Phenolic resin and preparation method thereof, photoresist composition and optical filter

Abstract

The invention provides phenolic resin and a preparation method thereof, a photoresist composition and an optical filter, and relates to the field of photoresist. The structural general formula of the phenolic resin is shown in the specification. R1 at any position independently comprises hydrogen or aryl, R2 at any position independently comprises alkyl or aryl, and n is 50-100. End groups are introduced into phenolic resin, alkyl groups on benzene rings of the end groups can increase heat resistance, and phenolic hydroxyl groups on the end groups can increase solubility in an alkaline developing solution.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of photoresist, in particular to a phenolic resin and a preparation method thereof, a photoresist composition and an optical filter. BACKGROUND

[0002] As a core material in semiconductor manufacturing, the performance of photoresist directly affects the precision and efficiency of chip manufacturing. As an important member of the photoresist field, i-line positive photoresist exhibits unique solubility characteristics under specific wavelength light, thereby realizing the transfer of fine patterns and being widely used in many high-end manufacturing fields such as integrated circuits, flat panel displays, micro-electro-mechanical systems, etc. With the rapid development of the semiconductor industry towards high precision and high integration, the research and innovation of i-line positive photoresist are accelerating to meet the increasingly stringent process requirements and continue to shine on the stage of semiconductor manufacturing.

[0003] However, there are still some problems that have not been well solved, such as the heat resistance, photosensitivity, resolution, etc. of i-line positive photoresist. Moreover, although the photoresist made of i-line (365 nm) high ortho-ortho connected resin usually has high resolution, it is still difficult to meet the requirements in terms of photosensitivity and heat resistance, etc.

[0004] Therefore, there is an urgent need to provide a resin to solve the above problems. SUMMARY

[0005] The present application aims to provide a phenolic resin and a preparation method thereof, a photoresist composition and an optical filter to solve the above problems.

[0006] To achieve the above purpose, the first aspect of the present application provides a phenolic resin, the structure general formula of which is as follows: ; In the formula, R1 at any position independently includes hydrogen or aryl, R2 at any position independently includes alkyl or aryl, and n is 50-100.

[0007] The second aspect of the present application provides a preparation method of the phenolic resin, comprising: mixing and reacting p-cresol, an aldehyde compound and a hydroxide to obtain a first reactant; It should be noted that the reaction of the first reaction is as follows: ; mixing and reacting the first reactant, p-cresol and to obtain a second reactant; It should be noted that the reaction of the second reaction is as follows: ; mixing, drying the second reactant and n-heptane to obtain the phenolic resin; wherein R2 at any position each independently comprises an alkyl group or an aryl group.

[0008] Optionally, the method for preparing the phenolic resin satisfies at least one of the following conditions: (1) the aldehyde compound comprises formaldehyde and / or aromatic aldehyde; (2) the hydroxide comprises one or more of potassium hydroxide, sodium hydroxide, and ammonium hydroxide; (3) the comprises 4-hydroxy-3,3-dimethylbenzyl alcohol.

[0009] Optionally, the method for preparing the phenolic resin satisfies at least one of the following conditions: (1) when the first mixing is performed, the molar ratio of the p-cresol, the aldehyde compound, and the hydroxide is 1:3-6:0.6-1; (2) when the second mixing is performed, the molar ratio of the first reactant, the p-cresol, and the is 1:2-3:1-4.

[0010] Optionally, the temperature of the first reaction and the second reaction is independently 80-100°C, and the time is independently 1-3h.

[0011] The third aspect of the present application provides a photoresist composition, the raw materials of which comprise, in terms of mass parts: 30-100 parts of the phenolic resin, 5-40 parts of diazonaphthoquinone photosensitive compound, 50-170 parts of solvent, and 0.1-2 parts of leveling agent.

[0012] Optionally, the diazonaphthoquinone photosensitive compound comprises 2,3,4-trihydroxybenzophenone-1,2-diazido naphthoquinone-5-sulfonate.

[0013] Optionally, the solvent comprises propylene glycol methyl ether acetate.

[0014] Optionally, the leveling agent comprises one or more of polymethylphenylsiloxane and / or polydimethylsiloxane.

[0015] The fourth aspect of the present application provides a filter prepared from the photoresist composition.

[0016] Compared with the prior art, the beneficial effects of the present application include: The phenolic resin provided in the application introduces an end group on the basis of a conventional phenolic resin, the benzene ring of the end group containing an alkyl group can increase heat resistance, and the end group containing a phenolic hydroxyl group can increase solubility in an alkaline developer (i.e., increase photosensitivity).

[0017] The preparation method of the phenolic resin provided in the application is simple, fast and low in cost.

[0018] The photoresist composition provided in the application solves the problems of poor heat resistance and poor photosensitivity. First, the hydroxyl group of the phenolic resin and the nitrogen naphthoquinone photosensitive compound can form a stable six-membered ring structure through hydrogen bonding, thereby inhibiting the dissolution of the phenolic resin in the alkaline developer. After the photoresist is exposed, the nitrogen naphthoquinone photosensitive compound decomposes, the six-membered ring structure is destroyed, the diazonaphthoquinone is converted into indene carboxylic acid and dissolved in the alkaline developer, and the phenolic resin itself is dissolved in the alkaline solution, thereby promoting the dissolution. The photoresist composition not only has high resolution, but also can improve the photosensitivity and heat resistance of the photoresist.

[0019] The filter provided in the application has excellent photosensitivity and heat resistance. BRIEF DESCRIPTION OF DRAWINGS

[0020] In order to more clearly illustrate the technical solutions of the embodiments of the application, the following will briefly introduce the drawings needed to be used in the embodiments. It should be understood that the following drawings only show some embodiments of the application, and therefore should not be regarded as a limitation on the scope of the application.

[0021] Figure 1 The nuclear magnetic resonance hydrogen spectrum of the phenolic resin provided for Example 1. DETAILED DESCRIPTION

[0022] First, the scheme provided in the application will be explained in more detail, as follows: To achieve the above purpose, the first aspect of the application provides a phenolic resin, the structure general formula of which is as follows: Among them, R1 at any position each independently includes hydrogen or aryl, R2 at any position each independently includes alkyl or aryl, and n is 50-100.

[0023] Alternatively, n can be 50, 60, 70, 80, 90, 100 or any value between 50 and 100.

[0024] The second aspect of the application provides a preparation method of the phenolic resin, comprising: mixing and reacting p-methyl phenol, an aldehyde compound and a hydroxide to obtain a first reactant; mixing and reacting the first reactant, p-methyl phenol and​ performing a second mixing, a second reaction to obtain a second reactant; performing a third mixing, drying the second reactant and n-heptane to obtain a phenolic resin; It should be noted that n-heptane can realize the precipitation of the phenolic resin in the second reactant; wherein R2at any position independently includes an alkyl group or an aryl group.

[0025] In some embodiments, the method for preparing the phenolic resin satisfies at least one of the following conditions: (1) the aldehyde compound includes formaldehyde and / or aromatic aldehyde; (2) the hydroxide includes one or more of potassium hydroxide, sodium hydroxide, and ammonium hydroxide; (3) the includes 4-hydroxy-3,3-dimethylbenzyl alcohol.

[0026] In some embodiments, the method for preparing the phenolic resin satisfies at least one of the following conditions: (1) when performing the first mixing, the molar ratio of the p-cresol, the aldehyde compound, and the hydroxide is 1:3-6:0.6-1; Optionally, when performing the first mixing, the molar ratio of the p-cresol, the aldehyde compound, and the hydroxide can be 1:3:0.6, 1:4:0.6, 1:5:0.6, 1:6:0.6, 1:3:0.8, 1:3:1, 1:6:1, or any value between 1:3-6:0.6-1. (2) when performing the second mixing, the molar ratio of the first reactant, the p-cresol, and the is 1:2-3:1-4.

[0027] Optionally, when performing the second mixing, the molar ratio of the first reactant, the p-cresol, and the can be 1:2:1, 1:2.5:1, 1:3:1, 1:2:2, 1:2:3, 1:2:4, or any value between 1:2-3:1-4.

[0028] In some embodiments, the temperature of the first reaction and the second reaction is independently 80-100℃, and the time is independently 1-3h.

[0029] Optionally, the temperature of the first reaction and the second reaction can be independently 80℃, 90℃, 100℃, or any value between 80-100℃, and the time can be independently 1h, 2h, 3h, or any value between 1-3h.

[0030] The third aspect of the present application provides a photoresist composition, raw materials of which include, by mass fraction: 30-100 parts of the phenolic resin, 5-40 parts of the diazonium naphthoquinone photosensitizer, 50-170 parts of the solvent, and 0.1-2 parts of the leveling agent.

[0031] Optionally, the raw materials of the photoresist composition, by mass fraction, the phenolic resin can be 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, or any value between 30-100 parts, the diazonium naphthoquinone photosensitizer can be 5 parts, 10 parts, 20 parts, 30 parts, 40 parts, or any value between 5-40 parts, the solvent can be 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 150 parts, 160 parts, 170 parts, or any value between 50-170 parts, and the leveling agent can be 0.1 parts, 0.5 parts, 1 parts, 1.5 parts, 2 parts, or any value between 0.1-2 parts.

[0032] In some embodiments, the diazonium naphthoquinone photosensitizer includes 2,3,4-trihydroxybenzophenone-1,2-diazido naphthoquinone-5-sulfonate.

[0033] In some embodiments, the solvent includes propylene glycol methyl ether acetate.

[0034] In some embodiments, the leveling agent includes one or more of polymethylphenylsiloxane and / or polydimethylsiloxane.

[0035] The fourth aspect of the present application provides a filter prepared from the photoresist composition.

[0036] The embodiments of the present application will be described in detail below with specific examples, but those skilled in the art will understand that the following examples are only for illustration of the present application and should not be regarded as limiting the scope of the present application. If the specific conditions are not specified in the examples, the conventional conditions or the conditions recommended by the manufacturer are used. If the reagents or instruments used are not specified by the manufacturer, they are all conventional products that can be purchased on the market.

[0037] Example 1 The first aspect of the present embodiment provides a phenolic resin and a preparation method thereof, and the specific preparation steps are as follows: S1: In a three-necked flask with a thermometer and mechanical stirring, 5 g (46.30 mmol, 1.0 eq) of p-methylphenol, 60 mL of formaldehyde 4.17 g (138.90 mmol, 3.0 eq), and potassium hydroxide 1.55 g (27.62 mmol, 0.6 eq) were added, and the mixture was reacted at 80°C for 1 hour to obtain a first reaction product; S2: 10 g (92.60 mmol, 2.0 eq) of p-methylphenol and 4.8 g (46.30 mmol, 1.0 eq) of 4-hydroxy-3,3-dimethylbenzyl alcohol were added to the first reactant and stirring was continued, the reaction progress was monitored by liquid chromatography, and the second reactant was obtained by reacting at 100°C for 6 hours; S3: 250 mL of n-heptane was added to the second reactant and stirred for 10 min, then filtered, the filter cake was washed with n-heptane, dried and weighed to obtain the crude phenolic resin 3.94 g, with a yield of 62%.

[0038] The structural formula of the phenolic resin is: The proton nuclear magnetic resonance spectrum of the phenolic resin is as shown in the figure Figure 1 A high-heat-resistant and high-sensitivity phenolic resin was synthesized.

[0039] The second aspect of the embodiment provides a photoresist composition, raw materials of which include, by mass fraction: 90 parts of the above phenolic resin, 8 parts of 2,3,4-trihydroxybenzophenone-1,2-diazido naphthoquinone-5-sulfonate photosensitizer, 2 parts of leveling agent polymethylphenylsiloxane, and 160 parts of propylene glycol methyl ether acetate.

[0040] The specific preparation steps of the photoresist composition patterning are as follows: S4: preparation and filtration of the glue solution, dissolving the components in the solvent to prepare a photoresist solution, mixing on a shaker for 48 hours to fully dissolve and uniformly mix; then filtering the obtained solution three times using a 0.5 μm filter membrane to obtain a pure photoresist solution; S5: coating, exposure and development, using an 8-inch silicon wafer as a substrate, sequentially performing spin coating at a pre-rotation speed of 2000 rpm and a main rotation speed of 3000 rpm on a glue uniformizer to form a uniform photoresist film; then baking at 110°C; using an I-line stepping photolithography machine for exposure, with an exposure dose of 200 mJ / cm 2 ; using a TMAH aqueous solution with a concentration of 2.38% as a developing solution, with a developing time of 75 s, to finally obtain the required pattern.

[0041] Example 2 The difference from Example 1 is that the raw materials of the photoresist composition include, by mass fraction: 83 parts of the above phenolic resin, 15 parts of 2,3,4-trihydroxybenzophenone-1,2-diazido naphthoquinone-5-sulfonate photosensitizer, 2 parts of leveling agent polydimethylsiloxane, and 160 parts of propylene glycol methyl ether acetate.

[0042] Comparative Example 1 The difference from Example 1 is that the phenolic resin in Example 1 is replaced by a conventional high-ortho-ortho phenolic resin (poly(methylene phenol), purchased from Xuyouguocai Resin (Nantong) Co., Ltd.), and other conditions are unchanged.

[0043] Comparative Example 2 The difference from Example 2 is that the phenolic resin in Example 2 is replaced by a conventional high-ortho-ortho phenolic resin (poly(methylene phenol), purchased from Xuyouguocai Resin (Nantong) Co., Ltd.), and other conditions are unchanged.

[0044] The photoresist compositions prepared in the above examples and comparative examples are tested for resolution, photosensitivity and heat resistance of the pattern after exposure and development, respectively; the morphology of the silicon wafer is observed under CD-SEM to determine whether it changes, and the specific test results are shown in Table 1.

[0045] Table 1 Performance Test

[0046] Analysis: From the above tests, it can be seen that Comparative Example 1 exhibits high heat resistance and high photosensitivity compared to Example 1, and the etching resistance is significantly improved; Comparative Example 2 exhibits high heat resistance and high photosensitivity compared to Example 2.

[0047] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application, and are not limiting; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that they can still modify the technical solutions described in the foregoing examples, or make equivalent substitutions for some or all of the technical features; and these modifications or substitutions do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

[0048] In addition, those skilled in the art will understand that although some of the embodiments herein include certain features rather than others included in other embodiments, the combination of features of different embodiments means that it is within the scope of the present application and forms different embodiments. For example, any one of the claimed embodiments can be used in any combination. The information disclosed in the BACKGROUND section is only intended to deepen the understanding of the overall background of the present application, and should not be considered as acknowledging or implying in any form that the information constitutes prior art known to those skilled in the art.

Claims

1. A phenolic resin, characterized in that, Its general structural formula is: ； In this context, R1 at any position independently includes either hydrogen or aryl, and R2 at any position independently includes either alkyl or aryl, with n being 50-100.

2. A method for preparing the phenolic resin according to claim 1, characterized in that, include: The first mixture and first reaction of p-methylphenol, aldehyde compound and hydroxide are carried out to obtain the first reactant; The first reactant, p-methylphenol, and A second mixing and a second reaction are carried out to obtain a second reactant; The second reactant and n-heptane were mixed in a third step and dried to obtain phenolic resin. In this context, each R2 at any position can independently be either alkyl or aryl.

3. The method for preparing phenolic resin according to claim 2, characterized in that, At least one of the following conditions must be met: (1) The aldehyde compounds include formaldehyde and / or aromatic aldehydes; (2) The hydroxide includes one or more of potassium hydroxide, sodium hydroxide, and ammonium hydroxide; (3) The above Including 4-hydroxy-3,3-dimethylbenzyl alcohol.

4. The method for preparing phenolic resin according to claim 2, characterized in that, At least one of the following conditions must be met: (1) When the first mixture is made, the molar ratio of the p-methylphenol, the aldehyde compound and the hydroxide is 1:3-6:0.6-1; (2) During the second mixing, the first reactant, the p-methylphenol, and the... The molar ratio is 1:2-3:1-4.

5. The method for preparing phenolic resin according to any one of claims 2-4, characterized in that, The temperature of the first reaction and the second reaction are each 80-100℃, and the time is each 1-3h.

6. A photoresist composition, characterized in that, Its raw materials, by weight, include: 30-100 parts of the phenolic resin as described in claim 1, 5-40 parts of the diazonoquinone photosensitive compound, 50-170 parts of solvent, and 0.1-2 parts of leveling agent.

7. The photoresist composition according to claim 6, characterized in that, The diazonaphthoquinone photosensitive compounds include 2,3,4-trihydroxybenzophenone-1,2-diazidonaphthoquinone-5-sulfonate.

8. The photoresist composition according to claim 6, characterized in that, The solvent includes propylene glycol methyl ether acetate.

9. The photoresist composition according to any one of claims 6-8, characterized in that, The leveling agent includes polymethylphenylsiloxane and / or polydimethylsiloxane.

10. A filter, characterized in that, It is prepared from the photoresist composition according to any one of claims 6-9.

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