JPH07183196A - Multi-stage removal method of resists and resist peeling sheets based on the method - Google Patents

Abstract

PURPOSE:To remove a resist film image easily and definitely by performing at least two-stage treatment which pastes a pressure sensitive adhesive sheet having affinity with a front layer to the front layer of a resist and peels the layer then removes the lower layer of a residual resist from a substrate. CONSTITUTION:A first pressure sensitive adhesive sheet is pasted on the front layer of a resist adulterated and modified by implanting ions. The adhesive sheets and the front layer of the resist are peeled in one piece. The first pressure sensitive adhesive sheets used here are not limited to any specific type as long as they have affinity with the front layer with the resist. However, it is more favorable to use such pressure sensitive adhesive which contains amine groups and or alcohol groups especially for a pressure sensitive polymer. Furthermore, from the viewpoint of preventing a semiconductor substrate from contaminating, it is more favorable to use a curing type pressure sensitive adhesive. Mechanical removal, such as conventional ashing or tape peeling may be cited applicable to remove the lower layer of the resist. Especially, the application of pressure sensitive adhesive sheets is more favorable to peel.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image (resist pattern) formed of a resist that is no longer needed during the manufacture of various types of microfabricated components such as semiconductors, circuits, various printed boards, various masks, and lead frames. The present invention relates to sheets, such as a resist stripping sheet or tape, which are preferably used for stripping and removing the remaining resist), and a resist stripping and removing method using the same.

Hereinafter, the present invention will be described with reference to the example of semiconductor device manufacturing, but the present invention is not limited to the use as long as it is an article having an image made of a resist material.

[0003]

2. Description of the Related Art For example, in the manufacture of semiconductor devices, a resist material is applied onto a semiconductor substrate such as a silicon wafer and a predetermined image (resist pattern) is formed by an ordinary photo process. Using this as a mask, various processes such as ion implantation, etching, and doping are performed. After that, the unnecessary image is removed and a predetermined circuit is formed. Next, in order to form the next circuit, the cycle of applying the resist material again is repeated. Also, when circuits are formed on various substrates, unnecessary images are removed after image formation. At this time, the image of the resist material that is no longer needed is removed by using an asher (ashing means), a solvent (peeling liquid),
It is generally performed with chemicals.

[0004]

However, if the asher is used for removing the image, the work may take a long time and the impurity ions in the resist material may be implanted into the wafer. In addition, the use of solvents and chemicals has caused a problem of damaging the working environment.

In order to solve this problem, the present applicants have the following advantages when removing the unnecessary resist on the semiconductor substrate.
A resist stripping method using a pressure-sensitive adhesive sheet has been proposed (Japanese Patent Application No. 3-88053). However, there are some cases where the adhesiveness of the pressure-sensitive adhesive sheet to the resist surface is low, and there are some places, which causes a problem that the releasability of the resist decreases. Therefore, it may be possible to improve the wettability of the pressure-sensitive adhesive to be used on the resist surface (for example, JP-A-4-345015), but the adhesiveness after curing is reduced and the cohesive force of the adhesive is reduced. Then, there was a problem that the adhesive residue was likely to remain.

Particularly when the above-mentioned ions are implanted into the upper surface layer of the resist film image, the upper surface layer of this image is cured,
Since the upper surface layer is deteriorated and has high heat resistance and low reactivity, there is a problem that the conventional ashing means requires a long time for the removing work and is practically difficult to remove. Furthermore, when the normal ashing means is used, the impurity ions in the resist material and the ions remain on the semiconductor substrate and are injected into the semiconductor substrate by the subsequent heat treatment, making it impossible to construct the semiconductor integrated circuit as designed. Therefore, there is a problem that the characteristics of the semiconductor device are deteriorated. Therefore, according to the present invention, an unnecessary resist film image on a semiconductor substrate, in particular, a surface layer of an ion-implanted resist whose removal is rate-determining can be simply and surely performed by a novel method completely different from the conventional method. The purpose is to provide a method that can be removed.

[0007]

The inventors of the present invention can easily and surely remove a resist film image on a product such as a semiconductor substrate by removing the unnecessary resist film image by a multi-step process of at least two steps. They found that they could be removed, and completed the present invention.

That is, according to the present invention, in a method of peeling and removing a resist existing on an article, a pressure-sensitive adhesive sheet having an affinity for this surface layer is attached on the surface layer of the resist, and the adhesive sheet and the resist are combined. The present invention relates to a multi-step method of removing a resist, which comprises removing the surface layer integrally, and then removing the remaining lower layer of the resist from the substrate, and resist stripping sheets used for this method.

[0009]

According to the multi-step method of removing a resist of the present invention, first, for example, the following first pressure-sensitive adhesive sheets are attached to the surface layer of a resist which has been modified by ion implantation and modified. The adhesive sheets and the surface layer of the resist are peeled together.

The first pressure-sensitive adhesive sheet used here is not particularly limited as long as it has an affinity with the surface layer of the resist, but in the present invention, particularly the pressure-sensitive adhesive polymer, amines and / or alcohol. It is preferable to use a pressure-sensitive adhesive containing a compound, and it is preferable to use a curable pressure-sensitive adhesive from the viewpoint of preventing contamination of the semiconductor substrate.

A curable pressure-sensitive adhesive containing such amines is a pressure-sensitive adhesive polymer containing or copolymerizing an amine compound or a monomer described below. The integration of the material and the adhesive can be promoted. As specific examples, for example, (1) a pressure-sensitive adhesive polymer, a curable pressure-sensitive adhesive obtained by containing an amine compound having a good affinity for a resist material, and (2) a pressure-sensitive adhesive polymer, A curable pressure-sensitive adhesive containing an amine-based compound having at least one reactive functional group in the molecule, and (3) a pressure-sensitive adhesive formed by copolymerizing an amine-based monomer with a pressure-sensitive adhesive polymer. Examples include pressure-sensitive adhesives.

The amine compound used in the above (1) must have good affinity with the resist material. Here, having a good affinity with the resist material means that the phenomenon of dissolving, swelling or destroying the resist material is remarkable, and also includes the phenomenon of migration or diffusion into the resist material. As a guideline for this, the resist material is sufficiently dried and the solvent is dipped in this amine compound and stored, for example, at 130 ° C. for 24 hours so that the resist material is dissolved, swelled or destroyed. Further, that the compound is non-volatile means that it is not easily volatilized in the step of coating and drying the adhesive.

Specific examples of such amine compounds include:
For example, tertiary amines such as triethylamine, trioctylamine and triethanolamine, secondary amines such as diisooctylamine and diethanolamine, stearylamine, aminonaphthol, 2-aminopropyl alcohol, m-xylylenediamine and the like. Other examples include primary amines, amine polymers such as polyethyleneimine and triethylenetetramine, and those having a primary to tertiary amino group. Among these, one kind or two or more kinds can be appropriately selected and used depending on the kind of the pressure-sensitive adhesive polymer used, the nonvolatile compound described later, the target resist material, and the like.

The amount of the amine compound used is usually 1 to 50 parts by weight, based on 100 parts by weight of the pressure-sensitive adhesive polymer.
It is preferably 5 to 30 parts by weight. If the amount used is too large, the adhesive may flow out during storage, and sometimes the adhesive may be cured, resulting in poor storage stability. On the other hand, if the amount is too small, the effect of removing the resist material becomes insufficient, which is not preferable.

In particular, this amine compound contributes to promoting the integration of the adhesive and the resist material when removing the resist which has been altered by the ion implantation step in the semiconductor wafer processing step.

At least 1 in the molecule in the above (2)
Examples of the amine-based compound having one reactive functional group include dialkylaminoalkyl (meth) acrylamide and / or (meth) represented by the following general formula [Chemical formula 1].
Acrylic acid dialkylaminoalkyl ester, an amine compound having at least one unsaturated double bond such as allylamine represented by the general formula [Chemical formula 2], or an epoxy group represented by the general formula [Chemical formula 3] Examples thereof include amine compounds having one or more compounds, compounds represented by the general formula [Chemical Formula 4], 3 or 4 vinylpyridine and its derivatives, and N-vinylcarbazole.

[0017]

[Chemical 1]

[0018]

[Chemical 2]

[0019]

[Chemical 3]

[0020]

[Chemical 4]

In the present invention, one or more of them are appropriately selected from these, depending on the type of the pressure-sensitive adhesive polymer to be used, the non-volatile compound described below, the target resist material and the like. Can be used.

The amount of the amine compound having at least one reactive functional group in the molecule is usually 1 to 100 parts by weight based on 100 parts by weight of the pressure sensitive adhesive polymer.
It is preferably 5 to 50 parts by weight. If the amount used is too large, the adhesive may flow out during storage, and sometimes the adhesive may be cured, resulting in poor storage stability. On the other hand, if the amount is too small, the effect of removing the resist material becomes insufficient, which is not preferable. In the present invention,
By using the amine compound having at least one reactive functional group in the molecule, the adhesive and the resist material as described above are used for removing the resist pattern which has been deteriorated due to, for example, the ion implantation step in the semiconductor wafer processing step. Has the effect of further promoting the integration with.

Examples of the amine-based monomer in the above (3) include dialkylaminoalkyl (meth) acrylamide and / or (meth) acrylic acid dialkylaminoalkyl ester represented by the following general formula [Chem. Examples thereof include allylamine represented by [Chemical formula 6], compounds represented by the general formula [Chemical formula 7], 3 or 4 vinylpyridine and its derivatives, vinylcarbazole and the like.

[0024]

[Chemical 5]

[0025]

[Chemical 6]

[0026]

[Chemical 7]

In the present invention, one or more of them are appropriately selected from these, depending on the type of the pressure-sensitive adhesive polymer to be used and the nonvolatile compound described below and the resist material to be targeted. Can be used.

The amount of these amine monomers used is usually 5 with respect to 100 parts by weight of the total amount of the other copolymerizable monomers.
˜200 parts by weight, preferably 5 to 50 parts by weight. If the amount used is too large, the elastic modulus of the polymer described below tends to be too low, and the releasability of the resist material tends not to improve. On the other hand, if it is too small, effects such as integration with the resist material become insufficient. It is not preferable.

In the present invention, by copolymerizing such an amine-based monomer, the same effects as those obtained by using the above-mentioned amine-based compound having a reactive functional group are obtained, and the stability of the obtained adhesive sheet itself or It also has the effect of increasing shelf life.

A curable pressure-sensitive adhesive containing alcohols is a pressure-sensitive adhesive polymer containing alcohols described below. By such a method, the resist material and the adhesive are combined. Integration can be promoted. Specific examples include oleyl alcohol, octyl alcohol, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol triacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl 2-hydroxypropyl. Examples include phthalate.

The content of such alcohols is usually 5 to
100 parts by weight, preferably 10 to 50 parts by weight are preferred. If the amount is too small, there is a problem that the releasability of the resist material may not be improved. On the other hand, if the amount is too large, the pressure-sensitive adhesive becomes extremely soft, sticky and practically difficult to handle. In addition, flow occurs during storage, resulting in poor storage resistance.

Means for removing the lower layer of the resist in the present invention include conventional mechanical removal such as ashing and tape peeling. In the present invention, peeling is particularly carried out using the following pressure-sensitive adhesive sheets. Preferably. As the pressure-sensitive adhesive of the second pressure-sensitive adhesive sheet, a pressure-sensitive adhesive obtained by containing a pressure-sensitive adhesive polymer with a hydrophilic oligomer and / or a monomer is preferably used.

The hydrophilic oligomer is not particularly limited as long as it has an affinity for the resist and can be copolymerized. Specific examples include urethane acrylate, oligoester acrylate, phenol novolac acrylate and bisphenol. The acrylic derivative of A and the like can be mentioned.

The hydrophilic monomer is not limited as long as it has an affinity for the resist and can be copolymerized. Specific examples include (poly) ethylene glycol (mono, di) (meth) acrylate and polypropylene. Glycol (mono, di) (meth) acrylate, various other polyfunctional acrylates, urethane acrylates, ester acrylates, polyhydric alcohol acrylates and the like can be mentioned.

The content of these hydrophilic oligomers and / or monomers is 5 to 150 parts by weight, preferably 10 to
It is 100 parts by weight. If it is less than such a range, the releasability of the resist material may not be improved, while if it is too large, the pressure-sensitive adhesive is softened and becomes extremely soft and sticky, resulting in difficult handling, or after UV irradiation. The pressure sensitive adhesive becomes extremely hard or brittle and "cracks"
May occur, or the tape base material may be cut to make it difficult to handle in practical use.

The first and second curable pressure-sensitive adhesives of the present invention have good affinity with the resist material for the pressure-sensitive adhesive polymer and have at least one unsaturated double bond in the molecule. Those containing the non-volatile compound have are preferable.

As the pressure-sensitive adhesive polymer, any of various known polymers applicable to general pressure-sensitive adhesives can be used, and particularly preferable polymers are alkyl acrylate and / or methacrylic acid. An acrylic polymer having an alkyl ester as a main monomer can be used.

This acrylic polymer is a main monomer described above, that is, an ester of acrylic acid or methacrylic acid with an alcohol having a carbon number of usually 12 or less, a monomer having a carboxyl group or a hydroxyl group if necessary, and other modifications. It can be obtained by polymerizing these using a monomer for use by a conventional method such as solution polymerization, emulsion polymerization, suspension polymerization and bulk polymerization.

Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, maleic acid,
Itaconic acid or the like is used, and as the hydroxyl group-containing monomer, for example, hydroxyethyl acrylate, hydroxypropyl acrylate or the like is used. The amount of these monomers used is preferably 20% by weight or less based on the total amount of all the monomers.

As the above-mentioned other modifying monomers, vinyl acetate, vinyl propionate, styrene, acrylonitrile, acrylamide, couglycidyl methacrylate and the like are used.

The molecular weight of the acrylic polymer composed of such monomers is usually 10 in terms of weight average molecular weight.
It is preferably from 10,000 to 2,000,000. If the molecular weight is too low, the viscosity will be low when the non-volatile compound described below is blended therein, and problems such as flowing during storage are likely to occur, and if it is too high, handling problems are likely to occur. Further, the acrylic polymer preferably has a glass transition point of 250 ° K or lower in consideration of workability at the time of image removal. If it is higher than this, it tends to be too hard after curing and the peeling tends to be heavy. However, it does not try to eliminate all the use of acrylic polymers having such a high glass transition point,
Of course, it can be used in some cases.

In the present invention, the pressure-sensitive adhesive polymer contains a non-volatile compound having a good affinity with a resist material and having at least one unsaturated double bond in the molecule. An adhesive sheet made of a pressure sensitive adhesive is preferably used. Here, having a good affinity with the resist material means that the phenomenon of dissolving, swelling or destroying the resist material is remarkable, and also includes the phenomenon of migration or diffusion into the resist material. As a guide for this, the resist material is sufficiently dried and the solvent is dipped in the non-volatile compound, and the resist material is dissolved, swelled or destroyed when stored at 130 ° C. for 24 hours. Further, that the compound is non-volatile means that it is not easily volatilized in the step of coating and drying the adhesive.

Such a non-volatile compound is said to be such that after adhesive sheets are pasted on an article such as a semiconductor substrate on which a resist film image is present, the resist material and the adhesive are integrated by the action of this compound and then cured. Have a function.
Therefore, this non-volatile compound is required to have at least one unsaturated double bond capable of being cured by heat or light in the molecule and to have good affinity with the resist material. It is also required that the polymer has good compatibility with the water-soluble polymer and does not flow out during storage.

Examples of such non-volatile compounds include phenoxy polyethylene glycol (meth) acrylate, ε-caprolactone (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and trimethylolpropane tri. (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, oligoester (meth) acrylate, and the like. Among these, the type of pressure-sensitive adhesive polymer to be used. One or two or more of them can be appropriately selected and used depending on the target resist material.

The amount of the non-volatile compound used is usually 5 to 20 with respect to 100 parts by weight of the pressure-sensitive adhesive polymer.
The amount is 0 parts by weight, preferably 10 to 100 parts by weight. If the amount used is too small, the peeling effect of the resist material may not be sufficient, and if it is too large, the adhesive may flow out during storage, which is not preferable.

In the above-mentioned curable pressure-sensitive adhesive used in the present invention, the pressure-sensitive adhesive polymer is cross-linked to increase cohesive force from the viewpoint of workability when applied to an article such as a semiconductor substrate. Is preferred. For example, an acrylic polymer obtained by copolymerizing a carboxyl group- or hydroxyl group-containing monomer as a pressure-sensitive adhesive polymer is used, and a polyfunctional compound that reacts with the functional group of the polymer, such as polyisocyanate, polyepoxy, various metal salts, By containing a chelate compound or the like in the adhesive, the above reaction can be promoted in the step of forming a sheet or the like to crosslink the polymer.

The amount of the polyfunctional compound used is usually 20 parts by weight or less with respect to 100 parts by weight of the pressure-sensitive adhesive polymer. Within this range, the higher the molecular weight of the polymer, the lower the molecular weight of the polymer. , May be selected as appropriate.
If the amount of the polyfunctional compound used is too large, the adhesive strength will decrease, which is not preferable.

The curable pressure-sensitive adhesive may also contain a filler such as finely divided silica for the same purpose as the use of the above polyfunctional compound. Further, various additives such as a tackifier, a colorant and an anti-aging agent may be contained if necessary. The amount of these used may be in the usual range.

To the curable pressure-sensitive adhesive which can contain such various components, a polymerization initiator suitable for the curing means can be added. For example, in the case of heat curing, benzoyl peroxide, a thermal polymerization initiator such as azobisisobutyronitrile that generates radicals by heating is used, and in the case of photocuring such as ultraviolet light, benzoin, benzoin ethyl ether, A photopolymerization initiator that generates radicals by light irradiation such as dibenzyl is used. These polymerization initiators are usually used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive polymer.

When used, such a curable pressure-sensitive adhesive can be formed into a sheet or tape by itself, but it is usually dried on a film substrate. To be about 10 to 180 μm, and the adhesive-peeling adhesive sheets of the present invention can be obtained. As such a film substrate, for example,
A resin film made of polyethylene, polypropylene, polyethylene terephthalate, polyurethane, polyvinyl chloride, saponified ethylene-vinyl acetate copolymer or the like and having a thickness of about 12 to 100 μm is usually used. In such a case, a material that transmits light such as ultraviolet rays is selected and used.

In the multi-step method of removing a resist according to the present invention, an adhesive sheet using the curable pressure-sensitive adhesive having the above-mentioned constitution is stuck on the surface layer of the resist existing on an article such as a semiconductor substrate to form a resist. After the surface layer and the adhesive are integrated, a predetermined curing treatment is performed by heating or light irradiation. At this time, when the thermal effect on the semiconductor substrate is taken into consideration, the curing treatment by light irradiation is particularly suitable, and the irradiation amount of ultraviolet rays is usually 100 to 5000 m.
j / cm ² and it is preferably in the range of 300~3000mj / 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 is remarkably increased, and accordingly, the adhesive force between the resist surface layer and the lower layer is greatly reduced. As a result, by peeling off the adhesive sheets after the curing, the resist surface layer on the substrate can be easily and completely peeled off together with the adhesive sheets.

In the present invention, the second pressure-sensitive adhesive sheet composed of the second pressure-sensitive adhesive is then attached onto the remaining resist on the article, and the adhesive sheet and the resist lower layer are integrated. The resist layer can be easily and completely removed by peeling.

From the viewpoint of preventing contamination of the semiconductor substrate, it is preferable that the adhesive sheets used in the present invention are affixed with a curable pressure-sensitive adhesive having particularly good affinity with the resist agent. At this time, the resist material and the adhesive are favorably adhered and integrated, but in order to promote the adherence and integration, heating and / or pressure may be applied during the adhering.

Further, in the present invention, the above steps may be carried out at least twice, and it is also possible to repeat them more than once.

[0056]

As described above, according to the present invention, the resist on an article such as a semiconductor substrate can be easily and surely removed.

[0057]

EXAMPLES The present invention will be described below based on examples. In addition, "parts" means "parts by weight".

Reference Example 1 A surface of a silicon wafer (semiconductor substrate) was coated with a resist material composed of cresol novolac resin and naphthoquinone diazide, heated, exposed and developed to form a resist film image on the entire surface. ⁺ Ion acceleration energy 8
The entire surface was implanted at a high concentration of 0 keV and a dose amount of 1 × 10 ¹⁶ ions / cm ² .

Example 1 (Production of Adhesive Sheet 1 for Removing Resist Surface Layer) 80 parts of n-butyl acrylate, 15 parts of ethyl acrylate
Part of the monomer mixture consisting of 5 parts of acrylic acid and 150 parts of ethyl acetate and 0.1 part of azobisisobutyronitrile were subjected to solution polymerization at 60 ° C. for 12 hours under a nitrogen stream to give a weight average molecular weight of 56. The glass transition point is 231 °
A solution of the acrylic polymer of K was obtained. In 250 parts of this acrylic polymer solution, 10 parts of triethanolamine as an amine compound, 100 parts of oligoester acrylate as a non-volatile compound, and DETX-S5 as a polymerization initiator.
The parts were uniformly mixed to obtain a curable pressure-sensitive adhesive solution. Next, this curable pressure-sensitive adhesive solution was added to a thickness of 5
On a 0μm polyester film, the thickness after drying is 5
It was applied so as to have a thickness of 0 μm and dried at 150 ° C. for 10 minutes to prepare an adhesive sheet 1 for peeling a resist surface layer of the present invention.

Example 2 (Production of Adhesive Sheet 2 for Removing Resist Surface Layer) A monomer mixture consisting of 60 parts of 2-ethylhexyl acrylate, 30 parts of butyl acrylate, 5 parts of vinyl acetate and 5 parts of acrylic acid was used in Example 1 Polymerization was carried out in the same manner as above to obtain a solution of an acrylic polymer having a weight average molecular weight of 620,000 and a glass transition point of 217 ° K. To 250 parts of this acrylic polymer solution, 10 parts of trioctylamine as an amine compound, 15 parts of epoxy acrylate and 1 part of polyethylene glycol dimethacrylate as a non-volatile compound.
0 part and 1843 parts of the photopolymerization initiator Irgacure were uniformly mixed to obtain a curable pressure-sensitive adhesive solution, and in the same manner as in Example 1, an adhesive tape for a resist surface layer peeling adhesive sheet 2 was obtained.

Comparative Example 1 An adhesive tape was obtained in the same manner as in Example 1 except that the triethanolamine of Example 1 was omitted.

Comparative Example 2 An adhesive tape was obtained in the same manner as in Example 2, except that 10 parts of trioctylamine in Example 2 was replaced with 3 parts of triphenylphosphine.

Example 3 (Production of adhesive sheet 3 for peeling resist surface layer) [0063] Adhesion for peeling resist surface layer in the same manner as in Example 1 except that 10 parts of triethanolamine in Example 1 was replaced with 5 parts of xylylenediamine. Sheet 3 was obtained.

Example 4 (Production of Adhesive Sheet 4 for Removing Resist Surface Layer) An adhesive sheet 4 was obtained in the same manner as in Example 2 except that 10 parts of trioctylamine in Example 2 was replaced with 5 parts of stearylamine. It was

Example 5 (Production of Adhesive Sheet 5 for Removing Resist Surface Layer) 250 parts of the acrylic polymer solution obtained in Example 1 was added to tetraglycidyl meta as an amine compound having at least one reactive group in the molecule. Xylene diamine 15
Parts, 50 parts of polyethylene glycol dimethacrylate as a non-volatile compound, and 3 parts of a photopolymerization initiator were uniformly mixed to obtain a curable pressure-sensitive adhesive solution. Next, 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 50 μm, and dried at 150 ° C. for 10 minutes to obtain the resist of the present invention. An adhesive sheet 5 for peeling the surface layer was produced.

Example 6 (Production of Adhesive Sheet 6 for Removing Resist Surface Layer) In the same manner as in Example 5 except that 15 parts of tetraglycidyl metaxylenediamine was replaced by 25 parts of dimethylaminopropylacrylamide. An adhesive sheet 6 was obtained.

Example 7 (Production of Adhesive Sheet 7 for Removing Resist Surface Layer) 250 parts of the acrylic polymer solution obtained in Example 2 was added to dimethylaminoethyl as an amine compound having at least one reactive group in the molecule. 20 parts of acrylate, 20 parts of epoxy acrylate as a non-volatile compound, and 3 parts of a photopolymerization initiator were uniformly mixed to obtain a curable pressure-sensitive adhesive solution, and then an adhesive sheet 7 was obtained in the same manner as in Example 5. It was

Example 8 (Production of Adhesive Sheet 8 for Removing Resist Surface Layer) 250 parts of the acrylic polymer solution obtained in Example 2 was added to diethylaminopropyl methacrylate as an amine compound having at least one reactive group in the molecule. 15
Part, 50 parts of polyethylene glycol dimethacrylate as a non-volatile compound, and 3 parts of a photopolymerization initiator are uniformly mixed to obtain a curable pressure-sensitive adhesive solution, and then an adhesive sheet 8 is obtained in the same manner as in Example 5. It was

Comparative Example 3 Diethylaminopropyl methacrylate 15 of Example 8
An adhesive tape was obtained in the same manner as in Example 8 except that the parts were omitted.

Example 9 (Production of Adhesive Sheet 9 for Removing Resist Surface Layer) A monomer mixture consisting of 80 parts of n-butyl acrylate, 25 parts of dimethylaminopropyl acrylamide, 15 parts of ethyl acrylate and 5 parts of acrylic acid was mixed with ethyl acetate. 15
Using 0 part and 0.1 part of azobisisobutyronitrile,
Solution polymerization was carried out at 60 ° C. for 12 hours under a nitrogen stream to obtain an acrylic polymer solution having a weight average molecular weight of 360,000 and a glass transition point of 241 ° K in which an amine monomer was copolymerized. To 250 parts of this acrylic polymer solution, 25 parts of epoxy acrylate as a non-volatile compound and 3 parts of a photopolymerization initiator were uniformly mixed to obtain a curable pressure-sensitive adhesive solution. Next, 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 50 μm, and dried at 150 ° C. for 10 minutes to obtain the adhesive of the present invention. Sheet 9 was prepared.

Comparative Example 4 An adhesive tape was prepared in the same manner using the acrylic polymer solution (weight average molecular weight: 560,000, glass transition point: 246 ° K) copolymerized except for dimethylaminopropylacrylamide in Example 9. Obtained.

Example 10 (Production of adhesive sheet 10 for peeling resist surface layer) 60 parts of 2-ethylhexyl acrylate, 30 parts of butyl acrylate, 5 parts of vinyl acetate, 5 parts of acrylic acid, 20 parts of dimethylaminoethyl methacrylate The monomer mixture was polymerized in the same manner as in Example 9 to obtain an acrylic polymer solution having a weight average molecular weight of 650,000 and a glass transition point of 228 ° K and copolymerized with an amine monomer. To 250 parts of this acrylic polymer solution, polyethylene glycol dimethacrylate 40 was added as a non-volatile compound.
Parts and 3 parts of a photopolymerization initiator were uniformly mixed to obtain a basic curable pressure-sensitive adhesive solution, and an adhesive sheet 10 was obtained in the same manner as in Example 9.

Comparative Example 5 Dimethylaminoethyl methacrylate 20 of Example 10
An adhesive tape was obtained in the same manner using a solution of an acrylic polymer (weight average molecular weight: 620,000, glass transition point: 207 ° K) copolymerized except for a part.

Example 11 (Production of Adhesive Sheet 1 for Removing Lower Layer of Resist) 100 parts of the acrylic polymer of Example 1 was mixed with 4 parts of polyethylene glycol acrylate (weight average molecular weight: 500).
What added 0 part and 3 parts of urethane type photocrosslinking agents was apply | coated so that the thickness after drying might be 30 micrometers on the polyester film, and the adhesive sheet 1 for lower layer peeling was obtained.

Example 12 (Production of adhesive sheet 2 for peeling resist underlayer) In Example 10, a polymer obtained from a monomer mixture except for dimethylaminoethyl acrylate (weight average molecular weight: 800,000, glass transition point 233 °). K) 10
1 part of pentaerythritol triacrylate to 0 part
A mixture obtained by adding 0 parts and 30 parts of diethylene glycol diacrylate and mixing 3 parts of a photopolymerization initiator was applied on a polyester film so that the thickness after drying was 50 μm, to obtain a lower layer peeling adhesive sheet 2. .

Example 13 (2-step removal) Examples 1 to 10 were formed on the surface layer of the resist in Reference Example 1.
And the adhesive sheets of Comparative Example 5 were respectively attached, the adhesive sheets and the surface layer of the resist were integrally peeled off, and then Example 11 or Example 1 was formed on the remaining lower layer of the resist.
The adhesive sheet No. 2 was attached, and the adhesive sheets and the surface layer of the resist were integrally peeled off.

The results are shown in Tables 1 and 2 below.
It is understood that the method of the present invention can surely remove and remove the resist on the wafer surface. Here, each peeling area (%) means the ratio of the area where the resist was actually peeled off to the peeled area.

[0078]

[0079]

Front page continuation (72) Inventor Kaoru Aizawa 1-2 1-2 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto Denko Corporation

Claims (5)

[Claims] 1. A method of peeling and removing a resist existing on an article, wherein a pressure-sensitive adhesive sheet having an affinity with this surface layer is attached onto the surface layer of the resist, and the adhesive sheet and the surface layer of the resist are bonded together. A multi-step method for removing a resist, which comprises removing the resist underlayer from the substrate after peeling off the resist integrally. 2. The method for removing resist in multiple steps according to claim 1, wherein the article is a semiconductor substrate, and the surface layer of the resist is a layer ion-implanted in a semiconductor manufacturing process. 3. The resist according to claim 1, wherein the means for removing the lower layer of the resist from the article attaches pressure-sensitive adhesive sheets and peels the adhesive sheet and the lower layer of the resist together. Multi-step removal method. 4. A pressure-sensitive adhesive sheet for peeling a surface layer of a resist in the multi-step method for removing a resist according to claim 1 or 2, wherein the pressure-sensitive adhesive is an amine on a pressure-sensitive adhesive polymer. A sheet for resist stripping, which is a pressure-sensitive adhesive containing a group and / or an alcohol. 5. A pressure-sensitive adhesive sheet for peeling a lower layer of a resist in the multi-step method for removing a resist according to claim 3, wherein the pressure-sensitive adhesive has a hydrophilic property to a pressure-sensitive adhesive polymer. Sheets for resist stripping, which are pressure-sensitive adhesives containing an oligomer and / or a monomer.