WO2006132008A1 - Organic film release agent, and method and appartus for removing organic film using said release agent - Google Patents

Organic film release agent, and method and appartus for removing organic film using said release agent Download PDF

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Publication number
WO2006132008A1
WO2006132008A1 PCT/JP2006/303019 JP2006303019W WO2006132008A1 WO 2006132008 A1 WO2006132008 A1 WO 2006132008A1 JP 2006303019 W JP2006303019 W JP 2006303019W WO 2006132008 A1 WO2006132008 A1 WO 2006132008A1
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WO
WIPO (PCT)
Prior art keywords
release agent
substrate
film
organic film
organic coating
Prior art date
Application number
PCT/JP2006/303019
Other languages
French (fr)
Japanese (ja)
Inventor
Katsuyoshi Harada
Tomohisa Iinuma
Hiroshi Niizuma
Original Assignee
Toagosei Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toagosei Co., Ltd. filed Critical Toagosei Co., Ltd.
Priority to JP2007520027A priority Critical patent/JPWO2006132008A1/en
Publication of WO2006132008A1 publication Critical patent/WO2006132008A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D9/00—Chemical paint or ink removers
    • C09D9/005—Chemical paint or ink removers containing organic solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/267—Heterocyclic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/34—Imagewise removal by selective transfer, e.g. peeling away
    • G03F7/343—Lamination or delamination methods or apparatus for photolitographic photosensitive material
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • C11D2111/22—

Definitions

  • the present invention relates to a release agent for removing an organic film adhering to a substrate for surface cleaning of a substrate for an electronic device, a method for removing an organic film using the release agent, and a removal method. Relates to the device.
  • the present invention particularly relates to a release agent useful for removing a photoresist film used in processing of a semiconductor wafer or a liquid crystal substrate, a method for removing a photoresist film using the release agent, and a removal method. Relates to the device.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2003-203856
  • Patent Document 2 Japanese Patent Laid-Open No. 2003-305418
  • Patent Document 3 Japanese Patent Laid-Open No. 2003-330206
  • An object of the present invention is to provide a release agent that is easy to handle and excellent in release performance. Specifically, it is a release agent that is liquid at room temperature, and it can remove the resist film at a high release rate, and it is sufficiently productive even if it is a resist film that has been altered by ion implantation and is difficult to peel off. Providing a stripping agent that can be removed at a high speed and with a high stripping rate, and that does not degrade the stripping performance of the resist film even after repeated use, and a resist film stripping method and stripping device. There is to do.
  • an organic coating release agent characterized by containing 20 wt% or more of ⁇ -petit-mouthed rataton.
  • the present invention also provides a method for removing an organic film, characterized in that the organic film is removed by bringing the organic film remover into contact with a substrate having an organic film on the surface.
  • a mixed release agent storage tank for introducing a new release agent solution and introducing a treated release agent
  • F. means for discharging the release agent that dissolves the organic coating from the contact tank;
  • G. A device for removing an organic film on a substrate surface having an organic film is also provided, characterized in that it has means for circulating the release agent discharged from the contact tank and returning it to the mixed release agent storage tank.
  • FIG. 1 shows an example of an organic coating film removal apparatus of the present invention, and is an overall view when no ozone-containing gas is used.
  • FIG. 2 shows an example of the organic coating film removing apparatus of the present invention, and is an overall view when an ozone-containing gas is used.
  • the release agent of the present invention is a release agent that uses ⁇ -petit-mouth rataton, which has not been attempted to be used for stripping and removing a resist film, and ⁇ -petit-mouth rataton alone, Alternatively, it is a mixed solvent of ⁇ _petit-mouth rataton and a compatible liquid.
  • the mixed solvent of the petit-mouthed ratataton and the liquid compatible with the y-petit-mouthed ratataton contains at least 20% by weight of the petit-mouthed rataton.
  • y-Buchiguchi Rataton is a colorless liquid at room temperature with a melting point of _45 ° C, a boiling point of 204 ° C, and a flash point of 98 ° C. It is water-soluble and can be used as an aprotic polar solvent.
  • the liquid compatible with y-petit-mouth rataton preferably has a boiling point of 60 ° C or higher.
  • liquids include alcohols such as ethanol and isopropanol, ethers such as polyethylene glycol, alkylene carbonates such as ethylene carbonate, propylene carbonate and vinylene carbonate, and aromatic hydrocarbons such as toluene and xylene.
  • ethers such as polyethylene glycol
  • alkylene carbonates such as ethylene carbonate, propylene carbonate and vinylene carbonate
  • aromatic hydrocarbons such as toluene and xylene.
  • ethylene carbonate melting point 36.4 ° C, boiling point 238 ° C, flash point 160 ° C
  • propylene carbonate melting point— 48 ⁇ 8 ° C, boiling point 242 ° C, flash point 160 ° C or higher.
  • water can also be used.
  • ⁇ -petit-mouth rataton When ⁇ -petit-mouth rataton is used alone as a release agent, it has excellent resist film solubility and low-temperature release performance, but its flash point is slightly lower, so handle with care when using it. is required. If the processing temperature is likely to exceed the flash point of ⁇ — Petit Mouth Rataton, use a mixture of ⁇ — Petit Mouth Rataton and a liquid compatible with ⁇ — Petit Mouth Rataton. Thus, the boiling point and flash point of the mixed liquid can be increased. It is preferable that ⁇ petit rataton in the mixture is 20% by weight or more.
  • the ratio of monolatato ratatones in the release agent is less than 20% by weight, the performance of removing the resist film is reduced. If it exceeds 90% by weight, the effect of increasing the boiling point and flash point is reduced.
  • the ratio of ⁇ _petit-mouth rataton in the release agent is more preferably 50% by weight or more and 80% by weight or less.
  • the release agent of the present invention is effective for removing a photoresist at a high temperature, and the effective temperature range is 0 to 200 ° C (y_100 to 100 ° C in the case of using petit petit rataton alone). In consideration of the use below the flash point, it is preferably 30 to 150 ° C. (30 to 90 ° C. in the case of using y_petit-mouth rataton alone).
  • the release agent can be safely operated in the atmosphere if the temperature at the time of treatment is below the flash point, or it can be wet treated at about 200 ° C if it is in an inert gas. There is no problem. When processing at high temperature, the amount of evaporation of the release agent is slightly increased. The toxicity of the steam is low, so this is not a problem. If necessary, the steam can be discharged using a draft.
  • a release agent comprising a liquid mixture of ⁇ -butyrolatatone, ⁇ -butyrolatatane and ethylene carbonate and / or propylene carbonate, or a liquid mixture of ⁇ -petit-latataton and water is excellent in wide use temperature range. It has an organic film removal performance.
  • the photoresist stripping ability of the stripping agent of the present invention is a modified resist film in which ions are implanted at 1 ⁇ 10 15 / cm 2 or more, which has been very difficult with the conventional wet stripping method, which is larger as the processing temperature is higher. However, it can be peeled off in a short time.
  • a liquid mixture of ⁇ -petit-mouth rataton and ethylene carbonate (1: 1 by weight) for example, even a 2 ⁇ m-thick modified resist film can be removed by treatment at 120 ° C for 2 minutes. .
  • the above-described peeling mechanism of the resist film is considered to be mainly due to dissolution of the resist main component.
  • the release agent of the present invention has a very high dissolving power at a high temperature, but has a sufficiently practical dissolving power even at a low temperature of 30 ° C. Dissolution is a diffusion phenomenon and becomes faster as the concentration difference is larger. Therefore, when a liquid film is formed on the surface of the object to be treated and a new release agent is supplied to the liquid film and moved continuously, the liquid film is moved. Therefore, the dissolution effect can be further improved.
  • the release agent of the present invention can easily remove an oil film such as dioctyl phthalate (D0P), which is an organic contamination film on the substrate surface, and at the same time adheres to the surface with these oil films. Contaminated particulates can also be removed. In addition, it is also suitable for removing the oil film of the processing oil on the substrate surface after machining or the coating film on the metal surface.
  • D0P dioctyl phthalate
  • the release agent of the present invention is usually removed by heating the release agent, but it should also be used when it is necessary to carry out the treatment under room temperature or slight heating conditions due to the nature of the substrate. Is possible. In particular, it can be suitably used at a temperature of 35 ° C or lower at which ethylene carbonate solidifies.
  • ⁇ petit mouth rataton alone or a mixture of ⁇ petit mouth rataton and a liquid compatible with ⁇ petit mouth rattan effectively removes and removes an organic film such as a photoresist film.
  • the release agent after the treatment contains dissolved (and dispersed) components derived from the organic film.
  • the organic film is peeled off visually.
  • ⁇ -Butyrolatatone has better solubility of this organic coating than ethylene carbonate or propylene carbonate, which is conventionally known as a release agent. Therefore, the treated release agent is peeled off without any treatment. It can be reused as an agent.
  • the conventional release agent causes problems such as generation of a residue when used repeatedly several times or more.
  • the release agent of the present invention hardly generates a residue even when used repeatedly 20 times or more. Can be reused. Therefore, the release agent of the present invention does not need to be subjected to ozone treatment in order to be reused after treatment, but it is preferable to perform ozone treatment because it has the following advantages.
  • the dissolved resist in the release agent after the above treatment is decomposed into a low molecular weight substance in a short time by passing ozone gas of 50 ° C or lower.
  • ozone gas of 50 ° C or lower.
  • the y-petit-mouth rataton alone or a mixture of ⁇ _petit-mouth rataton and a liquid compatible with ⁇ _petit-mouthed ratataton is substantially chemically unaffected by this ozone gas flow, and It has been found that the removal and removal performance of resist and the like does not deteriorate. Therefore, if ozone gas is passed through the stripping agent after the organic film removal treatment, it can be reused as a stripping stripper for removing resist or the like by removing it as it is or by filtering it as necessary.
  • the liquid compatible with ⁇ -petit rataton is preferably ethylene carbonate and / or propylene carbonate. Removing the resist after stripping the resist with ozone to decompose the resist components and micro-filtering to remove the decomposed material can increase the number of times that the stripper can be used repeatedly without replacing it with a new one. Become.
  • the ventilation rate and the ventilation time of ozone gas are not particularly limited, but vary depending on the type of resist to be peeled off and the process conditions. In reality, it is determined by judging the degree of decomposition of the organic film based on the point that the resist is visually decomposed and the color disappears, conductivity, transmittance, UV absorption, and CPC analysis.
  • the release agent after the organic film removal treatment described above is treated with ozone gas to regenerate and recycle the release agent.
  • ozone gas is preferably used for stripping after the ozone gas concentration in the liquid is dissolved to the upper limit, that is, the saturated dissolution amount.
  • the release agent consisting of a liquid mixture of y-buchi-mouth rataton or ⁇ _butyrolataton and ethylene carbonate or propylene carbonate has a high boiling point, so it is rinsed with a new release agent, a release agent, and spin-dried.
  • a new release agent a release agent
  • spin-dried there is a high possibility that these molecular films will remain adsorbed on the wafer surface. If the release agent remains on the wafer, the physical properties (especially electrical properties) of the processed substrate will be adversely affected. There is a possibility of drowning. Therefore, it is desirable to continue rinsing with ultrapure water.
  • the organic film to be peeled in the present invention is a photoresist film which is unnecessary at the end of the photolithographic process of the electronic material substrate.
  • positive resists such as phenol novolac resists, talesol novolac resists, burphenol derivative resists, polymetatalylate resists, cyclized polyisoprene derivative resist negative resists, and the like.
  • a positive resist that is not three-dimensionally crosslinked is preferred.
  • the release agent of the present invention is optionally used by dissolving ozone gas, whereby an organic film on the surface of the substrate, for example, an ion-implanted resist film that conventionally required ashing, etc. Can be removed in a very short time and efficiently.
  • the stripping agent of the present invention is easy to handle because it is a liquid at room temperature, and it can be applied even in processing under high temperature conditions because of its high boiling point and flash point resist solubility at low temperatures. There are few environmental problems with high nature.
  • the present invention can be applied to remove a general organic film such as an oil film or a paint film on a substrate.
  • a release agent in order to remove the organic coating on the substrate surface, a release agent is brought into contact with the organic coating.
  • a method of contact such as a method in which a substrate with an organic coating is dissolved by immersing it in a stripping solution, a method in which a stripping solution is sprayed on the organic coating on the substrate, a method of washing and flowing, a stripping solution It is possible to exemplify the method of applying an organic coating in the vapor of the water and exposing the substrate. In addition, it is advantageous to increase the removal rate of the organic coating by acting on the organic coating on the substrate by stirring, vibrating, shaking, or publishing the release agent solution.
  • the release agent of the present invention is circulated using a circulation device and re-applied. It is economically preferable to use it.
  • Example [0029] An outline of the organic film removing apparatus and the removing method in the present embodiment will be described below. First, an apparatus for removing the organic film on the substrate surface by circulating the release agent of the present invention will be described with reference to the accompanying drawings. .
  • FIG. 1 shows a case where no ozone-containing gas is used, and the release agent of the present invention is prepared and stored in a new solution storage tank 1 for the release agent.
  • the release agent is supplied from the mixed release agent storage tank 2 to the contact tank 4 via the pipe 3.
  • the release agent accumulates in the contact tank 4, the substrate having the organic film is taken out from the substrate holder 5 and is put into the contact tank 4, and the substrate is immersed in the release agent.
  • the substrate is lifted from the release agent and taken out from the contact tank 4.
  • a means for taking out the substrate having the organic coating from the substrate holder 5 and immersing it in the release agent, and lifting the substrate from the release agent in the next step manually using an instrument that can sandwich the substrate, for example, tweezers or the like. Can be done. It can also be performed manually or automatically using a device capable of performing such an operation, for example, a robot arm as described in JP-A-2003-203856.
  • the stripping agent containing the organic film-derived component is discharged from the pipeline 6 and circulated back to the storage tank 2 for the mixed stripping agent.
  • Organic in the release agent that circulates by removing a part of the release agent containing components derived from the organic coating continuously or intermittently from the pipeline 6 and supplying new solution from the new release agent storage tank 1 Do not increase the concentration of ingredients derived from the coating.
  • Fig. 2 shows a case where an ozone-containing gas is used.
  • ozone may be introduced into the release agent from the pipe 7 in some cases.
  • the stripping agent containing the component derived from the organic film discharged from the pipe 6 is sent to the ozone-containing gas contact tank 8.
  • Ozone-containing gas contact tank 8 is supplied with ozone-containing gas from line 9, and is bunched in a release agent containing components derived from the discharged organic film, and is contained in the release agent. Is decomposed into low molecular weight substances.
  • Stripping agent containing degraded low molecular weight material is discharged from line 10. Remove and circulate back to storage tank 2 for mixed release agent.
  • a stripping agent containing a component derived from an organic coating is continuously or intermittently withdrawn from the pipeline 6 to the outside of the system. Avoid increasing the concentration of low molecular weight substances.
  • the ozone gas used in the examples has an ozone concentration of about 250 mgZL obtained by flowing oxygen containing 0.4% nitrogen in a discharge-type ozone generator for about 2 to 10LZ.
  • ⁇ ⁇ -Platinata Lataton and propylene carbonate were of a reagent-grade purity, and ethylene carbonate was a high-purity product manufactured by Toagosei Co., Ltd.
  • a quartz glass cassette containing five 10 cm square glass substrates was immersed in a quartz glass release agent tank (hereinafter referred to as tank jar) filled with 3 L of ⁇ -petit-mouth rataton. After soaking for a certain period of time, it was then soaked for a certain period of time in a spray rinse bath (hereinafter referred to as bath ⁇ ) filled with fresh ⁇ _butyrolatatatone. Furthermore, it was immersed in an overflow rinse tank (hereinafter referred to as tank C) with ultrapure water to complete the resist stripping.
  • tank jar quartz glass release agent tank
  • tank C overflow rinse tank
  • the resist peeling effect of ⁇ -petit-mouth rataton with a liquid temperature of 60 ° C was investigated.
  • the sample used was a novolac resin-based positive resist for I-line (trade name: PR-200, manufactured by Shipley) with a film thickness of 4 ⁇ m on the surface of a 10 cm square glass substrate, and beta for 140 seconds at 140 ° C. It is a thing. First, one of these was placed in a cassette, and 250 mg / L high-concentration ozone gas was published at 2 L / min for 5 minutes in ⁇ -butyrolatatone in tank A, and ozone was dissolved in a 60 ° C solution.
  • the cassette was immersed in the liquid, and the resist peeling state was observed with the naked eye. As a result, it was confirmed that peeling was completed within 10 seconds after immersion. The peel rate was 24 x m / min.
  • the cassette is pulled up and sprayed with ⁇ -Buchiguchi Rataton spray rinsing for 2 seconds in tank B, followed by 3 minutes of overflow rinsing with ultrapure water in tank C, followed by spin drying and observation of the surface with a microscope. As a result, no part was peeled off. In the examples and comparative examples, the cassette was dipped and pulled up manually.
  • Example 2 When a cassette of one sample was immersed in the tank A without venting ozone in the same manner as in Example 1, peeling was completed with the naked eye in 15 seconds (peeling speed: 16 ⁇ m / min). It was shown that resist stripping can be performed in a sufficiently short time even without passing high ozone gas at 60 ° C. The solution after resist removal turned pale yellow.
  • Exfoliation performance was examined in the same manner as in the case of ozone gas ventilation described in Example 1, except that the temperature of the tank tub—the small- mouth rataton was changed to 80 ° C. under the same processing conditions as in Example 1. As a result, it was confirmed by the naked eye that peeling was completed in 6 seconds. The peeling speed at this time was 40 xm / min. Immediately after that, the cassette is pulled up, and ⁇ -petit-mouth rataton spray rinsing is performed in a tank ⁇ for 2 seconds, then an overflow rinse of ultrapure water is performed in tank C for 3 minutes, spin dried, and the surface is observed with a microscope. As a result, the part that was not peeled off was not observed.
  • the experiment was performed in the same manner as in Example 2 except that the temperature of the ⁇ -petit-mouth rataton in the tank was 80 ° C. As a result of observing the resist peeling condition with the naked eye after immersing the cassette in the release agent, it was confirmed that the peeling was completed in 7 seconds. The peeling rate at this time was 34 ⁇ m / min. Immediately after that, the cassette is pulled up, and ⁇ -butyrorataton spray rinsing is performed for 2 seconds in tank B, then overflow rinsing is performed for 3 minutes in tank C, spin-dried, and the surface is observed with a microscope. As a result, the part which was not peeled was not recognized.
  • Example 2 In the same treatment method as in Example 1, the liquid mixture of ⁇ -petit ratatone and ethylene carbonate (1: 1 by weight) was used as the treatment liquid at a liquid temperature of 100 ° C. Similarly, peeling performance was examined.
  • the cassette was immersed in a stripping agent and the resist stripping condition was observed with the naked eye. As a result, it was confirmed that stripping was completed in 4 seconds. The peeling speed at this time was 60 xm / min. Then straight Next, the cassette is pulled up and spray rinsed with a liquid mixture of gamma-petite rataton and ethylene carbonate (1: 1 by weight) in tank B for 2 seconds, and then an overflow rinse of ultrapure water in tank C. After 3 minutes, spin drying and observing the surface with a microscope, no unpeeled part was observed.
  • Example 5 An experiment was conducted in the same manner as in Example 5 except that ozone gas was not passed. As a result of observing the resist peeling condition with the naked eye by immersing the cassette in a release agent, it was confirmed that the peeling was completed in 3 seconds. The peeling speed at this time was 80 ⁇ m / min. Immediately after that, the cassette is pulled up and sprayed with a ⁇ _petit-mouth rataton liquid spray rinse for 2 seconds in a tank ⁇ , and then an ultrapure water overflow rinse is performed for 3 minutes in the tank C. As a result of observation, no unpeeled portion was observed.
  • a novolac resin-based positive resist product name: PR-200, manufactured by Shipley
  • PR-200 manufactured by Shipley
  • Tank A was not ventilated with ozone, the temperature in tank A was increased to 120 ° C, and 1 x 10 14 / cm 2 and 1 x 10 15 / cm 2 injected samples were placed in each cassette. The resist was peeled off and observed with the naked eye. The resist film was completely removed in 1 minute for the former and 2 minutes for the latter. The stripping rates were 2 ⁇ mZ and 1 ⁇ mZ, respectively, which were practically usable.
  • Example 7 the same release test as in Example 7 was performed using the regenerated release agent, and it was found that the resist film was completely removed in 1 minute and the release agent was reusable.
  • Example 3 After applying a resist film to the substrate, an experiment similar to that in Example 3 was performed using a sample that was subjected to post-beta treatment at 140 ° C for about 3 minutes. As a result, the resist was a novolak resin-based positive resist, chemically amplified type. The stripping rate was 20 ⁇ m / min or more regardless of whether the polybutanol derivative positive resist or the cyclized polyisoprene negative resist was used.
  • the release agent was neutral, the metal films for wiring such as Al, Mo, W, Ti, and IT ⁇ were not attacked.
  • C1-based and Br-based gases are used for dry etching of aluminum films.
  • these corrosive gases remain on the resist film and the altered film on the side wall of the force zone, and cannot be removed even by ashing. Therefore, subsequent wet processing is required.
  • the resist When the aluminum film is dry-etched with a C1-based reactive gas, the resist is usually removed by ashing, and the target is a novolac resin-based positive resist, which is close to the actual device pattern.
  • the formed TEG wafer was prepared as a sample.
  • the film thickness of the resist is l z m.
  • Example 2 20% by weight of propylene carbonate was added to y-petit-mouthed rataton, and the same procedure as in Example 1 was performed. Exfoliation was sufficient and the exfoliation rate was 23 x m / min.
  • the present invention can be used to remove an organic coating adhering to a substrate in order to clean the surface of an electronic device substrate or the like.
  • the present invention is useful for removing a photoresist film used for processing a semiconductor wafer or a liquid crystal substrate, and is particularly suitable for resist removal in an ultrafine pattern device.
  • the present invention can be applied to the removal of general organic coatings such as oil films and coatings on a substrate.

Abstract

Disclosed are (1) an organic film release agent comprising not less than 20% by weight of ?-butyrolactone useful for the removal of a photoresist film, (2) a method for removing an organic film, useful for the removal of a photoresist film using the above release agent, the method comprising bringing an organic film release agent into contact with a substrate having an organic film on its surface to remove the organic film, and (3) an apparatus for removing an organic film from a surface of a substrate having the organic film on its surface, the apparatus comprising A. a storage tank for storing a fresh liquid of a release agent, B. a mixed release agent storage tank into which the fresh liquid of the release agent is introduced and the release agent used for the treatment, C. means for feeding the release agent from the mixed release agent storage means into a contact tank, D. a substrate holder for housing therein a substrate having an organic film, E. means for taking out the substrate having an organic film from the substrate holder, introducing the substrate into the contact tank, bringing the release agent into contact with the substrate on its surface having an organic film in the contact tank to dissolve the organic film in the release agent and thus to remove the organic film from the surface of the substrate, and pulling up the substrate, from which the organic film has been removed, from the contact tank, F. means for discharging the release agent containing the organic film dissolved therein from the contact tank, and G. means for circulating the release agent discharged from the contact tank to return the used release agent to the mixed release agent storage tank.

Description

明 細 書  Specification
有機被膜剥離剤、該剥離剤を用いた有機被膜の除去方法および除去装 置  Organic film remover, organic film removal method and remover using the remover
技術分野  Technical field
[0001] 本発明は、電子デバイス用基板等の表面清浄化のために、基体上に付着する有 機被膜を除去するための剥離剤、該剥離剤を用いた有機被膜の除去方法、および 除去装置に関する。具体的には、本発明は、特に半導体用ウェハーまたは液晶用基 板などの加工に際して使用するフォトレジスト被膜の除去に有用な剥離剤、該剥離 剤を用いたフォトレジスト被膜の除去方法、および除去装置に関する。  [0001] The present invention relates to a release agent for removing an organic film adhering to a substrate for surface cleaning of a substrate for an electronic device, a method for removing an organic film using the release agent, and a removal method. Relates to the device. Specifically, the present invention particularly relates to a release agent useful for removing a photoresist film used in processing of a semiconductor wafer or a liquid crystal substrate, a method for removing a photoresist film using the release agent, and a removal method. Relates to the device.
背景技術  Background art
[0002] 酸化膜やポリシリコン膜の微細加工に使用したフォトレジストの除去に関しては、通 常、硫酸（3容または 4容）：過酸化水素（1容）の混合液 (通称、ピラニア）、あるいはァ ッシングとピラニア処理との組み合わせが使用され、配線金属膜力卩ェに使用したフォ トレジストの除去に関しては、 n_メチルピロリドン (NMP)やジメチルスルホキシド（D MSO)あるいはァミン類のような有機溶剤が使用される。  [0002] Regarding removal of photoresist used for microfabrication of oxide films and polysilicon films, a mixture of sulfuric acid (3 or 4 volumes): hydrogen peroxide (1 volume) (commonly known as piranha) Alternatively, a combination of ashing and piranha treatment is used, and for removal of the photoresist used for the wiring metal film strength, organic substances such as n_methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), or amines are used. A solvent is used.
[0003] ピラニア処理は大量の硫酸を排出するし、有機溶剤を使用する場合もその使用量 が多いので、環境面での負荷が問題となる。また、最近オゾン水を用いたレジスト除 去が試みられているが、 I線用ノボラック樹脂系ポジ型レジスト膜の場合、剥離速度が 0. 1 / m/分以下と遅ぐ実用的に十分なものではない。  [0003] In piranha treatment, a large amount of sulfuric acid is discharged, and even when an organic solvent is used, the amount of use is large. Recently, removal of the resist using ozone water has been attempted, but in the case of a novolak resin-based positive resist film for I-line, the peeling rate is as low as 0.1 / m / min or less, which is practically sufficient. It is not a thing.
[0004] 一方、ジメチルホルムアミド、 N—メチルピロリドン、アミン類等の有機溶剤による湿 式処理では、溶解したレジストが蓄積し、レジスト剥離能力が低下するため、有機溶 剤の繰り返し使用が制限されるという問題があった。  [0004] On the other hand, in wet processing with an organic solvent such as dimethylformamide, N-methylpyrrolidone, and amines, the dissolved resist accumulates and the resist stripping ability decreases, so that the repeated use of the organic solvent is limited. There was a problem.
[0005] 剥離剤の繰り返し使用性を改善するために、処理後の液をオゾン酸化してレジスト を分解する方法が提案されている。該方法においては、処理用液として、炭酸ェチレ ンおよび/または炭酸プロピレンが使用されている（特開 2003— 203856号公報、 特開 2003— 305418号公報及び特開 2003— 330206号公報）。  [0005] In order to improve the repeated usability of the release agent, a method for decomposing a resist by ozone-oxidizing the treated liquid has been proposed. In this method, ethylene carbonate and / or propylene carbonate is used as a treatment solution (Japanese Patent Laid-Open Nos. 2003-203856, 2003-305418, and 2003-330206).
[0006] しかし、炭酸エチレンは常温で固体であるため、貯蔵槽ゃ循環配管を保温しなけれ ばならず、取り扱いに不便であり、また、炭酸プロピレンはレジストの剥離性能が特に 低温において不足している。そのため、取り扱いが容易でありかつ剥離性能に優れ た剥離剤が要求されてレ、た。 [0006] However, since ethylene carbonate is a solid at room temperature, the storage tank must be kept warm. In addition, it is inconvenient to handle, and propylene carbonate lacks resist stripping performance, especially at low temperatures. Therefore, a release agent that is easy to handle and excellent in release performance is required.
[0007] 特許文献 1 :特開 2003— 203856号公報 [0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2003-203856
特許文献 2 :特開 2003— 305418号公報  Patent Document 2: Japanese Patent Laid-Open No. 2003-305418
特許文献 3 :特開 2003— 330206号公報  Patent Document 3: Japanese Patent Laid-Open No. 2003-330206
発明の開示  Disclosure of the invention
[0008] 本発明の目的は、取り扱いが容易でありかつ剥離性能に優れた剥離剤を提供する ことである。具体的には、常温で液状である剥離剤であり、レジスト膜を速い剥離速度 で除去することができ、またイオン注入等により変質された剥離しにくいレジスト膜で あっても十分に生産性の高レ、剥離速度で除去することができ、かつレジスト膜の溶解 性が大きいため、繰り返し使用してもレジスト膜の剥離性能が低下しない剥離剤、お よびレジスト膜の除去方法ならびに除去装置を提供することにある。  [0008] An object of the present invention is to provide a release agent that is easy to handle and excellent in release performance. Specifically, it is a release agent that is liquid at room temperature, and it can remove the resist film at a high release rate, and it is sufficiently productive even if it is a resist film that has been altered by ion implantation and is difficult to peel off. Providing a stripping agent that can be removed at a high speed and with a high stripping rate, and that does not degrade the stripping performance of the resist film even after repeated use, and a resist film stripping method and stripping device. There is to do.
[0009] 本発明によれば、 γ —プチ口ラタトンを 20重量％以上含有することを特徴とする有 機被膜の剥離剤を提供する。  [0009] According to the present invention, there is provided an organic coating release agent characterized by containing 20 wt% or more of γ-petit-mouthed rataton.
また、本発明によれば、表面に有機被膜を有する基体に、上記の有機被膜剥離剤 を接触させて、有機被膜を除去することを特徴とする有機被膜の除去方法も提供す る。  The present invention also provides a method for removing an organic film, characterized in that the organic film is removed by bringing the organic film remover into contact with a substrate having an organic film on the surface.
[0010] 更に、本発明によれば、  [0010] Furthermore, according to the present invention,
Α.剥離剤の新液を貯蔵する貯槽と、  貯. A storage tank for storing a new release agent solution;
Β.剥離剤の新液を導入しかつ処理後の剥離剤を導入する混合剥離剤貯槽と、 V. A mixed release agent storage tank for introducing a new release agent solution and introducing a treated release agent;
C.混合剥離剤貯槽から剥離剤を接触槽に供給する手段と、 C. means for supplying the release agent from the mixed release agent storage tank to the contact tank;
D.有機被膜を有する基体を収容する基体ホルダーと、  D. a substrate holder for accommodating a substrate having an organic coating;
Ε.基体ホルダーから有機被膜を有する基体を取り出して接触槽に導入し、接触槽 内において、基体の有機被膜を有する表面に剥離剤を接触させて、有機被膜を剥 離剤に溶解させて、有機被膜を基体表面から除去し、有機被膜が除去された基体を 接触槽から引き上げる手段と、  Remove the substrate having the organic coating from the substrate holder and introduce it into the contact tank. In the contact bath, the release agent is brought into contact with the surface of the substrate having the organic coating, and the organic coating is dissolved in the release agent. Means for removing the organic coating from the surface of the substrate and lifting the substrate from which the organic coating has been removed from the contact tank;
F.有機被膜を溶解する剥離剤を接触槽から排出する手段と、 G.接触槽から排出された剥離剤を循環させて混合剥離剤貯槽に戻す手段と を有することを特徴とする、有機被膜を有する基体表面の有機被膜の除去装置も提 供する。 F. means for discharging the release agent that dissolves the organic coating from the contact tank; G. A device for removing an organic film on a substrate surface having an organic film is also provided, characterized in that it has means for circulating the release agent discharged from the contact tank and returning it to the mixed release agent storage tank.
図面の簡単な説明  Brief Description of Drawings
[0011] [図 1]本発明の有機被膜の除去装置の例を示すものであり、オゾン含有ガスを用いな い場合の全体図である。  FIG. 1 shows an example of an organic coating film removal apparatus of the present invention, and is an overall view when no ozone-containing gas is used.
[図 2]本発明の有機被膜の除去装置の例を示すものであり、オゾン含有ガスを用いる 場合の全体図である。  FIG. 2 shows an example of the organic coating film removing apparatus of the present invention, and is an overall view when an ozone-containing gas is used.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0012] 本発明の剥離剤は、従来レジスト膜の剥離 '除去のためには、使用することが試み られなかった γ—プチ口ラタトンを使用する剥離剤であり、 γ—プチ口ラタトン単独、ま たは γ _プチ口ラタトンと相溶する液体との混合溶剤である。 —プチ口ラタトンと、 y—プチ口ラタトンと相溶する液体との混合溶剤は、 Ί—プチ口ラタトンを 20重量％ 以上含有する。 [0012] The release agent of the present invention is a release agent that uses γ-petit-mouth rataton, which has not been attempted to be used for stripping and removing a resist film, and γ-petit-mouth rataton alone, Alternatively, it is a mixed solvent of γ_petit-mouth rataton and a compatible liquid. The mixed solvent of the petit-mouthed ratataton and the liquid compatible with the y-petit-mouthed ratataton contains at least 20% by weight of the petit-mouthed rataton.
y—ブチ口ラタトンは、融点 _45°C、沸点 204°C、引火点 98°Cの室温で無色の液 体であり、水溶性であって、非プロトン性極性溶媒として用いることができる。  y-Buchiguchi Rataton is a colorless liquid at room temperature with a melting point of _45 ° C, a boiling point of 204 ° C, and a flash point of 98 ° C. It is water-soluble and can be used as an aprotic polar solvent.
[0013] y—プチ口ラタトンと相溶する液体は、沸点が 60°C以上のものが好ましい。かかる 液体として、エタノール、イソプロパノールなどのアルコール類、ポリエチレングリコー ルなどのエーテル類、炭酸エチレン、炭酸プロピレン、炭酸ビニレンなどの炭酸アル キレン類、トルエン、キシレンなどの芳香族炭化水素類などが例示される。中でも、沸 点が 200°C以上であり、引火点も高ぐ室温で無色無臭な、炭酸エチレン (融点 36. 4°C、沸点 238°C、引火点 160°C)または炭酸プロピレン（融点— 48· 8°C、沸点 242 °C、引火点 160°C以上）が好ましい。また、前記有機溶剤以外に、水も使用すること が可能である。 [0013] The liquid compatible with y-petit-mouth rataton preferably has a boiling point of 60 ° C or higher. Examples of such liquids include alcohols such as ethanol and isopropanol, ethers such as polyethylene glycol, alkylene carbonates such as ethylene carbonate, propylene carbonate and vinylene carbonate, and aromatic hydrocarbons such as toluene and xylene. . Among these, ethylene carbonate (melting point 36.4 ° C, boiling point 238 ° C, flash point 160 ° C) or propylene carbonate (melting point— 48 · 8 ° C, boiling point 242 ° C, flash point 160 ° C or higher). In addition to the organic solvent, water can also be used.
[0014] 剥離剤として、 γ—プチ口ラタトンを単独使用する場合には、レジスト膜の溶解性や 低温での剥離性能には優れるが、引火点が若干低いため、使用する際に取り扱いに 注意が必要である。処理温度が γ —プチ口ラタトンの引火点を超える恐れがある場合 は、 Ύ—プチ口ラタトンに、 Ί—プチ口ラタトンと相溶する液体を混合して使用すること により、混合液の沸点および引火点を上昇させることができる。混合液中の γ プチ 口ラタトンは、 20重量％以上であるのが好ましい。 y ブチロラタトンに混合する液体 として、例えば炭酸エチレンおよび/または炭酸プロピレンを使用する場合は、剥離 剤中の Ί一プチ口ラタトンの割合が 20重量％未満では、レジスト膜を剥離する性能 が低下し、 90%重量を超えると、沸点および引火点を上昇させる効果が少なくなる。 この場合の剥離剤中の γ _プチ口ラタトンの割合は、より好ましくは 50重量％以上で ありかつ 80重量％以下である。 [0014] When γ-petit-mouth rataton is used alone as a release agent, it has excellent resist film solubility and low-temperature release performance, but its flash point is slightly lower, so handle with care when using it. is required. If the processing temperature is likely to exceed the flash point of γ — Petit Mouth Rataton, use a mixture of 液体 — Petit Mouth Rataton and a liquid compatible with Ί — Petit Mouth Rataton. Thus, the boiling point and flash point of the mixed liquid can be increased. It is preferable that γ petit rataton in the mixture is 20% by weight or more. y When ethylene carbonate and / or propylene carbonate is used as the liquid to be mixed with butyrolatatane, if the ratio of monolatato ratatones in the release agent is less than 20% by weight, the performance of removing the resist film is reduced. If it exceeds 90% by weight, the effect of increasing the boiling point and flash point is reduced. In this case, the ratio of γ_petit-mouth rataton in the release agent is more preferably 50% by weight or more and 80% by weight or less.
[0015] 本発明の剥離剤は、高温下でのフォトレジスト剥離 '除去に有効であり、有効な温 度範囲は 0〜200°C ( y _プチ口ラタトン単独使用の場合は、 0〜100°C)、引火点以 下の使用を考慮して好ましくは 30〜150°C ( y _プチ口ラタトン単独使用の場合は、 30〜90°C)である。該剥離剤は、処理する際の温度が、引火点以下であれば、大気 下で安全に操作することができるし、不活性ガス中であれば、 200°C程度で湿式処 理しても、何ら問題がない。高温状態で処理する場合には、剥離剤の蒸発量がやや 多くなる力 蒸気の毒性は低いので問題とはならないし、必要に応じてドラフトを用い て蒸気を排出すればよい。  [0015] The release agent of the present invention is effective for removing a photoresist at a high temperature, and the effective temperature range is 0 to 200 ° C (y_100 to 100 ° C in the case of using petit petit rataton alone). In consideration of the use below the flash point, it is preferably 30 to 150 ° C. (30 to 90 ° C. in the case of using y_petit-mouth rataton alone). The release agent can be safely operated in the atmosphere if the temperature at the time of treatment is below the flash point, or it can be wet treated at about 200 ° C if it is in an inert gas. There is no problem. When processing at high temperature, the amount of evaporation of the release agent is slightly increased. The toxicity of the steam is low, so this is not a problem. If necessary, the steam can be discharged using a draft.
[0016] このように、 γ ブチロラタトン、 γ ブチロラタトンと炭酸エチレンおよび/または 炭酸プロピレンとの液状混合物、または γ プチ口ラタトンと水との液状混合物からな る剥離剤は、使用温度範囲が広ぐ優れた有機膜除去性能を有するものである。  [0016] As described above, a release agent comprising a liquid mixture of γ-butyrolatatone, γ-butyrolatatane and ethylene carbonate and / or propylene carbonate, or a liquid mixture of γ-petit-latataton and water is excellent in wide use temperature range. It has an organic film removal performance.
[0017] 本発明の剥離剤のフォトレジスト剥離能力は、処理温度が高い程大きぐ従来湿式 の剥離法では非常に難しかった 1 X 1015/cm2以上のイオン注入された変質レジスト 膜であっても、短時間で剥離することができる。 γ—プチ口ラタトンと炭酸エチレンとの 液状混合物（重量比で 1： 1)を用いれば、例えば、厚さ 2 μ mの変質レジスト膜でも、 120°Cにおいて 2分間処理することで剥離される。ドライエッチングで変質層を生じた レジストの場合も、同様である。シリコン酸化膜上に特に剥離の困難な有機膜が生じ た場合でも、上記の液状混合物を用いて、沸点に近レ、 200°C (不活性ガス中）程度 の高温における湿式処理により剥離することできる。また、処理温度が高い程、表面 張力や粘度が下がり、超微細パターンデバイスでのレジスト剥離に適している。このよ うな安全で強力な処理効果は従来の有機溶媒系のレジスト剥離剤ではみられなかつ たものである。 [0017] The photoresist stripping ability of the stripping agent of the present invention is a modified resist film in which ions are implanted at 1 × 10 15 / cm 2 or more, which has been very difficult with the conventional wet stripping method, which is larger as the processing temperature is higher. However, it can be peeled off in a short time. Using a liquid mixture of γ-petit-mouth rataton and ethylene carbonate (1: 1 by weight), for example, even a 2 μm-thick modified resist film can be removed by treatment at 120 ° C for 2 minutes. . The same applies to a resist in which an altered layer is produced by dry etching. Even when an organic film that is particularly difficult to peel off is formed on the silicon oxide film, it should be peeled off by wet processing at a high temperature of about 200 ° C (in an inert gas) using the above liquid mixture. it can. In addition, the higher the processing temperature, the lower the surface tension and viscosity, making it suitable for resist stripping in ultra-fine pattern devices. Such a safe and powerful treatment effect is not seen with conventional organic solvent-based resist strippers. It is a thing.
l X 1014/cm2のイオン注入されたレジスト膜の場合は、 γ—プチ口ラタトンと炭酸 エチレンとの液状混合物（重量比で 1： 1)を用いれば、 120°Cにおレヽて厚さ 2 μ mの 膜の剥離に力、かる時間は 1分と速い。 l In the case of a resist film implanted with X 10 14 / cm 2 , if a liquid mixture of gamma-petit-mouth rataton and ethylene carbonate (1: 1 by weight) is used, the thickness is increased to 120 ° C. It takes about 1 minute to peel off a 2 μm film.
[0018] レジスト被膜の上記剥離機構は、主としてレジスト主成分の溶解によるものと考えら れる。本発明の剥離剤は、高温での溶解力は極めて大きいが、 30°Cという低温でも 十分実用的な溶解力を有している。溶解は拡散現象であり、濃度差が大きい程速く なることから、被処理体表面に液膜を形成させ、連続にあるいは間欠にその液膜に 対して新たな剥離剤を供給して移動させると、溶解効果をさらに向上させることができ る。 [0018] The above-described peeling mechanism of the resist film is considered to be mainly due to dissolution of the resist main component. The release agent of the present invention has a very high dissolving power at a high temperature, but has a sufficiently practical dissolving power even at a low temperature of 30 ° C. Dissolution is a diffusion phenomenon and becomes faster as the concentration difference is larger. Therefore, when a liquid film is formed on the surface of the object to be treated and a new release agent is supplied to the liquid film and moved continuously, the liquid film is moved. Therefore, the dissolution effect can be further improved.
[0019] また、本発明の剥離剤は、基板表面の有機汚染膜であるジォクチルフタレート（D〇 P)等の油膜を簡単に除去することができ、同時にこれらの油膜で表面に固着してい る汚染微粒子も除去できる。その他、機械加工後の基体表面の加工油の油膜、或い は、金属表面の塗膜等の除去にも適している。  [0019] In addition, the release agent of the present invention can easily remove an oil film such as dioctyl phthalate (D0P), which is an organic contamination film on the substrate surface, and at the same time adheres to the surface with these oil films. Contaminated particulates can also be removed. In addition, it is also suitable for removing the oil film of the processing oil on the substrate surface after machining or the coating film on the metal surface.
なお、本発明の剥離剤は、通常は、剥離剤を加熱して除去処理を行うが、基体の 性質上、室温か僅かな加温条件下で処理を行う必要がある場合にも使用することが できる。特に、炭酸エチレンが固化する 35°C以下の温度で好適に使用することが可 能である。  The release agent of the present invention is usually removed by heating the release agent, but it should also be used when it is necessary to carry out the treatment under room temperature or slight heating conditions due to the nature of the substrate. Is possible. In particular, it can be suitably used at a temperature of 35 ° C or lower at which ethylene carbonate solidifies.
[0020] 上述したとおりに、 γ プチ口ラタトン単独、または γ プチ口ラタトンと γ プチ口 ラ外ンと相溶する液体との混合物は、フォトレジスト膜等の有機被膜を有効に剥離 · 除去することができるが、該処理後の剥離剤には、有機被膜由来の成分が溶解（お よび分散)して含有されている。有機被膜の剥離は、 目視によって判断する。 γ—ブ チロラタトンは、この有機被膜の溶解性が、従来より剥離剤として知られている炭酸ェ チレンあるいは炭酸プロピレンよりも優れているため、処理後の剥離剤に何ら処理を 施さないでそのまま剥離剤として再利用することができる。  [0020] As described above, γ petit mouth rataton alone or a mixture of γ petit mouth rataton and a liquid compatible with γ petit mouth rattan effectively removes and removes an organic film such as a photoresist film. However, the release agent after the treatment contains dissolved (and dispersed) components derived from the organic film. The organic film is peeled off visually. γ-Butyrolatatone has better solubility of this organic coating than ethylene carbonate or propylene carbonate, which is conventionally known as a release agent. Therefore, the treated release agent is peeled off without any treatment. It can be reused as an agent.
[0021] 例えば、従来の剥離剤は、数回以上繰り返して使用すると残渣が発生する等の問 題を生じるが、本発明の剥離剤は、 20回以上繰り返し使用しても残渣が生じ難ぐ再 利用することができる。 そのため、本発明の剥離剤は、処理後に、再利用するために、オゾン処理を施す 必要はないが、オゾン処理を施す方が、以下の利点を有するので好ましい。 [0021] For example, the conventional release agent causes problems such as generation of a residue when used repeatedly several times or more. However, the release agent of the present invention hardly generates a residue even when used repeatedly 20 times or more. Can be reused. Therefore, the release agent of the present invention does not need to be subjected to ozone treatment in order to be reused after treatment, but it is preferable to perform ozone treatment because it has the following advantages.
[0022] 上記処理後の剥離剤中の例えば溶解したレジストは、 50°C以下のオゾンガスを通 気することにより、短時間に低分子量物質にまで分解される。そして、 y—プチ口ラタ トン単独、または γ _プチ口ラタトンと γ _プチ口ラタトンと相溶可能な液体との混合 物は、このオゾンガス通気によって、実質上、化学的に変化しないこと、および、レジ スト等の剥離'除去性能が低下しないことがわかっている。したがって、有機膜除去 処理後の剥離剤にオゾンガスを通気すれば、そのまま、もしくは必要に応じて濾過し て分解物質を除くことにより、レジスト等の除去用剥離剤として再利用することができ る。オゾンガスに対する耐性を有する点で、 Ί—プチ口ラタトンと相溶可能な液体は、 炭酸エチレンおよび/または炭酸プロピレンが好ましい。レジスト剥離後の剥離剤を オゾン処理してレジスト成分を分解し、精密濾過して分解物質を除くと、剥離剤を新し レ、ものに交換することなく繰り返し使用する回数を増やすことが可能となる。 [0022] For example, the dissolved resist in the release agent after the above treatment is decomposed into a low molecular weight substance in a short time by passing ozone gas of 50 ° C or lower. The y-petit-mouth rataton alone or a mixture of γ_petit-mouth rataton and a liquid compatible with γ_petit-mouthed ratataton is substantially chemically unaffected by this ozone gas flow, and It has been found that the removal and removal performance of resist and the like does not deteriorate. Therefore, if ozone gas is passed through the stripping agent after the organic film removal treatment, it can be reused as a stripping stripper for removing resist or the like by removing it as it is or by filtering it as necessary. From the viewpoint of resistance to ozone gas, the liquid compatible with Ί -petit rataton is preferably ethylene carbonate and / or propylene carbonate. Removing the resist after stripping the resist with ozone to decompose the resist components and micro-filtering to remove the decomposed material can increase the number of times that the stripper can be used repeatedly without replacing it with a new one. Become.
[0023] オゾンガスの通気速度、通気時間に関しては、特に限定は無いが、剥離するレジス トの種類、工程条件によって変化する。現実には、 目視によりレジストが分解して着色 が消える点、電導度、透過率、 UV吸収、 CPC分析、等により有機被膜の分解程度 を判断して決める。  [0023] The ventilation rate and the ventilation time of ozone gas are not particularly limited, but vary depending on the type of resist to be peeled off and the process conditions. In reality, it is determined by judging the degree of decomposition of the organic film based on the point that the resist is visually decomposed and the color disappears, conductivity, transmittance, UV absorption, and CPC analysis.
上述した有機被膜除去処理後の剥離剤をオゾンガス処理して剥離剤を再生'循環 再利用する工程にとどまらず、有機被膜の除去工程においてもオゾンガスを溶解さ せた剥離剤を使用すると、剥離 ·除去における効率が著しく向上する。オゾンガスは、 液中のオゾンガス濃度が、上限すなわち飽和溶解量まで溶解させて剥離に使用する のが好ましい。  The release agent after the organic film removal treatment described above is treated with ozone gas to regenerate and recycle the release agent. In addition to the process of reusing and recycling, the use of a release agent that dissolves ozone gas in the organic film removal process The efficiency in removal is significantly improved. The ozone gas is preferably used for stripping after the ozone gas concentration in the liquid is dissolved to the upper limit, that is, the saturated dissolution amount.
[0024] このようにして、レジストを、 CPC測定で分子量が数千以下になる程度に分解させる ことにより、本発明の剥離剤の循環使用回数を更に増大させることができる。  [0024] Thus, by decomposing the resist to such an extent that the molecular weight becomes several thousand or less by CPC measurement, it is possible to further increase the number of times the release agent of the present invention is circulated.
y—ブチ口ラタトンまたは γ _ブチロラタトンと炭酸エチレンあるいは炭酸プロピレン との液状混合物からなる剥離剤は、レ、ずれも沸点が高レ、ので、新しレ、剥離剤でリンス してスピン乾燥してもこれらの分子の膜がゥヱハー表面に吸着残存する可能性が高 レ、。ウェハー上に剥離剤が残ると処理基板の物性 (特に電気的物性）に悪影響を及 ぼす可能性がある。したがって、超純水によるリンスを引き続き実施することが望まし レ、。 The release agent consisting of a liquid mixture of y-buchi-mouth rataton or γ_butyrolataton and ethylene carbonate or propylene carbonate has a high boiling point, so it is rinsed with a new release agent, a release agent, and spin-dried. However, there is a high possibility that these molecular films will remain adsorbed on the wafer surface. If the release agent remains on the wafer, the physical properties (especially electrical properties) of the processed substrate will be adversely affected. There is a possibility of drowning. Therefore, it is desirable to continue rinsing with ultrapure water.
[0025] 本発明で剥離する有機被膜としては、電子材料用基板のフォトリソグラフイエ程で 最後は不要となるフォトレジスト膜である。例えばフエノールノボラック型レジスト、タレ ゾールノボラック型レジスト、ビュルフエノール誘導体型レジスト、ポリメタタリレート型 レジスト等のポジレジスト、環化ポリイソプレン誘導体型レジストネガ型レジスト等を挙 げること力 Sできる。三次元架橋しないポジ型レジストが好ましい。  [0025] The organic film to be peeled in the present invention is a photoresist film which is unnecessary at the end of the photolithographic process of the electronic material substrate. For example, it is possible to list positive resists such as phenol novolac resists, talesol novolac resists, burphenol derivative resists, polymetatalylate resists, cyclized polyisoprene derivative resist negative resists, and the like. A positive resist that is not three-dimensionally crosslinked is preferred.
[0026] 本発明に従えば、本発明の剥離剤を、場合によりオゾンガスを溶解させて用いるこ とにより、基体表面上の有機被膜、例えば、従来アツシングが必要であったイオン注 入レジスト膜等を極めて短時間にかつ効率的に除去することができる。本発明の剥 離剤は、常温で液体であるから取り扱いが容易であり、低温でのレジスト溶解性が大 きぐ沸点、引火点ともに高いことから高温条件下の処理においても適用でき、また安 全性も高ぐ環境面での問題も少ない。  [0026] According to the present invention, the release agent of the present invention is optionally used by dissolving ozone gas, whereby an organic film on the surface of the substrate, for example, an ion-implanted resist film that conventionally required ashing, etc. Can be removed in a very short time and efficiently. The stripping agent of the present invention is easy to handle because it is a liquid at room temperature, and it can be applied even in processing under high temperature conditions because of its high boiling point and flash point resist solubility at low temperatures. There are few environmental problems with high nature.
[0027] さらに、本発明は、基体上の油膜や塗膜等の一般的な有機被膜を除去するのに適 用できるものである。 Furthermore, the present invention can be applied to remove a general organic film such as an oil film or a paint film on a substrate.
本発明において、基体表面上の有機被膜を除去するには、有機被膜に剥離剤を 接触させる。力かる接触させる方法は、特に限定するものではなぐ有機被膜の付い た基体を剥離液に浸漬して溶解する方法、基体上の有機被膜に剥離液をスプレー して洗レ、流す方法、剥離液の蒸気中に有機被膜の付レ、た基体を晒す方法等を例示 すること力 Sできる。また、剥離剤液を撹拌、振動、動揺、パブリング等することによって 、基体上の有機被膜に作用を与えるのが、有機被膜の除去速度を高めることから、 有利である。  In the present invention, in order to remove the organic coating on the substrate surface, a release agent is brought into contact with the organic coating. There are no particular limitations on the method of contact, such as a method in which a substrate with an organic coating is dissolved by immersing it in a stripping solution, a method in which a stripping solution is sprayed on the organic coating on the substrate, a method of washing and flowing, a stripping solution It is possible to exemplify the method of applying an organic coating in the vapor of the water and exposing the substrate. In addition, it is advantageous to increase the removal rate of the organic coating by acting on the organic coating on the substrate by stirring, vibrating, shaking, or publishing the release agent solution.
[0028] また、本発明の剥離剤を容器に入れ、その中に有機被膜を有する基体を浸漬する ことによって、接触を実施する場合、循環装置を用いて本発明の剥離剤を循環させ て再利用するのが経済的に好ましい。  [0028] In the case where contact is performed by placing the release agent of the present invention in a container and immersing a substrate having an organic film in the container, the release agent of the present invention is circulated using a circulation device and re-applied. It is economically preferable to use it.
以下に例を挙げて本発明を詳細に説明するが、本発明の主旨を超えない限り、本 発明は力かる実施例に限定されるものではない。  Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to powerful examples as long as the gist of the present invention is not exceeded.
実施例 [0029] 本実施例における有機被膜除去装置および除去方法の概要について以下に記す 先ず、本発明の剥離剤を循環させて基体表面の有機被膜を除去する装置を、添付 図を参照しながら説明する。 Example [0029] An outline of the organic film removing apparatus and the removing method in the present embodiment will be described below. First, an apparatus for removing the organic film on the substrate surface by circulating the release agent of the present invention will be described with reference to the accompanying drawings. .
[0030] 図 1は、オゾン含有ガスを用いない場合を示すもので、剥離剤の新液貯槽 1におい て、本発明の剥離剤を調製して貯蔵する。剥離剤を混合剥離剤の貯槽 2に供給する 。混合剥離剤の貯槽 2から剥離剤を管路 3を経て接触槽 4に供給する。接触槽 4に剥 離剤が溜まったら、基体ホルダー 5から有機被膜を有する基体を取り出して接触槽 4 に投入して、基体を剥離剤中に浸漬させる。接触槽 4において、接触槽 4内の剥離 剤液に、撹拌、振動、動揺、パブリング等によって動きを与えるのが、有機被膜の除 去速度を高めることから、有利である。基体表面上の有機被膜が基体表面から除去 されるのを目視で確認した後に、基体を剥離剤から引き上げて接触槽 4から出す。基 体ホルダー 5から有機被膜を有する基体を取り出して剥離剤中に浸漬させ、次レ、で 基体を剥離剤から引き上げる手段としては、基体をはさむことができる器具、例えば ピンセット等を用いて手動で行なうことができる。また、このような操作を行なうことがで きる装置、例えば特開 2003— 203856号公報に記載されているようなロボットアーム を使用して手動で又は自動で行なうこともできる。有機被膜由来の成分を含有する剥 離剤を管路 6から排出して混合剥離剤の貯槽 2に循環させて戻す。有機被膜由来の 成分を含有する剥離剤を管路 6から系外に連続に又は間欠に一部抜き出して、かつ 剥離剤の新液貯槽 1から新液を補給して循環する剥離剤中の有機被膜由来の成分 濃度が高くならないようにする。  FIG. 1 shows a case where no ozone-containing gas is used, and the release agent of the present invention is prepared and stored in a new solution storage tank 1 for the release agent. Supply release agent to tank 2 of mixed release agent. The release agent is supplied from the mixed release agent storage tank 2 to the contact tank 4 via the pipe 3. When the release agent accumulates in the contact tank 4, the substrate having the organic film is taken out from the substrate holder 5 and is put into the contact tank 4, and the substrate is immersed in the release agent. In the contact tank 4, it is advantageous to give the stripper solution in the contact tank 4 a motion by stirring, vibration, shaking, publishing, etc., because the removal speed of the organic coating is increased. After visually confirming that the organic coating on the substrate surface is removed from the substrate surface, the substrate is lifted from the release agent and taken out from the contact tank 4. As a means for taking out the substrate having the organic coating from the substrate holder 5 and immersing it in the release agent, and lifting the substrate from the release agent in the next step, manually using an instrument that can sandwich the substrate, for example, tweezers or the like. Can be done. It can also be performed manually or automatically using a device capable of performing such an operation, for example, a robot arm as described in JP-A-2003-203856. The stripping agent containing the organic film-derived component is discharged from the pipeline 6 and circulated back to the storage tank 2 for the mixed stripping agent. Organic in the release agent that circulates by removing a part of the release agent containing components derived from the organic coating continuously or intermittently from the pipeline 6 and supplying new solution from the new release agent storage tank 1 Do not increase the concentration of ingredients derived from the coating.
[0031] 図 2は、オゾン含有ガスを用いる場合を示すもので、接触槽 4中の剥離剤に有機被 膜を有する基体を浸漬させた後に、場合により、管路 7からオゾンを剥離剤中にパブ リングさせて有機被膜の除去処理を促進する。管路 6から排出した有機被膜由来の 成分を含有する剥離剤をオゾン含有ガス接触槽 8に送る。オゾン含有ガス接触槽 8に は、管路 9からオゾン含有ガスを供給し、排出した有機被膜由来の成分を含有する剥 離剤中にパブンリングさせて剥離剤中に含有される有機被膜由来の成分を分解して 低分子量物質にする。分解された低分子量物質を含有する剥離剤を管路 10から排 出して混合剥離剤の貯槽 2に循環させて戻す。有機被膜由来の成分を含有する剥 離剤を管路 6から系外に連続に又は間欠に一部抜き出して、かつ剥離剤の新液貯 槽 1から新液を補給して循環する剥離剤中の低分子量物質濃度が高くならないよう にする。 [0031] Fig. 2 shows a case where an ozone-containing gas is used. After the substrate having the organic film is immersed in the release agent in the contact tank 4, ozone may be introduced into the release agent from the pipe 7 in some cases. To remove the organic coating. The stripping agent containing the component derived from the organic film discharged from the pipe 6 is sent to the ozone-containing gas contact tank 8. Ozone-containing gas contact tank 8 is supplied with ozone-containing gas from line 9, and is bunched in a release agent containing components derived from the discharged organic film, and is contained in the release agent. Is decomposed into low molecular weight substances. Stripping agent containing degraded low molecular weight material is discharged from line 10. Remove and circulate back to storage tank 2 for mixed release agent. A stripping agent containing a component derived from an organic coating is continuously or intermittently withdrawn from the pipeline 6 to the outside of the system. Avoid increasing the concentration of low molecular weight substances.
[0032] 次に、本発明の剥離剤を用いた有機被膜の除去方法を例示する。  [0032] Next, an organic film removal method using the release agent of the present invention will be exemplified.
なお、実施例で使用したオゾンガスは、放電方式のオゾン発生装置に 0. 4%の窒 素を含む酸素を 2〜： 10LZ分程度流して得たオゾン濃度が約 250mgZLのものであ る。 Ί—プチ口ラタトンと炭酸プロピレンは試薬特級の純度のものを、炭酸エチレンは 東亞合成株式会社製高純度品を使用した。  The ozone gas used in the examples has an ozone concentration of about 250 mgZL obtained by flowing oxygen containing 0.4% nitrogen in a discharge-type ozone generator for about 2 to 10LZ.プ チ -Platinata Lataton and propylene carbonate were of a reagent-grade purity, and ethylene carbonate was a high-purity product manufactured by Toagosei Co., Ltd.
10cm角ガラス基板が 5枚入る石英ガラス製カセットを、 3Lの γ—プチ口ラタトンが充 填してある石英ガラス製の剥離剤槽 (以下、槽 Αと呼ぶ）に浸漬した。一定時間浸漬 後、次いでフレッシュな γ _ブチロラタトンを充填したスプレーリンス槽（以下、槽 Βと 呼ぶ）に一定期間浸漬した。さらに超純水によるオーバーフローリンス槽 (以下、槽 C と呼ぶ）に浸漬し、レジストの剥離を完了した。  A quartz glass cassette containing five 10 cm square glass substrates was immersed in a quartz glass release agent tank (hereinafter referred to as tank jar) filled with 3 L of γ-petit-mouth rataton. After soaking for a certain period of time, it was then soaked for a certain period of time in a spray rinse bath (hereinafter referred to as bath Β) filled with fresh γ_butyrolatatatone. Furthermore, it was immersed in an overflow rinse tank (hereinafter referred to as tank C) with ultrapure water to complete the resist stripping.
[0033] 〔実施例 1〕  [0033] [Example 1]
液温 60°Cの γ—プチ口ラタトンのレジスト剥離効果を調べた。使用した試料は、 10 cm角ガラス基板の表面にノボラック樹脂系 I線用ポジ型レジスト（商品名： PR— 200、 シプレイ製）を膜厚 4 μ mで塗布し、 140°Cで 60秒間ベータしたものである。まず、こ の 1枚をカセットにセットし、槽 A中の γ —ブチロラタトンに 250mg/Lの高濃度ォゾ ンガスを 2L/分で 5分間パブリングさせ、 60°Cの液にオゾンを溶解した結果、僅かに 青色になったのを確かめた後に、前記カセットを液に浸して、レジストの剥離状況を 肉眼で観察した。その結果、浸漬後 10秒間で剥離が完了したことを確認した。剥離 速度は 24 x m/分であった。その後、直ちにカセットを引き上げ、槽 Bで γ—ブチ口 ラタトン液スプレーリンスを 2秒間施し、次に槽 Cで超純水のオーバーフローリンスを 3 分行い、スピン乾燥して顕微鏡で表面の観察を行ったところ、剥離されていない部分 は認められなかった。なお、実施例に及び比較例において、カセットの浸漬及び引き 上げは、手動で実施した。  The resist peeling effect of γ-petit-mouth rataton with a liquid temperature of 60 ° C was investigated. The sample used was a novolac resin-based positive resist for I-line (trade name: PR-200, manufactured by Shipley) with a film thickness of 4 μm on the surface of a 10 cm square glass substrate, and beta for 140 seconds at 140 ° C. It is a thing. First, one of these was placed in a cassette, and 250 mg / L high-concentration ozone gas was published at 2 L / min for 5 minutes in γ-butyrolatatone in tank A, and ozone was dissolved in a 60 ° C solution. After confirming that the color turned slightly blue, the cassette was immersed in the liquid, and the resist peeling state was observed with the naked eye. As a result, it was confirmed that peeling was completed within 10 seconds after immersion. The peel rate was 24 x m / min. Immediately after that, the cassette is pulled up and sprayed with γ-Buchiguchi Rataton spray rinsing for 2 seconds in tank B, followed by 3 minutes of overflow rinsing with ultrapure water in tank C, followed by spin drying and observation of the surface with a microscope. As a result, no part was peeled off. In the examples and comparative examples, the cassette was dipped and pulled up manually.
[0034] 〔実施例 2〕 槽 Aにおいてオゾンを通気せずに、実施例 1と同様に試料 1枚のカセットを浸漬した ところ、肉眼では 15秒間で剥離が終了した（剥離速度： 16 μ m/分)。 60°Cにおける γ—プチ口ラタトン自体の溶解能力は高ぐオゾンガスを通気しなくても十分に短時 間でレジスト剥離が行われることが示された。なお、レジスト剥離後の液は淡黄色に 変化した。 [Example 2] When a cassette of one sample was immersed in the tank A without venting ozone in the same manner as in Example 1, peeling was completed with the naked eye in 15 seconds (peeling speed: 16 μm / min). It was shown that resist stripping can be performed in a sufficiently short time even without passing high ozone gas at 60 ° C. The solution after resist removal turned pale yellow.
[0035] 〔実施例 3〕 [Example 3]
実施例 1と同様の処理条件で槽 Αの Ί—プチ口ラタトンの液温を 80°Cに変更する 以外は実施例 1記載のオゾンガス通気の場合と同様にして、剥離性能を調べた。 その結果、肉眼での観察では 6秒間で剥離が完了したことを確認した。この時の剥 離速度は 40 x m/分であった。その後、直ちにカセットを引き上げ、槽 Βで γ—プチ 口ラタトン液スプレーリンスを 2秒間施し、次に槽 Cで超純水のオーバーフローリンスを 3分行い、スピン乾燥して顕微鏡で表面の観察を行ったところ、剥離されていない部 分は認められなかった。 Exfoliation performance was examined in the same manner as in the case of ozone gas ventilation described in Example 1, except that the temperature of the tank tub—the small- mouth rataton was changed to 80 ° C. under the same processing conditions as in Example 1. As a result, it was confirmed by the naked eye that peeling was completed in 6 seconds. The peeling speed at this time was 40 xm / min. Immediately after that, the cassette is pulled up, and γ-petit-mouth rataton spray rinsing is performed in a tank Β for 2 seconds, then an overflow rinse of ultrapure water is performed in tank C for 3 minutes, spin dried, and the surface is observed with a microscope. As a result, the part that was not peeled off was not observed.
[0036] 〔実施例 4〕 [Example 4]
槽 Αの γ—プチ口ラタトンの液温を 80°Cにする以外、実施例 2と同様にして実験を おこなった。カセットを剥離剤に浸してレジストの剥離状況を肉眼で観察した結果、 7 秒間で剥離が完了したことを確認した。この時の剥離速度は 34 μ m/分であった。 その後、直ちにカセットを引き上げ、槽 Bで γ —ブチロラタトン液スプレーリンスを 2秒 間施し、次に槽 Cで超純水のオーバーフローリンスを 3分行い、スピン乾燥して顕微 鏡で表面の観察を行ったところ、剥離されていない部分は認められなかった。  The experiment was performed in the same manner as in Example 2 except that the temperature of the γ-petit-mouth rataton in the tank was 80 ° C. As a result of observing the resist peeling condition with the naked eye after immersing the cassette in the release agent, it was confirmed that the peeling was completed in 7 seconds. The peeling rate at this time was 34 μm / min. Immediately after that, the cassette is pulled up, and γ-butyrorataton spray rinsing is performed for 2 seconds in tank B, then overflow rinsing is performed for 3 minutes in tank C, spin-dried, and the surface is observed with a microscope. As a result, the part which was not peeled was not recognized.
実施例 1〜4の比較より浸漬温度が高くなると剥離速度が顕著に大きくなつた。液の 高温化でレジストの溶解度が高まったためである。  From the comparison of Examples 1 to 4, when the immersion temperature was higher, the peeling rate was significantly increased. This is because the solubility of the resist has increased due to the higher temperature of the solution.
[0037] 〔実施例 5〕 [Example 5]
実施例 1と同様の処理方法で、 Ί—プチ口ラタトンと炭酸エチレンとの液状混合物（ 重量比で 1： 1)を処理液として液温 100°Cで実施例 1記載のオゾンガス通気の場合と 同様にして、剥離性能を調べた。 In the same treatment method as in Example 1, the liquid mixture of Ί -petit ratatone and ethylene carbonate (1: 1 by weight) was used as the treatment liquid at a liquid temperature of 100 ° C. Similarly, peeling performance was examined.
カセットを剥離剤に浸して、レジストの剥離状況を肉眼で観察した結果、 4秒間で剥 離が完了したことを確認した。この時の剥離速度は 60 x m/分であった。その後、直 ちにカセットを引き上げ、槽 Bで γ —プチ口ラタトンと炭酸エチレンとの液状混合物（ 重量比で 1： 1)でスプレーリンスを 2秒間施し、次に槽 Cで超純水のオーバーフローリ ンスを 3分行い、スピン乾燥して顕微鏡で表面の観察を行ったところ、剥離されてい ない部分は認められなかった。 The cassette was immersed in a stripping agent and the resist stripping condition was observed with the naked eye. As a result, it was confirmed that stripping was completed in 4 seconds. The peeling speed at this time was 60 xm / min. Then straight Next, the cassette is pulled up and spray rinsed with a liquid mixture of gamma-petite rataton and ethylene carbonate (1: 1 by weight) in tank B for 2 seconds, and then an overflow rinse of ultrapure water in tank C. After 3 minutes, spin drying and observing the surface with a microscope, no unpeeled part was observed.
[0038] 〔実施例 6〕  [Example 6]
オゾンガスを通気しない以外、実施例 5と同様の方法で実験をおこなった。 カセットを剥離剤に浸して、レジストの剥離状況を肉眼で観察した結果、 3秒間で剥 離が完了したことを確認した。この時の剥離速度は 80 x m/分であった。その後、直 ちにカセットを引き上げ、槽 Βで γ _プチ口ラタトン液スプレーリンスを 2秒間施し、次 に槽 Cで超純水のオーバーフローリンスを 3分行レ、、スピン乾燥して顕微鏡で表面の 観察を行ったところ、剥離されていない部分は認められなかった。  An experiment was conducted in the same manner as in Example 5 except that ozone gas was not passed. As a result of observing the resist peeling condition with the naked eye by immersing the cassette in a release agent, it was confirmed that the peeling was completed in 3 seconds. The peeling speed at this time was 80 × m / min. Immediately after that, the cassette is pulled up and sprayed with a γ_petit-mouth rataton liquid spray rinse for 2 seconds in a tank 、, and then an ultrapure water overflow rinse is performed for 3 minutes in the tank C. As a result of observation, no unpeeled portion was observed.
[0039] 〔実施例 7〕  [Example 7]
従来はアッシャーを使わないと十分な除去のできない高濃度イオン注入後のレジス ト膜に対する剥離効果を調べた。  Conventionally, the peeling effect on the resist film after high-concentration ion implantation, which cannot be sufficiently removed without using an asher, was investigated.
試料として、 10cm角ガラス基板にノボラック樹脂系ポジ型レジスト（商品名： PR— 2 00、シプレイ製）を 2 /i m塗布したものに、 130°C, 4分間のベーキングを行い、さらに 、全面に 11B+による 30keVのイオン注入を 1 X 1014/cm2および 1 X 1015/cm2施 したものを用いた。 As a sample, a novolac resin-based positive resist (product name: PR-200, manufactured by Shipley) applied to a 10cm square glass substrate with 2 / im was baked at 130 ° C for 4 minutes. 11B + ion implantation at 30keV and 1 X 10 14 / cm 2 and 1 X 10 15 / cm 2 were used.
槽 Aのオゾンの通気は行わず、槽 A内の液温を 120°Cに高め、 1 X 1014/cm2およ び 1 X 1015/cm2注入の試料を各 1枚カセットに入れて浸漬し、レジストの剥離状況 を肉眼で観察した。レジスト膜は、前者は 1分、後者は 2分で完全に剥離した。剥離 速度は、夫々 2 μ mZ分、 1 μ mZ分であり実用化できる剥離速度であった。 Tank A was not ventilated with ozone, the temperature in tank A was increased to 120 ° C, and 1 x 10 14 / cm 2 and 1 x 10 15 / cm 2 injected samples were placed in each cassette. The resist was peeled off and observed with the naked eye. The resist film was completely removed in 1 minute for the former and 2 minutes for the latter. The stripping rates were 2 μmZ and 1 μmZ, respectively, which were practically usable.
[0040] 〔実施例 8〕 [Example 8]
実施例 7の実験で得られたレジストを溶解した混合物にオゾンを吹き込みレジストを 分解し、再生する実験を行なった。  An experiment was conducted in which ozone was blown into the mixture obtained by dissolving the resist obtained in the experiment of Example 7 to decompose and regenerate the resist.
槽 A中のレジストが溶解して褐色となった混合物に、 250mg/Lの高濃度オゾンガ スを 2LZ分で 10分間パブリングさせた結果、褐色は消え、僅かに青色になった。こ の液中のレジストを確認するため、 GPCを測定したところレジストは分解されているこ とを確認した。 As a result of publishing 250 mg / L high-concentration ozone gas at 2 LZ for 10 minutes to the mixture in which the resist in bath A was dissolved, the brown color disappeared and the color turned slightly blue. In order to check the resist in this solution, GPC was measured and it was found that the resist was decomposed. And confirmed.
次いで、この再生された剥離剤を用いて、実施例 7と同じ剥離試験を行なったところ 、レジスト膜は 1分で完全に剥離し、剥離剤が再使用可能であることが分った。  Subsequently, the same release test as in Example 7 was performed using the regenerated release agent, and it was found that the resist film was completely removed in 1 minute and the release agent was reusable.
[0041] 〔実施例 9〕 [Example 9]
基板にレジスト膜を塗布した後に、ポストベータを 140°C, 3分間程度おこなった試 料を用い、実施例 3と同様の実験をおこなったところ、レジストがノボラック樹脂系ポジ 型レジスト、化学増幅型のポリビュルフヱノール誘導体系ポジ型レジスト、あるいは環 化ポリイソプレン系ネガ型レジストのいずれを問わず、その剥離速度は 20 μ m/分 以上であった。  After applying a resist film to the substrate, an experiment similar to that in Example 3 was performed using a sample that was subjected to post-beta treatment at 140 ° C for about 3 minutes. As a result, the resist was a novolak resin-based positive resist, chemically amplified type. The stripping rate was 20 μm / min or more regardless of whether the polybutanol derivative positive resist or the cyclized polyisoprene negative resist was used.
また、剥離剤が中性のため、配線用の Al, Mo, W, Ti， IT〇等の金属膜は侵され なかった。  Moreover, since the release agent was neutral, the metal films for wiring such as Al, Mo, W, Ti, and IT ○ were not attacked.
[0042] 〔実施例 10〕 [Example 10]
アルミニウム膜のドライエッチングには C1系や Br系のガスが使われる。この場合レジ スト面や力卩ェ部側壁の変質膜にこれらの腐食性ガスが残留し、アツシングでも除けな いので、後続して湿式処理が必要となっている。このような処理対象に本発明を適用 するには、残存ハロゲンによるアルミニウム腐食の危険を防ぐため、なるべく低温で処 理することが望ましい。そこで、オゾンを添加した室温の γ —プチ口ラタトンでレジスト を剥離する実験をおこなった。  C1-based and Br-based gases are used for dry etching of aluminum films. In this case, these corrosive gases remain on the resist film and the altered film on the side wall of the force zone, and cannot be removed even by ashing. Therefore, subsequent wet processing is required. In order to apply the present invention to such an object to be treated, it is desirable to treat at a temperature as low as possible in order to prevent the risk of aluminum corrosion due to residual halogen. Therefore, an experiment was conducted to remove the resist with a γ-petit-mouth rataton at room temperature to which ozone was added.
アルミニウム膜を C1系の反応ガスでドライエッチングをした場合の、通常はアツシン グでレジスト剥離をしてレ、るノボラック樹脂系ポジ型レジストを対象とし、実際のデバイ スパターンに近レ、パターンが形成された TEGウェハーを作成して試料とした。レジス トの膜厚は l z mである。  When the aluminum film is dry-etched with a C1-based reactive gas, the resist is usually removed by ashing, and the target is a novolac resin-based positive resist, which is close to the actual device pattern. The formed TEG wafer was prepared as a sample. The film thickness of the resist is l z m.
y—プチ口ラタトンを用いて、実施例 1と同様に試料 1枚のカセットを浸漬したところ 、肉眼的には 15秒間で剥離が終了した。この時の剥離速度は 16 z mZ分であった 。超純水洗浄'乾燥後の表面を電子顕微鏡で観察した。残存レジストは、加工部側 面の変質膜を含めて見出されなかった。  When the cassette of one sample was immersed in the same manner as in Example 1 using y-petit mouthed rataton, peeling was completed in 15 seconds. The peeling speed at this time was 16 z mZ min. The surface after drying with ultrapure water was observed with an electron microscope. No residual resist was found including the altered film on the side of the processed part.
[0043] 〔実施例 11〕  [Example 11]
y—プチ口ラタトンは消防法の危険物であるため水の混合を実施した。 10重量％ の水を含む以外は実施例 1と同様のオゾン添加処理をおこなった γ —ブチロラタトン により実験をおこなったところ、剥離は十分なされており、剥離速度は ΙΟ μ ΐη/分であ つに。 Since y-petit mouth Lataton is a dangerous material of the Fire Service Act, water was mixed. 10% by weight When γ-butyrolatatone was subjected to the same ozone addition treatment as in Example 1 except that water was included, peeling was sufficient and the peeling rate was ΙΟ μ ΐη / min.
[0044] 〔実施例 12〕  [Example 12]
y—プチ口ラタトンに炭酸プロピレンを 20重量％添加し、実施例 1と同様に実施し た。剥離は十分なされており、剥離速度は 23 x m/分であった。  20% by weight of propylene carbonate was added to y-petit-mouthed rataton, and the same procedure as in Example 1 was performed. Exfoliation was sufficient and the exfoliation rate was 23 x m / min.
[0045] 〔実施例 13〕 [Example 13]
図 2に示す装置を用い、オゾン含有ガス接触手段 8に、管路 9からオゾン含有ガスを 供給し、処理剤の温度を 60°Cにする外は、実施例 1と同様の処理条件で実験をおこ なった。その結果、基体の表面にはレジストが剥離されていない部分は認められなか つた。  Experiments were performed under the same processing conditions as in Example 1 except that ozone-containing gas contact means 8 was supplied with ozone-containing gas from conduit 9 and the temperature of the treatment agent was changed to 60 ° C using the apparatus shown in Fig. 2. I did it. As a result, no portion of the resist was peeled off on the surface of the substrate.
[0046] 〔比較例 1〕 [Comparative Example 1]
γ—プチ口ラタトンの代わりに炭酸エチレンを使用する以外、実施例 10と同様の方 法で実験をおこなったところ、炭酸エチレンが固化しているため剥離ができなかった  Except for using ethylene carbonate instead of γ-petit-mouth rataton, an experiment was conducted in the same manner as in Example 10. As a result, ethylene carbonate was solidified and could not be peeled off.
[0047] 〔比較例 2〕 [Comparative Example 2]
γ—プチ口ラタトンの代わりに炭酸プロピレンを使用する以外、実施例 10と同様の 方法で実験をおこなったところ、剥離速度は 5 μ m/分であり γ—プチ口ラタトンと比 較して遅かった。  An experiment was conducted in the same manner as in Example 10 except that propylene carbonate was used instead of γ-petit-mouthed rataton. The peel rate was 5 μm / min, which was slower than γ-petit-mouthed rataton. It was.
産業上の利用可能性  Industrial applicability
[0048] 本発明は、電子デバイス用基板等の表面清浄化のために、基体上に付着する有 機被膜を除去するために使用することができる。本発明は、半導体用ウェハーまたは 液晶用基板などの加工に際して使用するフォトレジスト被膜を除去するのに有用であ り、特に、超微細パターンデバイスでのレジスト剥離に適している。さらに、本発明は、 基体上の油膜や塗膜等の一般的な有機被膜の除去に適用できるものである。 [0048] The present invention can be used to remove an organic coating adhering to a substrate in order to clean the surface of an electronic device substrate or the like. The present invention is useful for removing a photoresist film used for processing a semiconductor wafer or a liquid crystal substrate, and is particularly suitable for resist removal in an ultrafine pattern device. Furthermore, the present invention can be applied to the removal of general organic coatings such as oil films and coatings on a substrate.

Claims

請求の範囲  The scope of the claims
[I] γ _プチ口ラ外ンを 20重量％以上含有することを特徴とする有機被膜の剥離剤。  [I] An organic coating remover characterized by containing 20% by weight or more of γ_petit opening.
[2] γ _プチ口ラ外ン単独である、請求項 1に記載の有機被膜の剥離剤。 [2] The organic coating remover according to [1], wherein γ_petit mouth is alone.
[3] γ—プチ口ラタトンと、 Ί—プチ口ラタトンと相溶する液体との混合物である、請求項 1 に記載の有機被膜の剥離剤。 [3] and γ- Petit port Rataton, it - is a mixture of compatible liquid and Petit port Rataton, release agents organic coating according to claim 1.
[4] y—プチ口ラタトンと相溶する液体が炭酸エチレンおよび/または炭酸プロピレンで ある、請求項 3に有機被膜の剥離剤 [4] The organic film remover according to claim 3, wherein the liquid compatible with y-petit-mouth rataton is ethylene carbonate and / or propylene carbonate.
[5] γ—プチ口ラタトンと相溶する液体が水である、請求項 3に記載の有機被膜の剥離剤 [5] The organic film remover according to claim 3, wherein the liquid compatible with γ-petit-mouth rataton is water.
[6] 表面に有機被膜を有する基体に、請求項：!〜 5のいずれかに記載の有機被膜剥離 剤を接触させて、前記有機被膜を除去する、有機被膜の除去方法。 [6] A method for removing an organic coating, wherein the organic coating is removed by bringing the organic coating remover according to any one of claims: to 5 into contact with a substrate having an organic coating on the surface.
[7] 前記有機被膜を有する基体に、有機被膜剥離剤を接触させる際に、予め該剥離剤 を 30〜200°Cに加熱する、請求項 6に記載の方法。 [7] The method according to claim 6, wherein the release agent is heated to 30 to 200 ° C in advance when the organic coating release agent is brought into contact with the substrate having the organic coating.
[8] 前記有機被膜を有する基体を前記剥離剤中に浸潰させることにより、基体表面と前 記剥離剤を接触させる、請求項 6〜7のいずれかに記載の方法。 [8] The method according to any one of claims 6 to 7, wherein the substrate surface and the release agent are brought into contact with each other by immersing the substrate having the organic coating in the release agent.
[9] 前記有機被膜の表面に前記剥離剤の液膜を形成させ、連続的または間欠的にその 液膜に対し新たな剥離剤を供給して液膜を移動させる、請求項 6〜8のレ、ずれかに 記載の方法。 [9] The liquid film of the release agent is formed on the surface of the organic coating, and the liquid film is moved by supplying a new release agent to the liquid film continuously or intermittently. The method described in reg.
[10] 高濃度オゾン含有ガスの雰囲気中で、前記基体表面に前記剥離膜の液膜を移動さ せる、請求項 9に記載の方法。  [10] The method according to claim 9, wherein the liquid film of the release film is moved to the surface of the substrate in an atmosphere of a high-concentration ozone-containing gas.
[II] A.剥離剤の新液を貯蔵する貯槽と、  [II] A. A storage tank for storing a new release agent solution,
B.剥離剤の新液を導入しかつ処理後の剥離剤を導入する混合剥離剤貯槽と、 B. A mixed release agent storage tank for introducing a new release agent liquid and introducing a release agent after treatment;
C.混合剥離剤貯槽手段から剥離剤を接触槽に供給する手段と、 C. means for supplying the release agent to the contact tank from the mixed release agent storage means;
D.有機被膜を有する基体を収容する基体ホルダーと、  D. a substrate holder for accommodating a substrate having an organic coating;
E.基体ホルダーから有機被膜を有する基体を取り出して接触槽に導入し、接触槽 内において、基体の有機被膜を有する表面に剥離剤を接触させて、有機被膜を剥 離剤に溶解させて、有機被膜を基体表面から除去し、有機被膜が除去された基体を 接触槽から引き上げる手段と、 F.有機被膜を溶解する剥離剤を接触槽から排出する手段と、 E. The substrate having the organic film is taken out from the substrate holder and introduced into the contact tank. In the contact tank, the release agent is brought into contact with the surface of the substrate having the organic film, and the organic film is dissolved in the release agent. Means for removing the organic coating from the surface of the substrate and lifting the substrate from which the organic coating has been removed from the contact tank; F. means for discharging the release agent that dissolves the organic coating from the contact tank;
G.接触槽から排出された剥離剤を循環させて混合剥離剤貯槽に戻す手段と を有することを特徴とする、有機被膜を有する基体表面の有機被膜の除去装置。 さらに  G. A device for removing the organic film on the surface of the substrate having an organic film, comprising: a means for circulating the release agent discharged from the contact tank and returning it to the mixed release agent storage tank. More
F.接触槽の下流にオゾン含有ガス接触槽を有し、接触槽から排出された剥離剤を オゾン含有ガス接触槽に導入し、剥離剤中にオゾン含有ガスをバブンリングさせて剥 離剤中に含有される有機被膜由来の成分を分解して低分子量物質にする請求項 11 に記載の除去装置。  F. There is an ozone-containing gas contact tank downstream of the contact tank, and the release agent discharged from the contact tank is introduced into the ozone-containing gas contact tank, and the ozone-containing gas is bubbled into the release agent. 12. The removing apparatus according to claim 11, wherein the component derived from the organic coating contained therein is decomposed into a low molecular weight substance.
PCT/JP2006/303019 2005-06-07 2006-02-21 Organic film release agent, and method and appartus for removing organic film using said release agent WO2006132008A1 (en)

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Publication number Priority date Publication date Assignee Title
WO2008152907A1 (en) * 2007-06-12 2008-12-18 Toagosei Co., Ltd. Agent for stripping resist film on electroconductive polymer, method for stripping resist film, and substrate with patterned electroconductive polymer
JP2018104571A (en) * 2016-12-27 2018-07-05 菊水化学工業株式会社 Coating peeling agent

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