JP2004241414A - Stripper/cleaner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resist film stripper/cleaner in which stripping/removing rate is increased furthermore when a resist film adhering to a substrate is stripped/removed by supplying ozonic fluid and an extra cleaning process is eliminated without requiring complete enclosure of a special facility for treating waste liquid and by-products or a facility and a unit for removing troubles caused by leakage of a large quantity of ozone gas. <P>SOLUTION: Immediately before being fed to a substrate to which a resist film is adhering, ozonic fluid is mixed with high temperature vapor so that liquid temperature of the ozonic fluid is raised and stripping/removing rate of the resist film is increased significantly without lowering ozone concentration which causes lowering of resist removing rate thus enhancing resist film removing power. No residue is present on the surface of the substrate after the resist film is stripped/removed, waste liquid or by-products having adverse effect on the environment are not generated nor a large quantity of ozone gas leaks out. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a peeling cleaning device.
[0002]
[Prior art]
In a lithography process in a semiconductor and liquid crystal substrate manufacturing process, an organic resist film is generally used as a patterning mask. The resist film is removed when the patterning of the substrate is completed. In order to remove the resist film, a method using a mixed solution of sulfuric acid and hydrogen peroxide solution (hereinafter referred to as “SPM”) heated to 100 ° C. or higher or a stripping solution made of an organic solvent is generally used. In this method, since a large amount of stripping solution waste liquid and by-products (organic volatile components, acid gas, etc.) that may have an adverse effect on the environment are generated, special processing equipment is required, which requires a large amount of equipment cost and running cost. Costly. Further, as the size of the semiconductor wafer and the mother substrate of the liquid crystal panel increases, the amount of waste liquid further increases, and it is a problem that the process load and the processing cost increase.
[0003]
Also, a resist stripping method utilizing the oxidative decomposition of organic substances by ozone is known. According to this method, hydrocarbon molecules, which are organic substances constituting the resist film, react with reactive species such as hydroxy radicals generated in the process of self-decomposition of ozone, and are converted into low molecular weight and water-soluble components. Denatured and further decomposed into carbon dioxide and water. On the other hand, ozone is decomposed into oxygen. Therefore, this method hardly generates waste liquids and by-products that have an adverse effect on the environment, does not require special treatment equipment, and greatly reduces equipment costs and running costs as compared with the method using SPM or an organic solvent. It is possible. Thus, the method using ozone has excellent advantages. However, in this method, it is desired to further improve the removal rate of the resist film, that is, the capability of removing the resist film.
[0004]
By the way, when ozone water is used as an ozone source and the contact condition between the ozone water and the resist film is constant, it is known that the decomposition rate of the resist film depends on the ozone concentration of the ozone water and the temperature of the ozone water. . However, ozone is hardly soluble in water, and its solubility in water at normal temperature and normal pressure is only about 60 ppm. Therefore, in an environment at normal temperature and normal pressure, the ozone concentration is so large that it affects the decomposition rate of the resist film. It cannot be enhanced. To increase the ozone concentration, the temperature of the ozone water may be lowered. However, since the decomposition rate of the resist film depends more on the water temperature than on the ozone concentration, low-temperature ozone water does not have a sufficient resist film decomposition rate even at a high concentration.
[0005]
In order to increase the temperature of the ozone water and, consequently, the decomposition rate of the resist film, a method of raising the temperature of the ozone water by a heater, a heat exchanger or the like (for example, see Patent Document 1), heating the substrate by a heater, -A method of supplying high-concentration ozone water (for example, see Patent Document 2) has been proposed. Since the solubility of ozone in ozone water decreases with increasing temperature, it is necessary to raise the temperature of ozone water quickly. However, in general, since water has a high specific heat, it takes a long time to sufficiently heat with a heater, a heat exchanger, or the like, and a temperature difference occurs between a portion near the heat source and a portion separated from the heat source, so that uniform heating is performed. I can't. Therefore, most of the ozone is released as a gas by heating before reacting with the resist film, and is decomposed by heat before reaching the substrate, and does not contribute much to the removal reaction of the resist film.
[0006]
Further, in order to promote the decomposition of a resist film, a method using both an ozone gas and water vapor has been proposed (for example, see Patent Document 3). However, in this method, since a residue remains on the substrate, an extra step of washing again is required. In addition, since highly reactive ozone gas is used at a high concentration, it is necessary to completely seal the apparatus and a large-scale abatement equipment, which causes an increase in equipment cost and running cost.
[0007]
[Patent Document 1]
JP-A-2000-058496
[Patent Document 2]
JP 2001-077069 A
[Patent Document 3]
JP 2001-257189 A
[0008]
[Problems to be solved by the invention]
An object of the present invention is to achieve a higher resist film removal rate and, therefore, a higher resist film removal capability than the conventional technology, no residue remains on the substrate surface after removal, and no waste liquid or by-product that has an adverse effect on the environment is generated. An object of the present invention is to provide a stripping / cleaning apparatus that does not require a treatment facility, a completely sealed apparatus, and a large-scale detoxification facility.
[0009]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above problems, and as a result, when stripping and removing the resist film on the substrate surface using an ozone fluid, immediately before supplying the ozone fluid to the substrate, an ozone fluid and By mixing with high-temperature steam and instantaneously heating, the ozone concentration is suppressed to a level that does not affect the removal and removal of the resist film, while the liquid temperature of the ozone fluid is increased and the removal and removal speed of the resist film is increased. The remarkable improvement was achieved, and the present invention was completed.
[0010]
The present invention is a stripping and cleaning apparatus for removing an organic thin film and organic substances attached to a substrate surface with an ozone-based fluid,
An ozone-fluid generator for generating an ozone-fluid,
A steam generator for generating steam,
A gas-liquid mixing unit that mixes the ozone-based fluid generated by the ozone-based fluid generation unit and the steam generated by the steam generation unit;
A substrate processing unit for supplying a heated ozone-based fluid generated by a gas-liquid mixing unit to a substrate surface.
[0011]
According to the present invention, the liquid temperature of the ozone fluid is increased without substantially lowering the ozone concentration by mixing the ozone fluid and the high-temperature steam immediately before supplying the ozone fluid to the substrate. By supplying the ozone-based fluid whose temperature has been increased to the substrate, the resist film adhering to the substrate can be removed very efficiently without leaving any residue.
[0012]
That is, the stripping and cleaning apparatus of the present invention has a very high stripping and removing rate of the resist film, and thus a very high stripping and removing capability, and since no residue remains on the substrate surface after the removal, an extra washing step can be omitted, and wastewater and harmful effects on the environment can be eliminated. No by-products are generated, and no special waste liquid treatment facility, completely enclosed equipment, and large-scale abatement equipment are not required.
[0013]
Further, in the stripping and cleaning apparatus of the present invention, the ozone-based fluid generation unit includes
Ozone gas generating means for generating ozone gas;
Ozone fluid pure solvent generating means for generating a pure solvent to be mixed with ozone gas,
An ozone fluid generating means for mixing the ozone gas and the pure solvent to generate an ozone fluid is included.
[0014]
According to the present invention, when an ozone fluid is produced by mixing an ozone gas and a solvent, the resist film on the substrate is removed by removing extra components, impurities and the like from the solvent to obtain a pure solvent. An ozone fluid suitable for the above is obtained.
[0015]
Further, the peeling and cleaning apparatus of the present invention is provided between the ozone fluid generating means and the ozone fluid pure solvent generating means,
It is characterized by including cooling means for cooling the pure solvent.
[0016]
According to the present invention, by cooling the pure solvent before mixing the ozone gas and the pure solvent, it becomes possible to generate an ozone-rich fluid having a high ozone concentration, and the removal rate of the resist film is further improved. .
[0017]
Further, in the peeling and cleaning apparatus of the present invention, the gas-liquid mixing unit includes
Gas-liquid mixing means;
It is provided between the gas-liquid mixing means and the ozone fluid generation unit,
It is characterized by including ozone fluid control means for controlling the supply pressure and / or supply amount of the ozone fluid supplied to the gas-liquid mixing means.
[0018]
Further, in the peeling and cleaning apparatus of the present invention, the gas-liquid mixing unit includes
Gas-liquid mixing means;
Provided between the gas-liquid mixing means and the steam generation unit,
It is characterized by including steam control means for controlling the supply pressure and / or the amount of steam supplied to the gas-liquid mixing means.
[0019]
According to the present invention, in mixing the ozone fluid and the steam, by adjusting the supply pressure and the supply amount of the ozone fluid or the steam, the ozone fluid and the steam can be smoothly mixed, It is possible to obtain a high-temperature ozone fluid in which a decrease in ozone concentration is suppressed as much as possible.
[0020]
Further, in the peeling and cleaning apparatus of the present invention, the substrate processing unit may include:
Substrate processing means;
Provided between the substrate processing means and the gas-liquid mixing unit,
It is characterized by including a stripping liquid control means for controlling the supply pressure and / or the supply amount of the heated ozone-based fluid supplied to the substrate processing means.
[0021]
According to the present invention, by adjusting the supply pressure and the supply amount of the high-temperature ozone-based fluid (stripping liquid) to the substrate processing section, the ozone gas is separated from the high-temperature ozone-based fluid and the ozone concentration is reduced. Can be suppressed.
[0022]
Further, the stripping cleaning apparatus of the present invention is characterized in that the ozone fluid is at least one selected from pure water containing ozone, an organic solvent containing ozone, and an aqueous acid solution containing ozone. I do.
[0023]
According to the present invention, a high resist film removal rate can be achieved by using a mixture of a specific solvent and ozone gas as an ozone fluid.
[0024]
Further, the stripping and cleaning apparatus of the present invention is characterized in that the steam is steam of pure water, an organic solvent, an alkali or an acid.
[0025]
According to the present invention, a high resist film removal rate is achieved by using a specific solvent vapor as the high-temperature vapor.
[0026]
BEST MODE FOR CARRYING OUT THE INVENTION
FIG. 1 is a flowchart showing a configuration of a peeling and cleaning apparatus 1 according to a first embodiment of the present invention.
[0027]
The stripping / cleaning apparatus 1 includes an ozone-based fluid generation unit 2 that generates an ozone-based fluid, a steam generation unit 3 that generates a steam, and an ozone-based fluid and a steam generation unit 3 that generate the ozone-based fluid. It is configured to include a gas-liquid mixing unit 4 that mixes the vapor and a substrate processing unit 5 that supplies an ozone-based fluid heated by the gas-liquid mixing unit 4 to the substrate surface.
[0028]
The ozone-fluid generation unit 2 generates the ozone-fluid pure solvent generation unit 6 that generates a pure solvent mixed with the ozone gas, the ozone gas generation unit 7 that generates the ozone gas, and the ozone-fluid pure solvent generation unit 6. An ozone fluid generation means 8 for mixing the pure solvent and the ozone gas generated by the ozone gas generation means 7 to generate an ozone fluid.
[0029]
The steam generation unit 3 includes a steam pure solvent generating means 9 for generating a pure solvent for converting into steam, and a steam generating means 10 for converting the pure solvent generated by the steam pure solvent generating means 9 into steam. Is done.
[0030]
The gas-liquid mixing unit 4 mixes the ozone-based fluid and the vapor to generate a stripping solution that is a heated ozone-based fluid, an ozone-based fluid generation unit 8, and a gas-liquid mixing unit 11. And an ozone-fluid control unit 12 that controls the supply pressure and / or supply amount of the ozone-based fluid supplied to the gas-liquid mixing unit 11, And a steam control means 13 provided between the steam control means and the supply pressure and / or the supply amount of the steam supplied to the gas-liquid mixing means 11.
[0031]
The substrate processing unit 5 is provided between the gas-liquid mixing unit 11 and the substrate processing unit 14, and is supplied to the substrate processing unit 14. The substrate processing unit 14 supplies a stripping solution to the substrate surface to remove the resist film. And a stripping liquid control unit 15 for controlling the supply pressure and / or the supply amount of the stripping liquid.
[0032]
FIG. 2 is a cross-sectional view schematically illustrating the configuration of the substrate processing unit 5 and the processing of the substrate 16 by the substrate processing unit 5. The substrate processing unit 5 includes a stripping solution supply nozzle 17 as a substrate processing unit, and a stripping solution control unit provided between the gas-liquid mixing unit (not shown) and the stripping solution supply nozzle 17 so as to be in contact with the stripping solution supply nozzle 17. 18 are included. The stripping liquid supply nozzle 17 is provided at a distance from the surface 16a of the substrate 16 to be treated, and is provided so that the stripping liquid 19 is jetted at an acute angle to the surface 16a.
[0033]
The substrate 16 is placed on a roller 20 serving as a substrate transfer means such that the surface 16 a faces the stripping liquid supply nozzle 17, and the direction opposite to the direction in which the stripping liquid 19 is ejected from the stripping liquid supply nozzle 17. Transported to
[0034]
A plurality of rollers 20 are arranged so as to have an axis in a direction perpendicular to the figure, and can be driven to rotate around the axis by a driving device (not shown), and can convey the substrate 16 in the direction of arrow 21. By transporting the substrate 16 by the roller 20, a flat flow process can be performed. Therefore, even on a large-sized substrate such as a liquid crystal panel, the resist film can be uniformly peeled and removed.
[0035]
As shown in FIG. 1, first, the solvent supplied from the solvent line 22 to the pure solvent generating means 6 for ozone fluid removes particles such as impurities, another kind of solvent, and the like, so that the solvent can be used for semiconductor production. Purified to a pure solvent of higher purity. As the solvent, a solvent that can dissolve ozone can be used, and examples thereof include water, a polar organic solvent such as an organic acid, a non-polar organic solvent, and an aqueous solution containing an acid such as an organic acid and an inorganic acid. For example, an ion exchange membrane, a filtration filter, a distillation apparatus, or the like can be used as the pure solvent generating means 6 for ozone fluid. The pure solvent is supplied to the ozone fluid generating means 8 via the pure solvent line 23. On the other hand, the ozone gas obtained by the ozone gas generation means 7 is also supplied to the ozone fluid generation means 8 via the ozone gas line 24. The pure solvent and ozone gas are mixed there, producing an ozone-like fluid. For example, a gas-liquid mixer, a gas dissolving module (gas dissolving film) or the like can be used as the ozone fluid generating means 8. The ozone-based fluid is gas-liquid mixed from the ozone-based fluid generation unit 8 via the ozone-based fluid line 25 while the pressure and / or flow rate is controlled by the ozone-based fluid control unit 12 provided on the ozone-based fluid line 25. It is supplied to the means 11. As the ozone fluid control means 12, a pressure flow control valve, a pressure control valve, or the like is used.
[0036]
On the other hand, the solvent supplied from the solvent line 26 to the pure solvent for vapor generating means 9 is subjected to removal of particles such as impurities, another type of solvent, and the like, and is purified to a pure solvent having a purity equal to or higher than a predetermined purity that can be used for semiconductor production. . As the solvent, a solvent that can dissolve the above-mentioned ozone can be used. Further, a solvent containing an alkali such as an aqueous alkali solution can also be used. As the pure solvent generating means 9 for vapor, the same device as the pure solvent generating means 6 for ozone fluid can be used. The pure solvent is supplied to the vapor generation means 10 via the pure solvent line 27, where it is converted to vapor. A device capable of heating the solvent to a temperature higher than the boiling point can be used as the steam generating means 10, and examples thereof include an electric boiler. The vapor of the pure solvent is supplied to the gas-liquid mixing unit 11 from the vapor generation unit 10 via the vapor line 28 while controlling the supply pressure and / or the supply amount by the vapor control unit 13 provided on the vapor line 28. Supplied. As the steam control means 13, a pressure adjusting valve (for example, a steam pressure reducing valve), a pressure flow adjusting valve, or the like is used.
[0037]
The ozone fluid and vapor supplied to the gas-liquid mixing means 11 are mixed there. The ozone-based fluid is heated by the heat of the steam, and a stripping solution, which is a heated ozone-based fluid, is generated. By controlling the supply pressure and / or the supply amount of the steam, the ozone concentration and the liquid temperature of the ozone fluid can be controlled. The same or different solvents can be used for the solvent of the ozone-based fluid and the solvent of the vapor. In addition, the vapor of a highly polar solvent such as pure water or a strongly hydrogen-bonding solvent has a large latent heat of vapor, has a large effect of raising the temperature of the ozone-based fluid even if the mixing amount is small, and the ozone concentration due to the mixture of the vapor. Can be preferably used because the decrease in the amount can be suppressed. As the gas-liquid mixing means 11, a mixer such as a static mixer, an ejector mixer, or a mixer mixer can be used. Further, it is preferable to use a gas-liquid mixer made of a material having corrosion resistance to an ozone-based fluid. Such a material is, for example, a fluorine resin such as polytetrafluoroethylene (PTFE), a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether (PFA), stainless steel, or the like.
[0038]
The stripping liquid flows through the stripping liquid line 29 from the gas-liquid mixing means 11 in a state where the stripping liquid is heated and pressurized as shown in FIG. 2, and the pressure and / or the supply amount are controlled by the stripping liquid control means 18. Meanwhile, the liquid is supplied to the surface 16a of the substrate 16 from the stripper supply nozzle 17. A pressure adjusting valve (for example, a liquid pressure reducing valve), a pressure flow adjusting valve, or the like is used as the stripping liquid control unit 18. The stripper is preferably supplied to the substrate surface 16a after reducing the pressure to atmospheric pressure by a liquid pressure reducing valve or the like. The stripping solution 19 supplied on the surface 16a reacts with the resist film to strip and remove the resist film.
[0039]
By controlling the pressure and / or flow rate (supply amount) using the ozone-based fluid control means 12, the vapor control means 13, and the stripping liquid control means 15, the ozone gas is kept at a pressure higher than the normal pressure while maintaining the pressure of the stripping liquid higher than normal pressure. A decrease in ozone concentration due to release can be prevented.
[0040]
FIG. 3 is a cross-sectional view schematically showing a configuration of the substrate processing unit 30 provided in the peeling and cleaning apparatus according to the second embodiment of the present invention and cleaning of the substrate 31 by the substrate processing unit 30. The peeling / cleaning apparatus of the present embodiment has the same configuration as the peeling / cleaning apparatus 1 of the first embodiment, except for the substrate processing unit 30, and therefore, the description of the configuration other than the substrate processing unit 30 and the description thereof will be omitted. I do.
[0041]
The substrate processing unit 30 includes a stripping liquid supply nozzle 32 serving as a substrate processing unit, and a stripping liquid control unit provided between the gas-liquid mixing unit (not shown) and the stripping liquid supply nozzle 32 so as to be in contact with the stripping liquid supply nozzle 32. 33.
[0042]
The stripping liquid supply nozzle 32 is provided at a distance from the surface 31a of the substrate 31 to be processed, and is provided so that the stripping liquid 34 is jetted at right angles to the surface 31a.
[0043]
A pressure adjusting nozzle (for example, a liquid pressure reducing valve), a pressure flow rate adjusting nozzle, or the like is used as the stripping liquid control unit 33 in order to control a supply pressure and / or a supply amount of the stripping liquid to the stripping liquid supply nozzle 32. You. The stripper is preferably depressurized to atmospheric pressure by the stripper controller 33 and supplied to the substrate surface 31a from the stripper supply nozzle 32.
[0044]
The substrate 31 is placed on the rotating disk 35 with the surface 31 a facing the stripping liquid supply nozzle 32 and directly below the same.
[0045]
The turntable 35 can be driven to rotate in the direction of an arrow 36 by a drive device (not shown) to rotate the substrate 31. By rotating the substrate 31 with the turntable 35, spin processing can be performed.
[0046]
The stripping liquid generated by the gas-liquid mixing means (not shown) flows through the stripping liquid line 29, and is controlled by the stripping liquid supply nozzle 32 and the rotating disk 35 while controlling the pressure and / or the supply amount by the stripping liquid control means 33. It is supplied to the surface 31a of the substrate 31 rotating in the direction of the arrow 36, reacts with the resist film, and removes the resist film.
[0047]
FIG. 4 is a flowchart showing a configuration of the peeling and cleaning apparatus 37 according to the third embodiment of the present invention. The peeling / cleaning apparatus 37 of the present embodiment is similar to the peeling / cleaning apparatus 1 of the first embodiment or the peeling / cleaning apparatus of the second embodiment, and the corresponding portions are denoted by the same reference numerals and will not be described. Omitted.
[0048]
The peeling and cleaning device 37 is characterized in that a cooling means 38 is provided between the ozone fluid pure solvent generating means 6 and the ozone fluid generating means 8 in the ozone fluid generating section 2a. The cooling means 38 is preferably provided with a temperature control function.
[0049]
The pure solvent generated by the ozone-fluid pure solvent generating means 6 flows through a pure solvent line 39 and is supplied to a cooling means 38, where it is cooled. The cooled pure solvent is introduced into the ozone fluid generating means 8 while maintaining the liquid temperature, and is mixed with the ozone gas introduced from the ozone gas line 24. The pure solvent is cooled to 5 to 15 ° C. by the cooling means 38. The solubility of ozone gas in a solvent depends on the temperature of the solvent, and the lower the liquid temperature, the higher the solubility.Therefore, using a pure solvent that has been cooled makes it more ozone-soluble than using a pure solvent that has not been cooled. The ozone concentration in the fluid can be further increased. Even if this low-temperature and high-concentration ozone-based fluid is supplied to the substrate surface as it is, the reactivity with the resist film is low because the liquid temperature is low, and a sufficient peeling removal rate cannot be obtained. However, the low-temperature and high-concentration ozone-based fluid is mixed with the vapor of the solvent in the gas-liquid mixing unit 4 and heated instantaneously according to the configuration of the stripping cleaning device 37 of the present invention, and is supplied to the substrate surface. As a result, a higher resist film stripping / removing speed can be achieved than in the case of using a stripping solution in which steam is mixed with an uncooled ozone-based fluid.
[0050]
Hereinafter, the effects of the present invention will be described with reference to FIGS. 5 to 7 in a case where ozone water is used as the ozone-based fluid and steam is used as the vapor in the stripping and cleaning apparatus of the present invention.
[0051]
FIG. 5 is a graph showing the relationship between the amount of water vapor mixed with ozone water and the resist film peeling speed in the peeling and cleaning apparatus of the present invention. In this specification, the amount of water vapor mixed indicates the mass of water vapor with respect to the mass of ozone water in M / M% (% by weight). The resist film stripping rate is shown as 1 with the resist stripping rate of ozone water having a liquid temperature of 25 ° C. and an ozone concentration of 60 ppm, which is not mixed with water vapor. FIG. 6 is a graph showing the relationship between the amount of water vapor mixed and the ozone concentration at the outlet of the stripping solution supply nozzle in the apparatus of the present invention. FIG. 7 is a graph showing the relationship between the amount of mixed steam and the water temperature at the outlet of the stripping solution supply nozzle in the apparatus of the present invention. In each figure, ◇, □, △, ×, +, and ○ are symbols indicating the water temperature when ozone gas and water are mixed. Specifically, Δ: 5 ° C., □: 10 ° C., Δ: 15 ° C., ×: 20 ° C., +: 25 ° C., and ○: 30 ° C.
[0052]
Note that ozone water is a saturated aqueous solution at each temperature, and the ozone gas reacts with the resist in a supersaturated state without being released out of the liquid by mixing with water vapor.
[0053]
From FIG. 5, it can be seen that the resist stripping rate increases with an increase in the amount of steam mixed with the ozone water, and that the resist stripping rate increases as the pure water temperature decreases. That is, as described in the section of the prior art, in the conventional method, a sufficient resist removal rate cannot be obtained with low-temperature and high-concentration ozone water. On the other hand, in the present invention, an extremely high resist stripping rate has been successfully obtained by mixing low-temperature and high-concentration ozone water and steam immediately before the reaction of the ozone water with the resist film. For example, as shown in FIG. 5, when 1 ml of ozone water having a water temperature of 5 ° C. and an ozone concentration of 120 ppm is mixed with 160 ml of water vapor (water vapor mixing amount = 16%), ozone having a water temperature of 25 ° C. and an ozone concentration of 60 ppm without water vapor is mixed. It can be seen that a resist stripping speed 13 times that of water can be obtained.
[0054]
This is because, as shown in FIG. 6, the saturated ozone concentration increases as the temperature of the pure water mixed with the ozone gas decreases, and as shown in FIG. This is apparent from the fact that the temperature of the stripping solution at the nozzle outlet (ozone water temperature) is high.
[0055]
However, in practice, the ozone water is not supplied to the substrate in a uniform state because the ozone water evaporates from the ozone water so as to have little or no effect on the resist removal rate due to the mixing with the water vapor. Since the substrate may not be uniformly processed, it is necessary to set the optimal amount of ozone water and the amount of steam in accordance with the temperature and concentration of ozone water. The amount of ozone water and the amount of steam can be adjusted by the ozone fluid control means and the steam control means.
[0056]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the peeling removal rate of a resist film and, consequently, the peeling removal capability are extremely high, and since there is no residue on the substrate surface after the removal, an extra washing step can be omitted, and wastewater and by-products that adversely affect the environment are eliminated. A peeling / cleaning apparatus which does not require any special waste liquid treatment facility, complete sealing of the apparatus, and large-scale abatement equipment is provided.
[0057]
According to the present invention, when an ozone fluid is produced by mixing an ozone gas and a solvent, the resist film on the substrate is removed by removing extra components, impurities, and the like from the solvent to obtain a pure solvent. An ozone fluid suitable for the above is obtained.
[0058]
According to the present invention, by cooling the pure solvent before mixing the ozone gas and the pure solvent, it becomes possible to generate an ozone-based fluid having a high ozone concentration, and the removal rate of the resist film is further improved. .
[0059]
According to the present invention, in mixing the ozone fluid and the steam, the mixing of the ozone fluid and the steam can be performed smoothly by adjusting the supply pressure and the supply amount of the ozone fluid or the steam, It is possible to obtain a high-temperature ozone-based fluid in which a decrease in ozone concentration is suppressed as much as possible.
[0060]
According to the present invention, by adjusting the supply pressure and the supply amount of the high-temperature ozone-based fluid (stripping liquid) to the substrate processing unit, the ozone gas is separated from the high-temperature ozone-based fluid and the ozone concentration is reduced. Can be suppressed.
[0061]
According to the present invention, a high resist film removal rate is achieved by using a mixture of a specific solvent and ozone gas as an ozone-based fluid.
[0062]
According to the present invention, a high resist film removal rate is achieved by using a specific solvent vapor as the high-temperature vapor.
[Brief description of the drawings]
FIG. 1 is a flowchart showing a configuration of a peeling and cleaning apparatus according to a first embodiment of the present invention.
FIG. 2 is a cross-sectional view schematically illustrating a configuration of a substrate processing unit provided in the peeling and cleaning apparatus according to the first embodiment of the present invention and processing of a substrate by the substrate processing unit.
FIG. 3 is a cross-sectional view schematically illustrating a configuration of a substrate processing unit provided in a peeling and cleaning apparatus according to a second embodiment of the present invention, and processing of a substrate by the substrate processing unit.
FIG. 4 is a cross-sectional view illustrating a configuration of a substrate processing unit provided in a peeling and cleaning apparatus according to a third embodiment of the present invention.
FIG. 5 is a graph showing the relationship between the amount of water vapor mixed and the resist film peeling speed in the peeling and cleaning apparatus of the present invention.
FIG. 6 is a graph showing the relationship between the amount of water vapor mixed and the ozone concentration at the outlet of a stripping solution supply nozzle in the stripping cleaning apparatus of the present invention.
FIG. 7 is a graph showing the relationship between the amount of water vapor mixed and the liquid temperature at the outlet of the stripping liquid supply nozzle in the stripping cleaning apparatus of the present invention.
[Explanation of symbols]
1,37 Peeling and cleaning equipment
2 Ozone fluid generation unit
3 Steam generator
4 Gas-liquid mixing section
5,30 Substrate processing unit
6 Pure solvent generation means for ozone fluid
7 Ozone gas generating means
8. Ozone fluid generation means
9 Pure solvent generation means for steam
10 Steam generation means
11 Gas-liquid mixing means
12 Ozone fluid control means
13 Steam control means
14 Substrate processing means
15, 18, 33 Stripper control means
16,31 substrate
16a, 31a Substrate surface
17, 32 Stripper supply nozzle
19,34 Stripping solution
20 rollers
21,36 arrow
22, 26 solvent line
23, 27, 39 Pure solvent line
24 Ozone gas line
25 Ozone fluid line
28 steam line
29 Stripper line
35 turntable
38 Cooling means

Claims (8)

A peeling and cleaning apparatus for removing an organic thin film and organic substances attached to a substrate surface by an ozone fluid,
An ozone-fluid generator for generating an ozone-fluid,
A steam generator for generating steam,
A gas-liquid mixing unit that mixes the ozone-based fluid generated by the ozone-based fluid generation unit and the steam generated by the steam generation unit;
A substrate processing unit for supplying an ozone-based fluid heated by the gas-liquid mixing unit to the surface of the substrate. The ozone fluid generation unit,
Ozone gas generating means for generating ozone gas;
Ozone fluid pure solvent generating means for generating a pure solvent to be mixed with ozone gas,
2. The stripping and cleaning apparatus according to claim 1, further comprising an ozone fluid generating means for mixing the ozone gas and the pure solvent to generate an ozone fluid. Provided between the ozone fluid pure solvent generation means and the ozone fluid generation means,
3. The apparatus according to claim 2, further comprising a cooling unit for cooling the pure solvent. The gas-liquid mixing unit,
Gas-liquid mixing means;
It is provided between the gas-liquid mixing means and the ozone fluid generation unit,
The peeling and cleaning apparatus according to any one of claims 1 to 3, further comprising an ozone fluid control unit that controls a supply pressure and / or a supply amount of the ozone fluid supplied to the gas-liquid mixing unit. . The gas-liquid mixing unit,
Gas-liquid mixing means;
Provided between the gas-liquid mixing means and the steam generation unit,
The peeling and cleaning apparatus according to any one of claims 1 to 3, further comprising steam control means for controlling a supply pressure and / or a supply amount of steam supplied to the gas-liquid mixing means. The substrate processing unit,
Substrate processing means;
Provided between the substrate processing means and the gas-liquid mixing unit,
The stripper according to any one of claims 1 to 5, further comprising a stripper control unit that controls a supply pressure and / or a supply amount of the heated ozone-based fluid supplied to the substrate processing unit. Cleaning equipment. 7. The method according to claim 1, wherein the ozone-based fluid is at least one selected from pure water containing ozone, an organic solvent containing ozone, and an aqueous acid solution containing ozone. The stripping / cleaning apparatus according to any one of the above. The stripping and cleaning apparatus according to any one of claims 1 to 6, wherein the steam is steam of pure water, an organic solvent, an alkali or an acid.

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