200937513 九、發明說明 【發明所屬之技術領域】 本發明係有關適用於尤其是半導體裝置之配線步驟中 之基板硏磨方法。 【先前技術】 近幾年來，隨著半導體積體電路（LSI)之高積體化 φ 、高性能化而已開發新的微細加工技術。化學機械硏磨（ CMP)亦爲其一種，其係於LSI製造步驟中，尤其是多層 配線形成步驟中頻繁地利用於層間絕緣膜之平坦化、金屬 栓形成、埋入配線形成中之技術（例如參見下述專利文獻 1 ) ° 近年，爲了使LSI之高性能化，已嘗試利用銅合金作 爲配線材料。然而，銅合金難以藉由以往在鋁合金配線之 形成中頻繁使用之乾蝕刻法加以微細加工。因此，主要採 φ 用有在預先形成溝部及隆起部之絕緣膜上堆積銅合金薄膜 將銅合金埋入溝部，接著藉由CMP去除堆積在隆起部上 之銅合金薄膜（溝部以外之銅合金薄膜）而形成埋入配線 "之所謂的鑲嵌法（例如參照下述專利文獻2 )。 金屬之CMP之一般方法，爲於圓形硏磨壓盤（壓板 )上貼附硏磨墊，將硏磨墊表面以金屬用硏磨液加以浸漬 ，壓附在基板之形成金屬膜之面上，以自其背面施加特定 壓力（硏磨壓力或硏磨荷重）之狀態旋轉硏磨壓盤’藉由 硏磨液與金屬膜之隆起部進行機械摩擦而去除金屬膜之隆 -5- 200937513 起部者。 於CMP中使用之金屬用硏磨液（以下簡稱爲「硏磨 液」）一般含有金屬氧化劑極固體硏磨粒，依據需要進而 添加氧化金屬溶解劑、金屬抗蝕劑等。首先藉由氧化使金 屬膜表面氧化，其氧化層藉由固體硏磨粒磨削認爲係基本 之機制。其中，絕緣磨之溝部之金屬表面之氧化層並未過 於接觸硏磨墊，藉由固體硏磨粒引起之磨削效果有限，故 在進行CMP之同時主要去除隆起部上之金屬層而使基板 表面平坦化（例如參考下述非專利文獻1 )。 專利文獻1 :美國專利第4944836號公報 專利文獻2 :特開平2-278822號公報 非專利文獻：Journal of Electrochemical Socity，第 138卷11號（1991年發行），第3460〜3464頁。 【發明內容】 〔發明欲解決之問題〕 由CMP進行埋入配線形成時，添加氧化金屬溶解劑 作爲提高CMP之硏磨速度之方法爲有效。可解釋爲若引 起由硏磨粒所磨削除之金屬氧化物粒溶解於硏磨液中（以 下稱爲「蝕刻」）則可增大硏磨粒之磨削效果之故。 然而，藉由添加氧化金屬溶解劑而提高CMP之硏磨 速度之情況，若埋入溝部之金屬層表面之氧化層亦被蝕刻 而使金屬層表面露出，則由於金屬氧化劑使金屬層表面進 一步氧化，若重複此，則對於埋入溝部之金屬層亦會進行 -6- 200937513 蝕刻。因此硏磨後於埋入之金屬配線表面中央部會發生如 盤狀之低窪現象（以下稱爲「淺碟化」），而損及被硏磨 面之平坦化效果。另一方面，若使氧化金屬溶解劑減量以 使淺碟化不發生，則無法獲得實用上充分的硏磨速度。 又，藉由提高硏磨壓盤、安裝晶圓之硏磨墊任一者或 兩者之旋轉數，或藉由上升對於晶圓之硏磨荷重雖亦可提 高硏磨速度，但相反地無法獲得充分的平坦化效果。 @ 本發明係鑑於上述情況而完成者，目的在於提供一種 在層間絕緣膜上介以阻隔層而硏磨設有金屬層之基板之該 金屬層之際，可兼顧高的硏磨速度及被硏磨面之平坦性之 基板硏磨方法。 〔用以解決問題之手段〕 爲解決上述問題，本發明提供一種硏磨方法，其爲具 備有一面側具有由相互鄰接之隆起部與溝部所規定之高低 Q 部的層間絕緣膜，與追隨該層間絕緣膜之具有前述高低部 之面所設置之阻隔層，與以被覆該阻隔層方式設置之金屬 層之基板的硏磨方法，其特徵爲具有， 將含有氧化金屬溶解劑、金屬抗蝕劑、氧化金屬溶解 調整劑與水之第一液，與含有金屬氧化劑之第二液，依所 定比例混合以製得第一硏磨液，使用該第一硏磨液以使前 述阻隔層不會露出之方式對前述金屬層進行硏磨之第一步 驟，與 將第一液與第二液，以第二液之比例大於第一硏磨液 200937513 之比例之方式混合以製得第二硏磨液’使用該第二硏磨液 硏磨前述第一步驟後之金屬層，使前述阻隔層中之位於層 間絕緣膜之隆起部上方之部份露出的第二步驟。 依據本發明之硏磨方法，於2個化學機械硏磨（CMP )步驟中作爲硏磨液，可使用將含有氧化金屬溶解劑、金 靥抗蝕劑、氧化金屬溶解調整劑與水之第一液，與含有金 屬氧化劑之第二液以改變混合比例而調製者，而可在各硏 磨步驟中控制硏磨速度之提高效果及淺碟化之抑制效果， 其結果，可以全體兼顧高的硏磨速度及最終所得基板之被 硏磨面之平坦性。 又，本發明之硏磨方法中使用之第一及第二硏磨液， 如上述，爲使如第一液及第二液之共通原料液混合而得者 。因此本發明之硏磨方法，由硏磨液之調製步驟簡便化及 原料成本降低之觀點而言，亦爲有用。 本發明之硏磨方法中，第一硏磨液中之金屬氧化劑之 含有比例，以第一硏磨液之全重量作爲基準，較好爲 0.5~ 15重量％。另一方面，第二硏磨液中之金屬氧化劑含 有比例，以第二硏磨液之全重量作爲基準，較好爲1 〇~20 重量％。 又，第一硏磨液中之氧化金屬溶解劑之含有比例，以 第一硏磨液之全重量作爲基準，較好爲0.01〜10重量％。 另一方面’第二硏磨液中之氧化金屬溶解劑含有比例，以 第二硏磨液之全重量作爲基準，較好爲〇〇〇1〜1〇重量％。 又，本發明中所用之金屬氧化劑較好爲選自過氧化氫 -8 - 200937513 、硝酸、過碘酸鉀、次氯酸及臭氧水所選出之至少一種。 又，金屬層爲由銅、銅合金、銅之氧化物、銅合金之 氧化物所選出之至少一種。 又，於準備本發明之硏磨方法中所供給之基板之際， 金屬層可藉濺鍍法、電鍍法將金屬堆積在阻隔層上而形成 ，但如此形成之金屬層，對應於層間絕緣膜之高低部具有 高低部。更詳言之，藉由在層間絕緣膜之溝部上方堆積金 @ 屬，而於該溝部埋入金屬，但其一方面，亦於層間絕緣膜 之隆起部上方堆積金屬。因此，金屬層之被硏磨面藉由實 質上在層間絕緣層之隆起部上方堆積之金屬所構成，金屬 層之層間絕緣層之構部上方部份被硏磨故而成爲低窪形狀 。在硏磨此等基板時，於第一步驟中，對於金屬層之高低 部較好藉由使硏磨前後之段差滿足下述式（1)表示之條 件之方式硏磨金屬層。又，此處所謂之「段差」意指於高 低部中距離被硏磨面之深度。又，金屬層具有複數高低部 0 時，Si及s2意指於個別複數高低部中之段差平均値。又 ，於金屬層之高低部中，硏磨前之段差8!有時稱爲「初 期段差」，硏磨後之段差S2有時稱爲「剩餘段差」。 0 ^ S2/Si ^0.2 ( 1 ) 〔式（1)中，Si表示金屬層之高低部硏磨前之段差（單 位：run) ，S2表示前述金屬層之高低部硏磨後之段差（ 單位：nm )〕。 -9- 200937513 又，分別於第一步驟及上述第二步驟中，較好一邊對 硏磨壓盤之硏磨布供給第一硏磨液或第二硏磨液，一邊使 硏磨布對金屬層之被硏磨面成押壓狀態，使硏磨壓盤與基 板相對運動，藉此硏磨金屬層。 〔發明效果〕 依據本發明之硏磨方法，於層間絕緣膜上介以阻隔層 對設有金屬層之基板之該金屬層進行硏磨之際，可同時兼 顧高的硏磨速度及被硏磨面之平坦性。 【實施方式】 以下，依序需要參考圖式，對本發明之較佳實施形態 加以詳細說明。又，圖式中，相同元件附與相同符號，省 略其重複說明。又，上下左右等之位置關係，若無特別限 制，則係基於圖示所示之位置關係。再者，圖式之比例尺 並未限定於圖式所示之比例。 圖1爲模式性地顯示本發明硏磨方法之較佳實施形態 之步驟剖面圖。首先，於步驟（a)，準備供於硏磨之基 板100。基板100具備有面14側具有由相互鄰接之隆起部 11與溝部12所規定之高低部13的層間絕緣膜10，與追 隨該層間絕緣膜10之具有高低部13之面14所設置之阻 隔層20，與以被覆該阻隔層20之方式設置之金屬層30。 又，於半導體裝置之配線形成步驟中，通常，雖在矽基板 等之基板上形成層間絕緣膜10、阻隔層20及金屬層30, -10- 200937513 但於圖1中省略了層間絕緣膜10之下層構造。 作爲層間絕緣膜10，舉例有矽系皮膜或有機聚合物膜 等。作爲矽系被膜，舉例有以二氧化矽、氟矽酸鹽玻璃、 三甲基矽烷或二甲氧基二甲基矽烷等作爲起始原料所得之 有機矽酸鹽玻璃、氧氮化矽、氫化倍半矽氧烷等之氧化矽 被膜，進而舉例爲碳化矽、氮化矽等。又，作爲有基聚合 物膜，舉例有例如全芳香族系定介電率層間絕緣膜。層間 Φ 絕緣膜10之形成，可使用CVD法、旋轉塗佈法、浸漬塗 佈法、噴霧法等。又，於層間絕緣膜10中形成高低部13 ，可使用光微影蝕刻法等。 阻隔層20具有防止金屬自金屬層30擴散至層間絕緣 膜1〇中且提高層間絕緣膜10與金屬層30之密著性之機 能。阻隔層20之構成材料，較好爲選自钽、氮化鉬、钽 合金及其他鉬化合物、鈦、氮化鈦、鈦合金及其他鈦化合 物以及錫、氮化錫、錫合金及其他鎮化合物之至少一種。 H 又，圖1中雖示出阻隔層20爲單層構造時之例，但阻隔 層20亦可爲2層以上之層合構造。 金屬層30係以銅、銅合金、銅之氧化物、銅合金之 氧化物、鎢、鎢合金、銀、金等之金屬作爲主成分所構成 。該等中，於金屬層30之構成材料係選自銅、銅合金、 銅之氧化物、銅合金之氧化物之至少一種時，可較佳地適 用本發明之硏磨方法。 金屬層30雖可藉由濺鍍法、電鍍法將上述金屬堆積 在阻隔層20上而形成’但如此所形成之金屬層3〇可具有 -11 - 200937513BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate honing method suitable for use in a wiring step, particularly a semiconductor device. [Prior Art] In recent years, new microfabrication technology has been developed with the high integration of φ and high performance of semiconductor integrated circuits (LSIs). Chemical mechanical honing (CMP) is also one of the techniques used in the LSI manufacturing process, especially in the multilayer wiring forming step, which is frequently used in the planarization of the interlayer insulating film, the formation of the metal plug, and the formation of the buried wiring ( For example, the following patent document 1) ° In recent years, in order to improve the performance of LSI, a copper alloy has been tried as a wiring material. However, it is difficult for the copper alloy to be microfabricated by a dry etching method which has been frequently used in the formation of aluminum alloy wiring. Therefore, it is mainly used to deposit a copper alloy film on the insulating film in which the groove portion and the ridge portion are formed in advance, and the copper alloy is buried in the groove portion, and then the copper alloy film deposited on the ridge portion is removed by CMP (the copper alloy film other than the groove portion) The so-called damascene method of forming the buried wiring is described (for example, refer to Patent Document 2 below). The general method of metal CMP is to attach a honing pad to a circular honing platen (pressing plate), and impregnate the surface of the honing pad with a metal honing liquid, and press it on the surface of the substrate to form a metal film. Rotating the honing platen by applying a specific pressure (honing pressure or honing load) from the back side to remove the metal film by the mechanical friction of the honing liquid and the ridge of the metal film-5-200937513 Part. The metal honing liquid (hereinafter referred to simply as "honing liquid") used in CMP generally contains a metal oxidizing agent extremely solid honing granule, and if necessary, an oxidizing metal dissolving agent or a metal resist is further added. First, the surface of the metal film is oxidized by oxidation, and the oxide layer is considered to be a basic mechanism by solid honing. Wherein, the oxide layer on the metal surface of the groove portion of the insulating mill does not contact the honing pad too much, and the grinding effect by the solid honing particles is limited, so the metal layer on the ridge portion is mainly removed while the CMP is being performed to make the substrate The surface is flattened (for example, refer to Non-Patent Document 1 below). Patent Document 1: U.S. Patent No. 4,944,836, Patent Document 2: JP-A-2-278822, Non-Patent Document: Journal of Electrochemical Socity, Vol. 138, No. 11 (published in 1991), pages 3460 to 3464. SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] When a buried wiring is formed by CMP, it is effective to add a metal oxide dissolving agent as a method of increasing the honing speed of CMP. It can be explained that if the metal oxide particles which are ground by the honing particles are dissolved in the honing liquid (hereinafter referred to as "etching"), the grinding effect of the honing particles can be increased. However, by adding a metal oxide dissolving agent to increase the honing speed of the CMP, if the oxide layer buried on the surface of the metal layer of the trench is also etched to expose the surface of the metal layer, the surface of the metal layer is further oxidized by the metal oxidizing agent. If this is repeated, the metal layer buried in the trench will also be etched -6-200937513. Therefore, after honing, a disk-like low-lying phenomenon (hereinafter referred to as "shallow dishing") occurs in the central portion of the surface of the buried metal wiring, and the flattening effect of the honed surface is impaired. On the other hand, if the amount of the metal oxide dissolving agent is reduced so that the dishing does not occur, a practically sufficient honing speed cannot be obtained. Moreover, by increasing the number of rotations of the honing platen, the honing pad on which the wafer is mounted, or both, or by increasing the honing load on the wafer, the honing speed can be increased, but conversely Get a full flatness effect. The present invention has been made in view of the above circumstances, and an object thereof is to provide a high honing speed and a bedding when a metal layer of a substrate provided with a metal layer is honed through a barrier layer on an interlayer insulating film. A substrate honing method for flatness of a surface. [Means for Solving the Problems] In order to solve the above problems, the present invention provides a honing method which is provided with an interlayer insulating film having high and low Q portions defined by mutually adjacent ridge portions and groove portions on one side, and follows a lining method of a barrier layer provided on a surface of the interlayer insulating film having the surface of the high and low portions and a substrate provided with a metal layer provided by the barrier layer, characterized in that it contains a metal oxide dissolving agent and a metal resist And the first liquid of the oxidizing metal dissolution adjusting agent and the water, and the second liquid containing the metal oxidizing agent are mixed in a predetermined ratio to obtain a first honing liquid, and the first honing liquid is used to prevent the barrier layer from being exposed. The first step of honing the metal layer is mixed with the first liquid and the second liquid in a ratio of the second liquid to the first honing liquid 200937513 to obtain a second honing liquid. 'The second step of honing the metal layer after the first step using the second honing liquid to expose a portion of the barrier layer above the ridge portion of the interlayer insulating film. According to the honing method of the present invention, as the honing liquid in the two chemical mechanical honing (CMP) steps, the first one containing the oxidizing metal dissolving agent, the gold lanthanum resist, the oxidized metal dissolving agent and the water can be used. The liquid is prepared by changing the mixing ratio with the second liquid containing the metal oxidizing agent, and the effect of improving the honing speed and the suppressing effect of the shallow disc can be controlled in each honing step, and as a result, the high enthalpy can be considered as a whole. The grinding speed and the flatness of the honed surface of the resulting substrate. Further, the first and second honing liquids used in the honing method of the present invention are obtained by mixing a common raw material liquid such as the first liquid and the second liquid as described above. Therefore, the honing method of the present invention is also useful from the viewpoint of simplification of the pulverizing liquid preparation step and reduction in raw material cost. In the honing method of the present invention, the content of the metal oxidizing agent in the first honing liquid is preferably from 0.5 to 15% by weight based on the total weight of the first honing liquid. On the other hand, the metal oxidizing agent in the second honing liquid contains a ratio of preferably from 1 〇 to 20% by weight based on the total weight of the second honing liquid. Further, the content of the metal oxide dissolving agent in the first honing liquid is preferably 0.01 to 10% by weight based on the total weight of the first honing liquid. On the other hand, the content of the metal oxide solubilizing agent in the second honing liquid is preferably 〇〇〇1 to 1% by weight based on the total weight of the second honing liquid. Further, the metal oxidizing agent used in the present invention is preferably at least one selected from the group consisting of hydrogen peroxide-8 - 200937513, nitric acid, potassium periodate, hypochlorous acid and ozone water. Further, the metal layer is at least one selected from the group consisting of copper, a copper alloy, an oxide of copper, and an oxide of a copper alloy. Further, in preparing the substrate to be supplied in the honing method of the present invention, the metal layer may be formed by depositing a metal on the barrier layer by sputtering or electroplating, but the metal layer thus formed corresponds to the interlayer insulating film. The high and low parts have high and low parts. More specifically, metal is deposited in the groove portion by depositing a gold genus over the groove portion of the interlayer insulating film, but on the other hand, metal is deposited on the ridge portion of the interlayer insulating film. Therefore, the honed surface of the metal layer is formed of a metal which is substantially deposited over the ridge portion of the interlayer insulating layer, and the upper portion of the interlayer insulating layer of the metal layer is honed to have a low-lying shape. When honing such substrates, in the first step, it is preferable to honing the metal layer in such a manner that the step before and after honing satisfies the condition expressed by the following formula (1) for the high and low portions of the metal layer. Here, the "step difference" as used herein means the depth of the honed surface in the middle and low portions. Further, when the metal layer has a complex high and low portion 0, Si and s2 mean the average value of the step difference in the individual complex high and low portions. Further, in the high and low portions of the metal layer, the step 8 before the honing is sometimes referred to as the "initial step difference", and the step S2 after the honing is sometimes referred to as the "remaining step difference". 0 ^ S2/Si ^0.2 ( 1 ) [In the formula (1), Si represents the step difference before the honing of the metal layer (unit: run), and S2 represents the step difference after the honing of the high and low portions of the metal layer (unit :nm )]. -9- 200937513 Further, in the first step and the second step, respectively, the first honing liquid or the second honing liquid is preferably supplied to the honing cloth of the honing platen, and the honing cloth is applied to the metal. The honed surface of the layer is pressed to make the honing plate and the substrate move relative to each other, thereby honing the metal layer. [Effect of the Invention] According to the honing method of the present invention, when the metal layer of the substrate provided with the metal layer is honed through the interlayer insulating film via the barrier layer, the high honing speed and the honing can be simultaneously considered. The flatness of the face. [Embodiment] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same components are denoted by the same reference numerals, and the repeated description thereof will be omitted. Further, the positional relationship such as up, down, left, and right is based on the positional relationship shown in the drawing unless otherwise specified. Furthermore, the scale of the drawings is not limited to the scale shown in the drawings. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing the steps of a preferred embodiment of the honing method of the present invention. First, in step (a), the substrate 100 for honing is prepared. The substrate 100 includes an interlayer insulating film 10 having a high and low portion 13 defined by the raised portions 11 and the groove portions 12 adjacent to each other on the surface 14 side, and a barrier layer provided on the surface 14 having the high and low portions 13 following the interlayer insulating film 10. 20. A metal layer 30 disposed in such a manner as to cover the barrier layer 20. Further, in the wiring forming step of the semiconductor device, the interlayer insulating film 10, the barrier layer 20, and the metal layer 30 are usually formed on a substrate such as a germanium substrate, and -10-200937513, but the interlayer insulating film 10 is omitted in FIG. Underlying structure. As the interlayer insulating film 10, a lanthanide film or an organic polymer film or the like is exemplified. Examples of the ruthenium-based coating film include organic bismuth silicate glass, bismuth oxynitride, and hydrogenation obtained by using cerium oxide, fluoroantimonate glass, trimethyl decane or dimethoxy dimethyl decane as a starting material. The cerium oxide film such as sesquiterpene oxide or the like is further exemplified by cerium carbide, cerium nitride or the like. Further, as the base polymer film, for example, a wholly aromatic-based dielectric constant interlayer insulating film is exemplified. Interlayer Φ The insulating film 10 can be formed by a CVD method, a spin coating method, a dip coating method, a spray method, or the like. Moreover, the high and low portions 13 are formed in the interlayer insulating film 10, and photolithography or the like can be used. The barrier layer 20 has a function of preventing metal from diffusing from the metal layer 30 into the interlayer insulating film 1 and improving the adhesion between the interlayer insulating film 10 and the metal layer 30. The constituent material of the barrier layer 20 is preferably selected from the group consisting of bismuth, molybdenum nitride, bismuth alloy and other molybdenum compounds, titanium, titanium nitride, titanium alloys and other titanium compounds, and tin, tin nitride, tin alloys and other cation compounds. At least one of them. Further, in Fig. 1, although the barrier layer 20 is a single-layer structure, the barrier layer 20 may have a laminated structure of two or more layers. The metal layer 30 is composed of copper, a copper alloy, an oxide of copper, an oxide of a copper alloy, a metal such as tungsten, a tungsten alloy, silver or gold as a main component. In the above, when the constituent material of the metal layer 30 is at least one selected from the group consisting of copper, a copper alloy, an oxide of copper, and an oxide of a copper alloy, the honing method of the present invention can be preferably applied. The metal layer 30 can be formed by depositing the above metal on the barrier layer 20 by sputtering or electroplating, but the metal layer 3 thus formed can have -11 - 200937513
對應於層間絕緣膜10之高低部13之高低部31。也就是說 ，藉由在層間絕緣膜10之溝部11上方堆積金屬而於溝部 11埋入金屬，但其一方面，亦於層間絕緣膜1〇之隆起部 12上方堆積金屬。因此，金屬層30之層間絕緣膜10之隆 起部12上方部份33實質上構成被硏磨面，金屬層30之 層間絕原膜1〇之溝部11上方的部份32成爲自硏磨面低 漥之形狀。圖1中之箭頭Si表示高低部31中之段差（初 期段差）。 具有如上述構成之基板100，供給至如後述之2階段 硏磨步驟（b) 、（C)(第一步驟及第二步驟）。接著， 於第一步驟及第二步驟中，使用如含有氧化金屬溶解劑、 金屬抗蝕劑、氧化金屬溶解調整劑及水之第一液以及含有 金屬氧化劑之第二液之共通原料液調至兩種類之硏磨液， 使用於金屬層30之硏磨。Corresponding to the high and low portions 31 of the high and low portions 13 of the interlayer insulating film 10. That is, the metal is buried in the groove portion 11 by depositing metal over the groove portion 11 of the interlayer insulating film 10, but on the other hand, metal is deposited on the ridge portion 12 of the interlayer insulating film 1A. Therefore, the upper portion 33 of the raised portion 12 of the interlayer insulating film 10 of the metal layer 30 substantially constitutes a honed surface, and the portion 32 above the groove portion 11 of the interlayer of the metal layer 30 becomes a low self-grinding surface. The shape of the dragonfly. An arrow Si in Fig. 1 indicates a step difference (initial step difference) in the high and low portions 31. The substrate 100 having the above configuration is supplied to the two-stage honing steps (b) and (C) (first step and second step) which will be described later. Next, in the first step and the second step, using a common raw material liquid such as a first liquid containing a metal oxide dissolving agent, a metal resist, a metal oxide dissolving agent and water, and a second liquid containing a metal oxidizing agent Two types of honing fluid are used for the honing of the metal layer 30.
作爲第一液中所含之氧化金屬溶解劑，較好爲一種類 以上之酸及銨鹽。氧化金屬溶解劑只要爲水溶性者，則無 特別限制，但可舉例爲丙二酸、檸檬酸、蘋果酸、乙醇酸 、榖胺酸、葡糖酸、草酸、酒石酸、吡啶甲酸、菸鹼酸、 扁桃酸、吡啶甲酸、乙酸、硫酸、硝酸、磷酸、乙酸、鹽 酸、甲酸、己二酸、戊二酸、苯甲酸、喹哪啶酸、丁酸、 戊酸、乳酸、苯二甲酸、富馬酸、馬來酸、胺基乙酸、水 楊酸、甘油酸、庚二酸等。雖然可維持實用的CMP速度 ，但就有效抑制蝕刻效果之方面而言，倂用兩種以上之酸 或銨鹽亦爲有效。 -12- 200937513 至於金屬抗蝕劑，可較好地使用具有三唑骨架、嘧啶 骨架、咪唑骨架、胍骨架、噻唑骨架或吡唑骨架之化合物 。硏磨液中之金屬抗蝕劑之含有比例若太低，則雖可維持 實用的CMP速度及蝕刻速度之平衡，但就可有效抑制硏 磨摩擦而言，倂用兩種以上之金屬抗蝕劑亦爲有效。 金屬抗蝕劑中，作爲具有三唑骨架之化合物，可例示 有2-疏基苯并噻唑、1，2,3-三唑、1，2,4-三唑、3-胺基-1H-1,2,4-三唑、苯并三唑、1-羥基苯并三唑、1-二羥丙基苯 并三唑、2，3-二羧基丙基苯并三唑、4-羥基苯并三唑、4-羧基（-1H-)苯并三唑、4-羧基（-1H-)苯并三唑甲酯、 4- 羧基（-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-1-甲基〕〔 1，2,4-三唑-1-甲基〕〔2-乙基己基〕胺、甲苯基三唑、萘 并三唑、雙〔（1-苯并三唑）甲基〕磺酸、3-胺基三唑、 5- 甲基苯并三唑等。其中，就CMP速度及蝕刻速度之平 衡觀點觀之，更好爲1，2,3-三唑、1，2,4-三唑、3-胺基-1H-1，2,4-三唑、4-胺基-411-1，2,4-三唑、苯并三唑、1-羥基苯 并三唑、5-甲基苯并三唑。該等金屬抗蝕劑可單獨使用一 種，或可混合兩種以上使用。 又，具有咪唑骨架之化合物，可例示有2-甲基咪唑、 2-乙基咪唑、2-異丙基咪唑、2-丙基咪嗖、2-丁基咪唑、 4-甲基咪唑、2,4-二甲基咪哇、2·乙基-4-甲基咪唑、2-十 一烷基咪唑、2-胺基咪唑等。該等金屬抗蝕劑可單獨使用 一種或可混合兩種以上使用。 -13- 200937513 又，具有嘧啶骨架之化合物，可例示有嘧啶、l,2,4-三唑并〔l，5-a〕嘧啶、l,3,4,6,7,8-六氫-2H-嘧啶并〔l，2-a〕嘧啶、l，3-二苯基-嘧啶·2,4,6-三酮、l，4,5,6-四氫嘧啶 、2,4,5,6-四胺基嘧啶硫酸鹽、2,4,5-三羥基嘧啶、2,4,6-三胺基嘧啶、2,4,6-三氯嘧啶、2,4,6-三甲氧基嘧啶、 2,4,6-三苯基嘧啶、2,4-二胺基-6-羥基嘧啶、2,4-二胺基嘧 啶、2-乙醯胺基嘧啶、2-胺基嘧啶、2-甲基-5,7-二苯基-( 1，2,4)三唑并（1,5-&)嘧啶、2-甲硫基-5,7-二苯基-( 我 1，2,4)三唑并（l，5-a)嘧啶、2-甲硫基-5,7-二苯基-4,7-二氫(l，2,4)三唑并（l，5-A)嘧啶、4-胺基吡唑并〔 3.4- d〕嘧啶等，尤其，就CMP速度與蝕刻速度之平衡觀 點觀之，較好爲4·胺基吡唑并〔3,4-d〕嘧啶、1，2,4-三唑 并〔1，54〕嘧啶、2-甲基-5,7-二苯基-(1,2,4)三唑并（ 1.5- a)嘧啶、2-甲硫基-5,7-二苯基-(1,2,4)三唑并（ 1.5- a)嘧啶。該等可單獨使用一種或混合兩種以上使用。The oxidizing metal solubilizing agent contained in the first liquid is preferably one or more kinds of acids and ammonium salts. The metal oxide dissolving agent is not particularly limited as long as it is water-soluble, but may, for example, be malonic acid, citric acid, malic acid, glycolic acid, lysine, gluconic acid, oxalic acid, tartaric acid, picolinic acid or nicotinic acid. , mandelic acid, picolinic acid, acetic acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, hydrochloric acid, formic acid, adipic acid, glutaric acid, benzoic acid, quinaldine, butyric acid, valeric acid, lactic acid, phthalic acid, rich Horse acid, maleic acid, amino acetic acid, salicylic acid, glyceric acid, pimelic acid, and the like. Although a practical CMP speed can be maintained, it is also effective to use two or more acid or ammonium salts in terms of effectively suppressing the etching effect. -12- 200937513 As the metal resist, a compound having a triazole skeleton, a pyrimidine skeleton, an imidazole skeleton, an anthracene skeleton, a thiazole skeleton or a pyrazole skeleton can be preferably used. If the content ratio of the metal resist in the honing liquid is too low, the balance between the practical CMP speed and the etching speed can be maintained, but in the case of effectively suppressing the honing friction, two or more kinds of metal resists can be used. The agent is also effective. In the metal resist, as the compound having a triazole skeleton, 2-carbylbenzothiazole, 1,2,3-triazole, 1,2,4-triazole, 3-amino-1H- may be exemplified. 1,2,4-triazole, benzotriazole, 1-hydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzene And triazole, 4-carboxy(-1H-)benzotriazole, 4-carboxy(-1H-)benzotriazole methyl ester, 4-carboxy(-1H-)benzotriazolebutyl, 4-carboxyl (-1H-) benzotriazole octyl ester, 5-hexyl benzotriazole, [1,2,3-benzotriazol-1-methyl][ 1,2,4-triazole-1-methyl [2-ethylhexyl]amine, tolyltriazole, naphthotriazole, bis[(1-benzotriazole)methyl]sulfonic acid, 3-aminotriazole, 5-methylbenzo Triazole and the like. Among them, in terms of the balance between CMP speed and etching rate, it is more preferably 1,2,3-triazole, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole 4-amino-411-1,2,4-triazole, benzotriazole, 1-hydroxybenzotriazole, 5-methylbenzotriazole. These metal resists may be used singly or in combination of two or more. Further, the compound having an imidazole skeleton may, for example, be 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-propylimidazole, 2-butylimidazole or 4-methylimidazole, 2 , 4-dimethylmethane, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-aminoimidazole, and the like. These metal resists may be used alone or in combination of two or more. Further, a compound having a pyrimidine skeleton, which may be exemplified by pyrimidine, 1,2,4-triazolo[l,5-a]pyrimidine, 1,3,4,6,7,8-hexahydro- 2H-pyrimido[l,2-a]pyrimidine, l,3-diphenyl-pyrimidine, 2,4,6-trione, 1,4,5,6-tetrahydropyrimidine, 2,4,5, 6-tetraaminopyrimidine sulfate, 2,4,5-trihydroxypyrimidine, 2,4,6-triaminopyrimidine, 2,4,6-trichloropyrimidine, 2,4,6-trimethoxypyrimidine , 2,4,6-triphenylpyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4-diaminopyrimidine, 2-ethylamidopyrimidine, 2-aminopyrimidine, 2- Methyl-5,7-diphenyl-(1,2,4)triazolo(1,5-&)pyrimidine, 2-methylthio-5,7-diphenyl-(I 1,2 , 4) Triazolo(l,5-a)pyrimidine, 2-methylthio-5,7-diphenyl-4,7-dihydro(l,2,4)triazolo(l,5- A) pyrimidine, 4-aminopyrazolo[3.4-d]pyrimidine, etc., in particular, in view of the balance between CMP rate and etching rate, it is preferably 4·aminopyrazolo[3,4-d] Pyrimidine, 1,2,4-triazolo[1,54]pyrimidine, 2-methyl-5,7-diphenyl-(1,2,4)triazolo( 1.5- a)pyrimidine, 2- Methylthio-5,7-diphenyl-(1,2,4)triazolo(1.5-a)pyrimidine. These may be used alone or in combination of two or more.
又，具有胍骨架之化合物，可例示有1,3-二苯基狐、 Q 1-甲基-3-硝基胍等。該等金屬抗蝕劑可單獨使用一種或混 合兩種以上使用。 氧化金屬溶解調整劑舉例有例如褐藻酸、果膠酸、羧 甲基纖維素、洋菜、卡德蘭糖（curdUn)、普魯蘭多糖（ pullulan )等之多糖類；聚天門冬胺酸、聚穀胺酸、聚離 胺酸、聚蘋果酸、聚甲基丙烯酸、聚甲基丙烯酸銨鹽、聚 甲基丙烯酸鈉鹽、聚醯胺酸、聚馬來酸、聚依康酸、聚富 馬酸、聚（對-苯乙烯羧酸）、聚丙烯酸、聚丙烯醯胺、 -14- 200937513 胺基聚丙烯醯胺、聚丙烯酸銨鹽、聚丙烯酸鈉鹽、聚醯胺 酸、聚醯胺酸銨鹽、聚醯胺酸鈉鹽及聚戊二酸等之聚羧酸 及其鹽。再者，作爲聚羧酸之鹽，舉例有鹼金屬鹽、鹼土 類金屬鹽、鹵化物等。基板100爲半導體積體電路用矽基 板時，由於不期望受到鹼金屬、鹼土類金屬、鹵化物等之 污染，故較好使用羧酸及其敍鹽。另一方面，基板100爲 玻璃基板等時則無此限制。上述之養化金屬溶解調整劑中 Q ，就硏磨速度、蝕刻速度之觀點而言’較好爲果膠酸、洋 菜、聚蘋果酸、聚甲基丙烯酸、聚丙烯酸銨鹽、聚丙烯醯 胺、其等之酯及其等之銨鹽。 又，第一液中所含之水可使用蒸餾水、離子交換水或 純水。 另一方面，第二液中所含之金屬氧化劑，舉例有過氧 化氫、過硫酸銨、硝酸鐵、硝酸、過碘酸鉀、次氯酸及臭 氧水等，其中最好爲過氧化氫。金屬氧化劑可單獨使用一 Q 種或組合兩種以上使用。又，基板1〇〇爲含有積體電路用 元件之矽基板時，因不期望受到鹼金屬、鹼土類金屬、鹵 化物等之污染，故較好使用不含有不揮發成分之金屬氧化 劑。但，由於臭氧水之組成經時變化大，故以過氧化氫最 適宜。又，基板100爲不含有半導體元件之玻璃基板等時 ，使用含不揮發成分之金屬氧化劑也無妨。 又，第二液亦可進而含有水。 前段硏磨步驟之步驟（b)係使用以特定比例混合上 述第一液及第二液之第一硏磨液，進行金屬層30之硏磨 -15- 200937513 。至於硏磨方法，可使用例如一邊對硏磨壓盤之硏磨布上 供給第一硏磨液，一邊使金屬層30之被硏磨面以押壓於 硏磨布之狀態使硏磨壓盤與基板相對移動藉此硏磨被硏磨 面之方法。至於硏磨裝置，可使用具備有保持半導體基板 之固持器（硏磨頭）及貼附有硏磨布（墊）之（安裝有可 變更旋轉數之馬達等）之壓盤之一般硏磨裝置。至於硏磨 布，可使用一般不織布、發泡聚胺基甲酸酯、多孔質氟樹 脂等，而無特別限制。硏磨條件並無特別限制，但較好爲 壓盤之旋轉速度爲不使基板飛出之200rpm以下之低旋轉 數。具有被硏磨膜之半導體基板押向硏磨布之壓力較好爲 1〜lOOkPa，自硏磨速度之晶圓面內均一性及被硏磨面之平 坦性觀點觀之，更好爲5〜5 OkPa。在硏磨期間，以泵等對 於硏磨布連續供給第一硏磨液。其供給量並無限制，但較 好爲硏磨布表面經常覆以第一硏磨液。硏磨結束後之基板 ’較好於流水中充分洗淨後，使用旋轉乾燥等將附著在半 導體基板上之水滴甩落，從而乾燥。 又，第一液與第二液之混合方法，只要是在該等液在 硏磨前加以混合作爲第一硏磨液使用則無特別限制，例如 ’可使第一液與第二液預先混合，並將混合液供給至硏磨 壓盤，或亦可分別供給第一液、第二液而再配管內混合兩 液。 第一硏磨液中氧化金屬溶解劑之含有比例，以第一硏 磨液之全重量爲基準，較好爲0_001〜10重量％，更好爲 0.01〜1重量％，最好爲〇·01〜〇.5重量％。該含有比例若未 -16- 200937513 達0.0 01重量％，則有硏磨速度降低之傾向。又，此含有 比例若超過1 〇重量％，則有蝕刻速度變大，容易引起金屬 配線腐蝕之傾向。又，雖可使金屬抗蝕劑之含有比例變高 而抑制蝕刻速度，但此情形有硏磨摩擦增加之傾向。 又，第一硏磨液中金屬抗蝕劑之含有比例，以第一硏 磨液之全重量爲基準，較好爲0.001 ~2.0重量％，更好爲 0.0 1~ 0.5重量％，最好爲0.0 2〜0.2重量％。此含有比例若 Q 未達0.001重量％，則有難以抑制蝕刻之傾向，若超過2 重量％，則有無法獲得實用上充分之硏磨速度之傾向。 又，第一硏磨液中氧化金屬溶解調整劑之含有比例， 以第一硏磨液之全重量爲基準，較好爲0.001〜10重量％， 更好爲0.01〜5重量％，最好爲0.1~2重量％。此含有比例 若未達0.0 0 1重量％，則有金屬配線之淺碟化惡化，被硏 磨物於硏磨布上之累積增加之傾向。又，此含有比例若超 過1 〇重量％，則有蝕刻速度變大，且難以兼顧硏磨速度及 〇 被硏磨面之平坦性之傾向。 又，第一硏磨液中金屬氧化劑之含有比例，以第一硏 磨液之全重量爲基準，較好爲〇.5~15重量％，更好爲 1 · 〇〜1 5重量％，最好爲3.0〜1 3重量％。金屬氧化劑之含有 比例未達0.5重量％時或超過15重量％時，有硏磨速度降 低之傾向。 又，第一硏磨液之pH較好爲2~5，更好爲2·5~4·5， 最好爲3.0〜4.3。pH若小於2，則容易發生金屬腐蝕或表 面粗糙等問題，爲了減低該問題而藉由使抗蝕劑之含有比 -17- 200937513 例變高亦會使硏磨摩擦變大，容易發生配線不良。又，pH 若大於5，由於金屬腐蝕作用減少故可減低抗蝕劑含有比 例，但難以獲得充分之硏磨速度。本發明中，硏磨液之 pH係使用pH計（例如，橫河電機（股）製之型號pH81 )。更具體而言，使用標準緩衝液（苯二甲酸鹽酸pH緩 衝液pH: 4.21 (25°C )，中性磷酸pH緩衝液ΡΗ6·86 (25 °C ))，進行兩點校正後，將電極浸入硏磨液中，測定經 過2分鐘以上穩定後之値。 第一硏磨液在上述材料中亦可進而含有氧化鋁、氧化 矽、氧化铈等之固體硏磨粒，界面活性劑，維多利亞純藍 等染料，酞青綠等之顏料等之著色劑等。 作爲硏磨粒，可爲氧化矽、氧化鋁、氧化鉻、氧化姉 、氧化鈦、碳化矽等之無機硏磨粒、聚苯乙烯、聚丙烯酸 、氯化聚乙烯等之有機硏磨粒之任一者，但就於硏磨液中 之分散性良好’由CMP所發生之硏磨傷痕（擦傷）發生 數少而言’較好爲平均粒徑爲100nm以下之膠體氧化矽、 膠體氧化鋁，更好爲平均粒徑爲8 Onm以下之膠體氧化矽 、膠體氧化鋁，最好爲平均粒徑爲60nm以下之膠體氧化 砂。膠體氧化矽已知有藉由使烷氧化矽水解或使矽酸鈉進 行離子交換之製造方法，膠體氧化鋁已知有藉由使硝酸鋁 水解之製造方法。又，本發明中，硏磨粒之粒徑係以光繞 射散射式粒度分布計（例如COULTER電子公司製之 COULTER N4SD)測定。又，粒子的凝集度係以透過型電 子顯微鏡（例如日立製作所（股）製之H-7100FA )測定 200937513 。（:oulter之測定條件爲測定溫度2 0 °C，溶劑折射率1 · 3 3 3 (水），粒子折射率未知（設定），溶劑黏度1.005cp ( 水），時間200秒，雷射入射角90°，強度（散射強度， 相當於濁度）落入5E + 04~4E + 05之範圍，高於4E + 05時 以水稀釋後測定。 第一硏磨液中硏磨粒之含有比例，以第一硏磨液全重 量爲基準，較好爲0.01〜10.0重量％，更好爲0.05〜2.0重 ❺ 量％，最好爲〜1.0重量％。硏磨粒之含有比例爲0.01 重量％，有無法獲得因硏磨粒添加引起之效果，又於10.0 重量％以上，有並未發現到與含有比例相稱之更進一歩提 高效果之傾向。 步驟（b)係使用第一硏磨液以不使阻隔層20露出之 方式硏磨金屬層30之步驟，以步驟（b)進行硏磨後之基 板200雖於高低部3 1之段差（剩餘段差）S2亦比初期段 差Si*，但層間絕緣膜10之隆起部12上方依然存在有 〇 金屬層30。於步驟（b)中之硏磨，較好以金屬層30之高 低部31之初期段差S!與殘餘段差S2滿足下述式（1)表 示之條件之方式硏磨金屬層。 0 ^ S2/S1 ^0.2 ( 1 ) 〔式（1)中，S,表示金屬層之高低部硏磨前之段差（單 位：nm) ，S2表示前述金屬層之高低部硏磨後之段差（ 單位：nm )〕。 -19- 200937513 接著，步驟（C)係使用將第一液與第二液，以第二 液之比例大於第一硏磨液之比例之方式混合而得之第二硏 磨液進行硏磨。又，步驟（C)中之硏磨方法、硏磨裝置 、硏磨布、硏磨條件以及第一液與第二液之混合方法與上 述步驟（b)之情況相同，故在此省略其說明。 第二硏磨液係以第二液之比例大於第一硏磨液之比例 之方式混合而得者。因此，第二硏磨液中，與第一硏磨液 比較，源自第一液之氧化金屬溶解劑等之含有比例較小， 0 源自第二液之金屬氧化劑之比例較大。再者，於第二硏磨 液中各成分之含有比例較好滿足後述條件。 第二硏磨液中之氧化金屬溶解劑之含有比例，以第二 硏磨液之全重量爲基準，較好爲0.001〜10重量％，更好爲 0.01〜1重量％，最好爲0.01〜0.5重量％。此含有比例若未 達0.001重量％，則有硏磨速度降低之傾向。又，此含有 比例若超過1 0重量％，則有蝕刻速度變大，容易引起金屬 配線腐蝕之傾向。又，雖可使金屬抗蝕劑之含有比例變高 © 而抑制蝕刻速度，但此情形有硏磨摩擦增加之傾向。 又，第二硏磨液中金屬抗蝕劑之含有比例，以第二硏 磨液之全重量爲基準，較好爲0.001〜2.0重量％，更好爲 0.01〜0.5重量％，最好爲〇.〇2〜0.15重量％。此含有比例 若未達0.00 1重量％，則有難以抑制蝕刻之傾向，若超過 2重量％，則有無法獲得實用上充分之硏磨速度之傾向。 又，第二硏磨液中氧化金屬溶解調整劑之含有比例， 以第二硏磨液之全重量爲基準，較好爲0.001〜10重量％， -20- 200937513 更好爲0.01 ~5重量％，最好爲0.1〜2重量％。此含有比例 若未達0.001重量％，則有金屬配線之淺碟化惡化被硏磨 面之平坦性降低，再者被硏磨物於硏磨布上之累積增加之 傾向。又，此含有比例若超過1 〇重量％，則有蝕刻速度變 大，且難以兼顧硏磨速度及被硏磨面之平坦性之傾向。 又，第二硏磨液中金屬氧化劑之含有比例，以第二硏 磨液之全重量爲基準，較好爲0.5〜15重量％，更好爲 φ 1.0〜1 5重量％，最好爲3 · 0〜1 3重量％。金屬氧化劑之含有 比例未達0.5重量％時或超過15重量％時，有硏磨速度降 低之傾向。 又，第二硏磨液之pH較好爲2〜5，更好爲2.5〜4.5, 最好爲3·0〜4.3。pH若小於2，則容易發生金靥腐蝕或表 面粗糙等問題，爲了減低該問題而藉由使抗蝕劑之含有比 例變高亦會使硏磨摩擦變大，容易發生配線不良。又，pH 若大於5，由於金屬腐鈾作用減少故可減低抗蝕劑含有比 Q 例，但難以獲得充分之硏磨速度。 又，第二硏磨液與第一硏磨液同樣，亦可進而含有固 體硏磨粒、界面活性劑、著色劑等。 步驟（C)係接續步驟（b)，使用第二硏磨液硏磨金 屬層30，使阻隔層20中位於層間絕緣膜10之隆起部12 上方之部份露出之步驟，以步驟（c)進行硏磨後之基板 300，成爲於層間絕緣膜10之溝部11中埋入有金屬層30 ，隆起部12上方露出被覆層間絕緣膜10之阻隔層20之 狀態。 -21 - 200937513 依據本實施形態之硏磨方法，2個CMP步驟（b)、 (c)中之硏磨液可使用將含有氧化金屬溶解劑 '金屬抗 蝕劑、氧化金屬溶解調整劑與水之第一液，與含有金屬氧 化劑之第二液以改變混合比例而調製者，可分別於步驟（ b) 、（c)中控制硏磨速度之提高效果及淺碟化之抑制效 果，其結果，全體的硏磨速度可維持在充分高的水準且步 驟（c)之後所得之基板300之被硏磨面充分平坦化。 又，步驟（b)中使用之第一硏磨液及步驟（c)中所 @ 用之第二硏磨液如上述，係使如第一液及第二液之共通原 料液混合而得者，由該硏磨方法之硏磨液調製步驟之簡便 化及原料成本降低之觀點而言，亦爲有用。 又，本發明不限定於上述實施形態。於上述實施形態 中雖例示步驟（b) 、（c)爲連續進行時之例，但依據需 要，在步驟（b)與步驟（c)之間亦可設有被硏磨面之洗 淨步驟或乾燥步驟等。再者，步驟（b)與步驟（c)之間 ，亦可進行爲了硏磨壓盤或硏磨布之交換、加工荷重之變 © 更、進而爲進行該等作業之裝置之停止。 實施例 以下，基於實施例及比較例更具體說明本發明，但本 發明不以任何方式限定於以下之實施例。 〔實施例1〜4、比較例1、2〕 (硏磨液之調製） -22- 200937513 首先，將聚丙烯酸成爲1·2重量％、平均粒徑35nm之 膠體氧化矽硏磨粒成爲0·40重量％、作爲金屬溶解劑之蘋 果酸成爲0.20重量％、琥珀酸成爲0.20重量％、作爲金屬 抗蝕劑之苯并三唑成爲〇.20重量％以及其餘部份爲純水（ 亦即合計爲100重量％ )之方式，混合上述成分’混合液 之pH使用氨水調整至3.6’獲得A液（相當於本發明第 一液）。又，準備過氧化氫水溶液（試藥特級’ 30%水溶 φ 液）作爲本發明之第二液。接著，分別於實施例1〜3及比 較例1~2中，以表1所示比例混合A亦及B液’調製兩 種硏磨液。 (基板） 準備下述基板1、2作爲供給於硏磨之基板。 基板1(無圖案之8吋裸矽基板）：矽基板/層間絕緣 膜（二氧化矽，平均膜厚300nm ) /阻隔層（氮化钽’平 φ 均膜厚25nm) /金屬層（銅，平均膜厚1.5 m)。 基板2(附有圖案之8吋矽基板）：形成有深度〇·5 溝之矽基板/層間絕緣膜（二氧化矽，平均膜厚3 0 0nm )/阻隔層（氮化鉬，平均膜厚25 nm) /金屬層（銅’平均 膜厚 8 50nm )。 上述基板2(附有圖案之8吋矽基板）係如下述製作 。首先，將矽基板上之作爲層間絕緣膜之二氧化矽（平均 膜厚：500nm)藉由CVD法成膜。於此層間絕緣膜上’藉 由微影蝕刻法，交互並設寬100ym、深度500nm之溝部 -23- 200937513 (對應於金屬配線）及寬度100 之隆起部（對應於層 間絕緣層）而形成高低部。接著，藉由濺鍍法，沿著層間 絕緣膜表面之高低部形狀，形成氮化鉬膜（平均膜厚 :2 5nm )作爲阻隔層。進而，藉由電鍍法，以使氮化钽膜 上之溝全部埋入之方式，形成銅膜（平均膜厚：850nm)作 爲金屬層。 (硏磨速度極被硏磨面之評價） 0Further, examples of the compound having an anthracene skeleton include 1,3-diphenyl fox and Q 1-methyl-3-nitroanthracene. These metal resists may be used alone or in combination of two or more. Examples of the metal oxide dissolution adjusting agent include polysaccharides such as alginic acid, pectic acid, carboxymethyl cellulose, amaranth, curducci, pullulan, and the like; polyaspartic acid, Polyglutamic acid, polylysine, polymalic acid, polymethacrylic acid, polymethylammonium methacrylate, polymethyl methacrylate, poly-proline, polymaleic acid, poly-aconic acid, polyrich Acid, poly(p-styrenecarboxylic acid), polyacrylic acid, polyacrylamide, -14- 200937513 Aminopolyacrylamide, ammonium polyacrylate, sodium polyacrylate, polylysine, polyamine A polycarboxylic acid such as an ammonium acid salt, a polyamidosodium salt or a polyglutaric acid or a salt thereof. Further, examples of the salt of the polycarboxylic acid include an alkali metal salt, an alkaline earth metal salt, a halide, and the like. When the substrate 100 is a ruthenium substrate for a semiconductor integrated circuit, it is preferably not used because it is contaminated with an alkali metal, an alkaline earth metal, a halide or the like. Therefore, a carboxylic acid and a salt thereof are preferably used. On the other hand, when the substrate 100 is a glass substrate or the like, there is no such limitation. In the above-mentioned nutrient metal dissolution adjusting agent, Q is preferably pectic acid, acacia, polymalic acid, polymethacrylic acid, polyacrylic acid ammonium salt, polypropylene hydrazine from the viewpoints of honing speed and etching speed. An amine, an ester thereof or the like and an ammonium salt thereof. Further, distilled water, ion-exchanged water or pure water may be used as the water contained in the first liquid. On the other hand, the metal oxidizing agent contained in the second liquid may, for example, be hydrogen peroxide, ammonium persulfate, iron nitrate, nitric acid, potassium periodate, hypochlorous acid or ozone water, and among them, hydrogen peroxide is preferred. The metal oxidizing agent may be used alone or in combination of two or more. Further, when the substrate 1 is a tantalum substrate containing an element for an integrated circuit, since it is not desired to be contaminated with an alkali metal, an alkaline earth metal, a halide or the like, it is preferred to use a metal oxide agent which does not contain a nonvolatile component. However, since the composition of ozone water changes greatly over time, hydrogen peroxide is most suitable. Further, when the substrate 100 is a glass substrate or the like which does not contain a semiconductor element, it is also possible to use a metal oxidizing agent containing a nonvolatile component. Further, the second liquid may further contain water. The step (b) of the honing step is performed by honing the metal layer 30 using the first honing liquid in which the first liquid and the second liquid are mixed in a specific ratio -15-200937513. As for the honing method, for example, the first honing liquid is supplied to the honing cloth of the honing platen, and the honed surface of the metal layer 30 is pressed against the honing cloth to make the honing plate. A method of honing the surface to be honed by moving relative to the substrate. As the honing device, a general honing device including a holder for holding a semiconductor substrate (honing head) and a pressure plate to which a honing cloth (pad) is attached (a motor having a variable number of rotations, etc.) can be used. . As the honing cloth, a general non-woven fabric, a foamed polyurethane, a porous fluororesin or the like can be used without particular limitation. The honing condition is not particularly limited, but it is preferable that the rotation speed of the platen is a low rotation number of 200 rpm or less which does not cause the substrate to fly out. The pressure of the semiconductor substrate having the honed film to the honing cloth is preferably 1 to 100 kPa, and the uniformity of the wafer surface from the honing speed and the flatness of the honed surface are better, 5~ 5 OkPa. During the honing, the first honing liquid is continuously supplied to the honing cloth by a pump or the like. There is no limit to the amount of supply, but it is preferred that the surface of the honing cloth is often covered with the first honing liquid. After the completion of the honing, the substrate ‘ is preferably washed sufficiently in the running water, and the water droplets adhering to the semiconductor substrate are dropped by spin drying or the like to be dried. Further, the method of mixing the first liquid and the second liquid is not particularly limited as long as it is mixed as the first honing liquid before the honing, for example, 'the first liquid and the second liquid can be premixed. And supplying the mixed liquid to the honing pressure plate, or separately supplying the first liquid and the second liquid, and mixing the two liquids in the piping. The content of the oxidizing metal solubilizing agent in the first honing liquid is preferably from 0 to 001 to 10% by weight, more preferably from 0.01 to 1% by weight, most preferably 〇·01, based on the total weight of the first honing liquid. ~〇.5 wt%. If the content ratio is 0.001% by weight from -16 to 200937513, the honing speed tends to decrease. When the content is more than 1% by weight, the etching rate is increased, and the metal wiring tends to be corroded. Further, although the content ratio of the metal resist can be increased to suppress the etching rate, in this case, the honing friction tends to increase. Further, the content of the metal resist in the first honing liquid is preferably 0.001 to 2.0% by weight, more preferably 0.01 to 0.5% by weight, based on the total weight of the first honing liquid, and is preferably 0.0 2 to 0.2% by weight. If the content ratio of Q is less than 0.001% by weight, the etching tends to be difficult to suppress, and if it exceeds 2% by weight, the practically sufficient honing speed tends not to be obtained. Further, the content of the oxidation metal dissolution adjusting agent in the first honing liquid is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight, based on the total weight of the first honing liquid, and most preferably 0.1 to 2% by weight. If the content ratio is less than 0.001% by weight, the dishing of the metal wiring is deteriorated, and the accumulation of the abrasive on the honing cloth tends to increase. On the other hand, if the content ratio exceeds 1% by weight, the etching rate becomes large, and it is difficult to achieve both the honing speed and the flatness of the honed surface. Further, the content ratio of the metal oxidizing agent in the first honing liquid is preferably from 5% to 15% by weight, more preferably from 1 to 5% to 15% by weight based on the total weight of the first honing liquid. Good for 3.0~1 3 wt%. When the content of the metal oxidizing agent is less than 0.5% by weight or exceeds 15% by weight, the honing speed tends to decrease. Further, the pH of the first honing liquid is preferably from 2 to 5, more preferably from 2. 5 to 4.5, and most preferably from 3.0 to 4.3. When the pH is less than 2, problems such as metal corrosion or surface roughness are likely to occur, and in order to reduce the problem, the content of the resist is increased as compared with the case of -17-200937513, and the honing friction is increased, and wiring defects are likely to occur. . Further, if the pH is more than 5, since the corrosion resistance of the metal is reduced, the resist content ratio can be reduced, but it is difficult to obtain a sufficient honing speed. In the present invention, the pH of the honing liquid is a pH meter (for example, Model No. 81 manufactured by Yokogawa Electric Co., Ltd.). More specifically, using standard buffer (pH HCl pH: 4.21 (25 ° C), neutral phosphate pH buffer ΡΗ6·86 (25 ° C)), after two-point calibration, the electrode Immerse in the honing liquid and measure the enthalpy after 2 minutes or more of stabilization. The first honing liquid may further contain a solid honing agent such as alumina, cerium oxide or cerium oxide, a surfactant, a dye such as Victoria Pure Blue, a coloring agent such as a pigment such as indigo green, or the like. As the honing particles, it may be an inorganic honing grain such as cerium oxide, aluminum oxide, chromium oxide, cerium oxide, titanium oxide or cerium carbide, or organic granules such as polystyrene, polyacrylic acid or chlorinated polyethylene. One, but the dispersibility in the honing liquid is good. 'The number of occurrences of honing scars (scratches) caused by CMP is preferably 'colloidal cerium oxide, colloidal alumina having an average particle diameter of 100 nm or less. More preferably, the colloidal cerium oxide or colloidal alumina having an average particle diameter of 8 Onm or less is preferably colloidal oxidized sand having an average particle diameter of 60 nm or less. The colloidal cerium oxide is known to have a production method by hydrolyzing a cerium alkoxide or ion-exchanged sodium citrate, and a colloidal alumina is known to have a production method by hydrolyzing aluminum nitrate. Further, in the present invention, the particle size of the honing particles is measured by a light diffraction scattering type particle size distribution meter (for example, COULTER N4SD manufactured by COULTER Electronics Co., Ltd.). Further, the degree of aggregation of the particles was measured by a transmission electron microscope (for example, H-7100FA manufactured by Hitachi, Ltd.) 200937513. (The measurement conditions of oulter are measurement temperature 20 °C, solvent refractive index 1 · 3 3 3 (water), particle refractive index unknown (set), solvent viscosity 1.005 cp (water), time 200 seconds, laser incident angle 90°, the intensity (scattering intensity, equivalent to turbidity) falls within the range of 5E + 04~4E + 05, and is determined by dilution with water when it is higher than 4E + 05. The proportion of honing particles in the first honing liquid, The basis weight of the first honing liquid is preferably 0.01 to 10.0% by weight, more preferably 0.05 to 2.0% by weight, most preferably 1.00% by weight. The content of the honing particles is 0.01% by weight, There is no possibility of obtaining the effect due to the addition of the honing particles, and it is more than 10.0% by weight, and there is no tendency to further improve the effect corresponding to the content ratio. Step (b) is to use the first honing liquid to not The step of honing the metal layer 30 in such a manner that the barrier layer 20 is exposed, the step 200 after the honing of the substrate 200 in the step (b) is also different from the initial step Si* in the step S1 of the high and low portions 3 1 , but the interlayer insulation A base metal layer 30 remains above the ridges 12 of the film 10. In step (b) In the honing, it is preferable to honing the metal layer in such a manner that the initial step S! of the high and low portions 31 of the metal layer 30 and the residual step S2 satisfy the condition expressed by the following formula (1). 0 ^ S2/S1 ^0.2 ( 1 ) 〔 In the formula (1), S represents a step (unit: nm) before the honing of the high and low portions of the metal layer, and S2 represents a step (unit: nm) after the honing of the high and low portions of the metal layer. -19- 200937513 And the step (C) is performed by mixing the first liquid and the second liquid in a ratio of the second liquid to the first honing liquid, and the second honing liquid is honed. Further, the step (C) The honing method, the honing device, the honing cloth, the honing condition, and the mixing method of the first liquid and the second liquid are the same as those in the above step (b), and thus the description thereof is omitted here. The liquid system is obtained by mixing the ratio of the second liquid to the ratio of the first honing liquid. Therefore, in the second honing liquid, the metal oxide dissolving agent derived from the first liquid is compared with the first honing liquid. The ratio of the content of the metal is small, and the proportion of the metal oxidant derived from the second liquid is larger. Further, in the second honing liquid, The content of the fraction is preferably such that the content of the metal oxide solubilizing agent in the second honing liquid is preferably 0.001 to 10% by weight, more preferably 0.01 based on the total weight of the second honing liquid. 〜1重量%, preferably 0.01 to 0.5% by weight. If the content is less than 0.001% by weight, the honing rate tends to decrease. Further, if the content exceeds 10% by weight, the etching rate is changed. If it is large, it tends to cause corrosion of the metal wiring. Further, although the content ratio of the metal resist can be made high and the etching rate is suppressed, in this case, the honing friction tends to increase. Further, the content of the metal resist in the second honing liquid is preferably 0.001 to 2.0% by weight, more preferably 0.01 to 0.5% by weight, based on the total weight of the second honing liquid, and most preferably 〇 .〇2~0.15 wt%. If the content ratio is less than 0.001% by weight, the etching tends to be difficult to suppress, and if it exceeds 2% by weight, the practically sufficient honing speed tends not to be obtained. Further, the content of the oxidation metal dissolution adjusting agent in the second honing liquid is preferably 0.001 to 10% by weight based on the total weight of the second honing liquid, and more preferably 0.001 to 200937513 and 0.01 to 5% by weight. Preferably, it is 0.1 to 2% by weight. If the content ratio is less than 0.001% by weight, the deterioration of the dishing of the metal wiring is lowered by the flatness of the honing surface, and the accumulation of the honing object on the honing cloth tends to increase. On the other hand, when the content ratio exceeds 1% by weight, the etching rate is increased, and it is difficult to achieve both the honing speed and the flatness of the honed surface. Further, the content of the metal oxidizing agent in the second honing liquid is preferably 0.5 to 15% by weight, more preferably φ 1.0 to 15% by weight, most preferably 3, based on the total weight of the second honing liquid. · 0~1 3 wt%. When the content of the metal oxidizing agent is less than 0.5% by weight or exceeds 15% by weight, the honing speed tends to decrease. Further, the pH of the second honing liquid is preferably from 2 to 5, more preferably from 2.5 to 4.5, most preferably from 3. 0 to 4.3. When the pH is less than 2, problems such as ruthenium corrosion or surface roughness are likely to occur, and in order to reduce the problem, the honing friction is increased by increasing the content ratio of the resist, and wiring defects are likely to occur. Further, if the pH is more than 5, since the effect of the metal humus is reduced, the resist content ratio can be reduced, but it is difficult to obtain a sufficient honing speed. Further, the second honing liquid may further contain solid honing particles, a surfactant, a coloring agent, etc., similarly to the first honing liquid. Step (C) is followed by the step (b) of honing the metal layer 30 using the second honing liquid to expose a portion of the barrier layer 20 above the ridge portion 12 of the interlayer insulating film 10, in step (c) In the substrate 300 after the honing, the metal layer 30 is embedded in the groove portion 11 of the interlayer insulating film 10, and the barrier layer 20 covering the interlayer insulating film 10 is exposed above the ridge portion 12. -21 - 200937513 According to the honing method of the present embodiment, the honing liquid in the two CMP steps (b) and (c) can be used to contain a metal oxide dissolving agent 'metal resist, a metal oxide dissolving agent and water The first liquid and the second liquid containing the metal oxidant are prepared by changing the mixing ratio, and the improvement effect of the honing speed and the suppression effect of the shallow disc can be controlled in the steps (b) and (c), respectively. The honing speed of the whole can be maintained at a sufficiently high level and the honed surface of the substrate 300 obtained after the step (c) is sufficiently flattened. Further, the first honing liquid used in the step (b) and the second honing liquid used in the step (c) are as described above, and the common raw material liquids such as the first liquid and the second liquid are mixed. It is also useful from the viewpoint of simplification of the honing liquid preparation step and reduction in raw material cost by the honing method. Further, the present invention is not limited to the above embodiment. In the above embodiment, the steps (b) and (c) are exemplified as being continuous, but a step of cleaning the honed surface may be provided between the steps (b) and (c) as needed. Or drying steps, etc. Further, between step (b) and step (c), the exchange of the platen or the honing cloth, the change of the processing load, and the stop of the apparatus for performing the above operations may be performed. EXAMPLES Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to the following examples. [Examples 1 to 4, Comparative Examples 1 and 2] (Preparation of honing liquid) -22- 200937513 First, a colloidal cerium oxide abrasive grain having a polyacrylic acid content of 1.2% by weight and an average particle diameter of 35 nm was made to 0. 40% by weight, malic acid as a metal dissolving agent is 0.20% by weight, succinic acid is 0.20% by weight, benzotriazole as a metal resist is 〇20% by weight, and the rest is pure water (that is, total In a manner of 100% by weight, the pH of the above-mentioned component 'mixture was adjusted to 3.6' using ammonia water to obtain a liquid A (corresponding to the first liquid of the present invention). Further, an aqueous hydrogen peroxide solution (a reagent-grade 30% water-soluble φ liquid) was prepared as the second liquid of the present invention. Next, in Examples 1 to 3 and Comparative Examples 1 and 2, the two honing liquids were prepared by mixing A and B liquids in the ratios shown in Table 1. (Substrate) The following substrates 1 and 2 were prepared as substrates to be honed. Substrate 1 (8 吋 bare 矽 substrate without pattern): 矽 substrate / interlayer insulating film (cerium oxide, average film thickness 300 nm) / barrier layer (tantalum nitride 'flat φ uniform film thickness 25 nm) / metal layer (copper, The average film thickness is 1.5 m). Substrate 2 (8 吋矽 substrate with pattern): 矽 substrate/interlayer insulating film (cerium oxide, average film thickness 300 nm)/barrier layer (molybdenum nitride, average film thickness) formed with a depth of 〇·5 groove 25 nm) / metal layer (copper 'average film thickness 8 50 nm). The substrate 2 (8-inch substrate with a pattern attached) was produced as follows. First, cerium oxide (average film thickness: 500 nm) as an interlayer insulating film on a ruthenium substrate was formed by a CVD method. On the interlayer insulating film, a lithography method is used to alternately form a trench portion -23-200937513 (corresponding to a metal wiring) having a width of 100 μm and a depth of 500 nm and a ridge portion having a width of 100 (corresponding to an interlayer insulating layer) to form a level. unit. Next, a molybdenum nitride film (average film thickness: 25 nm) was formed as a barrier layer along the high and low portions of the surface of the interlayer insulating film by a sputtering method. Further, a copper film (average film thickness: 850 nm) was formed as a metal layer by a plating method so that the grooves on the tantalum nitride film were entirely buried. (The honing speed is extremely evaluated by the honing surface) 0
分別對上述基板1、2，實施使用第一硏磨液之硏磨步 驟I及使用第二硏磨液之硏磨步驟II。硏磨步驟I、II中 ，一邊對硏磨壓盤之硏磨布供給硏磨液I或硏磨液Π，一 邊以硏磨布押壓於金屬層之被硏磨面之狀態，使硏磨壓盤 與基板相對移動藉此硏磨金屬層。硏磨步驟I、Π中硏磨 條件顯示如下。又，硏磨步驟I、II中，從由電阻値換算 之硏磨前後之金屬層膜厚與硏磨時間求得硏磨速度，使用 觸針式段差計求得基板2之殘餘段差。 Q 又，於硏磨步驟I，硏磨進行至隆起部12之Cu平均 殘膜厚爲180〜20Onm爲止，於硏磨步驟II，硏磨進行至於 晶圓全面之層間絕緣膜之隆起部.12上之氮化钽露出爲止 。於實施例4中，進行硏磨步驟I後之膜厚測定以及段差 測定，硏磨步驟I、Π係連續硏磨。 (硏磨條件） 硏磨墊：IC1010(Rodale公司製） -24- 200937513 硏磨壓力： 硏磨步驟I : 14·0 kPa 硏磨步驟II : 7·〇 kPa 硏磨壓盤旋轉數：93rpm 裝有晶圓之硏磨頭旋轉數：87rpm 硏磨液供給量：200毫升/分鐘 〔表1〕 實施例 1 實施例 2 實施例 3 實施例 4 比較例 1 比較例 2 硏磨步驟 I 硏磨液I B液/A液混合 比(體積比） 1/9 3/7 4/6 3/7 5/5 5/5 H2〇2濃度 (雷畳〇/〇) 3.0 9.0 12 9.0 15 15 基板I硏磨速度(nrn/min) 965 795 720 795 625 625 基板Π硏磨時間(秒） 65 80 87 79 95 95 Cu殘膜厚(nm) 190 185 190 192 190 mm 没差(麵） 10 8 7 . 5 5 硏磨步驟 II 硏磨液π B液/A液混合 比(體積比） 5/5 5/5 5/5 5/5 5/5 3/7 H2〇2濃度 (重量％) 15 15 15 15 15 9.0 基板I硏磨速度(nm/min) 400 400 400 400 400 660 基板Π硏磨時間(秒） 60 58 60 60 60 45 殘餘段差(nm) 40 38 39 40 41 100 硏磨步驟I、Π之硏磨時間合計(秒） 125 138 147 139 155 135 相較於硏磨液I ’硏磨液II之B液/A液混合比爲較大 之實施例1〜3之情況’顯示硏磨步驟I之良好硏磨速度， 另一方面，硏磨步驟II後之基板的被硏磨面顯示良好平坦 -25- 200937513 性。於硏磨步驟I、II連續硏磨之實施例4亦同樣顯示良 好平坦性。另一方面，硏磨液I、II具有相同組成之比較 例1’於硏磨步驟I中硏磨速度低，圖案基板之硏磨時間 變長。又’相較於硏磨液I，硏磨液II之B液/A液混合比 爲較小之比較例2之情況，硏磨步驟I中硏磨速度變低， 圖案基板之硏磨時間變長’另一方面，於硏磨步驟平坦 性惡化。 【圖式簡單說明】 圖1爲模式性地顯示本發明硏磨方法之較佳實施形態 之步驟剖面圖。 【主要元件符號說明】 10 :層間絕緣膜 11 :溝部The honing step I using the first honing liquid and the honing step II using the second honing liquid are carried out on the substrates 1 and 2, respectively. In the honing steps I and II, while the honing liquid I or the honing liquid is supplied to the honing cloth of the honing platen, the honing cloth is pressed against the honed surface of the metal layer to make the honing The platen moves relative to the substrate to thereby honing the metal layer. The honing step I and the honing condition are shown below. Further, in the honing steps I and II, the honing speed was determined from the thickness of the metal layer before and after the honing by the resistance 硏 and the honing time, and the residual step of the substrate 2 was obtained using a stylus type step difference meter. Q, in the honing step I, the honing proceeds until the average residual film thickness of the Cu of the ridge portion 12 is 180 to 20 nm, and in the honing step II, the honing proceeds to the ridge portion of the interlayer insulating film of the wafer. The tantalum nitride on it is exposed. In Example 4, the film thickness measurement and the step measurement after the honing step I were carried out, and the honing step I and the hydrazine system were continuously honed. (honing condition) Honing pad: IC1010 (made by Rodale) -24- 200937513 Honing pressure: honing step I: 14·0 kPa honing step II: 7·〇kPa honing platen rotation number: 93 rpm Number of honing head rotations with wafer: 87 rpm Supply of honing liquid: 200 ml/min [Table 1] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Honing step I honing liquid IB liquid/A liquid mixing ratio (volume ratio) 1/9 3/7 4/6 3/7 5/5 5/5 H2〇2 concentration (Thunder/〇) 3.0 9.0 12 9.0 15 15 Substrate I honing Speed (nrn/min) 965 795 720 795 625 625 Substrate honing time (seconds) 65 80 87 79 95 95 Cu residual film thickness (nm) 190 185 190 192 190 mm No difference (face) 10 8 7 . 5 5 Honing step II honing liquid π B liquid / A liquid mixing ratio (volume ratio) 5/5 5/5 5/5 5/5 5/5 3/7 H2〇2 concentration (% by weight) 15 15 15 15 15 9.0 Substrate I honing speed (nm/min) 400 400 400 400 400 660 Substrate honing time (seconds) 60 58 60 60 60 45 Residual section difference (nm) 40 38 39 40 41 100 Honing step I, Π Grinding time total (seconds) 125 138 147 139 155 135 compared to honing fluid I The case where the mixing ratio of the liquid B of the honing liquid II is larger than that of the first embodiment 1 to 3 'shows the good honing speed of the honing step I, and on the other hand, the honing of the substrate after the honing step II The surface shows a good flat-25- 200937513 sex. Example 4, which was continuously honed in the honing steps I and II, also showed good flatness. On the other hand, in Comparative Example 1' in which the honing liquids I and II have the same composition, the honing speed was low in the honing step I, and the honing time of the pattern substrate became long. Moreover, compared with the case of the honing liquid I, the mixing ratio of the B liquid/A liquid of the honing liquid II is smaller, the honing speed in the honing step I becomes lower, and the honing time of the pattern substrate becomes On the other hand, the flatness deteriorates during the honing step. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing the steps of a preferred embodiment of the honing method of the present invention. [Main component symbol description] 10 : Interlayer insulating film 11 : Groove
12 :隆起部 1 3 :高低部 14 :面 20 :阻隔層 3 0 ·_金屬層 3 1 :高低部 32 :溝部 33 :隆起部 100 ' 200 ' 300 ：基板 -26-12: ridge portion 1 3 : height portion 14 : surface 20 : barrier layer 3 0 · _ metal layer 3 1 : height portion 32 : groove portion 33 : ridge portion 100 ' 200 ' 300 : substrate -26-