Resin, resin composition, cured layer and etching method

Abstract

A resin, a resin composition, a cured layer and an etching method are provided. The resin includes a structural unit represented by the following Formula (A). In the resin, an amount of the propynyl group is not zero. Among the hydrogen and the propynyl group represented by R 1and R

Description

Technical Field

[0001] This invention relates to a resin, and more particularly to a propyne-containing resin, a resin composition, a hardened layer, and an etching method. Prior Technology

[0002] With the development of semiconductor technology, the demand for miniaturization of key dimensions in semiconductor devices is gradually increasing in order to expand their applications. However, the thinning of photoresist layers currently used in the manufacture of semiconductor devices may lead to incomplete exposure during the manufacturing process, resulting in pattern collapse and affecting the performance of semiconductor devices made using it. Summary of the Invention

[0003] The present invention provides a resin, resin composition, hardened layer, and etching method that can form a resin having good flatness and etch resistance.

[0004] This invention provides a resin. The resin comprises structural units represented by the following formula (A). In the resin, the content of propyne groups is not 0. In the hydrogen and propyne groups represented by R1 and R2, the molar ratio of hydrogen to propyne groups is from 90:10 to 55:45. Formula (A) In formula (A), R1 and R2 each represent hydrogen or propynyl group, and * indicates the bond position.

[0005] In one embodiment of the present invention, the weight-average molecular weight (MW) of the resin is from 1,000 g / mol to 7,000 g / mol.

[0006] In one embodiment of the present invention, the structural unit represented by formula (A) above includes at least one of the structural units represented by formulas (A-1) to (A-3) below: Equation (A-1), In formula (A-1), R3 represents hydrogen, and R4 represents propynyl group; Equation (A-2), In formula (A-2), R5 represents propynyl group, and R6 represents propynyl group; Equation (A-3), In formula (A-3), R7 represents propyne group and R8 represents hydrogen.

[0007] In one embodiment of the present invention, the resin further comprises a structural unit represented by the following formula (A-4): Equation (A-4).

[0008] A resin composition of the present invention includes a resin (A), a surfactant (B), and a solvent (C). The resin (A) is the resin described above. Based on a total usage of 100 parts by weight of the resin composition, the amount of resin (A) used is 1.5 to 10 parts by weight, the amount of surfactant (B) used is 0.1 to 5.0 parts by weight, and the amount of solvent (C) used is 80 to 98.5 parts by weight.

[0009] In one embodiment of the present invention, the surfactant (B) comprises a fluorinated surfactant or a polyoxyethylene ether surfactant. Fluorinated surfactants further comprise alcohol, ester, or carboxylic acid groups.

[0010] In one embodiment of the present invention, the above-mentioned fluorinated surfactant includes a compound represented by the following formula (B-1): Formula (B-1), In equation (B-1), the sum of x and y is an integer from 3 to 30, n represents an integer from 0 to 5, and q represents an integer from 0 to 5.

[0011] In one embodiment of the present invention, the above-mentioned polyoxyethylene ether surfactant includes a compound represented by the following formula (B-2): Formula (B-2), In equation (B-2), r represents an integer from 0 to 15, and t represents an integer from 0 to 15.

[0012] In one embodiment of the present invention, the solvent (C) includes propylene glycol methyl ether, tetraethylene glycol dimethyl ether, propylene glycol methyl ether acetate, diethylmethylamine, isopropanol, methanol, acetone, n-butyl acetate, butanone, ethyl acetate, diacetone alcohol, or combinations thereof.

[0013] A hardened layer of the present invention is formed by hardening the above-mentioned resin composition.

[0014] An etching method of the present invention includes: immersing the above-mentioned hardened layer in an etching solution to perform an etching process.

[0015] In one embodiment of the present invention, the etching solution is an alkaline etching solution.

[0016] Based on the above, the resin of the present invention comprises structural units having a specific structure and containing propyne groups. This enables the formation of a hardened layer with good flatness and etch resistance, as well as an etching method, from a resin composition comprising the specific resin.

[0017] To make the above features and advantages of the present invention more apparent and understandable, specific embodiments are described in detail below. Simple Explanation of the Diagram

[0018] none. Implementation

[0019] <Resin>

[0020] This invention provides a resin comprising a structural unit represented by the following formula (A). Additionally, the resin of this invention may include other suitable structural units as needed.

[0021] Formula (A)

[0022] In formula (A), R1 and R2 each represent hydrogen or propynyl group, and * indicates the bond position. The propynyl group can be *-CH2-C≡CH or *-C≡C-CH3, preferably *-CH2-C≡CH. For example, in the structural unit represented by formula (A), R1 can represent hydrogen and R2 can represent propynyl group; R1 can represent propynyl group and R2 can represent hydrogen; R1 can represent propynyl group and R2 can represent propynyl group; or R1 can represent hydrogen and R2 can represent hydrogen.

[0023] In the resin, the content of propyne groups is not zero. For example, the resin may include structural units of formula (A) where R1 represents hydrogen and R2 represents propyne groups, and structural units of formula (A) where R1 represents hydrogen and R2 represents hydrogen. In the resin, the molar ratio of hydrogen to propyne groups in R1 and R2 may be from 90:10 to 55:45, preferably from 70:30 to 55:45. That is, based on the total amount of hydrogen and propyne groups represented by R1 and R2 in the resin being 100%, the proportion of propyne groups may be from 10% to 45%, preferably from 30% to 45%.

[0024] In this embodiment, the structural unit represented by formula (A) may include at least one of the structural units represented by formulas (A-1) to (A-3) below, and may further include a structural unit represented by formula (A-4) below. The resin may include at least one of the structural units represented by formulas (A-1) to (A-3) below, and may further include a structural unit represented by formula (A-4) below.

[0025] Equation (A-1)

[0026] In formula (A-1), R3 represents hydrogen and R4 represents propyne group.

[0027] Equation (A-2)

[0028] In formula (A-2), R5 represents propynyl group and R6 represents propynyl group.

[0029] Equation (A-3)

[0030] In formula (A-3), R7 represents propyne group and R8 represents hydrogen.

[0031] Equation (A-4)

[0032] The resin may include a structure represented by the following formula (A'), where m represents an integer from 7 to 50.

[0033] Formula (A')

[0034] In formula (A'), m represents an integer from 7 to 50, preferably an integer from 10 to 37.

[0035] The weight average molecular weight of the resin can be from about 1,000 g / mole to about 7,000 g / mole, preferably from about 2,000 g / mole to about 5,000 g / mole. [<] [Resin Composition] [>]

[0036] This invention provides a resin composition comprising: a resin (A), a surfactant (B), and a solvent (C). Additionally, the resin composition of this invention may include other suitable additives as needed. The components will now be described in detail. [resin()] [A] [)] []

[0037] Resin (A) is the resin described above that includes the structural unit represented by formula (A). Based on a total amount of 100 parts by weight of resin components, the amount of resin (A) used is 1.5 to 10 parts by weight, preferably 3 to 6 parts by weight. Surfactants [B] [)] []

[0038] There are no particular limitations on the surfactant (B), and an appropriate surfactant can be selected according to requirements. In this embodiment, the surfactant (B) may include fluorinated surfactants, polyoxyethylene ether surfactants, or other suitable surfactants. The surfactant (B) may be used alone or in combination.

[0039] Fluorinated surfactants may further include alcohol groups, ester groups, carboxylic acid groups, combinations thereof, or other suitable functional groups. In this embodiment, fluorinated surfactants may include compounds represented by the following formula (B-1) or other suitable fluorinated surfactants including alcohol groups, ester groups, or carboxylic acid groups.

[0040] Equation (B-1)

[0041] In equation (B-1), the sum of x and y is an integer from 3 to 30, preferably an integer from 7 to 20; n represents an integer from 0 to 5, preferably an integer from 1 to 3; q represents an integer from 0 to 5, preferably an integer from 1 to 3.

[0042] In equation (B-1), x can be an integer from 0 to 20, preferably an integer from 4 to 10, and y can be an integer from 0 to 20, preferably an integer from 4 to 10. At least one of x and y is not 0, preferably both are not 0.

[0043] Polyoxyethylene ether surfactants may include compounds represented by the following formula (B-2) or other suitable polyoxyethylene ether surfactants.

[0044] Equation (B-2)

[0045] In equation (B-2), r represents an integer from 0 to 15, preferably an integer from 1 to 8; t represents an integer from 0 to 15, preferably an integer from 1 to 8. At least one of r and t is not 0, preferably both are not 0.

[0046] Based on the total amount of resin components used being 100 parts by weight, the amount of surfactant (B) used is from 0.1 parts by weight to 5.0 parts by weight, preferably from 0.1 parts by weight to 1.0 parts by weight. [solvent() [C] [)] []

[0047] There are no particular limitations on the solvent (C), and an appropriate solvent can be selected according to requirements. In this embodiment, the solvent (C) may include propylene glycol methyl ether, tetraethylene glycol dimethyl ether, propylene glycol methyl ether acetate, diethylmethyl amine, isopropanol, methanol, acetone, n-butyl acetate, butanone, ethyl acetate, diacetone alcohol, combinations thereof, or other suitable solvents. Solvent (C) may be used alone or in combination.

[0048] Based on the total amount of resin components used being 100 parts by weight, the amount of solvent (C) used being 80 to 98.5 parts by weight, preferably 89 to 98.5 parts by weight.

[0049] When the resin composition includes a solvent (C), it can give the resin composition an appropriate viscosity, thereby achieving good coating uniformity to form a hardened layer. [<] [Preparation method of resin composition] [>]

[0050] There are no particular limitations on the preparation method of the resin composition. For example, resin (A), surfactant (B) and solvent (C) are placed in a stirrer and stirred until they are uniformly mixed into a solution. Other suitable additives may also be added if necessary. After mixing them evenly, a liquid resin composition can be obtained. [<] [Method for manufacturing the hardened layer] [>]

[0051] An exemplary embodiment of the present invention provides a hardened layer formed by curing the above-described resin composition. In this embodiment, the hardened layer may be an etch-resistant layer.

[0052] The hardening layer can be formed by coating the above-mentioned resin composition onto a substrate to form a coating film, and then baking the coating film. For example, after coating the resin composition onto the substrate to form a coating film, it is baked at a temperature of 150~350°C (preferably about 250°C) for 1~10 minutes (preferably about 3 minutes) to form a hardening layer with a thickness of 120~150 nm on the substrate.

[0053] There are no particular restrictions on the substrate, but its material is preferably silicon, silicon oxide, aluminum, aluminum oxide, copper, metal oxide, or metal nitride. There are no particular restrictions on the type of substrate, but it can be a glass substrate, a plastic substrate (e.g., polyether ether (PES) board, polycarbonate (PC) board, or polyimide (PI) film) or other suitable substrate types.

[0054] There are no particular restrictions on the coating method, but spraying, roller coating, vortex coating, screen printing, spin coating, or similar methods can be used. Generally, spin coating is widely used. Furthermore, a coating film is formed, and in some cases, residual solvent can be partially removed under reduced pressure. [<] [Etching Method] [>]

[0055] An exemplary embodiment of the present invention provides an etching method comprising immersing the aforementioned hardened layer in an etching solution to perform an etching process.

[0056] There are no particular limitations on the etching solution; an appropriate etching solution can be selected according to requirements. In this embodiment, the etching solution is an alkaline etching solution. The alkaline etching solution may include ammonia, hydrogen peroxide, water, tetramethylammonium hydroxide, potassium hydroxide, sodium hydroxide, ammonium chloride, copper chloride, or combinations thereof, preferably a combination of ammonia, hydrogen peroxide, and water. When the alkaline etching solution is composed of ammonia, hydrogen peroxide, and water, the mixing ratio (by weight) of ammonia, hydrogen peroxide, and water can be from 1:1:4 to 1:2:8, preferably from 1:1:4 to 1:1:5.

[0057] Other steps included in the etching method are well known to those skilled in the art and will not be described separately here.

[0058] The invention will be described in detail below with reference to examples. The following examples are provided to illustrate the invention, and the scope of the invention includes the scope described in the following claims, as well as their substitutions and modifications, but is not limited to the scope of the examples. [Example of resin synthesis] []

[0059] The following describes the synthesis examples 1 to 5 of the resin: [] [Synthesis example] [1]

[0060] 122.8 g of 3,4-dihydroxystyrene was dissolved in ethyl acetate to prepare a 60% solids ethyl acetate solution of 3,4-dihydroxystyrene (204.7 g). Then, 482 g of tetrahydrofuran was added to the reaction flask. After stirring at 10°C for 10 minutes, a tetrahydrofuran solution containing 5% sulfuric acid (139.2 g) was added dropwise, and the mixture was allowed to react at room temperature for 50 hours. After the reaction was complete, a sample was taken, and 1156 g of water was added to the reaction flask. Then, sodium carbonate (57.34 g) and tetrabutylammonium iodide (8.496 g) were slowly added. After stirring at room temperature for 10 minutes, 53.65 g of 3-bromopropyne was added, and the mixture was heated to reflux for 18.5 hours. After the reaction was complete, the reaction mixture was cooled and transferred to a separatory funnel. Saturated brine was added for layer extraction. The aqueous layer was washed twice with ethyl acetate, and the combined organic layers were washed three times with saturated brine. The organic layer was dehydrated with anhydrous magnesium sulfate, and the anhydrous magnesium sulfate was removed by filtration. The filtrate was concentrated and heated under vacuum for 12 hours to obtain poly[3,4-dihydroxystyrene]-3-propyne derivative A-1 (brown solid). The molecular weight was confirmed by gel permeation chromatography (MW was about 3180 g / mol, MP was about 3608 g / mol, PDI was about 1.831), and the propyne group ratio was 9.2%. [] [Synthesis example] [2]

[0061] 122.8 g of 3,4-dihydroxystyrene was dissolved in ethyl acetate to prepare a 70% solids ethyl acetate solution of 3,4-dihydroxystyrene (197 g). Then, 734 g of tetrahydrofuran was added to the reaction flask. After stirring at 10°C for 10 minutes, a 5% sulfuric acid tetrahydrofuran solution (473.2 g) was added dropwise, and the mixture was allowed to react at room temperature for 40 hours. After the reaction was complete, a sample was taken, and 1404 g of water was added to the reaction flask. Then, sodium carbonate (96.73 g) and tetrabutylammonium iodide (18.719 g) were slowly added. After stirring at room temperature for 10 minutes, 108.56 g of 3-bromopropyne (108.56 g) was added. g, heated to reflux for 18 hours. After the reaction was complete, the reaction mixture was cooled and transferred to a separatory funnel, and saturated brine was added for layer extraction. The aqueous layer was washed twice with ethyl acetate, and the combined organic layers were washed three times with saturated brine. The organic layer was dehydrated with anhydrous magnesium sulfate, filtered to remove the anhydrous magnesium sulfate, and the filtrate was concentrated and heated under vacuum for 12 hours to obtain poly[3,4-dihydroxystyrene]-3-propyne derivative A-2 (brown solid). The molecular weight was confirmed by gel permeation chromatography (MW: approximately 2615 g / mol, MP: approximately 3118 g / mol, PDI: approximately 1.616), and the propyne group ratio was 32.3%. [] [Synthesis example] [3]

[0062] 100 g of 3,4-dihydroxystyrene was dissolved in ethyl acetate to prepare a 73% solids ethyl acetate solution (137.0 g). Then, 429 g of tetrahydrofuran and 5.3 g of dimethylacetamide were added to the reaction flask. After stirring at 10°C for 10 minutes, a 5% sulfuric acid tetrahydrofuran solution (105.9 g) was added dropwise, and the mixture was allowed to react at room temperature for 59 hours. After the reaction was complete, a sample was taken, and 677.2 g of water was added to the reaction flask. Then, sodium carbonate (116.69 g) and tetrabutylammonium iodide (5.422 g) were slowly added. After stirring at room temperature for 10 minutes, 122.24 g of 3-bromopropyne was added, and the mixture was heated to reflux for 18.5 hours. After the reaction was complete, the reaction mixture was cooled and transferred to a separatory funnel. Saturated brine was added for layer extraction. The aqueous layer was washed twice with ethyl acetate, and the combined organic layers were washed three times with saturated brine. The organic layer was dehydrated with anhydrous magnesium sulfate, and the anhydrous magnesium sulfate was removed by filtration. The filtrate was concentrated and heated under vacuum for 12 hours to obtain poly[3,4-dihydroxystyrene]-3-propyne derivative A-3 (brown solid). The molecular weight was confirmed by gel permeation chromatography (MW was about 2996 g / mol, MP was about 3615 g / mol, PDI was about 1.921), and the propyne group ratio was 32.2%. [] [Synthesis example] [4]

[0063] 100 g of 3,4-dihydroxystyrene was added to ethyl acetate to prepare a 73% solids ethyl acetate solution of 3,4-dihydroxystyrene (137 g). Then, tetrahydrofuran (429 g) and dimethylacetamide (5.3 g) were added to the reaction flask, followed by the addition of a 5% sulfuric acid tetrahydrofuran solution (105.9 g). The mixture was then moved to room temperature and reacted for 59 hours. After the reaction was complete, a sample was taken and water (677.2 g) was added to the reaction flask. Then, sodium carbonate (143.92 g), tetrabutylammonium iodide (5.422 g), and 3-bromopropyne (152.80 g) were slowly added, and the mixture was heated to reflux for 18.5 hours. After the reaction was complete, saturated brine was added for layer extraction. The aqueous layer was washed twice with ethyl acetate, and the organic layers were combined and washed three times with saturated brine. The organic layer was dehydrated with anhydrous magnesium sulfate, filtered to remove the anhydrous magnesium sulfate, and the filtrate was concentrated and heated under vacuum for 12 hours to obtain propyne-2-yn-1-yloxyhydroxyl type polystyrene resin A-4 (brown solid). The molecular weight was confirmed by gel permeation chromatography (MW: approximately 3068 g / mol, MP: approximately 3693 g / mol, PDI: approximately 1.955), and the propyne group ratio was 36.7%. [] [Synthesis example] [5]

[0064] 25 g of 3,4-dihydroxystyrene was dissolved in ethyl acetate to prepare a 60% solids ethyl acetate solution (41.7 g). Tetrahydrofuran (101.3 g) was added to the reaction flask, followed by dropwise addition of a 5% sulfuric acid tetrahydrofuran solution (25 g). The reaction was allowed to proceed at room temperature for 59 hours. After the reaction was complete, a sample was taken, and 168 g of water was added to the reaction flask. Then, sodium carbonate (34.13 g), tetrabutylammonium iodide (3.398 g), and 3-bromopropyne (32.83 g) were slowly added. The mixture was heated to reflux for 18 hours. After the reaction was complete, saturated brine was added for layer extraction. The aqueous layer was washed twice with ethyl acetate, and the combined organic layers were washed three times with saturated brine. The organic layer was dehydrated with anhydrous magnesium sulfate, and the anhydrous magnesium sulfate was removed by filtration. The filtrate was concentrated and heated under vacuum for 12 hours to obtain propyne-2-yn-1-yloxyhydroxy polystyrene resin A-5 (brown solid). The molecular weight was confirmed by gel permeation chromatography (MW: approximately 4056 g / mol, MP: approximately 4619 g / mol, PDI: approximately 1.975), and the propyne group ratio was 43.6%. [] [Examples of resin composition and hardened layer] []

[0065] Examples 1 to 7 and Comparative Examples 1 to 8 describe the resin composition and hardened layer: [Example] [1] [a.] [Resin Composition] []

[0066] 4.4 parts by weight of resin A-2 and 0.1 parts by weight of surfactant B-1 were added to a mixed solvent of 90.75 parts by weight of PM and 4.75 parts by weight of TEGDE, and stirred evenly with a stirrer to obtain the resin composition of Example 1. [b.] [Hardened layer] []

[0067] The resin compositions prepared in the examples were coated onto a substrate (e.g., an 8-inch silicon substrate) using a spin coater (model MK-8, manufactured by Tokyo Electron Ltd., TEL, with a rotation speed of approximately 1500 rpm). The substrate was then baked at 250°C for 3 minutes to form a hardened layer with a thickness of 150 nm. The hardened layers were evaluated using the following methods, and the results are shown in Tables 2-5. [Example] [2] [To the Example] [7] [And comparative examples] [1] [To the comparative example] [8]

[0068] The resin compositions of Examples 2 to 7 and Comparative Examples 1 to 8 were prepared using the same steps as in Example 1, except that the types and amounts of the resin composition components were changed (as shown in Table 2), where the components / compounds corresponding to the numbers in Table 2 are as shown in Table 1. The obtained resin compositions were formed into hardened layers and evaluated using the following evaluation methods, the results of which are shown in Table 2. In Table 2, those with flatness less than 30 Å and etch resistance less than 10 Å are listed as examples; those outside the aforementioned ranges are listed as comparative examples.

[0069] [Table 1] label Ingredients / Compounds Resin (A) A-1 The resin A-1 prepared by Synthesis Example 1 comprises a structural unit represented by formula (A'), wherein the molar ratio of hydrogen to propyne group in hydrogen and propyne group represented by R1 and R2 is 90.8:9.2. The weight-average molecular weight is approximately 3180 g / mol. A-2 The resin A-2 prepared by Synthesis Example 2 includes structural units represented by formula (A'), wherein the molar ratio of hydrogen to propyne in the hydrogen and propyne groups represented by R1 and R2 is 67.7:32.3. The weight-average molecular weight is approximately 2615 g / mol. A-3 The resin A-3 prepared by Synthesis Example 3 includes structural units represented by formula (A'), wherein the molar ratio of hydrogen to propyne in the hydrogen and propyne groups represented by R1 and R2 is 67.8:32.2. The weight-average molecular weight is approximately 2996 g / mol. A-4 The resin A-4 prepared by Synthesis Example 4 includes structural units represented by formula (A'), wherein the molar ratio of hydrogen to propyne in the hydrogen and propyne groups represented by R1 and R2 is 63.3:36.7. The weight-average molecular weight is approximately 3068 g / mol. A-5 The resin A-5 prepared by Synthesis Example 5 comprises a structural unit represented by formula (A'), wherein the molar ratio of hydrogen to propyne in the hydrogen and propyne groups represented by R1 and R2 is 56.4:43.6. The weight-average molecular weight is approximately 4056 g / mol. Surfactant (B) B-1 Fluorine surfactants are represented by equation (B-1), where n represents an integer from 1 to 3, q ​​represents an integer from 1 to 3, and the sum of x and y is an integer from 7 to 20. B-2 Polyoxyethylene ether surfactants represented by formula (B-2), where r represents an integer from 2 to 8, and t represents an integer from 2 to 8. B-3 Fluorine surfactants represented by formula (B-1), where n represents 1, q represents 1, and the sum of x and y is an integer from 7 to 19. Solvent (C) C-1 Propylene glycol monomethyl ether (PM) C-2 Tetraethylene glycol dimethyl ether (TEGDE) Crosslinking agent (D) D-1 2-Allylphenol D-2 Naphthol type epoxy resin D-3 Dipentaerythritol acrylate D-4 Acrylic resin D-5 Catechins

[0070] [Table 2] Ingredients (Unit: parts by weight) Example 1 2 3 4 5 6 7 Resin (A) A-1 - - - - - - - A-2 4.4 - - - - - - A-3 - 4.4 - - 4.4 4.4 10 A-4 - - 4.4 - - - - A-5 - - - 4.4 - - - Surfactant (B) B-1 0.1 0.1 0.1 0.1 - - 0.1 B-2 - - - - 0.1 - - B-3 - - - - - 0.1 - Solvent (C) C-1 90.75 90.75 90.75 90.75 90.75 90.75 85.4 C-2 4.75 4.75 4.75 4.75 4.75 4.75 4.5 Crosslinking agent (D) D-1 - - - - - - - D-2 - - - - - - - D-3 - - - - - - - D-4 - - - - - - - D-5 - - - - - - - evaluate result Flatness (Å) 22.0 24.0 13.0 14.0 18.0 20.0 25.0 Etching resistance (Å) 5.2 5.0 3.3 8.8 4.0 5.0 6.0

[0071] [Table 2] (continued) Ingredients (Unit: parts by weight) Comparative example 1 2 3 4 5 6 7 8 Resin (A) A-1 4.4 - - - - - - A-2 - - - - - - - A-3 - 4.5 2.64 2.64 3.52 3.52 4.4 20 A-4 - - - - - - - - A-5 - - - - - - - - Surfactant (B) B-1 0.1 - 0.1 0.1 0.1 0.1 0.1 0.1 B-2 - - - - - - - - B-3 - - - - - - - - Solvent (C) C-1 90.75 90.75 90.75 90.75 90.75 90.75 90.5 75.9 C-2 4.75 4.75 4.75 4.75 4.75 4.75 4.5 4.0 Crosslinking agent (D) D-1 - - 1.76 - - - - - D-2 - - - 1.76 - - - - D-3 - - - - 0.88 - - - D-4 - - - - - 0.88 - - D-5 - - - - - - 0.5 - evaluate result Flatness (Å) 27.0 35.0 9.0 33.0 46.0 20.0 5.0 45.0 Etching resistance (Å) 18.7 15.0 94.5 42.5 25.1 *Peeling *Peeling 7.0 *Peeling: The hardened layer peeled off from the substrate in less than 30 minutes during the etch resistance test. [<] [Evaluation Method] [>] [a.] [flatness]

[0072] Each of the prepared resin components was coated onto an 8-inch silicon substrate and baked to cure, forming a hardened layer. The Cauchy parameters of the formulation were then measured using an ellipsometer. These parameters were then fed into an optical film thickness gauge (DNS VM-1210, manufactured by SCREEN SPE Co., Ltd.) to measure the film thickness at 69 different points on the film surface. The maximum thickness was subtracted from the minimum thickness to obtain the film thickness difference. A smaller film thickness difference indicates better flatness, i.e., better uniformity, in the hardened layer. [b.] [Etching resistance]

[0073] Each of the prepared resin components was coated onto an 8-inch silicon substrate and baked to cure, forming a hardened layer. The hardened layer was then immersed in an alkaline etching solution (ammonia:hydrogen peroxide:water = 150:150:700 (weight ratio)) at room temperature (25°C). After immersion for 30 minutes, the film thickness change was measured. Smaller film thickness changes indicated better etching resistance, i.e., better alkali resistance. [<] [Evaluation Results] [>]

[0074] As shown in Table 2, the hardened layer formed by the examples where the resin composition includes resin (A) having a specific structure and containing propyne-based structural units exhibits good flatness and etch resistance, making it suitable for semiconductor manufacturing processes. In contrast, the hardened layer formed by the comparative examples where the resin composition does not include resin (A) having a specific structure and containing propyne-based structural units exhibits poor flatness and / or etch resistance.

[0075] Furthermore, as shown in Table 2, compared to the hardened layer prepared when the molar ratio of hydrogen and propyne groups represented by R1 and R2 of resin (A) in the resin composition was not in the range of 90:10 to 55:45 (Comparative Example 1), the hardened layers prepared when the molar ratio of hydrogen and propyne groups represented by R1 and R2 of resin (A) in the resin composition was in the range of 90:10 to 55:45 (Examples 1-7) had smaller film thickness differences and film thickness variations, i.e., better flatness and etch resistance. Therefore, it can be concluded that when the molar ratio of hydrogen and propyne groups represented by R1 and R2 of resin (A) is in the range of 90:10 to 55:45, the hardened layer formed by the resin composition including it can have better flatness and etch resistance.

[0076] Furthermore, as shown in Table 2, compared to the hardened layer prepared without surfactant (B) (Comparative Example 2), the hardened layers prepared with surfactant (B) (Examples 1-7) exhibit smaller film thickness differences and variations, resulting in better flatness and etch resistance. This demonstrates that when the resin composition includes surfactant (B) with different structures, the hardened layer formed by the resin composition can possess better flatness and etch resistance.

[0077] Furthermore, as shown in Table 2, when the resin composition consists of the same components, compared to the hardened layer prepared by the resin composition excluding surfactant (B) (Comparative Example 2), the hardened layer prepared by the resin composition including surfactant (B) (Examples 2, 5-6) has a smaller film thickness difference and film thickness variation, i.e., it has better flatness and etching resistance. Therefore, it can be concluded that when the resin composition includes surfactant (B) with different structures, the hardened layer formed by the resin composition can have better flatness and etching resistance.

[0078] Furthermore, as shown in Table 2, the hardened layers prepared without the crosslinking agent (D) (Examples 1-7) exhibit better etch resistance compared to the hardened layers prepared with the resin composition including the crosslinking agent (D) (Comparative Examples 3-7). Therefore, it can be concluded that when the resin composition includes a resin (A) with a specific structure and containing propyne-based structural units, and does not include the crosslinking agent (D), the hardened layer formed by the resin composition can have better etch resistance.

[0079] Furthermore, as shown in Table 2, when the only difference in the composition of the resin composition is the crosslinking agent (D), the hardened layer prepared without the crosslinking agent (D) (Example 2) exhibits better etch resistance compared to the hardened layer prepared with the resin composition including the crosslinking agent (D) (Comparative Examples 3-7). Therefore, it can be concluded that when the resin composition includes a resin (A) with a specific structure and containing propyne-based structural units and does not include the crosslinking agent (D), the hardened layer formed by the resin composition can have better etch resistance.

[0080] Furthermore, as shown in Table 2, compared to the hardened layer prepared by a resin composition with a total resin component usage of 100 parts by weight and a resin (A) usage amount not in the range of 1.5 to 10 parts by weight (Comparative Example 8), the hardened layers prepared by a resin composition with a resin (A) usage amount in the range of 1.5 to 10 parts by weight (Examples 1-7) have smaller film thickness differences, i.e., better flatness, and good etch resistance. Therefore, it can be concluded that when the resin (A) usage amount in the resin composition is in the range of 1.5 to 10 parts by weight, the hardened layer formed by the resin composition can have better flatness and good etch resistance.

[0081] Furthermore, as shown in Table 2, when the resin composition consists of the same components, compared to the hardened layer prepared by a resin composition with a total resin composition usage of 100 parts by weight and a resin (A) usage range of 1.5 to 10 parts by weight (Comparative Example 8), the hardened layer prepared by a resin composition with a resin (A) usage range of 1.5 to 10 parts by weight (Examples 2 and 7) has a smaller film thickness difference, i.e., better flatness, and good etch resistance. Therefore, it can be concluded that when the amount of resin (A) in the resin composition is in the range of 1.5 to 10 parts by weight, the hardened layer formed by the resin composition can have better flatness and good etch resistance.

[0082] In summary, the resin composition of the present invention comprises a resin (A) having a specific structure and containing propyne-based structural units. When the molar ratio of hydrogen to propyne in R1 and R2 is 90:10 to 55:45, the hardened layer formed by the resin composition has good flatness and etch resistance, making it suitable for semiconductor manufacturing processes and thereby improving the performance of semiconductor devices manufactured using it.

[0083] Although the present invention has been disclosed above by way of embodiments, it is not intended to limit the present invention. Anyone skilled in the art can make some modifications and refinements without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.

[0084] none.

Claims

1. A resin comprising a structural unit represented by the following formula (A): Formula (A), wherein R1 and R2 each represent hydrogen or propynyl group, * represents a bonding position, wherein the content of the propynyl group in the resin is not 0, and the molar ratio of hydrogen to propynyl group in R1 and R2 is from 90:10 to 55:

45.

2. The resin as claimed in claim 1, having a weight average molecular weight of 1,000 g / mol to 7,000 g / mol.

3. The resin as claimed in claim 1, wherein the structural unit represented by formula (A) includes at least one of the structural units represented by formulas (A-1) to (A-3): Formula (A-1), where R3 represents hydrogen and R4 represents propynyl; Formula (A-2), where R5 represents propynyl and R6 represents propynyl; Formula (A-3), where R7 represents propynyl and R8 represents hydrogen.

4. The resin as claimed in claim 3 further comprises a structural unit represented by the following formula (A-4): Formula (A-4).

5. A resin composition comprising: Resin (A) is the resin described in any one of claims 1 to 4; The surfactant (B) and solvent (C) are used in an amount of 100 parts by weight based on the total amount of the resin composition used, wherein the amount of the resin (A) used is from 1.5 parts by weight to 10 parts by weight, the amount of the surfactant (B) used is from 0.1 parts by weight to 5.0 parts by weight, and the amount of the solvent (C) used is from 80 parts by weight to 98.5 parts by weight.

6. The resin composition as claimed in claim 5, wherein the surfactant (B) comprises a fluorinated surfactant or a polyoxyethylene ether surfactant, and the fluorinated surfactant further comprises an alcohol group, an ester group, or a carboxylic acid group.

7. The resin composition as claimed in claim 6, wherein the fluorinated surfactant comprises a compound represented by the following formula (B-1): Formula (B-1), where the sum of x and y is an integer from 3 to 30, n represents an integer from 0 to 5, and q represents an integer from 0 to 5.

8. The resin composition as claimed in claim 6, wherein the polyoxyethylene ether surfactant comprises a compound represented by the following formula (B-2): Formula (B-2), where r represents an integer from 0 to 15 and t represents an integer from 0 to 15.

9. The resin composition as claimed in claim 5, wherein the solvent (C) comprises propylene glycol methyl ether, tetraethylene glycol dimethyl ether, propylene glycol methyl ether acetate, diethylmethyl amine, isopropanol, methanol, acetone, n-butyl acetate, butanone, ethyl acetate, diacetone alcohol, or combinations thereof.

10. A hardened layer formed by hardening a resin composition as described in any one of claims 5 to 9.

11. An etching method, comprising: The hardened layer described in claim 10 is immersed in an etching solution for an etching process.

12. The etching method as described in claim 11, wherein the etching solution is an alkaline etching solution.