TWI375099B - - Google Patents

Description

1375099 0) Description of the Invention [Technical Field of the Invention] The present invention relates to a transparent electrode used for a thin display or the like. More specifically, it relates to a transparent electrode having zinc oxide and tin oxide as a main component, a tapered electrode at the end of the electrode, and a method for producing the electrode. [Prior Art] Liquid crystal display devices are characterized by low power consumption and easy colorization, and are considered to be the most promising in thin-type displays. In recent years, the development of large-scale display kneading has been very enthusiastic. . In this case, a cc-Si type thin film crystal (TFT) or a p-Si type TFT is arranged in a matrix as a switching element in each pixel, and an active matrix type liquid crystal flat panel display is driven, even if it is high in fineness of 800×600 pixels or more. As a high-performance color display flat panel display, it is highly attracting attention. In such an active matrix type liquid crystal flat panel display, a transparent electrode such as indium oxide-tin oxide (ITO) is used as a pixel electrode, and an A1 alloy thin film is often used as a gate electrode, a power source, and an electric drain electrode. In this system, the sheet resistance is low and the light transmittance is high, and A1 can be easily patterned with low resistance and high density. Here, a configuration example of the TFT substrate will be described. Fig. 4 is a cross-sectional view showing the vicinity of the ?-Si TFT in the completion stage of the pattern formation of the pixel electrode in the manufacturing step of the liquid crystal flat display. In Fig. 4, a gate electrode pattern-5-(2) 1375099 22 is formed on a translucent glass substrate 21: secondly, a SiN gate insulating 23, ct-Si:H(i) film is continuously formed by a plasma CVD method. The 24' channel protective film 25 and the α-Si: H (r film 26 are patterned in a desired shape. Further, the metal film is deposited mainly by 真空1 by vacuum evaporation or sputtering. The lithography technique is used to form the power electrode pattern 27 and the electric drain electrode pattern 28 to complete the α-Si TFT device portion. Also, in this example, the protective film 30 is formed. The ITO film is deposited thereon by sputtering. The lithography technique is used as the pixel electrode pattern 29 electrically connected to the source electrode 27. The reason for stacking the ITO film after the A] film is that the contact characteristics of the a-Si: germanium film with the power source and the electric drain electrode are not deteriorated. ΑΙ ΑΙ 。 。 ΑΙ ΑΙ ΑΙ ΑΙ ΑΙ ΑΙ ΑΙ ΑΙ ΑΙ ΑΙ ΑΙ ΑΙ ΑΙ ΑΙ ΑΙ ΑΙ ΑΙ ΑΙ ΑΙ ΑΙ ΑΙ 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Α1 is the main power supply and drain electrode pattern, and the HC]-HN03-H20 etchant is used to make the ΙΤΟ 素 极 极At the time of processing, there is a problem that the A] pattern is frequently generated at the time of completion of the addition. This is due to the inherent properties of Al and ITO dissolved in the etching solution of the HCi-HN03-H20 etching solution. hno3 in the etching solution When a thin A1 oxide film is formed on the surface, it is difficult to prevent the elution of A], and the etching time of the ITO film increases, and the defect of the impurity or foreign matter of the A1 film mixed in the A1 stack exists due to the local battery reaction. The oxidation effect of A of the above HN〇3 is not sufficient. Also, 'A1 ITO is in the state of electrical connection, and the photoresist is immersed in the four layers of the hydrogen hydride solution of the developing liquid») The plate-shaped element electric power source can be electrically electric type A1 When the medium 5 is in a 2.38 wt% aqueous solution of a (3) 1375099-ammonium (TMAH), there is a problem of elution of AI due to electricity. In order to prevent the elution of the A1, the ITO film is made amorphous. For the etching liquid of the HC1-HN03-H20 system, the etching ratio of ITO/A1 is increased (see, for example, Patent Document 1). However, even if the ITO is amorphous, the etching liquid of HCl-HN〇3. cannot completely prevent the elution of A1, and the liquid crystal display cannot be made fine. In this case, the A1 gate, the power supply and the electric drain electrode are patterned by the indium oxide-zinc oxide transparent electrode and the pixel electrode by the etching solution of the oxalic acid system, so that the patterning is easy ( For example, refer to Patent Document 2). However, indium oxide-tin oxide or indium oxide-zinc oxide (IZO), which is generally used as a transparent electrode, is mainly composed of indium oxide, and indium is required for thin display applications. Increase, its price is high. Therefore, the price of the sputtering target used for the production of the transparent electrode is also problematic. Therefore, there is a proposal of a transparent conductive tin oxide-based transparent conductive film which does not have a zinc oxide-based zinc oxide-based indium oxide (see, for example, Non-Patent Documents 3 and 4). However, the zinc oxide film is not practical in terms of its properties in acid and alkali solutions. Further, in the film formation of zinc oxide, the crystallinity of the near-zinc oxide is lowered, and the surface of the transparent conductive film has a property of extracting property. In the etching step, the film in the vicinity of the substrate is more reactive than the surface cell, and the phase velocity is - Η20 is a proposal for a high-precision pattern (ΙΤΟ). In recent years, there has been an increase in the number of films, or a weak film. The substrate is highly crystalline. It is easy to be -7- (4) (4) 1375099 f. The etched electrode has a problem of being inverted trapezoidal (undercut). On the other hand, the chemical stability of tin oxide is too strong, and there is a problem that the strong acid aqua regia (a mixed acid of nitric acid and hydrochloric acid) cannot be etched. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japan Society for the Promotion of Science, Transparent Oxide, Optical and Electronic Materials, 166th Committee: Technology of Transparent Conductive Film, Ohm Corporation (1999) [Disclosure of the Invention] The present invention provides the above problems in view of the above problems. A transparent electrode using indium is used for the purpose of providing a transparent electrode excellent in alkali resistance or wet heat stability and excellent in etching property. Further, it is an object of the present invention to provide a method for producing a transparent electrode in which an electrode end portion is difficult to form (a tapered shape can be easily formed). In order to solve the above problems, the inventors of the present invention have found that a transparent electrode is formed by using a sputtering target having zinc oxide and tin oxide as a main component, or a transparent target is formed by using the sputtering target. At the time of the electrode, the end portion of the electrode can be easily formed into a tapered shape by using the predetermined etching liquid, and the invention is completed. According to the present invention, the following transparent electrode, a method for producing the same, and the like can be provided. -8 - (5) (5) 1375099 [1] A transparent electrode 'characterized by zinc oxide and tin oxide as main components, and the taper angle of the electrode end portion is 30 to 89 degrees. [2] The transparent electrode according to [1], wherein the ratio of the zinc atom [Zn/(Zn + Sn), atomic ratio] is 0.5 to 0.9 with respect to the total amount of the crushed atoms and the tin atoms in the transparent electrode. [3] A method for producing a transparent electrode, characterized in that a transparent conductive film containing zinc oxide and tin oxide as a main component is etched so that a tapered angle of an electrode end portion can reach 30 to 89 degrees. [4] The method for producing a transparent electrode according to [3], wherein a ratio of zinc atoms [Zn / (Zn + Sn), atomic ratio] is 0.5 to 0.5 with respect to the total amount of zinc atoms and tin atoms in the transparent electrode. [0] [5] The method for producing a transparent electrode according to [3] or [4], wherein an aqueous solution of a hydrohalic acid having a concentration of 1 w19b to 40% by weight is used in the etching. [6] The method for producing a transparent electrode according to any one of [3] to [5], which comprises: forming a ratio of zinc atoms to a total amount of zinc atoms and tin atoms [Zn/(Zn + a first step of forming a transparent conductive film containing zinc oxide and tin oxide as a main component of Sn to an atomic ratio of 0.5 to 0.9, a second step of forming a photoresist film on the transparent conductive film, and using a hydrogen peroxide 1~5wt% aqueous solution of methylammonium is a photoresist development liquid, wherein the temperature of the aqueous solution is in the range of 20 to 50 ° C, the third step of patterning the photoresist film, and the concentration of using hydrohalic acid The transparent conductive film is etched to form a transparent electrode having a taper angle of 30 to 89 degrees, and a fourth step of forming a transparent electrode having a taper angle of 30 to 89 degrees (6) (6) 1375099, and using an ethanolamine-containing solution The photoresist stripping solution is a fifth step of peeling off the photoresist film remaining on the transparent electrode. [7] The method for producing a transparent electrode according to [3], which comprises: forming a total amount of zinc atoms with respect to zinc atoms and a ratio of zinc atoms [Zn/(Zn + Sn), atomic ratio] is 0.5~ 0.85 of a transparent conductive film containing zinc oxide and tin oxide as a main component, and an aqueous solution having an oxalic acid concentration of 1 wt% to 1% by weight as an etching solution, in an etching temperature of 20 to 50 ° C, The transparent conductive film is etched to perform a patterning process. [8] The method for producing a transparent electrode according to [3] or [4], comprising a first step of forming a transparent conductive film containing zinc oxide and tin oxide as a main component, and forming light on the transparent conductive film a second step of the resist film, a third step of patterning the photoresist film, and a mixed solution of nitric acid 'hydrochloric acid and water to etch the transparent conductive film to form a cone angle of 30 to 8 The fourth step of the 9 degree electrode and the fifth step of peeling off the photoresist film remaining on the transparent electrode. [9] The method for producing a transparent electrode according to [8], wherein the composition of the mixed solution is in a ratio of nitric acid:hydrochloric acid:water in a three-component system of nitric acid-hydrochloric acid-water, at (A) 2: 2:96, (B) 2 : 2 : 96 ' (C ) 78 : 2 : 20 , and (D) 78 : 20 : 2 surrounded by the four sides of the 10- (7) (7) 1375099-shaped area Inside. [10] The method for producing a transparent electrode according to [8] or [9], wherein the temperature of the mixed solution of nitric acid: hydrochloric acid: water in the fourth step is 20 to 50 〇C. [11] The method for producing a transparent electrode according to any one of [8] to [10] wherein the photoresist solution used in the third step is a 1 to 5 wt% aqueous solution of tetramethylammonium hydroxide. The photoresist stripping solution used in the fifth step contains ethanolamine. [12] An etching method characterized in that a transparent conductive film containing zinc oxide and tin oxide as a main component is etched using an aqueous oxalic acid solution. [13] The etching method according to [12], wherein the concentration of the oxalic acid in the aqueous solution of the oxalic acid is from 1% by weight to 10% by weight. [14] An etching method characterized by using a mixture of nitric acid, hydrochloric acid and water. The solution is filled with a transparent conductive film containing zinc oxide and tin oxide as a main component. [15] The etching method according to [14], wherein the composition of the mixed solution of nitric acid, hydrochloric acid and water is in a ratio of nitric acid:hydrochloric acid:water in the three components of nitric acid-hydrochloric acid-water, in (A) 2: 2: 96, (B) 2: 2: 96, (C) 78: 2: 20 and (D) 7 8 : 20 : 2 is surrounded by the composition of the quadrilateral area. The transparent electrode of the present invention does not use indium, and has a low price regardless of the price variation of indium. By using zinc oxide and tin oxide as main components, the durability and heat and humidity resistance of the electrode can be made superior. Moreover, by using the predetermined etching liquid 'the electrode end can be prevented from being inverted - 11 - (8) (8) 1375099 trapezoid, and an electrode controlled to a certain taper angle can be obtained. [The best form for carrying out the invention. The transparent electrode of the present invention will be specifically described below. Figure 1 is a cross-sectional view of a transparent electrode of the present invention. The transparent electrode 11 of the present invention is formed on the substrate 10, and has zinc oxide and tin oxide as main components, and the taper angle (α) of the electrode end portion is 30 to 89 degrees. The so-called "zinc oxide and tin oxide are mainly composed. The term "atomic ratio" of zinc and tin oxide in the transparent electrode means that it is more than 51%. Further, in the present invention, the proportion of the oxide is preferably 75% or more, more preferably 90% or more. The form of zinc and tin oxides is in the form of zinc oxide such as ΖηΟ, the form of tin oxide such as Sn, 02, and SnO, and the form of a composite oxide between zinc oxide and tin oxide such as ZnSn03 'Zn2Sn04. The amorphous transparent conductive film is preferably a transparent conductive film of zinc oxide type and a transparent conductive film of tin oxide type, and has excellent etching characteristics. That is, unlike the zinc oxide-based transparent conductive film, it is difficult to form an inverted electrode shape after etching, and it is not preferable that the tin oxide-based etching property is poor. In the transparent electrode of the present invention, the taper angle of the electrode end portion is 30 to 89 degrees. When the taper angle is less than 30 degrees, the distance between the edge portions of the electrodes increases, and when the liquid crystal or the organic EL is driven, the peripheral portion of the pixel is different from the inside. When the taper angle exceeds 89 degrees, the electrode part of the edge is cracked or -12- 1375099

Further, when it is a liquid crystal, there is a case where the alignment film is defective, and when it is an organic EL, there is a case where the opposite electrode is broken. The film thickness of the transparent conductive film (transparent electrode) is preferably from 5 to 300 MPa. More preferably, it is preferably from 0 to 150 nm, and most preferably from 30 to 80 nm. When the film thickness is less than 5 nm, the resistance 値 is too high; when it exceeds 30,000 nm, the taper angle of the electrode end after etching may not reach 30 to 89 degrees.

In the present invention, the above-mentioned transparent conductive film containing zinc oxide and tin oxide as a main component can control the taper angle of the transparent electrode. The control of the taper angle is performed by adjusting the blending, concentration, temperature, and the like of the etching liquid to be used when etching the transparent conductive film. Specifically, an aqueous solution of oxalic acid, a mixed solution of nitric acid-hydrochloric acid-water, an aqueous solution of hydrohalic acid or the like can be used as the etching liquid. When an aqueous solution of oxalic acid is used, the cone angle can be controlled by the concentration of the aqueous oxalic acid solution. Specifically, it is adjusted to reduce the concentration of the aqueous oxalic acid solution in order to reduce the taper angle, and conversely, it is preferable to adjust the concentration of the aqueous solution of the oxalic acid in the case of the __ cone angle. Further, in this case, the ratio of zinc atoms [Zn/(Zn + Sn), atomic ratio] is preferably 0.5 to 0.85 with respect to the total amount of zinc atoms and tin atoms in the transparent electrode. When the [Zn/(Zn + Sn)] is larger than 0.85, the control is difficult, and the taper angle of the electrode end portion is 90 degrees or more, the side etching is too large, and the electrode is tapered or broken. Further, the contact resistance with the anisotropic conductive film (ACF) connecting the transparent electrode and the external circuit is increased, and in the endurance test (high temperature, high humidity), the #contact resistance of the ACF is increased. On the other hand, when [Zn/(Zn + Sn)] is less than 0.5, the etching rate is lowered by -13-(10) (10) 1375099, and there is a case where etching is impossible. [Zn/(Zn + Sn)] is preferably from 0.5 to 0.8, more preferably from 0.7 to 0.8. When a mixed solution of nitric acid-hydrochloric acid-water is used as the etching solution, the taper angle can be controlled by adjusting the composition ratio of the mixed solution. Specifically, in order to reduce the taper angle, it is preferable to increase the ratio of hydrochloric acid, and conversely to increase the taper angle, to reduce the ratio of hydrochloric acid. Further, when the encapsulation is carried out using a mixed solution of nitric acid-hydrochloric acid-water, the ratio of zinc atoms [Zn/(Zn + Sn), atomic ratio] is 0.5 with respect to the total amount of zinc atoms and tin atoms in the transparent electrode. It is preferably 0.9, which is the same as the case of the above oxalic acid. [Zn/(Zn + Sn)] is preferably from 0.55 to 0.85, more preferably from 0.57 to 0.8. It is particularly suitable for 0.60~0.77, and is particularly suitable for 0.64~0.74, and the best is 0.64~0.69. When an aqueous solution of hydrohalic acid is used as the etching solution, the taper angle can be controlled by the concentration of the hydrohalic acid or the temperature of the hydrohalic acid. Specifically, in order to reduce the taper angle, it is suitable to reduce the concentration of the hydrohalic acid or lower the temperature of the aqueous solution; conversely, to increase the cone angle, to increase the concentration of the hydrohalic acid or increase the temperature of the aqueous solution. More suitable. Further, when etching with a hydrohalic acid aqueous solution, the ratio of zinc atoms [Zn/(Zn + Sn), atomic ratio] is preferably 0.5 to 0.9 with respect to the total amount of zinc atoms and tin atoms in the transparent electrode. This reason is the same as the case of the above oxalic acid. [Zn/(Zn + Sn)] is preferably 〇·52 to 0.7, more preferably 0.55 to 0.67, most preferably 0.55 to 0.63. Further, in the present invention, a transparent conductive film containing zinc oxide and tin oxide as a main component is preferably an amorphous film. When it is not an amorphous film, the control of the taper angle is -14 (11) (11) 1375099 is difficult, and it cannot be 30 to 89 degrees. Further, the ratio of zinc atoms [Zn/ ( Zn + Sn ) , atomic ratio] is determined by ICP (High Frequency Induced Combined Plasma) analysis. Further, the atomic ratio of the actually obtained transparent conductive film is almost the same as the atomic ratio in the raw material of the sputtering target used for forming the transparent conductive film (transparent electrode). Therefore, by adjusting the atomic ratio in the raw material of the sputtering target, the atomic ratio [Zn/(Zn + Sn)] of the transparent conductive film can be controlled. The transparent electrode of the present invention is obtained by etching a transparent conductive film made of an amorphous conductive oxide containing zinc oxide and tin oxide as a main component. The description will be described below with reference to the drawings. Fig. 2 is a view showing a manufacturing step of the transparent electrode of the present invention. The manufacturing step is mainly formed by the formation of a transparent conductive film [first step, FIG. 2(a)], formation of a photoresist film [second step, FIG. 2(b)], and patterning of the photoresist film [third step, Fig. 2(c)] 'etching of the transparent conductive film [fourth step, Fig. 2(d)], peeling of the photoresist film on the transparent electrode [fifth step, Fig. 2(e)] Formation of Transparent Conductive Film A transparent conductive film ii is formed on the substrate 10 on which the transparent electrode is formed:» The substrate 10 can be a glass of a transparent substrate, a transparent resin plate such as polyfluorene or polycarbonate, or the like. The film formation method of the transparent conductive film 11' includes a vapor deposition method, a sputtering method, a CVD method, a spray method, a dipping method, and the like. Among them, sputtering is more suitable. Specifically, a sputtering target which is prepared by sintering and sintering with zinc oxide and tin oxide as a main raw material is suitable. Further, when the transparent conductive film 11' -15- (12) (12) 1375099 is formed as an amorphous transparent conductive film, the substrate temperature during sputtering is adjusted to 300 ° C or less, and the sputtering is performed during sputtering. It is preferred to add hydrogen (10% by volume or less) to the plating gas. Thus, by making the transparent conductive film 1 1 ' amorphous, the above etching liquid can be easily singular. (2) Formation of Transparent Electrode Next, the transparent conductive film was etched to form a desired electrode pattern. Patterning can be performed in the art by conventional methods such as lithography. That is, the photoresist film 12 is formed on the transparent conductive film 11 (Fig. 2(b)), and the photoresist film 12 is patterned by exposure and development [Fig. 2(c)]. Thereafter, the transparent conductive film 1 is etched using an etching solution to form a desired pattern. Finally, the photoresist film 12 remaining on the transparent electrode 11 is removed by using a stripping liquid [Fig. 2(d)] to form a transparent electrode [Fig. 2(e)]. In the present invention, the etching solution is preferably an aqueous solution of oxalic acid, a mixed solution of nitric acid-hydrochloric acid-water or an aqueous solution of hydrohalic acid. When an aqueous solution of oxalic acid is used as the etching solution, the concentration of the oxalic acid in the aqueous solution of the oxalic acid is preferably from 1% by weight to 10% by weight. When the concentration of oxalic acid is less than 1 wt%, the etching rate is slow, which is not practical; when it exceeds 10% by weight, the crystal of the oxalate may be precipitated. It is preferably 2 wt% to 7 wt%, more preferably 2 wt% to 5 wt%.

When a mixed solution of nitric acid-hydrochloric acid-water is used as the etching solution, it is preferred that the composition of the mixed solution is in a ratio of nitric acid:hydrochloric acid:water (volume ratio) at (A)2:9 6 :2, (B) 2 : 2 : 9 6. (C) 7 8 : 2 ·· 2 0, and (D •16- (13) 1375099 ) 78: 20: The area of the quadrilateral surrounded by the composition points. Figure 3 is suitable nitric acid in the present invention. A map of the composition of hydrochloric acid and water. In Fig. 3, the edge-shaped area (the area of the oblique line) of (A) to (D) is a suitable range. At this time, the etching speed is either too fast or too slow, and the taper of the electrode is in the range of 30 to 89 degrees. The composition of the mixed solution is composed of nitric acid:hydrochloric acid:water)4:48:48, (B')4:8:88, (C') 78:8 D')78:1 1 :1 1 The composition of the mixed solution of the enclosed quadrilateral region is composed of nitric acid:hydrochloric acid:water ratio 47:47, ( Β" ) 6 : 8 : 86, ( C" ) 50 : 8 : 42 50 : 25 : 25 The area of the quadrilateral surrounded by the point is still, nitric acid means the usual concentrated nitric acid (concentration of 60%), and hydrochloric acid means the usual hydrochloric acid (concentration of 35%, specific gravity: when using hydrogen-acid aqueous solution as etching liquid, Hydrogen halide HI, HBi·, HC or HF. Preferably HC], HI or HF. The concentration of hydrohalic acid in the aqueous solution of hydrohalic acid is 1 wt %~. When the concentration of hydrohalic acid is less than 1 wt %, The etching rate is slow; when it exceeds 40 wt%, the crystal of the hydrohalide salt may precipitate preferably from 2 wt% to 35 wt%, more preferably from 3 wt% to 15 wt%.

In the present invention, the use temperature of the etching liquid at the time of etching is preferable. When the temperature is less than 20 ° C, the etching rate is slow, and it is not practical to measure the concentration of the etching liquid or the etching liquid due to evaporation of water or hydrochloric acid. A preferred J spoon is preferred. The angle formed outside the four ranges of the mixed solution may not reach the ratio (A ' : 14 , and (the domain is better; this: (A " ) 6 : , and (D ") is the most suitable *, the specific gravity 1.4 0 18 It is possible to use, for example, '40% by weight is not a practical one. It is ί for 20~50°C; 25~45t -17- (14) (14) 1375099 for more than 50% concentration, more preferably 30 ~45 ° C. In the photoresist solution, it is better to use an aqueous solution of tetramethylammonium hydroxide (TMAH). When using an alkali component other than TMAH, the pattern of the photoresist pattern is caused to be uneven or dissolved. There is a fear of a major failure. In addition, when the AI is electrically connected to the transparent conductive film, it may cause a reaction when it comes into contact with the electrolyte solution. It is necessary to pay attention to it. The concentration of TMAH is preferably 1 to 5 wt%. When it is less than 1 wt%, there is a case where the photo-resistance is poor, and the formed transparent electrode is easily short-circuited. Further, when it exceeds 5 wt%, the photoresist pattern is thinned or peeled off, and the electrode pattern is formed. In the case of wire shrinkage or wire breakage, it is preferably 2 to 4 wt%. Photoresist stripper to use ethanolamine The amine is preferred. The ethanolamine amine is monoethanolamine, diethanolamine or triethanolamine, and it is suitable to use diethanolamine. Alternatively, an aqueous solution or a mixture with a polar solvent may be used. Such a polar solvent is DMF or DMSO. , NMP, etc. In the photoresist stripping solution, the concentration of the ethanolamine amine is preferably 10 wt% to 60 wt%, more preferably 20 wt% to 40 wt%. Further, when an inorganic base such as NaOH or KOH is used as the stripping solution, the electrode The surface is dissolved to be uneven, and is not suitable. The carrier mobility of the transparent electrode thus formed is preferably 10 cm 2 /V · SEC or more, more preferably 20 cm 2 /V · SEC or more. When the temperature is 10 cm2/V· SEC, the response speed is slowed down, and the picture quality of the liquid crystal is lowered. The lower the specific resistance, the better the distance from the TFT element to the end of the LCD drive electrode in the case of TFT driving. For short reasons, it is preferably 1 (Γ2 Ω <: ιη). -18- (15) 1375099 Also, the carrier mobility is measured by a through-hole measurement method (Vander). In the transparent electrode of the present invention, Adding a third gold without affecting carrier mobility The third metal is, for example, a metal oxide having a small transmittance to increase the transmittance. Such representative examples are MgO, B2〇3, Ge02, etc. Further, in order to reduce the specific resistance of the transparent electrode, a specific resistance may be added. Representative examples of such compounds are cerium oxide, cerium oxide, cerium oxide, and the like, and the heavy metal oxides may be colored, and the amount added is preferably added in a range that does not affect the light transmittance. [Examples] The present invention will be described in more detail with reference to the following examples: <Preparation of a sputtering target and a substrate with a transparent conductive film> [Production Example 1] (1) Preparation of a sputtering target to have an average particle diameter The following zinc oxide powder (manufactured by Shiraishi Seiki Co., Ltd.) and tin oxide powder (manufactured by Kogyo Co., Ltd.) having an average particle diameter of 1/m or less are blended according to the line of B/11/(211 + 511) = 0.79 (atomic ratio). It was placed in a resin can, and then pure water was added, and it was mixed by a wet ball mill using a Zr02 ball mill. The mixing time was 20 hours. The resulting mixed slurry was taken out, filtered, dried and granulated. • The wave method can be refracted by 'G a 2 〇 3 small oxygen. However, it is necessary to pay attention to the technical use of Mitsubishi. Proportion of hard -19- (16) (16) 1375099 This granulated product is formed by a cool hydraulic compressor applying a pressure of 294 MPa (3 t/cm 2 ). This molded product was sintered as follows. In the sintering furnace, sintering was carried out at 1500 ° C for 5 hours in a gas atmosphere in which the internal volume of each furnace was 0 L3 to 5 L/min. At this time, the temperature was raised to 1 °C /min up to 1000 °C, and i〇〇〇~1 500 °c was heated at 3 °c /min. Thereafter, the introduction of oxygen was stopped, and 1500 to 1300 eC was taken at 1 Torr. (: /min is cooled. In addition, it is kept at 1 300 ° C for 3 hours in a gas atmosphere in which argon gas is introduced at a ratio of 10 L/min per furnace, and then allowed to cool. Zinc oxide/tin oxide sinter with a density of more than 90%. The sputtered surface of the obtained sinter is honed by a cup-type grindstone, and processed into a back plate having a diameter of 100 mm and a thickness of 5 mm and bonded with an indium alloy to be sputtered. Target (sinter target 1). The density of this target is 5.72g/cm3. Also, it is preferable to disperse tin oxide in the target, especially to replace the zinc side which is dissolved in zinc oxide. The form of S η contained therein may be in the form of a dispersion of tin oxide such as SnO 2 or SnO, and may be dispersed in zinc oxide by a composite oxide of zinc oxide-tin oxide such as ZnSn03 or Zn2S η 04. The form of Sn is more preferably dispersed in the zinc oxide by atomic grade, and the discharge is stably discharged during sputtering, so that the obtained transparent conductive film becomes low in electrical resistance. Spectral image processing of Sn atoms by ray microanalysis, and the average grain diameter is 3_87 // m. In addition, the overall resistance (specific resistance) of the target 1 is 3 60 Ω cm, which is the target for stable RF sputtering. -20- (17) 1375099 The properties of the sintered target are shown in Table 1. f Table 1 ] Zn/(Zn + Sn) density grain average particle diameter specific resistance [atomic ratio] [g/cm3] [^ m] [Ω cm] Manufacturing Example 1 0.79 5.72 3.87 360 Manufacturing Example 2 0.75 5.86 3.32 350 Manufacturing Example 3 0.70 5.83 3.4 370 Manufacturing Example 4 0.67 5.92 3.5 420 Manufacturing Example 5 0.55 6.10 480 Manufacturing Example 6 0.97 5.42 280 Manufacturing Example 7 0.40 6.34 • 4400

(2) Production of Transparent Conductive Film The sintered target 1 was mounted on a sputtering apparatus. The glass substrate (thickness 1 mm or 1.1 mm) was moved into the apparatus to reach a degree of vacuum: 5 x l 〇 "Pa, film formation pressure: 0.1 Pa, substrate temperature: 200 t, and a transparent conductive film (thickness 100 nm) was formed on the substrate. Film formation. The ratio of the atom of the transparent conductive film [Zn/(Zn + Sn)], the specific resistance, the carrier mobility, and the light transmittance were evaluated. Also, the specific resistance and the carrier (charge) mobility were measured by through holes. In addition, the light transmittance is measured by a spectrophotometer with respect to a light having a wavelength of 50 nm. Further, the ratio of atoms [Zn/(Zn + Sn), atomic ratio] is determined by ICP (high frequency induction combined with electricity). Pulp) analysis method - 21 - (18) 1375099 The measurement results are shown in Table 2. [Table 2]

Zn/(Zn + Sn) specific resistance charge mobility transmittance [atomic ratio] [Ω cm] [cm2/V.sec] m Manufacturing Example 1 0.79 0.25 25 87.8 Manufacturing Example 2 0.75 0.04 45 86.3 Manufacturing Example 3 0.70 0.009 48 86.5 Production Example 4 0.67 0.006 46 86.3 Production Example 5 0.55 0.03 3 5 85.9 Production Example 6 0.97 0.86 15 79.8 Manufacturing Example 7 0.40 0.08 8 78.8 Light transmittance · 'wavelength of wavelength 55 0 nm. [Production Example 2-7] In addition to the use of zinc oxide powder having an average particle diameter of at most and tin oxide powder having an average particle diameter of the following as a raw material powder, zinc atoms and tin atoms were prepared as shown in Table 1, and were produced. In the same manner as in Example 1, a sputtering target (sinter target 2 to 7) was formed, and a substrate on which a transparent conductive film was formed was produced. Also, the sputtering target has a diameter of 152 mm and a thickness of 5 mm. The evaluation results of the properties of the sputter target and the transparent conductive film are shown in Table 丨 and Table 2. -22- (19) 1375099 <Production of Transparent Electrode> [Experimental Example 1] A photoresist solution was used on the permeation film of the transparent conductive film substrate prepared in Production Example 1 (HPR204 manufactured by Fujitsu Hahndo Co., Ltd.) A photoresist film is formed by spin coating. Next, a photoresist film and development image are applied using a photomask of a predetermined pattern. An aqueous solution of tetramethylammonium hydroxide (TM AM) is used as a developing solution. The substrate was etched with an aqueous solution of an etching solution of oxalic acid to etch the transparent conductive film to pattern the transparent electrode. The condition was that the concentration of the aqueous oxalic acid solution was 3.5 wt%, and the temperature was etched by immersion. The etching rate of this condition was also evaluated. The temperature at which the aqueous oxalic acid solution was used was 40 ° C, the concentration of the diacid aqueous solution was 5.0 wt%, and the use temperature was 35 t. The results are shown in Table 3. Finally, two were used. A solution of ethanolamine in DMSO (3 〇Wt%) was used to remove the photoresist film remaining on the transparent electrode. At this time, the strip was immersed for 1 minute at 40 Å: by forming a transparent electrode as described above (width 90 m 110# m) Substrate by SEM observation The cone of the electrode end of the transparent electrode was measured. The results are shown in Table 3. The conductivity is 440 wt%, and the temperature is 30 ° C ' at this time, and the etching of B is the peeling member, and the spacing Angle, • 23- (20) 1375099 [Table 3] Etching speed of the substrate with a transparent conductive film [A / min] (The following column: concentration of oxalic acid aqueous solution and temperature of use) Cone angle [degrees] 3.5 Wt % 3 0 ° C 3.5 wt % 4 0 ° C 5. Owt % 3 5 〇 C Example 1 Manufacturing Example 1 105,000 220,000 180,000 86 Example 2 Manufacturing Example 2 65,000 132,000 96,000 75 Example 3 Manufacturing Example 3 500 1,100 950 48 Example 4 Production Example 4 30 7 1 55 42 Example 5 Production Example 5 10 25 22 38 Comparative Example 1 Production Example 6 3,560,000 7, 210,000 6,800,000 134 Comparative Example 2 Production Example 7 • • - • * Tapered horn oxalic acid The concentration of the aqueous solution was 3.5 wt%, and the angle at which the temperature was 30 ° C was used. * Comparative Example 2 could not be etched. [Examples 2 to 5 'Comparative Examples 1 to 2> A transparent electrode substrate was produced and evaluated in the same manner as in Example 1 except that the transparent conductive film substrate produced in Production Examples 2 to 7 was used. The results are shown in Table 3. [Example 6] On a transparent conductive-24-(21) 1375099 film with a transparent conductive film substrate prepared in Production Example 1, a photoresist (HPR 204 manufactured by Fujitsu Honda Co., Ltd.) was used by spin coating. The cloth forms a photoresist film. Next, exposure/development of the photoresist film is performed using a photoresist mask of a predetermined pattern. As the developing solution, a 2.8 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) was used. Next, the substrate is treated with a mixed solution of nitric acid:hydrochloric acid:water of an etching solution (nitric acid:hydrochloric acid:water=25:1 3:62) to etch a transparent conductive film to pattern the transparent electrode. . This liquid was used at a temperature of 30 ° C and was etched by dipping. Evaluate the etch rate under these conditions. Further, it is also evaluated that the etching liquid is used at a temperature of 40 ° C, and a mixed solution of nitric acid, hydrochloric acid, and water (nitric acid: hydrochloric acid: water = 25:25:50), and etching at a temperature of 35 ° C is used. speed. The results are shown in Table 4. Finally, a DMSO solution (30 wt%) of diethanolamine was used as a stripping solution to remove the photoresist film remaining on the transparent electrode. The condition at this time was that φ was immersed at 4 ° C for 1 minute. A substrate on which a transparent electrode (width: 90 // m, pitch: I 1 0 /z m ) was formed as described above. The taper angle of the electrode end portion of the obtained transparent electrode was observed by SEM, and measurement was performed. The results are shown in Table 4. -25- (23) (23)

1375099 Secondly, use a photoresist mask of the specified pattern to perform a photoresist film. As the developing solution, an aqueous solution of tetramethylammonium hydroxide (TMAH) was used. Next, the substrate was subjected to uranium engraving of a transparent conductive film by treatment with hydrochloric acid (35 wt% aqueous solution) as an etching solution, and the electrode was patterned. The conditions at this time were by dipping at a temperature of 30 ° C. The etching rate under this condition was evaluated. Further, the use temperature of the aqueous hydrochloric acid solution was also evaluated to be 40 ° C. The concentration of the aqueous hydroiodic acid solution was 5 wt%, and the use temperature was 35 t. The results are shown in Table 5. The photoresist film remaining on the transparent electrode was removed using a solution of diethanolamine in DMSO (30 wt%). The conditions were then immersed for 1 minute at 4 ° C. The transparent electrode was formed as described above (width 90 μm) The substrate of 110/zm) was measured by SEM observation of the taper of the electrode end of the obtained transparent electrode. The results are shown in Table 5. Exposure of 2.8 wt% of HC1) When etching was performed transparently, and etching was performed as peeling, 、, pitch angle, -27- (27) 1375099 degrees: 5xl (T4Pa, film formation pressure: O.lPa' substrate temperature: room temperature, A1 film (thickness 200 n) was formed on a glass substrate. Make the area of the obtained glass substrate into a cappuccino tape The coatings 1 to 7 were prepared by using Production Examples 1 to 7, and a film having a thickness of 100 nm was formed on the substrate at room temperature. Thereafter, the Kabutong tape was peeled off to form a partial film of the gossip film. A glass substrate with a laminated film. Further, as a reference, a glass substrate having an additional laminated film of an ITO film formed on the A1 film is also prepared. The glass substrate with the laminated film is dipped. The dissolution of the AI film was observed for 2 minutes in a 24.0 wt% aqueous solution (20 ° C) of TMAH. The results are shown in Table 9. [Table 9] Change of laminated structure film A1 film / Transparent conductive film of Production Example 1 The transparent conductive film of the A1 film/manufacturing example 2 was not changed. The transparent conductive film of the A1 film/manufacturing example 3 was not changed. The AI film was not changed. The transparent conductive film of the example 4 was not changed. The transparent conductive film of the A1 film/manufacturing example 5 was not Change A] Film / Production Example 6 Transparent Electroconductive Film Dissolved Conductive Film Dissolved A1 Film / Production Example 7 Transparent Conductive Film Produced Conductive Film Coloring Reference Example: AI Film / ITO Film A1 Film Completely Dissolved

Further, the glass substrate on which only the pure A] film was formed was immersed in the aqueous solution -31 · (28) (28) 1375099, and the dissolution of the A1 layer was not observed. Therefore, the dissolution of A1 was observed in this evaluation, and it was confirmed that the battery reaction was caused by the laminated structure of the A1/transparent conductive film. <Evaluation 3 > The 100 nm-attached film-coated glass obtained in Production Example 1 was placed in a mixture of 3 vol% of diethanolamine and 70 vol% of dimethyl argon (DMSO) of a photoresist stripper, and 10% by volume was added. The water was immersed at 45 ° C for 5 minutes. Thereafter, the surface of the film was observed by a scanning electron microscope (SEM). As a result, no irregularities and no clutter on the surface were observed. On the other hand, as a result of the same operation, the film of the 〇〇nm-attached film obtained in the production example 6 was observed, and irregularities and surface disorder were observed on the surface of the film, and it was confirmed that it was not suitable as an electrode for liquid crystal or organic EL. . <Evaluation 4> The glass substrate was laminated using the transparent conductive film of the manufacturing examples 1 to 7 and the substrate of the AI film, and the transparent conductive film and the A film were each formed into a thin line having a line width of 5 〇 #m. The conductive thin wires are orthogonal (the intersection of the thin wires is in a laminated state). The contact resistance of the laminated interface is measured by the Kelvin probe method. The results are shown in Table 1. -32. (29) 1375099 [Table 10] Laminated structure contact resistance 値 (Ω) A1 film / system ί 0 Η Example 1 transparent conductive film 0.4 AJ film / system Du 2 Ξ. Example 2 transparent conductive film 0 .6 A1 film/manufacturing 'αε ε Example 3 transparent conductive film 0.7 A1 film / system, the transparent conductive film of the example 4 0.8 A1 film / transparent conductive film of the example 5 A1 film / system, 'example 6 transparent conductive film 0 4 A1 film / transparent conductive film of the example 7 2 Reference example: AI film / ITO film 130

[Industrial Applicability] The transparent electrode of the present invention is inexpensive because it does not use indium. Further, the stagnation characteristics are good, and the electrode end portion can be formed into a tapered shape. Therefore, it is suitable as a transparent electrode used in a thin display such as a liquid crystal display device, an organic electroluminescence display device, or a plasma display. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view of a transparent electrode. Fig. 2 is a view showing a manufacturing step of the transparent electrode of the present invention. Fig. 3 is a view showing the composition of a suitable mixture of nitric acid: hydrochloric acid: water in the present invention. 4 is a view showing an example of a TFT substrate. -33- (30) 1375099 [Description of Symbols of Main Components] (X: Tapered Angle 1 0 : Substrate 1 1 : Transparent Electrode 1 1 ': Transparent Conductive Film 1 2 : Photoresist Film

2 1 : Translucent glass substrate 2 2 : Gate electrode pattern 2 3 : S i N gate insulating film 24 : α-Si : H ( i ) Film 25 : Channel protective film 26 : a-Si : Η ( η ) Membrane 27: power supply electrode pattern 28: electric leakage electrode pattern 29: pixel electrode pattern 30: protective film - 34

Claims (1)

1375099 Patent application No. 095100652 Patent application for amendment of the scope of patent application in the Republic of China, July 30, 2003. Amendment 10. Patent application scope 1. A transparent electrode containing no indium, characterized by zinc oxide and tin oxide as main components. In the total amount of zinc atoms and tin atoms, the ratio of zinc atoms [Zn/(Zn + Sn), atomic ratio] is 0.5 to 0.9, and the taper angle at the end of the electrode is 30 to 89 degrees. Φ 2. A method for producing a transparent electrode for etching a tapered corner of an electrode end to 30 to 89 degrees, which comprises: forming a ratio of zinc atoms relative to the total amount of zinc atoms and tin atoms [Zn/ ( Zn + Sn), atomic ratio is 0.5 to 0.9, a first step of a transparent conductive film containing zinc oxide and tin oxide as a main component and containing no indium, and a second step of forming a photoresist film on the transparent conductive film And using a 1~5 wt% aqueous solution of tetramethylammonium hydroxide as a photoresist development liquid, wherein the temperature of the aqueous solution is in the range of 20 to 50 ° C, and the photoresist film is patterned into a third shape. And a fourth step of forming a transparent electrode having a cone angle of 30 to 8 9 degrees by using an aqueous solution having a concentration of hydrohalic acid of 1 wt% to 40 wt%/D to cause the transparent conductive film to be etched* And a fifth step of peeling off the photoresist film remaining on the transparent electrode using a photoresist stripping solution containing ethanolamine. 3. The method for producing a transparent electrode according to claim 2, which comprises: forming a ratio of zinc atoms of 1375099 f /' with respect to the total amount of zinc atoms and tin atoms. /year? The step of repairing the transparent conductive film containing zinc oxide and tin oxide as the main component of the Zn [(Zn + Sn), atomic ratio] of 0.5 to 0.85, and using the oxalic acid concentration of 1 wt% The aqueous solution of ~10 wt% is used as the contact liquid, and the transparent conductive film is etched in the range of the etching liquid temperature of 20 to 50 ° C, and the step of patterning is performed. 4. As claimed in the second or third patent scope The method for producing a transparent electrode, comprising: a first step of forming a transparent conductive film containing zinc oxide and tin oxide as a main component, and a second step of forming a photoresist film on the transparent conductive film a third step of patterning the photoresist film and a fourth step of etching the transparent conductive film by using a mixed solution of nitric acid, hydrochloric acid and water to form a transparent electrode having a taper angle of 30 to 89 degrees, and The fifth step of peeling off the photoresist film remaining on the transparent electrode. 5. The method for producing a transparent electrode according to item 4 of the patent application, wherein the composition of the mixed solution is a ratio of nitric acid:hydrochloric acid:water in a triangular coordinate indicating a ratio of nitric acid:hydrochloric acid:water (volume ratio) (volume ratio), a quadrangle surrounded by (A) 2 : 2 : 96, ( B ) 2 : 2 : 96 ' ( C ) 78 : 2 : 2〇 , and (D ) 78 : 20 : 2 In the region, the method for producing a transparent electrode according to the fourth aspect of the patent application, wherein the temperature of the mixed solution of nitric acid:hydrochloric acid:water in the fourth step is 2〇~5 0〇c. The method for manufacturing a transparent electrode according to the fourth aspect of the invention, wherein the photoresist solution used in the third step is a 1~5 wt% aqueous solution of tetramethylammonium hydroxide, which is used in the fifth step. The photoresist stripping solution contains ethanolamine.