TW521280B - Method of producing transparent conductive film-laminated substrate and method of producing color filter - Google Patents
Method of producing transparent conductive film-laminated substrate and method of producing color filter Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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521280 Α7 I --—------ 五、發明說明(1 ) 【技術領域】 本發明係有關於透明導電膜積層基板及彩色濾光片之 製造方法。 【習知技術】 成為筆記型電腦、桌上型電腦用之顯示器等之主流的 TFT顯示器係構成從光源來的光線通過TFT、液晶分子、彩 色濾光片而於基板上形成影像的狀態。 彩色遽光片之製造方法可知有例如特開昭63 — 197903 號公報、特開平6 — 28932號公報所記載的方法。 特開昭63 — 197903號公報係揭示有將形成有遮光膜及 彩色光阻劑膜之玻璃基板加熱至l8(rc而將錫一銦氧化物 燒結體所構成之靶子(target)予以濺鍍,或是藉著包含氧氣 之氬锿境氣體中將銦錫合金所構成之靶子施予反應性濺鍍 ,而於形成有遮光膜及彩色濾光阻劑膜之玻璃基板上形成 ITO導電膜的方法。 但是,以特開昭63一 197903號公報所揭示之之方法所 獲得之ιτο v電膜係由單層構成者,乃有導電率低(即電阻 率大)的缺點。若是要提昇IT0導電膜之導電率的話,則有 必要將導電膜之膜厚作得厚,然而,一旦將ΙΤ〇導電膜之膜 厚作厚,則無法避免導電膜之透明性受損的情形。因此, 以此方法所獲得之ΙΤ0導電膜無法滿足高導電率及透明性 之雙方。 特開平6一 28932號公報乃揭示有在形成有彩色光阻劑 膜上形成之有機樹脂表面形成ΙΤ〇導電膜的方法。此方法具 本紙張尺度適用中國國豕標準(CNS)A4規格(2〗〇 X 297公爱) {請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印521280 Α7 I --------- 5. Description of the invention (1) [Technical Field] The present invention relates to a method for manufacturing a transparent conductive film laminated substrate and a color filter. [Known Technology] TFT displays, which have become mainstream in displays for notebook computers and desktop computers, constitute a state where light from a light source passes through TFTs, liquid crystal molecules, and color filters to form an image on a substrate. As a method for producing a color phosphor film, there are known methods described in, for example, Japanese Patent Application Laid-Open No. 63-197903 and Japanese Patent Application Laid-Open No. 6-28932. Japanese Patent Application Laid-Open No. 63-197903 discloses that a glass substrate formed with a light-shielding film and a color photoresist film is heated to 18 (rc, and a target made of a tin-indium oxide sintered body is sputtered. Or a method of forming an ITO conductive film on a glass substrate having a light-shielding film and a color filter film formed by subjecting an indium tin alloy target to reactive sputtering in an argon atmosphere gas containing oxygen to a target. However, the ιτο v electrical film obtained by the method disclosed in JP-A-63-197903 is composed of a single layer, which has the disadvantage of low conductivity (ie, large resistivity). If it is necessary to improve the conductivity of IT0 If the conductivity of the film is necessary, it is necessary to make the film thickness of the conductive film thick. However, once the thickness of the ITO conductive film is made thick, the transparency of the conductive film cannot be avoided. Therefore, in this way, The ITO conductive film obtained by the method cannot satisfy both high conductivity and transparency. Japanese Patent Laid-Open No. 6-28932 discloses a method for forming an ITO conductive film on the surface of an organic resin formed on a color photoresist film. This side The standard of this paper is applicable to China National Standard (CNS) A4 specification (2) 0 X 297 public love. {Please read the notes on the back before filling this page.)
--------^--------- -4- 521280 A7 B7 五、發明說明( --------------裝--- (請先閱讀背面之注意事項再填寫本頁) 有(a)在有機樹脂表面,使用錫一銦氧化物燒結體作為靶子 ,而在包含氬氣或氧氣3容量%之氬氣與氧氣之混合氣體的 锿境氣體中,以直流磁控管(magnetr〇n)濺鍍法被覆厚度3 〜3 Onm之結晶核生成層(第}層)的步驟、(b)將結晶核生成層 在減壓的環境氣體中,並以10(rc以上之前述有機樹脂不會 劣之的溫度進行退火而成長結晶核的步驟,以及於結晶 核生成層上,在包含氬氣或氧氣3容量%之氬氣與氧氣之混 合氣體的環境氣體中,以直流磁控管(magnetr〇n)濺鍍法被 覆低電阻化層(第2層)的步驟。 要弄低ITO導電膜之電阻率,乃有兩種方法。其一係將 載體(自由電子)之移動度弄大的方法,其二係提高載體(自 由電子)之密度的方法。上述特開昭63一 1979〇3號公報所記 載的方法係將載體的密度弄大,其結果係要達到降低17〇 導電膜之電阻率,即,要達到提昇導電率者。 但是依據此方法的話,雖然載體之移動度會變大,惟 ,會伴隨著Φ體之密度會降低而使導電率之改善效果不充 足。 又’特開平6 — 28932號公報的方法因有必要進行所謂 退火的特別處理.,故無實用性。 而且,在形成ITO導電膜的方法上,可得知有例如特開 平2 — 189816號公報所記載的方法。 上述公報係揭示著具有,於包含經減壓之非活性氣體 或非活性氣體與氧氣之混合氣體的環境氣體中,使用銦一 錫氧化物燒結體的靶子而在維持2〇〇°C的基板上藉著磁控 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 χ 297公釐) 521280-------- ^ --------- -4- 521280 A7 B7 V. Description of the invention (-------------- install --- (please first Read the notes on the reverse side and fill in this page) (a) On the surface of the organic resin, use a tin-indium oxide sintered body as the target, and 锿Step of coating a crystal nucleation layer (layer) with a thickness of 3 to 3 Onm in a direct current magnetron (magnetron) sputtering method in an ambient gas, (b) decompressing the crystal nucleation layer to an ambient gas Step of growing the crystal nucleus by annealing at a temperature not lower than the aforementioned organic resin of 10 (rc), and on the crystal nucleation layer, an argon gas and an oxygen gas containing 3% by volume of argon or oxygen Step of coating a low-resistance layer (second layer) with a DC magnetron sputtering method in an ambient gas of a mixed gas. There are two methods for reducing the resistivity of an ITO conductive film. The first method is to increase the mobility of the carrier (free electron), and the second method is to increase the density of the carrier (free electron). Japanese Patent Application Laid-Open No. 63-11979 The method described in the bulletin is to increase the density of the carrier, and as a result, it is necessary to reduce the resistivity of the 170 conductive film, that is, to increase the conductivity. However, according to this method, although the carrier mobility will increase However, the effect of improving the conductivity is not accompanied by the decrease in the density of the Φ body. The method disclosed in Japanese Patent Application Laid-Open No. 6-28932 is not practical because it requires a special treatment called annealing. As a method for forming an ITO conductive film, for example, a method described in Japanese Patent Application Laid-Open No. 2-189816 is known. The above-mentioned publication discloses that a method including a depressurized inert gas or In an ambient gas of mixed gas, a target of indium-tin oxide sintered body is used, and a substrate maintained at 200 ° C is magnetized by a magnetron. Centimeters) 521280
經濟部智慧財產局員工消費合作社印製Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
官濺鍍法而形成第1層ITO膜的步驟;在減壓下將將該基板 加熱至300°C以上的步驟;於包含經減壓之非活性氣體與氧 氣之混合氣體的環境氣體中,使用前述靶子而在加熱至3〇〇 C以上之該基板的第丨層上,藉著磁控管濺鍍法而形成第2 層ITO膜的步驟;將該基板在經減壓的環境氣體中冷卻至 250它以下之後,將該環境氣體回復到大氣壓下的步驟。而 於基板上形成由二層所構成之ITQ導電膜的方法。 上述特開平6 — 28932號公報所記載的方法亦係將載體 的密度弄大,其結果係要達到降低IT〇導電膜之電阻率,即 ’要達到提昇導電率者。 然而,依據此方法固然可弄大載體的移動度,但是因 載體密度不會變大而使導電率之改善效果不充分。 又,由於上述方法係要將基板曝露在3〇(rc以上高溫的 情形下,以致於存在著可使用的基板受到限制的缺點。 而且,上述方法乃有必要在減壓下從2〇〇〇c以下加熱至 3〇〇°c以上的高溫,而從30(rc以上的溫度冷卻至25〇t以下 ,因此在此等加熱及冷卻上需要長的時間。上述方法包含 在經減壓的環境氣體中將基板冷卻至250。(:以下之後回復 到大氣壓下的步驟。此步驟乃在於若是將加熱至”❹艺以上 的基板就這樣子地回復到大氣壓下時,則經加熱至3001以 上的基板會與氧氣接觸而被氧化,其結果則有必要防止基 板的劣化。 爰此,特開平6— 28932號公報的方法由於有必要將基 板加熱至高溫並加以冷卻的繁雜操作,故非實用。 τ : --------tr---------線 (請先閱讀背面之注意事項再填寫本頁)A step of forming a first layer of ITO film by an official sputtering method; a step of heating the substrate to 300 ° C or more under reduced pressure; in an ambient gas containing a mixed gas of a reduced pressure inert gas and oxygen, A step of forming a second layer of ITO film on the first layer of the substrate heated above 300 ° C by a magnetron sputtering method using the aforementioned target; placing the substrate in a reduced-pressure ambient gas A step of returning the ambient gas to atmospheric pressure after cooling below 250 ° C. A method for forming an ITQ conductive film composed of two layers on a substrate. The method described in Japanese Patent Application Laid-Open No. 6-28932 also increases the density of the carrier. As a result, it is necessary to reduce the resistivity of the IT0 conductive film, that is, to increase the conductivity. However, although the mobility of the carrier can be increased according to this method, the effect of improving the conductivity is not sufficient because the density of the carrier does not increase. In addition, the above method involves exposing the substrate to a high temperature of 30 ° C or higher, so that there is a disadvantage that the usable substrate is limited. In addition, the above method is necessary to reduce the pressure from 20000 under reduced pressure. c is heated below 300 ° c to a high temperature above 300 ° c, and cooled from a temperature above 30 ° c to below 25 ° t, so it takes a long time to heat and cool down. The above method includes a reduced pressure environment The substrate is cooled to 250 in the gas. (The following steps are to return to atmospheric pressure. This step is to return the substrate heated to the above temperature to atmospheric pressure, and then heat it to 3001 or higher. The substrate is oxidized by contact with oxygen, and as a result, it is necessary to prevent the substrate from being deteriorated. Therefore, the method disclosed in Japanese Patent Application Laid-Open No. 6-28932 is not practical because of the complicated operation of heating and cooling the substrate to a high temperature. τ: -------- tr --------- line (please read the precautions on the back before filling this page)
本紙張尺度適用令國國家標iMCNS)A4規格(21〇 x撕 ) 521280 A7 五、發明說明(4 ) 【發明揭示】 本發明之其一目的係在於提供積層具有高導電率且透 明性優異之導電膜之基板的製造方法。 本發明之另一目的係在於提供具有高導電率且透明性 優異之據光片的製造方法。 本發明人等為了達到上述目的而一再地進行各種的研 究。其結果終能獲知於基板上形成ΙΤ〇膜之際,要在基板上 至少形成二層ΙΤΟ膜,而用以形成此各層ΙΤ0膜的電源乃要 分別使用特定的電源且藉著在特定的濺鍍氣體環境中進行 濺鍍,而能提高ΙΤΟ膜之載體濃度,因此可獲得積層具有高 導電率且透明性優異之導電膜之基板。 又’亦獲知於形成有遮光膜及彩色光阻劑膜之透明基 板上積層上述導電膜,藉此,可獲得積層具有高導電率且 透明性優異之導電膜之彩色濾光片。 而且更獲知即使將上述多數1丁〇膜的一部分置換成氧 化銦膜,亦可獲得所希望的導電膜積層基板及彩色濾光片 0 本發明乃依據此等獲知而完成者。 經濟部智慧財產局員工消費合作社印製 本發明提供一種透明導電膜積層基板之製造方法。此 方法具有(1)使用DC(直流)電源或DC+RF(高頻)電源,在非 活性氣體或非活性氣體與氧氣之混合氣體的環境氣體中, 濺鍍銦一錫氧化物燒結體之靶子而形成IT〇膜的步驟;及 (2)將從銦一錫氧化燒結體及銦氧化燒結體所構成之群所選 出之至少一種靶子,使用DC電源、RF電源或DC+ RF電源 本紙張尺度適用中國國豕標準(CNS)A4規格(210 X 297公爱) 五、發明說明(5 ) 而在非活性氣體環境氣體中施予濺鍍而在上述(1)所形成之 1丁〇膜上形成ITO膜及/或氧化銦膜的步驟。 本發明提供一種透明導電膜積層基板之製造方法。此 方法具有(1)使用DC電源或DC + RF電源將銦一錫氧化燒結 物之靶子在非活性氣體或非活性氣體及氧氣之混合氣^環 境氣體中施予濺鍍而於基板上形成第1層1丁〇膜的步驟;(2) 使用DC電源或DC + RF電源將上述靶子在非活性氣體及氧 氣之混合氣體環境氣體中施予濺鍍而於第丨層上形成第2層 ITO膜的步驟;及(3)使用£)(:電源或DC + RF電源將上述靶 子在非活性氣體或非活性氣體及氧氣之混合氣體環境氣體 中施予濺鍍而於第2層上形成第3層IT〇膜的步驟。 本發明乃提供一種依據上述各種方法而製造的透明導 電膜積層基板。 本發明提供一種濾光片之製造方法,係於透明基板上 順序地形成遮光膜、彩色光阻劑膜及至少二層導電膜的濾 光片之製造方法,其中導電膜形成步驟包含有(1)使用〇([:電 源或DC + RF電源,在非活性氣體或非活性氣體與氧氣之混 合氣體的環境氣體中,濺鍍銦一錫氧化物燒結體之靶子而 形成ITO膜的步驟;及(2)將從銦一錫氧化燒結體及銦氧化 燒結體所構成之群所選出之至少_餘子,使用DC電源、 RF電源或DC+RF電源而在非活性氣體環境氣體中施予滅 鍍而在上述(1)所至形成之IT〇膜上形成IT〇膜及/或氧化 銦膜的步驟。 本發明提供一種濾光片之製造方法,係於透明基板上 521280 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明說明( 順序地形成遮光膜、彩色光阻劑膜及至少三層導電膜的濾 光片之製造方法,其中導電膜形成步驟包含有(1)使用DC電 源或DC+ RF電源將銦一錫氧化燒結物之靶子在非活性氣 體或非活性氣體及氧氣之混合氣體環境氣體中施予濺鍍而 於基板上形成第1層ITO膜的步驟;(2)使用DC電源或DC + RF電源將上述靶子在非活性氣體及氧氣之混合氣體環境氣 體中施予濺鍍而於第1層上形成第2層ITO膜的步驟;及(3) 使用DC電源或DC+RF電源將上述靶子在非活性氣體或非 活性氣體及氧氣之混合氣體環境氣體中施予濺鍍而於第2 層上形成第3層ITO膜的步驟。 本發明乃提供一種依據上述各種方法而製造的濾光片 【發明之實施樣態】 透明導電膜積層基板之製造: 本發明之透明導電膜積層基板乃藉著在基板上形成至 少二層所構成之ITO膜或至少一層ITO膜及至少一層氧化 _膜的方法而製造。 形成在基板上的ITO膜可為2層、3層、4層、5層或是此 等以上。又,氧化銦膜可為1層、2層或是此等以上。 此等各ITO膜在習知的方法上,乃在基板上形成膜。而 本發明乃必須將二層或二層以上所構成之丨丁〇膜之至少其 中之一者,以(1)使用DC電源或DC + RF電源,在非活性氣 體或非活性氣體與氧氣之混合氣體的環境氣體中,濺鍍銦 一錫氧化物燒結體之靶子而形成IT0膜;而且在如此形成之 -------------. I---I--訂-------- (請先閱讀背面之注意事項再填寫本頁)This paper is suitable for the national standard iMCNS) A4 specification (21 × x tear) 521280 A7 V. Description of the invention (4) [Disclosure of the invention] One of the objectives of the present invention is to provide a laminate with high conductivity and excellent transparency. Manufacturing method of substrate of conductive film. Another object of the present invention is to provide a method for producing a light sheet having high electrical conductivity and excellent transparency. The present inventors have repeatedly conducted various studies in order to achieve the above-mentioned object. As a result, it can finally be known that when the ITO film is formed on the substrate, at least two ITO films must be formed on the substrate, and the power used to form each of the ITO films must use a specific power source and use a specific sputtering method. Sputtering in a plating gas environment can increase the carrier concentration of the ITO film, so a substrate with a conductive film laminated with high conductivity and excellent transparency can be obtained. It is also known that the above-mentioned conductive film is laminated on a transparent substrate on which a light-shielding film and a color photoresist film are formed, whereby a color filter can be obtained in which a conductive film having high conductivity and excellent transparency is laminated. Furthermore, it has been found that the desired conductive film laminated substrate and color filter can be obtained even if a part of the above-mentioned many 1-but films is replaced with an indium oxide film. The present invention has been completed based on these findings. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics The present invention provides a method for manufacturing a transparent conductive film laminated substrate. This method has (1) using a DC (direct current) power supply or a DC + RF (high frequency) power supply, and sputtering an indium-tin oxide sintered body in an inert gas or an ambient gas of a mixed gas of inactive gas and oxygen. A step of forming an IT0 film with a target; and (2) at least one target selected from the group consisting of an indium-tin oxide sintered body and an indium oxide sintered body, using a DC power source, an RF power source, or a DC + RF power source Applicable to China National Standard (CNS) A4 specification (210 X 297 public love) V. Description of the invention (5) Sputtering in an inert gas ambient gas on the 1-but film formed in (1) above A step of forming an ITO film and / or an indium oxide film. The invention provides a method for manufacturing a transparent conductive film laminated substrate. This method has the following features: (1) using a DC power source or a DC + RF power source to sputter the target of indium-tin oxide sintered in an inert gas or a mixed gas of inactive gas and oxygen ^ environment gas to form a first on a substrate; Step of 1 layer of 1 film; (2) Using a DC power supply or a DC + RF power supply to sputter the above target in a mixed gas of inert gas and oxygen to form a second layer of ITO on the first layer Film step; and (3) using £) (: power supply or DC + RF power supply to sputtering the above target in an inert gas or a mixed gas of inert gas and oxygen gas to form a first layer on the second layer 3 steps of IT0 film. The present invention provides a transparent conductive film laminated substrate manufactured according to the above-mentioned various methods. The present invention provides a method for manufacturing a filter, which sequentially forms a light-shielding film and colored light on a transparent substrate. A method for manufacturing a resist film and a filter with at least two conductive films, wherein the conductive film forming step includes (1) using 〇 ([: power supply or DC + RF power supply, inert gas or inert gas and oxygen Mixed gas A step of sputtering an indium-tin oxide sintered body in an ambient gas to form an ITO film; and (2) at least _ Yuzi selected from the group consisting of an indium-tin oxide sintered body and an indium oxide sintered body A step of forming an IT0 film and / or an indium oxide film on the IT0 film formed by the above (1) by using a DC power supply, an RF power supply, or a DC + RF power supply to extinguish plating in an inert gas ambient gas; The present invention provides a method for manufacturing an optical filter, which is printed on a transparent substrate 521280 Α7 Β7 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (sequentially forming a light-shielding film, a color photoresist film, and at least three layers A method for manufacturing a conductive film filter, wherein the conductive film forming step includes (1) using a DC power source or a DC + RF power source to indium-tin oxide sintered target in an inert gas or a mixed gas environment of inactive gas and oxygen A step of forming a first layer of ITO film on a substrate by sputtering in a gas; (2) using a DC power source or a DC + RF power source to perform sputtering on the target in a mixed gas environment gas of inert gas and oxygen, and On the 1st A step of forming a second layer of ITO film on the layer; and (3) using a DC power source or a DC + RF power source to perform sputtering on the target in an inert gas or a mixed gas of inert gas and oxygen, and apply The step of forming a third layer of ITO film on the layer. The present invention is to provide a filter manufactured according to the above-mentioned various methods [inventive mode of the invention] Manufacturing of transparent conductive film laminated substrate: The transparent conductive film laminated substrate of the present invention is Manufactured by a method of forming at least two ITO films or at least one ITO film and at least one oxide film on a substrate. The ITO film formed on the substrate may be two, three, four, or five layers. Or these and above. In addition, the indium oxide film may be one, two or more. Each of these ITO films is formed on a substrate by a conventional method. The present invention must use at least one of the two or more layers of the butadiene film formed by (1) using a DC power supply or a DC + RF power supply between an inactive gas or an inactive gas and oxygen. In an ambient gas of a mixed gas, an IT0 film is formed by sputtering a target of an indium-tin oxide sintered body; and in this way, I --- I--order -------- (Please read the notes on the back before filling this page)
521280 A7 _____B7__ 五、發明說明(7 ) (請先閱讀背面之注意事項再填寫本頁) 之ITO膜上,更(2)將從銦一錫氧化燒結體及銦氧化燒結體 之乾子’使用DC電源、RF電源或DC + RF電源而在非活性 氣體環境氣體中施予濺鍍而形成ITO膜及/或氧化銦膜。 經過上述(1)及(2)步驟而形成的導電膜之導電膜中的 導體密度會變高,且載體之移動度幾乎不降低,而在多少 的濺鍍條件下,導電膜中的載體密度會變高,且載體之移 動度亦會變大,故導電膜係具有高導電率者。 本發明之透明導電膜積層基板,更詳細而言例如可藉 著下述方法A〜方法C來製造。 方法A : 具有(1)使用DC電源或DC + RF電源,在非活性氣體或 非活性氣體與氧氣之混合氣體的環境氣體中,濺鍍銦一錫 氧化物燒結體之靶子而形成ITO膜的步驟;及(2)將從銦一 錫氧化燒結體及銦氧化燒結體所構成之群所選出之至少一 種靶子,使用DC電源、RF電源或DC+RF電源而在非活性 氣體環境氣體中施予濺鍍而在上述(1)所至形成之IT〇膜上 形成ΙΤΟ膜及/或氧化銦膜的步驟。 經濟部智慧財產局員工消費合作社印製 基板可使用公開眾所所知的基板,例如可舉例有玻璃 基板、玻璃壞氧樹脂基板、陶究基板、氧化紹基板、石夕基 板、氮化鋁基板、金屬基板、IMS基板、金屬芯基板、空心 基板、樹脂基板等。樹脂基板的樹脂材料例如可舉例有聚 碳酸酯、聚醚,風、聚酿亞胺、丙稀酸樹脂、環狀聚烤烴( 例如日本七才^ (株式會社)if才/ 了樹脂)、聚烯丙酸酯、 聚萘二曱酸乙二酯(PEN)、聚乙烯對苯二甲酸(pET)等。 -10- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 521280 經濟部智慧財產局員工消費合作社印製 A7 發明說明( 在此等基板之中以玻璃基板為佳。玻璃基板例如可廣 泛使用/慮光片用的玻璃基板,具體而言可例示如納舞破璃 基板。基板的大小、厚度可依據透明導電膜積層基板之使 用目的而適切地選擇。 A方法所使用之靶子為銦一錫氧化物燒結體。此燒結體 為眾所周知者,例如可使用將微粉末狀的氧化錫與微粉末 狀的氧化銦充分地混合而加壓成形預定的形狀,而例如以 1000〜約1500°C之高溫所燒成者。燒結體中的氧化錫含有 量並無限定,惟,一般約3〜約30重量%,最好是約5〜約 15重量%。 於A方法中,首先使用銦一錫氧化物燒結體作為靶子, 而於基板上進行濺鍍,使其在基板上形成第1層汀〇膜(以下 將此步驟稱為「第一步驟」)。 此第一步驟之濺鍍條件如以下所示。 電源設為DC電源或是DC + RF電源。電源最好是DC電 源。 施加電力的條件依據靶子的大小而不同,因此不能一 概而論,但是子若是設為5英叶X 15英忖大小的話,則 如以下所示。 施加電力為DC電源時,一般約0·1〜約1KW,最好約0.3 〜約0.6KW。DC + RF電源的話,DC電源的電力一般約0.1 〜約1KW ’最好約0.2〜約0.6KW,RF電源的電力一般約0.1 〜約3KW,最好約0.2〜約0.6KW。DC/RF電力比約在0.1 〜約10的範圍内適切地調整即可。使用RF電源的情形,頻 • 11 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) Μ--------^---------線 (請先閱讀背面之注意事項再填寫本頁) 521280 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(9 ) 率通常約6.78〜約27.12MHz,最好是約13·56ΜΗζ。 基板的溫度雖依據基板的種類而不同,然而在使用例 如玻璃基板的情形下,通常在室溫付近〜未滿300°C,最好 是約140〜約250°C。 濺鍍氣體以非活性氣體或非活性氣體及氧氣之混合氣 體、最好是非活性氣體及氧氣之混合氣體。非活性氣體可 廣泛使用公知的非活性氣體,其代表性的可舉出有氬氣等 氣體。 氣體壓力(濺鍍壓)通常約0.1〜約1P,最好是約0.2〜 0.8Pa。 在第一步驟使用非活性氣體及氧氣之混合氣體的情形 下’該混合氣體中的氧氣含有量約1容量%以下,最好是約 0.6容量%以下。 以第一步驟於基板上形成作為第1層之ITO膜的膜厚通 常約5〜約1 OOnm、較好約1 〇〜約70nm、最好是約15〜約50 nm ° 於方法A中,其次將銦一錫氧化物燒結體作為靶子使用 ,將此濺鍍於形成在基板上的第1層而於第1層上形成第2 層的ITO膜(以下將此步驟稱為「第二步驟」)。 此第二步驟之濺鍍條件如以下所述。 電源的種類設為DC電源、RF電源或DC + RF電源。電 源以RF電源為佳。 施加電力為DC電源時,一般約〇·ι〜約1KW,最好約〇·3 〜約0.6KW。RF電源的電力一般約〇·ι〜約3KW,最好約1 -12- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公髮) {請先閱讀背面之注意事項再填寫本頁) •-Ik 訂--------- 521280 A7 B7 10 五、發明說明( 〜約1.8KW。DC + RF電源的話,DC電源的電力一彀約〇1 〜約1KW,最好約0.2〜約〇6KW,RF電源的電力,一般約 0.1〜約3KW,最好約〇·2〜約〇 6KW。DC//RF電力比約在 〇·1〜約10的範圍内適切地調整即可。使用RF電源的情形, 頻率通常約6.78〜約27·12ΜΗζ,最好是約13.56MHz。 形成第1層之基板的溫度,通常在室溫付近〜未滿3〇〇 °C,最好是約140〜約250°C。 濺鍍氣體為非活性氣體。非活性氣體可廣泛使用公知 的非活性氣體,其代表性的可舉出有氬氣等氣體。 氣體壓力通常約0.1〜約1P,最好是約〇·2〜〇.8Pa。 以第二步驟於第1層上所形成作為第2層之IT〇膜的膜 厚通常約5〜約100nm、較好約1〇〜約70nm、最好是約3〇〜 約 70 nm 〇 於方法A中,以將基板的溫度維持在約14〇〜約25〇°c並 進行二次的濺鍵,而能在基板上形成由二層所構成的1丁〇 膜。此情形下’由於基板溫度十分低,故即使立刻將基板 之周圍的環境氣體回復到大氣壓亦不會有基板劣化之虞。 冷卻能在分鐘單位的短時間内完成。 於方法A包含以下的樣態。 (A— 1) 包含: (1)使用DC電源或DC+ RF電源,將銦一錫氧化物燒結 體之乾子在非活性氣體或非活性氣體及氧氣之混合氣體環 境氣體中進行濺鑛,而在基板上形成ITO膜,及, -13- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ^--------^---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 521280 A7 ____B7____ 五、發明說明(U ) (請先閱讀背面之注意事項再填寫本頁) (2)使用DC電源、RF電源或DC+ RF電源,將從銦一錫 氧化燒結體及銦氧化燒結體所構成之群所選出之至少一種 乾子’而在非活性氣體環境氣體中施予賤鍍而在上述(1)所 形成之ITO膜上形成ΓΓΟ膜及/或氧化銦膜的步驟的透明 導電膜積層基板之製造方法。 (A — 2),如(A— 1)所記載的透明導電膜積層基板之製 造方法,係將(1)步驟之電源設為DC電源而將(2)步驟之電 源設為RF電源。 (A — 3),如(A —2)所記載的透明導電膜積層基板之製 造方法’係將(1)步驟之濺鍍在非活性氣體及氧氣之混合氣 體環境氣體中進行,而將(2)步驟之濺鍍在非活性氣體環境 氣體中進行。 (A—4),如(A— 3)所記載的透明導電膜積層基板之製 造方法,係(1)步驟之非活性氣體及氧氣之混合氣體中的氧 氣含有量在1容量%以下。 (A—5),如(A — 4)所記載的透明導電膜積層基板之製 造方法,係(1)步驟之非活性氣體及氧氣之混合氣體中的氧 氣含有量在0.6容量%以下。 經濟部智慧財產局員工消費合作社印製 (A—6) ’如(A — 1)所記載的透明導電膜積層基板之製 造方法,係將(1)步驟之電源設為!)^電源,將(2)步驟之電 源設為DC電源。 (A—7) ’如(A — 6)所記載的透明導電膜積層基板之製 造方法’係將(1)步驟之濺鍍在非活性氣體及氧氣之混合氣 體環境氣體中進行’而將(2)步驟之濺鍍在非活性氣體環境 -14- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公H )521280 A7 _____B7__ 5. Description of the invention (7) (Please read the precautions on the back before filling out this page) on the ITO film, and (2) will be used from the indium-tin oxide sintered body and the dried indium oxide sintered body. A DC power source, an RF power source, or a DC + RF power source is formed by sputtering in an inert gas ambient gas to form an ITO film and / or an indium oxide film. The conductor density in the conductive film of the conductive film formed through the above steps (1) and (2) will become higher, and the mobility of the carrier will hardly decrease, and under some sputtering conditions, the carrier density in the conductive film It will become high, and the mobility of the carrier will also become large, so the conductive film has a high conductivity. The transparent conductive film laminated substrate of the present invention can be produced in more detail, for example, by the following methods A to C. Method A: (1) Use a DC power source or a DC + RF power source to form an ITO film by sputtering a target of an indium-tin oxide sintered body in an inert gas or a mixed gas of an inactive gas and oxygen. Step; and (2) applying at least one target selected from the group consisting of indium-tin oxide sintered body and indium oxide sintered body in a non-reactive gas ambient gas using a DC power source, an RF power source, or a DC + RF power source. A step of pre-sputtering to form an ITO film and / or an indium oxide film on the IT0 film formed in (1) above. The substrates printed by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs can use publicly known substrates. For example, glass substrates, glass bad oxygen resin substrates, ceramic substrates, oxide substrates, stone substrates, and aluminum nitride substrates can be used. , Metal substrate, IMS substrate, metal core substrate, hollow substrate, resin substrate, etc. Examples of the resin material of the resin substrate include polycarbonate, polyether, wind, polyimide, acrylic resin, and cyclic polybrominated hydrocarbons (for example, Nippon Chicai (Co., Ltd.)). Polyallylic acid ester, polyethylene naphthalate (PEN), polyethylene terephthalate (pET), etc. -10- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 521280 A7 printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (A glass substrate is preferred among these substrates. Glass The substrate can be widely used, for example, a glass substrate for a light-shielding sheet, and specifically, such as a glass substrate. The size and thickness of the substrate can be appropriately selected according to the purpose of use of the transparent conductive film laminated substrate. A method used The target is an indium-tin oxide sintered body. This sintered body is well known. For example, finely powdered tin oxide and finely powdered indium oxide can be sufficiently mixed to form a predetermined shape under pressure. Those fired at a high temperature of about 1500 ° C. The content of tin oxide in the sintered body is not limited, but is generally about 3 to about 30% by weight, and preferably about 5 to about 15% by weight. In method A First, a sintered body of indium-tin oxide is used as a target, and sputtering is performed on the substrate to form a first layer of a thin film on the substrate (hereinafter, this step is referred to as a "first step"). This first The sputtering conditions in the steps are shown below. The power source is set to DC power or DC + RF power. The power source is preferably DC power. The conditions for applying power vary depending on the size of the target, so it cannot be generalized, but if it is set to 5 The size of the Yingye X 15 inch is as follows. When the power is DC power, it is generally about 0.1 to 1KW, preferably about 0.3 to 0.6KW. For DC + RF power, the power of the DC power Generally about 0.1 to about 1 KW ', preferably about 0.2 to about 0.6 KW, and the power of the RF power supply is generally about 0.1 to about 3 KW, preferably about 0.2 to about 0.6 KW. The DC / RF power ratio is in the range of about 0.1 to about 10 It can be adjusted appropriately. In the case of using RF power, frequency • 11-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Μ -------- ^ ----- ---- Line (Please read the precautions on the back before filling this page) 521280 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (9) The rate is usually about 6.78 ~ 27.12MHz, preferably About 13.56MΗζ. Although the temperature of the substrate varies depending on the type of substrate, it is used for example glass-based In general, the temperature is usually close to 300 ° C at room temperature, preferably about 140 to 250 ° C. The sputtering gas is an inert gas or a mixed gas of inert gas and oxygen, preferably an inert gas and A mixed gas of oxygen. Known inert gas can be widely used as the inert gas. Typical examples include gases such as argon. Gas pressure (sputtering pressure) is usually about 0.1 to about 1P, and preferably about 0.2 to 0.8 Pa. When a mixed gas of inert gas and oxygen is used in the first step, the oxygen content of the mixed gas is about 1% by volume or less, and preferably about 0.6% by volume or less. In the first step, the film thickness of the ITO film as the first layer on the substrate is usually about 5 to about 100 nm, preferably about 10 to about 70 nm, and most preferably about 15 to about 50 nm. In method A, Next, an indium-tin oxide sintered body was used as a target, and this was sputtered on the first layer formed on the substrate and a second layer of ITO film was formed on the first layer (hereinafter, this step is referred to as the "second step" "). The sputtering conditions in this second step are as follows. The type of power supply is DC power, RF power, or DC + RF power. The power source is preferably an RF power source. When the applied power is a DC power source, it is generally about 0.00 to about 1 KW, and preferably about 0.3 to about 0.6 KW. The power of the RF power supply is generally about 0 ~~ 3KW, preferably about 1 -12- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 public) {Please read the precautions on the back before filling this Page) • -Ik Order --------- 521280 A7 B7 10 V. Description of the invention (~ about 1.8KW. If DC + RF power supply, the power of DC power supply is about 〇1 ~ about 1KW, the best About 0.2 ~ about 0.6KW, the power of RF power is generally about 0.1 ~ about 3KW, preferably about 0.2 ~ about 0.6KW. DC // RF power ratio is appropriately adjusted in the range of about 0.1 ~ about 10. That is, when using an RF power source, the frequency is usually about 6.78 to about 27 · 12 Μ 最好 ζ, preferably about 13.56 MHz. The temperature of the substrate forming the first layer is usually near room temperature to less than 300 ° C. It is preferably about 140 to about 250 ° C. The sputtering gas is an inert gas. Known inert gas can be widely used as the inert gas, and typical examples include gases such as argon. The gas pressure is usually about 0.1 to about 1P is preferably about 0.2 to 0.8 Pa. The thickness of the IT0 film as the second layer formed on the first layer in the second step is usually about 5 to about 100 nm, About 10 to 70 nm, preferably about 30 to 70 nm. In method A, the temperature of the substrate is maintained at about 14 to about 25 ° C. and the keying is performed twice, so that A 1-layer film composed of two layers is formed on the substrate. In this case, 'the substrate temperature is very low, so even if the ambient gas around the substrate is immediately returned to atmospheric pressure, there is no risk of the substrate being deteriorated. It can be completed in a short time in minutes. The following aspects are included in method A. (A— 1) Including: (1) Using a DC power source or a DC + RF power source, dry the indium-tin oxide sintered body in an inert gas. Or inert gas and mixed gas of oxygen and ambient gas to form ITO film on the substrate, and, -13- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ^- ------- ^ --------- line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 521280 A7 ____B7____ V. Invention Description (U ) (Please read the notes on the back before filling this page) (2) Use DC power, RF power DC + RF power supply, at least one dry element selected from the group consisting of indium-tin oxide sintered body and indium oxide sintered body, is subjected to base plating in an inert gas ambient gas and formed in the above (1) The manufacturing method of the transparent conductive film laminated substrate in the step of forming the ΓΓΟ film and / or the indium oxide film on the ITO film. (A-2), The manufacturing method of the transparent conductive film laminated substrate as described in (A-1), is The power of step (1) is set to DC power and the power of step (2) is set to RF power. (A-3), the manufacturing method of the transparent conductive film laminated substrate as described in (A-2), is performed by sputtering in step (1) in a mixed gas environment gas of inert gas and oxygen, and ( 2) The sputtering of the step is performed in an inert gas ambient gas. (A-4) The method for manufacturing a transparent conductive film laminated substrate as described in (A-3), wherein the oxygen content in the mixed gas of the inert gas and oxygen in step (1) is 1% by volume or less. (A-5) The method for manufacturing a transparent conductive film laminated substrate as described in (A-4), wherein the oxygen content in the mixed gas of the inert gas and oxygen in step (1) is 0.6% by volume or less. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (A-6) ′ The manufacturing method of the transparent conductive film laminated substrate as described in (A-1) is to set the power supply in step (1) to! ) ^ Power, set the power in step (2) to DC power. (A-7) 'The manufacturing method of the transparent conductive film laminated substrate as described in (A-6)' is performed by sputtering in step (1) in an inert gas and oxygen mixed gas ambient gas' and ( 2) Sputtering in a step in an inert gas environment -14- This paper size applies to China National Standard (CNS) A4 (210 X 297 male H)
521280 五、發明說明(12 ) 氣體中進行。 (Α—8) ’如(Α—7)所記載的透明導電膜積層基板之製 造方法,係(1)步驟之非活性氣體及氧氣之混合氣體中的氧 氣含有量在1容量%以下。 (Α — 9),如(Α — 7)所記載的透明導電膜積層基板之製 造方法,係(1)步驟之非活性氣體及氧氣之混合氣體中的氧 氣含有量在0·6容量%以下。 (Α — 1〇) ’如(a — 1)所記載的透明導電膜積層基板之製 造方法,係將(1)步驟之電源設為DC + RF電源,將(2)步驟 之電源設為RF電源。 (Α — Π),如(八一 10)所記載的透明導電膜積層基板之 製造方法,係將(1)步驟之濺鍍在非活性氣體環境氣體中進 仃 (Α — 12),如(Α— 10)所記載的透明導電膜積層基板之 製造方法,係將(1)步驟之濺鍍在非活性氣體及氧氣之混合 氣體環境氣體中進行。 (A — 13),如(A — 12)所記載的透明導電膜積層基板之 製造方法,係(1)步驟之非活性氣體及氧氣之混合氣體中的 氧氣含有量在0·6容量%以下。 (Α — 14),如(Α — 13)所記載的透明導電膜積層基板之 製造方法,係(1)步驟之非活性氣體及氧氣之混合氣體中的 氧氣含有量在0.4容量%以下。 (Α — 15),如(Α — 14)所記載的透明導電膜積層基板之 製造方法,係(1)步驟之非活性氣體及氧氣之混合氣體中的 -15- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -------— — — — —— ·1111111 ^ ·111111! (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 521280 A7 ----------B7____ 五、發明說明(13 ) 氧氣含有量在0.2容量%以下。 (A— 16),如(A— 1)所記載的透明導電膜積層基板之製 造方法,係將(1)步驟之電源設為DC電源,將(2)步驟之電 源設為DC+RF電源。 (A — 17),如(A — 16)所記載的透明導電膜積層基板之 製造方法,係將(1)步驟之濺鍍在非活性氣體及氧氣之混合 氣體環境氣體中進行。 (A— 18),如(A — 17)所記載的透明導電膜積層基板之 製造方法,係(1)步驟之非活性氣體及氧氣之混合氣體中的 氧氣含有量在1容量%以下。 (A — 19),如(A — 18)所記載的透明導電膜積層基板之 製造方法,係(1)步驟之非活性氣體及氧氣之混合氣體中的 氧氣含有量在0.6容量%以下。 方法B : 方法B具有: (1) 使用DC電源或DC + RF電源將銦一錫氧化燒結物之 靶子在非活性氣體或非活性氣體及氧氣之混合氣體環境氣 體中施予濺鍍而於基板上形成第丨,層IT〇膜的步驟; (2) 使用DC電源或DC+RF電源將上碟靶子在非活性 β 氣體及氧氣之混合氣體環境氣體中施予濺鍍而於第j層上 形成第2層ΙΤΟ膜的步驟;及 (3) 使用DC電源或DC + RF電源將上述靶子在非活性 氣體或非活性氣體及氧氣之混合氣體環境氣體中施予濺鍍 而於第2層上形成第3層ITO膜的步驟。 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) (請先閱讀背面之注意事項再填寫本頁) 0 ΊδΊ·1111111. 經濟部智慧財產局員工消費合作社印製 -16- 521280 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明(14 此方法所使用之基板及靶子乃與方法A相同。 於方法B中,首先,使用銦一錫氧化物燒結體作為靶子 ,而於基板上進行濺鍍,使其在基板上形成第1層1丁〇膜( 以下將此步驟稱為「第一步驟」)。 此第一步驟之滅鍍條件如以下所示。 電源设為DC電源或是DC + RF電源。電源最好是DC電 源。 施加電力的條件依據靶子的大小而不同,因此不能一 概而論,但是靶子若是設為5英吋x 15英吋大小的話,則 如以下所示。 施加電力為DC電源時,一般約〇·ι〜約1KW,最好約〇·3 〜約0.6KW。DC + RF電源的話,DC電源的電力一般約〇1 〜約1KW ,最好約〇·2〜約〇·6KW,RF電源的電力一般約〇· 1 〜約3KW,最好約〇·2〜約0.6KW。DC/RF電力比約在〇1 〜約10的範圍内適切地調整即可。使用RF電源的情形,頻 率通常約6.78〜約27·12ΜΗΖ,最好是約13.56MHz。 基板的溫度雖依據基板的種類而不同,然而在使用例 如玻璃基板的情形下,通常在室溫付近〜未滿3〇〇〇c ,最好 是約140〜約250°C。 賤鍍氣體以非活性氣體或非活性氣體及氧氣之混合氣 體。非活性氣體可廣泛使用公知的非活性氣體,其代表性 的可舉出有氬氣等氣體。 氣體壓力(濺鍍壓)通常約0.1〜約1P,最好是約0.2〜 0.8Pa 〇 -17- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ------II--— I- · I I I I I I I 訂·! 111!_ -^ (請先閱讀背面之注意事項再填寫本頁) 521280 A7 B7 五、發明說明(15 ) 在第一步驟使用非活性氣體及氧氣之混合氣體的情形 下,在DC電源的情形下,該混合氣體中的氧氣含有量約i 容量%以下,最好是約〇·6容量%以下,而在1)(: + 111?電源 的情形下,該混合氣體中的氧氣含有量約〇·6容量%以下, 較好是在約0.4容量%以下,最好是約〇·2容量%以下。 以第一步驟於基板上形成作為第1層之ΙΤ〇膜的膜厚通 常約5〜約l〇〇nm、較好約1〇〜約7〇nm、最好是約15〜約5〇 nm ° 於方法B中,其次將銦一錫氧化物燒結體作為靶子使用 ,將此濺鍍於形成在基板上的第丨層而於第丨層上形成第2 層的ITO膜(以下將此步驟稱為「第二步驟」)。 此第二步驟之濺鍍條件如以下所述。 電源的種類設為DC電源、RF電源或DC+RF電源。 施加電力為DC電源時,一般約〇·ΐ〜約1KW,最好約0.3 〜約0.6KW。RF電源的電力一般約〇·ι〜約3KW,最好約1 〜約1.8KW。DC + RF電源的話,DC電源的電力一般約0.1 〜約1KW,最好約0.2〜約0.6KW,RF電源的電力,一般約 〇·1〜約3KW,最好約〇·2〜約0.6KW。DC/RF電力比約在 〇·1〜約10的範圍内適切地調整即可。使用RF電源的情形, 頻率通常約6.78〜約27· 12MHz,最好是約13·56ΜΗζ。 形成第1層之基板的溫度,通常在室溫付近〜未滿300 °C,最好是約140〜約250°C。 濺鍍氣體為非活性氣體。非活性氣體可廣泛使用公知 的非活性氣體,其代表性的可舉出有氬氣等氣體。 -18- @張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) -0 tr---------線邊 經濟部智慧財產局員工消費合作社印製 521280 A7 _____ B7 五、發明說明(16 ) 氣體壓力通常約〇·1〜約1P,最好是約0.2〜〇.8Pa。 以第二步驟於第1層上所形成作為第2層之ITO膜的膜 厚通常約5〜約l〇〇nm、較好約10〜約70nm、最好是約30〜 約 70 nm 〇 於方法B中,其次將銦一錫氧化燒結物燒結體作為靶子 ’將此在非活性氣體或非活性氣體及氧氣之混合氣體環境 氣體中’而於形成在基板上的第2層進行濺鍍以在第2層上 形成第3層的ITO膜(以下稱此步驟為「第三步驟」)。 此第三步驟之濺鍍條件可與第一步驟之濺鍍條件相同 〇 此第三步驟之濺鍍條件如以下所示。 電源之種類設為DC電源或是DC+RF電源。 施加電力為DC電源時,一般約0.1〜約1KW,最好約0.3 〜約0.6KW。DC + RF電源的話,DC電源的電力一般約0.1 〜約1KW,最好約〇·2〜約〇.6KW,RF電源的電力一般約〇·1 〜約3KW,最好約〇·2〜約0.6KW。DC/RF電力比約在〇·1 〜約10的範圍内適切地調整即可。使用RF電源的情形,頻 率通常約6.78〜約27.12MHz,最好是約13.56MHz。 基板的溫度通常在室溫付近〜未滿300。(:,最好是約 140〜約 250°C。 濺鍍氣體以非活性氣體及氧氣之混合氣體。非活性氣 體可廣泛使用公知的非活性氣體,其代表性的可舉出有氬 氣等氣體。 氣體壓力(濺鍍壓)通常約〇·1〜約1P,最好是約〇.2〜 -19- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -------------裝--- (請先閱讀背面之注意事項再填寫本頁) · 線< 經濟部智慧財產局員工消費合作社印製 521280 A7521280 V. Description of the invention (12) Performed in gas. (A-8) The method for producing a transparent conductive film laminated substrate according to (A-7), wherein the oxygen gas content in the mixed gas of the inert gas and oxygen in step (1) is 1% by volume or less. (A-9) The method for manufacturing a transparent conductive film laminated substrate as described in (A-7), wherein the oxygen content in the mixed gas of the inert gas and oxygen in step (1) is equal to or less than 0.6% by volume . (Α — 1〇) 'The manufacturing method of the transparent conductive film laminated substrate as described in (a — 1), wherein the power supply in step (1) is set to DC + RF power, and the power supply in step (2) is set to RF power supply. (Α — Π), the manufacturing method of the transparent conductive film laminated substrate as described in (Aug. 10), the sputtering in step (1) is performed in an inert gas ambient gas, and (A-12), such as ( The manufacturing method of the transparent conductive film laminated substrate according to A-10) is performed by sputtering in the step (1) in an inert gas and oxygen mixed gas ambient gas. (A-13) The method for manufacturing a transparent conductive film laminated substrate as described in (A-12), wherein the oxygen content in the mixed gas of the inert gas and oxygen in step (1) is below 0.6% by volume . (A-14) The method for manufacturing a transparent conductive film laminated substrate as described in (A-13), wherein the oxygen content in the mixed gas of the inert gas and oxygen in step (1) is 0.4% by volume or less. (A-15), The manufacturing method of the transparent conductive film laminated substrate as described in (A-14), which is -15 in the mixed gas of inert gas and oxygen in step (1). This paper size applies to Chinese national standards (CNS) A4 specification (210 X 297 mm) --------- — — — — 1111111 ^ · 111111! (Please read the precautions on the back before filling out this page) Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by Consumer Cooperatives 521280 A7 ---------- B7____ 5. Description of the invention (13) The oxygen content is below 0.2% by volume. (A-16) The method for manufacturing a transparent conductive film laminated substrate as described in (A-1), where the power supply in step (1) is a DC power supply, and the power supply in step (2) is a DC + RF power supply . (A-17) The method for manufacturing a transparent conductive film laminated substrate as described in (A-16) is carried out by sputtering in step (1) in an inert gas and oxygen mixed gas ambient gas. (A-18) The method for manufacturing a transparent conductive film laminated substrate as described in (A-17), wherein the oxygen content in the mixed gas of the inert gas and oxygen in step (1) is 1% by volume or less. (A-19) The method for manufacturing a transparent conductive film laminated substrate as described in (A-18), wherein the oxygen content in the mixed gas of the inert gas and oxygen in step (1) is 0.6% by volume or less. Method B: Method B includes: (1) using a DC power source or a DC + RF power source to sputter the target of the indium-tin oxide sintered body in an inert gas or a mixed gas of an inactive gas and an oxygen gas to the substrate and sputter the substrate; Step of forming the first and the first layer of IT0 film; (2) Use a DC power supply or a DC + RF power supply to sputter the target on the dish in a mixed gas of inactive β gas and oxygen and place it on the j layer. A step of forming a second layer of ITO film; and (3) using a DC power source or a DC + RF power source to sputter the above target in an inert gas or a mixed gas environment gas of inert gas and oxygen on the second layer A step of forming a third layer of ITO film. This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 public love) (Please read the precautions on the back before filling out this page) 0 ΊδΊ · 1111111. Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-16- 521280 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (14 The substrate and target used in this method are the same as Method A. In Method B, first, an indium-tin oxide sintered body is used as the target And sputter plating on the substrate to form a first layer of 1 but film on the substrate (this step is hereinafter referred to as "the first step"). The conditions of the first step to remove the plating are shown below. Power supply Set to DC power supply or DC + RF power supply. The power supply is preferably a DC power supply. The conditions for applying power vary depending on the size of the target, so it cannot be generalized, but if the target is set to 5 inches x 15 inches, such as It is shown below. When the DC power is applied, it is usually about 0 ~ 1 ~ 1KW, preferably about 0.3 ~ 0.6KW. For DC + RF power, the power of DC power is generally about 0 ~ 1KW, most Good about 〇2 ~ 〇6KW, the power of RF power is generally about 0.1 ~ 3KW, preferably about 0.2 ~ 0.6KW. DC / RF power ratio can be adjusted appropriately within the range of about 0-1 ~ 10. Use In the case of an RF power supply, the frequency is usually about 6.78 to about 27 · 12 MHz, preferably about 13.56 MHz. Although the temperature of the substrate varies depending on the type of the substrate, when a glass substrate is used, for example, it is usually near room temperature. Over 300c, preferably about 140 ~ 250 ° C. The base plating gas is an inactive gas or a mixed gas of inactive gas and oxygen. The inert gas can be widely used as a known inert gas, and its representative Examples include gas such as argon. The gas pressure (sputtering pressure) is usually about 0.1 to about 1 P, preferably about 0.2 to 0.8 Pa. 〇-17- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------ II --- I- · IIIIIII Order! 111! _-^ (Please read the notes on the back before filling out this page) 521280 A7 B7 V. Description of the invention (15) In the case of using a mixed gas of inert gas and oxygen in the first step, in the case of a DC power supply The oxygen content of the mixed gas is about i% by volume or less, preferably about 0.6% by volume or less, and in the case of 1) (: + 111? Power, the oxygen content of the mixed gas is about 0.6% by volume or less, preferably about 0.4% by volume or less, and more preferably about 0.2% by volume or less. In the first step, the thickness of the ITO film as the first layer on the substrate is usually about 5 ~ About 100nm, preferably about 10 ~ about 70nm, most preferably about 15 ~ about 50nm In method B, the indium-tin oxide sintered body is used as a target, and this sputtering An ITO film formed on the first layer formed on the substrate and a second layer formed on the first layer (hereinafter, this step is referred to as a "second step"). The sputtering conditions in this second step are as follows. The type of power supply is DC power, RF power, or DC + RF power. When the applied power is a DC power supply, it is generally about 0 · ΐ to about 1 KW, and preferably about 0.3 to about 0.6 KW. The power of the RF power supply is generally about 0 to about 3 KW, and preferably about 1 to about 1.8 KW. In the case of DC + RF power, the power of the DC power is generally about 0.1 to about 1 KW, preferably about 0.2 to about 0.6 KW, and the power of the RF power is generally about 0.1 to about 3 KW, preferably about 0.2 to about 0.6 KW. . The DC / RF power ratio may be appropriately adjusted within a range of about 0.1 to about 10. When an RF power source is used, the frequency is usually about 6.78 to about 27 · 12 MHz, and preferably about 13.56 MHz. The temperature for forming the substrate of the first layer is usually from room temperature to less than 300 ° C, and preferably about 140 to 250 ° C. The sputtering gas is an inert gas. As the inert gas, a known inert gas can be widely used, and typical examples include a gas such as argon. -18- @ 张 码 量 Applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -0 tr --------- Economics Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau 521280 A7 _____ B7 V. Description of the invention (16) The gas pressure is usually about 0.1 to 1 P, and preferably about 0.2 to 0.8 Pa. The film thickness of the ITO film as the second layer formed on the first layer in the second step is usually about 5 to about 100 nm, preferably about 10 to about 70 nm, and most preferably about 30 to about 70 nm. In method B, secondly, the indium-tin oxide sintered body sintered body is used as a target 'this is in an inert gas or a mixed gas environment gas of inert gas and oxygen', and the second layer formed on the substrate is sputtered to A third layer of ITO film is formed on the second layer (hereinafter, this step is referred to as a "third step"). The sputtering conditions in this third step may be the same as those in the first step. The sputtering conditions in this third step are as follows. The type of power supply is DC power or DC + RF power. When the applied power is a DC power source, it is generally about 0.1 to about 1 KW, and preferably about 0.3 to about 0.6 KW. In the case of DC + RF power, the power of the DC power is generally about 0.1 to about 1 KW, preferably about 0.2 to about 0.6 KW, and the power of the RF power is generally about 0.1 to about 3 KW, preferably about 0.2 to about 2 0.6KW. The DC / RF power ratio may be appropriately adjusted within a range of about 0.1 to about 10. When an RF power source is used, the frequency is usually about 6.78 to about 27.12 MHz, and preferably about 13.56 MHz. The temperature of the substrate is usually near room temperature to less than 300. (:, Preferably about 140 to about 250 ° C. Sputtering gas is a mixed gas of inert gas and oxygen. Inert gas can be widely used as a known inert gas, and representative examples thereof include argon and the like. Gas. The gas pressure (sputtering pressure) is usually about 0.1 to 1P, preferably about 0.2 to -19. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)- ----------- Install --- (Please read the precautions on the back before filling out this page) · Thread & Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives 521280 A7
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521280 A7 18 五、發明說明( 本發明可將(1)步驟及(3)步驟的電源均設為DC+RF 電源而將(2)步驟之電源設為RF電源。此情形下,可在非活 性氣體或非活性氣體及氧氣的混合氣體之環境氣體下進行 (1)步驟及(3)步驟,而在非活性氣體之環境氣體下進行(2) 步驟。而且,(1)步驟及(3)步驟之非活性氣體及氧氣的混 合氣體中的氧含有量在約0.2容量%以下。 本發明可將(1)步驟及(3)步驟的電源均設為dc電源 而將(2)步驟之電源設為dc+ RF電源。此情形下,可在非活 性氣體及氧氣的混合氣體之環境氣體下進行(丨)步驟及(3) 步驟,而在非活性氣體之環境氣體下進行(2)步驟。而且, (1)步驟及(3)步驟之非活性氣體及氧氣的混合氣體中的氧 含有量在約0. 1〜約〇· 6容量%以下。 本發明可在第三步驟結束後,在與第二’步驟同樣的濺 鍍條件下進行濺鍍,而在第3層上形成由IT〇膜所構成的第4 層。此4層構造之ΙΤΟ膜所積層之透明導電膜積層基板特別 在高導電性及透明性方面為佳。 而且亦可4層構造之ιτο膜所積層之透明導電膜積層基 板的第4層上,在與第一步驟或第三步驟同樣的濺鍍條件下 進行濺鍍而形成由ΙΤΟ膜所構成的第5層。 本發明可交互地重複進行與第二步驟同樣的濺鍍條件 及第一步驟同樣的濺鍍條件,而於第5層上更形成丨或2以上 的ΙΤΟ膜。 於方法Β中,以將基板的溫度維持在約14〇〜約25〇t& 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公髮) -------II--I I ·1111111 ^ ·11111111 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -21- A7 A7521280 A7 18 V. Description of the invention (In the present invention, both the power supply in step (1) and step (3) can be set as DC + RF power supply and the power supply in step (2) can be set as RF power supply. In this case, Steps (1) and (3) are performed under an ambient gas of an active gas or a mixed gas of inactive gas and oxygen, and step (2) is performed under an ambient gas of an inert gas. Further, (1) step and (3 The content of oxygen in the mixed gas of inactive gas and oxygen in step) is about 0.2% by volume or less. In the present invention, both the power supply in step (1) and step (3) can be dc power supply, and the power supply in step (2) The power supply is set to dc + RF power supply. In this case, step (丨) and step (3) can be performed under the environment gas of a mixture of inert gas and oxygen, and step (2) can be performed under the environment gas of inert gas. In addition, the oxygen content in the mixed gas of the inert gas and oxygen in step (1) and step (3) is about 0.1 to about 0.6% by volume or less. In the present invention, after the third step, Sputtering was performed under the same sputtering conditions as in the second step, and in the third step A fourth layer consisting of an IT0 film is formed on the transparent conductive film laminated substrate laminated with the ITO film of this four-layer structure, which is particularly excellent in terms of high conductivity and transparency. Moreover, a ιτο film structure with a four-layer structure is also possible. On the fourth layer of the laminated transparent conductive film laminated substrate, sputtering is performed under the same sputtering conditions as in the first step or the third step to form a fifth layer composed of an ITO film. The present invention can be repeatedly performed interactively The same sputtering conditions as in the second step and the same sputtering conditions as in the first step, and an ITO film with a thickness of 2 or more was formed on the fifth layer. In the method B, the temperature of the substrate was maintained at about 14 °. ~~ 25〇t & This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 public) ------- II--II · 1111111 ^ · 11111111 (Please read the precautions on the back before (Fill in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-21- A7 A7
五、發明說明(19 ) (請先閱讀背面之注意事項再填寫本頁) 進行三次或是三次以上的濺鍍,而能在基板上形成由三層 或三層以上所構成的ITO膜。此情形下,由於基板溫度十分 低’故即使立刻將基板之周圍的環境氣體回復到大氣壓亦 不會有基板劣化之虞。冷卻能在分鐘單位的短時間内完成 〇 於方法B包含以下的樣態。 (B - 1) 包含: (1) 使用DC電源或DC + RF電源,將銦一錫氧化物燒結 體之靶子在非活性氣體或非活性氣體及氧氣之混合氣體環 境氣體中進行濺鍍,而在基板上形成第1層ITO膜; (2) 使用DC電源或DC + RF電源將上述靶子在非活性氣 體之環境氣體中施予濺鍍而於第1層上形成第2層ITO膜的 步驟;及 (3) 使用DC電源或DC + RF電源將上述靶子在非活性氣 體或非活性氣體及氧氣之混合氣體環境氣體中施予濺鍍而 於第2層上形成第3層ITO膜之步驟的透明導電膜積層基板 之製造方法。 經濟部智慧財產局員工消費合作社印製 (B—2),如(B — 1)所記載的透明導電膜積層基板之製造 方法,係將(1)步驟(2)步驟及(3)步驟之電源均設為DC電源 〇 (B — 3),如(B—2)所記載的透明導電膜積層基板之製造 方法’係將(1)步驟及(2)步驟在非活性氣體及氧氣之混合氣 體環境氣體中進行,而將(2)步驟在非活性氣體環境氣體中 22- 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 X 297公爱) 52128〇 Α7 _ Β7__ 五、發明說明(20 ) 進行。 (Β — 4),如(Β —3)所記載的透明導電膜積層基板之製造 方法’係(1)步驟及(3)步驟之非活性氣體及氧氣之混合氣體 中的氧氣含有量在1容量%以下。 (Β—5),如(Β - 1)所記載的透明導電膜積層基板之製造 方法,係將(1)步驟及(3)步驟之電源均設為DC電源,將(2) 步驟之電源設為RF電源。 (B — 6),如(B—5)所記載的透明導電膜積層基板之製造 方法,係將(1)步驟及(3)步驟之濺鍍在非活性氣體及氧氣之 混合氣體環境氣體中進行,而將(2)步驟之濺鍍在非活性氣 體環境氣體中進行。 (B—7),如(B —6)所記載的透明導電膜積層基板之製造 方法’係(1)步驟及(3)步驟之非活性氣體及氧氣之混合氣體 中的氧氣含有量在1容量%以下。 (B— 8),如(B — 5)所記載的透明導電膜積層基板之製造 方法’係(1)步驟、(2)步驟及(3)步驟係在非活性氣體的環境 氣體下進行。 (B —9),如(B — 1)所記載的透明導電膜積層基板之製造 方法’係將(1)步驟及(3)步驟之電源均設為DC+RF電源, 將(2)步驟之電源設為rf電源。 (B— 10),如(B—9)所記載的透明導電膜積層基板之製 造方法’係將(1)步驟及(3)步驟在非活性氣體及氧氣之混合 氣體環境氣體中進行,而將(2)步驟在非活性氣體環境氣體 中進行。 -23- I紙張尺度適用_7圈國家標準(CNS)A4規格(21〇 χ 297公釐)-;- -------------— (請先閱讀背面之注意事項再填寫本頁) 訂 線 經濟部智慧財產局員工消費合作社印製 521280 經濟部智慧財產局員工消費合作社印製 A7 — ____B7 _ 五、發明說明(21 ) (B — 11),如(B— 10)所記載的透明導電膜積層基板之製 造方法,係(1)步驟及(3)步驟之非活性氣體及氧氣之混合氣 體中的氧氣含有量在0.2容量%以下。 (B — 12),如(B — 1)所記載的透明導電膜積層基板之製 造方法,係將(1)步驟及(3)步驟之電源均設為Dc電源,將(2) 步驟之電源設為DC+RF電源。 (B— 13),如(B— 12)所記載的透明導電膜積層基板之製 造方法,係將(1)步驟及(3)步驟在非活性氣體及氧氣之混合 氣體環境氣體中進行,而將(2)步驟在非活性氣體環境氣體 中進行。 (B— 14),如(B — 13)所記載的透明導電膜積層基板之製 造方法,係(1)步驟及(3)步驟之非活性氣體及氧氣之混合氣 體中的氧氣含有量在1容量%以下。 方法C : 係具有: ⑴使用DC電源或DC + RF電源,將銦一錫氧化物燒結 體之靶子在非活性氣體或非活性氣體及氧氣之混合氣體環 境氣體中進行濺鍍,而在基板上形成第1層1丁〇膜的步驟; 及, (2)使用DC電源、RF電源或DC + RF電源,將銦一錫氧 化燒結體之靶子,在非活性氣體或非活性氣體及氧氣之混 合氣體環境氣體中施予濺鍍而在上述第1層1丁〇膜上形成第 2層1TO膜的步驟。 此方法之特徵在於(1)步驟所使用之靶子為銦一錫氧化 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) τ· —:---------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) •24- 521280 A7 五、發明說明(22 ) ' 燒結體,⑺步驟所使用之乾子為銦氧化燒結體。除了乾子 不同,其他條件與方法A相同。 本發明可將⑴步驟的電源均設為DC電源而將(2)步驟 之電源叹為RF電源。此情形下,可在非活性氣體及氧氣的 =乳體之環境氣體下進行⑴步驟,而在非活性氣體之環 ^氣體下進仃(2)步驟。而且,⑴步驟之非活性氣體及氧氣 的此〇氣體中的氧含有量在約丨容量%以下,最好是在〇.6 容量%以下。 以(1)步驟於基板上形成作為第丨層之IT〇膜的膜厚通 常約5〜約l00nm、較好約1〇〜約7〇nm、最好是約15〜約5〇 nm ° 以(2)步驟於第1層上形成作為第2層之氧化銦膜的膜厚 通常約5〜約l〇〇nm、較好約10〜約1〇〇nm、最好是約2〇〜 約 70 nm。 於方法c中,以將基板的溫度維持在約14〇〜約25〇t& 進行二次的濺鍍,而能在基板上形成ΠΌ膜及氧化銦膜。此 情形下,由於基板溫度十分低,故即使立刻將基板之周圍 的環境氣體回復到大氣壓亦不會有基板劣化之虞。冷卻能 在分鐘單位的短時間内完成。 C方法包含以下的樣態。 (C-1) 係具有: (1)使用DC電源或DC+RF電源,將銦一錫氧化物燒結 體之靶子在非活性氣體或非活性氣體及氧氣之混合氣體環 -25· 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) — — — — — — — — — · 11 (請先閱讀背面之注意事項再填寫本頁) i]· -線· 經濟部智慧財產局員工消費合作社印製 521280 A7 B7 五、發明說明(23 境氣體中進行藏鍍,而在基板上形成第1層][丁〇膜,及, (2)使用DC電源、RF電源或DC + RF電源,將銦氧化燒 結體之乾子’在非活性氣體或非活性氣體與氧氣之混合氣 體之環境氣體中施予濺鍍而在第丨層上形成第2層氧化銦膜 之步驟的透明導電膜積層基板之製造方法。 (C一2),如(C— 1)所記載的透明導電膜積層基板之製造 方法’係將(1)步驟之電源設為DC電源而將(2)步驟之電源 設為RF電源。 (C一 3) ’如(A—2)所記載的透明導電膜積層基板之製 造方法’係將(1)步驟及(2)步驟係在非活性氣體及氧氣之混 合氣體環境氣體中進行。 (C 一 4),如(C 一3)所記載的透明導電膜積層基板之製造 方法’係(1)步驟之非活性氣體及氧氣之混合氣體中的氧氣 含有量在1容量%以下,(2)步驟之非活性氣體及氧氣之混合 氣體中的氧氣含有量在0.6容量%以下。 (C 一 5),如(C—2)所記載的透明導電膜積層基板之製造 方法’係將(1)步驟之濺鍍在非活性氣體及氧氣之混合氣體 環境氣體中進行,而將(2)步驟之滅鑛在非活性氣體環境氣 體中進行。 (C 一 6),如(C 一 5)所記載的透明導電膜積層基板之製造 方法,係(1)步驟之非活性氣體及氧氣之混合氣體中的氧氣 含有量在1容量%以下。 上述之方法以外,本發明之透明導電膜積層基板能依 據下述方法D而製造。 -26- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) - 訂---------線赢 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 521280 Α7 _____ Β7 五、發明說明(24 ) 方法D : 係具有: (1) 使用DC電源或DC + RF電源,將銦一錫氧化物燒結 體之靶子在非活性氣體或非活性氣體及氧氣之混合氣體環 境氣體中進行濺鍍,而在基板上形成第1層汀〇膜; (2) 使用DC電源、RF電源或DC+ RF電源將上述靶子在 非活性氣體之環境氣體中施予濺鍍而於第丨層上形成第2層 ITO膜的步驟;及 (3) 使用DC電源或DC + RF電源將上述乾子在非活性氣 體或非活性氣體及氧氣之混合氣體環境氣體中施予濺鍍而 於第2層上形成第3層IT〇膜之步驟的透明導電膜積層基板 之製造方法0 此方法所使用之基板及靶子與方法Α相同。 除了在非活性氣體及氧氣之混合氣體環境氣體中施予 濺鍍岭步驟以外,其他條件與方法B相同。 在非活性氣體及氧氣之混合氣體環境氣體下進行(1)步 驟、(2)步驟及(3)步驟的情形下,⑺步驟之非活性氣體及氧 氣之混合氣體中的氧氣含有量可比⑴步驟中之混合氣體中 的氧氣含有量相同水準或比其低。具體而言,可將⑴步驟 及(3)步驟之非活性氣體及氧氣之混合氣體中的氧氣含有量 設在約1容量%以下,最好是約〇·2〜0.6容量%以下,將(2) 步驟之非活性氣體及氧氣之混合氣體中的氧氣含有量設在 約〇·3容量%以下,最好是約〇·2以下。 以(1)步驟於基板上形成作為第丨層之ιτ〇膜的膜厚通 11111111„ ^^ I I I I — — I— I I I — I I (請先閱讀背面之注意事項再填寫本頁) -27- A7V. Description of the invention (19) (Please read the precautions on the back before filling out this page) Three or more sputterings can be performed to form an ITO film composed of three or more layers on the substrate. In this case, since the temperature of the substrate is extremely low ', there is no risk of the substrate being deteriorated even if the ambient gas around the substrate is immediately returned to atmospheric pressure. The cooling can be completed in a short time in minutes. ○ Method B includes the following aspects. (B-1) Including: (1) Using a DC power supply or a DC + RF power supply, sputtering a target of an indium-tin oxide sintered body in an inert gas or a mixed gas of an inert gas and an oxygen gas, and Forming a first layer of ITO film on the substrate; (2) forming a second layer of ITO film on the first layer by sputtering the target in an inert gas atmosphere using a DC power supply or a DC + RF power supply; ; And (3) a step of forming a third layer of ITO film on the second layer by sputtering using the DC power supply or DC + RF power supply in the above target in an inert gas or a mixed gas of an inactive gas and an oxygen gas environment gas; Manufacturing method of transparent conductive film laminated substrate. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (B-2), as described in (B-1), the manufacturing method of the transparent conductive film laminated substrate is the combination of steps (1), (2), and (3). The power sources are all DC power sources (B-3). The manufacturing method of the transparent conductive film laminated substrate described in (B-2) is to mix steps (1) and (2) with inert gas and oxygen. It is carried out in a gas environment gas, and the step (2) is performed in an inert gas environment gas. 22- This paper size applies the Chinese National Standard (CNS) A4 specification (21〇X 297 public love) 52128〇Α7 _ Β7__ 5. Description of the invention (20) Proceed. (B-4). The method for manufacturing a transparent conductive film laminated substrate as described in (B-3) is that the oxygen content in the mixed gas of inert gas and oxygen in step (1) and step (3) is 1 Capacity% or less. (B-5) The method for manufacturing a transparent conductive film laminated substrate as described in (B-1), wherein the power supply in step (1) and step (3) is set to a DC power supply, and the power supply in step (2) is Set to RF power. (B-6) The method for manufacturing a transparent conductive film laminated substrate as described in (B-5), wherein the sputtering of steps (1) and (3) is performed in a mixed gas of inert gas and oxygen And the sputtering in step (2) is performed in an inert gas ambient gas. (B-7). The method for manufacturing a transparent conductive film laminated substrate as described in (B-6) is the oxygen content in the mixed gas of inert gas and oxygen in steps (1) and (3) is 1 Capacity% or less. (B-8) The method of manufacturing a transparent conductive film laminated substrate according to (B-5) is performed in steps (1), (2), and (3) under an inert gas atmosphere. (B-9), the manufacturing method of the transparent conductive film laminated substrate as described in (B-1) is to set the power supply of step (1) and step (3) to DC + RF power supply, and step (2) The power is set to rf power. (B-10), the method for manufacturing a transparent conductive film laminated substrate as described in (B-9), is performed in steps (1) and (3) in an inert gas and oxygen mixed gas environment gas, and Step (2) is performed in an inert gas ambient gas. -23- I paper size applies _7-round national standard (CNS) A4 specification (21〇χ 297 mm)-;--------------— (Please read the precautions on the back first Fill out this page again) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 521280 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy A7 — ____B7 _ V. Description of the invention (21) (B — 11), such as (B-10 The method for manufacturing a transparent conductive film laminated substrate according to (2) is that the oxygen content in the mixed gas of the inert gas and oxygen in steps (1) and (3) is 0.2% by volume or less. (B-12) The manufacturing method of the transparent conductive film laminated substrate as described in (B-1) is to set the power supply in step (1) and step (3) to Dc power supply, and set the power supply in step (2) Set to DC + RF power. (B-13) The method for manufacturing a transparent conductive film laminated substrate as described in (B-12), wherein the steps (1) and (3) are performed in an inert gas and oxygen mixed gas environment gas, and Step (2) is performed in an inert gas ambient gas. (B-14) The method for manufacturing a transparent conductive film laminated substrate as described in (B-13), wherein the oxygen content in the mixed gas of inert gas and oxygen in steps (1) and (3) is 1 Capacity% or less. Method C: The method includes: (1) using a DC power source or a DC + RF power source, sputtering a target of an indium-tin oxide sintered body in an inert gas or a mixed gas of an inert gas and an oxygen gas, and sputtering the target on the substrate; A step of forming a first layer of a 1-butadiene film; and (2) using a DC power source, an RF power source, or a DC + RF power source to mix the target of an indium-tin oxide sintered body with an inert gas or an inert gas and oxygen A step of forming a second layer of a 1TO film on the first layer of a 1-but film by sputtering in a gas atmosphere. The characteristic of this method is that the target used in step (1) is indium-tin oxide. The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) τ · —: --------- ------ Order --------- line (please read the precautions on the back before filling this page) • 24- 521280 A7 V. Description of the invention (22) 'Sintered body, used in ⑺ steps The dried seeds are indium oxide sintered bodies. The conditions are the same as Method A except that the dried seeds are different. According to the present invention, all the power sources in step (i) are set to DC power sources, and the power sources in step (2) are referred to as RF power sources. In this case, the step (2) can be performed under an inert gas and an ambient gas of oxygen = milk, and the step (2) is performed under a ring of inert gas. In addition, the oxygen content of the inert gas and oxygen gas in the step (i) is about ≤% by volume, and preferably about 0.6% by volume. The thickness of the IT0 film as the first layer formed on the substrate in step (1) is usually about 5 to about 100 nm, preferably about 10 to about 70 nm, and most preferably about 15 to about 50 nm. (2) The step of forming a film thickness of the indium oxide film as the second layer on the first layer is usually about 5 to about 100 nm, preferably about 10 to about 100 nm, and most preferably about 20 to about 100 nm. 70 nm. In the method c, the substrate is maintained at a temperature of about 140-1250 t & and a second sputtering is performed to form a ΠΌ film and an indium oxide film on the substrate. In this case, since the temperature of the substrate is extremely low, there is no risk of the substrate being deteriorated even if the ambient gas around the substrate is immediately returned to atmospheric pressure. Cooling can be completed in a short time in minutes. Method C includes the following aspects. (C-1) It has: (1) Using a DC power supply or a DC + RF power supply, the target of the indium-tin oxide sintered body is placed in an inert gas or a mixed gas of inert gas and oxygen. -25 · This paper size Applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) — — — — — — — — — — 11 (Please read the notes on the back before filling this page) i] · -Line · Ministry of Economic Affairs Intellectual Property Printed by the Bureau ’s Consumer Cooperatives 521280 A7 B7 V. Description of the Invention (23 Tibetan plating in an ambient gas, and the first layer is formed on the substrate] [Ding film, and, (2) DC power, RF power or DC + RF power supply, the step of forming a second layer of indium oxide film on the first layer by sputtering the indium oxide sintered body in an inert gas or an ambient gas of a mixed gas of inactive gas and oxygen to form a second layer of indium oxide film Manufacturing method of conductive film laminated substrate (C1-2), The manufacturing method of transparent conductive film laminated substrate as described in (C-1) is that the power source in step (1) is set to a DC power source and step (2) The power source is an RF power source. (C-3) The transparent conductive film as described in (A-2) The manufacturing method of the laminated substrate is that the steps (1) and (2) are performed in a mixed gas environment gas of inert gas and oxygen. (C1-4) The transparent conductive film as described in (C1-3) The manufacturing method of the laminated substrate is that (1) the oxygen content in the mixed gas of inert gas and oxygen in step 1 is 1% by volume or less, and the oxygen content in the mixed gas of inactive gas and oxygen in step (2) 0.6% by volume or less. (C-5) The manufacturing method of the transparent conductive film laminated substrate as described in (C-2) is the sputtering of the step (1) in a mixed gas of inert gas and oxygen. (C-6), the manufacturing method of the transparent conductive film laminated substrate as described in (C-5), is the step of (1) The content of oxygen in the mixed gas of inert gas and oxygen is less than 1% by volume. In addition to the above methods, the transparent conductive film laminated substrate of the present invention can be manufactured according to the following method D. -26- This paper size is applicable to China Standard (CNS) A4 Grid (210 X 297 mm) (Please read the precautions on the back before filling out this page)-Order --------- line wins the employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives printed the employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative 521280 Α7 _____ Β7 V. Description of the Invention (24) Method D: It has: (1) Using a DC power supply or a DC + RF power supply, the target of the indium-tin oxide sintered body is in an inactive gas or inactive The mixed gas of gas and oxygen is sputtered in the ambient gas to form the first layer of film on the substrate; (2) The DC target, RF power or DC + RF power is used to apply the above target in the inert gas environment gas. A step of pre-sputtering to form a second layer of ITO film on the first layer; and (3) using a DC power supply or a DC + RF power supply to dry the above-mentioned dry particles in an inert gas or a mixed gas of inert gas and oxygen Method for manufacturing a transparent conductive film laminated substrate in the step of forming a third layer IT0 film on the second layer by sputtering. The substrate and target used in this method are the same as method A. The conditions are the same as those of Method B, except that the sputtering ridge step is performed in an inert gas and oxygen mixed gas ambient gas. In the case of performing the steps (1), (2), and (3) under a mixed gas of inert gas and oxygen, the content of oxygen in the mixed gas of the inert gas and oxygen in the step is comparable to that in the step The oxygen content of the mixed gas in the same level or lower. Specifically, the oxygen content in the mixed gas of the inert gas and oxygen in step (3) and step (3) can be set to about 1% by volume or less, preferably about 0.2 to 0.6% by volume, and ( 2) The oxygen content in the mixed gas of the inert gas and oxygen in the step is set to about 0.3% by volume or less, preferably about 0.2 or less. In step (1), the thickness of the ιτ〇 film as the first layer is formed on the substrate. 11111111 „^^ I I I I — — I — I I I — I I (Please read the precautions on the back before filling this page) -27- A7
521280 五、發明說明(25 ) 常約5〜約i00nm、較好約1〇〜約7〇nm、最好是約ι5〜約5〇 nm 〇 以(2)步驟於第1層上形成作為第2層之IT〇膜的膜厚通 吊、、勺5〜約15〇nm、較好約1〇〜約i〇〇nm、最好是約2〇〜約 70 nm。 以(3)步驟於第2層上形成作為第3層之iTQ膜的膜厚通 常約5〜約i〇0nm、較好約1〇〜約7〇nm、最好是約15〜約5〇 nm 〇 本發明於(3)步驟結束後,亦可在與(2)步驟同樣的濺鍍 條件下進行濺鍍,而在第3層上形成由IT〇膜所構成之第4 層上,以與第(1)步驟或(3)步驟同樣的濺鍍條件下進行濺鍍 而形成由ΙΤΟ膜所構成的第5層。 本發明可交互地重複進行與(2)步驟同樣的濺鍍條件及 (1)步驟同樣的濺鍍條件,而於第5層上更形成1或2以上的 ΙΤΟ 膜。 於方法D中’以將基板的溫度維持在約14〇〜約25〇 t並 進行三次或是三次以上的濺鍍,而能在基板上形成由三層 或二層以上所構成的ITQ膜。此情形下,由於基板溫度十分 低’故即使立刻將基板之周圍的環境氣體回復到大氣壓亦 不會有基板劣化之虞。冷卻能在分鐘單位的短時間内完成 〇 於方法D包含以下的樣態。 (D - 1) 包含: -28- 本紐尺度顧中國國家標準(CNS)A4規格(210 X 297公釐)" " - (請先閱讀背面之注意事項再填寫本頁)521280 V. Description of the invention (25) Often about 5 to about 100 nm, preferably about 10 to about 70 nm, and most preferably about 5 to about 50 nm. (2) is formed on the first layer as the first The film thickness of the 2-layer IT0 film is 5 to about 150 nm, preferably about 10 to about 100 nm, and most preferably about 20 to about 70 nm. The thickness of the iTQ film as the third layer is formed on the second layer in the step (3), usually about 5 to about 100 nm, preferably about 10 to about 70 nm, and most preferably about 15 to about 50. nm 〇 In the present invention, after the step (3), the sputtering can be performed under the same sputtering conditions as in the step (2), and a fourth layer composed of an IT0 film is formed on the third layer to Sputtering was performed under the same sputtering conditions as in step (1) or (3) to form a fifth layer composed of an ITO film. According to the present invention, the same sputtering conditions as those in step (2) and the same sputtering conditions as in step (1) can be repeatedly performed, and an ITO film of 1 or more can be formed on the fifth layer. In method D ', an ITQ film composed of three or more layers can be formed on the substrate by maintaining the temperature of the substrate at about 140-1250 t and performing sputtering three or more times. In this case, since the temperature of the substrate is extremely low ', there is no risk of the substrate being deteriorated even if the ambient gas around the substrate is immediately returned to atmospheric pressure. The cooling can be completed in a short time in minutes. The method D includes the following aspects. (D-1) Contains: -28- The size of this button conforms to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) " "-(Please read the precautions on the back before filling this page)
P π---------線! 經濟部智慧財產局員工消費合作社印製 521280 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明(26 ,將銦一錫氧化物燒結 體之靶子在非活性氣體或非活性氣體及氧氣之混合氣體環 境氣體中進行濺鍍,而在基板上形成第1層1丁〇膜; (2) 使用DC電源、RF電源或DC+ RF電源將上述乾子在 非活性氣體及及氧氟之混合氣體之環境氣體中施予丨賤鍵而 於第1層上形成第2層ITO膜的步驟,·及 (3) 使用D C電源或D C + R F電源將上述靶子在非活性氣 體或非活性氣體及氧氣之混合氣體環境氣體中施予賤鍍而 於第2層上形成第3層ITO膜之步驟的透明導電膜積層基板 之製造方法。 (D — 2),如(D — 1)所記載的透明導電膜積層基板之製 造方法,係將(1)步驟(2)步驟及(3)步驟之電源均設為DC電 源。 (D — 3) ’如(D —2)所記載的透明導電膜積層基板之製 造方法’係將(1)步驟、(2)步驟及(3)步驟在非活性氣體及氧< 氣之混合氣體環境氣體中進行。 (D —4),如(D — 3)所記載的透明導電膜積層基板之製 造方法’係(1)步驟及(3)步驟之非活性氣體及氧氣之混合氣 _ 體中的氧氣含有量在1容量%以下,(2)步驟之非活性氣體及 氧氣之混合氣體中的氧氣含有量在〇.3容量%以下。 (D—5),如(D — 4)所記載的透明導電膜積層基板之製 造方法’係(1)步驟及(3)步驟之非活性氣體及氧氣之混合氣 體中的氧氣含有量在約〇·2〜約〇·6容量%以下,(2)步驟之 非活性氣體及氧氣之混合氣體中的氧氣含有量在〇·2容量 -29· 本紙張尺度適用中國國豕標準(CNS)A4規格(210 X 297公釐) I · I I--— II — II--- ·線 (請先閱讀背面之注意事項再填寫本頁) 521280 A7P π --------- line! Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 521280 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The mixed gas is sputtered in an ambient gas to form a first layer of a 1 butyl film on the substrate; (2) using a DC power source, an RF power source, or a DC + RF power source to mix the above-mentioned dried seeds in an inert gas and oxygen and fluorine; The step of applying a base bond in the ambient gas of the gas to form a second layer of ITO film on the first layer, and (3) using a DC power source or a DC + RF power source to place the above target in an inactive gas or inactive gas and A method for manufacturing a transparent conductive film laminated substrate in the step of forming a third layer of ITO film on the second layer by applying a base plating to a mixed gas of oxygen in an ambient gas. (D-2), as described in (D-1) The manufacturing method of the transparent conductive film laminated substrate is to set the power supply of the steps (1), (2) and (3) to DC power supply. (D — 3) The transparent conductive film as described in (D — 2) The manufacturing method of laminated substrates is (1) step Steps (2) and (3) are performed in a mixed gas environment gas of inert gas and oxygen < gas. (D-4) Manufacturing method of transparent conductive film laminated substrate as described in (D-3) 'It is the mixed gas of inactive gas and oxygen in steps (1) and (3) _ The content of oxygen in the body is less than 1% by volume, and the oxygen content of the mixed gas of inactive gas and oxygen in step (2) The amount is less than 0.3% by volume. (D-5), the manufacturing method of the transparent conductive film laminated substrate as described in (D-4) is the inert gas and oxygen in steps (1) and (3) The oxygen content in the mixed gas is about 0.2 to about 0.6% by volume, and the oxygen content in the mixed gas of the inert gas and oxygen in step (2) is 0.2 to -29. This paper size Applicable to China National Standard (CNS) A4 (210 X 297 mm) I · I I --- II — II --- · Cord (Please read the precautions on the back before filling this page) 521280 A7
五、發明說明(27 ) %以下。 (請先閱讀背面之注意事項再填寫本頁) (D—6),如(D〜1}所記載的透明導電膜積層基板之製 造方法,係將(1)步驟及(3)步驟之電源均設為Dc電源,將(2) 步驟之電源設為RF電源。 (D—7),如(D〜6)所記載的透明導電膜積層基板之製 造方法,係將(1)步驟及(3)步驟在非活性氣體環境氣體中進 行,而將(2)步驟在非活性氣體及氧氣之混合氣體環境氣體 中進行。 (D — 8),如(D—7)所記載的透明導電膜積層基板之製 造方法,係(2)步驟之非活性氣體及氧氣之混合氣體中的氧 氣含有量在1容量%以下。 (D —9),如(D—8)所記載的透明導電膜積層基板之製 造方法,係(2)步驟之非活性氣體及氧氣之混合氣體中的氧 氣含有量在0·3容量%以下。 上述方法Α〜D之中的濺鍍係公知的濺鍍,包含例如磁 控管濺鍍、反應性濺鍍、ECR濺鍍等。 濾光片的製造: 經濟部智慧財產局員工消費合作社印製 本發明之彩色濾光片係於透明基板上形成遮光膜、彩 色光阻劑膜及ITO導電膜而構成者。亦可於彩色光阻劑膜與 ITO導電膜之間保護層。 透明基板並無限定,能廣泛使用此一領域一般使用的 透明基板。透明基板之具體例乃可舉出例如鹼性玻璃、無 鹼性玻璃等玻璃板、聚碳酸酯、聚甲基丙烯酸酯等樹脂板 。此等材料之中以無鹼性樹脂為佳。透明基板之大小、厚 -30· ^張尺度適^中國國家標準(CNS)A4規格(210 X 297公釐) 經濟部智慧財產局員工消費合作社印製 521280 A7 ----—---E__— _ 五、發明說明(28 ) 度等可依彩色濾光片的使用目的而適宜地選擇。 形成遮光膜的材料可廣泛使用此領域常用之遮光膜形 《材料。遮光膜形成材料例如可舉出金屬、金屬之氧化物 、分散顏料的樹脂等。至於金屬具體而言可舉出鉻、鉬、 鈦、鋁等。金屬之氧化物具體而言可舉出氧化鉻、氧化鋁 等。分散顏料之樹脂具體而言可舉出碳分散樹脂、黑色顏 /料分散樹脂等。此等樹脂之中從遮紐、成膜性等的觀點 • 纟看以金屬鉻、氧化鉻、碳分散樹脂、黑色顏料分散樹脂 荨為佳。 形成彩色光阻劑膜的材料可廣泛使用此領域常用之彩 色光阻劑膜形成材料。彩色光阻劑膜形成材料例如可舉出 例如丙烯酸樹脂、聚酯樹脂、聚乙烯醇樹脂、聚醯亞胺樹 月曰或疋於此等樹脂之混合物分散紅色系、綠色系或藍色系 著色劑者。 構成保護層的樹脂可廣泛使用此領域常用之樹脂,而 可舉出例如環氧樹脂、丙烯酸樹脂、聚磑亞胺樹脂等。 對於在透明基板上形成遮光膜、彩色光阻劑膜及保護 膜的情形乃可廣泛使用公知的遮光膜形成方法、彩色光阻 劑膜形成方法及保護膜形成方法。 本發明之彩色濾光片可於遮光膜及彩色光阻劑膜、並 因應必要而更在形成保護膜的透明基板上,至少形成由二 層所構成之ITO導電膜。 本發明之彩色濾光片係以公知的方法於透明基板上形 成遮光膜及彩色光阻劑膜,並因應必要而更形成保護膜之 -31- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -------------裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 521280 A7 ----------B7____ 五、發明說明(29 ) ^ " 後’以上述方法Α〜方法Ε之其中任何導電膜形成方法而形 成導電膜來製造。 一省依據本發明之透明導電膜積層基板之製造方法,能提 同導電膜中的載體(自由電子)密度,且能幾乎不降低载體移 動度或可維持載體移動度或是可提高載體移動度,因此能 獲得具有高導電率之透明導電膜積層基板。 由於形成在基板上之導電膜具有高導電率,故不必要 將膜厚弄得厚而能確保優異的透明性。 因此,依據本發明乃能製造具有高導電率,即電阻率 小的透明導電膜積層基板。依據本發明可製造透明性優異 的透明導電膜積層基板。 於本發明的方法中,乃不必要將基板況度維持在3〇〇 c以上的溫度,而依情形即使在14〇〜25{rc之比較低的溫 度亦能在基板上形成良好的導電膜。因此,所使用之基板 的種類不受限制。本發明之方法不必要在真空下從3〇〇。匸以 上的南溫冷卻至250°C以下,故具實用性。 本發明之方法能僅變更濺鍍時之電源種類及濺鍍氣體 而能將所希望的ITO膜成膜在基板上,故具產業上利用性。 本發明的方法不必要進行回火處理等特別的處理,故 極具實用性。 依據本發明乃能製造具有高導電率,即能製造具有電 阻率低之ITO導電膜的彩色濾光片。 依據本發明乃能製造透明性優良的彩色渡光片。 【發明之最佳實施樣態】 •32- "^氏張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) --— τ : 41^--------tr---------線 (請先閱讀背面之注意事項再填寫本頁) 521280 A7 B7 五、發明說明(3Q ) 以下舉出實施例及比較例而更進一步說明本發明。 透明導電膜積層基板之製造例如以下所示。 (請先閱讀背面之注咅?事項再填寫本頁) 以1下的實施例及比較例中的操作概略如以下所述。 將玻璃基板(200mm χ 260mm、厚度〇·7mm)設置於預熱 區,在真空下預熱60分鐘至一定的溫度。 一旦基板被預熱至一定溫度時,將氬氣與氧氣以一定 的比例導入氣體,在調整全壓(濺鍍壓)呈〇.7Pa之後,使用 一定的電源施加於靶子而開始放電。 確認乾上的輝光放電(glow discharge)呈穩定之後,以 移動速度1.0m/分的速度使基板在放電中移動,而在基板 上形成一定厚度的第1層透明導電膜。往返於乾子上直到形 成一定膜厚為止。 其次將氬氣與氧氣以一定的比例導入氣體,在調整全 壓為一定壓力之後,使用一定的電源施加於靶子而開始放 電。 確認靶上的輝光放電呈穩定之後,以移動速度l 〇m/ 分的速度使經預熱的基板在放電中移動,而在基板上形成 經濟部智慧財產局員工消費合作社印製 一定厚度的第2層透明導電膜。往返於靶子上直到形成一定 膜厚為止。 而且,於第2層透明導電膜上形成第3層透明導電膜及 第5層透明導電臈的情形,係反覆進行與形成第1層透明導 電膜之操作相同的操作。於第3層透明導電膜上形成第4層 透明導電膜的情形,係反覆進行與形成第2層透明導電膜之 操作相同的操作。 •33- 本紙張尺錢中國國家標準(CNS)A4規格⑽χ挪公爱) 經濟部智慧財產局員工消費合作社印製 521280 A7 _B7_ 五、發明說明(31 ) 又,將成膜後的玻璃基板移動至真空室,經冷卻三分 鐘之後將基板從真空室置換成氮氣中,並取出已形成透明 導電膜的玻璃基板。 在氬氣與氧氣之混合氣體(氧氣含有量0.542容量%、 濺鍍壓0.7Pa)的環境氣體下,使用DC電源(電力0.5KW)將 銦一錫氧化物燒結體(氧化錫含有量10重量%,以下相同) 靶子予以濺鍍而在維持200°C之玻璃基板上形成由ITO膜所 構成的第1層(膜厚438.8人)。 其次在氬氣(濺鍍壓0. 7Pa)的環境氣體下,使用RF電源 (電力1.5KW、頻率13·56ΜΗζ)將銦一錫氧化物燒結體靶子 予以濺鍍而在第1層上形成由ITO膜所構成的第2層(膜厚 438.8人),以獲得本發明之透明導電膜積層基板。 比較例1 : 在氬氣(濺鍍壓0.7Pa)的環境氣體下,使用RF電源(電 子1.5KW、頻率13.56MHz)將銦一錫氧化物燒結體靶子予以 濺鍍而在維持200°C之玻璃基板上形成由ITO膜所構成的第 1層(膜厚553.9人)。 接著在氬氣與氧氣之混合氣體(氧氣含有量0. 542容量 %、濺鍍壓0. 7Pa)的環境氣體下,使用DC電源(電力0.5KW) 將銦一錫氧化物燒結體靶子予以濺鍍而在第1層上形成由 ITO膜所構成的第2層(膜厚553.9入),以獲得導電膜積層基 板。 對於從實施例1所獲得之本發明透明導電膜積層基板 及從比較例1所獲得之導電膜積層基板求出薄片電阻。 -34- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) --------訂---------線秦 521280 A7 B7 五、發明說明(32 ) 薄片電阻以其次的方式求出。即,於2〇〇mm x 260mm 、厚度0.7mm的玻璃基板上所形成的膜面均等地設置67點 的測定點,使用三菱化學製之四探針電阻計(MCP一 丁600) 而求出電阻值,並求出此等的平均值,而且乘上常數= 4.5424以求出薄片電阻。 膜厚藉由以下所述方式求出。即,使用小坂研究所製 之二維微細形狀測定器(ΕΤ4000)來測定已成膜在玻璃基板 上的導電膜的膜厚。測定係於玻璃基板上設定5點測定點, 以力:/卜 >膠帶來遮罩而於成膜後剝離遮罩並測定膜厚而 將該平均值作為膜的膜厚。 電阻率(Ω · cm)可藉著以上述四探針法所求出之薄片 電阻值乘上膜厚而求得。 又,對於從實施例1所獲得之本發明透明導電膜積層基 板及從比較例1所獲得之導電膜積層基板求出透過率(%)。 即,使用曰立製作所製分光光度計(u—2010)而測定在波長 200〜900nm的範圍内導電膜積層基板的透過率(%),成膜 前的玻璃基板(blank)的透過率(%)設為而算出62〇nm 、540nm及460nm的透過率(%)。 其結果如第1表所示。 第1表 (下頁續) -35- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) — — — — — — — — — —— — I· · I I (請先閱讀背面之注意事項再填寫本頁) 訂· --線- 經濟部智慧財產局員工消費合作社印製 521280 A7 B7 五、發明說明(33 ) 透明導電膜 之 全膜(A) 薄片電 阻 (Ω / □) 電阻率 透過率(%) (Ω cm) 620nm 540η m 460nm 實施例1 877.5 17.80 1·54x 10一4 90. 13 89. 0 5 91.82 實施例2 1107.8 27,01 2·99x 10-4 90. 17 92.6 2 93.97 (請先閱讀背面之注意事項再填寫本頁) 實施例2 : 在氬氣與氧氣之混合軋體(氧氣含有量GW容量%、濺 鍵壓0· 7Pa)的環境氣體下,使用Dc電源(電力〇· 將銦一 錫氧化物燒結體乾子予以錢錢而在維持2〇(rc之玻璃基板 上形成由ιτο膜所構成的第1層(膜厚433A)。 其次在氬氣(錢鑛壓0.7Pa)的環境氣體下,使用π電源 (電力0.5KW)將銦一錫氧化物燒結體靶子予以濺鍍而在第1層 上形成由ΙΤ0膜所構成的第2層(膜厚433A)。 其次在氬氣與氧氣之混合氣體(氧氣含有量〇.54容量 %、濺鍍壓0· 7Pa)的環境氣體下,使用DC電源(電力〇. 5KW)將 銦一錫氧化物燒結體靶子予以濺鍍而在第2層上形成由IT〇膜 所構成的第3層(膜厚433Α),以獲得本發明之透明導電膜積層 基板。 經濟部智慧財產局員工消費合作社印製 比較例2 ·· 在氬氣(濺鍍壓0.7Pa)的環境氣體下,使用Dc電源(電力〇 5KW)將銦一錫氧化物燒結體靶子予以濺鍍而在維持2⑼。〔之 玻璃基板上形成由ΙΤ0膜所構成的單層(祺厚1686·6Α),以獲 得導電膜積層基板。 36.5. Description of invention: (27)% or less. (Please read the precautions on the back before filling in this page) (D-6), The manufacturing method of the transparent conductive film laminated substrate as described in (D ~ 1) is the power supply of step (1) and step (3) Both are set to Dc power supply, and the power supply in step (2) is set to RF power supply. (D-7), the manufacturing method of the transparent conductive film laminated substrate as described in (D ~ 6), is the step (1) and ( 3) The step is performed in an inert gas ambient gas, and the step (2) is performed in a mixed gas ambient gas of inert gas and oxygen. (D-8) The transparent conductive film as described in (D-7) The manufacturing method of the laminated substrate is that the oxygen content in the mixed gas of the inert gas and oxygen in the step (2) is 1% by volume or less. (D-9) The transparent conductive film laminate as described in (D-8) The manufacturing method of the substrate is that the oxygen content in the mixed gas of the inert gas and oxygen in the step (2) is 0.3% by volume or less. The sputtering method in the above methods A to D is a well-known sputtering method and includes, for example, sputtering Magnetron sputtering, reactive sputtering, ECR sputtering, etc. Manufacturing of filters: Ministry of Economic Affairs The employee's cooperative of the Bureau printed the color filter of the present invention by forming a light-shielding film, a color photoresist film, and an ITO conductive film on a transparent substrate. It can also be protected between the color photoresist film and the ITO conductive film. The transparent substrate is not limited, and a transparent substrate generally used in this field can be widely used. Specific examples of the transparent substrate include glass plates such as alkaline glass and alkali-free glass, polycarbonate, and polymethacrylic acid. Resin plates such as esters. Among these materials, alkali-free resin is preferred. The size and thickness of the transparent substrate is -30. ^ The size is suitable. ^ China National Standard (CNS) A4 specification (210 X 297 mm). Printed by the Consumer Cooperative of the Property Bureau 521280 A7 ----——--- E __— _ V. Description of invention (28) The degree can be appropriately selected according to the purpose of use of the color filter. The material forming the light-shielding film can be widely A light-shielding film material commonly used in this field is used. Examples of the material for forming the light-shielding film include metals, metal oxides, and resins that disperse pigments. As the metal, specifically, chromium, molybdenum, titanium, aluminum, and the like are used. Metal Of Specific examples of the oxide include chromium oxide, aluminum oxide, and the like. Specific examples of resins for dispersing pigments include carbon-dispersed resins, black pigment / dispersion resins, and the like. Among these resins are barriers, film-forming properties, etc. Viewpoints • It is better to use metallic chromium, chromium oxide, carbon dispersing resin, and black pigment dispersing resin. The materials used to form color photoresist films can be widely used as color photoresist film forming materials commonly used in this field. Color photoresist Examples of the agent film-forming material include acrylic resin, polyester resin, polyvinyl alcohol resin, polyimide resin, or a mixture of these resins to disperse red, green, or blue colorants. As the resin constituting the protective layer, resins commonly used in this field can be widely used, and examples thereof include epoxy resin, acrylic resin, and polyimide resin. When a light-shielding film, a color photoresist film, and a protective film are formed on a transparent substrate, known light-shielding film formation methods, color photoresist film formation methods, and protective film formation methods can be widely used. The color filter of the present invention can form at least two layers of an ITO conductive film on a light-shielding film and a color photoresist film, and on a transparent substrate forming a protective film as necessary. The color filter of the present invention forms a light-shielding film and a color photoresist film on a transparent substrate by a well-known method, and further forms a protective film as necessary. -31- This paper standard applies to China National Standard (CNS) A4 (210 X 297 mm) ------------- install -------- order --------- line (please read the precautions on the back before filling (This page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 521280 A7 ---------- B7____ V. Description of the invention (29) ^ " After 'in any of the above methods A ~ Method E conductive film The formation method produces a conductive film. The manufacturing method of the transparent conductive film laminated substrate according to the present invention can improve the carrier (free electron) density in the conductive film, and can hardly reduce the carrier mobility or maintain the carrier mobility or improve the carrier mobility. Therefore, a transparent conductive film laminated substrate having high conductivity can be obtained. Since the conductive film formed on the substrate has high conductivity, it is not necessary to make the film thick to ensure excellent transparency. Therefore, according to the present invention, a transparent conductive film laminated substrate having high electrical conductivity, that is, small electrical resistivity can be manufactured. According to the present invention, a transparent conductive film laminated substrate having excellent transparency can be manufactured. In the method of the present invention, it is not necessary to maintain the substrate condition at a temperature of more than 300c, and depending on the situation, a good conductive film can be formed on the substrate even at a relatively low temperature of 14 ~ 25 {rc. . Therefore, the types of substrates used are not limited. The method of the invention need not necessarily be from 300 under vacuum. The temperature above 匸 is lower than 250 ° C, so it is practical. The method of the present invention can change a type of a power source and a sputtering gas during sputtering to form a desired ITO film on a substrate, and therefore has industrial applicability. The method of the present invention is extremely practical because it does not require special treatment such as tempering treatment. According to the present invention, a color filter having a high conductivity, that is, an ITO conductive film having a low resistivity can be manufactured. According to the present invention, it is possible to produce a color doped sheet having excellent transparency. [Best implementation of the invention] 32- " ^ 's scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) --- τ: 41 ^ -------- tr --------- Line (Please read the notes on the back before filling out this page) 521280 A7 B7 V. Description of the Invention (3Q) The following examples and comparative examples are given to further explain the present invention. An example of manufacturing a transparent conductive film laminated substrate is shown below. (Please read the note on the back? Matters before filling out this page.) The operations in the examples and comparative examples below are outlined as follows. A glass substrate (200 mm x 260 mm, thickness 0.7 mm) was set in a preheating zone, and preheated under vacuum to a certain temperature for 60 minutes. Once the substrate is preheated to a certain temperature, argon and oxygen are introduced into the gas at a certain ratio. After adjusting the full pressure (sputtering pressure) to 0.7 Pa, a certain power source is applied to the target to start discharging. After confirming that the glow discharge on the stem is stable, the substrate is moved during discharge at a moving speed of 1.0 m / min, and a first layer of transparent conductive film having a certain thickness is formed on the substrate. Back and forth on the dried seeds until a certain film thickness is formed. Next, argon and oxygen are introduced into the gas at a certain ratio, and after adjusting the total pressure to a certain pressure, a certain power source is applied to the target to start discharging. After confirming that the glow discharge on the target is stable, the preheated substrate is moved during the discharge at a moving speed of 10 m / min, and a substrate with a certain thickness printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is formed on the substrate 2 layers of transparent conductive film. Go back and forth on the target until a certain film thickness is formed. When the third transparent conductive film and the fifth transparent conductive film are formed on the second transparent conductive film, the same operations as those for forming the first transparent conductive film are repeated. In the case where the fourth transparent conductive film is formed on the third transparent conductive film, the same operations as those for forming the second transparent conductive film are repeated. • 33- This paper is printed in Chinese National Standard (CNS) A4 specification (⑽χ 挪 公公 爱) Printed by the Intellectual Property Bureau of the Ministry of Economy, Employee Consumer Cooperatives 521280 A7 _B7_ V. Description of the invention (31) In addition, the glass substrate after film formation is moved Go to the vacuum chamber, and after cooling for three minutes, replace the substrate from the vacuum chamber with nitrogen, and take out the glass substrate on which the transparent conductive film has been formed. A sintered body of indium-tin oxide (tin oxide content 10 wt. %, The same applies hereinafter) The target is sputtered to form a first layer (film thickness: 438.8 persons) made of an ITO film on a glass substrate maintained at 200 ° C. Next, an indium-tin oxide sintered target was sputtered under an argon gas (sputtering pressure 0.7 Pa) using an RF power source (electric power 1.5KW, frequency 13.56MΗζ) to form a layer on the first layer. The second layer (film thickness: 438.8 persons) made of ITO film to obtain the transparent conductive film laminated substrate of the present invention. Comparative Example 1: An indium-tin oxide sintered body target was sputtered using an RF power source (electron 1.5KW, frequency 13.56MHz) under an atmosphere of argon (sputter pressure 0.7Pa) and maintained at 200 ° C. A first layer made of an ITO film (film thickness: 553.9 persons) was formed on a glass substrate. Next, an indium-tin oxide sintered target was sputtered using a DC power supply (electricity 0.5KW) under an ambient gas of a mixed gas of argon and oxygen (oxygen content of 0.542% by volume and sputtering pressure of 0.7Pa). A second layer (film thickness: 553.9 mm) made of ITO film was formed on the first layer by plating to obtain a conductive film laminated substrate. The sheet resistance of the transparent conductive film laminated substrate of the present invention obtained in Example 1 and the conductive film laminated substrate obtained in Comparative Example 1 was determined. -34- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -------- Order ------ --- Line Qin 521280 A7 B7 V. Description of the invention (32) The sheet resistance is obtained in the following way. That is, 67 measurement points were uniformly set on the film surface formed on a glass substrate having a thickness of 200 mm x 260 mm and a thickness of 0.7 mm, and a four-probe resistance meter (MCP I-Ding 600) manufactured by Mitsubishi Chemical was used to obtain the measurement points. Resistance value, and find these average values, and multiply by constant = 4.5424 to find sheet resistance. The film thickness was determined as described below. That is, the two-dimensional fine shape measuring device (ET4000) manufactured by Kosaka Research Institute was used to measure the film thickness of the conductive film formed on the glass substrate. The measurement was performed by setting 5 measurement points on a glass substrate, and masking with a force: / bubble. After the film was formed, the mask was peeled off and the film thickness was measured. The average value was used as the film thickness of the film. The resistivity (Ω · cm) can be obtained by multiplying the sheet resistance value obtained by the above-mentioned four-probe method by the film thickness. The transmittance (%) of the transparent conductive film laminated substrate of the present invention obtained in Example 1 and the conductive film laminated substrate obtained in Comparative Example 1 was determined. That is, the transmittance (%) of the conductive film laminate substrate and the transmittance (%) of the glass substrate (blank) before film formation were measured using a spectrophotometer (u-2010) manufactured by Yueli Manufacturing Co., Ltd. ) Is set to calculate the transmittances (%) at 62 nm, 540 nm, and 460 nm. The results are shown in Table 1. Table 1 (continued on next page) -35- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) — — — — — — — — — — — — (I read first Note on the back, please fill out this page again) Order · --- Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives 521280 A7 B7 V. Description of the invention (33) Full film of transparent conductive film (A) Sheet resistance (Ω / □ ) Resistivity and transmittance (%) (Ω cm) 620nm 540η m 460nm Example 1 877.5 17.80 1.54x 10-4 90. 13 89. 0 5 91.82 Example 2 1107.8 27, 01 2.99x 10-4 90. 17 92.6 2 93.97 (Please read the precautions on the back before filling out this page) Example 2: Under the ambient gas of mixed rolling body of argon and oxygen (oxygen content GW capacity%, splash pressure 0 · 7Pa), Using a Dc power source (electricity: 0, the indium-tin oxide sintered body was dried and the first layer (film thickness 433A) made of a ιτο film was formed on a glass substrate maintained at 20 (rc). Next, argon was used. Gas (money pressure 0.7Pa), using a π power source (electricity 0.5KW) to indium-tin oxide sintered body target A second layer (film thickness 433A) made of ITO film was formed on the first layer by sputtering. Next, a mixed gas of argon and oxygen (oxygen content 0.54% by volume, sputtering pressure 0 · 7Pa), using a DC power supply (power 0.5KW) to sputter the indium-tin oxide sintered body target to form a third layer (film thickness 433A) made of IT0 film on the second layer. In order to obtain the transparent conductive film laminated substrate of the present invention. Comparative Example 2 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs.... Under an argon gas (sputter pressure 0.7Pa), a DC power supply (electricity 0KW) is used. A target of indium-tin oxide sintered body was sputtered and maintained at 2⑼. [The glass substrate was formed with a single layer composed of ITO film (Ki thickness 1686 · 6A) to obtain a conductive film laminated substrate. 36.
木紙張尺度適用中國國家標進Muorvr八,iT < U 1 r c / VJ r 1 ) \Wood paper scale is applicable to Chinese national standard Muorvr VIII, iT < U 1 r c / VJ r 1) \
~透明導電f 之 全膜(人) 片電f (Ω / □) [阻值~ 透過率 (%) (Ω · cm) 620nm 540η m 460η m 實施例1 1299. 1 13. 37 1. 74 X ΐ〇· 4 95. 16 97. 9 1 91. 2 1 實施例2 1686.6 15. 30 2. 58 X ΙΟ- 4 90. 16 90. 9 6 83. 8 5 實施例3 1504.3 15. 64^ 2. 35Χ ΙΟ- 4 96. 55 98. 0 1 88. 2 0 實施例3 : 521280 五、發明說明( 比較例3 : 、在鼠讀氧氣之混合氣體(氧氣含有量0· 54容量%、賤鍍 塵〇· 7Pa)的料亂體下,使·電源(電力⑴哪)將銦—錫氧 化物燒厂體乾子予以賤鍍而在維持2⑽。c之玻璃基板上形成 :斤構成的單層(膜厚丨5〇4·3入),以獲得導電膜積層基 板。 對於實施例2所獲得之本發明透明導電膜積層基板及從 比較例2及3所獲彳于之導電膜積層基板,與上述同樣地求出薄 片電阻值(Ω · □)、電阻率⑴· cm),以及6族爪、谓細及楊 nm的透過率(%)。 第2表 在鼠氣與氧氣之混合氣體(氧氣含有量Ο 542容量%、 賤錢壓0· 7Pa)的環境氣體下,使用dc電源(電力〇. 5KW)將銦 一錫氧化物燒結體乾子予以減錢而在維持2〇之玻璃基 板上形成由ITO膜所構成的第1層(祺厚446 5人)。 其次在氬氣G賤鍍壓0.7Pa)的環境氣體下,使用RF電源 -37- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公β " :- ------------ -裝-------—訂 1!111線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 521280 A7 _B7_ 五、發明說明(35 ) (電力1. 5KW、頻率13. 56MHz)將銦一錫氧化物燒結體靶子予 以濺鍍而在第1層上形成由ΙΤ0膜所構成的第2層(膜厚446. 5 (請先閱讀背面之注意事項再填寫本頁) A)。 其次在氬氣與氧氣之混合氣體(氧氣含有量0.542容量 %、濺鍍壓0.7Pa)的環境氣體下,使用DC電源(電力0.5KW)將 銦一錫氧化物燒結體靶子予以濺鍍而在第2層上形成由ΙΤ0膜 所構成的第3層(膜厚446. 5人),以獲得本發明之透明導電膜積 層基板。 實施例4 ·· 在氬氣與氧氣之混合氣體(氧氣含有量0.542容量%、 濺鍍壓0.7Pa)的環境氣體下,使用DC電源(電力0.5KW)將銦 一錫氧化物燒結體靶子予以濺鍍而在維持200°C之玻璃基 板上形成由ΙΤ0膜所構成的第1層(膜厚177. 8A)。 其次在氬氣(濺鍍壓0.7Pa)的環境氣體下,使用RF電源 (電力1. 5KW、頻率13. 56MHz)將銦一錫氧化物燒結體靶子予 以濺鍍而在第1層上形成由ITO膜所構成的第2層(膜厚177. 8 A) 〇 經濟部智慧財產局員工消費合作社印製 其次在氬氣與氧氣之混合氣體(氧氣含有量0. 542容量 %、濺鍍壓0.7Pa)的環境氣體下,使用DC電源(電力0.5KW)將 銦一錫氧化物燒結體靶子予以濺鍍而在第2層上形成由ITO膜 所構成的第3層(177· 8A)。 其次在氬氣(濺鍍壓0.7Pa)的環境氣體下,使用RF電源 (電力1. 5KW、頻率13. 56MHz)將銦一錫氧化物燒結體靶子予 以濺鍍而在第3層上形成由ITO膜所構成的第3層(膜厚177. 8 -38- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)~ Full film of transparent conductive f (person) Sheet electricity f (Ω / □) [Resistance value ~ Transmittance (%) (Ω · cm) 620nm 540η m 460η m Example 1 1299. 1 13. 37 1. 74 X ΐ0.495. 16 97. 9 1 91. 2 1 Example 2 1686.6 15. 30 2. 58 X 10- 4 90. 16 90. 9 6 83. 8 5 Example 3 1504.3 15. 64 ^ 2. 35Χ ΙΟ- 4 96. 55 98. 0 1 88. 2 0 Example 3: 521280 5. Description of the invention (Comparative Example 3: A mixed gas of oxygen read in a rat (oxygen content of 0.54% by volume, base plating dust) (7 · Pa), the power source (whatever the power is) will be indium-tin oxide sintering plant body dry plating to maintain 2 ⑽. C on the glass substrate is formed: a single layer composed of jin ( Film thickness 504 × 3) to obtain a conductive film laminated substrate. For the transparent conductive film laminated substrate of the present invention obtained in Example 2 and the conductive film laminated substrate obtained from Comparative Examples 2 and 3, and The sheet resistance value (Ω · □), resistivity (⑴ · cm), and the transmittance (%) of the Group 6 claw, so-called thin, and young nm were obtained in the same manner as described above. Table 2 The indium-tin oxide sintered body was dried using an dc power source (electricity 0.5 KW) under an ambient gas of a mixed gas of rat gas and oxygen (oxygen content of 0 542% by volume and a low pressure of 0 · 7Pa). The child reduced the amount of money and formed the first layer made of ITO film on the glass substrate maintained at 20 (with a thickness of 446 5 people). Secondly, under the environment gas of argon G (plating pressure 0.7Pa), use RF power supply -37- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 male β ":------- ------ -Install ----------- Order 1! 111 line (please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 521280 A7 _B7_ V. Invention Explanation (35) (electricity 1.5 KW, frequency 13. 56 MHz) The indium-tin oxide sintered target is sputtered to form a second layer (film thickness 446.5) composed of ITO film on the first layer. Please read the precautions on the back before filling in this page) A). Next, use a DC power supply (electricity 0.5KW) under an ambient gas of a mixed gas of argon and oxygen (oxygen content 0.542% by volume, sputtering pressure 0.7Pa). ) Sputtering an indium-tin oxide sintered body target to form a third layer (film thickness: 446.5 people) composed of an ITO film on the second layer to obtain the transparent conductive film laminated substrate of the present invention. Example 4 · DC power supply is used in an ambient gas of a mixed gas of argon and oxygen (oxygen content 0.542% by volume, sputtering pressure 0.7Pa) Power: 0.5KW) The indium-tin oxide sintered target was sputtered to form a first layer (film thickness 177.8 A) made of ITO film on a glass substrate maintained at 200 ° C. Next, argon (sputter Under an ambient gas of 0.7 Pa), an indium-tin oxide sintered target was sputtered using an RF power source (electric power 1.5 KW, frequency 13. 56 MHz) to form a first layer made of an ITO film on the first layer. 2 layers (film thickness 177.8 A) 〇 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, followed by an argon and oxygen mixed gas (oxygen content 0.542% by volume, sputtering pressure 0.7Pa) under ambient gas Using a DC power supply (power 0.5KW), an indium-tin oxide sintered target was sputtered to form a third layer (177 · 8A) made of an ITO film on the second layer. Next, argon (sputtering Under an ambient gas pressure of 0.7 Pa), an indium-tin oxide sintered body target was sputtered using an RF power source (electric power 1.5 KW, frequency 13. 56 MHz) to form a third layer made of an ITO film on the third layer. Layer (film thickness 177.8 -38-) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)
I 經濟部智慧財產局員工消費合作社印製 521280 A7 B7 五、發明說明(36 ) A)。 接著在氬氣與氧氣之混合氣體(氧氣含有量0.542容量 %、濺鍍壓0.7Pa)的環境氣體下,使用DC電源(電力0.5KW)將 銦一錫氧化物燒結體靶子予以濺鍍而在第4層上形成由ITO膜 所構成的第5層(膜厚177. 8人),以獲得本發明之透明導電膜積 層基板。 實施例5 : 在氬氣與氧氣之混合氣體(氧氣含有量0.542容量%、 濺鍍壓0. 7Pa)的環境氣體下,使用DC電源(電力0. 5KW)將銦 一錫氧化物燒結體靶子予以濺鍍而在維持200°C之玻璃基 板上形成由ITO膜所構成的第1層(膜厚182. 1A)。 其次在氬氣(濺鍍壓0.7Pa)的環境氣體下,使用RF電源 (電力1. 5KW、頻率13. 56MHz)將銦一錫氧化物燒結體靶子予 以濺鍍而在第1層上形成由ITO膜所構成的第2層(膜厚455. 3 人)。 接著在氬氣與氧氣之混合氣體(氧氣含有量0.542容量 %、濺鍍壓0. 7Pa)的環境氣體下,使用DC電源(電力0. 5KW)將 銦一錫氧化物燒結體靶子予以濺鍍而在第2層上形成由ITO膜 所構成的第3層(膜厚182. 1A),以獲得本發明之透明導電膜積 層基板。 實施例6 : 在氬氣與氧氣之混合氣體(氧氣含有量0.542容量%、 濺鍍壓0. 7Pa)的環境氣體下,使用DC電源(電力0. 5KW)將銦 一錫氧化物燒結體靶子予以濺鍍而在維持299°C之玻璃基 -39- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ^-------I ^---------^ (請先閱讀背面之注意事項再填寫本頁) 521280 A7 B7 五、發明說明(37 ) 板上形成由Π0膜所構成的第1層(膜厚208人)。 (請先閱讀背面之注意事項再填寫本頁) 其次在氬氣(濺鍍壓0.7Pa)的環境氣體下,使用RF電源 (電力1. 5KW、頻率13· 56MHz)將銦一錫氧化物燒結體靶子予 以濺鍍而在第1層上形成由ΙΤ0膜所構成的第2層(膜厚519. 9 A) 〇 其次在氬氣與氧氣之混合氣體(氧氣含有量〇· 542容量 %、濺鍍壓0.7Pa)的環境氣體下,使用DC電源(電力0.5KW)將 銦一錫氧化物燒結體靶子予以濺鍍而在第2層上形成由ΙΤ0膜 所構成的第3層(208A),以獲得本發明之透明導電膜積層基板。 對於實施例3〜6所獲得之本發明透明導電膜積層基板, 與上述同樣地求出薄片電阻值(Ω · □)、電阻率(Ω · cm),以及 620nm、540nm及460nm的透過率(%)。 其結果如第3表所示。 第3表 透明導電膜 之 薄片電阻 電阻率 透過率(%) 全膜厚(A) (Ω / (Q · cm) 620nm 540η m 460nm 實施例3 1339.5 12. 36 1. 65X 10' 4 94. 93 98. 2 9 93. 67 實施例4 888. 8 16. 70 1· 48X 10一 4 89. 96 89. 9 9 94. 06 實施例5 819. 5 18. 43 1. 51 X 10〕 4 89. 45 88. 2 9 90. 65 實施例6 935.8 15. 52 1.45X10- 4 92. 38 90. 4 5 91. 58 經濟部智慧財產局員工消費合作社印製 實施例7 : -40- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) 521280 A7 B7 五、發明說明(38 ) 除了將在第1層上形成第2層之濺鍍,在氬氣與氧氣之 混合氣體(氧氣含有量0.542容量%、濺鍍壓〇.7Pa)的環境氣 體下進行之外,與實施例3同樣地獲得本發明之透明導電膜積 層基板。此基板上所形成之第1層、第2層及第3層均為488· 1人。 實施例8 : 除了將在第1層上形成第2層之濺鍍,在氬氣與氧氣之 混合氣體(氧氣含有量0.542容量%、錢鍍壓〇.7Pa)的環境氣 體下進行之外,與實施例3同樣地獲得本發明之透明導電膜積 層基板。此基板上所形成之第1層、第2層及第3層均為432· 1人。 對於實施例7及8所獲得之本發明透明導電膜積層基板, 與上述同樣地求出薄片電阻值(Ω · □)、電阻率(Ω · cm),以及 620nm、540nm及460nm的透過率(%)。 其結果如第4表所示。 第4表 透明導電膜 之 薄片電阻 電阻率 透過率(%) 全膜厚(A) (Ω / □) (Ω · cm) 620nm 540η m 460η m 實施例7 1464.2 12.36 1. 81 X i〇- 4 95. 47 98. 6 9 92. 5 8 實施例8 1296.2 13. 92 1· 80 X 10 - 4 93. 10 97. 7 9 97. 2 0 經濟部智慧財產局員工消費合作社印製 ----------------- (請先閱讀背面之注意事項再填寫本頁) --線· 實施例9: 在氬氣與氧氣之混合氣體(濺鍍壓〇· 7Pa)的環境氣體 下,使用DC + RF電源(DC :電力0.4KW、RF :電力〇.4KW、 頻率13·56ΜΗζ)將銦一錫氧化物燒結體靶子予以濺鍍而在 -41- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 521280 A7 B7_______ 五、發明說明(39 ) 維持200°C之玻璃基板上形成由ΙΤ0膜所構成的第1層(膜厚 451. 9Α)。 其次在氬氣(濺鍍壓0.7Pa)的環境氣體下’使用RF電源 (電力1· 5KW、頻率13. 56MHz)將銦一錫氧化物燒結體靶子予 以濺鍍而在第1層上形成由ΙΤ0膜所構成的第2層(膜厚451· 9 A) 〇 接著在氬氣(濺鍍壓0.7Pa)的環境氣體下’使用dc + RF 電源(DC :電力〇. 4KW、RF _·電力0.4KW、頻率13.56MHz)將銦一 錫氧化物燒結體靶子予以濺鍍而在第2層上形成由1T0膜所構 成的第3層(膜厚451. 9人),以獲得本發明之透明導電膜積層基 板。 實施例10 : 除了將在玻璃基板上形成第1層之濺鍍及在第2層上形 成第3層之濺鍍,在氬氣與氧氣之混合氣體(氧氣含有量〇·18 容量%、濺鍍壓〇.7Pa)的環境氣體下進行之外,與實施例9同 樣地獲得本發明之透明導電膜積層基板。此基板上所形成之 第1層、第2層及第3層之膜厚均為470.6A。 其結果如第5表所示。 (請先閱讀背面之注意事項再填寫本頁)I Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 521280 A7 B7 V. Description of Invention (36) A). Next, in a gas mixture of argon and oxygen (oxygen content 0.542% by volume, sputtering pressure 0.7Pa), a DC power supply (electricity 0.5KW) was used to sputter the indium-tin oxide sintered target and A fifth layer made of an ITO film (with a film thickness of 177.8 persons) was formed on the fourth layer to obtain the transparent conductive film laminated substrate of the present invention. Example 5: A target gas of indium-tin oxide sintered body was produced using a DC power supply (electricity 0.5KW) under an ambient gas of a mixed gas of argon and oxygen (oxygen content 0.542% by volume, sputtering pressure 0.7Pa). 1A。 Sputtered to form a first layer (film thickness 182.1 1A) composed of an ITO film on a glass substrate maintained at 200 ° C. Next, an indium-tin oxide sintered body target was sputtered under an argon gas (sputtering pressure 0.7Pa) using an RF power source (electric power 1.5KW, frequency 13.56MHz) to form a layer on the first layer. The second layer of ITO film (455.3 film thickness). Next, an indium-tin oxide sintered target was sputtered using a DC power source (electricity 0.5KW) under an ambient gas of a mixed gas of argon and oxygen (oxygen content 0.542% by volume, sputtering pressure 0.7Pa). A third layer (film thickness 182.1A) made of an ITO film is formed on the second layer to obtain the transparent conductive film laminated substrate of the present invention. Example 6: In an ambient gas of a mixed gas of argon and oxygen (oxygen content 0.542% by volume, sputtering pressure 0.7Pa), a DC power source (electricity 0.5KW) was used to target an indium-tin oxide sintered body Glass substrate that is sputtered and maintained at 299 ° C-39- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ^ ------- I ^ ------ --- ^ (Please read the precautions on the back before filling out this page) 521280 A7 B7 V. Description of the invention (37) The first layer of Π0 film (film thickness 208 people) is formed on the board. (Please read the precautions on the back before filling in this page.) Next, sinter indium-tin oxide under an argon gas (sputter pressure: 0.7Pa) using an RF power source (power: 1.5KW, frequency: 13.56MHz). The target is sputtered to form a second layer (film thickness: 519. 9 A) composed of ITO film on the first layer. Secondly, a mixed gas of argon and oxygen (oxygen content: 0.542% by volume, sputtering Under the ambient gas of 0.7Pa), a DC power supply (0.5KW power) was used to sputter the indium-tin oxide sintered target to form a third layer (208A) composed of ITO film on the second layer. To obtain the transparent conductive film laminated substrate of the present invention. For the transparent conductive film laminated substrate of the present invention obtained in Examples 3 to 6, the sheet resistance value (Ω · □), resistivity (Ω · cm), and transmittances of 620nm, 540nm, and 460nm were obtained in the same manner as above. %). The results are shown in Table 3. Table 3 Sheet resistivity, resistivity, transmittance (%), full film thickness (A) (Ω / (Q · cm) 620nm 540η m 460nm Example 3 1339.5 12. 36 1. 65X 10 '4 94. 93 98. 2 9 93. 67 Example 4 888. 8 16. 70 1 · 48X 10-4 89. 96 89. 9 9 94. 06 Example 5 819. 5 18. 43 1. 51 X 10) 4 89. 45 88. 2 9 90. 65 Example 6 935.8 15. 52 1.45X10- 4 92. 38 90. 4 5 91. 58 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 7: -40- This paper standard applies China National Standard (CNS) A4 specification (210 X 297 public love) 521280 A7 B7 V. Description of the invention (38) In addition to the second layer of sputtering on the first layer, a mixed gas of argon and oxygen (oxygen A transparent conductive film laminate substrate of the present invention was obtained in the same manner as in Example 3 except that the content was 0.542% by volume and the sputtering pressure was 0.7 Pa). The first layer and the second layer formed on the substrate The third layer is 488. 1 person. Example 8: Except that the second layer is sputtered on the first layer, a mixed gas of argon and oxygen (oxygen content 0.542% by volume, coin plating pressure) The transparent conductive film laminated substrate of the present invention was obtained in the same manner as in Example 3 except that the process was performed under an ambient gas of 0.07 Pa). The first layer, the second layer, and the third layer formed on this substrate were all 432.1 For the transparent conductive film laminated substrates of the present invention obtained in Examples 7 and 8, the sheet resistance value (Ω · □), specific resistance (Ω · cm), and transmission at 620 nm, 540 nm, and 460 nm were obtained in the same manner as described above. The results are shown in Table 4. The sheet resistivity and transmittance of the transparent conductive film in Table 4 (%) Full film thickness (A) (Ω / □) (Ω · cm) 620nm 540η m 460η m Example 7 1464.2 12.36 1. 81 X i〇- 4 95. 47 98. 6 9 92. 5 8 Example 8 1296.2 13. 92 1.80 X 10-4 93. 10 97. 7 9 97. 2 0 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ----------------- (Please read the precautions on the back before filling this page)-Line · Example 9: In Argon In an ambient gas mixture of gas and oxygen (sputtering pressure: 0.7Pa), sintering of indium-tin oxide was performed using a DC + RF power supply (DC: 0.4KW, RF: 0.4KW, frequency: 13.56M56ζ). The target is sputtered and the ITO film is formed on -41- this paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 X 297 mm) 521280 A7 B7_______ V. Description of the invention (39) A glass substrate maintained at 200 ° C The first layer formed (film thickness 451.9A). Next, an indium-tin oxide sintered body target was sputtered under an argon gas (sputter pressure 0.7Pa) using an RF power source (electricity 1.5KW, frequency 13.56MHz) to form a layer on the first layer. The second layer of ITO film (film thickness: 45 · 9 A) 〇Then use dc + RF power source (DC: electric power 0.4KW, RF _ · electric power under an argon gas (sputter pressure 0.7Pa) ambient gas) 0.4KW, frequency 13.56MHz) sputtered the target of indium-tin oxide sintered body to form a third layer (film thickness 451.9 people) composed of 1T0 film on the second layer to obtain the transparency of the present invention Conductive film laminated substrate. Example 10: In addition to sputtering on which a first layer is formed on a glass substrate, and sputtering on which a third layer is formed on a second layer, a mixed gas of argon and oxygen (oxygen content of 0.18% by volume, sputtering A transparent conductive film laminated substrate of the present invention was obtained in the same manner as in Example 9 except that the plating pressure was performed under an ambient gas of 0.7 Pa). The film thickness of the first layer, the second layer, and the third layer formed on this substrate was 470.6A. The results are shown in Table 5. (Please read the notes on the back before filling this page)
經濟部智慧財產局員工消費合作社印製 第5表 透明導電膜 之 薄片電阻 電陴率 透過率(%) ~-- 全膜厚(A) (Q / □) (Ω · cm) 620nm 540η m 460η m 實施例9 ^----- 1355. 7 11. 34 1· 54X 1〇 4 95· 79 98. 2 4 92. 3 4 實施例10 1411· 9 12· 51 1· 77 X 1〇 4 97. 22 99. 3 9 91. 8 1 -42- 規格(210x 297公釐) 本紙張尺度賴巾(eNS)A4 521280 A7 B7 五、發明說明(4G ) 實施例11 : 在氬氣與氧氣之混合氣體(氧氣含有量0.542容量%、 濺鍍壓0. 7Pa)的環境氣體下,使用DC電源(電力0. 5KW)將銦 一錫氧化物燒結體靶子予以濺鍍而在維持200°C之玻璃基 板上形成由ITO膜所構成的第1層(膜厚467. 5人)。 其次在氬氣與氧氣之混合氣體(氧氣含有量0.542容量 %、濺鍍壓0.7Pa)的環境氣體下,使用RF電源(電力1.5KW、 頻率13. 56MHz)將銦一錫氧化物燒結體靶子予以濺鍍而在第 1層上形成由ITO膜所構成的第2層(膜厚467. 5A)。 接著在氬氣與氧氣之混合氣體(氧氣含有量〇. 542容量 %、濺鍍壓0.7Pa)的環境氣體下,使用DC電源(電力0.5KW)將 銦一錫氧化物燒結體靶子予以濺鍍而在第2層上形成由ITO膜 所構成的第3層(膜厚467. 5A),以獲得本發明之透明導電膜積 層基板。 實施例12 : 在氬氣(濺鍍壓0.7Pa)的環境氣體下,使用DC電源(電 力0. 5KW)將銦一錫氧化物燒結體靶子予以濺鍍而在維持 20(TC之玻璃基板上形成由ITO膜所構成的第1層(膜厚 470. 8A) 〇 其次在氬氣與氧氣之混合氣體(氧氣含有量0. 542容量 %、濺鍍壓0.7Pa)的環境氣體下,使用DC電源(電力0.5KW) 將銦一錫氧化物燒結體靶子予以濺鍍而在第1層上形成由ITO 膜所構成的第2層(膜厚470. 8人)。 接著在氬氣(濺鍍壓〇.7Pa)的環境氣體下,使用DC電源 -43- 本紙張尺度適用中國國家標準(CNS)A4規格(210 χ 297公釐) --- (請先閱讀背面之注意事項再填寫本頁) Γ 經濟部智慧財產局員工消費合作社印製 521280 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明() (電力0.5KW)將銦一錫氧化物燒結體靶子予以藏鐘而在第2層 上形成由ITO膜所構成的第3層(膜厚470.8人),以獲得本發明 之透明導電膜積層基板。 對於實施例11及12所獲得之本發明透明導電膜積層基 板,與上述同樣地求出薄片電阻值(Ω · □)、電阻率⑴· cm) ’ 以及620nm、540nm及460nm的透過率(%)。 其結果如第6表所示。 第6表 透明導電膜 之 薄片電阻 電阻率 透過率(% ) 全膜厚(Α) (Ω / □) (Ω · cm) 620nm 540η m 460η m 實施例11 1402·4 19. 22 2. 70X 10" 4 93. 84 98. 7 0 93. 3 6 實施例12 1412·3 19. 28 2. 72Χ 10' 4 95. 63 99. 7 7 92. 8 4 實施例13 : 在氬氣與氧氣之混合氣體(氧氣含有量〇· 36容量%、濺 鍍壓0.28Pa)的環境氣體下,使用DC電源(電力0.5KW)將銦 一錫氧化物燒結體靶子予以濺鍍而在維持15〇°C之玻璃基 板上形成由ITO膜所構成的第1層(膜厚288. 5A)。 其次在氬氣(濺鍍壓〇.28Pa)的環境氣體下’使用RF電源 (電力1.5KW、頻率13. 56MHz)將銦一錫氧化物燒結體靶子予 以濺鍍而在第1層上形成由ITO膜所構成的第2層(膜厚673, 3 A)。以獲得本發明之透明導電膜積層基板。 比較例4 : 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ^;---------------訂---------線 ^一^ (請先閱讀背面之注意事項再填寫本頁) 521280 A7 B7 五、發明說明(42 ) 在氬氣與氧氣之混合氣體(氧氣含有量〇·542容量%、濺 鍍壓0.7Pa)的環境氣體下,使用dc電源(電力〇.5KW)將銦一錫 氧化物燒結體靶子予以濺鍍而在維持丨50°c之玻璃基板上形 成由ΙΤ0膜所構成的第1層(膜厚1069· 2A),以獲得導電膜積層 基板。 比較例5 : 在氬氣(濺鍍壓0· 7Pa)的環境氣體下,使用DC電源(電力〇. 5KW)將銦一錫氧化物燒結體靶子予以濺鍍而在維持丨5〇〇c之 玻璃基板上形成由ιτο膜所構成的單層(膜厚928· 〇人),以獲得 導電膜積層基板。 比較例6: 在氬氣與氧氣之混合氣體(氧氣含有量〇 36容量%、、濺鍍 壓0· 7Pa)的環境氣體下,使用DC電源(電力〇· 5KW)將銦一錫氧 化物燒結體靶子予以濺鍍而在維持15〇〇c之玻璃基板上形成 由ITO膜所構成的單層(膜厚1406.5人),以獲得導電膜積層基 -------------裝— (請先閱讀背面之注意事項再填寫本頁) 訂 板 線 經濟部智慧財產局員工消費合作社印製 比較例7 : 在鼠氣(錢鑛壓0.7Pa)的環境氣體下,使用dc + rf電源 (DC ·電力 0.4KW、RF :電力 0.4KW、頻率13·56ΜΗζ)將銦一 錫氧化物燒結體靶子予以濺鍍而在維持15〇〇c之玻璃基板上 形成由ΙΤ0膜所構成的單層(膜厚1420· 2人)。以獲得導電膜積 層基板。 對於實施例13所獲得之本發明透明導電膜積層基板及比 較例4〜7所獲得之導電膜積層基板,與上述同樣地求出薄片電 -45- 本紙張尺度適用中國國家標準(CNS)A4規格(21(^297公釐) 521280 A7 B7 五、發明說明(43 ) 阻值(Ω · □)、電阻率(Ω · cm) ’ 以及620nm、540nm及460nm 的透過率(%)。 其結果如第7表所示。 第7表 導電膜之 薄片電阻 電阻率 透過率 (%) 全膜厚(A) (Ω / □) (Ω · cm) 620nm 540η m 460η m 實施例13 961. 8 17. 56 1. 69X 10~ 4 88. 52 89. 9 8 94. 8 8 比較例4 1069.2 40. 76 4. 36X 10' 4 88. 14 90. 6 3 95. 9 9 比較例5 928. 0 35. 62 3. 31 X 10' 4 87. 10 87. 9 2 90. 4 1 比較例6 1406.5 21. 64 3. 04X 10' 4 97. 58 100· 0 89. 7 3 比較例7 1 1420.2 23. 96 3. 40X 10' 4 98. 32 99. 9 4 87. 7 9 實施例14 ·· 在氬氣與氧氣之混合氣體(氧氣含有量0.36容量%、濺 鍍壓0.28Pa)的環境氣體下,使用DC電源(電力0.5KW)將銦 —錫氧化物燒結體靶子予以濺鍍而在維持15 0 °C之玻璃基 板上形成由ITO膜所構成的第1層(膜厚308. 6A)。 其次在氬氣(濺鍍壓0.28Pa)的環境氣體下,使用RF電源 (電力1. 5KW、頻率13. 56MHz)將銦一錫氧化物燒結體靶子予 以濺鍍而在第1層上形成由ITO膜所構成的第2層(膜厚720. 0 A) 〇 接著在氬氣與氧氣之混合氣體(氧氣含有量0.36容量%、 濺鍍壓0.28Pa)的環境氣體下,使用DC電源(電力0.5KW)將銦 -46· 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) 訂---------線應 經濟部智慧財產局員工消費合作社印製 521280Sheet No. 5 of the transparent conductive film printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Transmittance (%) of the sheet resistivity. --- Full film thickness (A) (Q / □) (Ω · cm) 620nm 540η m 460η m Example 9 ^ ----- 1355. 7 11. 34 1 · 54X 1〇4 95 · 79 98. 2 4 92. 3 4 Example 10 1411 · 9 12 · 51 1 · 77 X 104 0 97 22 99. 3 9 91. 8 1 -42- Specifications (210x 297 mm) The paper size of the paper (eNS) A4 521280 A7 B7 V. Description of the invention (4G) Example 11: Mixing argon and oxygen In an atmosphere of gas (oxygen content 0.542% by volume, sputtering pressure 0.7Pa), a DC power source (electricity 0.5KW) was used to sputter the indium-tin oxide sintered target while maintaining the glass at 200 ° C. The first layer (film thickness 467.5 people) composed of an ITO film was formed on the substrate. Next, an indium-tin oxide sintered target was RF-powered (electric power 1.5KW, frequency 13.56MHz) under an ambient gas of a mixed gas of argon and oxygen (oxygen content 0.542% by volume and sputtering pressure 0.7Pa). 5A) Sputtered to form a second layer (film thickness 467.5 5A) composed of an ITO film on the first layer. Next, an indium-tin oxide sintered target was sputtered using a DC power source (power 0.5KW) under an ambient gas of a mixed gas of argon and oxygen (oxygen content of 0.542% by volume and sputtering pressure of 0.7Pa). A third layer (film thickness 467.5 A) made of an ITO film is formed on the second layer to obtain the transparent conductive film laminated substrate of the present invention. Example 12: An indium-tin oxide sintered body target was sputtered on a glass substrate maintained at 20 (TC) using an argon gas (sputter pressure: 0.7 Pa) using a DC power source (power: 0.5 KW). The first layer (film thickness 470.8 A) made of ITO film was formed. Secondly, DC was used under an ambient gas of a mixed gas of argon and oxygen (oxygen content 0.542% by volume and sputtering pressure 0.7Pa). Power source (power: 0.5KW) The indium-tin oxide sintered body target was sputtered to form a second layer made of an ITO film (with a film thickness of 478.8 persons) on the first layer. Next, argon (sputtering Use DC power supply under ambient gas pressure of 0.7 Pa) -43- This paper size applies to China National Standard (CNS) A4 (210 χ 297 mm) --- (Please read the precautions on the back before filling this page ) Γ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 521280 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () (Electricity 0.5KW) The target of indium-tin oxide sintered body was placed on A third layer (a film thickness of 470.8 persons) made of an ITO film was formed on the second layer to obtain The transparent conductive film laminated substrate of the invention. For the transparent conductive film laminated substrate of the present invention obtained in Examples 11 and 12, the sheet resistance value (Ω · □), the specific resistance ⑴ · cm) ′, and the 620 nm and 540 nm were obtained in the same manner as described above. And 460nm transmittance (%). The results are shown in Table 6. Table 6 Sheet resistivity, resistivity, transmittance (%) of the transparent conductive film, full film thickness (Α) (Ω / □) (Ω · cm) 620nm 540η m 460η m Example 11 1402 · 4 19. 22 2. 70X 10 & quot 4 93. 84 98. 7 0 93. 3 6 Example 12 1412 · 3 19. 28 2. 72 × 10 '4 95. 63 99. 7 7 92. 8 4 Example 13: Mixing with argon and oxygen In an atmosphere of gas (oxygen content of 0.36% by volume and sputtering pressure of 0.28Pa), a DC power supply (electricity 0.5KW) was used to sputter the indium-tin oxide sintered target while maintaining the temperature at 15 ° C. 5A) A first layer made of an ITO film was formed on a glass substrate. Next, an indium-tin oxide sintered body target was sputtered using an RF power source (electric power 1.5KW, frequency 13.56MHz) under an ambient gas of argon (sputtering pressure 0.28Pa) to form a layer on the first layer. The second layer of ITO film (thickness 673, 3 A). To obtain the transparent conductive film laminated substrate of the present invention. Comparative Example 4: This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ^; --------------- Order --------- Line ^ 一 ^ (Please read the precautions on the back before filling out this page) 521280 A7 B7 V. Description of the invention (42) In a mixed gas of argon and oxygen (oxygen content: 0.542% by volume, sputtering pressure: 0.7Pa) ) In the ambient gas, using a dc power supply (power 0.5KW) to sputter the indium-tin oxide sintered target to form a first layer (film) made of ITO film on a glass substrate maintained at 50 ° C. 1069 · 2A) to obtain a conductive film laminated substrate. Comparative Example 5: An indium-tin oxide sintered body target was sputtered under an argon gas (sputtering pressure of 0.7 Pa) using a DC power source (power 0.5 KW) and maintained at a temperature of 500 ° C. A single layer (film thickness: 928 · 0) made of a ιτο film was formed on a glass substrate to obtain a conductive film laminated substrate. Comparative Example 6: Indium-tin oxide was sintered using a DC power source (electricity 0.5 kw) under an ambient gas of a mixed gas of argon and oxygen (oxygen content of 036% by volume and sputtering pressure of 0 · 7Pa). The bulk target is sputtered to form a single layer (film thickness: 1406.5 people) made of ITO film on a glass substrate maintained at 150 ° C to obtain a conductive film laminated base ------------ -Installation— (Please read the precautions on the back before filling this page) Printed Line Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Comparative Example 7: Use dc under ambient gas of rat gas (money pressure 0.7Pa) + rf power supply (DC · Power 0.4KW, RF: Power 0.4KW, Frequency 13.56MΗζ) Sputtering an indium-tin oxide sintered body target to form an ITO film on a glass substrate maintained at 150 ° C Single layer (film thickness 1420 · 2 persons). To obtain a conductive film laminated substrate. For the transparent conductive film laminated substrate of the present invention obtained in Example 13 and the conductive film laminated substrate obtained in Comparative Examples 4 to 7, the sheet electricity was obtained in the same manner as described above. -45- This paper applies the Chinese National Standard (CNS) A4 Specifications (21 (^ 297 mm) 521280 A7 B7 V. Description of the invention (43) Resistance (Ω · □), resistivity (Ω · cm) 'and transmittances (%) at 620nm, 540nm, and 460nm. Results As shown in Table 7. Sheet Resistivity, Resistivity, and Transmittance of the conductive film in Table 7 (%) Full film thickness (A) (Ω / □) (Ω · cm) 620nm 540η m 460η m Example 13 961. 8 17 56 1. 69X 10 ~ 4 88. 52 89. 9 8 94. 8 8 Comparative Example 4 1069.2 40. 76 4. 36X 10 '4 88. 14 90. 6 3 95. 9 9 Comparative Example 5 928. 0 35 62 3. 31 X 10 '4 87. 10 87. 9 2 90. 4 1 Comparative Example 6 1406.5 21. 64 3. 04X 10' 4 97. 58 100 · 0 89. 7 3 Comparative Example 7 1 1420.2 23. 96 3. 40X 10 '4 98. 32 99. 9 4 87. 7 9 Example 14 · Under an ambient gas of a mixed gas of argon and oxygen (oxygen content 0.36% by volume, sputtering pressure 0.28Pa), DC power (0.5KW) is used to convert indium-tin oxide The sintered body target is sputtered to form a first layer (film thickness 308.6 A) made of an ITO film on a glass substrate maintained at 15 ° C. Next, an atmosphere of argon (sputter pressure 0.28 Pa) is used. 0, using an RF power source (electric power 1.5KW, frequency 13.56MHz) to sputter the indium-tin oxide sintered target to form a second layer (film thickness 720.0) made of an ITO film on the first layer A) 〇 Next, indium-46 · is used in a mixed gas of argon and oxygen (oxygen content 0.36% by volume, sputtering pressure 0.28Pa) using a DC power supply (electricity 0.5KW). Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) Order --------- Printed by the Consumer Consumption Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs 521280
五、發明說明(44 ) —錫氧化物燒結體靶子予以濺鍍而在第2層上形成由ΙΤ0膜所 構成的第3層(膜厚308. 6A) 接著在氬氣(濺鍍壓〇.28Pa)的環境氣體下,使用RF電源 (電力1. 5KW、頻率13. 56MHz)將銦一錫氧化物燒結體靶子予 以濺鍍而在第3層上形成由ITO膜所構成的第4層(膜厚720. 0 A),以獲得本發明之透明導電膜積層基板。 與上述同樣地求出薄片電阻值(Ω ·□)為8.93、電阻率(Ω · cm)為 1.84 X 1 0-4。620nm、540nm及460nm的透過率(%)分別 為91.1%、87.0%、93.7%。 對於上述所獲得之若干代表性的透明導電膜積層基板, 以第8表表示導電膜之電氣特性(載體密度及移動度)。導電膜 之載體密度及移動度係使用東洋于夕二力(股份有限公司)製 之Resi Test 8320而以23°C來測定之值。 第8表 (下頁續) ----------------I (請先閱讀背面之注意事項再填寫本頁) 訂· 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 521280 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明(45 ) 載體密度 (個 / c m3) 移動度 (c m 2 / V s e c ) 實施例1 9 . 9 3 X 1 0 20 4 1 . 7 比較例1 7 . 2 1 X 1 0 20 3 3 . 7 實施例2 8 . 8 5 X 1 0 2 0 4 1.6 實施例5 1 . 0 4 X 1 0 21 4 2 . 1 實施例9 9 . 6 1 X 1 0 20 4 5 . 8 實施例10 8 . 3 6 X 1 0 20 45.8 實施例13 1 . 0 6 X 1 0 2 1 4 1 . 1 比較例4 5 . 9 9 X 1 0 20 2 6.0 比較例7 5 . 5 1 X 1 0 20 3 3 . 7 實施例14 9 . 9 1 X 1 0 20 4 0 . 1 接著說明彩色濾光片之製造例。 除了取代玻璃基板(200mm X 260mm、厚度0.7mm)而使用 經形成遮光膜、彩色光阻劑膜及保護層的玻璃基板(200mm X 260mm、厚度〇.7mm)之外,與上述同樣地製造經積層透明 導電膜之彩色濾光片。 實施例15 : 在氬氣與氧氣之混合氣體(氧氣含有量0.542容量%、 濺鍍壓0· 7Pa)的環境氣體下,使用電源(電力〇· 5KW)將銦 一錫氧化物燒結體靶子予以濺鍍而在維持2〇〇。〇之已形成 遮光膜、彩色光阻劑膜及保護層的玻璃基板上形成由IT〇 膜所構成的第1層(膜厚262· 0Α)。 其次在氬氣(濺鍍壓0.7Pa)的環境氣體下,使用RF電源V. Description of the invention (44)-a tin oxide sintered body target is sputtered to form a third layer (thickness 308.6 6A) composed of an ITO film on the second layer, followed by argon (sputtering pressure. 28Pa), an indium-tin oxide sintered target was sputtered using an RF power source (electric power 1.5KW, frequency 13.56MHz) to form a fourth layer (ITO film) on the third layer ( The film thickness is 720.0 A) to obtain the transparent conductive film laminated substrate of the present invention. The sheet resistance value (Ω · □) was calculated in the same manner as above, and the resistivity (Ω · cm) was 1.84 X 1 0-4. The transmittances (%) at 620nm, 540nm, and 460nm were 91.1% and 87.0%, respectively. , 93.7%. For some of the representative transparent conductive film laminated substrates obtained above, the electrical characteristics (carrier density and mobility) of the conductive film are shown in Table 8. The carrier density and mobility of the conductive film are measured at 23 ° C using Resi Test 8320 manufactured by Toyo Yukiji (Limited). Table 8 (continued on next page) ---------------- I (Please read the notes on the back before filling out this page) Order · Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 521280 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (45) Carrier density (pcs / c m3) Mobility ( cm 2 / V sec) Example 1 9. 9 3 X 1 0 20 4 1. 7 Comparative Example 17. 2 1 X 1 0 20 3 3. 7 Example 2 8. 8 5 X 1 0 2 0 4 1.6 Example 5 1. 0 4 X 1 0 21 4 2. 1 Example 9 9. 6 1 X 1 0 20 4 5 8 Example 10 8. 3 6 X 1 0 20 45.8 Example 13 1. 0 6 X 1 0 2 1 4 1. 1 Comparative Example 4 5. 9 9 X 1 0 20 2 6.0 Comparative Example 7 5. 5 1 X 1 0 20 3 3. 7 Example 14 9. 9 1 X 1 0 20 4 0. 1 Next, a manufacturing example of a color filter will be described. A glass substrate (200 mm X 260 mm, thickness 0.7 mm) formed with a light-shielding film, a color photoresist film, and a protective layer was used instead of the glass substrate (200 mm X 260 mm, thickness 0.7 mm). Color filter for laminated transparent conductive film. Example 15: An indium-tin oxide sintered target was applied using a power source (electricity 0.5 kw) under an ambient gas of a mixed gas of argon and oxygen (oxygen content 0.542% by volume, sputtering pressure 0 · 7Pa). Sputtering was maintained at 200. On the glass substrate on which the light-shielding film, the color photoresist film, and the protective layer have been formed, a first layer (film thickness 262.0A) made of the IT0 film is formed. Next, use an RF power supply under an argon gas (sputter pressure 0.7Pa).
T---:---------------訂--------- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 521280 A7 B7 五、發明說明(46 ) (電力1.5KW、頻率13. 56MHz)將銦一錫氧化物燒結體靶子予 以濺鍍而在第1層上形成由ITO膜所構成的第2層(膜厚611. 4 A) 〇 接著在氬氣與氧氣之混合氣體(氧氣含有量〇. 542容量 %、濺鍍壓0.7Pa)的環境氣體下,使用DC電源(電力0.5KW)將 銦一錫氧化物燒結體靶子予以濺鍍而在第2層上形成由ITO膜 所構成的第3層(膜厚262.0人),以獲得本發明之彩色濾光片。 實施例16 ·· 在氬氣與氧氣之混合氣體(氧氣含有量0.542容量%、 濺鍍壓0. 7Pa)的環境氣體下,使用DC電源(電力0· 5KW)將銦 —錫氧化物燒結體靶子予以濺鍍而在維持200°C之已形成 遮光膜、彩色光阻劑膜及保護層的玻璃基板上形成由ITO 膜所構成的第1層(膜厚232. 9A)。 其次在氬氣(濺鍍壓〇.7Pa)的環境氣體下,使用RF電源 (電力1. 5KW、頻率13. 56MHz)將銦一錫氧化物燒結體靶子予 以濺鍍而在第1層上形成由ITO膜所構成的第2層(膜厚698. 8 A)。 接著在氬氣與氧氣之混合氣體(氧氣含有量0. 542容量 %、濺鍍壓0.7Pa)的環境氣體下,使用DC電源(電力0.5KW)將 銦一錫氧化物燒結體靶子予以濺鍍而在第2層上形成由ITO膜 所構成的第3層(膜厚232.9A),以獲得本發明之彩色濾光片。 比較例8 : 在氬氣與氧氣之混合氣體(氧氣含有量0.542容量%、濺 鍍壓0.7Pa)的環境氣體下,使用DC電源(電力0.5KW)將銦一錫 -49- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -------------裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 521280T ---: --------------- Order --------- (Please read the precautions on the back before filling out this page) Staff Consumption of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the cooperative 521280 A7 B7 V. Description of the invention (46) (electric power 1.5KW, frequency 13.56MHz) The indium-tin oxide sintered body target is sputtered to form a second layer consisting of an ITO film on the first layer Layer (film thickness 611.4 A) 〇 Next, indium gas was mixed with argon and oxygen gas (oxygen content 0.542% by volume, sputtering pressure 0.7Pa) using a DC power supply (power 0.5KW) to indium A tin oxide sintered body target is sputtered to form a third layer (film thickness: 262.0 people) composed of an ITO film on the second layer to obtain the color filter of the present invention. Example 16 In a mixed gas of argon and oxygen (oxygen content 0.542% by volume, sputtering pressure 0.7Pa), an indium-tin oxide sintered body was DC-powered (electricity 0.5KW). The target is sputtered and a first layer (thickness: 232. 9A) made of an ITO film is formed on a glass substrate having a light-shielding film, a color photoresist film, and a protective layer maintained at 200 ° C. Next, an indium-tin oxide sintered body target was sputtered under an argon gas (sputter pressure: 0.7 Pa) using an RF power source (electric power: 1.5 KW, frequency: 13. 56 MHz) to form on the first layer. 8 A)。 The second layer composed of ITO film (film thickness 698.8 A). Next, an indium-tin oxide sintered target was sputtered using a DC power source (power 0.5KW) under an ambient gas of a mixed gas of argon and oxygen (oxygen content of 0.542% by volume and sputtering pressure of 0.7Pa). A third layer (thickness: 232.9A) made of an ITO film is formed on the second layer to obtain the color filter of the present invention. Comparative Example 8: An indium-tin-49- is used in a mixed gas of argon and oxygen (oxygen content 0.542% by volume, sputtering pressure 0.7Pa) using a DC power supply (electricity 0.5KW) China National Standard (CNS) A4 Specification (210 X 297 mm) ------------- Installation -------- Order --------- Line (Please (Please read the notes on the back before filling out this page) 521280
氧化物燒結體乾子予以濺鍍而在維持2 〇 o 〇c之已形成遮光 膜、彩色光阻劑膜及保護層的玻璃基板上形成由IT0膜所構成 的單層膜(膜厚1133· ΟΑ),以獲得彩色濾光片。 比較例9 : 在氬氣0賤鍍壓〇· 7Pa)的環境氣體下,使用DC + RF電源(D C ·電力0· 4KW、RF :電力0.4KW、頻率13.56MHz)將銦一錫 氧化物燒結體靶子予以濺鍍而在維持2〇(rc之已形成遮光 膜、衫色光阻劑膜及保護層的玻璃基板上形成由1了〇膜所構成 的單層膜(膜厚1145· 7A),以獲得彩色濾光片。 對以實施例15及16所獲得之本發明的彩色濾光片,以及 以比較例8及9所獲得之彩色濾、光片’求出薄片電阻值。 薄片電阻以其次的方式求出。即,於上述玻璃基板上 所形成的膜面均等地設置67點的測定點,使用三菱化學製 之四探針電阻計(MCP—T600)而求出電阻值,並求出此等 的平均值,而且乘上常數= 4.5424以求出薄片電阻。 膜厚藉由以下所述方式求出。即,使用小坂研究所製 之二維微細形狀測定器(ET4000)來測定已成膜在玻璃基板 上的導電膜的膜厚。測定係於玻璃基板上設定5點測定點, 以力7'、卜^膠帶來遮罩而於成膜後剝離遮罩並測定膜厚而 將該平均值作為膜的膜厚。 電阻率(Ω · cm)可藉著以上述四探針法所求出之薄片電 阻值乘上膜厚而求得。 又,對於從實施例15及16所獲得之本發明的彩色遽光 片’以及從比較例8及9所獲得之彩色濾光片求出透過率(% -50· 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) --------^---------. 經濟部智慧財產局員工消費合作社印製 521280 A7 B7 五、發明說明(48 ) )。即,使用曰立製作所製分光光度計(U—2010)而測定在 波長200〜900nm的範圍内導電膜積層基板的透過率(%), (請先閱讀背面之注意事項再填寫本頁) 成膜前之經形成遮光膜及彩色光阻劑膜的玻璃基板(blank) 的透過率(%)設為100%而算出62〇11111、54〇11111及46〇11111的透 過率(%)。 其結果如第9表所示。 第9表 導電膜之 薄片電阻 電阻率 透過率(%) 全膜厚(A) (Ω / □) (Ω · cm) 620nm 540η m 460η m 實施例15 1135.5 14. 13 1. 60X 10' 4 90. 89 92. 8 7 97. 7 3 實施例16 1164.6 13. 35 1. 56X 10' 4 91. 08 93. 9 9 98. 6 1 比較例8 1133. 0 21. 83 2.47X10" 4 88. 59 90. 7 2 99. 0 7 比較例9 1145·7 18· 07 2. 07X 10~ 4 91· 56 94. 4 8 98. 9 6 經濟部智慧財產局員工消費合作社印製 以實施例15及16所獲得彩色濾光片均在形成ITO膜所構 成之第1層之際,具有彩色光阻劑膜不受損傷而作為彩色濾光 片所期望的性能。 -51- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)The oxide sintered body was sputtered to form a single-layer film (film thickness 1133 ·) made of an IT0 film on a glass substrate having a light-shielding film, a color photoresist film, and a protective layer maintained at 200 ° C. OA) to obtain a color filter. Comparative Example 9: Indium-tin oxide was sintered using a DC + RF power source (DC · electric power 0.4 KW, RF: electric power 0.4 KW, frequency 13.56 MHz) under an ambient gas of argon gas (base plating pressure 0.7 Pa). The body target is sputtered to form a single-layer film (film thickness 1145 · 7A) made of 1.0 film on a glass substrate that has been formed with a light-shielding film, a shirt color photoresist film, and a protective layer maintained at 20 ° (rc). To obtain a color filter. The sheet resistance values of the color filters of the present invention obtained in Examples 15 and 16 and the color filters and filters obtained in Comparative Examples 8 and 9 were obtained. It is obtained by the following method. That is, 67 measurement points are evenly set on the film surface formed on the glass substrate, and the resistance value is obtained using a four-probe resistance meter (MCP-T600) manufactured by Mitsubishi Chemical, and calculated. These average values are calculated and multiplied by a constant value of 4.5424 to obtain the sheet resistance. The film thickness is determined as described below. That is, a two-dimensional micro shape measuring device (ET4000) manufactured by Kosaka Research Institute is used to measure the thickness. The thickness of the conductive film formed on the glass substrate. The measurement is on the glass substrate Set 5 measurement points, mask with force 7 ', tape, and peel off the mask after film formation, and measure the film thickness, and use the average value as the film thickness. Resistivity (Ω · cm) can be determined by It is obtained by multiplying the sheet resistance value obtained by the above-mentioned four-probe method by the film thickness. In addition, the color phosphor films of the present invention obtained from Examples 15 and 16 and the comparative examples 8 and 9 were obtained. The color filter is used to determine the transmittance (% -50 · This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling out this page) ---- ---- ^ ---------. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 521280 A7 B7 V. Description of Invention (48)). That is, a spectrophotometer (U— 2010) And measure the transmittance (%) of the conductive film laminated substrate in the range of 200 ~ 900nm, (Please read the precautions on the back before filling this page) Before forming the film, a light-shielding film and a color photoresist film are formed. The transmittance (%) of the glass substrate (blank) was set to 100%, and the transmittances (%) of 6201011, 5401111, and 4601011111 were calculated. The results are shown in Table 9. Sheet Resistivity, Resistivity, and Transmittance of the conductive film in Table 9 (%) Full film thickness (A) (Ω / □) (Ω · cm) 620nm 540η m 460η m Example 15 1135.5 14. 13 1. 60X 10 '4 90. 89 92. 8 7 97. 7 3 Example 16 1164.6 13. 35 1. 56X 10' 4 91. 08 93. 9 9 98. 6 1 Comparative Example 8 1133. 0 21. 83 2.47X10 " 4 88. 59 90. 7 2 99. 0 7 Comparative Example 9 1145 · 7 18 · 07 2. 07X 10 ~ 4 91 · 56 94. 4 8 98. 9 6 Employees' Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs When the color filters obtained in Examples 15 and 16 were printed to form the first layer of the ITO film, they had the desired performance as a color filter without damage to the color photoresist film. -51- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)
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WO2015192628A1 (en) * | 2014-06-18 | 2015-12-23 | 北京北方微电子基地设备工艺研究中心有限责任公司 | Method for depositing ito thin film and gan-based led chip |
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CN104465933B (en) * | 2013-09-18 | 2018-03-06 | 上海蓝光科技有限公司 | The preparation method of the LED chip of the preparation method and use of the ito thin film ito thin film |
WO2015192628A1 (en) * | 2014-06-18 | 2015-12-23 | 北京北方微电子基地设备工艺研究中心有限责任公司 | Method for depositing ito thin film and gan-based led chip |
CN105331936A (en) * | 2014-06-18 | 2016-02-17 | 北京北方微电子基地设备工艺研究中心有限责任公司 | ITO film deposition method and GaN-based LED chip |
CN105331936B (en) * | 2014-06-18 | 2018-05-08 | 北京北方华创微电子装备有限公司 | The deposition process and GaN base LED chip of ito thin film |
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