PHS resin as well as preparation method and application thereof
PHS resin is prepared through living anionic polymerization and hydrolysis, which solves the problem of unstable molecular weight and distribution in high-end semiconductor photoresist resin, achieves high-quality resin product consistency and stability, and is suitable for KrF photoresist.
Patent Information
- Application Number
- CN202410481338.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-04-22
- Publication Date
- 2025-10-24
AI Technical Summary
Existing technologies make it difficult to achieve high-quality polymer structure sequence composition distribution, molecular weight and extremely narrow PDI in high-end semiconductor photoresist resins, and it is difficult to ensure batch stability and consistency, which affects the photolithography effect and development rate.
The PHS resin is prepared by living anionic polymerization, wherein the compound of formula I monomer is polymerized by living anionic polymerization under the initiation of sec-butyl lithium, followed by hydrolysis and catalysis using hydrochloric acid to control the molecular weight and distribution. Post-processing includes precipitation, filtration and drying.
The obtained PHS resin has controllable molecular weight, low molecular weight distribution index, and low metal impurities, organic impurities and water content. It is suitable for KrF photoresist resin, ensuring the consistency and stability of each batch of products, and is suitable for small-scale tests, pilot tests and scale-up tests.
Smart Images
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of polymer synthesis, in particular to a PHS resin and a preparation method and application thereof. BACKGROUND
[0002] Polyhydroxystyrene system occupies a dominant position in photoresist film-forming resin. The synthesis of high-end semiconductor photoresist resin (KrF and ArF) faces the following main problems: first, from the micro perspective, the more fine process requires high-quality polymer structure sequence composition distribution, molecular weight and very narrow PDI, so that the photoresist can better achieve the photoetching effect on finer size, and the development rate and LWR technical indexes are better; second, from the engineering perspective, it is necessary to ensure the batch stability and consistency of all polymer products, and the technical parameter indexes such as molecular weight and molecular weight distribution are required to be very close in each batch, and the more high-end the resin is, the more consistent the quality is.
[0003] Several synthesis methods of polyhydroxystyrene are as follows:
[0004]
[0005] Method A is to prepare a hydroxystyrene derivative by decarboxylation of a derivative of cinnamic acid, which is more suitable for synthesizing ortho products. Method B is called Heck reaction, which has good selectivity when synthesizing ortho products, but the yield is relatively low (about 60%) due to the existence of steric hindrance, and the reaction conditions are also harsh. Method C is a traditional method for synthesizing acetoxy styrene, which starts from commercially available acetyl phenol and realizes by β-elimination reaction, which is commonly used to synthesize meta or para products. Method D uses Wittig reaction, and the raw material is cheap hydroxybenzaldehyde, the reaction conditions are mild and the yield is high, which is suitable for laboratory synthesis, but the preparation of the corresponding Wittig reagent is difficult. Method E uses a protected styrene derivative monomer to obtain a precursor polymer by free radical or living radical polymerization, and then hydrolysis to obtain poly-p-hydroxystyrene (PHS) target resin, which has the advantages of easy operation and simple process, but the disadvantages are that the molecular weight and its distribution are difficult to control and the distribution is wide, which is not conducive to its application in high-resolution etch-resistant process. Method F is a new synthesis method for preparing poly-p-hydroxystyrene (PHS), which starts from cheap and readily available polystyrene, and then acetylation, oxidation, and removal of acetyl group to obtain high yield product, which is expected to realize the scale production of poly-p-hydroxystyrene (PHS), but this method also has some disadvantages, such as the difficulty in preparing copolymer of poly-p-hydroxystyrene from it, and in addition, the molecular weight distribution of the obtained PHS will be wide after a series of reactions. SUMMARY
[0006] In view of the above-mentioned disadvantages of the prior art, the purpose of the present application is to provide a PHS resin, a preparation method and use thereof, for solving the problems in the prior art.
[0007] To achieve the above-mentioned purpose and other related purposes, the present application is obtained by the following technical solutions.
[0008] The present application provides a preparation method of a PHS resin, comprising the following steps:
[0009] The compound monomer of formula I is subjected to active anion polymerization under the action of an initiator to obtain a prepolymer;
[0010] The prepolymer is hydrolyzed;
[0011] The monomer is p-tert-butoxystyrene.
[0012] Preferably, the initiator is sec-butyllithium.
[0013] Preferably, the active anion polymerization reaction uses a first solvent, and the first solvent is tetrahydrofuran.
[0014] Preferably, the molar ratio of the initiator to the monomer is (0.004-0.006):1.
[0015] Preferably, the temperature for adding the initiator is the reaction temperature of the active anion polymerization reaction.
[0016] Preferably, the reaction temperature of the active anion polymerization reaction is -85 to -75℃. For example, it can be -85℃, -84℃, -80℃, -78℃, or -75℃.
[0017] Preferably, the active anion polymerization reaction uses a terminator, and the terminator is methanol. More preferably, the terminator is degassed methanol. The terminator functions to terminate the active anion polymerization reaction.
[0018] Preferably, the reaction time of the active anion polymerization reaction is 1-2h.
[0019] Preferably, the hydrolysis uses a catalyst, and the catalyst is hydrochloric acid. More preferably, the mass fraction of the hydrochloric acid is 36-38%. More preferably, the solvent of the hydrochloric acid is water.
[0020] More preferably, the molar ratio of the catalyst to the prepolymer is (10-15):1.
[0021] Preferably, the hydrolysis uses a second solvent, and the second solvent is acetone.
[0022] Preferably, the hydrolysis temperature is 55-70℃. For example, it can be 55-60℃ or 60-70℃.
[0023] Preferably, the hydrolysis time is 12-24h.
[0024] Preferably, the living anionic polymerization reaction further comprises a post-treatment step, which comprises separation, drying. More preferably, the separation comprises precipitation, filtration. Further preferably, the precipitation is precipitation by adding the solution into 10-20 times volume of methanol. Further preferably, the filtration is obtaining filtrate by solid-liquid separation, and the filtrate is adjusted to neutral with sodium hydroxide aqueous solution. More preferably, the drying is drying the precipitate in a vacuum oven at 55-65℃.
[0025] Preferably, the hydrolysis reaction further comprises a post-treatment step, which comprises separation, drying. More preferably, the separation comprises precipitation, filtration. Further preferably, the precipitation is precipitation by adding the solution into 10-20 times volume of n-hexane / water (v / v: volume ratio is 10:1). Further preferably, the filtration is obtaining filtrate by solid-liquid separation, and the filtrate is adjusted to neutral with sodium hydroxide aqueous solution. More preferably, the drying is drying the precipitate in a vacuum oven at 55-65℃.
[0026] The application also discloses a PHS resin obtained by the preparation method.
[0027] Preferably, the weight average molecular weight of the PHS resin is 29000-30000.
[0028] Preferably, the molecular weight distribution index of the PHS resin is <1.05.
[0029] Preferably, the metal impurity content of the PHS resin is <100ppb.
[0030] Preferably, the organic impurity content of the PHS resin is <100ppm.
[0031] Preferably, the water content of the PHS resin is <0.5%.
[0032] The application also discloses a use of the PHS resin obtained by the preparation method as a KrF photoresist resin.
[0033] The application discloses a PHS resin, a preparation method and a use thereof, and has the following beneficial effects:
[0034] (1) The molecular weight M of the PHS resin obtained by the preparation method is 29000-30000. WThe molecular weight is 29000-30000, the molecular weight distribution index is low, the content of metal impurities and organic impurities is low, the water content is low, the monomer conversion rate is stable at 100%, the molecular weight and the molecular weight distribution index of the PHS resin produced in each batch are the same, and the use requirements of the KrF photoresist resin are met.
[0035] (2) The reaction process is stable, and is suitable for small tests, and is still good in stability in pilot tests and scale-up tests, and has industrial operability. BRIEF DESCRIPTION OF DRAWINGS
[0036] Figure 1 The nuclear magnetic spectrum of the PHS resin prepared in Example 1 is shown. DETAILED DESCRIPTION
[0037] The embodiments of the present application are illustrated by specific, concrete examples below, and other advantages and effects of the present application can be easily understood by those skilled in the art from the disclosure. The present application can also be implemented or applied by other different specific embodiments, and each detail in the specification can be modified or changed based on different views and applications without departing from the spirit of the present application.
[0038] It should be understood that the process equipment or device not specifically mentioned in the following examples is the conventional equipment or device in the art.
[0039] In addition, it should be understood that the one or more method steps mentioned in the present application do not exclude that other method steps can exist before and after the combination steps or can be inserted between the explicitly mentioned steps, unless otherwise specified; it should also be understood that the combination connection relationship between the one or more devices / apparatuses mentioned in the present application does not exclude that other devices / apparatuses can exist before and after the combination devices / apparatuses or can be inserted between the two explicitly mentioned devices / apparatuses, unless otherwise specified. Moreover, unless otherwise specified, the numbering of each method step is only a convenient tool for identifying each method step, and is not a limitation on the arrangement order of each method step or a limitation on the range of implementation of the present application. The change or adjustment of the relative relationship, without substantial change of the technical content, is also regarded as the implementation range of the present application.
[0040] Example 1
[0041] The present embodiment provides a specific preparation method of a PHS resin, and the specific steps are as follows:
[0042] (1) Preparation of the prepolymer
[0043] In a vacuum system, 160 g of dried tetrahydrofuran was first added to a dry reaction vessel, cooled to -78°C, and then 1.3 mmol of sec-butyllithium and 40.7 g of p-tert-butoxy styrene (0.23 mol) were added in sequence. After 1 h of reaction, 0.5 mL of degassed methanol was added to terminate the reaction.
[0044] After the reaction was completed, the reaction solution was added to 20 times the volume of methanol for precipitation, and the filtrate was obtained by filtration. A 10% sodium hydroxide solution was added to the filtrate to adjust the pH to 7, and then added to 20 times the volume of methanol for precipitation. The precipitate was obtained by filtration and dried.
[0045] (2) Preparation of PHS resin
[0046] Under an inert atmosphere, the prepolymer was dissolved in acetone at 60°C, and 37% hydrochloric acid was added. After sealing and stirring overnight, the molar ratio of hydrochloric acid to prepolymer was 10:1.
[0047] After the hydrolysis reaction was completed, the reaction solution was added to n-hexane / water (v / v: volume ratio 10:1) for precipitation, and the filtrate was obtained by filtration. A 10% sodium hydroxide solution was added to the filtrate to adjust the pH to 7, and then added to 20 times the volume of methanol for precipitation. The precipitate was obtained by filtration and dried.
[0048] The PHS resin prepared in Example 1 was subjected to 1 HNMR analysis, and the detection spectrum is shown in Figure 1 .
[0049] Example 2
[0050] This example provides a specific preparation method of PHS resin, and the preparation method is basically the same as that of Example 1, except that in step (1), the reaction temperature is -84°C.
[0051] Comparative Example 1
[0052] This comparative example is a comparative example of Example 1, except that in step (1), the initiator is 1,1-diphenylstyrene and sec-butyllithium, and the mass ratio of 1,1-diphenylstyrene to sec-butyllithium is 1.3 mmol:1.3 mmol.
[0053] Comparative Example 2
[0054] This comparative example is a comparative example of Example 1, except that in step (1), the reaction temperature is -90°C.
[0055] Comparative Example 3
[0056] This comparative example is a comparative example of Example 1, except that in step (1), the reaction temperature is -95°C.
[0057] The PHS resins prepared in Examples 1-2 and Comparative Examples 1-3 were subjected to GPC analysis, and the results are shown in Table 1.
[0058] The PHS resins prepared in Examples 1-2 were subjected to ICP-MS detection of metal impurity content, and the results are shown in Table 1, with the detection conditions as follows:
[0059] Inductively coupled plasma mass spectrometer (instrument model NEXION 5000G)
[0060] Plasma power was 1500 W;
[0061] Plasma gas flow was 16 L / min;
[0062] Auxiliary gas flow was 1.2 L / min;
[0063] Atomizer temperature was -5°C;
[0064] Oxygen flow: 0.035 L / min;
[0065] Injection speed: 100 uL / min.
[0066] The PHS resins prepared in Examples 1-2 were subjected to GC-MS detection of organic impurity content, and the results are shown in Table 1, with the detection conditions as follows:
[0067] Instrument model was Agilent 8890-5977; gas chromatography conditions: GC column model: HP-5ms, length: 30 m, inner diameter: 0.25 mm; injection port temperature: 280°C; injection volume: 1 μL; split ratio: 20:1; column flow: 1.00 mL / min; solvent delay: 2.3 min; column oven temperature program: initial temperature 50°C for 1 min, then increased to 320°C at 30°C / min for 3 min.
[0068] Mass spectrometry conditions: transfer line temperature: 250°C; MS ion source temperature: 230°C; quadrupole rod temperature: 150°C; scan range m / z: 29-550; scan mode: double scan SCAN & SIM.
[0069] The PHS resins prepared in Examples 1-2 were subjected to moisture detector detection of moisture content, and the results are shown in Table 1.
[0070] Table 1
[0071]
[0072] The above embodiments are only illustrative of the principles of the present application and its efficacy, and are not intended to limit the present application. Any modification or change made by any person skilled in the art without departing from the spirit and scope of the present application shall be covered by the claims of the present application.
Claims
1. A method for preparing a PHS resin, characterized by, comprising the steps of: carrying out active anionic polymerization of the monomer under the action of an initiator to obtain a prepolymer; hydrolyzing the prepolymer; the monomer is p-tert-butoxystyrene.
2. The production method according to claim 1, characterized by, the initiator is sec-butyllithium; and / or, the active anionic polymerization employs a first solvent, and the first solvent is tetrahydrofuran.
3. The preparation method according to claim 1, characterized in that the temperature of adding the initiator is the reaction temperature of the active anionic polymerization.
4. The method of claim 1, wherein, the molar ratio of the initiator to the monomer is (0.004-0.006):
1.
5. The preparation method according to claim 1, characterized in that the reaction temperature of the active anionic polymerization is -85 to -75℃; and / or, the active anionic polymerization employs a terminating agent, and the terminating agent is methanol.
6. The method of claim 1, wherein, the hydrolysis employs a catalyst, and the catalyst is hydrochloric acid; and / or, the hydrolysis employs a second solvent, and the second solvent is acetone; and / or, the hydrolysis temperature is 55-70℃.
7. The preparation method according to claim 1, characterized in that the active anionic polymerization further comprises a post-treatment step, and the post-treatment step comprises separation and drying; and / or, the hydrolysis reaction further comprises a post-treatment step, and the post-treatment step comprises separation and drying.
8. A PHS resin obtained by the preparation method according to any one of claims 1-7.
9. The PHS resin of claim 8, wherein the weight average molecular weight of the PHS resin is 29000-30000; and / or, the molecular weight distribution index of the PHS resin is <1.05; and / or, the content of metal impurities in the PHS resin is <100 ppb; and / or, the content of organic impurities in the PHS resin is <100 ppm; and / or, the water content in the PHS resin is <0.5%.
10. Use of a PHS resin obtained by the preparation method according to any one of claims 1-7 as a KrF photoresist resin.