Coating composition for preventing semiconductor pattern collapse, and pattern coated using same

Abstract

The objective of the present invention is to provide a coating composition capable of preventing pattern collapse by causing the contact angle between a semiconductor device pattern and water to be close to 90°, and to provide a pattern coated with the coating composition, and the coating composition capable of preventing pattern collapse comprises: a coating material for preventing pattern collapse, comprising an amide compound represented by chemical formula (1) or a phosphorus compound represented by chemical formula (2); and an organic solvent.

Description

Coating composition for preventing semiconductor pattern collapse and pattern coated using the same

[0001] The present invention relates to a coating composition for preventing pattern collapse that can be used for a pattern having a high aspect ratio (aspect ratio of 15 or more) in the manufacture of memory semiconductors.

[0002] Due to miniaturization and integration of devices, implementation of fine patterns in semiconductor processes is required, and research and development are in progress on methods for forming such fine patterns, such as development of exposure equipment or miniaturization of patterns through introduction of additional processes. In order to increase the integration density of semiconductor devices and implement the formation of structures with dimensions in the nanometer range, development of process equipment or process technology is urgently required.

[0003] To increase the integration density of semiconductor devices and enable the formation of structures with dimensions in the nanometer range, patterns with high aspect ratios (the ratio of the pattern's length to its width) are being used, which has resulted in the pattern collapsing during the cleaning process.

[0004] When the aspect ratio of the micro-pattern formed on the device substrate was low, there was no problem with the wet cleaning method using distilled water. However, as the aspect ratio increased, the micro-pattern collapsed when the final cleaning was performed simply with distilled water.

[0005] The force that causes the collapse of the micro-pattern formed on the substrate increases in proportion to the surface tension and the cosine θ (cosθ) value of the contact angle that the material used in the pattern formation process and cleaning has on the micro-pattern. Therefore, an alternative was sought by applying the principle that the smaller the surface tension, the smaller the force. The following methods are actually being applied.

[0006] To solve the problem of micro-pattern collapse, semiconductor manufacturers have used alcohols such as isopropanol or surfactants to lower the surface tension applied to the pattern.

[0007] As semiconductor manufacturing processes have become more refined in recent years, the width of the pattern has become smaller and the height has become larger compared to the existing process, so the aspect ratio of the pattern has increased rapidly. This problem cannot be solved with the method introduced above, so a method to solve this has become necessary.

[0008] As briefly described above, factors affecting the force of micro-pattern collapse include the surface tension (Γ) of the cleaning solution, the aspect ratio according to the height (H) of the pattern, the spacing between patterns (D), the pattern width (W), and the contact angle between the pattern and the cleaning solution.

[0009] In the final wet process of the micro-pattern manufacturing process, the wafer is spin-dried. The above theory states that using a low surface tension detergent is an important factor in weakening the force of the detergent when it comes out during spin-drying. However, the micro-patterns currently being developed have such a high aspect ratio that it is impossible to see the effect by lowering the surface tension to a certain extent. Except for liquid helium, the surface tension is 0 J / m. 2 It is impossible to lower it to near 15 J / m, and the lowest surface tension value among commercially available substances, including surfactants, is 15 J / m. 2 It has been confirmed through numerous experiments that using a final cleaning solution having a surface tension value of this value or higher cannot prevent the collapse of micro-patterns.

[0010] That is, there is a problem in that the effect of controlling surface tension to prevent the collapse of micro-patterns can no longer be expected.

[0011] [Prior Art Literature]

[0012] [Patent Document]

[0013] (Patent Document 1) 1. Republic of Korea Patent Publication No. 10-1118437 B1

[0014] (Patent Document 2) 2. Republic of Korea Patent Publication No. 10-1535200 B1

[0015] (Patent Document 3) 3. Republic of Korea Patent Publication No. 10-1483484 B1

[0016] (Patent Document 4) 4. Republic of Korea Patent Publication No. 10-1525152 B1

[0017] The present invention provides a coating composition capable of preventing pattern collapse by making the contact angle of water close to 90° for a pattern including at least one element among polysilicon, silicon oxide, silicon nitride, titanium nitride, and tungsten, using a coating composition for preventing pattern collapse in the manufacture of a memory semiconductor device having a high aspect ratio, and provides a pattern device coated with such a coating composition.

[0018] Accordingly, the present invention provides, as a preferred first embodiment, a coating composition comprising at least one selected from an amide compound represented by the following chemical formula (1) and a phosphorus compound represented by the following chemical formula (2), wherein the coating composition forms a self-assembly monolayer (SAM) at a pattern interface by mixing the coating composition with an organic solvent, and the coating composition is characterized in that the contact angle of water with respect to the pattern is 80° to 100°.

[0019] Chemical formula (1)

[0020]

[0021]

[0022]

[0023] [Wherein R1, R2 and R3 are each hydrogen or an alkyl group having 1 to 8 carbon atoms or a fluoroalkyl group having 1 to 8 carbon atoms or a carbonyl group having 2 to 6 carbon atoms,

[0024] At least one of R1, R2 and R3 is hydrogen or an alkyl group having 1 to 8 carbon atoms,

[0025] At least one of R1, R2 and R3 is a fluoroalkyl group having 1 to 8 carbon atoms or a carbonyl group having 2 to 6 carbon atoms.]

[0026]

[0027] Chemical formula (2)

[0028]

[0029]

[0030]

[0031] [Here, R1, R2 and R3 are each hydrogen or an alkyl group having 1 to 16 carbon atoms or a fluoroalkyl group having 1 to 10 carbon atoms or a perfluoroalkyl group having 3 to 10 carbon atoms,

[0032] At least one of R1, R2 and R3 is hydrogen,

[0033] At least one of R1, R2 and R3 is an alkyl group having 1 to 16 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms or a perfluoroalkyl group having 3 to 10 carbon atoms.]

[0034] The coating composition for preventing pattern collapse according to the above embodiment may include 5 to 30 wt% of the pattern coating material and 70 to 95 wt% of an organic solvent.

[0035] The pattern coating material according to the above embodiment may include at least one selected from the amide compound represented by the above chemical formula (1) and the phosphorus compound represented by the above chemical formula (2).

[0036] The organic solvent according to the above embodiment may be at least one selected from among a glycol compound having 4 to 20 carbon atoms, a glycol ether compound having 4 to 20 carbon atoms, an alkylene glycol alkyl ether compound having 4 to 20 carbon atoms, a silylamine compound having 3 to 12 carbon atoms, an alcohol having 1 to 10 carbon atoms, and a hydrocarbon solvent having 6 to 10 carbon atoms.

[0037] The present invention also provides, as a second preferred embodiment, a pattern device coated with the coating composition for preventing pattern collapse.

[0038] The contact angle of water on the pattern device coated with the coating composition for preventing pattern collapse according to the above embodiment may be 80° to 100°.

[0039] The pattern coating composition according to the present invention uniformly coats a pattern on a substrate using a single spin method or a batch wet method, thereby preventing the pattern from collapsing when the semiconductor substrate is finally washed with water after oxide etching and dried, thereby reducing defects occurring in the memory semiconductor device manufacturing process stage, thereby increasing production through increased yield and reducing manufacturing process costs and process time.

[0040] Figure 1 shows the results of measuring whether or not a pattern collapses according to Example 1.

[0041] Figure 2 shows the results of measuring whether the pattern collapses according to Comparative Example 1.

[0042] Hereinafter, the coating composition for preventing pattern collapse according to the present invention will be described in more detail.

[0043] The present invention provides a coating composition for preventing pattern collapse, which comprises at least one selected from an amide compound represented by the following chemical formula (1) and a phosphorus compound represented by the following chemical formula (2), and is mixed with an organic solvent to form a self-assembled monolayer on a pattern interface, so that the contact angle of water with respect to the pattern is 80° to 100°.

[0044] Chemical formula (1)

[0045]

[0046]

[0047]

[0048]

[0049] [Wherein R1, R2 and R3 are each hydrogen or an alkyl group having 1 to 8 carbon atoms or a fluoroalkyl group having 1 to 8 carbon atoms or a carbonyl group having 2 to 6 carbon atoms,

[0050] At least one of R1, R2 and R3 is hydrogen or an alkyl group having 1 to 8 carbon atoms,

[0051] At least one of R1, R2 and R3 is a fluoroalkyl group having 1 to 8 carbon atoms or a carbonyl group having 2 to 6 carbon atoms.

[0052]

[0053] Chemical formula (2)

[0054]

[0055]

[0056]

[0057]

[0058] Here, R1, R2 and R3 are each hydrogen or an alkyl group having 1 to 16 carbon atoms or a fluoroalkyl group having 1 to 10 carbon atoms or a perfluoroalkyl group having 3 to 10 carbon atoms,

[0059] At least one of R1, R2 and R3 is hydrogen,

[0060] At least one of R1, R2 and R3 is an alkyl group having 1 to 16 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms or a perfluoroalkyl group having 3 to 10 carbon atoms.]

[0061] The present invention relates to a pattern treatment material that coats a pattern surface to make the contact angle between water and the pattern close to 90° to prevent the pattern from collapsing, based on the theory that among the elements of forces applied to a pattern in the manufacture of a semiconductor device for memory, more specifically, among the elements of forces applied to a pattern forming a cell, when the contact angle of a liquid becomes 90°, the cosine θ (cosθ) value becomes 0, so that the force applied to the pattern also becomes 0, thereby preventing collapse, and more specifically, to a coating composition that forms a hydrophobic self-assembled monolayer at the pattern interface to prevent the pattern from collapsing.

[0062] When coated with the above-described pattern collapse prevention coating composition, a self-assembled monolayer is formed by the compound represented by the chemical formula (1) on various pattern materials for devices used in the manufacture of semiconductor memory; for example, on substrates such as polysilicon (Poly Si), silicon oxide (SiO), silicon nitride (SiN), titanium nitride (TiN), and tungsten (W), so that the interface becomes hydrophobic, and when water drains out during the cleaning process after etching the oxide film, the force is minimized, thereby preventing the pattern collapse phenomenon.

[0063] Therefore, when applying the coating composition for preventing pattern collapse according to the present invention, the water contact angle for the pattern should be close to 90°, it should spread well between the fine patterns of a 300 mm wafer and be able to uniformly treat the surface, it should be miscible with a solvent such as water or alcohol, but it should also maintain bonding strength with the pattern, it can be used in a batch or spin manner, and it has the characteristic of being completely removable after drying by a dry method such as thermal, ultraviolet rays, or plasma.

[0064] Considering the above conditions, the coating solution of the present invention may include a coating material capable of forming a self-assembled monolayer on a pattern to enable coating treatment and having a contact angle with water close to 90°, and may also include an organic solvent capable of dissolving or diluting the coating material.

[0065] Typically, pattern materials used in the manufacture of memory semiconductor devices—polysilicon, silicon oxide, silicon nitride, titanium nitride, tungsten, etc.—are relatively hydrophilic inorganic materials. Consequently, their contact angle with water is small during the cleaning process, leading to pattern collapse due to capillary forces. Therefore, altering the pattern interface to be hydrophobic increases the contact angle with water, thereby preventing pattern collapse.

[0066] Accordingly, the coating material according to the present invention has a molecular structure in which at least one functional group has a hydrophilic group such as a hydroxyl group, an alkoxy group, an ester group, or an amide group to chemically bond with an inorganic interface, and at least one functional group has a hydrophobic group such as an alkyl group, a fluoroalkyl group, or a mixture of an alkyl group and a fluoroalkyl group (perfluoroalkyl group) to increase the contact angle of water therewith.

[0067] More specifically, the coating material that prevents the pattern from collapsing may include at least one selected from an amide compound represented by chemical formula (1) and a phosphorus compound represented by chemical formula (2).

[0068] Examples of amide compounds represented by chemical formula (1) include Acetamide, N-Propylamide, N-Butanamide, N,N-Dimethylbutanamide, N,N-Dimethylacetamide, 2,2,2-Trifluoroacetamide, 2,2,2-Trifluoro-N,N-bis(trifluoromethyl)acetamide, Pentafluoropropanamide, 2,2,3,3,4,4,4-heptafluorobutanamide, It may be selected from the group consisting of 2,2,3,3,4,4,5,5,5-Nonafluoropentanamide, Diacetamide, N-Propionylpropanamide, N-Butyrylbutanamide, 2,2,2-Trifluoro-N-(trifluoroacetyl)acetamide, 2,2,2-Trifluoro-N-(2-hydroxyethyl)acetamide, or a mixture thereof.

[0069] Examples of the phosphorus compound represented by the chemical formula (2) include monomethyl phosphate, monoethyl phosphate, propyl dihydrogen phosphate, butyl dihydrogen phosphate, monohexyl phosphate, monooctyl phosphate, decyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dihexyl phosphate, 3,3,3-trifluoropropyl dihydrogen phosphate, 3,3,4,4,5,5,6,6,6-Nonafluorohexyl dihydrogen phosphate, Perfluorooctyl phosphate, Perfluorodecyl phosphate, Bis(3,3,3-trifluoropropyl) hydrogen phosphate, Bis(3,3,4,4,5,5,6,6,6-nonafluorohexyl) hydrogen phosphate, Bisperfluorooctyl phosphate, Bisperfluorodecyl phosphate, mono-n-dodecyl phosphate, tributyl phosphate,It may be selected from the group consisting of 11-Phosphonoundecanoic acid, hexadecylphosphonic acid, octylphosphonic acid, tetradecylphosphonic acid, and phosphate monoesters, phosphate diesters having 8 to 18 carbon atoms, or mixtures thereof.

[0070] The coating composition for preventing pattern collapse according to the present invention may comprise 5 to 30 wt% of the pattern coating material and 70 to 95 wt% of an organic solvent.

[0071] If the content of the coating material is less than 5 wt%, there is a problem of the pattern collapsing in the form of clusters due to uniformity issues in the formation of a self-assembled monolayer at the pattern interface, and if it exceeds 30 wt%, a multilayer rather than a monolayer may be formed, or the pattern may collapse as the hydrophobic groups are randomly arranged by vertical polymerization.

[0072] When a coating composition for preventing pattern collapse is coated on materials such as polysilicon, silicon oxide, silicon nitride, titanium nitride, and tungsten, theoretically, the contact angle of water on the coated pattern must be 90° for the applied force to disappear. However, this is only assumed to be a correct theory for a flat plate after the coating is completed and dried. In an actual cleaning process, when different cleaning solutions are continuously supplied, it has been experimentally confirmed that coating materials showing a contact angle of about 80° to 100° on the flat plate can prevent pattern collapse.

[0073] This is estimated to be due to the difference in contact angle between the flat plate and the patterned substrate, which is caused by the degree to which the pattern coating material is coated on the pattern, the processing time, and mixing with water as a cleaning solution after processing.

[0074] When a pattern coating composition is used to treat a flat surface of materials such as polysilicon, silicon oxide, silicon nitride, titanium nitride, and tungsten, if the contact angle of water on the surface is about 80° to 100°, it can be said that the prevention of pattern collapse is satisfied.

[0075] It is thought that when the contact angle is less than 80° or more than 100°, the cosθ value increases and the force applied to the pattern also increases, causing the pattern to collapse.

[0076] The above pattern coating material may include a solvent depending on the content of the composition, and some of the solvent is involved in the coating and affects the contact angle of water on the pattern. The content of the solvent may be 70 to 95 wt% based on 100 wt% of the coating composition for preventing pattern collapse. If it is less than 70 wt%, a problem of residue occurs after the process of the coating composition for preventing pattern collapse, and if it is more than 95 wt%, there is a problem of using the coating composition for preventing pattern collapse in large quantities.

[0077] As mentioned above, usable organic solvents may be glycol compounds having 4 to 20 carbon atoms, glycol ether compounds having 4 to 20 carbon atoms, alkylene glycol alkyl ether compounds having 4 to 20 carbon atoms, silylamine compounds having 3 to 12 carbon atoms, alcohols having 1 to 10 carbon atoms, and hydrocarbon solvents having 6 to 10 carbon atoms.

[0078] Examples of usable solvents include tri(propylene glycol) methyl ether, tri(propylene glycol) monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol dibutyl ether, ethylene glycol, ethylene glycol acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol butyl ether, tripropylene glycol, propylene glycol, propylene glycol monomethyl ether acetate, petroleum ether, Minral Spritz, ethyl-3-ethoxypropionate, ethyl-2-hydroxypropanoate, 3-methoxybutyl acetate, ethyl lactate, cyclohexanone, gamma-butyrolactone, methyl cellosolve acetate, butyl cellosolve, cyclopentanone, cyclohexanone, It may be selected from the group consisting of 2-ethoxyethanol acetate, isopropyl alcohol, decane, methanol, ethanol, butanol, benzyl alcohol, mesitylene, glycol, trimethylsilylamine, trimethylsilylmethylamine, N-trimethylsilyldimethylamine, bis(trimethylsilyl)amine, tris(trimethylsilyl)amine, trimethyl-N-(2-phenylethyl)silylamine, trimethyl-N-(1-phenyl-2propyl)silylamine, N,N-diethyltrimethylsilylamine or mixtures thereof.

[0079] By coating the pattern with the coating composition for preventing pattern collapse as described above, a pattern having a contact angle of water with respect to the coating surface of 80° to 100° can be manufactured, thereby preventing the pattern from collapsing.

[0080] Hereinafter, the present invention will be described in detail by way of examples. However, the following examples are only intended to illustrate the present invention, and the content of the present invention is not limited by the following examples.

[0081] [Examples and Comparative Examples]

[0082] Example 1

[0083] A coating composition for preventing pattern collapse was prepared by adding 25 g of acetamide and 475 g of propylene glycol monomethyl ether acetate to a 1000 mL flask, stirring for 6 hours, and then passing the mixture through a 0.01 μm filter to remove fine impurities.

[0084]

[0085] Examples 2 to 90

[0086] A coating composition for preventing pattern collapse was prepared in the same manner as in Example 1 according to the compositions described in Tables 1 to 3.

[0087]

[0088] Comparative Examples 1 to 7

[0089] A coating composition for preventing pattern collapse was prepared in the same manner as in Example 1 according to the composition described in Tables 1 to 3.

[0090]

[0091] The composition components and composition ratios of Examples 1 to 90 and Comparative Examples 1 to 7 are described in Tables 1 to 3 below.

[0092]

[0093] Coating material (g) Organic solvent (g) Chemical formula (1) Chemical formula (2) Organic solvent 1 Organic solvent 2 Name Content (g) Name Content (g) Name Content (g) Name Content (g) Example 1 Acetamide 25 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 475 Bistrimethylsilylamine 0 Example 2 Acetamide 22.5 Monoethyl phosphate 2.5 Propylene glycol monomethyl ether acetate 450 Bistrimethylsilylamine 25 Example 3 Acetamide 20 Monoethyl phosphate 5 Propylene glycol monomethyl ether acetate 450 Bistrimethylsilylamine 25 Example 4 Acetamide 50 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 450 Bistrimethylsilylamine 0 Example 5 Acetamide 45 Monoethyl phosphate 5 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 50 Example 6 Acetamide 40 Monoethyl phosphate 10 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 50 Example 7 Acetamide 75 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 425 Bistrimethylsilylamine 0 Example 8 Acetamide 67.5 Monoethyl phosphate 7.5 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 25 Example 9 Acetamide 60 Monoethyl phosphate 15 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 25 Example 10 Acetamide 100 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 0 Example 11 Acetamide 90 Monoethyl phosphate 10 Propylene glycol monomethyl ether acetate 375 Bistrimethylsilylamine 25 Example 12 Acetamide 80 Monoethyl phosphate 20 Propylene glycol monomethyl ether acetate 375 Bistrimethylsilylamine 25 Example 13 Acetamide 125 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 375 Bistrimethylsilylamine 0 Example 14 Acetamide 112.5 Monoethyl phosphate 12.5 Propylene glycol monomethyl ether acetate 350 Bistrimethylsilylamine 25 Example 15 Acetamide 100 Monoethyl phosphate 25 Propylene glycol monomethyl ether acetate 350 Bistrimethylsilylamine 25 Example 16 Acetamide 150 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 350 Bistrimethylsilylamine 0 Example 17 Acetamide 135 Monoethyl phosphate 15 Propylene glycol monomethyl ether acetate 325 Bistrimethylsilylamine 25 Example 18 Acetamide 120 Monoethyl phosphate 30 Propylene glycol monomethyl ether acetate 325 Bistrimethylsilylamine 25 Example 19 Acetamide 22.5 Monoendodecyl phosphate 2.5 Propylene glycol monomethyl ether acetate 450 Bistrimethylsilylamine 25 Example 20 Acetamide 20 Monoendodecyl phosphate 5 Propylene glycol monomethyl ether acetate 450 Bistrimethylsilylamine 25 Example 21 Acetamide 45 Monoendodecyl phosphate 5 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 50 Example 22 Acetamide 40 Monoendodecyl phosphate 10 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 50 Example 23 Acetamide 67.5 Monoendodecyl phosphate 7.5 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 25 Example 24 Acetamide 60 Monoendodecyl phosphate 15 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 25 Example 25 Acetamide 90 Monoendodecyl phosphate 10 Propylene glycol monomethyl ether acetate 375 Bistrimethylsilylamine 25 Example 26 Acetamide 80 Monoendodecyl phosphate 20 Propylene glycol monomethyl ether acetate 375 Bistrimethylsilylamine 25 Example 27 Acetamide 11 2.5 Monoendodecyl phosphate 12.5 Propylene glycol monomethyl ether acetate 350 Bistrimethylsilylamine 25 Example 28 Acetamide 100 Monoendodecyl phosphate 25 Propylene glycol monomethyl ether acetate 350 Bistrimethylsilylamine 25 Example 29 Acetamide 135 Monoendodecyl phosphate 15 Propylene glycol monomethyl ether acetate 325 Bistrimethylsilylamine 25 Example 30 Acetamide 120 Monoendodecyl phosphate 30 Propylene glycol monomethyl ether acetate 325 Bistrimethylsilylamine 25 Comparative Example 1 Comparative Example 2 Acetamide 20 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 480 Bistrimethylsilylamine 0 Comparative Example 3-acetamide 200-monoethyl phosphate 0-propylene glycol monomethyl ether acetate 300-bistrimethylsilylamine 0.

[0094] Coating material (g) Organic solvent (g) Chemical formula (1) Chemical formula (2) Organic solvent 1 Organic solvent 2 Name Content (g) Name Content (g) Name Content (g) Name Content (g) Example 31 Butanamide 25 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 475 Bistrimethylsilylamine 0 Example 32 Butanamide 22.5 Monoethyl phosphate 2.5 Propylene glycol monomethyl ether acetate 450 Bistrimethylsilylamine 25 Example 33 Butanamide 20 Monoethyl phosphate 5 Propylene glycol monomethyl ether acetate 450 Bistrimethylsilylamine 25 Example 34 Butanamide 50 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 450 Bistrimethylsilylamine 0 Example 35 Butanamide 45 Monoethyl phosphate 5 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 50 Example 36 Butanamide 40 Monoethyl phosphate 10 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 50 Example 37 Butanamide 75 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 425 Bistrimethylsilylamine 0 Example 38 Butanamide 67.5 Monoethyl phosphate 7.5 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 25 Example 39 Butanamide 60 Monoethyl phosphate 15 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 25 Example 40 Butanamide 100 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 0 Example 41 Butanamide 90 Monoethyl phosphate 10 Propylene glycol monomethyl ether acetate 375 Bistrimethylsilylamine 25 Example 42 Butanamide 80 Monoethyl phosphate 20 Propylene glycol monomethyl ether acetate 375 Bistrimethylsilylamine 25 Example 43 Butanamide 125 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 375 Bistrimethylsilylamine 0 Example 44 Butanamide 112.5 Monoethyl phosphate 12.5 Propylene glycol monomethyl ether acetate 350 Bistrimethylsilylamine 25 Example 45 Butanamide 100 Monoethyl phosphate 25 Propylene glycol monomethyl ether acetate 350 Bistrimethylsilylamine 25 Example 46 Butanamide 150 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 350 Bistrimethylsilylamine 0 Example 47 Butanamide 135 Monoethyl phosphate 15 Propylene glycol monomethyl ether acetate 325 Bistrimethylsilylamine 25 Example 48 Butanamide 120 Monoethyl phosphate 30 Propylene glycol monomethyl ether acetate 325 Bistrimethylsilylamine 25 Example 49 Butanamide 22.5 Monoendodecyl phosphate 2.5 Propylene glycol monomethyl ether acetate 450 Bistrimethylsilylamine 25 Example 50 Butanamide 20 Monoendodecyl phosphate 5 Propylene glycol monomethyl ether acetate 450 Bistrimethylsilylamine 25 Example 51 Butanamide 45 Monoendodecyl phosphate 5 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 50 Example 52 Butanamide 40 Monoendodecyl phosphate 10 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 50 Example 53 Butanamide 67.5 Monoendodecyl phosphate 7.5 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 25 Example 54 Butanamide 60 Monoendodecyl phosphate 15 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 25 Example 55 Butanamide 90 Monoendodecyl phosphate 10 Propylene glycol monomethyl ether acetate 375 Bistrimethylsilylamine 25 Example 56 Butanamide 80 Monoendodecyl phosphate 20 Propylene glycol monomethyl ether acetate 375 Bistrimethylsilylamine 25 Example 57 Butanamide 11 2.5 Monoendodecyl phosphate 12.5 Propylene glycol monomethyl ether acetate 350 Bistrimethylsilylamine 25 Example 58 Butanamide 100 Monoendodecyl phosphate 25 Propylene glycol monomethyl ether acetate 350 Bistrimethylsilylamine 25 Example 59 Butanamide 135 Monoendodecyl phosphate 15 Propylene glycol monomethyl ether acetate 325 Bistrimethylsilylamine 25 Example 60 Butanamide 120 Monoendodecyl phosphate 30 Propylene glycol monomethyl ether acetate 325 Bistrimethylsilylamine 25 Comparative Example 4 Butanamide 20 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 480 Bistrimethylsilylamine 0 Comparative Example 5 Butanamide 200 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 300 Bistrimethylsilylamine 0.

[0095] Coating material (g) Organic solvent (g) Chemical formula (1) Chemical formula (2) Organic solvent 1 Organic solvent 2 Name Content (g) Name Content (g) Name Content (g) Name Content (g) Example 61 Pentafluoropropanamide 25 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 475 Bistrimethylsilylamine 0 Example 62 Pentafluoropropanamide 22.5 Monoethyl phosphate 2.5 Propylene glycol monomethyl ether acetate 450 Bistrimethylsilylamine 25 Example 63 Pentafluoropropanamide 20 Monoethyl phosphate 5 Propylene glycol monomethyl ether acetate 450 Bistrimethylsilylamine 25 Example 64 Pentafluoropropanamide 50 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 450 Bistrimethylsilylamine 0 Example 65 Pentafluoropropanamide 45 Monoethyl phosphate 5 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 50 Example 66 Pentafluoropropanamide 40 Monoethyl phosphate 10 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 50 Example 67 Pentafluoropropanamide 75 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 425 Bistrimethylsilylamine 0 Example 68 Pentafluoropropanamide 67.5 Monoethyl phosphate 7.5 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 25 Example 69 Pentafluoropropanamide 60 Monoethyl phosphate 15 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 25 Example 70 Pentafluoropropanamide 100 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 0 Example 71 Pentafluoropropanamide 90 Monoethyl phosphate 10 Propylene glycol monomethyl ether acetate 375 Bistrimethylsilylamine 25 Example 72 Pentafluoropropanamide 80 Monoethyl phosphate 20 Propylene glycol monomethyl ether acetate 375 Bistrimethylsilylamine 25 Example 73 Pentafluoropropanamide 125 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 375 Bistrimethylsilylamine 0 Example 74 Pentafluoropropanamide 112.5 Monoethyl phosphate 12.5 Propylene glycol monomethyl ether acetate 350 Bistrimethylsilylamine 25 Example 75 Pentafluoropropanamide 100 Monoethyl phosphate 25 Propylene glycol monomethyl ether acetate 350 Bistrimethylsilylamine 25 Example 76 Pentafluoropropanamide 150 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 350 Bistrimethylsilylamine 0 Example 77 Pentafluoropropanamide 135 Monoethyl phosphate 15 Propylene glycol monomethyl ether acetate 325 Bistrimethylsilylamine 25 Example 78 Pentafluoropropanamide 120 Monoethyl phosphate 30 Propylene glycol monomethyl ether acetate 325 Bistrimethylsilylamine 25 Example 79 Pentafluoropropanamide 22.5 Monoendodecyl phosphate 2.5 Propylene glycol monomethyl ether acetate 450 Bistrimethylsilylamine 25 Example 80 Pentafluoropropanamide 20 Monoendodecyl phosphate 5 Propylene glycol monomethyl ether acetate 450 Bistrimethylsilylamine 25 Example 81 Pentafluoropropanamide 45 Monoendodecyl phosphate 5 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 50 Example 82 Pentafluoropropanamide 40 Monoendodecyl phosphate 10 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 50 Example 83 Pentafluoropropanamide 67.5 Monoendodecyl phosphate 7.5 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 25 Example 84 Pentafluoropropanamide 60 Monoendodecyl phosphate 15 Propylene glycol monomethyl ether acetate 400 Bistrimethylsilylamine 25 Example 85 Pentafluoropropanamide 90 Monoendodecyl phosphate 10 Propylene glycol monomethyl ether acetate 375 Bistrimethylsilylamine 25 Example 86 Pentafluoropropanamide 80 Monoendodecyl phosphate 20 Propylene glycol monomethyl ether acetate 375 Bistrimethylsilylamine 25 Example 87 Pentafluoropropanamide 11 2.5 Monoendodecyl phosphate 12.5 Propylene glycol monomethyl ether acetate 350 Bistrimethylsilylamine 25 Example 88 Pentafluoropropanamide 100 Monoendodecyl phosphate 25 Propylene glycol monomethyl ether acetate 350 Bistrimethylsilylamine 25 Example 89 Pentafluoropropanamide 135 Monoendodecyl phosphate 15 Propylene glycol monomethyl ether acetate 325 Bistrimethylsilylamine 25 Example 90 Pentafluoropropanamide 120 Monoendodecyl phosphate 30 Propylene glycol monomethyl ether acetate 325 Bistrimethylsilylamine 25 Comparative Example 6 Pentafluoropropanamide 20 Monoethyl phosphate 0 Propylene glycol monomethyl ether acetate 480 Bistrimethylsilylamine 0 Comparative Example 7 pentafluoropropanamide 200 monoethyl phosphate 0 propylene glycol monomethyl ether acetate 300 bistrimethylsilylamine 0.

[0096] [Experimental and comparative experimental examples: Measurement of contact angle and pattern collapse]

[0097] Experimental examples 1 to 90

[0098] After coating a silicon substrate using the coating composition for preventing pattern collapse according to Examples 1 to 90, the contact angle of water on the coated pattern was measured.

[0099] The following processing steps were performed to spin the patterned wafer and check whether it fell over.

[0100] The pattern processing process is performed by rotating a semiconductor wafer at a speed of 0 to 1000 rpm and spraying at a speed of 1 to 30 mL / s for more than 1 second, first treating with an etchant such as hydrofluoric acid to remove the pattern oxide film, then sequentially treating with deionized water (DI water) and alcohol, coating with the coating composition for preventing pattern collapse manufactured above, and finally washing with water and alcohol and drying by spin drying to obtain a processed wafer, which was measured with an SEM (Hitachi S-4700 series) and as a result, it was possible to form a pattern in which the oxide film was completely removed without pattern collapse.

[0101]

[0102] Comparative Experimental Examples 1 to 7

[0103] In Comparative Experimental Example 1, the same process as in Experimental Example was performed except that the coating process with the above-mentioned pattern collapse prevention coating composition was not performed. That is, the pattern cleaning process was performed by first treating a semiconductor substrate on which an oxide film was formed with an etchant such as hydrofluoric acid to remove the pattern oxide film, then washing the silicon substrate with water without a separate coating and then drying it by spin drying to obtain a treated substrate, and when this was measured with an SEM (Hitachi S-4700 series), it was confirmed that the pattern oxide film was removed but the pattern collapsed.

[0104] In Comparative Experimental Examples 2 to 7, a coating composition for preventing pattern collapse was prepared in the same manner as Example 1 according to the composition components and composition ratios described in Tables 1 to 3, and after coating a silicon substrate, the contact angle of water on the coated pattern was measured. In addition, a wafer with a pattern was processed in the same manner as Example 1 to check whether it collapsed, and it was confirmed that all the patterns collapsed.

[0105] The measurement results of Experimental Examples 1 to 90 and Comparative Experimental Examples 1 to 7 are shown in Table 4 below.

[0106]

[0107] Contact angle (°) Pattern collapse (collapse X, not collapse O)Experimental example 180OExperimental example 282OExperimental example 382OExperimental example 482OExperimental example 584OExperimental example 684OExperimental example 783OExperimental example 885OExperimental example 985OExperimental example 1083OExperimental example 1185OExperimental example 1285OExperimental example 1383OExperimental example 1485OExperimental example 1585OExperimental example 1681OExperimental example 1782OExperimental example 1882OExperimental example 1983OExperimental example 2083OExperimental example 2185OExperimental example 2285OExperimental example 2386OExperimental example 2486OExperimental example 2587OExperimental example 2687OExperimental example 2787OExperimental example 2887OExperimental example 2983Experimental example 3083Experimental example 3182Experimental example 3284Experimental example 3384Experimental example 3484Experimental example 3586Experimental example 3686Experimental example 3785Experimental example 3887Experimental example 3987Experimental example 4085Experimental example 4188Experimental example 4288Experimental example 4385Experimental example 4488Experimental example 4588Experimental example 4682Experimental example 4783Experimental example 4883Experimental example 4985Experimental example 5085Experimental example 5187Experimental example 5287Experimental example 5389Experimental example 5489Experimental example 5590Experimental example 5690Experimental example 5790Experimental example 5890Experimental example 5985OExperimental example 6085OExperimental example 6185OExperimental example 6289OExperimental example 6389OExperimental example 6487OExperimental example 6592OExperimental example 6692OExperimental example 6789OExperimental example 6894OExperimental example 6994OExperimental example 7090OExperimental example 7195OExperimental example 7295OExperimental example 7390OExperimental example 7495OExperimental example 7595OExperimental example 7686OExperimental example 7788OExperimental example 7888OExperimental example 7993OExperimental example 8093OExperimental example 8197OExperimental example 8297OExperimental example 8399OExperimental example 8499OExperimental example 8599OExperimental example 8699OExperimental example 8798OExperimental example 8898OExperimental example 8993O Example 9093O Comparative Experimental Example 122X Comparative Experimental Example 268X Comparative Experimental Example 373X Comparative Experimental Example 470X Comparative Experimental Example 575X Comparative Experimental Example 675X Comparative Experimental Example 779X

[0108] While specific aspects of the present invention have been described in detail above, it will be apparent to those skilled in the art that these specific descriptions are merely preferred embodiments and do not limit the scope of the present invention. Therefore, the substantial scope of the present invention is defined by the claims and their equivalents.

Claims

1. A pattern collapse prevention coating material containing an amide compound represented by chemical formula (1) or a phosphorus compound represented by chemical formula (2); and a pattern collapse prevention coating composition comprising an organic solvent. Chemical formula (1) [Wherein R1, R2 and R3 are each hydrogen or an alkyl group having 1 to 8 carbon atoms or a fluoroalkyl group having 1 to 8 carbon atoms or a carbonyl group having 2 to 6 carbon atoms, At least one of R1, R2 and R3 is hydrogen or an alkyl group having 1 to 8 carbon atoms, At least one of R1, R2 and R3 is a fluoroalkyl group having 1 to 8 carbon atoms or a carbonyl group having 2 to 6 carbon atoms.] Chemical formula (2) [Here, R1, R2 and R3 are each hydrogen or an alkyl group having 1 to 16 carbon atoms or a fluoroalkyl group having 1 to 10 carbon atoms or a perfluoroalkyl group having 3 to 10 carbon atoms, At least one of R1, R2 and R3 is hydrogen, At least one of R1, R2 and R3 is an alkyl group having 1 to 16 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms or a perfluoroalkyl group having 3 to 10 carbon atoms.] 2. A coating composition for preventing pattern collapse, characterized in that it comprises 5 to 30 wt% of a pattern collapse prevention coating material containing an amide compound represented by chemical formula (1) or a phosphorus compound represented by chemical formula (2) in the first paragraph; and 70 to 95 wt% of an organic solvent.

3. In the second paragraph, the amide compound represented by the chemical formula (1) is acetamide, propylamide, butanamide, N,N-dimethylbutanamide, N,N-dimethylacetamide, 2,2,2-trifluoroacetamide, 2,2,2-trifluoro-N,N-bis(trifluoromethyl)acetamide, pentafluoropropanamide, 2,2,3,3,4,4,4-heptafluorobutanamide, A coating composition for preventing pattern collapse, characterized in that it is a compound selected from the group consisting of 2,2,3,3,4,4,5,5,5-nonafluoropentanamide, diacetamide, N-propionylpropanamide, N-butyrylbutanamide, 2,2,2-trifluoro-N-(trifluoroacetyl)acetamide, 2,2,2-trifluoro-N-(2-hydroxyethyl)acetamide, or a mixture of two or more thereof.

4. In the second paragraph, the phosphorus compound represented by the chemical formula (2) is monomethyl phosphate, monoethyl phosphate, propyl dihydrogen phosphate, butyl dihydrogen phosphate, monohexyl phosphate, monooctyl phosphate, decyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dihexyl phosphate, 3,3,3-trifluoropropyl dihydrogen phosphate, 3,3,4,4,5,5,6,6,6-Nonafluorohexyl dihydrogen phosphate, Perfluorooctyl phosphate, Perfluorodecyl phosphate, Bis(3,3,3-trifluoropropyl) hydrogen phosphate, Bis(3,3,4,4,5,5,6,6,6-nonafluorohexyl) hydrogen phosphate, Bisperfluorooctyl phosphate, Bisperfluorodecyl phosphate, mono-n-dodecyl phosphate, tributyl phosphate,A coating composition for preventing pattern collapse, characterized in that it is a compound selected from the group consisting of 11-phosphonoundecanoic acid, hexadecylphosphonic acid, octylphosphonic acid, tetradecylphosphonic acid, and phosphate monoester or phosphate diester having 8 to 18 carbon atoms, or a mixture of two or more thereof.

5. A coating composition for preventing pattern collapse, characterized in that in the second paragraph, the organic solvent is a compound selected from the group consisting of a glycol compound having 4 to 20 carbon atoms, a glycol ether compound having 4 to 20 carbon atoms, an alkylene glycol alkyl ether compound having 4 to 20 carbon atoms, a silylamine compound having 3 to 12 carbon atoms, an alcohol having 1 to 10 carbon atoms, and a hydrocarbon having 6 to 10 carbon atoms, or a mixture of two or more thereof.

6. A pattern coated with a coating composition for preventing pattern collapse according to any one of claims 1 to 5.

7. A pattern coated with a coating composition for preventing pattern collapse, characterized in that the material of the pattern in the 6th paragraph includes at least one element selected from polysilicon, silicon oxide, silicon nitride, titanium nitride, and tungsten.

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