KR100811839B1 - Cleaning solution for preparing insemiconductor device - Google Patents

Abstract

A cleaning solution composition for forming the pattern of a semiconductor device is provided to improve the CD uniformity of a pattern and to prevent the collapse of a pattern. A cleaning solution composition comprises 0.02-5 wt% of a first surfactant which is a fatty acid alkanol amide-based surfactant; 0.02-5 wt% of a second surfactant which can aid the dissolution of the first surfactant; and water. Preferably the composition comprises further 0.2-10 wt% of at least one bacteria inhibitor selected from ethylene glycol, 2-methoxy-1-ethanol, propylene glycol, 1-methoxy-2-propanol, 1,2-butadiene, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol and 1,2-octanediol; and 0.2-20 wt% of at least one bubble inhibitor selected from butanol, pentanol, hexanol, heptanol, octanol, nonanol and decanol.

Description

Cleaning liquid composition for semiconductor element pattern formation {CLEANING SOLUTION FOR PREPARING INSEMICONDUCTOR DEVICE}

Figure 1-Example 2 shows the production of bacteria according to Example 8 according to the period ((a) after 3 days culture; (b) after 5 days culture; (c) after 8 days culture)

Figure 2-a photograph showing the production of bacteria according to Example 7 in Example 2 according to the period ((a) after 3 days culture; (b) after 5 days culture; (c) after 8 days culture)

The present invention relates to a cleaning liquid composition required for the formation of a semiconductor device fine pattern, and more particularly to the semiconductor device pattern formation to improve the uniformity of the pattern and prevent the pattern collapse by using in the developing process used to form the fine pattern of the semiconductor device It relates to a cleaning liquid composition for.

In general, the thickness of the photoresist film should be lowered to 200 or less to prevent the collapse of the pattern when forming the micro pattern of 70 or less. In addition, in order to obtain a pattern of 80nm or less, 193nm exposure equipment should be used. The photosensitive agent used for the exposure source of 193 nm is not an aromatic aliphatic photosensitive agent. The aliphatic photosensitive agent has insufficient etching resistance, and after etching the lower layer such as poly, metal, SiO ₂ layer, the lower layer is deformed. Is impossible. In addition, the finer the pattern, the lower the uniformity of the pattern causes a problem in the characteristics of the semiconductor device. To overcome this, the photoresist must be thicker to form a pattern. However, when water is used as the final cleaning solution after development in a conventional developing process, the surface tension of the water acts to cause the pattern to collapse. In order to overcome this, it is proposed to treat with a cleaning solution added with a surfactant instead of water as a final cleaning solution. However, the following problems arise when using a conventional surfactant.

(1) Surfactants dissolved in water are difficult to sufficiently lower the surface tension.

(2) Bacterial fungi are generated from surfactants dissolved in water, which causes pattern defects.

(3) In the case of a cleaning liquid capable of sufficiently lowering the surface tension, bubbles are generated and the duration of the bubbles becomes long, which eventually causes a pattern failure caused by bubbles.

An object of the present invention is to provide a cleaning liquid composition for forming a semiconductor device pattern for solving the problems of the prior art.

In order to achieve the above object, the present invention (a) a first surfactant which is a fatty acid alkanol amide-based surfactant; And (b) a second surfactant capable of assisting dissolution of the first surfactant; It provides a cleaning liquid composition for forming a semiconductor device pattern comprising a.

Hereinafter, the present invention will be described in detail.

At this time, if there is no other definitions in the technical terms and scientific terms used herein, those having ordinary skill in the art to which this invention belongs have the meaning that is commonly understood.

In addition, repeated description of the same technical configuration and operation as in the prior art will be omitted.

In the present invention, the surfactant (surfactant) refers to a substance that is adsorbed to the interface in a dilute solution to reduce the surface tension, when the dissolved in water of the surfactant is ionized, the subject of the active agent is an anionic surfactant The cationic surfactant is used as the cationic surfactant, the cationic surfactant is used as the cationic surfactant, and the non-ionized surfactant is used as the cationic surfactant.

In addition, in the present invention, the auxiliary surfactant refers to a surfactant that can assist in dissolving in water the surfactant that is not dissolved in water, in the present invention, the fatty acid alkanol amide-based surfactant is dissolved in water to wash liquid composition It is a surfactant that can lower this surface tension as much as desired. At this time, the fatty acid alkanol amide-based surfactant in the present invention is a nonionic surfactant prepared by condensation reaction of alkanol amines and fatty acids or fatty acid derivatives, and in terms of effectiveness, such as diethanol amine or monoethanol amine among alkanol amines. It is preferable to use those prepared by condensation reaction of ethanol amine with a fatty acid or fatty acid derivative.

First, in order to solve the conventional problem of (1) "surfactant dissolved in water is difficult to sufficiently lower the surface tension" as described above, the present invention is a fatty acid alkanol amide-based interface that does not dissolve in water By combining the first surfactant composed of the active agent and the second surfactant composed of the auxiliary surfactant capable of dissolving the fatty acid alkanol amide surfactant, the surface active agent can be sufficiently reduced while the first surfactant is dissolved in water. The cleaning liquid composition for semiconductor element pattern formation which existed was developed.

At this time, the diethanol amide derivative or monoethanol amide derivative surfactant preferably used as the first surfactant is specifically coconut fatty acid diethanol amide, lauric acid diethanol amide, myristic acid diethanol amide, stearic acid diethanol amide, coconut fatty acid monoethanol amide, lauric acid monoethanol amide fatty acid alkanol amides selected from the group consisting of monoethanol amide, myristic acid monoethanol amide and stearic acid ethanethanol amide. However, the present invention is not limited to the surfactants described above, and other fatty acid alkanol amides may be used as long as they meet the object of the present invention.

The amount of the first surfactant is preferably used in an amount of 0.02 to 5% by weight based on the total weight of the cleaning liquid composition. This is because when it is less than 0.02% by weight, it is difficult to sufficiently lower the surface tension, and when it exceeds 5% by weight, the surfactant is coated to increase the pattern size during cleaning.

In addition, the second surfactant, which is an auxiliary surfactant capable of dissolving the first surfactant in water, may be a lauryl sulfate-based surfactant or a trimethyl ammonium chloride-based surfactant in view of the above-described effective aspects. Preference is given to using surfactants or amine oxide based surfactants.

At this time, the lauryl sulfate-based surfactant, trimethyl ammonium chloride-based surfactant or amine oxide-based surfactant preferably used as the second surfactant is specifically triethanolamine lauryl sulfate, ammonium lauryl Ammonium lauryl sulfate, Sodium lauryl ether sulfate, Lauryl trimethyl ammonium chloride, Cetyl trimethyl ammonium chloride, Stearyl trimethyl ammonium chloride (Stearyl trimethyl ammonium chloride), lauryl dimethylamine oxide (Lauryl dimethylamine oxide) and cocamido propylamine oxide (Cocamido propylamine oxide) is selected from the group consisting of. However, the present invention is not limited to the above-described auxiliary surfactant, and other lauryl sulfate-based surfactants, trimethyl ammonium chloride-based surfactants or amine oxide-based surfactants may be used as long as they meet the object of the present invention. Do.

In addition, the amount of the second surfactant is preferably used in an amount of 0.02 to 5% by weight relative to the total weight of the cleaning liquid composition, which is less than 0.02% by weight, it is difficult to increase the solubility of the first surfactant in water and 5% by weight. This is because when used in excess of the surfactant is coated to increase the pattern size during cleaning.

In addition, as described above, in order to solve the problem (2) "the problem of the occurrence of a pattern defect due to the generation of bacteria and mold in the dissolved surfactant", in the present invention, ethylene glycol (ethylene glycol), 2 2-methoxy-1-ethanol, propylene glycol, 1-methoxy-2-propanol, 1,2-butanediol (1, 2-butandiol), 1,2-pentandiol (1,2-pentandiol), 1,2-hexanediol (1,2-hexanediol), 1,2-heptandiol (1,2-heptandiol) and 1,2 It is preferable to further include 1,2-diol (1,2-diol) and derivatives thereof such as -octanediol (1,2-octandiol). At this time, the amount of the 1,2-diol and its derivatives is preferably used 0.2 to 10% by weight relative to the total weight of the cleaning liquid composition, which is less than 0.2% by weight is not enough bacteria removal ability and exceeds 10% by weight This is because the top of the photoresist surface is dissolved and the thickness of the photoresist is reduced. However, the present invention is not limited to the above-described bacteria removing agent, and other 1,2-diols and derivatives thereof may be used as long as they meet the object of the present invention.

In order to solve the above problem (3), in the case of the cleaning liquid capable of sufficiently lowering the surface tension, bubbles are generated and the duration of the bubbles becomes long, which eventually causes a pattern defect caused by the bubbles. As a defoamer, monoalcohol having 4 or more carbon atoms such as butanol, pentanol, hexanol, heptanol, heptanol, octanol, nonanol and decanol It is preferable to further include monoalcohol). In this case, the amount of the defoamer is preferably used in an amount of 0.2 to 20% by weight relative to the total weight of the composition, which is less than 0.2% by weight is not enough foam removal ability and 20% by weight of the manufacturing cost of the composition Because it increases. However, the present invention is not limited to the above-mentioned defoamer, and as long as it satisfies the object of the present invention, a monoalcohol having 4 or more carbon atoms may be used.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples, and it will be apparent to those skilled in the art that various changes or modifications can be made within the spirit and scope of the present invention.

Example 1 Preparation of Cleaning Liquid Composition for Forming Semiconductor Element Pattern According to the Present Invention

As shown in Table 1 below, the cleaning solution composition prepared with different components and its blending ratio was prepared.

TABLE 1

And, as a result of measuring the surface tension of Preparation Examples 1 to 6, it was measured by 33 to 35 it was confirmed that the surface tension is low enough so that the pattern does not fall.

In addition, as a result of washing the cleaning liquid composition in a semiconductor device that has undergone the developing step in the pattern forming step of the semiconductor device, it was found that the collapse of the pattern can be sufficiently prevented.

Example 2 Evaluation of Bacteria Removal Ability

In this example, the presence of bacteria was cultured by adding the cleaning solution composition prepared in the ingredients and blending ratios of Preparation Examples 7 to 15 to the culture medium capable of culturing bacteria as shown in Table 2 and Table 2 below.

First, 10 ml of the cleaning solution composition of Preparation Examples 7-15 was added to Tryptic Soy broth medium, and then cultured for 28 to 14 days to determine whether bacteria were generated.

TABLE 2

As a result, there was no bacterial development except for the composition of Preparation Example 7 that does not contain the bacterial additives. 1 and 2 show photographs showing whether bacteria of the composition of Preparation Example 8 and Preparation Example 7 were generated, respectively. As can be seen from FIG. 1, when the bactericidal agent was added, no bacteria were generated but the bactericidal agent was added. It can be seen that the bacteria are not generated in FIG. 2.

Example 3 Foam Sustainability Evaluation

In the present Example, it was intended to confirm the bubble duration time effect of the cleaning liquid composition prepared by the components and the preparation ratio of Preparation Examples 16 to 23 as shown in Table 3.

First, each of the cleaning solution compositions of Preparation Examples 16 to 23 prepared according to the present invention was put in a 1 liter measuring cylinder, and the lid was closed and shaken vigorously 10 times to generate bubbles.

Then, after measuring the height of the initial bubble, the bubble height was measured again after about 2 hours, and the height of the removed bubble was measured using the difference.

TABLE 3

The results are shown in Table 4 below. As can be seen from Table 4, it was found that the addition of monoalcohol improved the ability to remove bubbles.

TABLE 4

As described above, the cleaning liquid composition of the present invention has a low surface tension, no bacteria and excellent bubble removal effect, and thus can be used as a cleaning agent for semiconductor fine pattern formation.

Claims (7)

(a) a first surfactant which is a fatty acid alkanol amide surfactant; (b) a second surfactant capable of assisting dissolution of the first surfactant; And The cleaning liquid composition for semiconductor element pattern formation containing water. The method of claim 1, A cleaning liquid composition for forming a semiconductor device pattern comprising 0.02 to 5% by weight of the first surfactant and 0.02 to 5% by weight of the second surfactant, based on the total weight of the cleaning liquid composition. The method of claim 1, Ethylene glycol, 2-methoxy-1-ethanol, propylene glycol, 1-methoxy-2-propanol, 1,2-butadiene, 1,2-pentanediol, 1,2-hexanediol, 0.2-10% by weight of one or more bacterial inhibitors selected from the group consisting of 1,2-heptanediol and 1,2-octanediol; And butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol 0.2 to 20% by weight of at least one foam inhibitor selected from the group consisting of; each or a semiconductor device further comprises a mixture Cleaning liquid composition for pattern formation. The method of claim 2, Ethylene glycol, 2-methoxy-1-ethanol, propylene glycol, 1-methoxy-2-propanol, 1,2-butadiene, 1,2-pentanediol, 1,2-hexanediol, 0.2-10% by weight of one or more bacterial inhibitors selected from the group consisting of 1,2-heptanediol and 1,2-octanediol; And butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol 0.2 to 20% by weight of at least one foam inhibitor selected from the group consisting of; each or a semiconductor device further comprises a mixture Cleaning liquid composition for pattern formation. The method according to any one of claims 1 to 4, The fatty acid alkanol amide surfactant of (a) is a diethanol amide derivative or a monoethanol amide derivative; The second surfactant of (b) is a lauryl sulfate-based surfactant, trimethyl ammonium chloride-based surfactant or amine oxide-based surfactant, characterized in that the cleaning liquid composition for forming a semiconductor device pattern. The method of claim 5, wherein The fatty acid alkanol amide-based surfactants include coconut fatty acid diethanol amide, lauric diethanol amide, myristic acid diethanol amide, stearic acid diethanol amide, coconut fatty acid monoethanol amide, lauric acid monoethanol amide, myristic A cleaning liquid composition for forming a semiconductor device pattern, which is selected from the group consisting of acid monoethanol amide and stearic acid monoethanol amide. The method of claim 5, wherein The second surfactant is triethanolamine lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, lauryl dimethylamine oxide and A cleaning liquid composition for forming a semiconductor device pattern, characterized in that the surfactant is selected from the group consisting of cocamido propylamine oxide.

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