201111557 六、發明說明： 【發明所屬之技術領域】 、本發明係有關-種多層氧化結薄膜及其形成方 法，尤其是糊電漿氧化方式產生㈣相氧化銘層。 【先前技術】 ”氧化_膜可在大氣中於金屬銘表面形成，且氧化 紹薄膜本身具有緻密性以及抗化性，因此銘製器具或用 品-直以來便被大量的使用於不同的領域，包括蒸者用 的廚具、建築用的紹架與紹門窗、居家的紹傢俱，以及 運動用的棒球鋁棒及高爾夫球桿。 氧化鋁薄膜依據晶相主要可分成面心立方緊密堆 積的r晶相氧化紹（r -祕）以及立方緊密堆積晶體 ^晶相氧化紹u_Al2〇3)，其中α晶相氧化紹的晶格 能大於r晶純化!s ’使得在機械強度與耐衝擊力的物 性以及抗濕與抗驗的能力上，α晶相氧化銘皆優晶 相氧化鋁。 ' sa 目月ί ’氧她薄朗形成麟主要有H炫射技 術（Ceramic Arc Spray)及氧化鋁硬陽極膜（此付201111557 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a multilayer oxide film and a method for forming the same, in particular, a paste plasma oxidation method to produce (iv) a phase oxidation layer. [Prior Art] "Oxidation _ film can be formed on the surface of metal in the atmosphere, and the oxidized film itself has compactness and chemical resistance, so the original appliance or article - has been used in a large number of different fields. Including kitchen utensils for steamers, shelves and doors for construction, Shaoxing furniture for homes, and baseball aluminum rods and golf clubs for sports. Alumina film can be divided into face-centered cubically closely packed r crystals depending on the crystal phase. Phase oxidation (r-secret) and cubic compactly packed crystals ^ crystal phase oxidation of _u_Al2〇3), wherein the crystal lattice energy of α crystal phase oxidation is larger than that of r crystal purification! s 'make physical properties and impact resistance physical properties As well as the ability to resist moisture and anti-test, α-crystal phase oxidation is the best crystal phase alumina. ' sa 目月 ί ' Oxygen she thinly formed Lin mainly has H Arc technology (Ceramic Arc Spray) and alumina hard anode Membrane
Anodized Film)。 在陶瓷熔射技術中，氧化鋁粉材料被加熱至熔化 或”化狀態後於喷嘴褒置内藉高速氣流而噴出，並撞 擊附著於工件表面’在急速凝固後形成層狀堆積的塗 層。陶曼熔射技術所形成的氧化紹薄膜適合於特殊環境 中使用’可達到耐腐钱、抗磨耗、隔熱絕緣等功能。 但是，習用技術的陶瓷熔射技術的主要缺點包括： 201111557 =1。00嗔下之膜厚，其成膜厚度Μ控制且均勾度 2. 氧化__結合度猶密且麵過多微孔。 3. 對複雜外形及細薄之被噴塗件不易施工。 ί:機:：1:=能二容易造成剝離。 -全ttr更用陽極膜中，的陽極氧化是用1呂或銘 口金田％極’用錯、碳或不銹鋼當陰極，Anodized Film). In the ceramic spraying technique, the alumina powder material is heated to a molten or "stated state, and is ejected by a high-speed air stream in the nozzle chamber, and impinges on the surface of the workpiece to form a layered coating after rapid solidification. The Oxide film formed by Tauman's spray technology is suitable for use in special environments to achieve corrosion resistance, abrasion resistance, thermal insulation and other functions. However, the main disadvantages of conventional ceramic spray technology include: 201111557 =1膜 之 之 之 之 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔 嗔Machine::1:=2 can easily cause stripping. -All ttr is more used in the anode film, the anodizing is done with 1 Lu or Mingkou Jintian% pole' with the wrong, carbon or stainless steel as the cathode,
石ί酸、鉻酸等溶液中電解，形成六角晶柱之結晶構 k °人工配製屏障形成氧化膜時，膜厚度的增加與 附加電！成正比；但電壓不能無限制增加，^ _V左右的電解槽電壓下會引起絕緣破 展’缚膜受到損傷。因此陽極處理的目的即利用其易 氧化之特性，電化學方法控制氧化層之生成，轉止 銘材進步氧化，因此利用陽極電流強迫其繼續 以增厚此保護膜。 ' 然而，習用技術的氧化鋁硬陽極膜的主要缺點 括： 、 1·膜厚度有限制，通常在6〇喊上時，細相當困難。 2. 為六角晶柱結構，無高溫塑性、機械強度及韌性 不佳，容易脆裂。 3. 白為γ AhO3結構，於電聚及腐姓環境中，耐電漿及 孔钱性能不佳。 4. 經熱水或蒸氣封孔後，強度硬度大幅降低。 所以’ T晶相氧化銘的氧化紹硬陽極膜很容易產 生膜層裂解情形’尤其在緣角處，使得氧化硬陽極膜 201111557 不適合應用於電漿蝕刻（ETCH)、化學氣象沉積 (Chemical Vapor Deposition)、物理氣象沉積 (Physical Vapor Deposition)的電子、光電、太陽能、 半導體積體電路製造及傳統產業等設備環境，而只適用 於一般傳統輕金屬表層處理。 因此’需要一種具α晶相氧化銘的氧化銘薄膜， 以解決上述習用技術的所有問題。 【發明内容】 本發明之主要目的在提供一種電漿多層氧化鋁薄 膜至少包括介面層與主功能層，且介面層位於基材上而 主功能層位於介面層上，基材可包括鋁或鋁合金，介面 層可包括鋁及第一晶相氧化鋁，主功能層可包括第一氧 化鋁層及第二氧化鋁層，第一氧化鋁層位於介面層上， 第二氧化鋁層位於第一氧化鋁層上，且第一氧化鋁層包 括第一晶相氧化鋁及第二晶相氧化鋁，而第二氧化鋁層 只包括第二晶相氧化紹，第—晶相氧化紹為面心立方 緊密堆積的r晶相氧化!s(7_AhQ3)，該第二氧化銘層 為立方緊密堆積晶體的α晶相氧化鋁（α _Ah〇3)。 ,本發明之另一目的在提供一種電漿多層氧化鋁薄 =形，方法’係配置電解液，利用交流脈衝電壓施加到 當作陽極的基板，且以轉槽為陰極，將基板置入包含 在電解槽_電驗中，使驗鱗在適當溫度範圍， 且在適當電功率下，對基板中的銘進行電漿氧化，以形 成具有至少包含介面層與主功能層的電漿多層氧化鋁 薄膜。 201111557 【實施方式】 以下配合圖式及元件符號對本發明之實施方式做 更詳細的§兒明’俾使熟習該項技藝者在研讀本說明書後 能據以實施。 參閱第一圖，本發明電漿多層氧化鋁薄膜的示意 圖。如第一圖所示，本發明的電漿多層氧化鋁薄膜t包 括至少介面層20與主功能層30，且介面層2〇位於基Electrolysis in a solution of sulphuric acid, chromic acid, etc., forming a crystal structure of a hexagonal crystal column k ° artificially preparing a barrier to form an oxide film, the film thickness is increased and additional electricity! It is proportional to the voltage; however, the voltage cannot be increased without limit, and the insulation of the cell at about _V will cause the insulation to break. Therefore, the purpose of the anodizing treatment is to utilize the characteristics of its easy oxidation, the electrochemical method to control the formation of the oxide layer, and the progress of the oxidation of the material, so that the anode current is forced to continue to thicken the protective film. However, the main disadvantages of conventional aluminum oxide hard anodic films include: 1. There is a limit to the film thickness, which is usually quite difficult when 6 screams. 2. It is a hexagonal crystal column structure with no high temperature plasticity, poor mechanical strength and toughness, and easy brittle fracture. 3. White is a γ AhO3 structure, which is resistant to plasma and pores in the environment of electricity and corrosion. 4. After sealing with hot water or steam, the strength and hardness are greatly reduced. Therefore, 'T crystal phase oxidation of the hard anodic film is easy to produce film cracking situation' especially at the edge angle, making the oxidized hard anodic film 201111557 unsuitable for plasma etching (ETCH), chemical vapor deposition (Chemical Vapor Deposition) ), physical weathering (Physical Vapor Deposition) of electronics, optoelectronics, solar energy, semiconductor integrated circuit manufacturing and traditional industries and other equipment environment, and only for general traditional light metal surface treatment. Therefore, an oxidized film having an alpha crystal phase oxidation is required to solve all the problems of the above conventional techniques. SUMMARY OF THE INVENTION The main object of the present invention is to provide a plasma multilayer aluminum oxide film comprising at least an interface layer and a main functional layer, wherein the interface layer is on the substrate and the main functional layer is on the interface layer, and the substrate may comprise aluminum or aluminum. The alloy, the interface layer may include aluminum and the first crystalline phase alumina, and the main functional layer may include a first aluminum oxide layer and a second aluminum oxide layer, the first aluminum oxide layer is located on the interface layer, and the second aluminum oxide layer is located at the first layer On the aluminum oxide layer, the first aluminum oxide layer comprises a first crystalline phase alumina and a second crystalline phase alumina, and the second aluminum oxide layer comprises only the second crystalline phase oxidation, and the first crystalline phase is oxidized as a face center The cubically packed r crystal phase is oxidized!s(7_AhQ3), and the second oxide layer is a cubically phase-arranged alpha phase alumina (α_Ah〇3). Another object of the present invention is to provide a plasma multilayer alumina thinner shape, the method of which is to configure an electrolyte, apply an alternating pulse voltage to a substrate serving as an anode, and use a rotary channel as a cathode to place the substrate therein. In the electrolysis cell, the scale is subjected to plasma oxidation at a suitable temperature range and under appropriate electric power to form a plasma multilayer alumina film having at least an interface layer and a main functional layer. . [Embodiment] Hereinafter, embodiments of the present invention will be described in more detail with reference to the drawings and the component symbols, so that those skilled in the art can implement the present invention after studying the present specification. Referring to the first figure, a schematic view of a plasma multilayer alumina film of the present invention. As shown in the first figure, the plasma multilayer aluminum oxide film t of the present invention comprises at least the interface layer 20 and the main functional layer 30, and the interface layer 2 is located at the base.
材10上’而主功能層30位於介面層2〇上。基材1〇包 括鋁或鋁合金，介面層20包括鋁及第一晶相氧化鋁， 主功能層30包括第-氧化叙層及第二氧化紹層（圖中 未顯示），第一氧化鋁層位於該介面層上，第二氧化鋁 層位於該第-氧化_上H氛化域包括第一晶 相氧化缺第二晶純化，而帛二氧_層只包括第 二晶相氧化銘。 ^述的第-晶相氧化銘為面心立方緊密堆積的7 晶相氧化紹（r_Ah〇3) ’該第二氧化銘層為立方緊密堆 積晶體的α晶相氧她（α—Αΐ2〇3)。該介面層的在呂平均 佔，一百分比，該介面層的鋁平均佔第一百分比，該第 一氧化_的第—晶純化辦触第二百分比，該第 二百分比為50%至90%。 本矣明的賴乡層氧她_丨 =笛表面層40内可具有封閉性微錢。該表面層4〇 匕括第二晶相氧化鋁，因此具有較佳 性，進—錢聰_舰祕機顧度與耐用 201111557 、，閱第二圖’本發明電漿多層氧化銘薄膜形成方 法的流程圖。如第二圖所示，本發明的電漿多層氧化銘 薄膜形成方法係由步驟S1G開始，混合水、氫氧化銘、 無機酸以及無機脑，聰製該電驗，其t無機酸可 為醋酸，無機鹽類可包括磷酸鈉、矽酸鈉、碳酸鉀以及 -人&酸鹽類的至少其_之一。接著在步驟S2〇中，將基 板浸泡於電解液中，該電解液係包含於該電解槽内，然 後進入步驟S30 ’該基板連接至陽極，電解槽連接陰極。 • 接著在步驟S40中’在陽極與陰極分別饋入互為正相與 反相的交流脈衝電壓，產生一電流，對基板進行電漿氧 化’使基板所包含的銘因氧化反應而產生氧化銘，最後 進入步驟S50 ’形成電漿多層氧化鋁薄膜，並附著在該 基板的表面上。電漿多層氧化鋁薄膜的結構係如第一圖 所示，在此不再贅述。 由於基板附近會產生局部性的高溫電漿，因此整 體電解液的溫度係保持在某一溫度範圍内，比如5至 _ 30 C ’其目的為使電漿氧化銘急速冷卻以及避免電解液 過熱（而發生危險）。為使電漿多層氡化銘薄膜的成膜速 度達到所需範圍，且又需維持薄膜的品質，因此交流脈 衝電壓可為大於100至3000VAC，且電流可為大於1〇至 650安培。 本發明電漿多層氧化鋁薄膜及形成方法的主要特 點是，利用適當電功率的電漿氧化製程，配合適當組成 的電解液’在含鋁的基材表面上形成具較佳機械強度與 耐用性的α晶相氧化鋁層，尤其是在基板與α晶相氧^ 鋁層之間可進一步形成包含γ晶相氧化鋁與^晶相氧 201111557 化_中間層，或進-步在中間層與基板之間再 含有紹與7晶減化_介面層，其中α晶相氧化銘^ 結合中間層而在此稱作主功能層，因此在基板上I有^ 功能層及介_的多層結構，提錢強又 的機械強度及更佳的保護作用。The material 10 is on top and the main functional layer 30 is on the interface layer 2'. The substrate 1A includes aluminum or an aluminum alloy, the interface layer 20 comprises aluminum and a first crystalline phase alumina, and the main functional layer 30 comprises a first-oxidation layer and a second oxide layer (not shown), the first aluminum oxide The layer is located on the interface layer, the second aluminum oxide layer is located in the first oxidation-upper H region, and the second crystal phase is included in the second crystal phase oxidation. The first phase-crystal phase oxidation is described as a face-centered cubic close-packed 7-phase phase oxide (r_Ah〇3) 'The second oxide layer is a cubic densely packed crystal of alpha phase oxygen. (α-Αΐ2〇3 ). The interface layer occupies an average of a percentage, and the aluminum of the interface layer occupies the first percentage on average, and the first crystal oxidation of the first oxidation layer touches a second percentage, and the second percentage is 50% to 90%. Benjamin's Laixiang layer oxygen her _ 丨 = flute surface layer 40 can have closed micro-money. The surface layer 4 includes the second crystalline phase alumina, so it is preferable, and the method of forming the plasma multilayer oxide film of the present invention is as follows. Flow chart. As shown in the second figure, the method for forming a plasma multilayer oxide film of the present invention starts from step S1G, mixing water, hydroxide, inorganic acid and inorganic brain, and the test is performed, and the inorganic acid of t can be acetic acid. The inorganic salts may include at least one of sodium phosphate, sodium citrate, potassium carbonate, and a human & acid salt. Next, in step S2, the substrate is immersed in an electrolytic solution which is contained in the electrolytic cell, and then proceeds to step S30' where the substrate is connected to the anode, and the electrolytic cell is connected to the cathode. • Next, in step S40, 'the positive and negative phase AC pulse voltages are respectively fed to the anode and the cathode, and a current is generated to plasma-oxidize the substrate'. The inscription contained in the substrate is oxidized by the oxidation reaction. Finally, the process proceeds to step S50' to form a plasma multilayer alumina film and adhere to the surface of the substrate. The structure of the plasma multilayer aluminum oxide film is as shown in the first figure, and will not be described herein. Since local high-temperature plasma is generated near the substrate, the temperature of the overall electrolyte is maintained within a certain temperature range, such as 5 to -30 C', which is intended to rapidly oxidize the plasma and prevent the electrolyte from overheating ( And the danger occurs). In order to achieve a film formation speed of the plasma multilayer 氡化铭膜, and to maintain the quality of the film, the AC pulse voltage can be greater than 100 to 3000 VAC, and the current can be greater than 1 〇 to 650 amps. The main feature of the plasma multilayer alumina film and the forming method of the invention is that the plasma oxidation process with appropriate electric power is combined with the electrolyte of the appropriate composition to form a better mechanical strength and durability on the surface of the aluminum-containing substrate. The α-crystalline phase aluminum oxide layer, especially between the substrate and the α-crystalline phase oxygen aluminum layer, may further form a γ-phase phase alumina and a crystal phase oxygen 201111557 _ intermediate layer, or further in the intermediate layer and the substrate Between the 7-crystal reduction and the interfacial layer, wherein the α-crystal phase is oxidized, the intermediate layer is referred to herein as the main functional layer, so that the functional layer and the multi-layer structure are provided on the substrate. Qian Qiang's mechanical strength and better protection.
本發明電聚多層氧化銘薄膜及形成方法的另 =是’可在主魏層上進—步形成具不滑表面的表面 二，且表面層係只包含物性較強且化性較穩定的7晶相 乳化銘，尤其是表面層可進—步包含侧性微孔，提供 吸收外部衝擊力的機制，因此能提高耐衝擊性，藉以提 供更進一步的保護作用。 本土明的電漿多層氧化紹薄膜非常適合應用於電 漿钱刻^學氣象沉積、物理氣象沉積製㈣電子、光 電、太陽能、半導體積體電路製造及傳統產#等設備環 ,以上所述者僅為用以解釋本發明之較佳實施 例並非企圖據以對本發明做任何形式上之限制，是 以，凡有在相同之發明精神下所作有關本發明之任何修 飾或變更’皆仍應包括在本發明意圖保護之範轉。 【圖式簡單說明】 第:圖為本發明魏多層氧化_膜的示意圖。 第-圖為本發明電❹層氧化銘薄細彡成方法的流程圖。 【主要元件符號說明】 1電漿多層氧化鋁薄膜 201111557 ίο基材 20介面層 30主功能層 40表面層 42表面 44微孔 S10配製電解液 S20基板浸泡於電解液中 S30基板連接陽極而電解槽連接陰極 S40施加交流脈衝電壓以進行電漿氧化 S50形成電漿多層氧化鋁薄膜The electropolymerized multilayer oxide film of the invention and the method for forming the same can be formed on the main Wei layer to form a surface 2 having a non-slip surface, and the surface layer system only contains the physical property and the chemical stability is stable. The crystal phase emulsification, especially the surface layer can further include side micropores, providing a mechanism for absorbing external impact force, thereby improving impact resistance, thereby providing further protection. The local bright plasma multi-layer oxidation film is very suitable for the application of plasma engraving, meteorological deposition, physical meteorological deposition (4) electronics, optoelectronics, solar energy, semiconductor integrated circuit manufacturing and traditional production #, etc. It is to be understood that the preferred embodiment of the present invention is not intended to be construed as limiting the scope of the invention. It is intended to protect the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig.: is a schematic view showing the Wei multi-layer oxidation film of the present invention. The first-figure is a flow chart of the method for forming a thin layer of an electric layer of the present invention. [Main component symbol description] 1 plasma multilayer aluminum oxide film 201111557 ίο substrate 20 interface layer 30 main functional layer 40 surface layer 42 surface 44 microporous S10 preparation electrolyte S20 substrate immersed in electrolyte S30 substrate connected anode and electrolytic cell Connecting the cathode S40 to apply an alternating pulse voltage for plasma oxidation S50 to form a plasma multilayer aluminum oxide film