JP4966751B2 - Method and apparatus for removing conductive metal oxide thin film - Google Patents

Description

  The present invention relates to a method for removing a conductive metal oxide thin film formed on a substrate by, for example, sputter deposition so that it can be reused, and an apparatus for carrying out the method.

  For example, a high-performance glass substrate on which ITO (a film having transparent conductivity with an oxide of indium and tin) is excellent in optical performance (such as transmittance) and mechanical performance (such as flatness). Used for flat panel displays. However, since this high-performance glass substrate is expensive, when the ITO formed on the surface does not satisfy the quality control standard, the ITO is removed and reused to reduce the cost.

  As a method of removing the conductive metal oxide thin film such as ITO, there are a method of removing by mechanical abrasion and a method of removing by chemical etching. Among these, the former method is to remove the conductive metal oxide thin film 1 a formed on the surface of the workpiece 1 by rubbing with a polishing brush 2 as shown in FIG. 7.

In the latter method, as shown in FIG. 8, the conductive metal formed on the surface of the workpiece 1 is immersed in a chemical solution 3 for chemically dissolving the conductive metal oxide thin film 1a. The oxide thin film 1a is removed (for example, Patent Documents 1 and 2).
JP-A-6-321581 JP-A-9-86968

  However, since the method of removing by mechanical rubbing rubs the polishing brush, there are cases where rubbing marks (wrinkles) and stress deformation occur on the surface of the workpiece. When scratch marks are generated, it becomes impossible to reuse the glass substrate as it is. Moreover, when the object to be processed is a flat panel display, the glass thickness of the glass substrate is about 0.5 mm. Therefore, delicate pressure adjustment of the brush is necessary, and it takes a long time to completely peel off.

  On the other hand, the method of removing by chemical etching uses a strong acid or strong alkali chemical solution, so that chemical stress is generated on the surface of the substrate and an altered layer may be formed on the surface of the substrate. In addition, it is necessary to pay sufficient attention to handling, not only the workability is deteriorated, but also the electrolytic solution after use needs to be treated as a waste solution. Also, the collection of rare metals is very uneconomical because it requires a separate extraction operation.

  The problem to be solved by the present invention is that the method by mechanical abrasion causes scratch marks and stress deformation, and the substrate cannot be reused, and fine pressure adjustment of the brush is necessary, and a long time is required for complete peeling. It is necessary. On the other hand, the chemical etching method may cause a deteriorated layer on the surface of the substrate, and the workability is deteriorated. In addition, the used electrolytic solution needs to be treated as a waste solution, and is separately extracted for collecting rare metals. The work is necessary and uneconomical.

The method for removing the conductive metal oxide thin film of the present invention comprises:
In order to efficiently remove the conductive metal oxide thin film over almost the entire area without requiring precise position control,
In order to face the conductive metal oxide thin film formed on the surface of the base material, a positive electrode and a negative electrode are arranged in this order with an insulator interposed in the relative movement direction with respect to the base material. In contact with the conductive metal oxide thin film on the substrate surface,
And in the state which made electrolyte solution interpose between the said positive electrode and a negative electrode, and the electroconductive metal oxide thin film of the base-material surface, a voltage is applied to the said positive electrode and a negative electrode, The said positive electrode and a negative electrode, In the method for removing a conductive metal oxide thin film by removing the conductive metal oxide thin film on the surface of the base material by a reduction reaction by relatively moving the base material,
Forming the positive electrode with a porous body;
By supplying the electrolyte solution in a direction opposite to the direction from the positive electrode to the negative electrode, bubbles on the substrate surface generated by the reduction reaction are removed, and the positive electrode surface and the electrolyte solution, or the positive electrode surface or The main feature is that air bubbles in the electrolyte are sucked from the back side of the positive electrode.

In the method for removing a conductive metal oxide thin film of the present invention, a negative electrode is brought into contact with the conductive metal oxide on the surface of the base material, thereby converting the surface of the conductive metal oxide immediately below the positive electrode into a negative electrode. Electrolysis of the electrolyte solution between the positive electrode and the positive electrode generates OH ^{− on} the surface of the positive electrode and H ⁺ on the surface of the conductive metal oxide, and the conductive oxide surface is reduced by the generated H ⁺ .

At that time, the generated H ⁺ is flowed on the raw substrate by the electrolytic solution, and the conductive metal oxide thin film to be reduced is partially reduced, thereby inhibiting the conductivity and the conductivity. Metal oxide may not be reduced cleanly.

However, in the present invention, by supplying the electrolyte in the direction opposite to the direction from the positive electrode to the negative electrode, the generated bubbles such as H ⁺ are positively excluded to the substrate side where the reduction has been completed, Since the bubbles on the surface of the positive electrode and the electrolyte are sucked from the back side of the positive electrode, the above problem does not occur.

  In the present invention, instead of forming the positive electrode with a porous body, the positive electrode is formed in a rotatable cylindrical shape, and bubbles on the positive electrode surface and the electrolyte solution, or on the positive electrode surface or the electrolyte solution, Instead of suction from the back side of the electrode, the positive electrode formed in a cylindrical shape may be rotated in a direction opposite to the direction from the positive electrode to the negative electrode. This is the second method for removing a conductive metal oxide thin film of the present invention.

  In the second aspect of the present invention, if the positive electrode formed in the cylindrical shape is formed of a porous body, bubbles or bubbles and electrolyte are sucked from the inside, and the bubbles are attached to the surface of the positive electrode, Small bubbles that do not adhere to the electrode can also be attached to the surface of the positive electrode. This is the third method for removing a conductive metal oxide thin film of the present invention.

  In these methods for removing a conductive metal oxide thin film of the present invention, it is desirable to supply the electrolyte solution in the direction opposite to the direction from the positive electrode to the negative electrode from between the positive electrode and the negative electrode.

The method for removing the conductive metal oxide thin film of the present invention comprises:
Opposite to the conductive metal oxide thin film formed on the surface of the base material, and arranged in order in the direction of relative movement with the base material via an insulator so that only the negative electrode is in contact with the substrate A positive electrode and a negative electrode formed of a porous body;
An electrolytic solution for supplying an electrolytic solution in a direction opposite to the direction from the positive electrode to the negative electrode so that the electrolytic solution is interposed between the positive electrode and the negative electrode and the conductive metal oxide thin film on the surface of the base material. Supply means;
A power source for applying a voltage to the positive electrode and the negative electrode;
Means for relative movement of the positive and negative electrodes and the substrate;
Comprising suction means connected to the positive electrode;
The supplied electrolyte solution removes bubbles on the surface of the base material generated by the reduction reaction, and the suction means causes the positive electrode surface and the electrolyte solution, or the positive electrode surface or the bubbles in the electrolyte solution to be positive. This can be carried out by using the conductive metal oxide thin film removing apparatus of the present invention in which suction is performed from the back side of the electrode.

Moreover, the removal method of the electroconductive metal oxide thin film of 2nd this invention is the following.
Instead of forming the positive electrode with a porous body, it is formed in a rotatable cylindrical shape, and instead of the suction means, a positive electrode rotating means is provided,
Instead of sucking the positive electrode surface and the electrolyte solution, or bubbles in the positive electrode surface or the electrolyte solution from the back side of the positive electrode, by rotating the positive electrode formed in a cylindrical shape, This can be carried out by using the conductive metal oxide thin film removing apparatus according to the second aspect of the present invention, which discharges in the direction opposite to the direction toward the negative electrode.

Moreover, the removal method of the conductive metal oxide thin film of the third aspect of the present invention is as follows.
The electroconductive metal oxide film according to the third aspect of the present invention, wherein the positive electrode constituting the electroconductive metal oxide thin film removing device of the second aspect of the present invention is formed of a porous body, and further provided with suction means connected to the inside of the positive electrode. This can be done by using a metal oxide thin film removal apparatus.

  It is desirable that the electrolytic solution supply means in the conductive metal oxide thin film removing apparatus of the present invention is provided with an electrolytic solution supply nozzle between the positive electrode and the negative electrode.

  In the apparatus for removing a conductive metal oxide thin film of the present invention, when the insulator and the negative electrode are disposed to be inclined with respect to the relative movement direction with respect to the base material, the conductive metal oxide thin film is spread over a wider range. Can be removed.

  In the present invention, the electrolyte solution is supplied in the direction opposite to the direction from the positive electrode to the negative electrode to remove the bubbles on the substrate surface generated by the reduction reaction, so that the installation interval between the positive electrode and the negative electrode is increased. The conductive metal oxide thin film remaining unreduced at the rear end portion of the substrate can be reduced. In addition, the processing speed can be increased.

  In addition, the air in the positive electrode surface and the electrolyte solution is sucked from the back side of the positive electrode or discharged in the direction opposite to the direction from the positive electrode to the negative electrode by rotating the positive electrode. The conductive metal oxide thin film remaining unreduced can be further reduced.

  Further, since no strong acid or strong alkali chemical solution is used, the environmental load can be reduced, and resource cycles such as rare metals such as base materials can be realized, which is economically advantageous.

Hereinafter, the basic principle of the present invention will be described with reference to FIG. 1, and various embodiments will be described in detail with reference to FIGS. 2 to 6 together with the best mode for carrying out the present invention.
The present invention is a processing method that leaves as little wrinkles and stress deformation on a substrate as possible, and a method for removing a conductive metal oxide thin film that does not use strong acid or strong alkali.

  In FIG. 1, 14 is a metal positive electrode having a thickness of about 1 to 20 mm, and 15 is a metal negative electrode having a thickness of about 0.1 to 10 mm. These electrodes 14 and 15 are arranged to face a conductive metal oxide thin film (for example, ITO) 12 formed on the surface of a base material (for example, glass) 11 such as an insulator or a conductive material, and are applied by a DC voltage power supply 16. Has been. Reference numeral 17 denotes an insulator (for example, rubber or resin having a thickness of about 0.2 to 10 mm) installed on the positive electrode 14 side of the negative electrode 15.

Then, a part of the positive electrode 14 and the negative electrode 15 is immersed in the electrolytic solution 13, and the negative electrode 15 is brought into contact with the conductive metal oxide thin film 12 on the surface of the substrate 11. In this way, the surface of the conductive metal oxide thin film 12 located at a distance of 1 to 3 mm immediately below the positive electrode 14 is converted into a negative electrode, and the electrolytic solution 13 between the negative electrode and the positive electrode 14 is electrolyzed. Thus, OH ⁻ is generated on the surface of the positive electrode 14, and H ⁺ is generated on the surface of the conductive metal oxide thin film 12. Then, the surface of the conductive metal oxide thin film 12 is reduced and removed by the generated H ⁺ .

However, in such a removal method, the generated H ⁺ is caused to flow on the raw substrate 11 by the electrolytic solution 13 along with the movement of the substrate 11, and the conductive metal oxide thin film 12 to be reduced is partially removed. Therefore, there is a case where the conductivity is hindered and the conductive metal oxide thin film 12 is not reduced cleanly.

  Therefore, in the present invention, by supplying the electrolytic solution 13 in a direction opposite to the direction from the positive electrode 14 toward the negative electrode 15, the bubbles generated on the surface of the conductive metal oxide thin film 12 by the reduction reaction are It is pushed away to the side where the reduction is completed and actively eliminated.

  As means for supplying the electrolyte solution 13 from the positive electrode 14 in the direction opposite to the negative electrode 15, in the first example shown in FIG. 2, the negative electrode 15 tilted several degrees to several tens of degrees as viewed from the side. A box-shaped electrolyte supply nozzle 18 is installed on the upper surface via an insulator 17, and the electrolyte 13 supplied via a hose 19 flows uniformly below the positive electrode 14.

  By adopting such a configuration, the electrolytic solution 13 supplied from the electrolytic solution supply nozzle 18 flows from the negative electrode 15 toward the positive electrode 14 (the same direction as the movement direction of the base material 11), and the reduction Bubbles generated on the surface of the conductive metal oxide thin film 12 by the reaction are pushed away to the side where the reduction is completed. Therefore, the conductive metal oxide thin film 12 positioned between the negative electrode 15 and the positive electrode 14 is not partially reduced.

  In addition, although the distance of the closest part of the positive electrode 14 and the negative electrode 15 is based also on conditions, such as an applied voltage value, it shall be about 0.5-20 mm.

  Accordingly, the conductive metal oxide thin film 12 remaining unreduced at the rear end portion in the moving direction of the base material 11 is reduced, and the conductive metal oxide thin film 12 can be removed over almost the entire region. At that time, precise position control is not required.

In addition, since the electrolytic solution 13 flows in the same direction as the movement direction of the base material 11, the bubbles generated on the surface of the conductive metal oxide thin film 12 by the reduction reaction are pushed to the side where the reduction is completed. Even if the moving speed of 11 is increased, the H ⁺ is not flowed onto the unreduced substrate 11.

  In addition, in the first example shown in FIG. 2, the positive electrode 14 is formed of a porous body in which punching metal having a large number of holes of, for example, several μm are stacked, and the positive electrode (base) formed by this porous body is formed. The suction device 20 is connected to the back surface of the material 11 in the advancing direction of the material 11 so that the surface of the positive electrode 14 and bubbles in the electrolyte 13 can be sucked. Therefore, the conductive metal oxide thin film 12 remaining unreduced can be further reduced.

  In FIG. 3, the positive electrode 14 is formed in a cylindrical shape. By rotating the positive electrode 14 formed in the cylindrical shape, the surface of the positive electrode 14 and bubbles in the electrolytic solution 13 are actively based. The material 11 is discharged in the traveling direction.

  In this case, the thickness is not particularly limited as long as the shape of the cylindrical positive electrode 14 in the radial direction and the width direction can be kept uniform, but the thickness increases as the thickness increases. .

Further, the outer diameter of the cylindrical positive electrode 14 is not particularly limited, but is preferably about several tens of mm in consideration of the efficiency of removing bubbles and the cost due to the enlargement of the apparatus.
In the example shown in FIG. 3, the distance between the positive electrode 14 and the conductive metal oxide thin film 12 is set to about 1 to 2 mm so that the H ⁺ bubble and the positive electrode 14 can easily contact each other, thereby eliminating the bubble. Can be performed efficiently. Further, since the distance between the positive electrode 14 and the conductive metal oxide thin film 12 is shortened, it becomes easier for electricity to flow, so that it is possible to operate with less power.

  FIG. 4 shows the cylindrical rotatable positive electrode 14 shown in FIG. 3 formed of a porous body, and the inside of the positive electrode 14 and the suction device 20 are connected. In the third example shown in FIG. 4, by sucking bubbles or the electrolyte 13 and the bubbles from the inside, minute bubbles that do not come into contact with the positive electrode 14 can be attached to the surface of the positive electrode 14. Therefore, bubbles can be eliminated more efficiently than the second example shown in FIG.

  In this third example, the object is not to suck bubbles or electrolyte 13 into the positive electrode 14, but to adhere to the surface of the positive electrode 14, so the diameter of the hole is as small as several μm. Good.

  In the second and third examples, although not shown, by pressing the fixed brush against the surface of the rotating positive electrode 14 and removing the foreign matter adhering to the surface of the positive electrode 14 to keep it clean, A good reduction state can always be maintained.

  When bubbles are attached by suction from inside the positive electrode 14 as in the third example, the suction force is adjusted so as not to hinder the reduction and removal of the conductive metal oxide thin film 12 by the positive and negative electrodes 14 and 15. It is necessary.

  In this case, as shown in FIG. 5, if a shielding member 21 that prevents the suction action while the positive electrode 14 is immersed in the electrolytic solution 13 is provided inside the positive electrode 14, this suction trouble may be prevented. It can be easily prevented. The shielding member 21 is configured to keep the position where the positive electrode 14 is immersed in the electrolytic solution 13 regardless of the rotation of the positive electrode 14.

  In the present invention described above, the conductive metal oxide thin film 12 is finely divided (0.1 μm or less) as a metal solid after the electrolytic reduction treatment. Therefore, for example, as shown in FIG. What is necessary is just to peel a metal. In addition, in FIG. 6, what uses together mechanical peeling by the flexible material 23 as assistance is shown.

  After that, the reduced metal removed together with the electrolytic solution 13 is accumulated in the recovery tank 25 via the electrolytic solution collecting pan 24, and microbubbles are mixed by the microbubble generator 26. As a result, the metal bubbles are clustered using the microbubbles as nuclei and can be collected by the filter, and the reduced metal is collected through the filter 27. In addition, 28 in FIG. 6 shows a pump.

As described above, the present invention is a characteristic processing method for applying a negative voltage to a workpiece, not a general electrolytic elution removal reaction for applying a positive voltage to the workpiece, as described above. .
Note that since the electrolytic reaction here may generate H _{2 in} a very small region at the interface of the conductive metal oxide thin film, little current is required.

Accordingly, as the electrolytic solution 13 to be used, a generally used neutral salt solution or a mixture of a neutral salt solution in tap water, river water, or the like can be used. Preferably, the resistivity is 10 ² Ω · Those adjusted from cm to 10 ⁶ Ω · cm, more preferably from 10 ³ Ω · cm to 10 ⁴ Ω · cm are preferable.

That is, the resistivity of the electrolytic solution 13 in the present invention is equal to the resistance value of the electrolytic solution 13 between the positive electrode 14 and the negative electrode 15 and the resistance value between the negative electrode 15 to the conductive metal oxide thin film 12 to the positive electrode 14. The range is from 10 ² Ω · cm in consideration of the type of the conductive metal oxide thin film 12, the height of the positive electrode 14, and the distance between the positive electrode 14 and the negative electrode 15. 10 ⁶ Ω · cm.

When the resistivity of the electrolytic solution 13 is smaller than 10 ² Ω · cm, the conductive metal oxide thin film 12 is not passed through, and the positive electrode 14 and the negative electrode 15 are brought into conduction through the electrolytic solution 13. The reduction of the oxide in the physical thin film 12 hardly occurs. On the other hand, if it is larger than 10 ⁶ Ω · cm, the conductivity is lowered, and unless a high voltage is applied, the oxide cannot be completely reduced, which is economically undesirable.

  Thus, in the present invention, since the electrolytic solution 13 having a relatively high resistivity is suitable, it is possible to use tap water, river water, etc., which is not preferable as the electrolytic solution 13 conventionally, and is economical and safe. Also excellent in terms of sex.

The ITO of the present invention (negative electrode) shown in FIG. 2 described above is formed of ITO having a thickness of 1500 × 10 ⁻¹⁰ m formed on the entire surface of a glass substrate having a thickness of 0.7 mm and a size of 370 mm × 470 mm. : Thickness 0.1 mm, Positive electrode: Thickness 1 mm, Length 1 cm in the traveling direction of the glass substrate, Insulator: Thickness 0.2 mm, Distance at the closest part of the positive electrode and negative electrode: 0.9 mm, Between positive electrode and ITO The distance was removed by the method of the present invention using 1 mm).

  When removing ITO, tap water is used as the electrolyte, a DC voltage of 90 V is applied between the positive electrode and the negative electrode (both electrode widths are 600 mm) (current: 2 A), and the workpiece is processed at 2 m / min. When moved, good results were obtained with no reduction unevenness due to bubbles generated between the positive and negative electrodes.

The area of ITO remaining remains unreduced in the traveling direction back end portion of the glass substrate was reduced to 1.75 mm ² with respect to a conventional 365 mm ^2.

  The ITO on the same glass substrate as in Example 1 is removed by the method of the present invention using the device of the present invention (positive electrode: outer diameter 80 mm, thickness 2 mm, others are the same as in Example 1) shown in FIG. did.

  When removing ITO, tap water is used as the electrolyte, a 60V DC voltage is applied between the positive and negative electrodes (both electrode widths are 600 mm) (current: 2A), and the workpiece is processed at 2 m / min. When moved, good results were obtained with no reduction unevenness due to bubbles generated between the positive and negative electrodes. Moreover, the reduction amount of the area of ITO which remained unreduced in the rear-end part of a glass substrate was the same.

  Needless to say, the embodiments of the present invention may be changed as appropriate within the scope of the technical idea described in each claim.

For example, the suction of H ⁺ bubbles in the first example may be performed not only by providing a suction device but also by applying a negative pressure to the back side of the positive electrode 14.
The box-shaped electrolyte supply nozzle 18 may be provided with a baffle or the like inside the box as necessary so that the flow of the electrolyte 13 is uniform in the width direction.

It is a figure explaining the basic principle of this invention. It is the figure seen from the side in the schematic diagram explaining the 1st example of this invention. It is the figure seen from the side in the schematic diagram explaining the 2nd example of this invention. It is the figure seen from the side in the schematic diagram explaining the 3rd example of this invention. It is the figure seen from the side in the schematic diagram explaining the 4th example of the present invention. It is the figure which showed an example of the collection | recovery apparatus after carrying out the electrolytic reduction process of the electroconductive metal oxide thin film by this invention. It is a figure explaining the method of removing a metal thin film by mechanical abrasion. It is a figure explaining the method of removing a metal thin film by chemical etching.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Base material 12 Conductive metal oxide thin film 13 Electrolyte 14 Positive electrode 15 Negative electrode 16 DC voltage power supply 17 Insulator 18 Electrolyte supply nozzle 20 Suction device

Claims (9)

In order to face the conductive metal oxide thin film formed on the surface of the base material, a positive electrode and a negative electrode are arranged in this order with an insulator interposed in the relative movement direction with respect to the base material. In contact with the conductive metal oxide thin film on the substrate surface,
And in the state which made electrolyte solution interpose between the said positive electrode and a negative electrode, and the electroconductive metal oxide thin film of the base-material surface, a voltage is applied to the said positive electrode and a negative electrode, The said positive electrode and a negative electrode, In the method for removing a conductive metal oxide thin film by removing the conductive metal oxide thin film on the surface of the base material by a reduction reaction by relatively moving the base material,
Forming the positive electrode with a porous body;
By supplying the electrolyte solution in a direction opposite to the direction from the positive electrode to the negative electrode, bubbles on the substrate surface generated by the reduction reaction are removed, and the positive electrode surface and the electrolyte solution, or the positive electrode surface or A method for removing a conductive metal oxide thin film, wherein air bubbles in the electrolyte are sucked from the back side of the positive electrode. Instead of forming the positive electrode with a porous body, it is formed in a rotatable cylindrical shape,
Instead of suctioning the positive electrode surface and the electrolyte solution, or bubbles in the positive electrode surface or the electrolyte solution from the back side of the positive electrode, by rotating the positive electrode, the direction from the positive electrode to the negative electrode and 2. The method for removing a conductive metal oxide thin film according to claim 1, wherein the conductive metal oxide thin film is discharged in the opposite direction.   3. The conductive metal according to claim 2, wherein the cylindrical positive electrode is formed of a porous body, and bubbles or bubbles and an electrolytic solution are sucked from the inside to attach the bubbles to the surface of the positive electrode. Removal method of oxide thin film.   4. The conductive metal oxide according to claim 1, wherein the electrolyte solution is supplied in a direction opposite to the direction from the positive electrode to the negative electrode from between the positive electrode and the negative electrode. 5. Method for removing physical thin film. An apparatus for performing the method for removing a conductive metal oxide thin film according to claim 1,
Opposite to the conductive metal oxide thin film formed on the surface of the base material, and arranged in order in the direction of relative movement with the base material via an insulator so that only the negative electrode is in contact with the substrate A positive electrode and a negative electrode formed of a porous body;
An electrolytic solution for supplying an electrolytic solution in a direction opposite to the direction from the positive electrode to the negative electrode so that the electrolytic solution is interposed between the positive electrode and the negative electrode and the conductive metal oxide thin film on the surface of the base material. Supply means;
A power source for applying a voltage to the positive electrode and the negative electrode;
Means for relative movement of the positive and negative electrodes and the substrate;
Comprising suction means connected to the positive electrode;
The supplied electrolyte solution removes bubbles on the surface of the base material generated by the reduction reaction, and the suction means causes the positive electrode surface and the electrolyte solution, or the positive electrode surface or the bubbles in the electrolyte solution to be positive. An apparatus for removing a conductive metal oxide thin film, wherein suction is performed from the back side of the electrode. Instead of forming the positive electrode with a porous body, it is formed in a rotatable cylindrical shape, and instead of the suction means, a positive electrode rotating means is provided,
Instead of sucking the positive electrode surface and the electrolyte solution, or bubbles in the positive electrode surface or the electrolyte solution from the back side of the positive electrode, by rotating the positive electrode formed in a cylindrical shape, 6. The apparatus for removing a conductive metal oxide thin film according to claim 5, wherein discharge is performed in a direction opposite to the direction toward the negative electrode.   7. The apparatus for removing a conductive metal oxide thin film according to claim 6, further comprising a suction means formed of a porous body and connected to the inside of the positive electrode. An electrolyte supply nozzle is provided between the positive electrode and the negative electrode,
The conductive metal according to claim 5, wherein the electrolyte solution is supplied in a direction opposite to the direction from the positive electrode to the negative electrode by the electrolyte solution supply nozzle. Equipment for removing oxide thin films.   The apparatus for removing a conductive metal oxide thin film according to any one of claims 5 to 8, wherein the insulator and the negative electrode are disposed to be inclined with respect to a relative movement direction with respect to the base material.

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