201217563 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及一種鍍臈件及該鍍膜件的製備方法。 [先前技術] [0002] 透明導電薄膜由於具有良好的導電性和可見光透過率， 在太陽能電池和液晶顯示器等領域有著廣泛的應用。氧 化銦錫（ITO)薄膜係目前研究和應用最廣泛的透明導電薄 膜。由於Sn4 +可以替換晶格中In3 +的位置，產生自由電 子’故IT0薄膜具有較高的電導率。由於ITO薄膜含有貴 金屬銦，成本較高，研究者開始尋求另外的替代產品。 [0003] 氧化鋅原料豐富，價格便宜，無毒且穩定性高，因此摻 純化鋅（ΑΖΟ)薄膜係目前最有開發潘力的薄膜材料之一 。ΖΠ〇薄膜摻入A1後，Al3 +離子佔據晶格中W離子的位 置’形成一個—價正電荷中心和-個多餘的價電子，這 個價電子掙脫束缚而成為導電電子。JJ此掺雜A1導致淨 電子的增加’ ZnO薄膜的電導率増大。然鑛覆有AZ〇薄膜 〇 的鍵膜件在使用較長時間後，Az〇薄膜的導電性會不穩定 ’從而導致AZ0薄腺生4 , 联失效’極大縮短了鍍膜件的使用壽命 【發明内容】 [0004] 有鑒、U要提供—種有5切決上述問題的鍵膜件 [0005] 另外，還有必要提供一種製備j、+、 裡取備上述鍍膜件的方法。 [0006] 一種鍵膜件，包括基;bf· » $ ^ & 材及形成於基材表面的透明導電薄 〇99137〇76 表單编號 A_1 * 3 !/^ 9 ¥ 、H 0992064662-0 201217563 膜，該透明導電薄膜為Me摻雜的摻鋁氧化鋅薄膜，其中 Me為錫、叙、錄、组及銳中的兩種或兩種以上。 [0007] [0008] [0009] [0010] [0011] [0012] [0013] 099137076 一種鍍膜件的製備方法，其包括如下步驟： 提供基材； 在基材表面形成透明導電薄膜，該透明導電薄膜為Me摻 雜的摻鋁氧化鋅薄膜，其中Me為錫、鉍、銻、钽及鈮中 的兩種或兩種以上。 本發明所述鍍膜件在基材的表面沉積透明導電薄膜，該 透明導電薄膜藉由在摻鋁氧化鋅薄膜中引入錫、鉍、銻 、钽及鈮中的兩種或兩種以上，藉由高價態Sn4+、Bi3 + 、Sb5+、Ta5 +及Nb5+中的兩種或兩種以上取代部分Zn2 + ，從而產生自由電子，獲得較高的導電率。該透明導電 薄膜具有良好的穩定性，可有效地提高鍍膜件的使用壽 命。另外該透明導電薄膜還具有高透光性。 【實施方式】 請參閱圖1，本發明一較佳實施方式鍍膜件10包括基材11 、形成於基材11表面的透明導電薄膜13。 該基材11可為玻璃或陶瓷。 該透明導電薄膜13為Me摻雜的掺鋁氧化鋅（AZO)薄膜， 其中Me可為錫（Sn)、鉍（Bi)、銻（Sb)、钽（Ta)及鈮 (Nb)中的兩種或兩種以上，其中A1的質量百分含量可為1 〜5%，換雜的Sn的質量百分含量可為1〜4%，摻雜的Sb 的質量百分含量可為1〜2%，摻雜的Bi的質量百分含量可 為1〜3%，摻雜的Nb的質量百分含量可為1〜2%，摻雜的 表單編號A0101 第4頁/共9頁 0992064662-0 201217563201217563 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a rhodium-plated member and a method of preparing the coated member. [Prior Art] [0002] A transparent conductive film has a wide range of applications in fields such as solar cells and liquid crystal displays because of its good electrical conductivity and visible light transmittance. Indium tin oxide (ITO) films are currently the most widely studied and widely used transparent conductive films. Since Sn4 + can replace the position of In3 + in the crystal lattice, a free electron is generated, so the IT0 film has a higher conductivity. Since ITO films contain precious metal indium, the cost is higher, and researchers are looking for alternatives. [0003] Zinc oxide is rich in raw materials, inexpensive, non-toxic and highly stable. Therefore, the purified zinc (ruthenium) film system is currently one of the most developed film materials. After the ruthenium film is doped with A1, the Al3+ ions occupy the position of the W ion in the crystal lattice, forming a valence positive charge center and a redundant valence electron. This valence electron breaks away from binding and becomes a conductive electron. This J1 doping of A1 leads to an increase in net electrons. The conductivity of the ZnO thin film is large. However, after a long time of use, the bond film of AZ〇 film 矿 will be unstable, and the conductivity of Az〇 film will be unstable, which will lead to AZ0 thin gland 4, and the failure will greatly shorten the service life of the coated parts. Contents] [0004] There is a method to provide a key film that has 5 problems to solve the above problems. [0005] In addition, it is also necessary to provide a method for preparing the above-mentioned coated member in j, +, and lining. [0006] A key film member comprising a base; bf· » $ ^ & a material and a transparent conductive thin film formed on the surface of the substrate 99137〇76 Form No. A_1 * 3 !/^ 9 ¥ , H 0992064662-0 201217563 The transparent conductive film is a Me-doped aluminum-doped zinc oxide film, wherein Me is two or more of tin, ruthenium, ruthenium, group, and sharp. [0010] [0013] [0013] [0013] 099137076 A method for preparing a coated member, comprising the steps of: providing a substrate; forming a transparent conductive film on the surface of the substrate, the transparent conductive The film is a Me-doped aluminum-doped zinc oxide film, wherein Me is two or more of tin, antimony, bismuth, antimony and bismuth. The coated member of the present invention deposits a transparent conductive film on the surface of the substrate by introducing two or more of tin, antimony, bismuth, antimony and bismuth into the aluminum-doped zinc oxide film. Two or more of the high-valent states Sn4+, Bi3+, Sb5+, Ta5+, and Nb5+ substitute a part of Zn2+, thereby generating free electrons and obtaining higher conductivity. The transparent conductive film has good stability and can effectively improve the service life of the coated member. In addition, the transparent conductive film also has high light transmittance. Embodiments Referring to FIG. 1 , a coated article 10 according to a preferred embodiment of the present invention includes a substrate 11 and a transparent conductive film 13 formed on the surface of the substrate 11. The substrate 11 can be glass or ceramic. The transparent conductive film 13 is a Me-doped aluminum-doped zinc oxide (AZO) film, wherein Me can be two of tin (Sn), bismuth (Bi), antimony (Sb), tantalum (Ta), and niobium (Nb). Or more than two kinds, wherein the mass percentage of A1 may be 1 to 5%, the mass percentage of the mixed Sn may be 1 to 4%, and the mass percentage of the doped Sb may be 1 to 2 %, the mass percentage of doped Bi may be 1 to 3%, the mass percentage of doped Nb may be 1 to 2%, doped form number A0101, page 4 / total 9 pages 0992064662-0 201217563
Ta的質量百分含量可為1〜2°/〇。 [0014] 該透明導電薄膜13可以磁控濺射或蒸鍍的方式形成。該 透明導電薄膜13的厚度可為300〜80 Onm。 [0015] 本發明一較佳實施方式的鍍膜件10的製備方法，其包括 以下步驟： [0016] 提供一基材11，該基材11可為玻璃或陶瓷。 [0017] 將基材11放入無水乙醇中進行超聲波清洗，以去除基材 11表面的污潰，清洗時間可為5〜10mi η。 [0018] 對經上述處理後的基材11的表面進行氬氣電漿清洗，以 進一步去除基材11表面的油污，以及改善基材11表面與 後續塗層的結合力。該電漿清洗的具體操作及工藝參數 可為：將基材11放入一磁控濺射鍍膜機（圖未示）的鍍膜 室内，將該鍍膜室抽真空至1. 0〜2. 0xl(T5Torr，然後 向鍍膜室内通入流量為100〜300sccmC標準狀態毫升/分 鐘）的氬氣（純度為99. 999%)，並施加-10 0〜-300 V的偏 壓於基材11，對基材11表面進行氬氣電聚清洗，清洗時 間為1 0〜2 0 m i η。 [0019] 採用磁控濺射法在經氬氣電漿清洗後的基材11上濺鍍一 透明導電薄膜13，該透明導電薄膜13可為Me摻雜的ΑΖ0 薄膜，其中Me可為Sn、Bi、Sb、Ta及Nb中的兩種或兩種 以上。濺鍍該透明導電薄膜13在所述磁控濺射鍍膜機中 進行。使用Sn、Bi、Sb、Ta及Nb中的兩種或兩種以上組 成的合金靶、A1靶及Zn靶為靶材，以氧氣為反應氣體， 氧氣流量可為50〜200sccm，以氬氣為工作氣體，氬氣 099137076 表單編號 A0101 第 5 頁/共 9 頁 0992064662-0 201217563 流量可為100〜3〇〇SCCn^濺鍍時對基材施加_1〇〇〜_ 300V的偏壓，並加熱所述鍍膜室使基材u的溫度為2〇〇 〜350C，鍍膜時間可為3〇〜6〇mjn。該透明導電薄膜I〗 的厚度可為300〜800ηπ^ [0020] 本發明較佳實施方式鍍膜件1〇在基材丨丨的表面沉積透明 導電薄膜13，該透明導電薄膜13藉由在摻Α1的ΖηΟ薄膜 中引入Sn、Bi、Sb、Ta及Nb的兩種或兩種以上，藉由高 價態的Sn4+、Bi3+、Sb5+、Nb5 +及Ta5+中的兩種或兩種 以上取代部分Zn2+，從而產生自由電子，獲得較高的導 電率。該透明導電薄膜13真有良好的輪定性，可有效地 提高鍍膜件10的使用壽命。另外’該透明導電薄膜13還 具有1¾透光性。 【圖式簡單說明】 [0021] 圖1為本發明一較佳實施例鍍膜件的剖視圖。 【主要元件符號說明】 [0022] 鑛膜件：1〇 [0023] 基材：11 [0_ 透明導電薄膜：1 3 099137076 表單編號A0101 第6頁/共9頁 0992064662-0The mass percentage of Ta may be 1 to 2 ° / 〇. [0014] The transparent conductive film 13 can be formed by magnetron sputtering or evaporation. The transparent conductive film 13 may have a thickness of 300 to 80 Onm. [0015] A method of preparing a coated member 10 according to a preferred embodiment of the present invention includes the following steps: [0016] A substrate 11 is provided, which may be glass or ceramic. [0017] The substrate 11 is placed in absolute ethanol for ultrasonic cleaning to remove the stain on the surface of the substrate 11, and the cleaning time may be 5 to 10 mi η. [0018] The surface of the substrate 11 subjected to the above treatment is subjected to argon plasma cleaning to further remove the oil stain on the surface of the substrate 11, and to improve the adhesion of the surface of the substrate 11 to the subsequent coating. 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 T5Torr, then argon gas (purity of 99.999%) was introduced into the coating chamber at a flow rate of 100 to 300 sccm C standard state/min, and a bias voltage of -10 0 to -300 V was applied to the substrate 11, and the base was applied. The surface of the material 11 was subjected to argon electropolymer cleaning, and the cleaning time was 10 to 2 0 mi η. [0019] a transparent conductive film 13 is sputtered on the substrate 11 after argon plasma cleaning by a magnetron sputtering method, and the transparent conductive film 13 may be a Me-doped ΑΖ0 film, wherein Me may be Sn, Two or more of Bi, Sb, Ta, and Nb. The transparent conductive film 13 is sputtered in the magnetron sputtering coater. An alloy target composed of two or more of Sn, Bi, Sb, Ta, and Nb, an A1 target, and a Zn target are used as targets, and oxygen is used as a reaction gas, and the oxygen flow rate may be 50 to 200 sccm, and argon gas is used. Working gas, argon 099137076 Form No. A0101 Page 5 of 9 0992064662-0 201217563 Flow rate can be 100~3〇〇SCCn^ Apply a bias of 〇〇1 to _300V to the substrate during sputtering and heat The coating chamber has a temperature of the substrate u of 2 〇〇 to 350 C, and a coating time of 3 〇 to 6 〇 mjn. The transparent conductive film I can have a thickness of 300 to 800 η π ^ [0020] In the preferred embodiment of the present invention, the coated member 1 沉积 deposits a transparent conductive film 13 on the surface of the substrate ,, the transparent conductive film 13 is used in the erbium Two or more kinds of Sn, Bi, Sb, Ta, and Nb are introduced into the ΖηΟ film, and a part of Zn2+ is replaced by two or more of the high-valent states of Sn4+, Bi3+, Sb5+, Nb5+, and Ta5+. Produces free electrons and achieves higher conductivity. The transparent conductive film 13 has a good rounding property and can effectively improve the service life of the coated member 10. Further, the transparent conductive film 13 has a light transmittance of 13⁄4. BRIEF DESCRIPTION OF THE DRAWINGS [0021] FIG. 1 is a cross-sectional view of a coated member according to a preferred embodiment of the present invention. [Main component symbol description] [0022] Mineral film member: 1〇 [0023] Substrate: 11 [0_ Transparent conductive film: 1 3 099137076 Form No. A0101 Page 6 / Total 9 pages 0992064662-0