TWI422996B - Particle-containing resist peeling liquid and peeling method by using it - Google Patents

Description

Particle-containing photoresist stripping solution and peeling method using same

The present invention relates to a particle-containing photoresist stripping solution and a stripping method using the same.

In the manufacture of a semiconductor device, a general method of transferring a pattern to a semiconductor substrate such as a germanium wafer is photolithography. For example, by performing ion implantation to form a source region or a drain region at a predetermined position, it is then performed by selectively removing the photoresist in accordance with dry etching or the like to form a predetermined semiconductor element.

The photoresist has the property of being deteriorated by surface deterioration by ion implantation or heating or the like. For example, a photoresist having undergone ion implantation has a double structure composed of a photoresist layer having a surface hardened and a relatively soft photoresist layer which has not been deteriorated inside. In general, although the photoresist can be easily removed by using an organic solvent, the photoresist which has been subjected to ion implantation cannot be easily removed because its surface is hardened. Therefore, in this case, although it is intended to be removed by performing the ashing step, if only the ashing step is removed, there is a problem that the substrate is damaged. In addition, in another method, a method in which a paste such as cerium oxide is supplied to a surface-hardened photoresist while the polishing pad is subjected to mechanical processing by rubbing the surface hardened layer is disclosed (Patent Document 1).

Further, it has been disclosed that the surface hardening layer is removed by combining the mechanical processing steps with sulfuric acid washing, sulfuric acid washing with water, organic solvent washing, ozone washing, ozone vapor washing, steam washing or ultraviolet irradiation washing. Method Li literature 1).

Further, there has been disclosed a method of using at least one of the above-described mechanical processing, washing, megasonic cleaning, ultrasonic cleaning, two-fluid cleaning, steam cleaning, and supercritical cleaning. In the washing method, the surface hardened layer is removed without the necessity of supplying the paste (Patent Document 1).

However, in the removal method according to the above-described machining, in particular, there is a problem of the structure of the semiconductor substrate circuit in the case of damaging the fine wiring. In the method of combining the machining step and the cleaning step, since there are two steps, There will be problems that require time and unfavorable production. Further, in the cleaning method, the peeling property of the surface hardened layer from the semiconductor substrate is insufficient, and when it is strongly washed, there is a problem that the circuit structure of the semiconductor substrate is damaged.

In the manufacture of a liquid crystal display device, for example, in the case of a thin film transistor panel process of an active matrix type liquid crystal display device, a gate insulating film or a protective film is often formed by tantalum nitride. Then, the tantalum nitride film as the film to be processed is a mask formed thereon, and when the dry etching using a gas containing CF ₄ or SF ₆ is performed, the surface of the photoresist pattern is deteriorated. A surface metamorphic layer will form. Therefore, in this case, a method for removing a photoresist has been disclosed which comprises a step of treating with a photoresist stripping solution containing monoethanolamine as a main component, and performing megasonic cleaning or ultrasonic washing in ozone water. The net step (Patent Document 2).

In addition, a method for removing a photoresist is disclosed, which comprises the steps of performing a treatment using a photoresist stripping solution containing monoethanolamine as a main component, and performing megasonic cleaning or ultrasonic cleaning in hydrogen water ( Special Li literature 3).

However, in the photoresist removal method including the step of using a photoresist stripping solution containing monoethanolamine as a main component, and the step of performing megasonic cleaning or ultrasonic cleaning, since it is necessary to have two steps, There will be problems such as time and unfavorable production.

Patent Document 1: Japanese Patent Laid-Open No. 2006-186100

Patent Document 2: Japanese Patent Laid-Open No. 2006-24822

Patent Document 3: Japanese Patent Laid-Open No. 2006-24823

The problem to be solved by the present invention is to provide a photoresist stripping liquid excellent in peelability. Further, another object to be solved by the present invention is to provide a photoresist peeling liquid method which is excellent in photoresist peeling property and does not damage the circuit structure.

The above object is achieved by the following technical means disclosed: <1> A photoresist stripping liquid characterized by containing particles and at least one compound selected from the group consisting of an amine compound and an alkylene glycol. .

<2> The photoresist peeling liquid disclosed in <1>, which contains an amine compound and an alkylene glycol.

<3> The photoresist peeling liquid disclosed in <1>, wherein the primary particle diameter of the particles is 5 to 1,000 nm.

<4> The photoresist peeling liquid disclosed in <1>, wherein the particle is selected from the group consisting of cerium oxide, aluminum oxide, cerium oxide and titanium nitride. The inorganic particles, and/or the organic resin selected from the group consisting of epoxy resin, styrene resin and acrylic resin.

<5> The photoresist peeling liquid disclosed in <1>, wherein the concentration of the particles is 0.1 to 20% by weight with respect to the resist stripping solution.

<6> The photoresist peeling liquid disclosed in <1>, wherein the amine compound is monoethanolamine, diethylamine, N-ethylethanolamine, N-n-butylethanolamine, N,N-diethylethanolamine, four At least one selected from the group consisting of methylammonium hydroxides.

<7> The photoresist peeling liquid disclosed in <1>, wherein the alkylene glycol is ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether , ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol diacetate Ester, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol Selected from the group consisting of alcohol monobutyl ether, diethylene glycol diester ester, and triethylene glycol diacetate.

<8> The photoresist stripper disclosed in <1>, wherein the total amount of the amine compound and the alkylene glycol is from 10 to 90% by weight based on the resist stripper.

<9> A photoresist peeling method comprising the steps of: preparing a photoresist stripping liquid disclosed in <1>; and using the photoresist stripping liquid to strip the photoresist.

<10> The photoresist peeling method disclosed in <9>, wherein the step of peeling off the photoresist is a step of applying ultrasonic waves to the photoresist stripping liquid to peel off the photoresist.

<11> The photoresist peeling method disclosed in <9>, wherein the photoresist is a photoresist that is ion-implanted.

<12> A photoresist peeling method disclosed in <9>, which does not include a step of ashing treatment.

According to the invention, it is possible to provide a photoresist stripping liquid excellent in peelability. Further, according to the present invention, it is possible to provide a photoresist peeling method which is excellent in peelability and does not damage the circuit structure.

Embodiment of the invention

The photoresist stripping liquid of the present invention is characterized by comprising particles and at least one compound selected from the group consisting of an amine compound and an alkylene glycol. The details are as follows.

(particle)

The photoresist stripping liquid of the present invention contains particles. The particles include inorganic particles and organic particles. For example, examples of the inorganic particles include oxides and nitrides of cerium, aluminum, lanthanum, titanium, zirconium, manganese, chromium, iron, tin, antimony, and the like, and composite particles or the like can be used. Further, depending on the use, there are cases where hard particles such as diamonds are used. The inorganic particles preferably used are cerium oxide, aluminum oxide, cerium oxide and titanium nitride. The organic particles can be a styrene resin, a (meth)acrylic resin, a (meth)acrylate resin, a polyethylene resin, a polypropylene resin, a urethane resin, a polyvinyl chloride resin, a polyvinyl alcohol resin, or a polyvinyl fluoride resin. Organic particles such as a resin, a phenol resin, an epoxy resin, a silicone resin, and the like, and composite particles thereof. The organic particles that are preferably used are epoxy trees. Grease, polyethylene resin and acrylate resin.

The inorganic particles of the metal oxide can be obtained by a known method. The wet preparation method of metal oxide particles is a metal alkoxide as a starting material, and a method of obtaining colloidal particles according to a method of hydrolyzing the starting material can be mentioned. Specifically, at a certain setting rate, methyl n-decanoate can be dropped into an alkaline aqueous solution of a mixed alcohol to cause hydrolysis, and a colloidal body can be produced after undergoing a period of grain growth and a period in which grain growth is stopped according to quenching. Yttrium oxide. In addition to this, an alkoxide of aluminum or titanium or the like is used to obtain colloidal particles.

Further, as a dry method for producing metal oxide particles, a method of introducing a metal chloride into a hydrogen-oxygen flame and obtaining a soot particle by oxidizing the dechlorinated metal may be mentioned. Further, the metal or alloy to be contained in the target substance is pulverized to form a powder, and the powder is introduced into an oxygen flame containing a combustion-supporting gas to cause a continuous reaction according to the oxidation heat of the metal to obtain a fine The method of oxide particles has also been put into practical use. Particles produced according to such combustion methods are characterized in that the particles are amorphized due to the high heat experienced in the process, and if compared with the wet particles, the impurities are generally small. In other words, the density of the solid is high, and the density of the hydroxyl groups on the surface is also low.

It can be obtained by simultaneously raising the above-mentioned nitride and a reducing agent such as carbon in a nitrogen atmosphere. In this case, it is important to how to make the temperature distribution in the reactor uniform even if the reduction reaction is caused, but the fusion between the particles is not caused. In general, the case of particles containing molten adhesion is adopted by a method of dispersing such a powder against a shielding plate; or, in the case of a tough agglomerate, using a device such as a high-pressure homogenizer, imparting physical energy to be dispersed in a solvent to be pulverized The way in which things are dispersed.

Further, composite particles in which the oxide or nitride and the organic particles are combined can also be used. By covering the surface with the oxide having a smaller particle diameter than the organic particles, for example, the organic particles are not aggregated over a long period of time, and the composite particles which are present in stability can be formed.

The primary particle diameter contained in the photoresist stripping liquid of the present invention is preferably in the range of 5 to 1,000 nm. More preferably, it is 10 to 500 nm, preferably 20 to 500 nm. If it is within the above numerical range, it has superior peelability.

Further, the primary particle diameter indicates a weight average particle diameter, and can be measured in accordance with a dynamic light scattering method. When the measuring machine is listed, "Microtrack UPA150" manufactured by Nippon Denso Co., Ltd. is mentioned.

The concentration of the particles can be set to be about 0.1 to 20% by weight with respect to the resist stripping solution. When the concentration of the particles is less than 0.1% by weight, it becomes difficult to obtain a practical polishing rate. On the other hand, when it exceeds 20% by weight, it is feared that the dispersibility will deteriorate.

Further, the photoresist stripping liquid of the present invention contains at least one compound selected from the group consisting of an amine compound and an alkylene glycol.

(amine compound)

In the present invention, the amine compound contained in the photoresist stripping solution may, for example, be hydroxylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine or propanol. Amine, dipropanolamine, tripropanolamine, Isopropanolamine, diisopropanolamine, triisopropanolamine, butanolamine, N-methylethanolamine, N-methyldiethanolamine, N,N-dimethylaminoethanol, N-ethylethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine, N-n-butylethanolamine, di-n-butylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydrogen Oxide, tetrabutylammonium hydroxide, salts thereof, and the like.

Particularly preferred examples of the amine compound include monoethanolamine, diethylamine, N-ethylethanolamine, N-n-butylethanolamine, N,N-diethylethanolamine, and tetramethylammonium hydroxide.

In the case where the photoresist compound of the present invention contains an amine compound, it is also possible to use two or more kinds of amine compounds in combination.

(alkylene glycols)

The alkylene glycol contained in the photoresist stripping liquid of the present invention may, for example, be a glycol compound such as ethylene glycol, propylene glycol, hexanediol or neopentyl glycol, or a monoether or diether compound thereof. And the salt of this. Further, a compound having 2 to 4 alkylene glycols such as dialkylene glycol, trialkylene glycol or tetraalkylene glycol, and monoether or diether compounds thereof and salts thereof can be mentioned. In the present invention, a preferred alkyl group is an exoethyl group. That is, in the present invention, the alkylene glycol is preferably used as the alkylene glycol.

Specific examples thereof include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and ethylene glycol dimethyl ether. , ethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol diacetate and these compounds having a glycol number of 2 to 4 ( Diethylene glycol, triethylene glycol and tetraethylene glycol); preferably, diethylene glycol dimethyl ether, diethylene glycol diethyl ether Ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol monobutyl ether, diethylene glycol diacetate, and triethylene glycol Alcohol diacetate.

In the present invention, in the case where the resistive stripping solution contains an alkylene glycol, two or more kinds of alkylene glycols may be used in combination.

(concentration of amine compound)

The concentration of the amine compound is preferably from 10 to 90% by weight, more preferably from 20 to 70% by weight, most preferably from 20 to 50% by weight, based on the resist stripper. When the concentration of the amine compound is 10% by weight or more and 90% by weight or less, the peeling performance is high, which is preferable.

(concentration of alkylene glycols)

The concentration of the alkylene glycol is preferably from 10 to 90% by weight, more preferably from 15 to 70% by weight, most preferably from 20 to 50% by weight, based on the resist stripper. When the amount of the alkylene glycol to be added is 10% by weight or more, the peeling performance is high, which is preferable. Further, when the amount of the alkylene glycol to be added is 90% by weight or less, the viscosity of the resist release liquid is not excessively high, which is preferable.

The photoresist stripping liquid of the present invention contains particles and at least one compound selected from the group consisting of an amine compound and an alkylene glycol, and preferably contains particles, an amine compound and an alkylene glycol. In this case, the total amount of the amine compound and the alkylene glycol is preferably from 10 to 90% by weight, more preferably from 20 to 90% by weight, most preferably from 40 to 85% by weight, based on the stripping liquid. When the total amount of the amine compound and the alkylene glycol is within the above range, the peeling performance is high, and the damage to the substrate is small, which is preferable.

Further, in the photoresist stripping liquid of the present invention, it is preferred to add a solvent and a pH. Adjusting agent, etc.

(pH adjuster)

In the present invention, in order to prepare the photoresist stripper to a desired pH, the pH adjuster is preferably added with an acid or a buffer.

Examples of the acid or buffer include inorganic acids such as nitric acid, sulfuric acid, and phosphoric acid; formic acid, acetic acid, hydroxyacetic acid, propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and pimelic acid. Organic acids such as suberic acid, azelaic acid, sebacic acid, lactic acid, malic acid, tartaric acid, tropic acid, diphenyl glycolic acid, salicylic acid, citric acid, etc.; glycine, alanine, taurour A carbonate such as an acid or a carbonate such as sodium carbonate; a buffer such as a phosphate, a borate, a tetraborate or a hydroxybenzoate such as trisodium phosphate. Particularly preferred acids include lactic acid and hydroxyacetic acid.

Further, in the present invention, other components can also be added to the photoresist stripping solution.

The solvent which may be used in the photoresist stripping liquid of the present invention may, for example, be an alcohol such as water, methanol, ethanol, propanol, isopropanol or butanol; an ether such as tetrahydrofuran; butoxypropanol or butoxyethanol. An ether alcohol such as propoxypropanol; a carbonate such as diethyl carbonate, dimethyl carbonate, ethyl carbonate, or propyl carbonate; an ester of methyl acetate or ethyl acetate; Anthraquinone; N,N-dimethylformamide, N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, N,N-diethyl a decylamine such as acetamide; a lactone such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or N-propyl-2-pyrrolidone; 1,3-dimethyl- The polarities of imidazolidinone such as 2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, and 1,3-diisopropyl-2-imidazolidinone are Machine solvent. These solvents may be used singly or in combination of two or more. Among these solvents, water or isopropyl alcohol is preferably used.

A photoresist peeling method is described which comprises a step of preparing the photoresist stripper and a step of using the photoresist stripper to strip the photoresist.

In the present invention, the photoresist stripping can be carried out by any conventional method. Specifically, a method in which the photoresist stripping liquid and the stripped photoresist are in contact with each other can be mentioned.

Examples of the peeling method include a dipping method, a spray method, and a method using a vane type, and the treatment is carried out at an appropriate temperature and for an appropriate period of time. The peeling temperature varies depending on the solvent and method to be used, and is generally preferably from 20 to 80 ° C, more preferably from 40 to 60 ° C. When the peeling temperature is within the above range, since the change in concentration is small, the peeling performance can be maintained, which is preferable.

Preferably, the photoresist stripping method of the present invention is repeated twice or more and then stripped. By repeating the second or more peeling method, it is preferable because the removal ability of the photoresist is improved. The stripping method can be repeated any number of times until the photoresist is completely removed, preferably 1 to 3 times, more preferably 1 to 2 times.

In the photoresist peeling method of the present invention, a peeling method in which ultrasonic waves are applied to a resist stripping liquid will be described. According to this method, a minute eddy current is generated according to the vibration pressure of the ultrasonic wave, and the stirring of the photoresist peeling liquid around the photoresist can be accelerated, and the peeling of the photoresist and the photoresist residue can be accelerated. Further, since the peeling can be accelerated by the action of the particles contained in the resist release liquid of the present invention, the photoresist can be surely peeled off.

For example, in the case of the immersion method, after the photoresist is applied, prebaking is performed, and exposure is performed through the mask pattern, and the developed substrate (subject to be processed) is immersed in a processing tank filled with the resist stripping solution. Ultrasonic waves are applied to the back surface of the substrate to clean the surface of the substrate. The ultrasonic vibration transmitted under the substrate is propagated in the peeling liquid with almost no degradation, and the photoresist and the photoresist residue adhering to the upper surface can be peeled off. Propagating in the processing tank below the substrate, holding the ultrasonic oscillator and the substrate, it is preferable to provide a holding tool for irradiating the ultrasonic wave from the ultrasonic oscillator. Further, the treatment layer includes a cleaning device disclosed in Japanese Laid-Open Patent Publication No. 2002-222787.

The frequency of the ultrasonic wave is in the frequency band of 0.1 to 10 MHz, which is confirmed to be a high peeling ability. Further, it is preferably in the range of 0.8 to 1 MHz, and there is no fear of dissolving the photoresist attached to the substrate to damage the substrate.

It is preferred to use a modification step in accordance with the oxidizing agent before the step of stripping the photoresist. In particular, the ion-implanted photoresist uses this method to modify the photoresist surface, and the peeling ability is improved. The modification step can also use any of the conventional methods. Specifically, any one of a dipping method, a spraying method, a coating method, and the like can be used. Among these methods, the dipping method and the spraying method are more preferred, and the dipping method is more preferred.

In addition, the modification step is preferably carried out at 100 to 160 ° C, more preferably at 120 to 150 ° C.

In the modification step, it is preferred to contact the oxidant with the photoresist for 5 to 30 minutes, more preferably for 10 to 20 minutes. If the contact time is more than 5 minutes, the photoresist after ion implantation can be modified because the light of the subsequent stripping step The peeling resistance will be improved and better. Further, when the contact time is 30 minutes or shorter, the time required for the peeling method is preferably short. Further, the above modification step is preferably carried out prior to the use of the photoresist stripping liquid of the present invention to strip the photoresist.

(oxidant)

Specific examples of the oxidizing agent include hydrogen peroxide, peroxide, nitrate, iodate, periodate, hypochlorite, chlorite, chlorate, perchlorate, and persulfate. , dichromate, permanganate, ozone water and silver (II) salt, iron (III) salt and a mixture of hydrogen peroxide and sulfuric acid, it is preferred to use a mixture of hydrogen peroxide and sulfuric acid.

The oxidizing agent is preferably in the form of a solution, and examples of the solvent include various types of water such as ultrapure water ion-exchanged water and distilled water; alcohols such as methanol, ethanol, and butanol; and anthraquinones such as dimethyl hydrazine; N,N-dimethyl Amidoxime such as carbamide, N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, N,N-diethylacetamide; N- Indoleamines such as methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, etc.; 1,3-dimethyl-2-imidazolidinone, 1,3-two A polar organic solvent of an imidazolinone such as ethyl-2-imidazolidinone or 1,3-diisopropyl-2-imidazolidinone. The solvent is preferably water, an alcohol, an anthraquinone or an imidazolinone, more preferably water.

Further, in the present invention, the oxidizing agent is preferably a solution containing hydrogen peroxide, more preferably a mixed solution of hydrogen peroxide and sulfuric acid.

The oxidizing agent is preferably a solution of 5 to 30% by weight, more preferably 10 to 20% by weight, based on the resist stripping solution.

The photoresist stripping method of the present invention is suitable for ion implantation (ion injection) The photoresist peeling method after entering). It is possible to effectively peel off the photoresist-containing stripping liquid with respect to the resist which is difficult to peel by ion implantation. Further, by immersing the peeling liquid in the treatment layer, the surface of the substrate is washed by irradiating the ultrasonic wave from the back surface of the substrate, whereby the photoresist can be reliably peeled off.

The present invention is applicable to conventional photoresists that have been used in the semiconductor industry, and although particularly suitable for positive photoresists of KrF and ArF, the present invention is not limited by such photoresists.

According to the photoresist peeling method of the present invention, the ashing treatment can be omitted. In a semiconductor device, a technique of using a low-k film (low dielectric constant film) having a low dielectric constant to replace a SiO ₂ film has recently been developed. Accordingly, in the process of a semiconductor device, etching is formed. The necessity of a low-k film. Conventionally, after dry etching of a film, ashing is performed by plasma such as oxygen-ozone, and although the photoresist has been removed, such a treatment causes a problem of damage imparting a low-k film. In the method of ashing using an active plasma such as oxygen-ozone, in addition to the problem of substrate damage, since the number of steps is large, there is a problem that processing is time consuming.

In addition, since the ashing device has a chamber, the entire device will be enlarged. If the photoresist stripping method of the present invention can be used to omit the ashing treatment, the entire apparatus can be made space-saving because a large cavity is not required. In addition, since there is no need for vacuuming, there is no need to perform cavity vacuum processing. Therefore, the photoresist peeling can be performed in a short time.

[Examples]

Hereinafter, although the embodiment of the present invention is described in detail, the present invention It is not limited by these embodiments.

The photoresist peel test was performed as follows:

(production of sample)

On the wafer, a general-purpose photoresist (commercial KrF photoresist) was applied in such a manner that the thickness of the photoresist was about 1,000 Å. Next, the sample to which the photoresist has been applied is baked and passed through a mask pattern for exposure and development.

Thereafter, an ion implantation operation is performed. The ion was used as the ion, and the doping amount was set to 1E ¹⁶ atoms/cm ² to prepare a sample.

<Example 1> (Modulation of photoresist stripping solution)

(Resistance test of photoresist)

The obtained sample was immersed in a treatment bath containing a photoresist stripper, and an ultrasonic wave having a frequency of 0.8 to 1 MHz was applied from the lower surface of the substrate. The temperature of the peeling liquid was set to 50 ° C, the immersion time was set to 5 minutes, and washing was performed using ultrapure water.

Thereafter, the optical microscope was used to confirm the presence or absence of the photoresist, and the peeling property of the photoresist was evaluated.

The peeling resistance of the photoresist was evaluated in the following manner: ◎: excellent peelability

○: good peelability

△: Part of the remaining

×: Most of the remaining

<Examples 2 to 20>

The peeling property of the photoresist was evaluated in the same manner as in Example 1 except that the compound, pH adjuster, and water contained in the resist stripper were prepared as the substances and addition amounts shown in Table 1. The results are shown in Table 1.

<Comparative Examples 1 to 6>

The peeling property of the photoresist was evaluated in the same manner as in Example 1 except that the compound, pH adjuster, and water contained in the resist stripper were prepared as the materials and addition amounts shown in Table 2. The results are shown in Table 2.

<Comparative Example 7>

The peeling property of the photoresist was evaluated in the same manner as in Example 1 except that the compound, the pH adjuster, and the water contained in the resist stripper were prepared as the substances and addition amounts disclosed in Table 2, without applying ultrasonic waves. The results are shown in Table 2.

<Comparative Example 8>

The syrup of alumina was supplied while the hardened layer formed on the surface of the photoresist layer on the surface of the photoresist layer was removed by chemical mechanical polishing. After the hardened layer was removed, the sample was immersed in sulfuric acid to peel off the photoresist layer, and observed using a scanning electron microscope. As a result, numerous flaws were observed on the surface of the wafer after mechanical processing to peel off the photoresist.

The symbols in the table are as follows: P1: cerium oxide particles (primary particle size 30 nm)

P2: titanium nitride particles (primary particle size 100 nm)

P3: Epoxy resin particles (primary particle size 500 nm)

A1: monoethanolamine

A2: N-n-butylethanolamine

B1: diethylene glycol monobutyl ether

B2; triethylene glycol monobutyl ether

The symbols in the table are the same as in Table 1. As shown in Tables 1 and 2, the photoresist stripping liquid of the present invention is a photoresist stripping liquid having superior peelability.

<Example 21> (Modulation of photoresist stripping solution)

(Resistance test of photoresist)

The obtained sample was immersed in a treatment bath containing a photoresist stripper, and an ultrasonic wave having a frequency of 0.8 to 1 MHz was applied from the lower surface of the substrate. The temperature of the peeling liquid was set to 50 ° C, the immersion time was set to 5 minutes, and washing was performed using ultrapure water.

Thereafter, the presence or absence of the photoresist was confirmed by a scanning electron microscope, and the peeling property of the photoresist was evaluated.

The peeling resistance of the photoresist was evaluated in the following manner: ◎: excellent peelability

○: good peelability

△: Part of the remaining

×: Most of the remaining

<Examples 22 and 23 and Comparative Examples 9 and 10>

The peeling property of the photoresist was evaluated in the same manner as in Example 21 except that the primary particle diameter of the particles contained in the resist stripping liquid was set to the primary particle diameter disclosed in Table 3. The results are shown in Table 3.

As shown in Table 3, the photoresist stripping liquid of the present invention is a photoresist stripping liquid having a superior peeling property by containing particles having a primary particle diameter of 5 to 1,000 nm.

Claims (10)

A photoresist stripping liquid characterized by containing particles and at least one compound selected from the group consisting of an amine compound and an alkylene glycol, wherein the concentration of the particles is 0.1 to 20 with respect to the resist stripping solution. % by weight, wherein the total amount of the amine compound and the alkylene glycol is from 10 to 90% by weight based on the resist stripper. For example, the photoresist stripping solution of claim 1 contains an amine compound and an alkylene glycol. The photoresist stripping solution according to claim 1, wherein the particle has a primary particle diameter of 5 to 1,000 nm. The photoresist stripping solution according to claim 1, wherein the particles are inorganic particles selected from the group consisting of cerium oxide, aluminum oxide, cerium oxide and titanium nitride, and/or epoxy resin and benzene. An organic resin selected from the group consisting of vinyl resin and acrylic resin. The photoresist stripping solution according to claim 1, wherein the amine compound is monoethanolamine, diethylamine, N-ethylethanolamine, N-n-butylethanolamine, N,N-diethylethanolamine, tetramethyl At least one selected from the group consisting of ammonium hydroxides. For example, in the photoresist stripping solution of claim 1, wherein the alkylene glycol is ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and Glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, ethylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, triethylene glycol Selected from the group consisting of dimethyl ether, triethylene glycol monobutyl ether, diethylene glycol diacetate, and triethylene glycol diacetate. A photoresist stripping method comprising the steps of: preparing a photoresist stripping solution according to claim 1; and using the photoresist stripping solution to strip the photoresist. The photoresist stripping method of claim 7, wherein the step of stripping the photoresist is a step of applying ultrasonic waves to the photoresist stripper to strip the photoresist. The photoresist stripping method according to claim 7, wherein the photoresist is an ion-implanted photoresist. For example, the photoresist stripping method of claim 7 does not include the step of ashing.