JP2006148071A - Removing method of fouling on substrate surface, removing treatment liquid and removing device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a removing a treatment liquid, a treatment method and a removing device of an organic system fouling on a substrate surface capable of removing even a resist film hardened and denaturalized by high-concentration ion implantation at room temperature and provided with a multi-repeatable treatment capacity using environment-friendliness and ozone regeneration at almost the same level of ethylene carbonate (EC) treatment. <P>SOLUTION: (1) The removing method of the organic system fouling on the substrate surface, wherein the fouling is exfoliated by contacting the treatment liquid containing a mixed solvent composed of EC of a weight ratio 85/15 to 55/45 and γ-butyrolactone (GBL) with the substrate having the organic system fouling on the surface.(2) The removing treatment of the organic system fouling, wherein a reaction product of the mixed solvent and ozone and a reaction product of the organic system fouling and ozone are contained in 0 to 5 weight% in total and a residue is the mixed solvent.(3) The removing device of the organic system fouling, wherein the system has a treatment liquid introducing means, a fouling contacting means, a treatment liquid circulating means and an ozone containing gas contacting means. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention mainly relates to the removal of unnecessary organic substances adhering to a substrate surface during the manufacture of electronic devices and contaminants containing organic substances by a chemical solution, and particularly to the advancement of removal of a photoresist film in a photolithography process. . This removal technology is also used to clean organic substances such as solder flux used in the assembly of not only electronic parts but also precision parts.

  In the electronics industry, photolithography is often repeated many times during device manufacturing. Therefore, it is required that the resist stripping process is complete and that the device function is not damaged each time. Time required and expenses cannot be neglected. As for the resist to be stripped, the negative type tends to be gradually withdrawn in terms of resolution and environmental load, the positive type is the mainstream, and most of which is a novolac resin type, and chemically amplified polyvinylphenol. Resin systems continue. When the resist film is used as a mask for dry etching or high-concentration ion implantation, it is hardened and deteriorated. Therefore, ashing with plasma-excited oxygen is generally performed to remove these resists. However, this treatment is likely to damage the device, and a residue derived from a resist or the like is formed on the finished surface. Therefore, a wet treatment with a stripping solution with relatively little damage is used in combination with heated sulfuric acid + excess. Decomposition treatment with hydrogen oxide, or dissolution treatment with an organic solvent mainly composed of amines, n-methylpyrrolidone, dimethyl sulfoxide, propylene carbonate (for negative type), etc. has been used depending on the processed film and the material of the substrate .

  However, the sulfuric acid treatment has a social and economic problem because it requires a large measure for pollution to the air and rivers and requires a large amount of ultrapure water for rinsing. Most of the above solvents have appeared as substitutes for chlorinated solvents due to problems related to environmental destruction and toxicity, but they still have a large environmental impact, including the treatment of rinse wastewater, and the organic solvents themselves are expensive. Not economical. Therefore, in the case of peeling with an organic solvent, a waste solution is regenerated by distillation after being used a plurality of times with the same solution. As the number of treatments increases, the amount of solute in the liquid also increases in proportion thereto. Since a part of the solute is always brought into the rinse, the burden of the rinse liquid increases with each turn, and the risk that the solute and the like are recontaminated increases. Therefore, there is a limit to the number of times that can be repeated, and it is usually at most a dozen times. Further, recovery of this waste liquid by distillation is desired from the viewpoint of resource saving and economy, but distillation is not always easy, and a special measure has been proposed as it may involve harmful reactions (Patent Document 1). .

  The positive resist described above is reactive with ozone. Acetic acid has a weak solubility in this type of resist, but when a gas containing ozone (hereinafter abbreviated as ozone gas) is vented, the ozone concentration reaches several hundred mg / L at room temperature, and ozone is dissolved at this high concentration. The acetic acid thus obtained can be removed at a high peeling rate of about 5 μm / min if it is a general resist film, and the resist is decomposed into water-soluble carboxylic acid, water, etc., and the load of rinsing water is reduced. Moreover, acetic acid itself reacts very little with ozone. Therefore, it can be repeatedly peeled 100 times or more with the same treatment liquid, which is a preferable method in terms of resource saving and economy (Patent Document 2). However, since acetic acid has a high vapor pressure and is flammable, the burden on the apparatus is large, and acetic acid containing ozone damages copper wiring and the like. On the other hand, various ozone water treatments have been proposed as a stripping method that is expected to reduce environmental impact and save resources, but the stripping rate is insufficient, and even 180 mg / L high-concentration ozone water produced under high pressure is about 1 μm / min. Can only be removed (Non-Patent Document 1).

In ethylene carbonate of about 40 ° C (melting point 36 ° C), ozone is saturated at about 50 mg / L, but the resist stripping rate of the solution is several times higher than the ozone saturated acetic acid solution, and the ozone in the solution is The resist is decomposed into low molecular weight substances as in acetic acid. Even if ozone is not included, as with existing organic solvent-based stripping solutions, the higher the temperature, the higher the stripping performance and the higher the stripping rate than ozone treatment. In this case, ozone is dissolved in the stripped solution. If this is the case, repeated peeling treatment can be performed many times (Patent Document 3). The ethylene carbonate liquid has a boiling point of 238 ° C., a flash point of 160 ° C., and the vapor pressure at 80 ° C. is about 1/10 that of existing stripping liquids, and high-temperature wet processing at 150 ° C. is possible. A hardened and altered resist film obtained by 1 × 10 ¹⁵ / cm ² ion implantation of B ⁺ which is considered difficult can be peeled off by immersion for about 2 minutes. In addition, there is an advantage that the copper wiring is not damaged and there is almost no risk of ignition (not applicable to the dangerous materials of the Fire Service Act). The mixed solution of propylene carbonate in the same series of alkylene carbonate and ethylene carbonate is also inferior in peeling performance to ethylene carbonate, but can be used many times by similar ozone treatment.

Chlorine solvents and chlorofluorocarbon solvents have been used to clean precision parts with solder flux and epoxy resin before curing, but polymers have been used as alternative cleaning agents due to toxicity and environmental problems. The above-described stripping solutions of polar aprotic solvents that dissolve well, γ-butyrolactone, and the like have appeared. From the viewpoint of waste liquid recovery such as distillation regeneration, a treatment liquid without an auxiliary agent is preferable even if the cleaning ability is slightly inferior. Even in a single solution, in γ-butyrolactone, Patent Document 4 is effective for cleaning flux, Patent Document 5 is effective for cleaning uncured epoxy resin, and Patent Document 6 is effective for cleaning both. However, complete removal of deposits requires heating of the liquid and strong use of several tens of kilohertz ultrasonic waves, and there is a risk of damaging the function when applied to a complicated circuit board or nanodevice.
Japanese Patent No. 2501008 Japanese Patent No. 3538114 JP 2003-330206 A Japanese Patent Laid-Open No. 5-125396 Japanese Patent No. 3269593 JP-A-9-176696 Japanese Patent No. 643693 62nd Applied Physics Academic Lecture Proceedings 12p-W-10 p. 617 2001

  As described above, according to the ethylene carbonate solution, the resist film cured and altered by high-concentration ion implantation can be removed in a few minutes by high-temperature treatment at 150 ° C. However, at this temperature, the vapor pressure is 40 mmHg or more, and the structural burden on the apparatus is large. The ethylene carbonate treatment has a great advantage in that the dissolved resist can be decomposed with ozone and can be repeatedly removed many times. However, as shown in Patent Document 3, the higher the liquid temperature, the higher the liquid temperature. As a result, the generation of an oxidizing substance increases, so that a treatment at about 40 ° C. close to the melting point is required. Therefore, it becomes a circulation process that repeats the high-temperature treatment and the 40 ° C. treatment, and heat loss becomes a problem. It can be said that the liquid temperature of the stripping process and the liquid temperature of the resist decomposition process using ozone are the same and are preferably closer to room temperature.

  As a result of the study by the present inventors, it has been found that the oxidizing substance generated in ethylene carbonate by the reaction with ozone is an organic peroxide. This peroxide itself has little influence on the resist removing ability, but its concentration increases successively when ozone treatment is repeated with the same solution. Since an organic peroxide is generally a polymerization initiator, there is a risk that an intermediate product due to the ozone reaction is polymerized and a troublesome foreign substance is generated when its concentration increases. This is not preferable because it decreases the peeling rate, hinders the rinsing effect, and causes contamination in the liquid circulation system, thereby shortening the life of the circulation treatment. It is this ethylene carbonate liquid that does not generate peroxides relatively in alkylene carbonate, but it is necessary to suppress this generation as much as possible.

  The essential drawback of this ethylene carbonate treatment is that the melting point is 36 ° C, so that it is necessary to keep the main part of the equipment as well as the liquid at about 40 ° C at all times. This is in terms of equipment cost and maintenance. It is not preferable. As a countermeasure, Patent Document 3 proposes ozone treatment at room temperature with propylene carbonate characterized by a melting point of −49 ° C. and an ethylene carbonate / propylene carbonate mixed solvent having a mixing ratio capable of maintaining a liquid state. In the latter case, a considerably high ozone concentration can be obtained by aeration with ozone at 25 ° C., but on the other hand, since the processing temperature is low, the dissolving ability is lowered, and the resist stripping ability is slightly lowered. Propylene carbonate can be repeatedly treated many times by ozonolysis, but peroxides are likely to be generated even at room temperature treatment, and the number of cycles that can be circulated is poor. A particular problem is that when an ozone aeration treatment is performed with a stripping solution containing propylene carbonate and then direct rinsing with water, a white film-like residue is often produced on the stripped surface. In that case, it is necessary to reliably replace the treated solution with a new stripping solution before rinsing with water. Therefore, the application of the room temperature treatment of propylene carbonate system by ozone ventilation is limited.

  The present invention provides an ethylene carbonate-containing improved treatment solution having an improved peeling ability so that the cured and altered resist film can be peeled off at room temperature without heating the solution, and a removal treatment method thereby. The organic substance transferred to the treatment liquid is decomposed by ozone, and the liquid can be reused. At that time, the generation of peroxides is reduced, and the treatment capacity is repeated many times, and adheres to the surface of the substrate exceeding the ethylene carbonate treatment. The challenge is to improve the removal of organic substances.

  In order to solve the above-mentioned problems, first, the present invention provides a substrate having an organic deposit on the surface, ethylene carbonate (hereinafter sometimes abbreviated as EC) having a weight ratio of 85/15 to 55/45, and γ-butyrolactone. (Abbreviated as GBL hereinafter) is brought into contact with a processing solution containing a mixed solvent, and a removal method for peeling the deposits by a dissolving action is provided as a basic feature.

The mixed solvent of the above weight ratio provided by the present invention can be represented by the following four mixed solvents.
(1) EC85w% GBL15w% (hereinafter sometimes abbreviated as 85/15 solution)
(2) EC 75 w% GBL 25 w% (hereinafter sometimes abbreviated as 75/25 liquid)
(3) EC 65 w% GBL 35 w% (hereinafter sometimes abbreviated as 65/35 liquid)
(4) EC 55 w% GBL 45 w% (hereinafter sometimes abbreviated as 55/45 liquid)
The secondary component γ-butyrolactone added to ethylene carbonate has a freezing point of −41.5 ° C., and FIG. 1 is a freezing point diagram of this mixed solvent at normal pressure prepared by the present inventor. The freezing point of the 75/25 liquid is 21 ° C., and the freezing points of the 65/35 liquid and 55/45 liquid are below this. In an ordinary factory where air conditioning is performed, the environment does not become 21 ° C. or lower, so these can always be used in a liquid state. The 85/15 solution has a freezing point of 27 ° C., but at an average working environment control temperature of 25 ° C. (hereinafter, all treatments described as room temperature are treatments at 25 ° C.), it is almost liquid due to supercooling, Even if there is precipitation of ethylene carbonate crystals, there is usually no problem with the process of this application.

The present invention is primarily composed of two basic stripping methods, with the main purpose being to provide a stripping treatment method in which high stripping performance can be obtained with the processing solution prepared at room temperature. As a first feature, the present invention is a removal method described above as a basic feature, wherein the contact between the substrate and the treatment liquid forms a liquid layer of the treatment solution on the surface of the substrate. A method of removing a light beam having a peak wavelength of radiant energy of 0.24 to 2 μm that is irradiated through the liquid layer to the surface intermittently and / or while relatively moving the substrate and the light beam. I will provide a. The substrate may be a substrate on a flat plate. This removal method is suitable for so-called single wafer processing. Since the irradiation of the light beam is performed intermittently and / or while the substrate and the light beam are moved relative to each other, the temperature of the entire treatment liquid layer is slightly increased. On the other hand, the treatment liquid in the substrate surface and the region adjacent to the surface is rapidly heated, and the deposits are separated from the surface by a dissolving action enhanced by light energy. The effectiveness of this method indicates that the method using the present treatment liquid heated at a high temperature has a remarkable effect.
Furthermore, a gas containing ozone is preferably passed through the discharge treatment liquid that has taken in the release substance in the release treatment of the deposit on the substrate at a treatment liquid temperature of preferably 22 to 27 ° C. to decompose the substance into a low molecular weight substance. There is shown a removal method in which the decomposed processing solution is used as a regenerating processing solution for processing another substrate to improve the repeatability many times. That is, the treatment liquid can be recycled. By aeration of a gas containing ozone while irradiating the treatment liquid with ultrasonic waves, decomposition of the deposit into a low molecular weight substance can be promoted. As an ultrasonic wave, an ultrasonic wave of 20-400 KHz is mentioned, for example.

Further, as a second feature of the peeling method of the present invention, there is shown a deposit removing method which is suitable for so-called batch processing in which a large number of substrates are simultaneously processed and enables room temperature processing. That is, the present invention provides the above-described removal method as a basic feature, wherein the treatment liquid is an ozone-containing treatment liquid having an ozone concentration of 20 mg / L or more. By bringing the ozone-containing treatment liquid into contact with the substrate, the deposit is dissolved and simultaneously decomposed into a low molecular weight substance by the action of ozone. The liquid temperature when ozone is dissolved in the treatment liquid is preferably 22 to 27 ° C.
In this method, a gas containing ozone at a concentration of 100 mg / L or more is continuously passed through the treatment liquid, and the substrate is immersed in the treatment liquid while maintaining the ozone concentration in the treatment liquid. The treatment liquid may be brought into contact with the substrate. When the substrate is a flat substrate and at least one surface of the flat substrate has the organic deposit, the one surface having the organic deposit and the ozone-containing treatment liquid A gas containing ozone having a concentration of 100 mg / L or more in a state in which only one side or one side and one side opposite to the one side is covered with the ozone-containing treatment liquid in the form of a liquid film. You may carry out by hold | maintaining in. By doing in this way, the ozone concentration in the treatment liquid can be maintained at 20 mg / L or more, and removal of the deposit and decomposition of the deposit into a low molecular weight substance can be performed effectively. .
In the treatment liquid after the deposit on the substrate surface is removed by this method, the organic deposit is decomposed into a low molecular weight substance, so that the treatment liquid is circulated as a treatment liquid for treating another substrate. Can be used. In order to further sufficiently decompose the organic deposit, a gas containing ozone may be passed through the treatment liquid after the deposit is removed. Conditions such as the treatment liquid temperature and ozone concentration during aeration can be the same as described above. When removing or decomposing organic deposits with an ozone-containing treatment liquid, or when a gas containing ozone is passed through the treatment liquid after removing the deposits, irradiate the treatment liquid with ultrasonic waves. Also good. Thereby, decomposition | disassembly to this low molecular weight substance of this deposit can be accelerated | stimulated. As an ultrasonic wave, an ultrasonic wave of 20-400 KHz is mentioned, for example.

If the generation of peroxides can be reduced by lowering the ozone treatment and the life of the solution in the repeated treatment is significantly increased, impurities in the resist itself and metal elements derived from contamination from the equipment accumulate in the treatment solution and the substrate There is a risk of adsorbing contamination on the surface. In order to prevent this, when the treatment liquid is circulated and used in the removal method of the present invention, one or more filled with fine powders made of the same or similar material as the constituent material of the surface of the substrate to be removed. The concentration of metal impurities accumulated in the treatment liquid can be reduced by passing the treatment liquid through the metal impurity adsorption cylinder and the subsequent precision filter that prevents the fine powder from flowing out. If the adsorption purification mechanism composed of the metal impurity adsorption cylinder and the precision filter is deployed as a bypass of a liquid circulation system that repeatedly performs organic substance removal treatment many times, and used as a purification means that operates as needed, the treatment liquid It is possible to reduce the concentration of metal impurities accumulated in the substrate.
Furthermore, the treatment liquid which has been subjected to the regeneration process by ozone a number of times and turned into a waste liquid can be regenerated as described below and used as a treatment liquid for the removal method of the present invention. That is,
(A) Freely separating the crystals containing ethylene carbonate by leaving the processing solution recycled and used as waste to stand at a temperature of −30 to −15 ° C.,
(B) subjecting the frozen and separated crystals to a normal solidification method to obtain purified crystals containing ethylene carbonate;
(C) A weight ratio of 85/15 to 55/45 prepared by mixing the obtained crystal with γ-butyrolactone or with a distilled purified product of the treatment liquid after freeze-separating the crystal of the step (a). A treatment liquid containing a mixed solvent of ethylene carbonate and γ-butyrolactone can be used in the removal method of the present invention.

In addition, the present invention provides:
A. A treatment liquid introduction means for transporting a treatment liquid containing a mixed solvent containing ethylene carbonate and γ-butyrolactone as main components to a treatment area;
B. A deposit contacting means for bringing the treatment liquid into contact with a surface of the substrate having the organic deposit in the treatment area on the surface having the organic deposit;
C. C. treatment liquid circulating means for returning the treatment liquid discharged from the treatment area to the treatment area via one or more temporary storage means; An organic system attached to the surface of the substrate having an organic deposit, characterized by having an ozone-containing gas contact means for contacting an ozone-containing gas with a processing solution in the processing area and / or in the temporary storage means. A kimono removal apparatus is also provided. Examples of the treatment liquid include the treatment liquid described in the present specification. The means A may further be provided with a heating mechanism for the treatment liquid. The means D may further include a cooling mechanism for the ozone-containing gas. Furthermore, the apparatus may have means for pouring the treatment liquid into the treatment area by means of a high-pressure jet nozzle and / or a two-fluid jet nozzle.

The present invention is an improvement of the environment-friendly ethylene carbonate treatment provided in Patent Document 3. The problem requiring constant heat retention, which was the weak point, was solved by the mixed solvent treatment liquid to which γ-butyrolactone of the present invention was added. As a result, the disadvantage of the complexity of the device structure can be avoided. Moreover, it should be emphasized that the processing solution enabled a high-performance removal process that can be peeled off even at room temperature even in a hardened and denatured resist film that has been ion-implanted at a high concentration of about 1 × 10 ¹⁵ / cm ² . Conventionally, the treatment capable of peeling such a modified film with an organic solvent required optimization of the peeling ability by mixing several kinds of materials and further heating to near the flash point. The removal method of the present invention clearly exceeds the stripping ability of conventional methods with organic solvents.

It is known that γ-butyrolactone has excellent solubility in polymers. Needless to say, this mixed solvent has improved solubility compared to ethylene carbonate alone due to the synergistic effect of the dissolution performance of cyclic esters having slightly different properties. However, the reason why the present mixed solvent has brought about the high peeling effect in the room temperature treatment emphasized above is rather based on characteristics remarkably different from the conventional peeling solvents listed below.
1. The ethylene carbonate having a high boiling point (238 ° C.) is mixed with γ-butyrolactone having a boiling point lower by about 30 ° C. (204 ° C.).
2. It is transparent over a wide range of near infrared, visible light, and near ultraviolet light.
3. Ethylene carbonate has an extremely low viscosity at a high temperature of about 0.4 cP at 180 ° C., but with this mixed solvent, the viscosity is further reduced by about 0.03 cP, which is similar to acetone at room temperature where low viscosity is utilized. .
4). When ozone gas is passed at room temperature, the ozone concentration rises more rapidly than the ethylene carbonate solution, and ozone dissolves at a concentration approximately 50% higher. Also, the ozone dissolution behavior is significantly different from that of γ-butyrolactone, and the concentration does not decrease even if aeration continues, so it is suitable for continuous treatment at room temperature of about 20 minutes. The residual ratio of ozone 30 seconds after the stop of ventilation is 0% for γ-butyrolactone, while it is improved to nearly 80% for this mixed solvent, so that the ozone solution can be transported and used.
5). The amount of peroxide generated when ozone is dissolved is relatively small, and even if ozone gas is passed for 20 minutes at room temperature, it is about the same as when it is passed for 5 minutes through 40 ° C. ethylene carbonate.

The peeling method in which only the substrate / liquid contact area is rapidly heated to nearly 200 ° C. by light irradiation through the processing liquid layer, which is shown as the first feature, utilizes the characteristics 1 to 3. The irradiation control of light can be optimized using the micro-foaming (boiling point) of γ-butyrolactone. The above-mentioned cured and altered resist, which is suitable for single wafer processing and required 2 minutes for peeling by immersion in ethylene carbonate at 150 ° C., can be peeled off within 1 minute with a 75/25 solution prepared at room temperature. At this high temperature liquid interface, the viscosity is lowered and the wettability is remarkably improved, so that contaminants including fine via holes and altered resist in the wiring trenches can be eliminated. Since the thickness of the boundary layer that hinders the flow of liquid at the interface is proportional to the square root of the viscosity, ultra-low viscosity contributes to carrying out contaminants in the fine recess by thinning the boundary layer. Although depending on the thickness of the liquid layer, the temperature of the entire liquid usually rises only about several degrees Celsius, and since the vapor pressure near room temperature is low, there is almost no loss of liquid due to the treatment. The drained liquid after processing easily returns to room temperature and ozone gas is passed as it is, so that the ozone concentration of the liquid quickly rises to a high concentration and can efficiently decompose the resist. The process can be repeated many times at room temperature, eliminating the heat loss problem and further improving the economic effect of the circulation process.
The superiority of the organic deposit removal ability of the treatment liquid over the ethylene carbonate alone liquid increases as the liquid temperature increases. This is a natural consequence of the above description. The 75/25 liquid flash point measured in the Cleveland open-type flash point test is 131 ° C., that is, exceeds 130 ° C., so that a treatment liquid of 130 ° C. or lower, preferably 120 ° C. or lower can be used safely. To remove deposits that are particularly difficult to peel off, such as hardened degenerated resist films in which phosphorus is ion-implanted in high concentration, with high productivity, it is necessary to perform contact with high-temperature liquid while impacting with a high-pressure jet nozzle or two-fluid jet nozzle. It is extremely effective. However, in this case, when the resist in the treated liquid is decomposed with ozone, it is necessary to cool the liquid to 22 to 27 ° C. in order to suppress the generation of peroxide, and the energy loss increases. It is. On the other hand, the present inventor has found that the generation of peroxide can be substantially suppressed without cooling the liquid by sufficiently cooling and bubbling the ozone-containing gas. Examples of the temperature of the cooled ozone-containing gas include −40 to 20 ° C., preferably −30 to 15 ° C. The high temperature liquid may be brought into contact with the substrate while irradiating the high temperature liquid with ultrasonic waves.

  Utilizing the characteristics 4 and 5, the substrate is brought into contact with an ozone-containing treatment liquid in which ozone gas is aerated in a liquid of 27 ° C. or lower and 22 ° C. or higher, which is shown as the second feature, for example, by dipping, and deposits Is a peeling method that simultaneously dissolves and decomposes by ozone. When the substrate having the cured altered resist adhered thereto is immersed in a 75/25 solution prepared at room temperature and ozone gas having a concentration of 200 mg / L is vented, it is peeled off in 20 minutes, and during this time, the resist is completely decomposed and 20 minutes. Even in the treatment, the generation of peroxide is the same as the 5-minute treatment of ethylene carbonate, so that the resist can be repeatedly peeled many times satisfactorily for the altered resist. Even if the processing time is long, it is rather suitable for a batch processing tact type multi-tank immersion cleaning apparatus of about 25 batches that has been widely used, and can be easily implemented with sufficient productivity and economy.

  In this room temperature treatment, depending on the degree of resist alteration and the presence / absence of the resist, it is possible to remove and decompose normally in about 1 to 5 minutes including the first rise of ozone concentration, and thus the generation of peroxide is considerably reduced. Therefore, as far as the peeling performance is concerned, the ability to repeat many times is improved by 50% or more compared to the case of 40 ° C. ethylene carbonate treatment. If the life of the liquid in repeated processing is significantly extended, metal elements due to impurities in the resist itself accumulate in the liquid and there is a risk of adsorbing contamination on the substrate.In the present invention, however, a purification mechanism for purification using a metal impurity adsorption cylinder is provided. Since it can be arranged as a bypass of the liquid circulation system, the economical and resource saving effect by extending the liquid life is obvious, and the problem of improving the repetitive processing capacity according to the present invention has been achieved.

  The resist stripping with the mixed solvent of the present invention can provide a sufficient performance improvement effect by room temperature treatment by two complementary methods. The peeling performance was clearly improved over the ethylene carbonate treatment at 150 ° C. and the ozone-containing ethylene carbonate treatment at 40 ° C. In addition, ozone gas ventilation at room temperature achieved a rapid rise in ozone concentration and an increase in the concentration reached, and succeeded in reducing the generation of peroxide, greatly improving the performance of repeated treatment many times.

  Details of the present invention will be described below. The ozone gas described in this specification is generated by a discharge-type generator, and oxygen gas containing ozone at a concentration of about 200 mg / L is used unless otherwise specified. In the present invention, by adding an appropriate amount of γ-butyrolactone to ethylene carbonate, a high-concentration ozone-containing liquid can be obtained at a rapid rise when ozone gas is passed at room temperature, and processing that suppresses the generation of peroxide is enabled. . This is because the concentration of ozone in γ-butyrolactone can be grasped at any time by devising the analytical method as described below.

《Quantification of ozone concentration in treatment liquid and evaluation of peroxide generation amount》
In general, the analysis of ozone in a water-soluble liquid is typically performed by the iodine method in which iodine liberated immediately after potassium iodide is added to this liquid. When ozone is dissolved in an organic solvent, an organic peroxide is likely to be generated at the same time, and when the iodine method is performed, the peroxide immediately releases iodine and is added to the released amount by ozone. However, since ozone generally decomposes faster than peroxide, both can be analyzed using this property. However, since γ-butyrolactone itself immediately reacts with potassium iodide, the iodine method cannot be applied. Therefore, it was estimated that ozone, like most other organic solvents, hardly dissolved.

  As a result of studying an analytical method for measuring fading caused by a reaction with a blue indigo carmine solution, which was used for quantifying low-concentration ozone, the present inventor can quantitate even with high-concentration ozone with sufficient accuracy. As a result, we have devised a method that can relatively evaluate the generation amount of peroxides based on the results of studies on the discoloration reaction. Therefore, not only γ-butyrolactone but also a wide range of other organic solvents can be compared for both amounts.

<< Evaluation of ozone treatment of organic solvent for resist removal >>
Therefore, for organic solvents that have been used or announced for resist stripping in a conventional beaker, 50 ml in each beaker is ozone gas at 25 ° C. using a cylindrical fluororesin bubbler with a diameter of 25 mm and a thickness of 15 mm. Aeration was conducted at a flow rate of 3 L / min for 5 minutes, and the relative value of the ozone concentration and the amount of peroxide generated immediately after that was determined (the amount of generation at 40 ° C. ethylene carbonate during 5 minutes was 1). The results are shown in Table 1. Incidentally, the amount of peroxide generated in the 20 minute aeration of ethylene carbonate at 40 ° C. is 2, that is, twice the amount in the case of a 5 minute aeration, and approximately 4 in the 20 minutes aeration at 25 ° C. propylene carbonate.

  Regarding ozone concentration and peroxide generation, γ-butyrolactone was close to propylene carbonate. As for the other solvents, there was a result that ozone was not present at all or contained only a little, and in the former, white smoke was emitted and the reaction temperature was increased as the liquid temperature increased by 10 ° C. Therefore, only γ-butyrolactone was worth considering except for homologous series solvents as an additive for ethylene carbonate. Therefore, in order to compare the action of ozone for γ-butyrolactone and ethylene carbonate, the relationship between ozone gas ventilation time and ozone concentration was investigated at 40 ° C., where the latter kept liquid. The results are shown in the solid line graph of FIG. In both cases, the concentration rises rapidly until about 1 minute after aeration, and in the case of ethylene carbonate liquid, the rate of increase gradually decreases, but the ozone concentration increases. γ-Butyrolactone seems to be a byproduct of a substance that decomposes ozone because the rising ozone concentration quickly reaches its peak and then decreases rapidly. Since γ-butyrolactone reaches a peak in about 5 minutes in the 25 ° C. treatment and then shows a sharp drop, it is not suitable as a removing means for performing continuous ozone treatment.

<< Ozone concentration in room temperature ozone treatment of this mixed solvent >>
The results of time-measurement of the liquid ozone concentration when ozone gas was passed at room temperature under the same aeration conditions as above for the four mixed solvents representing the composition range of the present invention are shown by dotted lines in FIG. With a 5-minute aeration of 85/15 and 75/25, a concentration of about 75 mg / L, which is about 50% higher than that obtained with an ethylene carbonate solution at 40 ° C., is obtained. There is a slight increase trend. These compositions are suitable for the immersion removal treatment in which ozone is continuously bubbled. In this mixed solvent, the concentration of ozone obtained decreases as the ratio of γ-butyrolactone increases, but the ozone concentration hits the head after about 10 minutes of aeration in both 65/35 and 55/45 solutions, but the subsequent decrease is slow. Surprisingly, the effect of the plunging property of γ-butyrolactone is weak. After 20 minutes, a high concentration of about 60 mg / L is maintained, and this composition is often effective in stripping polymers other than resist.

<< Peroxide generation in room temperature ozone treatment of this mixed solvent >>
Table 2 shows the measurement results of the relative values of peroxide generation over time when ozone gas was passed through the four mixed solvents at room temperature under the same ventilation conditions as described above.

The amount of peroxide that governs the ability of repeated stripping treatment was evaluated by comparison with ethylene carbonate treatment at 40 ° C. for 5 minutes. The background is as follows. The undissolved particles are dispersed in the resist solution in the ethylene carbonate solution from which the hardened and altered resist is peeled off by ion implantation at 1 × 10 ¹⁴ / cm ² , but the resist is completely decomposed by aeration of ozone gas at 40 ° C. for 5 minutes. About 100 times of circulation processing was completed by reproduction. At the stage near the end, the peeling rate decreased considerably, but the practical range was acceptable. Since it is a track record in a process that is relatively difficult to peel off, the amount of peroxide generated in one ozone aeration process where a cyclic peeling process is practically possible is a concentration of 200 mg / L with respect to an ethylene carbonate solution at 40 ° C. The amount of ozone gas generated by a 5-minute ventilation was determined, and this was used as a reference amount for comparison. The actual measured value of the generated amount by the iodine method is 5 to 10 mg equivalent / L, although it varies depending on the number of circulations and the type of processed resist. The control generation amount relative value 1 in Table 2 indicates the standard. The peeling of propylene carbonate at 25 ° C. for 20 minutes reduces the ability of repeated treatment to about half. However, if this is a practical limit, the relative value of the generated amount in the 20-minute ventilation, that is, 4 is the permissible generation of peroxide. It becomes the upper limit of. γ-Butyrolactone is not suitable for repeated regeneration with ozone because it has a relative value of 7 to 8 at 20 minutes ozone ventilation, but it acts to suppress the generation of peroxide when it is added to ethylene carbonate. This effect greatly contributes to the present invention.

  From Table 2, the amount of peroxide generated in the 75/25 and 85/15 ozone treatments at room temperature is approximately half that of the 40 ° C ethylene carbonate treatment, and the life of the circulating fluid should double. However, even with room temperature treatment, there is evaporation and scattering of the liquid, and the elongation is substantially about 50%. The other two composition liquids also generate less peroxide than propylene carbonate, and can be expected to have a considerable circulation life, though inferior to the above two. When the γ-butyrolactone component is 45% by weight or more, peroxide generation is unacceptable.

<Best removal target for ozone treatment>
The organic substance to be removed, which can make use of the above high ozone concentration and excellent circulation peeling properties, reacts well with ozone and is decomposed into low molecular weight substances, which are dissolved in the mixed solvent and rinsing water. It must be easy. Accordingly, a substance having a large molecular weight, particularly a polymer substance, having a double bond, a benzene ring (including a condensed ring), a nucleophilic atom, or the like in the molecule is applicable. Since the present mixed solvent is involved in the decomposition reaction of ozone, that is, it is an active solvent, most of the decomposition products are often low molecular weight substances. Specifically, the organic deposit in the method of the present invention includes, for example, a photoresist and a solder flux, and more specifically as follows.

The organic substances to be removed by the present invention are optimum novolak resin resists and polyvinylphenol resin resists that occupy most of the positive resists, that is, polymer substances containing phenols in the molecule and react well with ozone. The product substance including the decomposition product of the present mixed solvent itself is carboxylic acid such as formic acid, acetic acid, oxalic acid, glycolic acid, its ester, carbon dioxide gas, water or the like. Even if the concentration of these low molecular weight products in the solvent is increased to about 5% by repeating ozone regeneration many times, the dissolving ability of the liquid in the resist film hardly decreases. In addition, when the resist is decomposed to a water-soluble substance as compared with the existing stripping agent dissolved in the form of resist molecules, it is much easier to remove the resist substance in rinsing, that is, to clean the surface after peeling.
More than 90% of epoxy resins used in electronic parts are phenolic, and those that are not cured are reactive with ozone, and rosin, which is also common in soldering fluxes, is a polycyclic aromatic compound that is decomposed by ozone. It is a good removal object of the invention. Regardless of the electronic component, there are many polymers that are reactive with ozone, and are other surface deposits. They are a preferred subject of the present invention.

<Processing liquid>
In the present invention, a treatment liquid that can be preferably used for removing organic deposits on the substrate surface is, for example, a mixed solvent composed of ethylene carbonate and γ-butyrolactone having a weight ratio of 85/15 to 55/45 and ozone. And the reaction product of the organic deposit and ozone in a total amount of 0 to 5% by weight, with the remainder being the mixed solvent. The treatment liquid may further contain 0.1 to 2% by weight of oxalic acid. Thereby, the organic deposit removal action of the treatment liquid according to the present invention can be further improved.
Propylene carbonate is known as a release agent for negative resist films, and as shown in Table 1, the properties against ozone are similar to γ-butyrolactone. Adding another solvent such as propylene carbonate or acetic acid having a very high ability to dissolve ozone to the treatment liquid of the present invention may have a new effect depending on the purpose of use. However, even if these solvents are added, the original effect of the present invention can be exhibited as long as the above weight ratio is maintained. Therefore, it goes without saying that the treatment liquid of the present invention is included in the scope of the present invention even if it contains this type of solvent.

《Hard and altered resist peeling ability in room temperature ozone treatment of this mixed solvent》
Regarding the contact of the ozone-containing mixed solvent at room temperature with the substrate, which is shown as the second feature of the stripping method of the present invention, the resist stripping performance is compared with 40 ° C. ozone-containing ethylene carbonate treatment. For the resist sample for comparison, a high-concentration ion-implanted and hardened film, which is generally considered to be difficult to remove by wet processing, which requires 2 minutes to remove with an ethylene carbonate solution at 150 ° C. described in Patent Document 3, It was created with the same specifications as the sample. That is, a 2 cm × 2 cm chip is obtained from a 1 × 10 ¹⁵ / cm ² implant of ¹¹ B ⁺ at 30 KeV on the entire surface of a 1.5 μm-thick novolak resist (IX500) film on a silicon oxide wafer. It cut out and it was set as the sample of the comparative experiment.

  The resist stripping process uses ozone ventilation means under the same conditions as the process used to create the data shown in Fig. 2. After aeration for 1 minute, the sample chip is immersed in the solution in the beaker and aerated for a predetermined time. Rinse and air dry. The peeling state was observed under a microscope. In an ethylene carbonate solution at 40 ° C., the resist undergoes only a slight change in immersion for 5 minutes where peroxide generation is acceptable, and complete peeling cannot be achieved even in immersion for 20 minutes, so that the surface appears jagged after immersion for 10 minutes. However, in both the 85/15 and 75/25 solutions, a considerable part was completely peeled off in 20 minutes when immersed for 10 minutes at room temperature. When MHz ultrasonic waves are used in combination, they are peeled off by immersion for 10 minutes, and when ultrasonic waves of about 40 KHz can be used, they are peeled off in 3 minutes. From Table 2, even when aeration of these liquids for 20 minutes, the generation of peroxides is within an acceptable range, and the peeling is accelerated little by little in the order of 65/35 liquid and 55/45 liquid, while peroxide generation increases. Regarding the peeling speed, it can be presumed that γ-butyrolactone has the ability to promote the resist dissolving power.

  Naturally, this room temperature ozone treatment can be applied to the immersion treatment with a wafer stored in a cassette. The completely stripped solution is also colorless and transparent as it is decomposed by ozone, and even a strongly denatured resist is sufficiently decomposed by ozone. rare. Therefore, the next wafer can be immersed in this solution as it is for peeling treatment, and repeated peeling treatment can be easily performed in many cases. Even if resist degeneration is very strong and undecomposed matter remains floating, if the treatment liquid is temporarily transferred to another tank and irradiated with ozone at 20 to 400 KHz and ozone is vented at room temperature, the suspended matter can be removed in a few minutes. The decomposition additional treatment solution can be returned to the dipping bath and used for peeling the next wafer, and the removal treatment can be repeated many times.

  According to the room temperature ozone treatment of the present invention, it is possible to remove even strongly altered deposits that cannot be removed by the 40 ° C. ozone-containing ethylene carbonate treatment, and the peeling performance is clearly improved. In addition to the simplification of the apparatus due to room temperature treatment, pollution to the atmosphere due to volatilization is reduced by lowering the treatment, and a remarkable improvement effect can be obtained in terms of maintenance. It seems that it takes too long to take 20 minutes or 10 minutes for the stripping process, but since it can be directly followed by overflow pure water rinsing, it is a batch-type multi-bath immersion process that has been widely used in the past and has been the mainstream of washing machines. It can be conveniently applied to the apparatus in terms of tact, and the present mixed solvent can be put into practical use without any special capital investment.

  Naturally, a resist film that is weakly modified or only baked at 150 ° C. or less can be stripped within several minutes or one minute, and in some cases about 10 seconds, if it is immersed in the present mixed solvent treatment solution at room temperature and vented with ozone gas. However, intermittently supplying ozone gas at a constant concentration for a short time complicates the generator, so it is more practical to lower the ozone concentration in accordance with the tact time and extend the processing time with a tact type processing device. If it is lowered too much, the decomposition ability will suddenly drop, so the ozone concentration of the liquid needs to be 20 mg / L or more. In addition, the ozone gas concentration for ventilation changes depending on the structure of the bubbler, the gas flow rate, etc., so that it is sufficient to set the concentration to 100 mg / L or more with a margin.

《Method of contact with substrate other than immersion method》
As described above, a resist film that can be quickly peeled is actually widely used on the surface of a semiconductor wafer or the glass substrate surface for a liquid crystal device. In addition, there are very many processes that require sheet processing other than immersion treatment. When separation can be performed in about 10 to 30 seconds, productivity and homogeneity can be generally satisfied by modifying an existing single wafer processing apparatus. Examples of the contact method between the processing liquid and the substrate other than the dipping method include, for example, transporting the ozone-containing mixed solvent processing liquid obtained by aeration of ozone gas from the ozone dissolution container and supplying the processing liquid to the substrate surface. There is a method in which a liquid film flowing above is brought into contact with the substrate. In order to bring the treatment liquid into a liquid film state that flows on the surface of the substrate, the liquid is moved onto the surface while rotating the substrate with a rotation axis perpendicular to the surface or moving the substrate in the extending direction of the surface. This can be done by supplying from the nozzle. The problem here is that the ozone concentration in the organic solvent decreases rapidly without the passage of ozone gas. Table 3 shows the residual ratio of ozone concentration with respect to the number of seconds elapsed after stopping the ozone gas ventilation.

  When the supply of ozone to the treatment liquid is stopped, the ozone concentration of the liquid rapidly decreases with γ-butyrolactone, but when γ-butyrolactone is contained in ethylene carbonate, the life of ozone is rather extended. When the ozone-containing mixed solvent treatment liquid at room temperature is transported from the ozone dissolution vessel and supplied to the treatment device, it is desirable that the transportation time is short, but practically there is no problem as long as it takes 30 seconds or less to reach the nozzle.

<< Advantage of dissolution performance of this mixed solvent >>
The superiority of the release performance of the room temperature ozone treatment of the present invention over the 40 ° C. ozone-containing ethylene carbonate treatment is that the 55/45 solution mentioned above is slightly more than the 65/35 solution but the release is faster. It can be said that the dissolving ability contributes to the improvement of the dissolving ability of the mixed solvent, and the synergistic effect is combined with the increase in the concentration of dissolved ozone. Originally γ-butyrolactone has excellent solubility in polymers, and ethylene carbonate is the same cyclic ester and has similar properties such as good water solubility and high solubility in aromatics, The solubility parameter (SP value) is about 1 and is about 13, which is close to a phenol resin (SP value: about 12) or an epoxy resin (SP value: about 11). Therefore, when this mixed solvent is applied to the adhesion of this kind of organic substance including a resist, the composition close to 55/45 liquid helps to contribute to the delamination of ozone. Qualitatively because the sample can be accurately compared, but this formulation at room temperature is clearer than the immersion in ozone-added ethylene carbonate solution for general phenol resin and epoxy resin paints The peeling was quick.

<< Peeling by light irradiation in a mixed solvent prepared at room temperature >>
In the method shown as the first feature of the peeling method of the present invention, a liquid layer of a mixed solvent prepared at room temperature is formed on the surface of a substrate on which deposits are present, and the substrate is irradiated with light through the liquid layer. This irradiation suppresses a rise in the temperature of the entire liquid and rapidly raises the temperature of only the surface of the substrate and the adjacent area of the liquid to be contacted, thereby enabling a treatment at a temperature substantially higher than the high-temperature treatment of ethylene carbonate. This efficient heating is preferably performed by condensing a light beam that is not absorbed by the treatment liquid in the vicinity of the surface of the substrate and scanning the surface with the collected light beam. More specifically, the heating is performed, for example, by condensing the light beam and scanning the surface with a condensing part that includes the focus or is slightly out of focus. Adjustment of the energy amount of the condensing unit is performed by intermittent irradiation and optimization of the scanning method according to the selected light source and optical system. Although the irradiation conditions are determined by examining specific peeling performance, the boiling point of the mixed solvent component γ-butyrolactone can be conveniently used in the preliminary stage. When the appearance of a few fine bubbles is taken as a guide, the temperature rise of the whole liquid is suppressed to 10 ° C. or less, and the conditions for the peeling treatment at a temperature slightly below 200 ° C. are in view.
When the substrate is a flat substrate transparent to the light beam and one surface of the flat substrate has an organic deposit, the above-mentioned peeling due to light irradiation may cause the organic attachment. Forming a liquid layer of the treatment liquid on one side having a kimono makes the treatment liquid contact with the substrate, and comprises a substance that absorbs the light beam on one side opposite to the one side having the organic deposit. By bringing the surface of the auxiliary plate into close contact and irradiating the surface of the auxiliary plate intermittently and / or while relatively moving the auxiliary plate and the light beam through the liquid layer and the substrate It can be carried out. The heating at that time is preferably performed by scanning the surface of the auxiliary plate with the light beam condensed near the surface of the auxiliary plate. More specifically, the operation can be performed in the same manner as described above.

Here, an infrared lamp was used as the light source. Peeling ability is 2cm x 2cm chip sample of 1x10 ¹⁵ / cm ² ion-implanted cured altered resist film that takes 2 minutes to dip in 150 ° C ethylene carbonate prepared for comparison of effects of room temperature ozone treatment Compared. FIG. 3 shows the concept of this peeling experiment for this ion-implanted resist chip. The sample chip 1 was submerged in a 75/25 liquid 3 at room temperature with a depth of about 6 mm filled in the dish 2 with the resist surface facing up. A 0.5KW straight tube type halogen lamp 4 is placed above the dish, the near-infrared ray 6 is condensed on the resist surface by the reflecting mirror 5, and the entire surface of the chip is intermittently moved by the condensing line by reciprocating the dish in the direction of the arrow. Scanned. This near-infrared radiation energy peak has a wavelength of 1.2 μm when a rated voltage is applied, and the skirt hardly spreads to the infrared region having the absorption peak of the present mixed solvent. On the other hand, there is no absorption peak of the present mixed solvent in the near infrared region having a wavelength of 2.5 μm or less, and since the thermal conductivity of the liquid is small, there is no rapid temperature rise of the whole liquid. The temperature of the base silicon that absorbs the light beam is rapidly increased, and the temperature of the substrate is increased to nearly 200 ° C. at which the microbubbles are observed along with the contact portion of the processing liquid with the chip surface. However, since the altered portion cannot be easily dissolved, this portion was peeled off so as to float in the form of a film, and a light brown resist solution containing it was obtained. The required time is about 1 minute, and the peeling rate is clearly larger than the high temperature immersion treatment of ethylene carbonate. The increase in the liquid temperature after the treatment is only a few degrees C., and virtually no solvent vapor is dissipated despite the high temperature treatment.

In short, this method peels off deposits on the substrate by a dissolving action enhanced by light energy. The light beam that can be used is not limited to infrared lamp light. A light beam in a wavelength region in which the absorption spectrum of the mixed solvent is not observed, that is, a light beam having a peak wavelength of radiant energy of 2.5 μm or less, preferably 2 μm or less, and 0.24 μm or more can be used. For example, all laser light having an oscillation wavelength in this range can be used, and a wavelength with a large absorption of the substrate may be selected. Specifically, Nd: YAG laser, which is widely used for laser processing in the semiconductor field, has a short pulse laser beam with a wavelength of 1.06 μm or a second harmonic of 0.532 μm and a fourth harmonic of 0.266 μm. Can be used.
When irradiating the light beam, the treatment liquid may be renewed by supplying a new treatment liquid to the liquid layer on the substrate surface to move the treatment liquid on the substrate surface in the liquid layer state. Thereby, the temperature rise of the whole processing liquid can be suppressed. The supply of new treatment liquid may be performed continuously or intermittently as necessary.

<Decomposition of resist solution with ozone>
The resist-dissolved coloring liquid containing the undissolved film becomes close to room temperature in a short time just by leaving it alone. Here, when ozone gas is ventilated, the coloration disappears within 10 seconds, and if ozone aeration is continued for 2 minutes while irradiating an ultrasonic wave of about 40 KHz, undissolved substances also disappear. The effect of ultrasonic waves is particularly strong, and the time required for decomposition is within the practical range even if the concentration of ozone gas to be vented is reduced to ½. The generated low molecular weight substance is similar to the decomposition products described above according to the analysis, and the amount of peroxide generated is almost half that of 40 ° C. ethylene carbonate. The mixed solvent treatment using light and the decomposition treatment with ozone according to the present invention enable a circulation treatment many times at room temperature, and the number of repetitions can be improved almost twice as much as the ethylene carbonate treatment.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1
The removal method of scanning the surface of the substrate with deposits in the condensing part of the halogen lamp light prepared in the mixed solvent treatment solution of the present invention prepared at room temperature has already been described. In this embodiment, a halogen lamp arranged in parallel is provided. A method of performing the same light irradiation immersion treatment by placing the substrate to be removed below the flat plate furnace will be described. Since the resist on the glass substrate for liquid crystal devices was targeted for removal, the glass does not absorb near-infrared energy. Therefore, the substrate was placed on an auxiliary plate that reliably absorbs light, and peeling was attempted.

  In this embodiment, the object of peeling is a resist used as a mask for dry etching an aluminum / molybdenum two-layer film test pattern on a glass substrate. The resist film is hardened and altered by reactive ions. ing. For the peeling test, the pattern-formed substrate was cut into 20 cm square. The test device is a modification of the rotating part of the existing single wafer spinner cleaning device with vacuum chuck and the wall surface and bottom surface of the chamber. An overhead view of the rotating part is shown in FIG. The rotating part is a stainless steel dish formed with a flat square bottom plate 7 and an edge 8 having a width of 3 cm with an inclination of 10 ° and coated with a thin fluororesin. The bottom plate 7 is an auxiliary plate. FIG. 5 is a sectional view showing the concept of this apparatus. The bottom plate 7 of the dish is fixed to a cruciform stainless steel support 10 via a heat insulating material 9, and the support 10 is a rotating shaft 11 of a drive mechanism (not shown). The dish is rotated by the drive mechanism. The substrate 12 is fixed at a position where the corner of the substrate 12 is sandwiched between a pair of pins 13 by vacuum suction (related mechanism is not shown). The processing liquid of the present invention is sent to the spray nozzle 16 by a pipe (which is shown in bold lines in the present embodiment, and the liquid flows in the direction of the arrow) in the storage tank 14 at room temperature. A liquid layer 17 is formed on the substrate 12 which is filled on the substrate from which suction is stopped. Incidentally, a liquid feed pump, a dust removal filter, valves and the like for sending the liquid attached to the pipe are omitted in the drawing.

  A flat plate furnace 20 (having a quartz glass plate on the lower surface of the furnace) in which a 0.5 KW straight tube type halogen lamp 18 is juxtaposed with the reflecting surface body 19 is disposed above the plate, and at the same time the processing liquid fills the plate. The pan is rotated slowly at 100 rpm or less, the lamp is operated at a rated voltage, and the light emission is intermittently turned on and off to control the upper surface of the pan bottom to a substantially uniform predetermined temperature. The energy of the radiated near infrared rays is hardly absorbed by the treatment liquid, and most of the energy is absorbed by the stainless steel dish, the substrate temperature rises due to heat conduction, the temperature of the adjacent liquid region also rises, and the solvent dissolving action is enhanced. Since it is indirect light heating, it takes longer to peel off than in the case of a silicon substrate, but the temperature rise of the whole liquid is usually 10 ° C. or less. If a long processing time is required, an increase in the liquid temperature can be sufficiently suppressed by instantaneously supplying the liquid from the spray nozzle between the radiation breaks and overflowing the liquid from the edge of the dish. When the light treatment is finished, the liquid is discharged beyond the edge of the dish by increasing the number of revolutions of the dish to 500 to 1000 rpm. Here, after spraying the treatment liquid from the nozzle and rinsing for a predetermined time, the liquid feeding is stopped, and if necessary, the rotation speed is increased to cut off the excess liquid, and the substrate 12 in a state covered with a thin liquid film is removed from the ultrapure water. Transfer to a spin rinser, rinse and spin dry. The substrate can be easily transferred if it is lifted by air supply from the vacuum suction hole and is held by a moving handle (not shown).

  In this peeling test, the 85/15 solution was used as the treatment solution. When the rotation of the dish was set at 60 rpm, the temperature of the dish bottom surface became 200 ° C. in 10 seconds (this rise time is preferably short. For this purpose, a heating plate is provided instead of the heat insulating material 9 and preheating is performed. Preferably). The irradiation interruption of the flat plate furnace was adjusted so that the temperature could be maintained. After 30 seconds, spray rinsing was performed at 1000 rpm for 5 seconds, followed by idle rotation at 1500 rpm for 5 seconds to stop, and the substrate was transferred to rinse with ultrapure water for 10 seconds and spin drying. The rise in the liquid temperature at the end of the lamp treatment was 10 ° C. or less. The substrate was observed with a scanning electron microscope and it was confirmed that the resist was completely peeled off and the metal film was not damaged at all. In order to obtain the same effect with ethylene carbonate, a dip peeling treatment at 100 ° C. or higher was necessary.

  Since the liquid splashes upward during rotation from the structure of the dish, the chamber wall 21 was modified in this apparatus to provide an inward ridge above. The chamber bottom 22 has a concave structure capable of recovering the processing liquid, and the recovered liquid is sent to an ozone processing tank 23 provided with a water cooling mechanism by piping. When the adsorbed liquid for several times collected in the tank 23, the ozone bubbling 24 at room temperature was performed, and the resist was decomposed in about 10 seconds. If the liquid is left for 10 minutes, the ozone will decompose and disappear. This liquid is returned to the storage tank 14 for re-use / circulation. Ozone aeration time is short, and since it is a room temperature treatment, less peroxide is generated and circulation of 150 times or more is possible. The life of the liquid is increased by 50% or more compared with the ethylene carbonate treatment.

Example 2
Dual damascene copper wiring is one of the standard processes in advanced ULSI ultrastructure. FIG. 6 shows a model of the structure after dry etching before copper is embedded. This process is related to the wiring on the CMP flattened surface in which the copper wiring 25 is embedded in the interlayer insulating film 26. In this embodiment, the interlayer insulating film 28 and the SiC etching in the film are formed on the SiC barrier layer 27. A stop film 29 is laminated, and a test wafer in which a via hole opening is provided in the film 29 and a copper wiring groove 31 and a via hole 32 are formed by a mask resist 30 is used. The film 28 is made of low dielectric constant methylsilsesquioxane (MSQ). A 2cm x 2cm chip was cut out from this wafer, and the ashing and removal of the resist hardened and altered by dry etching with 75/25 solution containing 2% by weight oxalic acid prepared at room temperature was attempted and cleaning in the micropores was attempted. It was.

  In the dry etching performed for forming the fine holes, the copper sputtered during the over-etching at the bottom of the via holes is scattered from the side walls of the fine holes to the outside, and the copper surface is oxidized. In addition, there are resist alterations and etching deposits on the side surfaces of both the via holes and the groove holes, and it is necessary to clean all of them including copper before filling with copper. In such fine pore cleaning, (1) the cleaning liquid surely enters, (2) the liquid quickly carries the object to be removed out of the hole, (3) the liquid is replaced with a rinsing liquid, and then ( 4) A procedure for removing the rinse solution and drying is required. This cleaning becomes more difficult as the pores become finer and deeper. As described above, when the mixed solvent of the present invention is heated near 200 ° C., the viscosity is remarkably lowered and the surface tension is also lowered, so that it easily penetrates into the fine pores. Therefore, when the liquid layer 33 is formed on the wafer surface with 75/25 liquid and the temperature of the film is rapidly increased by light heating, the temperature of the liquid in the region in contact with the substrate surface rapidly increases, and the resist and contaminants are removed and the above (1). The liquid permeation described in (1) proceeds efficiently.

  In the peeling experiment, four small protrusions for fixing the position of the tip to the processing liquid supply port, the drainage port, and the bottom are provided in the dish 2 of FIG. The liquid layer on the surface was crafted to flow in a certain direction. Light irradiation was carried out by changing the halogen lamp light to a short pulse laser light. A Q-switched Nd: YAG laser fourth harmonic 0.266 μm oscillator is used to collect energy even in a fine interlayer insulating film, and a 10 KHz laser beam is collected by a lens to form a spot having a diameter of 200 μm. Scanning was performed at 100 mm / second and a linear density of 10 lines / mm. Since this structure dislikes the remaining of water, the operation is repeated once more after rinsing with isopropyl alcohol, and the resist is peeled off and the inside of the hole and groove is cleaned by observation with a scanning electron microscope after drying. It was confirmed. When the amount of oxalic acid added to the treatment solution was 0.1% by weight, almost no residue was found after 3 repetitions. However, if oxalic acid was not added, sufficient residue could not be eliminated.

Example 3
This example relates to a method of peeling a resist on the surface of a glass substrate for a liquid crystal device conveyed by a roller conveyor with a peeling solution at room temperature. Peeling is desirably performed in a short time from the standpoint of productivity. Usually, the peeling solution is heated to about 50 to 70 ° C. and sprayed from a nozzle arranged on a line in the roller axis direction. . In the case of treating with an ethylene carbonate heating liquid, the vapor pressure is low, which is superior to other stripping liquids in that the substrate surface does not dry and can be directly transferred to water rinsing. The removal at room temperature with the mixed solvent of the present invention in which this advantage was utilized as it was was experimented with a resist-coated glass substrate cut into 20 cm square. A conceptual diagram of the experimental apparatus is shown in FIG. When the substrate 36 is transported at a speed of 1 m / min in the direction of the arrow by the roller 37, the novolac resist is applied to the substrate so that the peeling is incomplete when sprayed with ethylene carbonate at 70 ° C. for 3 seconds and peels in 6 seconds. Conditions and nozzle and spray conditions were determined.

  The mixed solvent 75/25 liquid 15 at room temperature in the storage tank 14 is sent to the ozone aeration tank 38 by piping, the ozone gas 40 is bubbled into the liquid 39 in the tank, and the ozone solution (ozone concentration 70 mg / L) is moved along with the movement of the substrate. The above was sprayed from the nozzle 41 for 6 seconds by the liquid feed pump P under the same discharge conditions as the heating liquid. The treated substrate was sprayed with pure water and then air-dried and observed with a microscope. As a result, it was confirmed that the resist was sufficiently removed. When resist stripping becomes difficult due to dry etching processing or the like, a stripping process in which a liquid 15 is separately provided and sprayed to the substrate surface by a high-pressure spray nozzle 42 from a liquid feed pump P for 6 seconds was added. Although the test was also performed on the substrate of Example 1, it was almost peeled off by this treatment. If the processing time is extended, it can be removed reliably. The metal film is not damaged at all by observation with a scanning electron microscope.

  A treatment liquid receiver 43 having a concave structure is provided under the roller 36, and the treated liquid is collected in the storage tank 23. When the nozzle 42 is used, ozone gas bubbling 24 is performed in the tank 23. Ozone ventilation usually does not require 30 seconds. In the case where only the nozzle 41 is used, the ozone decomposition in the tank 23 is unnecessary because the resist decomposition usually occurs simultaneously with the resist peeling. In any case, the liquid in the tank 23 is transferred to the tank 14, and the liquid is used repeatedly many times. Even if the resist is strongly cured by ion implantation, if the treatment of the nozzle 42 with the nozzle 41 is repeated, the resist can be removed although it takes time. In this case, it takes several minutes or more for the ozonolysis of the resist in the tank 23. However, if 20 to 400 kHz ultrasonic wave irradiation is used in combination, decomposition in 1 to 2 minutes is possible.

  When the nozzles of this experimental apparatus were restored to the old one and the ethylene carbonate treatment at 40 ° C. was performed, and this treatment with 75/25 liquid was compared, the latter was advantageous only because the treatment temperature was low. The repeatable number of times increased by more than 50%. However, if the process is repeated a number of times, there is a risk that the metal contamination derived from the resist or the device material will naturally increase and the substrate will be contaminated. Therefore, 50 times or 100 times or the like is a milestone, the processing liquid is bypassed to the storage tank 44, and the oxide film of the basic constituent material is the same as the tower 46 filled with the fine powder of high purity silicon which is the basic constituent material of the semiconductor device. If the liquid 45 is sequentially passed through the packed tower 47 of high-purity quartz glass fine powder of the same quality and subjected to particle removal processing with a precision filter and sent to the raw tank 14, there is a possibility that the device active region of the substrate will be adsorbed and contaminated from the liquid. It can be regenerated into a liquid in which certain harmful metals are selectively reduced (application of Patent Document 7). Since the metal adsorbed and fixed to the fine particles can be easily removed by flowing dilute hydrofluoric acid through each packed tower, if it is configured in parallel, it can be continuously purified by alternating regeneration.

Example 4
In the waste liquid after the ozone treatment of the present invention is repeated many times for the novolak-type positive resist, resist decomposition products such as water, glycolic acid, formic acid, acetic acid, oxalic acid and butyric acid are found by analysis, According to absorption analysis, several tens of ppb of Fe and Na are detected. A 85/15 or 75/25 solution was used as the treatment solution, and a combination of a crystal precipitation method and a normal solidification method was tried as an ethylene carbonate recovery method when the ratio of ethylene carbonate in the waste solution was large.

  The bottle was stored in a large-sized polyethylene wide-mouthed bottle, and a heat insulating cap made of polystyrene foam was put on the upper part of the bottle and left in a freezer warehouse at about −30 ° C. overnight. According to the freezing point diagram of FIG. 1, ethylene carbonate crystals are precipitated, a net lid is attached, the bottle is turned upside down, and the residual liquid in which γ-butyrolactone and ethylene carbonate are present in a mixing ratio of approximately 2: 1 is allowed to flow out. Move to the environment and heat, once melt the ethylene carbonate crystals in the bottle. Heating was stopped when a slight amount of crystals remained, and a typical normal solidification method was applied from below, and recrystallization purification was repeated twice to recover about 70% of the original ethylene carbonate component amount. According to liquid chromatography and atomic absorption analysis, the above-mentioned resist decomposition products and metal impurities are refined to 1/10 or less, and they are sufficiently reused to remove deposits that do not require special emphasis on substrate cleanliness. it can. In the case of 85/15 liquid waste, it is sufficient to leave it in the freezer at about -15 ° C.

Example 5
An embodiment in which the present invention is applied to cleaning of a soldering flux that affects the reliability of an electronic circuit board will be described. Since the main component of this type of flux is rosin, an experiment was conducted on a test substrate in which rosin (Kanto Chemical Reagent) was sprayed on a copper plate and melted at 150 ° C. for 20 minutes. The evaluation of removal was based on the residual rate calculated from the residual amount after washing the rosin adhesion amount in advance by weight difference. A conceptual diagram of the apparatus used is shown in FIG. Using a processing tank 49 having an upper edge 48 of a mating surface that allows the substrate to be immersed vertically, ozone gas can be bubbled (not shown in the illustration of the bubbler) from the supply pipe 51 at the bottom of the processing liquid 50 inside. It was configured as follows. Reference numeral 52 denotes an ozone exhaust gas discharge pipe. In a cap tank 54 having a lower edge 53 with a mating surface, a cleaning target substrate 55 can be set, and a mechanism (not shown) that can be lowered and raised in the processing liquid tank is incorporated.

  A series of cleaning starts by storing 55/45 liquid in the tank 49 and bubbling ozone gas. After covering the cap tank 54 on which the test substrate 55 is set, ozone gas is introduced from a gas introduction pipe 56 provided at the top of the tank to replace the air in the tank. Thereafter, the substrate is lowered, dipped for 1 second, returned to the original position, and left for 10 seconds. After repeating this operation three times, the cap tank is moved so that the lower edge 53 is aligned with the mating surface of the upper edge 58 of the rinse tank 57. After the substrate is lowered into the pure water 59 and overflow rinse is performed for about 1 minute, the substrate is returned and the cap tank is released. Next, hot air is introduced from the introduction pipe 56 to dry the substrate. The dry substrate was allowed to stand until it reached room temperature, and then gravimetric evaluation was performed. As a result, it was found that the residual ratio of rosin was within the range of measurement error, and the removal was performed satisfactorily. Since rosin, epoxy resin (uncured resin) and the like have an SP value smaller than that of phenol resin, a higher ratio of γ-butyrolactone is desirable in terms of solubility. Since the treatment liquid on the substrate is in contact with ozone in a liquid film state, the ozone concentration instantaneously increases to near 100 ppm. Moreover, γ-butyrolactone in the treatment liquid hardly changes in quality when contacted with high-concentration ozone for a short time. These dissolved organic substances are decomposed by the ozone of the liquid 50, but there is little adhesion of product substances to the substrate, and the efficiency of pure water rinsing is good.

Example 6
Resist peeling of the surface of the glass substrate for liquid crystal device of Example 3 In the example, even if the resist was strongly cured by ion implantation, peeling was possible if the treatment was repeated over time. In order to further increase productivity, the apparatus was slightly changed as shown in FIG. In FIG. 9, the 75/25 mixed solvent liquid supplied by the processing liquid supply pipe 60 is heated to a high temperature by a heater 61 without adding ozone, and the liquid is atomized by a two-fluid jet nozzle 62 using nitrogen gas. A high-speed air current was impacted on the resist-cured surface and a synergistic effect with heating was measured. Since the flash point of this mixed solvent exceeds 130 ° C, it can be safely operated even at 120 ° C. The drainage can be regenerated by ozone circulation in the device. Therefore, a sufficient flow rate can be used, and continuous operation can be easily performed even when the droplet velocity is 100 m / s or more. Under such operating conditions, even a resist film in which P is ion-implanted with 10 ¹⁵ / cm ² can be peeled off at an economical substrate transfer speed.
Even if it is peeled off with a high temperature liquid, it naturally cools when it enters the tank 23. However, the liquid temperature is much higher than room temperature, and in this case, the decomposition of γ-butyrolactone is quick in the ozone treatment. On the other hand, it is not preferable that the temperature of the drained liquid is too low from the viewpoint that the drained liquid is regenerated, circulated, and reused by heating. Therefore, the ozone bubbler 63 in the tank 23 has a structure in which a large amount of fine bubbles is generated, and the gas cooler 64 is provided in the ozone gas supply system so that the cooled gas enters the ozone bubbler 63.
In the example, when the gas cooled to −20 ° C. is sent to a solution browned with a dissolved resist, the color disappears instantly and the dissolved substance is decomposed in a short time. Fine needle-shaped undecomposed matter was dispersed in the liquid, but this could be easily separated and removed with a precision filter. The supply of ozone was stopped simultaneously with the decolorization, but reaction to γ-butyrolactone was hardly detected after 30 decomposition treatments. In this case, it is presumed that the resist decomposition reaction occurs in a narrow region at a low temperature very close to the gas-liquid interface of the foam, and hardly affects γ-butyrolactone itself.

Binary freezing point diagram of ethylene carbonate and γ-butyrolactone at normal pressure Diagram showing the relationship between ozone ventilation time and treatment solution ozone concentration Longitudinal sectional view showing the concept of resist stripping by near infrared irradiation through the treatment liquid layer Overhead view of rotating part of parallel near-infrared light source irradiation method over treatment liquid layer Longitudinal sectional view showing the concept of parallel near-infrared light source irradiation method over treatment liquid layer Longitudinal sectional view showing the concept of resist stripping and cleaning through liquid layer in dual damascene Longitudinal cross-sectional view of an apparatus that uses a roller transport substrate to separate with an ozone mixed solvent Longitudinal sectional view showing the concept of flux cleaning with a treatment liquid film in an ozone atmosphere FIG. 7 is a longitudinal sectional view of an apparatus obtained by improving the apparatus of FIG.

Explanation of symbols

1. Sample chip 2. Treatment liquid layer forming dish Treatment liquid layer 4. 4. Halogen lamp Reflector 6. Near infrared 7. Rotating part bottom plate 8. Rotating part bottom plate edge 9, heat insulating material 10. Bottom plate support 11. Rotating shaft 12. Substrate 13. Board stop pin 14. Storage tank 15. Treatment liquid 16. Spray nozzle 17. Treatment liquid layer 18. Halogen lamp 19. Reflective face 20. Flat plate furnace 21. Chamber wall 22. Chamber bottom 23. Ozonation tank 24. Ozone bubbling 25. Copper wiring 26. Interlayer insulating film 27. SiC barrier layer 28. Interlayer insulating film 29. Etching stop film 30. Resist film.
31. Copper wiring groove 32. Via hole 33. Treatment liquid layer 34. Laser light 35. Treatment liquid convection 36, glass substrate 37. Conveyor roller 38. Ozone ventilation tank
39. Ozone treatment liquid 40. Ozone gas 41. Ozone treatment liquid nozzle 42. High pressure nozzle 43. Treatment liquid receiver 44. Liquid storage tank 45. Purification pretreatment solution 46. Silicon fine powder tower 47. Quartz glass fine powder tower 48. Treatment liquid tank upper edge 49. Treatment liquid tank 50. Treatment liquid 51. Ozone gas supply pipe 52. Ozone gas discharge pipe 53. Cap tank lower edge 54. Cap tank 55. Substrate 56. Gas introduction pipe 57. Rinse tank 58. Rinse tank upper edge 59. Pure water for rinsing 60. Pipe for treatment liquid supply 61. Heater 62. Two-fluid jet nozzle 63. Ozone bubbler 64. Gas cooler

Claims (26)

  A substrate having an organic deposit on the surface is contacted with a treatment liquid containing a mixed solvent of ethylene carbonate and γ-butyrolactone having a weight ratio of 85/15 to 55/45 to peel off the deposit. A method for removing organic deposits on the substrate surface.   2. The method according to claim 1, wherein the substrate and the treatment liquid are contacted by forming a liquid layer of the treatment liquid on the surface of the substrate, and the wavelength of the peak of the radiant energy is 0.24 to 0.24. A method comprising irradiating the surface with a light beam having a diameter of 2 μm intermittently and / or while relatively moving the light beam through the liquid layer.   The method according to claim 2, wherein the substrate is a flat substrate.   4. The method according to claim 2, wherein the light beam is an infrared lamp light or a laser beam, and the surface is scanned with the light beam condensed near the surface of the substrate.   2. The method according to claim 1, wherein the substrate is a flat substrate transparent to a light beam having a peak wavelength of radiant energy of 0.24 to 2 [mu] m, and one surface of the flat substrate is One side having the organic deposit and the contact between the substrate and the treatment liquid is formed by forming a liquid layer of the treatment liquid on one side having the organic deposit. The surface of the auxiliary plate made of a substance that absorbs the light beam is brought into close contact with one side opposite to the surface of the auxiliary plate, intermittently and / or through the liquid layer and the substrate, and / or the auxiliary plate. And irradiating the light beam with relative movement.   6. The method according to claim 5, wherein the light beam is an infrared lamp light or a laser beam, and the surface of the auxiliary plate is scanned with the light beam condensed near the surface of the auxiliary plate.   7. The treatment liquid is renewed by moving the treatment liquid on the surface of the substrate in a liquid layer state by supplying a new treatment liquid to the liquid layer upon irradiation with light. A method according to any one of the above.   The method according to claim 1, wherein the temperature of the treatment liquid is 25 to 130 ° C.   The method according to any one of claims 1 to 8, wherein the deposit on the surface of the substrate is removed, and then a gas containing ozone is passed through the treatment liquid in which the deposit is taken in. Is decomposed into a low molecular weight substance, and the treatment liquid after the decomposition treatment is circulated and used as a treatment liquid for treating another substrate.   The method according to claim 9, wherein the temperature of the treatment liquid when a gas containing ozone is vented is 22 to 27 ° C.   9. The method according to claim 8, wherein after the deposits on the surface of the substrate are removed, a gas of −40 to 20 ° C. containing ozone is passed through the treatment liquid that has taken in the deposits to remove the deposits. A method comprising decomposing into a low molecular weight substance and circulatingly using the treatment liquid after the decomposition treatment as a treatment liquid for treating another substrate.   The method according to claim 1, wherein the treatment liquid is an ozone-containing treatment liquid having an ozone concentration of 20 mg / L or more.   13. The method according to claim 12, wherein a gas containing ozone at a concentration of 100 mg / L or more is continuously passed through the treatment liquid to maintain the ozone concentration in the treatment liquid while the substrate is removed from the treatment liquid. A method of bringing the treatment liquid into contact with the substrate by immersing in the substrate.   13. The method according to claim 12, wherein the substrate is a flat substrate, at least one side of the flat substrate has the organic deposit, the one surface having the organic deposit, and the surface In contact with the ozone-containing treatment liquid, the substrate is coated at a concentration of 100 mg / L or more in a state where only one side or the one side and one side opposite to the one side are covered with the ozone-containing treatment liquid. It is made | formed by hold | maintaining in the gas containing ozone of this.   13. The method according to claim 12, wherein the substrate is a flat substrate, at least one side of the flat substrate has the organic deposit, the one surface having the organic deposit, and the surface The contact with the ozone-containing treatment liquid causes the ozone-containing treatment liquid to flow out of the ozone dissolution vessel on one side while moving the substrate in the extending direction of the one side or rotating it on a rotation axis perpendicular to the one side. The method is characterized in that it is carried out by supplying the nozzle on one side within 30 seconds and flowing the liquid on the one side in a liquid film form.   The method according to any one of claims 12 to 15, wherein the treatment liquid is circulated and used as a treatment liquid for treating another substrate after removing deposits on the substrate surface. how to.   The method according to any one of claims 12 to 15, wherein after the deposits on the surface of the substrate are removed, a gas containing ozone is passed through the processing solution, and the processing solution after the ventilation is supplied to another substrate. A method characterized by being recycled as a treatment liquid for treating the liquid.   The method according to any one of claims 9, 10, 11 and 17, wherein a gas containing ozone is ventilated while irradiating the treatment liquid with ultrasonic waves.   The method according to any one of claims 8, 12, and 13, wherein the treatment liquid is brought into contact with the substrate while irradiating the treatment liquid with ultrasonic waves.   When the treatment liquid is circulated, one or more metal impurity adsorption cylinders filled with fine powder made of the same or similar material as the constituent material of the surface of the substrate, and a subsequent step for preventing the fine powder from flowing out. 18. The method according to claim 9, wherein the concentration of metal impurities accumulated in the processing liquid is reduced by passing the processing liquid through a precision filter. A method according to any one of claims 9, 16, 17 and 20, comprising:
(A) The processing solution used in circulation is allowed to stand at a temperature of −30 to −15 ° C. to freeze and separate crystals containing ethylene carbonate,
(B) subjecting the frozen and separated crystals to a normal solidification method to obtain purified crystals containing ethylene carbonate;
(C) A weight ratio of 85/15 to 55/45 prepared by mixing the obtained crystal with γ-butyrolactone or with a distilled purified product of the treatment liquid after freeze-separating the crystal of the step (a). A process liquid comprising a mixed solvent comprising ethylene carbonate and γ-butyrolactone.   A treatment liquid for removing organic deposits on the surface of a substrate, the reaction product of ozone and a mixed solvent of ethylene carbonate and γ-butyrolactone having a weight ratio of 85/15 to 55/45, and the organic A treatment liquid comprising a total of 0 to 5% by weight of reaction products of system deposits and ozone, with the remainder being the mixed solvent.   The processing liquid according to claim 22, further comprising 0.1 to 2% by weight of oxalic acid. A. A treatment liquid introduction means for transporting a treatment liquid containing a mixed solvent containing ethylene carbonate and γ-butyrolactone as main components to a treatment area;
B. A deposit contacting means for bringing the treatment liquid into contact with a surface of the substrate having the organic deposit in the treatment area on the surface having the organic deposit;
C. C. treatment liquid circulating means for returning the treatment liquid discharged from the treatment area to the treatment area via one or more temporary storage means; An organic system attached to the surface of the substrate having an organic deposit, characterized by having an ozone-containing gas contact means for contacting an ozone-containing gas with a processing solution in the processing area and / or in the temporary storage means. Kimono removal device.   25. The apparatus according to claim 24, wherein a heating mechanism for the treatment liquid is further attached to the means A, and a cooling mechanism for the ozone-containing gas is further attached to the means D. Device to do. 26. The apparatus according to claim 24 or 25, further comprising means for pouring a processing liquid into the substrate by a high-pressure jet nozzle and / or a two-fluid jet nozzle in the processing zone.

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