經濟部智慧財產局員工消費合作社印製 527429 A7 B7 五、發明说明（） 發明領i 本發明係與過渡金屬碳化物薄膜的沉積相關。更特定 說來，本發明係關於以連續地自我飽合（self-saturating)表 面反應的方式在各不同基材上形成過渡金屬碳化物。 發明背景 週期表中第四族（鈦、錘、铪）、第五族（釩、鈮、钽） 及第六族（鉻、鉬、鎢）之過渡金屬元素的碳化物具有諸多 吸引人的特性，例如其性質不波潑、具高熔點、高硬度及 抗磨損、具高熱導性及與金屬相當之導電性。因此，過渡 金屬碳化物已被提出作為半導體製造中低阻抗擴散阻障 層的材料。 金屬碳化物的一般相關介紹可見於 yilmann*s Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A5, VCH Verlagsgesellschaft，1 986，pp. 61-77 及 Kirk，Othmer Encyclopedia of Chemical Technology, 4th Edition, Vol. 4, John Wiley &Sons, Inc.，1992，pp. 841-878 等圖書刊物之 内容。其中，過渡金屬碳化物能形成很多的化學組成物， 其中具有排列整齊或排列混亂的碳缺陷形式，鎢之碳化物 W3C，W2C，WC及WCwx即為其中的代表例子。在這些形式 中，碳係存於金屬原子之間的縫隙處。 這些過渡金屬碳化物的沉積可以化學氣相沉積 (CVD)、金屬有機化學氣相沉積（MOCVD)及物理氣相沉積 (PVD)等方法為之。 --— _ 第 21_ 本紙張从適用中國國家樣準（CNS )八4驗（21G X297公釐) --Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 527429 A7 B7 V. Description of the Invention () Invention Field The invention relates to the deposition of transition metal carbide films. More specifically, the present invention relates to the formation of transition metal carbides on various substrates in a continuous self-saturating surface reaction. BACKGROUND OF THE INVENTION The carbides of the transition metal elements of the fourth group (titanium, hammer, hafnium), the fifth group (vanadium, niobium, tantalum) and the sixth group (chromium, molybdenum, tungsten) in the periodic table have many attractive properties. For example, its properties are not sloppy, with a high melting point, high hardness and abrasion resistance, with high thermal conductivity and electrical conductivity equivalent to metal. Therefore, transition metal carbides have been proposed as materials for low-resistance diffusion barriers in semiconductor manufacturing. A general introduction to metal carbides can be found in yilmann * s Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A5, VCH Verlagsgesellschaft, 1 986, pp. 61-77 and Kirk, Othmer Encyclopedia of Chemical Technology, 4th Edition, Vol. 4 , John Wiley & Sons, Inc., 1992, pp. 841-878. Among them, transition metal carbides can form many chemical compositions, including carbon defects in a neat or disorderly arrangement. Tungsten carbides W3C, W2C, WC, and WCwx are representative examples. In these forms, carbon exists in the gaps between the metal atoms. These transition metal carbides can be deposited by chemical vapor deposition (CVD), metal organic chemical vapor deposition (MOCVD), and physical vapor deposition (PVD). --- _ No. 21_ This paper is from China National Standards (CNS) 8-4 inspection (21G X297 mm)-
527429 A7 B7 五、發明説明（） --- 碳化物長久以來即可以Cvd方法加以沉積形成，其 中同時在反應區參與反應的化學物質可超過一種。其中， 一種利用六氣化鶴、氣及一種含碳氣體進行CVD製程以 沉積鶴之碳化物的例子可見於國際專利申請案W〇〇〇 /47796中的描述。該含碳氣體首先加以熱使成活潑物質， 而所有的氣體化學物質都同時在反應區中反應，於是在基 材上沉積一層非揮發性之鎢的碳化物。一種利用WF6與三 甲基碳氫基氨及氫進行CVD反應而沉積形成wc與冷· W C 1-χ膜層的例子可見於n a k a j i m a等人於J. Electrochem. 144: 209^2100(1997))中所揭示的内容，其中前者的 沉積溫度為700°C -800°C，而後者則為400°C -60(TC，而其 中氫流率會影響鎢之碳化物的沉積速率。 經濟部智慧財產局員工消費合作社印製 M0CVD製程的做法是將有機金屬化合物在基材上加 以熱分解，或對這些有機金屬化合物加以其它氣相有機化 合物，接著使這些化合物與基材接觸，其中的化學物質分 子就在基材上分解而形成最後的產物。鎢之碳化物也曾以 此法沉積於基材上，即利用有機鎢之衍生物W(CO)6於低 壓下進行熱分解（Lai等人發表於Chem. Mater· 7:2284-2292(1995)者）而進行沉積。同樣地，TiC也可以CVD製 程法將有機金屬鈦化合物加以分解而沉積形成（Girolami 等人與 lUater Re^ Soc. Svmp,_P_r_oc. 121:429-438(1988)) ° 另美國專利5,916,365中亦揭露五雙甲基-氨基短的熱分解 方式。在以上製程中’化學物質分子都包含有金屬及碳’ 然而其在複雜而不規則之表面的效用則仍不得而知° _第3頁 _ 本纸張尺度適用中國國家橾準（CNS ) A4規格（210X297公釐） 527429 A7 B7 五、發明説明（ PVD製程一般都沿一瞄準線進行，其中—種沉積纽之 碳化物以當作擴散阻障層的方法可見諸美國專利 5,9 73,400之揭露内容，其中鈕之碳化物層係以在氮/甲烷/ 氬環境下對姮或妲之碳化物濺擊形成。然而，沿瞄準線的 沉積方式會因基材表面的輪廓複雜而使得受遮蔽之處不 能得到足夠的沉積。此外，瞄準線沉積會使得低揮發性材 料直接從材料源處抵至基材處，並很可能因此而黏附在其 所碰到的第一個表面上，故如此形成之覆層的—致性不 佳。 鏗於以上所述，過渡金屬之氮化物的沉積方法實有其 改進之必要。 發明目的及概沭： 本發明之一樣怨在於介紹一種利用原子層沉積 (ALD)法沉積一過渡金屬碳化物薄膜的方法。在所圖示 之實施例中，至少一過渡金屬源化合物及至少—碳源化 合物之氣相脈衝輪流供入反應區中，而一基材就位於反 應區中。 經濟部智慧財產局員工消费合作社印製 該過渡金屬源化合物至少包含一金屬源，而該金屬 以選自由鈦、锆、铪、鈮、叙、絡、鉬及鎢所組成的群 組中為佳。金屬函化物是過渡金屬源氣體的一範例，六 氟化鎢即為其一；碳源化合物的範例則包含硼化合物、 矽化合物及磷化合物。此外，在以上之源氣體化合物的 範例中，不管是硼、矽或磷都以直接與碳鍵結為佳。 第4頁 本紙張尺度逋用中國國家標準（CMS ) Μ規格（2Η)χ^^ 527429 A7 B7 --------^ 五、發明説明（） 以上所述之方法在沉積超薄之高品質膜層時特別能 顯出其效能，而超薄之高品質膜層是半導體製造領域所 追求的目標。舉例來說’金屬碳化物薄膜可在積體電路 特徵表面（如雙鑲嵌溝渠及介電孔等）上形成同形具導電 的有效薄擴散阻障層。 1式簡單說明： 第1圖為雙鑲嵌結構及金屬碳化物擴散阻障層的設置圖； 第2圖為以原子層沉積（ALD)方法形成金屬碳化物的流程 圖。 1號對照說明： 2 介電孔 4 介電孔絕緣體 6 擴散阻障層 1 溝渠 3 蝕刻阻層 5 溝渠絕緣體 f明詳細說明： 經濟部智慧財產局員工消費合作社印製 "原子層沉積"或’’ A L Dπ製程指的是一種利用連續或相 間之自我飽合（self-saturating)表面反應方式而將薄膜沉 積於一基材上的製程，其中ALD之原理可見於美國專利 4,0 5 8,43 0及5,71 1，81 1等之說明，在此將該兩專利併入， 以利參考。 π基材溫度M指的是沉積製程中反應區内所有的溫 度。 第5頁 527429 五、發明説明（） ”過渡金屬”是週期表中第3至第12族之元素，而第5 族給）、第6族（訊、銳及短）及第7族（絡、銷及 鶴)則為其中之較佳者。這些金屬碳化物的碳都位於缝隙 處，並具有一些純金屬的特性。 ••反應區”指的是一反應器或反應室，其中的各條件可 加以調整，以進行ALD製程。 本發明之較佳實施例中，過渡金屬碳化物薄膜由一種 化學氣相沉積法製備而得，而較佳的化學氣相沉積法則為 原子層沉積（ALD)法，其製程原理並已為眾所周知。 在一較佳ALD製程中，過渡金屬碳化物薄膜係在一 反應區中的向溫裱境下在一基材上成長而得，因此基材以 置於反應區内、並以連續或交替加以至少兩氣相反應物在 表面上使發生反應的方式為佳；在反應區條件上則以能調 整至典氣相之反應發生為佳，如無氣態反應物之間的反 應。在較佳之ALD製程中，一金屬源化合物及一碳源化 合物以液態之形式交替送進反應區中，以使兩者在反應區 中不同時以液態形式存在，因此只有基材表面上化學吸收 作用所吸收之物質或複合物會與氣態反應物進行表面反 應’其中該反應以能達到自我飽合及自我限制為佳。 在較佳的ALD製程中，過渡金屬源化合物及碳源化 合物的氣相脈脈衝以連續並相間的方式送入反應區並與 基材表面相接觸’其中這些源化合物並以由惰性或載氣伴 送入反應區為佳，如以氮或氬等載氣為之等。基材之，，表 面”在起始時至少包含有基材材料。在一實施例中該基材 第6頁 表紙張又度適用中國國家揉準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項 寫本頁) -裝· 訂 經濟部智慧財產局員工消費合作社印製 527429 五、發明説明（ 被預先加熱，如使之與一化學物質直接接觸而改變表面特 性等。當過渡金屬碳化物層沉積完成時，其就成為後續待 沉積之過渡金屬碳化物的表面。 第2圖中圖示一脈衝序列或"循環，，，其中每一沉積循 環至少包含： 送入一過渡金屬源化合物之氣相脈衝至反應區 中’其中該過渡金屬化合物氣相脈衝由一惰性載農輔助送 入； 移除剩餘的過渡金屬源化合物及所有氣態副產 物（如利用一惰性氣體洗淨）； 送入一碳源化合物之氣相脈衝進入反應區中，其 中該碳源化合物氣相脈衝由一惰性載氣輔助送入；及 移除剩餘的碳源化合物及所有氣態副產物（如利 用一惰性氣體洗淨）。 循環進行的次數可為任意，但以使所形成之過渡金屬 碳化物膜達至所需的厚度為原則。至於每一循環中的洗淨 時間’其選定以長至足以清除氣態反應物及防止過渡金屬 碳化物薄膜的成長速率高於該過渡金屬碳化物之一晶格 常數為原則。 在一實施例中，沉積係於大氣壓力下進行。不過，沉 積的進行以在較低之壓力下為佳，其中反應器中的壓力以 介於約0. 〇 1毫巴爾至5 0毫巴爾之間為佳，並以介於約〇 i 毫巴爾至10毫巴爾之間為更佳。另一方面，基材溫度以 高至足以避免源物質的物理吸收及凝結發生為佳。再者， 第7頁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) •裝· 訂 經濟部智慧財產局員工消費合作社印製 527429 A7 ________B7_____ 五、發明説明（） 基材溫度以高至足以提供表面反應所需的活化能為佳，即 約為200°C至600°C之間，並以介於約250°C至400°C之間 為更佳。然而，熟知該項技術者皆知基材溫度及反應區壓 力的更佳值與反應物及基材種類有關。 如果氣相源混合物的部份壓力超過基材溫度的凝結 限度，那麼過渡金屬碳化物膜的成長便會失去控制。因 此，在一較佳實施例中，源容器之溫度以低於基材之溫度 為佳。 經濟部智慧財產局員工消費合作社印製 在較佳實施例中，過渡金屬源化合物在基材表面上有 化學吸收現象，於是表面就會為過渡金屬複合物所牽附， 牽附之量則與原表面本身相關，其中反應物分子與該表面 的牽附直至該表面上不再有多餘的鍵結位覃 '並至該單層 上的配位體不與仍留在氣相中過量的源化合物反應時終 止，這種現象稱之為”自我飽和’’。當所有的鍵結位置都被 佔據時，反應物分子的實際大小可能會使表面不能得到完 全的覆蓋，這端視所使用的反應物而定；而基材上在每一 脈波序列中沉積時’以沉積不超過一單層過渡金屬源複合 物的情況會有較佳之覆蓋特性，所以欲形成完整的單層過 渡金屬碳化物非得進行若干次的沉積循環不為功。 在商業生產的設定中，自我飽和反應時間的受限不部 份在於經濟因素。例如，欲使基材產出具經濟效率，那麼 自我飽和反應所需的時間就有所限制。 基材可為習用的各種材料，如參、碎化物、鐘碎物、 金屬、金屬氮化物、金屬氧化物、多孔材料、碎之碳化物 ----- _- -第 8頁 一 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐 1 -' 經濟部智慧財產局員工消費合作社印製527429 A7 B7 V. Description of the invention () --- Carbides can be deposited and formed by Cvd method for a long time, among which more than one chemical substance can participate in the reaction zone at the same time. Among them, an example of a CVD process using six gasification cranes, gas, and a carbon-containing gas to deposit the carbides of cranes can be described in the international patent application 5000/47796. The carbon-containing gas is first heated to make the active substance, and all the gas chemicals react in the reaction zone at the same time, so a layer of non-volatile tungsten carbide is deposited on the substrate. An example of the formation of wc and cold · WC 1-χ film by CVD reaction of WF6 with trimethylhydrocarbon ammonia and hydrogen can be found in Nakajima et al. J. Electrochem. 144: 209 ^ 2100 (1997) The content disclosed in the former is that the deposition temperature of the former is 700 ° C -800 ° C, while the latter is 400 ° C -60 ° C, and the hydrogen flow rate will affect the deposition rate of tungsten carbide. Ministry of Economic Affairs wisdom The method of printing the M0CVD process by the Consumer Cooperative of the Property Bureau is to thermally decompose organometallic compounds on the substrate, or to add other gas-phase organic compounds to these organometallic compounds, and then contact these compounds with the substrate. The chemical substances in them The molecules are decomposed on the substrate to form the final product. Tungsten carbides have also been deposited on the substrate in this way, using organic tungsten derivatives W (CO) 6 for thermal decomposition at low pressure (Lai et al. Published in Chem. Mater · 7: 2284-2292 (1995)) for deposition. Similarly, TiC can also be deposited by decomposition of organometallic titanium compounds by a CVD process (Girolami et al. And 1Uater Re ^ Soc. Svmp , _P_r_oc. 121 : 429-438 (1988)) ° Another US patent 5,916,365 also discloses a short thermal decomposition method of pentabismethyl-amino group. In the above process, 'chemical molecules contain metals and carbon', but it is complex and irregular. The effectiveness of the surface is still unknown ° _Page 3_ This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 527429 A7 B7 V. Description of the invention (PVD process generally follows a line of sight For a method of depositing carbides as a diffusion barrier, see the disclosure in US Patent No. 5,9,73,400, in which the carbide layer of the button is formed in a nitrogen / methane / argon atmosphere. Plutonium carbides are formed by sputtering. However, the deposition along the line of sight will not be adequately deposited due to the complex contour of the substrate surface. In addition, the line of sight deposition will allow low-volatile materials to be directly removed from the material. The source touches the substrate and is likely to adhere to the first surface it encounters. Therefore, the coating thus formed has poor consistency. As mentioned above, nitrides of transition metals Deposition There is a need for its improvement. Purpose and summary of the invention: One of the complaints of the present invention is to introduce a method for depositing a transition metal carbide film by atomic layer deposition (ALD). In the illustrated embodiment, at least one The gas phase pulses of the transition metal source compound and at least the carbon source compound are alternately supplied into the reaction zone, and a substrate is located in the reaction zone. The printing of the transition metal source compound by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics contains at least one metal Source, and the metal is preferably selected from the group consisting of titanium, zirconium, hafnium, niobium, Syria, complex, molybdenum, and tungsten. Metal halide compounds are an example of a transition metal source gas, tungsten hexafluoride is one of them; examples of carbon source compounds include boron compounds, silicon compounds, and phosphorus compounds. In addition, in the above examples of the source gas compound, whether it is boron, silicon, or phosphorus, it is preferable to directly bond with carbon. Page 4 This paper uses the Chinese National Standard (CMS) M specifications (2Η) χ ^^ 527429 A7 B7 -------- ^ V. Description of the invention () The high-quality film can show its performance especially, and the ultra-thin high-quality film is the goal pursued in the field of semiconductor manufacturing. For example, a 'metal carbide thin film' can form an effective thin diffusion barrier layer with a conductive shape on the characteristic surface of the integrated circuit (such as dual damascene trenches and dielectric holes). Formula 1 is briefly explained: Fig. 1 is a setup diagram of a dual damascene structure and a metal carbide diffusion barrier layer; Fig. 2 is a flow chart of forming a metal carbide by an atomic layer deposition (ALD) method. Comparative description of No. 1: 2 dielectric holes 4 dielectric hole insulators 6 diffusion barrier layer 1 trench 3 etching resist 5 trench insulator f detailed description: printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs " atomic layer deposition " The `` AL Dπ process '' refers to a process of depositing a thin film on a substrate by continuous or inter-self-saturating surface reaction. The principle of ALD can be found in U.S. Patent 4,05. The descriptions of 8,43 0 and 5,71 1,81 1 are incorporated herein by reference for ease of reference. π substrate temperature M refers to all temperatures in the reaction zone during the deposition process. Page 5 527429 V. Description of the invention () "Transition metals" are elements of Groups 3 to 12 in the periodic table, and Group 5 gives), Group 6 (new, sharp and short) and Group 7 (network , Pin and Crane) are the better ones. The carbon of these metal carbides is located in the gap and has some characteristics of pure metal. • "Reaction zone" refers to a reactor or reaction chamber, where various conditions can be adjusted for the ALD process. In a preferred embodiment of the present invention, the transition metal carbide film is prepared by a chemical vapor deposition method Therefore, the preferred chemical vapor deposition method is the atomic layer deposition (ALD) method, whose process principle is well known. In a preferred ALD process, the transition metal carbide film is oriented in a reaction zone. It is obtained by growing on a substrate under warm mounting environment. Therefore, the substrate is preferably placed in the reaction zone, and at least two gas-phase reactants are continuously or alternately applied on the surface to cause the reaction to occur; the conditions in the reaction zone In the above, it is better that the reaction can be adjusted to the classical gas phase, such as the reaction between no gaseous reactants. In the preferred ALD process, a metal source compound and a carbon source compound are alternately sent into the reaction zone in a liquid form. So that the two do not exist in liquid form in the reaction zone at the same time, so only the substance or compound absorbed by chemical absorption on the surface of the substrate will undergo a surface reaction with the gaseous reactant. The reaction is preferably able to achieve self-saturation and self-limitation. In a better ALD process, the gas phase pulses of the transition metal source compound and the carbon source compound are sent into the reaction zone in a continuous and interphase manner and are in phase with the surface of the substrate. It is better to contact 'these source compounds and feed them into the reaction zone with an inert or carrier gas, such as nitrogen or argon. The substrate, surface' includes at least the substrate material at the beginning . In an example, the sheet on page 6 of the substrate is again suitable for the Chinese National Standard (CNS) A4 (210X297 mm) (please read the precautions on the back first to write this page) Printed by the Bureau ’s Consumer Cooperative 527429 V. Description of the invention (Being pre-heated, such as directly contacting a chemical substance to change the surface characteristics, etc. When the transition metal carbide layer is deposited, it becomes a subsequent transition metal to be deposited The surface of the carbide. Figure 2 illustrates a pulse sequence or " cycle, where each deposition cycle includes at least: sending a gas phase pulse of a transition metal source compound into the reaction zone, where the transition metal compound The gas phase pulse is fed by an inert agricultural carrier; the remaining transition metal source compounds and all gaseous by-products are removed (such as cleaning with an inert gas); the gas phase pulse sent by a carbon source compound enters the reaction zone, The carbon source compound gas phase pulse is fed in by an inert carrier gas; and the remaining carbon source compound and all gaseous by-products (such as by using an inert gas) are removed. The number of cycles can be arbitrary, but the principle is to make the transition metal carbide film formed to the required thickness. As for the washing time in each cycle, it is selected to be long enough to remove It is a principle that the growth rate of the gaseous reactant and the transition metal carbide film is higher than the lattice constant of one of the transition metal carbides. In one embodiment, the deposition is performed under atmospheric pressure. However, the deposition is performed in Low pressure is preferred, where the pressure in the reactor is preferably between about 0.01 millibar and 50 millibar, and more preferably between about 0.1 millibar and 10 millibar. On the other hand, the temperature of the substrate should be high enough to avoid physical absorption and coagulation of the source material. Furthermore, page 7 of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (please (Please read the notes on the back before filling in this page) • Binding · Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperative 527429 A7 ________B7_____ V. Description of the invention () The temperature of the substrate is high enough to provide surface response The required activation energy is preferably between about 200 ° C and 600 ° C, and more preferably between about 250 ° C and 400 ° C. However, the substrate temperature is well known to those skilled in the art And the better value of the reaction zone pressure is related to the type of reactants and substrate. If the partial pressure of the gas source mixture exceeds the condensation limit of the substrate temperature, the growth of the transition metal carbide film will be out of control. In a preferred embodiment, the temperature of the source container is preferably lower than the temperature of the substrate. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In a preferred embodiment, the transition metal source compound has chemical absorption on the surface of the substrate Phenomenon, then the surface will be entrained by the transition metal complex, and the amount of entrainment is related to the original surface itself, where the reactant molecules are attached to the surface until there are no more excess bonding sites on the surface. This phenomenon is called "self-saturation" when the ligand on the monolayer does not react with the excess source compound still remaining in the gas phase. When all the bonding positions are occupied, the actual size of the reactant molecules may prevent the surface from being completely covered, depending on the reactants used; and the substrate is deposited in each pulse wave sequence In the case where no more than a single layer of the transition metal source composite is deposited, there will be better coverage characteristics, so it is not useful to perform several deposition cycles to form a complete single layer of transition metal carbide. In commercial production settings, the limitation of self-saturation response time is not partly due to economic factors. For example, to make substrate output economically efficient, the time required for a self-saturation reaction is limited. The substrate can be a variety of conventional materials, such as ginseng, shredded materials, bell broken materials, metals, metal nitrides, metal oxides, porous materials, broken carbides ----- _--page 8 a paper Standards are applicable to China National Standard (CNS) A4 specifications (210X 297 mm 1-'Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs
527429 •發明説明（） 及碎之氮化物等。在較佳余姓办丨由 1 , 只她例中，就如以上所述-旦過 渡金屬碳化物薄膜形成之後， 便泛層就成為後續待沉積層膜 的基材表面。 過渡金屬源化合物及碳源化合物以選擇成能符合氣 相壓力足夠、基材溫度時熱穩定度足夠及基材表面化合物 反應性足夠的要件者為佳，纟中^夠大的氣相壓力指的是 ,基材表面附近有足夠多的氣相化合物分子，以使表面處 能發生自我飽和反應。足夠的熱穩定度指的是源化學物質 本身不能在基材上經由熱分解而形&干擾成長的凝結相 態t在基材表面上留下過量有害之雜質，因此反應物的選 擇最好是能使其本身之原子或分子不會在基材上產生凝 結者。 本發明之較佳實施例中需要使用一過渡金屬源材料 及一碳源材料，其中碳源材料以為硼源化合物、矽源化合 物或磷源化合物。不過，在一實施例中需要使用到電漿， 而車父佳的碳源材料則為碳氮化物。 過渡金屬源材料 較佳之金屬源化合物為過渡金屬源化合物，因其能在 足夠低溫下揮發。這些過渡金屬化合物以至少包含一選自 於由鎢、鈥、锆、給、飢、說、組、鉻及鉬所組成之過渡 金屬群組中為佳，其中金屬源化合物以為金屬画化物為最 佳，金屬函化物則包含金屬氟化物及金屬氯化物。在一圖 示之較佳實施例中，金屬源材料為六氟化鎢。 2.硼源化会物 第9頁 本紙張尺度適用中國國家標準（CNS ) Μ規格（210X297公釐）527429 • Description of the invention () and broken nitrides. In the preferred Yuxing Office from 1, in her case, as described above, once the transition metal carbide film is formed, the pan layer becomes the substrate surface of the subsequent layer film to be deposited. The transition metal source compound and the carbon source compound are preferably selected to meet the requirements of sufficient gas phase pressure, sufficient thermal stability at the substrate temperature, and sufficient reactivity of the compound on the surface of the substrate. The reason is that there are enough gas-phase compound molecules near the surface of the substrate so that the surface can self-saturate. Sufficient thermal stability refers to the fact that the source chemical itself cannot be formed on the substrate through thermal decomposition & the condensed phase that interferes with growth t leaves excessive harmful impurities on the surface of the substrate, so the choice of reactants is the best It can prevent the atoms or molecules of itself from coagulating on the substrate. In a preferred embodiment of the present invention, a transition metal source material and a carbon source material are required. The carbon source material is a boron source compound, a silicon source compound, or a phosphorus source compound. However, in one embodiment, a plasma is required, and the carbon source material of the car parent is carbonitride. Transition metal source material The preferred metal source compound is a transition metal source compound because it can volatilize at a sufficiently low temperature. These transition metal compounds preferably include at least one selected from the group consisting of tungsten, tungsten, zirconium, zirconium, zinc, titanium, chromium, and molybdenum. Among them, the metal source compounds are most preferably metal paints. Preferably, metal halide compounds include metal fluorides and metal chlorides. In a preferred embodiment shown, the metal source material is tungsten hexafluoride. 2. Boron source compounds Page 9 This paper size is applicable to China National Standard (CNS) M specifications (210X297 mm)
527429 五、發明説明（） 較佳之硼化合物為，化合物，其中包含至少—碳原 子，且在基材溫度之下能夠揮發。更佳的做法是，以硼化 合物當作硼源材料，其中在該硼源化合物分子中具有至少 一硼-碳鍵。 硼源化合物以選自以下之物質者佳： 如分子式（1)之碳硼烷。 C 2 B n Η η+χ < I) 其中n為1至10的整數，並以介於2至6為佳；而χ為 一偶數整數’並以為2,4或6為佳。 分子式（1)之碳硼烷例子包含閉合型-碳硼烷 (C2BnHn+2)、巢型（nido)-碳硼烷（C2BnHn+4)及蛛網型·碳硼烷 (C2BnHn+6)。 碳氫基氨-碳硼烷化合物如分子式Π。 R3NBX3 (II) 其中R為線性或側鏈C1至C10的烷基，並以為C1至c4 之烷基、氫或函素者為佳。 氨基硼烷，其中硼上有一或多氨基群取代物，如分子 式II卜 r2n (111) C4 第10頁 I紙張纽家標準(CNS ) A4規格（210X297公釐 (請先閲讀背面之注意事項寫本頁) -裝· 經濟部智慧財產局員工消资合作社印製 其中R為線性或側鏈C 1至C 10的烷基，並以為C1至 之烷基或取代、未經取代的芳香族羥基群為佳。 一適用之氨基棚燒例為（CH3)2NB(CH3)2。 烷基硼或烷基硼烷，其中烷基典型上為線性成側键e 至CIO的淀基’並以為C2至C4的虎基為佳。 527429 五、發明説明（） 烷基硼化合物為其φ异^ .. _ 、中瑕佳者。在較佳實施例中，該硼 源材料為三乙基硼B j.矽源化合物 較佳之矽源化合材料A a ^ 料為含碳之碎化合物，其能在基材 溫度以下之溫度揮發。承 史佳的矽源材料為矽化合物，其在 矽源化學物質分子中且右$ , ^ ^ “百至少一矽-碳鍵。烷基矽化合物 則為其中最佳之矽源材料。 4. 磷源化合物 車又佳之蹲源材料為含碳之嶙源化合物，其能在基材溫 度以下之溫度揮發。更佳的鱗源材料為鱗化合物，其在墙 源化予物貝；7子中具有至少一磷·碳鍵。烷基磷化合物則 為其中最佳之磷源材料。 5. 碳氮化物 具冋氫/碳比之碳氫化物適於當作碳源化學物質，線性 或側鏈甲烷則為更佳之碳源化學物質。 在一較佳實施例中，金屬源氣體及碳源氣體並不同時 在反應區中以液相存在，其中兩源化學物質以交替之方式 送入反應區而與基材相接觸為佳，由此在基材上以AlD 法成長出金屬碳化物。 牽附有過渡金屬化合物的表面及碳源化合物間的反 應副產物以為氣態者為佳，因其易於從反應區中利用改變 反應區塵力及/或以惰性氣流載運的方式移出。此外，碳源 化合物以能在金屬碳化物中留下碳、並從基材表面帶走卣 素為佳。 第11頁 本纸張尺度適用中國國家樣準（CNS ) Μ規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) -裝· 訂 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 527429 A7 B7 _ 五、發明説明（） 淨反應WF6 + (CH3CH2)3B的副產物雖尚未被完全分析 出來，但目前暫時假設是由於三乙基硼分子在靠近鎢之氟 化物分子時，三乙基硼分子中的碳原子間鍵結斷開而釋放 出CH3F副產物。此外，目前也暫時假設副產物的來源是 由於三乙基硼分子在靠近鎢之氟化物分子時，三乙基硼分 子中的碳及硼間的鍵結斷開而釋放出氣相ch3ch2f及bf3 副產物。不過’本發明之理論並不僅限於此等暫時性之假 設。 此外，碳源化學物質也會改變牽附有過渡金屬化合物 分子之表面的氧化狀態。本發明之碳化物薄膜經分析後指 出其中存有高金屬/碳比（WsC)，這說明了表面上的鎢被部 份減少了。 在一實施例中，惰性氣流會稀釋碳源化合物及牽附有 過渡金屬化合物之表面間反應生成的副產物，直至氣相副 產物在反應區中的濃度顯得微不足道。 碳源化合物以在成長之過渡金屬碳化物薄膜中留下 碳為佳。當一過渡金屬iS化物被用作為一金屬源化合物 時，画化物副產物可在前者與碳源化合物反應時生成。例 如在使用者為硼碳源時，所生成之副產物即為硼函化物。 第1表格中的範例顯示所形成的齒化硼在一較佳基材溫度 時會揮發（如3 50°c )，因此不會在基材表面上凝結，並能 使其本身從反應區中移除，這在以上亦有述及。 第1至第5表格中的沸點溫度指出化合物的氣相恩力 為1013毫巴爾（760托爾），不過ALD製程所需之最低氣 __ 第12頁 ^紙張尺度遑用中國國家揉準（CNS ) A4規格（210X297公瘦1 (請先閲讀背面之注意事項再填寫本頁)527429 V. Description of the invention () The preferred boron compound is a compound which contains at least -carbon atoms and is volatile under the temperature of the substrate. More preferably, a boron compound is used as the boron source material, wherein the boron source compound has at least one boron-carbon bond in the molecule. The boron source compound is preferably selected from the following materials: Carborane of formula (1). C 2 B n Η η + χ < I) where n is an integer from 1 to 10 and preferably between 2 and 6; and χ is an even integer 'and is preferably from 2, 4 or 6. Examples of the carborane of the molecular formula (1) include closed-carborane (C2BnHn + 2), nido-carborane (C2BnHn + 4), and cobweb type · carborane (C2BnHn + 6). Hydrocarbon ammonia-carborane compounds such as molecular formula II. R3NBX3 (II) wherein R is an alkyl group having a linear or side chain C1 to C10, and is preferably an alkyl group, a hydrogen group, or a functional group having C1 to c4. Aminoborane, in which boron has one or more amino group substitutions, such as molecular formula II, r2n (111) C4, page 10 I New Zealand Standard (CNS) A4 specification (210X297 mm (please read the precautions on the back first) (This page)-Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs where R is a linear or side chain C 1 to C 10 alkyl group, and C 1 to C is an alkyl group or a substituted, unsubstituted aromatic hydroxyl group Groups are preferred. A suitable example of amino sintering is (CH3) 2NB (CH3) 2. Alkyl boron or alkyl borane, in which the alkyl group is typically a linear group with linear side bonds e to CIO and is considered C2 Tiger group to C4 is better. 527429 V. Description of the invention () The alkyl boron compound is φ iso ^ .. _, which has a good defect. In a preferred embodiment, the boron source material is triethylboron B j. Silicon source compound is a better silicon source compound material A a ^ The material is a carbon-containing crushed compound, which can volatilize at a temperature below the substrate temperature. Cheng Shijia's silicon source material is a silicon compound, which is in silicon source chemical molecules Center and right $, ^ ^ "One hundred silicon-carbon bonds. Alkyl silicon compounds are the best silicon source materials. 4. A good source of phosphorus source compounds is carbon-containing tritium source compounds, which can volatilize at a temperature below the substrate temperature. A better scale source material is a scale compound, which is converted to wall shell material; 7 Has at least one phosphorus · carbon bond. Alkyl phosphorus compounds are the best phosphorus source materials. 5. Carbonitrides Hydrocarbons with a hydrogen / carbon ratio are suitable as carbon source chemicals, linear or side chain. Methane is a better carbon source chemical. In a preferred embodiment, the metal source gas and the carbon source gas do not exist in the liquid phase in the reaction zone at the same time, wherein the two source chemicals are sent to the reaction zone in an alternating manner. It is better to contact with the substrate, so that metal carbides are grown on the substrate by the AlD method. The surface of the transition metal compound and the by-products of the reaction between the carbon source compounds are preferably gaseous because they are easy It is removed from the reaction zone by changing the reaction zone dust force and / or carried by an inert gas flow. In addition, the carbon source compound is preferably able to leave carbon in the metal carbide and remove the halogen from the surface of the substrate. 11 pages of paper China National Standards (CNS) M specifications (210X297 mm) (Please read the precautions on the back before filling out this page)-Binding and ordering printed by the Intellectual Property Bureau Employee Consumer Cooperatives of the Ministry of Economic Affairs Preparation 527429 A7 B7 _ 5. Description of the invention () Although the by-products of the net reaction WF6 + (CH3CH2) 3B have not been completely analyzed, it is temporarily assumed that the triethyl boron molecule is close to the tungsten fluoride molecule. The bond between the carbon atoms in the ethyl boron molecule is broken to release the CH3F by-product. In addition, it is temporarily assumed that the source of the by-product is due to the triethyl boron molecule near the tungsten fluoride molecule. The bond between carbon and boron in the molecule is broken and the gas phase ch3ch2f and bf3 by-products are released. However, the theory of the present invention is not limited to these temporary assumptions. In addition, the carbon source chemistry also changes the oxidation state of the surface on which the molecules of the transition metal compound are involved. The analysis of the carbide film of the present invention indicates that a high metal / carbon ratio (WsC) is present therein, which indicates that the tungsten coat portion on the surface is reduced. In one embodiment, the inert gas stream dilutes the carbon source compounds and by-products produced by the surface-to-surface reaction of the transition metal compounds, until the concentration of the gas-phase by-products in the reaction zone becomes negligible. The carbon source compound preferably leaves carbon in the growing transition metal carbide film. When a transition metal iS compound is used as a metal source compound, a by-product of the compound may be formed when the former reacts with a carbon source compound. For example, when the user is a boron-carbon source, the by-product generated is a boron compound. The example in Table 1 shows that the formed boronized teeth will volatilize at a preferred substrate temperature (such as 3 50 ° C), so it will not condense on the surface of the substrate and will allow it to escape from the reaction zone itself. Removed, which was also mentioned above. The boiling point temperatures in Tables 1 to 5 indicate that the gas phase power of the compound is 1013 millibar (760 Torr), but the minimum gas required for the ALD process __ page 12 ^ Paper dimensions are based on Chinese national standards ( CNS) A4 specifications (210X297 male thin 1 (Please read the precautions on the back before filling this page)
527429 A7 ____B7 _ 五、發明説明（） 相壓力低於該值，如低至約〇. 0 1至0 · 1毫巴爾即可。 (請先閲讀背面之注意事項再填寫本頁) 第1表格 鹵化硼範例 以下表格資料係得自於1^.1^.0“€11\¥00(1&11(1八· Earnshaw, MChemistry of Elements,M1st ed., Pergamon Press, Oxford，England 1 986，ρ·220,225π o 化合物 溶點（°c) 沸點（°C ) bf3 -127.1 -99.9 BC13 -107 + 12.5 BBr3 -48 + 91.3 βι3 + 49.9 + 210 b2f4 -56 -34 B2C14 -92.6 + 65.5 同樣地，函化碳氫化物在一較佳基材溫度時也會有高 揮發性（如第2表格所示），如3 50°C時。 經濟部智慧財產局員工消費合作社印製 第2表格 丈完基函化物範例 以下表格之資料係得自於 CRC Handbook of Chemistry and Physics, 61st ed., Editor:R.C. Weast, CRC Press，Florida，USA 1981 o 第13頁 本紙張尺>交適用中國國家揉準（CNS ) A4規格（210X297公釐） " 527429 A7 B7 五、發明説明（） 4匕合物 溶點[°C ] 沸點[°C ] ch3f -141.8 -78.4 CH3C1 -97.1 -24.2 CH3Br -93.6 + 3.6 CH31 -66.4 + 42.4 cf4 -150 -129 CC14 -23 + 76.5 CH3CH2F -143.2 -37.7 CH3CH2CI -136.4 + 12.3 CH3CH2Br -118.6 + 38.4 CH3CH2I -108 + 72.3 (請先閲讀背面之注意 填寫本育) -裝· 第3及第4表格顯示由碎及鹵化罐組成之副產物同樣 具有高氣相壓力，因此金屬碳化物的碳源可以為反應性有 機矽及磷化合物。 第u頁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 訂 經濟部智慧財產局員工消費合作社印製 527429 A7 _B7 __ 五、發明説明（） 第3表格 鹵化矽之辦例 CRC Handbook of Chemistry and Physics,61st ed., Editor:R. C. Weast, CRC Press, Florida, USA 1981, pp.B- (請先閲讀背面之注意事項再填寫本頁) -装- 訂 經濟部智慧財產局員工消費合作社印製 142-B-143. 化合物 溶點f°C i 沸點rc SiF4 -40.2 -86 SiCl4 -70 + 57.6 SiBr4 + 5.4 + 154 Sil4 + 120.5 +287.5 Si2Cl6 -1 + 145 SiCl2F2 -144 -31.7 SiClF3 -138 -70 SiBr2Cl2 -45.5 104 第15頁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 527429 A7 B7 五、發明説明（ 經濟部智慧財產局員工消費合作社印製 第4表格 鹵化磷範例 以下 表格之資料係得自 N. N. Greenwood and A Earnsha w. ，"Chemistry of Elements, 1st ed., Pergmon Press. Oxford，England 1 986, ρ568,572· 化合物 溶點rc 1 沸點rc 1 pf3 -151.5 -101.8 PC13 -93.6 + 76.1 PBr3 -41.5 +173.2 Pla + 61.2 P2F4 -86.5 -6.2 P2CI4 -28 P2I4 +125.5 pf5 -93·7 -84.5 PC15 + 167 + 1 60(subl.) Pis + 41 PCUF -59 + 67 pci2f3 -125 + 7.1 PC1F4 -132 -43.4 第16頁 (請先閲讀背面之注意事項 1?^寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 527429 A7 B7_ 五、發明説明（） 第5表格527429 A7 ____B7 _ V. Description of the invention () The phase pressure is lower than this value, such as as low as about 0.01 to 0.1 millibar. (Please read the precautions on the back before filling this page) Example of Form 1 Boron Halide The following form information is from 1 ^ .1 ^ .0 "€ 11 \ ¥ 00 (1 & 11 (1Earth · Earnshaw, MChemistry of Elements, M1st ed., Pergamon Press, Oxford, England 1 986, ρ · 220,225π o Compound melting point (° c) Boiling point (° C) bf3 -127.1 -99.9 BC13 -107 + 12.5 BBr3 -48 + 91.3 βι3 + 49.9 + 210 b2f4 -56 -34 B2C14 -92.6 + 65.5 Similarly, functional hydrocarbons are highly volatile at a preferred substrate temperature (as shown in Table 2), such as at 3 50 ° C The second form printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is an example of the basic functional compound. The information in the following form is from the CRC Handbook of Chemistry and Physics, 61st ed., Editor: RC Weast, CRC Press, Florida, USA 1981 o Page 13 This paper ruler> Apply to China National Standard (CNS) A4 (210X297 mm) " 527429 A7 B7 V. Description of the invention (4) Melting point [° C] Boiling point [° C] ch3f -141.8 -78.4 CH3C1 -97.1 -24.2 CH3Br -93.6 + 3.6 CH31 -66.4 + 42.4 cf4 -150 -129 CC14 -23 + 76.5 CH3CH2F -143.2 -37.7 CH3CH2CI -136.4 + 12.3 CH3CH2Br -118.6 + 38.4 CH3CH2I -108 + 72.3 (Please read the notes on the back first and fill in this education)-Equipment The by-products of the halogenated tank and the halogenated tank also have high gas pressure, so the carbon source of the metal carbides can be reactive organic silicon and phosphorus compounds. Page u The paper size applies the Chinese National Standard (CNS) A4 specification (210X 297) (%) Order printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 527429 A7 _B7 __ V. Description of Invention () Form 3 Example of Silicon Halide CRC Handbook of Chemistry and Physics, 61st ed., Editor: RC Weast, CRC Press, Florida, USA 1981, pp.B- (Please read the precautions on the back before filling out this page) -Packing-Ordered by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economy Printed 142-B-143. Compound melting point f ° C i Boiling point rc SiF4 -40.2 -86 SiCl4 -70 + 57.6 SiBr4 + 5.4 + 154 Sil4 + 120.5 +287.5 Si2Cl6 -1 + 145 SiCl2F2 -144 -31.7 SiClF3 -138 -70 SiBr2Cl2 -45.5 104 Page 15 This paper is applicable to Chinese national standards CNS) A4 specification (210X297 mm) 527429 A7 B7 V. Description of the invention (printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy, Form 4 Example of phosphorus halide, the information in the following form is from NN Greenwood and A Earnsha w., &Quot; Chemistry of Elements, 1st ed., Pergmon Press. Oxford, England 1 986, ρ568,572 · Compound melting point rc 1 Boiling point rc 1 pf3 -151.5 -101.8 PC13 -93.6 + 76.1 PBr3 -41.5 +173.2 Pla + 61.2 P2F4 -86.5 -6.2 P2CI4 -28 P2I4 +125.5 pf5 -93 · 7 -84.5 PC15 + 167 + 1 60 (subl.) Pis + 41 PCUF -59 + 67 pci2f3 -125 + 7.1 PC1F4 -132 -43.4 Page 16 (Please read first Note on the back 1? ^ Write this page) The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 527429 A7 B7_ V. Description of the invention () Form 5
Sigma Aldrich 商用磁溏化 本案揭露之金屬碳化物沉積用之碳源範例，其皆為市 面上可購得者： 化合物 同義字 沸點 (CH3CH2)3B 三乙基棚 + 95 (CH3CH2)4Si 四乙基矽 + 153 (CH3)4Si 四甲基矽 + 27 (CH3CH2)3P 三乙基磷 + 127 範例1 在一基材上形成一過渡金屬碳化物薄膜時，以六氟化 鶏當作金屬源化學物質，而碳源則以三乙基侧（c H 3 c Η 2) 3 B 為之。 一矽晶圓被載入至一 Pulsar™2000反應器的反應區中 以進行A L D製程，該反應器係購自a S Μ M i c r 〇 - c h e m i s t r y 〇y of Espoo, Finland者。其中，反應區為一機械式真空幫 浦抽空，之後再供入純度為99.9999%的氮氣，以將反應區 壓力調整至約5毫巴爾至1 0毫巴爾（絕對）之間。接著，反 應區穩定至約3 50。(：。WF6及（CH3CH2)3B由外部源供應， 其電子階數脈衝被加以氣化，並交替送進反應區中與基材 相接觸，其中這些源化合物脈衝彼此之間以利用通入氮氣 洗淨的方式加以隔開，因此脈衝週期就包含了兩源化合物 第17頁 _^_ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事填寫本頁) 裝 訂 -線 經濟部智慧財產局員工消費合作社印製 527429 A7 B7 五、發明説明（ 脈衝及兩氮洗淨氣流動作時 甘丄 于間Ε #又，其中該脈 進行167次。 復 脈衝週期的脈衝及洗淨次數如下·· 025秒鐘 3 · 0秒鐘 〇 · 5秒鐘 3 · 0分鐘 使上述週期内的洗淨時間縮 六氟化鎢脈衝 氮氣洗淨動作期間 (CH3CH2)3B 脈衝 氮氣洗淨動作期間 製程條件的最佳化可 短 當沉積結束之後，石夕基材從反應器中移出以進行檢測 及分析。結果顯示基材的整個表面上都覆有薄膜，且該薄 膜具有金屬灰色光澤，其與基材之附著情況良好，並具導 電性。薄膜樣品以T0F-EDRA(飛行時間彈跳偵測分析')分 析其組成，並利用EDS(電子繞射光譜儀）量測其厚度，而 利用四點探針測量薄片阻抗。另外，阻抗值由厚度及薄片 組抗推導而得。 根據TOF-EDRA結果可知，薄膜樣品的鎢及碳原子比 為WSC，而樣品的厚度為23奈米，因此得知鎢之碳化物 的成長速度為1 · 4埃/循環。上述之循環内所成長的厚度小 於鎢之碳化物的晶格常數，其中的部份原因可能是由於前 驅物的分子大小較鎢及碳原子佔去了更多的基材表面空 間之故《薄膜之阻抗為200微歐姆·公分。膜層中的氟雜 質濃度（原子比）僅約為1.0%至1.5%。 第18頁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 527429 A7 B7 五、發明説明（ 範例2 金屬碳化物薄3¾沉積之f般描述 I- -1 - -18 m ...... > · 將一基材送入一反應區中，該反應區則調整至一較佳 溫度及一較佳壓力。所進行之可重覆進行製程序列包含四 個步驟，四個步驟於此時開始進行。一過渡金屬源化合物 氣相脈衝被送入反應區並與基材表面相接觸。經過一段第 一接觸時間之後，過剩之過渡金屬源化合物及所有的反應 副產物被移出反應區之外，移出的方式則是利用將反應區 的壓力加以改變及/或利用惰性氣流帶出。在經過第一洗淨 時間之後，一碳源化合物的氣相脈衝被送入反應室並與基 材表面接觸。經過一段第二接觸時間之後，過剩的碳源化 合物及所有的反應副產物從反應區中移開，移除之方式為 對反應區之壓力加以改變及/或由惰性氣流帶出。經過第二 洗淨時間之後，製程序列持續進行，直至金屬碳化物薄膜 達至一特定厚度止。最後，生有一層薄膜的基材就由反應 室中移出。 碳源化合物可為硼、碎或鱗碳源化合物。 範例3 以ALD金屬碳化物當作積體電路之阻障層 如第1圖所示，一基材具有溝渠1及介電孔2、蝕刻 阻層3、介電孔絕緣體4及溝渠絕緣體5，其被置於一 ALD 反應器的反應區中。該反應區被抽至真空，接著由加入一 惰性氣體（以氮氣為佳）的方式調整至一較佳壓力。其中， 第19頁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐〉 請先閲讀背面之注意事\^^· 裝 :寫本頁) 訂 H— —ϋ —^ϋ 527429 A7 B7 鈮 經濟部智慧財產局員工消費合作社印製 五、發明説明（ 该較佳壓力介於約1毫巴爾至5 0毫巴爾之間，並以介於 約3宅巴爾至1 〇亳巴爾為更佳。反應區之溫度接著穩定 至較佳足製程溫度，以3〇〇t至425°C之間為佳，以約325 C至375°C之間為更佳，並以约為35(rc為最佳。接著， 過渡金屬碳化物層6由進行以下循環而沉積製得： 將一過渡金屬源化合物送入該反應區並與該基 材接觸一第一脈衝時間； 將過剩之過渡金屬源化合物分子及所有副產物 分子在第一洗淨時間中自該反應區中移除； 將一碳源化合物送入該反應區中，並使之與該基 材接觸一第二脈衝時間； 將過剩之碳源化合物分子及所有的副產物分子 在第二洗淨時間中自該反應區中移除。 乂上之過渡金屬源化合物以選自由鈥、錯、給、飢、 备、絡、I目及鎢化合物的群組中為佳，並以為金屬 鹵化物為更佳。碳源化合物以選自由包含碳之硼、梦及 磷化合物組成的群組中為佳，其中烷基硼、烷基矽及烷 基磷化合物又為更佳。 在洗淨期間中，惰性氣體或貴重氣體被導入反應區 中 ^將過剩之化合物及副產物的濃度稀釋至不明顯之 程度，其中稀釋係以將以上分子驅入幫浦線中的方式為 之。 每一脈衝循環可使層膜增加以一金屬碳化物分子層 之同的厚度，而脈衝循環的正確次數則視應用之領域及 第20頁 本紙張尺度逋用中國國家揉準（CNS ) Μ規格（210Χ297公釐） 請 先 閲 背 之 注 意 事 項 再 527429 A7 B7 五、發明説明（） — 層膜所欲達到的厚度而定。 過渡金屬碳化物層可當作一擴散阻障層，因此基材 上可再接著加以不同處理，如沉積一層金屬晶種層等。 範例4 牲―次方式處理金屬碳化物储嗅用之工具 孔洞中可加以鑽錐鑽孔的方式而達到延長其可用壽 命目的’對該洞鍍以一金屬碳化物即可達成該目的。由 於本發明之A L D製程對樣品之結構並不敏感，因此其可 以批次處理之方式為之，也因此需鍍以膜層之部份可以 是相當小的結構，每一結構的鍍膜成本於是就可大大降 低。 基材支撐器中有很多的鑽孔設置於其中，而該基材 支撐器在基材欲進行處理時被載進一批次反應器之反應 區中。將真空區抽至真空。接著，反應區的壓力以加入 一惰性氣體（以氮氣為佳）的方式調整至一較佳之壓力， 如约1毫巴爾至5 0毫巴爾之間，並以為約3毫巴爾至1 〇 毫巴爾之間為更佳。反應區的製程溫度接著加以穩定至 較佳值’如約300°C至425°C，並以約為3 25 °C至3 75 °C 之間為更佳，在所舉之實施例中則設定至約3 5 0 °C。 過渡金屬源化合物以選自由鈥、錄、給、訊、銳、 組、路、翻及鎢化合物組成之群組中為佳，並以為金屬 鹵化物為更佳。碳源化合物以選自由包含碳之揮發性 硼、矽及磷化合物組成的群組中為佳，其中烷基硼、烷 _ 第21頁 本纸張尺度適用中國國家橾準（CNS ) A4規格（210X297公釐） " ""~ (請先閲讀背面之注意事項用填寫本頁) 裝Examples of carbon sources for metal carbide deposition disclosed in this case by Sigma Aldrich commercial magnetization are commercially available: Compound Synonym Boiling Point (CH3CH2) 3B Triethyl Shed + 95 (CH3CH2) 4Si Tetraethyl Silicon + 153 (CH3) 4Si tetramethyl silicon + 27 (CH3CH2) 3P triethyl phosphorus + 127 Example 1 When forming a transition metal carbide film on a substrate, thorium hexafluoride is used as the metal source chemical , And the carbon source is the triethyl side (c H 3 c Η 2) 3 B. A silicon wafer was loaded into the reaction zone of a Pulsar ™ 2000 reactor for the AlD process, which was purchased from a S M M i c r 0-c h e mi i s t r y 0 y of Espoo, Finland. The reaction zone is evacuated by a mechanical vacuum pump, and then a nitrogen gas with a purity of 99.9999% is supplied to adjust the pressure in the reaction zone to about 5 millibar to 10 millibar (absolute). Then, the reaction zone stabilized to about 3 50. (: .WF6 and (CH3CH2) 3B are supplied by external sources, and their electronic order pulses are gasified and alternately fed into the reaction zone to contact the substrate, where these source compounds are pulsed between each other to make use of nitrogen The washing method is used to separate them, so the pulse period includes the two source compounds. Page 17 _ ^ _ This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the notes on the back and fill in this first Page) Binding-Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 527429 A7 B7 V. Description of the invention (Pulse and two nitrogen washing air flow Gan Gan Yu Jian E # Also, the pulse is performed 167 times. Multiple pulse cycle The pulses and washing times are as follows: 025 seconds 3 · 0 seconds 0 · 5 seconds 3 · 0 minutes The washing time in the above cycle is reduced by tungsten hexafluoride pulse nitrogen cleaning operation period (CH3CH2) 3B pulse The optimization of the process conditions during the nitrogen purge action can be short. After the deposition is completed, the Shi Xi substrate is removed from the reactor for inspection and analysis. The results show that the entire surface of the substrate is covered with a thin film, and The film has a metallic gray luster, its adhesion to the substrate is good, and it is conductive. The film samples were analyzed for their composition by TOF-EDRA (time-of-flight bounce detection analysis), and measured by EDS (electronic diffraction spectrometer) Its thickness is measured by a four-point probe. In addition, the impedance value is derived from the thickness and the group impedance. According to the TOF-EDRA results, it can be known that the tungsten and carbon atomic ratio of the thin film sample is WSC, and the thickness of the sample is 23 nanometers, so we know that the growth rate of tungsten carbide is 1.4 Angstroms / cycle. The thickness grown in the above cycle is smaller than the lattice constant of tungsten carbide, part of the reason may be due to the precursor The size of the molecule takes up more surface space of the substrate than tungsten and carbon atoms. "The impedance of the film is 200 microohm · cm. The fluorine impurity concentration (atomic ratio) in the film is only about 1.0% to 1.5%. Page 18 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 527429 A7 B7 V. Description of the invention (Example 2 Metal carbide thin film 3¾ F-description of deposition I- -1--18 m. ..... > · A substrate is sent into a reaction zone, and the reaction zone is adjusted to a better temperature and a better pressure. The repeatable process sequence includes four steps, and the four steps begin at this time. The gas phase pulse of the transition metal source compound is sent into the reaction zone and comes into contact with the surface of the substrate. After a period of first contact time, the excess transition metal source compound and all reaction byproducts are removed from the reaction zone, in a manner of removal Then, the pressure in the reaction zone is changed and / or brought out by an inert gas stream. After the first cleaning time, a gas-phase pulse of a carbon source compound is sent to the reaction chamber and contacts the surface of the substrate. After a second contact time, excess carbon source compounds and all reaction by-products are removed from the reaction zone by removing pressure from the reaction zone and / or being carried out by an inert gas stream. After the second cleaning time, the manufacturing process is continued until the metal carbide film reaches a specific thickness. Finally, the substrate with a thin film is removed from the reaction chamber. The carbon source compound may be a boron, crushed, or squamous carbon source compound. Example 3 Using an ALD metal carbide as a barrier layer of an integrated circuit as shown in FIG. 1, a substrate has a trench 1 and a dielectric hole 2, an etching resist layer 3, a dielectric hole insulator 4, and a trench insulator 5, It is placed in the reaction zone of an ALD reactor. The reaction zone is evacuated and then adjusted to a preferred pressure by adding an inert gas (preferably nitrogen). Among them, page 19 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) Please read the notes on the back first \ ^^ · Pack: write this page) Order H— —ϋ — ^ ϋ 527429 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the Niobium. 5. Description of the invention (the preferred pressure is between about 1 mbar to 50 mbar, and more preferably between about 3 mbar and 100 mbar. The temperature of the reaction zone is then stabilized to a better sufficient process temperature, preferably between 300t and 425 ° C, more preferably between approximately 325C and 375 ° C, and approximately 35 (rc is Best. Next, the transition metal carbide layer 6 is deposited by performing the following cycles: sending a transition metal source compound into the reaction zone and contacting the substrate for a first pulse time; and excess transition metal source compound Molecules and all by-product molecules are removed from the reaction zone in the first washing time; a carbon source compound is sent into the reaction zone and brought into contact with the substrate for a second pulse time; the excess is Carbon source compound molecules and all by-product molecules during the second wash The transition metal source compound on the substrate is preferably selected from the group consisting of a compound, a compound, a compound, a compound, a compound, a compound, and a tungsten compound, and more preferably a metal halide. The carbon source compound is preferably selected from the group consisting of carbon-containing boron, dream, and phosphorus compounds, of which alkylboron, alkylsilicon, and alkylphosphorus compounds are more preferred. During the washing, the inert Gas or precious gas is introduced into the reaction zone ^ The concentration of excess compounds and by-products is diluted to an insignificant level, where the dilution is made by driving the above molecules into the pump line. Each pulse cycle can make The thickness of the film is increased by the same thickness of a metal carbide molecular layer, and the correct number of pulse cycles depends on the field of application and page 20. This paper size uses the Chinese National Standard (CNS) M specifications (210 × 297 mm). Read the precautions at the back first, then 527429 A7 B7 V. Description of the invention ()-It depends on the thickness of the film. The transition metal carbide layer can be used as a diffusion barrier layer, so it can be added on the substrate. The same treatment, such as depositing a metal seed layer, etc. Example 4-Treatment of metal carbide storage tool holes can be drilled with a drill to achieve the purpose of extending its useful life. A metal carbide can achieve this goal. Since the ALD process of the present invention is not sensitive to the structure of the sample, it can be processed in batches, and the portion to be coated with the film layer can be quite small Structure, the coating cost of each structure can be greatly reduced. There are many drill holes in the substrate support, and the substrate support is loaded into a batch of reactors when the substrate is to be processed. In the vacuum zone, the vacuum zone is evacuated to vacuum. Then, the pressure in the reaction zone is adjusted to a better pressure by adding an inert gas (preferably nitrogen), such as between about 1 millibar and 50 millibar. More preferably between about 3 millibar and 10 millibar. The process temperature in the reaction zone is then stabilized to a preferred value, such as about 300 ° C to 425 ° C, and more preferably between about 3 25 ° C and 3 75 ° C. In the illustrated embodiment, Set to approximately 3 5 0 ° C. The transition metal source compound is preferably selected from the group consisting of 、, 、, 、, 、, 锐, 路, 路, 及, and tungsten compounds, and more preferably a metal halide. The carbon source compound is preferably selected from the group consisting of volatile boron, silicon, and phosphorus compounds containing carbon, among which alkylboron, alkanes_ page 21 This paper is applicable to China National Standard (CNS) A4 specifications ( 210X297 mm) " " " ~ (Please read the precautions on the back first to complete this page)
、1T 經濟部智慧財產局員工消費合作社印製 527429 A7 B7 五、發明説明（ 基碎及燒基磷化合物又為更佳。 在洗淨期間中，惰性氣體或貴重氣體被導入反應區 中’以將過剩之化合物及副產物的濃度稀釋至不明顯之 程度，其中稀釋係以將這些分子驅入幫浦線中的方式為 之。 每一脈衝循環可使層膜增加以一金屬碳化物分子層 之高的厚度’而脈衝循環的正確次數則視應用之領域及 層膜所欲達到的厚度而定。 範例5 以—Δ孓D成長出之合馬瑞化物當作合鋼鑽沉精的 耜始表面 過渡金屬碳化物層可當作一金鋼鑽薄膜成長的成核 表面’其中前者以本發明之ALD製程沉積於一基材之 上，並接著當作金鋼鑽沉積的起始表面。 範例6 利股一A.LD金屬碳化物遠成與碳化矽之電性接觸 為了得到與碳化矽表面有較佳電性接觸的目的，本發 明之ALD製程中特形成一中介薄膜，該中介層由一金屬 破化物薄膜組成。首先，提供一碳化矽基材，其中基材表 面具有該第一少量金屬碳化物分子層發生成核作用所需 要的反應位置。該製程的最關鍵點在於該碳化矽表面上 ALD源化學物質之第一分子層的吸收作用。此外，該沉積 第22頁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公簸） (請先閲讀背面之注意事項^填寫本頁) 裝· 訂 經濟部智慧財產局員工消費合作社印製 527429 A7 B7 五、發明説明（） 製程可以金屬源化學物質先送入、或也可以碳源化學物質 先送入的方式為之。 範例7 j^L.ALD金屬碳化物常作一黏荖層 金屬碳化物可在一基材上當作一中介層，以改善後續 將沉積於基材上之材料的附著情況，其中該金屬碳化物薄 膜係以上述之沉積方法形成者。 範例8 知··以電聚形成金屬磑化物的製程 加入些許脈衝電漿時，本發明之沉積製程的沉積溫度 可降低，同時也能利用ALD製程以分子團形式之有機化 合物碎片來進行金屬碳化物薄膜的沉積。 在該實施例中，一基材先置於該反應區中。反應區的 壓力由一真空幫浦及惰性氣體流調整至一較佳值，而溫度 也同樣調整至一較佳值❶沉積製程於以上設定完成之後開 始展開。 將過渡金屬源化合物分子送入該反應區並與該 基材接觸一第一脈衝時間； 將過剩之過渡金屬源化合物分子及所有副產物 分子在第一洗淨時間中自該反應區中移除； 將碳源化合物以分子團之形式送入該反應區 中’並使之與該基材接觸一第二脈衝時間； _'__第23頁 本紙張尺度通用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 裝- 訂 經濟部智慧財產局員工消費合作社印製 527429 a7 B7 ___^^--- H、發明说明（） 將過剩之碳源化合物分子及所有的副產物分子 在第二洗淨時間中自該反應區中移除。 金屬碳化物薄膜在可加以厚度均句性控制之條件下 的最大沉積速率為每一循環内沉積一分子層之厚度。碳 源化合物以為僅包含碳及氫的有機化合物為佳，並以能 轉變成為電漿者為佳，其方法可為利用一些習用技術或 利用紫外線輻射、電弧光及射頻產生器將氣體原子或分 子轉變成電漿等方式。所產生的分子團以具有高氫/碳比 為佳，以能改善這些物種的揮發性，並降低基材上沉積 之富含碳層的揮發性過低的可能性。由於該實施例中使 用了脈衡式電漿，因此在金屬源化合物脈衝出現的時間 區間内以能將電聚源關閉或將其導開為佳，以使基材上 之金屬沉積不致變得不可控制。 以上之循環行之次數以能形成所需要之層膜厚度為 原則。沉積完成之後’基材由反應區中載出。 範例9 經濟部智慧財產总員工消費合作社印製 _HD金屬碳化物做成气身保謹層 當各元件曝於腐蚀性環境中時，軸承是其中一能夠受 到一硬式外層保護的零件。一组軸承被送入一具穿孔之基 材支撐器處’其中基材支撐器上表面的洞為圓錐形開口， 而軸承就座落於這些淺圓錐的底部上。接著，基材支撐氣 被送進反應區中，此時基材支撐器與源氣流及惰性氣流線 呈連接狀態。接著，反應區被抽至真空，並接著通入惰性 第24頁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 527429 A7 B7 五、發明説明（） 氣體於反應區中而將其内的壓力調整至一較佳之製程壓 力《其中，惰性氣體係由基材支撐器之孔洞處進入，並將 軸承從圓錐體的底部處舉起，而軸承最好能在流通的氮氣 流中自由旋轉（白努利定律）、並在沉積進行時不與任何固 體表面接觸為佳。此外，反應區的溫度加以調整至較佳 值。 ALD金屬碳化物沉積製程於以上設定完成之後開 始，並至少包含下列步驟： 將金屬源化合物送入該反應區並與該基材接觸 一第一脈衝時間； 將過剩之金屬源化合物分子及所有副產物分子 在一第一洗淨時間中自該反應區中移除； 將碳源化合物送入該反應區中，並使之與該基材 接觸一第二脈衝時間； 將過剩之碳源化合物分子及所有的副產物分子 在一第二洗淨時間中自該反應區中移除。 源化學物質氣流流過基材支撐器的圓錐洞，並與固定 於垂直氣流中的軸承相接觸。該製程於每一脈衝循環 中形成高至一分子層的金屬碳化物。在沉積過程之 後，氮流逐漸降低，直至軸承會至圓錐體的底部為 止。接著，基材支撐器可經由一負載室載出；或是不 經由負載室載出，而以將反應室之壓力增至與外部相 同之壓力的方式加以載出，其中反應室壓力之增加係 以通入惰性氣體之方式為之。 第25頁 本紙張尺度逍用中國國家橾率（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項弈填寫本頁) 裝- 訂 經濟部智慧財產局員工消費合作社印製Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1T, 527429 A7 B7 V. Description of the invention (Base broken and burned base phosphorus compounds are more preferred. During the cleaning period, inert gas or precious gas is introduced into the reaction zone. Dilute the concentration of excess compounds and by-products to an insignificant level, where the dilution is to drive these molecules into the pump line. Each pulse cycle can increase the layer film with a metal carbide molecular layer High thickness' and the correct number of pulse cycles depends on the field of application and the desired thickness of the layer film. Example 5 The Hemareth compound grown with Δ 孓 D is used as the beginning of Hesteel's immersion. The surface transition metal carbide layer can be used as a nucleated surface for the growth of a gold diamond film. The former is deposited on a substrate by the ALD process of the present invention, and then used as the starting surface for the gold steel diamond deposition. 6 A.LD. A. LD metal carbide is formed into electrical contact with silicon carbide. In order to obtain better electrical contact with the surface of silicon carbide, an intermediary film is specially formed in the ALD process of the present invention. The layer is composed of a thin metal carbide film. First, a silicon carbide substrate is provided, wherein the surface of the substrate has a reaction position required for the first small amount of metal carbide molecular layer to undergo nucleation. The most critical point of the process lies in the Absorption of the first molecular layer of the ALD source chemical on the surface of silicon carbide. In addition, the paper size on page 22 applies the Chinese National Standard (CNS) A4 specification (210X297). (Please read the precautions on the back first ^ (Fill in this page) Bookmark and print 527429 A7 B7 printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention () The process can be sent in by metal source chemical substances or carbon source chemical substances first. Example 7 j ^ L. ALD metal carbide is often used as an adhesive layer. Metal carbide can be used as an interposer on a substrate to improve the adhesion of subsequent materials deposited on the substrate, where the metal is carbonized. The thin film is formed by the above-mentioned deposition method. Example 8 Knowing ······································································································································ The deposition temperature can be reduced, and at the same time, the metal carbide film can be deposited in the form of molecular clusters by using the ALD process. In this embodiment, a substrate is first placed in the reaction zone. The pressure in the reaction zone is determined by A vacuum pump and an inert gas flow are adjusted to a preferred value, and the temperature is also adjusted to a preferred value. The deposition process is started after the above settings are completed. The transition metal source compound molecules are sent to the reaction zone and communicated with the The substrate is contacted for a first pulse time; excess transition metal source compound molecules and all by-product molecules are removed from the reaction zone in a first wash time; carbon source compounds are sent to the reaction in the form of molecular clusters 'And in contact with the substrate for a second pulse time; _'__ page 23 This paper size is common Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before (Fill in this page) Binding-Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 527429 a7 B7 ___ ^^ --- H. Invention Description () Excess carbon source compound molecules and all secondary The product molecules are removed from the reaction zone in a second wash time. The maximum deposition rate of metal carbide films under the condition that the thickness uniformity can be controlled is the thickness of one molecular layer deposited in each cycle. The carbon source compound is preferably an organic compound containing only carbon and hydrogen, and preferably one that can be converted into a plasma. The method can be the use of some conventional techniques or the use of ultraviolet radiation, arc light and radio frequency generator to gas atoms or molecules Into plasma and other methods. The resulting molecular clusters preferably have a high hydrogen / carbon ratio to improve the volatility of these species and reduce the possibility that the carbon-rich layer deposited on the substrate is too low in volatility. Since a pulse-balanced plasma is used in this embodiment, it is better to turn off the electropolymerization source or conduct it away during the time interval of the pulse of the metal source compound, so that the metal deposition on the substrate does not become Uncontrollable. The above number of cycles is based on the principle of forming the required film thickness. After the deposition is complete, the substrate is carried out from the reaction zone. Example 9 Printed by the Consumer Cooperative of the Intellectual Property Staff of the Ministry of Economic Affairs _HD metal carbides are used as a body protection layer. When each component is exposed to a corrosive environment, the bearing is one of the parts that can be protected by a hard outer layer. A set of bearings is fed into a perforated substrate support. The holes on the top surface of the substrate support are conical openings, and the bearings are seated on the bottoms of these shallow cones. Then, the substrate support gas is sent into the reaction zone, and at this time, the substrate support is connected to the source gas flow and the inert gas flow line. Then, the reaction zone was evacuated, and then inert. Page 24 This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 527429 A7 B7 V. Description of the invention () The gas will be in the reaction zone. The internal pressure is adjusted to a better process pressure. Among them, the inert gas system enters from the hole of the substrate support, and the bearing is lifted from the bottom of the cone, and the bearing is preferably in a flowing nitrogen stream. It is better to rotate freely (Banuli's law) and not contact any solid surface while the deposition is in progress. In addition, the temperature of the reaction zone is adjusted to a preferable value. The ALD metal carbide deposition process begins after the above settings are completed and includes at least the following steps: sending the metal source compound into the reaction zone and contacting the substrate for a first pulse time; passing the excess metal source compound molecules and all secondary The product molecules are removed from the reaction zone in a first wash time; the carbon source compound is sent into the reaction zone and brought into contact with the substrate for a second pulse time; the excess carbon source compound molecules And all by-product molecules are removed from the reaction zone in a second wash time. The source chemical gas stream flows through the conical holes of the substrate holder and contacts the bearings fixed in the vertical air stream. This process forms up to one molecular layer of metal carbide in each pulse cycle. After the deposition process, the nitrogen flow gradually decreases until the bearing reaches the bottom of the cone. Then, the substrate support can be carried out through a load chamber; or it can be carried out in such a way that the pressure of the reaction chamber is increased to the same pressure as the outside without being carried out through the load chamber. The increase in the pressure of the reaction chamber is Do this by passing inert gas. Page 25 This paper uses the Chinese National Standard (CNS) A4 size (210X297 mm) (Please read the precautions on the back and fill out this page) Binding-Order Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs