1375734 【發明内容】 發明概要 本發明鑒於上述問題而作，其目的在於提供一種用於 真空等離子體工藝設備的腔室及其内部部件的塗布材料， 5 以便在熱喷塗陶瓷過程中，減少保護塗層的内部缺陷，從 而提高耐腐蝕性並延長部件壽命。 本發明還提供一種上述用於半導體製造設備的塗布材 料的製造方法。 另外，本發明還提供一種利用所述塗布材料，對用於 10 半導體製造設備的部件進行塗布的方法。 本發明的熱喷塗材料是用於半導體製造設備的熱喷塗 材料，其組成成分為(AlxY^hCMx的範圍是0.05-0.95)，且 具有非晶態（amorphous)結構。 其中，X可以是0.5-0.95。 15 而且，熱喷塗材料可以包括粒徑為1-100 μιη的粉末。 本發明的用於半導體製造設備的熱喷塗材料的製造方 法包括以下步驟：i)混合粒徑為0.1-30 μιη的Α12〇3粒子和 Υ203粒子，以製備組成成分為（AlxY^hCMx的範圍是 0.05-0.95 )的物質；ii)對所述物質進行噴霧乾燥，以製備合 20 成粉末；iii)在800-1500°C的溫度下，煆燒所述合成粉末。 其中，混合所述物質的步驟可進一步包括施加靜電之 步驟，所述步驟誘導並使ai2o3粒子和Y203粒子分別攜帶不 同極性的電荷。 而且，所述施加靜電之步驟包括以下步驟：1)在溶劑 6 1375734 中添加聚甲基丙稀酸曱敍鹽（Poly-methyl metacrylic ammonium salt)，使Al2〇3粒子攜帶負電荷；2)在溶劑中添 加聚鍵酿亞胺(Poly-ethylen imide)，使Υ203粒子攜帶正電 荷。 5 本發明的用於半導體製造設備的熱喷塗材料的塗布方 法包括以下步驟：i)準備組成成分為(AlxY^hOKx的範圍是 0.05-0.95)的熱喷塗材料；ii)向等離子體火焰注入熱喷塗材 料，藉此加熱所述熱喷塗材料；iii)將透過加熱處於完全熔 融或半熔融狀態的熱喷塗材料層積在用於半導體製造設備 10的部件之表面上，以形成非晶態塗層。 其中，形成塗層的步驟可進一步包括形成金屬中間層 的步驟。 而且’所述形成塗層的步驟可進一步包括，逐漸改變 所述熱噴塗材料的組成成分，以形成梯度塗層的步驟。 15 而且在進行塗布時，可利用將熱喷塗材料的組成從與 被塗基材相同或類似的組成，逐漸改變為(Α1χΥΐ χ)2〇3_ 範圍是0.05-0.95)的梯度塗層的形成方法，形成梯度塗層。 另外’在形成塗層的步驟中，部件可以是真空等離子 體设備的腔室或腔室内部部件。 20 本發明的塗布材料由Al2〇々Y2〇3的粉末組成， 因而作 為半導體製造設備部件之材料被廣泛使用，且價格低廉。 而且所述塗布材料恨早就在半導體工藝上所使用，其穩定 性已被驗證’因而在其他半導體工藝中不會引發問題。 利用本發明的塗布材料，在基材上形成熱喷塗陶曼塗 7 (S > 層時，會形成非晶態的塗層。因此，在變為固體時所產生 的體積變化不大，從而可減少塗層的内部缺陷。 而且，由於塗層的内部缺陷減少’塗層保持較高的機 械強度，從而可提高在腐蝕環境下的耐腐蝕性。 另外，利用本發明的塗布粉末及塗布方法，可在真空 等離子體工藝設備的腔室及其内部部件上形成機械強产及 耐腐蝕性高的塗層。因此，可延長部件的使用壽命無兩 頻繁地更換製造設備的部件或經常維修製造膂 , σ又两，從而可 提南半導體的生產效率。 由於污練子的生成率降 並且’半導體製造工藝中 低’從而可提高產品品質。 圖式簡單說明 餘刻設備 第1圖係為半導體製造設備之一的等 的縱剖視圖。 * 丁锻热贾罜設備之等 示意圖 第3圖係為利用外部形式的等 _面^=賴㈣增卿成之砂 卞鉀栺顯微鏡照片。 第5圖係為用以 龜裂的電子掃描顯微鏡:片陶餘子在冷卻時產生 第6圖係為液態物 時間產生料化現“料模⑽變相料，根據溫度和 第7圖係為用以顯示液態物質經冷卻而變為固態時所 產生的體積變化過程的模式圖。 第8圖係為用以顯示液態物質變為結晶態固體時所產 生的缺陷之形成原理模式圖。 5 第9圖係為用以說明按材料的種類，冷卻時形成結晶態 固相的條件各異的模式圖。 第1 〇圖係為用以說明液態物質經冷卻而形成非晶態 時，所發生的體積收縮過程的模式圖。 第11圖係為用以說明液態物質成為非晶態時，阻止產 10生龜裂等缺陷的過程模式圖。 第12圖係為用以說明混合不同類型的粉末，以製備粉 末大小較大的熱喷塗用複合粉末過程的模式圖。 第13圖係為根據本發明合成的熱喷塗用陶瓷粉末的電 子掃描顯微鏡照片。 15 第14圖係為純ai2o3的X線分析結果(χ=ι)。 第15圖係為（Α1χΥΝχ)2〇3(χ = 0.9)的X線分析結果 (x=0.9)。 第16圖係為（Α1χΥΝχ)2〇3(χ = 0.6)的X線分析結果 (x=0‘6) 〇 20 第17圖係為（A1xYKx)2〇3(x = 0.1)的X線分析結果 (x=0.1) 〇 第18圖係為高純度Y203的X線分析結果(x=0)。 第19圖係為在(ΑΙχΥ,.ΑΟα^Ο.ό)粉末未完全熔融的狀 態下，進行熱喷塗而形成的塗層的X線分析結果(x=0.6)。 9 1375734 第20圖係為透過熱喷塗而形成的A1, .56Υ0.44Ο3物質的非 晶態塗層的低倍率電子掃描顯微鏡照片（Χ200)。 第21圖係為透過熱喷塗而形成的Al, .56Υ0.44Ο3物質的非 晶態塗層的低倍率電子掃描顯微鏡照片（Χ650)。 5 第22圖係為透過熱喷塗而形成的A1, .56Υ〇.4403物質的非 晶態塗層的高倍率電子掃描顯微鏡照片。 第23圖係為透過熱喷塗而形成的Ah.25Υ0.75Ο3物質的非 晶態塗層的低倍率電子掃描顯微鏡照片。 第24圖係為透過使用靜電混合方法而形成的 10 Ali.25Y0.75O3物質的非晶態塗層之低倍率電子掃描顯微鏡照 片。 第25圖係為用以顯示Α1203、Υ203的熱喷塗塗層與本發 明實施例塗層的硬度比較結果之曲線圖。 第26圖係為用以顯示Α1203、Υ203的熱喷塗塗層與本發 15 明實施例塗層的抗劃性能比較結果之曲線圖。 第27圖係為用以顯示Υ203熱喷塗塗層與本發明實施例 塗層對鹽酸的抗腐#性比較結果之曲線圖。 第28圖係為用以顯示Α12〇3、Υ203熱喷塗塗層與本發明 實施例塗層對腐蝕環境（等離子體）的耐久性比較結果之曲 20 線圖。 第29圖係為用以顯示按照本發明的實驗例4的條件所 製造的塗層的X線分析結果之曲線圖。 第30圖係為用以顯示按照本發明的實驗例5的條件所 製造的塗層的X線分析結果之曲線圖。 10 1375734 cf3、CF4、SF6、nf3、f2、CH2f2、CHF3、c2F6等含有氣元 素F的氣體；Cl2、BCh、SiCl4、HCl等含有氯元素⑽氣體； HBr、Βι*2、CFsBr等含有溴元素Br的氣體；以及其他siN4、 〇2、Ar、Η:等氣體中的一種或兩種以上混合氣體。 5 但是，蝕刻氣體不僅影響被蝕刻物件即基板15，而且 還會影響其他部分。即，所述蝕刻設備的腔室及其内部部 件也會由於製造工藝中腔室内部的極限環境而受到化學、 物理損傷。 蝕刻工藝是利用腐蝕性氣體及加速離子、等離子體 10等，對基板的整個表面或其局部施加物理-化學衝擊，從而 使其受損之後，去除受損部分的工藝，因此腔室内壁及内 部部件也會在此過程中遭受損傷。具體而言，腔室及内部 部件會受到化學反應性較高的蝕刻氣體之化學侵钱 (chemical attack)。同時，還會由於在RF電磁場的作用下加 速的離子化氣體粒子的爲擊（Ion bombardment)而JL表面 受到物理侵链(phyical attack) » 如上所述，如果腔室及内部部件在上述過程十受損， 就需要更換或清洗/維修受損的部分蝕刻設備，因此需要額 外支出費用。而且，為更換或清洗/維修設備，需要停止生 20產線’從而會延長產品的工期。 不僅如此，受損的腔室及内部部件之表面所產生的污 染物質可能會污染被蝕刻物件-晶片或LCD玻璃基板，因此 會增加半導體及LCD的不良率。 因此’為提高真空等離子體設備的腔室及内部部件的 12 耐久性，出現了各種方法。τ 卜面對習知的防止眞空等離子 體腔室内部及其内部部件輕的典型方法詳細說明。 通常，真空等離子體腔室的㈣為_鋼合金 、鋁（或 。金)或欽（或。金)等金屬材料和幻〇2、以或八丨办等陶 瓷材料。 由紹σ金製成的部件，廣泛採用透過陽極化工藝在基 材表面上形成Μ03陶竟塗層的技術。但是透過這種方法所 形成的陶曼塗層内部存在諸多缺陷，因此不僅很難達到高 硬度和耐腐肺要求，而且還存在污染粒子生成率比較高 10的缺點。 另外，難以進行陽極化工藝的各種金屬材料及陶瓷材 料，則採用透過耐腐蝕性較高、污染粒子生成率較低的外 部物質而形成保護膜的方法。 而且’眾所周知的還有單獨或混合使用所述塗布材料 15來進行熱喷塗的技術。但是如果以這種方法塗布所述物 質’則由於所產生的内部缺陷，會使塗層的特性極度惡化。 最近，對可適用於陽極化技術的鋁合金材料也採用利 用異型陶瓷材料形成保護膜的方法。利用異型陶瓷材料形 成保護膜的最具代表性的方法就是熱喷塗法。 2〇 熱喷塗法是向高溫等離子體火焰注入金屬或陶瓷粉 末’藉此加熱所述粉末之後，在完全炫融或半疼融的狀態 下’將其層積在基材表面上從而形成塗層的技術。 第2圖是熱噴塗設備的重要部分一等離子體搶的結構 示意圖。下面詳細說明等離子體槍20的工作原理。 13 1375734 首先，透過氣體注入口 21注入的等離子體氣體(Ar、 N2、H2、He等），在透過被施加高電力（通常為30-100 V ’ 400-1000A)的負極22和正極24之間的間隙的過程中，其中 一部分氣體被解理，從而形成500(M5000°C的高溫等離子 5 體火焰25。 為防止等離子體生成部分一負極末端的腐蝕，負極22 通常使用鎢或鎮強化金屬材料，而正極24則由銅或銅合金 製成，且其内部設有冷卻通道23，其用於防止由於高溫等 離子體’正極壽命縮短。 1〇 透過等離子體熱喷塗法，可以在金屬、陶瓷等各種材 料表面上塗布相同或不同的材料，所述塗布材料使用粉末 或線型金屬或陶瓷。 其次’將塗布材料製成粉末之後，透過粉末注入口 27 注入到高温等離子體火焰25之中。粉末注入口 27可透過支 15架26固定在等離子體搶（以下簡稱“外部形式"(EXTERNAL TYPE))上，也可以設置在正極24(以下簡稱“内部形式” (INTERNAL TYPE))上。 透過粉末注入口 27注入的粉末在被高溫等離子體火焰 兀全熔融或部分熔融的狀態下，高速(200〜1〇〇〇 m/s)飛到 20被塗部件30 ’從而形成塗層29。 對氧化物陶瓷材料進行等離子體熱噴塗時，可在大氣 中進行作業。但是，在高溫條件下引起氧化反應或容易分 解的金屬材料或碳化物、氮化物等材料則要在真空或低壓 的腔室内進行等離子體熱喷塗。 14 1375734 丰導3、^過熱噴塗所形成的塗層，仍然無法完全解決 半導體製k工藝中所出現的各種問題。 =3圖及第4圖是用電子掃描顯微鏡拍攝的，經過孰喷 成的塗層剖面之照片。其中，⑽作為半導體 裝二備精的保護塗層材料，獲得廣泛的應用。 圖是利用所述外部形式的等離子體搶塗布的保護 膜的剖面照片’其存在多個不規則缺陷。 所述條件下域的塗層，其機械雜(如硬度)相對優 異’但是所述雜對㈣子體姊騎之_距離，He、 10 H2二等乳體的,主入置’所施加的電力等熱喷塗條件的變 化非书敏《巾且’進仃塗布的過程中需要施加過大的電 力’所以存在能效降低的缺點。而且，為熔融《等高炼 點的材料，須制有利於提高等離子體溫度的氫氣等氣 體’而此時Y2〇3塗層上會形成黑點。 15 第4圖是利用所述内部形式的等離子體搶所形成的塗 層剖面的照片。從圖中可見，在個別液滴與基材衝突所形 成的攤片（SPLAT)内部’縱向形成多個龜裂，而且在攤片之 間的介面上也產生了縫隙。 20 在上述條件下所形成的塗層不僅其機械特性(如硬度) 不佳’ ^，攤片的内部㈣和其介__會成為反應 氣體的擴散通道。因此，會促進塗層的腐蝕反應，最終加 快污染粒子的形成。而且’半導體製造過程或清洗過程中 所施加的機械衝擊會使塗層容易受損。 並且，透過熱喷塗法塗布所述陶究材料時，會形成所 15SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to provide a coating material for a chamber of a vacuum plasma processing apparatus and internal components thereof, 5 for reducing protection during thermal spraying of ceramics. Internal defects in the coating to improve corrosion resistance and extend component life. The present invention also provides a method of producing the above-described coating material for a semiconductor manufacturing facility. Further, the present invention provides a method of coating a member for a semiconductor manufacturing apparatus using the coating material. The thermal spray material of the present invention is a thermal spray material for a semiconductor manufacturing apparatus having a composition (AlxY^hCMx ranging from 0.05 to 0.95) and having an amorphous structure. Wherein X can be from 0.5 to 0.95. Further, the thermal spray material may include a powder having a particle diameter of from 1 to 100 μm. The method for producing a thermal spray material for a semiconductor manufacturing apparatus of the present invention comprises the steps of: i) mixing Α12〇3 particles and Υ203 particles having a particle diameter of 0.1 to 30 μm to prepare a composition composition of (AlxY^hCMx) It is 0.05-0.95); ii) spray-drying the substance to prepare a 20-millimeter powder; iii) calcining the synthetic powder at a temperature of 800-1500 °C. Wherein the step of mixing the substance may further comprise the step of applying static electricity, the step inducing and causing the ai2o3 particles and the Y203 particles to carry charges of different polarities, respectively. Moreover, the step of applying static electricity comprises the steps of: 1) adding a poly-methyl metacrylic ammonium salt to the solvent 6 1375734 to cause the Al2〇3 particles to carry a negative charge; 2) A poly-ethylen imide is added to the solvent to cause the Υ203 particles to carry a positive charge. 5 The coating method of the thermal spray material for a semiconductor manufacturing apparatus of the present invention comprises the steps of: i) preparing a thermal spray material having a composition of (AlxY^hOKx ranging from 0.05 to 0.95); ii) to a plasma flame Injecting a thermal spray material, thereby heating the thermal spray material; iii) laminating a thermal spray material in a fully molten or semi-molten state by heating on a surface of a component for the semiconductor manufacturing apparatus 10 to form Amorphous coating. Wherein the step of forming a coating layer may further comprise the step of forming a metal intermediate layer. Further, the step of forming a coating layer may further include the step of gradually changing the composition of the thermal spray material to form a gradient coating layer. 15 Also, when coating, the composition of the thermal spray material can be gradually changed from the composition of the same or similar to the substrate to be coated to the formation of a gradient coating of (Α1χΥΐ χ) 2〇3_ ranging from 0.05 to 0.95). The method forms a gradient coating. Further, in the step of forming the coating, the member may be a chamber or a chamber internal part of the vacuum plasma apparatus. The coating material of the present invention is composed of a powder of Al2〇々Y2〇3, and thus is widely used as a material for components of semiconductor manufacturing equipment, and is inexpensive. Moreover, the coating material has long been used in semiconductor processes, and its stability has been verified' so that it does not cause problems in other semiconductor processes. With the coating material of the present invention, when a thermal spray Taman coating 7 (S > layer is formed on a substrate, an amorphous coating layer is formed. Therefore, the volume generated when it becomes a solid does not change much, Thereby, the internal defects of the coating can be reduced. Moreover, since the internal defects of the coating are reduced, the coating maintains high mechanical strength, thereby improving corrosion resistance in a corrosive environment. In addition, the coating powder and coating using the present invention are utilized. The method can form a coating with high mechanical strength and high corrosion resistance on the chamber of the vacuum plasma processing equipment and its internal components. Therefore, the service life of the component can be extended without replacing the components of the manufacturing equipment frequently or frequently. Manufacturing 膂, σ and two, so that the production efficiency of South Semiconductor can be improved. The production rate of the smear is reduced and the 'semiconductor manufacturing process is low', which can improve the product quality. The figure shows that the first picture of the remaining equipment is Longitudinal section view of one of the semiconductor manufacturing equipments. * Schematic diagram of the Ding forging hot Jiayu equipment, etc. Figure 3 is the use of the external form of the _ surface ^ = Lai (four) Zeng Qingcheng Photograph of potassium strontium microscope. Fig. 5 is an electron scanning microscope for cracking: the piece of terracotta is produced when it is cooled. Figure 6 is a liquid material. Time is generated. The material is now "material (10) phase change material, according to temperature and Figure 7 is a schematic diagram showing the volume change process produced when a liquid substance is solidified by cooling. Figure 8 is a pattern showing the formation of defects when a liquid substance becomes a crystalline solid. Fig. 5 Fig. 9 is a schematic diagram for explaining the conditions for forming a crystalline solid phase upon cooling according to the type of material. The first graph is used to illustrate that when a liquid substance is cooled to form an amorphous state. The pattern diagram of the volume shrinkage process that occurs. Fig. 11 is a schematic diagram showing the process of preventing the occurrence of cracks such as cracks when the liquid material becomes amorphous. Fig. 12 is a diagram showing the difference in mixing. A pattern of a powder of the type to prepare a composite powder process for thermal spraying having a larger powder size. Fig. 13 is an electron scanning micrograph of a ceramic powder for thermal spraying synthesized according to the present invention. X-ray analysis result of ai2o3 (χ=ι). Figure 15 is the X-ray analysis result of (Α1χΥΝχ)2〇3 (χ = 0.9) (x=0.9). Figure 16 is (Α1χΥΝχ)2〇3 X-ray analysis result (x = 0'6) 〇20 Figure 17 is the result of X-ray analysis of (A1xYKx)2〇3 (x = 0.1) (x=0.1) 〇Fig. 18 It is the result of X-ray analysis of high-purity Y203 (x = 0). Figure 19 is the X of the coating formed by thermal spraying in a state where the powder is not completely melted (ΑΙχΥ,.ΑΟα^Ο.ό). Line analysis results (x = 0.6). 9 1375734 Figure 20 is a low-magnification electron-scan micrograph (Χ200) of an amorphous coating of A1, .56Υ0.44Ο3 material formed by thermal spraying. Figure 21 is a low-magnification electron-scan micrograph (Χ650) of an amorphous coating of Al, .56Υ0.44Ο3 material formed by thermal spraying. 5 Figure 22 is a high-magnification electron-scan micrograph of an amorphous coating of A1, .56Υ〇.4403 material formed by thermal spraying. Figure 23 is a low-magnification electron scanning micrograph of an amorphous coating of Ah.25Υ0.75Ο3 material formed by thermal spraying. Fig. 24 is a low-magnification electron scanning microscope photograph of an amorphous coating of 10 Ali.25Y0.75O3 substance formed by using an electrostatic mixing method. Figure 25 is a graph showing the results of comparing the hardness of the thermal spray coating of Α1203, Υ203 with the coating of the embodiment of the present invention. Figure 26 is a graph showing the results of comparison of the scratch resistance of the thermal spray coating of Α1203, Υ203 and the coating of the embodiment of the present invention. Fig. 27 is a graph showing the results of comparison of the anti-corrosion effect of the Υ203 thermal spray coating with the coating of the embodiment of the present invention on hydrochloric acid. Fig. 28 is a graph showing the results of comparing the durability of the thermal spray coating of Α12〇3 and Υ203 with the corrosion environment (plasma) of the coating of the embodiment of the present invention. Fig. 29 is a graph showing the results of X-ray analysis of the coating layer produced in accordance with the conditions of Experimental Example 4 of the present invention. Fig. 30 is a graph showing the results of X-ray analysis of the coating layer produced in accordance with the conditions of Experimental Example 5 of the present invention. 10 1375734 cf3, CF4, SF6, nf3, f2, CH2f2, CHF3, c2F6 and other gases containing gas element F; Cl2, BCh, SiCl4, HCl, etc. contain chlorine (10) gas; HBr, Βι*2, CFsBr, etc. contain bromine a gas of Br; and one or a mixture of two or more gases such as siN4, 〇2, Ar, Η:. 5 However, the etching gas affects not only the object to be etched, i.e., the substrate 15, but also other portions. That is, the chamber of the etching apparatus and its internal components are also chemically and physically damaged due to the extreme environment inside the chamber during the manufacturing process. The etching process is a process of removing a damaged portion by applying a physico-chemical impact to the entire surface of the substrate or a portion thereof by using a corrosive gas, an accelerated ion, a plasma 10, or the like, thereby damaging the damaged portion, and thus the inner wall and the interior of the chamber Parts also suffer damage during this process. Specifically, the chamber and internal components are subject to chemical attack by highly chemically etched etching gases. At the same time, due to the Ion bombardment of the ionized gas particles accelerated by the RF electromagnetic field, the JL surface is subjected to a physical attack. As described above, if the chamber and internal components are in the above process ten Damaged, it is necessary to replace or clean/repair damaged parts of the etching equipment, so additional costs are required. Moreover, in order to replace or clean/repair the equipment, it is necessary to stop the production line, which will extend the product's construction period. Moreover, the contamination of the damaged chamber and the surface of the internal components may contaminate the object to be etched - the wafer or the LCD glass substrate, thus increasing the defect rate of the semiconductor and LCD. Therefore, various methods have appeared in order to improve the durability of the chamber and internal components of the vacuum plasma apparatus. τ Bu is described in detail in the conventional method of preventing the light inside the plasma chamber and its internal components. Usually, (4) of the vacuum plasma chamber is a metal material such as _ steel alloy, aluminum (or gold) or chin (or gold), and ceramic materials such as illusion 2, or octahedron. The parts made of Shaoqijin are widely used to form a Μ03 ceramic coating on the surface of the substrate through an anodizing process. However, there are many defects in the interior of the Tauman coating formed by this method, so that it is difficult to achieve high hardness and corrosion-resistant lung requirements, and there is also a disadvantage that the generation rate of contaminating particles is relatively high. Further, in the case of various metal materials and ceramic materials which are difficult to perform the anodizing process, a method of forming a protective film by using an external substance having high corrosion resistance and a low particle generation rate is used. Further, it is also known that the coating material 15 is used alone or in combination for thermal spraying. However, if the substance is coated in this way, the properties of the coating are extremely deteriorated due to internal defects generated. Recently, a method of forming a protective film using a shaped ceramic material has also been applied to an aluminum alloy material which can be applied to anodizing technology. The most representative method of forming a protective film using a shaped ceramic material is thermal spraying. 2. The thermal spraying method is to inject a metal or ceramic powder into a high-temperature plasma flame. After heating the powder, it is laminated on the surface of the substrate to form a coating in a state of complete blooming or semi-pain. Layer technology. Figure 2 is a schematic diagram of the structure of a plasma grab in an important part of the thermal spray equipment. The operation of the plasma gun 20 will be described in detail below. 13 1375734 First, the plasma gas (Ar, N2, H2, He, etc.) injected through the gas injection port 21 passes through the negative electrode 22 and the positive electrode 24 to which high electric power (usually 30-100 V '400-1000 A) is applied. During the interstitial process, a part of the gas is cleaved to form 500 (high temperature plasma 5 body flame of M5000 ° C. 25) In order to prevent corrosion of the plasma generating portion and the negative electrode terminal, the negative electrode 22 usually uses tungsten or town strengthening metal. The material, while the positive electrode 24 is made of copper or a copper alloy, and is internally provided with a cooling passage 23 for preventing the life of the positive electrode from being shortened due to the high temperature plasma. 1〇 Through the plasma thermal spraying method, it is possible to The same or different materials are coated on the surface of various materials such as ceramics, which are powder or linear metal or ceramic. Next, the coating material is powdered and then injected into the high temperature plasma flame 25 through the powder injection port 27. The powder injection port 27 can be fixed to the plasma grab (hereinafter referred to as "external form" (EXTERNAL TYPE)) through the support frame 26, or can be disposed on the positive electrode 24 ( Hereinafter, it is referred to as "internal TYPE". The powder injected through the powder injection port 27 is flying at a high speed (200 to 1 〇〇〇 m/s) in a state of being fully melted or partially melted by a high temperature plasma flame. The coating member 30 is formed to 20 to form the coating layer 29. When the plasma ceramic material is subjected to plasma thermal spraying, it can be operated in the atmosphere. However, the metal material or carbide which causes an oxidation reaction or is easily decomposed under high temperature conditions. Materials such as nitrides should be plasma-thermally sprayed in a vacuum or low-pressure chamber. 14 1375734 The coating formed by the superheated spray can still not completely solve the various problems in the semiconductor process. Fig. 3 and Fig. 4 are photographs of the cross section of the coating sprayed by a scanning electron microscope. Among them, (10) is widely used as a protective coating material for semiconductors. A cross-sectional photograph of the externally formed plasma-stretched protective film 'having a plurality of irregular defects. The coating under the condition is mechanically miscellaneous (such as hardness) For the excellent 'but the miscellaneous (four) child body 姊 _ distance, He, 10 H2 second-class milk, the main input 'electric power applied to the change of thermal spray conditions, etc. In the process of coating, excessive power is required to be applied. Therefore, there is a disadvantage that the energy efficiency is lowered. Moreover, in order to melt the material of the isothermal point, a gas such as hydrogen gas which is advantageous for increasing the plasma temperature is required, and at this time, Y2〇3 is coated. Black spots are formed on the layer. 15 Figure 4 is a photograph of a cross-section of the coating formed by the internal form of the plasma. It can be seen that the individual droplets collide with the substrate to form a patch (SPLAT). The inside 'forms a plurality of cracks in the longitudinal direction, and a gap is also formed in the interface between the sheets. 20 Under the above conditions, the coating formed not only has poor mechanical properties (such as hardness), but also the inside (4) of the sheet and its diffusion channel. Therefore, the corrosion reaction of the coating is promoted, and finally the formation of contaminating particles is accelerated. Moreover, the mechanical impact exerted during the semiconductor manufacturing process or cleaning process can easily damage the coating. Moreover, when the ceramic material is coated by thermal spraying, it will form a place.
(S 1375734 述攤片的内部龜裂及攤片間的縫隙。第5圖示出了上述缺 陷’而第5圖是一個陶莞粒子被等離子體火焰熔融之後層積 在基材表面而形成攤片時，用電子掃描顯微鏡拍攝其表面 的照片。這樣的缺陷在透過熱噴塗形成塗層後進行半導體 5製造的實際工程時會引發諸多問題。 其次，參照第5圖至第11圖說明在利用熱噴塗法來塗布 習知陶瓷材料時’攤片產生内部龜裂及介面缝隙的原因。 如第5圖所示，在攤片中產生多個龜裂。熱喷塗時，熔 融陶瓷粉末層積於基材表面，並經過冷卻而產生攤片。下 10面對此進行詳細說明。 組成液態陶究的元素（如丫2〇3中的Y和〇)間結合得比較 鬆弛，而立元素的排列順序也保持不規則的狀態。這樣的 液態陶瓷如果冷卻到熔點（Tm)以下，就會變成固態，並且 其組成元素之間的結合也會變得緊密，且變為元素排列有 15 規則的結晶態。 如上所述，進行熱噴塗時，在熔融陶瓷粉末層積在基 材表面並經冷卻的過程中，熔融陶竟粉末經過相變轉移到 結晶態，而所述結晶態致使攤片形成龜裂。 第6_示將喊材料冷卻到祕以下時，根據時間和 20溫度形成結晶態的條件。 陶竞在特定溫度附近(如第6圖中Tm)具有最快的相變 由、在此胍度下迅速變為結晶態。從液態變為固態的 如果冷卻時間短於在此溫度下進行結晶化所需的 _中不為t。*)’就無法形成結晶態。因此，陶究材 16 1375734 料如同在液態狀態下，轉變為組成元素間的排列不規則的 固體非晶態。 第7圖表示液態物質經過冷卻而變為結晶態固體時的 體積變化。 5 當溫度下降時，陶瓷物質因其組成元素之相鄰原子間 的距離縮短而收縮，而當形成組成元素有序排列的結晶態 時，其體積會陡然變小（如第7圖中的AV)。體積如此的急 劇變小，是熱喷塗工藝中，產生攤片的内部龜裂和介面縫 隙的原因。第8圖表示這種缺陷的形成過程。 10 為使液態的熔融陶瓷經冷卻而相變為固體，需要其組 成元素均排列到規定位置上。因此，組成元素的種類越多， 結晶態的原子排列結構越複雜，諸多種類的元素需要移動 到各自規定的位置上，因此排列需要較長的時間。 因此，如第9圖所示，如果組成元素的種類增加，與一 15 般的情況相比，AmorM(表示非晶態材料（amorphous materials)，是組成成分為(ΑΙχΥ^ΑΟ] (X的範圍是〇·〇5-0.95) 的非晶邊塗布材料的統稱’以下將這種非晶態材料稱為 “AmorM”)在相同的溫度下，形成結晶態所需時間更長。因 此，AmorM更容易形成為非晶態。 20 本發明實施例的塗布材料包括多組分陶瓷，如第9圖所 示，形成結晶態時所需要的時間較長。即，熱喷塗時，容 易形成非晶態。 而且，本發明實施例的塗層利用本發明實施例的多組 分陶瓷，使大部分塗層成為非晶態。此時，所述塗層至少 17 1375734 包括50%以上的非晶態為佳，而最好形成100%的非晶態。 塗層中的非晶態少於50%，就等同於包含50%以上的結 晶態。因此如上所述，其由液態轉變為結晶態固體的過程 中，其體積會產生很大的變化，從而會在塗層產生缺陷。 5 第10圖表示從液態相變為非晶態時的體積變化。如第 10圖所示，從液態變為非晶態時，其體積不會有急劇的變 化<。其原因是非晶態固體的原子排列與液體狀態下的原子 排列幾乎相同。因此，利用本發明的多組分陶瓷塗布材料 形成塗層，就會形成非晶態結構的固體，所以在特定溫度 10 下其體積不會有急劇的縮小。因此，不會產生從液態相變 為結晶態固體時的體積收縮而引起的攤片内部縱向龜裂及 介面縫隙等内部缺陷。第11圖表示從液態相變為非晶態固 態的過程。 下面，詳細說明形成本發明實施例的塗層的塗布材料。 15 為了容易形成非晶態的塗層’本實施例的塗布材料包 括多組分陶瓷材料，而這一多組分陶瓷材料含有3種以上元 素。 所述多組分陶瓷材料可使用包含Al2〇3及Y203的組成 元素即Al、Υ、Ο的多組分陶瓷材料。 20 所述多組分陶瓷材料的組成元素比例最好要滿足化學 式（ΑΙχΥ,.ΑΟΜχ為0.05-0.95)。如果X值小於0.05或大於 0.95，就會在利用已製成的粉末形成塗層的工藝中無法形 成百分之百的非晶態的塗層。從而會導致抗腐蝕性下降等 物理、化學特性的變劣。其中，氧元素的含量可根據熱噴 18 1375734 塗過程中火焰的溫度、喷射距離等而改變。 其次，說明製備本發明實施例的多組分陶瓷材料的方 法。 本發明的多組分陶瓷材料可透過以下幾種陶究合成方 5 法來製成粉末狀。 陶瓷合成方法的一種方法是，將含有A1和Y的化學物質 混合之後，經過熱處理去除不必要的元素，從而最終製備 由元素Al、Y、〇組成的粉末。其中，含有A1的化學物質有 A1(0H)3、A1(C3H503)3、Al(Cl8H33〇2)3、A1(Ci5H31C〇〇)3、 10 A12(S〇4)3等’含有Y的化學物質有Y2(C〇3)33H20、Y2(s〇4)3 8H20 等。 下面進一步詳細說明陶瓷粉末的製備方法。 第一種方法.首先將所述含有A1和Y的化學物質混合形 成(AIxYkhOdx為0.05-0.95)。其次，將其用高溫加熱，以 15 使除A1-Y-0以外的不穩定物質分解並去除，從而去除c、 Η、Ο等雜質。 第二種方法：將所述化學物質溶解于水或乙醇等溶劑 之後進行加熱，以製備具有（ΑΙχΥ,^ΟΑχ為0.05-0.95)組成 的A1-Y-0粉末。(S 1375734 describes the internal crack of the sheet and the gap between the sheets. Figure 5 shows the above defect' and Figure 5 shows a pottery particle that is layered on the surface of the substrate after being melted by the plasma flame. In the case of a sheet, a photograph of the surface thereof is taken by an electron scanning microscope. Such a defect causes a problem in the actual engineering of manufacturing the semiconductor 5 after forming a coating by thermal spraying. Next, the use of FIG. 5 to FIG. Thermal spraying method to apply conventional ceramic materials to cause the internal crack and interface gap to be formed. As shown in Figure 5, multiple cracks are generated in the tile. During thermal spraying, the laminated ceramic powder is laminated. On the surface of the substrate, and cooling to produce a spread. The next 10 faces are described in detail. The elements that make up the liquid ceramics (such as Y and 〇 in 丫2〇3) are loosely combined, and the arrangement of the vertical elements. The order is also kept in an irregular state. If such a liquid ceramic cools below the melting point (Tm), it becomes solid, and the bond between its constituent elements becomes tight, and the element is arranged in 15 gauges. As described above, in the thermal spraying, during the process in which the molten ceramic powder is laminated on the surface of the substrate and cooled, the molten ceramic powder is subjected to phase transformation to a crystalline state, and the crystalline state causes the wafer to be spread. Forming a crack. The 6th shows the condition that the crystalline state is formed according to the time and the temperature of 20 when the material is cooled below the secret. Tao Jing has the fastest phase change near the specific temperature (such as Tm in Fig. 6). At this temperature, it rapidly changes to a crystalline state. If the cooling time is shorter than the temperature required to perform crystallization at this temperature, it is not t. *) 'The crystalline state cannot be formed. Therefore, the ceramic material 16 1375734 is converted into an irregular solid amorphous state between the constituent elements as in the liquid state. Fig. 7 shows the change in volume when the liquid substance is cooled to become a crystalline solid. 5 When the temperature drops, the ceramic material shrinks due to the shortening of the distance between adjacent atoms of its constituent elements, and when the crystalline state of the constituent elements is formed, the volume will suddenly become smaller (such as AV in Fig. 7). ). The volume is so small that it is the cause of the internal cracks and interface gaps in the thermal spray process. Figure 8 shows the formation of such a defect. 10 In order for the liquid molten ceramic to be solidified by cooling, it is necessary to arrange the constituent elements to a predetermined position. Therefore, the more the types of constituent elements, the more complicated the atomic arrangement of the crystalline state, and the various types of elements need to be moved to their respective positions, so the arrangement takes a long time. Therefore, as shown in Fig. 9, if the type of constituent elements is increased, AmorM (representing amorphous materials) is a composition of (ΑΙχΥ^ΑΟ) (X range) compared with a case of 15 It is a general term for the amorphous edge coating material of 〇·〇5-0.95) 'This amorphous material is hereinafter referred to as "AmorM"). It takes a longer time to form a crystalline state at the same temperature. Therefore, AmorM is more It is easy to form an amorphous state. 20 The coating material of the embodiment of the present invention includes a multi-component ceramic, as shown in Fig. 9, the time required for forming a crystalline state is long. That is, when it is thermally sprayed, it is easy to form amorphous. Moreover, the coating of the embodiment of the present invention utilizes the multi-component ceramic of the embodiment of the present invention to make most of the coating amorphous. At this time, the coating at least 17 1375734 includes more than 50% of the amorphous state. Preferably, it is preferably 100% amorphous. The amorphous state in the coating is less than 50%, which is equivalent to containing more than 50% of the crystalline state. Therefore, as described above, it changes from a liquid state to a crystalline solid. In the process, its volume will change a lot, so it will The coating produces defects. 5 Figure 10 shows the change in volume from a liquid phase to an amorphous state. As shown in Fig. 10, the volume does not change sharply from a liquid state to an amorphous state. The reason is that the atomic arrangement of the amorphous solid is almost the same as the arrangement of the atoms in the liquid state. Therefore, by forming the coating by using the multi-component ceramic coating material of the present invention, an amorphous structure solid is formed, so at a specific temperature of 10 The volume does not decrease sharply. Therefore, internal defects such as longitudinal cracks and interface gaps in the sheet are not caused by volume shrinkage when the liquid phase changes to a crystalline solid. Fig. 11 shows the liquid phase from the liquid phase. The process of changing to an amorphous solid state. Hereinafter, the coating material forming the coating layer of the embodiment of the present invention will be described in detail. 15 In order to easily form an amorphous coating layer, the coating material of the present embodiment includes a multi-component ceramic material, and The multi-component ceramic material contains three or more elements. The multi-component ceramic material may use a multi-component ceramic material containing Al, yttrium and lanthanum, which are constituent elements of Al2〇3 and Y203. The compositional element ratio of the multi-component ceramic material preferably satisfies the chemical formula (ΑΙχΥ, ΑΟΜχ is 0.05-0.95). If the X value is less than 0.05 or greater than 0.95, it will not be possible in the process of forming a coating using the prepared powder. Forming a 100% amorphous coating, which leads to deterioration of physical and chemical properties such as corrosion resistance. Among them, the content of oxygen can be changed according to the temperature of the flame during the coating process of the thermal spray 18 1375734, the spray distance, and the like. Next, a method of preparing the multi-component ceramic material of the embodiment of the present invention will be described. The multi-component ceramic material of the present invention can be made into a powder by the following several methods of ceramic synthesis. One method of the ceramic synthesis method is After mixing the chemicals containing A1 and Y, the unnecessary elements are removed by heat treatment, thereby finally preparing a powder composed of the elements Al, Y, and yttrium. Among them, the chemical substance containing A1 includes A1(0H)3, A1(C3H503)3, Al(Cl8H33〇2)3, A1(Ci5H31C〇〇)3, 10A12(S〇4)3, etc. The substance is Y2(C〇3)33H20, Y2(s〇4)3 8H20 and the like. The preparation method of the ceramic powder will be described in further detail below. The first method is to first mix the chemical substances containing A1 and Y (AIxYkhOdx is 0.05-0.95). Next, it is heated at a high temperature to decompose and remove unstable substances other than A1-Y-0, thereby removing impurities such as c, ruthenium and osmium. The second method: the chemical substance is dissolved in water or a solvent such as ethanol, and then heated to prepare an A1-Y-0 powder having a composition of (0.05 to 0.95).
20 第三種方法：首先製備粒徑為1-100 μιη的A1金屬及Y 金屬的混合粉末，或者Α1和Υ的合金粉末之後，對所述混合 粉末進行氧化處理而合成所述粉末。其中，Α1金屬在常溫 下若與氧氣接觸，其表面也會被氧化而形成αι2ο3陶瓷，但 是為了易於進行氧化反應，可提高溫度加快氧化反應速 19 1375734 度。而且，還可以將Ai金屬製成粉末，以加大其反應面積。 不僅是A1金屬粉末’ Y金屬粉末及A1和Y的合金粉末也 可透過與A1金屬粉末的高溫氧化法相同的方法進行氧化， 從而製備(A12〇3)x(y2〇3)| X陶瓷。 5 萆四種方法U昆合A1金屬和Y金屬粉末之後，對所述混 合粉末進行氧化處理，以製備以比狀陶瓷，然後將其粉碎 製成粒徑等於或小於100 pm的粉末。此合成法與上述高溫 氧化法相同，都是在高溫下氧化金屬元素而形成氧化物的 方法。前面所述的高溫氧化法是對粉末進行氧化，而本方 10法則對粒徑為幾毫米（mm)或幾釐米（cm)的塊狀物進行氧 化0 製備金屬粉末將存在工藝複雜，製造成本增高的問 題但疋不管金屬合金的大小或形狀如何，若在bulk狀態 下進行氧化，就可用低廉的價格製造陶瓷材料。 15 第五種方法.混合粒徑為0.1-30 μηι的Al2〇3粒子和Y203 粒子，以製備組成成分為（Α1χϋ〇3(χ*〇〇5 〇95)的物 質’並進行賁霧乾燥，製備含有Α1、Υ、〇元素且粒徑為1_1〇〇 μηι的乾燥的合成粉末。 第五種方法中，將Al2〇3、丫2〇3粉末製備成組成成分為 2〇 (Α1χΥι·χ)2〇3(χ為0.05_0.95)的物質之後，與溶劑、結合劑、 分散劑等-起混合。然後’利用川航的空氣等氣體喷 霧，或者在高速旋轉的圓盤上形成微細的槽，並透過此槽 噴潔•，從而製造粒徑為1-200 μηι的粉末。 透過本方法所製造的粉末由於其強度較弱，因此還需 20 1375734 要在900-1500°C溫度下加熱。經過這種加熱工序，溶劑、 結合劑、分散劑等物質汽化，最終只剩下陶瓷粉末，由於 剩餘陶瓷粉末被燒結，所以粉末強度會提高。 第六種方法：透過以下步驟製備多組分混合粉末：誘 5 導並使粒徑為0.1-30 μιη的Al2〇3和Y203粒子攜帶極性互不 相同的電荷；混合帶不同靜電的粒子以製成組成成分為 (ΑΙχΥ,-ΑΟΑχ的範圍是0.05-0.95)的物質。僅僅以機械方式 混合ai2o3粉末和Y203粉末時，A1203粉末和Y203粉末混合 得不夠均勻。但是在第六種方法中，如第12圖所示，兩種 10 粒子在特定酸鹼度（例如pH值為6)的溶劑中由於靜電作用 而形成塊，因而ai2o3和Y203可以混合得非常均勻。因此， 可製備品質優異的粉末。 其中，使粉末帶電的方法如下：為了使αι2ο3帶負電 荷，在所述溶劑中添加聚甲基丙烯酸曱銨鹽（Poly-methyl 15 metacrylic amonium salt)，而為了使Y2O3帶正電荷，在所述 溶劑中添加聚醚醯亞胺(Poly-ethylen imide)。 所述製造方法的後序工序與噴霧乾燥法相同，只改變 了為進行喷霧乾燥的粉末之準備過程，因此本發明省略了 對後序工序的詳細說明。 20 將透過上述多種製造方法所合成的陶瓷粉末在 900-1500°C的溫度下進行煆燒處理，以製備具有適當強度 的熱喷塗粉末。 另外，本發明實施例的陶瓷粉末合成方法中，當混合 ai2o3粉末和Y203粉末時，為了使粉末比較容易混合，並使 21 1375734 混合的粒子均勻地分散，可使用溶劑和分散劑。而且，在 煆燒工序等後處理過程中，為保持其形狀，可使用結合劑。 陶瓷合成過程中使用的溶劑是選自水、丙酮或異丙醇 (Isoprophyl alchole)中的一種以上的混合液，而分散劑使用 5 咼分子聚合物(high molecular polymer)，結合劑可使用高分 子化合物(PVB76)或鄰苯二甲酸丁基苯甲酯（benzyl butyl phthalate)等。 第13圖表示用電子掃描顯微鏡觀察混合粉末的外形之 結果，所述混合粉末為利用本發明實施例的粉末製備方法 10 製成的包含Ab Y、0元素的多組分混合粉末。 下面，詳細說明利用本發明實施例的粉末製備方法製 成的陶瓷粉末，形成塗層之方法。 本發明實施例的塗布方法包括熱噴塗法。熱喷塗法包 括以下步驟：向等離子體火焰注入陶瓷粉末進行加熱；將 15 完全炫融或半'熔融狀態的粉末層積在等離子體腔室部件 (以下簡稱“基材”)之表面上，以形成塗層。 首先’準備用於塗布的粉末。用於熱喷塗的陶瓷粉末 為本發明實施例的粉末’可使用粒徑為1-100 μηι的單一粉 末。而且，也可使用將幾十納米及幾微米（μΓη)的一次微細 20 粉末凝聚成大小的粉末。 其次，向等離子體火焰注入所述的單一粉末或凝聚粉 末。被注入的粉末被火焰加熱飛散，並層積在基材表面上。 之後，被層積的粉末急劇冷卻，而形成塗層。 為穩定地進行塗布作業，並為了提高塗布材料的特 22 (S ) 性’可設;t不㈣作業條件。所述作業㈣可根據使用設 備和所使用的塗布粉末的大小及種類而異。 f驗例 下面，透過實驗例進一步詳細說明本發明。本發明的 實驗例中使用了私士 Plazmatek公司生產的“ρτ_8〇〇”電力施 加系統和美國Sulzer-Metco公司生產的“F4_HBS，，型等離子 體搶。而且，為形成等離子體使用了氬氣和氫氣，其使用 量分別控制在36L/分、417分。另外，將施加功率設定為 36Kw(6〇OA，60V)，將塗布粉末的注入速度設定為1〇g/分。 並將等離子體槍和被塗部件之間的距離設定為約12〇mnl左 右。 而且’本發明的實驗例中還使用了瑞士plazmatek公司 生產的“PT-800”電力施加系統和美國praxair公司生產的 “SG-100”型等離子體搶’並將氬氣使用量設定為4〇L/分， 將氦氣使用量設定為20L/分，將施加功率設定為25Kw，將 喷射距離設定為120mm。 首先’參照第13圖至第17圖’說明使用本發明實施例 的塗布粉末與使用純金屬氧化物（指A1及Y氧化物）之間的 區別。 為了觀察在不同組成的粉末條件下，塗層中所形成的 非晶態程度，調節(A1xYNx)2〇3中的X值而製備粉末，並使用 所生成的粉末透過熱喷塗法在腔室用基材上形成塗層。 第14圖表示透過等離子體熱噴塗法塗布純Al2〇3粉末 而形成的塗層的X線衍射值。為了與本發明實施例的陶瓷粉20 Third method: First, a mixed powder of A1 metal and Y metal having a particle diameter of 1-100 μm, or an alloy powder of lanthanum 1 and lanthanum is prepared, and then the powder is synthesized by oxidizing the mixed powder. Among them, when the ruthenium metal is in contact with oxygen at normal temperature, the surface thereof is also oxidized to form αι2ο3 ceramic, but in order to facilitate the oxidation reaction, the temperature can be increased to accelerate the oxidation reaction rate of 19 1375734 degrees. Moreover, the Ai metal can also be powdered to increase its reaction area. Not only the A1 metal powder 'Y metal powder and the alloy powder of A1 and Y can be oxidized by the same method as the high-temperature oxidation method of the A1 metal powder, thereby preparing (A12〇3)x(y2〇3)|X ceramic. 5 萆 Four methods U Kunming A1 metal and Y metal powder, the mixed powder is oxidized to prepare a ceramic, and then pulverized to a powder having a particle diameter of 100 pm or less. This synthesis method is the same as the above-described high-temperature oxidation method, and is a method of oxidizing a metal element at a high temperature to form an oxide. The high-temperature oxidation method described above oxidizes the powder, and the 10th method of the present invention oxidizes agglomerates having a particle diameter of several millimeters (mm) or several centimeters (cm). The preparation of the metal powder has a complicated process and a manufacturing cost. The problem of increase is that regardless of the size or shape of the metal alloy, if the oxidation is performed in the bulk state, the ceramic material can be manufactured at a low price. 15 The fifth method is to mix Al2〇3 particles and Y203 particles having a particle diameter of 0.1-30 μηι to prepare a substance having a composition of (Α1χϋ〇3(χ*〇〇5 〇95)' and drying it by mist. A dry synthetic powder containing cerium 1, lanthanum, cerium and having a particle diameter of 1 〇〇 〇〇 μη is prepared. In the fifth method, Al 2 〇 3 and 丫 2 〇 3 powders are prepared to have a composition of 2 〇 (Α1χΥι·χ). After 2物质3 (χ0.05_0.95), it is mixed with a solvent, a binder, a dispersant, etc., and then 'use a gas spray such as air from Sichuan Airlines or a fine disc on a high-speed rotating disc. The tank is sprayed through the tank to produce a powder having a particle size of 1-200 μη. The powder produced by the method has a weak strength, so it needs 20 1375734 to be heated at 900-1500 ° C. After this heating process, the solvent, the binder, the dispersant and the like are vaporized, and finally only the ceramic powder remains, and since the remaining ceramic powder is sintered, the powder strength is improved. The sixth method: preparing the multicomponent by the following steps Mixed powder: induce 5 leads and make the particle size 0.1-30 μιη of Al2〇3 and Y203 particles carry different charges with different polarities; particles with different static electricity are mixed to form a substance whose composition is (ΑΙχΥ, -ΑΟΑχ ranges from 0.05 to 0.95). Mechanical only When mixing ai2o3 powder and Y203 powder, A1203 powder and Y203 powder are not uniformly mixed. However, in the sixth method, as shown in Fig. 12, the two 10 particles are in a specific pH (for example, pH 6) solvent. Since a block is formed by electrostatic action, ai2o3 and Y203 can be mixed very uniformly. Therefore, a powder of excellent quality can be prepared. Among them, the method of charging the powder is as follows: In order to make αι2ο3 negatively charged, polymethyl is added to the solvent. Poly-methyl 15 metacrylic amonium salt, in order to make Y2O3 positively charged, poly-ethylenimide is added to the solvent. The subsequent steps of the manufacturing method and The spray drying method is the same, and only the preparation process for the powder for spray drying is changed. Therefore, the detailed description of the subsequent steps is omitted in the present invention. The ceramic powder synthesized by the method is subjected to calcination treatment at a temperature of 900 to 1500 ° C to prepare a thermal spray powder having an appropriate strength. Further, in the ceramic powder synthesis method of the embodiment of the invention, when the ai 2o 3 powder is mixed In the case of the Y203 powder, a solvent and a dispersing agent can be used in order to make the powder relatively easy to be mixed, and the particles mixed by 21 1375734 can be uniformly dispersed. Further, in the post-treatment process such as the calcining step, a binder can be used to maintain the shape thereof. . The solvent used in the ceramic synthesis process is a mixture of one or more selected from the group consisting of water, acetone or isopropanol (Isoprophyl alchole), and the dispersant uses a high molecular polymer, and the binder can use a polymer. Compound (PVB76) or benzyl butyl phthalate. Fig. 13 is a view showing the result of observing the outer shape of the mixed powder by an electron scanning microscope which is a multi-component mixed powder containing Ab Y, 0 element, which is produced by the powder preparation method 10 of the embodiment of the present invention. Next, a method of forming a coating using the ceramic powder produced by the powder preparation method of the embodiment of the present invention will be described in detail. The coating method of the embodiment of the present invention includes a thermal spraying method. The thermal spraying method comprises the steps of: injecting ceramic powder into a plasma flame for heating; and laminating 15 completely fused or semi-melted powder on the surface of a plasma chamber component (hereinafter referred to as "substrate") A coating is formed. First, prepare the powder for coating. Ceramic powder for thermal spraying A powder of the embodiment of the present invention can be used as a single powder having a particle diameter of 1-100 μη. Further, it is also possible to use a powder of a primary fine 20 powder of several tens of nanometers and several micrometers (μΓη) to be condensed into a size. Next, the single powder or agglomerated powder is injected into the plasma flame. The injected powder is heated and scattered by the flame and laminated on the surface of the substrate. Thereafter, the laminated powder is rapidly cooled to form a coating. In order to carry out the coating work stably, it is possible to increase the specific 22 (S) property of the coating material; t does not (4) the working conditions. The above operation (4) may vary depending on the size and type of the equipment to be used and the coating powder to be used. f. EXAMPLES Hereinafter, the present invention will be described in further detail by way of experimental examples. In the experimental example of the present invention, the "ρτ_8〇〇" power application system produced by the company Plazmatek and the "F4_HBS, type plasma grab" produced by Sulzer-Metco, USA are used. Moreover, argon gas is used for forming the plasma. The amount of hydrogen used was controlled at 36 L/min and 417, respectively, and the applied power was set to 36 Kw (6 〇OA, 60 V), and the injection speed of the coating powder was set to 1 〇g/min. The distance between the member to be coated and the member to be coated is set to about 12 〇mnl. Moreover, the "PT-800" power application system produced by the Swiss plazmatek company and the "SG-100" produced by the American praxair company are also used in the experimental example of the present invention. "Type plasma grab" and set the argon gas usage amount to 4 〇 L / min, the helium gas usage amount to 20 L / min, the applied power to 25 Kw, and the spray distance to 120 mm. First, refer to the 13th Figure to Figure 17' illustrates the difference between the use of the coated powder of the embodiment of the present invention and the use of pure metal oxides (referred to as A1 and Y oxides). In order to observe the coating conditions under different powder conditions To the degree of amorphous state, the powder was prepared by adjusting the X value in (A1xYNx)2〇3, and the resulting powder was used to form a coating on the substrate for the chamber by thermal spraying. Fig. 14 shows the plasma transmission. X-ray diffraction value of a coating formed by coating a pure Al 2 〇 3 powder by a body thermal spraying method. For the ceramic powder of the embodiment of the present invention
進订比& $過熱噴塗法塗布純A1203粉末之後，對其X 線衍射狀態進行了檢測。 p如第14圖所7F ’當使用純Al2〇3粉末時，在特定衍射角 :(第14圖表不為▽)下可觀察到高強度的峰值⑽k)。這種 阿強度的峰值存在—定的反復結構時才能出現由此可 見，當使用純ai2〇3粉末時，塗層内部將存在結晶態。 第15圖表不用成分為(A1xYl-x)2〇3的塗布用粉末來進行 熱嘴塗時’所形成的塗層之X線分析結果，其中χ為0.9。 如第15圖所示，與比較物件第13圖不同’在特定衍射 角度下，並不存在高強度的峰值。由此可見，（Αΐ"γ〇搞 粉末適合形成本發明實施例的非晶態塗層。 其次’將χ值調整為0.6，製備組成成分為(Α10.6Υ0.4)2〇3 的粉末之後，進行等離子體喷塗而形成塗層，並對該塗層 進行了X線分析。 第16圖疋組成成分為(AU^4)2。3的塗層的X線分析结 果。可見，當X為〇·6時，塗層仍是非晶態結構。 然後’將X值調整為0」，製備組成成分為(Α1〇ιΥ〇9)2〇3 的塗布粉末之後，進行了熱喷塗。 第17圖疋組成成为為(AUo.9)2。3的塗層之X線分析会士 果。如第17圖所示，在X軸的角度(2Θ)30。和4〇。之間出現微 小的峰值。由此可見，用（Al^Yo^O3粉末所形成的塗層大 部分形成為非晶態，但是一部分形成為結晶態。 另外，第18圖表示透過等離子體熱喷塗法塗布純γ2〇3 粉末而形成的塗層的X線衍射值。為了與本發明實施例的陶 24 1375734 究粉末進行比較，透過等教子體熱喷塗法塗布純ΥΛ粉末 之後，利用X線分析設傷測定其衍射狀態。 由第18圖可見，在特定角度下出現較強的峰值。由此 可見，如上述說明，利用純他塗布時，大部分都形成為 結晶態。 战马 另外，透過由純彻3形成的塗層與由純⑽3形成的塗 層的X線衍射之比較結果可知，不僅結晶態峰值的位置不 同，而且由純Al2〇3形成塗層時，整體上衍射蜂值的強度 低’與此相反，由純Y2〇3形成塗層時，在3〇。_4 : 測到更大驗。 & 這說明’由純Α】2〇3形成的塗層並不會形成完整的往曰 態，而會形成與其混雜在-起的一部分非晶態態結構。^ 此可見，與Υ2〇3相比’ Al2〇3更容易形成非晶態。即，為了 15 更谷易形成非晶態，優選將χ的範圍設定為G5_G 9，在此 況下，A1成分多於γ 〇 月 從上述實驗例可知，（Α1χΥΐ-χ)2〇3中，當χ值在〇 1〇 9的 可變範圍内時，可形成優質的非晶態塗層。 ·， .其次，參照第19圖說明，在熱喷塗過程中，根據塗布 條件的變化可能會產生的缺陷。 20 第19圖表示利用本發明實施例的粉末進行等離子體埶 噴塗所形成的塗層之X線分析結果。在此，所使用的是具有' (Α1〇‘6Υ〇·4)2〇3組成的粉末，該組成符合本發明的條件，作Β 其在低的等離子體溫度條件下，或者在粉末未完全熔融= 狀態下進行了熱喷塗。 、After the order ratio & $superheat spray method was applied to the pure A1203 powder, the X-ray diffraction state was examined. p, as shown in Fig. 14, when the pure Al2〇3 powder was used, a high intensity peak (10)k was observed at a specific diffraction angle: (the 14th graph is not ▽). This peak of the intensity can exist in the presence of a repeating structure, and when pure ai2〇3 powder is used, there will be a crystalline state inside the coating. The fifteenth graph shows the result of X-ray analysis of the coating formed when the coating powder of the composition (A1xYl-x) 2〇3 is used for the hot-mouth coating, wherein χ is 0.9. As shown in Fig. 15, unlike the comparative object Fig. 13, 'at a certain diffraction angle, there is no peak of high intensity. It can be seen that (Αΐ"γ〇 powder is suitable for forming the amorphous coating of the embodiment of the invention. Secondly, the enthalpy value is adjusted to 0.6, and the powder having the composition of (Α10.6Υ0.4)2〇3 is prepared. The coating was formed by plasma spraying, and the coating was subjected to X-ray analysis. Figure 16 shows the X-ray analysis results of the coating composition of (AU^4) 2.3. It can be seen that when X When it is 〇6, the coating is still in an amorphous structure. Then, the X value is adjusted to 0, and a coating powder having a composition of (Α1〇ιΥ〇9)2〇3 is prepared and then thermally sprayed. The composition of Fig. 17 becomes the X-ray analysis of the coating of (AUo.9)2.3. As shown in Fig. 17, the angle between the X-axis (2Θ) 30 and 4〇 appears tiny. It can be seen that the coating formed by the (Al^Yo^O3 powder is mostly formed into an amorphous state, but a part thereof is formed into a crystalline state. In addition, Fig. 18 shows that the coating is pure by plasma thermal spraying. The X-ray diffraction value of the coating formed by the γ2〇3 powder. In order to compare with the powder of the ceramic 24 1375734 of the embodiment of the present invention, After coating the pure tantalum powder by coating, the diffraction state was measured by X-ray analysis. It can be seen from Fig. 18 that a strong peak appears at a specific angle. Thus, as described above, when using pure coating, it is large. The part is formed into a crystalline state. In addition, the comparison between the coating formed by pure 3 and the X-ray diffraction of the coating formed of pure (10) 3 shows that not only the positions of the crystalline peaks are different, but also pure Al 2 〇 3 When the coating is formed, the intensity of the diffraction bee value as a whole is low. In contrast, when the coating is formed from pure Y2〇3, it is at 3 〇. _4 : A greater test is detected. & This shows 'by pure Α 】 2 The coating formed by 〇3 does not form a complete enthalpy, but forms a part of the amorphous structure mixed with it. ^ It can be seen that 'Al2〇3 is more likely to form amorphous than Υ2〇3 That is, in order to form an amorphous state, it is preferable to set the range of χ to G5_G 9, in which case, the A1 component is more than γ. From the above experimental example, (Α1χΥΐ-χ) 2〇3 Medium, when the χ value is within the variable range of 〇1〇9, it can form high quality Amorphous coating. Next, referring to Fig. 19, defects which may occur depending on changes in coating conditions during thermal spraying. 20 Figure 19 shows plasma using the powder of the embodiment of the present invention. X-ray analysis results of the coating formed by the body spray coating. Here, a powder having a composition of '(Α1〇'6Υ〇·4) 2〇3 is used, and the composition conforms to the conditions of the present invention as Thermal spraying is carried out under low plasma temperature conditions or in the state where the powder is not completely melted.
25 如第19圖所不，整體上看，在部分角度下形成峰值。 因此可以看出，在非晶態結構中混雜一些結晶態。這是因 為熱喷塗時’由於等離子體溫度低或者粉末未完全炫融等 原因，粉末中的結晶態直接傳到塗層的結果。 5 另外，在塗布過程中，當基材或塗布表面的溫度高到 可使非晶態經過相變而轉移到結晶態時，一部分非結晶態 也會經過相變而轉移到結晶態，從而形成非晶態與結晶態 相混合的結構。 在上述條件下所形成的塗層中大部分為非晶態，並在 1〇其中分散有一部分結晶態，且塗層内部未形成氣孔及攤片 的介面間隙。可見，即使形成塗層時條件不夠充分，但是 與使用純A1或純Y氧化物的塗層相比，在上述條件下形成的 塗層更具有優異的特性。 下面，參照第20圖至第22圖，說明本發明第一實驗例 15的塗層。在第一實驗例中，先製備組成成分為(ai0.78 Υ〇.22)2〇3 的多組分粉末後’使用内部形式的等離子體搶形成非晶態 塗層。以下，將本發明第一實驗例的非晶態塗層稱為 AmorMl。 第20圖及第21圖是對Am〇rMl塗層的剖面進行鏡面處 20理之後，透過電子掃描顯微鏡觀察的結果。第20圖及第21 圖中雖然發現了少許龜裂現象，但是並沒有觀察到通常的 熱喷塗結晶態塗層中常見的攤片内部的縱向龜裂及攤片間 縫隙。 第22圖為用高倍率投射電子顯微鏡觀察AmorMl非晶 26 態塗層的結果。從第22圖中可以確認，AmorMl塗層具有非 結晶結構。 下面，透過第23圖說明本發明第二實驗例的塗層。 第二實驗例中，製備了組成成分為(ai0.625y0 375)2〇3的 5多組分粉末，並使用内部形式的等離子體搶形成非晶態塗 層。以下’將本發明第二實驗例的非晶態塗層稱為AmorM2。 第23圖是對所述AmorM2塗層的剖面進行鏡面處理之 後，拍攝到的電子掃描顯微鏡照片。如第23圖所示 ，AmorM2 具有與第22圖的AmorMl塗層類似的形狀。即，並未產生攤 10片内部的縱向龜裂及攤片間的縫隙。 另外，本發明第三實驗例的塗層雖然與Am〇rM2組成成 分相同，但採用的是為使Al2〇3粉末和γ2〇3粉末均勻分散， 誘導並使其分別攜帶負電荷及正電荷之後混合的方法。 第24圖表示用電子掃描顯微鏡觀察第三實驗例的塗層 15剖面之結果。從圖中可見，由於採用了靜電混合的方法， 喷塗用粉末在所有的部分都保持均句的組成，所以沒有形 成攤片介面’從而形成了優質的塗層。 而且’從第24圖中可知，部分結晶態粒子分散在被塗 部件的表面（照片中的下部）。這是由於等離子體火焰的溫度 20低，未完全熔融粉末中的結晶態，或者由於被塗部件表面 及基材的溫度過尚’從而導致非晶態物質經過相變轉移到 結晶態的結果。 下面’參照第25圖至第28圖，說明Am〇及Am〇rM2 蜜層的機械、化學彳紐。S25gj至第28圖表* Am〇rM1和 27 1375734 第28圖表示本發明實施例的等離子體真空腔室的对久 性測定結果。 參照第28圖，本發明實％例的塗層對等離子體環境的 耐久性，與比較例1相比優異5倍以上。對耐久性的評價， 5採用了透過半導體製造設備之一，即等離子體蝕刻設備， 並使用CF<i+〇2氣體來钱刻被塗部件之後，測定姓刻深度的 方法。 耐久性測定條件具體說明如下。 以Si〇2每分鐘被蝕刻l〇〇nm的條件為基準，即將cf4氣 10 體注入速度設定為 3〇sccm(standard cubic centimeters per minute)，〇2氣體注入速度設定為6sccm，對主電極的輸入功 率設定為900W，偏置功率設定為90W，蝕刻腔室壓力設定 為5mtorr，並將腔室内部溫度保持在25°C 〇 表1中比較了比較例1及比較例2的塗層和本發明實施 15 例的塗層的特性。表1中的資料是在上述耐久性測定條件下 進行測定的結果。 表1 試料特性 比較例l(Al2〇3) 比較例2(Υ2〇3) 實施例 (AmorM) 硬度(Hv.200g) 800-850 300(I)-500(E) 700-750 劃痕深度 (Scratch Depth, μηι) 1 10(E)-22(I) 1.2 耐腐蝕性(g/g) _ 0.55 0.09-0.11 ICP等離子體耐腐蝕 性(nm/min) 9.5 1.7-1.8 1.6-1.9 缺陷(攤片介面縫 隙，氣孔） 有 有 良好 如表1所示，本發明實施例的塗層硬度與比較例1相 (S ) 29 1375734 似，耐腐蝕性與比較例2相似或者比它優異，因而本發明實 施例的塗層不僅具有一般塗層的優點，而且不會容易產生 其他缺陷。因此，本發明實施例的塗層與比較例相比，具 有優異的物理、化學特性。 5 另外，為了更詳細地說明本發明的優異特性，在腐蝕 性較強的條件下進行了等離子體真空腔室的耐久性實驗。 表2 塗布 變數 D (mm) Ar (psi) He (psi) 粉末 供給 速度 (RPM) 載氣 供給 速度 (psi) 電流 (A) 電壓 (V) 等離子體搶 掃描速度 (mm/sec) 實驗 例4 30 115 3 20 900 39.5 實驗 例5 150 40 65 3 20 37.3 1000 實驗 例6 40 85 3.5 50 40.8 用於本實驗的組成成分與AmorM2的組成成分相同，且 其製備成粒徑大小為10- 60 μιη的粉末。而且，根據所述表2 10 的比較例及實驗例的條件製造塗層。 第29圖表示本發明實驗例3的塗層的X線分析結果。從 第29圖中可以觀察到多個峰值，塗層整體上是非晶態，但 是也存在部分結晶態。 第30圖及第31圖分別表示按照本發明實驗例4及實驗 15 例5的條件製成的塗層之X線分析結果。從第30圖及第31圖 中可以觀察到，實驗例4及實驗例5與實驗例3不同，在該條 件下形成幾乎100%的非晶態。 在測試抗腐蝕性之前，首先對各實驗例的塗層進行了 硬度測試。塗層硬度透過將負重設定為200g的維氏硬度計 20 進行了測定。其測試結果如表3所示。 30 1375734 表3的結果顯示’產生部分結晶態的實驗例4的硬度與 實驗例5及實驗例6相似，塗層在整體上形成非晶態時，即 使包含部分結晶態，也不會對硬度產生太大的影響。 5 另外，塗層由100%的非晶態構成，即塗層内部未形成 氣孔而緊密構成時，硬度值會增加。因此，如同實驗例5及 實驗例6所示’由100%的非晶態構成的塗層，其硬度值也 會根據塗布條件發生變化。 其次’如上所述’在易於發生腐蝕的條件下，測定了 10 各塗層的耐腐钱性。 15 條件 實驗例4 實驗例5 實驗例6 硬度值(Hv) 645 593 750 該實驗是在Si〇2以300nm/分的速度被ϋ刻的條件下進 行的。具體而言’將CF4氣體的注入速度設定為40sccm， 〇2的注入速度設定為lOsccm，主電極的輸入功率設定為 1000W，偏置功率設定為150W ’蝕刻腔室内的壓力設定為 5mtorr，並將腔室内部溫度保持在25七。而且，將暴露於等 離子體環境中的時間設定為1小時。 第32圖及第33圖表示透過電子掃描顯微鏡觀察蝕刻試 驗前後的塗層表面的結果。第32圖表示触刻前的塗層表 面，第33圖表示钱刻後的塗層表面。觀察結果如表4所示。 --------η 比較例1 比較例2 實驗例4 實驗例5 實驗例6 平均蝕刻速度 (nm/min) 77.2 20.22 15.83 10.5 3.58 31 (S ) 20 1375734 從表4的平均_速度來看，本發明實驗例的姓刻速度 大大It於比較例。由此可見，本發明實施例的塗層在強氧 化條件下’也具有很強的耐久性。實驗例4是形成部分結晶 態的實驗例，其與由ι00%的非晶態構成的實驗例5及實驗 5例6相比，顯示出較快的蝕刻（腐蝕）速度.可見，只有在塗 層構成100%的非晶態的情況下，才能最有效地防止腐钱。 而且，對表1和表4的結果進行比較可以得出，在較弱 的腐姓環境(以Si〇2為基準時，腐姓速度為削nm/分)下，本 發明實她例的塗層與比較例2相比時其腐餘速度相差無 10幾’但是在較強的腐钱環境（以Si〇2為基準時，腐蝕速度為 300nm/分)下’本發明實施例的塗層表現出遠遠慢於比較例 2的腐蚀速度。可見’本發明實施例的塗層在強腐蚀性環境 下，仍然具有非常優異的耐腐蝕性。 另外’本發明可進一步包括形成金屬中間層的步驟， 15其目的在於提高熱喷塗的粘結強度。本發明還可進一步包 括透過逐次改變基材和被塗部件的組成成分，形成多個塗 層的步驟(梯度塗層的形成方法）。 在基材上形成金屬中間層，從而在塗布與基材的物理 化學特性不同的材料時’也能夠解決塗層因其介面脆弱而 20 容易剝離的問題。 在本發明實施例的塗層及被塗部件之間，可透過下述 方法形成中間層之後，塗布本發明的非晶態材料。在鋁 基材上塗布Zr〇2時’可使用熱膨脹係數小的NiCrA1Y等物質 來形成中間層。2)在鋁金屬上可使用強度高、埘腐蝕性優 32 1375734 秀的FeCr類非晶態金屬來形成中間層。3)在金屬基材上， 可使用Cr、Ni、Fe或包括所述金屬的合金來形成中間層。 4)在Al2〇3、Si、Si02等基材上，可以使用相同物質來形成 中間層之後，塗布本發明的非晶態材料。 5 如此，透過本發明的金屬中間層的形成方法，可防止 塗層的剝離，並可進一步提高耐腐蝕性。 另外，本發明實施例的塗層及部件之間可以不具備斷 續的第二塗層（中間層），而是採用梯度塗層，具體而言，準 備與基材相同或類似的物質粉末之後，在塗布過程中逐漸 10 增加本發明非晶態塗布材料的含量。利用此種方法可提高 塗層的财久性。 而且，可採用與其它的塗層形成技術聯用，或者在部 分熱喷塗塗層上使用本發明的非晶態塗層等方式的改良技 術。 15 上面對本發明的優選實施例進行了說明，但是本發明 並不局限於此，在本發明的申請專利範圍、發明内容及圖 示範圍内所作的各種修飾及變更，均屬於本發明的保護範 圍。 【圖式簡單說明3 20 第1圖係為半導體製造設備之一的等離子體蝕刻設備 的縱剖視圖。 第2圖係為等離子體熱喷塗設備之等離子體搶的剖面 示意圖 第3圖係為利用外部形式的等離子體搶所形成之 33 氧化釔）塗層剖面的電子掃描顯微鏡照片。 第4圖係為利用内部形式的等離子體搶所形成之⑽ 塗層剖面的電子掃描顯微鏡照片。 第5圖係為用以顯示液態溶融陶竞粒子在^^ 龜裂的電子掃描顯微鏡照片。 7部時產生 第6圖係為液態物質經冷卻而變相態時，根 時間產生結晶化現象的條件模式圖。 '皿又 第7圖係為用以顯示液態物質經冷卻而變為固 產生的體積變化過程的模式圖。 第8圖係為用以顯示液態物質變為結晶態 生的缺陷之形成原理模式圖。 時所產 第9圖係為用以說明按材料的種類’冷卻時形成結晶熊 固相的條件各異的模式圖。 第10圖係為用以說明液態物質經冷卻而形成非曰熊 15時’所發生的體積收縮過程的模式圖。 一 第11圖係為用以說明液態物質成為非晶態時，阻止產 生龜裂等缺陷的過程模式圖。 第12圖係為用以說明混合不同類型的粉末，以製備於 末大小較大的熱噴塗用複合粉末過程的模式圖。 20 第13圖係為根據本發明合成的熱喷塗用陶竞粉末的電 子掃描顯微鏡照片。 第14圖係為純Al2〇3的X線分析結果(x= i)。 第15圖係為（ΑΙχΥ^ζΟ# = 0.9)的X線分析社果 (x=0.9)。 34 1375734 第16圖係為（Α1χΥΝχ)203(χ = 0.6)的X線分析結果 (χ=0·6) 〇 第17圖係為（AlxY^hO# = 0.1)的X線分析結果 (x=0.1) 〇 5 第18圖係為高純度Y203的X線分析結果(x=0)。 第19圖係為在(AlxY^hCMx^j)粉末未完全熔融的狀 態下，進行熱喷塗而形成的塗層的X線分析結果(x=〇.6)。 第20圖係為透過熱喷塗而形成的A1, .56Y〇.4403物質的非 晶態塗層的低倍率電子掃描顯微鏡照片（Χ200)。 10 第21圖係為透過熱噴塗而形成的Ah .56Υ〇.44 03物質的非 晶態塗層的低倍率電子掃描顯微鏡照片（Χ650)。 第22圖係為透過熱喷塗而形成的A1, .56Υ〇.4403物質的非 晶態塗層的高倍率電子掃描顯微鏡照片。 第23圖係為透過熱喷塗而形成的All.25Υ〇.75〇3物質的非 15 晶態塗層的低倍率電子掃描顯微鏡照片。 第24圖係為透過使用靜電混合方法而形成的 ΑΙ,.^Υο.^Οβ物質的非晶態塗層之低倍率電子掃描顯微鏡照 片。 第25圖係為用以顯示Α12〇3、Υ203的熱喷塗塗層與本發 20 明實施例塗層的硬度比較結果之曲線圖。 第26圖係為用以顯示Α12〇3、Υ203的熱喷塗塗層與本發 明實施例塗層的抗劃性能比較結果之曲線圖。 第27圖係為用以顯示Υ203熱噴塗塗層與本發明實施例 塗層對鹽酸的抗腐蝕性比較結果之曲線圖。 35 1375734 第28圖係為用以顯示Al2〇3、Υ203熱噴塗塗層與本發明 實施例塗層對腐蝕環境（等離子體）的耐久性比較結果之曲 線圖。 第29圖係為用以顯示按照本發明的實驗例4的條件所 5 製造的塗層的X線分析結果之曲線圖。 第3 0圖係為用以顯示按照本發明的實驗例5的條件所 製造的塗層的X線分析結果之曲線圖。 第31圖係為用以顯示按照本發明的實驗例6的條件所 製造的塗層的X線分析結果之曲線圖。 10 第32圖係為用以顯示本發明實施例的塗層之電子掃描 顯微鏡照片。 第33圖係為用以顯示在以300nm/分的速度蝕刻Si02的 條件下，對本發明實施例的塗層，進行一個小時蝕刻結果 之電子掃描顯微鏡照片。 15 【主要元件符號說明】 2···上部電極 22…負極 8···基板支架 23…冷卻通道 9···下部電極 24···正極 13…氣體分散盤 25…等粒子體火焰 14...孔 26…支架 15…基板 27…粉末注入口 20…等離子體搶 29…塗層 21…氣體注入口 30···被塗部件 3625 As shown in Figure 19, overall, peaks are formed at partial angles. It can thus be seen that some crystalline states are mixed in the amorphous structure. This is due to the fact that the crystalline state of the powder is directly transmitted to the coating due to low plasma temperature or incomplete melting of the powder during thermal spraying. 5 In addition, during the coating process, when the temperature of the substrate or the coated surface is so high that the amorphous state undergoes phase transformation and is transferred to the crystalline state, a part of the amorphous state is also transferred to the crystalline state through phase transformation, thereby forming A structure in which an amorphous state is mixed with a crystalline state. Most of the coating layer formed under the above conditions is amorphous, and a part of the crystalline state is dispersed therein, and no pores and interface gaps are formed inside the coating. It can be seen that even if the conditions for forming the coating are insufficient, the coating formed under the above conditions has more excellent characteristics than the coating using pure A1 or pure Y oxide. Next, the coating of the first experimental example 15 of the present invention will be described with reference to Figs. 20 to 22. In the first experimental example, a multi-component powder having a composition of (ai0.78 Υ〇.22) 2〇3 was first prepared, and then an internal coating was used to form an amorphous coating. Hereinafter, the amorphous coating layer of the first experimental example of the present invention is referred to as AmorMl. Fig. 20 and Fig. 21 show the results of observation by a scanning electron microscope after mirroring the cross section of the Am〇rMl coating. Although a few cracks were observed in Figs. 20 and 21, longitudinal cracks and gaps between the sheets in the usual thermal sprayed crystalline coatings were not observed. Fig. 22 is a view showing the results of observation of an AmorMl amorphous 26-state coating by a high magnification projection electron microscope. It can be confirmed from Fig. 22 that the AmorMl coating has an amorphous structure. Next, the coating layer of the second experimental example of the present invention will be described through Fig. 23. In the second experimental example, a 5-component powder having a composition of (ai0.625y0 375) 2〇3 was prepared, and an internal coating was used to form an amorphous coating. Hereinafter, the amorphous coating layer of the second experimental example of the present invention will be referred to as AmorM2. Figure 23 is a photograph of an electron scanning micrograph taken after mirroring the cross section of the AmorM2 coating. As shown in Fig. 23, AmorM2 has a shape similar to that of the AmorMl coating of Fig. 22. That is, there is no longitudinal crack in the inside of the 10 sheets and a gap between the sheets. Further, although the coating layer of the third experimental example of the present invention is the same as the composition of Am〇rM2, it is used to uniformly disperse the Al2〇3 powder and the γ2〇3 powder, and induce and carry a negative charge and a positive charge, respectively. Mixed method. Fig. 24 shows the results of observing the cross section of the coating layer 15 of the third experimental example by an electron scanning microscope. As can be seen from the figure, since the electrostatic mixing method is employed, the powder for spraying maintains a uniform composition in all parts, so that the patch interface is not formed, thereby forming a high-quality coating. Further, as can be seen from Fig. 24, partially crystalline particles are dispersed on the surface of the member to be coated (lower portion in the photograph). This is because the temperature of the plasma flame is low, the crystalline state in the powder is not completely melted, or the temperature of the surface of the coated member and the substrate is too high, resulting in the phase transition of the amorphous material to the crystalline state. The following is a description of the mechanical and chemical properties of the Am〇 and Am〇rM2 honey layers, with reference to Figs. 25 to 28. S25gj to 28th chart * Am〇rM1 and 27 1375734 Fig. 28 shows the results of the measurement of the durability of the plasma vacuum chamber of the embodiment of the present invention. Referring to Fig. 28, the durability of the coating layer of the present invention of the present invention was 5 times or more superior to that of Comparative Example 1. For the evaluation of durability, 5 is a method of measuring the depth of a surname after passing through a part of a semiconductor manufacturing apparatus, that is, a plasma etching apparatus, and using CF<i+〇2 gas to inscribe a part. The durability measurement conditions are specifically described below. Based on the condition that Si〇2 is etched by 10 nm per minute, the cf4 gas 10 body injection speed is set to 3 〇sccm (standard cubic centimeters per minute), and the 〇2 gas injection rate is set to 6 sccm to the main electrode. The input power was set to 900 W, the bias power was set to 90 W, the etching chamber pressure was set to 5 mtorr, and the chamber temperature was maintained at 25 ° C. The coatings and the comparisons of Comparative Example 1 and Comparative Example 2 were compared in Table 1. The characteristics of the coating of the 15 examples were invented. The data in Table 1 is the result of measurement under the above-described durability measurement conditions. Table 1 Sample Characteristics Comparative Example 1 (Al2〇3) Comparative Example 2 (Υ2〇3) Example (AmorM) Hardness (Hv. 200g) 800-850 300(I)-500(E) 700-750 Scratch depth ( Scratch Depth, μηι) 1 10(E)-22(I) 1.2 Corrosion resistance (g/g) _ 0.55 0.09-0.11 ICP plasma corrosion resistance (nm/min) 9.5 1.7-1.8 1.6-1.9 Defects The interface gap, the pores are good. As shown in Table 1, the hardness of the coating of the embodiment of the present invention is similar to that of the comparative example 1 (S) 29 1375734, and the corrosion resistance is similar to or superior to that of Comparative Example 2, and thus The coating of the inventive examples not only has the advantages of a general coating, but also does not easily cause other defects. Therefore, the coating layer of the embodiment of the present invention has excellent physical and chemical properties as compared with the comparative example. Further, in order to explain the excellent characteristics of the present invention in more detail, the durability test of the plasma vacuum chamber was carried out under conditions of high corrosiveness. Table 2 Coating Variable D (mm) Ar (psi) He (psi) Powder Supply Speed (RPM) Carrier Gas Supply Speed (psi) Current (A) Voltage (V) Plasma Grab Scan Speed (mm/sec) Experimental Example 4 30 115 3 20 900 39.5 Experimental Example 5 150 40 65 3 20 37.3 1000 Experimental Example 6 40 85 3.5 50 40.8 The composition used in this experiment is the same as that of AmorM2, and it is prepared to have a particle size of 10 - 60 μm Powder. Further, a coating layer was produced according to the conditions of the comparative example and the experimental example of Table 210. Fig. 29 shows the results of X-ray analysis of the coating of Experimental Example 3 of the present invention. A plurality of peaks can be observed from Fig. 29, and the coating as a whole is amorphous, but also a partially crystalline state. Fig. 30 and Fig. 31 show the results of X-ray analysis of the coatings prepared in accordance with the conditions of Experimental Example 4 and Experimental Example 5 of the present invention, respectively. It can be observed from Fig. 30 and Fig. 31 that Experimental Example 4 and Experimental Example 5 differ from Experimental Example 3 in that almost 100% of an amorphous state is formed under the conditions. Prior to testing for corrosion resistance, the coatings of the respective experimental examples were first tested for hardness. The hardness of the coating was measured by a Vickers hardness tester 20 having a load of 200 g. The test results are shown in Table 3. 30 1375734 The results of Table 3 show that the hardness of Experimental Example 4 which produces a partially crystalline state is similar to that of Experimental Example 5 and Experimental Example 6. When the coating forms an amorphous state as a whole, even if it contains a partially crystalline state, it does not have hardness. It has too much impact. 5 In addition, the coating is composed of 100% amorphous state, that is, when the inside of the coating is not formed with pores and is tightly formed, the hardness value is increased. Therefore, as shown in Experimental Example 5 and Experimental Example 6, the hardness of the coating composed of 100% amorphous state also varies depending on the coating conditions. Next, as described above, the corrosion resistance of each of the coating layers was measured under conditions prone to corrosion. 15 Conditions Experimental Example 4 Experimental Example 5 Experimental Example 6 Hardness value (Hv) 645 593 750 This experiment was carried out under conditions in which Si〇2 was etched at a rate of 300 nm/min. Specifically, 'the injection rate of CF4 gas is set to 40 sccm, the injection speed of 〇2 is set to 10 sccm, the input power of the main electrode is set to 1000 W, and the bias power is set to 150 W. The pressure in the etching chamber is set to 5 mtorr, and The temperature inside the chamber was maintained at 25 seven. Moreover, the time to be exposed to the plasma environment was set to 1 hour. Fig. 32 and Fig. 33 show the results of observing the surface of the coating layer before and after the etching test by an electron scanning microscope. Fig. 32 shows the surface of the coating before the touch, and Fig. 33 shows the surface of the coating after the engraving. The observation results are shown in Table 4. --------η Comparative Example 1 Comparative Example 2 Experimental Example 4 Experimental Example 5 Experimental Example 6 Average etching speed (nm/min) 77.2 20.22 15.83 10.5 3.58 31 (S) 20 1375734 Average _speed from Table 4 It can be seen that the experimental name of the experimental example of the present invention is greatly faster than that of the comparative example. Thus, the coating of the embodiment of the present invention also has a strong durability under strong oxidation conditions. Experimental Example 4 is an experimental example of forming a partially crystalline state, which shows a faster etching (corrosion) speed than Experimental Example 5 composed of 10% amorphous state and Experimental Example 5. It can be seen that only the coating is applied. In the case where the layer constitutes 100% amorphous, the most effective prevention of rotten money. Moreover, comparing the results of Table 1 and Table 4, it can be concluded that in the weaker environment of the survivor (when Si〇2 is used as the reference, the speed of the surname is cut by nm/min), the coating of the present invention is practical. When the layer is compared with Comparative Example 2, the residual speed differs by no more than 10', but in a strong rot environment (corrosion rate of 300 nm/min based on Si〇2), the coating of the embodiment of the present invention It showed a much slower rate of corrosion than Comparative Example 2. It can be seen that the coating of the embodiment of the present invention still has very excellent corrosion resistance in a highly corrosive environment. Further, the present invention may further comprise the step of forming a metallic intermediate layer, 15 which is intended to increase the bond strength of the thermal spray. The present invention may further comprise the step of forming a plurality of coating layers (the method of forming a gradient coating layer) by sequentially changing the composition of the substrate and the member to be coated. The formation of a metallic intermediate layer on the substrate allows the coating to be easily peeled off due to the fragile interface of the coating when a material different from the physicochemical properties of the substrate is applied. The amorphous material of the present invention is applied between the coating layer and the member to be coated of the embodiment of the present invention after the intermediate layer is formed by the following method. When Zr〇2 is coated on an aluminum substrate, an intermediate layer can be formed using a substance such as NiCrA1Y having a small thermal expansion coefficient. 2) An intermediate layer can be formed on the aluminum metal by using FeCr-based amorphous metal with high strength and excellent corrosion resistance. 3) On the metal substrate, an intermediate layer may be formed using Cr, Ni, Fe or an alloy including the metal. 4) On the substrate of Al2?3, Si, SiO2 or the like, the amorphous material of the present invention may be applied after the intermediate layer is formed using the same substance. 5 Thus, by the method of forming the metal intermediate layer of the present invention, peeling of the coating layer can be prevented, and corrosion resistance can be further improved. In addition, the coating and the component of the embodiment of the present invention may not have an intermittent second coating layer (intermediate layer), but a gradient coating layer, specifically, after preparing a powder of the same or similar substance as the substrate. The content of the amorphous coating material of the present invention is gradually increased by 10 during the coating process. This method can improve the durability of the coating. Moreover, improved techniques in conjunction with other coating forming techniques, or on the use of amorphous coatings of the present invention on a portion of the thermally sprayed coating may be employed. The preferred embodiments of the present invention have been described above, but the present invention is not limited thereto, and various modifications and changes made within the scope of the invention, the scope of the invention, and the scope of the invention are within the scope of the present invention. . BRIEF DESCRIPTION OF THE DRAWINGS 3 20 Fig. 1 is a longitudinal sectional view of a plasma etching apparatus which is one of semiconductor manufacturing apparatuses. Fig. 2 is a schematic diagram of a plasma grabbing profile of a plasma thermal spraying apparatus. Fig. 3 is an electron scanning micrograph of a cross section of a 33 yttrium oxide coating formed by an external plasma. Figure 4 is an electron scanning micrograph of a (10) coating profile formed using an internal plasma capture. Figure 5 is an electron scanning micrograph showing the cracking of liquid molten Tao Jing particles in ^^. When the seventh part is produced, the sixth picture shows the conditional pattern of the crystallization phenomenon at the root time when the liquid substance is cooled and transformed into a phase. Fig. 7 is a schematic view showing a volume change process in which a liquid substance is solidified by cooling. Fig. 8 is a schematic diagram showing the principle of formation of a defect in which a liquid substance becomes crystalline. Fig. 9 is a schematic view for explaining the conditions under which the crystalline bear solid phase is formed upon cooling by the type of material. Fig. 10 is a schematic view showing the volume contraction process occurring when the liquid substance is cooled to form a non-raccoon 15'. Fig. 11 is a schematic view showing a process for preventing defects such as cracking when the liquid substance becomes amorphous. Fig. 12 is a schematic view for explaining the process of mixing different types of powders to prepare a composite powder for thermal spraying at a larger size. 20 Fig. 13 is an electron scanning micrograph of a ceramic powder for thermal spraying synthesized in accordance with the present invention. Figure 14 is the X-ray analysis result (x = i) of pure Al2〇3. Figure 15 is the X-ray analysis of (ΑΙχΥ^ζΟ# = 0.9) (x=0.9). 34 1375734 Figure 16 is the result of X-ray analysis of (Α1χΥΝχ)203 (χ = 0.6) (χ=0·6) 〇 Figure 17 is the result of X-ray analysis of (AlxY^hO# = 0.1) (x= 0.1) 〇5 Figure 18 shows the X-ray analysis results of high purity Y203 (x=0). Fig. 19 is a X-ray analysis result (x = 6. 6) of a coating layer formed by thermal spraying in a state where (AlxY^hCMx^j) powder is not completely melted. Figure 20 is a low-magnification electron-scan micrograph (Χ200) of an amorphous coating of A1, .56Y〇.4403 material formed by thermal spraying. 10 Figure 21 is a low-magnification electron-scan micrograph (Χ650) of an amorphous coating of Ah.56Υ〇.44 03 material formed by thermal spraying. Figure 22 is a high-magnification electron scanning micrograph of an amorphous coating of A1, .56Υ〇.4403 material formed by thermal spraying. Figure 23 is a low-magnification electron scanning micrograph of a non-15 crystalline coating of All.25Υ〇.75〇3 material formed by thermal spraying. Fig. 24 is a low-magnification electron scanning microscope photograph of an amorphous coating of ΑΙ, . Υ . . 物质 β substance formed by using an electrostatic mixing method. Figure 25 is a graph showing the results of comparing the hardness of the thermal spray coating of Α12〇3, Υ203 with the coating of the embodiment of the present invention. Figure 26 is a graph showing the results of comparison of the scratch resistance of the thermal spray coatings of the Α12〇3, Υ203 and the coatings of the examples of the present invention. Fig. 27 is a graph showing the results of comparison of the corrosion resistance of the Υ203 thermal spray coating with the coating of the embodiment of the present invention against hydrochloric acid. 35 1375734 Fig. 28 is a graph showing the results of comparing the durability of the thermal spray coating of Al2〇3, Υ203 with the corrosion environment (plasma) of the coating of the embodiment of the present invention. Fig. 29 is a graph showing the results of X-ray analysis of the coating layer produced in accordance with the conditions of Experimental Example 4 of the present invention. Fig. 30 is a graph showing the results of X-ray analysis of the coating layer produced in accordance with the conditions of Experimental Example 5 of the present invention. Fig. 31 is a graph showing the results of X-ray analysis of the coating layer produced in accordance with the conditions of Experimental Example 6 of the present invention. 10 Fig. 32 is an electron scanning micrograph showing a coating of an embodiment of the present invention. Fig. 33 is an electron scanning micrograph showing the results of etching for one hour of the coating of the embodiment of the present invention under the condition that SiO 2 was etched at a rate of 300 nm / min. 15 [Description of main component symbols] 2··· Upper electrode 22...Negative electrode 8···Substrate holder 23...Cooling channel 9···Lower electrode 24···Positive electrode 13...Gas dispersion disk 25...Particle flame 14. .. hole 26...bracket 15...substrate 27...powder injection port 20...plasma grab 29...coating 21...gas injection port 30···coated member 36