Cleaning composition and method of preparing semiconductor device using the same

Abstract

This invention relates to a cleaning composition and a method of manufacturing a semiconductor device using the same. The cleaning composition according to embodiments of the invention comprises a fluorine-based compound; an organic acid salt compound; an inorganic acid compound; and water, wherein the water content is at least 50% by weight based on the total weight of the composition, and the cleaning composition has a pH of 0.5 to 4. This cleaning composition exhibits high cleaning capability for photoresist residues converted through high-energy processes, and does not etchinate wiring containing metals (e.g., Mo, W, Ru, etc.) or layers such as silicon oxide and silicon nitride layers.

Description

Technical Field

[0001] This invention relates to a cleaning composition and a method of manufacturing a semiconductor device using the same. Prior Technology

[0002] To form wiring or insulation patterns for use in highly integrated semiconductor devices, a photomask pattern can be formed by coating and curing photoresist on the etch target layer. After dry etching using the photomask pattern, the photomask pattern can be removed by, for example, an ashing process.

[0003] During dry etching and / or ashing processes, photoresist material can be converted, and the converted photoresist can remain on wiring, insulating layers, or semiconductor substrates. To remove the residual converted photoresist, a wet process using a cleaning composition can be employed.

[0004] However, cleaning compositions may damage wiring materials containing conductive metals, or insulation layers containing organic or silicon-based inorganic materials.

[0005] When using general cleaning compositions, wiring containing metals such as ruthenium may also be removed, or residual photoresist may not be fully dissolved. Therefore, there is a need to improve the selectivity of cleaning compositions. Summary of the Invention

[0006] According to one aspect of the present invention, a cleaning composition having enhanced cleaning power is provided.

[0007] According to one aspect of the present invention, a method for manufacturing a semiconductor device using the cleaning composition is provided.

[0008] (1) A cleaning composition comprising: a fluorinated compound; an organic acid salt compound; an inorganic acid compound; and water, wherein the water content is at least 50% by weight based on the total weight of the composition, and the cleaning composition has a pH of 0.5 to 4.

[0009] (2) The cleaning composition described in (1) above, wherein the cleaning composition has a pH of 1 to 3.

[0010] (3) The cleaning composition described in (1) above, wherein the fluorine compound comprises an ionic bond between a hydrogen cation or an ammonium cation and a fluorine anion.

[0011] (4) The cleaning composition of any one of (1) to (3) above, wherein the ammonium cation contains 4 to 20 carbon atoms.

[0012] (5) The cleaning composition of any one of (1) to (3) above, wherein the content of the fluorine compound is 0.005% to 10% by weight based on the total weight of the cleaning composition.

[0013] (6) The cleaning composition of any one of (1) to (3) above, wherein the organic acid salt compound comprises an ionic bond between an ammonium cation and an organic acid-derived anion.

[0014] (7) The cleaning composition described in (6) above, wherein the organic acid comprises at least one selected from the group consisting of: formic acid, acetic acid, propionic acid, butyric acid, palmitic acid, stearic acid, oleic acid, oxalic acid, malonic acid, succinic acid, tartaric acid, maleic acid, glycolic acid, glutaric acid, adipic acid, sulfosuccinic acid, valeric acid, hexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, lactic acid, malic acid, citric acid, tartaric acid, benzoic acid, salicylic acid, p-toluenesulfonic acid, naphthoic acid, nicotinic acid, toluene, anisic acid, cuminic acid, and phthalic acid.

[0015] (8) The cleaning composition of any one of (1) to (3) above, wherein the content of the organic acid salt compound is 0.01% to 10% by weight based on the total weight of the composition.

[0016] (9) The cleaning composition of any one of (1) to (3) above, wherein the inorganic acid compound comprises at least one selected from the group consisting of hydrochloric acid, phosphoric acid, sulfuric acid and boric acid.

[0017] (10) The cleaning composition of any one of (1) to (3) above, wherein the inorganic acid compound comprises a compound or a salt thereof having a redox potential of 650 mV or lower.

[0018] (11) The cleaning composition of any one of (1) to (3) above, wherein the water content is 80% by weight or more based on the total weight of the composition.

[0019] (12) The cleaning composition of any one of (1) to (3) above, wherein the cleaning composition does not contain amine compounds, ammonium hydroxide compounds, metal hydroxides, peroxide compounds, organic solvents or surfactants.

[0020] (13) A method of manufacturing a semiconductor device, comprising: forming a photoresist pattern on a substrate; removing the photoresist pattern after performing an etching process using the photoresist pattern; and cleaning residues from the photoresist pattern using a cleaning composition according to the above embodiments.

[0021] The cleaning composition according to an exemplary embodiment of the present invention has a high cleaning capability for photoresist residues converted through high-energy processes. Therefore, high-quality semiconductor devices can be provided.

[0022] Furthermore, this cleaning composition can avoid etching wiring containing metals (e.g., Mo, W, Ru, etc.) and layers such as silicon oxide and silicon nitride layers. Therefore, converted photoresist residues can be selectively removed by using a highly selective cleaning composition.

[0023] The method for manufacturing a semiconductor device according to an exemplary embodiment of the present invention can provide a high-quality semiconductor device with reduced conversion photoresist.

[0024] To provide a better understanding of the above and other aspects of the present invention, specific embodiments are described below in conjunction with the accompanying drawings: Simple Explanation of the Diagram

[0025] Figures 1 through 5 are schematic cross-sectional views illustrating a method of manufacturing a semiconductor device according to an exemplary embodiment. Implementation

[0026] Embodiments of the present invention provide a cleaning composition comprising a fluorinated compound, an organic acid salt compound, an inorganic acid compound, and water. Embodiments of the present invention also provide a method for manufacturing a semiconductor device using the cleaning composition.

[0027] The embodiments of the present invention will be described in detail below.

[0028] The cleaning composition according to the embodiments (hereinafter, it may be referred to as the composition) comprises a fluorine-based compound, an organic acid salt compound, an inorganic acid compound, and water.

[0029] Fluorine compounds can be a major component used to remove converted photoresist residues. Converted photoresist residues can be generated through dry etching or photoresist ashing processes.

[0030] Dry etching or ashing processes can be performed using high-energy sources (such as high-temperature heating and high-energy-density light irradiation). Therefore, photoresist can be removed or converted. Converted photoresist may not be completely removed and may remain on the surface of wiring or insulating layers.

[0031] The converted photoresist residue may contain, for example, strong carbon-carbon bonds, carbon-silicon bonds, carbon-oxygen bonds, etc. The cleaning composition may contain a fluorine-based compound capable of reacting with these bonds. The fluorine-based compound can react with silicon to form silicon-fluorine bonds and can dissociate the converted photoresist residue.

[0032] Fluoropolymers can contain ionic bonds between hydrogen cations or ammonium cations and fluoride anions. For example, fluoropolymers can contain ionic bonds between hydrogen cations, ammonium cations, or ammonium cations containing at least one hydrocarbon group and fluoride anions.

[0033] Ammonium cations may include one or more alkyl groups having 1 to 5 carbon atoms. For example, ammonium cations may include methyl, ethyl, propyl, butyl, etc.

[0034] In exemplary embodiments, the ammonium cation may contain 4 to 20 carbon atoms. In some embodiments, the ammonium cation may contain 8 to 20 carbon atoms. For example, the ammonium cation may include tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, etc.

[0035] For example, fluorinated compounds can include hydrofluoric acid (HF), ammonium fluoride, methyl ammonium fluoride, tetramethyl ammonium fluoride, tetraethyl ammonium fluoride, tetrapropyl ammonium fluoride, tetrabutyl ammonium fluoride, etc. These can be used alone or in combination of two or more.

[0036] In an exemplary embodiment, the content of the fluorinated compound may be 0.005% to 10% by weight, based on the total weight of the composition. In some embodiments, the content of the fluorinated compound may be 0.01% to 10% by weight, based on the total weight of the composition.

[0037] Within the aforementioned range, converted photoresist residues can be removed quickly without damaging the silicon substrate (e.g., SiO2, SiN, etc.).

[0038] The composition contains an organic acid salt compound. This organic acid salt compound can react with the carbon components of the converted photoresist residue to form a complex, thereby removing the converted photoresist residue. Furthermore, the organic acid salt compound can prevent etching of the silicon substrate.

[0039] In an exemplary embodiment, the organic acid salt compound may include an ionic bond between an ammonium cation and an organic acid-derived anion. The ammonium cation may be the same as the ammonium cation described in the fluorine-based compound.

[0040] Organic acid-derived anions may include one or more carboxyl anionic moieties, wherein hydrogen atoms are removed from the carboxyl groups of the organic acid in the molecule.

[0041] For example, organic acids can include formic acid, acetic acid, propionic acid, butyric acid, palmitic acid, stearic acid, oleic acid, oxalic acid, malonic acid, succinic acid, tartaric acid, maleic acid, glycolic acid, glutaric acid, adipic acid, sulfosuccinic acid, valeric acid, hexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, lactic acid, malic acid, citric acid, benzoic acid, salicylic acid, p-toluenesulfonic acid, naphthoic acid, nicotinic acid, tolueneic acid, anisic acid, cuminic acid, phthalic acid, etc.

[0042] In this embodiment, the organic acids may include acetic acid, lactic acid, oxalic acid, maleic acid, tartaric acid, citric acid, etc. These may be used alone or in combination of two or more.

[0043] In exemplary embodiments, the content of the organic acid salt compound can be from 0.01% to 10% by weight, based on the total weight of the composition. In some embodiments, the content of the organic acid salt compound can be from 1% to 10% by weight, based on the total weight of the composition.

[0044] Within the aforementioned range, the converted photoresist residue can be removed more effectively, and the surface adsorption of organic acid salt compounds can be prevented.

[0045] The cleaning composition includes inorganic acid compounds. Even with small amounts of strongly acidic inorganic acid compounds, the pH of the cleaning composition can be adjusted to 5 or lower.

[0046] In an exemplary embodiment, the inorganic acid compound may include a compound or its salt having a redox potential of 650 mV or less. For example, the inorganic acid compound may include hydrochloric acid, phosphoric acid, sulfuric acid, boric acid, or its salt.

[0047] In an exemplary embodiment, the inorganic acid compound may exclude compounds with a redox potential exceeding 650 mV. For example, the inorganic acid compound may exclude one or more of nitric acid, hydrobromic acid, iodic acid, metaperiodic acid, orthoperiodic acid, hypoiodic acid, hydroiodic acid, chloric acid, perchloric acid, chlorite, hypochlorous acid, etc., or their salts. For example, the inorganic acid compound may exclude any of the above-mentioned compounds.

[0048] In an exemplary embodiment, the inorganic acid compound may not include nitric acid. Therefore, damage to the metal layer or wiring caused by nitric acid can be avoided.

[0049] Redox potential can be measured by immersing a redox potential electrode in a measurement solution containing inorganic acid compounds while stirring the measurement solution.

[0050] The pH of the cleaning composition can be 0.5 to 4. In some embodiments, the pH of the cleaning composition can be 1 to 3 or 1.2 to 2. In exemplary embodiments, the type and content of the inorganic acid compound can be adjusted by considering the pH of the cleaning composition as described above.

[0051] Within the aforementioned range, the cleaning composition can become relatively acidic, and can more quickly remove converted photoresist residues through organic acid salt compounds and fluorinated compounds in an acidic atmosphere.

[0052] If the pH of the cleaning composition is less than 1, the content of inorganic acid compounds may be too high, causing them to adsorb onto the surface. Therefore, it may not be possible to adequately remove the converted photoresist residue.

[0053] If the pH of the cleaning composition exceeds 4, the cleaning composition may not be able to create a sufficiently acidic environment. Therefore, the chemical reactions between the organic acid salts and fluorinated compounds, as well as the converted photoresist residues, may not occur.

[0054] The cleaning composition includes water. Water may be the main component of the composition, and water may be present in excess relative to the total weight of the composition. For example, the water content may be at least 50% by weight based on the total weight of the composition.

[0055] In an exemplary embodiment, the water content may be at least 60% by weight, at least 70% by weight, or at least 80% by weight, based on the total weight of the composition. In this embodiment, water may be included in the remaining amount of the composition, in addition to the content of fluorinated compounds, organic acid salts, and inorganic acid compounds. The remaining amount may refer to a variable that is adjusted according to the addition of other additional components.

[0056] In an exemplary embodiment, the cleaning composition may not include an alkaline compound. Alkaline compounds can neutralize inorganic acid compounds, thereby increasing the pH and reducing the cleaning power of the cleaning composition.

[0057] In some embodiments, the cleaning composition may not include amine compounds, ammonium hydroxide compounds, and / or metal hydroxides. For example, amine compounds may include primary to tertiary amines that are soluble in water to have a pH of 7 or higher. For example, ammonium hydroxide compounds may include ionic bonds between ammonium cations and hydroxide ions (OH⁻). For example, metal hydroxides may include alkali metal hydroxides.

[0058] For example, basic compounds may include: amine compounds, including primary to tertiary aliphatic amines, alicyclic amines, heterocyclic amines, aromatic amines, etc.; ammonium hydroxide compounds, including ammonium hydroxide, trimethylammonium hydroxide, triethylammonium hydroxide, etc.; or metal hydroxides, including NaOH, KOH, Ca(OH)2, Al(OH)3, etc.

[0059] In some embodiments, the cleaning composition may not contain an oxidizing agent. For example, an oxidizing agent can etch the metal wiring of a semiconductor device during the cleaning process, thereby degrading the quality of the semiconductor device.

[0060] In some embodiments, the cleaning composition may not contain a peroxide compound. For example, the peroxide compound may include hydrogen peroxide, persulfate, persulfate, or a salt thereof.

[0061] In some embodiments, the cleaning composition may be free of organic solvents. Organic solvents can inhibit the reaction between fluorinated compounds and converted photoresist, and can reduce the solubility of fluorinated compounds, organic acid salts, and inorganic acid compounds.

[0062] For example, organic solvents may include propylene glycol methyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), tetrahydrofuran (THF), methanol, ethanol, isopropanol (IPA), methoxypropanol, dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), methyl ethyl ketone (MEK), acetone, hexane, methyl isobutyl ketone (MIBK), acrylonitrile, acetonitrile, ethyl acetate, phenol, benzene, toluene, xylene, etc.

[0063] In some embodiments, the cleaning composition may not include surfactants. When a cleaning process is performed using a cleaning composition containing surfactants, bubbles may form, reducing cleaning effectiveness. For example, surfactants can be anionic surfactants, such as sodium dodecyl sulfate (SDS), ammonium lauryl sulfate (ALS), sodium lauryl vinyl sulfate (SLES), linear alkylbenzene sulfonate (LAS), α-olefin sulfonate (AOS), alkyl sulfate (AS), alkyl ether sulfate (AES), sodium alkyl sulfonate (SAS), etc.; cationic surfactants, such as alkyl dimethyl benzyl chloride, tetradecyl dimethyl benzyl chloride, hexadecyl trimethyl ammonium chloride, docosyl trimethyl ammonium chloride, alkylpropylene diamine acetate, octadecylamine acetate, tetradecylamine acetate, didecyl dimethyl ammonium chloride, octadecyl dimethyl benzyl chloride, etc.; decylphosphonic acid, dodecylphosphonic acid, tetradecylphosphonic acid, hexadecylphosphonic acid, bis(2-ethylhexyl) phosphate, octadecylphosphonic acid, perfluoroheptanoic acid, perfluorodecanoic acid, trifluorodecanoic acid, trifluoromethanesulfonic acid, phosphonoacetic acid, dodecylbenzene sulfonic acid, dodecylamine, dodecylphenoxy polyethoxyethanol, etc.

[0064] In embodiments, the cleaning composition may consist essentially of a fluorinated compound, an organic acid salt compound, an inorganic acid compound, and water. For example, the cleaning composition may not include any other components besides the fluorinated compound, the organic acid salt compound, the inorganic acid compound, and water. For example, the sum of the contents of the fluorinated compound, the organic acid salt compound, the inorganic acid compound, and water may be 100% by weight, based on the total weight of the cleaning composition.

[0065] According to embodiments, a method for manufacturing a semiconductor device using a cleaning composition can be provided. The cleaning composition can be used in various processes for removing residual photoresist, and its application is not limited to the embodiments described below.

[0066] Figures 1 through 5 are schematic cross-sectional views illustrating a method for manufacturing a semiconductor device according to an embodiment.

[0067] Referring to Figure 1, a photoresist layer 120 can be formed by coating a photoresist layer on a substrate 100.

[0068] The substrate 100 may include semiconductor materials such as monocrystalline silicon or monocrystalline germanium, and may also include polycrystalline silicon.

[0069] An etching target layer 110 can be formed on the substrate 100. A photoresist layer 120 can be formed on the etching target layer 110.

[0070] The etched target layer 110 may include a metal layer for forming wiring, an insulating layer for insulating the wiring, and / or a semiconductor layer.

[0071] In some embodiments, a soft baking process can be performed after the photoresist layer 120 is formed. Therefore, the organic solvents included in the photoresist layer 120 can be evaporated.

[0072] Referring to Figure 2, the photoresist layer 120 can be divided into a non-exposed portion 120b and an exposed portion 120a. An exposure process can be performed using a light source (e.g., an EUV light source) and an exposure mask.

[0073] Light (e.g., EUV) passing through the opening of the exposure mask can illuminate the photoresist layer 120. Therefore, the photoresist layer 120 can be divided into an unexposed portion 120b that does not overlap with the opening and an exposed portion 120a that overlaps with the opening.

[0074] Referring to Figure 3, the exposed portion 120a or the unexposed portion 120b can be removed by a developing process using a developer solution to form a photoresist pattern 130 on the substrate 100 or the etch target layer 110. The developer solution can be an aqueous solution of tetramethylammonium hydroxide (TMAH).

[0075] As shown in Figure 3, when the photoresist layer 120 includes negative photoresist, the unexposed portion 120b can be removed through the development process, and the photoresist pattern 130 can be defined by the remaining exposed portion 120a.

[0076] Optionally, when the photoresist layer 120 includes positive photoresist, the exposed portion 120a can be removed through a development process, and the photoresist pattern 130 can be defined by the remaining unexposed portion 120b.

[0077] In some implementations, a post-baking process can be performed after the exposure process or after the development process.

[0078] The photoresist pattern 130 can be used as an etching mask to etch the target layer 110. Through etching, a bullseye pattern 115 can be formed from the target layer 110. The bullseye pattern 115 can be a fine wiring, insulating pattern, or semiconductor pattern of a semiconductor device. Etching can include dry etching or wet etching.

[0079] Referring to Figure 4, the photoresist pattern 130 can be removed through processes such as ashing.

[0080] In the ashing process, the photoresist pattern 130 can be essentially burned off and removed. For example, ashing can include plasma ashing and can be performed by injecting a reactive gas, such as oxygen.

[0081] The ashing process can be carried out at high temperatures, so a portion of the photoresist pattern 130 can react with the semiconductor material of the substrate 100 through high-temperature energy to form the transformed residue 135.

[0082] Referring to Figure 5, the conversion residue 135 can be removed using the cleaning composition according to the above embodiment. Therefore, a highly reliable semiconductor device can be provided without damaging the target pattern 115 of the semiconductor device formed on the substrate 100, such as metal wiring, silicon-containing layers, etc.

[0083] For example, the cleaning process using the above-described cleaning composition can be carried out by immersion and / or spraying with a batch etching apparatus or a single etching apparatus. [Example]

[0084] The present invention is described in more detail below with examples. However, the following embodiments are given only to illustrate the invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the invention. Such changes and modifications are suitably included in the appended claims. [Examples and Comparisons] [example]

[0085] As shown in Tables 1 and 2 below, the types and amounts of fluorinated compounds, organic acid salts, and inorganic acid compounds were used to prepare cleaning compositions, with the remainder being water. The content of each component is expressed as a percentage by weight based on the total weight of the composition. Tables 1 and 2 show the pH of each cleaning composition.

[0086] [Table 1] Fluorine compounds Organic acid salt compounds Inorganic acid compounds pH type content (weight%) type content (weight%) type content (weight%) Example 1 A-5 0.0005 B-7 2.5 C-1 3 1.4 Example 2 A-5 0.005 B-7 2.5 C-1 3 1.4 Example 3 A-5 0.01 B-7 2.5 C-1 3 1.4 Example 4 A-5 0.1 B-7 2.5 C-1 3 1.4 Example 5 A-5 2.5 B-7 2.5 C-1 3 1.4 Example 6 A-5 10 B-7 2.5 C-1 3 1.4 Example 7 A-5 15 B-7 2.5 C-1 3 1.4 Example 8 A-5 2.5 B-7 0.005 C-1 3 1.4 Example 9 A-5 2.5 B-7 0.01 C-1 3 1.4 Example 10 A-5 2.5 B-7 2.5 C-1 3 1.4 Example 11 A-5 2.5 B-7 10 C-1 3 1.4 Example 12 A-5 2.5 B-7 15 C-1 3 1.4 Example 13 A-5 2.5 B-7 2.5 C-1 0.001 4.5 Example 14 A-5 2.5 B-7 2.5 C-1 0.005 3.5 Example 15 A-5 2.5 B-7 2.5 C-1 0.01 3 Example 16 A-5 2.5 B-7 2.5 C-1 3 1.4 Example 17 A-5 2.5 B-7 2.5 C-1 7 1.1 Example 18 A-5 2.5 B-7 2.5 C-1 10 0.9 Example 19 A-5 2.5 B-7 2.5 C-1 20 0.1 Example 20 A-2 0.0005 B-7 2.5 C-1 3 1.4 Example 21 A-2 0.005 B-7 2.5 C-1 3 1.4 Example 22 A-2 0.01 B-7 2.5 C-1 3 1.4 Example 23 A-2 0.1 B-7 2.5 C-1 3 1.4 Example 24 A-2 2.5 B-7 2.5 C-1 3 1.4 Example 25 A-2 10 B-7 2.5 C-1 3 1.4 Example 26 A-2 15 B-7 2.5 C-1 3 1.4 Example 27 A-2 2.5 B-7 0.005 C-1 3 1.4 Example 28 A-2 2.5 B-7 0.01 C-1 3 1.4 Example 29 A-2 2.5 B-7 2.5 C-1 3 1.4 Example 30 A-2 2.5 B-7 10 C-1 3 1.4 Example 31 A-2 2.5 B-7 15 C-1 3 1.4 Example 32 A-2 2.5 B-7 2.5 C-1 0.001 4.5 Example 33 A-2 2.5 B-7 2.5 C-1 0.005 3.5 Example 34 A-2 2.5 B-7 2.5 C-1 0.01 3 Example 35 A-2 2.5 B-7 2.5 C-1 3 1.4 Example 36 A-2 2.5 B-7 2.5 C-1 7 1.1 Example 37 A-2 2.5 B-7 2.5 C-1 10 0.9 Example 38 A-2 2.5 B-7 2.5 C-1 20 0.1 Example 39 A-3 2.5 B-7 2.5 C-1 3 1.4 Example 40 A-4 2.5 B-7 2.5 C-1 3 1.4 Example 41 A-1 2.5 B-7 2.5 C-1 3 1.4 Example 42 A-6 2.5 B-7 2.5 C-1 3 1.4 Example 43 A-7 2.5 B-7 2.5 C-1 3 1.4 Example 44 A-8 2.5 B-7 2.5 C-1 3 1.4 Example 45 A-2 2.5 B-2 2.5 C-1 3 1.4 Example 46 A-2 2.5 B-3 2.5 C-1 3 1.4 Example 47 A-2 2.5 B-4 2.5 C-1 3 1.4 Example 48 A-2 2.5 B-5 2.5 C-1 3 1.4 Example 49 A-2 2.5 B-6 2.5 C-1 3.5 1.4 Example 50 A-2 2.5 B-1 2.5 C-1 3 1.4 Example 51 A-2 2.5 B-7 2.5 C-2 3 1.4 Example 52 A-2 2.5 B-7 2.5 C-3 3 1.4 Example 53 A-2 2.5 B-7 2.5 C-4 3 1.4

[0087] [Table 2] Fluorine compounds Organic acid salt compounds Inorganic acid compounds Other compounds pH type content (weight%) type content (weight%) type content (weight%) type content (weight%) Comparative Example 1 - - B-1 2.5 C-1 3 - - 1.4 Comparative Example 2 A-2 2.5 - - C-1 3 - - 1.4 Comparative Example 3 A-2 2.5 B-1 2.5 - - - - 6.5 Comparative Example 4 - - B-1 2.5 C-1 3 D-1 10 1.4 Comparative Example 5 A-2 2.5 - - C-1 3 D-2 10 1.4 Comparative Example 6 - - B-1 2.5 C-1 3 D-3 10 1.4 Comparative Example 7 A-2 2.5 - - C-1 3 D-4 10 1.4 Comparative Example 8 - - B-1 2.5 C-1 3 D-5 10 1.4 Comparative Example 9 A-2 2.5 - - C-1 3 D-6 10 1.4 Comparative Example 10 - - B-1 2.5 C-1 3 E-1 5 1.4 Comparative Example 11 A-2 2.5 - - C-1 3 F-1 10 13 Comparative Example 12 - - B-1 2.5 C-1 3 F-2 10 13 Comparative Example 13 A-2 2.5 B-1 2.5 - - F-3 10 11 Comparative Example 14 - - B-1 2.5 C-1 3 G-1 0.1 1.4 Comparative Example 15 A-2 2.5 - - C-1 3.5 G-2 0.1 1.4 Comparative Example 16 A-2 2.5 B-1 2.5 - - G-3 0.1 1.4 Comparative Example 17 - - B-1 2.5 C-1 3.5 G-4 0.1 1.4 Comparative Example 18 A-2 2.5 - - C-1 3.5 G-5 0.1 1.4 Comparative Example 19 A-2 2.5 B-1 2.5 C-1 3.5 D-1 40 1.0 A-1: Ammonium fluoride A-2: Tetramethylammonium fluoride (TMAF) A-3: Tetraethylammonium Fluoride (TEAF) A-4: Tetrapropylammonium Fluoride (TPropylAF) A-5: Tetrabutylammonium fluoride (TBAF) A-6: Tetrapentylammonium fluoride (TPentylAF) A-7: Ethyltrimethylammonium fluoride (ETMAF) A-8: Diethyldimethylammonium fluoride (DEDMAF) B-1: Tetramethylammonium (TMA) acetate B-2: TMA Formate B-3: TMA lactate B-4: TMA oxalate B-5: TMA malate B-6: TMA Tartrate B-7: TMA Citrate C-1: Phosphoric acid C-2: Sulfuric acid C-3: Hydrochloric acid C-4: Nitric acid D-1: Propylene glycol monomethyl ether acetate (PGMEA) D-2: Propylene glycol methyl ether (PGME) D-3: Tetrahydrofuran (THF) D-4: Isopropyl alcohol (IPA) D-5: Acetone D-6: Dimethyl sulfoxide (DMSO) E-1: Hydrogen peroxide (H2O2) F-1: Sodium hydroxide (NaOH) F-2: Tetramethylammonium hydroxide (TMAH) F-3: Ammonium hydroxide (NH4OH) G-1: Sodium dodecyl sulfate G-2: Hexadecylphosphonic acid G-3: Perfluorodecanoic acid G-4:2-(p-dodecylphenoxyethoxy)-ethoxyethanol G-5: Cetyltrimethylammonium chloride [Experimental Example]

[0088] The properties of the cleaning compositions of the examples and comparative examples were evaluated using the following methods, and the results are shown in Tables 3 and 4. [(1)] [Evaluation of photoresist residues from clean conversion]

[0089] A converted photoresist residue was formed on a silicon wafer and cut into 1.5cm × 1.5cm pieces to prepare samples. The initial residue was calculated using scanning electron microscopy (SEM) based on the pixel area of ​​the converted photoresist residue on the sample surface.

[0090] The samples were immersed in a beaker containing the cleaning compositions of the examples and comparative examples at 25°C for 100 seconds at 400 rpm. Afterward, the samples were removed, rinsed with water, and air-dried.

[0091] The photoresist residue remaining on the sample surface after processing was analyzed using SEM, and the amount of residue was calculated based on the pixel area.

[0092] Calculate the ratio of the treated residue to the initial residue and evaluate it according to the following criteria.

[0093] <Evaluation Criteria> Level 5: Approximately 80%~100% of the initial value. Level 4: Approximately 60% to 80% of the initial value. Level 3: Approximately 40% to 60% of the initial value. Level 2: Approximately 20% to 40% of the initial value. Level 1: Approximately 0% to 20% of the initial value. [(2) SiO, 2, ] [Evaluation of Etching Rate]

[0094] Silicon wafers with 5,000 Å of deposited SiO2 were cut into 1.5 cm × 1.5 cm pieces to prepare samples. The samples were immersed in a beaker containing the clean compositions of the examples and comparative examples at 25 °C for 600 seconds at 400 rpm. Afterward, the samples were removed, rinsed with water, and air-dried.

[0095] The SiO2 layer thickness of the treated sample was measured using an ellipsometry. The etch rate of the SiO2 layer was calculated using the variation in layer thickness and evaluated according to the following criteria.

[0096] <Evaluation Criteria> The etching rate of the O:SiO2 layer is 1 Å / min or lower. △: The etching rate of the SiO2 layer is greater than 1 Å / min and 10 Å / min or less. X: The etching rate of the SiO2 layer is greater than 10 Å / min [(3)] [right] [SiNx] [Evaluation of Etching Rate]

[0097] Silicon wafers with 1,000 Å of deposited SiNx were cut into 1.5 cm × 1.5 cm pieces to prepare samples. The samples were immersed in a beaker containing the clean compositions of the examples and comparative examples at 25 °C for 600 seconds at 400 rpm. Afterward, the samples were removed, rinsed with water, and air-dried.

[0098] The thickness of the SiNx layer in the treated sample was measured using an ellipsometry. The etch rate of the SiNx layer was calculated using the variation in layer thickness and evaluated according to the following criteria.

[0099] <Evaluation Criteria> The etching rate of the O:SiNx layer is 1 Å / min or less. △: The etching rate of the SiNx layer is greater than 1 Å / min and 10 Å / min or less. X: The etching rate of the SiNx layer is greater than 10 Å / min [(4)] [right] [Mo] [Evaluation of Etching Rate]

[0100] Silicon wafers with 200 Å of deposited Mo were cut into 3.0 cm × 3.0 cm pieces to prepare samples. The samples were immersed in a beaker containing the clean compositions of the examples and comparative examples at 25°C for 600 seconds at 400 rpm. Afterward, the samples were removed, rinsed with water, and air-dried.

[0101] The thickness of the Mo layer in the treated sample was measured using X-ray fluorescence spectroscopy (XRF). The etch rate of the Mo layer was calculated using the variation in layer thickness and evaluated according to the following criteria.

[0102] <Evaluation Criteria> The etching rate of the O:Mo layer is 1 Å / min or less. △: Mo layer etching rate greater than 1 Å / min and 10 Å / min or less X: Mo layer etching rate greater than 10 Å / min [(5)] [right] [W] [Evaluation of Etching Rate]

[0103] Silicon wafers with 200 Å of deposited W were cut into 3.0 cm × 3.0 cm pieces to prepare samples. The samples were immersed in a beaker containing the clean compositions of the examples and comparative examples at 25°C for 600 seconds at 400 rpm. Afterward, the samples were removed, rinsed with water, and air-dried.

[0104] The thickness of the W layer in the treated sample was measured using X-ray fluorescence spectroscopy (XRF). The etch rate of the W layer was calculated using the variation in layer thickness and evaluated according to the following criteria.

[0105] <Evaluation Criteria> The etching rate of the O:W layer is 1 Å / min or less. △: The etching rate of the W layer is greater than 1 Å / min and 10 Å / min or less. X:W layer etching rate greater than 10 Å / min [(6)] [right] [Ru] [Evaluation of Etching Rate]

[0106] Silicon wafers with 100 Å of Ru deposited were cut into 3.0 cm × 3.0 cm pieces to prepare samples. The samples were immersed in a beaker containing the clean compositions of the examples and comparative examples at 25°C for 600 seconds at 400 rpm. Afterward, the samples were removed, rinsed with water, and air-dried.

[0107] The thickness of the Ru layer in the treated sample was measured using X-ray fluorescence spectroscopy (XRF). The etch rate of the Ru layer was calculated using the variation in layer thickness and evaluated according to the following criteria.

[0108] <Evaluation Criteria> The etching rate of the O:Ru layer is 1 Å / min or less. △: Ru layer etching rate greater than 1 Å / min and 10 Å / min or less X:Ru layer etching rate greater than 10 Å / min

[0109] [Table 3] Level of residue after treatment Evaluation of corrosion resistance properties Mo W Ru SiO2 SiNx Example 1 3 O O O O O Example 2 1 O O O O O Example 3 1 O O O O O Example 4 1 O O O O O Example 5 1 O O O O O Example 6 1 O O O O O Actual example 7 1 O O O X X Actual example 8 2 O O O O O Actual example 9 1 O O O O O Actual example 10 1 O O O O O Actual example 11 1 O O O O O Actual example 12 2 O O O O O Actual example 13 3 O O O △ △ Actual example 14 1 O O O O O Actual example 15 1 O O O O O Actual example 16 1 O O O O O Actual example 17 1 O O O O O Actual example 18 1 O O O O O Actual example 19 1 O O O △ △ Actual example 20 3 O O O O O Actual example 21 1 O O O O O Actual example 22 1 O O O O O Actual example 23 1 O O O O O Actual example 24 1 O O O O O Actual example 25 1 O O O O O Actual example 26 1 O O O X X Actual example 27 2 O O O O O Actual example 28 1 O O O O O Actual example 29 1 O O O O O Actual example 30 1 O O O O O Actual example 31 2 O O O O O Actual example 32 3 O O O △ △ Actual example 33 1 O O O O O Actual example 34 1 O O O O O Actual example 35 1 O O O O O Actual example 36 1 O O O O O Actual example 37 1 O O O O O Actual example 38 1 O O O △ △ Actual example 39 1 O O O O O Actual example 40 1 O O O O O Actual example 41 1 O O O O O Actual example 42 1 O O O O O Actual example 43 1 O O O O O Actual example 44 1 O O O O O Actual example 45 1 O O O O O Actual example 46 1 O O O O O Actual example 47 1 O O O O O Actual example 48 1 O O O O O Actual example 49 1 O O O O O Actual example 50 1 O O O O O Actual example 51 1 O O O O O Actual example 52 1 O O O O O Example 53 2 △ △ △ O O

[0110] [Table 4] Level of residue after treatment Evaluation of corrosion resistance properties Mo W Ru SiO2 SiNx Comparative Example 1 5 O O O O O Comparative Example 2 4 O O O O O Comparative Example 3 5 O O O O O Comparative Example 4 5 O O O O O Comparative Example 5 4 O O O O O Comparative Example 6 5 O O O O O Comparative Example 7 4 O O O O O Comparative Example 8 5 O O O O O Comparative Example 9 4 O O O O O Comparative Example 10 5 X X X O O Comparative Example 11 5 O O O X X Comparative Example 12 5 O O O X X Comparative Example 13 5 O O O O O Comparative Example 14 5 O O O O O Comparative Example 15 4 O O O O O Comparative Example 16 5 O O O O O Comparative Example 17 5 O O O O O Comparative Example 18 4 O O O O O Comparative Example 19 5 O O O O O

[0111] Referring to Table 3, the cleaning compositions of the examples, which include fluorine-based compounds, organic acid salt compounds, inorganic acid compounds, and excess water with a pH of 0.5 to 4, provide high corrosion resistance to metals such as Mo, W, and Ru and silicon substrates such as SiO2 and SiNx, and provide high cleaning ability to converted photoresist residues.

[0112] In Example 53, which uses nitric acid as an inorganic acid compound, the etching rate of metals including Mo, W, and Ru was slightly increased compared to other examples.

[0113] Referring to Table 4, comparative cleaning compositions that do not contain fluorine compounds, organic acid salts, or inorganic acid compounds provide cleaning capabilities that reduce converted photoresist residues.

[0114] In particular, the cleaning compositions of Comparative Examples 6 and 11-13 exhibited excessively high pH values, resulting in reduced cleaning ability against converted photoresist residues.

[0115] In addition, the cleaning composition of Comparative Example 19 contains an excessive amount of organic solvent, which reduces its cleaning ability against converted photoresist residues.

[0116] The above description is merely an exemplary implementation of the application and principles of this disclosure, and may include other elements without departing from the scope of the invention.

[0117] In summary, although the present invention has been disclosed above with reference to embodiments, it is not intended to limit the invention. Those skilled in the art can make various modifications and refinements without departing from the spirit and scope of the invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.

[0118] 100:Substrate 110: Etching the target layer 115: Bullseye Chart Pattern 120: Photoresist layer 135: Residue

Claims

1. A cleaning composition comprising: a monofluoro group; an organic acid salt compound; an inorganic acid compound; and water, wherein, Based on the total weight of the composition, the water content is at least 50% by weight, and the cleaning composition has a pH of 0.5 to 4.

2. The cleaning composition as described in claim 1, wherein, This cleaning composition has a pH of 1 to 3.

3. The cleaning composition as described in claim 1, wherein, This fluorinated compound contains ionic bonds between hydrogen cations or ammonium cations and fluorine anions.

4. The cleaning composition as described in any one of claims 1 to 3, wherein, This ammonium cation contains 4 to 20 carbon atoms.

5. The cleaning composition as described in any one of claims 1 to 3, wherein, Based on the total weight of the cleaning composition, the content of the fluorinated compound is 0.005% to 10% by weight.

6. The cleaning composition as described in any one of claims 1 to 3, wherein, This organic acid salt compound contains an ionic bond between an ammonium cation and an organic acid-derived anion.

7. The cleaning composition as described in claim 6, wherein, The organic acid includes at least one selected from the group consisting of: formic acid, acetic acid, propionic acid, butyric acid, palmitic acid, stearic acid, oleic acid, oxalic acid, malonic acid, succinic acid, tartaric acid, maleic acid, glycolic acid, glutaric acid, adipic acid, sulfosuccinic acid, valeric acid, hexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, lactic acid, malic acid, citric acid, benzoic acid, salicylic acid, p-toluenesulfonic acid, naphthoic acid, nicotinic acid, tolueneic acid, anisic acid, cuminic acid, and phthalic acid.

8. The cleaning composition as described in any one of claims 1 to 3, wherein, Based on the total weight of the composition, the content of the organic acid salt compound is 0.01% to 10% by weight.

9. The cleaning composition as described in any one of claims 1 to 3, wherein, The inorganic acid compound includes at least one selected from the group consisting of hydrochloric acid, phosphoric acid, sulfuric acid, and boric acid.

10. The cleaning composition as described in any one of claims 1 to 3, wherein, The inorganic acid compounds include compounds or their salts having a redox potential of 650 mV or lower.

11. The cleaning composition as described in any one of claims 1 to 3, wherein, Based on the total weight of the composition, the water content is 80% by weight or more.

12. The cleaning composition as described in any one of claims 1 to 3, wherein, This cleaning composition does not contain amine compounds, ammonium hydroxide compounds, metal hydroxides, peroxide compounds, organic solvents, or surfactants.

13. A method of manufacturing a semiconductor device, comprising: A photoresist pattern is formed on the substrate; After using the photoresist pattern for etching, the photoresist pattern is removed. And to clean the residue from the photoresist pattern using a cleaning composition as described in any one of claims 1 to 12.

Images