Resin, resin composition, hardened layer, and etching method

Abstract

This invention provides a resin, a resin composition, a hardened layer, and an etching method. The resin comprises structural units represented by the following formula (A). In the resin, the content of propyne groups is not zero. In R... 1 and R 2 In the hydrogen and propynyl groups represented, the molar ratio of hydrogen to propynyl groups is from 90:10 to 55:45. In formula (A), R 1 and R 2 Each represents either hydrogen or propyne group, and * indicates the bond position.

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. Background 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 thinner photoresist layers currently used to manufacture semiconductor devices may result in incomplete exposure during the process, leading to pattern collapse and affecting the performance of semiconductor devices made from them. Summary of the Invention

[0003] The present invention provides a resin, a resin composition, a hardened layer, and an 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 zero. In R... 1 and R 2 In the hydrogen and propynyl groups represented, the molar ratio of hydrogen to propynyl groups is from 90:10 to 55:45.

[0005]

[0006] In formula (A), R 1 and R 2 Each represents either hydrogen or propyne group, and * indicates the bond position.

[0007] 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.

[0008] 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:

[0009]

[0010] In equation (A-1), R 3 R represents hydrogen. 4 Indicates propynyl group;

[0011]

[0012] In equation (A-2), R 5 Represents propynyl group, R 6 Indicates propynyl group;

[0013]

[0014] In equation (A-3), R 7 Represents propynyl group, R 8 It represents hydrogen.

[0015] In one embodiment of the present invention, the resin further comprises a structural unit represented by the following formula (A-4):

[0016]

[0017] 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 amount 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.

[0018] In one embodiment of the present invention, the surfactant (B) comprises a fluorinated surfactant or a polyoxyethylene ether surfactant. Fluorinated surfactants further comprise alcohol groups, ester groups, or carboxylic acid groups.

[0019] In one embodiment of the present invention, the above-mentioned fluorinated surfactant includes a compound represented by the following formula (B-1):

[0020]

[0021] 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.

[0022] In one embodiment of the present invention, the above-mentioned polyoxyethylene ether surfactant includes a compound represented by the following formula (B-2):

[0023]

[0024] In equation (B-2), r represents an integer from 0 to 15, and t represents an integer from 0 to 15.

[0025] In one embodiment of the present invention, the solvent (C) includes propylene glycol methyl ether, tetraethylene glycol dimethyl ether, propylene glycol methyl ether acetate, diethylformamide, isopropanol, methanol, acetone, n-butyl acetate, butanone, ethyl acetate, diacetone alcohol, or combinations thereof.

[0026] A hardened layer of the present invention is formed by hardening the above-mentioned resin composition.

[0027] An etching method of the present invention includes: immersing the hardened layer described above in an etching solution to perform an etching process.

[0028] In one embodiment of the present invention, the etching solution is an alkaline etching solution.

[0029] 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.

[0030] To make the above features and advantages of the present invention more apparent and understandable, specific embodiments are described in detail below. Detailed Implementation

[0031] <Resin>

[0032] 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.

[0033]

[0034] In formula (A), R 1 and R 2 Each represents either 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), R 1 It can represent hydrogen and R 2 Indicates propynyl group; R 1 It can represent propyne group and R 2 R represents hydrogen; 1 It can represent propyne group and R 2 Indicates propynyl group; or R 1 It can represent hydrogen and R 2 It represents hydrogen.

[0035] In the resin, the content of propyne groups is not zero. For example, the resin may include R... 1 Represents hydrogen and R 2 The structural unit represented by formula (A) for the propyne group and R 1 Represents hydrogen and R 2 The structural unit represented by formula (A) represents hydrogen. In the resin, in R... 1 and R 2 In the indicated hydrogen and propynyl groups, the molar ratio of hydrogen to propynyl groups can be from 90:10 to 55:45, preferably from 70:30 to 55:45. That is, based on R in the resin 1 and R 2The total amount of hydrogen and propynyl groups represented is 100%, and the proportion of propynyl groups can be from 10% to 45%, preferably from 30% to 45%.

[0036] 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.

[0037]

[0038] In equation (A-1), R 3 R represents hydrogen. 4 It represents the propynyl group.

[0039]

[0040] In equation (A-2), R 5 Represents propynyl group, R 6 It represents the propynyl group.

[0041]

[0042] In equation (A-3), R 7 Represents propynyl group, R 8 It represents hydrogen.

[0043]

[0044] The resin may include a structure represented by the following formula (A'), where m represents an integer from 7 to 50.

[0045]

[0046] In formula (A'), m represents an integer from 7 to 50, preferably an integer from 10 to 37.

[0047] The weight average molecular weight of the resin can be from about 1,000 g / mol to about 7,000 g / mol, more preferably from about 2,000 g / mol to about 5,000 g / mol.

[0048] <Resin Composition>

[0049] 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.

[0050] Resin (A)

[0051] 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 the resin composition, the amount of resin (A) used is 1.5 parts by weight to 10 parts by weight, preferably 3 parts by weight to 6 parts by weight.

[0052] Surfactant (B)

[0053] There are no particular limitations on the surfactant (B), and an appropriate surfactant can be selected according to requirements. In this embodiment, surfactant (B) may include fluorinated surfactants, polyoxyethylene ether surfactants, or other suitable surfactants. Surfactant (B) may be used alone or in combination.

[0054] 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.

[0055]

[0056] In equation (B-1), the sum of x and y is an integer from 3 to 30, preferably an integer from 7 to 20;

[0057] n represents an integer from 0 to 5, preferably an integer from 1 to 3;

[0058] q represents an integer from 0 to 5, preferably an integer from 1 to 3.

[0059] 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.

[0060] Polyoxyethylene ether surfactants may include compounds represented by the following formula (B-2) or other suitable polyoxyethylene ether surfactants.

[0061]

[0062] In equation (B-2), r represents an integer from 0 to 15, preferably an integer from 1 to 8;

[0063] 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.

[0064] Based on the total amount of resin composition 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.

[0065] Solvent (C)

[0066] 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, diethylformamide, 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.

[0067] Based on the total amount of resin composition used being 100 parts by weight, the amount of solvent (C) used is from 80 parts by weight to 98.5 parts by weight, preferably from 89 parts by weight to 98.5 parts by weight.

[0068] 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.

[0069] <Preparation method of resin composition>

[0070] 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.

[0071] <Method for manufacturing hardened layer>

[0072] 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.

[0073] The hardened layer can be formed by coating the above-described 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 to 350°C (preferably about 250°C) for 1 to 10 minutes (preferably about 3 minutes) to form a hardened layer with a thickness of 120 to 150 nm on the substrate.

[0074] 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 material (e.g., polyethersulfone (PES) board, polycarbonate (PC) board, or polyimide (PI) film) or other suitable substrate types.

[0075] 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 coated film is formed, and in some cases, residual solvent can be partially removed under reduced pressure.

[0076] <Etching Method>

[0077] 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.

[0078] 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.

[0079] Other steps included in the etching method are well known to those skilled in the art and will not be described separately here.

[0080] 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 set forth in the claims and its substitutions and modifications, but is not limited to the scope of the examples.

[0081] Example of resin synthesis

[0082] The following describes the synthesis examples 1 to 5 of the resin:

[0083] Synthesis example 1

[0084] 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 5% sulfuric acid tetrahydrofuran solution (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, 57.34 g of sodium carbonate and 8.496 g of tetrabutylammonium iodide 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%.

[0085] Synthesis example 2

[0086] 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 was added, and the mixture was heated to a warm temperature. The reaction mixture was allowed to react for 18 hours. After the reaction was complete, the reaction mixture was cooled and transferred to a separatory funnel, where 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). A sample was taken and the molecular weight was confirmed by gel permeation chromatography (MW approximately 2615 g / mol, MP approximately 3118 g / mol, PDI approximately 1.616), with a propyne group ratio of 32.3%.

[0087] Synthesis example 3

[0088] 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 (MW was approximately 2996 g / mol, MP was approximately 3615 g / mol, PDI was approximately 1.921) was confirmed by gel permeation chromatography. The propyne group ratio was 32.2%.

[0089] Synthesis example 4

[0090] 100g of 3,4-dihydroxystyrene was added to ethyl acetate to prepare a 73% solids ethyl acetate solution of 3,4-dihydroxystyrene (137g). Then, 429g of tetrahydrofuran and 5.3g of dimethylacetamide were added to the reaction flask, followed by the addition of 105.9g of tetrahydrofuran solution containing 5% sulfuric acid. 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%.

[0091] Synthesis example 5

[0092] 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%.

[0093] Examples of resin compositions and hardened layers

[0094] Examples 1 to 7 and Comparative Examples 1 to 8 describe the resin composition and hardened layer:

[0095] Example 1

[0096] a. Resin composition

[0097] 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.

[0098] b. Hardened layer

[0099] 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.

[0100] Examples 2 to 7 and Comparative Examples 1 to 8

[0101] The resin compositions of Examples 2 to 7 and Comparative Examples 1 to 8 were prepared using the same procedures as in Example 1, except that the types and amounts of components in the resin compositions 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, and the results are shown in Table 2. In Table 2, the flatness is less than... And its etch resistance is less than Examples of examples are listed below; examples outside the foregoing scope are listed below as comparative examples.

[0102] [Table 1]

[0103]

[0104]

[0105] [Table 2]

[0106]

[0107] [Table 2] (continued)

[0108]

[0109] *Peeling: The hardened layer peeled off the substrate in less than 30 minutes during the etch resistance test.

[0110] <Evaluation Method>

[0111] a. Flatness

[0112] Each of the prepared resin compositions 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 fitted into an optical film thickness gauge (DNS VM-1210, manufactured by Screenspe 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.

[0113] b. Etching resistance

[0114] Each of the prepared resin compositions was coated onto an 8-inch silicon substrate and baked to cure, forming a hardened layer. The substrate 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.

[0115] <Evaluation Results>

[0116] As shown in Table 2, the hardened layer formed by the examples of resin compositions including resin (A) having a specific structure and containing propyne-based structural units exhibits good flatness and etch resistance, making it suitable for semiconductor processes. In contrast, the hardened layer formed by the comparative examples of resin compositions not including resin (A) having a specific structure and containing propyne-based structural units exhibits poor flatness and / or etch resistance.

[0117] Furthermore, as shown in Table 2, compared to the R of resin (A) in the resin composition... 1 and R 2 The hardened layer prepared when the molar ratio of hydrogen and propyne groups is not in the range of 90:10 to 55:45 (Comparative Example 1), the resin (A) in the resin composition has a R 1 and R 2 The hardened layers (Examples 1-7) prepared with a hydrogen to propyne molar ratio in the range of 90:10 to 55:45 exhibit small film thickness differences and variations, resulting in better flatness and etch resistance. Therefore, it can be seen that when the R of resin (A) is in the range of 90:10 to 55:45, the resulting hardened layers have smaller film thickness differences and variations, resulting in better flatness and etch resistance. 1 and R 2 When the molar ratio of hydrogen and propyne groups 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.

[0118] Furthermore, as shown in Table 2, compared to the hardened layer prepared by the resin composition excluding surfactant (B) (Comparative Example 2), the hardened layers prepared by the resin composition including surfactant (B) (Examples 1-7) have smaller film thickness differences and film thickness variations, i.e., better flatness and etch resistance. Therefore, it can be seen that when the resin composition includes surfactant (B) with different structures, the hardened layer formed by the resin composition can have better flatness and etch resistance.

[0119] 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 without 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., better flatness and etching resistance. Therefore, it can be seen 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.

[0120] 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) having 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.

[0121] 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 by 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.

[0122] Furthermore, as shown in Table 2, 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 amount not in the range of 1.5 to 10 parts by weight (Comparative Example 8), the hardened layers prepared by resin compositions 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.

[0123] Furthermore, as shown in Table 2, when the resin composition has the same components, compared to the hardened layer prepared by a resin composition with a total resin composition usage of 100 parts by weight but a resin (A) usage amount not in the range of 1.5 parts by weight to 10 parts by weight (Comparative Example 8), the hardened layer prepared by a resin composition with a resin (A) usage amount in the range of 1.5 parts by weight to 10 parts by weight (Examples 2 and 7) has a smaller film thickness difference, i.e., better flatness, and also 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 parts by weight to 10 parts by weight, the hardened layer formed by the resin composition can have better flatness and good etch resistance.

[0124] In summary, the resin composition of the present invention comprises a resin (A) having a specific structure and containing propyne-based structural units, and in R... 1 and R 2 When the molar ratio of hydrogen to propyne in the indicated hydrogen and propyne groups is 90:10 to 55:45, the hardened layer formed from the resin composition has good flatness and etch resistance, making it suitable for semiconductor processes and thereby improving the performance of semiconductor devices manufactured using it.

[0125] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A resin comprising a structural unit represented by the following formula (A): In formula (A), R 1 and R 2 Each represents either a hydrogen or propynyl group, and * indicates the bond position. In the resin, the content of the propyne group is not 0, in R 1 and R 2 In the hydrogen and propynyl groups represented, the molar ratio of hydrogen to propynyl groups is from 90:10 to 55:

45.

2. The resin according to claim 1, wherein the weight average molecular weight is from 1000 g / mol to 7000 g / mol.

3. The resin according to claim 1, wherein the structural unit represented by formula (A) comprises at least one of the structural units represented by formulas (A-1) to (A-3): In equation (A-1), R 3 R represents hydrogen. 4 Indicates propynyl group; In equation (A-2), R 5 Represents propynyl group, R 6 Indicates propynyl group; In equation (A-3), R 7 Represents propynyl group, R 8 It represents hydrogen.

4. The resin according to claim 3 further comprises a structural unit represented by the following formula (A-4):

5. A resin composition comprising: Resin (A) is the resin according to any one of claims 1 to 4; Surfactant (B); as well as Solvent (C), The total amount of the resin composition used is 100 parts by weight, 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.

6. The resin composition according to 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 according to claim 6, wherein the fluorinated surfactant comprises a compound represented by the following 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.

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

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

10. A hardened layer formed by hardening the resin composition according to any one of claims 5 to 9.

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

12. The etching method according to claim 11, wherein the etching solution is an alkaline etching solution.

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