JP2013101790A - Manufacturing method of a substrate with a transparent conductive oxide film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide method to suitably manufacture a substrate with a transparent conductive oxide film whose maximum surface roughness (Rpv) is small.SOLUTION: A transparent conductive oxide film is formed on a substrate. A treatment process of scrubbing is performed while supplying alkaline solution or an acid solution without containing a polishing agent on the surface of the transparent conductive oxide film.

Description

  The present invention relates to a method for producing a substrate with a transparent conductive oxide film.

  Conventionally, transparent electrodes having translucency have been used for various elements such as organic EL elements. It is known that the transparent electrode can be composed of a transparent conductive oxide such as indium tin oxide (ITO), for example.

  For example, in an organic EL element, if there is a protrusion on the surface of the ITO film constituting the anode, the distance between the anode and the cathode in the portion where the protrusion is present becomes short, and a leak current is likely to occur. There's a problem.

  In view of such a problem, Patent Document 1 proposes that the maximum height (Rmax) of the surface roughness of the surface to be bonded to the organic film of the anode of the organic EL element is 50 mm or less. In Patent Document 1, as the method for setting the maximum surface roughness (Rmax) of the surface of the anode of the organic EL element to 50 mm or less, the surface of the ITO film formed by sputtering or electron beam method is polished, A method of polishing by a technique such as lapping or tape wrapping is described.

Japanese Patent Laid-Open No. 9-245965

  However, when the surface of the ITO film is polished with an abrasive, there is a problem that the surface of the ITO film is damaged. There is also a problem that it takes a long time to reduce the maximum height (Rmax) of the surface roughness by polishing the surface of the ITO film with an abrasive.

  The main object of the present invention is to provide a method capable of suitably producing a substrate with a transparent conductive oxide film having a small surface maximum roughness (Rpv) on the surface of the transparent conductive oxide film.

  In the method for producing a substrate with a transparent conductive oxide film according to the present invention, a transparent conductive oxide film is formed on the substrate. A processing step of rubbing while supplying an acidic solution or an alkaline solution containing no abrasive to the surface of the transparent conductive oxide film is performed.

  In the treatment step, it is preferable to rub the surface of the transparent conductive oxide film with a resin porous body impregnated with an acidic solution or an alkaline solution.

  The resin porous body is preferably made of polyolefin, more preferably polyethylene.

  The porosity of the resin porous body is preferably 30% by volume to 95% by volume.

  In the treatment step, it is preferable to rub the surface of the transparent conductive oxide film with a porous resin body in a state where the transparent conductive oxide film is immersed in an acidic solution or an alkaline solution.

  As the acidic solution, an aqueous hydrochloric acid solution is preferably used, and an aqueous potassium hydroxide solution is preferably used as the alkaline solution.

  The transparent conductive oxide film is preferably made of an oxide containing at least one of tin and zinc.

  The transparent conductive oxide film is preferably formed by a sputtering method, a vacuum evaporation method, or a CVD method.

  ADVANTAGE OF THE INVENTION According to this invention, the method which can manufacture suitably the board | substrate with a transparent conductive oxide film with small surface maximum roughness (Rpv) of the surface of a transparent conductive oxide film can be provided.

  Hereinafter, an example of the preferable form which implemented this invention is demonstrated. However, the following embodiment is merely an example. The present invention is not limited to the following embodiments.

  This embodiment demonstrates the manufacturing method of the board | substrate with a transparent conductive oxide film used for an organic EL element etc.

  First, a transparent conductive oxide film is formed on a substrate. The kind of board | substrate is not specifically limited. As the substrate, for example, a glass substrate, a plastic substrate, or the like can be used. The glass substrate includes a crystallized glass substrate.

  The transparent conductive oxide film can be made of an oxide containing at least one of tin and zinc, for example. Specific examples of the oxide containing at least one of tin and zinc include indium tin oxide (ITO), indium zinc oxide (IZO), aluminum zinc oxide (AZO), and the like.

  Examples of the method for forming the transparent conductive oxide film include a sputtering method, a vacuum deposition method, and a CVD method.

  The thickness of the transparent conductive oxide film is not particularly limited, and can be, for example, about 50 nm to 200 nm.

  When the transparent conductive oxide film is formed by sputtering or the like, protrusions are formed on the surface of the transparent conductive oxide film. Therefore, next, a processing step is performed to remove the protrusions of the transparent conductive oxide film.

  Specifically, in the treatment step, rubbing while supplying an acidic solution or an alkaline solution containing no abrasive to the surface of the transparent conductive oxide film. By doing so, the protrusions can be efficiently removed without damaging the surface of the transparent conductive oxide film. Therefore, according to the method for manufacturing a substrate with a transparent conductive oxide film of this embodiment, a substrate with a transparent conductive oxide film having a small surface maximum roughness (Rpv) on the surface of the transparent conductive oxide film is preferably used. Can be manufactured.

  In the present invention, the maximum surface roughness (Rpv) is the difference between the maximum peak height (Rp) and the maximum valley depth (Rv) in the roughness curve defined by JISB0601: 2001.

  For example, it is conceivable to remove the protrusions only by supplying an acidic solution or an alkaline solution to the surface of the transparent conductive oxide film without rubbing. In this case, the surface of the transparent conductive oxide film is not damaged. However, it takes a long time to remove the protrusions. On the other hand, as in this embodiment, the surface of the transparent conductive oxide film is rubbed without damaging the surface of the transparent conductive oxide film by rubbing while supplying an acidic or alkaline solution containing no abrasive to the surface of the transparent conductive oxide film. The protrusion can be removed during the time.

  Although the member which rubs a transparent conductive oxide film is not specifically limited, For example, a resin-made porous body is used preferably. Among these, a resin porous body made of polyolefin, and a resin porous body made of polyethylene are more preferably used. The porosity of the resin porous body is preferably 30% by volume to 95% by volume, and more preferably 60% by volume to 80% by volume. By impregnating these resin porous bodies with an acidic or alkaline solution and rubbing the surface of the transparent conductive oxide film, the protrusions can be removed more efficiently without damaging the surface of the transparent conductive oxide film. can do.

  In the treatment step, it is more preferable to rub the surface of the transparent conductive oxide film with a porous resin body in a state where the transparent conductive oxide film is immersed in an acidic solution or an alkaline solution. By doing so, a new acidic solution or alkaline solution can be efficiently supplied to the surface of the transparent conductive oxide film during rubbing. Therefore, the protrusion removal efficiency can be further increased.

  The kind of acidic solution is not particularly limited. As the acidic solution, a hydrochloric acid aqueous solution, a nitric acid aqueous solution, a sulfuric acid aqueous solution or the like is preferably used. Among these, a hydrochloric acid aqueous solution, particularly a dilute hydrochloric acid aqueous solution is more preferably used.

  The concentration of the acidic solution is preferably 0.5 N to 12 N, and more preferably 0.5 N to 1 N.

  The kind of alkaline solution is not particularly limited. As the alkaline solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution or the like is preferably used. Of these, an aqueous potassium hydroxide solution is more preferably used.

  The concentration of the alkaline solution is preferably 0.1 N to 1 N, and more preferably 0.1 N to 0.5 N.

  Hereinafter, the present invention will be described in more detail on the basis of specific examples. However, the present invention is not limited to the following examples, and may be appropriately modified and implemented without departing from the scope of the present invention. Is possible.

Example 1
An ITO film having a thickness of 150 nm was formed on a glass substrate made of non-alkali glass OA-10 manufactured by Nippon Electric Glass Co., Ltd. by a sputtering method. When the surface maximum roughness (Rpv) of the surface of the formed ITO film was measured using AFM, it was 31 nm in a measurement range of 10 μm square.

  Next, using a polyethylene porous body having a porosity of 60% by volume fixed to a vinyl chloride pipe having an outer shape of 40 mm, an ITO film immersed in a 1N dilute hydrochloric acid aqueous solution is applied in one direction. And then 70 times along another direction perpendicular to one direction. The time required for this process was approximately 240 seconds. Then, when the surface maximum roughness (Rpv) of the surface of the ITO film was measured again using AFM, it was 11 nm.

(Comparative Example 1)
An ITO film produced in the same manner as in Example 1 was immersed in a 1N dilute hydrochloric acid solution for 360 seconds and was not rubbed. Then, when the surface maximum roughness (Rpv) of the surface of the ITO film was measured again using AFM, it was 35 nm.

(Example 2)
The surface of the ITO film was rubbed in the same manner as in Example 1 except that a 0.5 N KOH aqueous solution was used instead of the 1 N dilute hydrochloric acid aqueous solution. Then, when the surface maximum roughness (Rpv) of the surface of the ITO film was measured again using AFM, it was 22 nm.

  From the above results, it can be seen that protrusions can be efficiently removed by rubbing while supplying an acidic solution or an alkaline solution to the surface of the ITO film.

(Example 3)
The surface of the ITO film was rubbed in the same manner as in Example 1 except that a porous body made of polyvinyl alcohol having a porosity of 90% by volume was used instead of the porous body made of polyethylene. Then, when the surface maximum roughness (Rpv) of the surface of the ITO film was measured again using AFM, it was 17 nm.

Example 4
The surface of the ITO film was rubbed in the same manner as in Example 1 except that a polyurethane porous body having a porosity of 83% by volume was used instead of the polyethylene porous body. Then, when the surface maximum roughness (Rpv) of the surface of the ITO film was measured again using AFM, it was 15 nm.

  From the results of Examples 1 to 4, it can be seen that the protrusions can be more efficiently removed by using the polyethylene porous body.

Claims (10)

Forming a transparent conductive oxide film on the substrate;
A treatment step of rubbing while supplying an acidic solution or an alkaline solution containing no abrasive to the surface of the transparent conductive oxide film;
A method for producing a substrate with a transparent conductive oxide film.   2. The production of a substrate with a transparent conductive oxide film according to claim 1, wherein in the treatment step, a surface of the transparent conductive oxide film is rubbed with a porous resin body impregnated with the acidic solution or the alkaline solution. Method.   The manufacturing method of the board | substrate with a transparent conductive oxide film of Claim 2 with which the said resin-made porous bodies consist of polyolefin.   The manufacturing method of the board | substrate with a transparent conductive oxide film of Claim 3 with which the said resin-made porous bodies consist of polyethylene.   The manufacturing method of the board | substrate with a transparent conductive oxide film as described in any one of Claims 2-4 whose porosity of the said resin porous body is 30 volume%-95 volume%.   In the treatment step, the surface of the transparent conductive oxide film is rubbed with the porous resin body in a state where the transparent conductive oxide film is immersed in the acidic solution or the alkaline solution. 6. The method for producing a substrate with a transparent conductive oxide film according to any one of 5 above.   The manufacturing method of the board | substrate with a transparent conductive oxide film as described in any one of Claims 1-6 which uses hydrochloric acid aqueous solution as the said acidic solution.   The manufacturing method of the board | substrate with a transparent conductive oxide film as described in any one of Claims 1-6 which uses potassium hydroxide aqueous solution as the said alkaline solution.   The said transparent conductive oxide film is a manufacturing method of the board | substrate with a transparent conductive oxide film as described in any one of Claims 1-8 which consists of an oxide containing at least one of tin and zinc.   The manufacturing method of the board | substrate with a transparent conductive oxide film as described in any one of Claims 1-9 which forms the said transparent conductive oxide film by sputtering method, a vacuum evaporation method, or CVD method.