KR100733650B1 - Edge bead remover - Google Patents

Abstract

The edge bead remover of this invention is alpha-hydroxyisobutyrate methyl, and the following general formula (I):

(R is hydrogen or acetyl group, R ¹ is hydrogen or methyl group, R ² is an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 3. However, when R is hydrogen, n is an integer of 1 to 3) It is a solvent composition containing the compound represented by.

This edge bead remover has a high resist dissolving ability, and a small amount of use can sufficiently remove the unnecessary resist with a short cleaning time.

In addition, the edge bead remover has high safety for the human body, very little unpleasant odor that may be present in the organic solvent and excellent workability.

Description

EDGE BEAD REMOVER}

The present invention relates to a novel edge bead remover and a method for removing unnecessary resist from an electronic component substrate during or after applying a resist-forming composition using the edge bead remover. .

Application of the resist-forming composition includes spin coating, roll coating, reverse roll coating, cast-coating, doctor-coating, dip-coating, land-coating, and the like. Various methods are employed, and spin coating is selected in the manufacture of integrated circuit devices.

In the spin coating method, a predetermined volume of the resist-forming liquid composition deposited on the substrate is spread out in the circumferential direction outside the substrate by the rotation of the substrate, and the excess resist-forming liquid composition is spun off at the substrate edge so that the substrate A resist film having a desired thickness is formed in the center portion.

However, spin coating methods involve an edge bead in which a portion of the resist-forming composition spreads around the edge of the substrate to reach the back side of the substrate or the resist-forming composition applied to the outer circumferential portion of the substrate becomes thicker than other portions of the substrate. There is a drawback that it is formed.

Such edge beads and unnecessary resist are removed by heat treatment in the next process and peeled into small scale pieces during transportation of the substrate, which causes contamination of the device. The exfoliated resist is attached to the resist surface on the substrate and causes serious problems in manufacturing high quality semiconductor devices.

Therefore, it is necessary to remove unnecessary edge beads from the substrate and to remove unnecessary resist from the side or back side of the substrate.

As with the spin coating method, other coating methods have a problem associated with deposition of unnecessary resist.

The solvent used for removing such unnecessary edge beads and resist is referred to as "edge bead remover".

As described in US Pat. No. 5,814,433, edge bead removers are used to remove resist prior to imagewise exposure and are significantly different from the resist release agent in terms of the required properties as well as the timing of use, which is the end of the etching process. This is because it is used to remove an unused resist pattern.

Japanese Unexamined Patent Publication No. 63-69563 proposes 1-methyl-2-pyrrolidone, acetone and xylene as a solvent used in edge bead removers. Japanese Patent Application Laid-Open No. 7-146562 discloses an ether such as ethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether, and propylene glycol monoalkyl acetate as a cleaning solvent for removing a resist together with a conventionally known solvent. B acetates; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate and alkoxycarboxylates or mixtures thereof Described.

However, some conventional cleaning agents do not have sufficient dissolving ability to resist, and residues or precipitates are liable to be generated at the time of cleaning, and a long time or a large amount of cleaning agents are required to perform sufficient cleaning.

Less volatile cleaning agents require a long time to dry and are disadvantageous for practical use. On the contrary, most ketones and esters have high vapor pressure, resulting in poor workability.

Moreover, many solvents, including highly soluble ethylene glycol solvents, are somewhat toxic and have an unpleasant odor. Therefore, there is a need for a detergent that simultaneously satisfies excellent solubility and better safety for the human body.

This demand is not limited to the manufacture of integrated circuit devices, but also appears in the manufacturing field of color filters, liquid crystal display devices and the like.

An object of the present invention is to provide an edge bead remover that has high solubility and good workability and excellent workability, which can sufficiently remove unnecessary resist in a short amount of time in a short time.

MEANS TO SOLVE THE PROBLEM As a result of earnestly research, the present inventors have shown that (alpha) -hydroxyisobutyrate and general formula (I):

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(R is hydrogen or acetyl group, R ¹ is hydrogen or methyl group, R ² is an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 3. However, when R is hydrogen, n is an integer of 1 to 3) The homogeneous solvent composition comprising the compound represented by the formula has a high solubility that can sufficiently remove unnecessary resist in a short amount of time with a small amount of use, has high safety for the human body, almost no unpleasant odor that may be present in the organic solvent, and workability It has been found to act as an excellent edge bead remover. We have accomplished the present invention based on this finding.

Therefore, the present invention provides α-hydroxyisobutyrate methyl and the following formula (I):

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(R is hydrogen or acetyl group, R ¹ is hydrogen or methyl group, R ² is an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 3. However, when R is hydrogen, n is an integer of 1 to 3) It relates to an edge bead remover comprising a mixture of compounds represented by. The present invention also secures the safety to the human body and suppresses the unpleasant odor that may be present in the organic solvent as low as possible, while removing the unnecessary resist from the substrate for an electronic component during or after application of the resist-forming composition. A method of removing in a short time using a small amount.

The compound of the general formula (I) is a glycol monoalkyl ether when R is hydrogen, R is an acetyl group, when n is an integer of 1 to 3, glycol monoalkyl ether acetate, R is an acetyl group, When n is zero, an acetate ester is shown.

As glycol monoalkyl ether represented by said general formula (I), for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol Monoethyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether It may include. Especially preferably, it is propylene glycol monomethyl ether.

As glycol monoalkyl ether acetate represented by said general formula (I), for example, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate. Especially preferably, it is propylene glycol monomethyl ether acetate.

As acetate acetate represented by said general formula (I), methyl acetate, ethyl acetate, butyl acetate, etc. are mentioned, for example. Especially preferably, it is butyl acetate.

Said glycol monoalkyl ether, glycol monoalkyl ether acetate, and acetate ester may be used independently, or may be used in combination of 2 or more type.

The edge bead remover of the present invention may be prepared by any method as long as a homogeneous mixture with α-hydroxyisobutyrate, a compound represented by the general formula (I), and an optional additive acceptable for removing the resist is obtained.

For example, at a temperature near room temperature, methyl α-hydroxyisobutyrate, the compound represented by the general formula (I), and optional additives are mechanically mixed under stirring until a homogeneous mixture is obtained.

The weight mixing ratio of the α-hydroxyisobutyrate and the compound represented by the general formula (I) is 9: 1 to 1: 9, preferably 7: 3 to 5: 5.

The edge bead remover of the present invention may further contain other solvents as necessary.

Such solvents may be selected from ethers, esters, ketones, ketoethers, ketols, alcohols, esters of alkoxycarboxylic acids, diketones, amides and aromatic hydrocarbons. These additional solvents can be used alone or in combination of two or more thereof.

The edge bead remover of the present invention can be applied to any of a known positive resist or a negative resist.

Representative examples of the positive resist to which the edge bead remover of the present invention can be applied include a resist composition or a chemically amplified resist based on a quinonediazide-based photosensitive compound and an alkali-soluble resin. Representative examples of the negative resist include a resist containing a high molecular compound having a photosensitive group such as polyvinyl cinnamate; A resist containing an aromatic azide compound; Resists containing azide compounds prepared from cyclized rubbers and bisdiazide compounds; Resists containing diazide resins; Photopolymerizable compositions containing addition polymerizable unsaturated compounds; And chemically amplified negative resists.

An antireflection film may be selectively formed on the surface of the chemically amplified negative resist. At this time, if the antireflection film is soluble in the organic solvent, unnecessary parts of the antireflection film can be removed together with unnecessary parts of the resist.

Examples of the film-forming substance effective for the present invention include novolak resins obtained by reacting phenol, cresol or xylenol with aldehydes; Acrylic resins; Copolymers of styrene and acrylic acid; Hydroxystyrene polymers; Polyvinylhydroxybenzoate; And alkali-soluble resins such as polyvinylhydroxybenzal.

In addition, to the resist-forming composition, compatible dyes such as coumarin-based dyes and azo dyes may be added as necessary. In addition, as other additives, conventional resins such as dissolution inhibitors, additive resins, plasticizers, stabilizers, and coloring agents or contrast sharpeners for further visualizing the pattern obtained by developing are commonly used in the industry. You may add it.

Edge bead removal is performed as follows. The resist-forming solution is applied to a silicon substrate, a glass substrate, or the like which has been pretreated as necessary by a conventional coating method such as a spin coating method.

When applied in a spin application process, the resist-forming solution usually spreads into a film in which the thickness of the peripheral film of the substrate is larger than that of the central film, whereby edge beads are formed. In addition, a portion of the resist-forming composition spreads around the edges to reach the edge side or the back side of the substrate.

The edge bead remover of the present invention is applied to the edge bead on the rotating substrate by a method such as spraying or back rinse to promote the flow of beads to remove the edge bead and have a substantially uniform thickness on the substrate. The resist film can be left.

In addition, the resist present on the edge side and the back of the substrate can be removed by spraying the edge bead remover.

Edge bead removers of the present invention are typically applied in an amount effective to sufficiently remove edge beads and / or other unnecessary resist at temperatures near room temperature.

The amount effective for removal depends on many factors such as edge bead remover and resist chemical composition, resist film thickness, but determining the optimal amount is within the skill of one of ordinary skill in the art.

The resist removal by the edge bead remover of the present invention may be performed after the resist film applied on the substrate is prebaked at 20 to 200 ° C. for 0.1 to 120 minutes.

In addition to the edge bead removal, the edge bead remover of the present invention is extremely excellent in solubility with respect to the resist, and thus is effectively used for cleaning and removing the resist adhered to a spinner cup or the like.

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Examples 1-9 and Comparative Examples 1-5

A commercially available positive photoresist (TFR-790, manufactured by Tokyo Corporation) was applied onto the silicon wafer in an amount such that the dry film thickness was 16000 kPa using a spinner, and then preheated at 120 ° C. for 30 minutes in a drying oven to form a resist film. .

Next, 100 ml of each solvent of the composition shown in the table was put into the beaker, and the wafer dried above was immersed in the solvent for 10 seconds. Immediately after removal from the solvent it was dried by air blowing. The film thickness on each wafer was measured by the film thickness meter (Nanometric Japan, Nano Spec M 5000), and the dissolution rate (Å / sec) was calculated | required.

Table 1 shows the results of Examples and Comparative Examples.

Incidentally, the solvents used in Comparative Examples 1 to 3 and 5 are actually used as edge bead removers.

Table 1

Chemical Composition of Edge Bead Remover (Weight Ratio) Dissolution rate (Å / sec) smell Example 1 HBM: PGME = 5: 5 1482 No unpleasant smell Example 2 HBM: PGME = 6: 4 1390 No unpleasant smell Example 3 HBM: PGME = 7: 3 867 No unpleasant smell Example 4 HBM: PGMEA = 5: 5 1152 No unpleasant smell Example 5 HBM: PGMEA = 6: 4 1086 No unpleasant smell Example 6 HBM: PGMEA = 7: 3 673 No unpleasant smell Example 7 HBM: AcOBu = 5: 5 776 No unpleasant smell Example 8 HBM: AcOBu = 6: 4 758 No unpleasant smell Example 9 HBM: AcOBu = 7: 3 498 No unpleasant smell Comparative Example 1 PGME 1517 Has an unpleasant smell Comparative Example 2 PGMEA 669 Has an unpleasant smell Comparative Example 3 Ethyl lactate 701 Peculiar smell Comparative Example 4 HBM 247 No unpleasant smell Comparative Example 5 AcOBu 1481 Peculiar smell HBM: α-hydroxyisobutyrate methyl PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl ether acetate AcOBu: butyl acetate

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The edge bead remover of the present invention has high dissolution rate to resist, extremely low toxicity, and biodegradability, and therefore is not accumulated in nature and thus is preferable for environmental conservation.

In addition, since the edge bead remover has a moderate volatility and has good drying properties, a flash point is relatively high, and there is almost no unpleasant smell, so there is an advantage in that workability and safety are high.

Claims (10)

methyl α-hydroxyisobutyrate and the following general formula (I):

(R is hydrogen or acetyl group, R ¹ is hydrogen or methyl group, R ² is an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 3. However, when R is hydrogen, n is an integer of 1 to 3) Edge bead remover comprising a mixture of compounds represented by. The method of claim 1, An edge bead remover, wherein the weight mixing ratio of the α-hydroxyisobutyrate methyl and the compound represented by the general formula (I) is from 9: 1 to 1: 9. The method according to claim 1 or 2, The above-mentioned compound represented by the general formula (I) is at least one compound selected from the group consisting of glycol monoalkyl ether, glycol monoalkyl ether acetate and acetate ester. The method of claim 3, The above-mentioned glycol monoalkyl ether is diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, propylene At least one compound selected from the group consisting of glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether. Edge bead remover. The method of claim 4, wherein An edge bead remover, wherein said glycol monoalkyl ether is propylene glycol monoethyl ether. The method of claim 3, The glycol monoalkyl ether acetate is diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether Edge bead remover, characterized in that at least one compound selected from the group consisting of acetate. The method of claim 6, An edge bead remover, wherein said glycol monoalkyl ether acetate is propylene glycol monomethyl ether acetate. The method of claim 3, The above-mentioned acetate ester is at least one compound chosen from the group which consists of methyl acetate, ethyl acetate, and butyl acetate, The edge bead remover characterized by the above-mentioned. The method of claim 8, An edge bead remover, wherein said acetate ester is butyl acetate. Applying a resist-forming composition to the substrate; And Removing the unwanted resist-forming composition deposited on the periphery, edge or back surface of the substrate using the edge bead remover according to claim 1 or 2. How to remove.