TW501191B - TiN-series thin film and method for depositing same - Google Patents

TiN-series thin film and method for depositing same Download PDF

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Publication number
TW501191B
TW501191B TW089118699A TW89118699A TW501191B TW 501191 B TW501191 B TW 501191B TW 089118699 A TW089118699 A TW 089118699A TW 89118699 A TW89118699 A TW 89118699A TW 501191 B TW501191 B TW 501191B
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Taiwan
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thin film
titanium
oxygen
nitrogen
containing gas
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TW089118699A
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Chinese (zh)
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Hayashi Otsuki
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Tokyo Electron Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
    • H01L21/02186—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing titanium, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02362—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment formation of intermediate layers, e.g. capping layers or diffusion barriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
    • H01L28/40—Capacitors

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Semiconductor Memories (AREA)
  • Chemical Vapour Deposition (AREA)
  • Electrodes Of Semiconductors (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Semiconductor Integrated Circuits (AREA)
  • Insulated Gate Type Field-Effect Transistor (AREA)

Abstract

A TiN-series thin film according to the present invention is formed by a CVD, and contains Ti, 0 and N to have a higher barrier characteristic than those of conventional TiN thin films, so that TiN-series thin film can suitably used as a barrier layer. In addition, a TiN-series thin film according to the present invention is formed by a CVD, and contains Ti, N and P to have a lower resistance than those of conventional TiN films, so that TiN-series thin film can suitably used as a barrier layer or a capacitor top electrode. Moreover, if a TiN-series thin film containing Ti, 0, N and P is formed by a CVD, the TiN-series thin film can have both of a high barrier characteristic and a low resistance characteristic.

Description

501191 A7 B7 _ 五、發明說明（1 ) 發明背景 發明領域 -----^---” ！丨裝 (請先閱讀背面之注意事項再填寫本頁) 本發明係關於一種氮化鈦系列薄膜，其係用作為例如 P旱壁層、電谷裔頂電極、閘極電極或接觸部件而用於半導 體裝置及其沈積方法。本發明亦係關於一種沈積氮化鈦系 ,列薄膜之方法，包括氮化鈦系列薄膜之薄膜構造，及其製 法以及利用氮化鈦系列薄膜之半導體裝置。 相關技術之說明 半導體裝置之製造中，電路構造隨著晚近對較高密度 及較高密度集成的需求而傾向於具有多層金屬化構造。因 此嵌置電連結於各層間之技術例如接觸孔其為底半導體裝 置層及底佈線層間的連結部件，及通孔其為底與頂佈線層 間的連結部件相當重要。此外隨著高密度之集成，以高遮 蓋率沈積電容器閘極材料製成的dr am記憶體部件之頂電 極技術變重要。晚近高電介質材料如五氧化二鈕用作為電 容器閘極材料。 經濟部智慧財產局員工消費合作社印製 前述技術嵌置接觸孔及通孔時，一般使用鋁、鎢或主 要含銘或鶴之合金。若此種金屬或合金直接接觸下方矽基 材或銘佈線，則可能由於金屬間邊界部份的鋁之矽抽吸效 應（反向擴散）而形成兩種金屬的合金。如此形成的合金具 有大電阻值’故由晚近對半導體裝置要求之降低電源消耗 及高速操作等觀點看來形成此等合金並不佳。 此外當鎢或鎢合金用作為接觸孔之嵌置層時，用以形 4 本紙張尺錢財目國家標準（CNS)A4規格（210 X 297公髮） 501191 A7 B7 五、發明說明（2 ) 成嵌置層的氟化鎢氣體傾向於與基材之矽反應而劣化電氣 特性獲得非期望的結果。 I I I I I I I · I I (請先閱讀背面之注意事項再填寫本頁) 因此為了防止此等缺點，於嵌置層形成於接觸孔或通 孔前，形成一障壁層於其内壁上以及嵌置層係形成於障壁 層上。此種情況下，通常使用鈦薄膜及氮化鈦薄膜之雙層 構造作為障壁層。 習知此種障壁層係藉物理氣相沈積（PVD)沈積。晚近 特別要求半導體裝置之尺寸的縮小及高密度集成且設計法 則特別苛刻。如此線寬及孔直徑進一步縮小而縱橫比增加 。結果PVD薄膜之嵌置性能不良，無法確保足夠接觸電阻 •線· 因此組成障壁層之鈦膜及氮化鈦膜係藉預期可形成較 佳品質薄膜的化學氣相沈積（CVD)沈積。當鈦膜係藉cvd 沈積使用四氣化鈦及氫氣作為欲被活化成為電漿沈積薄膜 之反應性氣體。當沈積氮化鈦膜時使用四氣化鈦及氨氣或 MMH(—甲基胼）作為反應氣體。 經 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 它方面’如前述使用高密度集成，高電介質材料如五 氧化二钽用作為電容器閘極材料俾獲得高電容而無需改變 尺寸。但此種高電介質材料不比習知用作為電容器閘極材 料的二氧化石夕穩定。因此當使用習知用作為頂電極的多晶 矽時，多晶矽於電容器製備後被加熱過程氧化，故無法妒 成穩定裝置。因此氮化鈦等較為難以被氧化的材料要求用 作為頂電極。501191 A7 B7 _ V. Description of the invention (1) Background of the invention Field of invention ----- ^ --- "! (Please read the precautions on the back before filling this page) This invention is about a titanium nitride series The thin film is used as, for example, a P drywall layer, a top electrode, a gate electrode or a contact member for a semiconductor device and a deposition method thereof. The present invention also relates to a method for depositing a titanium nitride-based thin film Including the thin film structure of titanium nitride series thin film, its manufacturing method and semiconductor device using titanium nitride series thin film. Description of Related Technology In the manufacture of semiconductor devices, the circuit structure is integrated with higher density and higher density. Demands tend to have a multi-layer metallization structure. Therefore, the technology of embedding electrical connections between layers such as contact holes is a connecting member between the bottom semiconductor device layer and the bottom wiring layer, and through holes are connecting members between the bottom and the top wiring layer. It is very important. In addition, with the high-density integration, the top electrode technology of dr am memory components made of capacitor gate materials with high coverage is becoming important. Materials such as the second pentoxide button are used as the capacitor gate material. When the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the aforementioned technology to embed contact holes and through holes, aluminum, tungsten or alloys mainly containing inscriptions or cranes are generally used. Such a metal or alloy directly contacts the underlying silicon substrate or the wiring, and may form an alloy of the two metals due to the silicon suction effect (back diffusion) of aluminum in the intermetallic boundary portion. The alloy thus formed has a large resistance Therefore, it is not good to form these alloys from recent viewpoints such as reducing power consumption and high-speed operation of semiconductor devices. In addition, when tungsten or a tungsten alloy is used as an embedded layer of a contact hole, it is used to form 4 sheets of paper. National Standard (CNS) A4 specification (210 X 297 issued) 501191 A7 B7 V. Description of the invention (2) The tungsten fluoride gas forming the embedded layer tends to react with the silicon of the substrate and deteriorate the electrical characteristics. Expected results IIIIIII · II (Please read the precautions on the back before filling this page) Therefore, in order to prevent these shortcomings, before the embedded layer is formed in the contact hole or through hole, A barrier layer is formed on the inner wall and an embedded layer is formed on the barrier layer. In this case, a double-layer structure of a titanium film and a titanium nitride film is usually used as the barrier layer. It is known that such a barrier layer is based on physical gas. Phase deposition (PVD) deposition. Recently, the size reduction and high-density integration of semiconductor devices are particularly demanded, and the design rules are particularly demanding. In this way, the line width and hole diameter are further reduced and the aspect ratio is increased. As a result, the PVD film has poor embedding performance and cannot be guaranteed Adequate contact resistance • Wire • Therefore, the titanium film and titanium nitride film that make up the barrier layer are deposited by chemical vapor deposition (CVD), which is expected to form a thin film of better quality. When the titanium film is deposited by cvd, four gaseous titanium and Hydrogen acts as a reactive gas to be activated into a plasma-deposited film. When the titanium nitride film is deposited, titanium tetragas and ammonia gas or MMH (-methylphosphonium) are used as a reaction gas. Printed by the Ministry of Economic Affairs and Intellectual Property Bureau's Consumer Cooperatives. It uses high-density integration as described above, and high-dielectric materials such as tantalum pentoxide are used as capacitor gate materials to obtain high capacitance without changing the size. However, this kind of high-dielectric material is not more stable than the dioxide that is conventionally used as a capacitor gate material. Therefore, when polycrystalline silicon conventionally used as a top electrode is used, polycrystalline silicon is oxidized by a heating process after the capacitor is prepared, so it cannot be jealous of a stable device. Therefore, materials that are relatively difficult to be oxidized such as titanium nitride are required as the top electrode.

A7 五、 發明說明（ 又以此種技術為例，氮化鈦膜等習知係藉前述pVD沈 積。但晚近高度集成電容器類型要求高遮蓋率例如冠型、 翅型、或RUG多晶石夕有不規則處形成於多晶石夕上俾當形 成越型或翅型日守加大電容器電容，此等類型之電容器無法 沈積作為頂電極。 因此組成電容器頂電極之氮化鈦膜也藉Cvd沈積， 預期CVD可形成咼遮蓋率之較佳品質薄膜。又於本例， 使用四氯化鈦及氨氣或MMH作為沈積氮化鈦膜的反應氣 體。如此，當氮化鈦膜係藉CVD沈積時，氣殘留於薄膜 内’故沈積薄膜具有高比電阻。若比電阻過高，則當應用 至電容器頂電極時無法獲得足夠特性。此外形成的薄膜為 高應力薄膜。有屬於柱晶的氮化鈦薄膜具有低障壁特性， 原因在於容易發生晶粒間擴散。特別當使用氮化鈦薄膜作 為銅佈線之障壁層時或當使用氮化鈦薄膜作為氧擴散障壁 (於形成五氧化二组電容器頂電極案例）時，低障壁性質造 成問題。換言之，因殘餘氣腐蝕銅佈線以及因氧擴散造成 五氧化二钽容量減低，增加五氧化二鈕厚度而引發問題。 發明概述 因此本發明之目的係消除前述問題以及提供一種具有‘ 比習知氮化鈦薄膜更高障壁特性之氮化鈦系列薄膜，該薄 膜係藉CVD形成，及其製法。 本發明之另一目的係提供一種具有比習知氮化鈦薄臈 更低電阻之氮化鈦系列薄膜，該薄膜係藉CVD形成及其 (請先閱讀背面之注意事項再填寫本頁) I I I I I — I I I!· — · — — · . 項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 6 501191 經辦部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（4 ) 製法。 本發明之另一目的係提供一種可形成氮化鈦系列薄膜 之氣化欽糸列薄膜沈積系統。 本發明之又一目的係提供一種包括此種氮化鈦系列薄 膜之薄膜構造及其製法。 本發明又有另一目的係提供一種使用此種氮化鈦系列 P 薄膜之半導體裝置。 發明人發現藉CVD沈積且含鈦、氧及氮（氮化物）之氮 化鈦系列薄膜具有比習知氮化鈦薄膜之障壁特性更高的障 壁性質且適合用作為障壁層。此外，發明人發現藉CVD 沈積且含有鈦、氮及磷之氮化鈦系列薄膜具有比習知氮化 鈦薄膜更低的電阻，且適合用作為障壁層及電容器頂電極 。此外’發明人發現同時含有氧及磷且具有前述功能之氮 化鈦系列薄膜具有高障壁特性及低電阻特性。 I 因此為了完成前述及其它目的，根據本發明之第一特 徵方面，提供一種氮化鈦系列薄膜其係藉CVD形成且含 有鈦、氧及氮。 也提供一種藉CVD形成且含有鈦、氮及磷之氮化鈦 系列薄膜。 也提供一種藉CVD形成且含有鈦、氧、氮及磷之氮 化鈦系列薄膜。 也提供一種氮化鈦系列薄膜，具有堆疊構造包含··一 第一薄膜其係藉CVD形成且含有鈦、氧及氮以及一第二 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） — — — — — — — — * — — — 111— ·ΙΙΙΙΙΙΙ (請先閱讀背面之注意事項再填寫本頁) 501191 A7 B7 五、發明說明（5 ) 薄膜其係藉CVD形成且含有鈦、氮及磷。此種情況下， 第一薄膜較佳進一步含有磷，或第二薄膜進一步含有氧。 也提供一種氮化鈦系列薄膜，具有堆疊構造包含··一 第一薄膜其係藉CVD形成且含有鈦、氧及氮以及一第二 薄膜其係藉CVD形成於第一薄膜之上且含有鈦、氮及磷 •，以及一第三薄膜其係藉CVD形成於第二薄膜之上且含 有鈦、氧及氮。又此種例中，第一薄膜及第三薄膜中之至 少一者較佳進一步含有磷，或第二薄膜進一步含有氧。 根據本發明之第二特徵方面，提供一種沈積一氮化鈦 系列薄膜之方法，該方法包含下列步驟：配置一基材於一 處理容器；以及將四氣化鈦氣體、含氮氣體、含氫氣體及 含氧氣體導入處理容器内部而藉CVD形成含鈦、氧及氮 之薄膜於基材上。此例中，該方法進一步包含於形成含鈦 、氧及氮之薄膜之步驟之前及/或之後，將含氧氣體導入 處理容器内部之步驟。 也提供一種沈積氮化鈦系列薄膜之方法，該方法包含 下列步驟：配置一基材於一處理容器；以及將四氣化鈦氣 體、含氮氣體、含氫氣體、含氧氣體及含磷氣體引進處理 谷器内部而藉CVD形成一層含鈦、氧、氮及填之薄膜於 基材上。又於本例，該方法較佳進一步包含於形成含鈦、 氧、氮及磷之薄膜之步驟之前及/或之後，將含氧氣體導 入處理容器内部之步驟。 也提供一種沈積氮化鈦系列薄膜之方法，該方法包含 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） (請先閱讀背面之注意事項再填寫本頁) 讎 a·· m MUM aas MW · 經濟部智慧財產局員工消費合作社印製 經^Ε部智慧財產局員工消費合作社印製 501191 A7 ------------B7 _____ 五、發明說明（6 ) 下列步驟：將四氣化鈦氣體、含既氣體、含氣氣體及含氧 氣體導入處理容器内部而藉CVD形成含欽、氧及氣之第 一―薄膜；以及將四氣化鈦氣體、含氮氣體、含氫氣體及含 ， 似體導入處理容器内部而藉CVD形成含鈦、氮及磷之 - 帛二薄膜。此例中’當形成第-薄膜時，較佳將進一步含 • 魏體導入處理容器内部而形成含鈦、氧、氮及磷之薄膜 ，或§形丨第二薄膜肖較佳進一步將含氧氣體導入處理容 器内部而形成含鈦、氧、氮及磷之薄膜。 也提供種'尤積氮化鈦系列薄膜之方法，該方法包含 下列步驟··將四氣化鈦氣體、含氮氣體、含氫氣體及含氧 氣體導入處理容器内部而藉CVD形成含鈦、氧及氮之第 薄膜’將E9氣化鈦氣體、含氮氣體、含氫氣體及含鱗氣 體導入處理容器内部而藉CVD於第—薄膜上形成含欽、 亂及磷之第二薄膜；以及將四氣化鈦氣體、含氮氣體、含 _ 虱氣體及含氧氣體導入處理容器内部而藉CVD於第二薄 膜上形成含欽、氧及氮之第三薄膜。此例中，#形成第一 — 薄膜及/或第三薄膜時，含磷氣體較佳進一步導入處理容 ，㈣部而形成含鈦、氧、氮及鱗之薄膜；或當形成第二薄 膜％，含氧氣體較佳進一步導入處理容器内部:而形成含鈦 、氧、氮及磷之薄膜。 前述沈積方法中，較佳使用氨氣作為含氮氣體及含氫 氣體，將含氧氣體容積轉成氧氣容積所得相對於氨氣之容 積比較佳係於0.0001至0·001之範圍。 本紙張尺度ϋ財關家標準（CNS)A4 i格（210 X 297公爱） ----^ ------ ^5^! (請先閱讀背面之注意事項再填寫本頁) 9 501191A7 V. Explanation of the invention (Taking this technology as an example, the conventional methods such as titanium nitride film are deposited by the aforementioned pVD. However, recently the type of highly integrated capacitors requires high coverage such as crown type, fin type, or RUG polycrystalline stone. There are irregularities formed on the polycrystalline stone. When the Yue type or wing type is used to increase the capacitor capacitance, these types of capacitors cannot be deposited as the top electrode. Therefore, the titanium nitride film that forms the top electrode of the capacitor also uses Cvd. It is expected that CVD can form a thin film of better quality with a high coverage. In this example, titanium tetrachloride and ammonia or MMH are used as the reaction gas for the deposited titanium nitride film. Thus, when the titanium nitride film is formed by CVD During deposition, gas remains in the film, so the deposited film has a high specific resistance. If the specific resistance is too high, sufficient characteristics cannot be obtained when applied to the top electrode of a capacitor. In addition, the formed film is a high-stress film. There are columnar crystals Titanium nitride film has low barrier properties because it is prone to inter-grain diffusion. Especially when using titanium nitride film as a barrier layer for copper wiring or when using titanium nitride film as an oxygen diffusion barrier (In the case of forming the top electrode of the second group of pentoxide capacitors), the low barrier properties cause problems. In other words, the residual gas corrodes the copper wiring and the reduction of the tantalum pentoxide capacity due to the diffusion of oxygen causes the problem of increasing the thickness of the second pentoxide button. SUMMARY OF THE INVENTION Therefore, the object of the present invention is to eliminate the aforementioned problems and provide a titanium nitride series thin film having higher barrier characteristics than the conventional titanium nitride thin film, which is formed by CVD and a method for manufacturing the same. The purpose is to provide a titanium nitride series thin film with lower resistance than the conventional titanium nitride thin film. The thin film is formed by CVD and (please read the precautions on the back before filling this page) IIIII — III! · — · — — ·. Please fill in this page again) Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6 501191 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (4) Manufacturing Law. Another object of the present invention is to provide a gasification Qinli thin film deposition system capable of forming a titanium nitride series thin film. Still another object of the present invention is to provide a thin film structure including such a titanium nitride series thin film and a manufacturing method thereof. Another object of the present invention is to provide a semiconductor device using such a titanium nitride series P film. The inventors have found that titanium nitride series films containing titanium, oxygen, and nitrogen (nitride) deposited by CVD have barrier properties higher than those of conventional titanium nitride films and are suitable for use as a barrier layer. In addition, the inventors found that the titanium nitride series thin film deposited by CVD and containing titanium, nitrogen, and phosphorus has lower resistance than the conventional titanium nitride thin film, and is suitable for use as a barrier layer and a capacitor top electrode. In addition, the inventors discovered that the titanium nitride series thin film containing both oxygen and phosphorus and having the aforementioned functions has high barrier characteristics and low resistance characteristics. I Therefore, in order to accomplish the foregoing and other objects, according to a first feature aspect of the present invention, a titanium nitride series thin film is provided which is formed by CVD and contains titanium, oxygen, and nitrogen. A titanium nitride series thin film formed by CVD and containing titanium, nitrogen, and phosphorus is also provided. A titanium nitride series thin film formed by CVD and containing titanium, oxygen, nitrogen, and phosphorus is also provided. A titanium nitride series film is also provided with a stacked structure including a first film formed by CVD and containing titanium, oxygen and nitrogen, and a second paper standard applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) — — — — — — — — — * — — — 111 — · ΙΙΙΙΙΙΙ (Please read the notes on the back before filling out this page) 501191 A7 B7 V. Description of the invention (5) The film is formed by CVD and Contains titanium, nitrogen and phosphorus. In this case, the first thin film preferably further contains phosphorus, or the second thin film further contains oxygen. Also provided is a titanium nitride series film having a stack structure including a first film formed by CVD and containing titanium, oxygen and nitrogen, and a second film formed on the first film by CVD and containing titanium , Nitrogen and phosphorus, and a third thin film formed on the second thin film by CVD and containing titanium, oxygen, and nitrogen. In another example, at least one of the first film and the third film preferably further contains phosphorus, or the second film further contains oxygen. According to a second characteristic aspect of the present invention, a method for depositing a titanium nitride series thin film is provided. The method includes the following steps: disposing a substrate in a processing container; and disposing a titanium tetragas, a nitrogen-containing gas, and a hydrogen-containing gas. The gas and the oxygen-containing gas are introduced into the processing container to form a thin film containing titanium, oxygen, and nitrogen on the substrate by CVD. In this example, the method further includes a step of introducing an oxygen-containing gas into the inside of the processing vessel before and / or after the step of forming a thin film containing titanium, oxygen, and nitrogen. A method for depositing a titanium nitride series thin film is also provided. The method includes the following steps: disposing a substrate in a processing container; and disposing a titanium tetragas, a nitrogen-containing gas, a hydrogen-containing gas, an oxygen-containing gas, and a phosphorus-containing gas. The inner part of the trough is introduced to process a layer containing titanium, oxygen, nitrogen and a film on the substrate by CVD. Also in this example, the method preferably further includes a step of introducing an oxygen-containing gas into the inside of the processing container before and / or after the step of forming a thin film containing titanium, oxygen, nitrogen, and phosphorus. A method for depositing titanium nitride series films is also provided. The method includes the paper size applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 public love) (Please read the precautions on the back before filling this page) 雠 a · · M MUM aas MW · Printed by the Consumers 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 501191 A7 ------------ B7 _____ V. Description of the Invention (6 ) The following steps: introducing a tetra-titanium gas, an existing gas, a gas-containing gas and an oxygen-containing gas into the inside of the processing container to form a first-thin film containing cyanine, oxygen and gas by CVD; and Nitrogen-containing gas, hydrogen-containing gas, and the like-like substance are introduced into the processing vessel to form a titanium-nitrogen-containing second film by CVD. In this example, when the first film is formed, it is preferable to further introduce the Wei body into the processing container to form a film containing titanium, oxygen, nitrogen, and phosphorus, or the second film. It is preferable to further include oxygen. The gas is introduced into the processing vessel to form a thin film containing titanium, oxygen, nitrogen, and phosphorus. A method for forming a thin film of titanium nitride series is also provided. The method includes the following steps: introducing titanium tetragas, a nitrogen-containing gas, a hydrogen-containing gas, and an oxygen-containing gas into the inside of the processing container to form titanium-containing by CVD, The second thin film of oxygen and nitrogen 'introduces E9 vaporized titanium gas, nitrogen-containing gas, hydrogen-containing gas, and scale-containing gas into the processing vessel to form a second thin film containing chin, chaos, and phosphorus by CVD on the first thin film; and A tetra-titanium gas, a nitrogen-containing gas, a lice-containing gas, and an oxygen-containing gas are introduced into the processing container to form a third thin film containing cyanine, oxygen, and nitrogen on the second thin film by CVD. In this example, when forming the first thin film and / or the third thin film, the phosphorus-containing gas is preferably further introduced into the processing volume, and a thin film containing titanium, oxygen, nitrogen, and scale is formed at the crotch; or when the second thin film is formed% The oxygen-containing gas is preferably further introduced into the inside of the processing vessel: a thin film containing titanium, oxygen, nitrogen, and phosphorus is formed. In the foregoing deposition method, it is preferable to use ammonia gas as the nitrogen-containing gas and hydrogen-containing gas, and the volume of the oxygen-containing gas to the volume of the oxygen relative to the ammonia gas is preferably in the range of 0.0001 to 0.001. This paper size: CNS Standard A4 i (210 X 297 public love) ---- ^ ------ ^ 5 ^! (Please read the precautions on the back before filling this page) 9 501191

經濟部智慧財產局員工消費合作社印製 五、發明說明（7 ) 也較佳提供一種沈積氮化鈦系列薄膜之方法，該方法 包含下列步驟：配置一基材於一處理容器；以及將四氯化 鈦氣體，含氮氣體，含氫氣體及含磷氣體導入處理容器内 部而藉CVD形成含鈦、氮及磷於基材上之薄膜。又於此 例’該方法較佳進一步包含於形成含鈦、氮及磷之薄膜之 步驟之別及/或之後，將含氧氣體導入處理容器之步驟。 月!1述沈積方法中，較佳使用膦作為含磷氣體，膦之進 給速率較佳於0.04至〇·3升/分鐘之範圍。本例膦之進給速 率較佳為0·1升/分鐘及以上俾致使形成的薄膜為非晶形。 根據本發明之第三特徵方面，提供一種沈積氮化鈦系 列薄膜之系統，該系統包含：一處理容器用以於其中罩住 一欲處理的基材；一支持件用以支持基材於處理容器；一 沈積氣體導入機構用以將沈積氣體導入處理容器内部；以 及一加熱機構声以加熱支持於支持件上之基材，其中該沈 積氣體導入機構具有來源用以供應四氣化鈦氣體、含氮氣 體及含氫氣體以及至少一來源用以供應含氧氣體及一供應 含磷氣體之來源。此例中，含鈦、氧及氮之薄膜以及含鈦 、氮及磷之薄膜較佳可藉調整來自供應含氧氣體來源之氣 體供應以及來自供應含磷氣體來源之氣體供應而連續形成 〇 根據本發明之第四特徵方面，提供一種薄膜構造包含 ·· 一第一層；一第二層；及一氮化鈦系列薄膜設置於第一 與第二層間’氮化鈦糸列薄膜包含含鈦、氧及氮之薄膜， 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ----^---·----0 Μ---- (請先閱讀背面之注意事項再填寫本頁) 訂----I----舞 10 501191 經 •ate - 濟r 部 智 慧 財 產 局 員 X 消 費 合 作 社 印 製 五、發明說明（8 ) 含鈦、氮及磷之薄膜以及含鈦、氧、氮及磷之薄膜之一， 此等薄膜係藉CVD形成或其中二或多種薄膜之堆疊層。 此例中，第一層較佳為鈦薄膜、石夕化鈦薄膜及石夕化銘薄膜 之一以及第二層較佳為金屬層。 · .根據本發明之第五特徵方面，提供一種製造薄膜構造 之方法’該方法包含下列步驟：形成一第一層；於一處理 A7 B7 谷為藉CVD沈積氮化鈦系列薄膜於第一層上，該氮化鈦 系列薄膜包含含鈦、氧及氮之薄膜，含鈦、氮及磷之薄膜 及含鈦、氧、氮及磷之薄膜之一或其中二或多層薄膜之堆 ®層；形成一第二層於氮化鈦系列薄膜上；以及於形成氮 化鈦系列薄膜之步驟之前及/或之後，將含氧氣體導入處 理容器内部。此例中，第一層較佳為鈦薄膜、矽化欽薄膜 及矽化鈷薄膜之一，以及第二層較佳為金屬層。 如前述’根據本發明之氮化鈦系列薄膜係藉CVD方 法形成且含有鈦、氧及I因而具有比習知氮化鈦薄膜更高 的障壁特性，故氮化鈦系列薄膜適合用於障壁層。此外， 根據本發明之氮化鈦系列薄膜係藉CVD形成且含鈦、氮 及磷而具有比習知氮化鈦薄膜更低的電阻，故氮化鈦系列 薄膜適合用作為障壁層或電容器頂電極。 此外，藉CVD形成且含有鈦、氧、氮及磷之氮化鈦 系列薄膜具有高障壁特性及低電阻特性。Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (7) It is also preferable to provide a method for depositing a titanium nitride series film, which method includes the following steps: disposing a substrate in a processing container; Titanium gas, nitrogen-containing gas, hydrogen-containing gas, and phosphorus-containing gas are introduced into the processing vessel to form a thin film containing titanium, nitrogen, and phosphorus on the substrate by CVD. Also in this example ', the method preferably further includes a step of introducing an oxygen-containing gas into the processing container after and / or after the step of forming a thin film containing titanium, nitrogen, and phosphorus. In the above-mentioned deposition method, phosphine is preferably used as the phosphorus-containing gas, and the feed rate of the phosphine is preferably in the range of 0.04 to 0.3 liters / minute. The feed rate of phosphine in this example is preferably 0.1 liters / minute or more, so that the formed film is amorphous. According to a third characteristic aspect of the present invention, a system for depositing a titanium nitride series film is provided. The system includes: a processing container for covering a substrate to be processed therein; and a supporting member for supporting the substrate during processing. A container; a deposition gas introduction mechanism for introducing the deposition gas into the inside of the processing container; and a heating mechanism for heating the substrate supported on the support member, wherein the deposition gas introduction mechanism has a source for supplying a tetragas titanium gas, A nitrogen-containing gas and a hydrogen-containing gas and at least one source are used to supply an oxygen-containing gas and a source to supply a phosphorus-containing gas. In this example, the thin film containing titanium, oxygen, and nitrogen, and the thin film containing titanium, nitrogen, and phosphorus are preferably formed continuously by adjusting the gas supply from the supply of the oxygen-containing gas source and the gas supply from the supply of the phosphorus-containing gas source. According to a fourth characteristic aspect of the present invention, there is provided a thin film structure including a first layer, a second layer, and a titanium nitride series film disposed between the first and second layers. The titanium nitride queue film includes titanium. , Oxygen and nitrogen film, this paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---- ^ --- · ---- 0 Μ ---- (Please read the back first Please pay attention to this page before filling in this page) Order ---- I ---- Dance 10 501191 Economics • Member of the Intellectual Property Bureau of the Ministry of Economic Affairs X Printed by Consumer Cooperatives V. Invention Description (8) Contains titanium, nitrogen and phosphorus One of thin films and thin films containing titanium, oxygen, nitrogen, and phosphorus, which are formed by CVD or a stacked layer of two or more of them. In this example, the first layer is preferably one of a titanium film, a titanium oxide film, and a silicon oxide film, and the second layer is preferably a metal layer. According to a fifth characteristic aspect of the present invention, a method for manufacturing a thin film structure is provided. The method includes the following steps: forming a first layer; and processing a A7 B7 valley to deposit a titanium nitride series thin film on the first layer by CVD. In the above, the titanium nitride series thin film includes a thin film containing titanium, oxygen, and nitrogen, a thin film containing titanium, nitrogen, and phosphorus, and one or two or more layers of the thin film containing titanium, oxygen, nitrogen, and phosphorus; Forming a second layer on the titanium nitride series film; and introducing an oxygen-containing gas into the processing container before and / or after the step of forming the titanium nitride series film. In this example, the first layer is preferably one of a titanium film, a silicide film, and a cobalt silicide film, and the second layer is preferably a metal layer. As mentioned above, the titanium nitride series thin film according to the present invention is formed by the CVD method and contains titanium, oxygen, and I. Therefore, it has higher barrier characteristics than the conventional titanium nitride thin film. Therefore, the titanium nitride series thin film is suitable for the barrier layer. . In addition, the titanium nitride series thin film according to the present invention is formed by CVD and contains titanium, nitrogen, and phosphorus, and has a lower resistance than the conventional titanium nitride thin film. Therefore, the titanium nitride series thin film is suitable for use as a barrier layer or a capacitor top. electrode. In addition, the titanium nitride series thin film formed by CVD and containing titanium, oxygen, nitrogen, and phosphorus has high barrier characteristics and low resistance characteristics.

此外，若氮化鈦系列薄膜具有堆疊構造：其中第一薄 膜係藉CVD形成且含有鈦、氧及氮以及第二薄膜係藉CVD 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） — 1 — ! — ·丨丨 1!· · I I I ! —訂！！ - (請先閱讀背面之注意事項再填寫本頁) 11 經濟部智慧財產局員工消費合作社印製 A7 '—-------— B7 __ 五、發明說明(Μ -- 形成且含有鈦、氮及鱗，則第一層之高障壁特性以及第二 d之低笔阻特性可提供相等或優於習知障壁層之特性，即 使厚度比習知障壁層更薄亦如此。 此外，若氮化鈦系列薄膜具有堆疊構造，包含藉cVD 形成且含鈦、氧及氮之第一薄膜，藉CVD形成且含鈦、 氮及磷之第二薄膜以及藉CVD形成且含鈦、氧及氮之第 二薄膜，則可於兩邊獲得障壁特性。 此外於半導體裝置，此等氮化鈦系列薄膜係用作為（1) I1羊壁層或嵌置佈線部份於一佈線層與一半導體基材間之接 觸部件或一導電層設置於基材上，（2) 一電容器部份之頂 黾極層、p早壁層或底電極具有五氧化二组或氧化釘之絕緣 層，（3)至少一閘極電極部件，以及（4) 一接觸構造於半導 體基材之一主面上故可獲得絕佳特性。 1式之簡單說明 由後文詳細說明以及本發明之較佳具體實施例之附圖 將更為了解本發明。但附圖絕非意圖限制本發明於特定具 體實施例，反而僅供解說了解之用。 附圖中： 第1圖為根據本發明之沈積氮化鈦系列薄膜用之沈積 系統之剖面圖； 第2圖為線圖顯示流量比氧/氨與氧氮化鈦薄膜之比電 阻值間之關係； 第3圖為線圖顯示流量比膦與氮化鈦系列薄膜之比電 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 12 !]__·_ 裝--------訂！ 1·· (請先閱讀背面之注意事項再填寫本頁) 501191 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（10 ) 阻值間之關係； 弟4圖為線圖顯示當使用膦及未使用鱗時，沈積溫度 與氮化鈦系列薄膜之比電阻值間之關係； 弟5圖為線圖顯示當使用及未使用膦時，流量比氧/氨 ’ 與氮化鈦系列薄膜之比電阻值間之關係； 第6圖為剖面圖顯示根據本發明之氮化鈦系列薄膜之 堆疊構造之實例（a)及（b); 第7圖為使用根據本發明之氮化鈦系列薄膜之薄膜構 造之剖面圖； 第8圖為剖面圖顯示根據本發明之氮化鈦系列薄膜 貫例（a)至（c) ’該薄膜係用作為金屬佈線層之接觸部份； 第9圖為剖面圖顯示根據本發明之氮化鈦系列薄膜 貝例（a)至（c) ’其係用於DRAM等電容器構造； 第10圖為示意圖顯示根據本發明可連續沈積氮化鈦系 列薄膜及其它薄膜之沈積系統之一例； 第11圖為剖面圖顯示根據本發明之氮化鈦系列薄膜之 實例（a)及（b)其係用於閘極電極； 第12圖為剖面圖顯示根據本發明之氮化鈦系列薄膜之 實例（a)及（b)其係用於閘極電極；以及 第13圖為剖面圖，顯示當佈線形成於半導體基材主 所形成的擴散區時，根據本發明之氮化欽系列薄膜之一 其係用於接觸構造。 較佳具體實施例之說明 ‘紙張尺度適用中國國家標準（CNS)A4 ‘格⑽x 297公釐）__ 之 之 面 例 — — — — — — — · I I I I I I I ^^ 111111 — (請先閱讀背面之注意事項再填寫本頁) 501191In addition, if the titanium nitride series thin film has a stacked structure: the first thin film is formed by CVD and contains titanium, oxygen and nitrogen, and the second thin film is formed by CVD. The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297). Mm) — 1 —! — · 丨 丨 1! · · III! — Order! !! -(Please read the notes on the back before filling out this page) 11 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 '—-------— B7 __ 5. Description of the invention (M-formed and contains titanium , Nitrogen, and scale, the high barrier characteristics of the first layer and the low pen resistance characteristics of the second layer can provide characteristics that are equal to or better than those of the conventional barrier layer, even if the thickness is thinner than the conventional barrier layer. In addition, if The titanium nitride series thin film has a stacked structure including a first thin film formed by cVD and containing titanium, oxygen, and nitrogen, a second thin film formed by CVD and containing titanium, nitrogen, and phosphorus, and a second thin film formed by CVD and containing titanium, oxygen, and nitrogen The second thin film can obtain barrier properties on both sides. In addition, in semiconductor devices, these titanium nitride series thin films are used as (1) I1 sheep wall layers or embedded wiring parts on a wiring layer and a semiconductor substrate. The contact part or a conductive layer is arranged on the substrate, (2) the top electrode layer, p-early wall layer or bottom electrode of a capacitor part has an insulating layer of two groups of pentoxide or oxide nails, (3) at least A gate electrode member, and (4) a contact structure on a semiconductor substrate Excellent characteristics can be obtained on a main surface. A brief description of the formula 1 will be better understood from the detailed description below and the accompanying drawings of preferred embodiments of the present invention. However, the drawings are by no means intended to limit the present invention to The specific embodiment is for illustrative purposes only. In the drawings: FIG. 1 is a cross-sectional view of a deposition system for depositing a titanium nitride series thin film according to the present invention; FIG. 2 is a line graph showing a flow rate ratio oxygen / The relationship between the specific resistance of ammonia and titanium oxynitride film; Figure 3 is a line chart showing the specific ratio of flow rate ratio of phosphine to titanium nitride series film. Paper size is applicable to China National Standard (CNS) A4 (210 X 297) (Mm) 12!] __ · _ Install -------- Order! 1 ·· (Please read the precautions on the back before filling out this page) 501191 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (10) The relationship between the resistance values; Figure 4 is a line chart showing the relationship between the deposition temperature and the specific resistance value of the titanium nitride series thin film when phosphine and scale are not used; Figure 5 is a line chart Shows the flow ratio of oxygen / ammonia 'and nitriding with and without phosphine The relationship between the specific resistance of a series of thin films; Figure 6 is a sectional view showing an example (a) and (b) of a stacked structure of a titanium nitride series thin film according to the present invention; Figure 7 is a view showing the use of nitride according to the present invention Sectional view of the thin film structure of the titanium series thin film; FIG. 8 is a sectional view showing the conventional examples (a) to (c) of the titanium nitride series thin film according to the present invention; the thin film is used as a contact portion of a metal wiring layer; FIG. 9 is a cross-sectional view showing examples of titanium nitride series thin films according to the present invention (a) to (c), which are used for capacitor structures such as DRAM; FIG. 10 is a schematic view showing that the titanium nitride series can be continuously deposited according to the present invention An example of a thin film and other thin film deposition system; FIG. 11 is a cross-sectional view showing examples (a) and (b) of a titanium nitride series thin film according to the present invention, which are used for a gate electrode; FIG. 12 is a cross-sectional view showing Examples (a) and (b) of the titanium nitride series thin film according to the present invention are used for gate electrodes; and FIG. 13 is a cross-sectional view showing when wiring is formed in a diffusion region formed by a semiconductor substrate, According to the present invention, Which system is configured for contacting. Explanation of the preferred embodiment 'Paper size applicable to Chinese National Standard (CNS) A4' Dimensions x 297 mm) __ Face example — — — — — — — IIIIIII ^^ 111111 — (Please read the note on the back first Matters refill this page) 501191

五、發明說明（11 經濟部智慧財產局員工消費合作社印製 /現在參照附圖，本發明之較佳具體實施例詳細說明如 後。 第1圖為根據本發明沈積氮化銳系列薄膜之沈積系統 i面圖沈積系統具有霄質圓柱形氣密處理容器11，其 中感測器12用於水平支持半導體晶DW作為欲處理的物件 ’該晶圓係配置同時支持於柱形支持件13上。於感測器12 之外緣部，設置一導環14用以導引半導體晶圓w。此外加 熱器15嵌置於感測器12内部。當由電源供應器陳電給加 …、器15日守，加熱器15加熱作為欲處理物件之半導體晶圓w 至預定溫度。電源供應器16連結至控制器17，控制器係根 據來自溫度感測器（圖中未顯示）的信號控制加熱器15的輸 出。 處理容器11之頂壁11 a設置有一喷淋頭20〇喷淋頭2〇 中’父替形成多個氣體排放孔2〇a及20b，用以排放氣體朝 向感測器12。氣體供應機構3〇之管路連結至噴淋頭2〇。容 後詳述，供給四氣化鈦之導管45連結至氣體排放孔20a , 供給氨氣之導管46連結至氣體排放孔2〇b，故預定氣體經 由噴淋頭20引進處理容器Η内部。如此喷淋頭2〇為矩陣型 喷淋頭，採用後混合系統，其中作為反應氣體之四氯化鈦 及氨氣係於由交替形成的排放孔20a及20b排放後混合。 氣體供應機構30具有三氟化氣供應源31用以供應清潔 氣體三氟化氣，氮氣供應源32用以供應氮氣，四氣化鈦供 應源33用以供應反應氣體四氣化鈦，膦供應源34用以供應 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 14 J---*----^-----------— II (請先閱讀背面之注意事項再填寫本頁) 501191 ， 經齋部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（12) 作為含磷氣體的膦，氨供應源35用以供應反應氣體且含氮 及氫之氨，以及氧氣供應源36用以供應作為含氧氣體的氧 氣。此外，氣體管路39連結至三氟化氯供應源31，氣體管 路40連結至氮氣供應源32，氣體管路41連結至四氣化鈦供 應源33，氣體管路42連結至膦供應源34，氣體管路43連結 至氨供應源35，以及氣體管路44連結至氧氣供應源36。管 I 路39至44設置有閥47及質量流量控制器48。 由氮氣供應源32伸出的氣體管路40會合由四氣化鈦供 應源33伸出的氣體管路41，故載於氮氣的四氣化鈦氣體流 經氣體管路40及導管45經由喷淋頭20之氣體排放孔20a被 導入處理容器11内部。由三氟化氣供應源31伸出的氣體管 路39會合氣體管路40,故作為清潔氣體之三氟化氣由氣體 排放孔20a經由氣體管路39及40以及導管45(藉由開啟設置 於氣體管路39的閥）而被導入處理容器11内部。此外氨氣 | 係由喷淋頭20的氣體排放孔20b經由氣體管路43及導管46 被導入處理容器11内部。連結至膦供應源34之氣體管路42 連結至氣體管路41，故膦氣由喷淋頭20之氣體排放孔20a 經由氣體管路42、41及40以及導管45被引進處理容器11内 部。連結至氧氣氣體源36之氣體管路44連結至氣體管路43 ，故氧氣由喷淋頭20之氣體排放孔20b經由氣體管路44及 43以及導管46被導入處理容器11内部。 此外，作為含氮氣體及含氫氣體，可使用一甲基胼 (MMH)替代氨氣，或含氮氣體及含氫氣體可作為分開氣 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 15 _ 裝· I 訂------- I!線 (請先閱讀背面之注意事項再填寫本頁) 五、 發明說明（13) 體導入。此外，作為含氧氣體，一氧化氮氣體或氧化亞氮 氣體可用於替代氧氣。此外氬氣可取代氮氣。 於處理容器11之底壁lib連結排氣管18。包括真空幫 浦之排氣系統19連結至排氣管18。經由作動排氣系統19， 處理容器11之壓力可降至預定真空程度。 後文將說明使用此種系統沈積氮化鈦系列薄膜於半導 體晶圓W之方法。 首先，半導體晶圓W架設於處理容器11之感測器12上 。然後當晶圓W由加熱器15加熱時，處理容器丨丨藉排氣系 統19被抽真空至咼度真空狀態。隨後氮氣及氨氣以預定流 量比導入處理容器11内部，故處理容器丨丨之壓力為133至 1333巴斯卡進行前置退火。 然後處理容器11之壓力改變成13 3至133巴斯卡，維 持氮氣及氨氣之流速，四氣化鈦氣體以及氧氣及膦氣中之 至少一者預先以預定流速流動約5至2〇秒。隨後預定氮化 鈦系列薄膜之沈積係於預先流動之相同條件下進行。此時 ，氮化鈦系列薄膜沈積係於約400至7〇〇。(：之溫度進行。 沈積後，半導體晶圓由處理容器u排放出。然後作為 清潔氣體的三1化氣氣體被導人處理容器u而清潔處理容 器11内部。 當氨氣、四氯化鈦氣體及氧氣用於前述沈積作為處理 氣體時，形成氮化鈦系列薄膜（氧氮化鈦薄膜）其含有欽、 氣及氧且具有高度障壁特性同時維持相對低電阻。換古之 ----一---«----Μ--------^----II (請先閱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 16 A7 五、發明說明（14) ，因氮化鈦薄膜之晶體為柱晶，故容易發生晶粒間擴散， 如此金屬或氧容易經由氮化欽晶體的晶粒邊界擴散。因此 若氮化鈦薄膜係藉熱CVD使用含氧氣體形成，則可改善 氮化鈦晶體晶粒邊界的障壁特性。此例中氧對氨之容積比 較佳係於0.0001至〇 00]之鉻囹 ,lL Λ 王υ·υυι之靶圍。如此電阻值係於預定範 _ 圍。 訂 第2圖顯示流速氧/氨與氧氮化鈦薄膜之比電阻值間之 關係。此例中，四氣化鈦氣體之流速為0 02升/分鐘，氨 氣流速為G.5升/分鐘，氮氣流速為G15升/分鐘，及氧氣流 速係於5xl0-5至4xl0-3升/分鐘之範圍改變（流速比氧/氨係 於〇.〇〇_至〇._之範圍）。此外於沈積過程基材溫度為55〇 c，處理容器愿力為3〇〇毫托耳，薄膜厚度為5〇毫微米。 如第2圖所示’當流量比氧/氨係於前述範圍時，氧氣化鈦 薄膜之比電阻（電阻係數）值係於36〇至75〇〇微歐姆•厘米 之範圍，此乃容許範圍。 此外即使使用另一種氣體例如氧化氮或氧化亞氮作為 圍 含氧氣體，電阻值經由轉換成前述氧氣範圍徐於適當範 内。 此外若比電阻值為約7〇〇微歐姆•厘米或以上則障壁 特丨生良好。因此由第2圖可知流量比氧/氨為〇〇〇〇6或以上 俾獲得良好障壁特性。 其次，說明形成含鈦、氮及磷之氮化鈦系列薄膜（氮 磷化鈦薄膜）之方法。 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 χ 297公釐 17 經濟部智慧財產局員工消費合作社印製 501191 Α7 五、發明說明（l5) 當使用氨氣、四氣化鈦氣及膦氣作為處理氣體時，形 成虱化鈦系列薄膜（氮磷化鈦薄膜）且含有鈦、氮及磷且具 有低電阻值同時維持相對良好障壁特性。經由使用膦氣， 可藉膦氣的還原功能去除剩餘氯氣，故可降低氮化鈦系列 薄膜之電阻值。此例中，膦之流速係於〇 〇4至〇 5升/分鐘 之fe圍。若流速低於0 04升/分鐘，則無法獲得良好效果 。此外，若膦氣流速為〇」升/分鐘或以上，則形成的薄膜 為非晶形且密實，故可降低電阻且障壁特性良好。 第3圖顯示膦氣流速與氮化鈦系列薄膜之比電阻值間 之關係。本例中四氯化鈦氣體流速為0·02升/分鐘，氨氣 流速為0.5升/分鐘，氮氣流速為〇15升/分鐘及膦氣流速係 於0至0.2升/分鐘間變化。此外於沈積期間，基材溫度為43〇 t至550°C，處理容器壓力為40巴斯卡，薄膜厚度為5〇毫 微米。如第3圖所示，當膦氣流速為〇〇4升/分鐘時，電阻 值明白降低。此外，當沈積溫度為550°C時，電阻值傾向 於更為降低。以於5501沈積為例，當膦氣流速為〇·2升/ 分鐘時’可獲得70微歐姆•厘米，此乃極低值。 此種情況下，氮化鈦系列薄膜之沈積溫度與比電阻值 間之關係顯示於第4圖。如第4圖所示，添加膦氣時，比電 阻值與溫度的相依性比較未添加膦氣時更小，故電阻值穩 定維持低值。此外於第4圖，四氣化鈦氣體流速為〇〇2升/ 分鐘，氨氣流速為0.5升/分鐘，氮氣流速為〇·ΐ5升/分鐘及 膦氣流速為0.2升/分鐘。此外處理容器壓力為4〇巴斯卡， 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） -----^---Ί I I ^ ill — — — — ^« — — — 1 — (請先閱讀背面之注意事項再填寫本頁) 18 501191 經濟部智慧財產局員工消費合作社印製 Α7 Β7 五、發明說明（16) 薄膜厚度為50毫微米。 其次說明含鈦、氮、氧及磷之氮化鈦系列薄膜（氧氣 磷化鈦薄膜）之形成方法。 當氨氣、四氣化鈦氣體、氧氣及膦氣用於沈積作為處 理氣體時，可獲得含鈦、t、氧及磷之氮化欽系列薄膜（ 氧氮磷化鈦薄膜）其具有高度障壁特性及低電阻特性。換 言之，雖然障壁特性係經由於沈積過程供給氧氣而改良， 但隨著氧（流量比氧/氨）數量的增高，電阻值增高（如第5圖 所不）。但經由供給膦氣而導入磷，電阻值比未導入磷時 更低，故可獲得具有高障壁特性及低電阻特性之氮化鈦系 列薄膜。此外於第5圖，四氯化鈦氣體流速為〇〇2升/分鐘 ，氨氣流速為0.5升/分鐘，氮氣流速為〇15升/分鐘，膦氣 流速係於0·2升/分鐘至〇升/分鐘，氧氣流速係於化1〇·5至 lxl〇·3升/分鐘範圍改變（流量比氧/氨係於〇 〇〇〇1至〇 〇〇1之 範圍）。此外處理容器壓力為40巴斯卡，薄膜厚度為5〇毫 微米。 前述沈積過程中，未變更氣體而形成單一氮化鈦系列 溥膜。它方面，若如下形成包含複數氮化鈦系列薄膜之堆 疊膜，則可以較小厚度獲得較高障壁特性。待別如第6(勾 圖所示，四亂化鈦氣體、氣氣及氧氣首先導入處理容器η 内部而形成於底層50上之含鈦、氧及氮之第一薄膜51。隨 後關閉氧氣管路44 ,開啟膦氣管路而將四氣化鈦氣、氨氣 及膦氣導入處理容器11内部而形成含鈦、氮及磷之第二 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） ^1 — — — — ！ — · ! I I 屢 I (請先閱讀背面之注意事項再填寫本頁) 19 A7 A7 經濟部智慧財產局員工消費合作社印製 五、發明說明（17) 膜52於第一薄膜51上。經由形成此種雙層構造，若膜厚度 小於習知膜厚度，可改良障壁特性同時維持與習知比電随 值相等的比電阻值。此種情況下，第一薄膜51之厚度較佳 係於1至10亳微米之範圍，第二薄膜52之厚度較佳係於3至 50¾微米之範圍。 特別當使用薄膜作為銅佈線層的障壁層時，習知氮化 鈦溥膜厚度須為5〇毫微米或以上俾獲得良好障壁效果。作 若形成此種堆疊構造，即使第一薄膜51(高障壁氧氮化鈦 薄膜）之厚度係於1至5毫微米之範圍以及第二薄膜52(含磷 低電阻氮化鈦系列薄膜）之厚度係於5至2〇毫微米之範圍， 故總厚度減至25毫微米或以下，該厚度係小於習知厚度， 障壁層可具有習知氮化鈦薄膜之相同障壁特性及電阻值。 此外第一薄膜及第二薄膜可以反向順序沈積。 此外如第6(b)圖所示，氮化鈦薄膜具有三層構造。此 例中，四氣化鈦氣、氨氣及氧氣首先導入處理容器n内部 而形成含鈦、氧及氮之第一薄膜51於底層5〇上。隨後關閉 氧氣管路44及開啟膦氣管路而將四氣化鈦氣、氨氣及膦氣 導入處理容器11内部形成含鈦、氮及磷之第二薄膜52於第 一薄膜51上。隨後關閉膦氣管路45及開啟氧氣管路料再度 將四氯化鈦氣、氨氣及氧氣導入處理容器u而形成含鈦、 氧及氮之第三薄膜於第二薄膜52上。 經由形成此種三層構造，可改良對兩邊薄膜之障壁特 性，同時維持相等比電阻，且膜厚度係小於習知膜厚度。 — III ΙΊ I I Λι I I ·1111111 ^ »1111111— f請先閱讀背面之注意事項再填寫本頁}V. Description of the Invention (11 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs / Now referring to the drawings, the preferred embodiment of the present invention is described in detail below. Figure 1 shows the deposition of a nitrided series of thin films according to the present invention. The system i-plane deposition system has a cylindrical cylindrical airtight processing container 11, in which a sensor 12 is used to horizontally support a semiconductor crystal DW as an object to be processed. The wafer system configuration is simultaneously supported on a columnar support 13. On the outer edge of the sensor 12, a guide ring 14 is provided to guide the semiconductor wafer w. In addition, the heater 15 is embedded inside the sensor 12. When the power is supplied from the power supply to the battery, the device 15 Rishou, the heater 15 heats the semiconductor wafer w to be processed to a predetermined temperature. The power supply 16 is connected to the controller 17, and the controller controls the heater based on a signal from a temperature sensor (not shown) The output of 15. The top wall 11a of the processing container 11 is provided with a shower head 200. The shower head 20 has a plurality of gas discharge holes 20a and 20b formed thereon for discharging gas toward the sensor 12. Gas Supply Agency 30 The pipe is connected to the shower head 20. As detailed later, the pipe 45 for supplying titanium tetragas is connected to the gas discharge hole 20a, and the pipe 46 for supplying ammonia gas is connected to the gas discharge hole 20b. The head 20 is introduced into the processing vessel Η. In this way, the shower head 20 is a matrix-type shower head, and a post-mixing system is adopted, in which titanium tetrachloride and ammonia gas, which are reaction gases, are discharged through alternately formed discharge holes 20a and 20b The gas supply mechanism 30 has a trifluoride gas supply source 31 for supplying a clean gas trifluoride gas, a nitrogen supply source 32 for supplying nitrogen, and a titanium tetraoxide supply source 33 for supplying a reaction gas titanium tetraoxide. Phosphine supply source 34 is used to supply the paper size applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 14 J --- * ---- ^ -----------— II (Please read the notes on the back before filling out this page) 501191, printed by A7 B7 of the Consumer Cooperatives of the Intellectual Property Bureau of Zhaibei 5. Description of the invention (12) As a phosphorus-containing gas, the ammonia supply source 35 is used to supply A reactive gas containing nitrogen and hydrogen, and an oxygen supply source 36 for supplying Oxygen containing oxygen. In addition, the gas line 39 is connected to a chlorine trifluoride supply source 31, the gas line 40 is connected to a nitrogen supply source 32, the gas line 41 is connected to a tetragas titanium supply source 33, and the gas line 42 is connected to a phosphine supply source 34, a gas line 43 is connected to an ammonia supply source 35, and a gas line 44 is connected to an oxygen supply source 36. Pipes I to 39 are provided with a valve 47 and a mass flow controller 48. Nitrogen The gas line 40 extending from the supply source 32 meets the gas line 41 extending from the four-titanium-titanium supply 33, so the four-titanium-titanium gas carried in nitrogen flows through the gas line 40 and the duct 45 through the shower head The gas discharge hole 20a of 20 is introduced into the processing container 11. The gas line 39 extending from the trifluoride gas supply source 31 meets the gas line 40, so the trifluoride gas as the clean gas is passed from the gas discharge hole 20a through the gas lines 39 and 40 and the conduit 45 (by opening the setting Into the gas line 39) and introduced into the processing container 11. In addition, the ammonia gas is introduced into the processing container 11 through the gas discharge hole 20b of the shower head 20 through a gas pipe 43 and a pipe 46. The gas line 42 connected to the phosphine supply source 34 is connected to the gas line 41, so the phosphine gas is introduced into the inside of the processing container 11 through the gas discharge holes 20a of the shower head 20 through the gas lines 42, 41 and 40, and the conduit 45. The gas line 44 connected to the oxygen gas source 36 is connected to the gas line 43, so that oxygen is introduced into the processing container 11 through the gas discharge holes 20 b of the shower head 20 through the gas lines 44 and 43 and the conduit 46. In addition, as a nitrogen-containing gas and a hydrogen-containing gas, monomethylphosphonium (MMH) can be used instead of ammonia gas, or a nitrogen-containing gas and a hydrogen-containing gas can be used as a separate gas. The paper standard is applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) 15 _ Install · I order ------- I! Line (Please read the precautions on the back before filling this page) V. Description of the invention (13) Body introduction. In addition, as the oxygen-containing gas, a nitrogen monoxide gas or a nitrous oxide gas may be used instead of oxygen. In addition, argon can replace nitrogen. An exhaust pipe 18 is connected to the bottom wall lib of the processing container 11. An exhaust system 19 including a vacuum pump is connected to the exhaust pipe 18. By activating the exhaust system 19, the pressure of the processing container 11 can be reduced to a predetermined vacuum level. A method for depositing a titanium nitride series thin film on a semiconductor wafer W using this system will be described later. First, the semiconductor wafer W is mounted on the sensor 12 of the processing container 11. Then, when the wafer W is heated by the heater 15, the processing container is evacuated to the high-vacuum state by the exhaust system 19. Subsequently, nitrogen gas and ammonia gas are introduced into the processing vessel 11 at a predetermined flow ratio, so the pressure of the processing vessel is 133 to 1333 Baska for pre-annealing. Then, the pressure of the processing vessel 11 is changed to 13 3 to 133 Baska, maintaining the flow rate of nitrogen and ammonia, and at least one of the titanium tetragas and the oxygen and phosphine flows at a predetermined flow rate for about 5 to 20 seconds in advance. . The subsequent deposition of the titanium nitride series thin film is performed under the same conditions as the flow in advance. At this time, the titanium nitride series thin film is deposited at about 400 to 700. (: The temperature is performed. After deposition, the semiconductor wafer is discharged from the processing container u. Then, the tri-gas gas, which is a cleaning gas, is led into the processing container u to clean the inside of the processing container 11. When ammonia gas, titanium tetrachloride When the gas and oxygen are used in the aforementioned deposition as a processing gas, a titanium nitride series film (titanium oxynitride film) is formed, which contains cyanine, gas, and oxygen and has high barrier characteristics while maintaining relatively low resistance. In ancient times ---- I ----------- M -------- ^ ---- II (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 16 A7 5 Explanation of the invention (14), since the crystal of the titanium nitride thin film is a columnar crystal, intergranular diffusion easily occurs, so that metal or oxygen easily diffuses through the grain boundary of the nitride crystal. Therefore, if the titanium nitride thin film is borrowed The formation of thermal CVD using an oxygen-containing gas can improve the barrier properties of the grain boundaries of titanium nitride crystals. In this example, the volume of oxygen to ammonia is better than 0.0001 to 0.0000] of chromium 囹, lL Λ King υ · υυι Target range. So the resistance value is within the predetermined range. Order Figure 2 shows the flow The relationship between the specific resistance of oxygen / ammonia and titanium oxynitride film. In this example, the flow rate of titanium tetragas is 0 02 liters / minute, the flow rate of ammonia gas is G.5 liters / minute, and the flow rate of nitrogen gas is G15. L / min, and the oxygen flow rate is changed in the range of 5xl0-5 to 4xl0-3 liters / min (the flow rate is lower than that of oxygen / ammonia in the range of 0.000_ to 〇._). In addition, the substrate temperature during the deposition process It is 55 ° C, the processing container is willing to have 300 millitorr, and the film thickness is 50 nanometers. As shown in Figure 2, when the flow ratio oxygen / ammonia is in the above range, the ratio of the titanium oxide film is The resistance (resistance coefficient) value is in the range of 36 to 750,000 microohms · cm, which is an allowable range. In addition, even if another gas such as nitrogen oxide or nitrous oxide is used as the oxygen-containing gas, the resistance value is converted into The aforementioned range of oxygen is within an appropriate range. In addition, if the specific resistance value is about 700 microohms · cm or more, the barrier characteristics are good. Therefore, it can be seen from the second figure that the flow ratio oxygen / ammonia is 0.0006 or In the above, good barrier properties are obtained. Next, the formation of nitrides containing titanium, nitrogen, and phosphorus will be described. The method of series film (titanium-nitrogen phosphide film). This paper size is applicable to Chinese National Standard (CNS) A4 specification (21〇χ 297 mm 17) Printed by the Employees' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 501191 Α7 V. Description of the invention (l5 ) When ammonia gas, titanium tetrafluoride gas, and phosphine gas are used as the processing gas, a titanium oxide series film (titanium phosphorus phosphide film) is formed, which contains titanium, nitrogen, and phosphorus and has a low resistance value while maintaining relatively good barrier properties. Through the use of phosphine gas, the residual chlorine gas can be removed by the reduction function of the phosphine gas, so the resistance value of the titanium nitride series film can be reduced. In this example, the flow rate of the phosphine is in the range of 0.04 to 0.05 liters per minute. . If the flow rate is lower than 0 04 liters / minute, good results cannot be obtained. In addition, if the flow rate of the phosphine gas is 0 liters / minute or more, the formed film is amorphous and dense, so that the resistance can be reduced and the barrier characteristics are good. Fig. 3 shows the relationship between the flow rate of the phosphine gas and the specific resistance of the titanium nitride series thin film. In this example, the titanium tetrachloride gas flow rate is 0.02 liters / minute, the ammonia gas flow rate is 0.5 liters / minute, the nitrogen gas flow rate is 0.15 liters / minute, and the phosphine gas flow rate is varied from 0 to 0.2 liters / minute. In addition, during the deposition, the substrate temperature was from 43 ° to 550 ° C, the processing vessel pressure was 40 Baska, and the film thickness was 50 nm. As shown in Fig. 3, when the phosphine gas flow rate was 4,000 liters / minute, the resistance value clearly decreased. In addition, when the deposition temperature is 550 ° C, the resistance value tends to decrease even more. Taking deposition at 5501 as an example, when the phosphine gas flow rate is 0.2 liters / minute, 70 microohms · cm can be obtained, which is an extremely low value. In this case, the relationship between the deposition temperature and the specific resistance of the titanium nitride series thin film is shown in FIG. 4. As shown in Fig. 4, the dependence of specific resistance value and temperature when phosphine gas is added is smaller than when no phosphine gas is added, so the resistance value remains stable at a low value. In addition, in Fig. 4, the flow rate of the titanium tetragas is 0.02 liters / minute, the flow rate of the ammonia gas is 0.5 liters / minute, the flow rate of the nitrogen gas is 0.5 liters / minute, and the flow rate of the phosphine gas is 0.2 liters / minute. In addition, the pressure of the processing vessel is 40 Baska, and this paper size applies the Chinese National Standard (CNS) A4 specification (210 x 297 mm) ----- ^ --- Ί II ^ ill — — — — ^ «— — — 1 — (Please read the notes on the back before filling this page) 18 501191 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 Β7 V. Description of the invention (16) The thickness of the film is 50 nm. Next, the formation method of titanium nitride series thin film (oxygen titanium phosphide thin film) containing titanium, nitrogen, oxygen and phosphorus will be described. When ammonia gas, tetra-titanium gas, oxygen and phosphine gas are used for deposition as a processing gas, a nitrided series film (titanium oxynitride film) containing titanium, t, oxygen, and phosphorus can be obtained, which has a high barrier. Characteristics and low resistance characteristics. In other words, although the barrier characteristics are improved by supplying oxygen during the deposition process, as the amount of oxygen (flow rate is higher than oxygen / ammonia) increases, the resistance value increases (as shown in Figure 5). However, when phosphorus is introduced by supplying a phosphine gas, the resistance value is lower than that when phosphorus is not introduced. Therefore, a titanium nitride series thin film having high barrier characteristics and low resistance characteristics can be obtained. In addition, in Figure 5, the titanium tetrachloride gas flow rate is 0.02 liters / minute, the ammonia gas flow rate is 0.5 liters / minute, the nitrogen gas flow rate is 0.15 liters / minute, and the phosphine gas flow rate is between 0.2 liters / minute and The flow rate of oxygen was changed in the range of 10.5 to 1 × 10 3 liters / minute (the flow ratio of oxygen / ammonia was in the range of 10,000 to 0.001). In addition, the treatment vessel pressure was 40 Baska and the film thickness was 50 nm. During the aforementioned deposition process, a single titanium nitride series hafnium film was formed without changing the gas. On the other hand, if a stacked film including a plurality of titanium nitride series thin films is formed as follows, higher barrier characteristics can be obtained with a smaller thickness. Wait as shown in the sixth figure (tick diagram), the first disordered titanium gas, gas and oxygen are first introduced into the processing vessel η to form a first film 51 containing titanium, oxygen and nitrogen on the bottom layer 50. Then the oxygen tube is closed Road 44. The phosphine gas pipeline is opened and the four gaseous titanium gas, ammonia gas and phosphine gas are introduced into the processing container 11 to form a second paper standard containing titanium, nitrogen and phosphorus. The Chinese paper standard (CNS) A4 specification (210 χ 297 mm) ^ 1 — — — —！ — ·! II Repeat I (Please read the notes on the back before filling out this page) 19 A7 A7 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (17 ) The film 52 is on the first thin film 51. By forming such a double-layer structure, if the film thickness is smaller than the conventional film thickness, the barrier characteristics can be improved while maintaining the specific resistance value equal to the conventional specific electrical value. In this case The thickness of the first thin film 51 is preferably in the range of 1 to 10 μm, and the thickness of the second thin film 52 is preferably in the range of 3 to 50 ¾ μm. Especially when using the film as a barrier layer of a copper wiring layer, The thickness of the titanium hafnium film must be 50 nm or less. A good barrier effect is obtained on the top. If this stacked structure is formed, even if the thickness of the first film 51 (high barrier titanium oxynitride film) is in the range of 1 to 5 nm and the second film 52 (phosphorus-containing low resistance) The thickness of titanium nitride series film is in the range of 5 to 20 nanometers, so the total thickness is reduced to 25 nanometers or less. The thickness is less than the conventional thickness. The barrier layer may have the same thickness as the conventional titanium nitride film. Barrier characteristics and resistance values. In addition, the first film and the second film can be deposited in the reverse order. In addition, as shown in Figure 6 (b), the titanium nitride film has a three-layer structure. In this example, four gaseous titanium gas, Ammonia and oxygen are first introduced into the processing vessel n to form a first film 51 containing titanium, oxygen, and nitrogen on the bottom layer 50. Subsequently, the oxygen pipeline 44 and the phosphine gas pipeline are closed to dissolve the tetragas titanium gas and ammonia gas. And phosphine gas is introduced into the processing container 11 to form a second film 52 containing titanium, nitrogen, and phosphorus on the first film 51. Subsequently, the phosphine gas pipeline 45 is closed and the oxygen pipeline material is opened, and the titanium tetrachloride gas, ammonia gas, and Oxygen is introduced into the processing vessel u to form titanium, oxygen and nitrogen The third film is on the second film 52. By forming such a three-layer structure, the barrier characteristics of the two films can be improved, while maintaining the same specific resistance, and the film thickness is less than the conventional film thickness. — III ΙΊ II Λι II · 1111111 ^ »1111111— f Please read the notes on the back before filling in this page}

發明說明（18) 此種情況下，第一薄膜51及第三薄膜53之厚度較佳為1至10 亳微米而第二薄膜52之厚度較佳為3至50毫微米。此種三 層構造可有效用作為電容器部份之頂電極，具有絕緣層五 氧化二钽或氧化釕。 前述雙層及三層構造可在短時間内毫無困難形成，原 因在於各層唯有於相同系統内轉換氣體時才連續形成。 此外，於前述雙層及三層構造之任一例中，當形成第 一薄膜51及/或第三薄膜53時，含磷氣體可導入處理容器 内部。當形成含鈦、氧、氮及磷之薄膜時，或當形成第二 薄膜52時，若含氧氣體被導入處理容器内部，則可行成含 鈦、氧、氮及磷之薄膜。如此可進一步根據所得薄膜改良 特性。 如前述，根據本發明所得氮化鈦系列薄膜具有高障壁 特性及低電阻特性中之至少一者而適合用於金屬佈線層及 電容器頂電極之障壁層，即使具有單純構造或堆疊構造亦 如此。 根據本發明之氮化鈦系列薄膜實際上用作為薄膜構造 堆宜於另一層上。特別例如第7圖所示，含鈦、氧及氮之 薄膜’含鈦、氮及磷之薄膜以及含鈦、氧、氮及磷之薄膜 中之任一種氮化鈦薄膜55設置於第一層54與第二層％間。 此種薄膜構造可應用至半導體裝置各部份。例如接觸 層如鈦薄膜，石夕化鈦薄I切化㈣膜形成作為第一層^ 而根據本發明之氮㈣_55形成於其上。然後金制如 501191 A7 B7 五、發明說明（19) (請先閱讀背面之注意事項再填寫本頁) 鎢、Is或銅層應用作為佈線層或嵌置佈線部份形成於其上 作為第二層。此外，作為第一層54之矽化鈷薄膜可用作為 閘極電極，用作為佈線層之金屬層可透過根據本發明之氮 化鈦糸列薄膜電極作為障壁層而形成。此外，此種薄膜構 造可應用至DRAM之電容器部份或金屬閘極電極部份，容 後詳述。 當如此使用根據本發明之氮化鈦系列薄膜係藉CVD 形成時，於氮化鈦系列薄膜藉前述第1圖所示系統形成前（ 亦即導入氨氣、四氯化鈦氣及氧氣及/或膦氣前），或於氨 氣及膦氣之供應中止而完成形成薄膜後，或於二時間，含 氧氣體（前文第1圖所示系統之氧氣）被導入處理容器u内 部。特別例如鈦薄膜、矽化鈦薄膜及矽化鈷薄膜之第一層 首先藉PVD或CVD(電漿CVD或熱CVD)形成。隨後於藉 CVD形成氮化鈦系列薄膜前，氧氣被導入cvd處理容器 内部；以及於氮化鈦系列薄膜形成後再度導入氧氣。隨後 ’第二鋁、鎢或銅等金屬層係藉PVD或CVD(電漿CVD或 熱CVD)形成。此外可刪除氧氣導入之任一者。 經濟部智慧財產局員工消費合作社印製 於此時經由導入氧氣，薄氧化物膜形成於下方第一層 及/或氮化鈦系列薄膜上，故可提升對抗毗鄰第一層及/或 第二層之障壁特性。因此當形成含鈦、氧及氮之薄膜，以 及含鈥、氧、氮及磷之薄膜時，可減少氧量俾維持良好障 壁特性。此外，即使氮化鈦系列薄膜為前述堆疊膜，於薄 膜連續沈積於處理容器11之前及/或之後，經由導入含氧 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 22 501191 A7 B7 經澈部智慧財產局員工消費合作社印製(18) In this case, the thickness of the first film 51 and the third film 53 is preferably 1 to 10 μm and the thickness of the second film 52 is preferably 3 to 50 nm. This three-layer structure can be effectively used as a top electrode of a capacitor portion, and has an insulating layer of tantalum pentoxide or ruthenium oxide. The aforementioned two-layer and three-layer structures can be formed without any difficulty in a short time, because the layers are formed continuously only when the gas is switched in the same system. Further, in any of the foregoing two-layer and three-layer structures, when the first thin film 51 and / or the third thin film 53 are formed, a phosphorus-containing gas can be introduced into the processing container. When a thin film containing titanium, oxygen, nitrogen, and phosphorus is formed, or when a second thin film 52 is formed, if an oxygen-containing gas is introduced into the processing vessel, a thin film containing titanium, oxygen, nitrogen, and phosphorus is feasible. This further improves the characteristics of the obtained film. As described above, the titanium nitride series film obtained according to the present invention has at least one of high barrier characteristics and low resistance characteristics and is suitable for use as a barrier layer of a metal wiring layer and a capacitor top electrode, even if it has a simple structure or a stacked structure. The titanium nitride series thin film according to the present invention is actually used as a thin film construction stack suitable for another layer. In particular, as shown in FIG. 7, any one of the film including titanium, oxygen, and nitrogen, including the film including titanium, nitrogen, and phosphorus, and the film including titanium, oxygen, nitrogen, and phosphorus, is provided on the first layer. Between 54 and the second floor. This thin film structure can be applied to various parts of a semiconductor device. For example, a contact layer such as a titanium thin film, a titanium oxide thin film, and a titanium oxide thin film are formed as the first layer, and nitrogen hafnium_55 according to the present invention is formed thereon. Then gold system such as 501191 A7 B7 V. Description of the invention (19) (Please read the notes on the back before filling this page) Tungsten, Is or copper layer should be used as the wiring layer or embedded wiring part formed on it as the second Floor. In addition, a cobalt silicide film as the first layer 54 can be used as a gate electrode, and a metal layer used as a wiring layer can be formed through the titanium nitride queue thin film electrode according to the present invention as a barrier layer. In addition, such a thin film structure can be applied to a capacitor portion or a metal gate electrode portion of a DRAM, which will be described in detail later. When the titanium nitride series thin film according to the present invention is thus formed by CVD, before the titanium nitride series thin film is formed by the system shown in the aforementioned FIG. 1 (that is, ammonia gas, titanium tetrachloride gas, oxygen gas, and / Or before the phosphine gas), or after the supply of ammonia and phosphine gas is stopped and the film formation is completed, or at two hours, an oxygen-containing gas (oxygen of the system shown in Fig. 1 above) is introduced into the processing container u. In particular, the first layer of a titanium film, a titanium silicide film, and a cobalt silicide film is first formed by PVD or CVD (plasma CVD or thermal CVD). Subsequently, oxygen is introduced into the cvd processing container before the titanium nitride series thin film is formed by CVD; and oxygen is introduced again after the titanium nitride series thin film is formed. Subsequently, a second metal layer such as aluminum, tungsten, or copper is formed by PVD or CVD (plasma CVD or thermal CVD). In addition, any one of the oxygen introductions can be deleted. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed at this time through the introduction of oxygen, a thin oxide film was formed on the first layer and / or titanium nitride series film below, so it can improve the resistance to the adjacent first layer and / or the second Layer barrier properties. Therefore, when forming a thin film containing titanium, oxygen, and nitrogen, and a thin film containing ", oxygen, nitrogen, and phosphorus, the amount of oxygen can be reduced and good barrier characteristics can be maintained. In addition, even if the titanium nitride series thin film is the aforementioned stacked film, before the thin film is continuously deposited on the processing container 11 and / or after the oxygen-containing paper is introduced, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applied. 22 501191 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Che

五、發明說明（20) 氣體可獲得此種效果。 參照第8(a)至第8(c)圖，後為說明根據本發明之氮化 鈦系列薄膜實例，其用作為金屬佈線層接觸部件。 第8(a)圖所示實例中，層間電介質薄膜61形成於矽基 材60上，接觸孔62向下延伸至矽基材6〇之雜質擴散區6〇a ，接觸孔形成於層間電介質層61。於層間電介質膜61及接 觸孔62表面上，形成鈦薄膜63及根據本發明之氮化鈦系列 薄膜64。於氮化鈦系列薄膜64上形成銅或鎢之金屬佈線層 66。金屬佈線層66也填補接觸孔62，故建立石夕基材6〇之雜 質擴散區60a與金屬佈線層66間的導通狀態。 因氮化鈦系列薄膜64具有比習知氮化鈦薄膜更高的障 壁特性，故存在有氮化鈦系列薄膜64可極為有效防止銅或 鎢與矽反應形成的化合物。此外因氮化鈦系列薄膜64具有 此種高障壁特性，故可極為有效防止氣氣的擴散。氮化鈦 系列薄膜64較佳為氧氮化鈦薄膜或氧氮磷化鈦薄膜俾獲得 高障壁特性。此外可使用氮磷化鈦薄膜，原因在於當該薄 膜為非晶形時具有相對較高障壁特性。此種情況下，並非 經常需要提供鈦薄膜63。 第8(b)圖顯示實例中，類似第8(a)圖顯示實例，層間 電介質膜61形成於矽基材60上，接觸孔62向下伸展至矽基 材60及雜質擴散區60a，接觸孔62形成於層間電介質層61 。於層間電介質膜61與接觸孔62之表面上，設置含鈦薄膜 69其具有氮磷化鈦薄膜67以及氧氮化鈦薄膜68的雙重堆疊 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I III — — — ^ - I I I I I I I ^ — — — — — — I (請先閱讀背面之注意事項再填寫本頁) 期191 經濟部智慧財產局員工消費合作社印製 A7 B7 i、發明說明（21) 構造。於Ml化欽糸列薄膜6 9上’形成銅或嫣製成之金屬佈 線層66。金屬佈線層66也填補於接觸孔62，故建立石夕基材 60之雜質擴散區60a與金屬佈線層66間的導通狀態。如此 ’氮填化鈦薄膜6 7作為接觸層，而氧氮化鈦薄膜$ $作為障 壁層，故可獲得比習知鈦/氮化鈦薄膜更優異的特性。 第8(c)圖所示實例中，類似第8(a)圖所示實例，層間 電介質膜61形成於石夕基材60上，接觸孔62向下伸展至石夕基 材60之雜質擴散區60a，接觸孔62形成於層間電介質層61 。於接觸孔62形成氮磷化鈦薄膜之嵌置佈線層（插塞）7〇， 以及經由氧氮化鈥障壁層71形成銅或嫣之金屬佈線層72於 其上。如前述，氮磷化鈦薄膜具有低電阻，如此可用作為 嵌置佈線層。 此外’金屬佈線層66及72可由銅及嫣以外之任一種金 屬或合金製成。此外金屬佈線層66及72除了接觸孔部份外 ，也可施用至導通至其它導電層的通孔部份。 參照第9(a)至9(c)圖，後文說明根據本發明之氮化鈦 系列薄膜應用至DRAM等之電容器構造實例。 第9(a)圖所示實例中，非晶形矽製成之底電極層81連 結至石夕基材80之雜質擴散區80a ^底電極層81上，透過氣 化矽障壁層82形成五氧化二钽或氧化釕之絕緣層83，氮化 矽障壁層係藉矽之快速熱氮化（RTN)方法製成。於絕緣層 83上，形成根據本發明之氮化鈦系列薄膜之頂電極層84。 於頂電極層84上形成金屬佈線層（圖中未顯示）。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 24 -----^--1.---1^1 裝--------訂------ (請先閱讀背面之注意事項再填寫本頁) 丄夕丄 丄夕丄 五 經濟部智慧財產局員工消費合作社印製 A7 " ----______ 發明說明（22) 、，氮化鈦薄膜用作頂電極層84。但有問題，後處理 過歡加熱處理造成五氧化二崔旦之氧擴散入氮化鈦薄膜而 改變成氧化鈦，故氮化鈦薄膜厚度縮小五氧化二經厚度加 大而使電容降低。此種問題可經由使用根據本發明之氣化 鈦系列薄膜之頂電極84解決。此例中，組成頂電極Μ之氮 化鈦系列薄膜較佳為氧氮化鈦薄膜或氧氮碟化欽薄膜俾保 有冋P早壁特性。此外，若設置氮化欽系列薄膜及氮碟化欽 薄膜之堆疊構造’則可獲得良好障壁特性’同時維持尋常 比電阻，即使堆疊構造之厚度小亦如此。此外，提供氧氮 化鈦薄膜或氧氮磷化鈦薄膜/氮磷化鈦薄膜/氧氣化欽薄膜 或氧氮碟化鈦薄膜之三層堆疊構造，可有效防止頂電極層 84兩邊之氧氣及金屬擴散。 第9(b)圖所示實例之基本構造同第9(幼圖所示實例。 但於第9(b)圖所示實例中，形成根據本發明之氮化鈦系列 薄膜障壁層85替代底電極層81上的氮化矽障壁層82。組成 障壁層85之氮化鈦系列薄膜較佳為氧氮化鈦薄膜或氧氮磷 化鈦薄膜俾保有高度障壁特性。此外，也可使用氮化鈦系 列薄膜及氮磷化鈦薄膜之堆疊構造。 雖然根據本發明之氮化鈦系列薄膜可應用至金屬隔離 矽（MIS)構造，但根據本發明之氮化鈦系列薄膜也可應用 至使用金屬如釕替代底電極之非晶形矽之金屬隔離金屬 (MIM)構造。此外，根據本發明之氮化鈦系列薄膜可用作 為具有MIM構造之底電極。此例顯示於第9(c)圖。本實例 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） — — — — — ί — !! * I! t · I ! !馨 (請先閱讀背面之注意事項再填寫本頁) 25 501191 經濟部智慧財產局員工消費合作社印製 Α7 Β7 五、發明說明（23) 中，設置氮磷化鈦薄膜之底電極86替代非晶形矽之底電極 81。於底電極86上，提供氧氮化鈦薄膜或氧氮磷化鈦薄膜 P早壁層87。此外絕緣層83及頂電極層84具有第9(a)及9(b) 圖所述實例之相同構造。 第8(a)至8(c)及第9(a)至9(c)圖所述實例中，根據本發 明之氮化鈦系列薄膜及五氧化二鈕或氧化釕之金屬佈線層 或絕緣層可使用第10圖所示叢集工具類型方法系統連續沈 積。此種系統包含：一移送腔室9〇其係設置於中心；以及 二匣式容器91及92，一除氣容器93, 一沈積單元97, 一前 置清潔單元95，一沈積單元96，一沈積單元97及一冷卻容 98 ’其係配置ί哀繞移送腔室9〇周圍。此外，半導體晶圓 W利用設置於移送腔室9〇之移送臂99而導入容器及由容器 排放。 此種沈積系統中，設置沈積單元94、96及97之一用以 形成根據本發明之氮化鈦系列薄膜，設置其它單元用以形 成五氧化二钽或氧化釕之金屬佈線層或絕緣層。以沈積方 法作業為例，第9(b)圖所示電容器構造之形成說明如後。 首先，利用移送臂99由匣式容器91中取出半導體晶圓 W，欲導入前置清潔單元95俾藉三氣化溴去除表面上的氧 化物等。如此半導體晶圓W利用移送臂99導入除氣容器93 而除氣晶圓。隨後根據本發明之氮化鈦系列薄膜障壁層利 用沈積單元94、96及97中之任一者沈積於半導體晶圓…上 。隨後晶圓W利用臂99被導入另一沈積單元内部，同時維 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 26 ----一---.----裝-----丨· —訂------ (請先閱讀背面之注意事項再填寫本頁)5. Description of the invention (20) Gas can obtain this effect. Referring to Figures 8 (a) to 8 (c), an example of the titanium nitride series thin film according to the present invention will be described later, which is used as a metal wiring layer contact member. In the example shown in FIG. 8 (a), the interlayer dielectric film 61 is formed on the silicon substrate 60, the contact hole 62 extends downward to the impurity diffusion region 60a of the silicon substrate 60, and the contact hole is formed in the interlayer dielectric layer. 61. On the surfaces of the interlayer dielectric film 61 and the contact hole 62, a titanium thin film 63 and a titanium nitride series thin film 64 according to the present invention are formed. A metal wiring layer 66 of copper or tungsten is formed on the titanium nitride series thin film 64. The metal wiring layer 66 also fills the contact hole 62, so that a conductive state between the impurity diffusion region 60a of the stone substrate 60 and the metal wiring layer 66 is established. Since the titanium nitride series thin film 64 has higher barrier characteristics than the conventional titanium nitride thin film, there is a compound which can extremely effectively prevent copper or tungsten from reacting with silicon. In addition, because the titanium nitride series thin film 64 has such a high barrier property, it is possible to extremely effectively prevent the diffusion of gas. The titanium nitride series thin film 64 is preferably a titanium oxynitride thin film or a titanium oxynitride phosphorous thin film, to obtain high barrier properties. In addition, a titanium nitrogen phosphide film can be used because it has relatively high barrier characteristics when the film is amorphous. In this case, it is not always necessary to provide the titanium film 63. In the example shown in FIG. 8 (b), similar to the example shown in FIG. 8 (a), an interlayer dielectric film 61 is formed on the silicon substrate 60, and the contact hole 62 extends downward to the silicon substrate 60 and the impurity diffusion region 60a. The hole 62 is formed in the interlayer dielectric layer 61. On the surfaces of the interlayer dielectric film 61 and the contact hole 62, a titanium-containing film 69 having a dual stack of a titanium nitride phosphide film 67 and a titanium oxynitride film 68 is provided. This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) I III — — — ^-IIIIIII ^ — — — — — — I (Please read the notes on the back before filling out this page) Issue 191 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 i, SUMMARY OF THE INVENTION (21) Construction. A metal wiring layer 66 made of copper or copper is formed on the Ml thin film 69. The metal wiring layer 66 is also filled in the contact hole 62, so that the conduction state between the impurity diffusion region 60a of the stone substrate 60 and the metal wiring layer 66 is established. In this way, the nitrogen-filled titanium film 67 is used as the contact layer, and the titanium oxynitride film is used as the barrier layer, so it can obtain more excellent characteristics than the conventional titanium / titanium nitride film. In the example shown in FIG. 8 (c), similar to the example shown in FIG. 8 (a), an interlayer dielectric film 61 is formed on the Shixi substrate 60, and the contact hole 62 extends downward to the impurity diffusion of the Shixi substrate 60 In the region 60 a, a contact hole 62 is formed in the interlayer dielectric layer 61. An embedded wiring layer (plug) 70 of a titanium nitride phosphide film is formed in the contact hole 62, and a copper or copper metal wiring layer 72 is formed thereon via the oxynitride barrier layer 71. As mentioned above, the titanium nitride phosphide film has low resistance, and thus can be used as an embedded wiring layer. In addition, the metal wiring layers 66 and 72 may be made of any metal or alloy other than copper and copper. In addition to the contact hole portions, the metal wiring layers 66 and 72 may be applied to the through hole portions that are conducted to other conductive layers. Referring to Figures 9 (a) to 9 (c), an example of a capacitor structure in which the titanium nitride series thin film according to the present invention is applied to a DRAM or the like will be described later. In the example shown in FIG. 9 (a), the bottom electrode layer 81 made of amorphous silicon is connected to the impurity diffusion region 80a of the Shixi substrate 80. The bottom electrode layer 81 is formed through the vaporized silicon barrier layer 82 to form a pentoxide. An insulating layer 83 of tantalum or ruthenium oxide, and a silicon nitride barrier layer are formed by a rapid thermal nitridation (RTN) method of silicon. On the insulating layer 83, a top electrode layer 84 of a titanium nitride series thin film according to the present invention is formed. A metal wiring layer (not shown) is formed on the top electrode layer 84. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 24 ----- ^-1 .--- 1 ^ 1 Packing -------- Order ---- -(Please read the precautions on the back before filling this page) 丄 夕 丄 丄 夕 丄 5 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 " ----______ Invention Description (22), Titanium Nitride A thin film is used as the top electrode layer 84. However, there is a problem. After post-treatment overheating treatment, the oxygen of Cui Dan pentoxide diffuses into the titanium nitride film and changes to titanium oxide. Therefore, the thickness of the titanium nitride film is reduced, and the capacitance is decreased by the thickness of the pentoxide. Such a problem can be solved by using the top electrode 84 of the vaporized titanium series thin film according to the present invention. In this example, the titanium nitride series film constituting the top electrode M is preferably a titanium oxynitride film or an oxynitride disc film, which has the characteristics of early wall of P. In addition, if a stacked structure of a nitride film and a nitride film is provided, a good barrier property can be obtained, while maintaining the ordinary specific resistance, even if the thickness of the stacked structure is small. In addition, a three-layer stack structure of titanium oxynitride film or titanium oxynitride phosphide film / titanium oxynitride phosphide film / oxygenation film or titanium oxynitride disk film can be provided to effectively prevent oxygen and oxygen on both sides of the top electrode layer 84. Metal diffusion. The basic structure of the example shown in Fig. 9 (b) is the same as that shown in Fig. 9 (young figure. However, in the example shown in Fig. 9 (b), a titanium nitride series thin film barrier layer 85 according to the present invention is formed instead of the bottom The silicon nitride barrier layer 82 on the electrode layer 81. The titanium nitride series film constituting the barrier layer 85 is preferably a titanium oxynitride film or a titanium oxynitride phosphide film, which has a high barrier property. In addition, nitride may also be used. Stacked structure of titanium series thin film and titanium nitride phosphide film. Although the titanium nitride series thin film according to the present invention can be applied to a metal isolation silicon (MIS) structure, the titanium nitride series thin film according to the present invention can also be applied to a metal using For example, ruthenium replaces the metal-isolated metal (MIM) structure of the amorphous silicon of the bottom electrode. In addition, the titanium nitride series thin film according to the present invention can be used as a bottom electrode with a MIM structure. This example is shown in Figure 9 (c). Example This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) — — — — — ί — !! * I! T · I!! Xin (Please read the precautions on the back before filling this page ) 25 501191 Employee Consumption Printed by the agency A7 B7 5. In the description of the invention (23), a bottom electrode 86 of a titanium oxynitride film is provided instead of the bottom electrode 81 of amorphous silicon. On the bottom electrode 86, a titanium oxynitride film or oxynitride is provided. The titanium thin film P early wall layer 87. In addition, the insulating layer 83 and the top electrode layer 84 have the same structure as the example shown in Figs. 9 (a) and 9 (b). 8 (a) to 8 (c) and 9 ( In the examples shown in a) to 9 (c), the titanium nitride series thin film and the metal wiring layer or insulating layer of the two pentoxide or ruthenium oxide according to the present invention can be continuously performed using the cluster tool type method shown in FIG. 10 This system includes: a transfer chamber 90, which is set at the center; and two cassette containers 91 and 92, a degassing container 93, a deposition unit 97, a front cleaning unit 95, and a deposition unit 96 A deposition unit 97 and a cooling capacity 98 'are arranged around the transfer chamber 90. In addition, the semiconductor wafer W is introduced into the container and discharged from the container by a transfer arm 99 provided in the transfer chamber 90. In such a deposition system, one of the deposition units 94, 96, and 97 is provided to form a titanium nitride series according to the present invention. The film is provided with other units to form a metal wiring layer or an insulating layer of tantalum pentoxide or ruthenium oxide. Taking the operation of the deposition method as an example, the formation of the capacitor structure shown in Fig. 9 (b) is described later. First, use transfer The arm 99 is taken out of the semiconductor wafer W from the cassette container 91, and is intended to be introduced into the front cleaning unit 95 to remove oxides on the surface by using trigas bromine. Thus, the semiconductor wafer W is introduced into the degassing container 93 by using the transfer arm 99 and Outgassing wafer. The titanium nitride series thin film barrier layer according to the present invention is then deposited on a semiconductor wafer using any one of the deposition units 94, 96, and 97. Subsequently, the wafer W was introduced into another deposition unit by using the arm 99, and the dimension of the paper was adapted to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 26 ---- 一 ---.---- Install ----- 丨 · --Order ------ (Please read the precautions on the back before filling this page)

五、發明說明（24) 經濟部智慧財產局員工消費合作社印製V. Description of the invention (24) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

持真空態而形成五氧化二钽絕緣層。隨後晶圓W被導入第 一沈積單元内部而沈積根據本發明之氮化鈦系列薄膜之頂 電極層。視情況而定，晶圓w被導入另一沈積腔室内部而 形成金屬佈線層於頂電極上。如此完成預定沈積處理，及 然後半導體晶圓W利用罩於匣式容器92内部的冷卻容器98 冷卻。 參照第11(a)、11(b)及12圖，後文說明根據本發明之 氮化鈦系列薄膜應用至閘極電極之實例。 第11(a)圖之實例中，包含多晶矽膜1〇2及氮磷化鈦薄 膜103於其上的閘極電極104經由絕緣膜ι〇1設置於矽基材 100上。於氮磷化鈦薄膜103上形成鎢佈線層1〇6。換言之 ’習知多晶矽及矽化鎢（WSi)之雙層構造閘極電極的矽化 鶴由氮磷化鈦置換。此外參考編號丨05表示氮化矽之間隔 件。因用於閘極電極的氮磷化鈦具有低電阻及絕佳障壁特 性且為熱穩定性，故第丨1(a)圖之構造具有比習知多晶矽 及矽化鎢雙層構造閘極電極更優異的特性。此外若為非晶 形，則可進一步提升障壁特性，故可獲得更佳特性。特別 可達成較高速度，且可縮小薄膜厚度。習知多晶矽及矽化 鎢雙層構造之閘極電極之多晶矽及矽化鎢（WSi)厚度為100 毫微米，故總厚度為200亳微米。它方面，氮磷化鈦層於 多晶石夕上厚度為10至50亳微米，故總厚度係kuosmo毫 微米之範圍，其遠比習知雙層構造閘極電極的厚度更薄。 當鼠磷化鈥為非晶形俾改良障壁特性時，厚度特薄。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公髮） -------------裝--------訂！！線 (請先閱讀背面之注意事項再填寫本頁) 27 經濟部智慧財產局員工消費合作社印製 A7 -----------—B7 ___:___ 五、發明說明（25) 第11(_之實例中，提供僅含氮魏鈦薄膜之間極 電極107替代第n⑷圖之閘極電極1()4。如前述，氮碟化 欽薄膜具有低電阻、高熱電阻及絕佳障壁特性。因此單獨 鼠碟化鈦薄膜也可獲得類似多晶碎/氮魏鈦生成構造作 為閘極電極的絕佳特性。本例中，氮碟化欽間極電極107 厚度足夠與約20毫微米至約50亳微米之範圍，故可實現極 薄的閘極電極。如此又於單獨氮磷化鈦層之例，特別可藉 使氮磷化鈦層變成非晶形改良障壁特性而縮小厚度。 此外，於第12(a)圖之實例，使用矽化鈷薄膜之閘極 電極108，鎢佈線層1〇6經由障壁層1〇9形成其上，障壁層 為根據本發明藉CVD形成的氮化鈦系列薄膜障壁層。矽 化鈷薄膜具有低電阻，可獲得作為閘極電極的絕佳特性， 故可縮小閘極電極本身厚度。此外經由根據本發明之氮化 鈦系列薄膜之障壁層109，可獲得絕佳障壁特性。 第12(b)圖之實例中，BST，PZT(錯（錘、鈦）〇3 :鍅酸 鈦酸鉛），五氧化二钽或氧化釕之高電介質材料之絕緣層 101形成於矽基材100上。然後根據本發明之CVD氮化鈦 系列薄膜障壁層110形成其上，銘、鎢或銅之金屬閘極電 極1Π形成其上。第12(b)圖中，參考編號112及Η3分別表 示源極及汲極。此種構造為可響應加速反應的構造。根據 本發明之CVD氮化鈦系列薄膜障壁層114可有效防止閘極 電極111與高電介質材料絕緣層110間之相對擴散。 根據本發明之氮化鈦系列薄膜實例，應用至接觸構造 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 28 ^ .---Μ--------^-----I (請先閱讀背面之注意事項再填寫本頁)A vacuum state is formed to form a tantalum pentoxide insulation layer. The wafer W is then introduced into the first deposition unit to deposit the top electrode layer of the titanium nitride series thin film according to the present invention. Depending on the situation, the wafer w is introduced into another deposition chamber to form a metal wiring layer on the top electrode. The predetermined deposition process is thus completed, and then the semiconductor wafer W is cooled by the cooling container 98 housed inside the cassette container 92. Referring to Figs. 11 (a), 11 (b), and 12, an example in which the titanium nitride series thin film according to the present invention is applied to a gate electrode will be described later. In the example of FIG. 11 (a), a gate electrode 104 including a polycrystalline silicon film 102 and a titanium nitride phosphide film 103 thereon is provided on a silicon substrate 100 via an insulating film ι01. A tungsten wiring layer 106 is formed on the titanium nitride phosphide film 103. In other words, the conventional double-layered gate electrodes of polycrystalline silicon and tungsten silicide (WSi) are replaced by titanium nitride phosphide. In addition, reference numeral 05 indicates a spacer of silicon nitride. Because titanium nitride phosphide used for the gate electrode has low resistance, excellent barrier properties and thermal stability, the structure in Figure 1 (a) has more advantages than the conventional polycrystalline silicon and tungsten silicide double-layered gate electrode. Excellent characteristics. In addition, if it is amorphous, the barrier characteristics can be further improved, so better characteristics can be obtained. In particular, higher speeds can be achieved and film thickness can be reduced. It is known that the thickness of polycrystalline silicon and tungsten silicide (WSi) of the gate electrode with a double-layer structure of polycrystalline silicon and tungsten silicide is 100 nanometers, so the total thickness is 200 μm. On the other hand, the thickness of the titanium nitride phosphide layer on the polycrystalline stone is 10 to 50 μm, so the total thickness is in the range of kuosmo nanometers, which is much thinner than the thickness of the conventional double-layered gate electrode. When the rat's phosphorylation is amorphous, the thickness is extremely thin. This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 issued) ------------- Installation -------- Order! !! (Please read the notes on the back before filling out this page) 27 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ------------- B7 ___: ___ V. Description of Invention (25) Article In the case of 11 (_, an electrode 107 with only nitrogen-containing titanium film is provided instead of the gate electrode 1 () 4 in the nth figure. As mentioned above, the nitrogen-dissolved thin film has low resistance, high thermal resistance, and excellent barriers. Characteristics. Therefore, a single mouse-disc titanium film can also obtain excellent characteristics similar to a polycrystalline broken / nitrogen-titanium generation structure as a gate electrode. In this example, the thickness of the nitrogen-disc interelectrode 107 is sufficient to be about 20 nm. In the range of about 50 μm, it is possible to realize a very thin gate electrode. In the case of a separate titanium nitrogen phosphide layer, the thickness can be reduced by making the titanium nitrogen phosphide layer amorphous to improve the barrier characteristics. In the example of FIG. 12 (a), a gate electrode 108 of a cobalt silicide film is used, and a tungsten wiring layer 10 is formed thereon via a barrier layer 109, and the barrier layer is titanium nitride formed by CVD according to the present invention. Series thin film barrier layer. Cobalt silicide film has low resistance and can be used as a gate electrode Excellent characteristics, so the thickness of the gate electrode itself can be reduced. In addition, the excellent barrier characteristics can be obtained through the barrier layer 109 of the titanium nitride series thin film according to the present invention. In the example in FIG. 12 (b), BST, PZT ( False (hammer, titanium) 〇3: lead titanate titanate), an insulating layer 101 of a high dielectric material of tantalum pentoxide or ruthenium oxide is formed on a silicon substrate 100. Then, a CVD titanium nitride series thin film according to the present invention The barrier layer 110 is formed thereon, and a metal gate electrode 1Π of indium, tungsten, or copper is formed thereon. In FIG. 12 (b), reference numerals 112 and Η3 indicate a source electrode and a drain electrode, respectively. This structure is responsive to acceleration Reactive structure. The CVD titanium nitride series thin film barrier layer 114 according to the present invention can effectively prevent the relative diffusion between the gate electrode 111 and the high dielectric material insulating layer 110. According to the example of the titanium nitride series thin film of the present invention, it is applied to contact Structure This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 28 ^ .--- M -------- ^ ----- I (Please read the precautions on the back first (Fill in this page again)

發明說明（26) A7 B7 ------- 用以於半導體基材主面形成的擴散區形成佈線，容後詳述 。第13圖之實例中，碎化鈦薄膜切化㈣膜之接觸層122 形成於擴散區（源極或汲極）12卜其係形成时基材⑶之 主面。然後根據本發明之氮化鈦系列薄膜障壁層123形成 其上，鋁、鎢或鋼佈線層124形成其上。此種情況下，因 石夕化鈦薄膜及石m薄膜具有低電阻，故此等薄膜具有作 為接觸層的良好特性，可藉根據本發明之氮化鈦系列薄膜 獲得良好障壁特性，故可獲得具有極佳特性之接觸構造。 此外參考編號12 5表示閘極電極。 此外’本發明非僅限於前述較佳具體實施例反而可以 多種方式修改。例如各方法及條件僅供舉例說明，故根據 該方法可適當設定製程條件。此外使用的基材非僅限於半 導體晶圓而可為其它基材。此外其它層可形成於基材表面 。此外’雖然於前述較佳具體實施例係藉熱CVD沈積氮 化鈦系列薄膜，但本發明非僅限於此反而可使用其它Cvd 。但若熱CVD用於沈積，則可相對容易形成氮化鈦系列 薄膜而無需任何複雜處理，故熱CVD較佳用於沈積。 雖然已經藉較佳具體實施例揭示本發明俾輔助更清楚 明白’但須了解本發明可未悖離本發明之原理以多種方式 具體表現。因此須了解本發明包括未悖離如隨附之申請專 利範圍陳述之本發明之原理具體表現之全部可能的具體實 施例及所示具體實施例之修改。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I 1—! — · t - I! — 屢· I (請先閱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 29 501191 A7 B7 五、發明說明（27 ) 元件標號對照 經濟部智慧財產局員工消費合作社印製 11…處理容器 45-6…管路 11 a…頂壁 4 7…閥 lib…底壁 48···質量流量控制器 12…感測器 5〇…底層 13…支持件 51 ···第一薄膜 14…導環 52…第二薄膜 15…加熱器 53…第三薄膜 16…電源供應器 54…第一層 Π…控制器 55…氮化鈦薄膜 18…氣體排放管 56···第二層 19…氣體排放系統 60…矽基材 20…喷淋頭 60a…雜質擴散區 20a-b···氣體排放孔 61…層間電介質薄膜 30…氣體供應機構 62…接觸孔 31…氟化氯供應源 63…鈦薄膜 32…氮供應源 64···氮化鈦系統薄膜 33…四氣化銥供應源 66…金屬佈線層 34…膦供應源 67…氮磷化鈦薄膜 35…氨供應源 68…氧氮化鈦薄膜 36…氧供應源 69…含鈦薄膜 39·44…氣體管線 71…氧氮化鈦障壁層 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 30 501191 A7 B7 五、發明說明（28) 經濟部智慧財產局員工消費合作社印製 72…金屬佈線層 80…砍基材 80a···雜質擴散區 81…底電極層 82…氮化矽障壁層 83···絕緣層 84…頂電極層 85…障壁層 86…底電極 87…障壁層 90…移送腔室 91-2…匣式容器 93…除氣容器 94…沈積單元 95…前置清潔單元 96-7···沈積單元 98…冷卻容器 99…移送臂 100…碎基材 101···絕緣膜 102···多晶矽薄膜 103···氮磷化鈦薄膜 104···閘極電極 105···氮化矽間隔件 10 6…嫣佈線層 10 7 - 8…閘極電極 10 9…障壁層 110…絕緣層 111…閘極電極 112…源極 113…汲極 114…障壁層 120…碎基材 121···擴散區 122…接觸層 123···障壁層 124···佈線層 125…閘極電極 -------------裝--------訂------線 (請先閱讀背面之注意事項再填寫本頁) 31 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）Description of the invention (26) A7 B7 ------- It is used to form wiring on the diffusion region formed on the main surface of the semiconductor substrate, which will be described in detail later. In the example of FIG. 13, the contact layer 122 of the shredded titanium film and the ytterbium film is formed on the diffusion region (source or drain) 12, which is the main surface of the substrate ⑶ when it is formed. Then, a titanium nitride series thin film barrier layer 123 according to the present invention is formed thereon, and an aluminum, tungsten or steel wiring layer 124 is formed thereon. In this case, because the Shixihua titanium film and Shim film have low resistance, these films have good characteristics as a contact layer, and good barrier properties can be obtained by the titanium nitride series film according to the present invention, and thus can be obtained with Excellent contact structure. Further, reference numeral 12 5 denotes a gate electrode. In addition, the present invention is not limited to the foregoing preferred embodiments, but may be modified in various ways. For example, each method and condition is for illustration only, so the process conditions can be appropriately set according to this method. In addition, the substrate used is not limited to semiconductor wafers but may be other substrates. In addition, other layers may be formed on the surface of the substrate. In addition, although the titanium nitride series thin film is deposited by thermal CVD in the foregoing preferred embodiment, the present invention is not limited to this but other Cvd may be used. However, if thermal CVD is used for deposition, it is relatively easy to form a titanium nitride series thin film without any complicated processing, so thermal CVD is preferably used for deposition. Although the present invention has been disclosed by means of preferred embodiments, and is more clearly understood, it must be understood that the present invention can be embodied in various ways without departing from the principles of the present invention. It is therefore to be understood that the invention includes all possible specific embodiments that do not depart from the principles of the invention as set forth in the scope of the appended patent application, as well as modifications of the specific embodiments shown. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) I 1—! — · T-I! — Repeatedly I (Please read the notes on the back before filling this page) Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives 29 501191 A7 B7 V. Description of the invention (27) The component numbers are printed with the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 11… Processing container 45-6… Piping 11 a… Top wall 4 7… ... bottom wall 48 ... mass flow controller 12 ... sensor 50 ... bottom layer 13 ... support 51 ... first film 14 ... guide ring 52 ... second film 15 ... heater 53 ... third film 16 ... power supply 54 ... first layer Π ... controller 55 ... titanium nitride film 18 ... gas exhaust pipe 56 ... second layer 19 ... gas exhaust system 60 ... silicon substrate 20 ... spray head 60a ... impurity diffusion Zones 20a-b ... Gas discharge holes 61 ... Interlayer dielectric film 30 ... Gas supply mechanism 62 ... Contact hole 31 ... Chloride fluoride supply 63 ... Titanium film 32 ... Nitrogen supply 64 ... Titanium nitride system film 33 … Quadurized iridium supply source 66… metal wiring layer 34… phosphine supply Source 67 ... Titanium nitride phosphide film 35 ... Ammonia supply source 68 ... Titanium oxynitride film 36 ... Oxygen supply source 69 ... Titanium containing film 39 · 44 ... Gas line 71 ... Titanium oxynitride barrier film Standard (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back before filling out this page) 30 501191 A7 B7 V. Description of invention (28) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 72 ... Metal Wiring layer 80 ... cutting substrate 80a ... impurity diffusion region 81 ... bottom electrode layer 82 ... silicon nitride barrier layer 83 ... insulating layer 84 ... top electrode layer 85 ... barrier layer 86 ... bottom electrode 87 ... barrier layer 90 ... transfer chamber 91-2 ... cassette container 93 ... degassing container 94 ... deposition unit 95 ... front cleaning unit 96-7 ... deposition unit 98 ... cooling container 99 ... transfer arm 100 ... crushed substrate 101 ... · Insulation film 102 ·· Polycrystalline silicon film 103 ·· Titanium nitride phosphide film 104 ··· Gate electrode 105 ··· Silicon nitride spacer 10 6… Wiring layer 10 7-8… Gate electrode 10 9 ... the barrier layer 110 ... the insulating layer 111 ... the gate electrode 112 ... the source 113 ... the drain 114 ... the barrier layer 120 ... Base material 121 ... Diffusion region 122 ... Contact layer 123 ... Barrier layer 124 ... Wiring layer 125 ... Gate electrode -------------- install ------- -Order ------ line (please read the precautions on the back before filling this page) 31 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

501 j-94—— ^ B8 :….—..........—D8 六、申請專利範圍 第89118699號專利申請案申請專利範圍修正本91年5月16曰 1· 一種氮化鈦系薄膜，其係藉利用含氧氣體之化學氣相沈 積（CVD)形成’且該薄膜含有鈦、氧及氮。 2· —種氮化鈦系薄膜，其係藉利用含鱗氣體之化學氣相沈 積（CVD)形成，且該薄膜含有鈦、氮及磷。 3· —種氮化鈦系薄膜，其係藉利用含氧氣體以及含磷氣體 之CVD形成，且該薄膜含有鈦、氧、氮及磷。 4. 一種亂化鈦系薄膜，其具有一堆疊構造，包含：第一薄 膜，其係藉CVD形成且含有鈦、氧及氮；以及第二薄膜 ’其係藉CVD形成且含有鈦、氮及填。 5·如申請專利範圍第4項之氮化鈦系薄膜，其中該第一薄 膜進一步含有磷，或該第二薄膜進一步含有氧。 6· —種氮化鈦系薄膜，其具有一堆疊構造，包含：第一薄 膜，其係藉CVD形成且含有鈦、氧及氮；第二薄膜，其 係藉CVD形成於該第一薄膜上且含有鈦、氮及磷；以及 第三薄膜，其係藉CVD形成於該第二薄膜上且含有鈦、 氧及氮。 7·如申請專利範圍第6項之氮化鈦系薄膜，其中該第一薄 膜與該第三薄膜中之至少一者進一步含有磷，或該第二 薄膜進一步含有氧。 8· 種’尤積氮化鈦系薄膜之方法，該方法包含下列步驟： 在處理容器内配置一基材；以及 將四氯化欽氣體、含氮氣體、含氫氣體及含氧氣體 導入該處理容器内而藉CVD於該基材上形成含鈦、氧 本紙張尺度適用中關家標準（⑽）M規格（2歡297公楚） 32 .............. 4 (請先閱讀背面之注意事項再填寫本頁) 訂丨 、申請專利範園 及氮之薄膜。 9·如申请專利範圍第8項之沈積氮化鈦系薄膜之方法，其 進一步包含在形成含鈦、氧及氮之薄膜之步驟之前及/ 或之後，將含氧氣體導入該處理容器内部之步驟。 io.如申請專利範圍第8項之沈積氮化鈦系薄膜之方法，其 中使用氨作為該含氮氣體以及含氫氣體，且藉由將含氧 氣體容積轉成氧氣容積對氨氣之容積比係於〇·〇〇〇 i至 〇·〇〇1之範圍。 U· 一種沈積氮化鈦系薄膜之方法，該方法包含下列步驟： 在處理容器内配置一基材；以及 將四氣化鈦氣體、含氮氣體、含氫氣體、含氧氣體 及含磷氣體導入處理容器内而藉CVD於該基材上形成 含敛、氧、氮及磷之薄膜。 12·如申請專利範圍第丨丨項之沈積氮化鈦系薄膜之方法，其 進一步包含於形成含鈦、氧、氮及磷之薄膜之步驟之前 及/或之後，將含氧氣體導入處理容器内部之步驟。 13·如申請專利範圍第丨丨項之沈積氮化鈦系薄膜之方法，其 中使用氨作為含氮氣體及含氫氣體，且藉由將含氧氣體 容積轉成氧氣容積對氨氣之容積比係於〇〇〇〇1至〇〇〇工 之乾圍。 从如申請專利範圍第”項之沈積氮化鈦系薄膜之方法，其 中膦係用作為含磷氣體，以及膦之進給逮率係於〇〇4 至〇·3升/分鐘之範圍。 本紙張认適财關家標準（CNS) Α4規格⑵〇χ297公楚) (請先閲讀背面之注意事項再填寫本頁) •訂丨 :線_ 33 ινι A8 B8 C8 ' ---—----— D8____ I .....................................................................................................................1111111111__i _丨丨·_μ 、申請專利範圍 15· —種沈積氮化鈦系薄膜之方法，該方法包含下列步驟： 將四氣化鈦氣體、含氮氣體、含氫氣體及含氧氣體 導入處理容器内而藉CVD形成含鈦、氧及氮之第一薄 膜；以及 將四氯化鈦氣體、含氮氣體、含氫氣體及含磷氣體 導入處理容器内而藉CVD形成含鈦、氮及磷之第二薄 16·如申請專利範圍第15項之沈積氮化鈦系薄膜之方法，其 中使用氨作為含氮氣體及含氫氣體，且藉由將含氧氣體 容積轉成氧氣容積對氨氣之容積比係於〇 〇〇〇1至〇.〇〇1 之範圍。 17·如申請專利範圍第15項之沈積氮化鈦系薄膜之方法，其 中膦係用作為含磷氣體，以及膦之進給速率係於〇.〇4 至〇·3升/分鐘之範圍。 18·種沈積氮化鈦系薄膜之方法，該方法包含下列步驟： 將四氣化鈦氣體、含氮氣體、含氫氣體及含氧氣體 導入處理容器内而藉CVD形成含鈦、氧及氮之第一薄 膜； 將四氯化鈦氣體、含氮氣體、含氫氣體及含磷氣體 導入處理容器内而藉CVD於該第一薄膜上形成含鈦、 氮及磷之第二薄膜；以及 將四氣化鈦氣體、含氮氣體、含氫氣體及含氧氣體 導入處理容器内而藉CVD於第二薄膜上形成含鈦、氧 本紙張尺度適用中國國家標準（CNS) Μ規格⑵似297公楚） 34 (請先閲讀背面之注意事項再填寫本頁) -,可丨 ,ψ ^υιΐ9ΐ Α8 Β8 C8 D8 申請專利範圍 及氮之第三薄膜。 19.如申請專利範圍第18項之沈積氮化鈦系薄膜之方法，其 中使用氨作為含氮氣體及含氫氣體，且藉由將含氧氣體 谷積轉成氧氣容積對氨氣之容積比係於0.0001至0.001 之範圍。 20·如申明專利範圍第丨8項之沈積氮化敛系薄膜之方法，其 中膦係用作為含磷氣體，以及膦之進給速率係於〇.〇4 至〇·3升/分鐘之範圍。 21·種沈積氮化鈦系薄膜之方法，該方法包含下列步驟： 在處理容器内配置一基材；以及 將四氣化鈦氣體、含氮氣體、含氫氣體及含磷氣體 導入處理容器内而藉CVD於基材上形成含鈦、氮及磷 之薄膜。 22·如申請專利範圍第21項之沈積氮化鈦系薄膜之方法，進 一步包含於形成含鈦、氧及氮薄膜之步驟之前及/或之 後’將含氧氣體導入處理容器内部之步驟。 23·如申凊專利範圍第21項之沈積氮化鈦系薄膜之方法，其 中膦係用作為含磷氣體，以及膦之進給速率係於〇,〇4 至〇·3升/分鐘之範圍。 24· 一種沈積氮化鈦系薄膜之系統，該系統包含： 一處理容器，用於覆蓋其中欲處理的基材； 一支持件，在處理容器中用於支持該基材； 一沈積氣體導入機構，用於將沈積氣體導入該處理 本紙藏格⑵⑽細 -35 (請先閲讀背面之注意事項再填寫本頁) •訂丨 :線丨 juuyi A8 B8 C8 __ D8__— 、申請專利範圍 容器内；以及 一加熱機構，用於加熱支撐於支持件上的基材， 其中該沈積氣體導入機構具有四氣化鈦氣體、含氮 氣體及含氫氣體之供應源，以及含氧氣體供應源及含璘 氣體供應源中之至少一者。 25.如申請專利範圍第24項之沈積氮化鈦系薄膜之系統，其 中該含鈦、氧及氮之薄膜以及含鈦、氮及磷之薄膜可經 由調整來自含氧氣體供應源之氣體供應以及來自含磷 氣體供應源之氣體供應而持續形成。 26· —種製造薄膜構造之方法，該方法包含下列步驟： 形成一第一層； 於一處理容器内藉CVD於第一層上沈積一氮化鈦 系薄膜，該氮化鈦系薄膜包含含鈦、氧及氮薄膜、含鈦 、氮及磷薄膜以及含鈦、氧、氮及磷薄膜之一，或其中 二或多薄膜之堆疊層； 形成一第二層於氮化鈦系薄膜上；以及 於形成該氮化鈦系薄膜步驟之前及/或之後，將含 氧氣體導入該處理容器内。 27·如申請專利範圍第26項之製造薄膜構造之方法，其中該 第一層為石夕化鈦層、石夕化姑層、石夕層及聚秒層中之一， 以及該第二層為|呂層、嫣層及銅層中之一。 28·如申請專利範圍第26項之製造薄膜構造之方法，其中該 第一層為聚矽層，以及該第二層為鋁層、嫣層及銅層中 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） -36 (請先閲讀背面之注意事項再填寫本頁) •訂丨 ♦Γ 川 1191 A8 B8 C8 D8 、申請專利範圍 — 〇 29·如申請專利範圍第28項之製造薄膜構造之方法，其中薄 膜構造係建構成一半導體元件之一多金屬閘極電極構 造。 30· —種用於沈積金屬氮化物系薄膜之方法，該方法包含下 列步驟： 在處理容器内配置一基材；以及 將含金屬元素氣體、含氮氣體、還原氣體以及含氧 氣體與含第五族元素之氫化物氣體兩者之一導入該處 理谷内而藉CVD於該基材上形成含至少氧與第五族 元素之一的金屬氮化物薄膜。 31· —種用於製造薄膜構造之方法，該方法包含下列步驟： 形成第一導電層； 在該第一導電層上形成介電層； 在該介電層上形成一金屬氮化物系薄膜；以及 在該金屬氮化物系薄膜上形成第二導電層； 其中該形成金屬氮化物系薄膜的步驟係藉由將含 金屬元素氣體、氮氣、氨氣以及含氧氣體與含第五族元 素之氫化物氣體兩者之一導入一處理容器中，藉由 CVD以形成該金屬氮化物系薄膜，該薄膜包含含有該 金屬元素、氧以及氮之薄膜；含有該金屬元素、氮以及 磷之薄膜；以及含有該金屬元素、氧、氮以及磷的薄膜 三者中至少一者。 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） 37 (請先閲讀背面之注意事項再填寫本頁) .訂丨 :線丨 •如申請專利範圍第31項之製造薄膜構造之方法，其中該 第一導電層係一矽層，以及該介電層包含二氧化矽、五 氧化二鈕、氧化釕、PZT以及BST五者中至少一，、 及该第二導電層係鋁層、鎢層以及銅層中之一。 33·如申請專利範圍第32項之製造薄膜構造之方法，其中該 薄膜構造係建構成為一半導體元件之閘極電極結構。 34·如申請專利範圍第31項之製造薄膜結構之方法，其中該 第一導電層係一矽層，該介電層包含二氧化矽、五氧化 二鈕、氧化釕、PZT以及BST五者中至少一者，以及該 第一導電層係聚碎層。 35·如申請專利範圍第34項之製造薄膜構造之方法，其中該 薄膜構造係構成為一半導體元件之閘極電極結構。 36. 如申請專利範圍第31項之製造薄膜構造之方法，其中該 第一導電層係聚矽層以及金屬層之一，該介電層包含二 氧化矽、五氧化二鈕、氧化釕、pZT及BST五者中至少 一者，以及該第二導電層係金屬層。 37. 如申請專利範圍第36項之製造薄膜結構之方法，其中該 4膜結構係構成為一半導體元件之電容電極結構。501 j-94—— ^ B8:… .—..........— D8 6. Application for Patent Scope No. 89118699 Patent Application Amendment for Patent Scope Amendment May 16, 1991 1. A kind of nitrogen A titanium-based thin film is formed by chemical vapor deposition (CVD) using an oxygen-containing gas, and the thin film contains titanium, oxygen, and nitrogen. 2. A titanium nitride-based thin film formed by chemical vapor deposition (CVD) using a scale gas, and the thin film contains titanium, nitrogen, and phosphorus. 3. A titanium nitride-based thin film formed by CVD using an oxygen-containing gas and a phosphorus-containing gas, and the film contains titanium, oxygen, nitrogen, and phosphorus. 4. A disordered titanium-based thin film having a stacked structure including: a first thin film formed by CVD and containing titanium, oxygen, and nitrogen; and a second thin film 'formed by CVD and containing titanium, nitrogen, and fill. 5. The titanium nitride-based thin film according to item 4 of the application, wherein the first thin film further contains phosphorus, or the second thin film further contains oxygen. 6. A titanium nitride-based thin film having a stacked structure including: a first thin film formed by CVD and containing titanium, oxygen, and nitrogen; and a second thin film formed on the first thin film by CVD And contains titanium, nitrogen, and phosphorus; and a third thin film, which is formed on the second thin film by CVD and contains titanium, oxygen, and nitrogen. 7. The titanium nitride-based thin film according to item 6 of the application, wherein at least one of the first thin film and the third thin film further contains phosphorus, or the second thin film further contains oxygen. 8. · A method for forming a titanium nitride-based thin film, the method including the following steps: disposing a substrate in a processing container; and introducing a tetrachloromethane gas, a nitrogen-containing gas, a hydrogen-containing gas, and an oxygen-containing gas into the Titanium-containing, oxygen-containing paper is formed on the substrate by CVD in the processing container, and the paper size is in accordance with Zhongguanjia standard (⑽) M specification (2,297,297) 32 ............. 4 (Please read the notes on the back before filling out this page) Order, apply for a patent garden and nitrogen film. 9. The method for depositing a titanium nitride-based thin film according to item 8 of the patent application scope, further comprising introducing an oxygen-containing gas into the inside of the processing container before and / or after the step of forming a thin film containing titanium, oxygen, and nitrogen. step. io. A method for depositing a titanium nitride-based thin film according to item 8 of the scope of patent application, wherein ammonia is used as the nitrogen-containing gas and hydrogen-containing gas, and the volume ratio of the oxygen-containing gas to the volume of the oxygen gas is converted by the volume of the oxygen-containing gas It is in the range of 0.0000i to 0.0001. U · A method for depositing a titanium nitride-based thin film, the method comprising the following steps: disposing a substrate in a processing container; and disposing a titanium tetragas, a nitrogen-containing gas, a hydrogen-containing gas, an oxygen-containing gas, and a phosphorus-containing gas It is introduced into a processing container to form a thin film containing oxygen, nitrogen, and phosphorus on the substrate by CVD. 12. The method for depositing a titanium nitride-based thin film according to item 丨 丨 of the patent application scope, further comprising introducing an oxygen-containing gas into the processing container before and / or after the step of forming a thin film containing titanium, oxygen, nitrogen, and phosphorus Internal steps. 13. A method for depositing a titanium nitride-based thin film according to item 丨 丨 in the scope of patent application, wherein ammonia is used as a nitrogen-containing gas and a hydrogen-containing gas, and the volume ratio of the oxygen-containing gas to the volume ratio of the oxygen gas to the ammonia gas is converted. Department of the perimeter of the 10,000 to 100,000 workers. From the method for depositing a titanium nitride-based thin film as described in the "Scope of Patent Application", in which a phosphine is used as a phosphorus-containing gas, and a feed rate of the phosphine is in a range of from 0.4 to 0.3 liters / minute. Paper recognition standards (CNS) Α4 size ⑵〇χ297 公 Chu) (Please read the precautions on the back before filling out this page) • Order 丨: Line_ 33 ινι A8 B8 C8 '-------- -— D8____ I .............................. ........................................ ........... 1111111111__i _ 丨 丨 · _μ, patent application scope 15 · —A method for depositing titanium nitride-based thin film, the method includes the following steps: Introducing titanium tetrachloride gas, nitrogen-containing gas, hydrogen-containing gas, and oxygen-containing gas into the processing vessel to form a first thin film containing titanium, oxygen, and nitrogen by CVD; and introducing titanium tetrachloride gas, nitrogen-containing gas, Hydrogen gas and phosphorus-containing gas are introduced into the processing vessel to form a second thin film containing titanium, nitrogen, and phosphorus by CVD16. A method for depositing a titanium nitride-based thin film, such as the scope of patent application No. 15, wherein ammonia is used as the nitrogen-containing film And the hydrogen-containing gas, and the volume ratio of the oxygen-containing gas to the volume of ammonia by converting the volume of the oxygen-containing gas to the volume of the ammonia gas is in the range of 20001 to 0.0001. A method for depositing a titanium nitride-based thin film, in which a phosphine is used as a phosphorus-containing gas, and a feed rate of the phosphine is in a range of from 0.004 to 0.3 liters / minute. A method comprising the following steps: introducing a titanium tetragas, a nitrogen-containing gas, a hydrogen-containing gas, and an oxygen-containing gas into a processing container to form a first thin film containing titanium, oxygen, and nitrogen by CVD; and titanium tetrachloride A gas, a nitrogen-containing gas, a hydrogen-containing gas, and a phosphorus-containing gas are introduced into the processing container to form a second film containing titanium, nitrogen, and phosphorus on the first film by CVD; and The hydrogen-containing gas and oxygen-containing gas are introduced into the processing container to form titanium-containing and oxygen-containing films on the second film by CVD. The size of the paper is applicable to Chinese National Standards (CNS) M specifications (approximately 297 cm) 34 (Please read the notes on the back first (Please fill in this page again)-, OK 丨, ψ ^ υιΐ 9ΐ Α8 Β8 C8 D8 Patent application scope and the third thin film of nitrogen 19. 19. The method for depositing titanium nitride-based thin film according to item 18 of the patent application scope, wherein ammonia is used as the nitrogen-containing gas and hydrogen-containing gas, and The volume ratio of the volume of the oxygen-containing gas to the volume of oxygen converted to the volume of ammonia is in the range of 0.0001 to 0.001. 20 · As stated in the patent claim No. 8 method of depositing a nitrogen-condensation film, in which phosphine is used as a phosphorus-containing The feed rates of gas and phosphine are in the range of from 0.04 to 0.3 liters / minute. 21. A method for depositing a titanium nitride-based thin film, the method comprising the following steps: disposing a substrate in a processing container; and introducing a tetra-titanium gas, a nitrogen-containing gas, a hydrogen-containing gas, and a phosphorus-containing gas into the processing container A thin film containing titanium, nitrogen, and phosphorus is formed on the substrate by CVD. 22. The method for depositing a titanium nitride-based thin film according to item 21 of the patent application scope, further comprising a step of introducing an oxygen-containing gas into the inside of the processing container before and / or after the step of forming a thin film containing titanium, oxygen, and nitrogen. 23. A method for depositing a titanium nitride-based thin film as claimed in item 21 of the patent application, in which phosphine is used as a phosphorus-containing gas, and the feed rate of the phosphine is in the range of 0.004 to 0.3 l / min. . 24. A system for depositing a titanium nitride-based film, the system comprising: a processing container for covering a substrate to be processed therein; a support member for supporting the substrate in the processing container; a deposition gas introduction mechanism For the introduction of deposition gas into the processed paper collection grid -35 (please read the precautions on the back before filling out this page) • order 丨: line 丨 juuyi A8 B8 C8 __ D8 __— in the scope of the patent application container; and A heating mechanism for heating a substrate supported on a supporting member, wherein the deposition gas introduction mechanism has a supply source of four gaseous titanium gas, a nitrogen-containing gas and a hydrogen-containing gas, and an oxygen-containing gas supply source and a thorium-containing gas At least one of the sources of supply. 25. The system for depositing a titanium nitride-based thin film according to item 24 of the application, wherein the thin film containing titanium, oxygen, and nitrogen, and the thin film containing titanium, nitrogen, and phosphorus can be adjusted by supplying gas from an oxygen-containing gas supply source And the gas supply from the phosphorus-containing gas supply source is continuously formed. 26 · A method for manufacturing a thin film structure, the method includes the following steps: forming a first layer; depositing a titanium nitride-based film on the first layer by CVD in a processing container, the titanium nitride-based film including A titanium, oxygen, and nitrogen film, a titanium-containing, nitrogen-, and phosphorus-containing film, and one or more of the titanium-, oxygen-, nitrogen-, and phosphorus-containing films; or a stacked layer of two or more of them; forming a second layer on the titanium nitride-based film; And before and / or after the step of forming the titanium nitride-based film, an oxygen-containing gas is introduced into the processing container. 27. The method for manufacturing a thin film structure according to item 26 of the patent application scope, wherein the first layer is one of a titanium layer, a silicon layer, a stone layer, and a polysecond layer, and the second layer It is one of Lu layer, Yan layer and copper layer. 28. The method for manufacturing a thin film structure according to item 26 of the patent application scope, wherein the first layer is a polysilicon layer and the second layer is an aluminum layer, an aluminum layer, and a copper layer ) A4 specification (210X297mm) -36 (Please read the precautions on the back before filling out this page) • Order 丨 ♦ 川 1191 A8 B8 C8 D8, patent application scope-〇29 · If the scope of patent application item 28 A method for manufacturing a thin film structure, wherein the thin film structure is a multi-metal gate electrode structure constituting a semiconductor element. 30 · —A method for depositing a metal nitride-based thin film, the method comprising the following steps: disposing a substrate in a processing container; and placing a metal element-containing gas, a nitrogen-containing gas, a reducing gas, an oxygen-containing gas, and a One of the Group 5 element hydride gas is introduced into the processing valley to form a metal nitride film containing at least one of oxygen and one of the Group 5 element on the substrate by CVD. 31 · A method for manufacturing a thin film structure, the method comprising the following steps: forming a first conductive layer; forming a dielectric layer on the first conductive layer; forming a metal nitride-based thin film on the dielectric layer; And forming a second conductive layer on the metal nitride-based thin film; wherein the step of forming the metal nitride-based thin film is performed by hydrogenating a metal element-containing gas, nitrogen, ammonia, an oxygen-containing gas, and a group 5 element-containing hydrogen One of the two gases is introduced into a processing vessel, and the metal nitride-based thin film is formed by CVD, the thin film including a thin film containing the metal element, oxygen, and nitrogen; a thin film containing the metal element, nitrogen, and phosphorus; and At least one of three films containing the metal element, oxygen, nitrogen, and phosphorus. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 37 (Please read the precautions on the back before filling out this page). Order 丨: Line 丨 • If you are manufacturing a thin film structure in the scope of patent application No. 31 Method, wherein the first conductive layer is a silicon layer, and the dielectric layer includes at least one of silicon dioxide, pentoxide, ruthenium oxide, PZT, and BST, and the second conductive layer is an aluminum layer , A tungsten layer, and a copper layer. 33. The method for manufacturing a thin film structure according to item 32 of the application for a patent, wherein the thin film structure is constructed as a gate electrode structure of a semiconductor element. 34. The method for manufacturing a thin film structure according to item 31 of the scope of patent application, wherein the first conductive layer is a silicon layer, and the dielectric layer includes silicon dioxide, pentoxide, ruthenium oxide, PZT, and BST. At least one of them, and the first conductive layer is an aggregated layer. 35. The method for manufacturing a thin film structure according to item 34 of the application, wherein the thin film structure is configured as a gate electrode structure of a semiconductor element. 36. The method for manufacturing a thin film structure according to item 31 of the application, wherein the first conductive layer is one of a polysilicon layer and a metal layer, and the dielectric layer includes silicon dioxide, pentoxide, ruthenium oxide, pZT And at least one of BST and the second conductive layer is a metal layer. 37. The method for manufacturing a thin film structure according to item 36 of the application, wherein the 4-film structure is a capacitor electrode structure of a semiconductor element.
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