JPH07263437A - Anodic oxidation equipment and anodic oxidation method - Google Patents

Abstract

PURPOSE:To improve the quality and the thickness uniformity of an anodic oxidation film which is formed when thin film metal on a substrate is subjected to anodic oxidation, by making anodic oxidation solution flowing out in the part between a cathode electrode and the thin film metal connect electrically the cathode electrode with anode wirings. CONSTITUTION:The title equipment is provided with the following; a cathode electrode 402, anode wirings 406, 407, thin film metal electrically connected with the anode wirings 406, 407, and anodic oxidation solution 408 flowing out in the part between the cathode electrode 402 and the thin film metal. The anodic oxidation solution 408 connects electrically the cathode electrode 402 with the anode wirings 406, 407. For example, a substrate 201 is fixed on a rotatable stage 401 by a vacuum chuck. Holes 403 through which the anodic oxidation solution flows out, and connectors 404, 405 connected with anode wirings 406, 407 are formed on the facing surfaces of the cathode electrode 402 and the substrate 201. The cathode electrode 402 fixed on a substrate 201 subordinately rotates to the rotation of the stage 401.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus and method for anodizing a metal film formed on a substrate.

The present invention also relates to an apparatus and method for anodizing a wiring or an electrode of a substrate having a thin film semiconductor element.

The present invention also processes substrates one by one,
The present invention relates to a single-wafer type anodizing apparatus and method.

[0004]

2. Description of the Related Art In recent years, much research has been conducted on a technique for providing an integrated circuit using a thin film semiconductor element such as a thin film transistor (TFT) or a thin film diode (TFD) on a substrate having an insulating surface such as glass. For example, it is an active matrix type liquid crystal display, an image sensor, or the like. In particular, an active matrix type liquid crystal display is preferred to have a monolithic type configuration in which a thin film semiconductor element for switching each pixel and a peripheral drive circuit for driving the liquid crystal display are formed on the same substrate.

In the manufacturing process for forming a circuit using a thin film semiconductor element on such a substrate having an insulating surface, an anodic oxidation technique is often used. The anodization is to connect a metal to be oxidized to the positive side of the direct current power supply, that is, the anode, and to connect this metal and the electrode connected to the negative side of the direct current power supply, that is, the cathode to the anodizing liquid (for performing anodization. It is a technique of immersing in a liquid containing an electrolyte and passing a current between both electrodes to oxidize the metal connected to the anode.

The anodic oxides formed by this anodic oxidation are roughly classified into two types: barrier type anodic oxides and porous type anodic oxides. The barrier type anodic oxide is a neutral anodic oxide solution containing 3 to 10% of tartaric acid, oxalic acid, acetic acid and the like.
It is obtained by using a weakly acidic electrolytic solution. The barrier type anodic oxide has a dense composition, has an extremely high insulating property, has few pinholes, and has a high breakdown voltage. It also has a light-transmitting property. In a circuit using a thin film semiconductor element, such a barrier type anodic oxide is formed, for example, on the surface portion of the wiring and used for preventing leakage between the wiring. Further, it is also used as an insulator forming a metal-insulator junction of a MIM (metal-insulator-metal) type diode.

On the other hand, the porous anodic oxide can be obtained by using an acidic aqueous solution of 3 to 20% citric acid, nitric acid, phosphoric acid, chromic acid, sulfuric acid or the like as an anodizing solution. Porous anodic oxide has porosity and can be easily processed by etching. Since it is porous, it is also used for coloring by mixing a dye in the pores.

Further, these anodic oxides are positively used in the process of manufacturing an insulating gate type thin film transistor using a crystalline semiconductor (usually a crystalline but not a single crystal, a non-single crystal semiconductor). This is shown in Japanese Patent Application No. 5-28990, which is an application by the present applicant.

According to this technique, at least the side surface of the gate electrode is anodized, and doping is carried out in a self-aligned manner by utilizing this oxide or a portion after the oxide, and a high resistance region of uniform width is used as a source / drain region. It is provided between the gate electrode and the gate electrode to prevent generation of leak current when a reverse voltage is applied to the gate electrode. Further, the width to be anodized is changed according to the application and purpose of the thin film transistor to obtain desired characteristics.

For example, in a monolithic circuit having an active matrix circuit and a driver circuit for driving the circuit on the same substrate, in the active matrix circuit, the width of anodization on the side surface of the gate electrode is widened to reduce the leakage current. The thin film transistor with a wide width in the high resistance region can be obtained, and in the driver circuit, the decoder circuit, the CPU (central processing unit), the memory (memory) circuit, etc. that require high-speed operation, the width to be anodized is narrowed. Thus, a thin film transistor in which the width of the high resistance region is narrow can be obtained. As described above, the anodic oxidation technique is also used when manufacturing a circuit using a thin film semiconductor element.

[0011]

On the other hand, the conventional anodic oxidation technology has various problems. FIG. 1 shows a conceptual diagram of a conventional apparatus for performing anodic oxidation. FIG. 2 shows an anodized film formed by a conventional anodizing device. 1 is a water tank, 2 is an anodizing solution, 3 is a substrate having thin film metal wiring on one surface,
Reference numeral 4 is a cathode electrode, and 5 is a clip. The metal wiring on the substrate 3 is connected to the positive side of the DC power source, that is, the anode, via the clip 5, and the cathode electrode 4 is connected to the negative side of the DC power source, that is, the cathode. One cathode may be provided facing each substrate.

The first problem with such a conventional apparatus was that the anodizing solution could not be stirred during the anodizing process. As shown in FIG. 1, in the conventional anodic oxidation technique, the substrate 3 is sandwiched between clips 5 and hung from above, and the substrate 3 is placed in the anodizing solution 2. In this state, particularly when barrier type anodic oxidation having a high resistivity is performed and oxidation progresses, a high resistivity anodic oxide film is formed from the surface of the wiring. Therefore, when the clip 5 on the anode side gets wet with the anodizing solution, a current flows between the clip 5 and the cathode electrode 4 through the anodizing solution, and the current supply to the wiring is reduced and stopped. As a result, the anodic oxidation of the wiring did not proceed.

In order to avoid such a situation, conventionally,
The anodizing solution was not stirred during the anodizing process to prevent the liquid surface from shaking and prevent the clip from getting wet with the anodizing solution.

As a result, the flow of the anodizing solution near the wiring on the substrate 3 is stopped, and the oxidation efficiency is locally reduced due to hydrogen generated by the oxidation reaction, ions in the solution, impurities, etc. However, the film thickness and film quality of the anodic oxide film formed are likely to be non-uniform within the same substrate surface. Further, especially in the porous type anodic oxidation, the film thickness of the anodic oxide film was likely to be different between the upper part and the lower part of the same substrate.

Further, in order to prevent the clip from getting wet, the hoisting position of the substrate 3 is set high so that the position of the connector 5 is separated from the liquid surface of the anodizing liquid 2 to some extent. Therefore, when a metal to be anodized is provided on the entire surface of the substrate,
As shown in FIG. 2, in addition to the anodized region 10, there was a large region 11 which was not anodized on the substrate 3. Therefore, it is difficult to form anodized wiring having a size that occupies most of the substrate area.

Further, in order to reduce the area which is not anodized, it is necessary to control the liquid surface so that the clip does not get wet with the anodizing liquid. In particular, during the anodizing step, the liquid surface of the anodizing liquid sways, and the anodizing liquid adheres to the non-anodized region and is anodized. In such a case, the oxidation of the portion where the anodic oxide film was already thick was stopped, the voltage rise became uneven, and it became difficult to obtain a high resistance film.

A further problem is that anodization is performed on wirings on a large number of substrates. Conventionally, when a large number of substrates are to be processed, as shown in FIG. 1, a large number of substrates are collectively put into a water tank as a batch and processed, which is performed in a batch system. However, as described above, since the anodizing solution cannot be stirred during the oxidation process, the state of the anodizing solution varies slightly depending on the location in the water tank. Therefore, even in the same batch, variations in the film thickness and film quality of each substrate are likely to occur. Even if stirring could be performed, it was extremely difficult to realize the same conditions for all the substrates.

In addition, the film thickness and film quality differed between different batches. It is considered that this is because the state of the anodizing solution is different before and after the treatment.

Therefore, one substrate is temporarily put in the water tank.
Even if the variation is prevented from occurring within the batch by limiting the number to only one sheet, a difference still occurs between a plurality of batches. However, replacing the anodizing solution in the water tank for each batch takes time, and it is difficult to improve productivity.

In the case where a substrate having a large area of several to several tens of cm is used such as an active matrix type liquid crystal display, and extremely high uniformity is required for each product within the same substrate surface, this is the case. However, the nonuniformity of the film thickness and film quality of the anodic oxide film within the same substrate surface, within a batch, and between batches changes the characteristics of the thin film semiconductor element, which is not preferable. Further, even in the case of making a trial under various conditions in order to obtain the desired characteristic, great difficulty is involved when the target characteristic, particularly the same characteristic is attempted to be obtained in a plurality of substrates.

A further problem is the problem of space utilization. At the production site, in order to improve the utilization efficiency of the limited space, it is required to reduce the installation space of the manufacturing apparatus. In particular, in active matrix type liquid crystal displays, etc., the display area is expanding, and
The area of substrates to be processed at one time is increasing in size in order to obtain a plurality of substrates from 2 to 9 or more from one glass substrate. From this point of view, reducing the installation space of the device is an important matter.

However, since the conventional anodizing apparatus uses the water tank, even if different types of anodizing, for example, two different types of anodizing are continuously performed, the anodizing is continuously performed. Only one kind of anodizing solution can be used in the container for oxidation, and there is no other way but to provide another water tank or to wash the water tank well and replace the anodizing solution. Even if the surface of the substrate is washed with pure water, it has to be performed in a region different from the place where the water tank containing the anodizing solution is provided, and a lot of installation space for the device is required.

The present invention solves the above various problems.

It is an object of the present invention to flow an anodizing liquid while maintaining electrical connection between the thin film metal and the anode wiring when anodizing the thin film metal on the substrate.

Another object of the present invention is to improve the film quality and the uniformity of the film thickness of the anodized film formed on the same substrate surface when anodizing the thin film metal on the substrate. .

Further, the present invention improves the film quality, the uniformity of film thickness and the controllability of the anodic oxide film on each substrate when anodizing the thin film metal on each substrate on many substrates. With the goal.

Another object of the present invention is to carry out anodization using different types of anodizing solutions in the same container.

Another object of the present invention is to carry out an anodic oxidation process and other processes such as water washing, resist stripping, etching and the like in the same container.

Another object of the present invention is to carry out anodization of a substrate having a thin film semiconductor element, which is suitable for electrodes and wirings connected to the thin film semiconductor element.

[0029]

In order to solve the above problems, the present invention provides a cathode electrode, an anode wiring, a thin film metal electrically connected to the anode wiring, the cathode electrode and the thin film metal. And an anodizing liquid which flows out between the cathode and the anode wiring, and the anodizing liquid electrically connects the cathode electrode and the anode wiring.

Further, according to the present invention, the cathode electrode, the anode wiring, the thin film metal existing on the rotating surface and electrically connected to the anode wiring, and the thin film metal flowing out between the cathode electrode and the thin film metal. And an anodizing solution which electrically connects the cathode electrode and the anode wiring.

Further, the present invention comprises a cathode electrode, an anode wiring, a thin film metal electrically connected to the anode wiring, and an anodizing liquid flowing out from at least a part of the cathode electrode. The oxidizing liquid flows out onto the thin film metal, which is an anodizing device.

Further, according to the present invention, the cathode electrode, the anode wiring, the thin film metal present on the rotating surface and electrically connected to the anode wiring, and the anodizing liquid flowing out from at least a part of the cathode electrode. And the anode wiring flows out onto the thin film metal.

Further, the present invention has at least a plurality of containers and a substrate transfer means, and at least one of the containers has the anodizing device described above, and the substrate transfer means allows the anodization to be performed. From a container with a device to another container,
Or from another container to a container having the anodizing device,
The anodizing device is characterized in that the substrate is transported.

Further, the present invention has at least a stage, a first cathode electrode, a second cathode electrode, and an anode wiring, and the stage has a substrate arranged on the upper surface, and the substrate is arranged on the upper surface. A thin film metal, the thin film metal is electrically connected to the anode wiring, the first cathode electrode is at least a portion of the first cathode electrode, the thin film metal and the cathode electrode During this period, an acidic anodizing solution that causes porous type anodic oxidation to the thin film metal is flown out, and the second cathode electrode is formed from at least a part of the second cathode electrode by the thin film metal and the cathode. An anodizing device, characterized in that a neutral anodizing liquid that causes barrier-type anodizing of the thin-film metal flows out between the electrode and the electrode.

Further, the present invention is the anodizing method characterized in that the anodizing liquid is flown out between the cathode electrode and the thin film metal electrically connected to the anode wiring.

Further, the present invention is the anodizing method characterized in that the anodizing liquid is flown out between the cathode electrode and the thin film metal on the rotating surface electrically connected to the anode wiring.

Further, according to the present invention, the anodizing solution is caused to flow out from at least a part of the cathode electrode, and the anodizing solution is caused to flow out onto the thin film metal electrically connected to the anode wiring. It is an oxidation method.

Further, the present invention is characterized in that the anodizing liquid flowing out from at least a part of the cathode electrode is discharged into a thin film metal on the rotating surface, which is electrically connected to the anode wiring. Is the way.

[0039]

According to the apparatus of the present invention, as described above, in the anodizing step, the connection between the wiring on the substrate and the anode wiring in the anodizing solution and the electrically insulating state between the anodizing solution and the anode wiring are maintained. By allowing the anodizing liquid to flow and stir, it is possible to rotate the stage on which the substrates are placed and to process the substrates one by one. The film quality and film pressure of the film could be homogenized in the plane of the substrate and between the substrates. Hereinafter, the present invention will be described in detail with reference to examples.

[0040]

EXAMPLE 1 In this example, an anodizing apparatus shown in FIG. 3 was used to anodize a substrate having a wiring pattern shown in FIG. Wiring 4 shown in FIG.
In Nos. 1 and 42, the regions 43 and 44 connected to the anode wiring are located on the diagonal of the substrate, and in order to simultaneously anodize all the wirings on the substrate, either region 43 or 44 must be It will be present in the anodizing liquid 22. For this reason,
It is extremely difficult to simultaneously oxidize the wirings 41 and 42 in a conventional hanging type anodic oxidation apparatus using a clip.

In FIG. 3, the anodizing solution 2 is placed in the water tank 21.
Contains 2. In the present embodiment, a barrier type anodic oxide film is formed on the wiring as the anodizing liquid, and therefore, as the anodizing liquid 22, 3 to 10% of tartaric acid, boric acid and phosphoric acid are dissolved in ethylene glycol, and ammonia is used. A solution of PH≈7 neutralized with water, here a 3% solution of tartaric acid in ethylene glycol was used.

In this anodizing solution 22, 600
Substrate 2 with wiring made of 0Å aluminum on top
3 is fixed on the stage 24. As the material of the wiring, tantalum, titanium, silicon or the like is used in addition to aluminum. The wiring pattern shown in FIG. 4 was used as the wiring pattern. The substrate 23 is fixed to the stage 24 by a vacuum chuck (not shown) provided on the stage 24.

The cathode electrode 25 is provided in parallel with the substrate 23 so as to face it. By doing so, it is possible to improve the uniformity of the film quality and film thickness of the formed anodic oxide film in the substrate surface. The interval is arbitrary, but 1 to 50
mm About 5 mm here. The cathode electrode 25 is
Although it is opposed to the substrate in parallel here for the purpose of improving the film quality and film thickness, it can be installed at any place in the anodizing liquid 22.

Further, on the substrate 23, the aluminum wiring and the first and second anode wirings 28 and 29 are connected via the connectors 26 and 27. Connector 2
6, 27, the contact areas 43, 4 of the first anode wiring 28, the second anode wiring 29 and the wirings 41, 42 shown in FIG.
4 has an electrical connection. And the connector 26,
By 27, this connection is electrically isolated from the anodizing liquid 22 and can be insulated.

Although the connectors 26 and 27 extend from the lower side to the water tank 21 and are connected to the wiring on the upper surface of the substrate in FIG. 3, they may be provided from the upper or side portions of the water tank.
The structure may extend from the inside of the cathode electrode toward the substrate. Alternatively, wirings extending from the wirings 41 and 42 on the upper surface may be formed on the side surface or the lower surface of the substrate 23, and the wirings may be connected to the connector formed on the upper surface of the stage 24.

The connectors 26 and 27 are shown in FIG.
The structure shown in (A) was used. The connector shown in FIG. 5A has a cylindrical main body 84 and a pressure reducing device (vacuum).
The internal space 83 and the terminal 85 which are connected to the main component are the main components. Further, an O-ring 82 for improving the airtightness of the space in which the terminal 85 is enclosed is provided between the tip of the main body 84 and the substrate 81. Anodizing liquid around the body 2
If 2 does not touch the terminal 85, the O-ring 82 may be omitted, and in addition to the O-ring, a suction cup 88 as shown in FIG. 5C may be used. In addition, it is possible to provide a means (sealing means) for confining the terminal 85 in the hermetically sealed space at the tip of the connector main body and / or around it by using a material such as plastic, rubber, vinyl, ceramic, metal, or Teflon. .

The connectors 26 and 27 are fixed to the substrate 81 by coming into contact with the substrate 81 on which the wiring is formed via the O-ring 82 and performing suction 86 by the pressure reducing device to reduce the pressure inside the connector 83. Is. Further, here, the terminal 85 is pressed against the substrate side by an elastic body (not shown) such as a spring or rubber provided in the main body, and good contact with the wiring can be maintained. Further, if the depressurized state inside the connector 83 is released, the connector can be easily removed. A plurality of terminals 85 may be present in one connector body 84, and a plurality of different electrical connections can be configured with one connector.

Further, here, the terminal 85 is provided in the internal space 83 of the cylindrical main body 84, and the sucked space for sucking and fixing the substrate also serves as the space where the terminal 85 exists. However, one or a plurality of spaces where the terminals 85 are present and suction spaces may be provided separately.

Further, as shown in FIG. 5 (B), it is also possible to fix the substrate only by pressing 87 without providing a space for suction. For the pressing, the connector may be pressed against the board from above the board, or a facing member integrated with the connector may be placed on the back surface (bottom surface in the figure) of the board, and the member and the connector may have screws, springs, or the like. The substrate may be sandwiched by the force of. Further, both pressing and suction may be used together. Further, the O-ring 82 may be a suction cup.

By using such connectors 26 and 27, it becomes extremely easy to connect and disconnect the wiring on the substrate and the anode wiring. In this example, the substrate 23 was placed in the anodizing solution 22 as follows.

The upper surface of the stage 24, the connectors 26, 2
7. The cathode electrode 25 has moved above the surface of the anodizing liquid 22 before the substrate 22 is installed. When the substrate 22 is placed on the stage 24 by the transfer means, the two connectors 26 connected to the anode wirings 28 and 29 are connected to the substrate 2.
It moves to the upper part of the connection regions 43 and 44 of the wiring on the upper part 2 and is fixed on the substrate by suction. Anode wiring 28, 2
9 and wirings 41 and 42 are connected more.

After that, the stage 24 and the substrate 2 on it
3. The connector 26 fixed on the substrate moves so as to be positioned below the liquid surface of the anodizing liquid 22, and at the same time or after that, at least the surface of the cathode electrode 25 facing the substrate is anodizing liquid 22. Move below the liquid surface.

After the oxidation step, the reverse step, that is,
After moving the cathode electrode 25, the upper surface of the stage 24, the substrate 23, and the connectors 26 and 27 onto the liquid surface of the anodizing liquid 22, the reduced pressure state in the connector is released and the connector 2
6 and 27 are removed from the wiring connection regions 43 and 44, and the substrate 2
3 is moved to a place where the next processing is performed. Before moving the substrate 23, it is effective to rotate the substrate 23 at a high speed to remove and dry the anodizing liquid on the substrate. Simultaneously with or after that, by placing a substrate to be subsequently oxidized on the stage, a large number of substrates can be continuously anodized. It is effective to rotate the stage 24 at a high speed to remove and dry the anodizing liquid on the stage before a new substrate is placed on the stage.

Here, via the connectors 26 and 27,
A circuit series composed of the wiring 41 and the first anode wiring 28 is referred to as a first series, and a circuit series composed of the wiring 42 and the second anode wiring 29 is referred to as a second series. The first and second series are connected to the positive side of a DC power source that can be controlled independently of each other. A cathode electrode 25 is provided in parallel with the substrate 23 and is connected to the negative side of the DC power source. The cathode electrode is platinum, gold, lead, carbon, stainless steel, aluminum,
Alternatively, any material such as aluminum, titanium, nickel, or copper coated with gold or platinum may be used as long as it is not easily corroded by the anodizing solution or is not easily corroded.

Next, the wirings 41 and 42 on the substrate were anodized by making the formed anodic oxide films different in thickness. A constant current was started to flow to the first and second series at the same time, and in the first series, the voltage was raised to the _first voltage V ₁ and kept in that state for 1 hour. Then the first
The sequence while maintaining the voltage V _1, the second series continue to apply a constant current, the voltage is increased to a second voltage V _2, maintaining the second voltage V ₂ for 1 hour. Since the two-step anodic oxidation is performed in this manner, the wiring 4 of the first series is
The thickness of the anodic oxide formed on the side surface and the upper surface of the wiring is different between the first and second series wirings 42, and the latter is thicker. V ₁ is 50 to 150 V, where
It was set to 100V. The V ₂ is 100 to 250V, and here, 200V. In the present example, in the constant current state, the rate of increase in voltage was 2 to 5 V / min. Naturally, V ₁ <V ₂ . As a result, the anodic oxide having a thickness of about 1200Å is formed on the wiring 41 of the first series, and the thickness of the anodic oxide 2400 is formed on the wiring 42 of the second series.
Å Anodized oxide was formed respectively.

Thus, even though the substrate 23 is completely present in the anodizing solution 22, the electrical connection between the first and second anode wirings and the wirings on the substrate is completed. I was able to get to. Moreover, the first and second anode wirings and the anodizing liquid 22 were electrically isolated from each other and were in an insulating state. Therefore, even if oxidation progresses and an anodic oxide film having a high resistance is formed on the surface of the wiring, the current does not leak from the anodic wiring into the anodic oxidation solution, and good anodic oxidation can be performed. . Further, the anodic oxide films having different film thicknesses could be formed on the wiring 41 and the wiring 42.

The anodizing solution 22 is agitated by a rotary blade or the like in a water tank. Then, the anodizing liquid 22 between the cathode electrode 25 and the substrate 23 does not remain and always flows. Therefore, the state of the anodizing liquid between the substrate 23 and the cathode electrode 25 was always kept uniform, and the formed anodized film could have a uniform film pressure and film quality within the substrate surface.

In this example, the substrate having the cathode electrode and the wiring to be anodized was present in the water tank containing the anodizing liquid, but the anodizing liquid was connected to the cathode electrode and the anode wiring. It suffices that the wiring be electrically connected to the wiring to be anodized. In other words, it suffices if the cathode electrode and the wiring on the substrate to be anodized are electrically connected via the anodizing liquid. Therefore, the anodizing liquid may be poured between the cathode electrode and the substrate,
For example, one or a plurality of holes may be provided on the surface of the cathode electrode facing the substrate, or the anodizing solution may flow out through the holes or the mesh as a mesh structure.

FIG. 6A shows, as an example of the shape of the surface of the cathode electrode facing the substrate, an example in which a plurality of holes 50 through which the anodizing liquid flows are provided. FIG. 6B shows a configuration in which the connectors 51 and 52 connected to the anode wiring are provided inside the cathode electrode of FIG. 6A. As shown in FIG. 7A, the shape of the hole 61 through which the anodizing liquid flows out may be specified so that the direction in which the anodizing liquid flows out between the cathode electrode and the substrate can be specified. In addition, FIGS. 6C, 6D, and 7B
As described above, the cathode electrode may be circular. Arrangement of the holes through which the anodizing liquid flows out is arbitrary, but it is desirable to arrange so that the anodizing liquid flows out uniformly within the surface of the substrate. It may be concentric or radial with respect to the center of the facing surface.

The cathode electrode is not limited to a flat plate parallel to the substrate,
For example, the anodizing liquid may flow out as a cathode electrode having a pipe or nozzle shape, and may be electrically connected to the wiring on the substrate via the anodizing liquid.

The angle of the substrate may be horizontal, vertical or tanned. For example, the substrate and the cathode electrode parallel to the substrate may be slanted, and the anodizing liquid may flow out from the upper portion to the lower portion between the substrate and the cathode electrode.

As described above, in the structure in which a new anodizing solution is always introduced and supplied between the substrate and the cathode electrode, the anodizing solution does not remain between the substrates at all.
In addition to obtaining the in-plane uniformity of the formed anodic oxide film, it was also possible to secure the uniformity of the film thickness and film quality among many lots.

Further, either one or both of the cathode electrode and the substrate may be rotated. As a result, the film quality of the anodized film and the in-plane uniformity of the film thickness can be further improved.

The area of the cathode electrode with respect to the area of the substrate is preferably the same as or larger than that of the substrate, but if the area of the portion to be oxidized is 20% or more, sufficient anodization is possible.

Further, in this embodiment, the cathode electrode is located above the substrate. As a result, hydrogen generated on the cathode side during the anodizing process was prevented from remaining on the substrate, and the efficiency of the anodizing reaction due to hydrogen generation could be prevented from lowering.

[Embodiment 2] In this embodiment, an example in which a plurality of different manufacturing processes including an anodic oxidation process are performed in the same container (chamber) will be described. In addition, this embodiment shows an example in which different anodic oxidation widths are formed in the same step. In addition, in this embodiment, an insulating gate type thin film transistor (TF) using a crystalline semiconductor having different characteristics is used.
An example in which T) is formed on the same substrate is shown.

FIG. 8 and FIG. 9 show steps of manufacturing a crystalline insulating gate type thin film transistor on a glass substrate manufactured in this embodiment. FIG. 8 is a cross section of a portion indicated by a chain line in FIG. First, the substrate (Corning 705
9,300mm × 400mm or 100mm × 10
0 mm) 201 as a base oxide film 202 with a thickness of 100
A silicon oxide film having a thickness of 0 to 3000 Å, for example, 2000 Å was formed. As a method for forming this oxide film, a sputtering method in an oxygen atmosphere was used. However, in order to further improve mass productivity, a film obtained by decomposing / depositing TEOS by the plasma CVD method may be used.

After that, an amorphous silicon film of 300 to 5000 is formed by plasma CVD method or LPCVD method.
Å, preferably 500-1000 Å deposited, 5
It was left to stand in a reducing atmosphere at 50 to 600 ° C. for 24 hours for crystallization. This step may be performed by laser irradiation. Then, the crystallized silicon film is patterned to form island-shaped active layer regions 203 and 2
04 was formed. Further, a silicon oxide film 205 having a thickness of 700 to 1500 Å was formed thereon by a sputtering method.

Thereafter, an aluminum film (containing 1 wt% Si or 0.1 to 0.3 wt% Sc) having a thickness of 1000 Å to 3 μm, for example, 6000 Å was formed by the electron beam evaporation method or the sputtering method. Then, a photoresist (for example, OFPR8 manufactured by Tokyo Ohka) is used.
00/30 cp) was formed by spin coating.
Before forming the photoresist, if an aluminum oxide film with a thickness of 100 to 1000Å is formed on the entire surface of the aluminum film by the anodic oxidation method, the adhesion with the photoresist is good and the By suppressing the current leakage, it was effective in forming the porous anodic oxide only on the side surface in the subsequent anodic oxidation step. Then, the photoresist and the aluminum film are patterned and etched together with the aluminum film to form wiring portions 206 and 209 and gate electrode portions 207 and 20.
8 and 210 were formed. (Figure 8 (A))

The above photoresist is left on these wirings and gate electrodes, and this photoresist functions as a mask for preventing anodic oxidation in the subsequent anodic oxidation process. FIG. 9 shows how this state is viewed from above. Gate electrode 20
7, 208 and the wiring 209, the wiring 206, and the gate electrode 210 are electrically independent, and the former is called the A series and the latter is the B series. (Fig. 9 (A))

FIG. 10 shows an example of an anodizing device using the present invention. Now move the substrate into the device shown in FIG.
The wiring and the gate electrode were anodized. Figure 10
In the above, the substrate 201 transferred from the side by a robot arm (not shown) is placed on the stage 401 and fixed on the stage 401 by a vacuum chuck. The stage 401 is rotatable and constitutes a so-called spinner.

Next, the cup 400 located below the upper surface of the stage 401 returned to the position shown in the figure. The cathode electrode 402 comes down from above, and A on the substrate 201
The connectors 404 and 405 provided in the cathode electrode 402 were fixed on the connection regions extending from the series and the series B. Here, the connection region is provided on a diagonal line of the substrate 201.

The state of the surface of the cathode electrode 402 facing the substrate is shown in FIG. 6 (D). Holes 403 through which the anodizing liquid flows out, connectors 404 and 405 connected to the first anode wiring 406 and the second anode wiring 407 are provided on this facing surface. The cathode electrode may be platinum, gold, lead, carbon, stainless steel, aluminum, or aluminum, titanium, nickel, or copper coated with gold or platinum, as long as it is not corroded or difficult to be corroded by the anodizing solution.

The connectors 404 and 405 have the structure shown in FIG. 5A and are fixed by suction. Connector 4
04 is electrically connected to the first anode wiring 406, and the connector 405 is electrically connected to the second anode wiring 407. Further, the cathode electrode 402 and the anode wirings 406 and 407 are electrically insulated. First and second anode wiring 406, 4
07 is connected to the positive side of a DC power source that can be controlled independently of each other.

The stage 401 is connected to a motor and has a rotating function. Cathode electrode 402 fixed to the substrate 201
Rotate depending on the rotation of the stage 401.
The cathode electrode 402 may also be provided with a motor. In this way, the stage and the cathode electrode rotate in the same direction on the same axis. First anode wiring 406 and second anode wiring 40
7 has a structure, such as a brush connection, in which the electrical connection with the DC power supply is not interrupted even when the cathode electrode rotates. The distance between the substrate 201 and the surface of the cathode electrode 402 facing the substrate is, for example, 1 to 50 mm, preferably 10 mm or less, and here, 2 mm. If this distance is small, it becomes easy to fill the gap between the cathode electrode and the substrate surface with the anodizing liquid.

While rotating the stage 401, the substrate 201 and the cathode electrode 402, the hole 4 of the cathode electrode 402 is rotated.
The anodic oxidation solution 408 was made to flow out from No. 03. Rotation speed is 1
00-500 rpm Here, it was 200 rpm. As the anodizing solution, an acidic aqueous solution of 3 to 20% citric acid or nitric acid, phosphoric acid, chromic acid, sulfuric acid, or the like, here a 3% sulfuric acid aqueous solution was used. Anodizing liquid is 30-80 ° C, here 30 ° C
Is kept at. A ceramic heater, a Peltier element, or the like may be provided in the cathode electrode to control the temperature of the anodizing liquid.

The anodizing solution 408 flows out to the extent that it fills the gap between the substrate and the cathode electrode, and due to the centrifugal force caused by the rotation, the anodizing solution scatters from the edges of the substrate and the cathode electrode toward the cup 400, and is discharged. It flowed out below the cup 400 from the liquid port 409, and was drained to the outside of the device through the drain pipe. It is preferable that the drain pipe system be different for each type of liquid.

At this time, among the above wirings and gate electrodes, only the second anode wiring to which the B series is connected is anodized by passing a current, and the thickness is 3000 Å to 25 μm, for example,
Anode oxides 211 and 212 having a thickness of 0.5 μm were formed on the side surfaces of the wiring and the gate electrode. The applied voltage was 5 to 30 V, for example, a constant voltage of 8 V was applied to the gate electrode for 5 to 240 minutes, here 20 minutes.

The rotation of the stage 401 and the cathode electrode 402 and the outflow of the anodizing liquid are stopped, and the connector 40
Release the suction (decompression) state of 4, 405
2 was pulled up.

The anodic oxide thus formed was a porous anodic oxide having a porosity. The thickness of the anodic oxide was controlled by the anodic oxidation time and temperature. At this time, since no current was applied to the A series, no anodic oxide was formed on the gate electrodes 207 and 208 and the wiring 209. (FIG. 8 (B), FIG. 9 (B))

Next, the stage 401 and the substrate 201 were rotated again, and the anodizing liquid remaining on the substrate 201 was shaken off and dried. Rotation speed is 2500-4000rp
m, here 3000 rpm and rotated for 30 seconds. Almost no anodizing liquid was present on the substrate 201.

Next, the stage 401 and the substrate 201 thereon are rotated again at a rotation speed of 100 to 1000 rpm, here 300 rpm, and the first nozzle 410 is moved so that the pure water is rotated on the substrate 201. It was made to flow to the central part of the substrate and the upper surface of the substrate 201 was washed. After rotating for 2 minutes, the outflow of pure water is stopped, the first nozzle 410 is returned to the original position, and the number of rotations of the stage is 2500 to 4
The rotation speed was 3,000 rpm, here 3,000 rpm, and rotation was performed for 30 seconds to shake off the pure water on the substrate 201 and dry it. The pure water discharged from the drain port 409 to the lower side of the cup 400 was discharged to the outside of the apparatus through a drain pipe of a system different from the anodizing liquid used previously.

Next, the mask made of resist was removed using a resist stripping solution. 10 stages and substrates
0 ~ 1000rpm Here, rotate at 500rpm,
The second nozzle 411 is moved, and 50 to 8 is moved by the heater.
Substrate 2 rotating resist stripping solution heated to 0 ° C.
It was drained to the center of 01. After the lapse of 5 minutes, the outflow of the resist stripping solution is stopped, the nozzle 411 is returned to the original position, and the number of rotations of the stage is set to 2500 rpm to 4000 rpm, here 3000 rpm, and the resist stripping solution on the substrate 201 is rotated for 30 seconds. Shake off and dry. The resist stripping liquid discharged from the liquid discharge port 409 was discharged to the outside of the apparatus through a drain pipe of a system different from the anodizing liquid and pure water.

Next, the stage 401 and the substrate 201 thereon are rotated again at a rotation speed of 100 to 1000 rpm, here 300 rpm, the first nozzle 410 is moved, and the pure water is rotated on the substrate 201. It was made to flow to the central part of the substrate and the upper surface of the substrate 201 was washed. After rotating for 2 minutes, the outflow of pure water is stopped, the first nozzle 410 is returned to the original position, and the number of rotations of the stage is 2500 to 4
The rotation speed was 3,000 rpm, here 3,000 rpm, and rotation was performed for 30 seconds to shake off the pure water on the substrate 201 and dry it. The pure water discharged was discharged to the outside of the apparatus through the drain pipe of the same system as the pure water discharged in the cleaning process after anodization.

Next, since barrier type anodic oxidation is performed,
The cathode electrode 402 was moved again, and the connector was fixed on the connection region on the substrate 201 by suction. As for the circuit system to be connected, the A series is electrically connected to the connector 404 and the B series is electrically connected to the connector 405, as in the case of the porous anodic oxidation previously performed.

The cathode electrode 402 may be the same as that used for the porous anodic oxidation, but another electrode having the same structure is used as the cathode electrode in order to prevent the solution remaining in the electrode from being mixed. It was used as 402. Further, the distance between the substrate 201 and the surface of the cathode electrode 402 facing the substrate is 1 to 50 mm, preferably 10 mm or less, and here, 2
mm.

While rotating the stage 401, the substrate 201 and the cathode electrode 402, the hole 4 of the cathode electrode 402 is rotated.
The anodic oxidation solution 408 was made to flow out from No. 03. Anodizing liquid 4
08 contains 3 to 10% of tartar solution, boric acid, and phosphoric acid,
An ethylene glycol solution with PH≈7 neutralized with ammonia was used. The number of rotations was 100 to 500 rpm, here 200 rpm. At the same time, a constant current was applied to the gate electrode / wiring. This time, both A series and B series were energized. A good oxide film was obtained when the temperature of the anodizing liquid was lower than room temperature around 10 ° C. The temperature control may be performed by providing a ceramic heater, a Peltier element, or the like in the cathode electrode 402.

The anodizing solution 408 flows out to the extent that it fills the gap between the substrate and the cathode electrode, and due to the centrifugal force caused by the rotation, the anodizing solution scatters from the edges of the substrate and the cathode electrode toward the cup 400, and is discharged. It flowed out below the cup 400 from the liquid port 409, and was drained to the outside of the device through the drain pipe.

Current was applied until the voltage reached 100V. After that, the rotation of the stage 401 and the cathode electrode 402 and the outflow of the anodizing solution are stopped, and the connector 4
Release the suction (decompression) state of 04 and 405 to make the cathode electrode 4
02 was pulled up.

In this way, the gate electrode / wiring 206
˜210 on the top and sides of barrier type anodic oxide 21
3-217 were formed. The thickness of the anodic oxides 213 to 217 is proportional to the applied voltage, and for example, the applied voltage is 100V.
Formed 1200Å of anodic oxide. In this example, since the voltage was raised to 100 V, the thickness of the obtained anodic oxide was 1200 Å. The thickness of the barrier type anodic oxide is arbitrary, but if it is too thin, there is a risk that aluminum will be eluted when the porous anodic oxide is etched later, so 500 Å or more was preferable. .

It should be noted that even though the barrier type anodic oxide is obtained in the later step, the barrier type anodic oxide is not formed outside the porous anodic oxide, but the porous anodic oxide is formed. A barrier type anodic oxide is formed between the oxide and the gate electrode. (Fig. 8 (C))

Next, the stage 401 and the substrate 201 were rotated again, and the anodizing liquid remaining on the substrate 201 was shaken off and dried. Rotation speed is 2500-4000rp
m, here 3000 rpm and rotated for 30 seconds. Almost no anodizing liquid was present on the substrate 201.

Next, the stage 401 and the substrate 201 thereon are rotated again at a rotation speed of 100 to 1000 rpm, here 300 rpm, the first nozzle 410 is moved, and the pure water is rotated on the substrate 201. It was made to flow to the central part of the substrate and the upper surface of the substrate 201 was washed. After rotating for 2 minutes, the outflow of pure water is stopped, the first nozzle 410 is returned to the original position, and the number of rotations of the stage is 2500 to 4
The rotation speed was 3,000 rpm, here 3,000 rpm, and rotation was performed for 30 seconds to shake off the pure water on the substrate 201 and dry it. The pure water discharged from the drainage port 409 to the lower side of the cup 400 was discharged to the outside of the apparatus through the drain pipe from which the pure water used previously was discharged.

Thus, the anodic oxidation process is completed,
The cup 400 was moved to the lower side, and the substrate 201 was carried out by a robot arm or the like and moved to a carrying cassette or a device for performing the next step. Furthermore, by disposing a new substrate on the stage, it was possible to continuously perform anodizing on a large number of substrates.

After that, by the ion doping method, T
Impurities are implanted into the active layers 203 and 204 of the FT in a self-aligned manner using the gate electrode portion (that is, the gate electrode and the anodic oxide film around the gate electrode) and the gate insulating film as a mask, and the impurity (source / drain) regions 218 and 219 , 220 was formed. Phosphine (PH
₃ ) and diborane (B ₂ H ₆ ) were used. Dose amount is 5 × 10 ^{14 to} 5 × 10 ¹⁵ cm ^-2 , acceleration energy is 50
˜90 keV. Regions 218 and 220 are N-type,
The impurity is introduced so that the region 219 becomes P-type. The area 218 causes the NTFT 228 and the area 219 causes the PT.
The FT 229, region 220, creates an NTFT 230.

As a result, in the two TFTs 228 and 229 on the left side of the drawing (these are complementary TFTs), the thickness of the anodic oxides 214 and 215 on the side surfaces of the gate electrode is about 12.
Since it is 00 Å, the widths x ₁ and x ₃ of the regions (offset regions) where the gate electrode and the impurity region do not overlap each other are about 1000 Å in consideration of the wraparound at the time of ion doping. On the other hand, in the TFT 230 on the right side, the anodic oxide 212
Since the thicknesses of and 217 are about 6200Å in total, the offset width x ₂ was about 6000Å.

Then, the porous anodic oxides 211 and 213 were etched using a mixed acid of phosphoric acid, acetic acid and nitric acid. In this etching, only the anodic oxides 211 and 213 were etched, and the etching rate was about 600Å / min. Barrier type anodic oxides 213 to 217 and silicon oxide film 2
05 remained as it was. After that, a KrF excimer laser (wavelength 248 nm, pulse width 20 nsec) was irradiated to activate the impurity ions introduced into the active layer. (Fig. 8 (E))

Then, the gate electrode / wiring was divided to have a required size and shape. (FIG. 9 (C).
As the interlayer insulator 221, a silicon oxide film having a thickness of 6000Å was formed by the CVD method. Then thickness 800
An ITO (indium tin oxide) film of Å is formed by a sputtering method, and this is patterned to form the pixel electrode 22.
Formed 2. Then, the interlayer insulator 221 and the gate insulating film 205 are etched to form contact holes in the source / drain of the TFT, and at the same time, the interlayer insulator 221 and the anodic oxides 213 to 217 are etched to form the gate electrodes / wirings. A contact hole was formed in.
Finally, aluminum wirings / electrodes 223 to 226 were formed and hydrogen annealing was performed at 200 to 400 ° C.

Note that the wiring 223 is a complementary type T to the wiring 206.
Connect the source of N-channel TFT of FT, and connect the wiring 22
Reference numeral 5 connects the source of the P-channel TFT of the complementary TFT to the wiring 209. The wiring 224 (that is, 226) connects the output terminal of the complementary TFT (that is, the drains of the N-channel TFT and the P-channel TFT) and the drain of the right TFT. Furthermore, the wiring 227
Connects the drain of the right TFT and the pixel electrode 222. Through the above steps, an integrated circuit having a TFT was completed. (Figure 8 (F))

Further, particularly in the A series, as shown in the embodiment, the driver is driven with a large current, so that the PTF
T (width of high resistance region is x ₁ ) ) And NTFT (the width of the high resistance region is x ₄ ) are less deteriorated. In addition, the decoder, the CPU, the shift register, the memory, and other driving circuits consume little power and operate at high frequency, so that the channel width and the channel length are small and deterioration due to hot carriers is likely to occur. NT used in these circuits
The width x ₃ of the high resistance region of the FT needs to be larger than the width x ₁ of the high resistance region of the PTFT. Further, since the required mobility of the NTFT (where the width of the high resistance region is x ₂ ) in the active matrix circuit to which a large voltage is applied is small, deterioration is very likely to occur, resulting in reliability. For improvement, x ₂ > x ₃ > x ₄ ≧ x ₁ is required. For example, x ₂ is 0.5 to 1 μm, x ₃
Is 0.2 to 0.3 μm, x ₄ is 0 to 0.2 μm, and x ₁ is 0 to 0.1 μm. Thus, the shift register could be operated at 1-50 MHz. In the present embodiment, the effect of suppressing the leak current is large when the offset width of the TFT (right TFT) that controls the pixel electrode is sufficiently large.

In this embodiment, the series of different anodic oxidation widths is set to two systems of A and B, but the number of connectors or the number of terminals in the connector may be increased to provide three or more systems.

As described above, the steps of porous type anodic oxidation, drying, substrate cleaning with pure water, resist stripping, and barrier type anodic oxidation could all be performed in the same container (chamber). That is, container (chamber)
These steps could be performed without removing the substrate from the substrate. The space is effectively used, which is unthinkable in the conventional anodizing device. Further, before the porous type anodic oxidation step, electrolytic etching can be performed in the same apparatus in the same manner as in the anodic oxidation.

Ordinary wet etching may be performed in the same container. In this case, the resist and the like are patterned, and the stage and the substrate are rotated so that the etchant flows out to the center of the rotation of the substrate.

Further, due to the rotation of the substrate, the outflow of the anodizing liquid from many holes, the inflow of the anodizing liquid between the cathode electrode and the wiring on the substrate connected to the anode wiring, etc., the same substrate surface It was possible to obtain an extremely uniform film pressure and film quality of the anodic oxide film. The inflow of the anodizing liquid between the cathode electrode and the wiring on the substrate connected to the anode wiring may be continuous or intermittent. Further, in this example, the substrate and the cathode electrode were rotated, but even if they were not rotated at all, it was possible to obtain a highly uniform film thickness and film quality in the same substrate plane. Further, in this case, the shape of the surface of the cathode electrode facing the substrate may be set to a pattern as shown in FIGS. 7A and 7B so that the outflowing anodizing liquid flows in a specific direction. Good.

In the structure of this embodiment, the rotation of the substrate during the anodizing process causes the anodizing liquid to be blown into the cup by the centrifugal force, and the back surface (stage side) of the substrate is hardly touched. Therefore, it is possible to almost completely prevent the back surface of the substrate from being corroded by immersing the substrate in an anodizing solution (particularly, an acidic anodizing solution for a porous type), which has often been a problem in the past.

Further, even when a large number of substrates are continuously processed, a new anodizing liquid, that is, an anodizing liquid containing no impurities generated by the anodizing process is always supplied, so that the amount of space between the substrates is increased. The film thickness and film quality in Example 2 could be made uniform. In the present embodiment, all the anodizing liquid flowing between the cathode electrode and the substrate was discharged and wasted, but a part or all of it is used as it is or after being purified by a filter or the like and circulated. You can also do it.

Arrangement of holes on the surface of the anode electrode facing the substrate is arbitrary. In addition to those shown in FIGS. 6 and 7, for example, holes may be provided to allow the solution to flow out only at the position facing the center of the substrate rotation on the surface facing the substrate of the cathode electrode.

In this embodiment, the liquid is outflowed using the cathode electrode and the first and second nozzles, but it is also possible to adopt a configuration in which all the liquid is outflowed from the cathode electrode. In this case, it is advisable to perform a step of flowing out a chemical solution such as an anodizing solution (for barrier type or porous type) or a resist stripping solution, and then flowing out pure water or the like to wash the chemical solution remaining in the cathode electrode. . The substrate may be cleaned at the same time.

Further, as a matter of course, the cathode electrode and the hole for outflowing the anodizing solution may be provided separately and independently. Anodization is possible as long as the anodizing liquid that flows out is not electrically connected between the cathode electrode and the wiring on the substrate.

Incidentally, the stage, the substrate, the cathode electrode and the like may have various configurations other than those shown in FIG. 11 to 13 show examples of other configurations such as a stage, a substrate, and a cathode electrode. For example, in FIG.
As shown in, a connector may be provided on the stage side instead of the cathode electrode. In this way, the rotation speed and rotation direction of the cathode electrode and the substrate / stage can be independently determined. For example, the cathode electrode can be rotated at all without rotating the cathode electrode, and the device has a simple structure. Conversely, the substrate may be fixed and the cathode electrode may be rotated. It is also possible to make the rotation directions of the cathode electrode and the substrate / stage different from each other (opposite directions on the same axis). Also, once the connector is fixed in the contact area on the substrate, it is not necessary to remove the connector until the anodizing process is completed. Therefore, the work of fixing and removing the connector is not required between the two or more types of anodic oxidation processes of the barrier type and the porous type, and the number of processes can be reduced.

Further, as shown in FIG. 12, the thin film metal wiring on the substrate may be connected on the upper surface of the stage. In this case, it is necessary to provide a connection area on the back surface of the substrate, which is electrically connected to the wiring on the front surface side. However, since there is no connector on the substrate, there is no obstruction to the flow of the anodizing solution, and this is an effective method for achieving homogenization of the film pressure and film quality within the substrate surface.

As shown in FIG. 13, the wiring on the substrate and the anode wiring may be brought into contact with each other at the center of rotation of the substrate, and the anodizing liquid may flow out to the outside. In this case, the anodizing solution spreads due to centrifugal force, and the anodizing solution does not touch the center of rotation at all, so the contact area between the anode wiring and the wiring on the substrate is insulated and isolated from the anodizing solution. Good power can be supplied without particularly providing the above configuration. Further, similar to the configuration of FIG. 12, there is no matter that obstructs the flow of the anodizing liquid in the direction in which the anodizing liquid spreads due to the centrifugal force, so that it is effective for homogenizing the film thickness and film quality. In this case, the cathode electrode may not be rotated but may be rotatable only with respect to the connector or the anode wiring inside thereof.

In the case of the structure shown in FIG. 13, a contact area between the anode wiring and the wiring on the substrate must be provided in the central portion of the substrate. Therefore, for example, when processing a substrate for an active matrix type liquid crystal display, it is often used. This is particularly effective when chamfering (using one substrate finally divided into a plurality of parts) and anodizing the substrate. The position of the contact area on the substrate is provided so as to be located at the peripheral portion of the finally divided substrate.

As a matter of course, when the cathode electrode or the stage is rotated, the shape of the cathode electrode and the stage, the position of the substrate and the connector, etc. are taken into consideration in order to prevent vibration and the like from rotating. Horizontal balance is required at the center of the electrode or stage.

[Embodiment 3] In this embodiment, a large number of substrates are formed by using a plurality of containers (chambers) shown in FIG.
Configured a single-wafer type anodizing device that continuously processes one by one,
An example in which an anodic oxidation process is performed on the integrated circuit having the TFT shown in Example 2 using the apparatus will be described. In each process, the required time, temperature, composition of the chemical solution, film thickness and other conditions are the same as in Example 2.

FIG. 14 shows a conceptual diagram of the apparatus of this embodiment.
A cleaning chamber 501, a porous type anodizing chamber 502, a resist stripping chamber 503, a barrier type anodizing chamber 504, a hot plate 505, a cool plate 506, and a robot arm 507 are provided on or inside the apparatus main body 500. There is.

The cleaning chamber 501 and the resist stripping chamber 503 each have a spinner with a vacuum chuck arranged in a cup and have a nozzle (movable type) through which pure water or a resist stripping solution flows out. The anodizing chambers 502 and 503 have the configuration shown in FIG. However, the first and second nozzles are not provided. Each chamber has an independent drain pipe, and it is possible to collect and discharge the water or the chemical solution discharged in each chamber without mixing.

In the cassette 508, a plurality of substrates 201 having the structure shown in FIGS. 8A and 9A, which is manufactured in the same process as that of the second embodiment, is set. The substrates 201 taken out one by one from the cassette 508 by the robot arm 507 are carried out and carried into each chamber and plate in a specific order, processed, and finally returned to the cassette 508.

The anodic oxidation process in this example is shown below. One substrate 201 is taken out from the cassette 508 by the robot arm 507, the substrate 201 is first transferred to the hot plate 505, and heated to the temperature required for the next step, porous type anodic oxidation, here, 30 ° C. .

Next, the substrate 201 was carried into the porous anodic oxidation chamber 502, where only the B series was anodized to form a porous anodic oxide film. After completion of the anodization, the anodizing solution on the substrate was removed by the high speed rotation of the stage and dried.

Next, the substrate 201 was unloaded from the chamber 502 and loaded into the cleaning chamber 501. Cleaning was performed with pure water while rotating with a spinner, and then pure water on the substrate was removed by high-speed rotation and dried.

Next, the substrate 201 is cleaned by the cleaning chamber 5
01 to the hot plate 505, and heated to a temperature required for further drying of the water content of the substrate and the next resist stripping step, here 50 ° C.

Next, the substrate 201 was carried into the resist stripping chamber 503, and the resist stripping liquid was stripped off by the resist stripping liquid while rotating by a spinner, and then the resist stripping liquid was removed by high speed rotation and dried.

Next, the substrate 201 was unloaded from the chamber 503 and loaded into the cleaning chamber 501. Cleaning was performed with pure water while rotating with a spinner, and then pure water on the substrate was removed by high-speed rotation and dried.

Next, the substrate 201 is a hot plate 505.
After further drying the water on the substrate,
It was placed on the cool plate 506, and the temperature required for the next step, the barrier type anodic oxidation step, was lowered to 10 ° C. here.

Next, the substrate 201 is loaded into the barrier type anodic oxidation chamber 504, and an electric current is applied to the A and B series to form a barrier type anodic oxide film. After the anodizing process is completed, the anodizing solution on the substrate is removed and dried by rotating the stage at a high speed.

Next, the substrate 201 is unloaded from the chamber 504 and loaded into the cleaning chamber 501. Cleaning was performed with pure water while rotating with a spinner, and then pure water on the substrate was removed by high-speed rotation and dried.

The substrate 201 carried out was dried by the hot plate 505, cooled by the cool plate 506, and stored in the cassette 508. Thus, the anodic oxidation process was completed. When the predetermined number of processed substrates was reached, the cassette 508 was replaced with a new one containing unprocessed substrates, and the next process was started. The anodized substrate in the cassette 508 was then completed as an integrated circuit by the same steps as in Example 2.

In the present embodiment, the flow of processing steps for one substrate has been described, but it is needless to say that a plurality of substrates can be processed simultaneously by considering the flow of each processing step and the time required therefor. When processing a large number of substrates one by one, it is possible to efficiently and uniformly control the film pressure and film quality of the anodic oxide film on each substrate surface and between the substrates with good controllability. Could be formed.

A container (chamber) for etching
May be provided on the main body.

If a plurality of chambers for performing the anodic oxidation process, which requires a relatively long processing time, are provided, further speedup can be expected. Since the anodizing apparatus of the present invention does not require a large water tank, it can be constructed extremely compactly, can be easily added, and is space-saving.

Further, in the case of batch processing, it is necessary to set the processing conditions when enlarging the batch. However, in the case of the apparatus of this embodiment, since each process is independent, the condition setting is made again even if the process is expanded. Is unnecessary.

Further, since the substrate is almost dried during the transfer of the substrate, other substrates are not contaminated with water or the like. Further, the robot arm used for the transportation can be simple. [Embodiment 4] This embodiment shows an example in which the present invention is applied to an inverted stagger type insulated gate type thin film transistor (TFT). Further, in this example, an aluminum wiring serving as a gate electrode on the substrate was anodized by using the anodizing device having the configuration shown in FIG. 13 to obtain 640 × 48.
An example is shown in which an active matrix circuit in which an insulating gate type thin film transistor is provided in each pixel having a matrix structure of 0 is formed. The anodizing device used in this example had the same configuration as that of the device of FIG. 10 except for the configuration shown in FIG. Further, in this embodiment, the size of the substrate to be processed is 200 mm × 200 mm, and this substrate is 100 mm.
An example of a four-chamfered structure in which the substrate is divided into four substrates having a size of 100 mm is shown.

FIG. 15 shows a manufacturing process of the insulating gate type thin film transistor on the glass substrate manufactured in this embodiment.
Although only one thin film transistor is shown in the figure, it is formed in a matrix on the substrate to be paired with the pixel electrode to be connected. First, the substrate (Corning 70
59, 200 mm × 200 mm) 701 on the base film 70
2 as thickness 1000-3000Å, for example 2000Å
Was formed by sputtering. Instead of the silicon nitride film, a silicon oxide film may be provided with a similar thickness.
In this case, a sputtering method in an oxygen atmosphere is used as a method for forming the silicon oxide film. However, in order to further improve mass productivity, a film obtained by decomposing / depositing TEOS by the plasma CVD method may be used.

Next, the thickness is 1000Å to 2 μm, for example,
A 2800Å aluminum film (containing 1 wt% Si or 0.1 to 0.3% wt Sc) was formed by an electron beam evaporation method or a sputtering method. The formed aluminum film is patterned by a wet etching process using a mixed solution of phosphoric acid, nitric acid, and acetic acid so as to have a tapered cross section, and the gate electrode portion 70 is formed.
Formed 3. (Fig. 15 (A))

FIG. 16 shows an aluminum pattern 801 on the substrate 701 formed here. In FIG. 16, a connection region 802 in contact with the first anode wiring 406 and the connector 404 in FIG. 13 was formed in the substantially central portion of the substrate 701 together with the patterning of the gate electrode portion 703. This connection region is electrically connected to all gate electrode portions 703 on the substrate 701. In this manner, the gate electrode portion 703 of each of the 1/4 of the substrates to be chamfered can be simultaneously anodized. In this example, the connector 405 and the second anode wiring 407 in FIG. 13 were not used, and only one anode wiring was used.

Next, this gate electrode portion 703 was anodized by using the apparatus having the structure shown in FIG. In FIG. 13, a substrate 701 transferred by a robot arm from the side is placed on the stage 401 and fixed on the stage 401 by a vacuum chuck. Stage 4
01 is rotatable and constitutes a so-called spinner.

Next, the cup 400 in FIG. 13 located below the upper surface of the stage 401 returned to the position shown in the figure. The cathode electrode 402 comes down from above, and on the connection region 802 provided in the central portion of the substrate 701,
The connector 404 provided inside the cathode electrode 402 was fixed. The anodizing liquid is configured to flow outside the connector 404.

Here, in the connection area, the connector 404 was fixed by pressing from the top using the structure of FIG. 5 (B). It may be used in combination with suction or suction. The connector 404 is electrically connected to the first anode wiring 406 and the connector 405 is electrically connected to the second anode wiring 407, and is connected to the positive side of the DC power source.

The stage 401 is connected to a motor and has a rotation function. Cathode electrode 402 fixed to the substrate 201
Rotate depending on the rotation of the stage 401.
The cathode electrode 402 may also be provided with a motor. The first anode wiring 406 has a structure such as a brush connection in which electrical connection with the DC power supply is not interrupted even when the cathode electrode rotates. Further, the distance between the substrate 701 and the surface of the cathode electrode 402 facing the substrate is set to 1 to 50 mm, preferably 10 mm or less, here 2 mm.

While rotating the stage 401, the substrate 201 and the cathode electrode 402, the hole 4 of the cathode electrode 402 is rotated.
The anodic oxidation solution 408 was made to flow out from No. 03. Anodizing liquid 4
As 08, an anodic oxidation solution of PH≈7 in which an ethylene glycol solution in which 3% tartaric acid was dissolved was neutralized with ammonia was used. The rotation speed is 100 to 500 rpm, 20 here.
It was 0 rpm. A better oxide film was obtained when the temperature of the anodizing solution 408 was lower than room temperature around 10 ° C. A ceramic heater, a Peltier element, or the like may be provided in the cathode electrode to control the temperature of the anodizing liquid.

Since the anodizing liquid 408 flows out to the outside of the connector 404 and is subjected to the centrifugal force due to the rotation, it receives a force in the direction away from the connector 404.
The anodizing solution 408 does not touch the. Therefore,
In particular, anodic oxidation can be performed without providing a structure for insulating and isolating the anodizing liquid.

The anodizing solution 408 flows out to the extent that it fills the gap between the substrate and the cathode electrode, and due to the centrifugal force of the rotation, the anodizing solution scatters from the peripheral edges of the substrate and the cathode electrode toward the cup 400, It flowed out of the drainage port 409 below the cup 400, and was drained to the outside of the apparatus through the drain pipe. It is preferable that the drain pipe system be different for each type of liquid.

At the same time, a current was passed between the aluminum wiring pattern 801 on the substrate 701 and the cathode electrode 402 to start anodization. The current value was constant, the current density was 0.5 mA / cm ² here, and the current was applied until the voltage reached 120V. After reaching 120V, it was maintained at 120V for 1 to 60 minutes, here 10 minutes. After that, the rotation of the stage 401 and the cathode electrode 402 and the outflow of the anodizing liquid are stopped, and the connector 404 and the cathode electrode 40 are stopped.
2 was pulled up.

In this way, the gate electrode portion 703 is
Barrier type anodized aluminum 705 was formed on the upper surface and the side surface of the gate electrode 704. The thickness of the anodized aluminum 705 was about 1600Å as the voltage was raised to 120V.

Next, the stage 401 and the substrate 701 were rotated again, and the anodizing liquid remaining on the substrate 701 was shaken off and dried. Rotation speed is 2500-4000rp
m, here 3000 rpm and rotated for 30 seconds. Almost no anodizing liquid was present on the substrate 701.

Next, the stage 401 and the substrate 701 thereon are rotated again at a rotation speed of 100 to 1000 rpm, here 300 rpm, the first nozzle 410 is moved, and pure water is rotated on the substrate 701. Of the substrate 701, and the upper surface of the substrate 701 was washed. After rotating for 2 minutes, the outflow of pure water is stopped, the first nozzle 410 is returned to the original position, and the number of rotations of the stage is 2500 to 4
The rotation speed was 3,000 rpm, here 3,000 rpm, and rotation was performed for 30 seconds to shake off the pure water on the substrate 701 to dry it. The pure water discharged from the drain port 409 to the lower side of the cup 400 was discharged to the outside of the apparatus through a drain pipe of a system different from the anodizing liquid used previously.

Thus, the anodic oxidation process is completed,
The cup 400 was moved to the lower side, and the substrate 701 was carried out and moved to the apparatus for performing the next step by the robot arm or the like. Furthermore, by disposing a new substrate on the stage, it was possible to continuously perform anodizing on a large number of substrates.

Pure water may be discharged from the hole 403 of the cathode electrode during the cleaning step other than the anodic oxidation step. Further, the anodizing step, the washing step, and the drying step may be performed while the connector is arranged in the connection region on the substrate.

Through the above steps, the gate electrode 704 made of aluminum and the gate insulating film 705 made of anodized aluminum could be formed. (Fig. 15
(B))

Thereafter, in the atmosphere, 200 to 300 ° C., for example, 2
When heated at 00 ° C. for several to several tens of minutes, the leak current of anodized aluminum was reduced by one digit or more, which was preferable.

Next, silane and ammonia are added in a ratio of 1: 3 to 1: 8.
Here, a silicon nitride film is used as the second-layer gate insulating film 706 by a plasma CVD method with a ratio of 1: 5.
000-3000Å, for example 2000Å. Instead of the silicon nitride film, a silicon oxide film may be provided with a similar thickness. As a method for forming the silicon oxide film, a sputtering method in an oxygen atmosphere or a plasma CVD method is used. When the plasma CVD method is used, TEOS is used as a raw material, and the substrate temperature is 150 to 400 ° C., preferably 20 with oxygen.
RF discharge was performed at 0 to 250 ° C. to decompose and deposit the source gas. The pressure ratio of TEOS and oxygen is 1: 1 to 1:10.
Further, the pressure was 0.05 to 0.5 torr and the RF power was 100 to 250W. Alternatively, TEOS may be formed with ozone gas as a raw material by a low pressure CVD method or a normal pressure CVD method at a substrate temperature of 150 to 400 ° C., preferably 200 to 250 ° C. The gate insulating film 706 need not be provided, but when it is provided, it is possible to reduce the short circuit between electrodes and improve the mutual conductance of the thin film transistor.

Two I-type amorphous silicon films 707 forming a channel forming region are formed on the gate insulating film 706.
It was formed in the range of 00 to 2000Å, for example 1000Å. Further thereon, a silicon nitride film of 500 to 3000 Å, here 1000 Å, was formed. The formed silicon nitride film was etched with pure hydrofluoric acid diluted to 1/10 to 1/50 to form a protective film 708. Further thereon, an n ⁺ amorphous silicon film 709 containing phosphorus was formed by plasma CVD to a thickness of 200 to 1000 Å, here 300 Å. (Figure 15 (C))

Next, the I-type amorphous silicon film 70 is formed.
7 and n ⁺ amorphous silicon film 709 were dry-etched and patterned. On the other hand, an ITO (indium oxide / tin) thin film to be the pixel electrode is also formed
Patterned (not shown). Then, an aluminum film is formed on the substrate by electron beam evaporation method or sputtering method to 1000
˜2 μm Here, it is formed to a thickness of 3000 Å. Then, this aluminum film and the n ⁺ amorphous silicon film thereunder are etched and patterned by dry etching to form a source electrode 710 and a drain electrode 711, and the n ⁺ amorphous silicon film thereunder is formed into a source region and a drain region. Then, the thin film transistor was completed. (Figure 15 (D))

By using the active matrix circuit thus formed in a liquid crystal electro-optical device, good characteristics could be obtained.

In the present embodiment, a four-chamfered substrate was used, but if the wiring on the substrate and the anode wiring can be connected at the central portion of the substrate, the present invention can be applied to a structure with six or more chamfers. Needless to say, can be carried out.

As described above, the anodizing device of the present invention has various effects. The present invention uses a connector or centrifugal force to insulate the anode wiring from the anodizing liquid while ensuring electrical connection between the anode wiring and the wiring on the substrate.
I was able to be isolated. Therefore, even if an anodic oxide film having a high resistance is formed on the surface of the wiring, the current does not leak from the anodic wiring into the anodic oxidation liquid, and good anodic oxidation can be performed. In addition, since a new anodizing solution is allowed to flow in and be supplied between the substrate and the cathode electrode, the anodizing solution does not stay between the substrates at all, so that in-plane uniformity of the formed anodizing film can be obtained. In addition, it was possible to secure uniformity of film thickness and film quality among many lots. Further, the steps of porous type anodic oxidation, drying, substrate cleaning with pure water, resist stripping, and barrier type anodic oxidation could all be performed in the same container (chamber). That is, these steps could be performed without taking out the substrate from the container (chamber). The space is effectively used, which is unthinkable in the conventional anodizing device. In addition, before the porous type anodic oxidation step, electrolytic etching can be performed in the same container in the same manner as in the anodic oxidation. Furthermore, normal wet etching is also possible in the same container.

Further, due to the rotation of the substrate, the outflow of the anodizing liquid from a large number of holes, the inflow of the anodizing liquid between the cathode electrode and the wiring on the substrate connected to the anode wiring, etc., the same substrate surface It was possible to obtain an extremely uniform film pressure and film quality of the anodic oxide film.

Further, due to the rotation of the substrate during the anodizing process, the anodizing liquid is blown into the cup by centrifugal force, and the back surface (stage side) of the substrate is hardly touched.
Therefore, it has been possible to almost completely prevent the back surface of the substrate from being corroded by immersing the substrate in an anodizing solution (particularly, an acidic anodizing solution for a porous type), which has often been a problem in the past.

Further, even when a large number of substrates were processed successively, the fresh anodic oxidation solution was constantly supplied, so that the film thickness and film quality between the substrates could be made uniform.

Further, in the present invention, the contact area between the anode wiring and the wiring on the substrate, which is conventionally provided only on one side of the substrate, is provided at any position on the substrate in the present invention. Also, the anode wiring can be connected, and even when the anodic oxidation width is made different for each series, a wiring pattern having a very high degree of freedom can be formed.

In this specification, the structure for processing the substrates one by one is mainly shown, but in the same container or water tank,
It goes without saying that a plurality of substrates may be processed.

In the present specification, a glass substrate was mainly used as the substrate, but in the anodizing apparatus of the present invention, other than quartz substrate, silicon wafer, metal substrate, etc., conductor or insulator may be used. Various things can be used. There is no particular limitation on the size or thickness of the substrate.

Further, according to the present invention, a state in which one surface of the substrate is not touched by the anodizing liquid is obtained, so that the substrate itself such as aluminum or copper is easily anodized or is oxidized by the anodizing liquid. Substances that are susceptible to
Even if a substrate made of a material is used, one surface or only a pattern or the like formed on one surface can be anodized and the other surface can be hardly oxidized.

Further, although a DC power source has been mainly described as the power source for anodization, an AC power source or an AC power source having a DC component may be used.

In this specification, aluminum (Al) and aluminum oxide (A) obtained by anodic oxidation are mainly used.
has been described l ₂ O _3), the present invention is not limited thereto, for example, tantalum (Ta) and tantalum oxide (Ta ₂ O _5), titanium (Ti) and titanium oxide (T
It is also effective for iO ₂ ), silicon (Si) and silicon oxide (SiO ₂ ), or a multilayer film of these.

[Brief description of drawings]

FIG. 1 shows a conceptual diagram of a conventional apparatus for performing anodic oxidation.

FIG. 2 shows an anodized film formed by a conventional anodizing device.

FIG. 3 shows an anodizing device used in Examples.

FIG. 4 shows a substrate having a wiring pattern.

FIG. 5 shows a structure of a connector.

FIG. 6 shows an example of the shape of the surface of the cathode electrode facing the substrate.

FIG. 7 shows an example of the shape of the surface of the cathode electrode facing the substrate.

FIG. 8 shows a process of manufacturing a crystalline insulating gate type thin film transistor on a glass substrate manufactured in an example.

FIG. 9 shows a manufacturing process of a crystalline insulating gate type thin film transistor on a glass substrate manufactured in an example.

FIG. 10 shows an example of an anodizing device using the present invention.

FIG. 11 shows an example of another configuration such as a stage, a substrate, and a cathode electrode.

FIG. 12 shows an example of another configuration such as a stage, a substrate, and a cathode electrode.

FIG. 13 shows an example of another configuration such as a stage, a substrate, and a cathode electrode.

FIG. 14 shows a single-wafer-type anodizing apparatus that successively processes a large number of substrates one by one using a plurality of containers (chambers).

FIG. 15 shows a manufacturing process of an insulating gate type thin film transistor on a glass substrate manufactured in an example.

FIG. 16 shows an aluminum pattern on a substrate.

[Explanation of symbols]

1 Water Tank 2 Anodizing Liquid 3 Substrate Having Thin Film Metal on One Side 4 Cathode Electrode 5 Clip 10 Anodizing Area 11 Non-Anodizing Area 21 Water Tank 22 Anodizing Solution 23 Substrate 24 Stage 25 Cathode Electrode 26, 27 Connector 28 1st Anode wiring 29 Second anode wiring 41, 42 Wiring 41, 42 43, 44 Area connected to the anode wiring 50 Holes through which anodizing liquid flows out 51, 52 Connector 61 Holes through which anodizing liquid flows out 81 Wiring is formed Substrate 82 O-ring 83 Connector inside 84 Main body 85 Terminal 86 Suction 87 Press 88 Sucker 201 Substrate 401 Stage 402 Cathode electrode 403 Cathode electrode 403 Hole through which anodizing solution flows 404, 405 Connector 406 First anode wiring 407 Second anode wiring 408 Anodizing liquid 409 Drainage port 410 First nose 411 Second nozzle 500 Device body 501 Cleaning chamber 502 Porous anodizing chamber 503 Resist stripping chamber 504 Barrier anodizing chamber 505 Hot plate 506 Cool plate 507 Robot arm 507 508 Cassette 701 Substrate 702 Base film 703 Gate Electrode portion 704 Gate electrode 705 Anodized aluminum 706 Silicon nitride film 707 I-type amorphous silicon film 708 Protective film 709 n ⁺ amorphous silicon 710 Source electrode 711 Drain electrode 801 Aluminum pattern on the substrate 701 Contact area

Claims (30)

[Claims] 1. A cathode electrode, an anode wiring, a thin-film metal electrically connected to the anode wiring, and an anodizing liquid flowing out between the cathode electrode and the thin-film metal. An anodizing device is characterized in that the anodizing liquid electrically connects the cathode electrode and the anode wiring. 2. A cathode electrode, an anode wiring, a thin film metal existing on a rotating surface and electrically connected to the anode wiring, and anodization flowing out between the cathode electrode and the thin film metal. An anodizing solution, wherein the anodizing solution electrically connects the cathode electrode and the anode wiring. 3. A cathode electrode, an anode wiring, a thin film metal electrically connected to the anode wiring, and an anodizing liquid flowing out from at least a part of the cathode electrode. Flowing out onto the thin-film metal. 4. A cathode electrode, an anode wiring, a thin film metal present on a rotating surface and electrically connected to the anode wiring, and an anodizing liquid flowing out from at least a part of the cathode electrode. The anodic oxidation device is characterized in that the anodic wiring flows out onto the thin film metal. 5. A cathode electrode, an anode wiring, a thin film metal electrically connected to the anode wiring, and an anodizing liquid flowing out from at least a part of the cathode electrode. The thin film metal is discharged so as to flow in a specific direction. 6. A stage, a cathode electrode, and an anode wire are provided, a substrate is installed on the upper surface of the stage, the substrate has a thin film metal on the upper surface, and the thin film metal is the anode wire. An anode characterized by being electrically connected, and between the thin film metal and the cathode electrode, an anodizing liquid flows out so that the thin film metal and the cathode electrode are electrically connected. Oxidizer. 7. A stage, a cathode electrode, and an anode wiring are provided, a substrate is installed on an upper surface of the stage, the substrate has a thin film metal on the upper surface, and the thin film metal is provided on the stage. Is electrically connected to the anode wiring via a connector, and between the thin film metal and the cathode electrode, an anodizing liquid is used so that the thin film metal and the cathode electrode are electrically connected. An anodizing device, wherein the anodizing device is discharged and the stage and the substrate on the stage rotate. 8. A stage, a cathode electrode, and an anode wiring are provided, and a substrate is installed on the upper surface of the stage, and the substrate has a thin film metal on the upper surface and at least a part of the lower surface of the substrate, The anode wiring is electrically connected to a thin film metal provided on the lower surface of the substrate, and the thin film metal and the cathode electrode are electrically connected between the thin film metal and the cathode electrode. Thus, the anodizing liquid flows out, and the stage and the substrate on the stage rotate, the anodizing device. 9. A stage, a cathode electrode, an anode wiring, a substrate is provided on an upper surface of the stage, the substrate has a thin film metal on the upper surface, and the cathode electrode electrically connects with the cathode electrode. An insulated anode wiring is provided, the thin film metal is electrically connected to the anode wiring, and the thin film metal and the cathode electrode are electrically connected between the thin film metal and the cathode electrode. An anodizing device in which an anodizing liquid is discharged so as to be connected, and the stage, the substrate on the stage, and the cathode electrode rotate in the same direction with the same rotation axis. 10. A stage, a cathode electrode, an anode wiring, a substrate is provided on an upper surface of the stage, the substrate has a thin film metal on the upper surface, and the cathode electrode is electrically connected to the cathode electrode. Having an insulated anode wiring, the thin film metal is electrically connected to the anode wiring in the central portion of the stage, between the thin film metal and the cathode electrode, the thin film metal and the cathode An anodizing device, characterized in that an anodizing liquid flows out so as to electrically connect with an electrode, and the stage and the substrate on the stage rotate. 11. A stage, a cathode electrode, an anode wiring, a substrate is installed on an upper surface of the stage, the substrate has a thin film metal on the upper surface, and the cathode electrode is electrically connected to the cathode electrode. Having an insulated anode wiring, the thin film metal is electrically connected to the anode wiring in the central portion of the stage, between the thin film metal and the cathode electrode, the thin film metal and the cathode An anodizing liquid is discharged so as to be electrically connected to the wiring, and the stage, the substrate on the stage, and the cathode electrode have the same rotation axis and rotate in the same direction. Anodizing device. 12. The anodizing device according to claim 10, wherein the anodizing liquid is flown out to a region outside the anode wiring in the center of the stage. 13. The anodizing device according to claim 7, wherein the anodizing liquid is discharged from at least a part of the cathode electrode. 14. The anodizing device according to claim 7, wherein the anodizing liquid is discharged onto a rotating shaft. 15. A stage, a first cathode electrode, a second cathode electrode, and at least an anode wiring, wherein the stage has a substrate arranged on an upper surface, and the substrate has a thin film metal on the upper surface. The thin film metal is electrically connected to the anode wiring, the first cathode electrode is at least a portion of the first cathode electrode, between the thin film metal and the cathode electrode, An acidic anodic oxidation solution that causes porous anodic oxidation to the thin film metal flows out, and the second cathode electrode is located between the thin film metal and the cathode electrode by at least a part of the second cathode electrode. In addition, a neutral anodic oxidation solution that causes barrier type anodic oxidation to the thin film metal is flowed out. 16. A stage, a cathode electrode, an anode wiring, and a nozzle, and at least a substrate is disposed on the upper surface of the stage, the substrate has a thin film metal on the upper surface, and the thin film metal is the Is electrically connected to the anode wiring, the cathode electrode, at least a portion of the cathode electrode,
An anodizing device, characterized in that an anodizing liquid is flown out between the thin film metal and the cathode electrode, and the nozzle flows pure water over the substrate and the thin film metal. 17. A substrate having at least a stage, a cathode electrode, an anode wiring, and a nozzle, wherein a substrate having a thin film metal on an upper surface is installed on the stage, and the thin film metal is electrically connected to the anode wiring. Connected, the cathode electrode is at least a portion of the cathode electrode,
An anodizing device, wherein an anodizing liquid flows out between the thin film metal and the cathode electrode, and the nozzle flows a resist stripping liquid onto the substrate and the thin film metal. 18. A substrate having at least a stage, a cathode electrode, an anode wiring, and a nozzle, wherein a substrate having a thin film metal on an upper surface is provided on the stage, and the thin film metal electrically connects with the anode wiring. Connected, the cathode electrode is at least a portion of the cathode electrode,
An anodizing device, wherein an anodizing liquid flows out between the thin film metal and the cathode electrode, and the nozzle flows out an etching liquid. An anodizing device, wherein an anodizing liquid flows out from at least a part of the cathode electrode between the thin film metal and the cathode electrode, and an etching liquid flows out from the nozzle. 19. The anodizing apparatus according to claim 16, wherein when the liquid flows out from the nozzle, the thin film metal and the anode wiring are electrically disconnected from each other. apparatus. 20. The anodizing apparatus according to claim 1, wherein the stage and the substrate on the stage, and / or the cathode electrode have the same rotation axis and rotate in the same direction, whereby the substrate on the substrate is rotated. An anodizing device, characterized in that the liquid is removed and / or dried. 21. The anodizing device according to any one of claims 1 to 18, comprising a plurality of anode wirings and a power source capable of independently controlling the plurality of anode wirings. 22. The anodizing device according to any one of claims 1 to 18, wherein the cathode electrode has a temperature control means. 23. At least one of a plurality of containers and a substrate transfer means is provided, and at least one of the containers has the anodizing device according to any one of claims 1 to 22; An anodizing device, wherein a substrate is transferred from a container having an anodizing device to another container, or from another container to a container having the anodizing device. 24. The container according to claim 23, other than the container having the anodizing device, is a substrate cleaning device, a resist stripping device, an etching device, or an anode using an anodizing liquid different from the anodizing device. An anodizing device having an oxidizing device. 25. The heating means and / or the heating device according to claim 23.
Alternatively, an anodizing device having a cooling means. 26. An anodizing method, characterized in that an anodizing solution is caused to flow out between a cathode electrode and a thin film metal electrically connected to an anode wiring. 27. An anodizing method, characterized in that an anodizing solution is flown out between a cathode electrode and a thin film metal on a rotating surface electrically connected to an anode wiring. 28. An anodizing method, characterized in that an anodizing solution is caused to flow out from at least a part of a cathode electrode, and the anodizing solution is caused to flow out onto a thin film metal electrically connected to an anode wiring. 29. An anodizing method, characterized in that the anodizing liquid flowing out from at least a part of the cathode electrode is discharged into a thin film metal on the rotating surface, which is electrically connected to the anode wiring. 30. An anodizing method, characterized in that the anodizing liquid flowing out from at least a part of the cathode electrode is caused to flow out in a specific direction over the thin film metal electrically connected to the anode wiring.