Negative photoresist composition for Krf thin film lithography, its preparation method and application

Abstract

The present invention discloses a negative photoresist composition for Krf thin film lithography, its preparation method and application. Specifically, the present invention discloses an application of a resist composition in Krf thin film lithography. The resist composition is prepared from the following raw materials, and the raw materials include the following components in parts by weight: 80 to 150 parts of resin A, 5 to 20 parts of resin B, 5 to 15 parts of resin C, 3 to 10 parts of photoacid generator, 2 to 10 parts of crosslinking agent, 0.5 to 2.5 parts of acid diffusion inhibitor, and 500 to 2000 parts of solvent; wherein, the ratio of the weight parts of resin A to resin C is 20:3 to 20:1, and the ratio of the weight parts of resin B to resin C is 1:2 to 2:1; resin A is a substituted styrene resin, which is composed of structural unit #imgabs0#, wherein, m is 1 or 2; R1 is H, acetyl or propionyl; the weight average molecular weight of resin A is 4000 to 10000, and the molecular weight distribution index is 1.2 to 3.0.

Description

Technical Field

[0001] The present invention relates to a negative photoresist composition for Krf thin film lithography, a preparation method thereof, and an application thereof. Background Art

[0002] Recently, with the development of semiconductor manufacturing process technology, miniaturization and high integration of semiconductor devices are required. Therefore, a technology for realizing ultra-fine patterns with a line width of several tens of nanometers or less is needed. Technological progress for forming such ultra-fine patterns has been brought about by developing light sources with smaller wavelengths, process technologies for light sources, and photoresists suitable for light sources.

[0003] Photoresists are used in photolithography for forming various patterns. A photoresist is a photosensitive resin that can change its solubility in a developer by the action of light to obtain an image corresponding to an exposure pattern. As the photoresist pattern formation methods, there are pattern formation methods using a negative tone developer (NTD, Negative Tone Development) and a positive tone developer (PTD, Positive Tone Development). The pattern formation method using a negative developer forms a pattern by selectively dissolving and removing non-exposed areas with a negative tone developer; the pattern formation method using a positive developer forms a pattern by selectively dissolving and removing exposed areas with a positive tone developer. When compared with the pattern formation method using a positive tone developer, the pattern formation method using a negative tone developer can achieve an inverted pattern even when it is difficult to form contact hole patterns or trench patterns due to insufficient exposure amount, and is easy to form a pattern when forming the same pattern. Moreover, an organic solvent is used as the developer for removing the unexposed part, so that a photoresist pattern can be formed more effectively.

[0004] On the other hand, a photolithography process using a conventional photoresist composition includes: a process of coating a photoresist on a wafer, a soft baking process of heating the coated photoresist to evaporate the solvent, a process of imaging using a light source passing through a photomask, a process of forming a pattern using a developer based on the solubility difference between the exposed part and the unexposed part, and a process of etching it to complete a circuit.

[0005] The photoresist composition contains a photoacid generator that generates acid upon exposure to excimer laser irradiation, a base resin, and other additives. The base resin basically uses a structure with a hydroxyl group in the phenol structure, specifically polystyrene polymers, cresol polymers, and novolak polymers; the photosensitizer only needs to generate acid (H+) of a specific wavelength, and mainly uses organic acids and inorganic acids such as sulfonium salts, sulfonyl diazo compounds, benzothioalkyl compounds, iodine compounds, chlorine compounds, and carboxylic acid compounds.

[0006] However, there are the following problems with the negative photoresist manufactured using the above composition: due to the disadvantage that the photosensitizer located at the lower part cannot generate a sufficient amount of acid (H+), etc., the desired shape cannot be formed, and a worse profile is generated in the case of forming a finer pattern. In addition, the light sources mainly used in the above process are in the wavelength range of 365 nm to 193 nm using I-ray, KrF excimer laser, and ArF excimer laser light sources, and the shorter the wavelength, the finer the pattern formed. Under each wavelength light source, the resist thickness is also one of the variables, which further increases the difficulty of resist research and development. Therefore, developing a KrF light source resist product with high resolution and high aspect ratio has become an urgent technical problem in this field. Summary of the Invention

[0007] The technical problem to be solved by the present invention is to provide a negative photoresist composition in order to overcome the defects that the negative photoresist in the prior art cannot form the desired shape and the finer the effect, the worse it is. The negative photoresist composition of the present invention has the advantages of high resolution and high aspect ratio.

[0008] The present invention mainly solves the above technical problems through the following technical means.

[0009] The present invention provides a resist composition, which is characterized in that it is prepared from the following raw materials, and the raw materials include the following components in parts by weight: 80 to 150 parts of resin A, 5 to 20 parts of resin B, 5 to 15 parts of resin C, 3 to 10 parts of photoacid generator, 2 to 10 parts of crosslinking agent, 0.5 to 2.5 parts of acid diffusion inhibitor, and 500 to 2000 parts of solvent; wherein, the ratio of the weight parts of resin A to resin C is 20:3 to 20:1, and the ratio of the weight parts of resin B to resin C is 1:2 to 2:1;

[0010] Resin A is a substituted styrene resin, which consists of structural units wherein, m is 1 or 2, and R1 is H, acetyl, or propionyl; the weight average molecular weight of resin A is 4000 to 10000, and the molecular weight distribution index is 1.2 to 3.0;

[0011] The structure of the resin B is as follows:

[0012]

[0013] The structure of the resin C is as follows:

[0014]

[0015] In the present invention, the photoacid generator used is a conventional photoacid generator in the art, and preferably triphenylsulfonium perfluorobutanesulfonate.

[0016] In the present invention, the crosslinking agent used is a conventional crosslinking agent in the art, and preferably tetramethoxymethyl glycoluril.

[0017] In the present invention, the acid diffusion inhibitor used is a conventional acid diffusion inhibitor in the art, and preferably tributylamine.

[0018] In the present invention, the solvent used is a conventional solvent in the art, and the solvent includes but is not limited to: ketones (such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone), polyols and their derivatives (such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether of ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol monoacetate, dipropylene glycol, and dipropylene glycol monoacetate), cyclic ethers (such as dioxane), esters (such as ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate), aromatic hydrocarbons (such as toluene and xylene), or combinations thereof.

[0019] The solvent used is preferably a combination of ethyl lactate and propylene glycol methyl ether acetate. Among them, the mass ratio of the ethyl lactate to the propylene glycol methyl ether acetate is preferably 3:14.

[0020] In the resist composition, the resin A is preferably 80 parts, 100 parts, or 150 parts by weight.

[0021] In the resin A, m is preferably 1.

[0022] The structural unit of the resin A is preferably

[0023] The weight-average molecular weight of the resin A is preferably 4,600 to 9,300, such as 4,608, 4,658, 5,428, 6,295, 7,521, 7,828 or 9,238.

[0024] The molecular weight distribution index of the resin A is preferably 1.2 to 2.9, such as 1.2, 1.8, 2.5, 2.7 or 2.9.

[0025] In some embodiments, the resin A is selected from any of the following:

[0026] Option 1: In the resin A, the structural unit is R1 is H, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 1.8;

[0027] Option 2: In the resin A, the structural unit is R1 is H, the weight-average molecular weight is 5,846, and the molecular weight distribution index is 2;

[0028] Option 3: In the resin A, the structural unit is R1 is H, the weight-average molecular weight is 9,798, and the molecular weight distribution index is 2;

[0029] Option 4: In the resin A, the structural unit is R1 is H, the weight-average molecular weight is 8,726, and the molecular weight distribution index is 1.8;

[0030] Option 5: In the resin A, the structural unit is R1 is H, the weight-average molecular weight is 5,753, and the molecular weight distribution index is 2.6;

[0031] Option 6: In the resin A, the structural unit is R1 is acetyl, the weight-average molecular weight is 5,399, and the molecular weight distribution index is 2.2;

[0032] Option 7: In the resin A, the structural unit is R1 is propionyl, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 2.9;

[0033] Option 8: In the resin A, the structural unit is R1 is H, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 1.8;

[0034] Option 9: In the resin A, the structural unit is R1 is H, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 1.8;

[0035] Option 10: In the resin A, the structural unit is R1 is H, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 1.8;

[0036] Scheme 11: In resin A, the structural unit is R1 is H, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 1.8;

[0037] Scheme 12: In resin A, the structural unit is R1 is H, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 1.8;

[0038] Scheme 13: In resin A, the structural unit is R1 is H, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 1.8;

[0039] Scheme 14: In resin A, the structural unit is R1 is H, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 1.8;

[0040] Scheme 15: In resin A, the structural unit is R1 is H, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 1.8;

[0041] Scheme 16: In resin A, the structural unit is R1 is H, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 1.8;

[0042] Scheme 17: In resin A, the structural unit is R1 is H, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 1.8;

[0043] Scheme 18: In resin A, the structural unit is R1 is H, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 1.8;

[0044] Scheme 19: In resin A, the structural unit is R1 is H, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 1.8;

[0045] Scheme 20: In resin A, the structural unit is R1 is H, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 1.8;

[0046] Scheme 21: In resin A, the structural unit is R1 is H, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 1.8.

[0047] The said resin A can be prepared from the monomer by a conventional polymerization reaction.

[0048] In the resist composition described above, the resin B is preferably 5 parts, 10 parts or 20 parts by weight.

[0049] In the resist composition described above, the resin C is preferably 5 parts, 10 parts or 15 parts by weight.

[0050] In the resist composition described above, the ratio of the weight parts of resin A and resin B can be 5:1 to 20:1, preferably 5:1, 8:1, 10:1, 15:1 or 20:1.

[0051] In the resist composition described above, the ratio of the weight parts of resin B and resin C is preferably 1:2, 2:3, 1:1 or 2:1.

[0052] In the resist composition described above, the ratio of the weight parts of resin A and resin C is preferably 20:3, 8:1, 10:1, 15:1 or 20:1.

[0053] In the resist composition described above, the photoacid generator is preferably 3 parts, 6 parts or 10 parts by weight.

[0054] In the resist composition described above, the crosslinking agent is preferably 2 parts, 5 parts or 10 parts by weight.

[0055] In the resist composition described above, the acid diffusion inhibitor is preferably 0.5 part, 1 part or 2.5 parts by weight.

[0056] In the resist composition described above, the solvent is preferably 500 parts, 850 parts or 2000 parts by weight.

[0057] Preferably, the raw materials of the resist composition are composed of 80 to 150 parts of the resin A, 5 to 20 parts of the resin B, 5 to 15 parts of the resin C, 3 to 10 parts of the photoacid generator, 2 to 10 parts of the crosslinking agent, 0.5 to 2.5 parts of the acid diffusion inhibitor and 500 to 2000 parts of the solvent by weight; wherein, the ratio of the weight parts of the resin A and the resin B is 20:3 to 20:1, and the ratio of the weight parts of the resin B and the resin C is 1:2 to 2:1.

[0058] In a preferred embodiment of the present invention, the raw materials of the resist composition may include the raw materials shown in any of the following schemes by weight, or be composed of the raw materials shown in any of the following schemes by weight:

[0059] Scheme 1: 100 parts of resin A, 10 parts of resin B, 10 parts of resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethylglycoluril, 1 part of tributylamine, and 850 parts of solvent; wherein, in resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8;

[0060] Scheme 2: 100 parts of resin A, 10 parts of resin B, 10 parts of resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethylglycoluril, 1 part of tributylamine, and 850 parts of solvent; wherein, in resin A, the structural unit is R1 is H, the weight-average molecular weight is 5846, and the molecular weight distribution index is 2;

[0061] Scheme 3: 100 parts of resin A, 10 parts of resin B, 10 parts of resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethylglycoluril, 1 part of tributylamine, and 850 parts of solvent; wherein, in resin A, the structural unit is R1 is H, the weight-average molecular weight is 9798, and the molecular weight distribution index is 2;

[0062] Scheme 4: 100 parts of resin A, 10 parts of resin B, 10 parts of resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethylglycoluril, 1 part of tributylamine, and 850 parts of solvent; wherein, in resin A, the structural unit is R1 is H, the weight-average molecular weight is 8726, and the molecular weight distribution index is 1.8;

[0063] Scheme 5: 100 parts of resin A, 10 parts of resin B, 10 parts of resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethylglycoluril, 1 part of tributylamine, and 850 parts of solvent; wherein, in resin A, the structural unit is R1 is H, the weight-average molecular weight is 5753, and the molecular weight distribution index is 2.6;

[0064] Scheme 6: 100 parts of resin A, 10 parts of resin B, 10 parts of resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethylglycoluril, 1 part of tributylamine, and 850 parts of solvent; wherein, in resin A, the structural unit is R1 is acetyl, the weight-average molecular weight is 5399, and the molecular weight distribution index is 2.2;

[0065] Scheme 7: 100 parts of resin A, 10 parts of resin B, 10 parts of resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethylglycoluril, 1 part of tributylamine, and 850 parts of solvent; wherein, in resin A, the structural unit is R1 is a propionyl group, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 2.9;

[0066] Scheme 8: 80 parts of resin A, 10 parts of resin B, 10 parts of resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethylglycoluril, 1 part of tributylamine, and 850 parts of solvent; among them, in resin A, the structural unit is R1 is H, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 1.8;

[0067] Scheme 9: 150 parts of resin A, 10 parts of resin B, 10 parts of resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethylglycoluril, 1 part of tributylamine, and 850 parts of solvent; among them, in resin A, the structural unit is R1 is H, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 1.8;

[0068] Scheme 10: 100 parts of resin A, 5 parts of resin B, 10 parts of resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethylglycoluril, 1 part of tributylamine, and 850 parts of solvent; among them, in resin A, the structural unit is R1 is H, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 1.8;

[0069] Scheme 11: 100 parts of resin A, 20 parts of resin B, 10 parts of resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethylglycoluril, 1 part of tributylamine, and 850 parts of solvent; among them, in resin A, the structural unit is R1 is H, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 1.8;

[0070] Scheme 12: 100 parts of resin A, 10 parts of resin B, 5 parts of resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethylglycoluril, 1 part of tributylamine, and 850 parts of solvent; among them, in resin A, the structural unit is R1 is H, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 1.8;

[0071] Scheme 13: 100 parts of resin A, 10 parts of resin B, 15 parts of resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethylglycoluril, 1 part of tributylamine, and 850 parts of solvent; among them, in resin A, the structural unit is R1 is H, the weight-average molecular weight is 7,828, and the molecular weight distribution index is 1.8;

[0072] Scheme 14: 100 parts of Resin A, 10 parts of Resin B, 10 parts of Resin C, 3 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 850 parts of solvent; among them, in Resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8;

[0073] Scheme 15: 100 parts of Resin A, 10 parts of Resin B, 10 parts of Resin C, 10 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 850 parts of solvent; among them, in Resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8;

[0074] Scheme 16: 100 parts of Resin A, 10 parts of Resin B, 10 parts of Resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 2 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 850 parts of solvent; among them, in Resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8;

[0075] Scheme 17: 100 parts of Resin A, 10 parts of Resin B, 10 parts of Resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 10 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 850 parts of solvent; among them, in Resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8;

[0076] Scheme 18: 100 parts of Resin A, 10 parts of Resin B, 10 parts of Resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 0.5 part of tributylamine, and 850 parts of solvent; among them, in Resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8;

[0077] Scheme 19: 100 parts of Resin A, 10 parts of Resin B, 10 parts of Resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 2.5 parts of tributylamine, and 850 parts of solvent; among them, in Resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8;

[0078] Scheme 20: 100 parts of resin A, 10 parts of resin B, 10 parts of resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 500 parts of solvent; among them, in resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8;

[0079] Scheme 21: 100 parts of resin A, 10 parts of resin B, 10 parts of resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 2000 parts of solvent; among them, in resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8.

[0080] The present invention also provides a preparation method of the resist composition described above, which includes the following steps: mixing the raw materials of the above resist composition evenly.

[0081] In the preparation method described above, the mixing method can be a conventional mixing method in the art, preferably shaking.

[0082] In the preparation method described above, preferably, a membrane filtration is also included after the mixing step, for example, filtering with a 0.1 μm membrane.

[0083] The present invention also provides an application of the above resist composition in Krf thin film lithography.

[0084] The application may include the following steps: coating the resist composition on a pretreated wafer, drying, exposing, baking, and developing.

[0085] The weight-average molecular weight and molecular weight distribution index described herein can be measured by conventional testing methods in the art, such as gel permeation chromatography.

[0086] On the basis of not violating the common knowledge in the art, the above preferred conditions can be combined arbitrarily to obtain various preferred examples of the present invention.

[0087] The reagents and raw materials used in the present invention are all commercially available.

[0088] The positive and progressive effects of the present invention are as follows: the resist composition of the present invention has high sensitivity, high resolution, and high aspect ratio, and a finer photoresist pattern can be produced in the application by using the resist composition of the present invention. Detailed embodiments

[0089] The present invention will be further described below by way of examples, but the present invention is not limited to the scope of the described examples. For the experimental methods without specific conditions in the following examples, they are carried out according to conventional methods and conditions, or selected according to the product specifications.

[0090] The resin A, resin B, resin C, triphenylsulfonium perfluorobutanesulfonate as a photoacid generator, tetramethoxymethyl glycoluril as a crosslinking agent, tributylamine as an acid diffusion inhibitor and a solvent were mixed uniformly according to the parts by weight listed in Tables 1 and 2 to prepare the resist compositions of Examples 1 to 21 and Comparative Examples 1 to 6.

[0091] In the following examples and comparative examples, resin A, resin B and resin C are commercially available, or resin B can be prepared by referring to the method disclosed in Patent CN110183654B, and resin C can be prepared by referring to the method disclosed in Patent CN107722265A.

[0092] In the following examples, the structural unit of resin A is The weight average molecular weight and molecular weight distribution were measured by gel permeation chromatography.

[0093] Table 1: Raw material components in the resist compositions of examples and comparative examples: Resin A

[0094]

[0095]

[0096] Table 2: Parts by weight of the remaining raw material components in the resist compositions of examples and comparative examples

[0097]

[0098]

[0099] The solvent in Table 2 is a combination of ethyl lactate and propylene glycol monomethyl ether acetate, and the mass ratio of ethyl lactate to propylene glycol monomethyl ether acetate is 3:14.

[0100] Effect examples

[0101] The resist compositions of Examples 1 to 21 and Comparative Examples 1 to 6 were filtered using a 0.1 μm Teflon material syringe filter, then coated on a silicon wafer using a spin coater, and soft baked at 100 °C for 90 seconds to confirm the target thickness of 500 nm. Then, an exposure process was carried out under a light source of 248 nm. After the exposure process was completed, a baking process was carried out at 110 °C for 90 seconds, and then a development process was carried out with 2.38% tetramethylammonium hydroxide to form a pattern.

[0102] For the resolution, use a Critical Dimension Scanning Electron Microscope (CD-SEM) capable of observing the line width (Critical Dimension) of the pattern to observe and confirm the minimum line width (resolution) based on L / S (Line, Space); for the sensitivity, measure the sensitivity with the energy (Energy) capable of determining the minimum line width (resolution).

[0103] For the effect, the smaller the numerical values of sensitivity, resolution, minimum pattern size, and aspect ratio, the better.

[0104] The test results are shown in Table 3.

[0105] Table 3: Sensitivity, Resolution, Minimum Pattern Size, and Aspect Ratio of Examples and Comparative Examples

[0106]

[0107]

[0108] In Examples 1 to 21, the sensitivity value < 50 mJ / cm 2 , the resolution value ≤ 0.20 μm, the minimum pattern size < 120 nm, and the aspect ratio < 1:3.5; in Comparative Examples 1 to 6, the sensitivity value > 50 mJ / cm 2 , the resolution value > 0.20 μm, the minimum pattern size > 130 nm, and the aspect ratio > 1:3.5. Compared with the comparative examples, the examples have significantly better effects in each index, and the examples have excellent resolution while having high sensitivity, indicating that the resist composition of the present invention has the advantages of high resolution and high aspect ratio, and can make the formed pattern finer in application.

Claims

1. Application of a resist composition in Krf thin film lithography, characterized in that, The resist composition is prepared from the following raw materials, and the raw materials include the following components in parts by weight: 80 to 150 parts of resin A, 5 to 20 parts of resin B, 5 to 15 parts of resin C, 3 to 10 parts of photoacid generator, 2 to 10 parts of crosslinking agent, 0.5 to 2.5 parts of acid diffusion inhibitor, and 500 to 2000 parts of solvent; wherein, the ratio of the weight parts of resin A to resin C is 20:3 to 20:1, and the ratio range of the weight parts of resin B to resin C is 1:2 to 2:1; The resin A is a substituted styrene resin and consists of structural units ; wherein, m is 1 or 2; R1 is H, acetyl or propionyl; The weight-average molecular weight of resin A is 4000 to 10000, and the molecular weight distribution index is 1.2 to 3.0; The structure of resin B is: The structure of resin C is: The weight-average molecular weight and molecular weight distribution index are measured by gel permeation chromatography.

2. The application according to claim 1, wherein The photoacid generator is triphenylsulfonium perfluorobutanesulfonate; and / or, the crosslinking agent is tetramethoxymethyl glycoluril; and / or, the acid diffusion inhibitor is tributylamine; and / or, the solvent is a combination of ethyl lactate and propylene glycol monomethyl ether acetate; and / or, the ratio of the weight parts of resin A to resin B is 5:1 to 20:1; and / or, the ratio of the weight parts of resin B to resin C is 1:2, 2:3, 1:1 or 2:1; and / or, the ratio of the weight parts of resin A to resin C is 20:3, 8:1, 10:1, 15:1 or 20:

1.

3. The application according to claim 2, characterized in that, The ratio of the weight parts of resin A to resin B is 5:1, 8:1, 10:1, 15:1 or 20:1; and / or, in the combination of ethyl lactate and propylene glycol monomethyl ether acetate, the mass ratio of ethyl lactate to propylene glycol monomethyl ether acetate is 3:

14.

4. The application according to claim 1, characterized in that The parts of resin A in parts by weight are 80 parts, 100 parts or 150 parts; and / or, the parts of resin B in parts by weight are 5 parts, 10 parts or 20 parts; and / or, the parts of resin C in parts by weight are 5 parts, 10 parts or 15 parts; and / or, the parts of the photoacid generator in parts by weight are 3 parts, 6 parts or 10 parts; and / or, the parts of the crosslinking agent in parts by weight are 2 parts, 5 parts or 10 parts; and / or, the parts of the acid diffusion inhibitor in parts by weight are 0.5 parts, 1 part or 2.5 parts; and / or, the parts of the solvent in parts by weight are 500 parts, 850 parts or 2000 parts.

5. The application according to claim 1, characterized in that In resin A, m is 1; and / or, the weight-average molecular weight of resin A is 4600 to 9300; and / or, the molecular weight distribution index of resin A is 1.2 to 2.

9.

6. The application according to claim 5, wherein, The structural unit of the resin A is and / or, the weight-average molecular weight of resin A is 4608, 4658, 5428, 6295, 7521, 7828 or 9238; and / or, the molecular weight distribution index of resin A is 1.2, 1.8, 2.5, 2.7 or 2.

9.

7. The application according to claim 1, characterized in that, Resin A is selected from any of the following schemes: Scheme 1: In Resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8; Scheme 2: In resin A, the structural unit is R1 is H, the weight-average molecular weight is 5846, and the molecular weight distribution index is 2; Scheme 3: In resin A, the structural unit is R1 is H, the weight-average molecular weight is 9798, and the molecular weight distribution index is 2; Solution 4: In Resin A, the structural unit is R1 is H, the weight-average molecular weight is 8726, and the molecular weight distribution index is 1.8; Scheme 5: In resin A, the structural unit is R1 is H, the weight-average molecular weight is 5753, and the molecular weight distribution index is 2.6; Scheme 6: In Resin A, the structural unit is R1 is an acetyl group, the weight-average molecular weight is 5399, and the molecular weight distribution index is 2.2; Scheme 7: In resin A, the structural unit is R1 is propionyl, the weight-average molecular weight is 7828, and the molecular weight distribution index is 2.

9.

8. The application according to claim 1, characterized in that, The resist composition is prepared from the following raw materials, and the raw materials consist of the following components by weight: 80 to 150 parts of the resin A, 5 to 20 parts of the resin B, 5 to 15 parts of the resin C, 3 to 10 parts of the photoacid generator, 2 to 10 parts of the crosslinking agent, 0.5 to 2.5 parts of the acid diffusion inhibitor, and 500 to 2000 parts of the solvent; wherein, the weight ratio of the resin A to the resin B is 20:3 to 20:1, and the weight ratio of the resin B to the resin C is 1:2 to 2:

1.

9. The application according to claim 1, wherein The raw materials of the resist composition include the raw materials shown in any of the following schemes by weight, or consist of the raw materials shown in any of the following schemes by weight: Solution 1: 100 parts of Resin A, 10 parts of Resin B, 10 parts of Resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 850 parts of solvent; wherein, in Resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8; Scheme 2: 100 parts of Resin A, 10 parts of Resin B, 10 parts of Resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 850 parts of solvent; among them, in Resin A, the structural unit is R1 is H, the weight-average molecular weight is 5846, and the molecular weight distribution index is 2; Scheme 3: 100 parts of resin A, 10 parts of resin B, 10 parts of resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 850 parts of solvent; wherein, in resin A, the structural unit is R1 is H, the weight-average molecular weight is 9798, and the molecular weight distribution index is 2; Solution 4: 100 parts of Resin A, 10 parts of Resin B, 10 parts of Resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 850 parts of solvent; among them, in Resin A, the structural unit is R1 is H, the weight-average molecular weight is 8726, and the molecular weight distribution index is 1.8; Solution 5: 100 parts of Resin A, 10 parts of Resin B, 10 parts of Resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 850 parts of solvent; among them, in Resin A, the structural unit is R1 is H, the weight-average molecular weight is 5753, and the molecular weight distribution index is 2.6; Scheme 6: 100 parts of Resin A, 10 parts of Resin B, 10 parts of Resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 850 parts of solvent; wherein, in Resin A, the structural unit is R1 is an acetyl group, the weight-average molecular weight is 5399, and the molecular weight distribution index is 2.2; Solution 7: 100 parts of Resin A, 10 parts of Resin B, 10 parts of Resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 850 parts of solvent; among them, in Resin A, the structural unit is R1 is propionyl, the weight-average molecular weight is 7828, and the molecular weight distribution index is 2.9; Solution 8: 80 parts of resin A, 10 parts of resin B, 10 parts of resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 850 parts of solvent; among them, in resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8; Scheme 9: 150 parts of Resin A, 10 parts of Resin B, 10 parts of Resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethylglycoluril, 1 part of tributylamine, and 850 parts of a solvent; among them, in Resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8; Scheme 10: 100 parts of Resin A, 5 parts of Resin B, 10 parts of Resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethylglycoluril, 1 part of tributylamine, and 850 parts of solvent; wherein, in Resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8; Scheme 11: 100 parts of Resin A, 20 parts of Resin B, 10 parts of Resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 850 parts of a solvent; among them, in Resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8; Scheme 12: 100 parts of resin A, 10 parts of resin B, 5 parts of resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 850 parts of solvent; wherein, in resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8; Scheme 13: 100 parts of Resin A, 10 parts of Resin B, 15 parts of Resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 850 parts of solvent; among them, in Resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8; Scheme 14: 100 parts of Resin A, 10 parts of Resin B, 10 parts of Resin C, 3 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 850 parts of solvent; among them, in Resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8; Scheme 15: 100 parts of Resin A, 10 parts of Resin B, 10 parts of Resin C, 10 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 850 parts of solvent; among them, in Resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8; Scheme 16: 100 parts of Resin A, 10 parts of Resin B, 10 parts of Resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 2 parts of tetramethoxymethylglycoluril, 1 part of tributylamine, and 850 parts of solvent; wherein, in Resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8; Scheme 17: 100 parts of resin A, 10 parts of resin B, 10 parts of resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 10 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 850 parts of solvent; among them, in resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8; Scheme 18: 100 parts of Resin A, 10 parts of Resin B, 10 parts of Resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 0.5 part of tributylamine, and 850 parts of solvent; wherein, in Resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8; Scheme 19: 100 parts of Resin A, 10 parts of Resin B, 10 parts of Resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethylglycoluril, 2.5 parts of tributylamine, and 850 parts of a solvent; wherein, in Resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8; Scheme 20: 100 parts of Resin A, 10 parts of Resin B, 10 parts of Resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 500 parts of a solvent; among them, in Resin A, the structural unit is R1 is H, the weight-average molecular weight is 7828, and the molecular weight distribution index is 1.8; Solution 21: 100 parts of Resin A, 10 parts of Resin B, 10 parts of Resin C, 6 parts of triphenylsulfonium perfluorobutanesulfonate, 5 parts of tetramethoxymethyl glycoluril, 1 part of tributylamine, and 2000 parts of solvent; wherein, in Resin A, the structural unit is R1 is H, the weight average molecular weight is 7828, and the molecular weight distribution index is 1.

8.

10. The application according to any one of claims 1-9, characterized in that The preparation method of the resist composition comprises the following steps: mixing the raw materials of the resist composition evenly.

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