KR20030061286A - Cleaning composition for a positive or negative photoresist - Google Patents

Abstract

0.1 to 20% by weight of alkyl oxide polymer (a) having a molecular weight of 50 to 2000, 1 to 20 parts by weight of dipropylene glycol methyl ether (DPGME), 10 to 50 parts by weight of N-methylpyrrolidone (NMP) and methyl 10 to 90 parts by weight of an organic solvent (b1) or dimethylformamide (DMF) containing 50 to 90 parts by weight of isobutyl ketone (MIBK) and an organic solvent (b2) or dimethylacetate containing 10 to 50 parts by weight of n-butyl acetate A composition for cleaning a positive or negative photoresist material comprising 80 to 99.9% by weight of any one of an organic solvent (b3) including 10 to 90 parts by weight of amide (DMAc) and 10 to 50 parts by weight of n-butyl acetate.

Description

Cleaning composition for positive or negative photoresist

The present invention relates to a composition for cleaning a photoresist, and more particularly to a device and a photosensitive material contacting a photosensitive material during a microcircuit processing process using a negative photoresist resist composition containing a positive or negative photoresist composition and a pigment. A photosensitive agent cleaning composition used to remove photosensitive material remaining in unwanted portions of a substrate to be coated.

Methods of making photoresist compositions are well known in the art and are described, for example, in US Pat. Nos. 3,666,473, 4,115,128, and 4,173,470. These compositions include phenol-formaldehyde nobulac resins and photosensitive materials, usually substituted naphthoquinone diazo compounds.

The nobulak resin component in such a photoresist composition is soluble in an aqueous alkali solution, but the naphthoquinone photosensitizer acts as a dissolution rate inhibitor for the resin. However, when a particular portion of the coated substrate is exposed to actinic radiation, the photosensitizer will cause radiation induced structural deformation and the exposed portion of the coating layer will be more soluble than the unexposed portion.

The relief pattern RELIEF PATTERN of the photoresist manufactured by the above method is used to make 1 um small lines and weirs, for example, in a semiconductor manufacturing process.

In addition, such a small circuit manufacturing process can increase the circuit density by increasing the resolution of the resist using photolithography technique. Such photoresists have been widely used in the manufacture of semiconductors and liquid crystal displays.

An example of using the photosensitive material of the color filter process in the liquid crystal display device will be described in more detail as follows.

The color filter process involves coating a negative photosensitive material containing a positive or pigment on a rectangular glass or conductive metal film (hereinafter referred to as a 'substrate'), soft-bake it, exposing it, and then developing it. Make a pattern of shapes to make.

In the process of forming such a microcircuit pattern, when the photoresist film is formed on the substrate, the photoresist film formed on the edge of the substrate becomes uneven compared with the photoresist film formed on the center of the substrate, and also the edge unevenly during the soft baking process or the exposure process. It needs to be removed to prevent contamination of the equipment due to the applied photoresist material.

As a method of removing a coated photoresist film by a physical method, a method of scraping a film is known, but this method has a problem in that the removal of the film is not uniform and damages the film.

BACKGROUND OF THE INVENTION A method of removing a photoresist film with a compound for chemically stripping or cleaning the photoresist film is generally known.

U.S. Patent No. 4,983,490 discloses a photoresist film treatment solution consisting of 1 to 10 parts by weight of propylene glycol alkyl ether (PGME) and 1 to 10 parts by weight of propylene glycol alkyl ether acetate (PGMEA).

However, such a general chemical composition mainly shows an excellent cleaning ability for the positive photosensitive agent, but has the following disadvantages for the negative photosensitive agent containing the pigment.

The negative photosensitive agent containing a pigment is a photosensitive agent used for a color filter among liquid crystal display devices, and its photosensitive agent is black, red, blue, and green.

When the photoresist containing such a pigment is washed with the above-described cleaning agent consisting of 1 to 10 parts by weight of PGME and 1 to 10 parts by weight of PGMEA, the photoresist residue is reduced on the interface between the cleaned and unwashed parts after development. Will remain.

SUMMARY OF THE INVENTION An object of the present invention is to provide a cleaning composition in which a negative photosensitive agent containing a pigment is soft-baked after cleaning, exposed to light, and no photosensitive residue remains on the cleaned and uncleaned interface after development. do.

Another object of the present invention is to provide a cleaning composition in which the build-up phenomenon does not occur, in which the photoresist rises higher than the original coated thickness by the cleaning liquid at the part where the photosensitive material is cleaned during cleaning and at the interface at which the photosensitive material is not cleaned. To provide.

Still another object of the present invention is to provide a cleaning composition having excellent cleaning ability of the photosensitive film.

1 is a graph showing the build-up characteristics of each of the positive photosensitive agent when cleaning the positive photoresist using the cleaning composition and the general organic solvent cleaning agent of the present invention.

Figure 2 is a photograph showing whether the photoresist remains when washing the color photosensitive agent using the cleaning composition of the present invention.

In order to achieve the above object, the present invention provides a cleaning composition comprising an alkyl oxide (a) of 0.1 to 20% by weight and an organic solvent (b) of 80 to 99.9% by weight of the molecular weight within 50-2000 to provide.

The organic solvent (b) is preferably a mixture (b1) of methyl isobutyl ketone (MIBK), dipropylene glycol methyl ether (DPGME) and N-methylpyrrolidone (NMP), or dimethylformamide (DMF). ) And a mixture of n-butyl acetate (b2), or a mixture of dimethylacetamide (DMAc) and n-butyl acetate (b3).

Hereinafter, the present invention will be described in detail.

The cleaning composition of the present invention comprises an alkyl oxide polymer (a) having a molecular weight of 50 to 2000, methyl isobutyl ketone (MIBK), dipropylene glycol methyl ether (DPGME) and N-methylpyrrolidone (NMP). An organic solvent (b1) or an organic solvent (b2) consisting of dimethylformamide (DMF) and n-butyl acetate or a mixture of an organic solvent (b3) consisting of dimethylacetamide (DMAc) and n-butylacetate.

Wherein the preferred amount of alkyloxide polymer (a) in the composition is 0.1 to 20% by weight relative to the total composition. If the amount of the polymer exceeds 20% by weight, it is not preferable because it is not completely volatilized during the soft-bake process. It is undesirable because there is a residual photoresist material at the interface.

In addition, even when the molecular weight of the polymer exceeds 2000 there is a problem that does not volatilize completely is not preferable. If the molecular weight is less than 50, the coated photoresist is undesired since there is a residual photoresist material at the cleaned and post-cleaned interface after exposure development.

Most preferred alkyl oxide polymers are ethylene or propylene oxide polymers, and either end group of the alkyl oxide polymer has no change in its performance no matter which group is substituted.

Next, the composition of the most preferable organic solvent (b) to be mixed with the alkyl oxide polymer (a) is as follows.

(b-1) Examples of preferred organic solvent mixtures include 1 to 20 parts by weight of dipropylene glycol methyl ether (DPGME), 10 to 50 parts by weight of N-methylpyrrolidone (NMP) and methyl isobutyl ketone (MIBK) 50 To 90 parts by weight of an organic solvent mixture. In the case of dipropylene glycol methyl ether (DPGME), when it exceeds 20 parts by weight, there is a characteristic that does not completely volatilize, when less than 1 part by weight, the washing power is not preferable because it is not preferable. In the case of N-methylpyrrolidone (NMP) when mixed to 10 parts by weight or less, the washing power is sharply dropped, it is not preferable, it is most preferably mixed within 50 parts by weight. When methyl isobutyl ketone (MIBK) is less than 50 parts by weight, the washing power is not preferable, and it is most preferable to mix within 90 parts by weight.

(b-2) Another most preferred organic solvent mixture is an organic solvent mixture consisting of 10 to 90 parts by weight of dimethylformamide (DMF) and 10 to 50 parts by weight of n-butyl acetate.

If the content of n-butyl acetate is more than 50 parts by weight, or less than 10 parts by weight, there is a problem that the washing ability is lowered.

(b-3) Another most preferred organic solvent mixture is an organic solvent mixture consisting of 10 to 90 parts by weight of dimethylacetamide (DMAc) and 10 to 50 parts by weight of n-butyl acetate.

Here, when the content of n-butyl acetate is more than 50 parts by weight or less than 10 parts by weight, there is a problem that the washing ability is lowered.

In the case of the compounds (b-1), (b-2) and (b-3), the coating thickness of the photosensitive agent is thicker at the interface between the cleaned and uncleaned portions when cleaning the positive photosensitive agent. -up) Excellent ability without phenomenon.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

<Example 1>

After coating AZ HKT501, a positive photoresist, on a 370mm × 470mm glass substrate using a spinner, 3% by weight of an alkyl oxide polymer having a molecular weight of 300, 80% by weight of DMF, and 17% by weight of n-butyl acetate were mixed in a DNS EBR apparatus. After dissolving and removing the resist layer from the periphery and the back of the glass plate using the result of observing the results using a microscope, it was confirmed that there is no photoresist remaining without being removed.

<Example 2>

As a removal solvent, a resist layer was formed from the periphery and the back of the glass plate by using a composition obtained by mixing 3% by weight of an alkyl oxide polymer having a molecular weight of 300, 7% by weight of DPGME, 20% by weight of NMP, and 70% by weight of MIBK, as a removal solvent. After dissolving and removing the result of observation using a microscope, it was confirmed that there was no photoresist remaining without being removed.

<Example 3>

Except for using 80% by weight of DMAc instead of 80% by weight of DMF and observed using the results as in Example 1, it was confirmed that there is no photosensitizer still remaining without being removed.

Comparative Example 1

As a removal solvent, the experiment was performed in the same manner as in Example 1 using a composition containing 30% by weight of propylene glycol monomethyl ether acetate (PGMEA) and 70% by weight of propylene glycol monomethyl ether (PGME). Marked on.

1 is a build-up after coating the substrate using the cleaning composition of the present invention prepared in Examples 1 and 2 and the general organic solvent cleaning agent in Comparative Example after coating the positive photosensitive agent AZ HKT 501 on the substrate (build -up) A graph showing the characteristics. As shown in FIG. 1, when cleaning using the cleaning composition of the present invention, there is no buildup phenomenon at the interface between the cleaned portion and the uncleaned surface, and organic solvent penetrates into the photosensitive agent so that the coating thickness does not change. Able to know.

Figure 2 is a photograph showing whether the photoresist remains when washing the color photosensitive agent using the cleaning composition of the present invention prepared in Examples 1 and 2. As can be seen in Figure 2, after coating the JSR color photosensitive agent (R, G, B) on the substrate, using the cleaning mixture of the present invention prepared in Examples 1 and 2 to wash, bake and develop the It can be seen that no residue is present.

As described above, the positive and negative photosensitive agent cleaning composition of the present invention is very excellent in cleaning power and no residue after cleaning, as well as build-up phenomenon or cleaning solution on the surface of the cleaned and uncleaned parts. There is also no problem of penetrating into the coated photoresist to change the coating thickness.

Claims (7)

Alkyl oxide polymers having a molecular weight of 50 to 2000 (a) from 0.1% to 20% by weight; Organic solvent (b) 80 to 1 to 20 parts by weight of dipropylene glycol alkyl ether (DPGME), 10 to 50 parts by weight of N-methylpyrrolidone (NMP) and 50 to 90 parts by weight of methyl isobutyl ketone (MIBK) A composition for cleaning a positive or negative photosensitive material comprising 99.9%. The composition of claim 1, wherein said alkyl oxide polymer is an ethylene oxide polymer. The composition of claim 1, wherein said alkyl oxide polymer is a propylene oxide polymer. The composition for cleaning a positive or negative photosensitive material according to any one of claims 1 to 3, wherein the dipropylene glycol alkyl ether is dipropylene glycol methyl ether. Alkyl oxide polymer having a molecular weight of 50 to 2000 (a) 0.1 to 20% by weight; And A composition for cleaning a positive or negative photoresist material comprising 80 to 99.9% of an organic solvent (b) comprising 10 to 90 parts by weight of dimethylformamide (DMF) or dimethylacetamide (DMAc) and 10 to 50 parts by weight of n-butyl acetate. The composition of claim 5, wherein said alkyl oxide polymer is an ethylene oxide polymer. The composition of claim 5, wherein the alkyl oxide polymer is a propylene oxide polymer.