High performance photoresist composition

Abstract

The invention discloses a photoresist composition with high performance. The photoresist composition is prepared from the following raw materials: a polymer, a photoacid generator, a solvent and a quenching agent. The photoresist composition disclosed by the invention has good ductility, crack resistance and the like.

Description

Technical Field

[0001] This invention relates to a high-performance photoresist composition. Background Technology

[0002] In the field of photoresist, resin, as a core functional component, directly determines key indicators such as the photoresist's ductility, developability, and film stability. The resin's preparation process is one of the core factors affecting its performance. Different polymerization processes result in significant differences in the resin's molecular chain structure, degree of polymerization distribution, and purity, leading to marked differences in the final application effect of the photoresist. Therefore, optimizing the resin polymerization process is of great significance for improving photoresist performance.

[0003] Currently, resin polymerization preparation processes are mainly divided into two categories: batch polymerization and continuous polymerization. Among them, batch polymerization is prone to uneven polymerization degree and molecular weight distribution among different batches of resin due to large fluctuations in reaction system parameters, making it difficult to meet the high requirements of photoresist for resin performance stability. On the other hand, continuous polymerization can effectively reduce product performance fluctuations and achieve uniform resin performance by precisely controlling and maintaining stable reaction temperature, pressure, monomer ratio and other conditions, and has become an important development direction for the preparation of high-quality photoresist resins.

[0004] However, existing continuous polymerization technologies still have technical shortcomings that urgently need to be addressed. For example, the continuous polymerization method disclosed by Nippon Shokubai Co., Ltd. in patent JP2009084549A still suffers from a wide degree of polymerization distribution, making it difficult to meet the stringent requirements of high-precision photoresists for resin polymerization uniformity. In addition, this type of method is prone to incomplete removal of reaction impurities, affecting resin purity and leading to pattern defects in the photoresist during development, thus limiting its application in advanced process photoresists.

[0005] Therefore, there is an urgent need in the field to develop a new continuous polymerization process to solve problems such as uneven degree of polymerization in existing technologies, so as to prepare polymers with uniform degree of polymerization and then obtain high-performance photoresists for research and development or application. Summary of the Invention

[0006] This invention overcomes the shortcomings of existing photoresist resins, such as wide molecular weight distribution or high residual monomer content. Therefore, it provides a polymer for photoresist resin and its applications. The polymer for photoresist resin of this invention has the advantages of high uniformity and low impurities.

[0007] This invention provides a polymer prepared by a method comprising the steps of: transferring a reaction solution to the working surface of a continuously circulating conveyor belt for polymerization reaction to obtain a polymer product;

[0008] The working surface of the conveyor belt is provided with heating zones 1, 2 and 3 in sequence along the forward direction of the conveyor belt. The temperature of heating zone 1 is 50-65℃, the temperature of heating zone 2 is 75-85℃, and the temperature of heating zone 3 is 90-105℃.

[0009] The reaction solution includes monomers, initiators, and organic solvents;

[0010] The monomers mentioned are one or two of the following monomers: monomer I, monomer II, monomer III, and monomer IV (e.g., "monomer I and monomer II", "monomer I and monomer III", or "monomer I and monomer IV"):

[0011] ;

[0012] Where R1 is C 1-4 Alkyl or 3-6 cyclic alkyl groups;

[0013] R2 is -C 1-4 Alkyl-OC 1-4 Alkyl or -C 1-4 alkyl-OH;

[0014] R3, R4, and R5 are independently C 1-4 alkyl;

[0015] The percentages of the molar amounts of monomer I, monomer II, monomer III, and monomer IV relative to the total molar amount of monomers are as follows: 50% < monomer I ≤ 100%, 0 ≤ monomer II < 50%, 0 ≤ monomer II < 50%, and 0 ≤ monomer IV < 50%.

[0016] In this invention, the weight-average molecular weight of the polymer is preferably 8000-23000.

[0017] In this invention, the dispersion index of the polymer is preferably 1.4-2.1.

[0018] In this invention, monomer I is preferably... (methyl methacrylate) (methacrylate), (methoxymethyl methacrylate) (methoxyethyl methacrylate) (2-hydroxyethyl methacrylate), (cyclohexyl methacrylate) and (isoborneol methacrylate) contains one, two, or three of the following; more preferably, " and (For example, the molar ratio of the two is 1:0.42), and (For example, the molar ratio of the two is 1:0.65), , and (For example, the molar ratio of the three components is 1:0.84:0.22) and (For example, a molar ratio of 1:0.7) or " , and (For example, the molar ratio of the three is 1: 1:0.71).

[0019] Wherein, monomer I preferably contains at least .

[0020] Wherein, monomer II is preferably (4-Isopropenylphenol).

[0021] Wherein, monomer III is preferably (Diethyl maleate).

[0022] In this invention, preferably, the percentage of the molar amount of monomer I to the total molar amount of monomers is: 70% ≤ monomer I ≤ 100%, for example 77%, 74%, 81%, 100%.

[0023] In this invention, preferably, the percentage of the molar amount of monomer II to the total molar amount of monomer is: 20 ≤ monomer II ≤ 30%, for example 23%.

[0024] In this invention, preferably, the percentage of the molar amount of monomer III to the total molar amount of monomers is: 20 ≤ monomer II ≤ 30%, for example 26%.

[0025] In this invention, preferably, the percentage of the molar amount of monomer IV to the total molar amount of monomer is: 15 ≤ monomer IV < 25%, for example 19%.

[0026] In some embodiments of the present invention, when the monomers are monomer I and monomer II, the percentage of the molar amount of monomer I to the total molar amount of monomers is: 75% ≤ monomer I ≤ 80%; the percentage of the molar amount of monomer II to the total molar amount of monomers is: 20% ≤ monomer II ≤ 25%.

[0027] In some embodiments of the present invention, when the monomers are monomer I and monomer III, the percentage of the molar amount of monomer I in the total molar amount of the monomers is: 70% ≤ monomer I ≤ 75%; the percentage of the molar amount of monomer II in the total molar amount of the monomers is: 25% ≤ monomer III ≤ 30%.

[0028] In some embodiments of the present invention, when the monomers are monomer I and monomer III, the percentage of the molar amount of monomer I in the total molar amount of the monomers is: 72% ≤ monomer I ≤ 82%; the percentage of the molar amount of monomer II in the total molar amount of the monomers is: 18% ≤ monomer III ≤ 25%.

[0029] In this invention, the monomers are preferably from any one of the following groups:

[0030] Group 1: Cyclohexyl methacrylate, 4-isopropenylphenol and isobornyl methacrylate;

[0031] Group 2: Cyclohexyl methacrylate, diethyl maleate, and 2-hydroxyethyl methacrylate;

[0032] Group 3: Cyclohexyl methacrylate, methyl methacrylate, and 2-hydroxyethyl methacrylate;

[0033] Group 4: Cyclohexyl methacrylate, methoxyethyl methacrylate, and N-phenylmaleimide;

[0034] Group 5: tert-butyl methacrylate, methoxymethyl methacrylate, and methyl methacrylate.

[0035] In this invention, the molar ratios of the monomers in groups 1 to 6 are as follows:

[0036] Group 1: 1:0.42:0.25;

[0037] Group 2: 1:1.17:0.65;

[0038] Group 3: 1:0.84:0.22;

[0039] Group 4: 1:0.7:0.39;

[0040] Group 5: 1:1:0.71.

[0041] In this invention, the conditions and operations described are those conventional in continuous conveyor belt heating polymerization methods. The present invention particularly prefers the following conditions and operations:

[0042] In this invention, preferably, the working surface of the conveyor belt is coated with an anti-stick resin coating.

[0043] In this invention, preferably, the temperature of the first heating zone is 55-65°C.

[0044] In this invention, preferably, the temperature of the second heating zone is 75-85°C.

[0045] In this invention, the working surface of the conveyor belt is sequentially set with heating zones 1, 2 and 3 at temperatures of 55-65℃, 75-85℃ and 90-105℃ along the forward direction of the conveyor belt.

[0046] In this invention, preferably, the working surface of the conveyor belt is provided with heating zones 1, 2, and 3 sequentially along the forward direction of the conveyor belt, and the temperatures are set as follows:

[0047] Group 1: 60℃, 80℃, 90℃;

[0048] Group 2: 65℃, 85℃, 100℃;

[0049] Group 3: 50℃, 70℃, 90℃;

[0050] Group 4: 60℃, 85℃, 105℃;

[0051] Group 5: 55℃, 75℃, 90℃.

[0052] In this invention, preferably, the heating time of the first heating zone is 2-3 minutes.

[0053] In this invention, preferably, the heating time of the second heating zone is 4-8 min, more preferably 4-7 min.

[0054] In this invention, preferably, the heating time of the third heating zone is 1-3 minutes.

[0055] In this invention, preferably, the total time for the first, second and third heating zones is 7-14 min; more preferably, it is 9-12 min.

[0056] In this invention, preferably, the time for which the first, second, and third heating zones are sequentially set along the forward direction of the conveyor belt is as follows:

[0057] Group 1: 2 min, 5 min, 2 min;

[0058] Group 2: 2 min, 7.6 min, 2.4 min;

[0059] Group 3: 2 min, 4 min, 1 min;

[0060] Group 4: 2 min, 4 min, 1 min;

[0061] Group 5: 2 min, 5 min, 2 min.

[0062] In this invention, preferably, the working surface of the conveyor belt is provided with heating zones 1, 2 and 3 at temperatures of 55-65℃, 75-85℃ and 90-105℃ respectively along the forward direction of the conveyor belt, and the heating time of the heating zones is 2-3 min, 4-7 min and 1-3 min respectively.

[0063] In this invention, preferably, the conveyor belt speed is 0.20-0.45 m / min, more preferably 0.25-0.3 m / min.

[0064] In this invention, the initiator is preferably an azo initiator.

[0065] In this invention, the initiator is preferably one, two, or three of AIBN, VAZO-67, and VAZO-52.

[0066] In this invention, the amount of the initiator is preferably 0.6wt%-5wt%, more preferably 0.6wt%~1.2wt%, and the percentage is the ratio of the mass of the initiator to the total mass of the monomer.

[0067] In this invention, the organic solvent can be any known solvent commonly used for monomer polymerization, especially for the polymerization of acrylic monomers to prepare resins. The solvent is preferably one or more of aromatic solvents (e.g., toluene or benzene), ether solvents (e.g., tetrahydrofuran (THF), diethyl ether, or dioxane), methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), and γ-butyrolactone, such as propylene glycol monomethyl ether acetate and / or γ-butyrolactone.

[0068] In this invention, the solid content of the reaction solution is preferably 40wt%~60wt%, more preferably 45wt%~60wt%.

[0069] In this invention, preferably, the reaction solution is applied to the working surface of the conveyor belt using a slot coating method. The reaction solution preferably forms a coating film on the working surface of the conveyor belt with a thickness of 100-300 μm, more preferably 150-200 μm, and most preferably 160-200 μm, for example, 180 μm or 170 μm.

[0070] In a preferred embodiment of the present invention, the working surface of the conveyor belt is sequentially set with heating zones 1, 2 and 3 at temperatures of 55-65°C, 75-85°C and 90-105°C along the forward direction of the conveyor belt, and the heating time of the heating zones is 2-3 min, 4-7 min and 1-3 min respectively.

[0071] The monomers mentioned above are monomer I, "monomer I and monomer I", "monomer I and monomer III", or "monomer I and monomer IV".

[0072] The initiator is one, two, or three of AIBN, VAZO-67, and VAZO-52.

[0073] The present invention also provides a photoresist composition prepared from the following raw materials, said raw materials including: the above-mentioned polymer, photoacidifier, solvent and quencher.

[0074] In this invention, the types and contents of the solvent, photoacid generator, and quencher are all conventional types and contents in the art.

[0075] In this invention, the content of the polymer, by weight, is preferably 15-25 parts, more preferably 17-20 parts, for example 18 parts.

[0076] Photoacidogens

[0077] In some embodiments of the photoresist composition, such as the phenylthionium salt of the photoacidifying agent.

[0078] The cation of the phenylthionium salt can be... or .

[0079] The anion of the phenylthionium salt can be a borate anion, preferably [B(C6H5)4]. - Or [B(C6F4H)4] - .

[0080] The photoacid-generating agent is preferably PAG1 and / or PAG2;

[0081] .

[0082] The content of the photoacid-generating agent, by weight, is preferably 0.3-0.7 parts, more preferably 0.4-0.6 parts, for example 0.5 parts.

[0083] In some embodiments of the photoresist composition, the solvent may be a conventional organic solvent in the art, such as ethyl lactate.

[0084] The solvent content, in parts by weight, is preferably 75-85 parts, more preferably 79-83 parts, for example 81.5 parts.

[0085] In some embodiments of the photoresist composition, the quencher is a quencher conventionally used in the art for adjusting the diffusion rate of materials such as generated acids, preferably triethanolamine.

[0086] The content of the quenching agent, in parts by weight, is preferably 0.02-0.07 parts, more preferably 0.04-0.05 parts, for example 0.05 parts.

[0087] In some embodiments of the photoresist composition, the photoresist composition may also contain other components, which are components that are conventionally added to photoresists in the art, such as leveling agents, adhesion promoters, crosslinking agents, etc.

[0088] In some embodiments of the photoresist composition, the photoresist composition is prepared from the following raw materials in parts by weight: 15-25 parts of the above-mentioned polymer, 0.3-0.7 parts of photoacidifier, 75-85 parts of solvent and 0.02-0.07 parts of quencher.

[0089] In some embodiments of the photoresist composition, the photoresist composition is prepared from the following raw materials in parts by weight: 17-20 parts of the above-mentioned polymer, 0.4-0.6 parts of photoacidifying agent, 79-83 parts of ethyl lactate and 0.04-0.05 parts of triethanolamine;

[0090] The photoacid-generating agent is PAG1 and / or PAG2.

[0091] In some embodiments of the photoresist composition, the photoresist composition is prepared from the following raw materials, which consist of the polymer described above, the photoacidifier described above, the solvent described above, and the quencher described above.

[0092] The present invention also provides a method for forming a photolithographic pattern, the method comprising the following steps:

[0093] Step 1: Coat the above photoresist composition onto the substrate surface to form a photoresist composition layer;

[0094] Step 2: Bake the photoresist composition layer;

[0095] Step 3: Cool the baked photoresist composition layer;

[0096] Step 4: Copy the pattern on the photomask onto the baked photoresist composition layer by exposure;

[0097] Step 5: Bake the exposed photoresist composition layer;

[0098] Step 6: Apply developer to the baked photoresist composition layer for development to obtain the photolithographic pattern.

[0099] All reagents used in this invention are commercially available.

[0100] The continuous conveyor belt device used in this invention is a coating-belt heating device commonly used in the art, and is equipped with a nitrogen protective cover and a precision belt speed control module, as detailed in [link to details]. Figure 1 .

[0101] The beneficial effects of this invention are as follows: This invention uses a conveyor belt heating polymerization method and sets a zoned temperature control for the polymerization reaction, resulting in a lower monomer residue in the obtained resin polymer; the PDI of the resin is below 2.0, which greatly improves the polymerization uniformity of the resin; the conversion rate can reach more than 90%; and the purity, high yield and uniformity of the photoresist resin are greatly improved.

[0102] The polymer of the present invention can be used to prepare photoresist compositions with excellent photolithography properties and crack resistance, resulting in clear photolithographic patterns. Attached Figure Description

[0103] Figure 1 The coating-belt heating device used in the embodiments of the present invention is described in which "1" is the working surface of the conveyor belt, "2" is the slit coater, "3" is the first, second and third heating reaction zones, and "4" is the cooling section of the conveyor belt. Detailed Implementation

[0104] The embodiments described in this invention are merely some embodiments of this application, and not all embodiments. As for the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0105] The abbreviations used in this invention and their corresponding names are as follows:

[0106] Chinese name Chemical name AIBN Azobisisobutyronitrile 2,2'-Azobis(2-methylpropionitrile) VAZO-67 Azobis(2,4-dimethylpentanonitrile) 2,2'-Azobis(2,4-dimethylpentanonitrile) VAZO-52 Azobis(2-methylbutyronitrile) 2,2'-Azobis(2-methylbutyronitrile) PGMEA Propylene glycol methyl ether acetate / γ-BL γ-Butyrolactone /

[0107] Example 1: Preparation of Polymers

[0108] Cyclohexyl methacrylate, 4-isopropenylphenol, and isobornyl methacrylate were mixed in a mass ratio of 60:20:20 (total mass of each monomer is 1 kg, with molar amounts of 0.356 mol, 0.149 mol, and 0.089 mol respectively). PGMEA solvent was added until the solid content was 60 wt%, and then AIBN was added as 0.8 wt% of the total initiator. The mixture was then mixed evenly to form a reaction solution. The reaction solution was then conveyed to the working surface of the conveyor belt of a belt heating device (the working surface was coated with polytetrafluoroethylene). A slit coater was used to apply the reaction solution to the working surface of the stainless steel belt to form a 180 μm thick liquid film. The conveyor belt speed was set to 0.35 m / min. Under a nitrogen atmosphere, the reaction liquid was sequentially heated through three independent temperature zones 1, 2, and 3 at 60°C, 80°C, and 90°C, respectively. The reaction time for each heating zone was 2 min, 5 min, and 2 min, respectively, for a total reaction time of 9 minutes, resulting in a polymerization product. After cooling, the polymerization product was peeled off, yielding 980 g of polymerization product.

[0109] Example 2: Preparation of Polymers

[0110] Cyclohexyl methacrylate, dimethyl maleate, and 2-hydroxyethyl methacrylate were mixed in a mass ratio of 40:40:20 (total mass of each monomer is 1 kg, molar amounts are 0.237 mol, 0.277 mol, and 0.153 mol respectively) to prepare a reaction solution. A mixed solvent of γ-butyrolactone and PGMEA (volume ratio 1:1) was added to adjust the solid content to 45 wt%. 1.2 wt% of VAZO-67 initiator was added and mixed thoroughly to form the reaction solution. The reaction solution was then conveyed to the working surface of a belt-heated device (the working surface was coated with polytetrafluoroethylene). A slit coater was used to apply the reaction solution to the stainless steel belt surface to form a 200 μm thick liquid film. The belt speed was set to 0.25 m / min. The reaction solution was then passed sequentially through three independent heating zones: 65℃, 85℃, and 100℃, with reaction times of 2 min, 7.6 min, and 2.4 min respectively. The polymerization product was obtained after 12 minutes of cooling. After cooling, the polymerization product was peeled off to obtain 950g of polymerization product.

[0111] Example 3: Preparation of Polymers

[0112] Cyclohexyl methacrylate, methyl methacrylate, and 2-hydroxyethyl methacrylate were mixed in a ratio of 60:30:10 (total mass of each monomer is 1 kg, with molar amounts of 0.356 mol, 0.299 mol, and 0.076 mol respectively) and dissolved in PGMEA, with a solid content of 40 wt%. 1.0 wt% of the total AIBN was added as an initiator to form a reaction solution. The reaction solution was then conveyed to the working surface of a belt-heated device (the working surface was coated with polytetrafluoroethylene). A slit coater was used to coat the reaction solution onto the stainless steel belt surface to form a 150 μm coating, with the belt speed set at 0.45 m / min. The reaction solution was then sequentially heated to polymerization in three independent temperature zones 1, 2, and 3 at 50℃, 70℃, and 90℃, with reaction times of 2 min, 4 min, and 1 min respectively, for a total reaction time of 7 minutes to obtain the polymerization product. After cooling, the polymerization product was peeled off, yielding 970 g of the polymerized product.

[0113] Example 4: Preparation of Polymers

[0114] Cyclohexyl methacrylate, methoxyethyl methacrylate, and N-phenylmaleimide were mixed in a ratio of 50:30:20 (total mass of monomers: 1 kg, molar amounts: 0.297 mol, 0.208 mol, and 0.115 mol, respectively). PGMEA solvent and γ-BL were added and mixed, resulting in a solid content of 55%. Then, 0.7 wt% of VAZO-52 initiator was added to form a reaction solution. The reaction solution was then conveyed to the working surface of a belt-heated device (coated with polytetrafluoroethylene). A slit coater was used to apply PTFE onto the stainless steel belt surface to form a 170 μm thick liquid film. The belt speed was set to 0.26 m / min. The reaction solution was sequentially passed through temperature zones 1, 2, and 3, set to 60℃, 85℃, and 105℃ for polymerization. The reaction times for each heating zone were 2 min, 7.6 min, and 2.4 min, respectively. The polymerization reaction lasted 12 minutes, yielding the polymer product. After cooling, the polymer product was peeled off, yielding 920 g of polymer product.

[0115] Example 5: Preparation of Polymers

[0116] A mixed monomer solution of tert-butyl methacrylate, methaneoxymethyl methacrylate, and methyl methacrylate was prepared in a mass ratio of 40:40:20 (total mass of each monomer is 1 kg, with molar amounts of 0.281 mol, 0.307 mol, and 0.199 mol respectively). This mixed monomer solution was dissolved in PGMEA to achieve a solid content of 48 wt%. Then, 0.6 wt% of the total AIBN was added as an initiator to form a reaction solution. The reaction solution was then conveyed to the working surface of a belt-heated device (the working surface was coated with polytetrafluoroethylene). A slit coater was used to apply the reaction solution to the stainless steel belt working surface to form a 160 μm thick coating. The reaction solution was then sequentially heated and polymerized through three temperature zones (55℃, 75℃, and 90℃) at a belt speed of 0.30 km / h. The reaction speed was m / min, and the reaction times for each heating were 2 min, 5 min, and 2 min respectively. After 9 minutes of reaction, the polymer product was obtained. After cooling, the polymer product was peeled off to obtain 930g of polymer product.

[0117] Example 6 Preparation of photoresist composition

[0118] At room temperature, the raw materials in Table 1 were added sequentially to a 1L three-necked flask and stirred thoroughly to dissolve them completely. The solution was then filtered through a 0.02-micron filter to obtain the photoresist composition.

[0119] Photoacidinogens:

[0120] , .

[0121] Quenching agent

[0122] Triethanolamine .

[0123] Table 1

[0124]

[0125] Comparative Example 1

[0126] Using the same formulation and dosage as in Example 2, but modified to a batch polymerization method, the reaction solution was placed in a glass reactor and reacted at a constant temperature of 85°C for 6 hours. The reaction solution was then concentrated and vacuum dried to obtain 920g of polymerization product.

[0127] Comparative Example 2

[0128] Except for setting the heating zone to be undivided and the uniform heating zone temperature to 80°C, all other conditions were the same as in Example 3, resulting in 800g of polymer product.

[0129] Comparative Example 3

[0130] The working surface of the conveyor belt of the belt heating device was not coated with polytetrafluoroethylene. The reaction was carried out directly on the steel surface of the conveyor belt of the belt heating device. All other conditions were the same as in Example 1, and 350g of polymer product was obtained.

[0131] Comparative Example 4

[0132] The polymer in Example 7 was replaced with the polymer in Comparative Example 1, and the photoresist performance was tested.

[0133] Comparative Example 5

[0134] The polymer in Example 8 was replaced with the polymer in Comparative Example 2, and the photoresist performance was tested.

[0135] Effect Test 1:

[0136] 1. Determination of weight-average molecular weight (Mn) and dispersion index (PDI)

[0137] The weight-average molecular weight (Mn) and dispersion index of the products in Examples 1-5 and Comparative Examples 1-3 were tested by gel permeation chromatography. The specific results are shown in Table 2.

[0138] 2. Determination of residual product content:

[0139] Quantitative detection was performed using high performance liquid chromatography (HPLC). The labeling procedure was as follows: Weigh 0.1000 g of resin sample, add 5.00 mL of acetonitrile solution, mix well, and sonicate for 10 min to ensure complete dissolution. Filter (using a 0.45 µm PTFE membrane) to obtain the test solution.

[0140] The analytical conditions are as follows: the chromatographic column used is C10. 18 Reversed-phase column (250 mm × 4.6 mm, 5 µm); mobile phase: acetonitrile / water = 70 / 30 (volume ratio); flow rate: 1.0 mL / min; column temperature: 30 °C; detector: ultraviolet detector (UV), detection wavelength: 210 nm; injection volume: 10 µL.

[0141] A series of standard solutions ranging from 1 to 500 ppm were prepared using monomer standards to establish an external standard calibration curve with a correlation coefficient R² of ≥0.999. The peak area of ​​the target monomer in the sample was determined under the same conditions, and its content was calculated using the calibration curve.

[0142] The residual content in the products of Examples 1-5 and Comparative Examples 1-3 was tested using the above method. The specific results are shown in Table 2.

[0143] Table 2

[0144]

[0145] Note: Conversion rate = (Mass of polymer obtained / Total mass of monomers) * 100%

[0146] As shown in the table above, the batch reactor polymerization (Comparative Example 1) resulted in a resin with a wide molecular weight distribution (PDI of 2.8) and uneven polymerization; residual monomer content was >1.5%, and the product was slightly yellow, failing to meet the requirements for photoresist. The continuous polymerization reaction without preheating and termination temperatures (Comparative Example 2) resulted in a resin with a wide molecular weight distribution (PDI of 3.0) and uneven polymerization. Directly applying the reaction solution to the steel surface of the conveyor belt caused the polymerization product to adhere heavily to the steel surface, interrupting the transmission and resulting in a low conversion rate.

[0147] The inventors of this invention have creatively discovered that by employing continuous band polymerization and setting zoned temperature control, the conversion rate of monomers, the purity of the product, and the molecular weight distribution are significantly improved. This invention provides a novel method for large-scale production of photoresists that reduces costs and increases efficiency.

[0148] Effect Test 2:

[0149] In the HMDS chamber of a spin coater, gaseous HMDS is deposited onto the surface of a wafer substrate. Then, the photoresists from Examples 6-10 and Comparative Examples 4-5 are spin-coated onto the HMDS-pretreated silicon wafer, spinning at 1000–3000 rpm to form a uniform film. The film is then baked on a hot plate at 120°C for 90 seconds, cooled to room temperature in a cold plate chamber, and then exposed on an exposure machine at a wavelength of 248 nm and an exposure intensity of 10–50 mJ / cm². 2 .

[0150] After exposure, the sample was baked on a hot plate at 110°C for 90 seconds, then developed in 2.38% TMAH developer for 60 seconds, rinsed with pure water, and then dried. The photolithography results were then examined under an electron microscope.

[0151] The lithography machine model is 248nm KrFstepper: Nikon S204B, 0.55NA, 0.33Sigma (NA: numerical aperture; Sigma: aperture).

[0152] 1. Crack resistance

[0153] The crack resistance of the photoresist film surface was observed using a SEM device (device name "S8840"; manufactured by Hitachi Corporation).

[0154] 2. Shape Evaluation

[0155] Based on the results of cross-sectional SEM of the developed wafer, those that can be resolved to the substrate and have good pattern straightness (rectangular pattern) are rated A, while those that cannot be resolved to the substrate but have poor pattern straightness (protruding bottom) are rated B.

[0156] 3. Evaluation of the rectangularity of the cross-sectional shape of the pattern

[0157] By observing the cross-sectional shape of the pattern using SEM, we define A as the pattern with almost vertically cut sides, B as the pattern that will become roughly conical, C as the pattern with wavy sides, and D as the pattern with wavy sides.

[0158] The test results are as follows:

[0159] Table 3

[0160] Photoresist composition Coating properties Film thickness (μm) Crack resistance shape Rectangularity of the cross-sectional shape of the pattern Example 6 good 3.2 No cracks A A Example 7 good 3.2 No cracks A A Example 8 good 3.2 No cracks B B Example 9 good 3.2 No cracks A A Example 10 good 3.2 No cracks A B Comparative Example 4 good 3.2 minor cracks A B Comparative Example 5 Uneven 3.2 minor cracks B C

[0161] The above results indicate that the resin obtained by heating and polymerization using a continuous conveyor belt exhibits good photolithographic properties, crack resistance, and makes it easier to obtain clear patterns.

Claims

1. A photoresist composition, characterized in that, It is made from the following raw materials, which include: polymer, photoacidin, solvent and quencher; The polymer is prepared by the following method, which includes the following steps: transferring the reaction solution to the working surface of a continuously circulating conveyor belt for polymerization reaction to obtain the polymer product; The working surface of the conveyor belt is provided with heating zones 1, 2 and 3 in sequence along the forward direction of the conveyor belt. The temperature of heating zone 1 is 50-65℃, the temperature of heating zone 2 is 75-85℃, and the temperature of heating zone 3 is 90-105℃. The reaction solution includes monomers, initiators, and organic solvents; The monomer is one or two of the following monomers: monomer I, monomer II, monomer III, and monomer IV: ； Where R1 is C 1-4 Alkyl or 3-6 cyclic alkyl groups; R2 is -C 1-4 Alkyl-OC 1-4 Alkyl or -C 1-4 alkyl-OH; R3, R4, and R5 are independently C 1-4 alkyl; The percentages of the molar amounts of monomer I, monomer II, monomer III, and monomer IV relative to the total molar amount of monomers are as follows: 50% < monomer I ≤ 100%, 0 ≤ monomer II < 50%, 0 ≤ monomer II < 50%, and 0 ≤ monomer IV < 50%.

2. The photoresist composition according to claim 1, characterized in that, The polymer has a weight-average molecular weight of 8,000-23,000 and a dispersion index of 1.4-2.

1.

3. The photoresist composition according to claim 1, characterized in that, It satisfies one or more of the following conditions: (1) The monomer I is , , , , , and One, two, or three types; (2) The monomer II is ; (3) The monomer III is ; (4) The percentage of the molar amount of monomer I to the total molar amount of monomers is: 70% ≤ monomer I ≤ 100%; (5) The percentage of the molar amount of monomer II to the total molar amount of monomer is: 20 ≤ monomer II ≤ 30%; (6) The percentage of the molar amount of monomer III to the total molar amount of monomer is: 20 ≤ monomer II ≤ 30%; And, (7) the percentage of the molar amount of monomer IV to the total molar amount of monomer is: 15≤monomer IV<25%.

4. The photoresist composition according to claim 1, characterized in that, The monomer I is a combination of any of the following monomers: and The molar ratio of the two is 1:0.42; and The molar ratio of the two is 1:0.65; , and The molar ratio of the three components is 1:0.84:0.22; and The molar ratio of the two is 1:0.7; or, , and The molar ratio of the three components is 1:1:0.

71.

5. The photoresist composition according to claim 1, characterized in that, The monomers mentioned are from any of the following groups: Group 1: Cyclohexyl methacrylate, 4-isopropenylphenol and isobornyl methacrylate; Group 2: Cyclohexyl methacrylate, diethyl maleate, and 2-hydroxyethyl methacrylate; Group 3: Cyclohexyl methacrylate, methyl methacrylate, and 2-hydroxyethyl methacrylate; Group 4: Cyclohexyl methacrylate, methoxyethyl methacrylate, and N-phenylmaleimide; Group 5: tert-butyl methacrylate, methoxymethyl methacrylate, and methyl methacrylate; Preferably, the molar ratios of the monomers in groups 1 to 6 are as follows: Group 1: 1:0.42:0.25; Group 2: 1:1.17:0.65; Group 3: 1:0.84:0.22; Group 4: 1:0.7:0.39; Group 5: 1:1:0.

71.

6. The photoresist composition according to claim 1, characterized in that, It satisfies one or more of the following conditions: (1) The content of the polymer, by weight, is 15-25 parts, preferably 17-20 parts; (2) The photoacid-generating agent is PAG1 and / or PAG2; ； (3) The content of the photo-induced acid-generating agent, by weight, is 0.3-0.7 parts, preferably 0.4-0.6 parts; (4) The solvent is ethyl lactate; (5) The content of the solvent, by weight, is 75-85 parts, preferably 79-83 parts; (6) The quenching agent is triethanolamine; The content of the quenching agent mentioned in (7) is 0.02-0.07 parts by weight, preferably 0.04-0.05 parts.

7. The photoresist composition according to any one of claims 1-6, characterized in that, It satisfies one or more of the following conditions: (1) The working surface of the conveyor belt is coated with an anti-stick resin coating; (2) The temperature of the first heating zone is 55-65℃; (3) The temperature of the second heating zone is 75-85℃; (4) The heating time of the first heating zone is 2-3 min; (5) The heating time of the second heating zone is 4-8 min; (6) The heating time of the third heating zone is 1-3 min; (7) The belt speed of the conveyor belt is 0.20-0.45 m / min; (8) The initiator is one, two or three of AIBN, VAZO-67 and VAZO-52; (9) The amount of the initiator is 0.6wt%-5wt%, and the percentage is the ratio of the mass of the initiator to the total mass of the monomer; (10) The organic solvent is one or more of the following: aromatic solvents, ether solvents, methyl ethyl ketone, propylene glycol monomethyl ether acetate and γ-butyrolactone; (11) The solid content of the reaction solution is 40wt%~60wt%; The reaction solution described in (12) forms a coating with a thickness of 100-300 μm on the working surface of the conveyor belt.

8. The photoresist composition according to any one of claims 1-6, characterized in that, The working surface of the conveyor belt is sequentially set with heating zones 1, 2, and 3 along the forward direction of the conveyor belt, and the temperatures are set as follows: Group 1: 60℃, 80℃, 90℃; Group 2: 65℃, 85℃, 100℃; Group 3: 50℃, 70℃, 90℃; Group 4: 60℃, 85℃, 105℃; Group 5: 55℃, 75℃, 90℃; The heating time for the first, second, and third heating zones, sequentially set along the forward direction of the conveyor belt, is as follows: Group 1: 2 min, 5 min, 2 min; Group 2: 2 min, 7.6 min, 2.4 min; Group 3: 2 min, 4 min, 1 min; Group 4: 2 min, 4 min, 1 min; Group 5: 2 min, 5 min, 2 min.

9. The photoresist composition according to claim 1, characterized in that, The photoresist composition is prepared from the following raw materials in parts by weight: 17-20 parts of the above-mentioned polymer, 0.4-0.6 parts of photoacidifying agent, 79-83 parts of ethyl lactate and 0.04-0.05 parts of triethanolamine; The photoacid-generating agent is PAG1 and / or PAG2; 。 10. The photoresist composition according to claim 1, characterized in that, The photoresist composition is prepared from the following raw materials in parts by weight: 15-25 parts of the polymer, 0.3-0.7 parts of the photoacidifying agent, 75-85 parts of the solvent, and 0.02-0.07 parts of the quencher.

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