TW589365B

TW589365B - Polishing composition and polishing method employing it

Info

Publication number: TW589365B
Application number: TW89108647A
Authority: TW
Inventors: Katsuyoshi Ina; Tadahiro Kitamura; Satoshi Suzumura
Original assignee: Fujimi Inc
Priority date: 1998-12-01
Filing date: 2000-05-05
Publication date: 2004-06-01

Abstract

A polishing composition comprising the following components: (a) an abrasive, (b) alpha-alanine, (c) hydrogen peroxide, and (d) water.

Description

589365 A7 __B7_ _ 五、發明説明（ί ) 發明背景發明範圍本發明係關於半導體、光罩及多種記憶硬碟之基材拋光用的拋光劑組成物，特定言之，係關於諸如半導體工業中裝置晶圓之表面平面化之拋光用的拋光劑組成物，以及使用此組成物的拋光方法。更特定言之，本發明係關於拋光劑組成物其具有高效率並在半導體裝置（有所謂的化學及機械硏磨（CMP)技術施用至彼）的拋光中及裝置晶圓的加工中提供高選擇性，以及使用此組成物的拋光方法。背景之討論近年來所謂的高科技產品（包括電腦）有長足的進展 ’並且使用於該等產品的零件（例如ULSI )亦逐年向高整合及局速度發展。半導體裝置的設計規則亦隨著此進展而逐年地漸趨精細，裝置製程中的聚焦深度有趨淺的傾向，並且圖樣成形表面所需的平面化亦愈趨嚴格。 ‘ 此外，因爲接線的精細化會使接線的電阻增加，已有人硏究以銅來替代鎢或鋁作爲接線材料。就本質而言，銅很難藉蝕刻施以加工，因此，其需要以下的製程。即，在絕緣層上形成接線槽及vias後，即利用濺射或電鍍形成銅接線，再以機械拋光及化摩拋光之組合的化學機械拋光（在下文中稱爲CMP)將澱積在絕緣層上的多餘銅層去除。本紙張尺度適用中國國家標準（CNS ) A4規格（210x297公慶)~771 " ~ (請先閱讀背面之注意事項再填寫本頁) . 訂經濟部智慧財產局員工消費合作社印製 589365 A7 B7 五、發明説明6 ) 請· 先閱讀· 背* 'έ 之注意 Φ 項再 I 頁然而，在此製程中，銅原子可能會擴散進入絕緣層而使裝置性質劣化。因此，爲防止銅原子的擴散，有人提出在具有接線槽-Vias的絕緣層上提供阻擋層的做法。金屬鉅或鉬化物（在下文中將通稱爲含鉅化合物）最適合作爲此阻擋層的材料，由裝置之信賴性的觀點而言亦然，並且預期未來會以彼爲主。訂線因此，在含有此銅層及鉅化物之半導體裝置的此CMP 製程中，首先是作爲最外層的銅層接著是作爲阻擋層的含鉅化合物層分別被施以拋光，並且當到達諸如二氧化矽或一氟氧化矽（SiOF)之絕緣層時拋光即完成。理想的製程是最好僅使用一種拋光劑組成物，銅層及含鉅化合物層係於單一拋光步驟中藉拋光被均勻地去除，當到達絕緣層時當然拋光即完成。然而，銅及含鉅化合物在厚度、化學安定性及其他機械性質上均不同，因此在加工性上亦不同，因而難以採用此理想的拋光製程，因此，以下的兩步驟拋光製程，即，分爲兩步驟的拋光製程刻正硏究中。經濟部智慧財產局員工消費合作社印製首先，在第一步驟拋光（在下文中稱爲第一拋光）中，使用能夠在高效率下使銅層拋光的拋光組成物，以諸如含鉅化合物層作爲制動裝置將銅層施以拋光直到到達此含鉬化合物層。此處，爲了不在銅層表面上生成多種表面傷害（例如凹痕、磨損、凹陷等），在到達含鉅化合物層之前拋光立即終止，即，銅層仍略微殘留時。.然後，在第二步驟拋光（在下文中稱爲第二拋光）中，使用能夠在高效率下主要使含鉬層拋光的拋光組成物，並以絕緣層作爲制本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）_ 5 _ 589365 Α7 Β7 經濟部智慧財產局員工消費合作社印製五、發明説明έ ) 動裝置將殘餘薄銅層及含鉅化合物層施以連續拋光，當到達絕緣層時拋光即完成。使用於第一拋光中的拋光組成物其具有的性質必須使銅層在高切削率下拋光並且不會在銅層表面上生成上述的多種表面缺陷（其無法被第二拋光所去除）。 JP-A-7-233485揭示一種銅型金屬層用的拋光液其可作爲銅層的此拋光組成物且包含至少一個選自包含胺基醋酸及醯胺硫酸的有機酸，氧化劑與水，及使用此拋光液之半導體裝置的製法。如果此拋光液係用於銅層的拋光，則可得相當高的切削率。咸信銅層表面上的銅原子會因氧化劑的作用而氧化，且氧化的銅元素會被螯合物所吸收，由是可得局切削率。然而，由發明人得到的試驗結果發現當以上的拋光液被用於具有銅層及含鉅化合物層之半導體裝置的拋光時，銅層之切削率對含鉅化合物層之切削率的比率（在下文中稱爲"選擇性比率"）並不適宜，如果組成等被施以調整以增加選擇性比率，拋光後銅層表面的平整度容易受到顯著的損害。即，上述拋光液具有選擇性比率及拋光表面平整度方面的問題並且仍有待進一步的改善。發明槪述本發明之用意係解決上述問題。即，本_發明之目的係提供拋光組成物及拋光方法，由是在具有至少一個銅層及含鉅化合物層之半導體裝置之製造的CMP製程中，銅層可 (請先閱讀背面之注意事項再填寫本頁) 1«· 訂線本紙張又度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -6 - 589365 A7 B7 五、發明説明4 ) 有高選擇性比率（即，高切削率）且含鉅化合物層可有低切削率，並且拋光表面可有極佳的平整度。本發明提供包含以下組份的拋光組成物： (a )磨蝕劑， (b ) α -丙胺酸， (c )過氧化氫，及 (d )水。此外’本發明提供半導體裝置（其具有形成於基材之上的銅層及含鉬化合物層）拋光用的拋光方法，其係利用包含以下組份的拋光組成物： (a) 磨蝕劑， (b) α -丙胺酸， (c) 過氧化氫，及 ⑷水。依據本發明，在具有至少一個銅層及含鉅化合物層之半導體裝置的CMP製程中，銅層可有高選擇性比率（即，高切削率）且含鉅化合物層可有低切削率，並且拋光表面可有極佳的平整度。此外，依據本發明，在半導體裝置的上述製造中半導體裝置可有良好的產率。589365 A7 __B7_ _ V. Description of Invention (ί) Background of the Invention The present invention relates to a polishing agent composition for polishing substrates of semiconductors, photomasks, and various memory hard disks. In particular, it relates to devices such as those used in the semiconductor industry. A polishing agent composition for polishing the surface of a wafer, and a polishing method using the same. More specifically, the present invention relates to a polishing composition which has high efficiency and provides high performance in polishing of semiconductor devices (so-called chemical and mechanical honing (CMP) technology is applied thereto) and processing of device wafers. Selectivity, and polishing method using this composition. Discussion of the background In recent years, the so-called high-tech products (including computers) have made considerable progress, and the parts used in these products (such as ULSI) have also been developed year by year to high integration and local speed. With this progress, the design rules of semiconductor devices have gradually become finer, the depth of focus in the device manufacturing process tends to be shallower, and the planarization required for the pattern forming surface has become more stringent. ‘In addition, because the fineness of the wiring will increase the resistance of the wiring, some people have investigated the use of copper instead of tungsten or aluminum as the wiring material. In essence, copper is difficult to be processed by etching, so it requires the following processes. That is, after forming the wiring grooves and vias on the insulating layer, the copper wiring is formed by sputtering or electroplating, and then chemical mechanical mechanical polishing (hereinafter referred to as CMP) of a combination of mechanical polishing and chemical polishing will be deposited on the insulating layer The excess copper layer is removed. This paper size applies to China National Standard (CNS) A4 specification (210x297 public holidays) ~ 771 " ~ (Please read the precautions on the back before filling out this page). Order Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 589365 A7 B7 V. Description of the invention 6) Please read it first. * Please note the item Φ and then page I. However, in this process, copper atoms may diffuse into the insulating layer and degrade the properties of the device. Therefore, in order to prevent the diffusion of copper atoms, it has been proposed to provide a barrier layer on an insulating layer having a wiring trench-Vias. Metal giants or molybdenum compounds (hereinafter collectively referred to as macro-containing compounds) are the most suitable materials for this barrier, from the viewpoint of the reliability of the device, and it is expected that they will be dominated in the future. Therefore, in this CMP process of a semiconductor device containing the copper layer and the giant compound, firstly the copper layer as the outermost layer and then the giant compound-containing layer as the barrier layer are polished separately, and when reaching a layer such as The polishing of the insulating layer of silicon oxide or silicon monoxide (SiOF) is completed. The ideal process is to use only one polishing composition. The copper layer and the macro compound-containing layer are uniformly removed by polishing in a single polishing step. Of course, the polishing is completed when the insulating layer is reached. However, copper and macro-containing compounds are different in thickness, chemical stability, and other mechanical properties, so they are also different in processability. Therefore, it is difficult to adopt this ideal polishing process. Therefore, the following two-step polishing process, namely, Research is underway for a two-step polishing process. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs First, in the first step polishing (hereinafter referred to as the first polishing), a polishing composition capable of polishing a copper layer with high efficiency is used, such as a layer containing a macro compound as a The brake device polishes the copper layer until it reaches the layer containing the molybdenum compound. Here, in order not to cause various surface damages (such as dents, abrasion, dents, etc.) on the surface of the copper layer, the polishing was terminated immediately before reaching the macro-compound-containing layer, that is, when the copper layer remained slightly. Then, in the second step polishing (hereinafter referred to as the second polishing), a polishing composition capable of mainly polishing a molybdenum-containing layer at a high efficiency is used, and an insulating layer is used as the paper standard. Chinese national standards apply (CNS) A4 specification (210X297 mm) _ 5 _ 589365 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention) The moving device will continuously polish the remaining thin copper layer and the layer containing giant compounds. Polishing is complete when the insulation is reached. The polishing composition used in the first polishing must have properties such that the copper layer is polished at a high cutting rate and does not generate the above-mentioned various surface defects on the surface of the copper layer (which cannot be removed by the second polishing). JP-A-7-233485 discloses a polishing liquid for a copper-type metal layer, which can be used as a polishing composition for a copper layer, and includes at least one organic acid selected from the group consisting of aminoacetic acid and ammonium sulphuric acid, an oxidizing agent, and water, and Manufacturing method of semiconductor device using this polishing liquid. If this polishing liquid is used for polishing a copper layer, a considerably high cutting rate can be obtained. The copper atoms on the surface of the salty copper layer will be oxidized by the action of the oxidant, and the oxidized copper element will be absorbed by the chelate, so that the local cutting rate can be obtained. However, the test results obtained by the inventors found that when the above polishing liquid is used for polishing a semiconductor device having a copper layer and a macro compound-containing layer, the ratio of the cutting rate of the copper layer to the cutting rate of the macro compound-containing layer The term "selectivity" is not appropriate. If the composition and the like are adjusted to increase the selectivity, the flatness of the surface of the copper layer after polishing is easily damaged. That is, the above-mentioned polishing liquid has problems in the selectivity ratio and the flatness of the polishing surface and still needs further improvement. Summary of the invention The purpose of the present invention is to solve the above problems. That is, the purpose of the present invention is to provide a polishing composition and a polishing method. In a CMP process for manufacturing a semiconductor device having at least one copper layer and a macro compound-containing layer, the copper layer may be used (please read the precautions on the back first). (Fill in this page again) 1 «· Binding paper is also applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) -6-589365 A7 B7 V. Description of the invention 4) High selectivity ratio (ie high cutting Rate), and the macro compound-containing layer can have a low cutting rate, and the polished surface can have excellent flatness. The present invention provides a polishing composition comprising: (a) an abrasive, (b) α-alanine, (c) hydrogen peroxide, and (d) water. In addition, the present invention provides a polishing method for polishing a semiconductor device having a copper layer and a molybdenum-containing compound layer formed on a substrate, using a polishing composition containing the following components: (a) an abrasive, ( b) α-alanine, (c) hydrogen peroxide, and tritium water. According to the present invention, in a CMP process of a semiconductor device having at least one copper layer and a macro compound-containing layer, the copper layer may have a high selectivity ratio (ie, a high cutting rate) and the macro compound-containing layer may have a low cutting rate, and The polished surface has excellent flatness. In addition, according to the present invention, the semiconductor device can have a good yield in the above-mentioned manufacturing of the semiconductor device.

較佳實施例的詳細說明磨蝕齊U 在本發明的拋光組成物中，磨蝕劑係作爲所謂的磨蝕顆粒並用以實施CMP加工中的機械拋光。即，磨蝕劑係利本紙張尺度適用中國國家標準（CNS ) Α4規格（210X加公釐）請先閱讀背之注意事項再馬本頁經濟部智慧財產局員工消費合作社印製經濟部智慧財產局員工消費合作社印製 589365 A7 B7 _ 五、發明説明έ ) 用將於下文中說明之多種化合物組份將形成於欲拋光之表面上的脆性層以機械方式去除者。本發明之拋光組成物含有至少一個選自包含二氧化矽、氧化鋁、氧化鈽、氧化鈦、氮化矽、氧化銷、碳化矽及二氧化錳的化合物作爲磨蝕劑。其中，二氧化矽包括膠態氧化矽、熔凝矽石及性質或製法上不同的多種其他類型。氧化銘亦包括^ -氧化銘、5 -氧化銘、0 -氧化銘、/C -氧化鋁及其他不同形態者。此外，就其製法而言，亦有所謂的熔凝氧化鋁。就氧化數而言，氧化铈包括三價及四價者，並且就結晶系統而言，其包括六方系統、tesseral系統及面心立方系統。就結晶系統而言，氧化鉻包括單斜系統、四方系統及非晶形系統。此外，就其製法而言，亦有所謂的熔凝氧化锆。此外，亦有所謂的部份安定的氧化鉻，其具有經固體溶解的鈣、鎂或釔以使立方系統的部份結晶安定化，及完| 全安定化的氧化锆，其具有的此元素之固體溶解的量增加而使得立方系統的所有結晶完全安定化。就結晶系統而言，氧化鈦包括一氧化鈦、三氧化二鈦、二氧化鈦及其他類型。此外，就其製法而言，亦有所謂的熔凝氧化鈦。氮化矽包括α -氮化矽、β -氮化矽、非晶形氮化矽及其他不同形態者。本紙張尺度適用中國@家標準（CNS ) Α4規格（2!GX297公釐） (請先閱讀背面之注意事項再填寫本頁)DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Abrasion uniform In the polishing composition of the present invention, an abrasive is used as so-called abrasive particles and is used to perform mechanical polishing in a CMP process. In other words, the abrasive paper is based on the Chinese National Standard (CNS) A4 specification (210X plus mm). Please read the precautions on this page before printing this page. Intellectual Property Bureau of the Ministry of Economic Affairs. Printed by the employee consumer cooperative 589365 A7 B7 _ V. Description of the invention) Those who use a variety of compound components to be described below to form a brittle layer on the surface to be polished are mechanically removed. The polishing composition of the present invention contains at least one compound selected from the group consisting of silicon dioxide, aluminum oxide, hafnium oxide, titanium oxide, silicon nitride, oxide pins, silicon carbide, and manganese dioxide as an abrasive. Among them, silica includes colloidal silica, fused silica, and many other types with different properties or manufacturing methods. The oxidation inscription also includes ^ -oxidation inscription, 5-oxidation inscription, 0-oxidation inscription, / C-alumina, and other different forms. In addition, in terms of its manufacturing method, it is also called fused alumina. In terms of oxidation number, cerium oxide includes trivalent and tetravalent ones, and in terms of crystalline systems, it includes a hexagonal system, a tesseral system, and a face-centered cubic system. In terms of crystalline systems, chromium oxide includes monoclinic systems, tetragonal systems, and amorphous systems. In addition, in terms of its production method, there is also a so-called fused zirconia. In addition, there are so-called partially stabilized chromium oxides which have calcium, magnesium, or yttrium dissolved in solids to stabilize part of the crystals of the cubic system, and fully stabilized zirconia, which has this element The amount of solids dissolved increases and all crystals of the cubic system are completely stabilized. In terms of crystallization systems, titanium oxide includes titanium monoxide, titanium dioxide, titanium dioxide, and other types. In addition, in terms of its production method, there are also so-called fused titanium oxides. Silicon nitride includes α-silicon nitride, β-silicon nitride, amorphous silicon nitride and other different forms. This paper size applies to China @ 家 standard (CNS) Α4 specification (2! GX297 mm) (Please read the precautions on the back before filling this page)

589365 Α7 Β7 五、發明説明6 ) 碳化矽亦包括α ·型及Θ -型。就形態學而言，二氧化錳包括α -二氧化錳、β -二氧化錳、r-二氧化錳、（5-二氧化錳、ε-二氧化錳、π-二氧化錳及其他不同形態者。對本發明的拋光組成物而言，該等磨蝕劑可以視情況需要而組合使用。當其倂用時，組合的方式或者其比例未有特別的限制。在該等磨蝕劑中，最好使用具有均勻小顆粒尺寸的膠態磨蝕劑以降低儲存期間拋光組成物中磨蝕劑的沉澱作用及防止刮痕在欲拋光的物件上生成（因爲磨蝕劑）。即，當使用二氧化矽時，其最好是熔凝氧化矽及/或膠態氧化矽，當使用氧化鋁時，其最好是熔凝氧化鋁及/或膠態氧化鋁〇經濟部智慧財產局員工消費合作社印製上述的黏著劑係藉機械作用將欲拋光的表面施以拋光。其中，二氧化矽或氧化鋁的顆粒尺寸通常爲0.0丨至0.2微米，並以0.015至0.1微米爲較佳（以掃瞄式電子顯微鏡觀察得到的平均顆粒尺寸）。同樣地，氧化鈽、氧化锆、氧化鈦、氮化矽、碳化矽或二氧化錳的顆粒尺寸通常爲0.03至 0.3微米，並以0.05至0.2微米爲較佳（以掃瞄式電子顯微鏡觀察得到的平均顆粒尺寸）。如果該等磨蝕劑的主要顆粒尺寸太大，則機械拋光作用會太高，由是使得含鉅化合物層的拋光速率增加，拋光期間刮痕即易於生成。另一方面，如果主要顆粒尺寸太小，則機械拋光作用會降低，由是使得銅層的切削率變低。本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）_ ς> - 589365 經濟部智慧財產局員工消費合作社印製 A7 _B7 __ 五、發明説明f ) 本發明之拋光組成物中的磨鈾劑含量通常爲10至200克/ 升，並以30至100克/升爲較佳。如果磨蝕劑的含量太小’則機械拋光力會降低，由是使得銅層的切削率降低。另一方面，如果磨餽劑的含量太高，則機械拋光力會增加’並且含鉅化合物層的拋光速率會變得太高且難以控制。 α -丙胺酸本發明之拋光組成物含有α -丙胺酸。α -丙胺酸具有光學異構物，並且對本發明的拋光組成物而言，D-型態、L-型態或DL-型態中的任一種均可使用。本發明之拋光組成物中的α -丙胺酸含量通常爲0.02至 0.20莫耳/升，並以0.05至0.1 5莫耳/升爲較佳。如果α -丙胺酸的含量太小，則銅層的切削率會變小。另一方面，如果其太大，則銅層的切削率會變得太高且難以控制，由是使得拋光後銅層表面的平整度變差。此外，丙胺酸包括異構物/3 -丙胺酸。/3 -丙胺酸在結構上不同於α -丙胺酸並且咸信其與本發明之拋光組成物中的 α -丙胺酸具有相同的功能。然而，在本發明的拋光組成物中，/3 -丙胺酸將不會損及本發明的效果並且可以內含於本發明的拋光組成物中。一般而言，α -丙胺酸及/3 -丙胺酸的混合物與純α -丙胺酸相較其價格便宜，並且就成本的觀點而言，最好以此混合物作爲工業應用。然而，在此情況中 ’ α -丙胺酸的含量最好在上述的範圍內。因此，當使用α -丙胺酸及/5 -丙胺酸的混合物時，應將摻合比率考慮在內以本紙張尺度適用中國國家標準（CMS ) Α4規格（210X297公釐） -10- (請先閲讀背面之注意事項再填寫本頁)589365 Α7 Β7 V. Description of the invention 6) Silicon carbide also includes α · type and Θ-type. In terms of morphology, manganese dioxide includes α-manganese dioxide, β-manganese dioxide, r-manganese dioxide, (5-manganese dioxide, ε-manganese dioxide, π-manganese dioxide, and other different forms For the polishing composition of the present invention, these abrasives can be used in combination as needed. When they are used, there is no particular limitation on the combination method or ratio. Among these abrasives, the best Use a colloidal abrasive with a uniformly small particle size to reduce the precipitation of the abrasive in the polishing composition during storage and prevent the formation of scratches on the object to be polished (because of the abrasive). That is, when using silicon dioxide, It is preferably fused silica and / or colloidal silica. When alumina is used, it is preferably fused alumina and / or colloidal alumina. The above-mentioned printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs The adhesive is used to polish the surface to be polished by mechanical action. Among them, the particle size of silicon dioxide or aluminum oxide is usually from 0.0 丨 to 0.2 microns, and preferably from 0.015 to 0.1 microns (with a scanning electron microscope). Observed To the average particle size). Similarly, the particle size of hafnium oxide, zirconia, titanium oxide, silicon nitride, silicon carbide, or manganese dioxide is usually 0.03 to 0.3 microns, and preferably 0.05 to 0.2 microns (with Scanning electron microscope observation of the average particle size). If the main particle size of these abrasives is too large, the mechanical polishing effect will be too high, so that the polishing rate of the layer containing giant compounds is increased, the scratches during polishing are Easy to generate. On the other hand, if the main particle size is too small, the mechanical polishing effect will be reduced, so that the cutting rate of the copper layer will be lower. ς >-589365 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _B7 __ V. Description of the invention f) The content of uranium grinding agent in the polishing composition of the present invention is usually 10 to 200 g / liter, and 30 to 100 g / Liter is better. If the content of the abrasive is too small ', the mechanical polishing force will be reduced, thereby reducing the cutting rate of the copper layer. On the other hand, if the content of the abrasive feed is too high, the mechanical polishing force will increase 'and the polishing rate of the macro compound-containing layer will become too high and difficult to control. α-Alanine The polishing composition of the present invention contains α-Alanine. α-alanine has optical isomers, and any of the D-type, L-type, or DL-type can be used for the polishing composition of the present invention. The α-alanine content in the polishing composition of the present invention is usually 0.02 to 0.20 mole / liter, and preferably 0.05 to 0.1 5 mole / liter. If the content of? -Alanine is too small, the cutting rate of the copper layer becomes small. On the other hand, if it is too large, the cutting rate of the copper layer becomes too high and difficult to control, so that the flatness of the surface of the copper layer after polishing becomes worse. In addition, alanine includes the isomer / 3-alanine. / 3-alanine is structurally different from α-alanine and is believed to have the same function as α-alanine in the polishing composition of the present invention. However, in the polishing composition of the present invention, / 3-alanine will not impair the effect of the present invention and may be contained in the polishing composition of the present invention. In general, a mixture of α-alanine and / 3-alanine is cheaper than pure α-alanine, and from the viewpoint of cost, it is preferable to use the mixture for industrial applications. However, in this case, the content of 'α-alanine is preferably within the above range. Therefore, when using a mixture of α-alanine and / 5-alanine, the blending ratio should be taken into account and the Chinese National Standard (CMS) A4 specification (210X297 mm) should be applied to this paper scale. -10- (please first (Read the notes on the back and fill out this page)

589365 A7 B7 五、發明説明6 ) 決定丙胺酸混合物的含量。 (請先閱讀背面之注意事項再填寫本頁) 過氧化氫本發明之拋光組成物含有過氧化氫。在本發明的拋光組成物中，咸信過氧化氫係作爲氧化劑。此處，過氧化氫的特徵在於具有足夠氧化力以使銅層氧化且不含金屬離子雜質者可以容易地購得，因此其特別適合用於本發明的拋光組成物。本發明之拋光組成物中的過氧化氫含量通常爲0.01至1 莫耳/升，並以0.05至0.3莫耳/升爲較佳，以0.08至0.15莫耳/ 升爲更佳。如果過氧化氫的含量太小或太大，則銅層的切削率會變小，因此需要適當的留意。589365 A7 B7 V. Description of the invention 6) Determine the content of alanine mixture. (Please read the notes on the back before filling this page) Hydrogen Peroxide The polishing composition of the present invention contains hydrogen peroxide. In the polishing composition of the present invention, hydrogen peroxide is used as an oxidant. Here, hydrogen peroxide is characterized in that it has a sufficient oxidizing power to oxidize the copper layer and contains no metal ion impurities, and can be easily purchased, so it is particularly suitable for use in the polishing composition of the present invention. The hydrogen peroxide content in the polishing composition of the present invention is usually from 0.01 to 1 mole / liter, more preferably from 0.05 to 0.3 mole / liter, and even more preferably from 0.08 to 0.15 mole / liter. If the content of hydrogen peroxide is too small or too large, the cut rate of the copper layer will be small, so proper attention is required.

ZL 本發明之拋光組成物的介質爲水。水最好爲雜質盡可能降低者，而使得上述個別組份可以精確地執行其角色。經濟部智慧財產局員工消費合作社印製即，水最好爲蒸餾氷，或者雜質離子爲離子交換樹脂所去‘ 除且懸浮物爲濾器所去除者。拋光組成物本發明之拋光組成物通常藉上述個別組份（即，磨鈾劑、α -丙胺酸及氧化劑）的混合、溶解或分散於水中而製得。此處，混合、溶解或分散的方法係視需要選用。例如，可以利用葉片式攪拌器或者超音波分散實施攪拌。利用ZL The medium of the polishing composition of the present invention is water. Water is preferably the one that reduces impurities as much as possible, so that the individual components described above can perform their role precisely. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs That is, the water is preferably distilled ice, or the impurity ions are removed by the ion exchange resin and the suspended matter is removed by the filter. Polishing composition The polishing composition of the present invention is usually prepared by mixing, dissolving or dispersing the above-mentioned individual components (i.e., uranium mill, α-alanine and oxidizing agent) in water. Here, the method of mixing, dissolving or dispersing is selected as needed. For example, stirring can be carried out by using a blade stirrer or ultrasonic dispersion. use

本纸張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）~7y\Z 589365 A7 B7 五、發明説明$ ) 此方法，可溶解的組份將會溶解且無法溶解的組份將會分散，由是組成物將爲均勻的分散液。本發明之拋光組成物可以視情況需要再含有抗蝕劑、 pH-調整劑（以調整pH )、多種界面活性劑及其他添加劑。抗蝕劑係用以抑制對銅層的腐鈾作用。因爲此效果，拋光中因表面缺陷（例如凹槽、凹陷或磨損）形成所造成的銅層降低得以抑制。至於可用於本發明之拋光組成物的抗蝕劑，任何抗鈾劑均可以視需要使用只要其能夠抑制對銅層的腐蝕作用。苯並三唑、甲苯基三唑、苯並咪唑、三唑、咪唑及其他者常被提及。其中，以苯並三唑或甲苯基三唑爲較佳。欲摻入之此抗鈾劑的量視使用之抗蝕劑的種類而定，但是其通常爲0.005至0.0012莫耳/升。當抗蝕劑加至本發明之拋光組成物時，切削率有時會降低。因此，必須小心地選用其種類及含量。在本發明中，pH-調整劑係用以改善拋光組成物的安定性，以改善使用中的安定性或者符合不同規範的要求。氫氯酸、硝酸、硫酸、氯乙酸、酒石酸、號拍酸、檸檬酸、‘ 蘋果酸、丙二酸、多種脂肪酸、多種聚羧酸等均可作爲pH-調整劑以降低本發明之拋光組成物的pH。另一方面，氫氧化鉀、氫氧化鈉、氨、乙二胺、哌嗉、聚乙烯亞胺等可用以增加pH。本發明之拋光組成物的pH未有特別的限制，但是其通常被調整至pH 3至10。在本發明的拋光組成物中，界面活性劑係用以增加磨蝕劑的可分配性或者用以調整拋光組成物的黏度或表面張本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂經濟部智慧財產局員工消費合作社印製 -12- 6 3 9 A7 B7 五、發明説明彳0 ) 力。界面活性劑包括諸如分散劑、潤濕劑、增稠劑、消泡劑、起泡劑、排水劑等。欲作爲分散劑的界面活性劑通常是磺酸型、磷酸型、羧酸型或非離子酸型。至於本發明之拋光組成物的製法，不同添加物的混合順序或者混合方法未有特別的限制。本發明之拋光組成物可以相當高濃度之原液的型態製得、儲存或運送，所以其可以在實際拋光操作時稀釋使用。上述較佳的濃度範圍係針對實際的拋光操作而言。無須贅言，當採用此方法時，儲存或運送期間的原液係具有較高濃度的溶液。此外，過氧化氫的特徵在於其在金屬離子、銨離子或胺的存在下會分解。因此，在本發明的拋光組成物中，最好在實際使用拋光操作之前立即將其加至及混入拋光組成物。過氧化氫的此分解作用可藉羧酸或醇系分子的摻入而得到抑制。即，此效果可藉上述的pH-調整劑來達成。然而，此分解作用亦爲儲存環境所影響，運送期間溫度的變化或者應力的形成可能使部份的過氧化氫發生分解作用。因‘ 此，最好在拋光之前立即實施過氧化氫的混合。拋光機帋丨j 本發明的拋光組成物對銅層提供局切削率，同時對含鉅化合物層提供低切削率，由是提供高選擇/性比率，並且平整度極佳的拋光表面亦可以獲得。此拋光機制尙未被淸楚地瞭解，但是可以解釋如下。本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）_ 13 - (請先閲讀背面之注意事項再填寫本頁)This paper size applies to Chinese National Standard (CNS) A4 specification (210X297mm) ~ 7y \ Z 589365 A7 B7 V. Description of the invention $) This method will dissolve the components and the insoluble components will Dispersion means that the composition will be a homogeneous dispersion. The polishing composition of the present invention may further contain a resist, a pH-adjusting agent (to adjust the pH), various surfactants, and other additives as needed. The resist is used to inhibit the uranium decay effect on the copper layer. Because of this effect, the reduction of the copper layer caused by the formation of surface defects such as grooves, dents or abrasion during polishing is suppressed. As for the resist that can be used in the polishing composition of the present invention, any anti-uranium agent can be used as needed as long as it can suppress the corrosive effect on the copper layer. Benzotriazole, tolyltriazole, benzimidazole, triazole, imidazole and others are often mentioned. Among them, benzotriazole or tolyltriazole is preferred. The amount of this anti-uranium agent to be incorporated depends on the type of resist used, but it is usually 0.005 to 0.0012 mol / liter. When a resist is added to the polishing composition of the present invention, the cutting rate sometimes decreases. Therefore, the type and content must be selected carefully. In the present invention, the pH-adjusting agent is used to improve the stability of the polishing composition, to improve the stability in use or to meet the requirements of different specifications. Hydrochloric acid, nitric acid, sulfuric acid, chloroacetic acid, tartaric acid, tartaric acid, citric acid, 'malic acid, malonic acid, various fatty acids, and various polycarboxylic acids can be used as pH-adjusting agents to reduce the polishing composition of the present invention. PH of the product. On the other hand, potassium hydroxide, sodium hydroxide, ammonia, ethylenediamine, piperidine, polyethyleneimine, etc. can be used to increase the pH. The pH of the polishing composition of the present invention is not particularly limited, but it is usually adjusted to a pH of 3 to 10. In the polishing composition of the present invention, the surfactant is used to increase the distributability of the abrasive or to adjust the viscosity or surface tension of the polishing composition. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). ) (Please read the notes on the back before filling out this page) Order printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -12- 6 3 9 A7 B7 V. Description of Invention 彳 0). Surfactants include, for example, dispersants, wetting agents, thickeners, defoamers, foaming agents, drainage agents, and the like. The surfactant to be used as a dispersant is usually a sulfonic acid type, a phosphoric acid type, a carboxylic acid type, or a nonionic acid type. As for the method for producing the polishing composition of the present invention, the mixing order or mixing method of different additives is not particularly limited. The polishing composition of the present invention can be prepared, stored, or transported in the form of a stock solution with a relatively high concentration, so it can be diluted and used during the actual polishing operation. The above-mentioned preferred concentration ranges are for practical polishing operations. Needless to say, when this method is used, the stock solution during storage or transportation has a higher concentration of solution. In addition, hydrogen peroxide is characterized in that it decomposes in the presence of metal ions, ammonium ions, or amines. Therefore, in the polishing composition of the present invention, it is preferable to add and mix it to the polishing composition immediately before the polishing operation is actually used. This decomposition of hydrogen peroxide can be suppressed by the incorporation of carboxylic acid or alcohol-based molecules. That is, this effect can be achieved by the aforementioned pH-adjusting agent. However, this decomposition is also affected by the storage environment. Temperature changes or stress formation during transportation may cause some hydrogen peroxide to decompose. Therefore, it is best to mix the hydrogen peroxide immediately before polishing. Polisher 帋丨 j The polishing composition of the present invention provides a local cutting rate for copper layers and a low cutting rate for macro compound-containing layers, thereby providing a high selection / sex ratio and a polished surface with excellent flatness. . This polishing mechanism is not well understood, but can be explained as follows. This paper size applies Chinese National Standard (CNS) Α4 specification (210X297 mm) _ 13-(Please read the precautions on the back before filling this page)

、1T 線經濟部智慧財產局員工消費合作社印製 589365 Α7 Β7 五、發明説明彳l ) 首先，咸信拋光期間α -丙胺酸會對銅形成螯合鍵因而提供銅的高切削率。而使用於先前技藝中的甘胺酸亦對銅層顯現螯合作用，但是此作用太過強烈，由是含鉅化合物層的切削率變得太高，並且無法得到適宜的選擇性比率。此外，拋光後銅膜表面的平整度亦受到損害。即，^ -丙胺酸在α -位置處含有羧基及胺基，其提供螯合作用，但是同樣出現在α -位置處的甲基具有調整羧基及胺基之效果的功能，由是含鉅化合物膜的切削率得到抑制，並且拋光後銅膜表面的平整度將不會失去。由此機制，應該可以瞭解Θ -丙胺酸無法提供本發明之效果。此外，在本發明的拋光組成物中，咸信過氧化氫係提供氧化作用。此作用被使用於習見的CMP加工中。然而，在本發明中，拋光會因α -丙胺酸之上述螯合效果芨過氧化氫之氧化作用的倂用而被更爲有效地加速。因此，當其平衡得到最適化時，銅層將有最大的切削率。因此，_當過氧化氫的含量太高或太低時，切削率均會變小。此外，可用於本發明之拋光組成物的抗鈾劑咸信可以較α -丙胺酸更爲緊固地吸附至銅膜表面因而提供保護銅膜表面的功能。因此，對銅層的腐蝕效果將被抑制，由是可以得到平整度極佳的表面。當本發明的拋光組成物用於固體印刷層（僅具有銅層或含鉅化合物的晶圓）的拋光時，銅層的切削率通常至少爲4,000埃/分鐘並且可以調整爲至少5,〇〇〇埃/分鐘（藉諸如拋光組成物的最適化）。反之，含鉅化合物層的切削率通本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）-*|4 - (請先閲讀背面之注意事項再填寫本頁) -·一tx Γ 經濟部智慧財產局員工消費合作社印製 589365 Α7 Β7 五、發明説明彳2 ) 常至多爲200埃/分鐘並且可以藉拋光組成物的最適化而調整爲至多100埃/分鐘。因此，銅層得以在高切削率下拋光，同時鉅化合物層得以在低切削率下拋光。如果以選擇性比率表示’選擇性比率通常至少爲20並且可以藉拋光條件的最適化而調整爲至少50。利用此高選擇性比率，拋光終點的慎測將變得容易，並且亦可得到高產率。此外，利用本發明的拋光組成物，拋光可在高效率下實施同時極佳的表面平整度亦得以維持，由是高生產量得以實現。現在，將參考實例對本發明作更爲詳細的說明。然而，此處應該瞭解本發明絕非爲該等特定的實例所限制。實例1至27與比較例1及2 拋光組成物的製備磨蝕劑膠態氧化矽、過氧化氫及α -丙胺酸或甘胺酸以表1中所示的比例加入及混合而得到實例1至27與比較例1及 2的拋光組成物。過氧化氫爲市售的31 %水溶液，並在拋光前立即混入。’ 拋光試驗具有藉濺射以約10,000埃之厚度形成之銅層的6吋矽晶圓，及具有藉濺射以約2,000埃之厚度形成之鉅層的6吋矽晶圓係作爲拋光之標的物，且各晶圓的層形成側被施以拋光拋光係利用單側拋光機（台直徑：570毫米）實施。將本纸張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐）_ 15- 請先，閲讀背· 面之注意事項再填赢· 頁訂線經濟部智慧財產局員工消費合作社印製 589365 A7 B7_____ 五、發明説明彳3 ) 聚胺基甲酸乙酯（IC- 1000/Suba400，Rodel 11^.,11.3.八.製造 )製成的層合拋光墊黏合至拋光機的機台。首先，安放銅層附著的晶圓且施以一分鐘的拋光，然後換成鉬層附著的晶圓，其同樣被施以一分鐘的拋光。拋光條件如下：拋光壓力爲490克/平方厘米，台轉速爲40 rpm，拋光組成物的進料速率爲50cc/分鐘，且晶圓的轉速爲40 rpm。拋光後，晶圓再施以洗滌及乾燥，各晶圓因拋光而造成的層厚度降低係於49點施以量測，由是得到個別試驗中的切削率。此外，拋光後的拋光表面係以光學顯微鏡實施觀察，且拋光後的表面條件係依據以下的標準實施評估。 ◎:極佳〇：平整度略微受損 △:平整度部份受損 X :表面有腐蝕現象，且平整度差 XX :腐蝕過於嚴重且平整度太差而無實際用途所得的結果及拋光組成物的組成共同示於表1巾。 (請先閱讀背面之注意事項再填寫本頁)Printed on line 1T Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 589365 Α7 B7 V. Description of Invention 彳 l) First, α-alanine will form chelate bonds to copper during salty polishing, thus providing high copper cutting rates. Glycine used in the prior art also shows chelation effect on the copper layer, but this effect is too strong, because the cutting rate of the giant compound-containing layer becomes too high, and an appropriate selectivity ratio cannot be obtained. In addition, the flatness of the surface of the copper film after polishing is also impaired. That is, ^ -alanine contains a carboxyl group and an amine group at the α-position, which provides chelation, but the methyl group also occurring at the α-position has a function of adjusting the effect of the carboxyl group and the amine group, and is a giant compound. The cutting rate of the film is suppressed, and the flatness of the copper film surface will not be lost after polishing. From this mechanism, it should be understood that Θ-alanine cannot provide the effect of the present invention. Further, in the polishing composition of the present invention, a salt of hydrogen peroxide provides oxidation. This effect is used in the conventional CMP process. However, in the present invention, polishing is more effectively accelerated by the above-mentioned chelating effect of? -Alanine and the application of hydrogen peroxide oxidation. Therefore, when the balance is optimized, the copper layer will have the largest cutting rate. Therefore, when the content of hydrogen peroxide is too high or too low, the cutting rate will become small. In addition, the anti-uranium agent that can be used in the polishing composition of the present invention can adhere to the surface of the copper film more tightly than α-alanine, thereby providing a function of protecting the surface of the copper film. Therefore, the corrosion effect on the copper layer will be suppressed, so that a surface with excellent flatness can be obtained. When the polishing composition of the present invention is used for polishing a solid printing layer (wafer having only a copper layer or a macro compound-containing wafer), the cutting rate of the copper layer is usually at least 4,000 angstroms / minute and can be adjusted to at least 5,00. 0 Angstroms / minute (by optimization such as polishing composition). On the contrary, the cutting rate of the layer containing giant compounds is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) through the paper size.-* | 4-(Please read the precautions on the back before filling this page)-· 一 tx Γ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 589365 Α7 Β7 V. Description of Invention 彳 2) It is usually at most 200 angstroms / minute and can be adjusted to 100 angstroms / minute by optimizing the polishing composition. Therefore, the copper layer can be polished at a high cutting rate, and the macro compound layer can be polished at a low cutting rate. When expressed as a selectivity ratio, the 'selectivity ratio is usually at least 20 and can be adjusted to at least 50 by optimizing the polishing conditions. With this high selectivity ratio, careful measurement of the polishing end point becomes easy, and high yields can also be obtained. In addition, with the polishing composition of the present invention, polishing can be performed at a high efficiency while maintaining excellent surface flatness, which is achieved by high throughput. The present invention will now be described in more detail with reference to examples. However, it should be understood here that the present invention is in no way limited by these specific examples. Examples 1 to 27 and Comparative Examples 1 and 2 Preparation of polishing composition Abrasive colloidal silica, hydrogen peroxide, and α-alanine or glycine were added and mixed in the proportions shown in Table 1 to obtain Examples 1 to 27 27 and polishing compositions of Comparative Examples 1 and 2. Hydrogen peroxide is a commercially available 31% aqueous solution and is mixed in immediately before polishing. '' Polishing test A 6-inch silicon wafer with a copper layer formed by sputtering at a thickness of about 10,000 Angstroms, and a 6-inch silicon wafer with a giant layer formed by sputtering at a thickness of about 2,000 Angstroms were used as polishing targets. The polishing layer is applied to the layer forming side of each wafer using a single-side polishing machine (table diameter: 570 mm). Apply this paper size to the Chinese National Standard (CNS) A4 specification (210X 297 mm) _ 15- Please read the back and front precautions and fill in the win page. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 589365 A7 B7_____ V. Description of the invention 彳 3) Laminated polishing pads made of polyurethane (IC-1000 / Suba400, manufactured by Rodel 11 ^., 11.3. VIII.) Are bonded to the machine of the polishing machine. First, the wafer with the copper layer attached was placed and polished for one minute, and then the wafer with the molybdenum layer attached was replaced with one minute of polishing. The polishing conditions were as follows: the polishing pressure was 490 g / cm2, the table rotation speed was 40 rpm, the feed rate of the polishing composition was 50 cc / min, and the wafer rotation speed was 40 rpm. After polishing, the wafers were further washed and dried. The reduction in the layer thickness of each wafer due to polishing was measured at 49 points to obtain the cutting rate in individual experiments. In addition, the polished surface after polishing was observed with an optical microscope, and the surface condition after polishing was evaluated according to the following criteria. ◎: Excellent 〇: The flatness is slightly damaged △: The flatness is partially damaged X: The surface is corroded and the flatness is poor XX: The corrosion is too severe and the flatness is too poor without practical results and the polishing composition The composition of the products is shown in Table 1. (Please read the notes on the back before filling this page)

、1T 經濟部智慧財產局員工消費合作社印製本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 589365 五、發明説明04 ) 經濟部智慧財產局員工消費合作社印製鹚1 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 <] If csi 〇 r- c〇 υη 00 un 1—H CN 0 寸 00 寸 a o\ o\ 〇\ 11 OO 00 un a\ CO 寸 cn tn CN 〇 1~1 0 卜〇\ 寸 VO 寸寸 ' 4 寸戰翻撒騸 —ί 七 cd Η Ύ—< CNl 1~I cn 0 <0 c<\ y—^ !>· 〇 CS v_H 寸 C<1 VO 卜 τ—H 00 CN OO CO 00 CO 00 r- CN 00 OO 0 〇〇 cn un 0 r- 寸卜 0 o\ cn η u 0 0 csl \o 0 CO 〇〇\ 寸 m #v 00 00 00 cn *1 00 CO ON 寸 cn 0 CN r—H v〇 r—Η OO un 0* 〇\ 〇\ 寸 m VO cn cn Cvl cn \k τ Ή 〇 r—H 〇 r—< 〇 r *H 〇 T—S 〇 r—H 〇 ! i 〇〇 r—H 〇 τ" H 〇 τ A 〇 1~i 〇 r—H 〇 γ··Η 〇 ! i 〇 r=z W 滕Μ 关 < < < < < < < < < < < < < < < ii J 1 i τ—H 11 τ i f H o 0 r—( cn 〇 r—H un 1—H CO o un 0 〇〇〇〇〇 0 〇〇〇〇〇〇 \ m"H τ—H ^ ¥ /^N \k ^、 wn 〇〇 cn 〇〇〇〇〇 υο 0 un 〇〇 m 〇 v〇〇〇 »0 〇 v〇〇 un 〇 v〇 v^' CN CN 蘅 Jf 難 > i τ—H ψ、 > i 1 i 1 < 1 < v ' i 1—H 1 4 > Ή 1 _ i T—< r-—H r—H r—H CSI 匡 CO 寸 υη 匡 m 卜 OO 匡〇 s < 匡 τ—H τ Ή 匡 CNl τ- < 匡 cn T ' ^ 寸 y—i 匡 un τ—H 匡 {_ {_ {_ K {Η K K 1¾ IK u w IK n (請先閲讀背面之注意事項再填寫本頁) 、11 線本纸張尺度適用中國國家標準（CNS ) A4規格（21 OX 297公釐）_ 17 _ 589365 A7 B7 五、發明說明（l5) 經濟部智慧財產局員工消費合作社印製 («1)1 嗽表面條件 ◎ ◎ ◎ ◎ 〇 < ◎ ◎ ◎ ◎ ◎ 〇 X X X 讲 Τ—Η cs OO 寸 V oo CSI CN o o N r—Η CT\ CN CO \o oo oo CO On CO ON LXJ r- \〇 Ce ΐ i 寸戰 /^V /-TV 〇 o Η ^sO \D 卜 oo CO oo Q n VO CM C· OO (N1 ON o 0^1 o CN 褂麵 sR \〇 o VO 寸 OO oo o \ < 寸寸 o O 寸 oo OO CO r—H ^T\ o 〇 1 j1 r· H r- r^\ \〇寸 χ··+· f < nv^\ o 1/^\ o U 〇\ V^J Λ τ—H ^•4 ) W a : ^sl CO 寸 vT ) v〇 \〇 un ^ ) cn OO \ i ο csi o WO 〇 v〇 i i CN 〇 un csi τ—H 〇 r—H 〇〇 H 〇 r-H 〇 r—H 〇 1 < 〇 τ—H 〇 ο o o 〇 O m 时腾 Μ ^〆 < < < < < < < < < < < < K· ϋ ϋ \k •^·— τ—Η ! ' 1 < t—H τ—H τ—H \ i 1 < 胃 i r~i r—H \ _婦 s i CO 祕 Ο o 〇〇 o 〇〇〇〇〇〇 o 〇 o Μ vk —^ Ο o vn o v〇〇 un o oo o oo o oo un u〇〇〇 uo 蘅 * 并并并并 -X· _ τ i t i 1 < r ' i ?' 1 i r i CN1 U cn U 寸 u u \〇 U r- U r—H r—H VO τ 1 Η 卜 r—ί OO r "H 〇\ ，一H o CnI r < C\1 CNl CN CO CO 寸 Csl CN VO CN CNl i—< CN m 匡匡匡匡匡匡匡匡匡匡鎰鎰 IK w IK 1« IK IK κ u {_ J_J ^LA Ϊλ 1 BJ ϋ ·ϋ βϋ βϋ I · ϋ n n ϋ ϋ I ϋ j、 n «ϋ —-— ·ϋ ϋ ·ϋ I I HJP^r I _ 口矣 j (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 589365 A7 B7 五、發明說明（Ιό) 磨蝕劑 - C1 :膠態氧化矽（主要顆粒尺寸：〇.〇3微米） (請先閱讀背面之注意事項再填寫本頁) C2 :膠態氧化矽（主要顆粒尺寸：0.005微米） C3 :膠態氧化矽（主要顆粒尺寸：〇.〇1微米） C4 :膠態氧化矽（主要顆粒尺寸：〇.〇15微米） C5 :膠態氧化矽（主要顆粒尺寸：0.1微米） C6 :膠態氧化矽（主要顆粒尺寸：0.2微米） C7 :膠態氧化矽（主要顆粒尺寸：0.3微米）添加劑 A : α -丙胺酸 G :甘胺酸由表1中所示的結果可以淸楚地得知使用本發明之拋光組成物，銅（Cu)層的切削率高，且鉅（Ta)膜的切削率低，並且選擇性比率高，同時拋光表面有極佳的平整度。經濟部智慧財產局員工消費合作社印製依據本發明，在包含至少銅層及含鉬化合物層之半導體裝置的CMP製程中，銅層的切削率可以調高，而含鉅化合物層的切削率可' 以調低，以提供高選擇性比率，並且平整度極佳的拋光表面亦得以獲得。此外，依據本發明，在半導體裝置的上述製造中，半導體裝置亦可以良好的產率製得。本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）， 1T Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs of the Consumer Cooperatives. This paper is printed according to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 589365 V. Description of the invention 04) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs ’Consumer Cooperatives 鹚 1 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ <] If csi 〇r- c〇υη 00 un 1-H CN 0 inch 00 inch ao \ o \ 〇 \ 11 OO 00 un a \ CO inchcn tn CN 〇1 ~ 1 0 Bu 〇 \ Inch VO Inch '4 inch war 骟 — 骟七 cd Η Ύ— < CNl 1 ~ I cn 0 < 0 c < \ y— ^! &Gt; · 〇CS v_H inch C < 1 VO BU τ—H 00 CN OO CO 00 CO 00 r- CN 00 OO 0 〇〇cn un 0 r- inch Bu 0 o \ cn η u 0 0 csl \ o 0 CO 〇〇 \ inch m #v 00 00 00 cn * 1 00 CO ON inch cn 0 CN r—H v〇r—Η OO un 0 * 〇 \ 〇 \ inch m VO cn cn Cvl cn \ k τ Ή 〇r-H 〇r- < 〇 r * H 〇T-S 〇r-H 〇! i 〇〇r-H 〇τ " H 〇τ A 〇1 ~ i 〇r-H 〇γ ·· Η 〇 ! i 〇r = z W TengMuan < < < < < < < < < < < < < < < ii J 1 i τ—H 11 τ if H o 0 r— (cn 〇r—H un 1—H CO o un 0 〇〇〇〇〇〇〇〇〇〇〇〇〇〇 \ m " H τ-H ^ ¥ / ^ N \ k ^, wn 〇〇 cn 〇〇〇〇〇〇υο 0 un 〇〇m 〇v〇〇〇 »0 〇v〇〇un 〇v〇v ^ 'CN CN 蘅 Jf difficult > i τ-H ψ, > i 1 i 1 < 1 < v 'i 1—H 1 4 > Ή 1 _ i T— < r-—H r—H r—H CSI Kuang CO inch υη Kuang m OO Kuang 0s < Kuang τ—H τ Ή Marina CNl τ- < Marina cn T '^ inch y—i Marina un τ—H Marina {_ {_ {_ K {Η KK 1¾ IK uw IK n (Please read the precautions on the back before filling this page ), 11-line paper size applies Chinese National Standard (CNS) A4 specification (21 OX 297 mm) _ 17 _ 589365 A7 B7 V. Description of invention (l5) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs («1 1 cough surface ◎ ◎ ◎ ◎ 〇 < ◎ ◎ ◎ ◎ ◎ XXX Talk Τ—Η cs OO inch V oo CSI CN oo N r—Η CT \ CN CO \ o oo oo CO On CO ON LXJ r- \ 〇Ce ΐ i inch battle / ^ V / -TV 〇o ^ sO \ D oo CO oo Q n VO CM C · OO (N1 ON o 0 ^ 1 o CN coat sR \ 〇o VO inch OO oo o \ < Inch o O Inch oo OO CO r—H ^ T \ o 〇1 j1 r · H r- r ^ \ \ 〇inch x ·· + · f < nv ^ \ o 1 / ^ \ o U 〇 \ V ^ J Λ τ—H ^ • 4) W a: ^ sl CO inch vT) v〇 \ 〇un ^) cn OO \ i ο csi o WO 〇v〇ii CN 〇un csi τ-H 〇r-H 〇〇 H 〇rH 〇r—H 〇1 < 〇τ-H 〇ο oo 〇0 m 时时Ｍ ^ 〆 < < < < < < < < < < < < K · ϋ ϋ \ k • ^ · — τ—Η! '1 < t-H τ-H τ-H \ i 1 < stomach ir ~ ir-H \ _ si CO secret 〇 o 〇〇o 〇〇〇〇〇〇〇 o 〇o Μ vk — ^ 〇 o vn ov〇〇un o oo o oo o oo un u〇〇〇uo 蘅 * and merge -X · _ τ iti 1 < r 'i?' 1 iri CN1 U cn U inch uu \ 〇U r- U r—H r—H VO τ 1 Η 卜 r—ί OO r " H 〇 \, one H o CnI r < C \ 1 CNl CN CO CO inch Csl CN VO CN CNl i— < CN m Kuang Kuang Kuang Kuang Kuang Kuang Kuang Kuang Kuang 镒镒 IK w IK 1 «IK IK κ u {_ J_J ^ LA Ϊλ 1 BJ ϋ · ϋ βϋ βϋ I · ϋ nn ϋ ϋ I ϋ j, n «Ϋ —-— · ϋ ϋ · ϋ II HJP ^ r I _ 口矣 j (Please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ) 589365 A7 B7 V. Description of the invention (Ιό) Abrasive-C1: Colloidal silica (main particle size: 0.03 microns) (Please read the precautions on the back before filling this page) C2: Colloidal silica (Main particle size: 0.005 microns) C3: Colloidal silica (main particle size: 0.01 micron) C4: Colloidal silica (main Particle size: 0.015 microns) C5: Colloidal silica (main particle size: 0.1 microns) C6: Colloidal silica (main particle size: 0.2 microns) C7: Colloidal silica (main particle size: 0.3 microns) ) Additive A: α-Alanine G: Glycine From the results shown in Table 1, it is clear that using the polishing composition of the present invention, the cutting rate of the copper (Cu) layer is high, and the giant (Ta) The cutting rate of the film is low, and the selectivity is high, and the polished surface has excellent flatness. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs According to the present invention, in a CMP process of a semiconductor device including at least a copper layer and a molybdenum-containing compound layer, the cutting rate of the copper layer can be increased, and the cutting rate of the giant compound-containing layer '' Lowered to provide a high selectivity ratio, and a polished surface with excellent flatness is also obtained. In addition, according to the present invention, in the above-mentioned manufacturing of the semiconductor device, the semiconductor device can also be manufactured in a good yield. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims

589365 8 8 8 8 ABCD Patent Application Scope Annex 2: Patent Application No. 89 1 08647 Amendment of Chinese Application Patent Scope This amendment amends the printing of the following components by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs: (a) Abrasives, It is at least one member selected from the group consisting of silicon dioxide, aluminum oxide, cerium oxide, hafnium oxide, titanium oxide, silicon nitride, and silicon carbide, (b) α-alanine, (c) hydrogen peroxide ', And swill. 2. The polishing composition according to item 1 of the application, wherein the abrasive is at least one compound selected from the group consisting of fused silica, colloidal silica, fused alumina, and colloidal alumina. 3. The polishing composition according to item 1 of the patent application range, wherein the main particle size of the uranium grinding agent is 0.01 to 0.3 micrometer, and the content of the abrasive is 10 to 200 g / liter based on the polishing composition. 4. The polishing composition according to item 1 of the scope of patent application, wherein the content of? -Alanine is 0.02 to 0.25 mol / liter based on the polishing composition. 5. The polishing composition according to item 1 of the patent application range, wherein the content of hydrogen peroxide is 0.01 to 1 mole / liter based on the polishing composition. 6. A polishing method, which uses a polishing composition according to item 1 of the patent application range to polish a semiconductor device having a copper layer and a group-containing compound layer formed on a substrate. 1. A polishing composition, characterized by (Please read the note on the back of the 4 items before filling and loading —; write this page), 11 paper size applicable to China National Standard (CNS) Α4 specifications (210 × 297 mm)