經濟部中央標準局負工消费合作社印家 4 3 6 3 twf . d〇C/0 06 404037 at B7 五、發明説明（f) 本發明是有關於一種積體電路的製造方法，且特別是 有關於一種金屬層/氮化金屬層的製造方法。 當積體電路的積集度增加，使得晶片的表面無法提供 足夠的面積以製作所需的內連線時，爲了配合金氧半電晶 體縮小後所需增加的內連線需求，多重金屬化製程已逐漸 成爲許多積體電路兀件所採用的方式。通常，金氧半電晶 體各個電極與金屬層吊以介電層加以隔離，再透過接觸窗 插塞（contact plug)予以連接。然而，爲了使接觸窗插塞 與電極（或金屬層）之間有更好的附著能力，以及避免金屬 插塞與矽介面的尖峰（spike)現象，常會在金屬插塞形成 之前，先形成一層黏著層或阻障層的導電材料。 氮化鈦（titanium nitride，TiN)是目前積體電路製程 裡’使用最頻繁的黏著層或阻障層材料。爲了增進金屬對 矽歐姆式接觸的能力，氮化鈦在接觸金屬化製程上是和欽 金屬一起搭配，而以鈦/氮化鈦的組合作爲阻障層或黏著 層。以合金的接觸製程爲例，整個金屬結構將是以鈦、氮 化鈦、合金等三種不同的材料組合而成，以使接觸面的功 函數降低，並達到抑制尖峰與電移現象的發生。 另外，在金屬材料中，由於金屬鎢具有熔點高、熱膨 脹係數與矽相當的優點，再加上以化學氣相沉積法所沉檳 的鎢其內應力並不高，且具備極佳的階梯覆蓋能力，因此 以化學氣相沉積法所沉積的金屬鎢來製作金屬插塞，已麋 泛使用於目前的次微米製程中。 第1A圖至第1C圖繪示爲習知製作鈦/氮化鈦的製作 3 本紙張尺度適用中國國家榡準（CNS ) A4規格（210X297公釐） Μ裝 . . ，訂. '線 (請先閲讀背面之注意事項再4-寫本頁> ：3 6 3 twf . doc/0 06 404037 A7 B7 經濟部中央標準局另工消費合作社印製 五、發明説明（之） 結構剖面圖。首先，請參照第1A圖，在已完成MOS電晶 體102製作的半導體基底100,沈積並定義一層介電層 104，此介電層104中具有接觸窗開口 106，暴露出基底中 部分的源極/汲極區108。 請參照第1B圖，以磁控DC濺鍍的方式，沿著介電層 104的表面上，形成一層欽金屬層110。爲了提昇欽金屬 層110在接觸窗開口 106底部的沈積能力，進行濺鍍時會 在金屬靶與晶片之間加上一個準直管（collimator)。 請參照第1C圖，以物理氣相沈積法（PVD)在鈦金屬層 110上沈積一層氮化鈦層112。由於積集度增加的同時， 接觸窗的高寬比（aspect ratio)會提高，以PVD沈積之氮 化鈦層112並無法提供足夠的階梯覆蓋（step coverage) 效果，在接觸窗開口 106底部角落的鈦金屬層110，會因 此被暴露出來，如圖中標號1H所示。 一般在沈積鎢金屬時，是以六氟化鎢（WF6)做爲化學 氣相沈積法的氣源。一旦氮化欽層的階梯覆蓋能力不佳而 裸露出鈦金屬層，或是氮化鈦層有任何缺陷，WF6所釋放 出的F原子，則會穿透氮化鈦層，和位於其下方的金屬鈦 反應而形成四氟化鈦（TiF4)。由於四氟化鈦係屬於易於揮 發的氣體，因此，當鎢金屬沉積在接觸窗或介層窗開口之 時，會有類似爆裂的現象發生，因此稱作火山效應（vo 1 cano effect)。而此效應的發生，將使得氮化鈦層因此而剝離 或彎曲，讓金屬鎢在剝落的氮化鈦層之兩面沈積。若此現 象係發生於接觸窗開口或介層窗開口的頂端邊角處’將會 4 本紙張尺A適用中國國家梂準（CNS ) A4規格（210X297公釐） ---------.裝-- (請先閲讀背面之注意事項再填寫本頁) 訂 ，線. 經濟部中央標準局貝工消費合作社印裝 A7 £7______________ 五、發明説明（3 ) 使得金屬鎢層的表面產生突起的現象。當突起的現象過於 嚴重時，通常以反應性蝕刻程序都不易將其去除。如此一· 來，將導致瞎窗（b 1 i nd wi ndow)、短路、晶片污染及低產 量等問題。 因此，本發明提供一種金屬層/氮化金屬層的製造方 法，係在已形成有一介電層之半導體基底上進行’妣介電 層中至少具有一接觸窗開口，暴露出部分位於半_體基底 中的導電區域。以物理氣相沈積法’使用準直管在接觸窗 開口中形成一層金屬層，在金屬層上形成一層氮化金屬 層。進行一道植入步驟’以含氮元素的氣體作爲氣體源’ 使因爲階梯覆蓋效果不佳而裸露的金屬層與氮反應’而形 成氮化金屬，藉以覆蓋金屬層。 本發明利用含氣之氣體作爲氣體源，進行植入步驟， 藉以強化氮化金屬層的結構，並使裸露的金屬層可以與氮 反應而形成氮化金屬層，在後續沈積金屬插塞的過程中， 可以避免火山效應的發生。 爲讓本發明之上述目的、特徵、和優點能更明顯易懂， 下文特舉一較佳實施例，並配合所附圖式，作詳細說明如 下： 圖式之簡單說明： 第1A圖至第1C圖繪示爲習知製作鈦/氮化鈦的製作結 構剖面圖；以及 第2A圖至第2D圖繪示依照本發明一較佳實施例，一 種金屬層/氮化金屬層的製造流程圖。 5 本紙張尺度通用中囷固家榇準（CNS ) M規格（210X297公釐） -----------裝--------訂 I ------- 線 (請先聞讀背面之注意事項再填寫本頁) 4363twf.doc/006 404037 A7 B7 經濟部中央標準局貝工消费合作社印製 五、發明説明（>) 圖示標記說明： 100,200 半導體基底 102 MOS電晶體 104,204 介電層 106,206 接觸窗開口 108 源極/汲極區 110 鈦金屬層 112 氮化鈦層 202 導電結構 208,208a 金屬層 210,210a,210b 氮化金屬層 212 氮化金屬層未覆蓋金屬層的部分 I 植入步驟 214 金屬插塞 實施例 在本發明的實施例中，以形成在接觸窗開口中的金屬 層與氮化金屬層爲說明，此並非用以限定本發明之範圍， 在實際的應用上，本發明可適用於接觸窗開口與介層洞 中，形成的金屬層與氮化金屬層適合作爲黏著層或阻障 層。 第2A圖至第2D圖繪示依照本發明一較佳實施例，一 種金屬層/氮化金屬層的製造流程圖。 請參照第2A圖，其繪示爲一半導體基底的剖面示意 圖，導線結構202位於基底200上，可以是許多不同的元 6 本紙張尺度逋用中國國家標準（CNS ) A4規格（21〇X297公釐） ---------_裝—-------訂--------線 (锖先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消费合作社印聚 404037 4363twf.doc/〇〇6 A7 _B7 五、發明説明（夕） 件結構，比如爲金氧半電體的閘極或是源極/汲極區、金 屬內連線、或是介層插塞，在導線結構202中有間隙。導 線結構202可以是各種不同的材料，例如：鋁、鋁與矽的 合金、鋁與銅的合金或銅，合金包括銅與其他多層結構， 其他多層結構包括其他比較便宜的金屬，或比較貴像是高 熔點的金屬。基底200可能包括不同的組成，譬如··包括 電晶體、二極體、或習知裡所能運用的其他半導體組成， 基底200也可能包括其他互連的金屬層。 在此基底200上覆蓋有一層介電層204，可作爲內金 屬介電層（inter-metal dielectric layer，IMD))或是內 層介電層（inter-layer dielectric layer, ILD)。其中， 介電層204至少具有一接觸窗開口 206，以暴露出位於基 底200中的導電結構202。介電層204之材質比如是化學 氣相沈積法形成之二氧化矽、磷矽玻璃（PSG)或是硼磷矽 化玻璃（BPSG)，或是以塗佈方式形成的旋塗式玻璃（S0G)。 另外，可進行平坦化製程，比如化學機械硏磨法（CMP)， 使介電層204具有平坦的上表面。 請參照第2B圖，在介電層204上形成一層共形的金屬 層208，金屬層208之材質比如爲鈦金屬（Τι)，形成的方 式比如利用準直管，以濺鍍的方式進行。在金屬層208上 形成一層氮化金屬層210，氮化金屬層210之材質包括氮 化鈦（ΊΊΝ)，形成方式與形成金屬層208的方法相同，比 如利用準直管將氮化金屬濺鍍在金屬層208上。由於濺鍍 的方法其階梯覆蓋性較差，故氮化金屬層210在接觸窗開 7 本紙張尺度適用中國國家榡準（CNS ) A4規格（210X297公釐） --------^-裝--r-----^訂丨------'線 (請先聞讀背面之注意事項再填寫本頁) 404037 4363twf.doc/ΟΟβ A7 B7 五、發明説明（6) 口 206底部的角落的覆蓋形並不好，如標號212所示’會 暴露出部分的金屬層208。 請參照第2C圖，進行一道植入步驟I，以含氮的氣體 比如氮氣（N2)或氨氣（NH3)作爲氣體源，使未被氮化金屬層 210覆蓋，而外露的金屬層208部分可以與氮反應’而形 成氮化金屬層210a，藉以覆蓋其下方的金屬層208。因此’ 當後續塡入鎢金屬時，原本外露的金屬層208因反應成氮 化金屬，其結構可以阻擋氟化鎢（WF6)所釋放的氟，避免 氟與金屬層208反應形成易揮發的氟化金屬，而造成火山 效應。其中，植入步驟的植入能量約爲10-20Kev ;植入劑 量約爲3χ105-3χ105原子/平方公分，較佳爲1.5χ105原子 /平方公分；_入步驟進行的溫度約爲攝氏200度-400度， 較佳約爲攝氏200度；而進行的壓力約爲lxlO_6Torr。 經濟部中央標準局負工消費合作社印聚 C請先聞讀背面之注意事項再填寫本頁) 請參照第2D圖，在接觸窗開口 206中形成金屬插塞 214，其材質比如爲鎢，形成方式比如以氟化鎢和氫氣作 爲氣體源，進行化學氣相沈積法，在氮化金屬層210a上 形成一層鎢，再去除介電層204上方的鎢、氮化金屬層210a 與金屬層208,使留在接觸窗開口 206中的金屬插塞214、 氮化金屬層210b與金屬層208a組合形成一接觸窗。 本發明利用含氮之氣體作爲氣體源，進行植入步驟’ 藉以強化氮化金屬層的結構，並使裸露的金屬層可以與氮 反應而形成氮化金屬層’在接觸窗開口中形成金屬插塞的 過程中，可以避免反應氣體與金屬層接觸而產生的火山效 應，進而增進元件的可靠度。 8 本紙張尺度適用中國國家梯準（CNS ) A4規格（2K)X297公釐） 4 3 6 3 twf . do c/0 404G37 A7 B7 五、發明説明（7) 雖然本發明已以一較佳實施例揭露如上，然其並非用 以限定本發明，任何熟習此技藝者，在不脫離本發明之精 神和範圍內，當可作各種之更動與潤飾，因此本發明之保 護範圍當視後附之申請專利範圍所界定者爲準。 ---------·1 裝--„---„--^訂—.-----.線 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印裝 本紙張尺度適用中國國家揉準（CNS ) Α4規格（210X297公釐〉The Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4 3 6 3 twf. Doc / 0 06 404037 at B7 V. Description of the invention (f) The present invention relates to a method for manufacturing integrated circuits, and in particular A method for manufacturing a metal layer / nitride metal layer. When the integration degree of integrated circuits increases, so that the surface of the wafer cannot provide enough area to make the required interconnects, in order to meet the increased interconnect requirements required by the shrinkage of metal-oxide semiconductors, multiple metallization The manufacturing process has gradually become the method adopted by many integrated circuit components. Generally, each electrode of the metal oxide semiconductor is separated from the metal layer by a dielectric layer, and then connected through a contact plug. However, in order to have better adhesion between the contact plug and the electrode (or metal layer), and to avoid spikes between the metal plug and the silicon interface, a layer is often formed before the metal plug is formed. Conductive material for the adhesive or barrier layer. Titanium nitride (TiN) is currently the most frequently used adhesive or barrier layer material in integrated circuit manufacturing processes. In order to improve the metal-to-silicon ohmic contact ability, titanium nitride is used with the metal in the contact metallization process, and a titanium / titanium nitride combination is used as a barrier layer or an adhesive layer. Taking the alloy contact process as an example, the entire metal structure will be composed of three different materials, such as titanium, titanium nitride, and alloy, to reduce the work function of the contact surface and to suppress the occurrence of spikes and electromigration. In addition, in metallic materials, because tungsten metal has the advantages of high melting point and thermal expansion coefficient equivalent to that of silicon, coupled with tungsten deposited by chemical vapor deposition, its internal stress is not high, and it has excellent step coverage. The ability to use metal tungsten deposited by chemical vapor deposition to make metal plugs has been widely used in current sub-micron processes. Figures 1A to 1C show the conventional production of titanium / titanium nitride. 3 This paper size is applicable to China National Standard (CNS) A4 (210X297 mm). Packing.., Order. 'Line (Please Read the precautions on the back first and then write this page >: 3 6 3 twf .doc / 0 06 404037 A7 B7 Printed by the Central Standards Bureau of the Ministry of Economic Affairs and other consumer cooperatives Please refer to FIG. 1A, and deposit and define a dielectric layer 104 on the semiconductor substrate 100 on which the MOS transistor 102 has been completed. The dielectric layer 104 has a contact window opening 106 to expose a portion of the source / Drain region 108. Referring to FIG. 1B, a magnetic metal layer 110 is formed along the surface of the dielectric layer 104 by magnetron DC sputtering. In order to improve the metal metal layer 110 on the bottom of the contact window opening 106, Deposition ability, a collimator is added between the metal target and the wafer during sputtering. Please refer to Figure 1C, and deposit a layer of nitride on the titanium metal layer 110 by physical vapor deposition (PVD). Titanium layer 112. As the degree of accumulation increases, the height and width of the contact window The aspect ratio will increase. The titanium nitride layer 112 deposited by PVD does not provide sufficient step coverage. The titanium metal layer 110 at the bottom corner of the contact window opening 106 will be exposed as a result. The middle reference number is 1H. Generally, when tungsten metal is deposited, tungsten hexafluoride (WF6) is used as the gas source for the chemical vapor deposition method. Once the step coverage of the nitride layer is not good, the titanium metal layer is exposed. Or, if there are any defects in the titanium nitride layer, the F atoms released by WF6 will penetrate the titanium nitride layer and react with the metal titanium below it to form titanium tetrafluoride (TiF4). Titanium is a volatile gas, so when tungsten metal is deposited in the contact window or interstitial window opening, a phenomenon similar to bursting occurs, so it is called the vo 1 cano effect. This effect occurs Will cause the titanium nitride layer to be peeled off or bent, so that metal tungsten is deposited on both sides of the exfoliated titanium nitride layer. If this phenomenon occurs at the top corners of the contact window opening or the via window opening, it will be 4 This paper rule A is applicable China National Standard (CNS) A4 (210X297 mm) ---------. Installation-(Please read the precautions on the back before filling this page) Order, line. Central Bureau of Standards, Ministry of Economic Affairs Industrial and consumer cooperative printing A7 £ 7 ______________ 5. Description of the invention (3) The surface of the metal tungsten layer is protruded. When the protuberance is too serious, it is usually not easy to remove it by reactive etching process. Will cause problems such as blind window (b 1 in nd wi ndow), short circuit, wafer contamination and low yield. Therefore, the present invention provides a method for manufacturing a metal layer / nitride metal layer, which is performed on a semiconductor substrate on which a dielectric layer has been formed. The dielectric layer has at least one contact window opening, and the exposed part is located in a semi-body. A conductive region in a substrate. A physical vapor deposition method is used to form a metal layer in the opening of the contact window using a collimator tube, and a nitrided metal layer is formed on the metal layer. An implantation step is performed 'using a nitrogen-containing gas as a gas source' so that a bare metal layer reacts with nitrogen due to poor step coverage effect to form a nitrided metal to cover the metal layer. The present invention uses a gas containing gas as a gas source to perform an implantation step, thereby strengthening the structure of the nitrided metal layer, and allowing the exposed metal layer to react with nitrogen to form a nitrided metal layer, and the subsequent process of depositing a metal plug In order to avoid volcanic effects. In order to make the above-mentioned objects, features, and advantages of the present invention more comprehensible, a preferred embodiment is given below in conjunction with the accompanying drawings for detailed description as follows: Brief description of the drawings: FIG. 1A to FIG. FIG. 1C is a cross-sectional view of a conventional structure for manufacturing titanium / titanium nitride; and FIGS. 2A to 2D are flowcharts of a metal layer / nitride metal layer manufacturing process according to a preferred embodiment of the present invention. . 5 This paper is a universal medium-sized household standard (CNS) M specification (210X297 mm) ----------- installation -------- order I ------- (Please read the precautions on the reverse side before filling out this page) 4363twf.doc / 006 404037 A7 B7 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (>) Symbol description: 100,200 semiconductor substrate 102 MOS transistors 104, 204 dielectric layers 106, 206 contact window openings 108 source / drain region 110 titanium metal layer 112 titanium nitride layer 202 conductive structure 208, 208a metal layer 210, 210a, 210b metal nitride layer 212 metal nitride layer not covered Part I of the metal layer. Implantation step 214. Metal plug embodiment In the embodiment of the present invention, the metal layer and the nitrided metal layer formed in the opening of the contact window are described as illustrations, which is not intended to limit the scope of the present invention. In practical applications, the present invention can be applied to contact window openings and via holes, and the formed metal layer and metal nitride layer are suitable as an adhesion layer or a barrier layer. FIG. 2A to FIG. 2D show a manufacturing flow chart of a metal layer / nitride metal layer according to a preferred embodiment of the present invention. Please refer to FIG. 2A, which is a schematic cross-sectional view of a semiconductor substrate. The wire structure 202 is located on the substrate 200, which can be many different sizes. This paper uses the Chinese National Standard (CNS) A4 specification (21 × 297 mm). Li) ---------_ installation ----------- order -------- line (锖 first read the notes on the back before filling this page) Central Bureau of Standards, Ministry of Economic Affairs Industrial and Consumer Cooperatives Printed Poly 404037 4363twf.doc / 〇〇6 A7 _B7 V. Description of the invention (Even) The structure of the device, such as the gate or source / drain region of metal-oxide semiconductors, metal interconnects, or It is a via plug, and there is a gap in the wire structure 202. The wire structure 202 may be of various materials, such as aluminum, an alloy of aluminum and silicon, an alloy of aluminum and copper, or copper. The alloy includes copper and other multilayer structures, and other multilayer structures include other less expensive metals, or more expensive images. It is a high melting point metal. The substrate 200 may include different compositions, for example, including a transistor, a diode, or other semiconductor components that can be used in the art, and the substrate 200 may also include other interconnected metal layers. A dielectric layer 204 is covered on the substrate 200, which can be used as an inter-metal dielectric layer (IMD) or an inter-layer dielectric layer (ILD). The dielectric layer 204 has at least one contact window opening 206 to expose the conductive structure 202 in the substrate 200. The material of the dielectric layer 204 is, for example, silicon dioxide, phosphosilicate glass (PSG) or borophosphosilicate glass (BPSG) formed by chemical vapor deposition, or spin-on glass (S0G) formed by coating. . In addition, a planarization process may be performed, such as a chemical mechanical honing method (CMP), so that the dielectric layer 204 has a flat upper surface. Referring to FIG. 2B, a conformal metal layer 208 is formed on the dielectric layer 204. The material of the metal layer 208 is, for example, titanium (Ti). The forming method is, for example, using a collimator tube and sputtering. A metal nitride layer 210 is formed on the metal layer 208. The material of the metal nitride layer 210 includes titanium nitride (ΊΊN), and the formation method is the same as the method of forming the metal layer 208, such as sputtering a nitride metal using a collimator. On the metal layer 208. Due to the poor step coverage of the sputtering method, the metal nitride layer 210 is opened at the contact window. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -------- ^- Install --r ----- ^ Order 丨 ------ 'line (please read the notes on the back before filling in this page) 404037 4363twf.doc / ΟΟβ A7 B7 V. Description of the invention (6) 口The covering shape at the bottom corner of 206 is not good. As indicated by reference numeral 212, a part of the metal layer 208 is exposed. Referring to FIG. 2C, an implantation step I is performed, using a nitrogen-containing gas such as nitrogen (N2) or ammonia (NH3) as a gas source, so that the exposed metal layer 208 is not covered by the nitrided metal layer 210, It can react with nitrogen to form a metal nitride layer 210a to cover the metal layer 208 below it. Therefore, when tungsten metal is subsequently implanted, the originally exposed metal layer 208 reacts to form a nitride metal, and its structure can block the fluorine released by tungsten fluoride (WF6) and prevent the fluorine from reacting with the metal layer 208 to form volatile fluorine. Metal, which causes a volcanic effect. Among them, the implantation energy of the implantation step is about 10-20 Kev; the implantation dose is about 3x105-3x105 atoms / cm2, preferably 1.5x105 atoms / cm2; the temperature at which the implantation step is performed is about 200 degrees Celsius- 400 degrees, preferably about 200 degrees Celsius; and the applied pressure is about lxlO_6 Torr. Please read the notes on the back before filling out this page. Please refer to Figure 2D. A metal plug 214 is formed in the contact window opening 206. Its material is, for example, tungsten. For example, tungsten tungsten and hydrogen are used as gas sources, and a chemical vapor deposition method is performed to form a layer of tungsten on the metal nitride layer 210a, and then the tungsten, the metal nitride layer 210a, and the metal layer 208 above the dielectric layer 204 are removed. The metal plug 214, the metal nitride layer 210b, and the metal layer 208a remaining in the contact window opening 206 are combined to form a contact window. In the present invention, a nitrogen-containing gas is used as a gas source to perform the implantation step 'to strengthen the structure of the nitrided metal layer and allow the exposed metal layer to react with nitrogen to form a nitrided metal layer' to form a metal plug in the opening of the contact window. During the plugging process, the volcanic effect caused by the contact of the reaction gas with the metal layer can be avoided, thereby improving the reliability of the component. 8 This paper size applies to China National Standard (CNS) A4 (2K) X297 mm 4 3 6 3 twf. Do c / 0 404G37 A7 B7 V. Description of the invention (7) Although the present invention has been implemented in a preferred way The example is disclosed as above, but it is not intended to limit the present invention. Any person skilled in the art can make various modifications and retouches without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be attached as the following. The ones defined in the scope of patent application shall prevail. --------- · 1 Pack ---------- ^ Order --.-----. (Please read the notes on the back before filling this page) Central Bureau of Standards, Ministry of Economic Affairs The paper size of the printed paper for employee consumer cooperatives is applicable to China National Standard (CNS) Α4 (210X297 mm)