KR102629621B1 - Cleaning solution composition for photoresist nozzle - Google Patents

Abstract

The present invention contains a carbonate-based solvent and an anionic surfactant and has a pH of 1 to 7, so that it has excellent cleaning power for photoresist containing inorganic particles or metal oxides, and removes photoresist deposited in the spray nozzle. It can be effectively cleaned without leaving any residue, preventing the spray nozzle from clogging, thereby preventing defects in the substrate that may occur when the residue falls on the substrate, and controlling the pH over time. It relates to a photoresist cleaning liquid composition with excellent stability.

Description

Photoresist nozzle cleaning liquid composition {CLEANING SOLUTION COMPOSITION FOR PHOTORESIST NOZZLE}

The present invention relates to a photoresist nozzle cleaning liquid composition.

In the manufacturing process of display devices, lithography technology is used to produce electronic circuits or pixels for implementing colors. The lithography process is a method used to create fine patterns on a substrate. By irradiating light through a mask with a desired pattern printed on a substrate coated with a photosensitive material (also called photoresist), the circuit pattern of the mask is transferred to the substrate. It is a process.

During the development process, the applied photosensitive material selectively interacts with the developing solution in parts that receive light or do not receive light, depending on the type of photosensitive agent, and are removed from the substrate, thereby obtaining a photosensitive agent pattern similar to the desired circuit pattern. .

In this way, the method of applying the photosensitive material to the substrate uses a coating device, such as a nozzle. As this process is performed repeatedly, some residue of the photosensitive material remains in the coating device, and in severe cases, the nozzle This clogging phenomenon may occur.

In particular, research on high color reproduction of color filters has been actively conducted in recent years, and in relation to this, the use of metal oxides or inorganic particles as scattering particles along with various quantum dots is increasing. Specifically, the quantum dot is a nanometer-sized semiconductor nanocrystal, and has the characteristic of changing energy band gap (Bandgap, Eg) depending on size and shape, and emits light only by adjusting the size of the quantum dot due to the quantum confinement effect. Since the wavelength can be adjusted, excellent color purity, and high PL (photoluminescence) efficiency can be achieved, it has recently been receiving attention in various fields. The quantum dots may have a single homogeneous structure, but may also have a core-shell structure, a gradient structure, etc. In some cases, it has a dual structure. In particular, the core and shell of the quantum dots contain materials containing metal atoms such as CdSe, CdS, etc.

However, when photosensitive materials containing metal oxides or inorganic particles are applied through a coating device, metal oxides or inorganic particles are deposited inside the nozzle, clogging the coating device, and the deposits are deposited on the substrate during the process. It falls on the table and causes defects. Therefore, a cleaning process to remove the photosensitive material deposited inside the photosensitive material application device is absolutely necessary.

In this regard, Republic of Korea Patent No. 10-0954639 describes a nozzle plate cleaning liquid composition in which TMAH (trimethylammonium hydride) carbonate is added to a TMAH (trimethylammonium hydride) solution of pH 8 to pH 12, but it is a strong base. There is a problem that the nozzle is corroded and the durability of the nozzle is reduced due to the use of .

In addition, Republic of Korea Patent No. 10-1820310 includes 55-70 parts by weight of glycol ethers, based on 100 parts by weight of the total composition; 25-35 parts by weight of ethyl 3-ethoxypropionate; 3-7 parts by weight of methyl 3-methoxypropionate; and 1-5 parts by weight of glycerin; wherein the glycol ethers are composed of a single compound of propylene glycol monomethyl ether or a mixture of propylene glycol monomethyl ether and propyl cellosolve. Although a composition for cleaning equipment is described, it has the problem of poor cleaning power against metal oxides or inorganic particles.

Republic of Korea Patent No. 10-0954639 (2010.04.16.) Republic of Korea Patent No. 10-1820310 (2018.01.15.)

The present invention is intended to solve the above problems, and its purpose is to provide a cleaning liquid composition with excellent cleaning power for photoresist containing inorganic particles and metal oxides.

The cleaning liquid composition of the present invention for achieving the above object includes a carbonate-based solvent and an anionic surfactant, and has a pH of 1 to 7.

The cleaning liquid composition of the present invention has excellent cleaning power for photoresist containing inorganic particles or metal oxides, and can effectively clean without leaving residues of photoresist deposited in the spray nozzle, preventing clogging of the spray nozzle. This has the advantage of being able to eliminate process defects that may arise as a result. Additionally, there is an advantage that stability over time is improved by adjusting the pH.

In the present invention, when a part "includes" a certain component, this means that it may further include other components rather than excluding other components, unless specifically stated to the contrary.

Hereinafter, the present invention will be described in more detail.

The photoresist cleaning liquid composition according to one aspect of the present invention includes a carbonate-based solvent and an anionic surfactant and has a pH of 1 to 7, thereby providing excellent cleaning power for photoresist containing inorganic particles or metal oxides. As a result, photoresist residues deposited in the spray nozzle can be effectively cleaned without leaving any residue, preventing the spray nozzle from clogging, thereby preventing substrate defects that may occur when the residue falls onto the substrate. There are benefits to doing this. In addition, there is an advantage of excellent stability over time by adjusting the pH. When the pH range is outside the above range, stability over time is reduced. In particular, when amines and alkaline compounds are included together, stability over time is further reduced.

Carbonate type solvent

As described above, the photoresist cleaning liquid composition according to one aspect of the present invention has the advantage of excellent cleaning power for photoresist containing inorganic particles or metal oxides by including a carbonate-based solvent.

According to one embodiment of the present invention, the carbonate-based solvent may include a compound represented by the following formula (1). In this case, the compound represented by the following formula (1) penetrates into the photoresist containing inorganic particles or metal oxides. The photoresist can be melted and detached from the injection nozzle.

[Formula 1]

(In Formula 1 above,

R ₁ and R ₂ are each independently hydrogen, a C6 to C20 aromatic hydrocarbon group substituted or unsubstituted with a halogen group, a C1 to C8 alkyl group substituted or unsubstituted with a halogen group, or a C2 to C8 group substituted or unsubstituted with a halogen group. An alkenyl group, -COOR ₃ , a metal ion, or an ammonium ion, or

R ₁ and R ₂ are bonded to each other and represent a C1 to C8 alkyl group substituted or unsubstituted with a hydroxy group; C6 to C20 aromatic hydrocarbon group; or a halogen group; forming a saturated or unsaturated ring consisting of a carbon atom substituted or unsubstituted,

R ₃ is a C1 to C8 alkyl group).

In the present invention, aromatic hydrocarbon groups include, for example, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, 4-n-butylphenyl group, 4-tert-butylphenyl group, naphthyl group, and anthryl group. , phenanthryl group, biphenyl group, terphenyl group, etc.

In the present invention, the alkyl group may be straight chain or branched, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-hexadecyl group, n-icosyl group, isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group, etc. You can.

In the present invention, an alkenyl group has one or more carbon-carbon double bonds and may be straight chain or branched. For example, ethenyl, propenyl, butenyl, pentenyl, etc. can be mentioned.

In the present invention, metal atoms include Na, Ca, K, Al, Li, Mg, etc.

More specifically, the compound represented by Formula 1 is monoethyl carbonate, diethyl carbonate, dimethyl carbonate, vinyl ethyl carbonate, propylene carbonate, ditertbutyl dicarbonate, diethyl dicarbonate, ethyl methyl carbonate, aryl methyl carbonate, Propyl carbonate, 1,2-divinylethylene carbonate, 4-fluoro-1,3-dioxolan-2-one, 4-phenyl-1,3-dioxolan-2-one, 4-hydroxymethyl -1,3-dioxolane-2-one, 4-butyl-1,3-dioxolane-2-one, 1,2-butylene carbonate, etc. are mentioned, but are not limited to these, and each of them alone Alternatively, two or more types can be mixed and used.

Among the compounds exemplified above, monoethyl carbonate, dimethyl carbonate, propylene carbonate, diethyl dicarbonate, 4-hydroxymethyl-1,3-dioxolan-2-one, and 1,2-butylene carbonate are preferably used. In this case, it may be desirable because the cleaning power of the photoresist may be further improved.

The photoresist cleaning liquid composition of the present invention can be used by mixing the carbonate-based solvent and the non-carbonate-based solvent, but when the carbonate-based solvent is used alone, the cleaning power for photoresist containing inorganic particles or metal oxides is improved. In addition, it is desirable because the cleaning effect of the cleaning liquid composition can be maintained for a long period of time even over time.

At this time, the non-carbonate-based solvent may be used without particular limitation as long as it is a solvent used for photoresist cleaning in the art, and examples include water-soluble organic solvents such as glycol ether-based solvents.

The glycol ether-based solvent refers to a solvent in which at least one of the two hydroxyl groups of glycol forms an ether. The glycol refers to a compound in which one hydroxy group is substituted for each two carbon atoms of an aliphatic hydrocarbon. . The aliphatic hydrocarbon may be a chain-type aliphatic hydrocarbon or a cyclic aliphatic hydrocarbon. The glycol ether-based solvent is, for example, 3-methoxy-3-methyl-1-butanol (MMB), diisopropylene glycol monomethyl ether (DPM), methyl diglycol (MDG), and ethyl diglycol (EDG). , and butyl diglycol (BDG), ethylene glycol monobutyl ether (EGBE), etc., but are not limited thereto.

According to one aspect of the present invention, the carbonate-based solvent may be included in an amount of 90 to 99.995% by weight, preferably 90 to 99.990% by weight, more preferably 95 to 95% by weight, based on the total 100% by weight of the cleaning liquid composition containing the carbonate solvent. It may be contained at 99.990% by weight. If the content of the carbonate-based solvent is contained within the above range, the cleaning power of the photoresist can be further improved. If the content of the carbonate-based solvent is contained below the above range, the cleaning power may be reduced. If the content exceeds the above range, an anionic surfactant may be used. Since it cannot be included, it may be difficult to expect an increase in cleaning power.

anion meter Surfactants

The photoresist cleaning liquid composition according to one aspect of the present invention includes an anionic surfactant, thereby improving the permeability of the carbonate-based solvent into the photoresist to be removed, thereby improving the penetration of the carbonate-based solvent into the photoresist to be removed. It has the effect of further improving the cleaning power of the carbonate-based solvent on the resist and preventing the inorganic particles, metal oxides, etc. from re-adhering within the spray nozzle.

The anionic surfactant may mean having an anionic functional group in the molecular structure, and in this case, the anionic functional group may mean a group that generates anions in water.

The anionic surfactant may be used without particular limitation as long as it is classified as an anionic surfactant in the art. For example, carboxylate-based alkyl ether carbonate, fatty acid alkali salt, acrylic amino acid, etc.; Sulfonate or sulfate ester series, alkyl sulfate sodium such as sodium laurate sulfate, alkyl sarcosinate salt, alkyl sulfate ester salt, polyoxyethylene alkyl sulfate ester salt, alkylaryl sulfate ester salt, alkylbenzene sulfonate, alkyl naphthalene sulfonic acid. Salts, higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecyl benzenesulfonate and sodium dodecylnaphthalenesulfonate, etc. alkylaryl sulfonates, etc.; Phosphoric acid ester salts or phosphate series include, but are not limited to, alkyl phosphates, polyoxyethylene alkyl phosphoric acid esters, alkylaryl ether phosphates, alkyl phosphoric acid ester salts, and ammonium fluoroalkyl sulfonamides.

According to one embodiment of the present invention, the anionic surfactant is contained in an amount of 0.005 to 10% by weight, preferably 0.010 to 10% by weight, more preferably 0.010 to 0.010% by weight, based on 100% by weight of the photoresist cleaning liquid composition containing the anionic surfactant. It may be included at 5% by weight. If the content of the anionic surfactant is less than the above range, the effect of preventing re-adhesion of inorganic particles such as inorganic pigments or metal particles may be reduced, thereby reducing the cleaning power, and if it exceeds the above range, the viscosity of the composition may improve, making it a self-raw material. And agglomeration may occur between the melted raw materials and inorganic particles and metal particles in the photoresist.

The photoresist cleaning liquid composition of the present invention may further contain various additives depending on the user's needs within the range that does not deteriorate the effect of the present invention.

Hereinafter, preferred embodiments are presented to aid understanding of the present invention. However, the following examples are merely illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and technical spirit of the present invention. , it is natural that such variations and modifications fall within the scope of the attached patent claims. In the following examples and comparative examples, “%” and “part” indicating content are based on weight, unless otherwise specified.

Manufacturing example : Preparation of cleaning liquid composition

A cleaning liquid composition was prepared with the composition and content shown in Table 1 below.

(Unit: weight%) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Carbonate-based solvent A-1 99.95 - - - 97.64 - - 91.42 - - A-2 - 99.54 - 98.43 - 100 - - 92.67 - A-3 - - 98.97 - - - - - - 98.35 Solvents other than carbonate-based A-4 - - - - - - 99.16 - - - A-5 - - - 1.16 - - - 8.58 - - A-6 - - - - 0.82 - - - 7.33 - Anionic surfactant B-1 0.05 - - 0.41 1.54 - 0.84 - - - B-2 - 0.46 - - - - - - - - B-3 - - 1.03 - - - - - - - B-4 - - - - - - - - - 1.65 pH 3.65 2.15 1.41 2.36 5.32 7.03 1.53 11.23 9.5 7.12 A-1: Diethylene carbonate
A-2: Propylene carbonate
A-3: Bisphenyl carbonate
A-4: Propylene glycol methyl ether acetate
A-5: Tetramethylammonium hydroxide (aqueous solution with concentration of 2.38% by weight)
A-6: Diethanolamine
B-1: Phosphate ester (BYK-106, @BYK chemical company)
B-2: Phosphate ester (BYK-110, @BYK chemical company)
B-3: Ammonium fluoroalkyl sulfonamide (Novec 4200, @3M)
B-4: Polyester silicone oil (SH-8400 @Dowcorning)

Experiment example : photoresist Cleansing power evaluation

A photoresist containing titanium oxide (SIJ_W1400, manufactured by DWFC) was uniformly coated with a film thickness of 5㎛ on a 5 × 5cm glass using a spin coater, and then naturally dried at room temperature for 30 minutes to prepare a substrate. . Thereafter, the substrate was immersed in the cleaning solution composition prepared in the examples and comparative examples for 1 minute at room temperature, and then the degree of peeling of the photoresist was measured with the naked eye and a Haze meter, and the results are listed in Table 2 below. The evaluation criteria when observed with the naked eye are as follows.

[Evaluation standard]

◎: Very good (more than 99% of stains and residues removed)

○: Good (more than 90% but less than 99% of stains and residues removed)

△: Normal (removes more than 80% but less than 90% of stains and residues)

×: Poor (less than 80% of photoresist removed)

Immediately after preparing the cleaning solution 1 week after preparing the cleaning solution draft Haze draft Haze Example 1 ◎ 0.7 ◎ 0.7 Example 2 ◎ 0.3 ◎ 0.3 Example 3 ◎ 1.5 ◎ 1.5 Example 4 ○ 10.7 △ 56.5 Example 5 ○ 8.9 △ 49.8 Comparative Example 1 △ 46.3 △ 46.2 Comparative Example 2 × 78.9 × 78.8 Comparative Example 3 △ 54.4 × 89.2 Comparative Example 4 △ 52.7 × 87.4 Comparative Example 5 △ 39.4 △ 40.2

Referring to Table 2 above, in the case of Examples 1 to 5 containing both a carbonate-based solvent and an anionic surfactant as presented in the present invention, and containing only a carbonate-based solvent without an anionic surfactant ( It was confirmed that the cleaning power was superior to Comparative Examples 1, 3, 4, and 5) and the case without carbonate solvent (Comparative Example 2).

In addition, it was confirmed that the effect of the cleaning solution was maintained for a long period of time when it contained only carbonate-based solvents (Examples 1 to 3) rather than when solvents other than carbonate-based were included (Examples 4 and 5). In particular, this When the pH range was outside the range suggested by the invention (Comparative Examples 3 and 4), it was confirmed that the stability over time was worse.

Claims (6)

A photoresist cleaning liquid composition containing a carbonate-based solvent and an anionic surfactant and having a pH of 1 to 7,
The carbonate-based solvents include monoethyl carbonate, diethyl carbonate, dimethyl carbonate, vinyl ethyl carbonate, propylene carbonate, ditertbutyl dicarbonate, diethyl dicarbonate, ethyl methyl carbonate, aryl methyl carbonate, dipropyl carbonate, 1,2- Divinylethylenecarbonate, 4-fluoro-1,3-dioxolane-2-one, 4-phenyl-1,3-dioxolane-2-one, 4-hydroxymethyl-1,3-dioxolane -2-one, 4-butyl-1,3-dioxolane-2-one, bisphenyl carbonate, and 1,2-butylene carbonate;
The carbonate-based solvent is contained in an amount of 90 to 99.995% by weight, based on 100% by weight of the entire cleaning liquid composition containing it,
A photoresist cleaning liquid composition, wherein the photoresist contains metal oxide or inorganic particles. delete delete According to paragraph 1,
A photoresist cleaning liquid composition characterized in that the anionic surfactant is contained in an amount of 0.005 to 10% by weight based on 100% by weight of the total cleaning liquid composition containing the anionic surfactant. delete According to paragraph 1,
The carbonate-based solvent is selected from the group consisting of monoethyl carbonate, dimethyl carbonate, propylene carbonate, diethyl dicarbonate, 4-hydroxymethyl-1,3-dioxolan-2-one, and 1,2-butylene carbonate. A photoresist cleaning liquid composition comprising at least one.