JPH09266162A - Removal method of resist, and adhesive and bonding sheets used for it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily and securely remove an unnecessary resist material on an article, by setting exfoliation bonding force against a resist of a bonding agent layer upon exfoliation at a specific value or above and setting exfoliation bonding force for an article of a part of the bonding agent layer where no resist exists at less than a specific value. SOLUTION: When an unnecessary resist material on an article, for example, a semiconductor wafer and the like, is removed, 180 exfoliation bonding force of a resist of a bonding agent layer upon exfoliation is set at 5g/10mm or above, and 180 exfoliation bonding force for an article of a part of the bonding agent layer where no resist exists is set 150g/10mm. A bonding agent layer, preferable a pressure sensitive bonding agent layer, is provided on an article such as a semiconductor wafer where a resist pattern exists, and heating or pressurizing means is additionally provided for improving adhesion at need. With the hardening processing, the bonding agent is hardened in an integrated state with the resist material, and its elastic modules is sharply increased to ensure necessary tensile strength.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to, for example, a semiconductor,
The present invention relates to a method for removing an unnecessary resist material on an article such as a semiconductor wafer when manufacturing finely processed parts such as circuits, various printed boards, various masks, and lead frames, and an adhesive or an adhesive sheet used therefor.

An example of manufacturing a semiconductor device will be described below. The present invention is directed to a pattern made of a resist material,
That is, if the resist material is an article that partially exists,
The present invention is not limited to the application, and is preferably used for removing unnecessary ion-implanted resist material on a wafer, particularly in semiconductor device manufacturing.

[0003]

2. Description of the Related Art In the manufacture of semiconductor devices, for example, a resist material is applied on a wafer, an image composed of a resist pattern is formed by a normal photo process, and the resist is used as a mask. The material is removed to form a circuit. In order to form the next circuit, a resist material is applied again, and image formation-etching-
The cycle of removing the resist material is repeated. When a circuit is formed on various substrates, an unnecessary resist material is removed after forming a resist pattern.

Here, the unnecessary resist material is generally removed with an asher (ashing means) or a solvent (stripping solution). However, if an asher is used to remove the resist material, it may take a long time to perform the operation, or impurity ions in the resist material may be implanted into the wafer, which is not preferable. In addition, when a solvent is used, there is a problem that the working environment is impaired.

Accordingly, the applicant of the present application has disclosed in Japanese Patent Laid-Open No. Hei 4-345
No. 015, No. 5-275324, etc., adhesive sheets such as a sheet or tape are used to remove the resist material, and the adhesive sheet is attached to the upper surface of the resist pattern and then peeled integrally with the resist material. Proposing a method. This method is expected to be put into practical use as a simple and reliable removal method without the problem that impurity ions in the resist material are implanted into the wafer or harm the working environment.

[0006]

However, according to the study of the present inventors, according to the method using the above-mentioned adhesive sheets,
A high dose of As ions (for example, 1
(× 10 ¹⁵ ions / cm ² or more) or a high energy amount (for example, 1.0 MeV or more), and if the surface layer of the resist pattern is altered by this ion implantation, the peelability of the adhesive sheet deteriorates and the wafer surface Therefore, there is a problem that it is difficult to remove the resist without leaving the entire surface. Furthermore, at the time of peeling, a silicon wafer surface (for example, an oxide film (SiO ₂ film) or a nitride film (S
There is a problem in that the adhesive force between the i ₃ N ₄ film)) and the adhesive layer becomes too large, the wafer surface is contaminated by the adhesive, and the releasability of the resist decreases.

Therefore, the present invention does not depend on alteration of the surface layer of the resist material due to ion implantation or the thickness of the resist, does not cause the problem of contamination of articles such as wafers, and is unnecessary for articles. It is an object of the present invention to provide a method for easily and surely removing a resist material that has become defective, and an adhesive or an adhesive sheet used for the method.

[0008]

Means for Solving the Problems As a result of intensive studies on the above-mentioned objects, the present inventors have found that when a specific physical property of an adhesive layer provided on a resist material is specified, the adhesive layer Good results were obtained for the integral peelability with the resist material, and the resist material was easily and reliably peeled off from the article, regardless of whether the surface layer of the resist material was altered or not, without causing the problem of contamination of the article. Knowing what can be done, the present invention has been completed.

That is, the present invention provides a method of removing a resist in which an adhesive layer is provided on an article in which a resist is partially present, and the adhesive layer and the resist material are integrally peeled from the article. 180 for adhesive layer resist
° A peeling adhesive force of 5 g / 10 mm or more, and a 180 ° peeling adhesive force of less than 150 g / 10 mm with respect to an article in which the resist of the adhesive layer does not exist are set to less than 150 g / 10 mm. It is related.

The present invention also provides an adhesive or an adhesive sheet used in the above method of removing a resist, wherein the 180 ° peeling adhesive force of the adhesive layer to the resist at the time of peeling is 5
g / 10 mm or more, and the 180 ° peeling adhesive force to the part of the adhesive layer where the resist does not exist is 150 g / 10
The present invention relates to an adhesive or an adhesive sheet for resist removal set to be less than mm.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the method of removing a resist of the present invention, first, on an article on which a resist pattern is present,
A layer of adhesive is provided. This method of providing may be performed by a method of directly applying an adhesive onto the article, but in the present invention, an adhesive sheet such as a sheet or tape having an adhesive layer previously provided on a substrate is used. I made it,
A method is preferred in which the adhesive sheets are attached to the article.

The adhesive used here may be a non-curable type or a curable type, but in the non-curable type, the 180 ° peeling adhesive force of the adhesive itself to the resist is obtained. In the case of a hardening type, the 180 ° peeling adhesive strength of the cured adhesive to the resist is 5 g / 10 mm or more, especially 5 to 5000 g / 10 mm, and further 10 to 5000 g / 10
It is desirable to set it to about mm. This 18
If the 0 ° peel adhesion is less than the above value, the resist material cannot be peeled at all. In particular, about 3000 to 5000 g / 10 mm for high dose implantation resist, and 2000 to 4 for high energy implantation resist.
It is desirable to set it to about 000 g / 10 mm. On the other hand, if it is too large, the wafer may be damaged, or the anchor may be destroyed between the base material and the adhesive.

Further, peeling is performed on the article of the adhesive layer where the resist does not exist (for example, when the article is a silicon wafer, an oxide film (SiO ₂ film) or a nitride film (Si ₃ N ₄ film)). 180 ° peeling adhesive strength is 150
It is desirable to set it to be less than g / 10 mm, preferably 5 to 120 g / 10 mm. This adhesion is 150g /
If it is 10 mm or more, the adhesive force to the article where the resist does not exist is too large, the resist peeling operation cannot be easily performed, and the article surface may be contaminated with the adhesive, which is not preferable, while it is too small. If it is too much, a portion where the wafer and the adhesive layer of the adhesive sheet do not come into contact with each other is generated, and uniform peeling may not be performed. Even when a curable type is used as the adhesive, the same phenomenon as described above may occur. Therefore, the 180 ° peeling adhesive force to the article of the adhesive layer before curing where the resist does not exist is 150 g /
It is desired to be 10 mm or more, preferably 200 to 1000 g / 10 mm. Here, the 180 ° peeling adhesive force means an adhesive force defined in Examples described later.

The adhesive used in the present invention is a resist, and one specific for resist-free articles.
The adhesive is not particularly limited as long as it can exhibit 80 ° peel adhesive strength, and may be a pressure-sensitive adhesive or an ordinary adhesive. For example, non-curable adhesives include polyvinyl acetate, polyvinyl acetal, polyvinyl alcohol, Examples thereof include thermoplastic resins such as poly (meth) acrylic acid, poly (meth) acrylic acid ester, and various natural polymers. Particularly, the weight average molecular weight thereof is 10,000 to 10,000,000, preferably 100,000 to 5
Those having a number of, 000,000 are preferably used. If the molecular weight is too small, it is difficult to set the 180 ° peeling adhesive force to the resist and the article in the portion where the resist does not exist to the above specific value. On the other hand, if it is too large, it may be difficult to process it into a sheet or the like. As the curable adhesive, a thermosetting adhesive or a photocurable adhesive obtained by adding a polymerizable monomer or oligomer described below together with heat or a photopolymerization initiator to an adhesive polymer composed of the thermoplastic resin, And other thermosetting resins such as urea resin, phenol resin and epoxy resin.

In the present invention, a photo-curable pressure-sensitive adhesive, particularly an ultraviolet-curable pressure-sensitive adhesive, is preferably used from the viewpoint of curing workability and from the viewpoint of not having a thermal adverse effect on articles such as wafers and circuit boards. To be The UV-curable pressure-sensitive adhesive is not particularly limited as long as it can express the specific 180 ° peel adhesive force, but a compound having one or more unsaturated double bonds in the molecule is included in the pressure-sensitive adhesive polymer. It is preferable that the pressure-sensitive adhesive polymer is contained, and examples of such a pressure-sensitive adhesive polymer include (meth) acrylic acid and / or (meth) acrylic acid ester selected from acrylic acid, acrylic acid alkyl ester, methacrylic acid, and methacrylic acid alkyl ester. An acrylic polymer having as a main monomer is mentioned.

This acrylic polymer has the above-mentioned main monomer, that is, acrylic acid, methacrylic acid, an ester of acrylic acid or methacrylic acid and an alcohol having a carbon number of usually 12 or less, and optionally a carboxyl group or a hydroxyl group. It can be obtained by using a monomer or other modifying monomer and polymerizing them by a method such as solution polymerization, emulsion polymerization, suspension polymerization or bulk polymerization according to a conventional method.

Examples of the carboxyl group-containing monomer include acrylic acid and methacrylic acid which can also be used as main monomers, as well as maleic acid and itaconic acid, and examples of the hydroxyl group-containing monomer include hydroxyethyl acrylate and hydroxypropyl. Acrylate and the like are used respectively. The amount of these monomers used when necessary is usually 2 in all the monomers.
The content is preferably 0% by weight or less. As other modifying monomers, vinyl acetate, vinyl propionate, styrene, acrylonitrile, acrylamide, glycidyl methacrylate and the like are used. When these modifying monomers are used, the amount used is usually preferably 50% by weight or less based on the total amount of the main monomers.

The weight average molecular weight of the acrylic polymer composed of such monomers is usually 10,000 to 10,000,000, preferably 100,000 to 5,000,000. If the molecular weight is too low, the
It is difficult to set the 80 ° peeling adhesive force to the above-mentioned specific value, and on the other hand, if it is too large, it may be difficult to process it into a sheet or the like.

When synthesizing an acrylic polymer, an unsaturated double bond in the molecule is used as a copolymerization monomer.
Unsaturation in the molecule of the acrylic polymer by using a compound having more than one or by chemically bonding a compound having an unsaturated double bond in the molecule to the acrylic polymer after synthesis by a reaction between functional groups. By introducing a double bond, this polymer itself can be made to participate in the polymerization-curing reaction by ultraviolet irradiation.

Here, the compound having one or more unsaturated double bonds in the molecule (hereinafter referred to as a polymerizable unsaturated compound) is a low molecular weight compound which is nonvolatile and has a weight average molecular weight of 10,000 or less. In particular, it preferably has a molecular weight of 5000 or less so that the three-dimensional reticulation of the adhesive layer during curing can be efficiently performed. Such a polymerizable unsaturated compound is excellent in compatibility with the acrylic polymer and contributes to fluidization of the entire adhesive, and gives good results in fluid immersion and adhesion to the concave portions of the resist pattern. Further, it is desirable that the material has excellent affinity with the resist material, has a large adhesive force with the resist material, and does not flow to the side surface when stored in a tape or sheet state.

Specific examples of the polymerizable unsaturated compound include phenoxy polyethylene glycol (meth) acrylate, ε-caprolactone (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and triglyceride. Methylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, urethane (meth) acrylate, epoxy (meth)
Acrylate, oligoester (meth) acrylate,
Examples include ethoxylated trimethylolpropane tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, and polyester diacrylate. Of these, the type of acrylic polymer used and the type of target resist material Depending on the type, one or more types can be selected.

Such a polymerizable unsaturated compound is usually used in an amount of 5 to 30 relative to 100 parts by weight of the pressure-sensitive adhesive polymer.
It is used in an amount of 0 part by weight, preferably 20 to 300 parts by weight. If the amount is too small, the fluidization of the entire adhesive is low, and the effect of removing the resist material may not be sufficient. If the amount is too large, the adhesive may flow out during storage.

The polymerization initiator added to the curable pressure-sensitive adhesive used in the present invention is not particularly limited, and known ones can be used. For example, in the case of a thermosetting type, benzoyl peroxide, azobisisobutyi. Thermal polymerization initiators such as ronitrile, and in the case of photo-curing type, benzoin, benzoin ethyl ether, dibenzyl, isopropyl benzoin ether, benzophenone, Michler's ketone chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, acetophenone diethyl ketal, benzyl dimethyl ketal. , Α-hydroxycyclohexyl phenyl ketone, 2-hydroxymethylphenyl propane,
Photopolymerization initiators such as 2,2-dimethoxy-2-phenylacetophenone are exemplified. These polymerization initiators are usually added in an amount of 0.1 to 100 parts by weight of the pressure-sensitive adhesive polymer.
It is used in the range of 1 to 15 parts by weight, preferably 0.5 to 10 parts by weight.

The curable pressure-sensitive adhesive improves workability when it is attached to an article such as a semiconductor wafer,
And from the point that the resist material can be peeled off efficiently, a cross-linking agent for cross-linking the pressure-sensitive adhesive polymer to increase the cohesive force as an adhesive, for example, an acrylic polymer having a carboxyl group or a hydroxyl group, this functional group and It is preferable to include polyisocyanates such as diphenylmethane diisocyanate and tolylene diisocyanate, polyepoxy, various metal salts, and chelate compounds as the reactive polyfunctional compound. The amount of these polyfunctional compounds used is 2 parts by weight based on 100 parts by weight of the pressure-sensitive adhesive polymer.
The amount is 0 parts by weight or less, and the molecular weight of the polymer may be appropriately selected so that the molecular weight is small and the molecular weight is small within the range. It is not preferable to use too much because the adhesive strength between the adhesive layer and the resist material is reduced.

Further, such a curable pressure-sensitive adhesive may contain a filler such as finely divided silica for the same purpose of use as the above-mentioned polyfunctional compound, and other tackifying resins. If desired, various known additives such as a colorant, an antiaging agent and the like can be included. These various additives may be used in the usual amounts used for general adhesives.

In the present invention, the above-mentioned adhesive itself or, particularly preferably, the adhesive layer made of this adhesive is provided on the substrate to obtain adhesive sheets in the form of a sheet or tape. be able to. As the base material, a plastic film made of polyethylene, polypropylene, polyethylene terephthalate, polyurethane, polyvinyl chloride, ethylene-vinyl acetate copolymer, etc., a plastic nonwoven fabric, a cloth made of plastic synthetic fiber or glass fiber, aluminum, stainless steel, etc. Metal foil, paper, etc. are used. The thickness of the base material is usually about 10 to 500 μm. When a photo-curing adhesive is used as the adhesive, a material that transmits light such as ultraviolet rays is selectively used as the substrate.

In particular, in the present invention, a UV-curable pressure-sensitive adhesive is applied on a film substrate which transmits ultraviolet rays so that the thickness after drying is about 10 to 180 μm, whereby a film form is obtained. UV-curable pressure-sensitive adhesive sheets in the form of tape or tape are preferably used. The film substrate is made of polyethylene, polypropylene, polyethylene terephthalate, etc. and has a thickness of 12 to 1
A plastic film that transmits ultraviolet rays of about 00 μm is preferably used.

In the resist removing method of the present invention, an adhesive layer, preferably a pressure sensitive adhesive layer, is provided on an article such as a semiconductor wafer having a resist pattern, and if necessary, the resist material and the adhesive layer are brought into close contact with each other. A heating or pressurizing means for improving the property is added, and if the adhesive is a curable adhesive, an appropriate curing treatment by heating or light irradiation is performed. In consideration of the thermal effect on wafers and other articles, it is desirable to perform the curing treatment by irradiation with ultraviolet rays using the above-mentioned photocurable pressure-sensitive adhesive sheets. The irradiation dose of 30
It is preferable to set it to about 0 to 3000 mj / cm ² .

By this hardening treatment, the adhesive is hardened in the state of being integrated with the resist material, and the elastic modulus thereof can be remarkably increased to give the necessary tensile strength. The adhesive force between the adhesive layer and the resist can be increased to a certain value or more, and the adhesive force between the adhesive layer and the wafer portion where the resist does not exist can be increased because the adhesive layer and the resist penetrate into the concave portions of the substrate and harden. It can be lowered to a specific value or less, and as a result, an article such as a wafer can be easily peeled without leaving any resist material without contaminating the article.

[0030]

As described above, according to the resist removing method of the present invention, there is no fear that the work time when using the asher is prolonged and that impurity ions in the resist material are injected into the wafer, and the solvent is used. The effect of being able to remove the resist material very easily and surely without deteriorating the work environment and without causing the problem of contamination of the article because of not using.

[0031]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments. Hereinafter, “parts” means “parts by weight”. Reference Example 1 A naphthol quinone diazide of a cresol novolac resin and a polyhydroxy compound was formed on a wafer having a 5-inch silicon wafer with an oxide film (SiO ₂ film) or nitride film (Si ₃ N ₄ film) processed by CVD. Positive photoresist consisting of sulfonic acid ester and ethyl lactate 1μm
To form a resist pattern (film image) on the entire surface, and then apply P ⁺ ions at an acceleration energy of 80 keV with a high dose of 1 × 10 ¹⁶ ions / cm ^2. Was injected over the entire surface (hereinafter referred to as resist film image A).

Reference Example 2 A positive photoresist consisting of cresol novolac resin, naphthoquinone diazide sulfonic acid ester of polyhydroxy compound and ethyl lactate was coated on the surface of a 5-inch silicon wafer to a thickness of 5 μm, and heated, exposed and developed. After forming a resist pattern (film image) on the entire surface, P ⁺ ions are implanted over the entire surface at a high energy of acceleration energy of 3.0 MeV and a dose of 5 × 10 ¹³ ions / cm ^2. Resist film image B).

Example 1 80 parts of n-butyl acrylate, 15 ethyl acrylate
Part of the monomer mixture consisting of 5 parts of acrylic acid and 150 parts of ethyl acetate and 0.2 part of azobisisobutyronitrile were subjected to solution polymerization at 60 ° C. for 12 hours in a nitrogen atmosphere to give a weight average molecular weight of 560,000. Acrylic polymer solution A was obtained. In this solution A, 30 parts of polyester diacrylate as a polymerizable unsaturated compound, 3 parts of diphenylmethane diisocyanate as a polyfunctional compound, and 3 parts of α-hydroxycyclohexyl phenyl ketone as a polymerization initiator were uniformly added to 100 parts of an acrylic polymer. To prepare a curable pressure-sensitive adhesive solution. This curable pressure-sensitive adhesive solution was applied onto a polyester film having a thickness of 50 μm so that the thickness after drying would be 40 μm, and dried at 130 ° C. for 3 minutes to prepare a resist-removing adhesive sheet. The obtained adhesive sheet for resist removal has a 180 ° peeling adhesive force of the cured adhesive to the resist film, and the oxide film (SiO ₂ film) and nitride film (Si) on the wafer surface.
_The 180 ° peel adhesion strength to ₃ N ₄ film) was measured in the following manner, and the results are shown in Table 1.

[Measurement of 180 ° Peeling Adhesive Force] For measuring the adhesive force with respect to the resist film, a silicon wafer prepared in the same manner as in Reference Example 1 without applying a pattern was used. As an uncoated part, an oxide film (1000 Å, CVD) to be processed on the silicon wafer when the resist film is formed.
Process) and a wafer with a nitride film (1000 Å, CVD process) were used. Width 10 mm, length 1 on these wafers
Adhere a strip of adhesive sheet of 00mm, 130 ℃
After being heated for 30 seconds, the film was irradiated with ultraviolet rays from the film substrate side with a high pressure mercury lamp at an irradiation amount of 1 J / cm ² to be cured, and the adhesive strength after curing was measured. Each measurement is at 23 ℃, 65% RH, peeling speed 300mm
/ Min, and the peeling angle was 180 °.

Next, the obtained resist removing adhesive sheet was attached to the entire surface of the resist film image of the above-mentioned reference example,
After heating and pressing at 130 ° C. for 30 seconds, ultraviolet rays were irradiated with a high pressure mercury lamp at an irradiation amount of 1 J / cm ² to cure the adhesive sheet. Then, the adhesive sheet, 23 ℃, 65%
Peeling speed 300 mm / min, peeling angle 18 in RH atmosphere
When peeled off at 0 °, the resist was easily peeled off together with the adhesive sheet. Further, when the surface of the wafer after peeling was observed with a fluorescence microscope, no adhesion of an adhesive was observed and no contamination of the surface of the wafer was observed.

Example 2 To the solution A of the acrylic polymer obtained in Example 1, 50 parts of polyethylene glycol dimethacrylate as a polymerizable unsaturated compound was added to 100 parts of the acrylic polymer.
A curable pressure-sensitive adhesive solution was prepared by uniformly mixing 50 parts of epoxy acrylate, 3 parts of tolylene diisocyanate as a polyfunctional compound, and 5 parts of α-hydroxycyclohexyl phenyl ketone as a polymerization initiator. Using this curable pressure-sensitive adhesive solution, in the same manner as in Example 1,
An adhesive sheet for resist removal was produced. The resist film of the adhesive after curing of the obtained adhesive sheet for resist removal, the oxide film (SiO ₂ film) and the nitride film (Si ₃ N) on the wafer surface
_The 180 ° peeling adhesive force to the ₄ films) was measured in the same manner as above, and the results are shown in Table 1. Next, using this resist removing adhesive sheet, in the same manner as in Example 1,
When the resist film image on the silicon wafer was peeled and removed, the resist was easily peeled and removed integrally with the adhesive sheet. Further, when the surface of the wafer after peeling was observed with a fluorescence microscope, no adhesion of an adhesive was observed and no contamination of the surface of the wafer was observed.

Example 3 50 parts of polyethylene glycol dimethacrylate as a polymerizable unsaturated compound was added to 100 parts of the acrylic polymer in the solution A of the acrylic polymer obtained in Example 1.
A curable pressure-sensitive adhesive solution was prepared by uniformly mixing 50 parts of urethane acrylate, 3 parts of tolylene diisocyanate as a polyfunctional compound, and 5 parts of α-hydroxycyclohexyl phenyl ketone as a polymerization initiator. Using this curable pressure-sensitive adhesive solution, in the same manner as in Example 1,
An adhesive sheet for resist removal was produced. The resist film of the adhesive after curing of the obtained adhesive sheet for resist removal, the oxide film (SiO ₂ film) and the nitride film (Si ₃ N) on the wafer surface
_The 180 ° peeling adhesive force to the ₄ films) was measured in the same manner as above, and the results are shown in Table 1. Next, using this resist removing adhesive sheet, in the same manner as in Example 1,
When the resist film image on the silicon wafer was peeled and removed, the resist was easily peeled and removed integrally with the adhesive sheet. Further, when the surface of the wafer after peeling was observed with a fluorescence microscope, no adhesion of an adhesive was observed and no contamination of the surface of the wafer was observed.

Example 4 50 parts of trimethylolpropane triacrylate as a polymerizable unsaturated compound, 100 parts of ethoxylated pentaerythritol tetraacrylate, and 100 parts of a polyfunctional compound with respect to 100 parts of polyacrylic acid having a weight average molecular weight of 4,000,000. A curable pressure-sensitive adhesive solution was prepared by uniformly dissolving and mixing 2 parts of tolylene diisocyanate and 5 parts of α-hydroxycyclohexyl phenyl ketone as a polymerization initiator. Using this curable pressure-sensitive adhesive solution, an adhesive sheet for resist removal was prepared in the same manner as in Example 1. The 180 ° peeling adhesive strength of the obtained adhesive sheet for removing resist to the resist film of the cured adhesive, the oxide film (SiO ₂ film) and the nitride film (Si ₃ N ₄ film) on the wafer surface was the same as above. The measurement was performed, and the results are shown in Table 1. Next, using this resist removing adhesive sheet, Example 1
When the resist film image on the silicon wafer was peeled and removed in the same manner as above, the resist was easily peeled and removed integrally with the adhesive sheet. In addition, when the surface of the wafer after peeling was observed with a fluorescence microscope, no adhesion of adhesive was observed,
No contamination of the wafer surface was observed.

Example 5 100 parts of polyacrylic acid having a weight average molecular weight of 4,000,000, 100 parts of ethoxylated trimethylolpropane triacrylate as a polymerizable unsaturated compound, 3 parts of diphenylmethane diisocyanate as a polyfunctional compound, polymerization initiation A curable pressure-sensitive adhesive solution was prepared by uniformly dissolving and mixing 3 parts of α-hydroxycyclohexyl phenyl ketone as an agent. Using this curable pressure-sensitive adhesive solution, an adhesive sheet for resist removal was prepared in the same manner as in Example 1. The resist film of the adhesive after curing of the obtained adhesive sheet for resist removal, the oxide film (SiO 2) on the wafer surface
_The 180 ° peel adhesion strength to the _two films) and the nitride film (Si ₃ N ₄ film) was measured in the same manner as above, and the results are shown in Table 1. Next, when the resist film image on the silicon wafer was peeled off by using this resist removing adhesive sheet in the same manner as in Example 1, the resist was easily peeled off together with the adhesive sheet. Further, when the surface of the wafer after peeling was observed with a fluorescence microscope, no adhesion of an adhesive was observed and no contamination of the surface of the wafer was observed.

Comparative Example 1 In the solution A of the acrylic polymer obtained in Example 1, 50 parts of polyethylene glycol methacrylate as a polymerizable unsaturated compound and tolylene diisocyanate 3 as a polyfunctional compound were added to 100 parts of the acrylic polymer. Parts and 3 parts of α-hydroxycyclohexyl phenyl ketone as a polymerization initiator were uniformly mixed to prepare a curable pressure-sensitive adhesive solution. Using this curable pressure-sensitive adhesive solution, an adhesive sheet for resist removal was prepared in the same manner as in Example 1. Resist film of the adhesive after curing the obtained adhesive sheet for resist removal, oxide film (SiO ₂ film) on the wafer surface
The 180 ° peel adhesion strength to the nitride film (Si ₃ N ₄ film) and the nitride film (Si ₃ N ₄ film) were measured in the same manner as above, and the results are shown in Table 1. Next, using this resist removal adhesive sheet,
When the resist film image on the silicon wafer was peeled and removed in the same manner as in Example 1, the resist was not peeled and removed integrally with the adhesive sheet, and the adhesive force to the wafer peripheral portion (resist uncoated portion) was too large. As a result, the peeling work could not be performed easily, and the wafer surface was also contaminated.

Comparative Example 2 In the solution A of the acrylic polymer obtained in Example 1, 100 parts of the acrylic polymer, 50 parts of epoxy acrylate as a polymerizable unsaturated compound, and 3 parts of tolylene diisocyanate as a polyfunctional compound. , As a polymerization initiator
-Hydroxycyclohexyl phenyl ketone (3 parts) was uniformly mixed to prepare a curable pressure-sensitive adhesive solution. Using this curable pressure-sensitive adhesive solution, an adhesive sheet for resist removal was prepared in the same manner as in Example 1. The resist film of the adhesive after curing of the obtained adhesive sheet for resist removal, the oxide film (SiO ₂ film) and the nitride film (S) on the wafer surface
The 180 ° peel adhesive strength to the i ₃ N ₄ film) was measured in the same manner as above, and the results are shown in Table 1. Next, using this adhesive sheet for resist removal, the resist film image on the silicon wafer was peeled and removed in the same manner as in Example 1. The resist was not peeled and removed integrally with the adhesive sheet, and the wafer peripheral portion was removed. The adhesive strength to the (non-resist coated portion) was too large, the peeling work could not be easily performed, and the wafer surface was also contaminated.

Comparative Example 3 Polyester tape No. 31 manufactured by Nitto Denko (base material: polyethylene terephthalate film (80 μm thick), adhesive:
Acrylic) is used at room temperature (20 ° C.) for resist, oxide film (SiO ₂ film) and nitride film (Si ₃ N) on the wafer surface.
_The 180 ° peeling adhesive force to the ₄ films) was measured in the same manner as described above, and the results are shown in Table 1. Next, using this adhesive sheet for resist removal, the resist film image on the silicon wafer was peeled and removed in the same manner as in Example 1. The resist was not peeled and removed integrally with the adhesive sheet, and the wafer peripheral portion was removed. The adhesive strength to the (non-resist coated portion) was too large, the peeling work could not be easily performed, and the wafer surface was also contaminated.

From the above table, it can be seen that the resist material can be satisfactorily removed from the wafer by the resist removing method of the present invention.

[0044]

[Table 1]

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Claims (4)

[Claims] 1. A method for removing a resist in which an adhesive layer is provided on an article in which a resist is partially present, and the adhesive layer and the resist material are integrally peeled from the article. The 180 ° peeling adhesive strength to the resist is 5g / 10mm or more, and the 180 ° peeling adhesive strength to the article of the adhesive layer where the resist does not exist is 150g.
A resist removing method characterized by being set to be less than / 10 mm. 2. The method for removing a resist according to claim 1, wherein the adhesive layer is an adhesive sheet having an ultraviolet curable adhesive on a base material. 3. An adhesive or an adhesive sheet used for peeling and removing a resist existing on an article, comprising:
The 180 ° peeling adhesive strength of the adhesive layer to the resist at the time of peeling is 5 g / 10 mm or more, and the 180 ° peeling adhesive force of the adhesive layer to the article where the resist does not exist is 15
Adhesives or adhesive sheets for resist removal set to be less than 0 g / 10 mm. 4. The adhesive removing adhesive sheet according to claim 3, wherein the adhesive layer is an adhesive sheet having an ultraviolet curable adhesive on a substrate.