KR102157278B1 - Cleanig composition for photoresist - Google Patents

Abstract

The present invention relates to a cleaning liquid composition for photoresist removal, and more particularly, comprises at least one compound of a fluorine-based compound, an organic technology phonic acid, and an organic solvent, and the organic solvent is sulfolane or N-ethylpyrroly By including at least one compound of N-ethylpyrrolidone, it has excellent removal power to the photoresist, and the antireflection coating formed on or under the photoresist can be easily removed. In addition, the present invention relates to a cleaning solution composition for removing photoresist that can minimize damage to a lower silicon oxide film while removing the etching residue, and a method of manufacturing a semiconductor substrate using the same.

Description

Cleaning liquid composition for photoresist removal {CLEANIG COMPOSITION FOR PHOTORESIST}

The present invention relates to a cleaning liquid composition for removing a photoresist, and more particularly, to a cleaning liquid composition capable of effectively removing a photoresist and an antireflection coating without damaging a lower silicon oxide film and a metal film.

Photoresist is a chemical film that can shape a micropattern drawn in advance on a photomask on a desired substrate by using a photochemical reaction by light. It is a polymer material applied to exposure technology along with a photomask. It is recognized as a major factor that directly affects the degree of integration of the image and determines the ultimate resolution limit. According to Moore's law (the theory that the degree of integration of semiconductors doubles every two years), in order to put the degree of integration of a circuit that increases every year into a semiconductor of a limited size, it is necessary to pattern the designed circuit to a smaller size. Increasing the degree of semiconductor integration inevitably requires the development of new photoresists.

In order to manufacture a (semiconductor device or) high-resolution flat panel display, a photolithography process in which fine wiring is formed on a substrate using such a photoresist is generally used, and this is a substrate using the thermal, mechanical, and chemical properties of the photoresist. This is a method of applying a photoresist to, then exposing to light of a certain wavelength, and performing dry or wet etching.

In the fine patterning technology using a photoresist, a field that is considered important with the development of a new photoresist is a resist stripper (or Photoresist Remover). The photoresist must be removed by a solvent called a stripper or photoresist remover after the process is finished, which is an unnecessary photoresist layer after the etching process, and metal residues or altered photos remaining on the substrate through etching and washing processes. This is because resist residues cause problems such as lowering the yield of semiconductor manufacturing.

Typical dry etching methods include plasma etching and ion implantation etching. In the case of plasma etching, an etching process using a gas phase-solid phase reaction between a plasma gas and a material film such as a conductive layer. Since ions and radicals of the plasma etching gas cause a chemical reaction with the photoresist, the photoresist film is cured and denatured, making removal difficult. In addition, the ion implantation process is a process in which elements such as phosphorus, arsenic, boron, etc. are diffused in order to impart conductivity to a specific area of the substrate in the manufacturing process of semiconductor/LED/LCD devices, and the ions react chemically with the positive photoresist. Because it causes degeneration, it is also difficult to remove.

On the other hand, before the photoresist is etched, an antireflection coating is formed on the top or bottom of the photoresist. After etching, the residue of the antireflection coating can also reduce the yield of semiconductor manufacturing. And need to be removed at the same time.

Accordingly, there is a need for a cleaning solution composition capable of preventing damage to the lower metal wiring and silicon oxide film while at the same time having excellent peeling power for the deteriorated photoresist residue and removal power for the etching residue of the photoresist and antireflection coating.

Korean Patent Publication No. 2011-0130563 discloses a photoresist stripper composition.

Korean Patent Publication No. 2011-0130563

An object of the present invention is to provide a cleaning liquid composition having an excellent removal power for photoresist.

An object of the present invention is to provide a cleaning liquid composition for removing photoresist having excellent removal power even for anti-radiation coating.

In addition, an object of the present invention is to provide a cleaning liquid composition for removing photoresist that can minimize damage to the lower silicon oxide film.

In addition, an object of the present invention is to provide a method for manufacturing a semiconductor substrate using the cleaning liquid composition of the present invention.

1.Including at least one compound, an organic phonic acid, and an organic solvent among the compounds represented by the following Formula 1 or Formula 2,

The organic solvent comprises at least one compound of sulfolane or N-ethylpyrrolidone, a cleaning solution composition for photoresist removal:

[Formula 1]

^{_{(R 1) 4 N + F}} -

[Formula 2]

^{_{(R 2) 4 N + HF}} 2 -

(In the formula, R ₁ and R ₂ are each independently a linear alkyl group having 1 to 8 carbon atoms).

2. In the above 1, wherein the cleaning liquid is a non-aqueous, photoresist removal cleaning liquid composition.

3. In the above 1, the compound represented by Formula 1 is tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, tetrapentylammonium fluoride, tetrahexylammonium fluoride , Tetraheptyl ammonium fluoride and tetraoctyl ammonium fluoride, comprising at least one selected from the group consisting of, photoresist removal cleaning liquid composition.

4. In the above 1, the compound represented by Formula 2 is tetramethylammonium bifluoride, tetraethylammonium bifluoride, tetrapropylammonium bifluoride, tetrabutylammonium bifluoride, tetrapentylammonium bifluoride, A cleaning solution composition for removing a photoresist comprising at least one selected from the group consisting of tetrahexylammonium bifluoride, tetraheptylammonium bifluoride, and tetraoctylammonium bifluoride.

5. In the above 1, the organic phonic acid is at least one of the compounds represented by the following formulas 3 and 4, a cleaning solution composition for removing photoresist:

[Formula 3]

R ₃ SO ₃ H

[Formula 4]

(In the formula, R ₃ is a C 1 to C 12 linear alkyl group,

R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms).

6. In the above 1, 1 to 20% by weight of at least one of the compounds represented by Formula 1 or Formula 2 based on the total weight of the composition, 1 to 20% by weight of organic phonic acid and 60 to 98% of an organic solvent, photo Resist removal cleaning liquid composition.

7. The method of 1 above, wherein the photoresist is an antireflection coating (ARC), a cleaning solution composition for removing photoresist.

8. The method of 1 above, wherein the photoresist has a metal film formed under the photoresist, a cleaning solution composition for removing photoresist.

9. The method of 1 above, wherein the photoresist has a silicon oxide film formed under the photoresist, a cleaning solution composition for removing photoresist.

10. I) forming a metal film on the substrate;

Ⅱ) forming a silicon oxide film on the metal film;

Ⅲ) forming a photoresist pattern on the silicon oxide film by a photolithography process;

Ⅳ) etching the silicon oxide layer on which the photoresist pattern is formed; And

V) cleaning the substrate with the cleaning liquid composition according to claims 1 to 9;

A method of manufacturing a semiconductor substrate comprising a.

11. The method of manufacturing a semiconductor substrate according to the above 10, further comprising forming an antireflection coating before or after the step of forming the photoresist pattern in step Ⅲ).

The cleaning liquid composition of the present invention is excellent in removing power to photoresist.

The cleaning liquid composition of the present invention has excellent removal power for anti-reflective coating formed on or under the photoresist (ANTIREFLECTION COATING).

The cleaning liquid composition of the present invention can minimize damage to the lower silicon oxide film during cleaning.

In addition, the cleaning liquid composition of the present invention is excellent in stability over time.

The present invention relates to a cleaning solution composition for photoresist removal, and more particularly, comprises at least one compound of fluorine-based compounds, an organic technology phonic acid, and an organic solvent, and the organic solvent is sulfolane or N-ethylpyrroly By including at least one compound of N-ethylpyrrolidone, it has excellent removal power to the photoresist, and the antireflection coating formed on or under the photoresist can be easily removed. In addition, the present invention relates to a cleaning solution composition for removing photoresist that can minimize damage to a lower silicon oxide film while removing the etching residue, and a method of manufacturing a semiconductor substrate using the same.

The photoresist is formed on the silicon oxide film and the metal film. In the case of a conventional photoresist cleaning liquid composition, the antireflection coating formed on the upper or lower part of the photoresist is not removed together, or only the resist removal force is excessively increased to There was a problem of damaging the oxide film or the like.

The cleaning liquid composition for removing photoresist of the present invention can have excellent removal power for photoresist and antireflection coating, while minimizing damage to the lower silicon oxide film.

Hereinafter, the present invention will be described in detail.

< Photoresist Cleaning liquid composition for removal>

The cleaning liquid composition for removing a photoresist of the present invention includes at least one compound of the compounds represented by Formula 1 or Formula 2, an organic technology phonic acid, and a specific type of organic solvent.

It is preferable that the cleaning liquid composition for removing photoresist according to the present invention is non-aqueous. In the present invention, "non-aqueous" means that water is not used as a solvent, and "substantially not used" means that the present invention It means that it does not exclude the case where a trace amount of water is included within the range and effect of.

The non-aqueous cleaning liquid composition for photoresist removal of the present invention does not use water as a solvent, so it does not excessively increase the activity of hydrogen fluoride (HF) in the composition, and thus it is possible to effectively remove the photoresist without damaging the lower silicon film. have.

Represented by Formula 1 or 2 Alkyl ammonium fluoride

The cleaning liquid composition of the present invention contains at least one compound from among the compounds represented by the following formulas 1 or 2.

[Formula 1]

^{_{(R 1) 4 N + F}} -

[Formula 2]

^{_{(R 2) 4 N + HF}} 2 -

(In the formula, R ₁ and R ₂ are each independently a linear alkyl group having 1 to 8 carbon atoms).

The compound represented by Formula 1 or 2 is a component for removing photoresist, and it can effectively remove photoresist and antireflection coating by generating hydrogen fluoride (HF) through reaction with the organic sulfonic acid of the present invention to be described later. To be.

On the other hand, in the case of using inorganic ammonium fluoride, it is impossible to dissolve the organic solvent alone, so water must be used as a solvent. In this case, the activity of hydrogen fluoride (HF) is excessively increased by water, and the lower silicon oxide film or There was a problem that caused over-etching of the lower metal film.

However, in the present invention, by using the alkyl ammonium fluoride represented by Formula 1 or 2, it is possible to remove the photoresist effectively without damaging the lower silicon oxide film and the lower metal film.

The type of the compound represented by Formula 1 is not particularly limited, but for example, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, tetrapentylammonium fluoride, tetra Hexyl ammonium fluoride, tetraheptyl ammonium fluoride, tetraoctyl ammonium fluoride, and the like, and these may be used alone or in combination of two or more.

The type of the compound represented by Formula 2 is not particularly limited, but for example, tetramethylammonium bifluoride, tetraethylammonium bifluoride, tetrapropylammonium bifluoride, tetrabutylammonium bifluoride, tetrapentylammonium Bifluoride, tetrahexylammonium bifluoride, tetraheptylammonium bifluoride, tetraoctylammonium bifluoride, and the like, and these may be used alone or in combination of two or more.

The content of the compound represented by Formula 1 or 2 is not particularly limited, but may be included in 1 to 20% by weight, preferably 2 to 10% by weight, based on the total weight of the cleaning liquid composition. When the above range is satisfied, the photoresist and the reflective ring coating can be removed at an appropriate rate, and at the same time, defects on the lower wiring and damage to the lower silicon oxide film can be suppressed. On the other hand, when it exceeds 20% by weight, the solubility of the composition decreases, so that a fluoride compound may be precipitated, and a defect in the metal film may be caused.

Organic technology

The organic phonic acid used in the cleaning liquid composition of the present invention is a component that generates hydrogen fluoride (HF) through reaction with the compound of Formula 1 or 2 to remove the modified photoresist.

In the cleaning liquid composition of the present invention, since hydrogen fluoride (HF) is generated in the composition, hydrogen fluoride (HF) is not separately added, so it is safer in use.

In addition, it is believed that the sulfone group of the organic technology can significantly improve the corrosion prevention effect by forming a film made of a chelate compound on the surface of the metal film.

The type of the organic sulfonic acid according to the present invention is not particularly limited, but may be, for example, at least one of the compounds represented by the following Formula 3 or Formula 4.

[Formula 3]

R ₃ SO ₃ H

[Formula 4]

(In the formula, R ₃ is a C 1 to C 12 linear alkyl group,

R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms).

The kind of organic technology phonic acid represented by Formula 3 is not particularly limited, but examples thereof include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, and the like, and these may be used alone or in combination of two or more, Preferably, methanesulfonic acid may be used.

The kind of organic technology phonic acid represented by Formula 4 is not particularly limited, but examples thereof include benzene sulfonic acid, paratoluene sulfonic acid, aminobenzene sulfonic acid, and the like, and these may be used alone or in combination of two or more. For example, paratoluenesulfonic acid may be used.

The content of the organic technology phonic acid according to the present invention is not particularly limited, but, for example, may be included in 1 to 20% by weight, and preferably 1 to 10% by weight, based on the total weight of the cleaning liquid composition. If the above range is satisfied, the modified photoresist can be removed at an appropriate speed, and at the same time, defects on the lower wiring can be suppressed. On the other hand, if it exceeds 20% by weight, the stability of the cleaning liquid composition may be lowered to cause a color change, the antireflection coating property or the removal rate of the photoresist may be lowered, and defects in the silicon oxide film or the metal film may be caused.

Organic solvent

The organic solvent used in the cleaning liquid composition of the present invention contains at least one compound of sulfolane or N-ethylpyrrolidone.

The sulfolane and N-ethylpyrrolidone can effectively dissolve the aforementioned organic phonic acid and alkyl ammonium fluoride, and at the same time improve the wettability with the film to be cleaned, especially the antireflection coating film. , It is a component that can significantly improve the removal speed of the antireflection coating.

The components of sulfolane and N-ethylpyrrolidone may be used alone or in combination, and the mixing ratio is not particularly limited, but, for example, 1:9 to 9:1 days I can.

Further, if necessary, in addition to the above components, glycols, alkylene glycol monoalkyl ethers, alkylene glycol alkyl ether acetates, alkyl acetates, aromatic hydrocarbons, ketones, alcohols; Cyclic esters and the like can be further used.

The content of the organic solvent is not particularly limited, but, for example, may be included in an amount of 60 to 98% by weight, and preferably 80 to 90% by weight, based on the total weight of the cleaning liquid composition. If the above range is satisfied, an appropriate etching rate and solubility may be exhibited.

The cleaning liquid composition of the present invention may further contain conventional additives as necessary in addition to the above-described components. Examples of the additive include, but are not limited to, an etch control agent, a metal ion sequestering agent, a corrosion inhibitor, a surfactant, a pH control agent, and the like.

The cleaning object of the cleaning liquid composition according to the present invention may be an antireflection coating formed on or below the photoresist as well as a general photoresist. A metal film and/or a silicon oxide film may be formed under the photoresist.

<Method of manufacturing semiconductor substrate>

The present invention relates to a method of manufacturing a semiconductor substrate using the cleaning liquid composition of the present invention.

A method of manufacturing a semiconductor substrate according to an embodiment of the present invention includes the steps of: Ⅰ) forming a metal film on the substrate; Ⅱ) forming a silicon oxide film on the metal film; Ⅲ) forming a photoresist pattern on the silicon oxide film by a photolithography process; Ⅳ) etching the silicon oxide layer on which the photoresist pattern is formed; And V) cleaning the substrate with the cleaning liquid composition according to the present invention.

The type of the metal film is not particularly limited, but may be, for example, an aluminum-based metal film, and the aluminum-based metal film includes aluminum (Al) as a component of the film, and is a multilayer film such as a single film, a double film, and a triple film. It is a concept that includes.

For example, it may include a single film of aluminum or an alloy of aluminum, and the aluminum alloy film is nickel (Ni), indium (In), magnesium (Mg), manganese (Mn), beryllium (Be), together with aluminum (Al), Hafnium (Hf), niobium (Nb), tungsten (W) and vanadium (V), silver (Ag), molybdenum (Mo), titanium (Ti), copper (Cu), palladium (Pd), lanthanum ( La) means an aluminum alloy containing at least one selected from the group consisting of, or an aluminum alloy film composed of nitrides (eg, TiAlN) or carbides (eg, TiAlC) of the aluminum alloy.

In addition, the method of manufacturing a semiconductor substrate according to the present invention may further include forming an antireflection coating before or after the photoresist pattern forming step of step III).

The method of manufacturing a semiconductor substrate according to the present invention includes a cleaning step using the cleaning liquid composition of the present invention described above, so that the photoresist and the antireflection coating can be effectively removed, and at the same time, damage to the lower silicon oxide film and the metal film is prevented. Can be minimized.

Hereinafter, preferred embodiments are presented to aid the understanding of the present invention, but these examples are only illustrative of the present invention and do not limit the scope of the appended claims, and examples within the scope and spirit of the present invention It is obvious to those skilled in the art that various changes and modifications are possible, and it is natural that such modifications and modifications fall within the scope of the appended claims.

Example And Comparative example

division
(weight%) Organic acid Alkyl ammonium
Fluoride ammonium
Fluoride Organic solvent Deionized water ingredient content ingredient content ingredient content ingredient content Example 1 A-1 5 B-1 5 - - D-1 90 - Example 2 A-1 10 B-1 5 - - D-1 90 - Example 3 A-1 20 B-1 5 - - D-1 75 - Example 4 A-2 5 B-1 5 - - D-1 90 - Example 5 A-1/
A-2 2.5/
2.5 B-1 5 - - D-1 90 - Example 6 A-1 5 B-1 10 - - D-1 85 - Example 7 A-1 5 B-1 20 - - D-1 75 - Example 8 A-1 5 B-2 5 - - D-1 90 - Example 9 A-1 5 B-1/
B-2 2.5/
2.5 D-1 90 - Example 10 A-1 20 B-1 20 - - D-1 60 - Example 11 A-1 5 B-1 5 - - D-2 90 - Example 12 A-1 5 B-1 5 - - D-1/
D-2 45/
45 - Example 13 A-1 5 B-1 5 - - D-1/
D-2 20/
70 - Example 14 A-1 5 B-1 5 - - D-1/
D-2 70/
20 - Comparative Example 1 A-1 10 - - - - D-1 90 - Comparative Example 2 - - B-1 10 - - D-1 90 - Comparative Example 3 - - - - C-1 10 D-1 90 - Comparative Example 4 - - - - C-1 10 D-3 90 - Comparative Example 5 - - - - C-2 10 D-1 90 - Comparative Example 6 - - - - C-2 10 D-1 70 20 Comparative Example 7 A-1 5 B-1 5 - - D-3 90 - Comparative Example 8 A-1 5 B-1 5 - - D-4 90 - Comparative Example 9 A-1 5 - - C-2 5 D-1 90 - Comparative Example 10 A-1 5 B-1 5 - - D-1 85 5 A-1: methanesulfonic acid (99%)
A-2: Para-toluenesulfonic acid
B-1: tetrabutylammonium fluoride
B-2: tetramethylammonium bifluoride
C-1: Foshan
C-2: ammonium fluoride
D-1: Sulfolane
D-2: ethylpyrrolidone
D-3: propylene carbonate
D-4: pyridine

Test Methods

One) Photoresist Removal, silicone Oxide Damage assessment

After a silicon oxide film was formed on the silicon wafer on which aluminum was deposited, a photoresist (193 nm) was applied and exposed, and then a patterned wafer was prepared by developing a plasma-etched patterned wafer thereon. The substrate was sampled in a size of 2x2cm, each of the compositions in Table 1 was prepared, heated to 60°C, the substrate was immersed for 2 to 5 minutes, washed with water, and a scanning electron microscope (SEM, Hitachi S-4700) and an ellipsometer (Ellipsometer, SE-MG-1000), the removability of the modified polymer (dipping for 2 minutes) and the defect of the silicon oxide film (dipping for 5 minutes) were determined based on the following criteria, and the results are shown in Table 2.

<Photoresist removal evaluation criteria>

◎: More than 95% removed

○: More than 90% removed

△: More than 80% removed

Х: less than 70% removed

<Evaluation of removal of anti-reflective coating>

◎: The removal speed of the antireflection coating exceeds 400Å/min.

○: Anti-reflection coating removal speed 200Å/min or more and 400Å/min or less

△: Anti-reflection coating removal speed less than 200Å/min

Х: Anti-reflection coating not etched

<attck standard of silicon oxide film>

◎: Less than 1Å/min of oxide film etching rate

○: Oxide etching rate 1Å/min or more and less than Å/min

△: Oxide etching rate 5Å/min or more and less than 10Å/min

Х: Oxide etching rate exceeds 10Å/min

3) Solubility evaluation (time stability evaluation)

The solubility of the compositions of Examples and Comparative Examples was observed with the naked eye, and the results are also shown in Table 2.

<Solubility evaluation criteria>

○: No sedimentation occurs at the bottom and is transparent

△: No precipitation occurs in the lower part, but the solution is suspended.

X: Both precipitation and suspension of solution occurred in the lower part

division Photoresist removal Anti-reflection coating
remove Silicon oxide film
damaged Solubility Example 1 ◎ ◎ ◎ ○ Example 2 ◎ ◎ ◎ ○ Example 3 ◎ ○ ◎ ○ Example 4 ◎ ◎ ○ ○ Example 5 ◎ ◎ ◎ ○ Example 6 ◎ ◎ ○ ○ Example 7 ◎ ○ ○ ○ Example 8 ◎ ◎ ◎ ○ Example 9 ◎ ◎ ◎ ○ Example 10 ◎ ◎ ○ ○ Example 11 ◎ ◎ ◎ ○ Example 12 ◎ ◎ ◎ ○ Example 13 ◎ ◎ ◎ ○ Example 14 ◎ ◎ ◎ ○ Comparative Example 1 ○ Ⅹ ◎ ○ Comparative Example 2 ○ Ⅹ ◎ ○ Comparative Example 3 ○ ◎ Ⅹ ○ Comparative Example 4 ○ ◎ Ⅹ ○ Comparative Example 5 - - - Ⅹ Comparative Example 6 ○ Ⅹ △ ○ Comparative Example 7 ○ ○ △ ○ Comparative Example 8 ○ ○ △ ○ Comparative Example 9 - - - Ⅹ Comparative Example 10 ◎ ◎ Ⅹ ○

Referring to Table 2, it was confirmed that the etchant compositions (Examples 1 to 14) according to the present invention effectively removed the photoresist and the antireflection coating, did not cause damage to the lower silicon oxide film, and had excellent stability over time.

However, in the case of Example 3 in which a little organic acid was used, the removal performance of the antireflection film was slightly lowered, and in the case of Example 7 in which the alkylammonium fluoride was slightly used, it was confirmed that some damage to the silicon oxide film occurred.

In comparison, in the case of Comparative Examples 1 to 6 in which the organic acid and/or alkyl ammonium fluoride according to the present invention was not used, it was confirmed that the removal power for the antireflection coating film was slightly lowered.

In addition, in the case of Comparative Examples 3 and 4 using hydrofluoric acid, damage to the silicon oxide film occurred greatly, and Comparative Examples 7 and 8 without using the organic solvent according to the present invention had both antireflection coating and photoresist removal ability. It could be confirmed that it fell.

Claims (11)

Including at least one compound of the compounds represented by the following Formula 1 or Formula 2, an organic solvent, and an organic solvent,
The organic solvent comprises at least one compound of sulfolane or N-ethylpyrrolidone, a cleaning liquid composition for removing a non-aqueous photoresist:
[Formula 1]
^{_{(R 1) 4 N + F}} -
[Formula 2]
(R ₂ ) ₄ N ⁺ HF ^2-
(In the formula, R ₁ and R ₂ are each independently a linear alkyl group having 1 to 8 carbon atoms).
delete The method according to claim 1, wherein the compound represented by Formula 1 is tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, tetrapentylammonium fluoride, tetrahexylammonium fluoride, tetra A cleaning liquid composition for removing a non-aqueous photoresist comprising at least one selected from the group consisting of heptyl ammonium fluoride and tetraoctyl ammonium fluoride.
The method according to claim 1, wherein the compound represented by Formula 2 is tetramethylammonium bifluoride, tetraethylammonium bifluoride, tetrapropylammonium bifluoride, tetrabutylammonium bifluoride, tetrapentylammonium bifluoride, tetrahexyl Ammonium bifluoride, tetraheptyl ammonium bifluoride, and tetraoctyl ammonium bifluoride, comprising at least one selected from the group consisting of, non-aqueous photoresist cleaning liquid composition for removing.
The method of claim 1, wherein the organic phonic acid is at least one of the compounds represented by the following formulas 3 and 4, the non-aqueous photoresist removal cleaning liquid composition:
[Formula 3]
R ₃ SO ₃ H
[Formula 4]

(In the formula, R ₃ is a C 1 to C 12 linear alkyl group,
R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms).
The non-aqueous photo of claim 1, comprising 1 to 20% by weight of at least one compound of the compound represented by Formula 1 or 2, 1 to 20% by weight of organic phonic acid, and 60 to 98% of an organic solvent based on the total weight of the composition. Resist removal cleaning liquid composition.
The method of claim 1, wherein the photoresist is an antireflection coating (ARC), a non-aqueous photoresist removal cleaning liquid composition.
The cleaning liquid composition of claim 1, wherein the photoresist has a metal film formed under the photoresist.
The cleaning liquid composition of claim 1, wherein the photoresist has a silicon oxide film formed under the photoresist.
Ⅰ) forming a metal film on the substrate;
Ⅱ) forming a silicon oxide film on the metal film;
Ⅲ) forming a photoresist pattern on the silicon oxide film by a photolithography process;
Ⅳ) etching the silicon oxide layer on which the photoresist pattern is formed; And
V) cleaning the substrate with the cleaning liquid composition for removing a non-aqueous photoresist according to any one of claims 1, 3 to 9;
A method of manufacturing a semiconductor substrate comprising a.
The method of claim 10, further comprising forming an antireflection coating before or after the step of forming the photoresist pattern in step III).