518712 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（） 發明領域： 本發明係有關於銅金屬化製程之阻障層（Barder 之製k方法’特別是有關於積體電路銅製程中，形成具梯 度濃度變化之低電阻值氮化鈕（TaNx)阻障層之製造方法。 發明背景：518712 Printed by A7 B7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs 5. Description of the invention () Field of the invention: The present invention relates to the barrier layer of the copper metallization process (barder's method of k's), especially to the copper of integrated circuits In the process, a manufacturing method of forming a low resistance value nitride button (TaNx) barrier layer with a gradient concentration change. BACKGROUND OF THE INVENTION
Ik著積體電路製程的迅速發展，後段多層導體連線製 程越來越受到重視。進入深次微米元件領域，積體電路元 件中元件運算速度的提升一直是各家必爭的要點，同時也 是購買者選擇時的重要訴求。其中，由於金屬連接線所造 成的時間常數（RC Time Constant)延遲現象嚴重影響元件 操作的速度，'其改善方法之一係為選用低電阻的金屬材料 來做為金屬連線結構，例如銅、金、銀等金屬材料已被列 入考量中。其中，由於銅金屬本身具有許多優勢，例如： (1)較金金屬與鋁金屬具有低電阻；（2)抗電遷移阻抗 (Electromigration Resistance)佳；（3)良好的熱導性。再加 上可以物理氣相沈積與化學氣相沈積與電鍍的方式長成， 因此，銅製程已漸成為各積體電路廠所採用的製程。 但是，銅金屬的一些化學性質卻阻礙了其在積體電路 元件上的應用，其中包括：（1)銅金屬在約200 °C的低溫下 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) — — .............---->----訂.........^ (請先閱讀背面之注意事项再塡寫本頁) ^/12 ^/12 經濟部智慧財產局員工消費合作社印製 、發明説明（） 極易與許多元素反應，例如蛊 巧郭興石夕或矽基材反應，形成如 3Si的化合物於積體電路結構中，而造成元件失效。⑺ 鋼金屬無法像銘金屬一樣生成自我保護的氧化層，因此容 易氧化與腐钱，而影響金屬連線的導電穩定性。⑺銅金屬 與介電層的附著性不良’使得積體電路中薄膜結構之機械 強度不足。（4)銅原子具有快速的擴散性，在電場的加速 下，銅原子能穿透介電層而快速的擴散，尤其一旦銅原子 擴散至石夕基材中，造成元件的特性退化與失效。因此，便 需要在基材或介電層與銅金屬間形成一阻障層來解決上述 問題。 良好的阻障層必需可做為有效的黏著層，不但與銅金 屬的附著性良好，且與介電層附著良好。同時，也需要高 溫下能有效抑'制銅原子擴散到矽元件内部，並具有良好的 熱穩定性以提高元件的壽命與可靠度。其中現今較常在鋼 製耘中使用的阻障層材料為氮化鈕（TaN)材料，其擁有較佳 的阻障效果。第1圖所繪示為一般利用氮化钽做為阻障層 材料的銅金屬内連線之結構示意圖。請參照第丨圖，其中 在基材10中已形成一銅金屬内連線14，並在基材上形 成具有一開口 20的介電層18，並。而在基材1〇與介電層 1 8間具有蝕刻終止層} 2，以方便形成例如金屬鑲嵌結構之 開口 20時的製程所需。接著，在開口 2〇中，沈積一層以 氮化纽所構成之阻障層22，再藉由銅晶種層（Seed Layer)、 裝 訂 (請先閲讀背面之注意事項再填寫本頁)Ik focused on the rapid development of integrated circuit manufacturing processes, and the subsequent multi-layer conductor connection process has received increasing attention. Entering the field of deep sub-micron components, the improvement of component computing speed in integrated circuit components has always been a must-have point for various companies, and it is also an important demand when buyers choose. Among them, the RC Time Constant delay phenomenon caused by the metal connection wire seriously affects the speed of the operation of the device. One of the improvement methods is to use a low-resistance metal material as the metal connection structure, such as copper, Metal materials such as gold and silver have been considered. Among them, copper metal has many advantages, such as: (1) lower resistance than gold metal and aluminum metal; (2) good electromigration resistance; (3) good thermal conductivity. Coupled with physical vapor deposition and chemical vapor deposition and electroplating, the copper process has gradually become the process used by various integrated circuit factories. However, some chemical properties of copper metal have prevented its application in integrated circuit components, including: (1) Copper metal is applicable to Chinese National Standard (CNS) A4 specifications at low temperatures of about 200 ° C ( 210X297 mm) — — ............. > ---- Order ......... ^ (Please read the precautions on the back before 塡(Write this page) ^ / 12 ^ / 12 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed and described by the invention () It is very easy to react with many elements, such as the coincidence of Guo Xingshi Xi or silicon substrate, to form compounds such as 3Si. Components in the body circuit structure. ⑺ Steel metal cannot generate self-protecting oxide layer like Ming metal, so it is easy to be oxidized and corrupted, which affects the conductive stability of the metal connection.不良 Poor adhesion between copper metal and dielectric layer 'makes the mechanical strength of the thin film structure in the integrated circuit insufficient. (4) Copper atoms have fast diffusivity. Under the acceleration of the electric field, copper atoms can penetrate the dielectric layer and diffuse rapidly. Especially once the copper atoms diffuse into the Shixi substrate, the characteristics of the components are degraded and invalidated. Therefore, it is necessary to form a barrier layer between the substrate or the dielectric layer and the copper metal to solve the above problems. A good barrier layer must be used as an effective adhesive layer, which not only has good adhesion to copper metal, but also good adhesion to the dielectric layer. At the same time, it is also necessary to effectively suppress the diffusion of copper atoms into the silicon device at high temperature and have good thermal stability to improve the life and reliability of the device. Among them, the material of the barrier layer more commonly used in steel processing today is a nitride button (TaN) material, which has a better barrier effect. Figure 1 shows the structure of a copper metal interconnect using tantalum nitride as the barrier material. Referring to FIG. 丨, a copper metal interconnect 14 has been formed in the substrate 10, and a dielectric layer 18 having an opening 20 has been formed on the substrate. An etching stopper layer 2 is provided between the substrate 10 and the dielectric layer 18 to facilitate the process required for forming the opening 20, such as a metal damascene structure. Next, in the opening 20, deposit a barrier layer 22 made of nitride nitride, and then use a copper seed layer (Seed Layer) and binding (please read the precautions on the back before filling this page)
518712 A7 厂 _B7____ 五、發明説明（） 銅電鑛（Electroplating)與化學機械研磨（Chemical Mechanical Polishing)等製程以形成銅金屬層24,便可完成 另一銅金屬内連線結構。 但是，在習知技術中，常會出現如第1圖所示之銅金 屬層24的回拉（pull Back)現象26。此回拉現象26有可能 是因為構成阻障層22之氮化钽材料與銅金屬層24間的附 著性不良，或後續製程或實際產品應用時之電與熱的加壓 所導致。由於回拉現象26的存在，會影響銅製程中多層金 屬内連線（Multilevel Interconnect)的導電穩定性與產品可 靠度。 發明目的及概述： 鑒於上述之發明技術具有導電穩定性與產品可靠度不 良的缺點’因此’本發明的目的之一係為提供一種銅金屬 化製程之低電阻值阻障層之製造方法，可獲得品質較為良 好的阻障層，以突破現有銅製程的技術瓶頸。 另外’本發明的目的之一係為提供一種銅金屬化製程 之氮化組阻障層之製造方法，以解決習知鋼金屬内連線製 程中’利用氮化鈕材料做為阻障層所遭遇到銅金屬内連線 回拉的問題。 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) ...............¥: (請先閲tII背面之注意事項再填寫本頁) 玎 線 經濟部智慧財產局員工消費合作社印製 518712 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（） 根據上述之目的，本發明所提供銅金屬化製程之低電 阻值阻障層之製造方法包括：提供一基材；形成一開口於 基材中’以及’進行一沈積步驟，在沈積具一厚度之阻障 層後’使含氮反應氣體流量遞減，並繼續形成阻障層覆蓋 於開口，此阻障層係由數個金屬原子與數個氮原子（N)所構 成，而此氮原子之濃度係由阻障層之底面向表面遞減。本 發明銅金屬之阻p早層之製造方法中，上述之開口可為溝渠 (Trench)結構、介層窗（Via)結構、或金屬鑲嵌（Damascene) 結構。而上述之沈積步驟可利用物理氣相沈積法（physical Vapor Deposition)、或化學氣相沈積法（chemical Vap〇r Deposition)來進行。在本發明一較佳實施例中，上述之金 屬原子係為钽原子（Ta)，含氮反應氣體為氮氣，而所形成 的阻障層係由氮化鈕（TaNx)材料所構成，並在阻障層之底 面中，组原子與氮原子之具有之較佳X值係介於〇.5至〇8 之間’其值視實際應用時之需求而定。另外，更可將上述 之含氮反應氣體流量遞減為零，因此，所形成的阻障層表 面，氮原子之濃度係為零。本發明更可在上述開口中形成 銅金屬，即可形成銅金屬内連線之結構。 利用本發明銅金屬化製程之低電阻值阻障層之製造方 法，可製造具有梯度濃度變化的氮化钽阻障層，其與銅金 屬間的附著性較習知應用氮化鈕材料好，而可降低阻障層 5 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) ...............苹·----、----、可.........^ (請先閲讀背面之注意事項再填寫本頁) 518712 、 A 7518712 A7 plant _B7____ 5. Description of the invention () Copper electro-mineralization (Electroplating) and chemical mechanical polishing (Chemical Mechanical Polishing) and other processes to form the copper metal layer 24, you can complete another copper metal interconnect structure. However, in the conventional technology, a pull back phenomenon 26 of the copper metal layer 24 as shown in FIG. 1 often occurs. This pullback phenomenon 26 may be caused by poor adhesion between the tantalum nitride material and the copper metal layer 24 constituting the barrier layer 22, or by electrical and thermal pressure during subsequent processes or actual product applications. The existence of the pullback phenomenon 26 will affect the conductive stability and product reliability of the multilevel metal interconnects in the copper process. Purpose and summary of the invention: In view of the above-mentioned invention technology has the disadvantages of poor conductivity stability and product reliability, so one of the objectives of the present invention is to provide a method for manufacturing a low-resistance barrier layer in a copper metallization process. Obtain a better quality barrier layer to break the technical bottleneck of the existing copper process. In addition, one of the objectives of the present invention is to provide a method for manufacturing a nitride group barrier layer in a copper metallization process, in order to solve the problems encountered when using a nitride button material as a barrier layer in the conventional steel metal interconnection process. The problem of copper metal internal wire pullback. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) ............... ¥: (Please read the precautions on the back of tII before filling this page) 玎 线Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 518712 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () According to the above purpose, the low-resistance barrier layer of the copper metallization process provided by the present invention The manufacturing method includes: providing a substrate; forming an opening in the substrate; and 'performing a deposition step, after depositing a barrier layer having a thickness,' decreasing the flow rate of the nitrogen-containing reaction gas, and continuing to form a barrier layer cover At the opening, the barrier layer is composed of several metal atoms and nitrogen atoms (N), and the concentration of the nitrogen atom decreases from the bottom surface of the barrier layer to the surface. In the method for manufacturing an early p-layer of copper metal of the present invention, the aforementioned opening may be a trench structure, a via structure, or a damascene structure. The above-mentioned deposition step can be performed by a physical vapor deposition method (physical vapor deposition method) or a chemical vapor deposition method (chemical vapor deposition method). In a preferred embodiment of the present invention, the above metal atom system is tantalum atom (Ta), and the nitrogen-containing reaction gas is nitrogen gas, and the barrier layer formed is made of a nitride button (TaNx) material, and In the bottom surface of the barrier layer, the preferable X value of the group atom and the nitrogen atom is between 0.5 and 08. The value depends on the actual application requirements. In addition, the flow rate of the nitrogen-containing reaction gas can be reduced to zero. Therefore, the surface of the formed barrier layer has a nitrogen atom concentration of zero. In the present invention, copper metal can be formed in the openings, that is, a structure of copper metal interconnects can be formed. By using the manufacturing method of the low-resistance barrier layer of the copper metallization process of the present invention, a tantalum nitride barrier layer with a gradient concentration change can be manufactured, and the adhesion between the barrier layer and the copper metal is better than that of conventionally used nitride button materials. It can reduce the barrier layer 5 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) ............... Can ......... ^ (Please read the notes on the back before filling out this page) 518712 、 A 7
之電阻及提升元件的抗電遷移阻抗與導電穩定性。 圖式簡單說明： ...............裝：…----訂 ί請先閲fm背面之注意事項再填寫本頁} 本發明的較佳實施例將於往後之說明文字中辅以下* 圖形做更詳細的闡述，其中： 第1圖所繪示為一般利用氮化钽做為阻障層材料的鋼 金屬内連線之結構示意圖； 第2圖所繪示為本發明銅金屬化製程之低電阻值阻障 層之結構示意圖； 第3圖所繪示為本發明銅金屬化製程之低電阻值阻障 層之放大結構示意圖；以及 第4圖所緣示為利用本發明低電阻值阻障層的銅金屬 内連線之結構示意圖。 圖號對照說明： 線 經濟部智慧財產局員工消費合作社印製 10 基材 12 姓刻終止層 14 銅金屬内連線 18 介電層 20 開口 22 阻障層 24 銅金屬層 26 回拉現象 50 基材 52 钮刻終止層 6 本紙張尺度適用中國國家標準(CNS)A4規格(210X297公釐) 518712 A7 五 、發明説明（ 54 60 64 70 74 銅金屬内連線 開口 位置 最先沈積部分 最後沈積部分 58 6266 72 80 介電層 阻障層 鼠原子 中段沈積部分 銅金屬層 發明詳細說明： 由於習知技術形成一層氮化鈕材料於金屬鑲嵌結構中 以做為阻障層，卻因後續製程或實際產品應用時之電與熱 的加壓，形成鋼金屬内連線的空洞（v〇id)與回拉現象，造 成鋼製程中内連接導線的不穩定導電性，使得積體電路的 可靠度下降。因此，本發明係提供一種銅金屬化製程之低 電阻值阻障層之製造方法，係可製造改善鋼金屬回拉現象 的氮化钽阻障層，以提高銅製程之積體電路元件的產品可 靠度。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 第2圖所繪示為本發明銅金屬化製程之低電阻值阻障 層之結構示意圖。請參照第2圖，首先，基材5 〇中係具有 已形成之銅金屬内連線54，但本發明不限於基材5〇中一 定具有銅金屬内連線54之結構。接著，在基材5〇上形成 隔離金屬連線所需的介電材料，例如介電層58,並在介電 材料中形成一開口 60,此開口可為溝渠結構、介層窗結構、 518712 Α7 _____ Β7 五、發明説明（） (請先閲tli背面之注意事項再填寫本頁) 或如第2圖中所示的金屬鑲嵌結構。若要以如金屬鑲嵌製 程來形成開口 60，則可在基材5〇與介電層58間形成蝕刻 終止層52，以防止過度蝕刻。其中，上述形成溝渠結構、 "層®結構或金屬鑲嵌結構之方法並非本發明之重點，且 其操作原理為熟悉此技藝者所知，故本發明不在此贅述。 經濟部智慧財產局員工消費合作社印製 形成開口 6 0後，本發明即利用物理氣相沈積法或化學 氣相沈積法在開口 60上形成阻障層62。其中，若為提高 鐘膜時的階梯覆蓋率，則可選擇化學氣相沈積法較能得到 厚度均勻的膜’但以例如氮化鈕做為銅金屬阻障層材料而 吕’在而真空下以物理氣相沈積法所鍍出的氮化鈕阻障層 薄膜品質較佳，操作者可依所需而加以選擇，本發明不限 於此。氮化鈕氣相沈積法中，含氮反應氣體與鈕原子結合， 以在基材中形成氮化鈕的薄膜，其中上述之含氮反應氣體 可為例如氮氣或其他氮化物氣體等，本發明不限於此。習 知幵y成氮化组薄膜過程中，不論是物理氣相沈積法或化學 氣相沈積法，其中所使用的氮氣反應氣體之流量是固定 的’因此所製造出來的氮化钽薄膜成分非常均勻，亦即氮 原子在薄膜中的分佈非常均勻。但是’本發明的特點在於， 在物理或化學氣相沈積法中，於沈積一定厚度之氮化鈕 後改炎含氮反應氣體的流量，使含氮反應氣體流量慢慢 遞減，並Μ續沈積氮化钽阻障層。因此，所製造出來的氮 化叙薄膜中的氮原子會呈現逐漸下降的梯度濃度。 8Resistance and improve the resistance to electromigration and conductive stability of components. Brief description of the drawings: ............... Equipment: ...---- Order, please read the precautions on the back of fm before filling out this page} The preferred embodiment of the present invention will In the following explanatory text, the following * graphs are used to explain in more detail, in which: Figure 1 shows a schematic diagram of the structure of steel metal interconnects generally using tantalum nitride as the barrier material; Figure 2 The diagram shows the structure of the low-resistance barrier layer of the copper metallization process of the present invention; FIG. 3 shows the enlarged structure diagram of the low-resistance barrier layer of the copper metallization process of the present invention; and FIG. 4 The reason is a schematic structural diagram of a copper metal interconnect using the low-resistance barrier layer of the present invention. Comparative description of drawing numbers: Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 10 Substrate 12 Last name engraved termination layer 14 Copper metal interconnect 18 Dielectric layer 20 Opening 22 Barrier layer 24 Copper metal layer 26 Pull back phenomenon 50 bases Material 52 Button cut-off layer 6 This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 518712 A7 V. Description of the invention (54 60 64 70 74 Copper metal interconnect opening position First deposited part Last deposited part 58 6266 72 80 Dielectric barrier layer deposited part of the copper metal layer in the middle of the mouse atom Detailed description of the invention: Due to the conventional technology, a layer of nitrided button material is formed in the metal mosaic structure as a barrier layer, but due to subsequent processes or actual Pressurization of electricity and heat during product application forms voids and pull-back phenomena in steel metal interconnects, causing unstable electrical conductivity of the interconnecting wires in the steel manufacturing process, which reduces the reliability of integrated circuits Therefore, the present invention provides a method for manufacturing a low-resistance barrier layer in a copper metallization process, which is capable of manufacturing a tantalum nitride barrier layer to improve the pullback phenomenon of a steel metal in order to improve Product reliability of integrated circuit components made of copper. (Please read the notes on the back before filling out this page.) Printed in Figure 2 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Schematic diagram of the structure of the resistance value barrier layer. Please refer to FIG. 2. First, the substrate 50 has a copper metal interconnect 54 formed thereon, but the present invention is not limited to the substrate 50 having a copper metal interconnect. The structure of the line 54. Next, a dielectric material, such as a dielectric layer 58, is formed on the substrate 50 to isolate the metal connection, and an opening 60 is formed in the dielectric material. This opening can be a trench structure, a dielectric Layer window structure, 518712 Α7 _____ Β7 V. Description of the invention () (Please read the precautions on the back of tli before filling out this page) or the metal mosaic structure as shown in Figure 2. If you want to use a metal mosaic process to form The opening 60 can form an etch stop layer 52 between the substrate 50 and the dielectric layer 58 to prevent over-etching. Among them, the method for forming a trench structure, " layer® structure or metal damascene structure is not the focus of the present invention. And its operation The working principle is known to those skilled in the art, so the present invention is not repeated here. After the opening 60 is printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the present invention uses physical vapor deposition or chemical vapor deposition to open the opening. A barrier layer 62 is formed on 60. Among them, in order to improve the step coverage of the bell film, a chemical vapor deposition method can be selected to obtain a film with a uniform thickness. However, for example, a nitride button is used as a copper metal barrier layer. The quality of the material of the nitrided button barrier layer deposited by the physical vapor deposition method under vacuum is better, and the operator can choose according to the needs, and the present invention is not limited thereto. In the nitrided button vapor deposition method, a nitrogen-containing reaction gas is combined with a button atom to form a thin film of a nitrided button in a substrate. The nitrogen-containing reaction gas may be, for example, nitrogen or another nitride gas. The present invention Not limited to this. It is known that during the process of forming nitride films, no matter whether it is physical vapor deposition or chemical vapor deposition, the flow rate of the nitrogen reaction gas used is fixed. Therefore, the composition of the produced tantalum nitride film is very Uniform, that is, the distribution of nitrogen atoms in the film is very uniform. However, the present invention is characterized in that in the physical or chemical vapor deposition method, the flow rate of the nitrogen-containing reaction gas is changed after the nitride button of a certain thickness is deposited, so that the flow rate of the nitrogen-containing reaction gas is gradually decreased, and the deposition is continued. Barrier layer of tantalum nitride. Therefore, the nitrogen atoms in the nitrided film produced will show a gradually decreasing gradient concentration. 8
經濟部智慧財產局員工消費合作社印製 518712 A 7 B7 五、發明説明（） 第3圖所繪示為本發明銅金屬化製程之低電阻值阻障 層之放大結構示意圖，此第3圖係為第2圖中位置64的放 大結構。請參照第3圖，沈積在開口 60中的阻障層62具 有數個氮原子66，其中，在最先沈積部分70中，由於參 與反應的含氮反應氣體流量最大，因此所含有的氮原子66 數量也最多。接著，由於含氮反應氣體流量遞減，因此在 中斷沈積部分72所含有的氮原子66數量即少於最先沈積 部分70所含有的氮原子66數量。隨後，當含氮反應氣體 流量非常微小時，最後沈積部分74中的氮原子66數量即 非常稀少。 在本發明一較佳實施例中沈積氮化組（TaNx)阻障層， 此X係用來代表氮化钽阻障層中，钽原子數量比上氮原子 數量的比值。其中，在阻障層底面，亦即最先沈積部分中， X值大約在0.5至0.8之間（視實際應用時之需求而定），而 當含氮反應氣體流量逐漸遞減的情況下，使X值逐漸下 降’甚至下降至零。亦即在沈積氮化组的製程中，最後可 將含氮反應氣體關閉，如此可在阻障層表面形成僅有超原 子的金屬結構，如此可結合鈕金屬與氮化鈕材料的特性， 以做為特性良好之阻障層結構。值得注意的是，本發明雜^ 金屬化製程之低電阻值阻障層之製造方法除了可應用在氮 化組阻障層之製造中，更可應用在其他氮化金屬之阻障層 ...............苹------、一叮.........^ (請先閲讀背面之注意事項再填寫本頁} 9Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 518712 A 7 B7 V. Description of the Invention () Figure 3 shows the enlarged structure of the low resistance barrier layer of the copper metallization process of the present invention. It is the enlarged structure of position 64 in FIG. 2. Referring to FIG. 3, the barrier layer 62 deposited in the opening 60 has a plurality of nitrogen atoms 66. Among the first deposition portions 70, since the nitrogen-containing reaction gas participating in the reaction has the largest flow rate, the nitrogen atoms contained therein 66 is also the largest. Next, since the flow rate of the nitrogen-containing reaction gas decreases, the number of nitrogen atoms 66 contained in the interrupted deposition portion 72 is less than the number of nitrogen atoms 66 contained in the first deposition portion 70. Subsequently, when the flow rate of the nitrogen-containing reaction gas is very small, the number of nitrogen atoms 66 in the final deposition portion 74 becomes very scarce. In a preferred embodiment of the present invention, a nitride group (TaNx) barrier layer is deposited, and X is used to represent the ratio of the number of tantalum atoms to the number of nitrogen atoms in the tantalum nitride barrier layer. Among them, in the bottom surface of the barrier layer, that is, the first deposition part, the X value is about 0.5 to 0.8 (depending on the actual application demand), and when the flow rate of the nitrogen-containing reaction gas gradually decreases, the The X value gradually decreases' or even drops to zero. That is, in the process of the deposition of the nitrided group, the nitrogen-containing reaction gas can be turned off at last, so that a super atom-only metal structure can be formed on the surface of the barrier layer, so that the characteristics of the button metal and the nitride button material can be combined to As a barrier layer structure with good characteristics. It is worth noting that the manufacturing method of the low-resistance barrier layer of the hybrid metallization process of the present invention can be applied to the barrier layer of a nitride group, and can also be applied to the barrier layers of other nitride metals .. ............. ping ------, a ding ......... ^ (Please read the notes on the back before filling out this page) 9
518712 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（） 結構製程中，本發明不限於此◊另外，本發明製造方法中， X值遞減至零僅為舉例，更可視產品或製程需要，選擇含 氮反應氣體流篁的遞減程度’亦即控制X的變化值，以製 造所需梯度濃度變化的阻障層，本發明並不限於此。本發 明低電阻值阻障層之製造方法除了可應用在底部為基材= 介電層之開口結構外，更可應用在内連線金屬介電層之開 口中，亦即銅製程中，需要形成低電阻值阻障層的位置， 皆可應用本發明之製造方法。 最後，請參照第4圖，形成銅金屬層8〇於第2圖之鲈 構中’即可形成銅金屬内連線之結構。利用本發明上述之 製造方法可製造具有梯度濃度變化的例如氮化鈕阻障層， 其中於表面形成的组金屬與銅金屬間的附著性較習知所麻 用的單純氮化钽材料好。另外，再加上本發明之阻障層^ 部係應用氮化钽材料，而可獲得良好的阻隔效果。如此一 來，利用本發明銅金屬化製程之低電阻值阻障層之製造方 法，可獲得同時具有良好附著性與阻隔特性的阻障層，應 用在銅金屬鑲嵌製程中，即可降低介層窗阻值，並提升I 多層金屬内連線之抗電遷移阻抗，使元件的導電穩定性提 升。 如熟悉此技術之人員所瞭解的，以上所述僅為本發明 之較佳實施例而已，並非用以限定本發明之申請專利範 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公爱)-------- ...............-----、玎.........^ (請先閲fm背面之注意事項再填寫本頁) 518712 A7 _ B7_ 五、發明説明（） 圍；凡其它未脫離本發明所揭示之精神下所完成之等效改 變或修飾，均應包含在下述之申請專利範圍内。 經濟部智慧財產局員工消費合作社印製 ..............苹—-----、可.........^ (請先閲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(210X297公釐)518712 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () In the manufacturing process, the present invention is not limited to this. In addition, in the manufacturing method of the present invention, the X value is reduced to zero for example only. The manufacturing process needs to select the decreasing degree of the nitrogen-containing reaction gas flow ', that is, to control the change value of X to manufacture a barrier layer with a desired gradient concentration change, and the present invention is not limited thereto. In addition to the manufacturing method of the low-resistance barrier layer of the present invention, in addition to the opening structure whose bottom is the substrate = dielectric layer, it can also be used in the opening of the interconnecting metal dielectric layer, that is, in the copper manufacturing process. Wherever a low-resistance barrier layer is formed, the manufacturing method of the present invention can be applied. Finally, please refer to FIG. 4 to form a copper metal layer 80 in the structure of FIG. 2 to form a copper metal interconnect structure. By using the above-mentioned manufacturing method of the present invention, for example, a nitride button barrier layer having a gradient concentration change can be manufactured, wherein the adhesion between the group metal formed on the surface and the copper metal is better than that of a simple tantalum nitride material known in the art. In addition, in addition to the application of the tantalum nitride material in the barrier layer ^ of the present invention, a good barrier effect can be obtained. In this way, by using the method for manufacturing a low-resistance barrier layer in the copper metallization process of the present invention, a barrier layer having both good adhesion and barrier properties can be obtained. When applied to a copper metal damascene process, the interlayer can be reduced Window resistance value, and improve the anti-electromigration resistance of I multi-layer metal interconnects, so that the component's conductive stability is improved. As understood by those familiar with this technology, the above description is only a preferred embodiment of the present invention, and is not intended to limit the patent application template of the present invention. The paper size applies to the Chinese National Standard (CNS) A4 specification (210x297 public love). -------- ...............-----, 玎 ......... ^ (Please read the precautions on the back of fm before (Fill in this page) 518712 A7 _ B7_ V. Description of the invention (); all other equivalent changes or modifications made without departing from the spirit disclosed by the present invention shall be included in the scope of patent application described below. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs .............. Ping —-----, but ......... (Please read the note on the back first Please fill in this page for more details) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm)