Resin for KrF photoresist and preparation method thereof

Abstract

The invention discloses resin for a KrF photoresist and a preparation method of the resin. The preparation method of the resin for the KrF photoresist comprises the following steps: in a continuous flow reactor, in the presence of an initiator, carrying out polymerization reaction on monomers in parts by weight in a solvent to obtain a polymer; 50-65 parts of a monomer A, 2-15 parts of a monomer B and 25-45 parts of a monomer C are included. The molecular weight distribution of the resin obtained by adopting the preparation method is relatively narrow, the thermal performance requirement of the KrF photoresist can be met, and the KrF photoresist prepared from the resin is clear and straight in pattern circuit after being developed, relatively good in resolution ratio and corrosion resistance and good in application prospect. # imgabs0 #

Description

Technical Field

[0001] The invention relates to a resin for KrF photoresist and a preparation method thereof. Background Art

[0002] Over the past half century, microelectronics technology has become one of the most promising technologies in this century with its extremely fast development speed and strong vitality. The upgrading of the microelectronics industry is inseparable from the support of photoresist and photolithography technology. Photoresist, also known as photoresist, has significant changes in solubility and adhesion before and after photolithography, which transfers circuit patterns to substrates to prepare microelectronic circuits.

[0003] As the line width of integrated circuits gradually enters the deep submicron level (less than 0.35μm). Against this background, 248nm photoresist based on KrF lithography technology has gradually developed. The light source wavelength of KrF photoresist is 248nm, which is a deep ultraviolet photoresist and is mainly used for the production of 8-inch wafers. Polyparahydroxystyrene (PHS) is often used as a film-forming resin in this type of photoresist, but polyparahydroxystyrene (PHS) has a single structure and cannot be effectively regulated, making it difficult to meet the various performance requirements of photoresists, such as wide molecular weight distribution, poor resolution, heat resistance or corrosion resistance.

[0004] Therefore, there is an urgent need in the art to develop a resin for KrF photoresist that can achieve good narrow molecular weight distribution, better resolution and corrosion resistance. Summary of the invention

[0005] The present invention provides a KrF photoresist resin and a preparation method thereof which are completely different from the prior art. The resin molecular weight distribution obtained by the preparation method of the present invention is relatively narrow, and the KrF photoresist prepared by the resin has clear and straight pattern lines after development, and has good resolution and corrosion resistance.

[0006] The present invention solves the above technical problems through the following technical solutions.

[0007] The present invention provides a method for preparing a KrF photoresist resin, which comprises the following steps: in a continuous flow reactor, in the presence of an initiator, polymerizing the following monomers in parts by weight in a solvent to obtain a resin polymer;

[0008] 50-65 parts of monomer A, 2-15 parts of monomer B, 25-45 parts of monomer C;

[0009]

[0010] The polymerization reaction temperature is 40-70°C.

[0011] The polymerization reaction conditions and operations are the conditions and operations of this type of reaction in the art. The present invention particularly prefers the following operations and conditions:

[0012] In the present invention, the continuous flow reactor is preferably a microreactor.

[0013] In the present invention, the type and amount of the initiator are the types and amounts of initiators commonly used in the polymerization reaction in the art. The initiator can be an azo initiator and / or a peroxide initiator, and further preferably 1, 2, 3 or 4 of benzoyl peroxide, azobisisobutyronitrile, azobisisoheptanenitrile and dimethyl azobisisobutyrate, and more preferably azobisisobutyronitrile. The mass ratio of the initiator to the total weight of the monomer can be (0.01-0.05):1, preferably (0.02-0.04):1, for example 0.03:1.

[0014] In the present invention, the weight portion of the monomer A is preferably 55-60 parts, preferably 55 parts.

[0015] In the present invention, the weight portion of the monomer B is preferably 5-10 parts, preferably 5 parts.

[0016] In the present invention, the weight portion of the monomer C is preferably 30-40 parts, preferably 40 parts.

[0017] In the present invention, the mass ratio of the monomer A to the monomer B is preferably (5.5-11):1, more preferably 5.5:1.

[0018] In the present invention, the mass ratio of the monomer C to the monomer B is preferably (3-8):1, more preferably 8:1.

[0019] In the present invention, the residence time of the polymerization reaction is the common time of such reaction in continuous flow reaction, preferably 10-25 min, more preferably 10-18 min, most preferably 15-18 min.

[0020] In the present invention, the type and amount of the solvent are the type and amount of the initiator commonly used in the polymerization reaction in the art. The solvent is preferably an alcohol solvent and / or an ether solvent, and more preferably ethanol. The mass ratio of the mass of the solvent to the total mass of the monomer is preferably (2-5):1, for example 3:1.

[0021] In the present invention, the monomer and the initiator may be injected simultaneously or separately to carry out the continuous flow reaction, for example, injected simultaneously. When the monomer and the initiator are injected simultaneously, the injection method may be as follows:

[0022] The monomer, the initiator and the solvent are formed into a single material and then injected to carry out the continuous flow reaction;

[0023] Alternatively, the monomer and the solvent form material A, the initiator and the solvent form material B, and material A and material B are injected simultaneously.

[0024] The reacted material can be transported by various methods, such as pumping. The pumping device can be conventional in the art, such as a metering pump. In some embodiments, the flow rate of the material is preferably 10 ml / min-40 ml / min, and can also be 10 ml / min-20 ml / min.

[0025] The polymerization reaction temperature is preferably 50-70°C, more preferably 50-60°C.

[0026] In a preferred embodiment, the mass ratio of the monomer A to the monomer B is preferably (5.5-11):1; the initiator is azobisisobutyronitrile; the residence time of the polymerization reaction is 10-18 min; and the temperature of the polymerization reaction is 50-60°C.

[0027] In a preferred embodiment, the preparation method of the resin polymer is any one of the following preparation methods (1) to (13):

[0028] (1): 60 parts of monomer A, 10 parts of monomer B and 30 parts of monomer C;

[0029] The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 50°C; the residence time of the polymerization is 10 minutes;

[0030] The monomer, the initiator and the solvent are injected into a single material and then subjected to the continuous flow reaction; the flow rate of the material is 10 ml / min;

[0031] (2): 55 parts of monomer A, 10 parts of monomer B and 35 parts of monomer C;

[0032] The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 50°C; the residence time of the polymerization is 10 minutes;

[0033] The monomer, the initiator and the solvent are injected into a single material and then subjected to the continuous flow reaction; the flow rate of the material is 10 ml / min;

[0034] (3): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C;

[0035] The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 50°C; the residence time of the polymerization is 10 minutes;

[0036] The monomer, the initiator and the solvent are injected into a single material and then subjected to the continuous flow reaction; the flow rate of the material is 10 ml / min;

[0037] (4): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C;

[0038] The initiator is benzoyl peroxide; the solvent is ethanol; the polymerization temperature is 50°C; the residence time of the polymerization is 10 minutes;

[0039] The monomer, the initiator and the solvent are injected into a single material and then subjected to the continuous flow reaction; the flow rate of the material is 10 ml / min;

[0040] (5): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C;

[0041] The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 40°C; the residence time of the polymerization is 10 minutes;

[0042] The monomer, the initiator and the solvent are injected into a single material and then subjected to the continuous flow reaction; the flow rate of the material is 10 ml / min;

[0043] (6): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C;

[0044] The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 60°C; the residence time of the polymerization is 10 minutes;

[0045] The monomer, the initiator and the solvent are injected into a single material and then subjected to the continuous flow reaction; the flow rate of the material is 10 ml / min;

[0046] (7): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C;

[0047] The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 70°C; the residence time of the polymerization is 10 minutes;

[0048] The monomer, the initiator and the solvent are injected into a single material and then subjected to the continuous flow reaction; the flow rate of the material is 10 ml / min;

[0049] (8): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C;

[0050] The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 60°C; the residence time of the polymerization is 10 minutes;

[0051] The monomer, the initiator and the solvent are injected into a single material and then subjected to the continuous flow reaction; the flow rate of the material is 15 ml / min;

[0052] (9): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C;

[0053] The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 60°C; the residence time of the polymerization is 10 minutes;

[0054] The monomer, the initiator and the solvent are injected into a single material to perform the continuous flow reaction; the flow rate of the material is 20 ml / min;

[0055] (10): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C;

[0056] The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 60°C; the residence time of the polymerization is 10 minutes;

[0057] The monomer, the initiator and the solvent are injected into a single material to perform the continuous flow reaction; the flow rate of the material is 40 ml / min;

[0058] (11): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C;

[0059] The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 60°C; the residence time of the polymerization is 14 minutes;

[0060] The monomer, the initiator and the solvent are injected into a single material and then subjected to the continuous flow reaction; the flow rate of the material is 15 ml / min;

[0061] (12): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C;

[0062] The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 60°C; the residence time of the polymerization is 18 minutes;

[0063] The monomer, the initiator and the solvent are injected into a single material and then subjected to the continuous flow reaction; the flow rate of the material is 15 ml / min;

[0064] (13): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C;

[0065] The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 60°C; the residence time of the polymerization is 22 minutes;

[0066] The monomer, the initiator and the solvent form a single material and then are injected to carry out the continuous flow reaction; the flow rate of the material is 15 ml / min.

[0067] After the polymerization reaction is completed, the post-treatment step preferably includes solid precipitation, slurrying, filtering and drying.

[0068] The precipitated solid is preferably prepared by adding the reaction solution dropwise into water at room temperature, wherein the mass ratio of water to the solvent is (3-6):1, for example 4:1.

[0069] The pulping (purification) is preferably performed using a mixed solvent of water and ethanol in a mass ratio of (3-6):1 (eg 4:1).

[0070] The present invention also provides a KrF photoresist resin prepared by the above-mentioned preparation method of the KrF photoresist resin.

[0071] The present invention also provides a KrF photoresist, which comprises the following components in parts by weight: 15-30 parts of the above-mentioned resin polymer, a photoacid generator and a solvent.

[0072] The weight proportion of the resin polymer may also be 15-20 parts.

[0073] The weight proportion of the photoacid generator may be a conventional amount, preferably 0.75-1.5 parts, for example 1 part.

[0074] Among them, the photoacid generator can use onium salt series, such as iodonium salt or sulfonium salt, and more preferably

[0075]

[0076] The weight percentage of the solvent may be the conventional weight percentage in the art, preferably 60-85 parts, more preferably 68-85 parts, for example 79 parts.

[0077] Wherein, the solvent can be a conventional solvent in the art, preferably 1, 2 or 3 of ketone solvents, ester solvents and ether solvents, such as ketone solvents or ester solvents. When the solvent is a ketone solvent, the ketone solvent can be cyclohexanone. The ester solvent can be ethyl acetate and / or propylene glycol monomethyl ether acetate. The ether solvent can be ethylene glycol monomethyl ether and / or dipropylene glycol monomethyl ether.

[0078] In the present invention, the KrF photoresist comprises any combination of the following components:

[0079] Combination 1: 15-30 parts of the resin polymer prepared by the above-mentioned method for preparing the resin polymer tree, 0.75-1.5 parts of the photoacid generator and 68-85 parts of a solvent;

[0080] Combination 2: 15-30 parts of the resin polymer prepared by the above-mentioned method for preparing the resin polymer tree, a photoacid generator and a solvent;

[0081] The photoacid generator is

[0082] The solvent is one, two or three of cyclohexanone, ethyl acetate or propylene glycol methyl ether acetate.

[0083] Combination 3: 15-30 parts of the resin polymer prepared by the above-mentioned method for preparing the resin polymer tree, 0.75-1.5 parts of the photoacid generator and 68-85 parts of a solvent;

[0084] The photoacid generator is

[0085] The solvent is one, two or three of cyclohexanone, ethyl acetate or propylene glycol methyl ether acetate.

[0086] The KrF photoresist is composed of the following components in parts by weight: 15-30 parts of the resin polymer prepared by the preparation method of the resin polymer tree, 0.75-1.5 parts of the photoacid generator and 68-85 parts of the solvent.

[0087] Based on the common knowledge in this field, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present invention.

[0088] The reagents and raw materials used in the present invention are all commercially available, or can be obtained by those skilled in the art according to conventional methods in the art using conventional technical means.

[0089] The beneficial effects of the present invention are: the resin prepared by the preparation method of the present invention can be obtained with high yield and has a narrow molecular weight distribution. The resin prepared by the method is used to prepare KrF photoresist, which can meet the requirements of the thermal performance of the photoresist. After development, the pattern circuit is clear and straight, and the resolution and corrosion resistance are both good. DETAILED DESCRIPTION

[0090] The present invention is further described below by way of examples, but the present invention is not limited to the scope of the examples. The experimental methods in the following examples without specifying specific conditions are carried out according to conventional methods and conditions, or selected according to the product specifications.

[0091] The following examples do not limit the specific operating temperature, and are all carried out at room temperature.

[0092] Microreactor: LTMR-X2, Guizhou Microchemical Technology.

[0093] Monomer A: Monomer B: Monomer C:

[0094] Resin preparation

[0095] Example 1

[0096] Monomer A (60 g), monomer B (10 g), monomer C (30 g) and azobisisobutyronitrile (3 g) were dissolved in ethanol (300 g) to prepare a liquid material, which was used as a reaction liquid to wait for feeding.

[0097] Use the reaction solvent ethanol to fully rinse the reaction pipe at a flow rate of 5 ml / min for 30 minutes, then blow nitrogen through the reaction pipe for 30 minutes to fully dry the pipe. Control the temperature heater to 50°C, adjust the flow rate of the pump to 5 ml / min, then blow nitrogen through the reaction pipe for 30 minutes to fully dry the pipe. Adjust the flow rate of the regulating pump to 10 ml / min, pass the reaction solution into the microreactor at a flow rate of 10 ml / min, carry out polymerization reaction at 50°C for 10 minutes, and collect the obtained reaction solution.

[0098] The obtained reaction solution was cooled to room temperature within 1 hour (to avoid too long cooling time and continuous reaction of residual monomers), and the reaction solution was slowly added dropwise to 1200 g of water (to precipitate the polymer), and stirring was continued for 20 minutes; then filtered and the solid was collected; the obtained solid was slurried in a mixed solvent of water and ethanol with a weight ratio of 4:1 (to remove residual organic matter on the surface of the precipitate and purify) for 30 minutes, filtered and washed the filter cake, the solid was collected and placed in a vacuum drying oven at 60°C to dry until the moisture content was constant, and 85 g of resin polymer P1 was obtained.

[0099] The product was tested by GPC, with Mw=10672 and PDI=1.52.

[0100] Example 2

[0101] The monomer A (60 g) and the monomer C (30 g) in Example 1 were replaced by the monomer A (55 g) and the monomer C (35 g), and the other conditions and operations were the same as those in Example 1, to obtain 80 g of the resin polymer P2.

[0102] The product was tested by GPC, with Mw=10320 and PDI=1.51.

[0103] Example 3

[0104] The monomer B (10 g) and monomer C (35 g) in Example 2 were replaced by monomer B (5 g) and monomer C (40 g), and the other conditions and operations were the same as those in Example 2, to obtain 83 g of resin polymer P3.

[0105] The product was tested by GPC, with Mw=10672 and PDI=1.52.

[0106] Example 4

[0107] The initiator azobisisobutyronitrile in Example 3 was replaced by benzoyl peroxide, and the other conditions and operations were the same as those in Example 3, to obtain 78 g of resin polymer P4.

[0108] The product was tested by GPC, with Mw=15739 and PDI=1.62.

[0109] Embodiment 5-7

[0110] The reaction temperature in Example 3 was replaced by the temperature in Table 1, and the other conditions and operations were the same as in Example 3.

[0111] Table 1

[0112]

[0113] The preparation method of the present invention can obtain a resin polymer with a low PDI in a high yield, and especially at 50-60° C., the PDI of the obtained resin polymer is better.

[0114] Embodiment 8-10

[0115] The flow rate in Example 6 was replaced by the amount in Table 2, and the other conditions and operations were the same as in Example 6.

[0116] Table 2

[0117]

[0118] The preparation method of the present invention can obtain a relatively small PDI resin polymer with a high yield, and especially at a flow rate of 15-20 ml / min, the PDI and yield of the obtained resin polymer are relatively good.

[0119] Examples 11-13

[0120] The residence time of 10 min in Example 8 was replaced by the residence time in Table 3, and the other conditions and operations were the same as in Example 8.

[0121] Table 3

[0122]

[0123] The preparation methods of the present invention can obtain smaller PDI resin polymers with high yield.

[0124] Example 14-26 Preparation of Photoresist

[0125] The resin polymer P1-13 obtained in Examples 1-13, the photoacid generator and the solvent are dissolved in the solvent according to the material and ligand ratio in Table 4, and then filtered with a 0.2 um filter membrane to prepare a photoresist composition.

[0126] Table 4 Material types and quantities

[0127]

[0128]

[0129] Photoacid generator:

[0130]

[0131] Solvent: propylene glycol methyl ether acetate (PGMEA), cyclohexanone or ethyl acetate.

[0132] Test case performance test:

[0133] In the HMDS chamber of the coating machine, gaseous HMDS is deposited on the surface of the wafer substrate, and the photoresists G1-G13 are spin-coated on the HMDS pre-treated silicon wafer at a speed of 2500 rpm to form a film, baked on a 120°C hot plate for 90 seconds, cooled to room temperature in a cold plate chamber, and then photolithography (exposure) is performed on the photolithography machine. The wavelength of the photolithography machine is 248nm and the photolithography intensity is 16mJ / cm 2After photolithography, bake on a 110°C hot plate for 90 seconds, and finally develop in a 2.38% TMAH developer for 60 seconds, quickly take it out and place it in pure water for rinsing, then dry it and inspect the photolithography results under an electron microscope. The specific test process is as follows, and the performance results are shown in Table 5.

[0134] The photolithography machine model is 248nm KrFstepper:Nikon S204B,0.55NA,0.33Sigma (NA:numerical aperture; Sigma: aperture).

[0135] 1. Lithography accuracy test:

[0136] The photolithography patterns are observed and measured using a scanning electron microscope (CDSEM) to obtain the minimum line width that can be separated by the photolithography patterns; the narrower the line width, the higher the photolithography accuracy.

[0137] 2. Shape evaluation

[0138] From the results of cross-sectional SEM of the wafer after development, the substrate could be discerned and the pattern had good linearity (rectangular) and was evaluated as A, while the substrate could not be discerned but the pattern had poor linearity (protruding bottom) and was evaluated as B.

[0139] 3. Evaluation of the rectangularity of the cross-sectional shape of the pattern

[0140] The cross-sectional shape of the pattern was observed by SEM, and the one with the side surface cut almost vertically was designated as A, the one with a substantially conical shape was designated as B, and the one with the side surface being wavy was designated as C.

[0141] 4. Etching resistance test

[0142] At room temperature, each silicon wafer coated with the film was placed in a LAM REASECH etcher and etched for 30 seconds under the conditions of 40CF4 / 240Ar / 60O2. The etching rate was calculated from the film thickness before and after etching and the etching time. The smaller the etching rate, the better the etching resistance.

[0143] Table 5

[0144]

[0145]

Claims

1. A method for preparing a KrF photoresist resin, characterized in that: The method comprises the following steps: in a continuous flow reactor, in the presence of an initiator, polymerizing the following monomers in parts by weight in a solvent to obtain a resin polymer; 50-65 parts of monomer A, 2-15 parts of monomer B, 25-45 parts of monomer C; The polymerization reaction temperature is 40-70°C.

2. The method for preparing a KrF photoresist resin according to claim 1, wherein: The continuous flow reactor is a microreactor.

3. The method for preparing a KrF photoresist resin according to claim 1 or 2, characterized in that: It meets one or more of the following conditions: (1) The weight portion of the monomer A is preferably 55-60 parts; (2) The weight portion of the monomer B is preferably 5-10 parts; (3) The weight portion of the monomer C is preferably 30-40 parts; (4) The residence time of the polymerization reaction is 10-25 min; (5) the monomer and the initiator are injected simultaneously or separately and successively to carry out the continuous flow reaction; and (6) The polymerization reaction temperature is 50-60°C.

4. The method for preparing a KrF photoresist resin according to claim 3, wherein: It meets one or more of the following conditions: (1) The weight portion of monomer A is 55 parts; (2) The weight portion of the monomer B is 5 parts; (3) The weight portion of the monomer C is 40 parts; (4) The residence time of the polymerization reaction is 10-18 min; (5) the monomer and the initiator are injected simultaneously and the continuous flow reaction is carried out; and (6) The polymerization reaction temperature is 50-60°C.

5. The method for preparing a KrF photoresist resin according to claim 4, characterized in that: The residence time of the polymerization reaction is 15-18min; And / or, the monomer, the initiator and the solvent are injected into a single material and the continuous flow reaction is carried out; the flow rate of the material is 10ml / min-40ml / min, and can also be 10ml / min-30ml / min.

6. The method for preparing a KrF photoresist resin according to claim 1 or 2, characterized in that: It meets one or more of the following conditions: (1) The initiator is an azo initiator and / or a peroxide initiator; (2) The mass ratio of the initiator to the total weight of the monomer is (0.01-0.05):1; (3) The solvent is an alcohol solvent and / or an ether solvent; and (4) The mass of the solvent and the total mass of the monomers are (2-5):

1.

7. The method for preparing a KrF photoresist resin according to claim 6, wherein: It meets one or more of the following conditions: (1) The initiator is one, two, three or four of oxybenzoyl, azobisisobutyronitrile, azobisisoheptanenitrile and dimethyl azobisisobutyrate, preferably azobisisobutyronitrile; (2) The mass ratio of the initiator to the total weight of the monomer is (0.02-0.04):1, for example 0.03:1; (3) The solvent is ethanol; and (4) The mass of the solvent and the total mass of the monomers are 3:

1.

8. The method for preparing a KrF photoresist resin according to claim 1 or 2, characterized in that: The mass ratio of the monomer A to the monomer B is preferably (5.5-11):1; the initiator is azobisisobutyronitrile; the residence time of the polymerization reaction is 10-18 min; and the temperature of the polymerization reaction is 50-60°C.

9. The method for preparing a KrF photoresist resin according to claim 1 or 2, characterized in that: The preparation method of the resin polymer is any one of the following preparation methods (1) to (13): (1): 60 parts of monomer A, 10 parts of monomer B and 30 parts of monomer C; The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 50°C; the residence time of the polymerization is 10 minutes; The monomer, the initiator and the solvent are injected into a single material and then subjected to the continuous flow reaction; the flow rate of the material is 10 ml / min; (2): 55 parts of monomer A, 10 parts of monomer B and 35 parts of monomer C; The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 50°C; the residence time of the polymerization is 10 minutes; The monomer, the initiator and the solvent are injected into a single material and then subjected to the continuous flow reaction; the flow rate of the material is 10 ml / min; (3): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C; The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 50°C; the residence time of the polymerization is 10 minutes; The monomer, the initiator and the solvent are injected into a single material and then subjected to the continuous flow reaction; the flow rate of the material is 10 ml / min; (4): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C; The initiator is benzoyl peroxide; the solvent is ethanol; the polymerization temperature is 50°C; the residence time of the polymerization is 10 minutes; The monomer, the initiator and the solvent are injected into a single material and then subjected to the continuous flow reaction; the flow rate of the material is 10 ml / min; (5): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C; The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 40°C; the residence time of the polymerization is 10 minutes; The monomer, the initiator and the solvent are injected into a single material and then subjected to the continuous flow reaction; the flow rate of the material is 10 ml / min; (6): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C; The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 60°C; the residence time of the polymerization is 10 minutes; The monomer, the initiator and the solvent are injected into a single material and then subjected to the continuous flow reaction; the flow rate of the material is 10 ml / min; (7): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C; The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 70°C; the residence time of the polymerization is 10 minutes; The monomer, the initiator and the solvent are injected into a single material and then subjected to the continuous flow reaction; the flow rate of the material is 10 ml / min; (8): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C; The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 60°C; the residence time of the polymerization is 10 minutes; The monomer, the initiator and the solvent are injected into a single material and then subjected to the continuous flow reaction; the flow rate of the material is 15 ml / min; (9): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C; The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 60°C; the residence time of the polymerization is 10 minutes; The monomer, the initiator and the solvent are injected into a single material to perform the continuous flow reaction; the flow rate of the material is 20 ml / min; (10): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C; The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 60°C; the residence time of the polymerization is 10 minutes; The monomer, the initiator and the solvent are injected into a single material to perform the continuous flow reaction; the flow rate of the material is 40 ml / min; (11): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C; The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 60°C; the residence time of the polymerization is 14 minutes; The monomer, the initiator and the solvent are injected into a single material and then subjected to the continuous flow reaction; the flow rate of the material is 15 ml / min; (12): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C; The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 60°C; the residence time of the polymerization is 18 minutes; The monomer, the initiator and the solvent are injected into a single material to perform the continuous flow reaction; the flow rate of the material is 15 ml / min; and (13): 55 parts of monomer A, 5 parts of monomer B and 40 parts of monomer C; The initiator is azobisisobutyronitrile; the solvent is ethanol; the polymerization temperature is 60°C; the residence time of the polymerization is 22 minutes; The monomer, the initiator and the solvent form a single material and then are injected to carry out the continuous flow reaction; the flow rate of the material is 15 ml / min.

10. A KrF photoresist resin prepared by the method for preparing a KrF photoresist resin according to any one of claims 1 to 9.

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