KR20180110488A - Resist stripper composition - Google Patents

Abstract

The present invention relates to a resist stripping liquid composition, which comprises 0.1 to 20 wt% of a tertiary amine containing a hydroxymethylamino group represented by chemical formula 1; and 79 to 99.9 wt% of a polar organic solvent. In the chemical formula 1, R_1 and R_2 are respectively an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. The present invention aims to provide the resist stripping liquid composition, which is excellent in the hydrostatic pressure, solubility, and peeling force for a lower metal film including aluminum, copper, titanium, molybdenum, and the like.

Description

RESIST STRIPPER COMPOSITION [

The present invention relates to a resist stripper composition.

Photoresist is a chemical film that can form a fine pattern pre-drawn on a photomask on a desired substrate by using photochemical reaction by light. It is used as a polymer material applied to exposure technology together with a photomask. Is directly recognized as a major factor in determining the ultimate resolution limit. In order to put the increasing degree of circuit integration into the semiconductor of a limited size every year according to the so-called Moore's law (the theory that the degree of integration of a semiconductor doubles every two years), the designed circuit must be patterned much smaller Increasing semiconductor density is inevitably demanding the development of new photoresists.

In order to produce semiconductor devices or high resolution flat panel displays, a photolithography process is generally used in which fine wirings are formed on a substrate using such photoresist. This is accomplished by using photolithography, mechanical, Applying a resist, exposing to light of a certain wavelength, and performing dry or wet etching.

In the fine patterning technique using a photoresist, a development that has been emphasized with respect to a new photoresist is a resist stripper (or a photoresist remover). The photoresist must be removed by a solvent called Stripper (or Photoresist Remover) after the etching process. This is because unnecessary photoresist layer after the etching process and etching of the metal residue or deteriorated photo This is because the resist residues cause problems such as a decrease in the yield of semiconductor production.

Typical examples of the dry etching method include plasma etching and ion implantation etching. In the plasma etching, a gas-solid reaction between a plasma gas and a material layer such as a conductive layer is used to perform an etching process The ions and radicals of the plasma etching gas chemically react with the photoresist to harden and denature the photoresist film, which makes it difficult to remove the photoresist film. The ion implantation process is a process of diffusing phosphorus, arsenic, boron, or the like phosphorus in order to impart conductivity to a specific region of a substrate in a manufacturing process of a semiconductor / LED / LCD device. So that the removal becomes difficult.

Therefore, a considerable level of exfoliating property is demanded with respect to the removal power against etching residues and the excellent peeling force against the deteriorated photoresist residue, the corrosion inhibiting ability against the lower metal wiring, and the like.

Korean Patent No. 10-0672102 discloses a photoresist stripping liquid composition, but it has a problem in that the anticorrosive force against the copper film is insufficient and the dissolving power and peeling power are lowered.

Korean Patent No. 10-0672102

An object of the present invention is to provide a resist stripping liquid composition which is excellent in a detergency, a dissolving power and a peeling force for a lower metal film including aluminum, copper, titanium, molybdenum and the like in order to solve the above problems.

The present invention relates to a pharmaceutical composition comprising 0.1 to 20% by weight of a tertiary amine containing a hydroxymethylamino group represented by the formula (1); And 79 to 99.9% by weight of a polar organic solvent.

[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

The present invention relates to a resist stripping liquid having excellent anticorrosion, dissolution and barrier properties against a lower metal film including aluminum, copper, titanium, molybdenum and the like by including a tertiary amine containing a hydroxymethylamino group and a polar organic solvent Lt; / RTI >

The present invention relates to a resist stripper composition. The resist stripping liquid composition of the present invention contains a tertiary amine containing a hydroxymethylamino group represented by the general formula (1) and a polar organic solvent, whereby a resist stripping liquid having excellent anticorrosion, dissolution and barrier properties against the copper film and aluminum film Composition can be provided.

Hereinafter, the configuration of the present invention will be described in detail.

The present invention provides a resist stripping liquid composition having improved resistance to copper and aluminum film and improved solvency and peel strength.

(1) Hydroxymethylamino group  Including tertiary Amine  compound

The resist stripping composition of the present invention comprises a tertiary amine compound having a hydroxymethylamino group represented by the following general formula (1).

[Chemical Formula 1]

The tertiary amine compound having the hydroxymethylamino group represented by Formula 1 may be modified or crosslinked under various process conditions such as dry or wet etching, ashing or ion implant processing, Of the polymer matrix, and breaks bonds existing in the molecule or between molecules. Thereby forming an empty space in a structurally weak portion in the resist remaining on the substrate, thereby allowing the resist to be easily removed by deforming the resist into an amorphous polymer gel lump state. In addition, the tertiary amine compound having the hydroxymethylamino group represented by the above formula (1) has less corrosive power against metals than other amine compounds, thereby effectively minimizing the attack on the metal film while peeling off the resist.

[Chemical Formula 1]

In Formula (1), R ₁ and R ₂ each independently represent an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. Representative examples of the above Formula 1 include 2 - ((hydroxymethyl) (methyl) amino) ethanol, 2 - ((hydroxymethyl) Methyl) amino) ethanol, 3 - ((hydroxymethyl) (methyl) amino) propanol and the like.

The content of the tertiary amine compound having a hydroxymethylamino group represented by the general formula (1) is preferably 0.1 to 20% by weight based on the total weight% of the composition, more preferably 0.5% To 15% by weight. If it is less than the above range, it is difficult to secure a fast peeling performance. If it exceeds the above range, corrosion of the metal wiring becomes severe.

Polar organic solvent

The polar organic solvent used in the present invention includes a proton-polar organic solvent and an aprotic polar organic solvent, which may be used alone or in combination.

The polar organic solvent serves to dissolve the gelled resist polymer. In addition, it facilitates the removal of the peeling liquid by the water during the rinsing of the deionized water after the peeling of the resist, so that the peeling liquid and the resorption / Minimize it. It is preferable that the polar organic solvent does not have a boiling point too high or low for an appropriate peeling force, and may be mixed and used. The polar organic solvent may be added according to the performance required in the peeling process.

Preferable examples of the protonic polar organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, polyethylene glycol, polypropylene glycol , Polyethylene glycol monomethyl ether, polyethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, alkylene glycol monoalkyl ether, propylene Recall monomethyl ether acetate and the like, and tetra-hydroperoxide furyl alcohol, one kinds of these may be used alone or in combinations of two or more.

Preferable examples of the aprotic polar organic solvent include pyrrolidone compounds such as N-methyl pyrrolidone and N-ethyl pyrrolidone; Imidazolidinone compounds such as 1,3-dimethyl-2-imidazolidinone and 1,3-dipropyl-2-imidazolidinone; lactone compounds such as? -butyrolactone; Sulfoxide compounds such as dimethylsulfoxide (DMSO) and sulfolane; Phosphate compounds such as triethyl phosphate, tributyl phosphate and the like; Carbonate compounds such as dimethyl carbonate, ethylene carbonate, and the like; N, N-dimethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N - (2-hydroxyethyl) acetamide, N, N-dimethylpropionamide, 3- methoxy-N, N-dimethylpropionamide, 3- (2-ethylhexyloxy) -N, N-dimethylpropionamide , And 3-butoxy-N, N-dimethylpropionamide. These compounds may be used singly or in combination of two or more.

The content of the polar organic solvent may be 79 to 99.9% by weight, preferably 80 to 99.9% by weight based on the total weight% of the total composition. If the amount is less than the above range, the solubility may be lowered, and re-adsorption / redeposition of the resist may occur in the rinsing step with deionized water. Also, when the amount exceeds the above range, the content of the tertiary amine containing a hydroxymethylamino group may be relatively decreased, and the peeling force may be lowered.

The corrosion inhibitor represented by the general formula (2)

The photoresist stripper composition of the present invention may further comprise a corrosion inhibitor represented by the general formula (2).

(2)

In Formula 2, R ₃ , R ₄ , R _5, and R ₆ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms.

The corrosion inhibitor represented by the above formula (2) serves to prevent corrosion of the film including copper and copper.

Specific examples of the corrosion inhibitor represented by the formula (2) include 6-methyl-4,5,6,7-tetrahydro-1H-benzo [1,2,3] triazole, 5,6- Tetrahydro-1H-benzo [1,2,3] triazole, 4,6-dimethyl-4,5,6,7-tetrahydro-1H- benzo [1,2,3] But is not limited thereto. The amount of the corrosion inhibitor represented by Formula 2 may be 0.001 to 1.0% by weight based on the total weight% of the composition, and more preferably 0.005 to 0.5% by weight based on the total weight% of the composition. If the amount is less than 0.001% by weight, the corrosion inhibiting ability is insufficient. If the amount is more than 1.0% by weight, it is difficult to obtain the effect of improving the performance of the hydrostatic pressure due to the increase of the content.

The resist stripping liquid composition of the present invention has an excellent antistatic effect on a lower metal film containing at least one of metals such as aluminum (Al), molybdenum (Mo), copper (Cu) and titanium (Ti) It has good resistance to copper. Thereby providing a resist stripping liquid composition.

Example  And Comparative Example : Resist  Preparation of release liquid composition

The ingredients shown in the following Table 1 and the content (unit: wt%) were mixed to prepare a resist stripping liquid composition.

[Table 1]

[Table 2]

Note: A1: 2 - ((hydroxymethyl) (methyl) amino)) Ethanol

A2: 2 - ((hydroxymethyl) (ethyl) amino)) ethanol

A3: 2,2 - ((hydroxyethyl) (hydroxymethyl) amino) ethanol

A4: N-hydroxymethylethanolamine

MEA: Monoethanolamine

DEA: N, N-diethanolamine

MDEA: N-methyldiethanolamine

MTBT: 6-methyl-4,5,6,7-tetrahydro-1H-benzo [1,2,3] triazole

DMTBT: 5,6-Dimethyl-4,5,6,7-tetrahydro-1H-benzo [1,2,3] triazole

Sorbitol: Sorbitol

Cat .: Catekol

NMP: N-methylpyrrolidone

NMF: N-methylformamide

MDG: diethylene glycol monomethyl ether

EDG: diethylene glycol monoethyl ether

BDG: diethylene glycol monobutyl ether

DEF: N, N-diethylformamide

DMPA: N, N-dimethylpropionamide

Experimental Example  1: Peel force  evaluation

In order to confirm the peeling effect of the resist stripper composition having compositions of Examples and Comparative Examples, resist was coated on a glass substrate using a spin coater according to a conventional method. The substrate coated with the resist was hard-baked at 170 캜 for 10 minutes to prepare a 2 cm x 2 cm area. The peelability was evaluated by a method in which the peeling liquid composition was kept at a constant temperature of 50 캜 and then the object was immersed and the peeling time was visually observed. The results are shown in Table 1 below. The resist removal time was expressed as?, Less than 1 minute, less than 3 minutes?, Less than 3 minutes to less than 10 minutes?, And X minutes longer than 10 minutes.

Experimental Example  2: Separation liquid metal wiring Corrosion resistance  evaluation

To evaluate the corrosion inhibiting ability of the resist stripper composition having compositions of Examples and Comparative Examples for metal wiring, a substrate on which Mo / Al / Mo and Cu / Ti wirings were exposed was used. The stripper composition was uniformly heated to 50 ° C The substrate was immersed for 30 minutes, then washed and dried, and evaluated using a scanning electron microscope (SEM, Hitachi S-4700). The results are shown in the following Table 3, and no corrosion was observed at all, and it is suitable for use in the process application. ⊚, slight corrosion on the surface is observed, but the level of use for the process application is ○, △ indicates that there is a high possibility of failure after the application of the process, △ indicates that the internal corrosion is observed as well as surface corrosion and the process is not applicable.

Experimental Example  3: solvency  Evaluation (number of processing)

To evaluate the number of treatments of the resist stripper composition having the compositions of Examples and Comparative Examples, 5 wt% of solidified PR was added to the stripper composition and dissolved at 300 rpm for 30 minutes. The remaining amount of PR was filtered through a filter paper The weight was measured and the degree of dissolution was calculated. When 5 wt% of PR is completely dissolved and the remaining amount is not measured, it is 100%. It can be said that the higher the value, the higher the amount of PR can be dissolved. The results are shown in Table 1 below. When the calculated value is 95% or more,?, Less than 95%? 90% or more?, Less than 90%? 80%?

[Table 3]

Examples 1 to 10 satisfying the constitution of the present invention were found to have excellent abilities for both aluminum, molybdenum, copper and titanium films while having excellent peeling force and dissolving power. In particular, through Examples 6, 9 and 10, 15% by weight or more of a tertiary amine containing a hydroxymethylamino group represented by the general formula (1) was contained, and thus the detergency against metals was also excellent I could confirm.

On the other hand, in Comparative Examples 1 to 9, it was confirmed that the peeling force and the dissolving power were poor, and the corrosion ability of aluminum and copper was poor. In the case of Comparative Examples 1 to 3 in which the tertiary amine containing hydroxymethylamino group represented by the formula (1) is not contained or the content range is not satisfied, peeling force and dissolving power are lowered, and aluminum and copper have surface corrosion and internal corrosion And the ability of the system was remarkably deteriorated. In addition, in the case of Comparative Examples 4 to 9 including compounds other than the tertiary amine containing the hydroxymethylamino group represented by the formula (1) of the present invention, the ability to cope with aluminum or copper was inferior and the peeling force and the dissolution power And it was confirmed that a bad case occurred. Particularly, in Comparative Examples 7 to 9, although the corrosion inhibitor was contained in an amount of 3% by weight or more, it was confirmed that the ability to cope with copper was significantly lowered.

Claims (7)

0.1 to 20% by weight of a tertiary amine containing a hydroxymethylamino group represented by the formula (1); And 79 to 99.9% by weight of a polar organic solvent.
[Chemical Formula 1]

(Wherein R ₁ and R ₂ are each independently an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms) The resist stripping composition according to claim 1, further comprising 0.001 to 1.0% by weight of a compound represented by the general formula (2).
(2)

(Wherein R _3, R ₄ , R ₅ and R ₆ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms) [2] The method according to claim 1, wherein the tertiary amine having a hydroxymethylamino group represented by Formula 1 is 2 - ((hydroxymethyl) (methyl) amino) ethanol, 2- (hydroxymethyl) Which is at least one selected from the group consisting of ethanol, 2,2 - ((hydroxyethyl) (hydroxymethyl) amino) ethanol and 3 - ((hydroxymethyl) Composition. The resist stripper composition according to claim 1, wherein the polar organic solvent comprises at least one of a proton-polar organic solvent and an aprotic polar organic solvent. [5] The method of claim 4, wherein the protonic organic solvent is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, polyethylene glycol, polypropylene Glycols, polyethylene glycol monomethyl ether, polyethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, alkylene glycol monoalkyl ether, Glycol monomethyl ether acetate and tetra-hydroperoxide will furyl least one selected from the group consisting of alcohols; Wherein the aprotic polar organic solvent is selected from the group consisting of N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, But are not limited to, butyrolactone, dimethylsulfoxide (DMSO), sulfolane, triethylphosphate, tributylphosphate, dimethylcarbonate, ethylene carbonate, formamide, N-methylformamide, N, N-dimethylacetamide, N, N-dimethylpropionamide, N, N-dimethylacetamide, N, N-dimethylacetamide, 1-methylpropionamide, 3-methoxy-N, N-dimethylpropionamide, 3- (2-ethylhexyloxy) -N, N-dimethylpropionamide and 3-butoxy- Or more of the resist stripper composition. [2] The compound according to claim 2, wherein the compound represented by Formula 2 is 6-methyl-4,5,6,7-tetrahydro-1H-benzo [1,2,3] triazole, 5,6- , 6,7-tetrahydro-1H-benzo [1,2,3] triazole and 4,6-dimethyl-4,5,6,7-tetrahydro-1H- benzo [1,2,3] triazole , Wherein the resist stripping liquid composition is at least one selected from the group consisting of: The method according to claim 1,
Al, Mo, Cu and Ti. ≪ RTI ID = 0.0 > 11. < / RTI >