JP2003027210A - Surface treatment method and method for manufacturing display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To effectively prevent the corrosion of wiring, electrodes, or the like, on a substrate, to make resistance lower while maintaining the transparency of transparent electrodes, to impart the ability of surface treatment, such as oxidation, to liquid exposed to a gas discharge and to form an alignment layer without contact on the surface of a glass substrate for a liquid crystal panel. SOLUTION: The gas discharge is generated in gas for the discharge containing at least oxygen under the atmosphere pressure or the pressure near the same and a metal oxide film 9 is formed on the surface of a metallic film 7 on the substrate 6 by the gaseous active species formed by this discharge. When the gas for the discharge contains at least hydrogen or organic matter, the metal oxide film 9 of the transparent electrode, or the like, on the surface of the substrate 6 is exposed to the gaseous active species, by which the metal oxide film is reduced. The gas discharge is generated on the liquid surface, by which the liquid itself is surface treated or the surface of the substrate or the like, is treated by using this liquid. The gaseous active species by the gas discharge are cast in a diagonal direction, by which the alignment layer is formed on the glass substrate for the liquid crystal panel.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for oxidizing / reducing the surface of a material to be treated, removing or cleaning organic substances / inorganic substances, and various other surface treatments, and particularly to semiconductor parts such as ICs and circuits. The present invention relates to a method and a device for surface-treating a surface of a substrate, a liquid crystal substrate or the like and wirings, electrodes formed on the surface.

[0002]

2. Description of the Related Art Conventionally, various surface treatment techniques have been used in the field of manufacturing semiconductor devices. For example, when removing organic substances such as flux residue used for soldering, wet cleaning method using organic solvent, or dry cleaning method that removes organic substances by irradiating them with ozone or ultraviolet rays to cause a chemical reaction There is. In the case of the wet method, the cleaning agent may affect electronic parts and the like, and in the case of the dry method, the ability to remove organic substances having a particularly large molecular weight is low, and a sufficient cleaning effect cannot be expected. Therefore, recently, a method for surface treatment using plasma generated in vacuum has been developed.

For example, in Japanese Patent Laid-Open No. 58-147143, a method of treating the surface of a lead frame with oxygen gas activated by microwave discharge in a reduced pressure environment to improve adhesion with a resin. Is disclosed in Japanese Patent Laid-Open No. 4-1
In Japanese Patent No. 16837, the plasma etching apparatus has
A method of introducing 10 Torr hydrogen gas and discharging to remove oxides is disclosed. In Japanese Patent Laid-Open No. 5-160170, by applying a high frequency voltage to an electrode in a depressurized processing chamber, argon oxygen plasma or hydrogen is generated. A method of generating a reducing plasma to etch a lead frame is described.

However, when plasma discharge is generated in a vacuum or reduced pressure environment, special equipment such as a vacuum chamber and a vacuum pump is required, and the entire apparatus becomes large and complicated and expensive. Further, since it is necessary to depressurize and maintain the inside of the chamber at the time of discharging, the processing itself takes a long time, and the workability is low, but the productivity is low, so the productivity is reduced. Furthermore, in plasma discharge under vacuum or under reduced pressure,
Since the number of electrons and ions is larger than that of the excited species, there is a risk of thermal or electrical damage, resulting in great damage or influence on a portion other than the portion to be processed.

On the other hand, recently, there has been proposed a method of performing various surface treatments such as ashing and etching by generating plasma by using a rare gas and a slight reaction gas at atmospheric pressure. These often generate a direct discharge between the high-frequency electrode and the material to be treated. For example, in JP-A-4-334543, a plasma is generated inside the tube to A method of treating a flowable substance passing through the inner surface of a pipe or a pipe is disclosed, and like the surface treatment device described in Japanese Patent Laid-Open No. 3-219082, discharge is performed between a power electrode and a ground electrode, and plasma activation thereof is performed. There is also known a method in which a seed is sprayed on a material to be processed to form a film.

[0006]

In recent years, in accordance with the demand for higher performance and smaller size of semiconductor devices, IC parts and circuit boards using multi-layer wiring are widely used. When forming a multi-layered wiring on a substrate, first, a metal wiring such as aluminum is formed by patterning on the substrate by using a photolithography technique, and an insulating film such as SiO ₂ is coated thereon. A metal layer to be the second wiring is formed on this insulating film, and the metal layer is also etched using the photolithography technique to form a desired wiring pattern. However, since pinholes are easily generated in the SiO ₂ film, when patterning the metal layer formed thereon, there is a possibility that the metal wiring below the metal layer may be etched at the same time. Therefore, in general, a method of forming a SiO ₂ film as an insulating layer with a thickness larger than a necessary thickness is adopted. However, it takes a lot of time and labor to form the SiO ₂ film, and the cost is increased to reduce the productivity, and the substrate itself is very thick, so that the substrate and the electronic parts can be made smaller and thinner. There was a problem that it was against the request of.

In addition, a glass substrate using a transparent electrode made of ITO or the like is generally used in a liquid crystal display (LCD). Particularly in the case of a liquid crystal display element used in a word processor, a personal computer, etc., a relatively large current flows during driving, and thus it is required that the wiring resistance of the transparent electrode is low. For this reason, the method of increasing the thickness of the transparent electrode has been conventionally adopted, but since the ITO electrode is usually formed by a vacuum film forming method, the film forming time is long and the cost is high. However, there is a problem that as the thickness increases, the transparency decreases and the liquid crystal display function itself is affected.

In order to solve these problems, the inventor of the present application can cover the surface of the lower metal wiring with an oxide in advance, even if the SiO ₂ film formed thereon has a pinhole. Attention was paid to the fact that by patterning the upper metal wiring, the lower metal wiring is not etched. Further, even if the metal wiring or electrode is exposed on the surface of the substrate, by coating the surface with a metal oxide, it is possible to have corrosion resistance against various contaminations, and the reliability of wiring and the like is improved, and The life can be extended. Further, since the ITO electrode is a metal oxide, the inventor of the present application achieves a desired low resistance by reducing and metallizing the ITO electrode without increasing the thickness of the transparent electrode more than necessary. Focused on gaining points. However, in any case, the above-mentioned conventional surface treatment technique has various difficulties in practice.

Further, in the manufacture of a liquid crystal display device, in order to form an alignment film on the surface of a liquid crystal panel in the related art, a conventional method for forming an alignment film in a liquid crystal panel is, for example, a heat-resistant synthetic material having electrical insulation such as polyimide. A method of forming a resin coating on a substrate and rubbing the surface with a roller wound with a cloth in one direction, that is, rubbing the surface to impart orientation is adopted. However, in such a physical rubbing method, the synthetic resin film is peeled from the substrate,
There has been a problem that the coating surface is damaged due to the cloth wound around the roller and the dust adhering to the coating surface.
In addition, the uniformity of orientation is important, but in the conventional method,
The angle of the alignment film and the inclination of the liquid crystal molecules largely depend on experience and trial and error, and in reality, the variation is large, and it is impossible to judge the result at the time of rubbing treatment. Furthermore, it was impossible to control the angle of the alignment film.

Therefore, the substrate surface treatment method of the present invention is
The present invention has been made in view of the above-mentioned conventional problems, and the purpose thereof is to easily surface metal wiring or electrodes formed on the surface of the substrate without causing thermal or electrical damage. By processing, it is possible to impart corrosion resistance to improve the reliability of the wiring, or to reduce the resistance, if necessary, and, for that purpose, there is no need for special equipment for vacuum or decompression, An object of the present invention is to provide a surface treatment method capable of easily and compactly constructing the entire apparatus, safely and locally treating a material to be treated, and at low cost and having high treatment ability.

Further, it is an object of the present invention to utilize such a surface treatment method to achieve thinning of the substrate without making the interlayer insulating film thicker than necessary, and to easily, at low cost and with high reliability. It is to provide a method capable of forming a wiring board.

Another object of the present invention is not only oxidation / reduction but also etching, removal of organic / inorganic substances, cleaning, etc. by a relatively simple structure which does not require special equipment for vacuuming or depressurizing. To provide a surface treatment method capable of easily and effectively performing various surface treatments at low cost, and also capable of single-wafer treatment or batch treatment, and an apparatus for realizing the same. is there.

Still another object of the present invention is to provide a liquid crystal panel which is capable of imparting a uniform orientation without damaging or peeling the surface of the synthetic resin film by the non-contact treatment, especially in the manufacture of a liquid crystal display device. Another object of the present invention is to provide a method for forming an alignment film. Another object of the present invention is to provide a method capable of directly forming an alignment film on the substrate surface of a liquid crystal panel.

[0014]

According to the present invention, a step of causing a gas discharge in a gas containing at least hydrogen or an organic substance under atmospheric pressure or a pressure in the vicinity thereof, and an active species of the gas generated by the discharge. And exposing the electrode formed on the substrate.

Further, a step of causing a gas discharge in a gas containing at least hydrogen or an organic substance under atmospheric pressure or a pressure in the vicinity thereof, and an activated species of the gas generated by the discharge are formed in the display device. Exposing the electrode.

Further, a gas discharge is generated in a gas containing at least oxygen under atmospheric pressure or a pressure in the vicinity thereof, and the metal film formed on the surface of the substrate is exposed to a gas active species generated by the discharge. Thereby, the surface of the metal layer is oxidized.

The first metal wiring formed on the substrate surface is
In the step of patterning the second metal wiring by covering with an insulating film formed thereon, forming a metal film on the insulating film and etching the metal film,
Before forming an insulating film on the first metal wiring, a gas discharge is generated in the gas under atmospheric pressure or a pressure in the vicinity thereof, and the first metal wiring is exposed to a gas active species generated by the discharge. It is characterized by

A gas discharge is generated in a gas containing at least hydrogen or an organic substance under atmospheric pressure or a pressure in the vicinity thereof, and a layer of metal oxide formed on the surface of the substrate is added to the gas active species generated by the discharge. Exposure, thereby reducing the metal oxide layer.

It is characterized in that the gas for generating the gas discharge further contains water vapor. Further, it is characterized in that an organic substance is applied to the surface of the substrate in advance, and the vaporized organic substance is added to a gas which causes gas discharge.

It is characterized in that a gas discharge is generated in a predetermined gas under atmospheric pressure or a pressure in the vicinity of the surface of the liquid.

The material to be treated is surface-treated with the liquid after the gas discharge is generated, and the material to be treated is further immersed in the liquid.

A liquid container, a means for causing a gas discharge in a predetermined gas under atmospheric pressure or a pressure in the vicinity thereof near the liquid surface of the container, and supplying the predetermined gas near the liquid surface of the container. And a means for doing so. In addition to this, it is characterized by further comprising means for circulating the liquid from the container to clean it. Further, it is characterized in that the material to be treated is immersed in the liquid in the container, or means for delivering the liquid in the container to the material to be treated is provided.

Further, a gas discharge is generated in a predetermined gas under atmospheric pressure or a pressure in the vicinity thereof, and a gas containing a gas active species generated by the gas discharge is supplied into a liquid, and this liquid is used. It is characterized in that the material to be treated is surface-treated. In addition to this, the material to be treated is immersed in the liquid.

Alternatively, a liquid container, a means for generating a gas discharge in a predetermined gas under atmospheric pressure or a pressure in the vicinity thereof, and a gas containing a gas active species generated by this discharge in the liquid in the container. And a means for supplying to. In addition to this, the material to be treated is immersed in the liquid in the container, or means for delivering the liquid in the container to the material to be treated is provided.

Further, a gas discharge is generated in a predetermined gas under atmospheric pressure or a pressure in the vicinity thereof, and a gas flow containing gas active species generated by this discharge is applied toward the substrate surface of the liquid crystal panel. It is characterized in that the gas active species is exposed to the surface of the substrate by obliquely jetting in accordance with the intended orientation direction. In addition to this, a synthetic resin film serving as an alignment film is previously formed on the substrate surface of the liquid crystal panel, and the synthetic resin film is exposed to a gas active species. On the other hand, a predetermined gas contains an organic substance that is liquid at room temperature, and after forming a film on the substrate surface by its active species,
A second gas discharge is generated under a pressure at or near atmospheric pressure, and the second gas active species generated thereby is exposed to the film formation surface of the substrate.

Further, a gas discharge is generated under atmospheric pressure or a pressure in the vicinity thereof, and a predetermined gas containing a liquid organic substance at room temperature is applied toward the substrate surface of the liquid crystal panel exposed to the discharge. It is characterized in that the film is formed on the surface of the substrate by spraying in the orientation direction and by the active species of the gas generated by the discharge.

[0027]

Therefore, according to the substrate surface treatment method of the first aspect, by generating a gas discharge under a pressure near the atmospheric pressure with a relatively simple structure, oxygen radicals such as oxygen radicals and ozone are generated. It is possible to oxidize the metal layer on the surface of the substrate, which is generated, and to coat the surface with the metal oxide.

According to the method for forming a multilayer wiring board according to claim 2, by using the surface treatment method according to claim 1, the surface of the first metal wiring is coated with a metal oxide.
Even when a pinhole is formed in the insulating film formed thereon, when the second metal wiring is patterned, the first
It is possible to prevent even the metal wiring of the above from being etched.

According to the substrate surface treatment method of claim 3, hydrogen is generated by generating a gas discharge under a pressure near atmospheric pressure with a relatively simple structure similar to the surface treatment method of claim 1. Radicals are generated, or organic substances are dissociated, ionized, or excited to generate active species such as organic matter, carbon, and hydrogen ion-excited species, and by their action, the metal oxide layer on the substrate surface is reduced and metalized. can do.

Further, according to the substrate surface treatment method of the fourth aspect, the rate of the reduction treatment with the gas active species can be accelerated by including the water vapor in the gas which causes the gas discharge. According to the substrate surface treatment method of claim 5, by coating the substrate surface with an organic substance, it is possible to effectively dissociate, ionize, and excite the organic substance by gas discharge. According to the method described in No. 6, by supplying the vaporized organic substance to the generation region of the gas discharge, the dissociation, ionization, and excitation thereof are similarly promoted, and the effect of the reduction treatment can be enhanced.

According to the surface treatment method of claim 7, the surface of the liquid is treated by the action of the gas containing the active species generated by the gas discharge under the pressure near the atmospheric pressure, or the gas is in the liquid. The surface treatment ability can be imparted to the liquid itself. Further, according to the method of claim 8, the surface treatment ability imparted to the liquid enables the material to be treated to be surface-treated without causing thermal or electrical damage irrespective of the discharge generation position, According to the method of claim 9, the material to be treated can be directly surface-treated with the liquid.

According to the surface treatment apparatus of claim 10,
The method according to claim 7 can be realized, in which a gas active species generated by plasma generated under a pressure near atmospheric pressure is applied to a liquid in a container to treat the liquid itself, or The material to be treated can be surface-treated via the liquid. Furthermore, according to the apparatus of the eleventh aspect, it is possible to remove impurity ions, dust, and the like generated in the liquid by the surface treatment, and maintain the cleanliness of the liquid high.
Further, according to the apparatus of claim 12, the material to be treated can be directly surface-treated in the liquid. According to the apparatus of claim 13, the position of gas discharge for generating the liquid is generated. The material to be treated can be surface-treated at a position different from the above.

According to the surface treatment method of claim 14,
By using a liquid containing a gas containing a gas active species generated by gas discharge, the material to be treated can be surface-treated by its action, and the material to be treated is placed at a position different from the position where the gas discharge occurs. Because you can prepare
The processing capacity can be appropriately adjusted according to the shape, size and number of the material to be processed, the environment in which gas discharge is generated, and other processing conditions. Further, according to the method of claim 15, the material to be treated can be directly surface-treated with the liquid.

According to the surface treatment apparatus of claim 16,
The method according to claim 14 can be realized, and the size, size and shape of the material to be treated, etc. are provided by separately providing the liquid container and the gas discharge generating means and connecting them by the gas supply means. Various conditions or as required
It is possible to control the type and amount of the gas active species supplied into the liquid, appropriately change the supply method, and change the size and shape of the liquid container. Further, according to the apparatus of claim 17, the material to be processed can be directly surface-treated in the liquid, and according to the apparatus of claim 18, the material to be processed can be surface-treated at a desired position. it can.

Further, according to the method for forming an alignment film of a liquid crystal panel of the nineteenth aspect, a gas active species is caused to act obliquely on the substrate surface so that the substrate surface is not in contact with the gas flow direction. The alignment film can be formed with. According to the method of claim 20, the synthetic resin film on the surface of the substrate can be oriented in the direction of the gas flow.
According to the method described in 1, the desired alignment film can be directly formed by polymerizing the organic substance on the surface of the substrate.

According to the method for forming an alignment film of a liquid crystal panel of claim 22, a synthetic resin film is formed by polymerizing an organic substance on the surface of a substrate relatively easily by using plasma under atmospheric pressure, and this is used. It can be oriented in a desired direction without contact.

[0037]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT A preferred embodiment of the present invention will now be described in detail with reference to the accompanying drawings.

FIG. 1 schematically shows an apparatus for use in the method for surface treating a substrate according to the present invention. The surface treatment apparatus 1 includes a pair of electrodes 3 which are connected to a power source 2 and are vertically arranged so as to face each other with a predetermined gap. A discharge gas is supplied from a gas supply device 5 to the space 4 defined between the electrodes. Immediately below both electrodes 3, a substrate 6 for horizontally performing a desired surface treatment is horizontally arranged. A metal wiring 7 made of aluminum is formed on the upper surface of the substrate 6.

A discharge gas is supplied from the gas supply device 5 to the space 4, and the atmosphere between the tips of both electrodes 3 and the substrate 6 and in the vicinity thereof is replaced with the discharge gas. When a predetermined voltage is applied from the power source 2 to the electrode 3, gas discharge is generated between both electrodes 3 and the substrate 6. In the discharge region 8, various reactions such as dissociation, ionization and excitation of the discharge gas due to plasma exist. The discharge is particularly strongly generated between the aluminum metal wiring 7 formed on the upper surface of the substrate 6.

In this embodiment, a mixed gas of helium and oxygen is used as the discharge gas. As a result, active species such as oxygen ions and excited species are generated in the discharge region 8. The surface of the metal wiring 7 is oxidized by being exposed to these active species, and a thin metal oxide film 9 as shown in FIG. 2A is formed.

Generally, when a high frequency voltage is applied using a rare gas such as helium under atmospheric pressure or a pressure in the vicinity of the atmospheric pressure, gas discharge is easily generated and the discharge becomes uniform, and the exposed material to be treated is exposed. The damage done to can be reduced. Further, even if compressed air or a mixed gas of nitrogen and oxygen is used as the discharge gas, the metal wiring can be similarly oxidized. Also, since helium is expensive as a gas itself, the manufacturing cost will increase.Therefore, use a rare gas such as helium or argon only at the start of discharge, and change to an appropriate inexpensive gas such as compressed air after discharge occurs. You can also

Regarding the temperature condition, it is possible to carry out the treatment at room temperature, which does not cause problems such as thermal damage to the elements on the substrate. However, it goes without saying that it is better to heat the substrate only to increase the oxidation rate.

In this way, the substrate 6 in which the surface of the metal wiring 7 is covered with the metal oxide film 9 has the insulating film 1 made of, for example, SiO ₂ on the metal wiring 7 as shown in FIG. 2B.
0 is formed to a predetermined thickness. Next, a metal film 11 made of, for example, aluminum is deposited on the insulating film 10 and is etched by using the photolithography technique as in the conventional case to form the second-layer metal wiring in a desired wiring pattern. According to the present invention, since the surface of the lower metal wiring is oxidized and covered with the metal oxide as described above, even if the interlayer insulating film is not formed thicker than necessary for electrical insulation, the pin Regardless of the presence or absence of holes, there is no risk of etching the lower metal wiring when etching the upper metal wiring. In this way, two-tiered multilayer wiring can be formed on the substrate 6, and by repeating the above steps, the third-layer and fourth-layer multilayer wiring can be formed.

In the present embodiment, the metal wiring 7 formed on the substrate 6 is made of aluminum, but the same can be applied to wiring made of other metal such as copper or ITO. Further, even if the wiring has a multilayer structure as in the present embodiment, it is possible to provide corrosion resistance by surface-treating the metal wiring and electrodes exposed on the substrate surface as described above, so that it is possible to prevent contamination and the like. Also has improved reliability and a longer life.

FIG. 3 shows a glass substrate 12 for applying the substrate surface treatment method according to the present invention. The glass substrate 12 is used for a liquid crystal display device, and a large number of transparent electrodes 13 made of, for example, ITO are formed on the surface thereof. In this embodiment, the surface treatment apparatus shown in FIG. 1 is used in the same manner as in the above-described embodiment, a gas containing at least hydrogen or an organic substance is supplied as a discharge gas, and a gas is supplied between the electrode 3 and the glass substrate 12. Generate a discharge. By making plasma in this way,
When the discharge gas contains hydrogen, hydrogen ions, active species such as excited species are generated, and in the case of a gas containing organic matter, the organic matter is dissociated, ionized, and organic matter generated by excitation,
Active species such as ion-excited species of carbon and hydrogen are generated.
These active species are exposed only to the portion of the transparent electrode 13 other than the display region 14 by disposing a means such as a mask on the glass substrate 12, for example.

As described above, the transparent electrode 13 is made of ITO.
Since it is formed of an oxide of a metal such as, it is reduced and metallized by the action of the active species. Thereby, the electric resistance of the transparent electrode 13 can be reduced. Therefore, it is possible to secure the electrical performance required as an electrode while maintaining good transparency for use in a liquid crystal display device without forming a film thicker than necessary as in the conventional case.

The organic substance for generating active species does not necessarily have to be included in the discharge gas. In another embodiment, the surface of the glass substrate 12 can be pre-applied. In this case, the gas is dissociated by the plasma in the discharge region between the electrode 3 and the glass substrate 12,
Since the energy state becomes high due to ionization and excitation, a part of the applied organic substance is evaporated and exposed to discharge to dissociate, ionize, and excite, and generate active species in the same manner as described above. Further, other part of the organic matter receives energy from the active species of the gas having a high energy state, and thereby dissociates, ionizes, and excites to similarly generate active species such as organic matter, carbon and hydrogen ions, and excited species. Becomes As a result, the same reducing action as when the discharge gas contains an organic substance can be obtained. In still another embodiment, a separate gas supply means may be used to supply the vaporized organic material to the discharge region. In this case as well, the same operational effects as described above can be obtained.

When the discharge gas contains an organic substance, the organic substance may be polymerized to form a polymer thin film on the surface of the material to be treated. When the formation of such a polymer thin film is not preferable, it is convenient to use a gas containing a low molecular weight organic substance or to include water in the discharge gas.

FIG. 4 to FIG. 6 show a specific structure for allowing the discharge gas to contain water or a low-molecular organic material in this way. In the embodiment shown in FIG. 4, a bypass is provided in the middle of a pipe line 15 for supplying the discharge gas from the gas supply device 5 to the surface treatment apparatus 1, and a branch is made, and a part of the discharge gas is adjusted by a valve 16. And send it into the tank 17. Water (preferably pure water) or liquid organic matter 18 is stored in the tank 17, and the heater 19 facilitates generation of water vapor or vaporized gas of the organic matter. The discharge gas introduced into the tank 17 is returned to the conduit 15 containing water vapor or vaporized gas of the organic substance 18 and mixed with the discharge gas directly fed from the gas supply device 5 for surface treatment. It is supplied to the device 1. The amount of water vapor or organic matter mixed with the discharge gas is adjusted by adjusting the circuit of the valve 16 and the heater 19.

In the embodiment shown in FIG. 5, a spraying device 20 is provided in the middle of a pipe line 15 connected to the surface treatment device 1 from the gas supply device 5, to which water or a liquid organic substance 18 is supplied from a tank 17. The gas is atomized and added to the discharge gas sent from the gas supply device 5. Also in this case, by providing a heater similar to that shown in FIG. 4 in the tank 17 for heating, atomization of water and liquid organic matter can be promoted.

In the embodiment shown in FIG. 6, the water or the liquid organic substance 18 stored in the tank 17 is heated by the heater 19 to generate steam or vaporized gas of the liquid organic substance, which is supplied from the gas supply device 5. The surface treatment apparatus 1 or the discharge area 8 is provided by a conduit 21 separate from the discharge gas.
Supply directly to. The pipe line 21 can be connected in the middle of the pipe line 15 connecting the gas supply device 5 and the surface treatment device 1, and the vaporized gas of water vapor or organic matter can be mixed with the discharge gas and supplied to the discharge region. .

An experiment was conducted on the effect of reducing the material to be treated using the surface treatment method of the present invention, and the following results were obtained. As the discharge gas, four kinds of gas were used: only helium, a mixed gas of helium and propane, a mixed gas of helium and oxygen, and a mixed gas of helium and hydrogen. Regarding the water vapor or the organic substance added to the discharge gas, the decane (C ₁₀ H ₂₂ ) was added, decane and water were added, and nothing was added. Power supply voltage for generating gas discharge is 200W
And The flow rate of helium was 20 liters per minute. The results obtained from this experiment are shown in Table 1 below.

[0053]

[Table 1] In Table 1, the flow rate of the liquid indicates the flow rate as a gas when the liquid is vaporized. At the time of gas discharge, at least hydrogen or organic substances are supplied as gas or liquid. Generally, when reduction is performed, it is preferable that no polymer is formed on the surface of the material to be treated. As can be seen from Table 1, when oxygen is mixed with the discharge gas, the polymerization can be suppressed, but the reducing property also becomes small. Further, it is understood that the addition of water can suppress the polymerization without affecting the reducibility.

FIG. 7 shows another embodiment of the surface treatment apparatus used in the method according to the invention. The surface treatment device 22 includes a rod-shaped electrode 24 connected to a power source 23.
Is vertically held in an electrically floating state by an insulating fixture 26 at the center of a box-shaped metal cover 25 opened downward. The metal cover 25 is grounded, completely houses the electrode 24 therein, and has a lower end 27 extending to the vicinity of the tip of the electrode 24 and defining an opening 28 therebelow. This lower end 27 is the electrode 2
4 counter electrodes. The inside of the metal cover 25 communicates with a gas supply device 29 that supplies a discharge gas. Opening 28
Is provided with a metal mesh 30, and a material to be processed of a substrate to be surface-treated is arranged below the metal mesh 30.

A predetermined discharge gas is supplied from the gas supply device 29 to replace the inside of the metal cover 25 with the discharge gas. When a voltage is applied from the power source 23 to the electrode 24, the electrode 2
A gas discharge occurs between the tip of 4 and the lower end 27 of the metal cover. Since the discharge gas is continuously supplied from the gas supply device 29 into the metal cover 25, the gas active species generated in the discharge region 31 become the reactive gas flow 32 together with the discharge gas and are opened. It is jetted downward from 28. The substrate is surface-treated by the gas activated species contained in the reactive gas flow. At this time, the reactive gas stream 32
The ions generated by the discharge are the metal mesh 30.
Since it is trapped and neutriated by, it is possible to further reduce the damage given to the surface-treated substrate.

In another embodiment, a conduit such as a flexible tube can be connected to the lower end opening 28 of the metal cover 25, and a reactive gas flow can be ejected from a nozzle provided at the tip of the conduit. The substrate to be surface-treated is arranged at a position separate from the main body of the surface treatment apparatus 22 and exposed to the reactive gas flow through the conduit.
As a result, it is possible to perform processing by changing the flow rate of the gas flow, the shape of the nozzle, etc., according to the processing conditions such as the shape and dimensions of the substrate to be processed, so that the processing capacity can be adjusted as necessary. It is possible and workability can be improved.

FIG. 8 shows a surface treatment apparatus for use in another embodiment of the surface treatment method according to the present invention. The surface treatment device 33 has a flat plate-shaped electrode 35 connected to a power source 34 and arranged horizontally. Electrode 35
A container 37 for storing a predetermined liquid 36 is arranged on the lower side, and a gas supply device 3 for supplying a discharge gas is provided.
8 is arranged so that the gas ejection port 39 faces the narrow space defined between the electrode 35 and the liquid surface of the liquid 36.
At the bottom of the container 37, a grounded metal plate 40 that serves as a counter electrode of the electrode 35 is arranged in parallel at a position corresponding to the electrode 35. The material 41 to be surface-treated is the liquid 36.
It is dipped in and placed on the bottom of the container 37 at a position corresponding to the metal plate 40.

As in each of the above-described embodiments, a predetermined discharge gas is jetted from the gas jet port 39 of the gas supply device 38 to discharge the space between the liquid surface of the electrode 35 and the liquid 36 for the discharge. Replace with gas. Next, when a voltage is applied from the power source 34 to the electrode 35, gas discharge is generated between the electrode 35 and the liquid surface. In the discharge region 42, active species of the discharge gas are generated by the plasma, and the active species generate the liquid 3.
6 is mixed into 6 and the material 41 to be processed is surface-treated.

When a gas containing oxygen, for example, a mixed gas of helium and oxygen is used as a discharge gas, active species such as oxygen radicals and ozone are generated in the discharge region 42 by the gas discharge. When the liquid 36 is water, preferably pure water, the ozone is mixed into the liquid 36 to turn it into ozone water, and the material 41 to be treated has an oxidative decomposition power similar to that of hydrogen peroxide water. Demonstrate. On the other hand, when the surface treatment is actually performed using a hydrogen peroxide solution by the wet method, the treatment cost is high because the hydrogen peroxide solution itself is expensive, and it is harmful to the human body. Work is complicated and complicated. According to the present invention, a sufficiently high oxidation treatment capacity can be obtained at low cost, and handling is easy and workability is improved.

In another embodiment, CF is used as the discharge gas.
Gases containing fluorine compounds such as ₄ , C ₂ F ₆ and SF ₆ can be used. In this case, the gas discharge produces active species such as fluorine ions and excited species.
When water is used as the liquid 36, the fluorine ions are mixed in the water and the liquid 36 becomes hydrogen fluoride (HF) water, so that the surface of the material 41 to be processed can be etched. It can be used, for example, in wet etching of silicon wafers to remove oxide from its surface.

A gas containing nitrogen as a discharge gas,
For example, a single gas of nitrogen, a mixed gas of nitrogen and helium,
Compressed air or the like can be used. When the liquid 36 is sulfuric acid, nitrogen gas, active species such as excited species are generated by the gas discharge, and the nitrogen ions are mixed into sulfuric acid to be converted to ammonium perhydrogen sulfate. As a result, the liquid 36 has the same cleaning ability as that of the ammonia-hydrogen peroxide mixture, and the organic substances and the like adhering to the surface of the material 41 to be processed can be removed. In particular, this method is effective when applied to wet etching of a resist formed on a substrate or the like after ashing.

According to the surface treatment method of this embodiment, various surface treatments such as oxidation, etching and cleaning can be inexpensively performed by appropriately selecting and combining the discharge gas and the liquid 36 as described above. And it can be done easily.
Then, by maintaining the cleanliness of the liquid in which the material to be treated is immersed at a constant high level, the material to be treated can be protected from contamination of substances generated by the surface treatment. A modified embodiment of such a surface treatment apparatus is shown in FIG.

In the embodiment shown in FIG. 9, an inlet 43 and an outlet 44 for the liquid are respectively provided at both ends of a container 37 for storing the liquid 36, and pure water is provided in the middle of a circulation pipe 45 connecting these. A playback device 46 is provided. The liquid 36 in the container 37 is sent from the outlet 44 to the pure water regenerator 46 via the circulation pipe 45, and after removing the impurity ions and dust generated by the surface treatment of the material 41 to be treated, the inlet 43. Is returned to the container 37. Therefore, the liquid 36 in the container 37 can always be maintained at a high degree of cleanliness, the risk of contamination is eliminated, and there is no need to replace the liquid 36 during the surface treatment work, which improves workability and productivity. Is improved. The pure water regenerator 46 is a known means that has been conventionally used, and is composed of activated carbon, ion exchange resin, various filters, etc., and these are appropriately selected or combined. When the liquid 36 is other than pure water, it is constructed and used as a filtering means corresponding to the type of the liquid.

FIG. 10 shows another embodiment of the surface treatment apparatus for similarly treating the surface of the material to be treated in the liquid. The surface treatment apparatus 47 of this embodiment includes an electrode 49 connected to a power source 48 and a grounded electrode 5 which is a counter electrode thereof.
0 and 0 are arranged in the casing 51 so as to face each other at a constant interval. The casing 51 is connected at one end thereof to a gas supply device 52 for supplying a discharge gas, and at the other end thereof to a nozzle 55 composed of a perforated plate arranged at the bottom of a container 54 for storing the liquid 53. There is. For example, the material 56 to be processed, which is a substrate, is stored in the container 54.
It is immersed in the liquid 53, and is arranged above the nozzle 55. In the present embodiment, as shown in the figure, a large number of materials 56 to be processed are arranged vertically in parallel in the liquid 53 in accordance with the size of the container 54.

A discharge gas is supplied from the gas supply device 52 into the casing 51, and the space between the electrodes 49 and 50 is replaced with the discharge gas. When a voltage is applied from the power source 48 to the electrode 49, gas discharge is generated in the space between the electrodes. The active species of the discharge gas generated in the discharge region 57 are sent to the nozzle 55 as a reactive gas flow by the continuous supply of the discharge gas from the gas supply device 52, and the active species in the liquid 53. It spouts into bubbles. By arranging the nozzle 55 at the bottom of the container 54, the bubbles of the reactive gas act to stir the liquid 53, and as a result, the liquid 53 is more uniformly mixed with the gas active species, so that the liquid 53 is totally mixed. Can be surface-treated. Further, in order to increase the dissolution efficiency of the reactive gas in the liquid 53, it is more convenient to make the hole diameter of the perforated plate forming the nozzle 55 smaller.

As a result, similar to the embodiment shown in FIGS. 8 and 9, the material 56 to be processed can be subjected to surface treatment such as oxidation, etching and cleaning depending on the type of discharge gas and the liquid 53. Moreover, in this embodiment, since the container 54 and the discharge part for generating the gas active species are separately provided and connected to each other through an appropriate conduit, the size of the container can be changed according to the processing conditions. By adjusting the supply amount of the sheath gas and the like, it is possible to surface-treat many materials to be processed or materials having various shapes and sizes at one time.

11 and 12 show modified examples of the embodiments of FIGS. 8 and 9, respectively. In these modified examples, the material 41 to be processed is arranged outside the container 37. Similar to the embodiment of FIGS. 8 and 9, the electrode 35 and the liquid 3
By the gas discharge generated between the six surfaces, the excited active species of the discharge gas supplied from the gas supply device 38 is generated, and the liquid 36 mixed with this is distributed toward the material 41 to be treated, It flows on the surface of the material to be processed while controlling the flow rate with the stopper 58. According to the present invention, by appropriately combining the types of the liquid 36 and the discharge gas, it is possible to similarly perform various surface treatments such as oxidation, etching and ashing on the material 41 to be treated.

In particular, in the embodiment of FIG. 12, as in the embodiment of FIG. 9, the liquid 36 is circulated in the container 37 while being regenerated by the pure water regenerator 46 and mixed with the excited active species. Is distributed from the container 37 to the material 41 to be processed. Further, in these modified examples, while the pure water is continuously supplied or circulated to the container 37 to perform the surface treatment of the material 41 to be processed, the plug 58 is closed in the middle of the treatment, and the discharge is supplied from the gas supply device 38. After changing the type of the working gas to change the property of the liquid 36, the surface of the material 41 to be processed can be continuously subjected to different surface treatments by opening the plug 58 again.

As described above, according to the modified embodiments of FIGS. 11 and 12, since the material 41 to be treated is arranged outside the container 37 for generating the gas discharge, the container 37 can be arranged in accordance with its size, size and shape. Therefore, the entire device can be miniaturized. Furthermore, the processing capacity can be easily controlled according to the scale of the required processing, single-wafer processing and batch processing can be performed as necessary, and cost reduction can be achieved.

FIG. 13 shows another embodiment of the surface treatment method according to the present invention. In this embodiment, a relatively large material to be processed 4 such as a glass for liquid crystal panel or a wafer substrate is used.
1 is placed in the cleaning tank 59, and is subjected to cleaning treatment using pure water continuously supplied therein. The used pure water discharged from the cleaning tank 59 is sent to the container 37. The pure water after use contains organic substances and the like removed from the material 41 to be treated and floats on the liquid surface of the container 37. Similar to the embodiment of FIGS. 11 and 12, an electrode 35 connected to a power source 34 is arranged above the container 37 with a slight gap between the electrode 35 and the liquid surface, and is grounded to the bottom of the container 37. The electrode 40 is provided.

Gas discharge is generated between the electrode 35 and the surface of the liquid 36 by supplying the discharge gas from the gas supply device 38, and the gas 36 is generated by using the gas active species generated thereby.
Treat the surface. By using compressed air as the discharge gas, a mixed gas of oxygen and helium or nitrogen,
The organic substances floating on the liquid surface of the container 37 are removed by ashing. The purified water thus purified is sent to the cleaning tank 59 and reused for cleaning the material 41 to be processed.

As described above, according to the present invention, the material 41 to be treated is
Irrespective of its size, shape and size, it can be continuously washed by cleaning while circulating pure water while being fixed at a desired position. Therefore, it is possible to easily cope with an increase in the size of the wafer, and it is possible to perform the single-wafer processing and the batch processing. Further, according to the present invention, even when a treatment such as cleaning is performed using a liquid other than pure water, the cleanliness of the used liquid is easily restored by reuse of the ashing treatment, and reused. can do.

FIG. 14 shows a method for forming an alignment film for a liquid crystal display device to which the surface treatment method according to the present invention is applied. TFT, MIM (Metal Insulator Metal), IT
A synthetic resin coating 61 such as an organic polymer resin is applied to the upper surface of a counter substrate 60 of a liquid crystal panel on which elements such as O, an electrode pattern, or a color filter are formed. An alignment treatment device 62 to which the surface treatment method using plasma under atmospheric pressure of the present invention is applied is arranged above the substrate 60. This alignment treatment device is provided with an electrode 6 connected to a power source 63.
4 and a grounded electrode 65 as its counter electrode. The electrode 64 on the power source side is entirely covered with an insulator 66 such as glass or ceramic. The electrode 64 and the electrode 65 covered by the insulator 66 face each other with a constant gap and, as shown in the drawing, the substrate 60.
And, it is arranged so as to be inclined at a certain angle a with respect to the surface of the synthetic resin coating 61. The angle a is 0 degree <a
It is set appropriately within the range of <90 degrees. Both electrodes 64, 6
The space defined between 5 is connected to a gas supply device 67 that supplies a discharge gas.

When a voltage is applied from the power source 63 to the electrode 64 while supplying the discharge gas from the gas supply device 67 to the space between the electrodes 64 and 65, gas discharge occurs in the space under atmospheric pressure or a pressure close to it. Occurs. The gas discharge may be any discharge such as glow discharge, corona discharge, and arc discharge as long as it produces active species in the discharge gas. By covering the electrode 64 with the insulator 66, the discharge state between both electrodes can be made uniform. At this time, the electrode 65 on the ground side instead of the electrode 64 on the power source side may be covered with an insulator, or both electrodes may be covered with an insulator.

The active species of the discharge gas generated in the discharge region 68 by the gas discharge are generated as a reactive gas flow by the discharge gas continuously supplied from the gas supply device 67 to the surface of the synthetic resin film 61. It is sprayed obliquely from above with a. As a result, the surface of the synthetic resin film 61 is oriented rightward in FIG. Further, the substrate 6
By moving 0 in the front-rear and left-right directions relative to the alignment treatment device 62, it is possible to uniformly align the entire surface of the synthetic resin film 61.

FIG. 15 shows an embodiment of a line type alignment treatment apparatus according to the present invention. The alignment treatment device 69 includes a gas supply device 67, a discharge generator 70 having a power electrode and a ground electrode, and a blowout nozzle 71, as in the embodiment of FIG. The blow-out nozzle 71 is made of an insulating material such as glass or ceramics, and has a straight and narrow blow-out port 72 like a so-called air knife, which is directed to the vicinity of the surface of the substrate 60 on which the synthetic resin coating 61 is formed and the surface thereof. They are arranged at an angle a (0 degree <a <90 degrees).

By supplying a predetermined discharge gas from the gas supply device 67 to the discharge generator 70 and applying a voltage to the power supply electrode, a gas discharge is generated in the discharge gas under atmospheric pressure or a pressure in the vicinity thereof. Cause The active species of the discharge gas generated in the discharge generation unit 70 by this gas discharge become a reactive gas flow due to continuous discharge of the discharge gas from the gas supply device 67, and FIG.
As shown in B, from the tip outlet 72 of the outlet nozzle 71,
The synthetic resin coating 61 on the substrate 60 is jetted at an angle a from diagonally above over the entire width thereof.

As a result, the synthetic resin film 61 is oriented in the same manner as in the embodiment of FIG. At this time, for example, 7 kg / cm
Stronger injection of the gas flow at a pressure of about ² is preferable because the alignment treatment can be performed more effectively and quickly. Further, by moving the substrate 60 relative to the alignment treatment device 69 in the left-right direction, the coating film 61 can be easily formed.
The entire surface of can be processed. In addition, the discharge generator 70
The blow-off nozzle 71 and the blow-off nozzle 71 can be connected to each other by a suitable conduit such as a flexible tube.

As the gas species of the discharge gas, compressed air,
A gas containing at least oxygen, such as a mixed gas of nitrogen and oxygen or a mixed gas of oxygen and helium, is used. In this case, excited active species such as ozone and oxygen radicals are generated by the gas discharge. When compressed air or a mixed gas of nitrogen and oxygen is used as the discharge gas, a high voltage is applied between the both electrodes of the discharge generator 70. The discharge at this time is corona discharge. When a mixed gas of helium and oxygen is used as the discharge gas, a high frequency power supply of, for example, 13.56 MHz is used to generate glow discharge.

FIG. 16 shows another embodiment of the method for forming an alignment film of a liquid crystal panel according to the present invention. In this embodiment, the substrate 73 to be oriented is a metal plate 7 that is grounded.
The metal electrode 7 placed on top of and directly above it.
5 are arranged. The electrode 75 has an air knife structure similar to that of the blowing nozzle 71 of the embodiment of FIG. 15, and has a passage 76 connected to the gas supply device 67 and an elongated slit-shaped outlet 77.

The electrode 75 is formed on the substrate 73 as shown in FIG.
The discharge gas is arranged so as to be ejected obliquely from above toward the surface of the discharge gas from the air outlet 77.
While supplying a predetermined discharge gas from the gas supply device 67 into the passage 76 and ejecting the discharge gas from the blowout port 77 onto the substrate surface,
A high frequency voltage is applied to the electrode 75 from the power source. The metal plate 74 serves as a counter electrode of the electrode 75, and discharge is generated between the tip of the electrode 75 and the substrate 73. In this discharge region 78, excited active species of the discharge gas are generated, and the outlet 7
The discharge gas continuously ejected from 7 sprays the surface of the substrate 73. As a result, a desired alignment treatment is performed on the surface of the substrate.

When the surface of the substrate 73 is previously formed with a synthetic resin film as in the embodiment of FIGS. 14 and 15,
A mixed gas of helium and oxygen is used. In this case, excited active species such as ozone and oxygen radicals are generated in the same manner as in the above-described embodiment, and the synthetic resin film is subjected to orientation treatment by the same surface treatment as ashing.

As described above, according to the present invention, since the alignment treatment can be carried out in a non-contact manner, there is no possibility of damaging or peeling the surface of the synthetic resin film, and it is possible to give a uniform alignment. . Further, the control of the angle of the alignment film mainly depends on the angle at which the reactive gas is blown, and partly depends on the voltage applied to the electrode and the gas species of the discharge gas, so that the control is relatively easy. can do.

In another embodiment, the alignment film can be directly formed on the surface of the substrate by selecting the discharge gas so as to contain an appropriate organic substance which is liquid at room temperature. For example,
When decane (C ₁₀ H ₂₂ ) is added to helium or when silicone is added to helium, a resin film is formed on the surface of the substrate 73 by polymerizing in a desired orientation direction. When oxygen and silicone are added to helium, a silicon oxide (SiO ₂ ) film is formed.

FIG. 17 shows a modification of FIG. 16 for directly forming an alignment film on a substrate. In this modification, the electrodes 75 are arranged vertically so that the discharge gas is blown from the blow-out port 77 to the substrate 73 at a substantially right angle. The substrate 73 is moved relative to the electrode 75 in either the left or right direction simultaneously with the discharge. Thereby, by appropriately setting the moving speed of the substrate in accordance with the film forming speed, the resin film can be grown obliquely and a desired alignment film can be obtained.

Next, the method for forming the alignment film of the liquid crystal panel according to the present invention will be specifically described with reference to examples.

(Example 1) The polyimide coating on the surface of the MIM substrate 80 on which the wiring pattern was formed was subjected to orientation treatment using the spot type surface treatment device 81 shown in FIG. 18 under the following conditions. In the surface treatment device 81, the electrode 83 is arranged at the center of the quartz tube 82 having a double structure and the control circuit 8 is provided.
It was connected to a power source 85 via 4 and was discharged between a ground electrode 86 arranged outside the quartz tube 82. A discharge gas was continuously supplied from the outside into the quartz tube 82, and a gas flow containing active species of the gas generated in the discharge region 87 was jetted from the gas jet port 88 to the surface of the substrate 80. . The substrate 80 was arranged obliquely to the gas flow at an angle of θ = 10 to 30 degrees.

Gas to be used: Compressed air gas pressure: 3 to 7 kg / cm ² Power to be used: 100 to 200 W Treatment time: 20 minutes Between the substrate 80 thus oriented and the substrate on which an orientation film is formed by a conventional rubbing treatment. The alignment state was observed by sandwiching a liquid crystal in between and arranging polarizing plates on both sides of the liquid crystal and irradiating with light. As a result, the portion of the polyimide coating that was exposed to the gas flow was oriented in the direction of the gas flow.

(Embodiment 2) Similarly, a polyimide coating on the surface of the MIM substrate 80 provided with a wiring pattern is shown in FIGS.
Using the line type surface treatment device 89 shown in
The alignment treatment was performed under the following conditions. In the surface treatment device 89, a long and narrow gas outlet 91 is opened along the longitudinal direction of the bottom surface of the power source 90 connected to the power source 85, and the discharge gas is jetted to the surface of the substrate 80 which is horizontally conveyed immediately below the gas outlet 91. While exposing, the polyimide coating was directly exposed to electrical discharge.

[0090] When the orientation of the polyimide coating film was observed in the same manner as in Example 1, it was found that the polyimide film was well oriented over the entire surface of the substrate.

(Embodiment 3) The polyimide coating on the surface of the MIM substrate 80 similarly provided with the wiring pattern is formed as shown in FIGS.
Using the spot type surface treatment device 92 shown in FIG. The surface treatment device 92 has an elongated glass tube 95 sandwiched between a power supply electrode 93 and a ground electrode 94, and discharges gas between the electrodes while flowing a discharge gas from one end to the other end. It was The substrate 80 was arranged in the vicinity of the other end of the glass tube 95 at an angle of θ = 10 to 30 degrees obliquely with respect to the gas flow ejected from the other end opening.

[0092] When the orientation of the polyimide coating film was observed in the same manner as in Example 1, it was confirmed that the polyimide coating was oriented in the treatment times of 1 minute and 3 minutes. In the case of this embodiment, the substrate 80
Is not exposed to direct discharge, there is no risk of charge-up on the substrate, and the processing speed is relatively slow, so that the alignment process can be controlled more easily.

In any of the above Examples 1 to 3, it is considered that the polyimide coating on the substrate 80 was subjected to the alignment treatment by the same surface treatment as ashing, depending on the type of the discharge gas used.

Example 4 An orientation film was directly formed on the surface of the glass substrate 96 on which no wiring pattern was formed, using the surface treatment apparatus shown in FIG. 21 under the following conditions. This surface treatment apparatus has the same configuration as that of the embodiment of FIG. 16, and discharges directly between the power electrode 75 and the glass substrate 96 on the ground electrode 74. The discharge gas is obtained by mixing the organic substance 99, which is liquid at room temperature in the container 98, into the gas sent from the gas supply device 97 by appropriately adjusting the control valves 100 and 101 and mixing the gas through the passage 76 inside the electrode 75. The polymer film 102 of the organic substance 99 was formed on the surface of the glass substrate by ejecting the air from the air outlet 77 obliquely onto the surface of the substrate 96. The gap between the electrode 75 and the surface of the substrate 96 was 1 mm, and the inclination angle of the electrode 75 with respect to the substrate 96 was θ = 60 degrees.

Gas used: Helium gas flow rate: 20 liters / minute Liquid organic substance: OH-modified silicone, silicone oil, n-decane Power consumption: 150 W Same as sandwiching liquid crystal between two substrates 96 on which the polymer film 102 is formed. When the orientation state was observed, the portion 103 of the polymer film 102 near the gas outlet 77 was not oriented, but the portion 102 far from the gas outlet 77 was oriented.

(Example 5) The same glass substrate 9 as in Example 4
An alignment film was directly formed on the surface of No. 6 under the following conditions.

As shown in FIG. 22, a discharge is directly generated between the surface of the glass substrate 96 disposed on the ground electrode 74 and the power electrode 105, and a discharge gas is jetted from the gas outlet 106 to the discharge region in the lateral direction. Let In the discharge gas,
The same one as in Example 4 was used, and the polymer film 1 was formed on the substrate surface.
02 was formed.

Gas used: Helium gas flow rate: 20 liters / minute Liquid organic matter: OH-modified silicone, silicone oil, n-decane Power consumption: 150W The polymer film 102 was the same as in Example 4, and the gas outlet 106 was used.
The portion 103 close to was not oriented, but the far portion 104 was oriented.

Example 6 The same glass substrate 9 as in Example 4
An alignment film was directly formed on the surface of No. 6 using the surface treatment apparatus shown in FIG. 23 under the following conditions. This surface treatment device
As in the fourth embodiment, a discharge gas mixed with a liquid organic substance 99 at room temperature is supplied into the dielectric 107 to generate a discharge between the power electrode 108 inside the dielectric and the external ground electrode 109. The gas flow containing the active species of the gas due to the discharge is jetted obliquely from the gas outlet 110 onto the surface of the glass substrate 96 at an angle of 60 degrees, and the polymerized film 11 is spread over the entire surface.
1 was formed. This polymer film has a liquid crystal pretilt angle of 9
It was 0 degree and was not oriented.

Gas used: Helium gas flow rate: 20 liters / minute Liquid organic substance: OH-modified silicone Power used: 150 W Next, as shown in FIG. 24, the glass substrate 96 placed on the ground electrode 112 is conveyed horizontally. While the power electrode 11
Direct discharge between 3 and 4. As the discharge gas, helium, nitrogen, compressed air and the like, which are often used for surface treatment for improving wettability, were supplied from the gas supply device 114. As a result,
The polymer film 111 was favorably oriented on the entire surface of the substrate 96.

(Embodiment 7) MIM provided with a wiring pattern
The same experiment as in Example 6 was conducted using the substrate. On the surface of the substrate, a well-oriented polymer film was formed as in the example.

The preferred embodiments of the present invention have been described above in detail, but the present invention is within the technical scope thereof.
Various modifications and changes can be added to the above embodiment. For example, in the surface treatment apparatus of FIGS. 1 and 7, as in the embodiment of FIG. 14, the electrodes are covered with an insulator or a dielectric material to generate a more uniform discharge, and the wear of the electrodes due to the discharge, and It is possible to prevent the material to be treated from being contaminated by the substance generated by. Further, by forming the electrodes of the surface treatment device in a flat plate shape and arranging them vertically, discharge is generated linearly in the longitudinal direction,
It can be used as a so-called line type surface treatment device. Further, as the electrode structure of the surface treatment apparatus, in addition to the electrode structure of the above-mentioned embodiment, for example, Japanese Patent Application No. 5-1
No. 13204, a discharge gas is introduced into a gas flow path formed of a dielectric material, and a high frequency voltage is applied to an electrode arranged outside the discharge gas to generate gas in the gas flow path. A structure having a structure in which a gas discharge is generated under a pressure near the atmospheric pressure and a surface treatment is performed by utilizing a gas active species generated thereby can be used as well.

[0103]

Since the present invention is constituted as described above, it has the following effects.

According to the method of treating the surface of a substrate of claim 1, the metal layer on the surface of the substrate is easily and rapidly oxidized to oxidize other portions of the substrate, for example, electronic parts without damaging the metal layer. Since a metal oxide film can be formed on the surface, corrosion of wiring and electrodes formed on the substrate can be effectively prevented, the reliability of electronic circuits can be improved, and the service life can be extended. You can

According to the method for forming a multilayer wiring board according to claim 2, by using the surface treatment method according to claim 1, the surface of the first metal wiring is covered with a metal oxide and has corrosion resistance. Therefore, when etching the second metal wiring, there is no fear that the first metal wiring on the lower side is also etched, and the interlayer insulating film formed between them becomes unnecessary more than its original insulating function. Since it is not necessary to form a thick film and the film can be thinned, the time required for the film formation can be shortened and the cost can be reduced, the productivity can be improved, and the substrate can be made thinner. it can.

According to the substrate surface treatment method of the third aspect, the metal oxide layer on the surface of the substrate can be damaged easily and at high speed on other parts of the substrate, such as electronic parts. Since it can be reduced and metallized without
When the metal oxide layer is a transparent electrode such as ITO, the desired electrical performance can be ensured by reducing the film thickness to maintain the desired transparency and lowering the resistance.

According to the surface treatment method of claim 7, by appropriately selecting the liquid and the discharge gas to be used, the liquid can be oxidized to the same extent as that of, for example, hydrogen peroxide solution, ammonia-hydrogen peroxide solution or the like. , Imparting surface treatment capabilities such as etching and cleaning at low cost, or the liquid itself used for surface treatment such as cleaning can be easily cleaned and reused at low cost, and the cost can be reduced. , The handling is relatively easy and safe, and the workability is greatly improved. In particular, by separately performing the discharge on the liquid and the surface treatment of the material to be treated using the liquid, the surface treatment is performed irrespective of the size, shape and location of the material to be treated. Batch processing becomes possible, and different surface treatments can be continuously performed on the material to be treated, and the apparatus can be downsized and the treatment capacity can be improved. And, such a surface treatment method,
By configuring the surface treating apparatus according to the tenth aspect, it can be realized at a low cost with a relatively simple configuration.

Further, according to the surface treatment method of the fourteenth aspect, a portion for causing gas discharge and a portion for subjecting the material to be treated to surface treatment are provided at different positions, and these are connected to each other to contain a gas active species. Since gas can be supplied to a liquid and surface treatment can be performed using this as a material to be treated, processing conditions such as the purpose of treatment, the shape and dimensions of the material to be treated, the number of materials to be treated at one time, or gas discharge. The surface treatment can be performed according to the type of gas used in the above, the environment for discharging, and the treatment capacity can be adjusted appropriately. Further, it is possible to selectively use single-wafer processing or batch processing depending on the purpose and application, the processing work such as handling the discharge gas is relatively easy and safe, and the productivity can be improved. Further, such a surface treatment method can be realized at a low cost with a relatively simple configuration by configuring the surface treatment apparatus according to the sixteenth aspect.

According to the method for forming an alignment film of a liquid crystal panel of claim 19, by injecting a gas flow containing a gas active species obliquely onto the surface of the substrate, the alignment treatment can be performed without contact with the synthetic resin film on the surface of the substrate. According to the method of claim 22, since the alignment film can be formed directly on the surface of the substrate, there is no risk of damaging or peeling the alignment film as in the conventional case, the yield is improved, and the processing time is increased. Since it is short and single-wafer processing is possible, productivity is greatly improved and cost can be reduced.

Furthermore, the surface treatment method and apparatus according to the present invention does not require a depressurized environment in any of the above-mentioned cases, so that the overall structure of the apparatus can be easily and miniaturized, and the atmospheric pressure can be reduced. Since the gas discharge is generated under the pressure of, the number of electrons and ions is smaller than that of the excited species, so that the damage to the material to be treated can be reduced, and the surface treatment can be performed at a high speed, so the cost can be reduced. You can

[Brief description of drawings]

FIG. 1 is a diagram schematically showing a configuration of a surface treatment apparatus used in a substrate surface treatment method according to the present invention.

2A and 2B are diagrams showing a process of forming a multilayer wiring by using the substrate surface treatment method according to the present invention, which includes FIGS.

FIG. 3 is a plan view showing a glass substrate to be reduced according to the present invention.

FIG. 4 is a block diagram showing a configuration for allowing the discharge gas to contain water vapor or a vaporized gas of an organic substance in the reduction treatment according to the present invention.

FIG. 5 is a block diagram showing another configuration different from FIG.

FIG. 6 is a block diagram showing another embodiment different from that of FIG.

FIG. 7 is a diagram showing another embodiment of the surface treatment apparatus used in the surface treatment method of the present invention.

FIG. 8 is a diagram showing a surface treatment apparatus used in an example of a surface treatment method different from that in FIG.

9 is a diagram showing a modified example of FIG.

FIG. 10 is a view showing a surface treatment apparatus used in another embodiment different from that of FIG.

FIG. 11 is a diagram showing another modification of FIG. 8.

FIG. 12 is a diagram showing a modified example of FIG.

FIG. 13 is a diagram showing another embodiment of the surface treatment method according to the present invention.

FIG. 14 is a diagram illustrating a method for forming an alignment film of a liquid crystal panel using the surface treatment method according to the present invention.

FIG. 15 is a side view schematically showing an embodiment of a line type alignment treatment apparatus, and FIG. B is a top view thereof.

16 is a diagram showing an embodiment of an alignment treatment device different from that in FIG.

FIG. 17 is a diagram showing a modification of the embodiment of FIG.

FIG. 18 is a diagram showing an alignment treatment method for a liquid crystal panel using a spot type surface treatment device.

FIG. 19 is a side view showing a line type surface treatment apparatus used in a method for aligning a liquid crystal panel, and FIG. B is a partial sectional view thereof.

FIG. 20A is a side view showing a spot type surface treatment apparatus which is also used in the liquid crystal panel alignment treatment method;
FIG. B is an end view thereof.

FIG. 21 is a diagram schematically showing a method for forming an alignment film of a liquid crystal panel according to the present invention.

FIG. 22 is a diagram showing a modification of FIG. 21.

FIG. 23 is a diagram showing a first half of steps in another embodiment of the method for forming an alignment film of a liquid crystal panel according to the present invention.

FIG. 24 is a diagram showing a second half of the process in the example of FIG. 23.

[Explanation of symbols]

1 Surface Treatment Device 2 Power Supply 3 Electrode 4 Space 5 Gas Supply Device 6 Substrate 7 Metal Wiring 8 Discharge Area 9 Metal Oxide Film 10 SiO ₂ Layer 11 Metal Film 12 Glass Substrate 13 Transparent Electrode 14 Display Area 15 Pipeline 16 Valve 17 Tank 18 Water or liquid organic matter 19 Heater 20 Spraying device 21 Pipe line 22 Surface treatment device 23 Power source 24 Electrode 25 Metal cover 26 Insulation fixture 27 Lower end 28 Opening 29 Gas supply device 30 Metal mesh 31 Discharge region 32 Reactive gas flow 33 Surface treatment Device 34 Power source 35 Electrode 36 Liquid 37 Container 38 Gas supply device 39 Gas ejection port 40 Metal plate 41 Processing material 42 Discharge region 43 Injection port 44 Discharge port 45 Circulation pipeline 46 Pure water regenerating device 47 Surface treatment device 48 Power source 49, 50 electrode 51 casing 52 gas supply device 53 liquid 54 container 55 nozzle 56 material to be treated 7 Discharge Area 58 Plug 59 Cleaning Tank 60 Substrate 61 Synthetic Resin Coating 62 Orientation Processing Device 63 Power Sources 64, 65 Electrode 66 Insulator 67 Gas Supply Device 68 Discharge Area 69 Orientation Processing Device 70 Discharge Generation Unit 71 Blow-out Nozzle 72 Tip Outlet 73 Substrate 74 Metal plate 75 Electrode 76 Passage 77 Air outlet 78 Discharge region 80 MIM substrate 81 Surface treatment device 82 Quartz tube 83 Electrode 84 Control circuit 85 Power supply 86 Ground electrode 87 Discharge region 88 Gas jet 89 Surface treatment device 90 Power supply 91 Gas blow Outlet 92 Surface treatment device 93 Power electrode 94 Ground electrode 95 Glass tube 96 Glass substrate 97 Gas supply device 98 Container 99 Organic matter 100, 101 Control valve 102 Polymerized film 103, 104 Part 105 Power electrode 106 Gas outlet 107 Dielectric 108 Power electrode 109 ground electrode 110 gas outlet 111 polymerization 112 ground electrode 113 power electrodes 114 gas supply device

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Katsuhiro Takahashi             Seiko, 3-3-3 Yamato, Suwa City, Nagano Prefecture             -In Epson Corporation (72) Inventor Takeshi Miyashita             Seiko, 3-3-3 Yamato, Suwa City, Nagano Prefecture             -In Epson Corporation (72) Inventor Satoru Katagami             Seiko, 3-3-3 Yamato, Suwa City, Nagano Prefecture             -In Epson Corporation F-term (reference) 2H088 FA18 FA21 HA02 MA20                 2H092 HA02 HA04 HA06 JB01 MA25                       NA28 PA01                 4K028 BA05 BA13

Claims (3)

[Claims] 1. A step of causing a gas discharge in a gas containing at least hydrogen or an organic substance under atmospheric pressure or a pressure in the vicinity thereof, and an electrode formed on a substrate by an active species of the gas generated by the discharge. And a step of exposing the surface treatment method. 2. A step of causing a gas discharge in a gas containing at least hydrogen or an organic substance under atmospheric pressure or a pressure in the vicinity thereof, and an active species of the gas generated by the discharge formed in a display device. Exposing the electrodes,
A method for manufacturing a display device, comprising: 3. The method for manufacturing a display device according to claim 2, wherein the electrode is ITO.