CN116410089A

CN116410089A - Photoresist film-forming monomer and preparation method and application thereof

Info

Publication number: CN116410089A
Application number: CN202310012236.6A
Authority: CN
Inventors: 王涛; 战海涛
Original assignee: Anqing Beihuada Science And Technology Park Co ltd; Beijing University of Chemical Technology
Current assignee: Anqing Beihuada Science And Technology Park Co ltd; Beijing University of Chemical Technology
Priority date: 2023-01-05
Filing date: 2023-01-05
Publication date: 2023-07-11

Abstract

The invention discloses a photoresist film-forming monomer, a preparation method and application thereof, wherein the photoresist film-forming monomer is a compound with the following general formulaAnd (3) the following substances:

wherein R is C ₁ ～C ₆ Or a hydrogen atom. The 3-ethyl substituted adamantane acrylic ester photoresist film forming monomer synthesized by the method has the advantages of simple synthesis line and easy operation, and the monomer is more excellent in adhesion to a silicon substrate than the traditional adamantane methacrylate photoresist.

Description

Photoresist film-forming monomer and preparation method and application thereof

Technical Field

The invention relates to the technical field of photoresist, in particular to a photoresist resin monomer structure, a preparation method and application thereof.

Background

193nm photoresist is basically a chemical amplification photoresist, which is a photoresist based on the chemical amplification principle, and its main components are polymer resin, photoacid generator, and corresponding additives (alkaline additive, dissolution inhibitor, etc.) and solvents. Wherein the polymer resin is formed by copolymerization between resin monomers of different side chain structures, the side chain structures are key components for endowing the polymer resin with required functions, and polar groups and acid-sensitive groups are generally provided for the polymer resin. Wherein the polar groups balance the hydrophilicity and hydrophobicity of the resin, improve adhesion between the resin and the substrate, and provide developability to the host resin.

Adamantane is selected as a typical alicyclic skeleton, and since this structure is considered as the most compact and effective dry-etching-resistant alicyclic structure, the structure of adamantane is introduced into a methacrylic resin monomer so that it has the advantages of both polymethacrylate and adamantane, shows good controllability, excellent resolution, excellent corrosion resistance, and the like, and is a photoresist resin monomer widely used for 193 nm.

The adhesion of the photoresist represents the strength of the photoresist to adhere to the substrate and the photoresist must adhere to many different types of surfaces including silicon, polysilicon, silicon dioxide and different metals. The photoresist, if not adhesive enough, can cause deformation of the pattern on the wafer surface. The adhesion of the photoresist must ensure that the photoresist withstands exposure, development and subsequent processing. However, the existing adamantane methacrylate resin compositions have low adhesion to a substrate. Resins produced by reacting ethyladamantane with maleic anhydride as in CN105295802a can be used in sealant compositions for bonding narrow-frame display devices, but require compounding with other curing agents to provide the required higher viscosity so that it can bond narrow-frame and even borderless devices such as cell phones, displays, televisions.

Disclosure of Invention

The invention aims to overcome the defects of the prior art, provides a 3-ethyl substituted adamantane acrylic ester type photoresist resin monomer with better adhesiveness with a silicon substrate, and also provides a preparation method thereof.

In order to achieve the purpose of the invention, the application provides the following technical scheme:

a photoresist film forming monomer, characterized in that: the monomer is a compound of the following general formula:

wherein R is C ₁ ～C ₆ Or a hydrogen atom.

Further, the monomer is selected from the following compounds:

the second object of the present invention is to provide a method for preparing the photoresist film-forming monomer, which comprises the following steps:

dissolving a compound of a formula III and an acid binding agent in an organic solvent, dropwise adding a compound of a formula II, and carrying out esterification reaction and purification to obtain a monomer of the formula I;

wherein X is a halogen atom, R is C ₁ ～C ₆ Or a hydrogen atom.

Further, the molar ratio of the compound of formula III, the compound of formula II and the acid binding agent is 1: (1.2-2): (1.2-2); the acid binding agent is selected from one of triethylamine, 2, 6-dimethylpiperidine and pyridine.

Further, the solvent is selected from dichloromethane, chloroform, ethyl acetate or dichloroethane.

Further, the temperature of the compound of the formula II is 0-35 ℃; the temperature of the esterification reaction is 5-35 ℃ and the time is 12-24 h.

Further, the purification comprises the steps of:

1) Quenching the reacted reaction solution by adding water, and layering the mixed solution into a first aqueous phase and a first organic phase;

2) Washing the first organic phase with saturated sodium bicarbonate aqueous solution, and layering the mixed solution into a second aqueous phase and a second organic phase;

3) Washing, drying and rotary steaming the second organic phase to obtain a crude product;

4) The crude product is subjected to column chromatography, added with polymerization inhibitor and concentrated by rotary evaporation to obtain the monomer of the formula I.

The polymerization inhibitor is selected from hydroquinone, p-hydroxyanisole and 2-tertiary butyl hydroquinone; the mol ratio of the compound of the formula III to the compound of the formula II to the acid binding agent to the polymerization inhibitor is 1: (1.2-2): (1.2-2): (0.01-2).

A third object of the present invention is to provide the use of the above-described photoresist film forming monomer as a photoresist comprising the above-described photoresist film forming monomer and at least one initiator.

The 3-ethyl substituted adamantane acrylic ester photoresist film forming monomer is synthesized, the synthetic line is simple, the operation is easy, and the adhesion of the monomer to a silicon substrate is more excellent than that of the traditional adamantane methacrylate photoresist.

Drawings

FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a photoresist film-forming monomer prepared in example 1,

FIG. 2 is a nuclear magnetic resonance spectrum of the photoresist film forming monomer prepared in example 1,

FIG. 3 is a comparative test of adhesion of the photoresist film forming monomer prepared in example 1 and 1-adamantane methacrylate.

Detailed Description

Numerical ranges in this application are approximations, so that it may include the numerical values outside of the range unless otherwise indicated. The numerical range includes all values from the lower value to the upper value that increase by 1 unit, provided that there is a spacing of at least 2 units between any lower value and any higher value. For example, if a component, physical or other property (e.g., molecular weight, etc.) is recited as 100 to 1000, it is intended that all individual values, e.g., 100, 101, 102, etc., as well as all subranges, e.g., 100 to 166,155 to 170,198 to 200, etc., are explicitly recited. For ranges containing values less than 1 or containing fractions greater than 1 (e.g., 1.1,1.5, etc.), then 1 unit is suitably considered to be 0.0001,0.001,0.01, or 0.1. For a range containing units of less than 10 (e.g., 1 to 5), 1 unit is generally considered to be 0.1. These are merely specific examples of what is intended to be provided, and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application. It should also be noted that the terms "first," "second," and the like herein do not limit the order of precedence, but are used merely to distinguish materials of different structures.

As used with respect to chemical compounds, the singular includes all isomeric forms and vice versa unless explicitly stated otherwise (e.g., "hexane" includes all isomers of hexane, either individually or collectively). In addition, unless explicitly stated otherwise, the use of the terms "a," "an," or "the" include plural referents.

The terms "comprises," "comprising," "including," and their derivatives do not exclude the presence of any other component, step or procedure, and are not related to whether or not such other component, step or procedure is disclosed in the present application. For the avoidance of any doubt, all use of the terms "comprising," "including," or "having" herein, unless expressly stated otherwise, may include any additional additive, adjuvant, or compound. Rather, the term "consisting essentially of … …" excludes any other component, step or process from the scope of any of the terms recited below, except as necessary for operability. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. The term "or" refers to the listed individual members or any combination thereof unless explicitly stated otherwise.

Example 1:

1. 3-ethyl-1-adamantanol (30 g,0.165 mol), methylene chloride (400 ml), triethylamine (28 g,0.277 mol) were successively added to a 1L three-port reaction flask equipped with a thermometer and mechanical stirring, and after stirring at 15℃for 1 hour, a mixture of methacryloyl chloride (26 ml,0.25 mol) and methylene chloride (50 ml) was slowly added dropwise under the protection of nitrogen, and the reaction was completed at 15℃for 20 hours, followed by detection of the completion of the reaction by TCL.

2. 100ml of water was added to the reaction solution, stirred sufficiently for 1 hour, left to stand for delamination, the aqueous phase was removed, the organic phase was washed with 100ml of saturated aqueous sodium hydrogencarbonate solution, the aqueous phase was removed, the organic phase was washed with 100ml of water, the aqueous phase was removed, the organic phase was dried over anhydrous sodium sulfate, filtered, the organic phase was added to 0.03g of hydroquinone, and concentrated by rotary evaporation at 35℃to give 44g of brown liquid.

3. The brown liquid was subjected to column chromatography using petroleum ether: washing with ethyl acetate (50:1) gave 33.8g of a colorless transparent liquid product, 82.6% molar yield and 98.7% purity.

Proved by nuclear magnetic resonance hydrogen spectrum and carbon spectrum (shown in figures 1 and 2), the colorless transparent liquid product is 3-ethyl-1-adamantyl methacrylate.

Example 2:

1. 3-ethyl-1-adamantanol (30 g,0.165 mol), methylene chloride (400 ml), triethylamine (26 g,0.257 mol) were successively added to a 1L three-port reaction flask equipped with a thermometer and mechanical stirring, and after stirring at 15℃for 1 hour, a mixture of methacryloyl chloride (22 g,0.211 mol) and methylene chloride (50 ml) was slowly added dropwise under the protection of nitrogen, and the reaction was completed at 15℃for 20 hours, followed by detection of the completion of the reaction by TCL.

2. 100ml of water was added to the reaction solution, stirred sufficiently for 1 hour, left to stand for delamination, the aqueous phase was removed, the organic phase was washed with 100ml of saturated aqueous sodium hydrogencarbonate solution, the aqueous phase was removed, the organic phase was washed with 100ml of water, the aqueous phase was removed, the organic phase was dried over anhydrous sodium sulfate, filtered, the organic phase was added to 0.03g of hydroquinone, and concentrated by rotary evaporation at 35℃to give 42.7g of brown liquid.

3. The brown liquid was subjected to column chromatography using petroleum ether: washing with ethyl acetate (50:1) gave 31.4g of a colorless transparent liquid product in a molar yield of 76.7% and a purity of 98.1%.

The colorless transparent liquid product is the methacrylic acid-3-ethyl adamantan-1-yl ester through nuclear magnetic resonance hydrogen spectrum and carbon spectrum verification.

Example 3

1. 3-ethyl-1-adamantanol (30 g,0.165 mol), methylene chloride (400 ml), triethylamine (26 g,0.257 mol) were successively added to a 1L three-port reaction flask equipped with a thermometer and mechanical stirring, and after stirring at 15℃for 1 hour, a mixture of acryloyl chloride (25 g,0.27 mol) and methylene chloride (50 ml) was slowly added dropwise under nitrogen protection, and the reaction was completed at 15℃for 20 hours, followed by detection of the completion of the reaction by TCL.

3. The brown liquid was subjected to column chromatography using petroleum ether: washing with ethyl acetate (50:1) gave 31.4g of a colorless transparent liquid product in a molar yield of 81.3% and a purity of 98.1%.

Example 4:

1. 3-ethyl-1-adamantanol (30 g,0.165 mol), methylene chloride (400 ml), triethylamine (26 g,0.255 mol) were successively added to a 1L three-port reaction flask equipped with a thermometer and mechanical stirring, and after stirring at 15℃for 1 hour, a mixture of acryloyl chloride (20 g,0.222 mol) and methylene chloride (50 ml) was slowly added dropwise under nitrogen protection, and the reaction was completed at 15℃for 20 hours, followed by detection of the completion of the reaction by TCL.

2. 100ml of water was added to the reaction solution, stirred sufficiently for 1 hour, left to stand for delamination, the aqueous phase was removed, the organic phase was washed with 100ml of saturated aqueous sodium hydrogencarbonate solution, the aqueous phase was removed, the organic phase was washed with 100ml of water, the aqueous phase was removed, the organic phase was dried over anhydrous sodium sulfate, filtered, the organic phase was added to 0.03g of hydroquinone, and concentrated by rotary evaporation at 35℃to give 40.1g of brown liquid.

3. The brown liquid was subjected to column chromatography using petroleum ether: washing with ethyl acetate (50:1) gave 29.3g of a colorless transparent liquid product in a molar yield of 75.5% and a purity of 98.1%.

Example 5:

1. 3-ethyl-1-adamantanol (30 g,0.165 mol), dichloroethane (400 ml), triethylamine (28 g,0.277 mol) were successively added to a 1L three-port reaction flask equipped with a thermometer and mechanical stirring, and after stirring at 15℃for 1 hour, a mixture of methacryloyl chloride (26 ml,0.25 mol) and dichloroethane (50 ml) was slowly added dropwise under the protection of nitrogen, and the reaction was completed at 15℃for 20 hours, followed by detection of the completion of the reaction by TCL.

2. 100ml of water was added to the reaction solution, stirred sufficiently for 1 hour, left to stand for delamination, the aqueous phase was removed, the organic phase was washed with 100ml of saturated aqueous sodium hydrogencarbonate solution, the aqueous phase was removed, the organic phase was washed with 100ml of water, the aqueous phase was removed, the organic phase was dried over anhydrous sodium sulfate, filtered, the organic phase was added to 0.03g of hydroquinone, and concentrated by rotary evaporation at 60℃to give 41.2g of brown liquid.

3. The brown liquid was subjected to column chromatography using petroleum ether: washing with ethyl acetate (50:1) gave 25.7g of a colorless transparent liquid product, 62.8% molar yield and 98.1% purity.

Example 6:

1. 3-ethyl-1-adamantanol (30 g,0.165 mol), methylene chloride (400 ml), pyridine (20.1 g,0.255 mol) were sequentially added to a 1L three-port reaction flask equipped with a thermometer and mechanical stirring, and after stirring at 15℃for 1 hour, a mixture of methacryloyl chloride (26 ml,0.25 mol) and methylene chloride (50 ml) was slowly added dropwise under the protection of nitrogen, and the reaction was completed at 15℃for 20 hours, followed by detection of the completion of the reaction by TCL.

2. 100ml of water was added to the reaction solution, stirred sufficiently for 1 hour, left to stand for delamination, the aqueous phase was removed, the organic phase was washed with 100ml of saturated aqueous sodium hydrogencarbonate solution, the aqueous phase was removed, the organic phase was washed with 100ml of water, the aqueous phase was removed, the organic phase was dried over anhydrous sodium sulfate, filtered, the organic phase was added with 0.03g of hydroquinone, concentrated by rotary evaporation at 35 ℃, and then concentrated at 60℃to give a light brown liquid of 44.7g.

3. The brown liquid was subjected to column chromatography using petroleum ether: washing with ethyl acetate (50:1) gave 31.9g of a colorless transparent liquid product, 77.9% molar yield and 98.4% purity.

Example 7:

2. 100ml of water was added to the reaction solution, stirred sufficiently for 1 hour, left to stand for delamination, the aqueous phase was removed, the organic phase was washed with 100ml of saturated aqueous sodium hydrogencarbonate solution, the aqueous phase was removed, the organic phase was washed with 100ml of water, the aqueous phase was removed, the organic phase was dried over anhydrous sodium sulfate, filtered, 0.03g of 2-t-butylhydroquinone was added to the organic phase, and concentrated by rotary evaporation at 35℃to give 44.7g of brown liquid.

3. The brown liquid was subjected to column chromatography using petroleum ether: washing with ethyl acetate (50:1) gave 34.9g of a colorless transparent liquid product in a molar yield of 85.2% and a purity of 99.2%.

Comparative example 1:

1. 3-ethyl-1-adamantanol (30 g,0.165 mol), tetrahydrofuran (400 ml), triethylamine (26 g,0.255 mol) were sequentially added to a 1L three-port reaction flask equipped with a thermometer and mechanical stirring, and after stirring at 15℃for 1 hour, a mixture of methacryloyl chloride (22 g,0.211 mol) and tetrahydrofuran (50 ml) was slowly dropped under nitrogen protection, and the reaction was completed at 15℃for 20 hours, followed by detection of the completion of the TCL reaction.

2. 100ml of water and 150ml of dichloromethane were added to the reaction solution, stirring thoroughly for 1 hour, the aqueous phase was removed, 100ml of dichloromethane was added to the aqueous phase, stirring thoroughly, the aqueous phase was removed, the organic phases were combined and washed with water (100 ml x 2) to neutrality, the aqueous phase was removed, the organic phases were dried over anhydrous sodium sulfate, 0.03g of hydroquinone was added, and concentrated by rotary evaporation at 35 ℃ to give a brown liquid of 30.2g.

3. The brown liquid was subjected to column chromatography using petroleum ether: ethyl acetate (50:1) to give 16.5g of 3-ethyl adamantan-1-yl methacrylate as a colorless transparent liquid, 40.3% molar yield and 98.1% purity.

Comparative example 2

1. 3-ethyl-1-adamantanol (30 g,0.165 mol), tetrahydrofuran (400 ml), triethylamine (26 g,0.255 mol) were sequentially added to a 1L three-port reaction flask equipped with a thermometer and mechanical stirring, and after stirring at 15℃for 1 hour, a mixture of acryloyl chloride (20 g,0.222 mol) and methylene chloride (50 ml) was slowly added dropwise under nitrogen protection, and the reaction was completed at 15℃for 20 hours, followed by detection of the completion of the TCL reaction.

3. The brown liquid was subjected to column chromatography using petroleum ether: ethyl acetate (50:1) to give 15.2g of 3-ethyl adamantan-1-yl acrylate as a colorless transparent liquid, 39.2% molar yield and 98.3% purity.

Comparative examples 1 and 2 illustrate that the use of tetrahydrofuran as a solvent has a side reaction, severely reducing the yield of the product.

Adhesion test

1.1 g of 3-ethyl adamantan-1-yl methacrylate prepared in example 1 and 1g of commercially available 1-adamantan methacrylate were weighed into a 2ml centrifuge tube, respectively, and 1% of initiator was added thereto, followed by ultrasonic dissolution for 5 minutes.

2. A layer of prepared 1-adamantane methacrylate and 3-ethyladamantane-1-yl methacrylate with an initiator is smeared on a glass slide, a silica gel film with the thickness of 2cm multiplied by 2cm is completely covered on the surface of the glass slide, and the glass slide is completely solidified by using a light source, wherein the thickness of the glass slide is 70-80 mu m.

3. The cured sample was dried for 16 hours and the adhesion was determined by cross-hatch. As a result, as shown in FIG. 3, it can be seen from the figure that the adhesion of the left 1-adamantane methacrylate was 0B in GB/T9286-1998, and the adhesion of the right 3-ethyladamantan-1-yl methacrylate was 3B in GB/T9286-1998, which is significantly superior to 1-adamantane methacrylate.

The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A photoresist film forming monomer, characterized in that: the monomer is a compound of the following general formula:

wherein R is C ₁ ～C ₆ Or a hydrogen atom.

2. A photoresist film forming monomer according to claim 1, wherein: the monomer is selected from the following compounds:

3. a method for preparing a photoresist film-forming monomer according to claim 1 or 2, characterized in that: the preparation method comprises the following steps:

wherein X is a halogen atom, R is C ₁ ～C ₆ Or a hydrogen atomAnd (5) a seed.

4. A method of preparation according to claim 3, characterized in that: : the molar ratio of the compound of the formula III to the compound of the formula II to the acid binding agent is 1: (1.2-2): (1.2-2).

5. A method of preparation according to claim 3, characterized in that: the acid binding agent is selected from one of triethylamine, 2, 6-dimethylpiperidine and pyridine.

6. A method of preparation according to claim 3, characterized in that: the solvent is selected from dichloromethane, chloroform, ethyl acetate or dichloroethane.

7. A method of preparation according to claim 3, characterized in that: the temperature of the compound of the formula II is 0-35 ℃; the temperature of the esterification reaction is 0-35 ℃ and the time is 6-24 h.

8. A method of preparation according to claim 3, characterized in that: the purification comprises the following steps:

9. The method of manufacturing according to claim 8, wherein: the polymerization inhibitor is selected from hydroquinone, p-hydroxyanisole and 2-tertiary butyl hydroquinone; the mol ratio of the compound of the formula III to the compound of the formula II to the acid binding agent to the polymerization inhibitor is 1: (1.2-2): (1.2-2): (0.01-2).

10. Use of a photoresist film forming monomer according to claim 1 or 2, characterized in that: is used as a photoresist comprising a photoresist film forming monomer and at least one initiator.