KR102445663B1 - Cleaning composition for photoresist supply nozzles - Google Patents

Abstract

The present disclosure relates to a composition for cleaning a photoresist supply nozzle. The composition for cleaning a photoresist supply nozzle comprises: alkylene glycol alkyl ether acetate (component A); and compounds having a structure of at least three kinds of formula 1 (component B), wherein the compounds of component B all belong to the structure of formula 1, but are different compounds. (In formula 1, R1, R2, and R3 are hydrogen or a C1 to C4 straight or branched alkyl group, and R4 is a C1 to C4 straight or branched alkylene group or a ketone group, wherein the C1 to C4 straight or branched alkylene group can or cannot include a ketone group.) The composition for cleaning a photoresist supply nozzle according to the present disclosure has excellent cleaning power so as to remove a photoresist component remaining in a photoresist supply device or the photoresist supply nozzle.

Description

Composition for cleaning photoresist supply nozzles {CLEANING COMPOSITION FOR PHOTORESIST SUPPLY NOZZLES}

The present disclosure relates to a cleaning composition for removing a photoresist used during a semiconductor or display manufacturing process. Specifically, when photoresist remaining on equipment or supply nozzles for supplying photoresist, or modified or cured photoresist remains on equipment or supply nozzles, etc., it relates to a composition for removing and cleaning the modified or cured photoresist will be.

In a manufacturing process of a display device, a lithography technique is used to manufacture an electronic circuit or a pixel for realizing a color. The lithography process is a method used to create a fine pattern on a substrate. The circuit pattern of the mask is transferred to the substrate by irradiating light through a mask on which a desired pattern is printed on a substrate on which a photosensitive material (also called photoresist) is applied. is a process that

The applied photosensitive material is removed from the substrate by selectively interacting with the developer in the light-receiving part or the non-lighting part depending on the type of the photosensitive agent in the developing process, thereby obtaining a photosensitive agent pattern such as a target circuit pattern. .

In a lithography process for semiconductor manufacturing, a photosensitive material is uniformly applied to a wafer by a rotation coating method, and a lithography process of a large substrate for display manufacturing uses a linear coating method rather than a rotation coating method. In this linear coating method, the photosensitive material is uniformly applied to the entire surface of the substrate while linearly moving the spray nozzle. The photosensitive material present at the edge of the wafer used during the semiconductor process or unnecessarily applied to the rear surface of the wafer during the coating process as described above may act as a contamination source that reduces the process yield in the subsequent process, so it must be removed. One of the processes for this is an EBR (edge bead removing) process, and at this time, a cleaning solution for removing unnecessary photosensitive materials is a thinner composition. In addition, the thinner composition is also used in the reducing resist consumption (RRC) process, in which the surface of the wafer is first treated with a thinner before applying the photosensitive material to the wafer so that it can be evenly applied to the entire surface of the wafer using only a small amount of the photosensitive agent.

In the process of applying the photoresist, it is required to clean not only the substrate to be coated but also the supply nozzle of the photoresist supply device to which the photoresist is supplied.

As the process of applying the photosensitive material on the substrate through the nozzle structure is repeatedly performed, some residues of the photosensitive material remain in the coating device, and in severe cases, the nozzle may be clogged. In addition, since the photosensitive material is a liquid, after supplying the photosensitive material through the nozzle, the photosensitive material condensed on the tip of the nozzle may drop onto the substrate little by little in the form of droplets. In this case, if the photosensitive material falling in the form of droplets after time is contaminated, it may adversely affect the lithography process. In particular, the photosensitive solution condensed on the tip of the nozzle may undergo a phenomenon such as evaporation of the solvent to form unnecessary photoresist, so it is necessary to clean the supply nozzle.

Korean Patent Application Laid-Open No. 10-2020-0079655 discloses a cleaning solution using a carbonate solvent and an anionic surfactant.

Korean Patent Application Laid-Open No. 10-2020-0025651 discloses alkoxy propionate, propylene glycol ether-based compounds and propylene glycol ether acetate-based thinner compositions applicable to RRC (Reduce Resist Coating) and EBR (Edge Bead Removal) processes. Compositions of the compounds are disclosed.

On the other hand, the photosensitive material supply nozzle is a part of the device for supplying the photoresist, and is made of a stainless material different from the silicon wafer or glass substrate to which the photoresist component is applied. Therefore, since there is a difference between the interaction between the semiconductor substrate or the display substrate and the photoresist and the interaction between the stainless steel and the photoresist, there is a need for the development of a cleaning agent optimized for cleaning the supply nozzle made of stainless steel material.

Korean Patent Application Laid-Open No. 10-2020-0079655 (published date: 2020.07.06) Korean Patent Application Laid-Open No. 10-2020-0025651 (published date: March 10, 2020)

An object of the present disclosure is to provide a composition for cleaning a photoresist supply nozzle having excellent cleaning power.

In order to achieve the above object, the present disclosure provides a composition for cleaning a photoresist supply nozzle, the composition comprising:

- alkyleneglycol alkylether acetate (component A); and

- at least three compounds having the structure of the formula (1) (component B);

including,

Here, the compounds of component B all belong to the structure of formula 1, but are different compounds:

[Formula 1]

(In Formula 1,

R1, R2, and R3 are hydrogen or a C1 to C4 linear or branched alkyl group;

R4 is a C1-C4 straight-chain or branched alkylene group or ketone group, wherein the C1-C4 straight-chain or branched alkylene group does not include or includes a ketone group).

The sum of the contents of the compounds of component B is 80 to 90% by weight, based on the total weight of the composition.

The content of the compound having the largest content among the compounds of component B is 70 to 95% by weight, based on the sum of the contents of the compounds of component B.

In addition, the present disclosure provides a method of cleaning a photoresist supply nozzle, the cleaning method comprising cleaning the supply nozzle through which the photoresist is discharged using the photoresist supply nozzle cleaning composition.

Since the photoresist supply nozzle cleaning composition according to the present disclosure has excellent cleaning power, it is possible to remove photoresist components remaining in the photoresist supply device or the photoresist supply nozzle.

In addition, it is possible to increase the production yield of the display manufacturing process by removing contamination sources such as residual photoresist remaining in the supply device or the supply nozzle.

1 shows the removal result of the i-line-B performed on the SUS substrate.
2 shows the result of PSPI removal performed on the SUS substrate.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. However, since various changes may be made to the embodiments, the scope of the patent application is not limited or limited by these embodiments. It should be understood that all modifications, equivalents and substitutes for the embodiments are included in the scope of the rights.

The terms used in the examples are used for the purpose of description only, and should not be construed as limiting. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present specification, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It is to be understood that this does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the embodiment belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

In addition, in describing the components of the embodiment, terms such as first, second, A, B, (a), (b), etc. may be used. These terms are only for distinguishing the elements from other elements, and the essence, order, or order of the elements are not limited by the terms.

Components included in one embodiment and components having a common function will be described using the same names in other embodiments. Unless otherwise stated, descriptions described in one embodiment may be applied to other embodiments as well, and detailed descriptions within the overlapping range will be omitted.

It is understood that the term “about” refers to a range of numbers that one of ordinary skill in the art would consider equivalent to the recited value in terms of achieving the same function or result.

All numerical ranges set forth throughout this specification include their upper and lower values, as well as all narrower numerical ranges falling therein, and all such narrower numerical ranges are considered to be expressly and specifically set forth herein.

As used herein, the term “alkyl” refers to a straight-chain or branched saturated C1 to C4 hydrocarbon radical, which may be substituted or unsubstituted. In this case, the substituent may include halogen, alkyl, hydroxy, and the like. Specific alkyls may include methyl, ethyl, propyl, isopropyl, tert-butyl, sec-butyl, n-butyl, and the like.

A composition for cleaning a photoresist supply nozzle according to the present disclosure, the composition comprising:

- alkyleneglycol alkylether acetate (component A); and

- at least three compounds having the structure of formula (1) (component B);

including,

In this case, a composition for cleaning a photoresist supply nozzle is provided, wherein all of the compounds of component B belong to the structure of Formula 1, but are different compounds:

[Formula 1]

(In Formula 1,

R1, R2, and R3 are hydrogen or a C1 to C4 linear or branched alkyl group;

R4 is a C1-C4 straight-chain or branched alkylene group or ketone group, wherein the C1-C4 straight-chain or branched alkylene group includes or does not include a ketone group).

According to one embodiment, the alkylene glycol alkyl ether acetate is propylene glycol alkyl ether acetate. According to a specific embodiment, the propylene glycol alkyl ether acetate is propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol pentyl ether acetate, propylene glycol hexyl ether acetate, or these may be a combination of Propylene glycol alkyl ether acetate is preferably propylene glycol methyl ether acetate.

The content of component A is from about 10 to about 20% by weight, based on the total weight of the composition. When it satisfies the weight percent range, it may have better photoresist cleaning power.

According to one embodiment, the compound having the structure of Formula 1 may be as follows.

[Formula 1]

(In Formula 1,

R1, R2, and R3 are hydrogen or a C1 to C4 linear or branched alkyl group;

R4 is a C1-C4 straight-chain or branched alkylene group or ketone group, wherein the C1-C4 straight-chain or branched alkylene group includes or does not include a ketone group).

Each of the compounds having the structure of Formula 1 may be a compound selected from among alkylene glycol alkyl ether-based compounds, glycorate-based compounds, lactate-based compounds, butyrate-based compounds, and pivalate-based compounds, and in particular, Compounds having the structure of Formula 1 include (i) at least one compound selected from among alkylene glycol alkyl ether compounds; (ii) at least one compound selected from glycorate-based compounds and lactate-based compounds; and (iii) at least one compound selected from a butyrate-based compound and a pivalate-based compound;

As the alkylene glycol alkyl ether compound, a propylene glycol alkyl ether compound may be used, and more specifically, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, or their can be a combination. Among the alkylene glycol alkyl ether compounds, propylene glycol monomethyl ether is preferable.

The glycorate-based compound may be methyl glycorate, ethyl glycorate, or a combination thereof.

The lactate-based compound may be methyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, tert-butyl lactate, or a combination thereof. Among the lactate compounds, ethyl lactate is preferable.

The butyrate-based compound may be a hydroxybutyrate-based compound, and more specifically, methyl 2-hydroxyisobutyrate, methyl 3-hydroxyisobutyrate, ethyl 2-hydroxybutyrate, ethyl 2-hydroxyisobutyrate, propyl 2 -Hydroxyisobutyrate, isopropyl 2-hydroxyisobutyrate, butyl 2-hydroxyisobutyrate, isobutyl 2-hydroxyisobutyrate, isopropyl 3-hydroxybutyrate, butyl 2-hydroxyisobutyrate, t- butyl alpha-hydroxyisobutyrate, or a combination thereof. Of the above butyrate compounds, methyl 2-hydroxyisobutyrate is preferable.

The pivalate-based compound may be methyl 3-hydroxypivalate.

According to one embodiment, the sum of the contents of the compounds of the component B is 80 to 90% by weight, based on the total weight of the composition, and the content of the compound having the highest content among the compounds of the component B is the component B Based on the sum of the contents of the compounds, it is 70 to 95% by weight, more preferably 80 to 90% by weight. The compound having the largest content among the compounds of component B is a compound that does not contain a ketone group. When the above weight percentage range is satisfied and the maximum content compound does not contain a ketone group, a better photoresist cleaning power is obtained.

According to an aspect, the cleaning composition according to the present disclosure may further include a polar solvent within a range that does not affect the nozzle cleaning effect. The polar solvent may be a protic polar solvent and an aprotic polar solvent. Polar solvents include alcoholic compounds such as ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, and glycerol; It may be one or more of a cyclic compound such as a nate compound, cyclohexanone (CHN), tetrafurfuryl alcohol (THFA), and an acetate compound such as ethyl acetate, propyl acetate, and butyl acetate, but the solvent is not limited thereto.

The photoresist material that can be removed with the cleaning composition according to the present disclosure is not particularly limited, and any photoresist material commonly used in the art may be removed from the supply nozzle. The present disclosure has been developed for the purpose of providing a composition for cleaning a supply nozzle that, unlike a thinner composition, can remove a wide variety of photoresist materials from the supply nozzle. In one embodiment, various types of photoresists such as i-line PR, g-line, and PSPI were evaluated and it was confirmed that the cleaning power was excellent.

A method of cleaning a photoresist supply nozzle using a cleaning composition according to the present disclosure is also provided. The cleaning method may be performed by a commonly known method such as a dip method, a spray method, or a method of passing the nozzle in cleaning the supply nozzle from which the photoresist is discharged, and the cleaning method is not limited to a specific method.

A cleaning composition according to the present disclosure is described in more detail below.

Examples 1 to 11 and Comparative Examples 1 to 11

Cleaning compositions of Examples 1 to 11 and Comparative Examples 1 to 11 were prepared as described in Table 1 below.

Component A Component B: Component of Formula 1 other ingredients Total content of compounds of Formula 1 (wt%) % by weight of the maximum content compound of the compounds of formula (1) PMA PM ML EL PL HBM HE EEP CHN Example 1 10 65 10 15 90 72.2 Example 2 10 70 5 15 90 77.8 Example 3 10 70 10 10 90 77.8 Example 4 15 60 5 20 85 70.6 Example 5 18 65 8 10 82 75.6 Example 6 15 70 5 10 85 82.3 Example 7 15 75 5 5 85 88.2 Example 8 15 72 5 8 85 84.7 Example 9 15 75 5 5 85 88.2 Example 10 15 75 5 5 85 88.2 Example 11 20 75 2 3 80 93.8 Comparative Example 1 70 30 30 100 Comparative Example 2 10 50 20 20 90 55.6 Comparative Example 3 20 30 45 5 80 56.5 Comparative Example 4 22 70 3 5 78 89.7 Comparative Example 5 15 85 85 100 Comparative Example 6 10 40 20 30 90 44.4 Comparative Example 7 30 65 2 3 70 92.8 Comparative Example 8 5 85 5 5 95 89.5 Comparative Example 9 10 60 5 25 90 66.6 Comparative Example 10 10 60 20 10 90 66.6 Comparative Example 11 10 60 10 20 90 66.6

PMA: propylene glycol monomethyl ether acetate PM: propylene glycol monomethyl ether

ML: methyl lactate,

EL: ethyl lactate

PL: propyl lactate

HBM: methyl 2-hydroxyisobutyrate

HE: ethyl 2-hydroxyisobutyrate

EEP: Ethyl-3-ethoxy propionate

CHN: cyclohexanone

In order to evaluate the cleaning ability on the photoresist of each of the prepared cleaning compositions, it was carried out as follows:

A photoresist-coated specimen with a thickness of 10 μm was prepared by applying a photoresist to a SUS 304 specimen having a size of 5 cm*2 cm and soft baking in an oven at 110° C. for 5 minutes. In the case of the photosensitive polyimide insulating film (PSPI), soft baking was performed for 30 minutes. 50ml of each of the compositions of Examples 1 to 11 and Comparative Examples 1 to 11 was put into a 100ml beaker, and the previously prepared specimen was immersed in a beaker containing the cleaning composition for 30 seconds, and then the specimen was taken out and washed with water. The specimens were visually observed, and the cleaning power was compared and shown in Table 2.

In this case, the evaluation criteria were as follows:

<Evaluation criteria (visual evaluation criteria)>

Δ: Residual photoresist (PR) material can be reliably discerned from the entire surface.

○: Residual PR material can be confirmed in some parts.

(double-circle): It is difficult to confirm the residual of a PR substance.

i line PR-A i line PR-B g line PR PSPI Example 1 ○ ○ ○ ○ Example 2 ○ ○ ○ ○ Example 3 ○ ○ ○ ○ Example 4 ○ ○ ○ ○ Example 5 ○ ○ ○ ○ Example 6 ○ ○ ○ ◎ Example 7 ◎ ◎ ◎ ◎ Example 8 ◎ ◎ ◎ ◎ Example 9 ◎ ○ ○ ○ Example 10 ○ ○ ○ ○ Example 11 ○ ○ ○ ○ Comparative Example 1 ○ △ ○ △ Comparative Example 2 ○ △ ○ △ Comparative Example 3 △ ○ ◎ △ Comparative Example 4 △ ○ ○ △ Comparative Example 5 △ △ △ ○ Comparative Example 6 △ △ △ ○ Comparative Example 7 ◎ ○ ◎ △ Comparative Example 8 △ ○ ○ △ Comparative Example 9 △ ○ △ △ Comparative Example 10 ○ △ ○ △ Comparative Example 11 ○ △ △ △

In addition, the removal result of the i-line PR-B performed on the SUS substrate according to Example 6 is shown in FIG. 1 compared with the result according to Comparative Example 1, and the PSPI removal result performed on the SUS substrate according to Example 6 is shown. Compared with the results according to Comparative Example 1, it is shown in FIG. 2 .

Examples 1 to 11 were confirmed to have excellent cleaning power for various photoresist materials. However, Comparative Examples 1 and 5, which were set not to include three or more compounds of Formula 1, showed poor cleaning power for some photoresists. In addition, Comparative Examples 2, 6, and 10 set so that the weight % of the compound having the maximum content among the compounds having the structure of Formula 1 (based on the total weight of the compounds having the structure of Formula 1) is out of 70 to 95% by weight It was also found that the cleaning power for some photoresists decreased. The compound having the largest content among the compounds having the structure of Formula 1 is set to be a compound containing a ketone group, and the weight % of the compound having the largest content among the compounds having the structure of Formula 1 (compound having the structure of Formula 1) (based on the total weight) of Comparative Example 3, which is set to deviate from 70 to 95% by weight, and the weight% of the sum of the contents of the compounds having the structure of Formula 1 (based on the total weight of the total composition) is set to deviate from 80 to 90% by weight It can be seen that Comparative Examples 4, 7, and 8 also have poor cleaning power for some photoresists. Furthermore, the weight % of the compound having the largest content among the compounds having the structure of Formula 1 (compound having the structure of Formula 1) Comparative Examples 9 and 11, which were set to deviate from 70 to 95% by weight), were also found to have poor cleaning power. Therefore, three or more compounds of Formula 1, the weight % of the sum of the content of the compounds having the structure of Formula 1 satisfy 80 to 90% by weight, and the compound having the maximum content among the compounds having the structure of Formula 1 is a ketone It should not contain a group, and when it satisfies the range of 70 to 95 wt%, the cleaning power for all photoresists was excellent.

Although the embodiments have been described as described above, those skilled in the art may apply various technical modifications and variations based on the above. For example, even if the described techniques are combined or combined in other forms, or substituted or substituted by other elements or equivalents, appropriate results may be achieved.

Therefore, other implementations, other embodiments, and equivalents to the claims are also within the scope of the following claims.

Claims (10)

A composition for cleaning a photoresist supply nozzle, the composition comprising:
- alkyleneglycol alkylether acetate (component A); and
- at least three compounds having the structure of the formula (1) (component B);
including,
At this time, all of the compounds of component B belong to the structure of Formula 1, but are different compounds,
The content of the compound having the largest content among the compounds of the component B, based on the sum of the contents of the compounds of the component B, will be 70 to 95% by weight, the photoresist supply nozzle cleaning composition:
[Formula 1]

(In Formula 1,
R1, R2, and R3 are hydrogen or a C1-C4 straight-chain or branched alkyl group;
R4 is a C1-C4 straight-chain or branched alkylene group or a ketone group, wherein the C1-C4 straight-chain or branched alkylene group includes or does not include a ketone group).
According to claim 1, wherein the sum of the content of the compounds of the component B, based on the total weight of the composition, 80 to 90% by weight, the content of the component A, based on the total weight of the composition, 10 to 20 weight %, the photoresist supply nozzle cleaning composition.
delete The composition for cleaning a photoresist supply nozzle according to claim 1, wherein the compound having the highest content among the compounds of component B is a compound that does not contain a ketone group.
According to claim 1, wherein the component B,
(i) at least one compound selected from among alkylene glycol alkyl ether compounds;
(ii) at least one compound selected from glycorate-based compounds and lactate-based compounds; and
(iii) at least one compound selected from a butyrate-based compound and a pivalate-based compound;
A composition for cleaning a photoresist supply nozzle comprising a.
According to claim 1, wherein the alkylene glycol alkyl ether acetate is propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol propylene glycol butyl ether acetate, propylene glycol pentyl ether acetate, propylene glycol hexyl ether acetate, or a combination thereof. for composition.
The composition for cleaning a photoresist supply nozzle according to claim 5, wherein the alkylene glycol alkyl ether-based compound is propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, or a combination thereof.
The composition for cleaning a photoresist supply nozzle according to claim 5, wherein the glycorate-based compound is methyl glycolate, ethyl glycolate, or a combination thereof.
The method of claim 5, wherein the lactate-based compound is methyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, tert-butyl lactate, or a combination thereof. A composition for cleaning a photoresist supply nozzle.
The method of claim 5, wherein the butyrate-based compound is methyl 2-hydroxyisobutyrate, methyl 3-hydroxyisobutyrate, ethyl 2-hydroxybutyrate, ethyl 2-hydroxyisobutyrate, propyl 2-hydroxyisobutyrate, Isopropyl 2-hydroxyisobutyrate, butyl 2-hydroxyisobutyrate, isobutyl 2-hydroxyisobutyrate, isopropyl 3-hydroxybutyrate, butyl 2-hydroxyisobutyrate, t-butyl alpha-hydroxyiso Butyrate, or a combination thereof, the photoresist supply nozzle cleaning composition.

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