Cleaning composition and method for forming photoresist pattern using cleaning composition

Abstract

A cleaning composition according to an embodiment of the present invention comprises an alcohol solvent and a zeolite. The zeolite content is greater than 0 and less than or equal to 1 ppb based on the total weight of the cleaning composition. The cleaning composition may exhibit improved temporal stability and improved semiconductor substrate residue cleaning performance.

Description

Technical Field

[0001] The present invention relates to a cleaning composition and a method for forming a photoresist pattern using the cleaning composition. Background Art

[0002] The composition comprising an alcohol solvent can be used to clean electronic devices (such as semiconductor devices) or remove photoresist residues in a photolithography process during the manufacture of semiconductor devices.

[0003] For example, a photoresist may be coated on a substrate, exposed to light of a specific wavelength, and then dry or wet etched to manufacture a semiconductor device or a high-resolution flat panel display having a fine wiring pattern formed on the substrate.

[0004] After forming a photoresist pattern through exposure and development processes, a cleaning solution is used to remove any residue remaining on the semiconductor substrate. However, if micron-sized impurities are present in the cleaning solution, these impurities may remain on the surface of the semiconductor device, potentially causing defects.

[0005] These impurities may be inevitably mixed into the cleaning solution during the manufacturing process, or may be formed due to side reactions between components during storage. Therefore, even if the cleaning solution is stored for a long time, it is preferable to suppress the generation of impurities. Summary of the Invention

[0006] An object of the present invention is to provide a cleaning composition having improved temporal stability and cleaning power.

[0007] Another object of the present invention is to provide a method for forming a photoresist pattern using the cleaning composition.

[0008] To achieve the above object, the present invention adopts the following technical solutions:

[0009] 1. A cleaning composition comprising: an alcohol solvent; and zeolite, wherein the zeolite is present in an amount greater than 0 and less than or equal to 1 ppb based on the total weight of the composition.

[0010] 2. The cleaning composition according to item 1 above, wherein the content of the zeolite is 0.1 ppt to 0.5 ppb based on the total weight of the composition.

[0011] 3. The cleaning composition according to 1 above, wherein the zeolite comprises A-type zeolite, X-type zeolite or Y-type zeolite.

[0012] 4. The cleaning composition according to item 1 above, wherein the water content in the composition is 1 ppm to 30 ppm based on the total weight of the composition.

[0013] 5. The cleaning composition according to 1 above, wherein the alcohol solvent comprises an alcohol having 2 to 5 carbon atoms.

[0014] 6. The cleaning composition according to 1 above, wherein the alcohol solvent comprises at least one selected from the group consisting of ethanol, 1-propanol, 2-propanol, 1-butanol, and 1-pentanol.

[0015] 7. The cleaning composition according to 1 above, wherein the alcohol solvent comprises 2-propanol and further comprises at least one selected from the group consisting of ethanol, 1-propanol, 1-butanol, and 1-pentanol.

[0016] 8. The cleaning composition according to item 7 above, wherein the content of 2-propanol is greater than or equal to 99 wt % and less than 100 wt %, based on the total weight of the composition.

[0017] 9. The cleaning composition according to 1 above, wherein the composition satisfies the following formula 1:

[0018] [Formula 1]

[0019] C≤(X / Y)-1≤D

[0020] (In the above formula 1, X is the total content of aldehyde compounds and ketone compounds based on the total weight of the cleaning composition measured after storing the composition at 60° C. for 90 days, Y is the total content of aldehyde compounds and ketone compounds based on the total weight of the composition measured before the storage, C is greater than 0 and less than or equal to 0.05, and D is 0.07 to 0.2).

[0021] 10. The cleaning composition according to 9 above, wherein in the above formula 1, C is 0.03, and D is 0.1.

[0022] 11. A method for forming a photoresist pattern, comprising: forming a photoresist film on a substrate; partially removing the photoresist film to form a photoresist pattern; and cleaning the substrate on which the photoresist pattern is formed using the cleaning composition according to 1 above.

[0023] The cleaning composition according to an embodiment of the present invention can suppress the generation of impurities even after long-term storage. Therefore, the temporal stability of the cleaning composition can be enhanced, and the cleaning performance of the semiconductor substrate can also be improved.

[0024] Therefore, when manufacturing electronic devices such as semiconductors or displays, it is possible to prevent impurities from being formed on the surface of the electronic devices and to suppress the occurrence of defects, thereby improving the production yield of the electronic devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings:

[0026] Figures 1 to 4 is a schematic cross-sectional view for describing a method of forming a pattern according to an exemplary embodiment. DETAILED DESCRIPTION

[0027] Embodiments of the present invention provide a cleaning composition comprising an alcohol solvent and a zeolite. This improves the temporal stability and purity of the cleaning composition. Furthermore, a method for forming a photoresist pattern using the cleaning composition is provided.

[0028] The abbreviation "ppb" used herein means "parts per billion (10 -9 )” and the abbreviation “ppt” stands for “parts per trillion (10 -12 )", wherein the ppb and ppt may be based on a weight basis.

[0029] Hereinafter, embodiments of the present invention will be described in detail.

[0030] <Cleaning Composition>

[0031] A cleaning composition according to an exemplary embodiment (hereinafter may be simply referred to as “composition”) may include an alcohol solvent and zeolite.

[0032] The alcohol solvent can remove process residues such as undeveloped photoresist or residual developer on the semiconductor substrate. For example, organic and inorganic residues remaining between photoresist patterns after exposure and development can be effectively removed from the semiconductor substrate.

[0033] In some embodiments, the alcohol solvent may include an alcohol having 2 to 5 carbon atoms.

[0034] For example, the alcohol solvent may include at least one selected from the group consisting of ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, tert-pentanol, 3-methyl-2-butanol, 3-methyl-1-butanol, and 2,2-dimethyl-1-propanol.

[0035] For example, methanol has high volatility, which leads to deterioration in cleaning power and stability, while alcohols with more than 5 carbon atoms may remain on the surface of the semiconductor substrate after cleaning. Therefore, when the alcohol solvent includes an alcohol with 2 to 5 carbon atoms, the occurrence of defects in the semiconductor device manufacturing process can be reduced.

[0036] According to an exemplary embodiment, the alcohol solvent can be obtained by refining crude oil. The purity of the alcohol solvent can be increased through a purification process.

[0037] For example, as crude oil before purification, 2-propanol derived from fossil resources such as coal, petroleum, and natural gas can be used, and 2-propanol derived from biomass (bio-2-propanol) can also be used.

[0038] Examples of bio-2-propanol may include: 2-propanol produced using bacteria that produce 2-propanol from biomass raw materials (see International Patent Publication No. 2009 / 008377); 2-propanol obtained by hydrating propylene produced using biomethanol; 2-propanol obtained by reducing acetone produced using bioethanol; and 2-propanol obtained by hydrating propylene produced using bioethanol.

[0039] In some embodiments, the alcohol solvent may include a secondary alcohol. For example, examples of the secondary alcohol may include 2-propanol, 2-butanol, 2-pentanol, 3-pentanol or 3-methyl-2-butanol, preferably 2-propanol.

[0040] In some embodiments, the alcohol solvent may include at least one selected from the group consisting of ethanol, 1-propanol, 2-propanol, 1-butanol, and 1-pentanol.

[0041] In some embodiments, the alcohol solvent includes 2-propanol and may include other alcohol solvents different from 2-propanol. For example, the alcohol solvent may include 2-propanol and at least one selected from the group consisting of ethanol, 1-propanol, 1-butanol, and 1-pentanol.

[0042] For example, alcohols containing 2 or 3 carbon atoms may have a low boiling point, thereby preventing them from remaining on the surface of the semiconductor substrate after cleaning, thereby improving the yield of the manufactured semiconductor devices.

[0043] In some embodiments, the alcohol solvent may include an alcohol having a boiling point of 110° C. or less. For example, the alcohol having a boiling point of 110° C. or less may include ethanol, 1-propanol, 2-propanol, 2-butanol, isobutanol, tert-butanol, or tert-amyl alcohol.

[0044] For example, alcohol having a boiling point of 110° C. or lower can be evaporated at a relatively low temperature, thereby preventing it from remaining on the surface of the semiconductor substrate after cleaning.

[0045] In some embodiments, the alcohol solvent may have a vapor pressure of 0.5 kPa or greater at 25° C. For example, the alcohol having a vapor pressure of 0.5 kPa or greater at 25° C. may include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 2-pentanol, 3-pentanol, tert-pentanol, or 2,2-dimethyl-1-propanol.

[0046] For example, alcohol having a vapor pressure of 0.5 kPa or higher at 25° C. can be more easily evaporated, thereby preventing it from remaining on the surface of the semiconductor substrate after cleaning.

[0047] According to exemplary embodiments, the alcohol solvent may be present in an amount of 99 weight % ("wt %) to less than 100 wt % based on the total weight of the composition. In some embodiments, the 2-propanol may be present in an amount of 99 wt % or more and less than 100 wt % based on the total weight of the composition. In one embodiment, the 2-propanol may be present in an amount of 99.9 wt % or more, 99.95 wt % or more, or 99.99 wt % and less than 100 wt % or more based on the total weight of the composition.

[0048] In some embodiments, the cleaning composition may include 2-propanol and, in addition to the zeolite content, an amount of an alcohol solvent other than 2-propanol. For example, the cleaning composition may include the zeolite content described below and the 2-propanol content described above, and may include an amount of an alcohol solvent other than 2-propanol.

[0049] As used herein, the term "balance" refers to a variable amount that may vary with the addition of other components.

[0050] When the composition is stored for a long time, the alcohol solvent may undergo natural oxidation reaction, resulting in the formation of impurities such as aldehydes and ketones. These impurities may aggregate into particles with large molecular weight and micron size, which may remain on the surface of the semiconductor substrate after cleaning.

[0051] The composition may include a temporal inhibitor that inhibits oxidation of the alcohol solvent, thereby preventing the formation of aldehydes and ketones. Thus, the temporal stability of the cleaning composition can be enhanced, and high purity can be ensured.

[0052] The composition may include water. The content of water in the composition (water content) may be 1ppm to 30ppm. According to some embodiments, the water content in the composition may be 3ppm to 20ppm, or 5ppm to 15ppm. Within the above range, when using the composition, residues or water marks may be prevented from forming on the surface of the object to be cleaned.

[0053] For example, the temporal inhibitor may include a zeolite, and the zeolite may be in the form of a fine particle dispersion.

[0054] According to exemplary embodiments, the zeolite may include silicon and aluminum. According to some embodiments, the zeolite may include A-type zeolite, X-type zeolite, or Y-type zeolite.

[0055] The silicon to aluminum atomic ratio (Si / Al) of type A zeolite may be about 1. The Si / Al ratio of type X zeolite may be 1 to 1.5. The Si / Al ratio of type Y zeolite may be 1.5 or higher.

[0056] According to one embodiment, the zeolite may include type Y zeolite. For example, type Y zeolite may be zeolite with CAS No. 1318-02-1.

[0057] According to one embodiment, the zeolite may include a compound represented by Formula 1 below.

[0058] [Formula 1]

[0059] M x / n [(Al2O) x (SiO2) y ]·zH2O

[0060] (In Formula 1, M is the metal, x and y are any positive numbers, z is the number of hydrated water molecules, and n is the charge of the metal cation).

[0061] Zeolite can suppress side reactions by absorbing moisture, thereby improving the temporal stability of the cleaning composition.

[0062] According to an exemplary embodiment, the composition may be prepared by introducing zeolite into an alcohol solvent. According to one embodiment, zeolite may be included and retained during the preparation of the alcohol solvent.

[0063] In an exemplary embodiment, the zeolite is present in an amount greater than 0 and less than 1 ppb based on the total weight of the composition. According to some embodiments, the zeolite may be present in an amount of 0.1 ppt to 0.5 ppb or 0.1 ppt to 10 ppt based on the total weight of the composition.

[0064] Within the above range, the temporal stability of the composition may be improved, and the residue cleaning performance of the composition on a semiconductor substrate may also be improved.

[0065] If the composition does not contain zeolite, the amount of aldehydes and / or ketones formed due to decomposition of the alcohol solvent may increase rapidly during long-term storage of the composition. Consequently, uniform production speed may not be ensured during semiconductor manufacturing processes using the composition, and the cleaning power of the composition may also be reduced, thereby deteriorating the quality of semiconductor products.

[0066] If the amount of zeolite in the composition exceeds 1 ppb, residues may be generated after cleaning due to the metal components contained in the zeolite. In addition, the excess zeolite may act as a decomposition catalyst for the alcohol solvent (e.g., 2-propanol). As a result, the content of acetal compounds formed by the decomposition reaction may increase, resulting in a decrease in the temporal stability of the composition.

[0067] According to an exemplary embodiment, the cleaning composition may satisfy the following Formula 1:

[0068] [Formula 1]

[0069] C≤(X / Y)-1≤D

[0070] In the above formula 1, X may be the total content of aldehyde compounds and ketone compounds based on the total weight of the cleaning composition measured after storing the cleaning composition at 60° C. for 90 days, and Y may be the total content of aldehyde compounds and ketone compounds based on the total weight of the composition measured before the storage.

[0071] In the above Formula 1, C may be greater than 0 and less than or equal to 0.05, and D may be 0.07 to 0.2.

[0072] The rate of change in the content of aldehyde compounds and ketone compounds before and after high-temperature storage of the composition may be, for example, 20% or less, 15% or less, 10% or less, or 7% or less.

[0073] The rate of change in the content of aldehyde compounds and ketone compounds before and after high-temperature storage of the composition may be, for example, greater than 0, 0.01% or greater, 0.02% or greater, or 0.03% or greater.

[0074] For example, in Formula 1, D may be 0.2, 0.15, 0.1, or 0.07, and C may be 0.01, 0.02, or 0.03.

[0075] Within the above range, the cleaning composition can exhibit improved temporal stability, and its long-term storage stability can also be enhanced.

[0076] Aldehyde compounds and ketone compounds may be trace impurities formed by natural oxidation of the alcohol solvent. The composition can exhibit improved temporal stability, thereby suppressing the increase of impurities including aldehyde compounds and ketone compounds even during long-term storage.

[0077] In one embodiment, in Formula 1, X may be the total content of acetaldehyde and acetone based on the total weight of the cleaning composition measured after storing the composition at 60° C. for 90 days, and Y may be the total content of acetaldehyde and acetone based on the total weight of the composition measured before the storage.

[0078] In Formula 1 above, X and Y are greater than 0, X may be 2600 ppb or less, 2500 ppb or less, 2400 ppb or less, or 2300 ppb or less, and Y may be 2300 ppb or less, or 2200 ppb or less.

[0079] <Photoresist Pattern Formation Method>

[0080] Figures 1 to 4 Schematic cross-sectional view illustrating a pattern forming method according to an exemplary embodiment. For example, Figures 1 to 4 A patterning process using a negative photoresist is shown and described.

[0081] However, the cleaning composition according to the exemplary embodiment is not limited to Figures 1 to 4 The process shown can also be used for patterning using positive photoresist.

[0082] refer to Figure 1 , a photoresist material may be applied to the substrate 100 to form a photoresist film 110 .

[0083] The substrate 100 may include a semiconductor material such as single crystal silicon or single crystal germanium, and may also be formed to include polycrystalline silicon.

[0084] In some embodiments, after forming the photoresist film 110 , a soft bake process may be performed, thereby evaporating an organic solvent that may be included in the photoresist film 110 .

[0085] refer to Figure 2 An unexposed portion 113 and an exposed portion 115 may be formed on the substrate 100 through an exposure process. The exposure process may be performed using a light source (eg, an extreme ultraviolet light source) and an exposure mask 50.

[0086] The photoresist film 110 may be irradiated with light (eg, extreme ultraviolet light) through the exposure mask 50. Thus, the photoresist film 110 may be patterned to have an unexposed portion 113 and an exposed portion 115.

[0087] refer to Figure 3 A photoresist pattern 120 may be formed on the substrate 100 through a development process. For example, the photoresist film 110 may be partially removed to form the photoresist pattern. Specifically, the unexposed portion 113 may be removed from the substrate 100 using a developer, thereby forming the photoresist pattern 120 consisting of the exposed portion 115. The developer may be an aqueous solution of tetramethylammonium hydroxide (TMAH).

[0088] Figure 3The patterning process using a negative photoresist is shown and described, but is not limited thereto. For example, a positive photoresist may alternatively be used for the patterning process. In this case, the exposed portion 115 may be removed to form a photoresist pattern consisting of unexposed portions 113.

[0089] In some embodiments, a post-baking process may be further performed after the exposure process or after the development process.

[0090] After the pattern forming process, development residue 130 may remain on substrate 100. Development residue 130 may include undeveloped photoresist or developer residue. If development residue 130 remains on substrate 100 or photoresist pattern 120, defects may occur during semiconductor device manufacturing.

[0091] refer to Figure 4 The substrate 100 on which the photoresist pattern 120 is formed can be cleaned using the cleaning composition according to the exemplary embodiment. Specifically, the cleaning composition according to the exemplary embodiment can be applied to the substrate 100 or used to immerse the substrate 100. Thus, the development residue 130 formed on the substrate 100 or the photoresist pattern 120 can be removed.

[0092] The cleaning step may be performed by applying the above-described cleaning composition according to the exemplary embodiment to the substrate 100 under generally known cleaning conditions.

[0093] In some embodiments, the temperature during cleaning is typically 25° C. to 70° C., preferably 25° C. to 50° C. When immersed in the cleaning composition, the residence time of the substrate 100 can be about 5 seconds to 10 minutes, preferably 10 seconds to 5 minutes.

[0094] In some embodiments, the cleaning step may include a first cleaning using deionized water to remove development residues, followed by a second cleaning using the above-described cleaning composition according to the exemplary embodiment.

[0095] As described above, the cleaning composition includes a predetermined amount of an alcohol solvent and an organometallic compound, thereby improving temporal stability and purity, thereby suppressing the occurrence of defects in semiconductor devices and improving production yield.

[0096] The cleaning composition according to the exemplary embodiment may be used not only in a pattern forming process using a photoresist but also in a cleaning process of electronic devices such as semiconductors or displays, and may also be applicable to other fields using an alcohol solvent.

[0097] The following experimental examples including specific embodiments and comparative examples are proposed to facilitate understanding of the present invention. However, the following examples are merely illustrative of the present invention and are not intended to limit the appended claims. Obviously, those skilled in the art can make various changes and modifications within the scope and spirit of the present invention, and these changes and modifications are appropriately included in the appended claims.

[0098] Examples and Comparative Examples

[0099] The cleaning compositions in Examples and Comparative Examples were prepared by mixing the components described in Table 1 according to their respective contents. The content of each component is expressed based on the total weight of the cleaning composition.

[0100] [Table 1]

[0101]

[0102]

[0103] (A) Zeolite

[0104] A-1: Zeolite (Sigma-Aldrich; CAS No. 1318-02-1)

[0105] (B) Alcohol solvent

[0106] B-1: 2-Propanol (isopropyl alcohol)

[0107] B-2: 1-Propanol

[0108] B-3: Ethanol

[0109] B-4: 1-Butanol

[0110] B-5: 1-Pentanol

[0111] Experimental Example

[0112] The properties of the cleaning compositions of Examples and Comparative Examples were evaluated according to the following methods. The results are shown in Table 2.

[0113] (1) Initial assessment

[0114] The total content (Y) of acetaldehyde and acetone contained in the cleaning compositions of Examples and Comparative Examples was measured using an Agilent 7890A / 5975C GC-MS device and an Agilent CP-Volamine (60 m, 0.32 mm) chromatography column.

[0115] Specifically, standard substances of acetaldehyde and acetone were prepared, and then the acetaldehyde and acetone detected as the analysis results of the cleaning compositions in Examples and Comparative Examples were quantitatively analyzed by comparing the peak areas of the acetaldehyde and acetone detected as the analysis results of the cleaning compositions in Examples and Comparative Examples with the peak areas of the pre-quantified standard substances.

[0116] (2) Time evaluation

[0117] The cleaning compositions of Examples and Comparative Examples were stored at 60° C. for 90 days, and then the total content (X) of acetaldehyde and acetone was measured in the same manner as in (1) above.

[0118] (3) Evaluation of temporal stability

[0119] The total content change rate of acetaldehyde and acetone was calculated (using the formula (X / Y)-1), and the temporal stability of the cleaning compositions according to Examples and Comparative Examples was evaluated according to the following evaluation criteria.

[0120] <Evaluation Criteria>

[0121] ◎: Content change rate is 0.1 or less

[0122] ○: Content change rate is greater than 0.1 and less than 0.3

[0123] △: Content change rate is 0.3 or greater

[0124] (4) Assessment of water content

[0125] The water contents of the cleaning compositions according to Examples and Comparative Examples were measured at room temperature in anhydrous methanol using a moisture analyzer V20 (manufactured by METTLER TOLEDO) using the Karl Fischer measurement method as its measurement principle.

[0126] [Table 2]

[0127]

[0128]

[0129] In Table 2 above, C-1 represents acetaldehyde and C-2 represents acetone.

[0130] Referring to Table 2 above, the cleaning composition in the examples contains zeolite. Therefore, the rate of change in the content of aldehyde compounds and ketone compounds does not increase significantly, and the water content ranges from 1 ppm to 30 ppm even after the composition is exposed to high temperature for a long time.

[0131] On the other hand, the cleaning composition in Comparative Examples does not include zeolite or includes an excessive amount of zeolite, and thus the content of aldehyde compounds and ketone compounds increases rapidly, resulting in a significant decrease in temporal stability.

[0132] In particular, the composition containing no zeolite in Comparative Example 2 contained a high content of water, which may result in the formation of water marks after cleaning and drying.

[0133] The above contents are merely examples of applying the principles of the present invention, and other configurations may be further included without departing from the scope of the present invention.

[0134] [Explanation of Reference Numerals]

[0135] 50: Exposure mask

[0136] 100: substrate

[0137] 110: Photoresist film

[0138] 113: Unexposed part

[0139] 115: Exposure

[0140] 120: Photoresist pattern

[0141] 130: Development residue.

Claims

1. A cleaning composition comprising: alcohol solvent; and zeolite, in, The zeolite is present in an amount greater than 0 and less than or equal to 1 ppb based on the total weight of the composition.

2. The cleaning composition according to claim 1, wherein The zeolite is present in an amount of 0.1 ppt to 0.5 ppb based on the total weight of the composition.

3. The cleaning composition of claim 1, wherein the zeolite comprises A-type zeolite, X-type zeolite, or Y-type zeolite.

4. The cleaning composition according to claim 1, wherein The water content in the composition is 1 ppm to 30 ppm based on the total weight of the composition. 5 . The cleaning composition of claim 1 , wherein the alcohol solvent comprises an alcohol having 2 to 5 carbon atoms. The cleaning composition according to claim 1 , wherein the alcohol solvent comprises at least one selected from the group consisting of ethanol, 1-propanol, 2-propanol, 1-butanol, and 1-pentanol. 7 . The cleaning composition according to claim 1 , wherein the alcohol solvent comprises 2-propanol, and further comprises at least one selected from the group consisting of ethanol, 1-propanol, 1-butanol, and 1-pentanol.

8. The cleaning composition according to claim 7, wherein The content of 2-propanol is greater than or equal to 99 wt % and less than 100 wt % based on the total weight of the composition.

9. The cleaning composition according to claim 1, wherein the composition satisfies the following formula 1: [Formula 1] C≤(X / Y)-1≤D In the above Formula 1, X is the total content of the aldehyde compound and the ketone compound based on the total weight of the cleaning composition measured after storing the composition at 60° C. for 90 days, Y is the total content of the aldehyde compound and the ketone compound based on the total weight of the composition measured before the storage, C is greater than 0 and less than or equal to 0.05, and D is 0.07 to 0.

2. 10 . The cleaning composition according to claim 9 , wherein in the above Formula 1, C is 0.03, and D is 0.

1.

11. A method for forming a photoresist pattern, comprising: forming a photoresist film on a substrate; partially removing the photoresist film to form a photoresist pattern; as well as The substrate on which the photoresist pattern is formed is cleaned using the cleaning composition according to claim 1 .

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