KR101392551B1 - Stripper composition for removal photoresist residue and stripping method of photoresists using the same - Google Patents

Abstract

The present invention relates to a peeling liquid composition for removing photoresist residue comprising (A) an organic sulfonic acid compound, (B) a hydroxycarboxylic acid compound, (C) a polyhydric alcohol and (D) water and a peeling method using the same. According to the present invention, in the manufacturing process of a semiconductor device and a flat panel display device, a photoresist residue containing a hardened and / or altered photoresist that may occur during an ashing process can be removed by a deposition method or a sheet- Or a spraying method, as well as a detachment liquid composition for removing photoresist residues which can prevent corrosion of a metal film and an insulating film on a lower part exposed to the stripping solution composition, and a stripping method using the same.

Organic sulfonic acid compound, hydroxycarboxylic acid compound, polyhydric alcohol, photoresist, exfoliation

Description

TECHNICAL FIELD The present invention relates to a peeling liquid composition for removing photoresist residues and a peeling method using the same.

The present invention relates to a photoresist residue or the like containing a cured and / or altered photoresist remaining on a substrate subjected to etching and ashing during the manufacturing process of a semiconductor device or a flat panel display device, The present invention relates to a peeling liquid composition for removing photoresist residues which can be effectively removed without corrosion of the exposed underlying metal film or insulating film, and a peeling method using the same.

The semiconductor device and the flat panel display device are manufactured by a process including the steps of forming a metal film or an insulating film, forming a photoresist, exposing the mask pattern to a photoresist, etching the film along the pattern, To the peeling step. In the peeling step, the photoresist applied on the wafer or the substrate is removed by wet ashing or dry ashing. After such wet ashing or dry ashing processes, some altered and / or cured photoresist residues and the like will be present. If the modified and / or cured photoresist is not completely removed, the photoresist residue may act as a factor of shorting or breaking the wiring in the subsequent process, which may cause a decrease in the yield of production.

To overcome this problem, residual and / or cured photoresist remaining after the ashing process has been removed through a wet process. The removal solution composition used for removing the photoresist in the above-mentioned wet process may be a combination of [amine + organic solvent + corrosion inhibitor], [acid + organic acid salt or inorganic acid salt + water] or [fluorine compound + quaternary ammonium compound + water ], [Fluorine compound + quaternary ammonium compound + organic solvent + water].

For example, U.S. Patent No. 4,617,251 discloses a process for the preparation of a compound of formula (I) wherein a specific amine compound [eg, 2- (2-aminoethoxy) ethanol, 2- (NMP), tetrahydrofurfuryl alcohol, dimethyl glutarate, sulfolane, gamma-butyrolactone (GBL), N, N-dimethylacetamide, and mixtures thereof. Discloses a positive photoresist stripper composition. Also, U.S. Patent No. 5,279,771 discloses a stripping composition comprising a hydroxylamine, an alkanolamine and optionally a polar solvent.

However, the above-mentioned amine-based stripping solution has serious problems such as the plasma etching, the residual polymer after high-temperature ashing, the complete removal of the cured photoresist after ion implantation, and the corrosion of a metal film such as aluminum.

Korean Patent Laid-Open No. 10-2004-75058 discloses a composition further comprising a corrosion inhibitor in a) a water-soluble organic solvent, b) a sulfonic acid or a corresponding salt thereof, and c) water. Korean Patent Laid-Open No. 10-2006-98333 also discloses a photoresist stripper composition containing at least one of a) an acetylenic alcohol compound and an organic sulfonic acid compound and b) a polyhydric alcohol and a derivative thereof .

As an example of a composition to which a fluorine compound is added, a composition comprising [fluorine compound + ascorbic acid + polar organic solvent] has been reported in Japanese Patent Laid-Open No. 2001-5200, but the instability of the composition has been a problem. Korean Patent Laid-Open No. 10-2006-50601 proposes a composition comprising a fluorine compound, a sulfonic acid and water, but has a high content of fluorine added.

In the case of a composition containing a fluorine compound, there is a problem that the margin of the peeling condition is narrow in addition to the instability of the composition. In addition, the organic peeling composition has a problem in that it has a long cleaning time after peeling and a high environmental treatment cost, and also has a problem in terms of cost to apply to a single-wafer method in which a wafer is cured in a large size. Accordingly, there is a demand for a remover which is excellent in removability of the photoresist, excellent in the effect of the system for the metal film and the insulating film, and capable of shortening the cleaning treatment time, more effectively and at a low cost.

The present inventors have made extensive efforts to solve the above-mentioned problems. As a result, the present inventors have found that, when the release liquid composition of the present invention comprising an organic sulfonic acid compound, a hydroxycarboxylic acid compound, a polyhydric alcohol compound, And the corrosion resistance of the metal film or the insulating film is low, thereby completing the present invention.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a peeling liquid composition for removing photoresist residues containing photoresist, which is hardened and / or altered after ashing, without corrosion of a metal film and an insulating film in a process of manufacturing semiconductor devices and flat panel display devices The present invention provides a peeling liquid composition for removing photoresist residues, which is effective for manufacturing a device including an aluminum film, and a peeling method using the same.

In order to achieve the above object,

(A) an organic sulfonic acid compound,

(B) a hydroxycarboxylic acid compound,

(C) a polyhydric alcohol compound, and

(D) water. The present invention also provides a detachment liquid composition for removing photoresist residues.

Further, the present invention provides a photoresist stripping method using the stripper composition for removing the photoresist residue.

The stripper composition for removing photoresist residue of the present invention can effectively remove photoresist residues including photoresist hardened and / or altered by hard baking, plasma etching, hot ashing during the manufacturing process of semiconductor devices and flat panel display devices And the corrosion of the metal film and the insulating film can be prevented. Particularly, the release liquid composition of the present invention is suitable for a production process of an aluminum wiring and an aluminum via hole and the like, and deionized water cleaning is easy, and the cleaning time can be shortened.

Hereinafter, the present invention will be described in detail.

The present invention relates to a method for manufacturing a semiconductor device and a method for manufacturing a semiconductor device, which is a process for manufacturing a semiconductor device and a flat panel display device, in which a residue of a photoresist containing cured and / or altered photoresist generated in a photolithography process, The present invention provides a peeling liquid composition for removing photoresist residues, which can be effectively removed without corrosion of a metal included in the peeling liquid, and a peeling method using the same.

Specifically, the present invention relates to a composition comprising,

(A) 0.1 to 20% by weight of an organic sulfonic acid compound;

(B) 0.1 to 20% by weight of a hydroxycarboxylic acid compound;

(C) 0.1 to 20% by weight of a polyhydric alcohol compound; And

(D) a residual amount of water so that the total weight of the entire composition becomes 100% by weight.

The organic sulfonic acid compound contained in the detachment liquid composition for removing the photoresist residue of the present invention is an organic sulfonic acid or a salt thereof and has high dissociation constant or acidity when dissociated into an aqueous solution.

Sulfuric acid is generally used in the process of removing organic substances in a semiconductor process because sulfuric acid has a high acidity and a strong oxidizing ability. That is, when dissolved in water, the amount of generated hydrogen ions is high, so that the hydrogen ion index is indicated to be small. Such a hydrogen ion, that is, an acid ion reacts with a hydrophobic photoresist as a polymer to convert it into a hydrophilic photoresist, and can act to relax the bond in the photoresist, and the relaxed photoresist can be modified by other functional groups And has a characteristic of being easily dissolved. Due to these properties, when an organic sulfonic acid having an acid dissociation constant similar to sulfuric acid, that is, an acidity, is used, the photoresist can be easily removed by strong acidity such as sulfuric acid. Accordingly, the photoresist modified layer and the sidewall protective deposited layer, which have been difficult to remove with the conventional peeling solution, can be removed together with the photoresist.

The organic sulfonic acid compound

(a) an alkylsulfonic acid having 1 to 4 carbon atoms;

(b) an arylsulfonic acid having 6 to 8 carbon atoms;

(c) a heteroarylsulfonic acid having 5 to 7 carbon atoms;

(d) an alkylbenzenesulfonic acid having 7 to 18 carbon atoms; And

(e) salts thereof, or a mixture of two or more thereof. The organic sulfonic acid compound may have a substituent, and the substituent may be a mercapto group, an amino group or a fluoro group.

The alkylsulfonic acid having 1 to 4 carbon atoms is preferably one or more compounds selected from the group consisting of methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid and aminomethanesulfonic acid.

The arylsulfonic acid having 6 to 8 carbon atoms is preferably one or more selected from the group consisting of benzenesulfonic acid and phenolsulfonic acid.

The heteroarylsulfonic acid having 5 to 7 carbon atoms is preferably pyridine sulfonic acid.

The alkylbenzenesulfonic acid having 7 to 18 carbon atoms is preferably selected from the group consisting of dodecylbenzenesulfonic acid, toluenesulfonic acid (4-methylbenzenesulfonic acid), pyridinium p-toluenesulfonic acid, cresylsulfonic acid (methylphenolsulfonic acid), cumenesulfonic acid and xylenesulfonic acid It is preferable that one kind or two kinds or more of them are selected.
In particular, the cresol sulfonic acid (methyl phenol sulfonic acid) may be 0-cresol sulfonic acid (2-methylphenol sulfonic acid), and the xylene sulfonic acid may be 2,5-xylene sulfonic acid and / or 2,4-xylene sulfonic acid.

In addition, camphorsulfonic acid and the like can be used.

Among the organic sulfonic acids listed above, dodecylbenzenesulfonic acid, toluenesulfonic acid, cumenesulfonic acid, aminomethanesulfonic acid, xylenesulfonic acid, camphorsulfonic acid and salts thereof are preferably used.

The amount of the organic sulfonic acid compound to be added is not particularly limited, but may be varied depending on the object to be removed and the removal conditions, and is preferably 0.1 to 20% by weight, particularly preferably 0.5 to 10% by weight based on the total weight of the total composition . If the organic sulfonic acid compound is contained in an amount of less than 0.1% by weight based on the total weight of the total composition, removal of the photoresist residue is unreasonable and if it is contained in an amount exceeding 20% by weight, corrosion of a metal film such as aluminum There is a problem that the manufacturing cost is increased.

The hydroxycarboxylic acid compound contained in the peeling liquid composition for removing the photoresist residue of the present invention has a function of removing the photoresist residue but also functions as a corrosion inhibitor for suppressing the corrosion of the metal film do.

The hydroxycarboxylic acid compound generally refers to a compound containing a carboxyl group and a hydroxy group. The composition of the present invention may be prepared by mixing one or more compounds selected from the group consisting of glycolic acid, gluconic acid, salicylic acid and salts thereof, Is preferably used.

The amount of the hydroxycarboxylic acid compound to be added is not particularly limited, but it may be increased or decreased depending on the object to be removed and the removal conditions, and is preferably 0.1 to 20% by weight, particularly preferably 0.1 to 10% by weight based on the total weight of the entire composition . When the hydroxycarboxylic acid is contained in an amount of less than 0.1% by weight based on the total weight of the composition, it becomes a cause of corrosion of a metal film such as aluminum. When the hydroxycarboxylic acid is contained in an amount of more than 20% by weight, There is a problem that removal of the photoresist residue is inadequate.

The polyalcohol compound contained in the release liquid composition for removing the photoresist residue of the present invention functions as a corrosion inhibitor to suppress the corrosion of the metal film. The polyhydric alcohol compound generally refers to a compound containing two or more hydroxy groups. The composition of the present invention may contain one or more compounds selected from glycols, glycerol, erythritol, arabitol, xylitol, mannitol, sorbitol, It is preferable to use a mixture of these compounds.

The blending amount of the polyhydric alcohol compound is not particularly limited, but it may be increased or decreased depending on the object to be removed and the removal conditions, and may be preferably 0.1 to 20% by weight, particularly preferably 0.1 to 10% by weight based on the total weight of the total composition have. When the polyhydric alcohol is contained in an amount of less than 0.1% by weight based on the total weight of the composition, it becomes a cause of corrosion of a metal film such as aluminum. When the polyhydric alcohol is contained in an amount of more than 20% by weight, There is a problem that removal of the resist residue is inadequate.

Water contained in the stripper solution composition for removing photoresist residue of the present invention is not particularly limited, but it is preferable to use deionized water having a specific resistance value of 18 M? / Cm or more as water for semiconductor processing. The water content can be adjusted according to the content of the other constituents.

The release liquid composition for removing the photoresist residue of the present invention may further contain a fluorine compound. The fluorine compound plays a role in promoting the removal of the hardened and deteriorated photoresist remaining on the substrate. It also serves to remove contaminants, such as fine dust, on the substrate.

The fluorine compound is not particularly limited, but is preferably a mixture of at least one member selected from the group consisting of hydrofluoric acid, ammonium fluoride, boron monochloride and fluoroboric acid.

The blending amount of the fluorine compound is not particularly limited, but may be increased or decreased depending on the object to be removed and the removal conditions, and preferably 0.0001 to 5% by weight based on the total weight of the entire composition. When the fluorine compound is contained in an amount of less than 0.0001% by weight based on the total weight of the entire composition, removal of the photoresist residue is unreasonable, and if it exceeds 5% by weight, a metal film such as aluminum, an insulating film such as SiO ₂ or SiNx Which may be a cause of corrosion.

The removing solution composition for removing the photoresist residue of the present invention can be prepared by mixing the above-mentioned compounds in an appropriate amount, and the mixing method is not particularly limited and various known methods can be applied.

The pH of the peeling liquid composition for removing photoresist residue produced by the present invention is preferably adjusted to 1 to 7. When the pH of the peeling liquid composition for removing the photoresist residue is less than 1, the corrosion of the metal film such as aluminum is intensified, and when the pH is more than 7, the photoresist residue removal effect is remarkably deteriorated.

The peeling liquid composition for removing the photoresist residue of the present invention can be used as a photoresist residue containing a photoresist hard baking, plasma etching, curing after high temperature ashing and / or altered photoresist in the manufacturing process of a semiconductor device or a flat panel display device It can be used in a peeling process for effectively removing water.

The detachment liquid composition for removing photoresist residues of the present invention is a water system type which can increase the activity of a compound in a composition to remove photoresist residues and is more cost effective than an organic release agent Do. Compared with the organic peeling liquid, since the composition is low in viscosity similar to water and can be sprayed, it is applicable to a sheet-like method. Therefore, the peeling liquid composition for removing photoresist residue of the present invention can be applied to both a batch method for peeling a plurality of wafers at a time or a single wafer processor for peeling a wafer at a time.

The present invention is also characterized by the use of the release liquid composition of the present invention and is a photoresist material that can effectively remove photoresist residues including hard baking, plasma etching, curing after hot etching and / A resist stripping method is provided.

In the photoresist stripping method,

(I) forming a photoresist film on a substrate;

(II) selectively exposing the photoresist film;

(III) developing the exposed photoresist film to form a photoresist pattern;

(IV) etching the substrate using the photoresist pattern as a mask;

(V) subjecting the photoresist pattern to ashing; And

(VI) peeling the photoresist residue after the ashing from the substrate using the peeling liquid composition for removing the photoresist residue of the present invention.

In addition, in the removing method of the present invention, a dry etching process such as an etchback process or a CMP (Chemical Mechanical Polishing) process is performed without performing a photoresist pattern forming process using a mask, And a method of peeling the film with the release liquid composition of the present invention.

The photoresist film formation, exposure, development, etching, and ashing processes in the peeling method can be performed by a method commonly known in the art, and are not particularly limited. A photoresist film containing a photoresist that is hardened or modified with a polymer If the substrate on which the resist residues are present and the peeling liquid composition can be brought into contact with each other, good peeling results can be obtained.

The peeling method may be a deposition method, a spraying method, or a deposition and spraying method. In the case of peeling by immersion, spraying or immersion and spraying, the temperature for peeling is usually from 10 to 100 캜, preferably from 20 to 80 캜, and the immersion, spraying or immersion and spraying time is usually from 30 seconds to 40 minutes, Preferably 1 minute to 20 minutes, but is not strictly applied in the present invention, and can be modified in a condition that is easy and suitable for a person skilled in the art.

The stripping liquid composition for removing the photoresist residue and the stripping method using the same according to the present invention can be used for manufacturing semiconductor devices and flat panel display devices and can be used for metal wiring such as aluminum and a method for insulating films such as SiO ₂ or SiN x There is an advantage of goodness.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples and comparative examples are provided for illustrating the present invention, and the present invention is not limited by the following examples and comparative examples, and various modifications and changes may be made.

Example  1 to 8 and Comparative Example  1 to 7

The photoresist stripping solution compositions of Examples 1 to 8 and Comparative Examples 1 to 7 were prepared by mixing the components as shown in Table 1 below.

Sulfonic acid
compound
(weight%) Hydroxy
Carboxylic acid
(weight%) Fluorine compound
(weight%) Polyhydric alcohol
(weight%) etc
(weight%) water
(weight%) Example 1 PSA 5 HC-3 10 - - Ask One - - Balance Example
2 DBSA 5 HC-1 3 - - Gl 10 - - Balance Example
3 TSA 10 HC-2 3 - - Gl 3 - - Balance Example 4 TSA 2 HC-3 5 - - Ery 5 - - Balance Example
5 TSA 2 HC-3 0.5 NH ₄ F 0.005 Search 0.5 - - Balance Example
6 TSA 5 HC-2
One
FBA
0.0005
Xyl
One
-
-
Balance
PSA 5 Example
7 TSA 10 HC-1 5 FBA 0.001 Man 5 - - Balance Example
8 TSA 2 HC-3 5
FBA
0.001
Ask
5
-
-
Balance
PSA 2 Comparative Example
One DBSA 2 - - - - - - - - Balance Comparative Example
2 DBSA 10 HC-3 0.05 NH ₄ F 0.5 - - - - Balance Comparative Example
3 TSA 2 - - NH ₄ F One - - - - Balance Comparative Example
4 TSA 25 HC-2 5 NH ₄ F 0.1 - - - - Balance Comparative Example
5 - - HC-3 3 - - - - TMAH 2 Balance Comparative Example
6 TSA 5 - - FBA 0.001 - - H ₂ SO ₄ 5 Balance Comparative Example
7 TSA 5 - - NH ₄ F 0.01 - - BDG 20 Balance

Note) DBSA: Dodecylbenzenesulfonic acid

TSA: toluenesulfonic acid

PSA: phenolsulfonic acid

HC-1: glycolic acid

HC-2: succinic acid

HC-3: gluconic acid

FBA: fluoroboric acid

TMAH: tetramethylammonium hydroxide

BDG: diethylene glycol monobutyl ether

Gl: Glycol

Ery: Erythritol

Ara: Arabitol

Xyl: Xylitol

Man: Mannitol

Sor: Sorbitol

Test Example : Peelability  And Improvisation  exam

A specimen having an Al metal wiring in an SiO ₂ insulating film and adhered to the metal film and the insulating film with deteriorated photoresist residue and polymer residue generated after plasma etching or high temperature ashing was applied to a peeling liquid Comparative Example) After each sample was immersed for 20 minutes, the specimen was taken out from the peeling solution, rinsed with ultrapure water for 1 minute, and dried using nitrogen gas. The removal of residual photoresist and polymer after dry or high temperature ashing using a scanning electron microscope and the corrosion resistance of the metal film and insulating film exposed to the chemical solution were evaluated. The peelability and corrosion resistance were evaluated according to the following criteria, and the results are shown in Table 2 below.

[Evaluation criteria for peelability]

⊚: very good, ∘: good, △: presence of some residues, X: impossible to remove residues

[Evaluation Criteria for Aluminum Anchoring Properties]

?: No corrosion,?: Almost no corrosion,?: Partial corrosion, Change in surface roughness, X: Etching

As shown in the above Table 2, the compositions of Examples 1 to 8, which are compositions comprising the organic sulfonic acid, hydroxycarboxylic acid compound, polyhydric alcohol and water of the present invention, are superior to the compositions of Comparative Examples 1 to 7, Peelability and corrosion resistance to aluminum.

Claims (12)

For the total weight of the composition, (A) 0.1 to 20% by weight of an organic sulfonic acid compound, (B) 0.1 to 20% by weight of a hydroxycarboxylic acid compound, (C) 0.1 to 20% by weight of a polyhydric alcohol compound, and (D) a residual amount of water such that the total weight of the entire composition is 100 wt% And removing the photoresist residue. delete The organic electroluminescent device according to claim 1, wherein the organic sulfonic acid compound (a) an alkylsulfonic acid having 1 to 4 carbon atoms; (b) an arylsulfonic acid having 6 to 8 carbon atoms; (c) a heteroarylsulfonic acid having 5 to 7 carbon atoms; (d) an alkylbenzenesulfonic acid having 7 to 18 carbon atoms; And (e) its salt Wherein the photoresist residue is at least one compound selected from the group consisting of a photopolymerization initiator and a photopolymerization initiator. [Claim 4] The method according to claim 3, wherein the alkyl sulfonic acid having 1 to 4 carbon atoms is at least one compound selected from the group consisting of methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid and aminomethanesulfonic acid. And The peeling liquid composition for removing photoresist residue according to claim 3, wherein the arylsulfonic acid having 6 to 8 carbon atoms is at least one compound selected from the group consisting of benzenesulfonic acid and phenolsulfonic acid. The peeling liquid composition for removing photoresist residue according to claim 3, wherein the heteroarylsulfonic acid having 5 to 7 carbon atoms is pyridine sulfonic acid. [Claim 4] The method according to claim 3, wherein the alkylbenzenesulfonic acid having 7 to 18 carbon atoms is selected from the group consisting of dodecylbenzenesulfonic acid, toluenesulfonic acid (4-methylbenzenesulfonic acid), pyridinium paratoluenesulfonic acid, cresylsulfonic acid (methylphenolsulfonic acid), cumenesulfonic acid and xylenesulfonic acid Wherein the photoresist residue is at least one compound selected from the group consisting of a photopolymerization initiator and a photopolymerization initiator. The peelable liquid composition for removing photoresist residue according to claim 1, wherein the hydroxycarboxylic acid compound is at least one compound selected from the group consisting of glycolic acid, gluconic acid, salicylic acid and salts thereof. The photoresist residue of claim 1, wherein the polyhydric alcohol compound is one or more compounds selected from the group consisting of glycols, glycerol, erythritol, arabitol, xylitol, mannitol, and sorbitol Removing composition. The removing solution composition for removing photoresist residue according to claim 1, wherein the stripper solution composition for removing photoresist residue further comprises a fluorine compound. The removing solution composition for removing photoresist residue according to claim 1, wherein the pH of the peeling solution composition for removing the photoresist residue is 1 to 7. (I) forming a photoresist film on a substrate; (II) selectively exposing the photoresist film; (III) developing the exposed photoresist film to form a photoresist pattern; (IV) etching the substrate using the photoresist pattern as a mask; (V) subjecting the photoresist pattern to ashing; And (VI) separating the photoresist residue after the ashing from the substrate using the peeling liquid composition for removing the photoresist residue according to any one of claims 1 and 3 to 11, Peeling method.