200923129 九、發明說明： 【發明所屬之技術領域】 本發明關於一種金屬母材之鎢塗層方法’特別關於一種可提高用作 半導體及TFT-LCD製造工序中所使用之真空室或電極輔材之銘母材之 耐等離子性、耐熱龜裂性（Heat and crack resistance)、耐腐蝕性，從而 延長真空室之使用壽命且降低污染度之金屬母材之鎢塗層方法。 【先前技術】 半導體或TFT-LCD之製造，係在真空室中利用電極提供蝕刻及蒸鍍氣 C 體，並對上述氣體施加電力而活化成等離子狀態’從而進行蝕刻或在基板 上通過高溫將物質進行化學蒸鍍等操作。 . 通過這些工序等，構成真空室或電極之鋁（A1)制輔材’在高溫中將 裸露于腐蝕性等離子氣體中。其結果，鋁制輔材會發生龜裂或腐蝕，嚴重 之將導致從鋁輔材中發生微粒污染，不僅影響鋁制輔材之使用壽命，還將 導致将該不利影響帶到即將蒸鍍之半導體或TFT-LCD基板等，導致產品受 損或導致中段加工過程。 I 爲解決上述問題，提出了耐真空室內惡劣環境之耐等離子性和耐熱龜 裂性之多種技術，以便對鋁制輔材表面進行工序。 美國專利第5,641，375號中揭示有，爲減少等離子腐蝕及壁之磨損 (wear)而對鋁真空室壁進行陽極氧化工序（anodized)，從而形成陽極氧 化塗膜之技術。但係，陽極氧化之情況下雖然通過調整高溫下塗膜厚度之 方式，在一定程度上確保耐等離子性或耐熱龜裂性，但由於等離子氣體之 腐蝕而導致發生塗膜損傷嚴重等其他問題。 200923129 日本申請公開第62-103379號中揭示有在鋁制物質上形成A1203、A1C、200923129 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for coating a tungsten metal coating of a metal base material, in particular, a vacuum chamber or an electrode auxiliary material which can be used in a semiconductor and TFT-LCD manufacturing process. The tungsten coating method of the metal base material which is resistant to plasma, heat and crack resistance and corrosion resistance, thereby prolonging the service life of the vacuum chamber and reducing the pollution degree. [Prior Art] Semiconductor or TFT-LCD is manufactured by using an electrode to provide etching and vapor deposition of a gas C body in a vacuum chamber, and applying electric power to the gas to be activated into a plasma state to perform etching or high temperature on the substrate. The substance is subjected to operations such as chemical vapor deposition. By these steps or the like, the aluminum (A1) auxiliary material constituting the vacuum chamber or the electrode is exposed to a corrosive plasma gas at a high temperature. As a result, aluminum auxiliary materials may crack or corrode, which will cause particulate contamination from aluminum auxiliary materials, which will not only affect the service life of aluminum auxiliary materials, but also bring the adverse effects to the upcoming evaporation. Semiconductor or TFT-LCD substrates, etc., cause damage to the product or cause intermediate processing. In order to solve the above problems, various techniques for resistance to plasma and heat cracking resistance in a harsh environment in a vacuum chamber have been proposed in order to carry out a process on the surface of an aluminum auxiliary material. A technique for anodizing an aluminum vacuum chamber wall to reduce plasma corrosion and wall wear to reduce the plasma corrosion and wall wear is disclosed in U.S. Patent No. 5,641,375. However, in the case of anodizing, although the thickness of the coating film at a high temperature is adjusted to ensure plasma resistance or heat cracking resistance to some extent, other problems such as serious damage of the coating film due to corrosion of the plasma gas occur. Japanese Patent Publication No. 62-103379 discloses the formation of A1203, A1C, on aluminum materials.
TiN、TiC、及A1N等之防腐膜之技術。但係上述防腐膜雖可提高耐等離子 性，但由於與鋁之粘附力而存在發生龜裂之問題。 並且，還揭示有在鋁制輔材表面進行氧化鉻(Cr203)塗膜之塗層方法，但 係僅通過該氧化鉻塗膜提高耐腐蝕性有其限度。 在大韓民國發明專利公開第2000-59295號中揭示有通過電鍍對金屬表 面進行鎢合金塗層，從而提高表面硬度及耐腐蝕性，在大韓民國發明專利 公開第2004-272號中揭示有通過無電解濕法鍍金方法將鎢、鈀、鎳、及鱗 塗於鋁合金表面之技術。 這些能通過鎢鍍金來一定程度上確保鋁制輔材之耐等離子性。但即使 在鋁制輔材上進行鎢鍍金，由於工序溫度本身高而鋁制輔材和鎢鍍金層之 間之熱膨脹特性差異較大，存在由此弓丨起之龜裂及剝離、起泡等會導致先 前塗層技術製備之真空室內鋁制輔材誘發急劇之微粒污染等新之問題。 在大韓民國發明專利公開第2005-22184號中揭示有在半導體零件之金 屬模組表面依次設置第1鎳鍍金層/第2鎳鍍金層/鎢鍍金層/第3鎳鍍金層/ 铑鍍金層之技術，以便延長裝備之使用壽命。通過這種技術雖然可解除金 屬模組之耐腐蝕性和金屬層間之剝離，但需要形成5層薄膜而存在導致工 序複雜、製造費用增加等問題。 【發明内容】 爲解決上述問題之不足，本發明提供一種可提高用於半導體及 TFT-LCD製造工序中之真空室或電極鋁制輔材之耐等離子性、耐熱龜裂 性、耐腐鈾性，從而延長真空室使用壽命且降低污染度之金屬母材之鎢塗 200923129 層方法。 本發明之另一目的在于’提供一種通過上述方法制造的半導體及 TFT-LCD 零件。 本發明係以如下方式實現之。本發明之第一個方面關於一種金屬母材 之鎢塗層方法，包括如下步驟： 對包括鋁或鋁合金之金屬母材進行陽極氧化工序而形成陽極氧化塗膜 之階段； 對上述金屬母材之陽極氧化塗膜上進行電解或無電解鍍金工序而形成 ^ 鎢鍍金膜之階段； 及熱處理階段； 其中，上述鎢電解鍍金，係通過製備包括Na£)WOH2〇 (5〜50g/l)、Na2CCb (10〜30g/l)、NftOH (1 〜15g/l)、CHOHCOONa (1 〜5g/l)、及 Na3GH5〇7 (20〜 5〇£/1)之水溶液(?116〜7)後，將其溫度調至75〜85°〇，以1〜10从11112之電流 密度施加電力而進行， f 上述鎢無電解鍍金，係通過製備包括Na2W〇4弧0 (10~30g/l)、NiC12.6H2〇 l, (5〜15g/l)、NaH2P〇2.H2〇 (10~30g/l)、CftOHCOONa (5〜15g/l)、Na3GH5〇7 (5〜 10g/l)、CH4N2S (5〜10g/l)、Na2C〇3 (10〜25g/l)、NftNR (5〜15%)之水溶液(pH 8〜 10)後，將其溫度調至80~90°C而進行。 其中，上述陽極氧化工序係，在包括磷酸、草酸、磺酸及其組合所構 成之群中選擇之一種酸之陽極氧化電解質中，施加0.1〜100V之電壓，以 25〜KXTC溫度進行〇·5〜5小時。 200923129 其中，上述熱處理係在350〜600°C溫度條件下進行。 並且，進一步包括’在形成上述陽極氧化塗膜後’通過電解鍍金工序 在上述陽極氧化塗膜上形成鎳鍍金膜之階段。 上述鎳電解鍍金，係以電解鎳鍍金液製備包括NiSCk6H2〇(100〜 500g/l)、NiCk6H2〇 (20〜80g/l)、ttBCh (20〜50g/l)之水溶液(pH 8〜10)後’將其 溫度調至40〜80°C，以1〜KWdm2之電流密度施加電力而進行。 本發明第2個方面關於一種半導體及TFT-LCD製造用真空室零件’根 據本發明第1個方面之方法形成且在表面依次形成鋁氧化塗膜、鎢鍍金膜 之。 其中，在上述鋁氧化塗膜和鎢鍍金膜之間形成鎳鍍金膜。 通過本發明，在鋁制金屬母材表面形成陽極氧化塗膜層和鎢鍍金膜， 從而提高金屬之耐等離子性、耐熱龜裂性及耐腐蝕性。 【實施方式】 以下結合圖面對本發明進行更爲詳細之說明。爲進行更爲形象之說 明’對各圖面中之結果進行擴大表示。此時，圖面中相同符號表示相同之 結構。缒且，描述爲某層在另一層“上”時，可以理解爲上述某層可以直 接與上_其他層接觸，也可以在他們之間存在第三之層。 第1實境例 圖面1係表示本發明第1實現例之金屬母材鎢塗層方法之流程圖，圖 面2〜®面4係該模式圖。 首先，準備銘或銘合金制之金屬母材（11)(圖面2)。 200923129 上述金屬母材（11)經過包括脫脂工序、水洗工序、蝕刻工序及電解 脫脂工序等之前處理工序。 爲了使金屬母材（11)容易形成塗膜，在上述前處理工序中爲去除表 面油垢而將金屬母材（11)放入60〜80°C之脫脂液中進行脫脂工序(Cleamng， Degreesing)後，進行水洗工序來去除上述脫脂液及雜質。而後進行蝕刻工 序（etching)來增力暖面積，之後進行電解脫脂工序（electrocleamng)。這 種前處理工序，除上述工序外還可以增加或代替施加超聲波等之前處理工 序。 而後，對金屬母材（11)表面進行陽極氧化，從而形成在上述金屬母 材（11)表面設有氣孔之陽極氧化塗膜（13)(圖面3)。 具體說明係，將金屬母材（11)作爲陽極(positive electrode)，並將該金 屬母材（11)浸漬於包括酸之陽極酸性電解質後施加電壓而發生陽極化 (Anodization)。此時，通過所施加之電壓使金屬母材（11)從表面電氧化， 使上述金屬母材（11)表面轉化爲作爲陽極氧化塗膜（13)之鋁氧化膜 (Al£b)。而後施加持續之電壓而相對金屬母材（11)形成垂直方向之陽極 氧化塗膜（13)。 此時，用於氧化之陽極氧化電解質包括磷酸、草酸、磺酸及其組合所 構成之群中選擇之一種酸，其稀釋液（Dilute solution) ’最好係15~18重量％ 之磺酸或者1〜5雷量％之草酸水溶液。 此时，阳极氧化为，施加0·1〜100V之电压’在25〜100°C温度条件进 行0.5〜5小时’本技術领域之技术人员可考虑酸之种类、纳米气孔之直径 200923129 及高有序性（highly ordered pore)等各种因素进行各种变形。 这种阳极氧化需要进行1次以上，必要时可进行2〜4次’从而提高 气孔之高有序性。 具有這樣形成之多數氣孔之陽極氧化塗膜（13)並非係完全之結晶型 塗膜，而形成非結晶型Al£b塗膜。該陽極氧化塗膜（13)雖向著金屬木材 (11)側成長50%且向外部成長50%而顯示出陶瓷特性，但無與金屬母材 (11)之龜裂性。在完全之結晶型塗膜（即利用噴塗形成在A1母材之Al2〇3 塗膜）之情況下，因爲係完全之陶瓷結晶，從而與A1母材相比時體現出4 倍之熱膨脹特性。 爲提高上述陽極氧化後後續塗層工序之效率而進行洗滌工序。由於這 種工序需要很高之精度，所以工序和工序之間必須進行徹底之水洗工序。 然後，在上述氧化塗膜（13)上進行電解或無電解塗層工序’從而形 成鎢鍍金膜（15)(圖面4)。 鎢具有優秀之耐腐鈾性、耐等離子性及耐熱龜裂性’從而可提高金屬 母材（11)之物性。 特別係在本發明中，在多孔性陽極氧化塗膜（13)上形成鎢鍍金膜（15) ’ 此時，如圖面3所示，陽極氧化塗膜（13)之氣孔內部存在鎢’在其上部 進行鎢塗層。從而，提高了金屬母材（11)和鎢鍍金膜（15)之間之粘附力’ 形成鎢鍍金膜（15)，最大程度上提高了其效果。 上述鎢鍍金膜（15)通過電解及鎢電解塗層工序所形成。 首先，電解鍍金工序，係通過製備作爲電解鎢塗層液之包括 10 200923129Technology of anti-corrosion film of TiN, TiC, and A1N. However, although the above-mentioned anticorrosive film can improve plasma resistance, there is a problem that cracking occurs due to adhesion to aluminum. Further, a coating method of performing a chromium oxide (Cr203) coating film on the surface of an aluminum auxiliary material has been disclosed, but there is a limit to improving the corrosion resistance only by the chromium oxide coating film. In the Korean Patent Publication No. 2000-59295, it is disclosed that a tungsten alloy coating is applied to a metal surface by electroplating to improve surface hardness and corrosion resistance, which is disclosed in the Republic of Korea Patent Publication No. 2004-272. A method of applying gold, tungsten, palladium, nickel, and scales to the surface of an aluminum alloy by a gold plating method. These can ensure the plasma resistance of aluminum auxiliary materials to a certain extent by tungsten gold plating. However, even if tungsten gold plating is performed on the aluminum auxiliary material, the thermal expansion characteristics between the aluminum auxiliary material and the tungsten gold plating layer are largely different due to the high process temperature itself, and there is cracking, peeling, foaming, etc. due to the bowing. It will lead to new problems such as rapid particle pollution caused by aluminum accessories in vacuum chambers prepared by previous coating technology. In the Korean Patent Publication No. 2005-22184, there is disclosed a technique of sequentially providing a first nickel gold plating layer / a second nickel gold plating layer / a tungsten gold plating layer / a third nickel gold plating layer / a ruthenium plating layer on the surface of the metal module of the semiconductor component. In order to extend the life of the equipment. Although this technique can release the corrosion resistance of the metal module and the peeling between the metal layers, it is necessary to form a five-layer film, which causes problems such as complicated processes and increased manufacturing costs. SUMMARY OF THE INVENTION In order to solve the above problems, the present invention provides a plasma, thermal cracking resistance, and uranium resistance resistance of a vacuum chamber or an electrode made of aluminum used in a semiconductor and TFT-LCD manufacturing process. The tungsten coating 200923129 layer method of metal base material which prolongs the service life of the vacuum chamber and reduces the pollution degree. Another object of the present invention is to provide a semiconductor and TFT-LCD part manufactured by the above method. The present invention is achieved in the following manner. A first aspect of the invention relates to a tungsten coating method for a metal base material, comprising the steps of: performing an anodizing process on a metal base material comprising aluminum or an aluminum alloy to form an anodized coating film; a step of forming an electroplating or electroless gold plating process on the anodized coating film to form a tungsten gold plating film; and a heat treatment stage; wherein the tungsten electroless gold plating is prepared by including Na£)WOH2〇 (5 to 50 g/l), After an aqueous solution (?116~7) of Na2CCb (10~30g/l), NftOH (1~15g/l), CHOHCOONa (1~5g/l), and Na3GH5〇7 (20~5〇£/1), The temperature is adjusted to 75 to 85 ° 〇, and the power is applied from 1 to 10 from the current density of 11112. f The above-mentioned tungsten electroless gold plating is prepared by preparing Na2W〇4 arc 0 (10-30 g/l), NiC12. .6H2〇l, (5~15g/l), NaH2P〇2.H2〇(10~30g/l), CftOHCOONa (5~15g/l), Na3GH5〇7 (5~10g/l), CH4N2S (5 After an aqueous solution (pH 8 to 10) of ~10 g/l), Na2C〇3 (10 to 25 g/l) and NftNR (5 to 15%), the temperature was adjusted to 80 to 90 °C. In the above anodizing step, a voltage of 0.1 to 100 V is applied to an anodic oxidation electrolyte of an acid selected from the group consisting of phosphoric acid, oxalic acid, sulfonic acid, and a combination thereof, and 〇·5 is performed at a temperature of 25 to KXTC. ~5 hours. 200923129 wherein the heat treatment is carried out at a temperature of 350 to 600 °C. Further, it further includes a step of forming a nickel gold plating film on the anodized film by an electrolytic gold plating process after the formation of the anodized film. The nickel electroplating is performed by preparing an aqueous solution (pH 8 to 10) comprising NiSCk6H2 〇 (100 to 500 g/l), NiCk6H2 〇 (20 to 80 g/l), and ttBCh (20 to 50 g/l) by electrolytic nickel plating. 'The temperature was adjusted to 40 to 80 ° C, and electric power was applied at a current density of 1 to KWdm 2 . According to a second aspect of the invention, a vacuum chamber component for semiconductor and TFT-LCD manufacturing is formed according to the method of the first aspect of the invention, and an aluminum oxide coating film or a tungsten gold plating film is sequentially formed on the surface. Among them, a nickel gold plating film is formed between the aluminum oxide coating film and the tungsten gold plating film. According to the present invention, an anodized coating layer and a tungsten gold plating film are formed on the surface of an aluminum metal base material, thereby improving the plasma resistance, heat crack resistance and corrosion resistance of the metal. [Embodiment] The present invention will be described in more detail below with reference to the drawings. For the purpose of making a more vivid statement, the results in each drawing are expanded. At this time, the same symbols in the drawing indicate the same structure. Moreover, when a layer is described as being "on" another layer, it can be understood that the above-mentioned layer may be directly in contact with the other layer or the third layer may be present between them. First Example of the Drawing Fig. 1 is a flow chart showing a method of coating a metal base material with a tungsten coating according to a first embodiment of the present invention, and Fig. 2 to the surface 4 is a schematic view. First, prepare the metal base material (11) made of Ming or Ming alloy (Fig. 2). 200923129 The above-mentioned metal base material (11) undergoes a pretreatment process including a degreasing step, a water washing step, an etching step, and an electrolytic degreasing step. In order to facilitate the formation of a coating film on the metal base material (11), in the pretreatment step, the metal base material (11) is placed in a degreasing liquid at 60 to 80 ° C to remove the surface grease, and a degreasing step (Cleamng, Degreesing) is performed. Thereafter, a water washing step is performed to remove the above-mentioned degreasing liquid and impurities. Then, an etching process is performed to increase the warming area, and then an electrolytic degreasing process (electrocleamng) is performed. In this pretreatment step, in addition to the above steps, a pretreatment process such as applying ultrasonic waves may be added or replaced. Then, the surface of the metal base material (11) is anodized to form an anodized coating film (13) having a pore on the surface of the above-mentioned metal base material (11) (Fig. 3). Specifically, the metal base material (11) is used as a positive electrode, and the metal base material (11) is immersed in an anodic acid electrolyte including an acid, and a voltage is applied thereto to cause anodization. At this time, the metal base material (11) is electrically oxidized from the surface by the applied voltage, and the surface of the above metal base material (11) is converted into an aluminum oxide film (Al£b) as an anodized film (13). Then, a continuous voltage is applied to form a vertical anodic oxide coating film (13) with respect to the metal base material (11). At this time, the anodic oxidation electrolyte for oxidation includes an acid selected from the group consisting of phosphoric acid, oxalic acid, sulfonic acid, and a combination thereof, and the dilution solution (Dilute solution) is preferably 15 to 18% by weight of sulfonic acid or 1 to 5 liters of oxalic acid aqueous solution. At this time, the anodic oxidation is performed by applying a voltage of 0·1 to 100 V '0.5 to 5 hours at a temperature of 25 to 100 ° C. Those skilled in the art can consider the type of acid, the diameter of the nanopore 200923129, and the high Various factors such as highly ordered pores are variously modified. This anodization needs to be carried out once or twice, and if necessary, 2 to 4 times, thereby increasing the order of the pores. The anodized coating film (13) having a plurality of pores thus formed is not a completely crystalline coating film, but forms an amorphous Al£b coating film. The anodized coating film (13) exhibits ceramic properties by 50% growth toward the metal wood (11) side and 50% growth to the outside, but has no cracking property with the metal base material (11). In the case of a completely crystalline coating film (i.e., an Al2〇3 coating film formed by spraying on the A1 base material), since it is completely ceramic crystal, it exhibits 4 times thermal expansion characteristics as compared with the A1 base material. A washing step is performed to increase the efficiency of the subsequent coating step after the anodization. Since this process requires high precision, a thorough water washing process must be performed between the process and the process. Then, an electrolytic or electroless plating process is performed on the above oxide coating film (13) to form a tungsten gold plating film (15) (Fig. 4). Tungsten has excellent uranium resistance, plasma resistance and heat crack resistance, which improves the physical properties of the metal base material (11). In particular, in the present invention, a tungsten gold plating film (15) is formed on the porous anodized coating film (13). At this time, as shown in Fig. 3, tungsten is present inside the pores of the anodized coating film (13). The upper part is coated with tungsten. Thereby, the adhesion between the metal base material (11) and the tungsten gold plating film (15) is increased to form a tungsten gold plating film (15), which maximizes the effect. The tungsten gold plating film (15) is formed by an electrolysis and tungsten electrolytic coating process. First, the electrolytic gold plating process is prepared by preparing as an electrolytic tungsten coating liquid. 10 200923129
Na2〇WOH2〇 (5 〜50g/l)、Na2C〇3 (10 〜30β/1)、ΝΗ4〇Η (1 〜15g/l)、CH2〇HCO〇Na (1〜5§/1)、及咖〇压〇(2〇〜5〇2/1)之水溶液(0{16〜7)後，將其溫度調至75 〜85°C，以1〜10A/dm2之電流密度施加電力而進行。 並且，無電解鍍金工序，通過製備作爲無電解鎢塗層液之包括 Na2W〇4.2H2〇 (10~30g/l) ' NiCk6H2〇 (5〜15g/l)、NaH2P〇H£) (10〜30g/l)、 CBOHCOONa (5~15g/l)、NasG· (5〜_)、C祕S (5〜10g/l)、NazCO (10〜 25g/l)、NftNF2 (5〜15%)之水溶液(pH 8〜10)後，將其溫度調至80〜90°C而進行。 , 此時，在鎢鍍金膜（15)具有5〜50 ί/m厚度爲止的時間内，進行上述電 解及無電解鍍金工序。如果上述鎢鍍金膜（15)之厚度未滿5 μιη，會導致 嚴重降低耐等離子特性之問題，如果上述鎢鍍金膜（15 )之厚度超過50卿， 會發生上面提及之先前鎢鍍金膜之氣泡問題及界面剝離問題，從而維持在 上述範圍。 在形成上述鎢鍍金膜（15 )後進行水洗工序及乾燥工序。 而後對上述金屬母材進行熱處理來完成工序。 , 上述熱處理係在350〜600°C的氧化還原條件下進行，通過這種熱處 理，來獲得提高鎢鍍金膜（15)之膜之密度且提高陽極氧化塗膜（13)之粘 附力之效果。如果熱處理溫度未滿35CTC，會導致降低鎢塗膜之機械特性， 與此相反地如超過600 °C，會導致母材損傷及陽極氧化塗膜發生龜裂等問 題，從而維持在上述範圍。 如上所述’本發明中通過陽極氧化在金屬母材（11)表面形成多孔結 構之陽極氧化塗膜（13)來確保耐等離子性及耐熱龜裂性，在其上部形成 11 200923129 鎢鍍金膜（15)而具有耐腐蝕性，在多孔結構之陽極氧化塗膜（13)之氣孔 內部存在鎢，從而具有可解除陽極氧化塗膜（13)和鎢鑛金膜（15)之間剝 離之效果。 在先前金屬母材（11)上進行如鎢等金屬層之塗層時’由於金屬母材 (11)和金屬層之間之粘附力低，爲提高粘附力而需進行鋅酸鹽(Zmcate)處理 或在金屬母材（11)與金屬層之間附加設置粘附層，而在本發明中無需進 行這些工序，從而具有使工序變得簡單化、降低製造成本之效果。 並且，本發明進一步包括，在上述陽極氧化塗膜形成後，通過電解鍍 金工序在上述陽極氧化塗膜上形成鎳鍍金膜之階段。 上述鎳鍍金膜位於陽極氧化塗膜及鎢鍍金膜之間，從而提高與這些之 介面粘附性，提高上述陽極氧化塗膜和鎢鍍金膜之間之粘附性。 第2實現例 圖面5係表示本發明第2實現例之金屬母材鎢塗層方法之流程圖，圖 面6〜圖面7係該模式圖。 具體說明係，在金屬母材之表面將陽極氧化而形成氧化塗膜。 對此時陽極氧化之具體內容可參照第1實現例中記載。 然後，通過電解鍍金在上述形成陽極氧化塗膜（13)之金屬母材（11) 形成鎳鍍金膜（17 )(參照圖面7)。 上述電解鍍金工序，係以電解鎳鍍金液製備包括NiSO6H20 (100~ 500g/l)、NiCl2,6H2〇 (20〜80g/l)、ΒΒα (20〜50g/l)之水溶液(pH 8〜10)後，將其 溫度調至40〜80t，以1〜20A/dm2之電流密度施加電力而進行。 12 200923129 此時，鎳鍍金膜（Π)如圖面6所示，在陽極氧化塗膜（13)之氣孔內 部存在鎳，在其上部塗覆有鎳。其結果’提高了金屬母材（11)和鎳鍍金 膜（17)間之粘附力，在其上部形成後續之鎢鍍金膜（19)。 然後，通過在上述鎳鍍金膜（丨7)上進行電解或無電解鍍金工序來形 成鎢鍍金膜（19)(參照圖面7) ° 上述鎢鍍金膜（19)通過電解或無電解工序進行’詳細之工序參照上 述第1實現例中記載。 苴次，對上述金屬母材進行熱處理來完成工序。 f 此時，在熱處理之前形成上述鎢鍍金膜（19)，而後進行乾燥工序。 通過上述各階段，順次在本發明金屬母材表面形成陽極氧化塗膜/鎢鍍 ' 金膜或者陽極氧化塗膜/鎳鍍金膜/鎢鍍金膜。 _ 根據本發明之金屬母材之表面工序用於半導體及TFT-LCD製造裝置之 真空室及真空室內部所使用之加熱器及噴頭（空氣擴散器）等之各種輔材 之表面處理。 . 上述輔材之主要材料爲鋁或鋁合金所構成，在這種輔材之表面塗覆 鎢，從而具有提高耐腐蝕性、耐等離子性及耐熱龜裂性之效果。如上所述， 根據本發明之方法可最大限度地提高物性，提高鎢鍍金膜和輔材之間之粘 附力’因工序簡單而具有與先前表面處理工序相比效果更爲優秀且可降低 費用之優點。 爲更易於理解本發明，以下公開優選之實施例。但係下述實施例僅爲 更易於理解本發明而提供，本發明之內容並不限於實施例中之內容。 13 200923129 實施例1 通過先前方法對銘基板進行脫脂、水洗、蝕刻及電解脫脂來進行前處 理工序。 然後，將經過前處理工序之鋁基板浸漬於磺酸及草酸之重量比爲1 : 5 之0.5M濃度之酸溶液後，以此作爲陽極，在28°C條件下供給0.2A/cii電流 60分鐘，從而形成陽極氧化塗膜。 用DI水將上述鋁基板水洗干净後浸漬於鎢鍍金膜形成用無電解鍍金槽 (Na2WO,2H2〇(30g/l)、NiC12_6H2〇 (5g/l)、NaHzPOHaO (12g/l)、 CH2〇HC〇〇Na(5.5g/l)、Na3GH5〇7 (10g/l)、CH4N2S (5g/l)、NaCCh (15g/l)、NH4NR (12%))中，pH 10、90°C溫度條件下攪拌、沉澱30分鐘。利用這種無電解 方式在陽極氧化塗膜上形成25卿厚度之鎢鍍金膜。 而後，水洗干淨後在常溫下乾燥1個小時，而後在氧氣環境下以400 °C條件進行熱處理2個小時。 實施例2 通過先前方法對鋁基板進行脫脂、水洗、蝕刻及電解脫脂來進行前處 理工序。 然後，將經過前處理工序之鋁基板浸漬於磺酸及草酸之重量比爲1 : 5 之0.5M濃度之酸溶液後，以此作爲陽極，在28°C條件下供給0.2A/cii電流 60分鐘，從而形成陽極氧化塗膜。 用DI水將上述鋁基板水洗干净後浸漬於鎢鍍金膜形成用電解槽 (Na2〇WOH2〇(20g/l)、Na£CK10g/l)、NH4〇H(5g/l)、CH£)HC00Na(lg/l)、及 14 200923129Na2〇WOH2〇(5~50g/l), Na2C〇3 (10~30β/1), ΝΗ4〇Η (1~15g/l), CH2〇HCO〇Na (1~5§/1), and coffee After the aqueous solution (0{16 to 7) of 〇(2〇~5〇2/1) was pressed, the temperature was adjusted to 75 to 85 ° C, and electric power was applied at a current density of 1 to 10 A/dm 2 . In addition, the electroless gold plating process is prepared by preparing Na2W〇4.2H2〇(10~30g/l) as a non-electrolytic tungsten coating liquid. [NiCk6H2〇(5~15g/l), NaH2P〇H£) (10~30g) /l), CBOHCOONa (5~15g/l), NasG·(5~_), C secret S (5~10g/l), NazCO (10~25g/l), NftNF2 (5~15%) After (pH 8 to 10), the temperature was adjusted to 80 to 90 °C. At this time, the above electrolysis and electroless gold plating are performed in a time period in which the tungsten gold plating film (15) has a thickness of 5 to 50 ί/m. If the thickness of the tungsten gold plating film (15) is less than 5 μm, the problem of severely resisting plasma characteristics may be caused. If the thickness of the tungsten gold plating film (15) exceeds 50 Å, the above-mentioned prior tungsten gold plating film may occur. The bubble problem and the interface peeling problem are maintained in the above range. After the tungsten gold plating film (15) is formed, a water washing step and a drying step are performed. Then, the above metal base material is subjected to heat treatment to complete the process. The heat treatment is carried out under the redox condition of 350 to 600 ° C, and the heat treatment is used to obtain the effect of increasing the density of the film of the tungsten gold plating film (15) and improving the adhesion of the anodized film (13). . If the heat treatment temperature is less than 35 CTC, the mechanical properties of the tungsten coating film are lowered. On the contrary, if it exceeds 600 °C, the base material is damaged and the anodized coating film is cracked, and the like, and the above range is maintained. As described above, in the present invention, an anodized coating film (13) having a porous structure formed on the surface of a metal base material (11) by anodization is used to ensure plasma resistance and heat crack resistance, and 11 200923129 tungsten gold plating film is formed on the upper portion thereof ( 15) It is corrosion-resistant, and tungsten is present inside the pores of the anodic oxide coating film (13) having a porous structure, thereby having the effect of releasing the peeling between the anodized coating film (13) and the tungsten ore gold film (15). When a coating of a metal layer such as tungsten is applied to the prior metal base material (11), since the adhesion between the metal base material (11) and the metal layer is low, zincate is required to improve adhesion ( In the Zmcate treatment, an adhesion layer is additionally provided between the metal base material (11) and the metal layer, and in the present invention, it is not necessary to carry out these steps, and the effect is simplified and the manufacturing cost is reduced. Furthermore, the present invention further includes a step of forming a nickel gold plating film on the anodized film by an electrolytic gold plating process after the anodized film is formed. The nickel gold plating film is disposed between the anodized coating film and the tungsten gold plating film to improve the adhesion to the interface and improve the adhesion between the anodized coating film and the tungsten gold plating film. (Second Embodiment) Fig. 5 is a flow chart showing a method of coating a metal base material with a tungsten coating according to a second embodiment of the present invention, and Figs. 6 to 7 are schematic views. Specifically, the surface of the metal base material is anodized to form an oxide coating film. The details of the anodization in this case can be referred to in the first embodiment. Then, a nickel gold plating film (17) is formed on the metal base material (11) on which the anodized coating film (13) is formed by electrolytic gold plating (see Fig. 7). In the above electroplating gold plating process, an aqueous solution (pH 8 to 10) comprising NiSO6H20 (100 to 500 g/l), NiCl2, 6H2 (20 to 80 g/l), and ΒΒα (20 to 50 g/l) is prepared by electrolytic nickel plating. Thereafter, the temperature was adjusted to 40 to 80 t, and electric power was applied at a current density of 1 to 20 A/dm 2 . 12 200923129 At this time, as shown in Fig. 6, the nickel gold plating film (Π) has nickel in the pores of the anodized coating film (13), and nickel is coated on the upper portion thereof. As a result, the adhesion between the metal base material (11) and the nickel gold plating film (17) was increased, and a subsequent tungsten gold plating film (19) was formed on the upper portion thereof. Then, a tungsten gold plating film (19) is formed by performing electrolysis or electroless gold plating on the above nickel gold plating film (丨7) (see Fig. 7). The tungsten gold plating film (19) is subjected to electrolysis or electroless process. The detailed steps are described in the first embodiment. In this order, the metal base material is heat-treated to complete the process. f At this time, the tungsten gold plating film (19) is formed before the heat treatment, and then a drying step is performed. Through the above stages, an anodized coating film/tungsten plating gold film or an anodized coating film/nickel gold plating film/tungsten gold plating film is sequentially formed on the surface of the metal base material of the present invention. The surface of the metal base material according to the present invention is used for surface treatment of various auxiliary materials such as a heater and a shower head (air diffuser) used in a vacuum chamber and a vacuum chamber of a semiconductor or TFT-LCD manufacturing apparatus. The main material of the above-mentioned auxiliary material is aluminum or aluminum alloy, and tungsten is coated on the surface of the auxiliary material to have an effect of improving corrosion resistance, plasma resistance and heat crack resistance. As described above, according to the method of the present invention, the physical properties can be maximized, and the adhesion between the tungsten gold plating film and the auxiliary material can be improved. The process is simple and the effect is superior to the previous surface treatment process and the cost can be reduced. The advantages. For a better understanding of the invention, the preferred embodiments are disclosed below. However, the following examples are provided for easier understanding of the present invention, and the contents of the present invention are not limited to the contents of the examples. 13 200923129 Example 1 The pretreatment process was carried out by degreasing, water washing, etching, and electrolytic degreasing of the substrate by the prior method. Then, the aluminum substrate subjected to the pretreatment step is immersed in an acid solution having a concentration of sulfonic acid and oxalic acid of 0.5 M in a weight ratio of 1:5, and then used as an anode to supply a current of 0.2 A/cii at 28 ° C. Minutes to form an anodized coating film. The aluminum substrate was washed with DI water and immersed in an electroless gold plating bath for forming a tungsten gold plating film (Na2WO, 2H2 〇 (30 g/l), NiC12_6H2 〇 (5 g/l), NaHz POHaO (12 g/l), CH2 〇 HC 〇〇Na (5.5g/l), Na3GH5〇7 (10g/l), CH4N2S (5g/l), NaCCh (15g/l), NH4NR (12%), pH 10, 90 °C Stir and precipitate for 30 minutes. A tungsten-plated film of 25 Å thick was formed on the anodized film by this electroless method. Then, after washing with water, it was dried at normal temperature for 1 hour, and then heat-treated at 400 ° C for 2 hours in an oxygen atmosphere. Example 2 A pretreatment process was carried out by degreasing, water washing, etching, and electrolytic degreasing of an aluminum substrate by a prior method. Then, the aluminum substrate subjected to the pretreatment step is immersed in an acid solution having a concentration of sulfonic acid and oxalic acid of 0.5 M in a weight ratio of 1:5, and then used as an anode to supply a current of 0.2 A/cii at 28 ° C. Minutes to form an anodized coating film. The aluminum substrate was washed with DI water and immersed in an electrolytic cell for forming a tungsten gold plating film (Na2〇WOH2〇(20g/l), Na£CK10g/l), NH4〇H(5g/l), CH£)HC00Na (lg/l), and 14 200923129
NasGftO (15g/l))中，而後供給5A電流40分鐘。利用這種電解方式在陽 極氧化塗膜上形成25 μιη厚度之鎢鑛金膜。 而後，水洗乾淨後在常溫下乾燥1個小時，而後在氧氣環境下以400 °C條件熱處理2個小時。 實施例3 通過先前方法對鋁基板進行脫脂、7]C洗、蝕刻及電解脫脂來進行前處 理工序。 然後，將經過前處理工序之鋁基板浸漬於磺酸及草酸之重量比爲1 : 5 之0.5M濃度之酸溶液後，以此作爲陽極，在28°C條件下供給0.2Α/αί電流 60分鐘，從而形成陽極氧化塗膜。 將上述鋁基板水洗干净後浸漬於鎳鍍金膜形成用電解槽（Ν6〇4·6Η2〇 (400g/l)、NiCk6H£)(20g/l)，H3Ba (30g/l))，而後供給 20Α 電流 10 分鐘，在 陽極氧化塗膜上形成5 _厚度之鎳鑛金膜。 而後，用DI 7jc仔細清洗後，再次將上述鋁基板浸漬於鎢鍍金膜形成用 電解槽（Na2〇W〇3.BO(20g/l)、Na2C〇3 (10g/l)、NH4〇H (5g/l)、CH2〇HCOONa (lg/1)、及Na3GH5Cb (15g/l))，而後供給5A電流40分鐘，形成30 μιη厚度之 鎢鑛金膜。 而後，在4°C條件乾燥4個小時，而後在氧氣環境下以400°C條件熱處 理4個小時。 比較例1 通過先前方法對鋁基板進行脫脂、水洗、鈾刻及電解脫脂來進行前處 15 200923129 理工序。 將上述鋁基板水洗千净後浸漬於鎳鍍金膜形成用電解槽（NiSCV6H2〇 (400g/l)、NiCk6H2〇(20g/l),H3B〇3 (30g/l))，而後供給 20A 電流 10 分鐘，在 陽極氧化塗膜上形成5 μπι厚度之鎳鍍金膜。 比較例2 通過先前方法對鋁基板進行脫脂、水洗、蝕刻及電解脫脂來進行前處 理工序。 然後，將經過前處理工序之鋁基板浸漬於磺酸及草酸之重量比爲1 : 5 之〇_5Μ濃度之酸溶液後，以此作爲陽極，在28°C條件下供給0.2Α/αί電流 60分鐘，從而形成陽極氧化塗膜。 試驗例1 爲確認通過上述實施例1係否在上述基板上形成鎢鍍金膜，通過掃描 電子顯微鏡（SEM)和EDAX對其表面成分進行分析，其結果如圖面8所 不。 圖面8之係表示實施例1之鎢鍍金膜表面成分之吸收光譜。 參照圖面8之，可知在陽極氧化塗膜上形成30%之鎢（W)。 圖面9係表示實施例1中製造之鎢鍍金膜正面相片’圖面1〇係表示實 施例1中積層在基板上之陽極氧化塗膜/鎢鍍金膜之側面相片。參照上述圖 面9及圖面10，可知在Α1母材上形成陽極氧化塗膜（Anodmng膜）’在其 上形成鎢鍍金膜。 試驗例2 :耐腐蝕性測定 16 200923129 爲測定由上述實施例1〜實施例3及比較例1和比較例2所製造之基板 之耐腐蝕性，將基板浸漬於HC110%溶液(251)後測定經時腐蝕程度，其測 定結果如圖面8所示。 圖面11係袠示實施例1〜實施例3和比較例1及比較例2中之基板經 時腐蝕程度之曲線圖。參照圖面11，可知在實施例1〜實施例3之基板之情 況T塗層膜之腐蝕程度低微。 試驗例3 :耐等離子性測定 , 爲測定上述實施例丨〜實施例3和比較例1及比較例2所製造之基板之 耐等離子性，將基板放入PECVD室後，在38(TC條件下利用NB氣體發生 等離子’來確定係否存在表面損傷，其結果如表1所示。 表1 區分 24小時 48小時 96小時 實施例1 基板/陽極氧化 塗_|鍍金膜 無損傷 無損傷 無損傷 實施例2 基板/陽極氧化 塗膜顧鍍金膜 無損傷 無損傷 無損傷 實施例3 基板/陽極氧化 塗膜顧鍍金膜 /鎢鍍金膜 無損傷 無損傷 無損傷 比較例1 基_臬鍍金膜 無損傷 輕微損傷 嚴重損傷 比較例2 基臟極氧化 塗膜/ 輕微損傷 嚴重損傷 嚴重損傷 試驗例4 :耐熱龜裂性測定 爲測定上述實施例1〜實施例3所製造之基板之耐熱龜裂性，重複10 次以500°C加熱後通過常溫下之水冷卻之過程，而後通過掃描電子顯微鏡對 基板表面進行測定。 17 200923129 圖面12係表示實施例1之鎢鍍金膜之掃描電子顯微鏡相片，圖面13係 表示比較例1之鎳鍍金膜之掃描電子顯微鏡相片，圖面14係表示比較例2之 陽極氧化塗膜之掃描電子顯微鏡相片。 參照圖面12可知’通過本發明所製造之鎢鍍金膜不發生龜裂。於此相 比地’可確認在圖面13及圖面14中之在基板上單純形成鎳鍍金膜或陽極氧 化塗膜之情況下發生龜裂。 產業上可利用性 根據本發明之金屬母材之表面工序劑用於半導體及TFT-LCD製造裝置 之真空室及真空室內部所使用之加熱器及噴頭（空氣擴散器）等之各種輔 材之表面處理。 【圖式簡單說明】 圖面1係表示本發明第1實現例之金屬母材鎢塗層方法之流程圖，圖 面2〜圖面4係該模式圖。 圖面5係表示本發明第2實現例之金屬母材鎢塗層方法之流程圖，圖 面6〜圖面7係該模式圖。 圖面8之（a)係表示實施例1之鎢鑛金膜表面成分之吸收光譜。 圖面9係表示實施例1中製造之鎢鍍金膜正面相片。 圖面10係表示實施例1中積層在基板上之陽極氧化塗膜/鎢鍍金膜之側 面相片。 圖面11係表示實施例1〜實施例3和比較例1及比較例2中之基板按 時間之腐飩程度之曲線圖。 圖面12係表示實施例1之鎢鍍金膜之掃描電子顯微鏡相片。 18 200923129 圖面13係表示比較例1之鎳鍍金膜之掃描電子顯微鏡相片。 圖面14係表示比較例2之陽極氧化塗膜之掃描電子顯微鏡相片。 【主要元件符號說明】 11:金屬母材 13:陽極氧化塗膜 15,19:鎢鍍金膜 17:形成鎳鍍金膜 19In NasGftO (15 g/l)), a 5 A current was supplied for 40 minutes. A tungsten ore gold film having a thickness of 25 μm was formed on the anode oxide film by this electrolysis. Then, after washing with water, it was dried at normal temperature for 1 hour, and then heat-treated at 400 ° C for 2 hours in an oxygen atmosphere. Example 3 A pretreatment process was carried out by degreasing, 7]C washing, etching, and electrolytic degreasing of an aluminum substrate by a conventional method. Then, the aluminum substrate subjected to the pretreatment process is immersed in an acid solution having a concentration of sulfonic acid and oxalic acid of 0.5 M in a weight ratio of 1:5, and then used as an anode to supply a current of 0.2 Α/αί at 28 ° C. Minutes to form an anodized coating film. The aluminum substrate was washed with water and immersed in an electrolytic cell for forming a nickel-plated gold film (Ν6〇4·6Η2〇(400g/l), NiCk6H£) (20g/l), H3Ba (30g/l), and then supplied with 20Α current. A nickel-gold gold film of 5 _ thickness was formed on the anodized film for 10 minutes. Then, after carefully washing with DI 7jc, the aluminum substrate was again immersed in an electrolytic cell for forming a tungsten gold plating film (Na2〇W〇3.BO (20 g/l), Na2C〇3 (10 g/l), NH4〇H ( 5 g/l), CH2〇HCOONa (lg/1), and Na3GH5Cb (15 g/l)), and then supplied a 5 A current for 40 minutes to form a tungsten ore gold film having a thickness of 30 μm. Thereafter, it was dried at 4 ° C for 4 hours, and then heat-treated at 400 ° C for 4 hours in an oxygen atmosphere. Comparative Example 1 The aluminum substrate was subjected to degreasing, water washing, uranium engraving, and electrolytic degreasing by a prior method to carry out the first step. The aluminum substrate was washed with water and then immersed in an electrolytic cell for forming a nickel gold plating film (NiSCV6H2 (400 g/l), NiCk6H2 (20 g/l), H3B〇3 (30 g/l)), and then supplied with a current of 20 A for 10 minutes. A nickel-plated gold film having a thickness of 5 μm was formed on the anodized film. Comparative Example 2 The aluminum substrate was subjected to degreasing, water washing, etching, and electrolytic degreasing by a conventional method to carry out a pretreatment process. Then, the aluminum substrate subjected to the pretreatment process is immersed in an acid solution having a concentration of sulfonic acid and oxalic acid of 1:5 〇5 ,, and then used as an anode to supply a current of 0.2 Α/α at 28 ° C. For 60 minutes, an anodized coating film was formed. Test Example 1 In order to confirm whether or not a tungsten gold plating film was formed on the substrate by the above-described Example 1, the surface components were analyzed by a scanning electron microscope (SEM) and EDAX, and the results are shown in Fig. 8. Fig. 8 shows the absorption spectrum of the surface component of the tungsten gold plating film of Example 1. Referring to Fig. 8, it is understood that 30% of tungsten (W) is formed on the anodized film. Fig. 9 is a side view showing the front side of the tungsten gold plating film produced in the first embodiment. Fig. 1 shows the side surface of the anodized film/tungsten plated film laminated on the substrate in Example 1. Referring to Fig. 9 and Fig. 10, it is understood that an anodized film (Anodmng film) was formed on the base material of the crucible 1 to form a tungsten gold plating film thereon. Test Example 2: Corrosion resistance measurement 16 200923129 To measure the corrosion resistance of the substrates produced in the above Examples 1 to 3, Comparative Example 1 and Comparative Example 2, the substrate was immersed in a HC110% solution (251) and then measured. The degree of corrosion over time is shown in Figure 8. Fig. 11 is a graph showing the degree of corrosion of the substrate in Examples 1 to 3, Comparative Example 1, and Comparative Example 2. Referring to Fig. 11, it can be seen that in the case of the substrates of Examples 1 to 3, the degree of corrosion of the coating film was low. Test Example 3: Plasma resistance measurement, in order to measure the plasma resistance of the substrate produced in the above Examples to 3, Comparative Example 1 and Comparative Example 2, the substrate was placed in a PECVD chamber, and then 38 (TC conditions) The NB gas generation plasma was used to determine whether there was surface damage. The results are shown in Table 1. Table 1 Distinguish 24 hours, 48 hours, 96 hours Example 1 Substrate/anodized coating_|Gold plated film without damage, no damage, no damage Example 2 Substrate/anodized coating film: gold-plated film without damage, no damage, no damage, example 3 substrate/anodized coating film, gold-plated film/tungsten-plated gold film, no damage, no damage, no damage, comparative example 1, base_臬 gold-plated film, no damage Severe damage damage Comparative Example 2 Base smear extreme oxidation coating film/Slight damage Serious damage Serious damage Test Example 4: Heat-resistant cracking property measurement To measure the heat-resistant cracking property of the substrate manufactured in the above Examples 1 to 3, repeat 10 After heating at 500 ° C, it was cooled by water at normal temperature, and then the surface of the substrate was measured by a scanning electron microscope. 17 200923129 Figure 12 shows the embodiment 1 A scanning electron microscope photograph of the tungsten gold plating film, a drawing 13 showing a scanning electron microscope photograph of the nickel gold plating film of Comparative Example 1, and a drawing 14 showing a scanning electron microscope photograph of the anodized coating film of Comparative Example 2. 12 It is understood that the tungsten-plated gold-plated film produced by the present invention does not cause cracking. In contrast, it can be confirmed that the nickel-plated film or the anodized film is simply formed on the substrate in the surface 13 and the surface 14 Industrial Applicability The surface process agent for a metal base material according to the present invention is used for a heater and a shower head (air diffuser) used in a vacuum chamber and a vacuum chamber of a semiconductor and TFT-LCD manufacturing apparatus. [Simplified description of the drawings] Fig. 1 is a flow chart showing a method for coating a metal base material with a tungsten coating according to a first embodiment of the present invention, and Fig. 2 to Fig. 4 are schematic views. Fig. 5 is a flow chart showing a method for coating a metal base material with a tungsten coating according to a second embodiment of the present invention, and Fig. 6 to Fig. 7 are the same. Fig. 8(a) shows the tungsten ore gold of the embodiment 1. The absorption spectrum of the surface component of the film. Fig. 9 is a front view showing a tungsten gold plating film produced in Example 1. Fig. 10 is a side view showing an anodized coating film/tungsten gold plating film laminated on a substrate in Example 1. Fig. 11 shows an example. 1 to a graph of the degree of corrosion of the substrate in Example 3 and Comparative Example 1 and Comparative Example 2. The surface 12 shows a scanning electron microscope photograph of the tungsten gold plating film of Example 1. 18 200923129 A scanning electron microscope photograph of the nickel-plated gold film of Comparative Example 1. Fig. 14 shows a scanning electron microscope photograph of the anodized coating film of Comparative Example 2. [Explanation of main component symbols] 11: Metal base material 13: anodized coating film 15,19: tungsten gold plating film 17: forming a nickel gold plating film 19