—1469300—1469300
i-V A7 B7 五、發明説明（。 第88100264號專利申請案說明書修正頁 修正日期：9〇年2月 技術領域 本發明係有關於一種以CVD形成鈦膜之方法，該膜係 於半導體裝置中作為諸如傳導金屬層或粘著層者。 習知技術 於半導體裝置之製造中’為因應最近高密度化以及高 積體化之要求而有將電路構造作成多層配線的傾向，因此 ，用於形成下層半導體裝置與上層配線層之接續部（即傳導 孔）’或者用於形成上下同配線層間之接續部（即介層孔）等 於層間形成電接續的埋入技術遂變得非常重要。 如此之傳導孔或介層孔之埋入一般上係使用鋁 (Aluminium)或鎢（Tungsten)或者以此等為主體之合金，但 如此之金屬或合金與下層之矽（SiHc〇ne)基板或鋁配線直 揍接觸，則於此等之邊界部分由於鋁之抽吸效果等而有形 成兩金屬之合金之虞。如此所形成之合金的電阻值大，形 成如此之合金從最近裝置所要求之省電化以及快速運轉的 觀點視之是不佳的。 又’使用鶴或鎢合金作為傳導孔之埋入層時，為形成 埋入層所使用之六氟化鎢（WFe)氣體會侵入矽基板而有使 電特性等劣化之傾向，終究得到不好的結果。 所以，為了防止此等之不適情形，於傳導孔或介層孔 形成埋入層之前，於此等之内壁形成屏障層，由其上形成 埋入層。此時之屏障層者，通常係使用鈦（Titan)膜以及氮 化鈦（TiN)膜之2層構造者。 向來，如此之屏障層係利用物理性蒸鍍（pvD)而形成 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ---;--^----^--^ X-- (請先聞讀背面之注意事項再填寫本頁) 訂_ 經濟部智慧財產局員工消費合作社印製 4 經濟部中央標準局貝工消费合作社印製 693 0 0 A7 _______ B7 五、發明説明（2 ) 膜，但是’如最近’裝置之微細化以及高積體化特別地受 要求，設計規定特別是變得嚴格，隨著線幅或孔之開口徑 變得更小，且使得面縱横比化，在pVD膜電阻增加，對付 要求變得困難。 因此，以可期待形成更良質膜之化學蒸鑛（CVD)法形 成構成屏障層之欽膜以及氣化鈦膜β此時，首先於孔底之 矽上形成為傳導金屬之欽膜。此時，，通常為了降低傳導電 阻，於前步驟中將於基底梦，上所形成之矽的自然氧化臈利 用l·%稀氟酸以洗淨處理而除去。 然而’如此地進行為了除去自然氧化膜之洗淨處理， 則依洗淨條件以及洗淨後其次之步驟為止的時間管理如何 而有所謂傳導形成時之電特性相異的問題。 又’於形成鈦膜時，使用四氯化鈦作為形成膜氣體則 形成膜時基底之梦與欽反應而形成二妙化欽，但在其反應 之過程’與基底之矽的界面形態會惡化，於傳導孔形成之 流程中使用下’變得易造成接合缝隙，於介層孔之情形下 使用亦造成壞影響》 本發明係鑑於此等情事而為者，其目的在於提供—利 用CVD形成献膜的方法，可形成一呈傳導電阻安定，與 與基底之矽之界面形態良好的鈦膜。 發明之揭示 為了解決上述問題，本發明為一利用CVD形成鈦膜 之方法，其係於如矽基板或聚矽配線之矽層之表面上採用 含有四氣化鈦氣體之形成膜氣體而利用CVD形成鈦膜， 本紙張尺度適用中國國家標準（CNS) M祝格（210><297公釐） ----------痒-------訂-------懷.- (請先閱讀背面之注意事項再<^··本頁) 5 693 0 0 A7 B7 經濟部中央標隼局員工消費合作社印製 五、發明説明（3 ) 其係提供-利用CVD形成鈦膜之方法，其特徵在於：包 含一能於前述矽層表面形成矽氧化臈之步驟，與一在使前 述氧化關存之狀態下㈣層表φ上供給含有四氣化数氣 體之成膜氣體而形成鈦琪的步驟。 於典型例子中’々層或在♦基板上之絕緣膜上形成之 傳導孔的底處露出其表面，或在聚石夕配線層上之絕緣膜上 形成之介層孔的底處露出其表面。 在成膜步驟中，以使成膜氣體之電漿激磁為宜。又， - 前述矽自然氧化膜為約1〇埃（人）以上厚度之膜。 當採用含有四氣化鈦氣體之成膜氣體利用CVD形成 鈦膜時，本發明者累積檢討欲使傳導電阻安定化同時鈦膜 與基底之矽的界面狀態良好的結果，發明使基底之矽上所 形成之例如自然氧化膜以一定厚度殘留狀態下形成膜為佳。 向來’作為傳導金屬之鈦膜多以PVD形成，其時，因 為基底之矽上殘存著自然氡化膜則形成鈦膜後之傳導電阻 變高，故除去自然氧化膜。在此，以CVD形成鈦膜時亦 同樣地除去自然氧化膜。 另一方面’以CVD形成鈦膜時，針對鈦膜與基底之 矽的界面形態惡化的原因加以調查的結果，發現在鈦與麥 之界面伴隨此等之相互擴散大而界面之凹凸變大，以及由 於四氣化鈦氣體而基底之矽被等向侵蝕是其原因^當時之 反應式如其次。iV A7 B7 V. Description of the Invention (. No. 88100264 Patent Application Specification Revision Page Revision Date: February 90. TECHNICAL FIELD The present invention relates to a method for forming a titanium film by CVD. The film is used in a semiconductor device as Such as a conductive metal layer or an adhesive layer. Known technology in the manufacture of semiconductor devices has a tendency to structure circuits into multilayer wirings in response to recent demands for higher density and higher integration. Therefore, it is used to form lower layers. The connection between semiconductor devices and the upper wiring layer (ie, conductive holes) 'or the embedding technology used to form the upper and lower same wiring layers (ie, vias) is equivalent to the formation of electrical connections between the layers, which has become very important. Holes or interlayer holes are generally buried using aluminum (Aluminium) or tungsten (Tungsten) or an alloy with these as the main body, but such metal or alloy is directly connected to the underlying silicon substrate (SiHcone) or aluminum wiring. If it is in contact, there may be a risk of forming an alloy of two metals at these boundary parts due to the effect of aluminum suction, etc. The alloy thus formed has a large resistance value and forms Such alloys are not good from the viewpoints of power saving and fast operation required by recent devices. Also, when using cranes or tungsten alloys as buried layers for conductive holes, hexafluoride is used to form buried layers. Tungsten (WFe) gas will penetrate into the silicon substrate and tend to deteriorate the electrical characteristics and the like. In the end, bad results will be obtained. Therefore, in order to prevent these discomforts, before forming a buried layer in a conductive hole or a via hole, These inner walls form a barrier layer from which a buried layer is formed. The barrier layer at this time is usually a two-layer structure using a titanium (Titan) film and a titanium nitride (TiN) film. Such a barrier has always been The layer system is formed by physical vapor deposition (pvD). The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ---;-^ ---- ^-^ X-- (please first Please read the notes on the back of the page and fill in this page) Order _ Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 Printed by the Shelling Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 693 0 0 A7 _______ B7 V. Description of the invention However, the miniaturization and high accumulation of 'as recent' devices In particular, the design requirements become stricter. As the width of the line width or the opening of the hole becomes smaller, and the aspect ratio is increased, the resistance of the pVD film is increased, and it is difficult to cope with the requirements. The chemical vapor deposition (CVD) method, which is expected to form a better film, forms a barrier film and a vaporized titanium film β. At this time, a barrier film is first formed on the silicon at the bottom of the hole as a conductive metal. At this time, usually In order to reduce the conduction resistance, in the previous step, the natural oxide of silicon formed on the substrate is removed by a washing treatment with l% difluoric acid. However, the cleaning treatment for removing the natural oxide film is performed in this way. However, there is a problem that the electric characteristics at the time of so-called conduction formation are different depending on the washing conditions and the time management until the next step after washing. Also, when forming a titanium film, using titanium tetrachloride as a film-forming gas, the substrate dream and Chin react during the film formation to form a dioxin, but during the reaction process, the interface morphology of the substrate and the silicon will deteriorate. "When used in the process of forming conductive holes, it becomes easy to cause joint gaps, and it also has a bad effect when used in the case of vias." The present invention is made in view of these circumstances, and its purpose is to provide-using CVD to form The method of film donation can form a titanium film with stable conduction resistance and good interface with the silicon on the substrate. DISCLOSURE OF THE INVENTION In order to solve the above-mentioned problems, the present invention is a method for forming a titanium film by CVD, which uses a film-forming gas containing a tetra-titanium gas on the surface of a silicon layer such as a silicon substrate or polysilicon wiring and utilizes CVD. Form titanium film, this paper size is applicable to Chinese National Standard (CNS) M Zhuge (210 > < 297mm) ---------- itch --------- order ----- --Huai.- (Please read the precautions on the back first, and then ^ this page) 5 693 0 0 A7 B7 Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (3) It is provided- The method for forming a titanium film by CVD is characterized in that it includes a step capable of forming silicon hafnium oxide on the surface of the aforementioned silicon layer, and supplying a gas containing four gasification numbers on the surface of the hafnium layer in a state where the aforementioned oxide is stored. The step of forming a gas into a titanium oxide. In the typical example, the surface is exposed at the bottom of the conductive layer formed on the insulating film on the substrate or the bottom of the via hole formed on the insulating film on the polysilicon wiring layer. . In the film formation step, it is preferable to plasma-magnetize the film formation gas. In addition, the aforementioned natural silicon oxide film is a film having a thickness of about 10 angstroms or more. When forming a titanium film by CVD using a film-forming gas containing a tetra-titanium gas, the inventors cumulatively reviewed the results of stabilizing the conduction resistance and the good interface state between the titanium film and the silicon of the substrate. The formed natural oxide film is preferably formed in a state where a certain thickness remains. Conventionally, titanium films that are used as conductive metals are mostly formed of PVD. At this time, since the natural siliconized film remains on the base silicon, the conductive resistance after the titanium film is formed becomes high, so the natural oxide film is removed. Here, when the titanium film is formed by CVD, the natural oxide film is similarly removed. On the other hand, when the titanium film was formed by CVD, the cause of the deterioration of the interface morphology of the titanium film and the silicon on the substrate was investigated. And the isotropic erosion of the substrate silicon due to the tetra-titanium gas is the reason ^ the reaction formula at that time was second.
TiCl4+H2+3 Si-> TiSi2+SiCl2+2HCt 然後1此等係由於基底之矽露出而產生，見識到藉由 本紙張尺度適用中國國家標準（匚阳）八4現#(210：><297公釐） I—I—JI裝------^訂------·> (請先閱請背面之注意事項寫本頁) 7 469300 A7 B7 五、發明説明（4 ) 使矽之自然氧化膜殘存可解消此種之不當情形。即，藉由 殘存一定厚度之氧化膜，抑制鈦與矽之相互擴散，又作為 四氣化欽氣體侵敍之屏障作用者。此時之反應式如其次。 TiCl4+4H2+Si02+Si^TiSi2+2H20+4HCl 又，於CVD形成膜之情形下，由於氧化膜藉由流程 氣體以還原反應而從矽與鈦之間的界面消失，故即使殘存 自然氧化膜也不會產生所謂鈦膜傳導電阻高的問題，因為 無除去氧化膜之必要，故傳導電阻之安定性亦高。 '再者，因可省略在前步驟之洗淨步驟，故可藉由步驟 數減少而將製造效率作到極高。 本發明係對抗所謂除去矽上之矽自然氧化膜的固有觀 念而成者，亦且為藉此達到如上述之極大效果者，其工業 上價值很高。 (請先間讀背面之注意事項再魂寫本頁) -裝·TiCl4 + H2 + 3 Si- > TiSi2 + SiCl2 + 2HCt and then these are due to the exposure of the silicon on the substrate. It is understood that the Chinese national standard (Liyang) 8 4 is now applicable by this paper standard # (210: > < 297 mm) I—I—JI equipment -------- ^ Order ------ &>; (Please read the notes on the back first to write this page) 7 469300 A7 B7 V. Description of the invention (4) Residual natural oxide film of silicon can eliminate such improper situations. That is, by remaining an oxide film of a certain thickness, the interdiffusion of titanium and silicon is suppressed, and it acts as a barrier to the invasion of the four gaseous gases. The reaction formula at this time is as follows. TiCl4 + 4H2 + Si02 + Si ^ TiSi2 + 2H20 + 4HCl In addition, in the case of forming a film by CVD, the oxide film disappears from the interface between silicon and titanium by the reduction reaction of the process gas, so even if a natural oxide film remains The problem that the so-called titanium film has high conduction resistance does not occur, because it is not necessary to remove the oxide film, so the stability of the conduction resistance is also high. 'Furthermore, since the washing step in the previous step can be omitted, the number of steps can be reduced and the manufacturing efficiency can be made extremely high. The present invention is made against the inherent idea of removing the natural oxide film of silicon on silicon, and in order to achieve the great effect as described above, it has high industrial value. (Please read the precautions on the back before writing this page)
'•IT 圖示之簡單說明 經濟部中央標準局貝工消费合作社印製 第1圖係表示為實施本發明之利用CVD形成鈦膜的方 法的形成膜裝置一例的截面圖。 第2圖係表示本發明適用之矽圓的截面圖。 第3圖係說明本發明中形成鈦膜的模式圖。 第4圖係說明向來之鈦媒形成的模式圖。 實施發明之最佳樣態 以下，參照添附圖示，針對本發明之實施樣態詳細說 明。 第1圖係表示實施本發明之形成鈦骐裝置一例的截面 圖。此形成膜之裝置具有以氣密所構成之略圓筒狀室】， 本紙張从iSf國國家標準(CNS)八4齡(210χ;97公釐)'• Introduction of IT diagrams Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Printed by the Shellfish Consumer Cooperative, FIG. 1 is a cross-sectional view showing an example of a film forming apparatus that implements the method for forming a titanium film by CVD according to the present invention. Fig. 2 is a cross-sectional view showing a silicon circle to which the present invention is applied. Fig. 3 is a schematic view illustrating the formation of a titanium film in the present invention. Fig. 4 is a schematic diagram illustrating the formation of a conventional titanium medium. Best Mode for Carrying Out the Invention Hereinafter, an embodiment of the present invention will be described in detail with reference to the accompanying drawings. Fig. 1 is a cross-sectional view showing an example of a titanium hafnium forming apparatus embodying the present invention. This film-forming device has a slightly cylindrical chamber formed by airtightness.] This paper is from the iSf National Standard (CNS) eighty-four years old (210χ; 97 mm).
469300 - 五、發明説明（5 ) 在其中’為了水平支持被處理體發圓W的支座2係以藉由 可昇降其中央之圓筒狀支持部材3所支持的狀態而配置。 又，加熱器4被嵌入於支座2中，此加熱器4係藉由未圖示 之電源所供電對被處理體矽晶W加熱至所'定的溫度。 在室1之上端部分，喷淋頭10係以與支座2所支持之半 導體圓W對向地設置著，於與其圓w對向之下面形成多數 之氣體排出孔10a »於嘴淋頭10之内部形成空間η，於其 中水平地設置著形成了多數之孔的分散板丨2。於喷淋頭1〇 之上部形成有氣體導入口 13以將氣體導入其中，於此氣體 導入口 13連結著氣體供給管15。 於氣體供給管15上連结著112(氫）氣體源16、Ar(氬）氣 體源17、TiCl4(四氣化鈦）氣體源18，各氣體從此等氣體源 通過氣體供給管15以及喷淋頭10而供給於室1内，於矽晶 圓W形成欽膜。又，在被連結於各氣體源之配管上皆設置 有闕19以及質量流輞節器20。 經濟部中央標率局員工消費合作社印笨 (請先間讀背面之注意事項再"!寫本頁) 高頻電源23係透過耦合電路22而連結於喷淋頭1〇上， 從此高頻電源23高頻電力可被外加於噴淋頭10上。藉由此 高頻電力，在室1内可形成膜氣體之電漿。又，喷淋頭10 與室1之間，藉由絕緣部材14被絕緣，室1接地。 於室1之底壁設置著排氣埠8，於此排氣埠8上連接著 將室1内排氣之排氣系統9 *又，於室1之侧壁下部設置有 晶圓W之搬出入口 24，此搬入出〇 24可藉由閘式閥25開閉 。晶圓W之搬出入係以使支座2下降之狀態進行。 為形成鈦膜，藉由如此之成膜裝置，將閘式閥25打開 本紙張尺度適用中國國家標準（CNS ) Α4祝格（210X297公釐） 469300 Α7 Β7 經濟部中央標率局員工消費合作社印製 五、發明説明（ό ) ，將矽晶圓W裝入室1内而載置於支座2上，一邊以加熱器 4加熱矽晶圓w一邊以排氣系9之真空泵抽真空而呈高真空 狀態，接著，將TiCU氣體、％氣體、心氣體導入之同時 ’藉由從高頻電源23外加高頻電力而使電'漿產生。 在此’形成鈦膜之對象者可例示：如第2 A圖所示， 於矽基板41上形成Si〇2膜42以為絕緣膜，於其處形成了傳 導孔43者；以及如第2B圖所示，於矽基板41上直接或透 過絕緣膜所形成之聚矽膜”上，形成3〗〇2膜45以為層間絕 緣膜，於其處形成介層孔46者。 於本實施樣態中，未將基底發上所形成之自然氧化膜 預先除去地如上述般形成欽膜。此時，具體上如第3八圖 般，在孔43之底的矽基板41上殘存了矽自然氧化膜5〇的狀 態下’在導入TiC〗4氣體、H2氣體、Ar氣體之同時，藉由 從高頻電源23外加高頻電力而使電漿產生而形成鈦膜。此 時’籍由自然氧化膜50之存在而抑制鈦與;g夕之相互擴散， 且-由於四氣化欽造成梦侵截亦被抑制。所以如第3β圖所 示般，由鈦與矽之擴散所產生之二矽化鈦膜51與基底矽基 板41的界面形態良好。 對比，如向來般地將自然氧化膜除去則如第4Α圖所 示地，四氣化鈦直接侵蝕基底之矽基板41之同時，由於矽 以及鈦之間無介在之層’故此等之相互擴散變得激烈，結 果如第4Β所示般，二矽化鈦膜51與基底之矽基板41之界 面形態變差。此時，因為四氣化鈦之侵蝕為各向同性，矽 基板不僅在縱方向在橫方向亦受侵敍，而易產生接合缝隙 本紙張尺度適用中國國家標率（CNS ) Α4規格（210X297公釐） US' •- :.〕 (請先閲讀背面之注意事項再，城寫本頁) -9 Γ 4 6 9 3 Ο Ό 經濟部中央標準局員工消費合作社印製 Α7 __;___Β7 _五、發明説明（7 ) ο 如此，在矽上以CVD形成鈦膜時，未經除去自然氧 化膜之步驟’藉由以使自然氧化膜殘存之狀態而形成膜， 不會如向來之除去自然氧化膜般產生形經惡化，變得不易 產生接合縫隙等。又，因為變成毋需洗淨步驟，有所謂步 驟數減少之流程上的大優點，又變得也不必要考慮到因經 過洗淨步騍而電特性紛亂。又，矽之自然氧化膜（8丨02膜） 係於矽表面被呈露於大氣時於瞬間所形成。於瞬間所形成 之矽氧化膜厚度約10埃。矽基之面被繼續呈露於大氣則氧 化膜厚度漸次增大，一般在30〜40埃之膜厚下飽和。 又，CVD之情形異於PVD，即使未除去自然氧化膜， 氧在最終也不會殘存於界面，以化學反應被除去。 其次，針對本發明之較佳條件予以說明。從維持著良 好界面形態而得到良好電傳導的觀點視之，自然氧化膜之 厚度以10〜40埃程度之範圍為宜。更宜在20〜30埃程度之 範.圍。又，為成膜之TiCl4氣體、H2氣體、Ar氣體量分別 地以在3〜30SCCM、50〜3SLM、0.5〜3SLM之範圍為宜 。再者，設定基板溫度：400〜700°C、對高頻電源之輸入 電力：100〜1000W、室内壓力：0.5〜3.0Torr之範圍為宜 〇 舉一為例，在室内壓力：1.5Torr、對高頻電源 (13.56MH2)之輸入電力：300W、112氣體流量：0.5SLM、 Ar氣體流量：1.0SLM、四氣化鈦氣體流量：7SCCM、基 板溫度600°C條件下，未除去自然氧化膜，於二氧化矽膜 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家摞準（CNS ) A4祝格（210X297公釐） 10 4693 00 經濟部中央標準局員工消費合作社印製 A7 ~~~~ -- --B7_ 五、發明説明（8 ) 所形成之傳導孔上形成鈦膜 。為了比較，對於在前步驟已 ‘除去自然氧化膜之晶圓亦形成同樣之鈦膜〇 其結果，在除去自然氧化膜後立即形成鈦膜時，如上 述第4圖所示’孔部分之二矽化鈦與基底-矽基板之界面形 態差’又其界面由於矽因四氣化鈦而受侵蝕，可確認朝橫 方向擴張。另一方面，在殘存了約10埃以上厚度之自然氧 化膜的本發明例中係如上述第3圓所示，確認可得到二矽 化鈦層薄度均一、良好之界面β /_ 、又，本發明不為上述實施樣態所限，可為種種之變形 。例如在上述實施樣態中，雖採用TiCl4氣體、Η2氣體、Ar 氣體以作為成膜氣體，但含有其他之氣體亦可。又，針對 製造條件亦不限於上述條件，可依能形成所希望之欽膜而 適宜設定。 又’在以上之說明中係利用矽表面之矽氧化膜為自然 氧化膜之例來說明’因為自然氧化膜係僅將矽表面呈露於 大氣所形成’故毋需為形成氧化膜另設步驟。但，石夕表面 上殘存之矽氧化膜不限於自然氧化膜。例如，在侵蝕等之 前步驟中矽表面露出之後，在同_室或其他室内以減壓氧 化之氛圍下形成約10〜40埃厚之;6夕氧化膜亦可》 即，於CVD —鈦膜形成時，在矽表面上殘存一定範 圍厚度之梦氧化膜是重要的，無論該妙氧化膜是如何形成 的》又氧化膜將以約10〜40埃之厚度形成者照原狀地殘存 亦可’ 一度比40埃更厚地形成後，再侵蝕成10〜4Ό埃之厚 度為止亦可。 本紙張尺度適用中國國家標準（CNS ) A4祝格（2丨0X297公釐） (請先閱讀背面之注意事項界%ί寫本頁} 、裝· 1訂 泉- 11 46 93 0 0 $ 五、發明説明（9 ) 如以上說明，依本發明，當於矽基板上或其上矽膜上 所形成絕緣膜之觸點利用CVD形成鈦膜時，由於未除去 基底之自然氧化膜地形成膜，故傳導電阻安定，可作到與 基底之矽的界面形態良好。 ’ 經濟部中央標準局貝工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4現格（210X297公釐） 12 693 0 0 A7 B7469300-V. Description of the invention (5) Among them, the support 2 for supporting the round W of the object to be processed horizontally is arranged in a state supported by a cylindrical support member 3 that can lift and lower its center. The heater 4 is embedded in the support 2. The heater 4 is heated by a power source (not shown) to heat the silicon wafer W to a predetermined temperature. In the upper end portion of the chamber 1, the shower head 10 is arranged opposite to the semiconductor circle W supported by the support 2, and a plurality of gas exhaust holes 10a are formed below the circle W opposite the circle w. A space η is formed inside, and a dispersion plate 2 in which a large number of holes are formed is horizontally disposed. A gas introduction port 13 is formed in the upper part of the shower head 10 to introduce gas thereinto, and a gas supply pipe 15 is connected to the gas introduction port 13. A gas supply pipe 15 is connected to a 112 (hydrogen) gas source 16, an Ar (argon) gas source 17, and a TiCl4 (titanium tetragas) gas source 18, from which each gas passes through the gas supply pipe 15 and a shower. The head 10 is supplied into the chamber 1 to form a film on the silicon wafer W. In addition, each of the pipes connected to each of the gas sources is provided with a 阙 19 and a mass rim controller 20. Yin Ben, an employee consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before writing this page!) The high-frequency power supply 23 is connected to the showerhead 10 through the coupling circuit 22, and from this high-frequency The high-frequency power of the power source 23 may be applied to the shower head 10. With this high-frequency power, a plasma of a film gas can be formed in the chamber 1. The shower head 10 and the chamber 1 are insulated by an insulating member 14, and the chamber 1 is grounded. An exhaust port 8 is provided on the bottom wall of the chamber 1, and an exhaust system 9 for exhausting the inside of the chamber 1 is connected to the exhaust port 8. * In addition, a wafer W is provided at the lower part of the side wall of the chamber 1. The inlet 24, which is moved in and out, can be opened and closed by a gate valve 25. The loading and unloading of the wafer W is performed with the holder 2 lowered. In order to form a titanium film, by using such a film forming device, the gate valve 25 is opened. The paper size is applicable to Chinese National Standards (CNS) Α4 Zhuge (210X297 mm) 469300 Α7 Β7 Preparation 5. Description of the invention: The silicon wafer W is loaded into the chamber 1 and placed on the support 2. The silicon wafer w is heated by the heater 4 while being evacuated by a vacuum pump of the exhaust system 9. In a high vacuum state, the TiCU gas, the% gas, and the core gas are introduced, and the plasma is generated by applying high-frequency power from the high-frequency power source 23 at the same time. Here, the object of forming a titanium film can be exemplified: as shown in FIG. 2A, a Si02 film 42 is formed on a silicon substrate 41 as an insulating film, and a conductive hole 43 is formed thereon; and as shown in FIG. 2B As shown, on the polysilicon film formed on the silicon substrate 41 directly or through the insulating film, a 3 〇2 film 45 is formed as an interlayer insulating film, and a via hole 46 is formed thereon. In this embodiment, The Qin film was formed as described above without removing the natural oxide film formed on the base hair in advance. At this time, as shown in Figure 38, a silicon oxide film remained on the silicon substrate 41 at the bottom of the hole 43. In the state of 50 °, while introducing TiC gas, H2 gas, and Ar gas, a plasma is generated by applying high-frequency power from a high-frequency power source 23 to form a titanium film. At this time, a natural oxide film is used. The existence of 50 inhibits the interdiffusion of titanium and g; and-the dream interception caused by the four gasification is also suppressed. Therefore, as shown in Figure 3β, the second titanium silicide produced by the diffusion of titanium and silicon The morphology of the interface between the film 51 and the base silicon substrate 41 was good. In contrast, the natural oxide film was removed as usual Then, as shown in FIG. 4A, at the same time as the tetra-gasified titanium substrate directly erodes the silicon substrate 41 of the base, since there is no intervening layer between silicon and titanium, the mutual diffusion becomes fierce, and the result is as shown in FIG. 4B. The morphology of the interface between the titanium disilicide film 51 and the silicon substrate 41 of the base becomes worse. At this time, because the erosion of titanium tetraoxide is isotropic, the silicon substrate is not only invaded in the vertical direction but also in the horizontal direction, and it is easy to produce Joint gap This paper size is applicable to China National Standard (CNS) Α4 specification (210X297mm) US '•-:.] (Please read the precautions on the back before writing this page) -9 Γ 4 6 9 3 〇印 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 __; ___ Β7 _V. Description of the Invention (7) ο In this way, when the titanium film is formed by CVD on silicon, the step of removing the natural oxide film is not used. The oxide film remains in the state to form a film, which will not cause the deterioration of the menstruation like conventional natural oxide films are removed, and it is difficult to produce joint gaps. Also, because there is no need for a washing step, there is a process called a reduction in the number of steps. The great advantages of It is necessary to consider that the electrical characteristics are chaotic due to the washing step. In addition, the natural oxide film of silicon (8 丨 02 film) is formed on the silicon surface in an instant when exposed to the atmosphere. The thickness of the silicon oxide film formed in an instant Approximately 10 angstroms. The surface of the silicon substrate continues to be exposed to the atmosphere, and the thickness of the oxide film gradually increases, generally saturated at a film thickness of 30 to 40 angstroms. Moreover, the situation of CVD is different from PVD, even if the natural oxide film is not removed, oxygen In the end, it will not remain at the interface and will be removed by chemical reaction. Second, the preferred conditions of the present invention will be described. From the viewpoint of maintaining good interface morphology and obtaining good electrical conduction, the thickness of the natural oxide film is 10 A range of about 40 angstroms is preferred. A range of about 20 to 30 angstroms is more suitable. The TiCl4 gas, H2 gas, and Ar gas for film formation are preferably in the range of 3 to 30 SCCM, 50 to 3 SLM, and 0.5 to 3 SLM, respectively. In addition, set the substrate temperature: 400 ~ 700 ° C, the input power to the high-frequency power supply: 100 ~ 1000W, the room pressure: 0.5 ~ 3.0Torr is suitable. For example, the indoor pressure: 1.5Torr, the Input power of high frequency power supply (13.56MH2): 300W, 112 gas flow rate: 0.5SLM, Ar gas flow rate: 1.0SLM, titanium tetragas flow rate: 7SCCM, substrate temperature 600 ° C, without removing natural oxide film, On the silicon dioxide film (please read the notes on the back before filling this page) This paper size is applicable to China National Standards (CNS) A4 Zhuge (210X297 mm) 10 4693 00 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 ~~~~---B7_ V. Description of the invention (8) A titanium film is formed on the conductive hole formed. For comparison, the same titanium film was also formed on the wafer that had been 'removed' the natural oxide film in the previous step. As a result, when the titanium film was formed immediately after the natural oxide film was removed, as shown in the above figure 4 The interface morphology of titanium silicide and the substrate-silicon substrate is poor, and its interface is eroded by titanium tetraoxide, and it can be confirmed that it expands in the horizontal direction. On the other hand, in the example of the present invention in which a natural oxide film with a thickness of about 10 Angstroms or more remained, as shown in the third circle above, it was confirmed that a uniform and favorable interface β / _ of the titanium disilicide layer can be obtained. The present invention is not limited to the above embodiments, and may be variously modified. For example, in the above embodiment, although TiCl 4 gas, Krypton 2 gas, and Ar gas are used as the film-forming gas, other gases may be contained. Moreover, the manufacturing conditions are not limited to the above-mentioned conditions, and can be appropriately set as long as a desired film can be formed. Also, in the above description, an example is described in which the silicon oxide film on the silicon surface is a natural oxide film. Because the natural oxide film is formed by exposing the silicon surface to the atmosphere, no additional step is required for forming the oxide film. However, the silicon oxide film remaining on the surface of Shi Xi is not limited to a natural oxide film. For example, after the silicon surface is exposed in the previous steps such as erosion, a thickness of about 10 to 40 Angstroms is formed under the atmosphere of reduced pressure oxidation in the same room or other rooms; the oxide film can also be used. During the formation, it is important to leave a dream oxide film with a certain thickness on the silicon surface, no matter how the wonderful oxide film is formed, and the oxide film will remain as it is at about 10 ~ 40 angstrom thickness. Once formed thicker than 40 angstroms, it may be eroded to a thickness of 10 to 4 angstroms. This paper size applies the Chinese National Standard (CNS) A4 Zhuge (2 丨 0X297 mm) (Please read the notes on the back of the page% ί write this page}, installed · 1 order spring-11 46 93 0 0 $ 5, Description of the invention (9) As explained above, according to the present invention, when a titanium film is formed by CVD on the contact of an insulating film formed on a silicon substrate or on a silicon film thereon, since the natural oxide film of the substrate is not removed, the film is formed. Therefore, the conduction resistance is stable, and the interface with the silicon on the substrate is in good shape. '' Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, this paper is printed in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 12 693 0 0 A7 B7
五、發明説明（10) 第88100264號專利申請案說明書修正頁V. Description of Invention (10) Amendment Sheet of Patent Application Specification No. 88100264
修正曰期：90年2月 元件標號對照 1...筒狀室 17...氬氣體源 2...支座 18...四氯化鈦氣體源 3...支持部材 19·.·閥 4...加熱器 20...質量流調節器 8...排氣埠 22...耦合電路 9...排氣系統 23...高頻電源 10...喷淋頭 41...砂基板 10a…氣體排出孔 42..Si〇2 膜 11...空間 43...傳導孔 12...分散板 44...聚矽膜 13··.氣體導入口 45...Si〇2 膜 14...絕緣部材 46…傳導孔、介層孔 15.··氣體供給管 50...矽自然氧化膜 16…氫氣體源 51…二石夕化欽層 _(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 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公嫠) 13Revised date: February 1990, component number comparison 1 ... cylindrical chamber 17 ... argon gas source 2 ... support 18 ... titanium tetrachloride gas source 3 ... support parts 19 ... · Valve 4 ... Heater 20 ... Mass flow regulator 8 ... Exhaust port 22 ... Coupling circuit 9 ... Exhaust system 23 ... High frequency power supply 10 ... Sprinkler 41 ... sand substrate 10a ... gas exhaust hole 42.Si〇2 film 11 ... space 43 ... conducting hole 12 ... dispersion plate 44 ... polysilicon film 13 ... gas inlet 45 ... Si〇2 film 14 ... insulating member 46 ... conducting hole, interlayer hole 15 .... gas supply tube 50 ... silicon natural oxide film 16 ... hydrogen gas source 51 ... two stone layers (Please read the notes on the back before filling out this page) The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy applies the Chinese National Standard (CNS) A4 specification (210X297)