Reaction kettle for settling and purifying deep ultraviolet photoresist resin

Abstract

The utility model discloses a reaction kettle for settling and purifying deep ultraviolet (DUV) photoresist resin, which belongs to the technical field of photoresist and comprises a first jacket kettle, a second jacket kettle and a third jacket kettle, the first jacket kettle, the second jacket kettle and the third jacket kettle are sequentially connected in series. Most of DUV photoresist resin in the prior art is a solid discharged material, a large number of residual solvents and residual unreacted substances exist, the subsequent photoresist performance, stability and batch-to-batch stability are seriously influenced, and the production efficiency is reduced due to the fact that the DUV photoresist resin is difficult to filter. According to the DUV photoresist resin amplification device, the problems that in the DUV photoresist resin amplification process, a large amount of residual solvents and residual unreacted substances exist, the environmental pollution amount is large due to synthesis exhaust, and filtering is difficult can be effectively solved.

Description

Technical Field

[0001] This utility model relates to the field of photoresist technology, and more specifically to a reaction vessel for the sedimentation and purification of deep ultraviolet photoresist resin. Background Technology

[0002] Photoresist is one of the eight core materials in the semiconductor field, contributing up to 12% to chip manufacturing costs, second only to large silicon wafers and electronic gases, firmly ranking third among integrated circuit manufacturing materials. Resin, as a key component of photoresist, not only provides mechanical and chemical support but also plays a crucial role in the processing of fine patterns at the micron and even nanometer scales.

[0003] In the paper "Advanced Photolithography Theory and Applications for Very Large Scale Integrated Circuits," authors Wei Ya-yi and others described that the design concept of ArF photoresist is similar to that of KrF photoresist. Its main components include polymer resin, photoacid generator, and a base quencher to neutralize the photoacid. Currently, the resins used for 193nm photoresist mainly fall into the following categories: methyl methacrylate (MMA), cycloolefin-maleic anhydride (COMA), cycloolefin, and vinyl ether-maleic anhydride (VEMA). Existing ArF photoresist resin processes and equipment are unstable in terms of resin stability and monomer residue, which may affect the performance of the photoresist.

[0004] Patent CN 117608164A describes a polymerization reaction using acetoxystyrene, styrene, tert-butyl methacrylate, initiator AIBN, and solvent tetrahydrofuran. After cooling, tetrahydrofuran is added, followed by the slow dropwise addition of a mixed solution of triethylamine and water to the reaction system. The reaction is deprotected, and the mixed solution is dropped into 5 L of deionized water for sedimentation, resulting in a white solid compound. The filter cake is then collected through filter paper and transferred to a vacuum drying oven for drying. After complete drying, the solid compound is dissolved in tetrahydrofuran to obtain a 20% crude resin solution. This solution is then precipitated into deionized water to obtain a white solid. This process is repeated twice, and the collected solid compounds are transferred to a 45°C vacuum oven for drying for 48 hours to finally obtain the desired polymer resin.

[0005] Patent JP 2006309186A describes a reaction involving the polymerization of acetoxystyrene, tert-butyl acrylate, styrene, initiator AIBN, and molecular weight regulator tert-dodecyl mercaptan in propylene glycol monomethyl ether. The polymerization reaction was carried out for 16 hours at 70°C under a nitrogen atmosphere. After polymerization, the reaction mixture was added dropwise to n-hexane to allow the resulting resin to solidify and purify. Next, propylene glycol monomethyl ether, methanol, triethylamine, and water were added to the purified resin, and the reaction was hydrolyzed under reflux at boiling point for 8 hours. After the reaction, the solvent and triethylamine were removed by vacuum distillation. The resulting resin was redissolved in acetone to a solids concentration of 20% by weight, and then added dropwise to water for curing. The mixture was filtered and vacuum dried overnight at 50°C.

[0006] After the polymerization reaction is completed, the polymerization solution is cooled with water to below 30°C, then added to methanol, and the precipitated white powder is filtered out. The obtained white powder is washed twice with methanol in a slurry state, filtered again, and dried at 50°C for 17 hours to obtain a white powder polymer.

[0007] However, patent CN 117608164A uses tetrahydrofuran as the solvent, and its residue may affect the stability of subsequent photoresists. Propylene glycol methyl ether is used, and residues at levels <1000ppm do not affect photolithography performance. AIBN is used as the initiator, resulting in higher color intensity. Patent JP 2006309186A uses dodecyl mercaptan as a molecular weight regulator, which has a strong odor and is unfriendly to subsequent processes. Patent CN 102077144B uses pure methanol for precipitation, which is difficult to scale up and filter, and the solid discharge method results in some solvent and moisture residue.

[0008] Currently, DUV photoresists encompass three main types of light sources: KrF (krypton fluoride laser), ArF (argon fluoride laser), and ArFi (argon fluoride laser combined with immersion lithography). Each of these three types of DUV photoresists plays a crucial role in semiconductor manufacturing. KrF light sources have a wavelength of 248 nanometers. KrF lasers were among the earliest DUV lithography light sources, suitable for larger feature patterns, and are typically used in more mature process nodes (such as 90 nanometers and above). KrF photoresists perform well in terms of resolution and image quality, but are gradually being replaced by other light sources in smaller-size applications. ArF light sources have a wavelength of 193 nanometers. ArF lasers have a shorter wavelength than KrF, enabling higher resolution and smaller feature sizes, and are therefore widely used in advanced process nodes (such as 65 nanometers, 45 nanometers, and below). The chemical properties and optical performance of ArF photoresists are optimized to meet the requirements of high-density integrated circuits. ArFi light sources have a wavelength of 193 nanometers. ArFi technology combines ArF lithography with immersion lithography. Immersion lithography further improves resolution and imaging quality by introducing a liquid (typically deionized water) between the photoresist and the lens. ArFi photoresist is particularly suitable for manufacturing smaller feature sizes (such as 7nm and 5nm nodes) and enables higher lithographic precision.

[0009] Currently, KrF photoresist is mainly used in mature processes, while ArF and ArFi photoresists are widely used in advanced process nodes, especially with technological advancements towards smaller sizes. As integrated circuit technology continues to evolve, the development and optimization of photoresists are also ongoing to meet increasingly stringent manufacturing requirements. Through the combination of the three existing light sources and technological advancements, DUV photoresist plays an indispensable role in modern semiconductor manufacturing.

[0010] Existing technologies all suffer from problems such as difficulty in filtering resin precipitation and residual solvent in the resin solid discharge. Therefore, providing a reaction vessel suitable for various light sources and capable of controlling solvent residue for the precipitation and purification of deep ultraviolet photoresist resin is a technical problem that urgently needs to be solved by those skilled in the art. Utility Model Content

[0011] This utility model aims to at least partially solve one of the aforementioned technical problems in the prior art.

[0012] Therefore, one objective of this utility model is to provide a reaction vessel for the precipitation and purification of deep ultraviolet photoresist resin, comprising a first jacketed vessel, a second jacketed vessel, and a third jacketed vessel.

[0013] The first jacketed vessel, the second jacketed vessel, and the third jacketed vessel are connected in series in sequence.

[0014] The first jacketed vessel has an intermediate bottle on its side, which is connected to the discharge port of the first jacketed vessel and to the inlet of the second jacketed vessel.

[0015] A filter is provided between the bottom of the second jacketed vessel and the outlet, and a filtrate receiving bottle is provided on the side of the second jacketed vessel. The outlet of the second jacketed vessel is connected to the inlet of the third jacketed vessel, and the outlet of the second jacketed vessel is also connected to the filtrate receiving bottle.

[0016] The third jacketed vessel is provided with a distillation receiving bottle on its side, and the distillation bottle at the top of the third jacketed vessel is connected to the distillation receiving bottle.

[0017] Preferably, a first diaphragm pump is provided between the first jacketed vessel and the second jacketed vessel.

[0018] Preferably, a second diaphragm pump is provided between the second jacketed vessel and the third jacketed vessel.

[0019] Preferably, the filter has a metal filter plate inside, a cross-shaped PTFE agitator above the metal filter plate, and a PTFE top plate below the metal filter plate.

[0020] In this invention, the filtrate receiving bottle is used for subsequent waste liquid tank treatment; the filtrate from the second jacketed kettle enters the filtrate receiving bottle (three-way valve, not transferred at the same time); the filter cake from the second jacketed kettle is dissolved and then undergoes alcoholysis, and after alcoholysis is completed, it is transferred to the third jacketed kettle.

[0021] The beneficial effects of this invention are as follows: This invention is a continuous production device for ESCAP liquid discharge, solving the difficulties in filtering ESCAP resin precipitation and the problem of solvent residue in solid ESCAP resin discharge. This invention features a continuous three-reactor system, reducing the number of reactors and operating steps. The process is closed, and the use of liquid discharge controls solvent residue. The reactor of this invention is suitable for the preparation of various photoresists such as KrF, ArF, and ArFi. Attached Figure Description

[0022] To more clearly illustrate the technical solutions in the embodiments of this utility model or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of this utility model. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0023] Figure 1 This is a schematic diagram of the reaction vessel structure for sedimentation and purification of deep ultraviolet photoresist resin provided by this utility model.

[0024] Figure 2 This is a schematic diagram of the structure of the filter provided by this utility model.

[0025] The structures represented by each number in the attached diagram are listed below: 1-First jacketed vessel; 2-Intermediate bottle; 3-First diaphragm pump; 4-Second jacketed vessel; 5-Filtrate receiving bottle; 6-Second diaphragm pump; 7-Third jacketed vessel; 8-Distillation receiving bottle; 9-Filter;

[0026] 91-Metal filter plate; 92-Cross-type PTFE agitator; 93-PTFE top plate. Detailed Implementation

[0027] The embodiments of this utility model are described in detail below. Examples of these embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain this utility model, and should not be construed as limiting this utility model.

[0028] In the description of this utility model, it should be understood that the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this utility model and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this utility model.

[0029] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this utility model, "a plurality of" means two or more, unless otherwise explicitly specified.

[0030] In this utility model, unless otherwise explicitly specified and limited, the terms "installation," "connection," "joining," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this utility model according to the specific circumstances.

[0031] In this invention, unless otherwise explicitly specified and limited, "above" or "below" the second feature can include direct contact between the first and second features, or contact between the first and second features through another feature between them. Furthermore, "above," "over," and "on top" of the second feature includes the first feature directly above or diagonally above the second feature, or simply indicates that the first feature is at a higher horizontal level than the second feature. "Below," "below," and "under" the second feature includes the first feature directly below or diagonally below the second feature, or simply indicates that the first feature is at a lower horizontal level than the second feature.

[0032] A reaction vessel for sedimentation and purification of deep ultraviolet photoresist resin, characterized in that it comprises a first jacketed vessel 1, a second jacketed vessel 4, and a third jacketed vessel 7.

[0033] The first jacketed vessel 1, the second jacketed vessel 4, and the third jacketed vessel 7 are connected in series in sequence.

[0034] The first jacketed vessel 1 has an intermediate bottle 2 on its side, which is connected to the discharge port of the first jacketed vessel 1 and to the inlet of the second jacketed vessel 4.

[0035] A filter 9 is provided between the bottom of the second jacketed vessel 4 and the outlet. A filtrate receiving bottle 5 is provided on the side of the second jacketed vessel 4. The outlet of the second jacketed vessel 4 is connected to the inlet of the third jacketed vessel 7, and the outlet of the second jacketed vessel 4 is also connected to the filtrate receiving bottle 5.

[0036] The third jacketed vessel 7 is provided with a distillation receiving bottle 8 on its side, and the distillation bottle at the top of the third jacketed vessel 7 is connected to the distillation receiving bottle 8.

[0037] In some embodiments, a first diaphragm pump 3 is provided between the first jacketed vessel 1 and the second jacketed vessel 4.

[0038] In some embodiments, a second diaphragm pump 6 is provided between the second jacketed vessel 4 and the third jacketed vessel 7.

[0039] In some embodiments, the filter 9 has a metal filter plate 91 inside, a cross-shaped PTFE agitator 92 above the metal filter plate, and a PTFE top plate 93 below the metal filter plate.

[0040] In this invention, the production process of the aforementioned reactor is as follows: Under nitrogen protection, 4-acetoxystyrene, styrene, and tert-butyl acrylate are added sequentially to the first jacketed reactor, followed by the initiator dimethyl azobisisobutyrate (AIBME). The reaction is carried out at 70-90°C for 16 hours using propylene glycol methyl ether (PGME) as the solvent. The polymerization product is transferred to a second jacketed reactor containing a methanol / water = 6 / 1 settling agent. The settling agent is removed by vacuum filtration, and the reactor is not completely dried. Then, methanol and water are pumped in for slurrying. The settling agent is removed again by vacuum filtration, and PGME is pumped in. The reactor is heated to 70°C for dissolution, and then methanol and triethylamine are added for alcoholysis at 65-70°C for 16 hours. The alcoholysis product is pumped into a third jacketed reactor, where the solvent is replaced with butyl acetate under vacuum. Then, 1% oxalic acid is pumped in, and the reactor is heated to 70°C for acid washing. After phase separation, pure water is pumped in for two water washes. After water washing and phase separation, the solvent is replaced with PGMEA. The deep ultraviolet photoresist resin was purified by sedimentation, and the finished product was a 35% PGMEA resin solution.

[0041] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. In addition, those skilled in the art can combine and integrate the different embodiments or examples described in this specification.

[0042] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A reaction vessel for the precipitation and purification of deep ultraviolet photoresist resin, characterized in that, It includes a first jacketed vessel, a second jacketed vessel, and a third jacketed vessel; The first jacketed vessel, the second jacketed vessel, and the third jacketed vessel are connected in series in sequence. The first jacketed vessel has an intermediate bottle on its side, which is connected to the discharge port of the first jacketed vessel and to the inlet of the second jacketed vessel. A filter is provided between the bottom of the second jacketed vessel and the outlet, and a filtrate receiving bottle is provided on the side of the second jacketed vessel. The outlet of the second jacketed vessel is connected to the inlet of the third jacketed vessel, and the outlet of the second jacketed vessel is also connected to the filtrate receiving bottle. The third jacketed vessel is provided with a distillation receiving bottle on its side, and the distillation bottle at the top of the third jacketed vessel is connected to the distillation receiving bottle.

2. The reaction vessel for sedimentation and purification of deep ultraviolet photoresist resin according to claim 1, characterized in that, A first diaphragm pump is provided between the first jacketed vessel and the second jacketed vessel.

3. The reaction vessel for sedimentation and purification of deep ultraviolet photoresist resin according to claim 1, characterized in that, A second diaphragm pump is provided between the second jacketed vessel and the third jacketed vessel.

4. The reaction vessel for sedimentation and purification of deep ultraviolet photoresist resin according to claim 1, characterized in that, The filter has a metal filter plate inside, a cross-shaped PTFE stirring paddle above the metal filter plate, and a PTFE top plate below the metal filter plate.

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