JP2003045842A - Method and apparatus of removing foreign matters deposited on surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method and apparatus for removing foreign matters (such as resist) deposited on the surfaces of various sorts of products including an electronic device substrate such as a liquid crystal glass substrate and cleaning the surfaces efficiently in a short time. SOLUTION: The method can remove foreign matters deposited on the surface of an object 1, by applying an ozone-soluble solvent on the surface of the object 1 to form a solution film thereon, and introducing a gas containing a high concentration of ozone into a lamellar gap between the surface and a ceiling plate 14 or another object to contact the gas with the solution film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for cleaning an article surface requiring removal of contaminants, and more particularly to a method for cleaning the surface of an electronic device substrate. Specifically, the present invention relates to removal of an organic film such as a photoresist used in processing a semiconductor wafer or a liquid crystal substrate, and cleaning / removal of organic contaminants generated throughout the wafer process. Furthermore, it relates to cleaning and removal of organic pollutants in precision metal products and glass products.

[0002]

2. Description of the Related Art Regarding the stripping of a photoresist after it has been used for microfabrication of an oxide film or a silicon film, a mixed solution of sulfuric acid (3 volumes or 4 volumes) and hydrogen peroxide (1 volume) is usually called piranha. Heated to 110-140 ℃
A method of dipping for 10 to 20 minutes is adopted. When high-concentration ion implantation is performed on the resist mask, the resist is denatured and cannot be removed by the piranha treatment, so ashing with plasma-excited oxygen is generally used. However, only ashing leaves organic alteration products derived from resist, fine particles, and trace metals on the wafer surface. Therefore, normally, even after the ashing process, the piranha process is further performed.

Since the piranha treatment uses high temperature sulfuric acid, there are many environmental problems regarding drainage and exhaust. Therefore, instead of this piranha treatment, resist stripping with ozone water has been attempted. When water is cooled to near 0 ° C, the solubility of ozone reaches 70-100ppm. However, in the case of a novolac resin-based positive resist film for I-line, which is widely used in LSI manufacturing, the stripping rate is 70 to 80n in ozone water treatment.
It is inefficient because it is slow at m / min. However, performing the resist stripping by ozone water treatment is effective in that the resist can be sufficiently decomposed by ozone, so a method of further increasing the resist stripping rate by ozone water treatment has been attempted, and it has been proposed to use a gas containing moist ozone. Methods of handling have been proposed.

An organic solvent such as n-methylpyrrolidone is usually used for stripping the resist used for fine processing of a metal film such as aluminum used for wiring. Further, although Freon has been widely used for precision cleaning of electronic parts, it cannot be used due to environmental problems, and a water-based alternative cleaning agent such as an alkaline cleaning agent or a surfactant is used.

[0005]

With the increasing miniaturization of semiconductor devices, especially VLSI, the need for reduction of organic contaminants on the wafer surface is becoming more and more important. The piranha cleaning process, which is effective in removing organic pollutants, is widely practiced in device manufacturing plants, but when the amount of high-temperature sulfuric acid used increases, environmental measures become troublesome, and since sulfuric acid has a strong viscosity, it is not suitable for rinsing. Since a large amount of ultrapure water is required, there are many social and economic problems.

In the case of stripping a novolac resin-based positive resist on a metal surface, organic bases such as n-methylpyrrolidone are often used as described above, but the degree of heating of the processing liquid and the processing time are long. Some corrode the metal surface.
Therefore, the treatment requires precise control, and in many cases, rinsing with an organic solvent such as isopropyl alcohol is performed before transferring to ultrapure water rinsing, which is also a problem in terms of economy.

Therefore, it is expected that ozone water will be treated. However, high-purity ozone water used for semiconductor-level treatment is a method in which high-purity oxygen containing ozone (hereinafter referred to as ozone gas) is passed through ultrapure water. It is manufactured by absorbing ozone. When a gas containing ozone at a concentration of C _G [mg / liter] is in equilibrium with a liquid at a concentration of ozone C _L [mg / liter] at a certain temperature, C _L and C _G are proportional to Henry's law, and their proportions are proportional. The constant distribution coefficient D = C _L / C _G is constant. Here, when the liquid is water, in one research example, at 25 ° C, D = 0.2,
It has been reported that D = 0.28 at 20 ° C and D = 0.47 at 5 ° C. The ozone concentration obtained by a normal discharge type ozone gas generator is about 200 mg / liter.
At 40 ppm and 5 ° C, 94 ppm is the saturated concentration. When water actually absorbs ozone, only a concentration lower than this saturation concentration can be obtained. Although ozone concentration can be increased with low-temperature water, the reaction rate usually decreases when the temperature decreases, and the resist stripping rate does not reach a sufficient value as described above.
It takes 20 to 30 minutes to remove and remove the novolac resin-based positive resist film of μm.

Some of the commercially available high-concentration ozone gas generators can generate ozone gas having a concentration of up to 300 mg / liter. It has been reported that when the concentration of ozone and the treatment temperature are raised by the treatment method using moist ozone gas, which appeared as an improvement of the ozone water treatment method, the peeling rate of the novolac resin-based positive resist film can be significantly improved. In this case, if the ozone concentration of the gas is 230 mg / liter and the treatment is performed at about 80 ° C., the peeling rate is about 1 μm / min.

The present inventor has found that ozone in gas and the partition coefficient D
Invents a method of sufficiently dissolving ozone in an organic solvent having a value of 0.6 or more and bringing it into contact with the surface to be cleaned to obtain a strong cleaning action, and has already applied for a patent (Japanese Patent Application No. 2000-101064, hereinafter,
Prior invention). When ozone gas with a concentration of 250 mg / liter is bubbled into pure acetic acid at room temperature, the ozone concentration in acetic acid usually reaches about 300 ppm in about 5 minutes. According to this acetic acid solution in which ozone is dissolved (hereinafter referred to as "ozone acetic acid"), the peeling rate of the above-mentioned novolac resin-based positive resist is 5 to 6 µm / min at room temperature, and the normal film thickness is about 1.5 µm. Then, it can be peeled off in 15-18 seconds.

However, when the bubbling means is used, the ozone molecules dissolved in the solvent are degassed at the same time when the ozone molecules of the gas are dissolved in the solvent, so that the distribution coefficient obtained from the static equilibrium is obtained. The ozone concentration in the solvent does not rise. There have been several reports of partition coefficients for acetic acid at room temperature, between 1.5 and 1.9, which should give ozone acetic acid with an ozone concentration of at least 380 ppm at 250 mg / l of ozone gas, but a fairly complicated bubbling device. Is used and the amount of acetic acid is decreased with respect to the gas flow rate or the bubbling time is not increased, the desired concentration is not easily reached. In addition, since ozone is easily degassed especially with high-concentration ozone acetic acid, even if such a high-concentration ozone acetic acid generator is used, if ozone acetic acid is used for treatment after being stored for a short time, The ozone concentration during the peeling process is likely to drop to around 300 ppm.

In the above-mentioned prior invention, a method for forming a liquid film of an ozone-soluble organic solvent on the surface of an object to be treated in an atmosphere containing ozone to remove adhering foreign substances, and ozone gas in a treatment chamber. An apparatus for removing an adhering foreign substance, which forms a solvent liquid film on the surface of an object to be treated, is provided. In this case, a bubbling device is not necessary, but the required amount of ozone gas is large, and a large amount of high-concentration ozone gas is used, so economically and practically there is a difficulty in implementing it. In the embodiment of the invention of the prior application, the ozone concentration introduced into the chamber is 200 mg / liter or less, and if the liquid film is formed with ozone acetic acid having a concentration that can be easily obtained by bubbling, the above-mentioned high concentration of ozone acetic acid can be obtained. It is practical because the removal performance is similar to that in the case of supplying liquid to form a liquid film.
However, naturally, an ozone dissolver by bubbling is required.

The present invention is a further improvement of the prior invention, in which an ozone dissolver for an organic solvent is unnecessary and a solvent liquid film in which ozone is dissolved is formed on the surface of the object to be treated by a high concentration ozone gas which is not large in quantity. The present invention provides a method and a device therefor, and as a result, it is possible to reduce the amount of high-concentration ozone gas used and to significantly improve the removal performance for foreign substances adhering to the surface.

[0013]

In order to achieve the above object, the present invention provides a surface of an object to which a foreign substance is attached,
An ozone-soluble solvent capable of sufficiently wetting the surface is applied, and a layer formed between the top plate adjacent to the surface of the object to be processed and another object to be processed with respect to the liquid film formed thereby. Used for removing a foreign substance adhering to a surface, which is characterized by removing a foreign substance adhering to the surface of an object to be treated by bringing a gas containing a high concentration of ozone introduced into a gap into contact therewith. The present invention relates to a removing device.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In a preferred embodiment of the method of the present invention, a gas having an ozone concentration of 200 mg / liter or more is applied to the surface of an article having a surface-attached foreign substance at a distance from the article surface to the surface of the article. After being introduced into the layered space between the top plate and another object to be treated within 10 mm, an ozone-soluble solvent capable of sufficiently wetting the surface of the article is supplied to the surface to form a liquid film, and ozone gas is generated. It is to contact.

Furthermore, according to the method of the present invention, after forming a liquid film of an ozone-soluble solvent capable of sufficiently wetting the surface of an article having surface-attached foreign matter, the ozone concentration is 200%.
It also includes a mode in which mg / liter or more of gas is supplied to the layered gap between the top plate or another object to be processed and the distance from the surface is within 10 mm.

The present invention is most effective when the article is a substrate for the electronic industry, and particularly when the foreign substance adhering to the surface is a photoresist. It is particularly effective against novolak resin-based positive resists that are widely used in the LSI and liquid crystal fields, and even with chemically amplified polyvinylphenol derivative-based positive resists, the peeling speed is slightly inferior, but at the same level. effective. Furthermore, for the cyclized polyisoprene type, which is a typical negative type resist, an even faster peeling rate is obtained. Therefore,
The present invention is applicable to most of the photoresists commonly used in the electronics industry.

In the present invention, in order to achieve the rapid removal of foreign substances from the surface of an article, a liquid film must be formed quickly on the surface of the article. That is, in order to sufficiently wet the article surface in an extremely short time, the surface tension of the solvent used at the treatment temperature must be small. Therefore, a solvent of 40 dyn / cm or less, preferably 30 dyn / cm or less is used. The thickness of the liquid film varies depending on the inclination of the article surface and the rotating state, but it is desirable that it be around 100 μm, 10 μm
But you can reach the goal enough. In the case of a chemically amplified resist, it may be preferable to set the thickness to about 300 μm.

The solvent for forming the liquid film is preferably one capable of swelling all or at least a part of the attached foreign substance, and more preferably all or at least a part of the attached foreign substance. It is extremely important to adopt a material that can be dissolved in order to accelerate the removal rate in the method of the present invention. Solubility should be at least as much as the total amount of attached pollutants.
It is preferably 50% by weight or more. Even if there are some dissolved residues, these are usually easily decomposed by ozone,
After all, it is completely removed as a decomposed product, so there is no problem.
Generally, when the temperature is raised, the solubility is remarkably improved, so it is highly preferable to heat the solvent at a temperature not higher than the flash point of the solvent. For that purpose, the solvent may be heated, ozone gas may be heated, or the article to be treated itself may be heated. A field in which it is effective to have solubility in all or at least the surface layer of adhered pollutants is the removal of adhered foreign substances such as fine particles adhered by oils and fats, etc. The application of certain solvents has a very pronounced effect.

The fact that the solvent forming the liquid film has a high solubility in ozone is the next most important point in order to enhance the speed of removal of foreign substances adhering to the surface. The method of the present invention attaches great importance to this quickness, and it is desirable that the partition coefficient of the solvent with respect to ozone gas is 1.0 or more, preferably about 1.5. However, when the surface-adhered contaminant is a metallic component and its purpose is limited for its removal, it can be sufficiently applied as long as the solubility is satisfied even if the partition coefficient is considerably small.

The most preferable solvent satisfying the above conditions is a low molecular weight aliphatic carboxylic acid, and in particular, a compound having the formula: C _n H _{2n + 1} COOH (where n = 1, 2 or 3 is an integer). The compound represented by () is preferable because it has low reactivity with ozone. Of these, acetic acid has good stability when it contains ozone, as it has been used as a reaction solvent for ozone oxidation, and has a large partition coefficient for ozone, as described above, and a high surface tension. Is about 25
Since it is dyn / cm, a liquid film can be easily formed on the article surface. In particular, when the surface-attached contaminant is an organic substance having a double or triple hydrocarbon bond, oxidative decomposition by ozone is strongly achieved in a liquid film using acetic acid as a solvent.
Also, even if propionic acid or butyric acid is used, in the same manner as acetic acid,
It has almost the same effect.

In addition to the above, halogenated hydrocarbons are often used as the effective organic solvent for the liquid film treatment. In particular, hydrochlorofluorocarbon (HCFC) is preferable, the distribution coefficient for ozone is close to 2.0, and the surface tension is 20 dy.
Since it is n / cm or less, the effect of cleaning the surface of precision metalworking products and glassworking products against oil and flux is further enhanced. The cleaning action of ozone with such a liquid film is possible even with an inorganic solvent such as heated sulfuric acid, and it is effective in removing inorganic surface-adhering pollutants.

As provided in the above-mentioned prior invention, a liquid film of an ozone-soluble solvent is formed on the surface of an article having a foreign substance adhering to the surface and placed in an ozone gas atmosphere, and the resulting ozone-containing solvent and the article surface. Surface foreign contaminants can be removed by contacting with. This is because if the ozone concentration in the atmosphere in contact with the liquid film is higher than the ozone concentration in the liquid, ozone easily diffuses in the liquid film and the ozone concentration in the liquid film rises to near the saturation point in a short time. However, the method of the invention of the prior application has a practical problem in that a large-capacity high-concentration ozone gas generator with good economy is required.

According to the present invention, a high concentration ozone gas of 250 mg / liter or more fills a layered gap whose distance from the surface to be treated is within 10 mm, preferably about 1 to 5 mm, and a liquid film which contacts the gas is formed. Whether it is intentionally stopped or is made to flow at a slow speed of several cm / sec or less, or several c
A method for removing a novolac resin-based positive resist having a thickness of 1.5 μm within 10 seconds by swinging at a moving distance of about m. The peeling speed reaches 10 μm / min or more. The mechanism is that the high-concentration ozone layer with a narrow and limited layered gap is in contact with a thin liquid film whose thickness is less than 100 μm due to the small surface tension, resulting in supersaturation of the ozone concentration in the liquid film. It is estimated that this is due to reaching. Further, in the case of a polyvinylphenol derivative resist having a film thickness of 0.5 μm or less, the same degree of peeling performance can be achieved by controlling the layered gap to about 1 mm to increase the effective flow rate of ozone gas.

It is known that the partition coefficient of ozone acetic acid solution prepared by bubbling ozone into acetic acid with ozone in gas decreases to about 60% when the temperature of the solution changes from 20 ° C to 40 ° C. However, even if the temperature rises and the reaction rate of the solvent itself with respect to the resist rises, when it is treated as a liquid film, the peeling rate is about twice at maximum, that is, about 10 μm / min. However, in the method of the present invention, when the temperature of the acetic acid liquid film is set to 40 ° C., the above-mentioned novolac resin-based positive resist film having a thickness of 1.5 μm is peeled off within several seconds, and the peeling speed at this time is as high as 20 μm / min or more. Presumed to have reached.

In the method of the present invention, since the resist can be stripped in a short time of about 5 seconds, a relatively small high-concentration ozone generator is used to temporarily store the generated gas, and this gas is stored on the resist surface in a short time. When released rapidly at a high flow rate, the ozone gas-occupying layered gap on the surface of the article is limited, so that the ozone concentration of the surface liquid film sufficient for resist stripping can be maintained for a required time.

As an apparatus for forming a high-concentration ozone gas layer having a required thickness on the surface of an article, a hood having a removable top plate is used, and the entire surface of the surface to be treated or the surface of the surface to be moved is supplied only when ozone gas is supplied. A structure that covers a part of it is desirable. In the case of processing an electronic industrial substrate surface in a cassette or spin processing a cassette containing a plurality of substrates, a high-concentration ozone gas layer can be formed in the layered gap between the substrate surfaces.

An example of a method of forming a liquid film that is brought into contact with ozone gas is as follows. (1) The solvent is sprayed onto the inclined surface of the substrate to be processed with a nozzle for a short time or intermittently, and the spraying is stopped when the entire surface of the substrate becomes wet. (2) When using the single-wafer spin processing mechanism, the solvent is discharged to the central portion, and low-speed spin processing at about 50 rpm is performed for a very short time to stop the rotation when the entire surface of the substrate becomes wet. (3) In the chamber, the solvent is discharged from a nozzle above the cassette into a cassette on which a plurality of substrates are placed, so that the entire surface of the substrate is wetted. (4) When using a spin processing mechanism that rotates a cassette on which multiple substrates are placed on a horizontal rotation axis, the solvent is discharged from the nozzle above the cassette, and low speed spin processing at about 50 rpm is performed for a very short time. The rotation is stopped when the entire surface of the substrate gets wet.

In any of the above cases, the ozone gas is released after the liquid film is formed on the entire surface. Since the time required for peeling is short, there is sufficient time margin to perform the peeling / removing treatment twice including the rinse with the solvent, and it is desirable to repeat the operation to ensure the effect. In the case of single-wafer spin processing, if resist removal / removal is difficult due to the resist after dry etching or ion implantation, the substrate should be repeatedly inverted at a relatively small angle during the ozone gas release time. Is effective.

[0029]

[Examples] The ozone-containing gas used in the following examples was obtained by flowing oxygen containing 0.4% of nitrogen into a small discharge type ozone generator, and having a high ozone concentration of about 250 mg / liter. It is ozone gas. As the organic solvent for dissolving ozone, as described in the specification of the prior application, acetic acid is preferable in that the effect of removing attached foreign substances and economical efficiency are compatible, so that the organic solvent in this example has a purity of
99.7% acetic acid was used.

When acetic acid in which ozone is sufficiently dissolved by bubbling, the peeling performance of the novolak resin-based positive resist reaches 6 μm / min at room temperature, the peeling performance is good, and if a small amount of hydrofluoric acid is added. In addition, fine particles and metal contamination on the semiconductor wafer can be effectively removed. Therefore, in the present invention, if stronger resist peeling than the above can be performed by acetic acid contacted with ozone gas, the same action as a chemical solution
Since an effect can be expected, it is considered that foreign substances adhering to the surface such as fine particles and metals can be similarly removed.

In order to clarify that the resist removal performance of the present invention is superior to that of the prior invention, it is shown in Example 13 of the prior invention specification as a resist coating sample in Examples 1 to 4. The same novolak resin-based positive resist "IX555" (JSR Corporation)
Manufactured by the same process as in the above embodiment, that is,
It was applied to the surface treated with HMDS (hexamethyldisizan), the coating thickness was 1.5 μm in each case, and baking was performed at 140 ° C. for 60 seconds. The amount of residual organic carbon after stripping / removing the resist was measured by charged particle activation analysis using a sample preparation device described in JP-A-10-39410, and it was confirmed that the stripping / removal was performed sufficiently.

Example 1 Spin cleaning in which the spin rotation speed is variable from low speed to high speed,
A single wafer cleaning machine capable of spin rinsing and spin drying was modified to create a single wafer spin resist stripping device for silicon wafers. FIG. 1 is a vertical sectional conceptual view of the device. A 200 mm diameter silicon wafer 1 with a 100 nm thick oxide film coated with a resist has a spin axis 2
It is configured to be held and rotated by the wafer holder 3 attached to the. Like the bearing 8 of the rotatable acetic acid supply pipe 7, which can discharge acetic acid to the center of the wafer through the acetic acid discharge port 6 at the tip of the chamber 5 having the spin bearing 4 only while the wafer is being loaded, the tip thereof has A bearing 11 of a rotatable gas supply pipe 10 for discharging high-concentration ozone gas is attached to the center of the wafer at the discharge port 9. Also,
While the ozone gas is being supplied, an exhaust liquid for exhausting acetic acid solution after the ozone gas is dissolved and the resist is stripped off and removed on the side wall of the exhaust pipe 12 having substantially the same height as the wafer for exhausting the ozone gas. A tube 13 is provided at the bottom.

While the ozone gas is discharged to the wafer surface, the entire surface of the wafer is covered, and the roof-like quartz glass hood is formed so that the layered gap between the wafer surface and the acetic acid supply pipe and the ozone gas supply pipe is not larger than about 5 mm. Body 14
Are placed. When the wafer is attached or detached, the hood body 14 moves upward and stands by. A heat exchanger 16 is connected to the acetic acid supply pipe 7 near the valve 15.
Further, the gas supply pipe 10 is connected to a compact high-concentration ozone gas generator (not shown) that generates ozone gas with an ozone concentration of 250 mg / l and a gas flow rate of 4 l / min. The pipe is close to the valve 17 and the three-way valve 18 temporarily stores the ozone gas generated from the generator to automatically store the generated ozone gas.
A cylinder 20 capable of discharging about 2 liters of ozone gas from the gas discharge port 9 in about 10 seconds is connected.

The resist stripping / removing process is performed as follows. First, high-concentration ozone gas is previously sent to the cylinder from the three-way valve 18 for about 30 seconds to fill the cylinder having a storage volume of about 2 liters in a full tank. After the hood body 14 is lifted up and the resist-attached wafer 1 is loaded on the holder 3, the acetic acid discharge port 6 and the gas discharge port 9 are positioned at the center of the wafer, and the hood body 14 is lowered to cover the entire surface of the wafer. The wafer is rotated at a low speed of about 60 rpm, and acetic acid heated to about 40 ° C. by the heat exchanger 16 is transferred to the valve 1
When about 5 cc is discharged by opening and closing 5, an acetic acid liquid film is instantaneously formed on the entire surface. Here, the rotation is stopped once. By operating the three-way valve 18 and the valve 17, about 1 liter of high-concentration ozone gas stored in the cylinder 20 is discharged to the wafer surface in 5 seconds, and most of the resist is peeled off in several seconds. Simultaneously with the release, the wafer is rotated at a medium speed of 500 to 1,000 rpm, and acetic acid is released at a flow rate of 200 cc / min for about 5 seconds to perform the first spin rinse. After the rinse, the rotation and the discharge of the liquid are stopped again, and about 1 liter of high-concentration ozone gas in the cylinder 20 is discharged on the wafer for about 5 seconds to complete the peeling, and then the second rinse is performed similarly to the first rinse. Next spin rinse. After the rinsing is completed, the hood body is moved upward, the rotation speed is increased to about 3,000 rpm, the rinse acetic acid adsorbed on the wafer surface is released, and spin drying is performed to complete the peeling / removing treatment.

The resist stripping rate at the primary ozone gas releasing stage was estimated to be close to 20 μm / min, and extremely fast stripping could be performed. The amount of residual organic carbon on the wafer surface immediately after peeling / removing is (3 to 5) × 10 ¹³ atoms / cm ²
Met. From this analysis result, it can be seen that the resist was removed and removed sufficiently. Even if it takes about 20 seconds for the total peeling and rinsing time, about 20 seconds for spin-drying, and about 20 seconds for exchanging the wafer, the processing time is 1 minute per wafer, and the productivity is considered to be sufficient for practical use. Since the amount of acetic acid used in this example is about 40 cc, the amount of liquid is 1/4 or less as compared with the case of performing the single-wafer spin treatment with a liquid in which ozone is dissolved in acetic acid in advance, and the economical efficiency is improved. ing.

Example 2 An example in which the present invention is applied to a manufacturing system in which a resist coated and baked on a rectangular glass substrate for liquid crystal having a silicon film formed on the surface is moved horizontally to advance the processing. Show. FIG. 2 is a conceptual sectional view of the device as seen from the side with respect to the traveling direction of the rectangular glass substrate. A large 650 × 550 mm square glass substrate 21 advances on the long side in a leftward direction of FIG. 2 on the feed rotation roll 22 at a speed of about 1 cm / sec. The feed rotation roll axis is orthogonal to the traveling direction of the glass substrate, is inclined by 3 to 4 ° with respect to the horizontal plane, and is arranged so as to have a slope shape in which the back direction of the paper surface is relatively low. There is a first fan-shaped nozzle 23 for spraying acetic acid almost horizontally to the substrate surface on the upper part of the slope, and a channel-shaped hood 24 made of quartz glass has a space between its top plate and the substrate surface of about 10 to 20 mm. In addition, a space of about 2 mm is maintained between the hem of the side wall and the substrate surface to cover a narrow region of about 50 mm in width including both ends of the substrate. When the tip of the substrate reaches the position A indicated by the arrow, acetic acid is intermittently sprayed from the nozzle 23 to form a liquid film of acetic acid in the narrow region. A rectangular exhaust pipe 26 having an exhaust port 25 is provided on the wall of the hood 24 on the side opposite to the advancing direction side, and exhaust is always performed to both sides in the direction orthogonal to the advancing direction.

A quartz glass channel hood 27 having a different shape is arranged adjacent to the channel hood 24 on the advancing direction side. The top plate of this hood is designed to be low and preferably has a height of about 5 mm from the substrate surface. A plurality of quartz glass high-concentration ozone gas supply pipes 28 are provided on the top plate, and are connected to a stainless (SUS 316 L) gas supply pipe 30 via a heat exchanger 29 for heating the ozone gas. At the same time as the start of acetic acid spraying to form a liquid film, a high-concentration ozone gas heated to approximately 40 ° C was supplied from the gas supply pipe.
Air is supplied at 50 cc / sec to fill the hood 27. A rectangular exhaust pipe 31 is arranged to face the hood 27 for exhaust at the time of start, and exhausts ozone gas leaked until the inner space of the hood is closed by the substrate surface.

FIG. 3 is a conceptual sectional view of the inner surface of the side wall of the hood 27 as seen from the base end in the traveling direction of the rectangular substrate. Since the substrate 21 is inclined, a head portion 32, which is a step portion for supporting the substrate, is provided at the axial end of the feed rotation roll 22. The exhaust pipes 33 at both ends of the hood 27 are
The gas filled between the substrate and the substrate is exhausted. At the stage of filling in this way, the introduction of ozone gas from the supply pipe 28 can be reduced to 1/2 or less of the initial amount.

When the substrate tip reaches the position (FIG. 2) B shown by the arrow at the end of the hood 27, the liquid film on the substrate surface in the hood is almost stationary, and the ozone concentration is sufficiently increased. However, almost all of the resist is decomposed by ozone dissolved in the acetic acid liquid film. The time required for the completion of decomposition was about 10 seconds even when combined with the acetic acid solution film formation time, which means that the resist peeling was performed at a speed of 9 μm / min or more.

The hood 2 is adjacent to the hood 27 in the traveling direction.
4, a hood 34 having the same shape as the hood 27, a hood 35 having the same shape as the hood 27, and a supply pipe 3 for supplying ozone gas at the same flow rate as the ozone supply pipe 28 of the hood 27.
6 are provided in order, the second fan-shaped nozzle 37 is arranged in the area of the hood 34 in the same manner as the first nozzle 23, and the hood 3
A rectangular exhaust pipe (not shown) having the same shape as the rectangular exhaust pipe 31 of the hood 27 is disposed below the hood 5, and an ozone exhaust pipe (not shown) similar to the ozone exhaust pipe 33 of the hood 27 is provided at both ends of the hood 35. No) is provided. In addition, channel-shaped hood 4
The acetic acid spray is performed by the third and fourth fan-shaped nozzles 38 and 39 covering the narrow area of the substrate having a width of about 100 mm. A rectangular exhaust pipe 41 similar to the rectangular exhaust pipe 26 is provided inside the side wall of the hood 40 in the traveling direction.

The substrate that has passed the position B is spray-rinsed by the nozzle 36 in the hood 34, and when the substrate enters the region of the hood 35, the peeling process is performed in the same manner as the region of the hood 27. This stage corresponds to the second stage treatment prepared when the unpeeled portion remains. In the area of the hood 40, spray rinse of acetic acid is performed, and the rinse liquid flows down and is removed along the inclined surface.

Finally, the substrate enters the tunnel hood 42. In the substrate area covered with the hood, the rinse acetic acid in the liquid film becomes almost stationary, and the air knife 43 scatters and removes the acetic acid from the substrate to obtain a dry surface. In addition,
A vaporized acetic acid exhaust line 44 is shown. The flow rate of acetic acid discharged from the second, third and fourth nozzles is 20
0 cc / min is sufficient. These acetic acids are collected and collected in a drainage pipe (not shown) below the feed rotary roll. The amount of acetic acid used per substrate is about 700 cc. The productivity of this device is about 1 minute per sheet, which is practically sufficient. Further, 18 liters of gas with an ozone concentration of 250 mg / liter were used per minute, but the substrate area of this example was about 11 times that of Example 1, and when compared per unit area, it was about the same. It can be said to be economical.

Example 3 An example of a batch process in which a large number of glass substrates for photomasks are placed in a fluorocarbon resin cleaning cassette and the resist is stripped at once is shown. 4 and 5 are conceptual views of the apparatus, FIG. 4 is a vertical sectional view seen from a direction perpendicular to the substrate surface, and FIG. 5 is a vertical sectional view seen from a direction parallel to the substrate.

The substrate 45 is 20 cm square and has a chromium thin film formed on its surface, and a resist is applied and baked on this surface. The layer gap of the substrate in the cassette 46 is 6 mm, a dummy substrate 45 ′ is put in the groove at the end of the cassette, and the substrate to be processed is set with the resist surface facing this direction and loaded in the processing container 47. The container is in the shape of a rectangular funnel with a drainage pipe 48 attached to the lower part. In the cassette, the resist surface of the substrate faces upward, and 1 to 1 from the vertical direction.
The exhaust pipe 50 is mounted on a quartz glass ozone gas discharger 49 which also serves as a mounting stand for the cassette and is positioned so as to be held at an inclination of 2 °, and is vertically movable waiting in the upward direction.
The container 47 is covered with the hood 51 attached with.

An acetic acid supply pipe 52 and an ozone gas supply pipe 53 penetrate the wall of the processing container 47, and the tip of the acetic acid supply pipe is a full-pyramidal spray nozzle 54 capable of spraying acetic acid over the substrate from above the substrate. Is provided, and the acetic acid supply pipe is supplied with acetic acid heated by the heat exchanger 56 by the valve 55. The ozone gas supply pipe is
It is connected to an ozone generator (not shown) via a valve 57. Ozone gas is supplied to the substrate layered gaps directly below each layered gap, and a net-like structure is formed by arranging a plurality of quartz glass tubes 59 having an outer diameter of 5 mm and having an outer diameter of 5 mm and having a plurality of openings 58 above. Done in. One side of the net is a quartz glass tube 60 for introducing ozone gas into the opening side of each quartz glass tube, and the opposite side is a quartz glass rod for fixing the sealing side, and the other 2
The sides are made of a quartz glass plate that reinforces the net structure, the net constitutes the main part of the ozone gas discharger 49, and the quartz glass pipe 60 is connected to the ozone gas supply pipe.

The resist stripping process is carried out as follows.
A cassette that can accommodate 25 substrates was used, and the substrates were set in all the grooves. The ozone generator used was one capable of generating an ozone gas concentration of 250 mg / l at a flow rate of 10 l / min. Prior to processing, valve 61 of drain 48
Is closed, and the valve 62 of the hood exhaust pipe 50 is opened. After opening the valve 57 and supplying ozone gas at a flow rate of 10 l / min for about 2 minutes to fill the layered gap of the substrate with ozone gas, the valve 55 is opened and the acetic acid heated to about 40 ° C. by the heat exchanger 56. Is sprayed from the nozzle 54 onto the resist surface for a few seconds, and the valve 55 is closed once the entire substrate surface is wet. When the flow of acetic acid from the substrate has almost stopped and the liquid film has almost stopped, the dissolution of ozone from the high-concentration ozone gas into the liquid film is accelerated, and the resist is stripped in a few seconds.
The peeling rate is estimated to be 10 μm / min or more, including the liquid film formation time by the acetic acid spray.

After opening the valve 61, the valve 55 is opened again.
After spraying and rinsing the substrate surface for about 10 seconds, the valve 55 is closed to suppress the flow of the liquid, the ozone concentration of the liquid film is increased, and the resist removal is ensured by the peeling operation again.
Subsequently, the valve 57 and the valve 62 are closed, the valve 55 is opened, and the spray rinse is performed from the nozzle 54 for about 10 seconds. When the valve 55 is closed and the flow of acetic acid from the substrate is almost stopped, the hood 51 is lifted up, the cassette is unloaded, and pure water is sprayed by a separately prepared general cleaning device.
dry.

As a result of scrutinizing the resist peeled surface with an electron microscope, the resist was completely removed and the chromium surface was not corroded at all. It is presumed that this is because the contact time of the chromium surface with the acetic acid liquid film containing a high concentration of ozone is extremely short. Since this treatment is a batch method, there is no problem in productivity, it can be matched with the conventional cleaning system, and the required amount of ozone gas and acetic acid per sheet is smaller than those in the previous Examples 1 and 2.

Example 4 An example similar to the existing apparatus for vertically rotating a silicon wafer in a closed chamber and spraying an organic solvent for resist stripping in the same batch processing as in Example 3 will be described with reference to FIGS. To do. FIG. 6 is a horizontal cross-sectional view including the rotation axis, and FIG. 7 is a vertical cross-sectional view perpendicular to the rotation axis.

The wafer 66 is housed in a dedicated cassette 65 which can be set on the rotary shaft 64 inserted into the chamber 63, and the wafer 66 is stored at a low speed of 20 rpm to 2,000 rpm for spin drying.
A mechanism (not shown) capable of controlling the rotation is provided. Fluorine resin-coated stainless steel (SUS316 stainless steel (SUS316) that flows the gas supplied from the valve 67 in a laminar flow between the wafers so that a layered gap of about 5 mm in the wafer becomes a high-concentration ozone gas layer.
Fin group 68, 69 made of L) is attached to the chamber wall. The valve 70 needs to be opened and closed at the same time as the valve 67,
It is for exhausting to assist the laminar flow between the wafers 71.

The wafer cassette is set, rotation is performed at the lowest speed, the valves 67 and 70 are opened, and ozone gas is supplied. When the ozone gas fills the space between the wafers, acetic acid carried by the acetic acid supply pipe 72 is sprayed from the grounded stainless (SUS 316L) full-pyramidal spray nozzle 74 by the valve 73, and once the entire wafer is wet, the spray is sprayed. Stop. The valves 67 and 70 are closed, the upper valve 75 and the lower valve 76 are opened, and a rinse spray of acetic acid is performed at 1,000 rpm for about 20 seconds. After the rinse is completed, the rotation speed is increased to about 2,000 rpm, the rinse acetic acid adsorbed on the wafer is removed, and spin drying is performed.

Specifically, for a cassette of 25 wafers with a diameter of 200 mm with a resist prepared in the same manner as in Example 1, a gas having an ozone concentration of 200 mg / liter was applied to the fin 68 for 1 minute at a flow rate of 20 liter / minute. After being sent in, the wafer layered gap is filled with high-concentration ozone gas and then acetic acid heated to 40 ° C. is sprayed. When the entire surface is wet in a few seconds, spraying is stopped for 20 seconds. Subsequently, a rinse with acetate was performed for 20 seconds, and spin drying was performed. Due to the structure of the device, the peeling state of the resist cannot be observed, so processing was performed with this schedule.
As in Example 1, the resist was completely stripped and removed. The amount of gas and acetic acid used is large, but since it is a batch process, the amount used per sheet is sufficiently small and the productivity is very good.

Example 5 On the surface of a silicon wafer exposed to a clean room for semiconductors, harmful organic pollution derived from the atmosphere occurs, but most of the pollutant is dioctyl phthalate (DOP).
Is known to be. Therefore, 30 wt% of ammonium fluoride was added to buffered hydrofluoric acid (dilute hydrofluoric acid aqueous solution (concentration: 6 wt%)) in which ⁶⁴ Cu, which is a radioisotope, is dissolved at a concentration of 2 × 10 ¹³ atoms / cc.・ Dissolved), 6 silicon wafers stored in a fluorocarbon resin cassette are immersed for 10 minutes, rinsed and dried with pure water, the radioactivity of each wafer is measured, and the surface of each wafer is adsorbed from the liquid. Concentration of ⁶⁴ Cu intentionally polluted with 10 ¹² atoms
It was confirmed to be / cm ² .

Further, the cassette containing the six wafers was placed in the middle stage of a closed plastic case with a glass dish filled with DOP solution set at the bottom, and left overnight in a constant temperature bath at 60 ° C. Although the vapor pressure of DOP is extremely low, the atmosphere inside the sealed case is saturated with the vapor of DOP.
The surface of the silicon wafer that easily absorbs OP vapor is DOP
It is strongly and intentionally contaminated. The monovalent Cu ions dissolved in the hydrofluoric acid-containing liquid are adsorbed on the silicon surface in the state of metal atoms due to the ionization tendency, and this adsorption state is known to be a group of Cu fine particles having an extremely small particle size. ing. Due to this intentional contamination, the surface tension of DOP is 30 dyn / cm.
Due to the degree, it goes under the ⁶⁴ Cu fine particles and sticks the individual fine particles to the silicon surface. That is, as a result, a surface contamination state in which Cu particles are strongly adhered with DOP is formed.

Prior to the cleaning treatment, in the apparatus of Example 1, the heat exchanger 16 was changed in order to change the acetic acid of about 5 cc discharged for forming the liquid film to acetic acid containing 2% by volume of hydrofluoric acid at room temperature. It was removed, a branch pipe and a valve were provided, and a supply mechanism of hydrofluoric acid-added acetic acid was attached. Two wafers were arbitrarily selected from the above-mentioned six intentionally contaminated wafers, and the wafers were processed one by one in the same manner as the resist stripping. That is, after loading the wafer into the holder 3, a liquid film of acetic acid containing hydrofluoric acid was formed on the wafer by the same procedure as in Example 1 to release a high-concentration ozone gas for 5 seconds.
After that, the primary spin rinse is performed with acetic acid at room temperature. Resist stripping and then spin drying is performed in the same manner as in reprocessing, ⁶⁴ Cu
The residual rate of was measured by comparing the radioactivity intensities of the wafers before and after cleaning. As a result, it was found that when the acetic acid containing hydrofluoric acid was used, the residual rate of Cu was 0.1% for both sheets, and a strong cleaning effect was obtained. This effect is that acetic acid quickly dissolves DOP first, and then ozone oxidizes Cu fine particles to convert them into copper oxide, and at the same time grows an oxide film on the silicon surface, but the silicon oxide film and Cu ²⁺ ions are hydrofluoric acid. It is presumed that the added acetic acid was dissolved and the dissolved solution was separated by centrifugal force by the rinse with acetic acid.

Comparative Example 1 The RCA cleaning method is the most typical cleaning method for silicon wafers, and is "SC-2" (a typical composition is hydrochloric acid: hydrogen peroxide: water = 1 volume: 1 volume: 6 volumes). ) To "SC-1" (a typical composition is ammonia: hydrogen peroxide: water = 1 volume: 1)
It is standard to put a large number of wafers in a cassette, immerse them at the same time, and treat them at 70 ° C for 10 minutes. In particular, the former is for heavy metal pollution such as Cu, and the latter is Cu for easily complexing with organic pollution,
It is said that strong cleaning can be performed. Therefore, in order to compare the cleaning effect on Cu in the case of DOP contamination with Example 5, a "SC-1" solution and a "SC-2" solution were filled in a quartz glass square tank, both of which were at 70 ° C. The remaining DOP / Cu-contaminated wafers prepared in Example 5 were heated to 2 each, and after measuring the radioactivity in each case, they were immersed and washed for 10 minutes, rinsed with ultrapure water, and dried after air-drying. The strength was measured, and the residual rate of ⁶⁴ Cu was determined by comparing with the measured value before cleaning.

^{64 on} wafer after "SC-2" cleaning
The Cu residual rates were 43% and 47%, and the residual rates in the case of the wafer after "SC-1" cleaning were 2.0% and 2.2%. The former can be presumed to have a high residual rate because the cleaning action on Cu does not work because DOP cannot be removed and Cu is buried in the silicon oxide film grown by hydrogen peroxide. In the latter, the DOP can be removed, but the growing silicon oxide film remains C before Cu has a sufficient complexing action.
It is presumed that washing will be insufficient due to the capture of u. From the comparison of the Cu residual ratio, the superiority of the cleaning method according to the present invention of Example 5 is clear.

Example 6 KrF Consisting of Polyvinylphenol Derivative and Acid Generator
A 200 mm diameter silicon wafer coated with a chemically amplified resist for excimer lasers to a thickness of O.75 μm,
For samples that were hard baked at 140 ℃ for 90 seconds,
An example in which the resist is removed with acetic acid and ozone gas using the apparatus of Example 1 will be shown. However, the coaxial rotation mechanism was modified so that the spin axis could be repeatedly rotated clockwise and counterclockwise by 30 ° each at a cycle of 4 times / second.

The resist stripping and removing treatment was performed in exactly the same manner as in Example 1 except for the following points. That is, when the hood body 14 is lowered to cover the entire surface of the wafer and then the wafer is repeatedly inverted, and about 15 cc of heated acetic acid is discharged, the solution spreads over the entire surface of the wafer to form a liquid film having a thickness of about 300 μm. Thereafter, similar to Example 1, about 1 liter of highly concentrated ozone gas stored in the cylinder is discharged for 5 seconds. Simultaneously with the end of discharge, the repetitive inversion is stopped, and thereafter, the first spin rinse is performed as in the first embodiment. This treatment is performed because the solubility of the resist in acetic acid is slightly weaker than that in the case of the novolak type resist, and a thick acetic acid liquid film swings well in repeated inversion of the wafer, and the ozone gas decomposing ability is high. Can also be added to rapidly dissolve the resist. By this treatment, most of the resist film is peeled off within a few seconds.

After the first rinse, when the rotation of the wafer is completely stopped and then the release of acetic acid is stopped, a thick liquid film is again formed on the wafer surface. Here, the repetitive wafer is repeatedly inverted for 5 seconds, during which the remaining gas in the cylinder 20 is released to complete the resist stripping, and the same process as in Example 1 is performed.

The amount of residual organic carbon on the wafer surface immediately after peeling was 5 × 10 ¹³ atoms / cm ² or less, and the polyvinylphenol-based chemically amplified resist could be removed at a high peeling rate of 10 μm / min or more.

[0062]

The present invention is an improvement of the above-mentioned prior invention. When acetic acid is used as a solvent, the stripping rate is improved by about 2 to 5 times in the case of a novolac resin-based positive resist, for example. Since the composition itself of the chemical solution is not different from the above-mentioned prior invention, the effect of removing surface-adhered contaminants of the present invention is also effective for metal contaminants and fine particles, and if a small amount of hydrofluoric acid is added, the surface of an oxide film, etc. In this case, this removal effect is extremely high. That is, the present invention significantly improved the adhesion removing performance. In addition, the peeling time can be greatly shortened, which greatly contributes to productivity.

In the present invention, the time during which the liquid in which high-concentration ozone is dissolved is in contact with the substrate surface is usually ten seconds or less, which is extremely short. Therefore, according to the present invention, not only the surface of silicon or a silicon oxide film, but also the surface of aluminum, tungsten, molybdenum, TiN, ITO or the like can be removed without corroding the surface. Further, while the ozone gas is in contact with the solvent liquid film, the liquid film is usually kept stationary, which not only contributes to the improvement of the peeling performance, but also can significantly reduce the amount of solvent used. Since the peeling time is short and ozone gas is supplied only to a narrow space, a method of temporarily storing a high-concentration gas and flowing it at a large flow rate for a required short time can be used. Therefore, there are advantages that the ozone generator used is downsized and the amount of ozone used is reduced. That is, in terms of economy, it is a significant improvement over the invention of the prior application.

When the ozone generator is used as described above,
The generator can be used for other purposes while being treated with stored ozone gas. If the generated ozone gas is bubbled in the solvent drainage after the resist is stripped, the undecomposed resist in the drainage can be completely decomposed. Therefore, by bubbling ozone gas, it becomes possible to recycle the used solvent by a simple treatment such as filtration or distillation if necessary.

[Brief description of drawings]

FIG. 1 is a conceptual diagram showing a vertical section of a single-wafer spin resist peeling apparatus.

FIG. 2 is a conceptual view of an apparatus for moving a large rectangular substrate in a surface direction to remove a resist, as viewed from the side in the moving direction.

FIG. 3 is a conceptual diagram of a cross section orthogonal to the moving direction of the device.

[Fig. 4] Placing a large number of rectangular substrates in a cassette and allowing them to stand,
It is a figure which shows the concept of the batch processing apparatus which removes a resist at once, and is a longitudinal sectional view seen from the direction perpendicular to the substrate surface.

FIG. 5 is a view showing a concept of the device, and is a vertical cross-sectional view seen from a direction parallel to a substrate.

FIG. 6 is a conceptual view of a processing apparatus including a chamber in which a large number of circular substrates are placed in a cassette and can be rotated about the center of the substrates, and a cross-sectional view including a rotation axis.

FIG. 7 is a conceptual view of the apparatus, which is a vertical cross-sectional view perpendicular to the rotation axis.

[Explanation of symbols]

1. Silicon wafer 2. Spin axis 3.
Wafer holder 4. Spin bearing 5. Chamber 6.
Acetic acid outlet 7. Acetic acid supply pipe 8. Acetic acid supply pipe bearing 9.
Ozone gas outlet 10. Gas supply pipe 11. Gas supply pipe bearing 1
2. Exhaust pipe 13. Drainage pipe 14. Hood body 1
5. Acetic acid supply valve 16. Heat exchanger 17. Gas supply valve 1
8. Three-way valve 19. Automatic piston 20. Cylinder 2
1. Large square substrate 22. Feed rotation roll 23, 37, 38, 3
9. Fan-shaped acetic acid nozzle 24, 34. Channel type hood 2
5. Exhaust port in hood 26, 41. Square exhaust pipe in hood 27, 35. Channel type low roof hood 28, 36. Quartz glass gas supply pipe 2
9. Heat exchanger 30. Metal gas supply pipe 31. Bottom square exhaust pipe 3
2. Rotating shaft head 33. Both side exhaust pipe 40. Wide channel type hood 4
2. Tunnel hood 43. Air knife 44. Exhaust pipe for acetic acid 4
5. Square quartz glass substrate 45 '. Dummy substrate 46. Cassette 4
7. Processing container 48. Drainage pipe 49. Ozone gas ejector 5
0. Exhaust pipe 51. Hood 52. Acetic acid supply pipe 5
3. Gas supply pipe 54. Full-pyramidal spray nozzle 55. Acetic acid supply valve
56. Heat exchanger 57. Gas supply valve 58. Opening hole for ozone release 5
9. Ozone discharge tube 60. Ozone gas introduction tube 61. Drain valve 6
2. Exhaust valve 63. Chamber 64. Cassette rotation axis 6
5. Cassette 66. Silicon wafer 67. Gas introduction valve 6
8,69. Laminar flow fin 70. Gas exhaust valve 71. Wafer layered gap
72. Acetic acid supply pipe 73. Acetic acid supply valve 74. Full-pyramidal spray nozzle 75. Upper valve 76. Lower valve

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Asuka Sato             735 Shinba-cho, Kohoku Ward, Yokohama City, Kanagawa Prefecture             Inside the company Purelex F term (reference) 2H088 FA21 FA30 HA01 MA20                 2H096 AA25 LA02                 5F046 MA02 MA05 MA13 MA17

Claims (14)

[Claims] 1. A surface of an object to be processed to which foreign substances are attached,
An ozone-soluble solvent capable of sufficiently wetting the surface is applied, and a liquid film formed thereby is provided between the object to be processed and a top plate or another object to be processed adjacent to the surface. A method for removing a foreign substance adhering to a surface, which comprises contacting a gas containing a high concentration of ozone introduced into a layered gap to remove a foreign substance adhering to the surface of a target object. 2. The method according to claim 1, wherein after introducing the gas into the layered gap with respect to the surface, the solvent is supplied to the surface to form a liquid film, and the liquid film is contacted with the gas. 1. The method for removing foreign substances adhering to the surface according to 1. 3. The method for removing foreign substances adhering to the surface according to claim 1, wherein after the liquid film of the solvent is formed on the surface, the gas is supplied to the layered gap for treatment. . 4. The method for removing a foreign substance adhering to a surface according to claim 1, wherein the liquid film is heated. 5. The surface-attached foreign substance according to claim 1, wherein the solvent is capable of dissolving all or at least a part of the foreign substance. Removal method. 6. The solvent is of the formula: C _n H _{2n + 1} COO.
The surface adhesion according to any one of claims 1 to 5, wherein the main component is an aliphatic carboxylic acid represented by H (in the formula, an integer of 1, 2, or 3). How to remove foreign substances. 7. The substrate to be processed is a substrate for electronic industry,
The said surface-attached foreign substance is a photoresist, and the main component of the solvent is acetic acid.
5. The method for removing surface-attached foreign matter according to any one of claims 4 to 4. 8. A hood having a top plate which covers all or a part of the surface of the object to be treated to which foreign contaminants to be removed are attached, and which has a structure in which the top plate does not come into contact with the surface. A body, a gas discharger attached to the hood wall for filling the space inside the hood with an ozone-containing gas and a gas supply pipe connected to the body, and a liquid film of an ozone-soluble solvent capable of sufficiently wetting the surface. The solvent supply device for forming on the surface and the solvent liquid film attached thereto are kept stationary or flow at a slow speed or a short moving distance, and finally the liquid film after treatment and A device for removing foreign substances adhering to a surface, comprising a mechanism for removing residual foreign substances from the surface. 9. A case where the removing device has a mechanism for spin-processing and cleaning an electronic industrial substrate in a single-wafer manner, and is provided with a mechanism capable of arbitrarily changing a rotation speed of the cleaning substrate, A gas discharger that is located close to the substrate for the processing time and supplies an ozone-containing gas onto the substrate surface; and a solvent supplier that discharges the solvent onto the substrate surface to form a liquid film, and 9. The apparatus for removing foreign substances adhering to a surface according to claim 8, further comprising a hood body provided with a vertically movable top plate capable of being filled with an ozone-containing gas during processing. 10. The removing device moves a rectangular substrate having a photoresist adhered to the surface thereof, tilts the rectangular substrate from a horizontal plane in a direction perpendicular to the traveling direction of the rectangular substrate, and removes the solvent. A hood having a channel type low top plate that covers a plurality of narrow regions including both ends in a direction perpendicular to the traveling direction of a square substrate surface, in the case of having a mechanism for forming a liquid film by flowing down in a direction perpendicular to the rectangular substrate surface. A body is applied, and an emitter for forming a solvent liquid film by flowing a solvent along the slopes of the rectangular substrate is disposed above the narrow regions in the plurality of narrow regions. 9. The apparatus for removing foreign substances adhering to the surface according to claim 8, wherein: 11. A plurality of substrates having the same shape and having different shapes adhered to the surface of a substrate for electronic industry in a cleaning container,
An apparatus for processing a cassette housed in a layered gap close to each other, comprising a gas discharger for introducing a high-concentration ozone-containing gas into the layered gap between the respective substrates, and a surface of each substrate positioned above the cassette. A nozzle for spraying a sufficiently wettable ozone-soluble solvent on the surface of each substrate, a gas discharger fixing base, a supply pipe for the gas, a solvent supply pipe for supplying the solvent to the nozzle, and each substrate A device for removing foreign substances adhering to a surface, characterized in that a drainage port for the solvent after the cleaning process that flows down from the layered gap between them is attached. 12. A plurality of substrates having the same shape for electronic industry,
A washing device for spin-processing a cassette housed in a layered gap close to each other, wherein the cassette is supported by a rotary shaft inserted through a horizontal wall of a closed container and is configured to be vertically rotatable. The rotation speed of the rotating shaft can be arbitrarily changed, and the hermetically sealed container is provided with a high-concentration ozone-containing gas discharge port and discharge port, and an ozone-soluble solvent capable of sufficiently wetting each substrate surface with each substrate surface. Nozzle located above the cassette for spraying on, a drain port is provided below, and through the rotary shaft in the steps of releasing the high-concentration ozone-containing gas, spraying the solvent, rinsing and draining liquid. A device for removing foreign substances adhering to a surface, characterized in that the cassette can be stopped or rotated at a desired rotation speed from low speed to high speed. 13. The removing device further stores an ozone-containing gas generated by an ozone gas generating device,
13. A cylinder-shaped gas reservoir provided with a piston for releasing gas so that the stored gas can be discharged at a high flow rate in a short time, and the gas reservoir according to any one of claims 8 to 12, characterized in that. Removal device for foreign substances adhering to the surface. 14. The solvent used in the removing device is capable of dissolving all or at least a part of the foreign substance, according to any one of claims 8 to 13. Equipment for removing foreign substances adhering to the surface of.