8 Example 2 A 0.06 B0.12 E0.8 0.2 10.1 3.8 Example 3 B0.12 C0.08 E0.8 0.2 10.1 3.8 Example 4 Β0·06 C0.08 Ε0·8 0.2 10.1 3.8 Example 5 Β0.06 C0.08 F0.8 0.2 10.1 3.8 Example 6 Β0.06 C0.08 G0.8 0.2 10.1 3.8 Example 7 Β0.06 C0.08 Η 0.8 0.2 10.1 3.8 Example 8 A 0.2 Ε1·2 0.3 J0.5 3.6 Example 9 A 0.15 B0.05 Ε1.2 0.3 J0.5 3.6 Comparative Example 1 B0.07 D0.3 Ε0.8 0.2 10.1 3.8 Comparative Example 2 B0.38 D0.1 Ε0.8 0.2 10.1 3.7 Comparative Example 3 ΒΘ.38 D0.3 £0.8 0.2 10.1 3.7 Ratio Example 4 Β0Λ3 Ε0·8 0.2 10.1 3.8 Comparative Example 5 B0J8 Ε0.8 0.2 10.1 3.7 Comparative Example 6 D0.25 Ε1·2 0.3 J0.5 3.6 27 201002805 The above symbols in Table 1 indicate the following substances (prevention Residual agent) A: benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.), B: 1,2,3 benzotriazine (manufactured by Tokyo Chemical Industry Co., Ltd. C: I, 3-diphenyl hydrazine (manufactured by Tokyo Chemical Industry Co., Ltd.) ) D: I, 2, 4- Triazole (manufactured by Wako Pure Chemical Industries, Ltd.) (oxidized metal dissolution modifier) E. Polyacrylic acid (weight average molecular weight: 200,000) Salty acid F: acrylic acid-methacrylic acid copolymer ((acrylic acid / methyl hydrazine. '(8〇/2〇), average molecular weight of smoked: 200,000) 酉 know G: acrylic acid-mercaptoacrylic acid copolymer ((acrylic acid / methacrylic long = (90/10), weight average molecular weight: 2 million Η : Acrylic-methacrylic acid copolymer ((acrylic acid/methacrylic acid) = (95/5), weight average molecular weight: 2 million) (paper particles) I. Secondary particle hollowing for 35 nm Acid gel J. A core material with a secondary particle size of 45 nm (substrate) (1) A tantalum substrate (BTW) having a metal layer (copper film) with a film thickness of 1 melon (2) formed with depth Multilayer substrate with 400 nm groove (矽 substrate/interlayer insulation film (2 Oxide film, film thickness 300 nm)) / barrier layer (film thickness of film 50 nm) / metal layer (copper, film) Patterned substrate (PTW) having a thickness of 900 nm) 28 201002805 Further, the above substrate (2) was produced in the following manner. First, a dioxide film having a thickness of 3 (8) nm is formed on a tantalum substrate by a chemical vapor deposition (CVD) method. On the ceria film, a groove portion having a wiring width of 〇25 (four) to just (four) and a depth of 4 〇〇nm is formed by a photolithography method so that the wiring density reaches 1 〇 to 90% (corresponding to the metal wiring) Then, this groove = a step portion which is alternately arranged with the ridge portion adjacent to the groove portion is formed. Next, a nitride film having a thickness of 5 〇 nm as a barrier layer is formed along the shape of the step portion of the surface of the interlayer insulating film by a sputtering method known in the art, and then a copper film of 900 nm is formed by the method. The metal layer is buried in all the grooves on the ruthenium dioxide film by a well-known heat treatment. The first polishing step is performed on the substrate (1) and the substrate (2) using the polishing nights produced. In the polishing step, on the one hand, the polishing liquid is supplied to the polishing cloth of the polishing platen, and the polishing layer is moved relative to the substrate while the polishing cloth is pressed against the metal layer, thereby polishing the metal layer. The polishing conditions in the first polishing step are shown below. V (CMP polishing conditions) Grinding device: Mirra (manufactured by APPLIED MATERIALS) Flow rate: 200 mL/min Grinding cloth: Foamed polyurethane resin with closed cells (Rodale, model "IC1000") Grinding pressure: 13.7 kPa Relative speed of substrate and grinding platen: 80 m/mm Rotating speed of grinding platen: 90 rpm 29 201002805 (cleaning after CMP) After CMP treatment, using polyethylene glycol (p〇iyVinyi aic〇) H〇i, PVA) After washing with brush and ultrasonic water, 'drying with a spin dryer'. (Blasting product evaluation item) CMP polishing rate: Example 1 to Example 9 and Comparative Example 1 to Comparative Example 6 'The CMP polishing of the substrate (PTW and BTW) was obtained by converting the amount of change in the resistance value of the metal layer. The difference in thickness between the front and the back is calculated, and the polishing rate is calculated based on the difference in film thickness and the polishing time. The amount of depression: In the polishing of PTW, as the first polishing step, polishing was performed for a time of exactly 30 seconds on the entire surface of the substrate by exposing the barrier layer on the interlayer insulating film (cerium oxide). Using a stylus profiler, the wiring metal is calculated relative to the barrier based on the surface shape of the stripe pattern portion (the recess evaluation portion) in which the wiring metal (width is 100 em) and the barrier layer (width is 100 em) are alternately arranged. The amount of film reduction in the layer. Grinding friction (friction ratio): The operating current value of the motor driven by the grinding platen of Mirra is output as an analog signal (voltage (V)), and is read by the model "NR-250" manufactured by Keyence Corporation. The average value of this value is set as the frictional force, and the frictional force obtained in the PTW and BTW is relatively compared to obtain the grinding friction ratio. (Evaluation of contact angle of the complex layer)

測定溫度：25±5°C 測定方法：使被研磨金屬片（銅片，2 cmx5 cm)於 5〇 mL的上述研磨液中含浸30分鐘’用純水沖洗5秒後， 30 201002805f 利用協和界面科學公司製造的商品名「DROPMASTER500」來測定金屬表面的錯合物層與純水的接觸角。將實施例1〜實施例9以及比較例丨〜比較例6中的各基板（PTW、BTW)的研磨速度、打”與BTW的研磨速度比、PTW與BTW的研磨時的摩擦力（研磨摩擦比）、 PTW的第1研磨步驟中的研磨時間以及凹陷量的價纟士示於表2中。又，將實施例2、實施例3、實施例4、'士施例7以及比較例1、比較例4、比較例6中的錯合物層的接觸角的評價結果示於表2中。另外，研磨速度比表示「pTW 研磨速度/BTW研磨速度χΙΟΟ」’研磨摩擦比表示「pTW研磨摩擦/BTW研磨摩擦χΙΟΟ」。 [表2]Measurement temperature: 25±5°C Measurement method: The ground metal piece (copper piece, 2 cmx5 cm) was immersed in 5 〇mL of the above slurry for 30 minutes. After rinsing with pure water for 5 seconds, 30 201002805f utilized the Concord interface. The trade name "DROPMASTER 500" manufactured by Science Corporation measures the contact angle of the complex layer on the metal surface with pure water. The polishing rate of each of the substrates (PTW, BTW) in Examples 1 to 9 and Comparative Examples ～ to 6 was compared with the polishing rate of BTW and the polishing force of PTW and BTW (grinding friction) The polishing time and the amount of the depression in the first polishing step of PTW are shown in Table 2. Further, Example 2, Example 3, Example 4, 'Scheme 7 and Comparative Example 1 The results of the evaluation of the contact angle of the complex layer in Comparative Example 4 and Comparative Example 6 are shown in Table 2. The polishing rate ratio indicates "pTW polishing rate / BTW polishing rate χΙΟΟ" and the polishing friction ratio indicates "pTW polishing". Friction / BTW grinding friction χΙΟΟ". [Table 2]

由表2可知，於實施例丨〜實施例9中，BTW研磨速 31 201002805 度均大於科· nm/min，PTW喃速度均大於等於彻 nm/min’PTW與BTW的研磨速度比均大於等於60%，Btw 與ptw的研磨摩擦比均大於等於观，對pTw的銅膜進行研f所需的_均小於等於UG秒，且均可使金屬層的凹陷量小於100 nm。又可知，於實施例2、實施例3、實施例4、實&例7 t，金屬層表面上生成的錯合物層與水的接觸角超過30度（疏水性高）。一由表2可知，相對於此，於比較例〗、比較例4中， BTW研磨速度、錯合物層的接觸角、PTW與BTW的研磨速度比、PTW與BTW的研磨摩擦比低，所耗研磨時間大於等於200秒，故欠佳。又可知，於比較例2中，BTw研磨速度低，所耗研磨時間為135秒，凹陷量大至1〇〇nm，故欠佳。可知，於比較例3中，BTW研磨速度、pTw與 BTW的研磨速度比、PTW與bTW的研磨摩擦比低，所^ 研磨時間為175秒，凹陷量大而平坦性低，故欠佳。可知，於比較例5中，BTW研磨速度低，所耗研磨時間為129 秒，故欠佳。可知，於比較例6中，雖然BTW研磨速度快，但ptw研磨速度低，錯合物層的接觸角小至23度， PTW與BTW的研磨速度比、PTW與BTW的研磨摩擦比低，結果所耗研磨時間為182秒，故欠佳。雖然本發明已以實施例揭露如上，然其並非用以限定本發明’任何所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍内，當可作些許之更動與潤掷，故本發明之保§蔓範圍當視後附之申请專利範圍所界定者為準。 32 201002805」【圖式簡單說明】圖1是表示CMP的研磨步驟的一例的剖面示意圖。【主要元件符號說明】 10 :層間絕緣膜 11 :槽部 12 :隆起部 13 :階差部 14 :面 20 :阻障層 30 :金屬層 100、200、300、400 :基板As can be seen from Table 2, in the embodiment 丨 to the embodiment 9, the BTW polishing speed 31 201002805 degrees are larger than the ke·nm/min, and the PTW spur speeds are greater than or equal to the nm/min'. The polishing speed ratios of the PTW and the BTW are both greater than or equal to 60%, the grinding friction ratio of Btw and ptw is greater than or equal to the view, the _ required for the pTw copper film is less than or equal to UG seconds, and the metal layer can be less than 100 nm. Further, in Example 2, Example 3, Example 4, and Example 7 t, the contact angle of the complex layer formed on the surface of the metal layer with water exceeded 30 degrees (high hydrophobicity). As can be seen from Table 2, in Comparative Example and Comparative Example 4, the BTW polishing rate, the contact angle of the complex layer, the polishing rate ratio of PTW to BTW, and the polishing friction ratio of PTW and BTW were lower. The grinding time is greater than or equal to 200 seconds, so it is not good. Further, in Comparative Example 2, the BTw polishing rate was low, the polishing time consumed was 135 seconds, and the amount of depression was as large as 1 〇〇 nm, which was not preferable. In Comparative Example 3, the BTW polishing rate, the polishing rate ratio of pTw and BTW, and the polishing friction ratio of PTW and bTW were low, and the polishing time was 175 seconds. The amount of depression was large and the flatness was low, which was not preferable. It can be seen that in Comparative Example 5, the BTW polishing rate was low, and the polishing time consumed was 129 seconds, which was not preferable. It can be seen that in Comparative Example 6, although the BTW polishing rate is fast, the ptw polishing rate is low, the contact angle of the complex layer is as small as 23 degrees, the polishing rate ratio of PTW to BTW, and the polishing friction ratio of PTW and BTW are low, and as a result, The grinding time is 182 seconds, so it is not good. Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention to those skilled in the art, and it is possible to make some modifications and simplifications without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the patent application. 32 201002805" BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of a polishing step of CMP. [Description of main component symbols] 10: interlayer insulating film 11: groove portion 12: ridge portion 13: step portion 14: surface 20: barrier layer 30: metal layer 100, 200, 300, 400: substrate

(J 33(J 33

Claims

201002805 VII. Patent application scope: i A metal polishing liquid containing: water; an oxidizing agent; an oxidizing metal dissolving agent; an anti-money agent; and a polishing liquid for oxidizing metal dissolution adjusting agent, wherein 'the above-mentioned polishing liquid The pH value is in the range of 1 to 5, and the anti-agent described above contains at least one of triphenyltriazole and diphenylguanidine. 2. The polishing liquid for metal according to claim 1, wherein the oxidized metal dissolution adjusting agent comprises a water-soluble polymer having an anionic group. The metal polishing liquid according to claim 2, wherein the water-soluble polymer having an anionic group is selected from the group consisting of methacrylic acid, crotonic acid, 2-mercaptobutenoic acid, and 3- a copolymer of at least one unsaturated carboxylic acid compound and an acrylic acid or a salt thereof in a group consisting of methyl crotonic acid, and a copolymerization ratio (acrylic acid/unsaturated carboxylic acid compound) of the above copolymer is (99.5/0.5)~ (80/20). 4. The polishing liquid for metal according to any one of claims 1 to 3, wherein the oxidizing agent comprises a selected from the group consisting of hydrogen peroxide, ammonium persulfate, nitric acid, periodate, hypochlorous acid, and At least one of the groups consisting of ozone water. The polishing solution for gold 34 201002805 f according to any one of claims 1 to 4, wherein the metal oxide dissolving agent comprises an inorganic acid, a machine, an aminoacetic acid, an amine group. At least one of a group consisting of a continuous acid and a salt of the above. 6. The gold use solution according to any one of claims 1 to 5, wherein the above-mentioned agent further comprises a salt selected from the group consisting of a nitrogen-containing heterocyclic compound, a compound containing a heterocyclic compound, and sulfur. At least one of a group consisting of alcohol, glucose, and cellulose. 7. The polishing slurry according to any one of claims 1 to 3, which contains the abrasive particles in a total amount of less than or equal to the weight of the polishing liquid. 8. The polishing slurry for metal according to claim 7, wherein the abrasive particles comprise a group selected from the group consisting of dioxo, oxidized, cerium oxide, titanium emulsified, oxidized, and cerium oxide. At least one of them. The polishing liquid for metal according to any one of the preceding claims, wherein the substrate is provided with a layered insulating layer having a surface on which a ridge portion and a groove portion are formed. a film, a barrier layer provided along the surface of the interlayer of the interlayer film, and a metal layer provided to cover the layer of the layer, and at least one of the metal layer of the substrate by the polishing liquid for the substrate Grinding or grinding at least one of the metal layer and the barrier layer. 10. The polishing liquid for metal according to the ninth aspect of the invention, wherein at least the above-mentioned J step of the polishing step of the first step and the second step is carried out, 35 201002805, the first step is The substrate is polished on the metal layer side to expose at least a portion of the barrier layer above the raised portion, and the second step is to polish the barrier layer 1 and the metal layer above the raised portion. At least a part of the interlayer insulating film of the raised portion is exposed. The metal polishing liquid according to the above, wherein the barrier layer comprises a group selected from the group consisting of a group, an atmosphere group, a group, a compound, a titanium nitride, and a titanium alloy. An alloy, other titanium compound, tungsten, alloy, other bismuth compound, bismuth, bismuth nitride, bismuth alloy, and at least one of the group consisting of compounds. The metal is patented to turn the machine according to item 9 to the eleventh shot, the machine for the towel, the __ is the H (four), the organic film or the organic polymer film. ^ Grinding method, which is the grinding method of the substrate, and the pot:::: two bases: the surface to be ground is pressed against the grinding item to the second shape, and the next side will be the first one as claimed And the fm is supplied to the surface movement by the polishing liquid for metal according to any one of the tenth aspects; and the polishing method according to Item 13 of the above-mentioned substrate is described in the above-mentioned substrate, wherein the upper film is a barrier layer provided on the surface of the interlayer insulating two-insulating film having a surface of the ridge portion and the groove portion, and a metal layer provided in a manner of covering the melon layer, 36 201002805 --- — 八In the polishing method, at least a part of the metal layer of the substrate is polished, or at least a part of the metal layer and the barrier layer are polished. The polishing method according to claim 14, wherein at least the Jth step of performing the polishing step of the first step and the second step is performed, and the substrate is polished from the metal layer side to be located At least a part of the barrier layer above the raised portion is exposed, and in the second step, the barrier layer and the upper layer located above the secret portion are polished to expose a part of the upper portion of the upper portion. The method of claim 14, wherein the barrier layer comprises a group selected from the group consisting of a group, a nitride group, a combination gold, another compound, tantalum, titanium nitride, a titanium alloy, and the like. At least one of a group consisting of a titanium compound, a crane, a nitrogen strontium chicken σ gold, other crane compounds, strontium, tantalum nitride, a bismuth alloy, and other bismuth compounds. The polishing method according to any one of claims 14 to 16, wherein the interlayer insulating film is a dream film, an organic inorganic mixed film or an organic polymer film. 37