Acrylate block polymer resin for directional self-assembly as well as preparation method and application of acrylate block polymer resin

Abstract

The invention provides acrylate block polymer resin for directional self-assembly as well as a preparation method and application of the acrylate block polymer resin. The number average molecular weight of the acrylate block polymer resin is 5000 to 20000, and preferably, the number average molecular weight of the acrylate block polymer resin is 5000 to 13000; molecular weight distribution lt; 1.30, preferably from 1.0 to 1.2; the impurity content of any key metal ion in the acrylate block polymer resin is less than 5ppb; the line edge roughness of the film of the acrylate-based block polymer resin is lt; the phase region is smaller than 200 nm, preferably 10 nm, preferably 4-10 nm, and the period length of the phase region repetition structure is smaller than 200 nm, preferably 10-200 nm. The prepared acrylate block polymer resin with narrow molecular weight distribution and low metal impurity content can be used as film-forming resin in a photoresist, and the line edge roughness and phase region period length of the photoresist in a photoetching process are improved.

Description

Technical Field

[0001] The present invention relates to the field of polymer materials. Further, it relates to an acrylate block polymer resin for directed self-assembly, its preparation method and applications. Background Art

[0002] In recent years, large-scale and very large-scale integrated circuits have developed rapidly. As one of the key materials for microfabrication in microelectronics technology, photoresists have also entered a period of rapid development. Photoresists, also known as photoresist materials or photoresist agents, are the most critical materials in the lithography process. Through photochemical reactions, the required fine patterns are transferred from the mask to the substrate to be processed through lithography processes such as exposure and development. Photoresists mainly consist of film-forming resins, photosensitizers (photoinitiators, photosensitizers or photoacid generators, etc.), organic solvents, additives and other auxiliary agents. To meet the requirements of higher integration and more precise integrated circuit manufacturing, shorter-wavelength light sources must be used in the lithography process, and the lithography resolution is correspondingly improved. The exposure light sources of lithography machines have evolved from broadband ultraviolet light to I-line (365 nm), KrF line (248 nm), ArF line (193 nm) and the current most advanced EUV (13.5 nm) light source. Different light sources require the use of different photoresists. As a key material in photoresists, film-forming resins have also evolved from polyvinyl cinnamate, cyclized rubber, phenolic resins, acrylate derivatives to polyacrylates, metal oxides, etc.

[0003] Among them, ArF photoresist products have excellent resolution and can be used in the integrated circuit manufacturing processes of 90 nm to 14 nm and even 7 nm technology nodes. Usually, in the 90 nm lithography process, the molecular weight distribution of the photoresist resin should reach below 1.2, and at the same time, the metal content of the resin is required to be very low. Further reducing the critical dimension of the pattern to below 50 nm in the lithography process is greatly limited by the cost of equipment and processes. To overcome these difficulties, block copolymers (BCPs) have received extensive attention because they can spontaneously form periodic layered, spherical or columnar structures with a size of 5 - 50 nm and can be used for directed self-assembly (DSA) to overcome these difficulties.

[0004] Patent CN111718439A uses methacrylate monomers as the starting monomers, and polyacrylic acid resin is obtained through traditional radical polymerization. After the obtained polymer undergoes multiple steps of complex and cumbersome purification operations, a polymethacrylic acid polymer is obtained. The molecular weight distribution of the polymethacrylic acid polymer obtained by the above synthesis method is relatively wide, greater than 1.6.

[0005] The molecular weight and molecular weight distribution of the film-forming resin have a significant impact on the performance of the photoresist. The film-forming resin with a narrow molecular weight distribution can greatly improve the lithography resolution and reduce the edge roughness of the lithography size. Therefore, how to synthesize a film-forming material for photoresist with controllable components and a narrow molecular weight distribution has attracted the attention of researchers. At present, in order to reduce the molecular weight distribution of the resin for photoresist, some polymerization methods with low molecular weight distribution have been disclosed, such as reversible addition-fragmentation chain transfer polymerization (RAFT), atom transfer radical polymerization (ATRP), etc. Patent CN112175133A discloses a method for polymerizing polyacrylates with a narrow number-average molecular weight distribution, which synthesizes a polyacrylic acid polymer with a narrow number-average molecular weight distribution by atom transfer radical polymerization (ATRP) of acrylate monomers. Although this method can obtain a resin with a narrow molecular weight distribution, it is necessary to introduce a transition metal complex (such as copper salt halide) during the resin preparation process, which is not consumed during the polymerization process. The heavy metal residues encapsulated in the resin are difficult to remove, the purification process is complex, and the presence of trace metal impurities will seriously affect the electrical properties of semiconductor materials.

[0006] At the same time, the existing organic photocatalytic reactions have problems such as low catalytic efficiency and long reaction time. The present invention improves the existing organic photocatalytic ATRP reaction. By adding an ionic liquid to use a mixed solvent, the reaction rate of acrylate monomers is significantly faster than that in traditional polar solvents, which improves the reaction rate and polymerization efficiency. At the same time, in terms of block copolymers, using the selective distribution of ionic liquids, phase separation of disordered block copolymers is promoted, the interaction parameter between the two blocks is increased, the line edge roughness is improved, the phase region period length can be regulated, and the surface energy and nanostructure orientation of the film are not changed, which has high compatibility with the existing guided assembly process and verifies the compatibility with chemical modification methods. Summary of the Invention

[0007] In order to solve the technical problems existing in the prior art, the present invention provides an acrylate block polymer resin for directed self-assembly, a preparation method thereof, and an application thereof.

[0008] In the prior art, polystyrene and poly(meth)acrylate block copolymers are usually used. The present invention uses 3 kinds of acrylate monomers to prepare block copolymers, aiming to obtain a larger Flory-Huggins interaction parameter, thereby reducing the molecular weight (i.e., the degree of polymerization) of the block polymer and obtaining a pattern with a narrower period length.

[0009] The present invention provides an acrylate block polymer resin with a narrow molecular weight distribution and low metal impurity content to improve the sensitivity of photoresist in the lithography process and can regulate the period length of the phase region, so as to solve the problems of the existing wide molecular weight distribution (>1.6), easy introduction of metal impurities during the resin preparation process, poor sensitivity, and slow phase separation. At the same time, the problem of insufficient photocatalytic reaction efficiency is solved.

[0010] One of the objectives of the present invention is to provide an acrylate block polymer resin with a number average molecular weight of 5000 to 20000, preferably 8000 to 13000; the molecular weight distribution <1.30, preferably 1.0 to 1.2; the content of any key metal ion impurity in the acrylate block polymer resin is less than 5 ppb; the line edge roughness of the film of the acrylate block polymer resin <10 nm, preferably 4 to 10 nm; the period length of the phase region repeating structure of the film of the acrylate block polymer resin <200 nm, preferably 10 to 200 nm, more preferably 80 to 200 nm.

[0011] The key metal ion impurities include Na, Ag, Ca, K, Fe, Cu, Mg, Al, Cr, Sn, Zn, Mn, Cr, and Co, and the content of any key metal ion impurity in the acrylate block polymer resin is less than 5 ppb.

[0012] The line edge roughness describes the deviation of the photoresist line width from the target value due to edge roughness. For the patterns obtained by high-resolution electron microscope scanning, the line width is measured at the same height interval in the vertical direction for each pattern, and the average value is taken as the target line width value. The line edge roughness is quantitatively described by three times the standard error between the measured line width value and the average line width.

[0013] The period length of the phase region repeating structure is the length when the diblock copolymer is fully extended, which can be understood as the length of a set of repeating patterns.

[0014] In a preferred embodiment of the present invention,

[0015] The acrylate resin contains three structural units derived from the following acrylic or acrylate monomers: acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, glycidyl methacrylate, 2-methyl-2-adamantyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 1,1,5-trihydroperfluoropentyl acrylate, N-propyl perfluorooctanesulfonamidoethyl acrylate; preferably three of acrylic acid, n-butyl acrylate, methyl methacrylate, tert-butyl acrylate, 2-methyl-2-adamantyl methacrylate, and further preferably,

[0016] First, two acrylic or acrylate monomers are subjected to photopolymerization, and then the third acrylic or acrylate monomer is added for photopolymerization to obtain the acrylate block polymer resin for directed self-assembly.

[0017] The second object of the present invention is to provide a method for preparing an acrylate block polymer resin, comprising the following steps:

[0018] (1) Mix acrylic or acrylate monomer I, an initiator, an ionic liquid, and a solvent uniformly to obtain a mixed solution A;

[0019] (2) Under the protection of a protective gas, add acrylic or acrylate monomer II and a photocatalyst to the mixed solution A obtained in step (1), mix uniformly, and then carry out a photocatalytic polymerization reaction A under light irradiation to obtain a mixed solution B;

[0020] (3) Under the protection of a protective gas, add acrylic or acrylate monomer III to the mixed solution B obtained in step (2), carry out a photocatalytic polymerization reaction B under light irradiation, and subject the obtained product to post-treatment to obtain the acrylate block polymer resin.

[0021] In a preferred embodiment of the present invention,

[0022] Step (1),

[0023] The initiator is at least one of α-haloaromatic compounds and α-haloaliphatic compounds; and / or,

[0024] The solvent is at least one of hydroxyl-containing solvents, ester solvents, ketone solvents, ether solvents, and polar group-containing cyclic solvents; and / or,

[0025] The ionic liquid is at least one of 1-allyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.

[0026] The ionic liquid has two functions. One is to increase the solution viscosity and significantly reduce the reaction chain termination rate coefficient, accelerating the chain growth rate, similar to the auto-acceleration effect in free radical polymerization.

[0027] The other is that the ionic liquid has a stronger interaction with one of the blocks. The microphase separation of the block copolymer is directly related to the Flory-Huggins interaction parameter change χN, where N is the total degree of polymerization of the block copolymer and χ is the change in the Flory-Huggins interaction parameter between the two blocks. Phase separation can occur only when χN is large enough. Moreover, the larger χ is, the less the two blocks interleave in the perpendicular region, and the clearer the pattern boundary formed. The ionic liquid changes χ between the two blocks, thereby reducing the degree of polymerization to make the period length smaller, achieving higher resolution and clearer line edges.

[0028] In a preferred embodiment of the present invention,

[0029] The α-haloaromatic compound is at least one of α-chloroethylbenzene, α-bromoethylbenzene, benzyl chloride, and benzyl bromide; and / or,

[0030] The α-haloaliphatic compound is at least one of ethyl α-chloropropionate, ethyl α-bromopropionate, ethyl α-bromoisobutyrate, α-chloroacetonitrile, α-chloropropionitrile, carbon tetrachloride, and chloroform; and / or,

[0031] The solvent is at least one of methanol, ethanol, isopropanol, methyl formate, ethyl acetate, methyl acetate, n-propyl acetate, acetone, methyl ethyl ketone, and cyclohexanone.

[0032] In a preferred embodiment of the present invention,

[0033] In steps (1) to (3),

[0034] The acrylic or acrylate monomer I, acrylic or acrylate monomer II, and acrylic or acrylate monomer III are each selected from acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, glycidyl methacrylate, 2-methyl-2-adamantyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 1,1,5-trihydroperfluoropentyl acrylate, N-propyl perfluorooctanesulfonamidoethyl acrylate; preferably one of acrylic acid, n-butyl acrylate, methyl methacrylate, tert-butyl acrylate, 2-methyl-2-adamantyl methacrylate;

[0035] The photocatalyst is at least one of diphenyldihydrophenazine, 10-phenylphenothiazine, dihydrophenazine, 2-trifluoromethyldihydrophenazine, dicyanodihydrophenazine, perylene, oxygen-doped anthracene.

[0036] The protective gas is at least one of nitrogen and inert gas, and the inert gas is preferably argon; before the reaction, the air and moisture in the reaction vessel are displaced with the protective gas;

[0037] The light source is visible light or ultraviolet light.

[0038] In a preferred embodiment of the present invention,

[0039] The molar ratio of the acrylic or acrylate monomer I, acrylic or acrylate monomer II, and acrylic or acrylate monomer III is 1:(0.1-10):(0.1-10), preferably 1:(0.5-2):(0.5-2); and / or,

[0040] The molar ratio of the initiator to the total amount of acrylic or acrylate monomers is (0.01-10):100, preferably (0.1-5):100; and / or,

[0041] The mass ratio of the ionic liquid to the total amount of acrylic or acrylate monomers is (0.01-100):1, preferably (0.1-50):1, more preferably (0.1-6):1;

[0042] The mass ratio of the solvent to the total amount of acrylic or acrylate monomers is (0.1-50):1, preferably (1-25):1, more preferably (1-6):1; and / or,

[0043] The molar ratio of the photocatalyst to the total amount of acrylic or acrylate monomers is (0.01-10):100, preferably (0.1-1):100.

[0044] In a preferred embodiment of the present invention,

[0045] In step (2), the reaction conditions of the photocatalytic polymerization reaction A are as follows:

[0046] The reaction temperature is 0 to 100 °C, preferably 25 to 50 °C; and / or,

[0047] The reaction time is 1 to 24 hours, preferably 8 to 16 hours; and / or,

[0048] In step (3), the reaction conditions of the photocatalytic polymerization reaction B are as follows:

[0049] The reaction temperature is 0 to 100 °C, preferably 25 to 50 °C; and / or,

[0050] The reaction time is 1 to 24 hours, preferably 8 to 16 hours; and / or,

[0051] The post-treatment includes precipitating the reaction product. The precipitation method can use the common solvents and precipitants in the art, dissolve and precipitate the system several times, and then dry to obtain the product. For example, using acetone as the solvent and water as the precipitant, dissolve and precipitate 3 times, and place the solid in a vacuum oven for drying.

[0052] The third object of the present invention is to provide an acrylate block polymer resin obtained by the above preparation method.

[0053] The fourth object of the present invention is to provide an application of the acrylate block polymer resin in a photoresist.

[0054] The prepared acrylate block polymer resin can be used as a film-forming resin in a photoresist; preferably,

[0055] The photoresist includes the acrylate block polymer resin and a solvent; more preferably,

[0056] The solvent is at least one of methyl acetate, ethyl acetate, ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol phenyl ether acetate, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,4-dioxane, tetrahydrofuran, methanol, ethanol, isopropanol, n-hexane, n-heptane, benzene, toluene, xylene, acetone, ethylene glycol, propylene glycol, and ether, preferably at least one of propylene glycol methyl ether acetate, methanol, isopropanol, acetone, and N-methylpyrrolidone; the mass ratio of the solvent to the acrylate block polymer resin is (20 to 200):1, more preferably (50 to 100):1;

[0057] The line edge roughness of the thin film of the photoresist is < 10 nm, preferably 4 - 10 nm; the period length of the phase region repeating structure of the thin film of the photoresist is < 200 nm, preferably 10 - 200 nm, more preferably 80 - 200 nm.

[0058] Compared with the prior art, the present invention has the following beneficial effects:

[0059] (1) In the present invention, for the acrylate resin, on the basis of the traditional atom transfer radical polymerization (ATRP) process, an organic photocatalyst is used to replace the transition metal catalyst, reducing the introduction of metal impurities in the resin preparation process and further improving the performance of the photoresist resin product.

[0060] (2) In the organic-catalyzed photo-controlled ATRP polymerization reaction, the reaction conditions are mild and it is easy to carry out low-temperature polymerization, making the living polymerization process more controllable.

[0061] (3) Under visible light irradiation by the organic photocatalyst, a polymer with a relatively small difference in molecular weight and a number-average molecular weight very close to the theoretical value is synthesized. Specifically, the molecular weight distribution of the acrylate resin obtained is < 1.2, effectively overcoming the problem that it is difficult to prepare a resin with a narrow molecular weight distribution at present.

[0062] (4) By improving the existing organic photocatalytic reaction and adding an ionic liquid to use a mixed solvent, the reaction rate of the acrylate monomer is significantly accelerated, improving the polymerization efficiency.

[0063] (5) Utilizing the selective distribution of the ionic liquid, that is, the ionic liquid has different interactions with different blocks and will preferentially bind to one of the blocks. It can be known from DSC analysis that the ionic liquid will selectively bind to a homopolymer to change the glass transition temperature, promoting the phase separation of the disordered block copolymer and increasing the interaction parameter between the two blocks.

[0064] (6) By preparing a block polymer with a low degree of polymerization, the period length of the phase region and the line edge roughness are improved. Detailed implementation mode

[0065] The present invention will be specifically described below in conjunction with specific embodiments. It is necessary to point out here that the following embodiments are only used for further illustration of the present invention and should not be construed as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention still fall within the protection scope of the present invention.

[0066] For the raw materials used in the examples and comparative examples, if not specifically defined, they are all disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0067] The raw materials used in the examples are all conventional commercially available raw materials.

[0068] Testing method:

[0069] Molecular weight and molecular weight distribution: Dissolve the polymer powder sample in chromatographic grade tetrahydrofuran to prepare a solution with a concentration of about 1.5 mg / mL. Test with a gel permeation chromatograph, the mobile phase is tetrahydrofuran, the flow rate is 1.0 mL / min, the injection volume is 50 μL, the standard sample is narrow-distribution medium molecular weight polystyrene, the weight-average molecular weight range is 266 - 125000, and the column temperature and detection temperature are both 35 °C.

[0070] Metal ion content: Prepare a set of standard solution of Na; Ag; Ca; K; Fe; Cu; Mg; Al; Cr; Sn; Zn; Mn; Cr; Co with different concentrations. Inject these standards into the sample cell of a graphite furnace atomic absorption spectrometer respectively, and record the corresponding absorbance values to establish a standard curve. Dissolve the polymer in methanol, dilute it by a specific multiple, inject it into the sample cell of a graphite furnace atomic absorption spectrometer, record the absorbance, and obtain the metal ion content through the standard curve.

[0071] Line edge roughness: Dissolve the prepared acrylate block polymer resin in an organic solvent to prepare a photoresist. The organic solvent is propylene glycol monomethyl ether acetate (PGMEA), methanol, isopropanone or N-methylpyrrolidone. Different solvent types and small concentration changes have almost no effect on phase formation. Spin-coat the photoresist on a silicon wafer, heat-treat it at 200 °C for 30 min in a vacuum drying oven, and then quench it to room temperature to obtain a thin film of the photoresist (i.e., a thin film of the acrylate block polymer resin). Obtain an electron microscope image through atomic force microscope characterization. Measure the line width at the same height intervals in the vertical direction for any one pattern, take the average value as the target line width value, and three times the standard error of the measured line width value from the average line width is the line edge roughness.

[0072] Phase region repeat structure period length: Dissolve the prepared acrylate block polymer resin in an organic solvent to prepare a photoresist. The organic solvent is propylene glycol monomethyl ether acetate (PGMEA), methanol, isopropanone or N-methylpyrrolidone. Different solvent types and small concentration changes have almost no effect on phase formation. Spin-coat the photoresist on a silicon wafer, heat-treat it in a vacuum drying oven, and then quench it to room temperature to obtain a thin film of the photoresist (i.e., a thin film of the acrylate block polymer resin). Obtain an electron microscope image through atomic force microscope characterization, and measure the width of a group of repeating patterns, which is the phase region repeat structure period length.

[0073]

Example 1

[0074] The round-bottom reaction flask after washing and drying was purged with nitrogen three times. 70 g (0.3 mol) of 2-methyl-2-adamantyl methacrylate, 0.001 mol of α-chloroethylbenzene, 14.8 g of 1-allyl-3-methylimidazolium chloride, and 740 g of methanol were added to the round-bottom flask and stirred to mix. Under a nitrogen atmosphere, 40 g (0.4 mol) of methyl methacrylate was added. After stirring evenly, 0.001 mol of diphenyldihydrophenazine as a photocatalyst was added, and after mixing and stirring evenly, it was irradiated under a white light lamp, and the polymerization reaction was started. The reaction temperature was 25 °C. After reacting for 12 h, the monomer conversion rate was 95%; then 38 g (0.3 mol) of tert-butyl acrylate was added, and polymerization was continued under a white light lamp. The reaction temperature was 25 °C. After reacting for 12 h, the monomer conversion rate was 95%.

[0075] After the reaction was completed, acetone was used as the solvent and water was used as the precipitant. It was dissolved and precipitated three times, and the solid was placed in a vacuum oven for drying to obtain a white solid.

[0076] The acrylate resin prepared in this example was analyzed by GPC. The results were as follows: the number-average molecular weight was 11252, and the molecular weight distribution was 1.08. Determined by graphite furnace atomic absorption spectrometry, the metal ion contents (Na; Ag; Ca; K; Fe; Cu; Mg; Al; Cr; Sn; Zn; Mn; Cr; Co) were all less than 5 ppb.

[0077] 5 g of the above white solid was dissolved in 500 g of propylene glycol methyl ether acetate. After heat treatment, it was characterized by atomic force microscopy. The line edge roughness was 10 nm, and the phase region period length was 186 nm.

[0078]

Example 2

[0079] The round-bottom reaction flask after washing and drying was purged with nitrogen three times. 35.24 g (0.2 mol) of benzyl methacrylate, 0.05 mol of α-bromoethylbenzene, 604.75 g of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, and 120.95 g of acetone were added to the round-bottom reaction flask and stirred to mix. Under a nitrogen atmosphere, 34.44 g (0.4 mol) of methyl acrylate was added. After stirring evenly, 0.001 mol of 10-phenylphenothiazine as a photocatalyst was added, and after mixing and stirring evenly, it was irradiated under a white light lamp, and the polymerization reaction was started. The reaction temperature was 50 °C. After reacting for 8 h, the monomer conversion rate was 90%; then 51.27 g (0.4 mol) of n-butyl acrylate was added, and polymerization was continued under a white light lamp. The reaction temperature was 25 °C. After reacting for 16 h, the monomer conversion rate was 97%.

[0080] After the reaction was completed, acetone was used as the solvent and water was used as the precipitant. It was dissolved and precipitated three times, and the solid was placed in a vacuum oven for drying to obtain a white solid.

[0081] The acrylate resin prepared in this example was analyzed by GPC. The results showed that the number-average molecular weight was 5,895 and the molecular weight distribution was 1.10. Determined by graphite furnace atomic absorption spectrometry, the metal ion contents (Na; Ag; Ca; K; Fe; Cu; Mg; Al; Cr; Sn; Zn; Mn; Cr; Co) were all less than 5 ppb.

[0082] 5 g of the above white solid was dissolved in 400 g of propylene glycol methyl ether acetate. After heat treatment, it was characterized by atomic force microscopy. The line edge roughness was 4 nm and the phase region periodic length was 89 nm.

[0083]

Example 3

[0084] The round-bottom reaction flask after washing and drying was purged with nitrogen three times. 49.58 g (0.25 mol) of 2-ethylhexyl methacrylate, 0.02 mol of benzyl chloride, 117.66 g of 1-butyl-3-methylimidazolium chloride, and 705.96 g of ethyl acetate were added to the washed and dried round-bottom reaction flask and stirred and mixed. Under argon atmosphere, 43.05 g (0.5 mol) of methacrylic acid was added and stirred evenly. Then, 0.005 mol of dihydrophenazine as a photocatalyst was added, and after mixing and stirring evenly, it was irradiated under a white light lamp and the polymerization reaction was started. The reaction temperature was 25 °C. After 12 h of reaction, the monomer conversion rate was 98%; then 25.03 g (0.25 mol) of ethyl acrylate was added and the polymerization continued under the white light lamp. The reaction temperature was 50 °C. After 8 h of reaction, the monomer conversion rate was 99%.

[0085] After the reaction was completed, acetone was used as the solvent and water was used as the precipitant. It was dissolved and precipitated three times, and the solid was placed in a vacuum oven for drying to obtain a white solid.

[0086] The acrylate resin prepared in this example was analyzed by GPC. The results showed that the number-average molecular weight was 8,982 and the molecular weight distribution was 1.06. Determined by graphite furnace atomic absorption spectrometry, the metal ion contents (Na; Ag; Ca; K; Fe; Cu; Mg; Al; Cr; Sn; Zn; Mn; Cr; Co) were all less than 5 ppb.

[0087] 5 g of the above white solid was dissolved in 250 g of methanol. After heat treatment, it was characterized by atomic force microscopy. The line edge roughness was 8 nm and the phase region periodic length was 156 nm.

[0088]

Example 4

[0089] After replacing the nitrogen in the washed and dried round-bottom reaction flask three times, 111.16 g (0.5 mol) of isobornyl methacrylate, 0.001 mol of benzyl bromide, 171.74 g of 1-butyl-3-methylimidazolium tetrafluoroborate, and 858.7 g of methanol were added to the washed and dried round-bottom reaction flask and stirred and mixed. Under a nitrogen atmosphere, 35.55 g (0.25 mol) of n-butyl methacrylate was added and stirred evenly, then 0.01 mol of dicyanodihydro-phenazine as the photocatalyst was added, and after mixing and stirring evenly, it was irradiated under a white light lamp and the polymerization reaction was started. The reaction temperature was 40 °C. After 12 h of reaction, the monomer conversion rate was 98%; then 25.03 g (0.25 mol) of methyl methacrylate was added, and the polymerization continued under a white light lamp. The reaction temperature was 40 °C. After 12 h of reaction, the monomer conversion rate was 98%.

[0090] After the reaction was completed, acetone was used as the solvent and water was used as the precipitant, and the solution was dissolved and precipitated three times. The solid was placed in a vacuum oven for drying to obtain a white solid.

[0091] The acrylate resin prepared in this example was analyzed by GPC. The results were as follows: the number-average molecular weight was 12067, and the molecular weight distribution was 1.06. Determined by graphite furnace atomic absorption spectrometer, the metal ion contents (Na; Ag; Ca; K; Fe; Cu; Mg; Al; Cr; Sn; Zn; Mn; Cr; Co) were all less than 5 ppb.

[0092] 5 g of the above white solid was dissolved in 250 g of isopropanone. After heat treatment, it was characterized by atomic force microscopy. The line edge roughness was 8 nm, and the phase region period length was 190 nm.

[0093]

Example 5

[0094] After replacing the nitrogen in the washed and dried round-bottom reaction flask three times, 40.61 g (0.29 mol) of glycidyl methacrylate, 0.01 mol of ethyl α-bromopropionate, 232.26 g of 1-butyl-3-methylimidazolium hexafluorophosphate, and 464.52 g of acetone were added to the washed and dried round-bottom reaction flask and stirred and mixed. Under a nitrogen atmosphere, 57.21 g (0.57 mol) of methyl methacrylate was added and stirred evenly, then 0.002 mol of 2-(trifluoromethyl)dihydro-phenazine as the photocatalyst was added, and after mixing and stirring evenly, it was irradiated under a white light lamp and the polymerization reaction was started. The reaction temperature was 35 °C. After 16 h of reaction, the monomer conversion rate was 97%; then 18.31 g (0.14 mol) of tert-butyl acrylate was added, and the polymerization continued under a white light lamp. The reaction temperature was 35 °C. After 16 h of reaction, the monomer conversion rate was 98%.

[0095] After the reaction was completed, acetone was used as the solvent and water was used as the precipitant. The mixture was dissolved and precipitated three times. The solid was placed in a vacuum oven for drying to obtain a white solid.

[0096] The acrylate resin prepared in this example was analyzed by GPC. The results showed that the number-average molecular weight was 10,213 and the molecular weight distribution was 1.10. Determined by graphite furnace atomic absorption spectrometry, the metal ion contents (Na; Ag; Ca; K; Fe; Cu; Mg; Al; Cr; Sn; Zn; Mn; Cr; Co) were all less than 5 ppb.

[0097] 5 g of the above white solid was dissolved in 500 g of N-methylpyrrolidone. After heat treatment, it was characterized by atomic force microscopy. The line edge roughness was 7 nm and the phase region period length was 175 nm.

[0098]

Example 6

[0099] The round-bottom reaction flask after washing and drying was purged with nitrogen three times. 87.04 g (0.29 mol) of 1,1,5-trihydroperfluoropentyl acrylate, 0.03 mol of ethyl α-bromoisobutyrate, 348.24 g of 1-allyl-3-methylimidazolium chloride, and 522.36 g of methyl ethyl ketone were added to the round-bottom flask and stirred and mixed. Under a nitrogen atmosphere, 14.02 g (0.14 mol) of methyl methacrylate was added. After stirring evenly, 0.004 mol of diphenyldihydrophenazine as a photocatalyst was added, and the mixture was stirred evenly and irradiated under a white light lamp to start the polymerization reaction. The reaction temperature was 45 °C. After reacting for 12 h, the monomer conversion rate was 95%; then 73.06 g (0.57 mol) of tert-butyl acrylate was added and polymerization continued under a white light lamp. The reaction temperature was 45 °C. After reacting for 12 h, the monomer conversion rate was 99%.

[0100] After the reaction was completed, acetone was used as the solvent and water was used as the precipitant. The mixture was dissolved and precipitated three times. The solid was placed in a vacuum oven for drying to obtain a white solid.

[0101] The acrylate resin prepared in this example was analyzed by GPC. The results showed that the number-average molecular weight was 8,319 and the molecular weight distribution was 1.11. Determined by graphite furnace atomic absorption spectrometry, the metal ion contents (Na; Ag; Ca; K; Fe; Cu; Mg; Al; Cr; Sn; Zn; Mn; Cr; Co) were all less than 5 ppb.

[0102] 5 g of the above white solid was dissolved in 500 g of propylene glycol methyl ether acetate. After heat treatment, it was characterized by atomic force microscopy. The line edge roughness was 7 nm and the phase region period length was 138 nm.

[0103]

Example 7

[0104] The round-bottom reaction flask after washing and drying was purged with nitrogen three times. Then, 181.34 g (0.29 mol) of N-propyl perfluorooctylsulfonamidoethyl acrylate, 0.004 mol of α-chloroacetonitrile, 1025.4 g of 1-allyl-3-methylimidazolium chloride, and 512.78 g of methanol were added to the round-bottom flask and stirred to mix. Under a nitrogen atmosphere, 57.07 g (0.57 mol) of methyl methacrylate was added. After stirring evenly, 0.01 mol of perylene as a photocatalyst was added, and the mixture was stirred evenly and irradiated under a white light lamp to start the polymerization reaction. The reaction temperature was 50 °C. After 12 h of reaction, the monomer conversion rate was 95%. Then, 17.94 g (0.14 mol) of tert-butyl acrylate was added, and the polymerization continued under the white light lamp. The reaction temperature was 50 °C. After 12 h of reaction, the monomer conversion rate was 99%.

[0105] After the reaction was completed, acetone was used as the solvent and water as the precipitant. The mixture was dissolved and precipitated three times, and the solid was placed in a vacuum oven for drying to obtain a white solid.

[0106] The acrylate resin prepared in this example was analyzed by GPC. The results showed that the number-average molecular weight was 7089 and the molecular weight distribution was 1.12. Determined by graphite furnace atomic absorption spectrometry, the metal ion contents (Na; Ag; Ca; K; Fe; Cu; Mg; Al; Cr; Sn; Zn; Mn; Cr; Co) were all less than 5 ppb.

[0107] 5 g of the above white solid was dissolved in 500 g of propylene glycol methyl ether acetate. After heat treatment, it was characterized by atomic force microscopy. The line edge roughness was 5 nm and the phase region period length was 119 nm.

[0108]

Example 8

[0109] The round-bottom reaction flask after washing and drying was purged with nitrogen three times. Then, 93.73 g (0.4 mol) of 2-methyl-2-adamantyl methacrylate, 0.05 mol of chloroform, 66.01 g of 1-allyl-3-methylimidazolium chloride, and 825.15 g of methyl ethyl ketone were added to the round-bottom flask and stirred to mix. Under a nitrogen atmosphere, 20.02 g (0.2 mol) of methyl methacrylate was added. After stirring evenly, 0.008 mol of oxygen-doped anthracene as a photocatalyst was added, and the mixture was stirred evenly and irradiated under a white light lamp to start the polymerization reaction. The reaction temperature was 25 °C. After 12 h of reaction, the monomer conversion rate was 95%. Then, 51.28 (0.4 mol) of tert-butyl acrylate was added, and the polymerization continued under the white light lamp. The reaction temperature was 25 °C. After 12 h of reaction, the monomer conversion rate was 94%.

[0110] After the reaction was completed, acetone was used as the solvent and water as the precipitant. The mixture was dissolved and precipitated three times, and the solid was placed in a vacuum oven for drying to obtain a white solid.

[0111] The acrylate resin prepared in this example was analyzed by GPC. The results showed that the number-average molecular weight was 6,079 and the molecular weight distribution was 1.15. Determined by graphite furnace atomic absorption spectrometry, the metal ion contents (Na; Ag; Ca; K; Fe; Cu; Mg; Al; Cr; Sn; Zn; Mn; Cr; Co) were all less than 5 ppb.

[0112] 5 g of the above white solid was dissolved in 500 g of propylene glycol methyl ether acetate. After heat treatment, it was characterized by atomic force microscopy. The line edge roughness was 8 nm and the phase region period length was 96 nm.

[0113]

Example 9

[0114] The round-bottom reaction flask after washing and drying was purged with nitrogen three times. 93.73 g (0.4 mol) of 2-methyl-2-adamantyl methacrylate, 0.05 mol of carbon tetrachloride, 47.83 g of 1-allyl-3-methylimidazolium chloride, and 817.1 g of methanol were added to the round-bottom flask and stirred and mixed. Under a nitrogen atmosphere, 40.05 (0.4 mol) of methyl methacrylate was added. After stirring evenly, 0.01 mol of diphenyldihydrophenazine as a photocatalyst was added, and after mixing and stirring evenly, it was irradiated under a white light lamp, and the polymerization reaction was started. The reaction temperature was 25 °C. After reacting for 12 h, the monomer conversion rate was 95%; then 25.64 (0.2 mol) of tert-butyl acrylate was added, and the polymerization was continued under a white light lamp. The reaction temperature was 25 °C. After reacting for 12 h, the monomer conversion rate was 95%.

[0115] After the reaction was completed, acetone was used as the solvent and water was used as the precipitant. It was dissolved and precipitated three times, and the solid was placed in a vacuum oven for drying to obtain a white solid.

[0116] The acrylate resin prepared in this example was analyzed by GPC. The results showed that the number-average molecular weight was 5,879 and the molecular weight distribution was 1.17. Determined by graphite furnace atomic absorption spectrometry, the metal ion contents (Na; Ag; Ca; K; Fe; Cu; Mg; Al; Cr; Sn; Zn; Mn; Cr; Co) were all less than 5 ppb.

[0117] 5 g of the above white solid was dissolved in 500 g of propylene glycol methyl ether acetate. After heat treatment, it was characterized by atomic force microscopy. The line edge roughness was 10 nm and the phase region period length was 105 nm.

[0118]

Example 10

[0119] The round-bottom reaction flask after washing and drying was purged with nitrogen three times. 77.33 g (0.33 mol) of 2-methyl-2-adamantyl methacrylate, 0.05 mol of α-chloroethylbenzene, 30.74 g of 1-allyl-3-methylimidazolium chloride, and 768.45 g of methanol were added to the round-bottom flask and stirred to mix. Under a nitrogen atmosphere, 34.05 g (0.34 mol) of methyl methacrylate was added. After stirring evenly, 0.001 mol of diphenyldihydrophenazine, a photocatalyst, was added. After mixing and stirring evenly, it was irradiated under a white light lamp, and the polymerization reaction was started. The reaction temperature was 25 °C. After 12 h of reaction, the monomer conversion rate was 94%. Then 42.31 g (0.33 mol) of tert-butyl acrylate was added, and the polymerization was continued under a white light lamp. The reaction temperature was 25 °C. After 12 h of reaction, the monomer conversion rate was 96%.

[0120] After the reaction was completed, acetone was used as the solvent and water was used as the precipitant. It was dissolved and precipitated three times. The solid was placed in a vacuum oven for drying to obtain a white solid.

[0121] The acrylate resin prepared in this example was analyzed by GPC. The results were as follows: the number-average molecular weight was 6234, and the molecular weight distribution was 1.10. Determined by graphite furnace atomic absorption spectrometry, the metal ion contents (Na; Ag; Ca; K; Fe; Cu; Mg; Al; Cr; Sn; Zn; Mn; Cr; Co) were all less than 5 ppb.

[0122] 5 g of the above white solid was dissolved in 500 g of propylene glycol methyl ether acetate. After heat treatment, it was characterized by atomic force microscopy. The line edge roughness was 7 nm, and the phase region period length was 99 nm.

[0123]

Comparative Example 1

[0124] According to the preparation method described in Chinese invention patent CN112175133A (invention name: "Acrylic Resin and Its Preparation Method and Application"), atom transfer radical polymerization (ATRP) was used to prepare acrylate resin. The raw material ratios of the three acrylates were the same as those in Example 1. The specific preparation method was as follows:

[0125] 70 g (0.3 mol) of 2-methyl-2-adamantyl methacrylate, 40 g (0.4 mol) of methyl methacrylate, 38 g (0.3 mol) of tert-butyl acrylate, 3.6 g of copper bromide as the catalyst, 6 g of methyl-triamine as the reducing agent, 0.15 g of silver as the reducing agent, and 740 g of methanol were added to the washed and dried round-bottom reaction flask and stirred. After heating to 60 °C, 0.3 g of 2-bromoethyl isobutyrate, the initiator, was added, and the reaction was carried out for 12 h. After the reaction was completed, acetone was used as the solvent and water was used as the precipitant. It was dissolved and precipitated three times. The solid was placed in a vacuum oven for drying to obtain a white solid.

[0126] The acrylate resin prepared in this comparative example was analyzed by GPC. The results were as follows: the number-average molecular weight was 12,067, and the molecular weight distribution was 1.31. Determined by graphite furnace atomic absorption spectrometry, the contents of Cu ions and Ag ions were both greater than 100 ppb.

[0127]

Comparative Example 2

[0128] The raw material ratios of the 3 acrylates were the same as those in Example 1, and the specific preparation method was as follows:

[0129] 40 g of methyl methacrylate, 38 g of tert-butyl acrylate, 70 g of 2-methyl-2-adamantyl methacrylate, 0.01 mol of AIBN, and 740 g of methanol were put into a washed and dried round-bottom reaction flask and stirred and mixed at a temperature of 60 °C. After reacting for 12 h, acetone was used as the solvent and water was used as the precipitant, and the solution was dissolved and precipitated 3 times. The solid was placed in a vacuum oven for drying to obtain a white solid.

[0130] The acrylate resin prepared in this comparative example was analyzed by GPC. The results were as follows: the number-average molecular weight was 11,453, and the molecular weight distribution was 2.05. Determined by graphite furnace atomic absorption spectrometry, the contents of metal ions (Na; Ag; Ca; K; Fe; Cu; Mg; Al; Cr; Sn; Zn; Mn; Cr; Co) were all less than 50 ppb.

[0131]

Comparative Example 3

[0132] 40 g of methyl methacrylate, 38 g of tert-butyl acrylate, 70 g of 2-methyl-2-adamantyl methacrylate, 0.001 mol of α-chloroethylbenzene, and 740 g of methanol were put into a 1 L washed and dried round-bottom reaction flask and stirred and mixed. Under a nitrogen atmosphere, 0.001 mol of diphenyldihydrophenazine as a photocatalyst was added, and after mixing and stirring evenly, it was irradiated under a white light lamp, and the polymerization reaction was started. The reaction temperature was 25 °C. After reacting for 12 h, the monomer conversion rate was 65%.

[0133] After the reaction was completed, acetone was used as the solvent and water was used as the precipitant, and the solution was dissolved and precipitated 3 times. The solid was placed in a vacuum oven for drying to obtain a white solid.

[0134] The acrylate resin prepared in this example was analyzed by GPC. The results were as follows: the number-average molecular weight was 11,879, and the molecular weight distribution was 1.33. Determined by graphite furnace atomic absorption spectrometry, the contents of metal ions (Na; Ag; Ca; K; Fe; Cu; Mg; Al; Cr; Sn; Zn; Mn; Cr; Co) were all less than 5 ppb.

[0135] Dissolve 5 g of the above-mentioned white solid in 500 g of propylene glycol methyl ether acetate. After heat treatment, it was characterized by atomic force microscopy. The line edge roughness was 48 nm, and the phase region period length was 494 nm.

[0136] From the test results of Examples 1 to 10 and Comparative Examples 1 to 3, it can be seen that:

[0137] (1) For the acrylate resins obtained in Examples 1 to 10, the molecular weight distribution was narrow (PDI < 1.2), and the metal ion contents (Na; Ag; Ca; K; Fe; Cu; Mg; Al; Cr; Sn; Zn; Mn; Cr; Co) were all less than 5 ppb. After heat treatment, the pattern edge roughness was all less than 10 nm, and the phase region period length was less than 200 nm.

[0138] (2) Compared with Comparative Example 1, the metal ion content in the resin prepared in Example 1 was low. The results showed that the traditional ATRP polymerization method was prone to introducing metal impurities, and the metal impurities could be reduced or avoided by using organocatalytic photo-controlled ATRP.

[0139] (3) Compared with Comparative Example 2, the acrylate resins obtained in Examples 1 to 10 had a narrow molecular weight distribution (PDI < 1.2), indicating that the organocatalytic photo-controlled ATRP synthesis method could obtain resins with a narrow molecular weight distribution.

[0140] (4) Compared with Comparative Example 3, when the reaction time was 12 h, the monomer conversion rate was greater than 95%. This showed that by adding ionic liquid, when using a mixed solvent in Examples 1 to 10, the polymerization reaction rate of acrylate monomers was significantly accelerated, and the polymerization efficiency could be improved.

[0141] (5) Compared with Comparative Example 3, the resins prepared in Examples 1 - 10 could improve the line edge roughness and reduce the phase region period length after heat treatment.

[0142] In Examples 1 to 10, on the basis of the traditional atom transfer radical polymerization (ATRP) process, an organophotocatalyst was used to replace the transition metal catalyst, reducing the introduction of metal impurities in the resin preparation process, further improving the performance of the photoresist resin product, and the reaction conditions were mild, being easy for low-temperature polymerization, making the living polymerization process more controllable.

[0143] The acrylate block polymer resins prepared in Examples 1 to 10 for directed self-assembly had a molecular weight distribution < 1.2, improved the phase region period length and line edge roughness, and were more suitable as film-forming resins for photoresists.

Claims

1. An acrylate block polymer resin for directed self-assembly, having a number average molecular weight of 5000 to 20000, preferably 5000 to 13000; a molecular weight distribution < 1.30, preferably 1.0 to 1.2; the content of any key metal ion impurity in the acrylate block polymer resin is less than 5 ppb; the line edge roughness of the film of the acrylate block polymer resin < 10 nm, preferably 4 to 10 nm; the phase region repeating structure period length of the film of the acrylate block polymer resin < 200 nm, preferably 10 to 200 nm, more preferably 80 to 200 nm.

2. The acrylate block polymer resin according to claim 1, wherein: The acrylate resin contains three structural units derived from the following acrylic acid or acrylate monomers: acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, glycidyl methacrylate, 2-methyl-2-adamantyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 1,1,5-trihydroperfluoropentyl acrylate, N-propyl perfluorooctanesulfonamidoethyl acrylate.

3. A method for preparing the acrylate block polymer resin according to claim 1 or 2, comprising the following steps: (1) Mix acrylate or acrylate monomer I, an initiator, an ionic liquid and a solvent evenly to obtain a mixed solution A; (2) Under the protection of a protective gas, add acrylate or acrylate monomer II and a photocatalyst to the mixed solution A obtained in step (1), mix evenly and carry out a photocatalytic polymerization reaction A under light irradiation to obtain a mixed solution B; (3) Under the protection of a protective gas, add acrylate or acrylate monomer III to the mixed solution B obtained in step (2), carry out a photocatalytic polymerization reaction B under light irradiation, and post-treat the obtained product to obtain the acrylate block polymer resin.

4. The method for preparing the acrylate block polymer resin according to claim 3, wherein: In step (1), The initiator is at least one of an α-haloaromatic compound and an α-haloaliphatic compound; and / or, The solvent is at least one of a hydroxyl-containing solvent, an ester solvent, a ketone solvent, an ether solvent, and a polar group-containing cyclic solvent; and / or, The ionic liquid is at least one of 1-allyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.

5. The method for preparing the acrylate block polymer resin according to claim 4, wherein: The α-halo aromatic compound is at least one of α-chloroethylbenzene, α-bromoethylbenzene, benzyl chloride, and benzyl bromide; and / or, The α-halo aliphatic compound is at least one of ethyl α-chloropropionate, ethyl α-bromopropionate, ethyl α-bromoisobutyrate, α-chloroacetonitrile, α-chloropropionitrile, carbon tetrachloride, and chloroform; and / or, The solvent is at least one of methanol, ethanol, isopropanol, methyl formate, ethyl acetate, methyl acetate, n-propyl acetate, acetone, methyl ethyl ketone, and cyclohexanone.

6. The method for preparing an acrylate block polymer resin according to claim 3, wherein: In steps (1) to (3), The acrylic acid or acrylate monomer I, the acrylic acid or acrylate monomer II, and the acrylic acid or acrylate monomer III are each selected from acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, glycidyl methacrylate, 2-methyl-2-adamantyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 1,1,5-trihydroperfluoropentyl acrylate, and N-propyl perfluorooctanesulfonamidoethyl acrylate; and / or, The photocatalyst is at least one of diphenyldihydrophenazine, 10-phenylphenothiazine, dihydrophenazine, 2-trifluoromethyldihydrophenazine, dicyanodihydrophenazine, perylene, and oxygen-doped anthracene; and / or, The protective gas is at least one of nitrogen and inert gas, and the inert gas is preferably argon; and / or, The light source is visible light or ultraviolet light.

7. The method for preparing an acrylate block polymer resin according to claim 3, wherein: The molar ratio of the acrylic acid or acrylate monomer I, the acrylic acid or acrylate monomer II, and the acrylic acid or acrylate monomer III is 1:(0.1 - 10):(0.1 - 10), preferably 1:(0.5 - 2):(0.5 - 2); and / or, The molar ratio of the initiator to the total amount of the acrylic acid or acrylate monomers is (0.01 - 10):100, preferably (0.1 - 5):100; and / or, The mass ratio of the ionic liquid to the total amount of the acrylic acid or acrylate monomers is (0.01 - 100):1, preferably (0.1 - 50):1, more preferably (0.1 - 6):1; and / or, The mass ratio of the solvent to the total amount of the acrylic acid or acrylate monomers is (0.1 - 50):1, preferably (1 - 25):1, more preferably (1 - 6):1; and / or, The molar ratio of the photocatalyst to the total amount of the acrylic acid or acrylate monomers is (0.01 - 10):100, preferably (0.1 - 1):

100.

8. The method for preparing an acrylate block polymer resin according to claim 3, wherein: In step (2), the reaction conditions for the photocatalytic polymerization reaction A are: The reaction temperature is 0 to 100 °C, preferably 25 to 50 °C; and / or, The reaction time is 1 to 24 hours, preferably 8 to 16 hours; and / or, In step (3), the reaction conditions of the photocatalytic polymerization reaction B are: The reaction temperature is 0 to 100 °C, preferably 25 to 50 °C; and / or, The reaction time is 1 to 24 hours, preferably 8 to 16 hours; and / or, The post-treatment includes precipitating the reaction product.

9. An acrylate block polymer resin obtained by the preparation method according to any one of claims 3 to 8.

10. Use of an acrylate block polymer resin according to any one of claims 1 to 2, 9 in a photoresist, preferably, The line edge roughness of the film of the photoresist < 10 nm, preferably 4 to 10 nm; the period length of the phase region repeating structure of the film of the photoresist < 200 nm, preferably 10 to 200 nm, more preferably 80 to 200 nm.