JP3508789B2 - Substrate surface treatment method - Google Patents

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 and the like 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.

[0013]

In one aspect, the substrate surface treatment method of the present invention produces a gas discharge in a gas containing an organic substance under atmospheric pressure or a pressure in the vicinity thereof, and the gas discharge is generated by the discharge. The metal oxide layer formed on the surface of the substrate is exposed to the gas activated species, thereby reducing the metal oxide layer.

[0014] By thus generating a gas discharge under a pressure near atmospheric pressure by a relatively simple structure, Yes
The organic matter is dissociated, ionized, and excited to generate active species such as organic matter, carbon, and hydrogen ion-excited species, and the metal oxide layer on the surface of the substrate can be reduced and metalized by their action.

In one embodiment, the
The organic substance does not necessarily have to be included in the discharge gas.
Ku, due to be pre-organics were applied to the substrate surface
Therefore, the dissociation, ionization, and excitation of the organic substance by the gas discharge can be effectively performed. It is also possible to add vaporized organic matter to the gas that causes gas discharge ,
Similarly, its dissociation, ionization, and excitation are promoted, and reduction treatment
It is possible that.

In one embodiment, the gas for generating the gas discharge further comprises water vapor. By including water vapor in the gas that causes gas discharge, the rate of reduction treatment by the gas active species can be accelerated.

[0017]

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 a method for treating a surface of 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. Both electrodes 3
Immediately below the substrate is a substrate 6 for performing a desired surface treatment.
Are arranged horizontally. 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 thereof, 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 troubles 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 an 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 embodiment, since the surface of the lower metal wiring is oxidized and covered with the metal oxide as described above, it is possible to form the interlayer insulating film thicker than the thickness necessary for electrical insulation. Regardless of the presence or absence of pinholes, 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 substance 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, water or liquid organic matter 18 stored in the tank 17 is heated by a heater 19 to generate steam or vaporized gas of the liquid organic matter, 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.

[0032]

[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 you can see 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 pipe 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 pipe. 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 the case of 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 electrode 35 and the liquid surface of 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 the discharge gas, the gas discharge produces active species such as oxygen radicals and ozone in the discharge region 42. 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. Book
According to the embodiment , 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 provided at both ends of a container 37 for storing the liquid 36, and pure water is provided in the middle of a circulation conduit 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 to replace the space between the electrodes 49 and 50 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 the liquid 36 containing the excited active species mixed therein. 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, the material 41 to be treated is arranged outside the container 37 for generating the gas discharge, so that the container 37 can be formed according to 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.

Further, FIG. 13 shows another embodiment of the surface treatment method related to the present invention. In the present embodiment, a relatively large material to be processed 41 such as a glass for a liquid crystal panel and a wafer substrate is placed in a cleaning tank 59, and is cleaned by 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 from the gas supply device 38 between the electrode 35 and the surface of the liquid 36, and a gas discharge is generated.
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.

According to this embodiment , regardless of the size, shape and size of the material to be treated 41, the material 41 is fixed at a desired position and is continuously cleaned by circulating pure water for cleaning. Therefore, it is possible to easily deal with the recent increase in size of glass substrates for liquid crystal panels and wafers, and single-wafer processing and batch processing are possible. Further, according to the present embodiment , even when a treatment such as cleaning is performed using a liquid other than pure water, the cleanliness thereof can be easily recovered by performing the ashing treatment on the used liquid similarly.
Can be reused.

[0053] Figure 14 is an alignment film formation method of the liquid crystal display device related to the present invention have been described. TFT, MIM
A synthetic resin coating 61 such as an organic polymer resin is applied to the upper surface of the counter substrate 60 of the liquid crystal panel on which elements such as (Metal Insulator Metal) and ITO, electrode patterns, or color filters are formed. Above the substrate 60, a large
An alignment treatment device 62 to which a surface treatment method using plasma under atmospheric pressure is applied is arranged. This alignment treatment device has an electrode 64 connected to a power source 63 and a grounded electrode 65 as a counter electrode thereof. The electrode 64 on the power source side is entirely covered with an insulator 66 such as glass or ceramic. Electrode 64 covered by insulator 66
The electrode 65 and the electrode 65 are arranged so as to face each other at a constant interval and incline at an angle a with respect to the surfaces of the substrate 60 and the synthetic resin coating 61 as shown in the drawing. The angle a is appropriately set within the range of 0 degree <a <90 degrees. The space defined between the electrodes 64 and 65 is connected to a gas supply device 67 that supplies a discharge gas.

When a voltage is applied from the power supply 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 at or near atmospheric pressure. 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 on 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 related to the present invention. The alignment treatment device 69 includes a gas supply device 67 and a discharge generator 70 including a power electrode and a ground electrode as in the embodiment of FIG.
And the blowing nozzle 71. 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 the alignment film of the liquid crystal panel according to the present invention. In this embodiment, a substrate 73 to be oriented is placed on a grounded metal plate 74, and a metal electrode 75 is arranged immediately above it. 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. Since the alignment treatment can be performed in a non-contact manner as described above, there is no risk of damaging or peeling the surface of the synthetic resin film, and moreover, uniform alignment can be provided. 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 formed directly 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 the alignment film on the 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, specifically described alignment film forming method of the liquid crystal panel by way of 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, an electrode 83 is arranged at the center of a quartz tube 82 having a double structure, is connected to a power source 85 via a control circuit 84, and is connected to a ground electrode 86 arranged outside the quartz tube 82. It was discharged. 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 used: Compressed air gas pressure: 3 to 7 kg / cm ² Power consumption: 100 to 200 W Processing time: 20 minutes

The liquid crystal is sandwiched between the substrate 80 thus oriented and the substrate on which an alignment film is formed by the conventional rubbing treatment, and polarizing plates are arranged on both sides of the liquid crystal to irradiate light to obtain an alignment state. Was observed. 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.

Example 2 Similarly, the polyimide coating on the surface of the MIM substrate 80 provided with the wiring pattern was subjected to orientation treatment using the line type surface treatment device 89 shown in FIGS. 19A and 19B under the following conditions. The surface treatment device 89 has a power source 9 connected to a power source 85.
Elongated gas outlet 91 along the longitudinal direction on the bottom surface of 0
The board 80 is opened and is horizontally conveyed immediately below.
The polyimide coating was directly exposed to the discharge while the discharge gas was ejected onto the surface. Gas used: Mixed gas of helium and oxygen Gas flow rate: Helium 20 liters / minute Oxygen 100 ccm Power used: 100 V, 13.56 MHz Processing time: 1 minute

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.

Example 3 Similarly, the polyimide coating on the surface of the MIM substrate 80 provided with the wiring pattern was subjected to orientation treatment under the following conditions by using the spot type surface treatment device 92 shown in FIGS. 20A and 20B.
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 is formed in the vicinity of the other end of the glass tube 95 at an angle θ with respect to the gas flow ejected from the other end opening.
= 10 to 30 degrees. Gas used: Mixed gas of helium and oxygen Gas flow rate: Helium 20 liters / min Oxygen 100 ccm Power used: 100 V, 13.56 MHz Processing time: 1 to 3 minutes

When the orientation of the polyimide coating 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, since the substrate 80 is not directly exposed to the 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 Examples 1 to 3 above, 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 alignment film was directly formed on the surface of a Pyrex 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 treating apparatus has the same structure as that of the embodiment of FIG.
And the glass substrate 96 on the ground electrode 74 is directly discharged. As the discharge gas, the organic substance 99, which is liquid at room temperature in the container 98, is changed to the gas sent from the gas supply device 97 by the control valve
The electrode 75
The polymer film 102 of the organic substance 99 was formed on the surface of the glass substrate by obliquely ejecting the gas from the gas outlet 77 to the surface of the substrate 96 through the passage 76 inside. Electrode 75 and substrate 9
The gap with the six surfaces 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 matter: OH-modified silicone, silicone oil, n-decane Power consumption: 150W

When the liquid crystal was sandwiched between the two substrates 96 on which the polymerized film 102 was formed and the orientation was observed in the same manner, the portion 103 of the polymerized film 102 near the gas outlet 77 was not oriented. The part 102 far from the gas outlet 77
Were oriented.

Example 5 An alignment film was directly formed on the same surface of the glass substrate 96 as in Example 4 under the following conditions. As shown in FIG. 22, the surface of the glass substrate 96 disposed on the ground electrode 74 and the power supply electrode 105.
And a discharge gas was ejected laterally from the gas outlet 106 to the discharge region. The same discharge gas as in Example 4 was used, and the polymer film 102 was formed on the surface of the substrate. Gas used: Helium gas flow rate: 20 liters / minute Liquid organic matter: OH-modified silicone, silicone oil, n-decane Power consumption: 150W

In the polymer film 102, the portion 103 near the gas outlet 106 was not oriented, but the portion 104 far from the gas outlet 106 was oriented, as in Example 4.

Example 6 An alignment film was directly formed on the surface of the same glass substrate 96 as in Example 4 using the surface treatment apparatus shown in FIG. 23 under the following conditions. In this surface treatment apparatus, as in the case of the fourth embodiment, the discharge gas mixed with the organic substance 99 that is liquid at room temperature is used as the dielectric 107.
The gas is supplied to the inside and a discharge is generated between the power electrode 108 inside the dielectric and the ground electrode 109 outside, and a gas flow containing the active species of the gas due to the discharge is discharged from the gas outlet 110 to the surface of the glass substrate 96. Spray at an angle of 60 degrees to
A polymer film 111 was formed over the entire surface. The polymer film had a liquid crystal pretilt angle of 90 degrees and was not oriented. Gas used: Helium gas flow rate: 20 liters / min Liquid organic matter: OH-modified silicone Power used: 150W

Next, as shown in FIG. 24, the ground electrode 11
While horizontally transporting the glass substrate 96 placed on 2,
It was directly discharged to the power supply electrode 113. 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.

Example 7 The same experiment as in Example 6 was conducted using an MIM substrate provided with a wiring pattern. 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.

[0079]

According to the substrate surface treatment method of the present invention,
Since the metal oxide layer on the surface of the substrate can be reduced and metallized easily and at high speed without damaging other parts of the substrate, for example, electronic parts, the metal oxide layer is ITO. In the case of a transparent electrode such as the above, the desired electrical performance can be secured by reducing the resistance while reducing the film thickness to maintain the desired transparency.

Further, according to the surface treatment method of the present invention, it is possible to perform the surface treatment by providing the portion for generating the gas discharge and the portion for the surface treatment of the material to be treated at different positions. It is possible to perform surface treatment according to the purpose of treatment, the shape and size of the material to be treated, the number of materials to be treated at one time, the type of gas used for gas discharge, the environment to be discharged, etc., and adjust the treatment capacity appropriately. You can 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.
The surface treatment method can be realized at a low cost with a relatively simple structure.

[0081]

[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 .

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 .

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

FIG. 23 is a diagram showing a first half of the process in another example of the method for forming an alignment film of a liquid crystal panel .

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

[Explanation of symbols]

1 surface treatment equipment, 2 power supply, 3 electrodes, 4 space, 5
Gas supply device, 6 substrates, 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 conduits, 16 valves, 17 tank , 18
Water or liquid organic matter, 19 heaters, 20 atomizers,
21 conduits, 22 surface treatment equipment, 23 power supply, 24
Electrode, 25 metal cover, 26 insulating fixture, 27 lower end, 28 opening, 29 gas supply device, 30 metal mesh, 31 discharge region, 32 reactive gas flow, 33
Surface treatment equipment, 34 power supply, 35 electrodes, 36 liquid,
37 container, 38 gas supply device, 39 gas outlet,
40 metal plate, 41 processed material, 42 discharge area, 43
Inlet, 44 outlet, 45 circulation line, 46 pure water regenerator, 47 surface treatment device, 48 power supply, 49, 5
0 electrode, 51 casing, 52 gas supply device, 5
3 liquids, 54 containers, 55 nozzles, 56 treated materials,
57 discharge area, 58 stopper, 59 cleaning tank, 60 substrate,
61 synthetic resin film, 62 orientation treatment device, 63 power supply, 64, 65 electrode, 66 insulator, 67 gas supply device, 68 discharge area, 69 orientation treatment device, 70 discharge generation part, 71 blow nozzle, 72 tip blow outlet, 73
Substrate, 74 metal plate, 75 electrode, 76 passage, 77
Air outlet, 78 discharge area, 80 MIM substrate, 81
Surface treatment device, 82 quartz tube, 83 electrode, 84 control circuit, 85 power supply, 86 ground electrode, 87 discharge area,
88 gas outlet, 89 surface treatment device, 90 power supply,
91 gas outlet, 92 surface treatment device, 93 power supply 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, 1
04 part, 105 power electrode, 106 gas outlet,
107 dielectric, 108 power electrode, 109 ground electrode, 110 gas outlet, 111 polymerized film, 112 ground electrode, 113 power electrode, 114 gas supply device

─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Takeshi Miyashita 3-5 Yamato, Suwa City, Nagano Prefecture Seiko Epson Co., Ltd. (72) Inventor Satoru Katagami 3-5 Yamato, Suwa City, Nagano Prefecture (56) References JP-A-5-235541 (JP, A) JP-A-4-273442 (JP, A) JP-A-2-281734 (JP, A) JP-A-61-203655 ( JP, A) JP 3-153037 (JP, A) JP 6-108257 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C23C 8/36 H01L 21/2305 H01L 21/28 H01L 21/316 H01L 21/768

Claims (2)

(57) [Claims] 1. Organic matter under pressure at or near atmospheric pressure
Causing gas discharge in the gas containing, in the active species of the gas generated by the discharge, it is exposed a layer of metal oxide formed on the substrate, thereby reducing the metal oxide layer Engineering
In advance, the organic substance is pre-coated on the surface of the substrate.
A surface treatment method for a substrate, characterized in that 2. The method for surface treatment of a substrate according to claim 1, wherein the gas further contains water vapor.