201114936 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種含α鈕之被覆膜之成膜方法及其被覆 膜。 本案係基於2009年7月21日於日本申請之日本專利特願 2009-170577號並主張優先權，且將其内容引用於此。 【先前技術】 於 LSI(large scale integration，大規模積體電路）或1(： (integrated circuit ’積體電路）等半導體元件之配線中採取 如此措施，即藉由在基體與配線之間設置阻隔金屬層而防 止構成配線之導電材料向基體側擴散所引起之配線劣化。 上述阻隔金屬層係藉由利用濺鍍等pVD(physical vap〇r deposition，物理氣相沈積）法或氣相成長法將含金屬或金 屬化合物之薄膜成膜於基體而形成。 例如，揭示一種具有如下銅配線之半導體元件（曰本專 利特開2〇〇3-179133號公報），該銅配線係於含低介電常數 (hnv-k)材料或二氧化邦i〇2)之基體上，形成有包含氮化 鈕（TaN)、鈕（Ta)及組合著該等之膜之阻隔金屬層。 先前之用作阻隔金屬層之薄膜之Ta存在比電阻較高之問 題。 /其原因在於鈕之薄膜包含晶系為立方晶之组(a|a)與晶 系為正方晶之钽（β钽），難以充分降低比電阻。 【發明内容】 本發明所涉及之態樣之目的在於提供一種將含α钽之被 149719.doc 201114936 覆膜成膜於基體之方法及含α鈕之被覆膜，該被覆膜係藉 由該成膜方法而形成，且自上述基體朝上述含α鈕之被覆 膜方向觀察，於上述含α鈕之被覆膜前後之至少任一方配 置有導體或半導體。 本發明所涉及之態樣中之含α鈕之被覆膜之成膜方法的 特徵在於：其係使用濺鍍法將含之被覆膜成膜於基體 之方法，將含惰性氣體及氮氣之第丨處理氣體導入至真空 槽，於導入上述第丨處理氣體之後，以成為形成含α鈕之被 覆膜之氮分壓之方式將含惰性氣體及氮氣中之至少一者之 第2處理氣體導入至上述真空槽而控制電漿，藉此將含α鈕 之被覆膜形成於基體。 上述含α鈕之被覆膜之成膜方法之特徵在於，於導入上 述第1處理氣體之後，將含氮化钽之基礎層形成於基體， 且於將上述含氮化鈕之基礎層形成於上述基體之後，將上 述含α鈕之被覆膜形成於上述基體。 上述含α钽之被覆膜之成膜方法之特徵在於，使用矽作 為上述基體材料。 上述含α钽之被覆膜之成膜方法之特徵在於，使用二氧 化石夕或石英作為上述基體材料。 本發明所涉及之態樣中之含_之被覆膜之特徵在於： 其係藉由上述成膜方法而形成者，於自上述基體朝上述含 «鈕之被覆膜之方向’在上述含α鈕之被覆膜之前的位置及 之後的位置之至少任一方配置有導體或半導體。 根據本發明所涉及之態樣中之含α纽之被覆膜的成膜方 149719.doc 201114936 法，可容易地進行先前難以進行之將含他之被覆膜形成 於基體。 本發明所涉及之態樣中之含α组之被覆膜係於自基體觀 察該含α钽之被覆膜時，在含α鈕之被覆膜之前後之至少一 ㈣置有導體或半導體，其作為比電阻較低之阻隔金屬膜 防止上述導體或半導體材料向基體擴散，且可提高上述導 體或半導體向基體之密接性。 【實施方式】 以下，根據較佳之實施方式並參照圖式來說明本發明所 涉及之態樣。 本實施形態之含α鈕之被覆膜之成膜方法係使用濺鍍法 將含α钽之被覆膜成膜於基體之方法，其依次包含：導入 含惰性氣體及氮氣之第1處理氣體之步驟A ;及以成為形成 含α鈕之被覆膜之氮分壓之方式設定含惰性氣體及/或氮氣 之第2處理氣體而控制電漿，藉此將含α钽之被覆膜形成於 基體之步驟Β。 作為上述濺鍍法，可適用能夠將金屬薄膜成膜於基板上 之通常之濺鍍法，例如可列舉磁控濺鍍、反應性濺鍍等濺 * 鍍法。 - 作為上述濺鍍法中之靶材，使用含Ta之靶材（以下稱為BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film forming method of a coating film containing an alpha button and a coating film therefor. The present application is based on Japanese Patent Application No. 2009-170577, filed on Jan. 27, 2009, the entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire [Prior Art] This measure is adopted in wiring of semiconductor elements such as LSI (large scale integration circuit) or 1 (: (integrated circuit 'integrated circuit), that is, by providing a barrier between the substrate and the wiring The metal layer prevents deterioration of wiring caused by diffusion of the conductive material constituting the wiring to the substrate side. The barrier metal layer is formed by pVD (physical vap〇r deposition) or vapor phase growth method such as sputtering. A film containing a metal or a metal compound is formed on a substrate. For example, a semiconductor device having a copper wiring is disclosed (Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei No. 3-179133). On the substrate of the constant (hnv-k) material or the oxidized state, a barrier metal layer including a nitride button (TaN), a button (Ta), and a film in combination is formed. The Ta which was previously used as a film for the barrier metal layer has a problem that the specific resistance is high. The reason is that the film of the button includes a group in which the crystal system is cubic (a|a) and a crystal in which the crystal is tetragonal (β钽), and it is difficult to sufficiently reduce the specific resistance. SUMMARY OF THE INVENTION An object of the present invention is to provide a method for forming a film comprising a film of 149719.doc 201114936 on a substrate and a film containing a button, which is coated with The film formation method is carried out, and a conductor or a semiconductor is disposed on at least one of the front and back of the coating film including the alpha button as viewed from the direction of the film containing the alpha button. The film forming method of the coating film containing the alpha button in the aspect of the invention is characterized in that the coating film is formed on the substrate by sputtering, and the inert gas and nitrogen gas are contained. The second processing gas is introduced into the vacuum chamber, and after introducing the second processing gas, the second processing gas containing at least one of the inert gas and the nitrogen gas is formed so as to form a nitrogen partial pressure of the coating film containing the alpha button. The film is introduced into the vacuum chamber to control the plasma, whereby the coating film containing the alpha button is formed on the substrate. The film forming method of the coating film containing the alpha button is characterized in that after introducing the first processing gas, a base layer containing tantalum nitride is formed on the substrate, and the base layer containing the nitride button is formed on the base layer. After the substrate, the coating film containing the alpha button is formed on the substrate. The film forming method of the above-mentioned α-containing coating film is characterized in that ruthenium is used as the above-mentioned base material. The film forming method of the above-mentioned α-containing coating film is characterized in that silica or quartz is used as the above-mentioned base material. The coating film containing the film according to the aspect of the invention is characterized in that it is formed by the film forming method, and the direction from the substrate toward the coating film containing the button is in the above-mentioned At least one of the position before and after the coating of the alpha button is disposed with a conductor or a semiconductor. According to the method of film formation of the film containing α-nucleus in the aspect of the present invention, the film of 149719.doc 201114936 can be easily formed on the substrate by a coating film containing it. In the aspect of the present invention, the coating film containing the alpha group is formed by observing the coating film containing α钽 from the substrate, and at least one (four) after the coating film containing the alpha button is provided with a conductor or a semiconductor. The barrier metal film having a lower specific resistance prevents the conductor or the semiconductor material from diffusing into the substrate, and the adhesion of the conductor or the semiconductor to the substrate can be improved. [Embodiment] Hereinafter, aspects of the present invention will be described based on preferred embodiments and with reference to the drawings. The film forming method of the coating film containing the alpha button of the present embodiment is a method of forming a coating film containing α钽 on a substrate by a sputtering method, and sequentially includes introducing a first processing gas containing an inert gas and nitrogen gas. Step A; and setting a second processing gas containing an inert gas and/or nitrogen gas so as to form a nitrogen partial pressure of the coating film containing the alpha button, and controlling the plasma to form an α-containing coating film In the step of the substrate. As the sputtering method, a usual sputtering method in which a metal thin film can be formed on a substrate can be applied, and examples thereof include sputtering/plating methods such as magnetron sputtering and reactive sputtering. - As a target in the above sputtering method, a target containing Ta is used (hereinafter referred to as
TaJfe 材）。 作為上述濺鍍法中之壓力，可以周知之濺鍍法中所使用 之壓力進行滅鍍’例如可以l.〇xl〇-6 Pa以上且4〇〇 以下 進行濺鍍。 H9719.doc 201114936 作為上述濺錢法中之基體溫度，可以周知之雜法中所 使用之溫度進行濺鍍’例如可以鐵以上且議。c以下進 行濺鍍。 :為上述基體’若為包含可承受利用㈣法進行成膜時 :溫度之材料者則無特別限制，例如可列舉含⑦之基板、 氧化夕之基板、含石英之基板、含金屬之基板等。 —作為上述基體，亦可為於上述基板上預先成膜有其他 薄膜等作為基礎層者。 作為上述惰性氣體，若為濺鍍.法中所使用之惰性氣體則 無特別限制，例如可列舉氬（Ar)、氪（Kr)、氦（He)等。其 中’更好的是通常容易獲得且價格低之Are 上述氮氣（NO只要為通常於濺鍍法中所使用之純度之氮 氣即可，且純度越高越好。 根據本實施形態之含α钽之被覆膜之成膜方法，可進行 先前難以進行之將含α钽之被覆膜成膜於基體。 於先則之利用濺鍍法進行之含组之薄膜之成膜方法中， 藉由在心等惰性氣體環境下使用Ta靶材進行濺鍍而成膜含 組之薄膜’但所形成的是含β钽及α鈕之薄膜。 另一方面，於本實施形態中’在使用丁3靶材進行濺鍍時 依次進行下述步驟Α與下述步驟Β，藉此可將含α钽之被覆 膜成膜於基體。 以下’透過第一態樣與第二態樣來說明本實施形態之含 α组之被覆膜之成膜方法。 <第一態樣> 149719.doc 201114936 參照圖1所示之濺鍍裝置1來說明本實施形態之含α鈕之 被覆膜之成膜方法之第一態樣。 於真空槽10之頂板固定有陰極電極4’並於該陰極電極4 之表面配置有Ta靶材5。於陰極電極4上連接有施加負電壓 之直流電源9。 於真空槽10外部之陰極電極4之背面位置設置有含永久 磁鐵之磁路8 ’並以如下方式構成：該磁路8所形成之磁通 貝穿陰極電極4與Ta靶材5，並於Ta靶材5表面形成洩漏磁 場。於進行_時電子被該㈣磁場捕獲，從而使電聚高 密度化。 於真空槽10之底面設置有基體電極6，並於該基體電極6 之表面呈大致平行地對向配置有基體7與Ta靶材5。 基體電極6連接於施加高頻偏壓電力之高頻電源13。 ,，於基體電極6設置有藉由絕緣部na而電性絕緣之加熱 器U，可將基體7之溫度調節為_5〇t〜6〇〇t。 於真空槽1G中設置有氣體導入口2與真空排氣口3。構成 處理氣體之Ar及氛氣之儲氣罐以可個別地㈣各自之流量 之方式連接於氣體導入口 2。於真空排氣口 3連接有真空泵 (未圖示儲氣罐及真空泵’ ，實施形態之上述步驟八係將含惰性氣體及氫氣之第^ 理氣體導入至真空槽10之步驟。 J氣體導入口 2導入至真空槽10之上述第〗處理氣體之 Ϊ為惰性氣體之流量與氮氣之流量之和。 作為上述第1處理氣體中之惰性 π肢 < 机量無特別丨 149719.doc 201114936 制’例如可以1 .〇 seem以上且30 seem以下流動。 作為上述第1處理氣體中之氮氣之流量無特別限制，例 如可以0.01 seem以上且30 seem以下流動。 再者’上述seem係以cm3/分（1 atm，0。(：）表示之單位。 藉由如上述般於步驟A中預先導入上述第1處理氣體，而 可使真空槽10内之氣體流量及壓力穩定，進而，可於於後 述之步驟B中藉由濺鍍法而形成含α鈕之被覆臈時穩定地產 生電漿。 作為於上述步驟Α導入有上述第1處理氣體之真空槽1〇内 之壓力’較好的是適於濺鍍法之壓力範圍1〇xl〇-6 Pa以上 且400 pa以下，更好的是〇〇〇1 pa以上且1〇〜以下進而 好的是0.01 Pa以上且1.0 Pa以下。 若為上述範圍之壓力，則於後述之步驟B中，可將含&组 之被覆膜效率良好地成膜於基體。 本實施形態之上述步驟B係如下步驟：以成為形成含〇鈕 之被覆膜之氮分壓之方式設定含惰性氣體及/或氮氣之第2 處理氣體而控制電漿，藉此將含α钽之被覆膜形成於基 體。 & 於上述步驟B中，將上述第2處理氣體導入至處於上述步 驟A中所導入之上述第丨處理氣體之環境下的真空槽1〇中， 將真空槽10之氮分壓設為適於形成含〇鈕之被覆膜者。 自氣體導入口 2導入至真空槽10之上述第2處理氣體之流 量為惰性氣體之流量與氮氣之流量之和。 上述第2處理氣體中，作為惰性氣體之流量，較好的是 149719.doc 201114936 5.0 seem以上且2〇 sccm以下，更好的是5 〇似爪以上且15 SCCm以下’進而好的是8·〇 seem以上且π sccm以下。 上述第2處理氣體中’作為氮氣之流量，較好的是〇 seem以上且5.0 sccnm下’更好的是〇 〇5 sccm以上且2 5 SCCm以下’進而好的是0·1 seem以上且1.0 sccm以下。 再者，上述seem係以cm3/分（]atm , 〇。〇）表示之單位。 作為導入至真空槽10中之上述第2處自氣體之惰性氣體 與氮氣之流量比（惰性氣體之流量：氮氣之流量），較好的 是2000:1〜1:1，更好的是300:1〜2:1，進而好的是 120:1〜8:1。於此，上述範圍係含其兩端之流量比者。 藉由在上述流量範圍設定構成上述第2處理氣體之斛及 氮氣，而可將真空槽10内設為形成含α鈕之被覆膜之氮分 壓。设定有該第2處理氣體之真空槽1〇之惰性氣體及氮氣 之各自之分壓的較佳範圍為如下所述。 作為設定有上述第2處理氣體之真空槽1〇中之惰性氣體 的分壓，較好的是〇.〇3 pa以上且5〇 Pa以下，更好的是 0.03 Pa以上且1.0 pa以下，進而好的是〇〇3 pa以上且〇5 Pa以下》 作為設定有上述第2處理氣體之真空槽1〇中之氮分壓（氮 氣分壓）’較好的是0.001 Pa以上且〇 〇2 Pa以下，更好的是 0.001 Pa以上且0.01 Pa以下，進而好的是〇〇〇3 Pa以上且 0.007 Pa以下。 於真空槽10内穩定在形成上述含α钽之被覆膜之氮分壓 後，接通直流電源9將負電壓施加至陰極電極4而開始放 149719.doc 201114936 電’於Ta靶材5表面產生電漿’藉此可進行濺鍍。此時， 亦可藉由高頻電源13而將高頻偏壓施加至基體電極6。 作為直流電源9之電力’自使本實施形態之效果優異之 方面考慮，較好的是5.0 kW以上且30 kW以下，更好的是 10 kW以上且25 kW以下’最好的是15 kW以上且20 kW以 下。 於施加向頻電源1 3之情形時，作為其頻率，自使本實施 形態之效果優異之方面考慮’較好的是丨〇 MHz以上且 13.56 MHz以下。 藉由如此般進行濺鍍而可將含〇1钽之被覆膜成膜於基體 7 〇 所成膜之含α钽之被覆膜之厚度，可藉由適當地調整濺 鍍時間而成為所需之厚度，例如可以1 nm以上且2〇〇 μηια 下之厚度成膜。 作為成膜有上述含α鈕之被覆膜之基體7之表面並無特別 限制例如可為含矽之基板之表面，可為含二氧化矽之基 板之表面，亦可為含TaN等之薄膜等作為基礎層而預先形 成於該等基板之面。 <第二態樣> 參照圖1所示之濺鍍裝置丨來說明本實施形態之含(1鈕之 被覆膜之成膜方法的第二態樣。 濺鍍裝置1之構成與第一態樣中所說明之濺鍍裝P之構 成相同。 本實轭形態中之上述步驟A係將含惰性氣體及氮氣之第i 149719.doc 201114936 處理氣體導入至真空槽10之步驟。 自氣體導入口 2而導入至真空槽10之上述第1處理氣體之 流量為惰性氣體之流量與氮氣之流量之和。 作為上述第1處理氣體中之惰性氣體之流量，較好的是 5.0 seem以上且2〇 sccm以下，更好的是5〇 sccm以上且15 seem以下，最好的是8.0 seem以上且12 sccm以下。 作為上述第1處理氣體中之氮氣之流量，較好的是15 seem以上且60 sccm以下，更好的是2〇 sccm以上且4〇 sccm 以下’最好的是25 seem以上且35 seem以下。 再者，上述seem係以cm3/分（1 atm，ot)表示之單位。 作為導入至真空槽10之上述第丨處理氣體之惰性氣體與 氮氣之流量比（惰性氣體之流量：氮氣之流量），較好的是 1:2〜1:5，更好的是1:2〜1:4，最好的是l:2 5〜1:3 $。於此， 上述範圍係包含其兩端之流量比者。 作為於上述步驟八中導入有上述第1處理氣體之真空槽10 内之壓力，可如上所述般Hi 〇xl〇.6〜以上且彻Pa以下 進=設定，但更好的是0·01 Pa以上且10 Pa以下，進而好 的疋0.1 Pa以上且ι·〇 pa以下。 又’作為於上述步驟中導人有上述第以理氣體之真空 槽10之氮分麗’較好的是周知之以濺鐘法形成含TaN之薄 膜時之氮分壓，例如，較好的是G.G3 Pa以上且5_〇 pa以 下’更好的是0.03 Pari V Η1 Λ 上且1.0 Pa以下，進而好的是〇〇3TaJfe wood). The pressure in the sputtering method can be subjected to sputtering by a pressure used in a sputtering method, for example, and sputtering can be carried out, for example, at a temperature of at most 〇xl 〇 -6 Pa or less. H9719.doc 201114936 As the substrate temperature in the above-described splashing method, sputtering can be carried out at a temperature used in a well-known hybrid method, for example, iron can be used. Sputtering is performed below c. The substrate is not particularly limited as long as it contains a material that can withstand the film formation by the method of (4), and examples thereof include a substrate containing 7, a substrate for oxidizing, a substrate containing quartz, a substrate containing metal, and the like. . As the substrate, a film or the like may be formed on the substrate as a base layer. The inert gas to be used in the sputtering method is not particularly limited, and examples thereof include argon (Ar), krypton (Kr), and helium (He). Among them, 'the better is the above-mentioned nitrogen which is usually easily available and low in price (the NO is only required to be a nitrogen gas which is usually used in the sputtering method, and the higher the purity, the better. The α钽 according to the embodiment) In the film forming method of the coating film, the coating film containing α钽 can be formed on the substrate in a previously difficult manner. In the film forming method of the film containing the group by sputtering first, In the inert gas atmosphere such as a heart, a Ta target is used for sputtering to form a film containing a film, but a film containing β钽 and α buttons is formed. On the other hand, in the present embodiment, 'the target of D3 is used. When the material is sputtered, the following steps and subsequent steps are sequentially performed, whereby the coating film containing α钽 can be formed on the substrate. Hereinafter, the first embodiment and the second aspect will be described. The film formation method of the coating film containing the alpha group. <First aspect> 149719.doc 201114936 The coating device containing the alpha button of the present embodiment will be described with reference to the sputtering apparatus 1 shown in Fig. 1 . The first aspect of the membrane method. The cathode electrode 4' is fixed on the top plate of the vacuum chamber 10. A Ta target 5 is disposed on the surface of the cathode electrode 4. A DC power source 9 to which a negative voltage is applied is connected to the cathode electrode 4. A magnetic circuit 8 including a permanent magnet is disposed on the back surface of the cathode electrode 4 outside the vacuum chamber 10. And being configured in such a manner that the magnetic flux formed by the magnetic circuit 8 penetrates the cathode electrode 4 and the Ta target 5, and forms a leakage magnetic field on the surface of the Ta target 5. When the _ is performed, the electron is captured by the (four) magnetic field, thereby The base electrode 6 is provided on the bottom surface of the vacuum chamber 10, and the substrate 7 and the Ta target 5 are disposed substantially in parallel with each other on the surface of the base electrode 6. The base electrode 6 is connected to the application high. The high-frequency power source 13 of the frequency-biased power is provided with a heater U electrically insulated by the insulating portion na on the base electrode 6, and the temperature of the substrate 7 can be adjusted to _5〇t~6〇〇t. The gas inlet port 2 and the vacuum exhaust port 3 are provided in the vacuum chamber 1G. The gas tanks constituting the processing gas Ar and the atmosphere are connected to the gas introduction port 2 so as to be individually (four). A vacuum pump is connected to the port 3 (a gas tank and a vacuum pump are not shown) The above-mentioned step 8 of the embodiment is a step of introducing a gas containing an inert gas and a hydrogen gas into the vacuum chamber 10. The J gas introduction port 2 is introduced into the vacuum tank 10, and the 处理 process gas is the flow rate of the inert gas. The sum of the flow rate of the nitrogen gas and the flow rate of the nitrogen gas. The inert gas body in the first process gas is not particularly large. 149719.doc 201114936 The system can be used as the first process gas, for example, 1. 〇seem or more and 30 seem or less. The flow rate of the nitrogen gas is not particularly limited, and may be, for example, 0.01 seem or more and 30 seem or less. Further, the above seek is in cm3/min (1 atm, 0). (:) indicates the unit. By introducing the first processing gas in advance in the step A as described above, the gas flow rate and pressure in the vacuum chamber 10 can be stabilized, and further, α can be formed by sputtering in the step B described later. The plasma is stably generated when the button is covered. The pressure in the vacuum chamber 1〇 into which the first processing gas is introduced in the above step 较好 is preferably a pressure range suitable for the sputtering method of 1 〇 xl 〇 -6 Pa or more and 400 Pa or less, more preferably It is more preferably 0.01 Pa or more and 1.0 Pa or less. In the case of the pressure in the above range, in the step B described later, the coating film containing the & group can be efficiently formed on the substrate. In the step B of the present embodiment, the second processing gas containing an inert gas and/or nitrogen gas is set so as to form a nitrogen partial pressure of the coating film containing the button, and the plasma is controlled, whereby α is contained. The coating of the crucible is formed on the substrate. & In the above step B, the second processing gas is introduced into the vacuum chamber 1〇 in the environment of the second processing gas introduced in the step A, and the nitrogen partial pressure of the vacuum chamber 10 is adjusted. For forming a film containing a button. The flow rate of the second processing gas introduced into the vacuum chamber 10 from the gas introduction port 2 is the sum of the flow rate of the inert gas and the flow rate of the nitrogen gas. In the second processing gas, the flow rate of the inert gas is preferably 149719.doc 201114936 5.0 seem or more and 2 〇 sccm or less, more preferably 5 〇 like a claw or more and 15 SCCm or less 'and further preferably 8· 〇seem above and below π sccm. In the second processing gas, the flow rate of nitrogen gas is preferably 〇seem or more and 5.0 sccnm is more preferably 〇〇5 sccm or more and 2 5 SCCm or less. Further preferably 0·1 seem or more and 1.0. Below sccm. Furthermore, the above seek is expressed in units of cm3/min (] atm, 〇.〇). The ratio of the flow rate of the inert gas to the nitrogen gas introduced into the vacuum tank 10 (the flow rate of the inert gas: the flow rate of the nitrogen gas) is preferably 2000:1 to 1:1, more preferably 300. :1~2:1, and then good is 120:1~8:1. Here, the above range includes the flow ratio between the two ends. By setting the helium and nitrogen constituting the second processing gas in the above flow rate range, the inside of the vacuum chamber 10 can be used as the nitrogen partial pressure of the coating film containing the ? button. The preferred range of the partial pressure of the inert gas and the nitrogen gas in the vacuum chamber 1 of the second processing gas is as follows. The partial pressure of the inert gas in the vacuum chamber 1〇 in which the second processing gas is set is preferably pa3 kPa or more and 5 〇 Pa or less, more preferably 0.03 Pa or more and 1.0 Pa or less. It is preferable that 〇〇3 pa or more and 〇5 Pa or less ” The partial pressure of nitrogen (nitrogen partial pressure) in the vacuum chamber 1 设定 in which the second processing gas is set is preferably 0.001 Pa or more and 〇〇 2 Pa. Hereinafter, it is more preferably 0.001 Pa or more and 0.01 Pa or less, and further preferably 〇〇〇3 Pa or more and 0.007 Pa or less. After the nitrogen partial pressure of the above-mentioned α-containing coating film is stabilized in the vacuum chamber 10, the DC power source 9 is turned on to apply a negative voltage to the cathode electrode 4 to start discharging 149719.doc 201114936 Electric 'on the surface of the Ta target 5 A plasma is produced 'by which sputtering can be performed. At this time, a high frequency bias voltage can also be applied to the base electrode 6 by the high frequency power source 13. The electric power of the DC power source 9 is preferably 5.0 kW or more and 30 kW or less, more preferably 10 kW or more and 25 kW or less, and more preferably 15 kW or more, from the viewpoint of the effect of the present embodiment. And less than 20 kW. In the case where the power source 13 is applied, the frequency is preferably 丨〇 MHz or more and 13.56 MHz or less from the viewpoint of the effect of the present embodiment being excellent. By performing sputtering as described above, the thickness of the coating film containing α钽 can be formed by coating the coating film containing 〇1钽 on the substrate 7 ,, and the sputtering time can be appropriately adjusted by the sputtering time. The thickness required may be, for example, a film formed at a thickness of 1 nm or more and 2 〇〇μηια. The surface of the substrate 7 on which the coating film containing the α button is formed is not particularly limited. For example, the surface of the substrate containing ruthenium may be the surface of the substrate containing cerium oxide, or may be a film containing TaN or the like. The surface is formed in advance on the surface of the substrates as a base layer. <Second Aspect> A second aspect of the film formation method of the coating film of the first embodiment is described with reference to the sputtering apparatus 图 shown in Fig. 1. The configuration and the sputtering apparatus 1 The composition of the sputtering apparatus P described in the aspect is the same. The above step A in the embodiment of the yoke is a step of introducing the processing gas of the i 149719.doc 201114936 containing inert gas and nitrogen into the vacuum chamber 10. The flow rate of the first processing gas introduced into the vacuum chamber 10 at the inlet 2 is the sum of the flow rate of the inert gas and the flow rate of the nitrogen gas. The flow rate of the inert gas in the first processing gas is preferably 5.0 seem or more. 2 〇 sccm or less, more preferably 5 〇 sccm or more and 15 seem or less, and most preferably 8.0 seem or more and 12 sccm or less. The flow rate of the nitrogen gas in the first processing gas is preferably 15 seem or more. 60 sccm or less, more preferably 2 〇 sccm or more and 4 〇 sccm or less 'best is 25 seem or more and 35 seem or less. Further, the above seek is expressed in units of cm 3 /min (1 atm, ot). As the inertia of the above-mentioned third processing gas introduced into the vacuum chamber 10. The flow ratio of gas to nitrogen (flow of inert gas: flow rate of nitrogen) is preferably 1:2 to 1:5, more preferably 1:2 to 1:4, and most preferably 1:2 5~ 1:3 $. Here, the above range includes the flow ratio between the two ends. As the pressure in the vacuum chamber 10 into which the first processing gas is introduced in the above step 8, Hi 〇 xl 可 can be as described above. .6~ or more and the following is the setting of the Pa, but it is more preferably 0·01 Pa or more and 10 Pa or less, and further preferably 疋0.1 Pa or more and ι·〇pa or less. Also as a guide in the above steps The nitrogen partial pressure of the vacuum tank 10 having the above-mentioned first reason gas is preferably a nitrogen partial pressure when a film containing TaN is formed by a sputtering clock method, for example, preferably G.G3 Pa or more and 5_ 〇pa below 'better is 0.03 Pari V Η1 Λ on and below 1.0 Pa, and then good 〇〇 3
Pa以上且〇.5 pa以下。 S於上述範圍之氮分壓中推;^千她1 #。+ 乳刀i 7進仃濺鍍時，可將含TaN之基 1497I9.doc -11 - 201114936 礎層形成於基體7。 作為該濺鍍之方法，接通直流電源9將負電壓施加至陰 極電極4而開始放電，於Ta靶材5表面產生電漿，藉此可進 行滅:鍍。此時’亦可藉由高頻電源13而將高頻偏壓施加至 基體電極6。 本實施形態中之上述步驟B係如下步驟：以成為形成含α 叙之被覆膜之氮分壓之方式設定含惰性氣體及/或氮氣之 第2處理氣體而控制電漿，藉此將含α鉅之被覆膜形成於基 體7。 於上述步驟Β中’僅將惰性氣體作為第2處理氣體導入至 處於上述步驟Α中所導入之第1處理氣體環境下之真空槽 1〇’並一面連續降低真空槽10中之氮分壓一面如上述般進 行濺錢，藉此可將含α钽之被覆膜成膜於基體7。 就上述步驟Β中連續地降低真空槽10之氮分壓之方法而 言’可於設定第2處理氣體時，設定為停止氮氣之流入而 僅流入惰性氣體。在真空槽丨〇中排出與所流入之氣體相同 之量之氣體而將真空槽10之壓力保持於固定，由此可藉由 切換為僅流入惰性氣體而連續地降低真空槽1〇中所殘存之 氮氣之濃度。因此，於持續地僅流入惰性氣體之情形時， 真空槽10之氮分壓最後實質上成為〇。 於如此般使真空槽10之氮分壓連續降低而至實質上為〇 之過程中’通過於基體7形成含α鈕之被覆膜之氮分壓。 即，於真空槽10之氮分壓為可形成TaN膜之氮分壓時， 一面開始濺鍍而將TaN之基礎層形成於基體7, 一面如上述 149719.doc -12· 201114936 般連續地降低該氮分壓並且持續濺鑛，藉此在達到於基體 7形成含α钽之被覆膜之氮分壓時，開始於基體7形成含α钽 之被覆膜。此後，進一步降低氮分壓並且持續濺鍍，藉此 於之前形成之含α鈕之被覆膜上形成含α鈕之被覆膜。該氮 分壓最後實質上成為0，但藉由在該情形時亦持續濺鍍而 持續形成含α钽之被覆膜。 如上所述’就若一旦於基體7形成有α鈕則此後積層之组 均會成為α組之機制，可考慮作如下假設··之前形成之含α 钽之被覆膜作為晶體成長之核而發揮功能，從而使得此後 積層之鈕成為α钽而成膜。 所成膜之含α鈕之被覆膜之厚度可藉由適當地調整濺鍍 時間而成為所需之厚度，例如可以i nm以上且2 〇 〇 以下 之厚度進行成膜。 作為上述步驟B中設定有上述第2處理氣體之真空槽1〇内 之壓力，較好的是適於濺鍍法之壓力範圍1〇χΐ〇·6 h以上 且400 Pa以下，更好的是〇〇〇1 pa以上且ι〇〜以下進而 好的是0.01 Pa以上且1.0 Pa以下。 自氣體導人口 2流人至真空槽1G之上述第2處理氣體之流 量為惰性氣體之流量與氮氣之流量之和❶ 上述第2處理氣體中’作為惰性氣體之流量，較好的是 5.0 seem以上且20 sccm以下，更好的是5〇 s·以上且η seem以下’進而好的是8 〇似爪以上且mccm以下。 上述第2處理氣體中 seem以上且 〇.5 sccmw ’作為氮氣之流量，較好的是〇 下’更好的是〇 seem以上且0.25 149719.doc -J3- 201114936 seem以下，最好的是〇 seem。 再者，上述sc cm係以cm3/分（1 atm，〇°C )表示之單位。 於上述濺鍍中，作為直流電源9之電力，自使本實施形 態之效果優異之方面考慮，較好的是5.0 kW以上且30 kw 以下’更好的是10 kW以上且25 kW以下，最好的是15 kw 以上且20 kW以下。 於上述賤鑛中’在施加南頻電源13之情形時，作為其頻 率’自使本實施形態之效果優異之方面考慮，較好的是 1_〇 MHz以上且13.56 MHz以下。 藉由如上述般進行濺鍍而可將含TaN之基礎層形成於基 體7上，進而可將含α鈕之被覆膜成膜於該基礎層上。 於不將上述含TaN之基礎層形成於基體7上之情形時，至 真空槽10内之氮分壓成為形成含(^^鈕之被覆膜之氮分壓為 止，以遮板等覆蓋基體7而防止含TaN之基礎層形成於基體 7上即可。 作為成膜有上述含α鈕之被覆膜之基體7之面並無特別限 制，例如，可為含矽之基板之表面，可為含二氧化矽之基 板之表面，亦可為含TaN等之薄膜等作為基礎層而預先形 成於該等基板之面。 藉由如上述般設定第2處理氣體而成為形成含〇1鈕之被覆 膜之氮分壓，可根據由本發明者等人之研究所獲得之圖2 之結果而明確。即，藉由如圖2所示將氮氣與惰性氣體一 同流入而可發現如下傾向：氮氣為圖2之流量F時所成膜之 Ta薄膜之比電阻變得極小。 149719.doc • 14· 201114936 圖2之橫軸表示導入至真空槽10之氮氣之流量(單位為 seem) ° ^ 2之縱軸表示以橫軸所示之氮氣流量使真空槽10充分 穩定之後，藉由進行濺鑛而形成之Ta薄膜之比電阻（翠位 為μΩ.^ρ再者，所形成之^薄膜之厚度為約a，复 基礎層為TaN。 根據X射線繞射之結果’可確認出以圖2之氮氣流量為5 seem以上所形成之^薄膜為含TaN之薄膜。 氮氣流量為5 sccm以下時，所形成之仏薄膜之比電阻低 於TaN薄膜’於氮氣流量F為〇.1 seem以上且1.〇 sccm以下 之範圍内比電阻降為最低。根據X射線繞射之結果，確認 出於該氮氣流量之範圍所形成之Ta薄膜為含(31鈕之薄膜。 另方面，氮氣流量為〇 seem時，Ta薄膜之比電阻與含 TaN之薄膜相同。根據χ射線繞射之結果而確認出該^薄 膜為含β鈕之薄膜。 [實施例] 其次，透過實施例更詳細地說明本實施形態，但本發明 並非受該等例限定。 貫施例1及比較例1〜2中，使用圖1所示之賤鍵裝置1進行 濺鍍。 [實施例1 ] 以表1所示之步驟A、C、B、D之順序調整處理氣體而控 制電衆’並藉由濺鍍法而於矽晶圓21上形成含TaN之基礎 層22 ’進而將含α钽之被覆膜23成膜於該基礎層22上（參照 1497I9.doc •15· 201114936 圖 3A)。 [表1] 步驟 (秒） 直流電力 (kW) 高頻電力 (W) Ar流量 (seem) N2流量 (seem) A ΓΤ5Γ〇 0.0 0 10.0 30.0 C 3.0 18.0 600 10.0 30.0 B 10.0 18.0 600 10.0 1 0.0 D 15.0 0.0 0 0.0 0.0 於步驟A中，將Ar流量1〇.〇 sccin及氮氣流量30.0 sccm2 第1處理氣體自氣體導入口 2導入至真空槽10中，並為使真 空槽10之氣體流量穩定而保持15秒。 其次’於步驟C中’將電漿產生用直流電源9之電力設定 為18.0 kW，將基體偏壓高頻電源13(1.〇〜13.56 MHz)之電 力設定為600 W，並使用與步驟A相同之處理氣體進行3 〇 秒之濺鍍’於矽晶圓21上形成含TaN之基礎層22(厚度：約 20 nm)。 繼而，於步驟B中，一面將電漿產生用直流電源9之電力 及基體偏壓高頻電源1 3之電力保持於與步驟c相同之條 件，一面自第1處理氣體切換至第2處理氣體。該第2處理 氣體係將Ar流量設為1〇.〇 sccm及將氮氣流量設為〇 〇 seem ^切換至第2處理氣體進行15 〇秒之濺鍍，將含α鈕之被 覆膜23(厚度.約l〇〇nm)成膜於上述含TaN之基礎層上。 於最後之步驟D中，斷開電漿產生用直流電源9及基體偏 壓高頻電源13，並停止處理氣體而進行15〇秒之處理氣體 之排氣。 當以X射線繞射（波長λ=1.5418 A)分析所成膜之含〇1鈕之 149719.doc -16- 201114936 被覆膜23時，如圖3B所示，於2Θ=38.3度附近存在α鈕之 (110)之陡峭峰值。另一方面，於20=33.5度附近不存在β钽 之（002)之峰值。根據結果可確認出所成膜之被覆膜係不含 β钽而含α组之被覆膜。 [比較例1] 以表2所示之步驟S101〜S105之順序調整處理氣體而控制 電槊’並藉由濺鍍法而於矽晶圓24上形成含TaN之基礎層 25，進而將含β鈕及α钽之鈕之被覆膜26成膜於該基礎層乃 上。（參照圖4Α)。 [表2] 步驟 #間 (秒） 直流電力 (kW) 高頻電力 (W) Ar流量 (seem) N2流量 (seem) 1 15.0 0.0 "〇 10.0 30.0 2 3.0 18.0 600 10.0 30.0 3 20.0 0.0 0 10.0 0.0 4 10.0 18.0 600 10.0 0.0 5 15.0 0.0 ^0 0.0 0.0 於步驟S101中’將Ar流量1〇_〇 sccm及氮氣流量3〇 〇 seem之處理氣體自氣體導入口 2導入至真空槽1〇，並為使 真空槽10之氣體流量穩定而保持15秒。 其次’於步驟S102中’將電漿產生用直流電源9之電力 »又定為18·0 kW，將基體偏壓高頻電源13(i 〇〜13 56 MHz) 之電力设定為600 W ’並使用與步驟s丨〇丨相同之處理氣體 而進订3.0秒之滅鍛’於矽晶圓以上形成含TaN之薄膜層 25(厚度：約2〇11111)。 此後’於步驟S103中，切換至Ar流量H).0 seem及氮氣 149719.doc -17- 201114936 流量0.0 seem之處理氣體並保持20秒，自真空槽10中去除 IL氣而使真空槽10為Ar環境。 繼而，於步驟S 1 04中，將電漿產生用直流電源9之電力 友基體偏壓高頻電源13之電力設定為與步驟S102相同之條 件’處理氣體係保持於與步驟S103相同之條件而進行15 〇 秒之濺鍍，並將含β钽及α钽之被覆膜26(厚度：約100 nm) 成膜於上述含TaN之基礎層25上（厚度：約1〇〇 nm)。 於最後之步驟S1 05中，斷開電漿產生用之直流電源9及 基體偏壓高頻電源13 ’並停止處理氣體而進行15 〇秒之處 理氣體之排氣。 以X射線繞射（波長λ=1.5418 A)分析所成膜之含p钽及α 钽之被覆膜26時，如圖4Β所示’於2Θ=38.3度附近存在 之（Π0)之寬峰值◦另一方面，於20=33.5度附近存在β鈕之 (002)之比較陡峭的峰值。根據該結果可確認出所成膜之被 覆膜係含β鈕及α鈕之被覆膜。 [比較例2] 以表3所示之步驟S201〜S204之順序調整處理氣體而控制 電聚’並藉由濺鍍法而將含β鈕之钽之被覆膜28成膜於石夕 晶圓27上（參照圖5Α)。 [表3] 步驟 時間 (秒） 直流電力 (kW) 高頻電力 (W) Ar流量 (seem) A流量 iscr.m\ a 15.0 0.0 0 — 10.0 b 〇 ~ b 3.0 18.0 600 ' 10.0 0 0 c 10.0 18.0 600 ' 10.0 0 0 d Γΐ5.0 0.0_ 0 ' ------1 Γαο ^.0 149719.doc -18- 201114936 於步驟S201中Above Pa and below 55. S is pushed in the nitrogen partial pressure of the above range; ^ thousand her 1 #. + When the latex knife i 7 is sputtered, the base layer of the TaN-containing base 1497I9.doc -11 - 201114936 can be formed on the base 7. As a method of the sputtering, the DC power source 9 is turned on to apply a negative voltage to the cathode electrode 4 to start discharge, and plasma is generated on the surface of the Ta target 5, whereby the plating can be performed. At this time, a high frequency bias can also be applied to the base electrode 6 by the high frequency power source 13. In the above-described step B of the present embodiment, the second processing gas containing an inert gas and/or nitrogen gas is set so as to form a nitrogen partial pressure of the coating film containing α, and the plasma is controlled, thereby including The α-large coating film is formed on the substrate 7. In the above step ', the inert gas is introduced as the second processing gas into the vacuum chamber 1〇' in the first processing gas atmosphere introduced in the step 并, and the nitrogen partial pressure in the vacuum chamber 10 is continuously reduced. The money is splashed as described above, whereby the coating film containing α钽 can be formed on the substrate 7. In the above-described step, the method of continuously reducing the partial pressure of nitrogen in the vacuum chamber 10 can be set such that when the second processing gas is set, the inflow of nitrogen gas is stopped and only the inert gas is introduced. The gas in the same amount as that of the inflowing gas is discharged into the vacuum chamber, and the pressure of the vacuum chamber 10 is kept constant, whereby the residual in the vacuum chamber 1 can be continuously reduced by switching to only the inert gas. The concentration of nitrogen. Therefore, in the case where only the inert gas is continuously supplied, the nitrogen partial pressure of the vacuum chamber 10 finally becomes substantially 〇. Thus, the nitrogen partial pressure of the vacuum chamber 10 is continuously lowered to substantially 〇, and the nitrogen partial pressure of the coating film containing the alpha button is formed by the substrate 7. In other words, when the partial pressure of nitrogen in the vacuum chamber 10 is a nitrogen partial pressure at which the TaN film can be formed, the base layer of TaN is formed on the substrate 7 by sputtering, and the continuous reduction is performed as described in 149719.doc -12 201114936. The nitrogen partial pressure continues to be splashed, whereby the formation of the α-containing coating film on the substrate 7 is started when the nitrogen partial pressure of the α-containing coating film is formed in the substrate 7. Thereafter, the partial pressure of nitrogen was further lowered and sputtering was continued, whereby a coating film containing an alpha button was formed on the previously formed coating film containing the alpha button. The partial pressure of nitrogen is finally substantially zero, but by continuous sputtering in this case, the coating film containing α钽 is continuously formed. As described above, if the α button is formed on the substrate 7, the group of layers will become the mechanism of the α group. Consider the following assumptions: The previously formed α 钽-coated film is used as the core of crystal growth. The function is made such that the button of the subsequent layer becomes a film of α钽. The thickness of the film containing the ? button formed by the film can be a desired thickness by appropriately adjusting the sputtering time, and for example, it can be formed into a film having a thickness of i nm or more and 2 Å or less. The pressure in the vacuum chamber 1〇 in which the second processing gas is set in the above step B is preferably a pressure range suitable for the sputtering method of 1 〇χΐ〇·6 h or more and 400 Pa or less, more preferably It is more preferably 0.01 Pa or more and 1.0 Pa or less. The flow rate of the second processing gas from the gas-conducting population 2 to the vacuum chamber 1G is the sum of the flow rate of the inert gas and the flow rate of the nitrogen gas. 流量 The flow rate of the inert gas in the second processing gas is preferably 5.0. The above is preferably 20 sccm or less, more preferably 5 〇s· or more and η seem or less. Further preferably, 8 〇 is more than a claw and mccm or less. The second processing gas has a concentration of seem or more and 〇.5 sccmw ' as a flow rate of nitrogen, preferably 〇下' is more preferably 〇seem or more and 0.25 149719.doc -J3- 201114936 seem below, and most preferably 〇 Seem. Further, the above sc cm is expressed in units of cm3/min (1 atm, 〇 °C). In the above-described sputtering, the electric power of the DC power source 9 is preferably 5.0 kW or more and 30 kw or less from the viewpoint of the effect of the present embodiment. More preferably, it is 10 kW or more and 25 kW or less. Good is 15 kw or more and 20 kW or less. In the case of the above-mentioned antimony ore, when the south-frequency power source 13 is applied, the frequency is excellent in the effect of the present embodiment, and is preferably 1_〇 MHz or more and 13.56 MHz or less. The base layer containing TaN can be formed on the substrate 7 by sputtering as described above, and the coating film containing the ? button can be formed on the base layer. When the base layer containing the TaN is not formed on the substrate 7, the partial pressure of nitrogen in the vacuum chamber 10 is such that the nitrogen partial pressure of the coating film containing the button is formed, and the substrate is covered with a mask or the like. 7. The base layer containing TaN may be prevented from being formed on the substrate 7. The surface of the substrate 7 on which the coating film containing the alpha button is formed is not particularly limited, and may be, for example, a surface of a substrate containing ruthenium. The surface of the substrate containing the cerium oxide may be formed on the surface of the substrate as a base layer, such as a film containing TaN or the like. The second processing gas is set as described above to form a yttrium-containing button. The nitrogen partial pressure of the coating film can be clarified by the results of Fig. 2 obtained by the inventors of the present invention, etc. That is, by introducing nitrogen gas together with an inert gas as shown in Fig. 2, the following tendency can be found: nitrogen gas The specific resistance of the Ta film formed at the flow rate F of Fig. 2 becomes extremely small. 149719.doc • 14· 201114936 The horizontal axis of Fig. 2 indicates the flow rate of nitrogen gas introduced into the vacuum chamber 10 (unit is see) ° ^ 2 The vertical axis indicates that the vacuum chamber 10 is sufficiently stabilized by the flow rate of nitrogen indicated by the horizontal axis. Then, the specific resistance of the Ta film formed by sputtering is (the position is μΩ.^ρ, the thickness of the formed film is about a, and the complex base layer is TaN. According to the result of X-ray diffraction 'It can be confirmed that the film formed by the nitrogen flow rate of Fig. 2 is 5 seem or more is a film containing TaN. When the flow rate of nitrogen is 5 sccm or less, the specific resistance of the formed tantalum film is lower than that of the TaN film 'at nitrogen flow rate F The specific resistance was minimized in the range of seem.1 seem or more and 1. 〇sccm. According to the result of the X-ray diffraction, it was confirmed that the Ta film formed by the range of the nitrogen gas flow was a film containing (31 button). On the other hand, when the flow rate of nitrogen gas is 〇seem, the specific resistance of the Ta film is the same as that of the film containing TaN. It is confirmed that the film is a film containing a β button as a result of diffraction of the χ ray. [Embodiment] The present embodiment will be described in more detail, but the present invention is not limited to these examples. In the first embodiment and the comparative examples 1 and 2, sputtering is performed using the key device 1 shown in Fig. 1. [Example 1] The process gas is adjusted in the order of steps A, C, B, and D shown in Table 1. The base layer 22' containing TaN is formed on the tantalum wafer 21 by sputtering, and the coating film 23 containing α钽 is formed on the base layer 22 (refer to 1497I9.doc • 15 · 201114936 Fig. 3A). [Table 1] Step (seconds) DC power (kW) High frequency power (W) Ar flow (seem) N2 flow (seem) A ΓΤ5Γ〇0.0 0 10.0 30.0 C 3.0 18.0 600 10.0 30.0 B 10.0 18.0 600 10.0 1 0.0 D 15.0 0.0 0 0.0 0.0 In the step A, the Ar flow rate is 1 〇. 〇 sccin and the nitrogen flow rate is 30.0 sccm2. The first process gas is introduced into the vacuum chamber 10 from the gas introduction port 2, and the vacuum chamber is used. The gas flow rate of 10 is stable for 15 seconds. Next, in step C, the power of the plasma generating DC power supply 9 is set to 18.0 kW, and the power of the base bias high frequency power supply 13 (1. 〇 to 13.56 MHz) is set to 600 W, and used in step A. The same process gas was subjected to 3 seconds of sputtering to form a TaN-containing base layer 22 (thickness: about 20 nm) on the tantalum wafer 21. Then, in step B, the electric power of the plasma generating DC power source 9 and the power of the base bias high-frequency power source 13 are maintained under the same conditions as in the step c, and the first processing gas is switched to the second processing gas. . In the second process gas system, the flow rate of Ar is set to 1 〇.〇sccm, and the flow rate of nitrogen gas is set to 〇〇seem ^, the second process gas is switched to perform sputtering for 15 seconds, and the coating film 23 containing the α button is used. A thickness of about 10 nm is formed on the above TaN-containing base layer. In the final step D, the DC power source 9 for plasma generation and the high-frequency power source 13 for the plasma are turned off, and the processing gas is stopped to exhaust the processing gas for 15 seconds. When the 149719.doc -16-201114936 coating film 23 containing the 〇1 button was formed by X-ray diffraction (wavelength λ = 1.5418 A), as shown in Fig. 3B, α was present at 2 Θ = 38.3 degrees. The steep peak of the button (110). On the other hand, there is no peak of (002) of β钽 around 20 = 33.5 degrees. According to the results, it was confirmed that the film to be coated was a film containing the α group without β钽. [Comparative Example 1] The process gas was adjusted in the order of steps S101 to S105 shown in Table 2 to control the electrode 槊', and a base layer 25 containing TaN was formed on the ruthenium wafer 24 by sputtering, and further, β was contained. The coating film 26 of the button and the button of the 钽 button is formed on the base layer. (Refer to Figure 4Α). [Table 2] Step #Between (seconds) DC power (kW) High-frequency power (W) Ar flow (seem) N2 flow (seem) 1 15.0 0.0 "〇10.0 30.0 2 3.0 18.0 600 10.0 30.0 3 20.0 0.0 0 10.0 0.0 4 10.0 18.0 600 10.0 0.0 5 15.0 0.0 ^0 0.0 0.0 In step S101, a process gas of Ar flow rate 1〇_〇sccm and nitrogen flow rate 3〇〇seem is introduced from the gas introduction port 2 into the vacuum chamber 1〇, and In order to stabilize the gas flow rate of the vacuum chamber 10, it was maintained for 15 seconds. Next, in step S102, 'the electric power of the direct current power source 9 for plasma generation» is set to 18·0 kW, and the power of the base bias high-frequency power source 13 (i 〇 to 13 56 MHz) is set to 600 W ' And using the same process gas as the step s, the 3.0-second forging was performed to form a TaN-containing film layer 25 (thickness: about 2〇11111). Thereafter, in step S103, switching to Ar flow rate H).0 seem and nitrogen 149719.doc -17- 201114936 flow rate 0.0 seem process gas for 20 seconds, removing IL gas from vacuum tank 10 to make vacuum tank 10 Ar environment. Then, in step S104, the power of the power friend base bias high frequency power source 13 of the plasma generating DC power source 9 is set to the same condition as the step S102. The process gas system is maintained under the same conditions as the step S103. Sputtering was performed for 15 sec., and a coating film 26 (thickness: about 100 nm) containing β 钽 and α 成 was formed on the TaN-containing base layer 25 (thickness: about 1 〇〇 nm). In the last step S1 05, the DC power source 9 for plasma generation and the base bias high frequency power source 13' are turned off and the process gas is stopped to exhaust the gas for 15 seconds. When the film 26 containing p钽 and α 成 formed by the X-ray diffraction (wavelength λ = 1.5418 A) is analyzed, as shown in FIG. 4A, the width peak of Π(Π0) existing near 2Θ=38.3 degrees. On the other hand, there is a relatively steep peak of the (002) β button near 20 = 33.5 degrees. From the results, it was confirmed that the film to be formed was a coating film containing a β button and an α button. [Comparative Example 2] The process gas was adjusted in the order of steps S201 to S204 shown in Table 3 to control the electropolymerization', and the coating film 28 containing the ? button was formed into a film by a sputtering method. 27 (refer to Figure 5Α). [Table 3] Step time (seconds) DC power (kW) High-frequency power (W) Ar flow (seem) A flow iscr.m\ a 15.0 0.0 0 — 10.0 b 〇~ b 3.0 18.0 600 ' 10.0 0 0 c 10.0 18.0 600 ' 10.0 0 0 d Γΐ 5.0 0.0_ 0 ' ------1 Γαο ^.0 149719.doc -18- 201114936 in step S201
Sccm 真空 將八1·流量10.0 seem及氮氣流量〇.〇 之處理氣體自氣體導入口 2導入至真空槽1〇,並為使 槽1 〇之氣體流量穩定而保持15秒。 其次，於步驟S202中，將電漿產生用直流電源9之電力 設定為18.0 kW，將基體偏壓高頻電源13(1〇〜13 56 Μ# 之電力設定為600 W，並使用與步驟82〇1相同之處理氣體 而進行3.0秒之濺鍍，於矽晶圓27上形成含p钽之被覆膜（厚 度：約 20 nm)。 此後，於步驟S203中，進而以與步驟82〇2相同之條件進 行1〇.〇秒之濺鍍，進而成膜有含p鈕之被覆膜28(厚度：約 100 nm)。 於最後之步驟S204中，斷開電渡產生用直流電源9及基 體偏壓高頻電源13，並停止處理氣體而進行15 〇秒之處理 氣體之排氣。 以X射線繞射（波長λ=ΐ.5418 A)分析所成膜之含卩钽之被 覆膜28時，如圖5B所示，於20=38 3度附近不存在以鉅之 (no)之峰值。另一方自’於削35度附近存在ρ鈕之 (002)之陡峭峰值。根據該結果可確認出所成膜之被覆膜係 含β钽之被覆膜。 【圖式簡單說明】 圖1係可用於本發明所涉及之態樣之含&鈕之被覆膜的成 膜方法之濺鍍裝置之一例； 圖2係表示氮氣流量與所形成之Ta薄膜之比電阻之關係 之圖； 149719.doc 201114936 圖3 A係藉由本發明所涉及之態樣之含α钽之被覆膜的成 膜方法而成膜於基體之含α钽之被覆膜的剖面圖； 圖3Β係圖3Α所示之含α钽之被覆膜之X射線繞射光譜； 圖4Α係成膜於基體之含β钽及α鈕之被覆膜之剖面圖； 圖4Β係圖4Α所示之含β鈕及α钽之被覆膜之X射線繞射光 譜； 圖5Α係成膜於基體之含β钽之被覆膜之剖面圖；及 圖5Β係圖5Α所示之含β钽之被覆膜之X射線繞射光譜。 【主要元件符號說明】 1 濺鍍裝置 2 氣體導入口 3 真空排氣口 4 陰極電極 5 Ta乾材 6 基體電極 7 基體 8 磁路 9 直流電源 10 真空槽 11 加熱器The Sccm vacuum was introduced into the vacuum chamber 1 from the gas introduction port 2 by the gas flow rate of 10.0 seem and the nitrogen flow rate of 0.0. 保持, and was kept for 15 seconds in order to stabilize the gas flow rate of the tank 1 。. Next, in step S202, the power of the plasma generating DC power source 9 is set to 18.0 kW, and the power of the base bias high-frequency power source 13 (1〇~13 56 Μ# is set to 600 W, and is used and step 82 is used.相同1 is the same processing gas and is subjected to sputtering for 3.0 seconds to form a coating film containing p钽 on the germanium wafer 27 (thickness: about 20 nm). Thereafter, in step S203, further with step 82〇2 Under the same conditions, sputtering is performed for 1 〇. 〇 second, and a coating film 28 having a p-button (thickness: about 100 nm) is formed into a film. In the last step S204, the DC power source 9 for generating electric power is turned off. The substrate is biased with the high-frequency power source 13 and the processing gas is stopped to perform the exhaust gas of the processing gas for 15 sec. The X-ray diffraction (wavelength λ = 54.5418 A) is used to analyze the film-formed ruthenium-containing coating film. At 28 o'clock, as shown in Fig. 5B, there is no peak of no (no) near 20 = 38 3 degrees. The other side has a sharp peak of (002) of p button near '35 degrees. It can be confirmed that the film to be coated is a coating film containing β钽. [Schematic Description of the Drawing] Fig. 1 can be used in the aspect of the present invention. An example of a sputtering apparatus for forming a film of a button film; FIG. 2 is a view showing a relationship between a flow rate of nitrogen gas and a specific resistance of a formed Ta film; 149719.doc 201114936 FIG. 3A is by the present invention The film formation method of the coating film containing α钽 is formed into a cross-sectional view of the α含-containing coating film formed on the substrate; FIG. 3 is the X of the α-containing coating film shown in FIG. Ray diffraction spectrum; Fig. 4 is a cross-sectional view of a film containing β钽 and α buttons formed on the substrate; Fig. 4 is an X-ray diffraction of the coating containing β button and α钽 shown in Fig. 4Α Fig. 5 is a cross-sectional view of a film containing β钽 formed on a substrate; and Fig. 5 is an X-ray diffraction spectrum of a film containing β钽 shown in Fig. 5Α. 1 Sputtering device 2 Gas inlet 3 Vacuum exhaust port 4 Cathode electrode 5 Ta dry material 6 Base electrode 7 Base 8 Magnetic circuit 9 DC power supply 10 Vacuum chamber 11 Heater
Ha 絕緣部 13 高頻電源 21 基體（矽晶圓） 22 基礎層 149719.doc •20- 201114936 23 24 25 26 27 28 含α组之被覆膜 基體 基礎層 含β钽及α钽之被覆膜 基體 含β钽之被覆膜 149719.doc •21 ·Ha Insulation 13 High-frequency power supply 21 Substrate (矽 wafer) 22 Base layer 149719.doc •20- 201114936 23 24 25 26 27 28 Coating film base layer containing α group containing β钽 and α钽 coating Substrate containing β钽 coating 149719.doc •21 ·