JP4701072B2 - 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-functional 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. Of these methods, 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. 10.

In the latter method, as shown in FIG. 11, the conductive metal formed on the surface of the workpiece 1 is immersed in a chemical solution 3 that chemically dissolves 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 cannot be reused. 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 problems to be solved by the present invention are that mechanical scratching causes scratch marks and stress deformation, making it impossible to reuse the substrate, and delicate pressure adjustment of the brush is necessary, and complete peeling takes a long time. In the method using chemical etching, a deteriorated layer may be formed on the surface of the substrate, and workability is deteriorated. In addition, it is necessary to dispose the used electrolytic solution as a waste liquid. This requires that a separate extraction operation is required for collection, which is uneconomical.

The method for removing the conductive metal oxide thin film of the present invention comprises:
Without leaving scratch marks or stress deformation on the base material, and without using a strong acid or strong alkali chemical solution, the conductive metal oxide thin film of the base material has no residual film up to the edge of the base material. In order to remove efficiently,
In order to face the conductive metal oxide thin film formed on the surface of the substrate, a plurality of pairs of positive and negative electrodes are alternately arranged,
A voltage is applied to both of the positive electrode and the negative electrode while the electrolyte is interposed between the positive electrode, the negative electrode and the conductive metal oxide thin film , and the positive electrode and the negative electrode are connected to the conductive metal oxide. in order to change the relative position of the thin film, in Rukoto move to the adjacent electrode direction, and the most important feature be removed by a reduction reaction a conductive metal oxide thin film of the substrate surface.

  In this method for removing a conductive metal oxide thin film according to the present invention, a plurality of pairs of positive and negative electrodes are alternately arranged to face the conductive metal oxide thin film, thereby forming a conductive film formed on the surface of the substrate. The conductive metal oxide thin film can be removed over a wide range.

In removing method of the conductive metal oxide thin film of the present invention, the positive and negative electrodes, in order to change the relative position between the conductive metal oxide thin film, Runode move to the adjacent electrode direction by slightly moving The conductive metal oxide thin film in the electrode arrangement direction can be removed at a time.

In the method for removing a conductive metal oxide thin film of the present invention, the conductive metal oxide formed on the surface of the substrate is used by using an electrolyte having a resistivity of 10 ³ Ω · cm to 10 ⁶ Ω · cm. It is possible to efficiently remove the physical thin film.

The apparatus for removing a conductive metal oxide thin film of the present invention comprises:
A plurality of positive and negative electrodes alternately arranged to face the conductive metal oxide thin film formed on the surface of the substrate;
Means for supplying an electrolytic solution between the positive electrode, the negative electrode and the conductive metal oxide thin film formed on the surface of the substrate, or the positive electrode, the negative electrode and the substrate are immersed in the electrolytic solution An electrolyte tank for storing the electrolyte as much as possible,
1) Preparations to give a power source for applying a voltage to the positive and negative electrodes,
The plurality of alternately arranged positive electrodes and negative electrodes are arranged such that a plurality of rows of positive electrodes pass through a planar negative electrode arranged to face the conductive metal oxide thin film.
Or
2) a power supply that applies voltage to these positive and negative electrodes;
It is provided with a moving device that moves the positive electrode and the negative electrode in the direction of the adjacent electrode in order to change the relative position of the conductive metal oxide thin film,
The most important feature .

The latter in apparatus for removing conductive metal oxide thin film of the present invention, the positive and negative electrodes in which a plurality pairs arranged alternately Said, etc. were also placed as linear or plate-like in one row is adopted The

In the latter apparatus for removing a conductive metal oxide thin film according to the present invention, comprising a positive electrode and a negative electrode in which linear or plate-like ones are arranged in a row, a positive electrode facing the conductive metal oxide thin film, If the linear or plate-like direction of the negative electrode is disposed so as to be oblique with respect to the adjacent electrode direction , a wider range of conductive metal oxide thin film can be removed.

Also in the apparatus for removing conductive metal oxide thin film of the latter invention of this, the positive electrode and the negative electrode, in order to change the relative position between the conductive metal oxide thin film is moved to the adjacent electrode direction When the moving device is provided, the conductive metal oxide thin film in the electrode arrangement direction can be removed at a time by a slight movement.

  In the present invention, since a plurality of pairs of positive electrodes and negative electrodes are alternately arranged, the conductive metal oxide thin film can be removed over a wide range at a time. At that time, if the conductive metal formed on the substrate is removed after weakening the adhesive force by electrolytic elution, the conductive metal oxide thin film can be formed without leaving wrinkles or stress deformation on the substrate. It can be efficiently removed to the end of the material, and it becomes possible to recycle an expensive functional glass substrate used in the semiconductor field. 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 method of the present invention will be described with reference to FIG. 1, and then the best mode for carrying out the present invention will be described in detail with reference to FIGS.
The present invention is a processing method that does not leave wrinkles or stress deformation on a substrate, and a method for removing a conductive metal oxide thin film that does not use strong acid or strong alkali.

  That is, as shown in FIG. 1, a base material 11 such as an insulator or a conductive material having a conductive metal oxide thin film 12 formed on the surface thereof, and a positive electrode 13 and a negative electrode disposed above the base material 11 with a predetermined interval therebetween. 14 is immersed in the electrolytic solution 15 in the electrolytic solution tank, and a DC voltage or a pulse voltage is applied from the power source 16.

In this way, a closed circuit of the power source 16 (+)-positive electrode 13-electrolytic solution 15-conductive metal oxide thin film 12-electrolytic solution 15-negative electrode 14-power source 16 (-) is formed. H ₂ fine bubbles are generated from the surface of the conductive metal oxide thin film 12 in the vicinity of the electrode 13.

At this time, H ₂ generated on the surface of the conductive metal oxide thin film 12 in the vicinity of the positive electrode 13 serves as a reducing agent, and an action of removing O ₂ in the conductive metal oxide thin film 12 occurs. Furthermore, since the generation of H ₂ occurs at the interface of the conductive metal oxide thin film 12, an efficient reduction reaction occurs.

The conductive metal oxide thin film 12 that is no longer bonded by O ₂ contains only a metal element, and exists on the surface of the base material 11 in a state where the bonding force is weakened. The conductive metal 12a whose bond with the base material 11 has been weakened is reliably removed from the base material 11 by a flexible material such as a rotating sponge body that is rubbed with a weak stress.

  However, in the electrode arrangement as shown in FIG. 1, at the final end, the distance D between the conductive metal oxide thin film 12 and the negative electrode 14 becomes long, and the amount of current flowing through the conductive metal oxide thin film 12 is reduced by the electrolyte. 15 and the current efficiency is deteriorated.

  Therefore, in the present invention, for example, the positive electrode 13 and the negative electrode 14 immersed in the electrolytic solution 15 in the electrolytic solution tank are opposed to the conductive metal oxide thin film 12 formed on the surface of the substrate 11 as shown in FIG. As shown in FIG. 3, a plurality of pairs are alternately arranged.

  For example, FIG. 2 shows an example in which linear or plate-like electrodes such as rods and wires are arranged in a line. FIG. 3 shows the arrangement of the negative electrode 14 formed in a mesh shape, for example, so that the positive electrode 13 penetrates the entire mesh. In this case, the net-like negative electrode 14 is disposed so as to face the conductive metal oxide thin film 12 formed on the surface of the substrate 11, and the positive electrode 13 and the negative electrode 14 are disposed via the insulator 17. ing. Note that reference numeral 20 in FIG. 2 denotes a substrate.

  Among these, in the case of the configuration of FIGS. 2 and 3, for example, as shown in FIG. When configured to be horizontally movable by the distance between the positive electrode 13 and the adjacent positive electrode 13, the conductive metal oxide thin film 12 can be efficiently removed over a wide range.

At that time, the linear or plate-like directions of the positive electrode 13 and the negative electrode 14 arranged in the one row facing the conductive metal oxide thin film 12 are adjacent to each other as shown in FIG. When arranged so as to be inclined with respect to the direction , for example, the first region E1 in the first electrode pair above the paper surface, the second region E2 in the next second electrode pair, etc., the conductive metal oxide. The thin film 12 can be removed over a wider range. In addition, since the conductive metal oxide thin film 12 can be reduced over a wider range by the movement of the base material 11, the length L of the electrodes 13, 14 can be shortened. Moreover, the horizontal movement of the base material 11 becomes unnecessary.

  However, when the electrodes 13 and 14 are provided obliquely as shown in FIG. 5, when the electrode angle is θ, the interval between the positive electrodes 13 is X, and the length is L, the relationship is X / L ≦ sin θ. Must do so. This is because when X / L> sin θ, the region where the reduction reaction does not occur between the first region E1 and the second region E2.

  In such an electrode arrangement, since a plurality of pairs of positive electrodes 13 and negative electrodes 14 are alternately arranged, the negative electrodes 14 are separated from the conductive metal oxide thin film 12 only at the corners of the substrate 11. Thus, the remaining portion of the conductive metal oxide thin film 12 can be reduced as much as possible.

By the way, the rate at which the conductive oxide thin film 12 undergoes the reduction reaction is mainly determined by the applied voltage and the distance between the electrodes 13 and 14. The larger the applied voltage / electrode distance, the faster the reduction reaction rate. This is because when the electrode interval is shorter and the voltage is higher, the current flowing through the circuit becomes larger and the amount of H ⁺ generated increases.

  However, if the applied voltage is increased in order to increase the reduction reaction rate, a high-voltage power source is required, resulting in poor efficiency. In addition, if the applied voltage / electrode interval is too large, dielectric breakdown may occur between the electrodes, and a discharge may be generated to damage the substrate 11.

  Therefore, in the present invention, a plurality of pairs of the positive electrode 13 and the negative electrode 14 are alternately arranged so that a large area corresponding to the lower portion of the electrode can be reduced at a time without applying a high voltage. Increased speed.

  Further, FIG. 6 employs an electrode having the configuration shown in FIG. 3 so that the substrate 11 is pulled up above the electrolyte solution 15. In such a configuration, the conductive metal oxide thin film 12 can be efficiently removed with a small apparatus installation area by disposing the rotating sponge body 18 at the lifting position of the substrate 11.

  In addition, in such an electrode configuration, the positive electrode 13 penetrates all the inside of the mesh of the negative electrode 14 formed in a mesh shape, and the range to be removed by one positive electrode 13 is only within one mesh. . Therefore, even if a low voltage is applied between the short positive electrode 13 and the negative electrode 14, the entire net-like negative electrode 14 can be reduced at once and the processing speed is improved.

Also, electrolytic concentration occurs around the positive electrode 13 penetrating through the mesh, thereby concentrating current at the tip of the positive electrode 13 and increasing the current density. Therefore, the generation density of H ⁺ at that portion increases. The efficiency of the reduction reaction can be increased even when a low voltage is applied.

  3 is provided also on the back surface side of the electrode shown in FIG. 6, as shown in FIG. 7, the two substrates 11 can be processed with one set of electrodes.

When the electrode having the configuration shown in FIG. 3 is employed, the conductive metal oxide of the substrate 11 passes through the inside of the positive electrode 13 as shown in FIG. 8 instead of being immersed in the electrolyte solution 17 as shown in FIG. By injecting the electrolyte solution 15 toward the physical thin film 12, the conductive metal oxide thin film 12 whose O ₂ is eliminated and the bonding force with the base material 11 is weakened may be removed.

  In the above-described present invention, the positive electrode 13 and the negative electrode 14 are moved in the direction of the adjacent electrodes in order to change the relative position with the conductive metal oxide thin film 12 (the distance between the positive electrode 13 and the adjacent positive electrode 13). If the substrate 11 is moved horizontally or pulled up while moving the electrodes 13, 14 in the direction of the white arrow in FIG. 6A, for example, the entire surface of the conductive metal oxide thin film 12 is efficiently removed. it can.

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, the electrolytic solution 15 to be used can be used as a neutral salt solution which is generally used. However, when both the positive electrode 13 and the negative electrode 14 are not in contact with the base material 11, it is preferable to use a resistance as described above. The rate is from 10 ³ Ω · cm to 10 ⁶ Ω · cm, more preferably from 10 ⁴ Ω · cm to 10 ⁵ Ω · cm.

In the present invention, when both the positive electrode 13 and the negative electrode 14 are not in contact with the base material 11, a highly conductive electrolyte 15 having a resistivity of less than 10 ³ Ω · cm is applied between the electrodes 13 and 14. This is because, since the voltage does not pass through the conductive metal oxide thin film 12 and becomes conductive through the electrolytic solution 15 between the electrodes 13 and 14, the removal efficiency of the conductive metal oxide thin film 12 decreases. Further, if the resistivity exceeds 10 ⁶ Ω · cm, it is necessary to apply a high voltage, which is economically undesirable.

  Thus, in the present invention, since the electrolytic solution 15 having a relatively high resistivity is suitable, tap water, river water, and the like, which are not preferable as the electrolytic solution 15 conventionally, can be used. Also excellent in terms of sex.

  The present invention is not limited to the above-described examples, and it goes without saying that the embodiments may be appropriately changed within the scope of the technical idea described in each claim.

  For example, the configuration in which a plurality of rows of positive electrodes 13 pass through the planar negative electrode 14 is not limited to the negative electrode 14 formed in a mesh shape as shown in FIG. 3, and is patterned by plating the surface of the insulator 17. The negative electrode 14 may be formed.

  When such a negative electrode 14 is used, only the conductive metal oxide thin film 12 at a desired position on the substrate 11 can be removed. Further, if the substrate 11 is moved, the entire surface of the conductive metal oxide thin film 12 can be removed without moving the electrodes 13 and 14.

In addition, in the case where the linear or plate-like electrodes 13 and 14 are arranged in a row as shown in FIG. 2, the electrodes 13 and 14 are in contact with each other through the electrolyte membrane 19 as shown in FIG. You may do it. In this case, the use of the electrolyte membrane 19 prevents the reduction of the reduction reaction due to O ₂ generated from the positive electrode 13 and enables the conductive metal oxide thin film to be removed stably.

  This method can also be used in a configuration in which a plurality of rows of positive electrodes 13 pass through the planar negative electrode 14. In this case, in order to remove the entire surface of the conductive metal oxide thin film 12, it is necessary to move both electrodes 13 and 14. Therefore, the planar electrode is the positive electrode 13, and the electrode penetrating the planar electrode is formed. The negative electrode 14 may be used.

It is a figure explaining the basic principle of this invention. It is the schematic explaining the 1st example of the electrode which comprises this invention apparatus, and is the figure which showed the example which has arrange | positioned linear or plate-like electrodes, such as a rod and a wire, in 1 row. It is the schematic explaining the 2nd example of the electrode which comprises this invention apparatus, and is the figure which showed the example arrange | positioned so that the positive electrode may penetrate all the insides of the net | network of the negative electrode formed in mesh shape. It is the schematic explanatory drawing of this invention apparatus using the electrode of FIG. 2, and is the figure seen from upper direction. It is a schematic explanatory drawing of this invention apparatus at the time of arrange | positioning an electrode diagonally in FIG. It is a schematic explanatory drawing of this invention apparatus using the electrode of FIG. 3, (a) is a perspective view, (b) is a principal part enlarged view. It is a schematic explanatory drawing of the apparatus of this invention shown in FIG. 6 of the structure which provided the electrode of FIG. 3 also in the back side. It is a principal part enlarged view of the apparatus of this invention of FIG. 6 which injects electrolyte solution toward the electroconductive metal oxide thin film of a base material through the inside of a positive electrode. It is the figure which showed the example at the time of comprising so that both electrodes may contact via an electrolyte membrane. 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 12a Conductive metal 13 Positive electrode 14 Negative electrode 15 Electrolytic solution 16 Power supply 18 Rotating sponge body

Claims (7)

In order to face the conductive metal oxide thin film formed on the surface of the substrate, a plurality of pairs of positive and negative electrodes are alternately arranged,
A voltage is applied to both of the positive electrode and the negative electrode while the electrolyte is interposed between the positive electrode, the negative electrode and the conductive metal oxide thin film , and the positive electrode and the negative electrode are connected to the conductive metal oxide. in order to change the relative position of the thin film, in Rukoto move to the adjacent electrode direction, the conductive metal oxide thin film, and removing by a reduction reaction a conductive metal oxide thin film of the substrate surface Removal method. The electrolyte, a method for removing the electrically conductive metal oxide thin film according to claim 1, resistivity, characterized in that you use those from 10 ³ Ω · cm of 10 ⁶ Ω · cm. A plurality of positive and negative electrodes alternately arranged to face the conductive metal oxide thin film formed on the surface of the substrate;
Means for supplying an electrolytic solution between the positive electrode, the negative electrode and the conductive metal oxide thin film formed on the surface of the substrate, or the positive electrode, the negative electrode and the substrate are immersed in the electrolytic solution An electrolyte tank for storing the electrolyte as much as possible,
It has a power supply that applies voltage to these positive and negative electrodes,
The positive electrode and the negative electrode arranged alternately in pairs are arranged so that a plurality of rows of positive electrodes pass through the planar negative electrode arranged to face the conductive metal oxide thin film. conductive you wherein Rukoto metal oxide thin film removal device. A plurality of positive and negative electrodes alternately arranged to face the conductive metal oxide thin film formed on the surface of the substrate;
Means for supplying an electrolytic solution between the positive electrode, the negative electrode and the conductive metal oxide thin film formed on the surface of the substrate, or the positive electrode, the negative electrode and the substrate are immersed in the electrolytic solution An electrolyte tank for storing the electrolyte as much as possible,
A power supply for applying a voltage to these positive and negative electrodes ;
A conductive metal oxide comprising a moving device for moving the positive electrode and the negative electrode in the direction of an adjacent electrode so as to change a relative position of the conductive metal oxide thin film . Thin film removal device.   The removal of the conductive metal oxide thin film according to claim 4, wherein the plurality of alternately arranged positive electrodes and negative electrodes are linear or plate-like ones arranged in a line. apparatus. The positive electrode and the negative electrode in which the linear or plate-like ones are arranged in a line are electrodes in which the linear or plate-like directions of the positive and negative electrodes facing the conductive metal oxide thin film are adjacent to each other. The apparatus for removing a conductive metal oxide thin film according to claim 5, wherein the apparatus is disposed obliquely with respect to the direction . The electroconductive material according to claim 3 , further comprising a moving device that moves the positive electrode and the negative electrode in the direction of an adjacent electrode so as to change a relative position of the electroconductive metal oxide thin film . Metal oxide thin film removal device.

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