CN103524355A - 1,3, 5-tri (4-N, N' -dialkyl aniline) benzene organic compound and synthetic method thereof - Google Patents

Abstract

The invention relates to a micromolecule photoresist compound which can be dissolved and removed by using water as a developing solution, in particular to an organic compound with a structure of 1,3, 5-tri (4-N, N' -dialkyl aniline) benzene and a synthetic method thereof. The invention takes N, N ' -dialkyl aniline and 1,3, 5-tribromobenzene as raw materials, bromizes N, N ' -dialkyl aniline at 4-position to obtain product 4-bromine-N, N ' -dialkyl aniline, borates 4-bromine-N, N ' -dialkyl aniline at bromine atom position, and reacts the product 4-boric acid-N, N ' -dialkyl aniline with 1,3, 5-tribromobenzene to generate the organic compound with the following structure. The organic compound of the invention realizes the conversion from hydrophobic property to hydrophilic property under the action of strong acid generated by a photo-acid generator, can be dissolved and removed by using water as a developing solution, can avoid the pollution of other alkaline developing solutions to the environment, and is beneficial to reducing the cost.

Description

1,3,5-tri(4-N,N'-dialkylaniline) benzene organic compound and its synthesis method

technical field

The invention relates to a small molecule photoresist compound that can be dissolved and removed by using water as a developer, in particular to a 1,3,5-tri(4-N,N'-dialkylaniline) benzene Organic compounds and methods of their synthesis.

Background technique

Photoresists are used in microlithography to make miniaturized electronic components, such as those used to make computer chips and integrated circuits. Generally, a photoresist solution is first applied to the surface of a substrate material, such as a silicon wafer used to manufacture integrated circuits. Then the substrate coated with photoresist solution is baked to evaporate the solvent in the photoresist solution, and the formed photoresist film coating is fixed on the substrate, and then coated with photoresist film Layered substrates are exposed to light for imaging.

Photoresist is usually exposed in the ultraviolet band or a smaller wavelength (less than 400nm), according to the light source used for different wavelength exposure, such as KrF (248nm), ArF (193nm) and EUV (13.5nm), the corresponding light Resist composition will also have some changes. For example, poly(p-hydroxystyrene) and its derivatives are commonly used as photoresist host materials for 248nm photoresist, polyester cycloacrylate and its copolymer are commonly used for 193nm photoresist, polyester derivatives and molecular glass are commonly used for EUV photoresist Single-component materials and the like are host materials. In addition to the main material, the photoresist is generally added with a photoresist solvent, a photoacid generator, a crosslinking agent or other additives.

In the early 1980s, the lithography process based on the concept of chemical amplification greatly accelerated the development of lithography technology. Chemical amplification refers to the generation of strong acid through the decomposition of photoacid generator under the action of ultraviolet light, which diffuses under the action of heat and decomposes the acid-sensitive part of the photoresist host material into alkali-soluble groups, and in Part of the host material is dissolved in the developer according to the difference in solubility, so as to obtain a positive or negative image.

At present, the most widely used photoresist with acid-sensitive part is the hydroxyl compound protected by tert-butoxycarbonyl, but it will generate carbon dioxide gas during the acidolysis process, and the amount of carbon dioxide gas produced will affect the imaging of the photoresist after exposure Quality; and the developer is an alkaline solution, which will pollute the environment.

Contents of the invention

The object of the present invention is to provide a water-soluble organic photoresist with the structure of 1,3,5-tris(4-N,N'-dialkylaniline) benzene series under the action of photoacid generator compound.

Another object of the present invention is to provide a method for synthesizing a 1,3,5-tris(4-N,N'-dialkylaniline) benzene-based small molecule photoresist organic compound.

The 1,3,5-tris(4-N,N'-dialkylaniline) benzene-based small molecule photoresist organic compound of the present invention has the following general structure:

Wherein, R is a C ₁ -C ₂ alkyl group.

The synthesis method of the 1,3,5-tris(4-N,N'-dialkylaniline) benzene-based small molecule photoresist organic compound of the present invention uses N,N'-dialkylaniline and 1,3, 5-tribromobenzene is raw material, comprises the following steps successively:

(1) Bromination of N,N'-dialkylaniline at 4-position: bromination is based on N,N'-dialkylaniline as raw material. Dissolve N,N'-dialkylaniline, tetrabutylammonium bromide, and methanol in dichloromethane at a molar ratio of 1:0.1:0.5; add N, N, The dichloromethane solution of liquid bromine in an amount 1 times the number of moles of N'-dialkylaniline is reacted; after the reaction is completed, the solution obtained from the reaction is washed with water and saturated aqueous sodium bicarbonate solution, and then the washed solution is concentrated and then added into a mixed solution of ethanol and water (preferably use a mixed solution of ethanol and water with a volume ratio of 1:1) to precipitate solids, filter the solution containing solids and use a mixed solution of ethanol and water (preferably use a volume ratio of 1:1 mixed solution of ethanol and water) to wash the obtained solid, and vacuum-dry to obtain the brominated product——4-bromo-N,N'-dialkylaniline;

Wherein, R is a C ₁ -C ₂ alkyl group;

(2) Borylation of 4-bromo-N,N'-dialkylaniline: The brominated product obtained in step (1)—4-bromo-N,N'-dialkylaniline is used as a raw material. Dissolve the 4-bromo-N,N'-dialkylaniline and metal magnesium obtained in step (1) in anhydrous tetrahydrofuran at a molar ratio of 1:1.2, and carry out a reaction at room temperature under nitrogen protection (the general reaction time is 2 hours or so); then, under ice-bath conditions, add dropwise anhydrous tetrahydrofuran solution of trimethyl borate dissolved in 4-bromo-N,N'-dialkylaniline molar amount to the solution obtained from the reaction; dropwise add After the completion, continue the reaction at room temperature (the general reaction time is about 10 hours). After the reaction is completed, pour the reaction solution into 0.5M dilute hydrochloric acid, remove THF under reduced pressure, and then add sodium bicarbonate to the remaining solution to adjust the pH of the solution. >7 to generate a white solid (when the pH>7, that is, a white solid is generated), the solution containing the white solid is suction-filtered to obtain a white solid and a filtrate respectively; the obtained filtrate is extracted with dichloromethane, and the obtained organic phase Dry over sodium sulfate and concentrate to obtain a large amount of white solid; combine the above two parts of white solid obtained after suction filtration and concentration, and dry in vacuum to obtain the borated product——4-boronic acid-N,N'-dialkylaniline;

Wherein, R is a C ₁ -C ₂ alkyl group;

(3) Reaction of 4-boronic acid-N,N'-dialkylaniline with 1,3,5-tribromobenzene to generate the target compound. The borated product obtained in step (2)——4-boric acid-N,N'-dialkylaniline and 1,3,5-tribromobenzene, anhydrous potassium carbonate, tetrakistriphenylphosphine palladium according to the molar ratio It is 5:1:10:0.15 dissolved in the mixed solution of water and tetrahydrofuran (preferably using a mixed solution of water and tetrahydrofuran with a volume ratio of 1:10), and heated to reflux reaction under nitrogen protection (the general reaction time is about 5 hours) ); after the reaction was completed, most of the water and tetrahydrofuran were removed under reduced pressure, and the residue was washed with water and then extracted with dichloromethane, and the gained organic phase was separated by silica gel chromatography (eluent was V _{petroleum ether} : V _{ethyl acetate} : V _{triethylamine} =10:1:0.001) to obtain the target compound——1,3,5-tris(4-N,N'-dialkylaniline) benzene organic compound;

Wherein, R is a C ₁ -C ₂ alkyl group.

The synthesized structure of the present invention is 1,3,5-tris(4-N,N'-dialkylaniline) benzene small molecule photoresist compound, under the action of the strong acid produced by the photoacid generator, the hydrophobic The property is changed to hydrophilicity, and _CO2 gas will not be generated, and it can be dissolved and removed by using water as a developing solution. The present invention can avoid environmental pollution by using other alkaline developing solutions, and is beneficial to reduce costs.

Description of drawings

Fig. 1 is a thermogravimetric analysis (TGA) change diagram of compound A in Example 1 of the present invention.

Fig. 2 is the proton nuclear magnetic spectrum ( ¹ HNMR) of compound A in Example 1 of the present invention.

Detailed ways

The synthesis method in Example 1 was synthesized by referring to the literature Sophie Gervat, Eric Leonel, Jean-Yves Barraud, Victorin Ratovelomanana, Tetrahedron Letters, Vol.34, No.13,2115.

Example 1. Synthesis and characterization of 1,3,5-tris(4-N,N'-dimethylaniline)benzene compound A with the following structure.

The synthetic scheme of A is represented by the following formula:

1. Liquid bromine, tetrabutylammonium bromide, methanol, dichloromethane, ice bath

2. ①Magnesium, anhydrous tetrahydrofuran, iodine; ②Trimethyl borate, nitrogen protection

3. Tetrakistriphenylphosphine palladium, potassium carbonate, water, tetrahydrofuran, nitrogen protection, reflux

Specific steps are as follows:

(1) Preparation of compound 1b

Compound 1a (24.2g, 0.2mol), tetrabutylammonium bromide (6.4g, 0.02mol) and methanol (3.2g, 0.1mol) were dissolved in 100mL of dichloromethane solution, and mixed to the above Slowly add 25 mL of dichloromethane solution dissolved with liquid bromine (32 g, 0.2 mol) in the solution for reaction; Add it to the mixed solution of ethanol/water (V _ethanol : V _water = 1:1), and a large amount of white solids will be precipitated. Suction filter the solution containing the solids, and use the mixed solution of ethanol/water (V _ethanol : V _water = 1:1) The obtained solid was washed and dried in vacuum to obtain 31.2 g of compound 1b as a white solid with a yield of 78%.

(2) Preparation of compound 1c

Add polished magnesium chips (1.44g, 0.06mol) (treated with 1M dilute hydrochloric acid, acetone and then vacuum-dried) and catalytic amount of iodine particles (to accelerate the reaction, use catalytic amount of iodine particles) into 200mL of anhydrous tetrahydrofuran 30mL of anhydrous tetrahydrofuran solution dissolved in compound 1b (10g, 0.05mol) prepared in step (1) was added dropwise to it under the protection of nitrogen, and the reaction was initiated by slight heating. After the reaction started, the heat source was removed, and continued in React at room temperature for 2 hours; then add dropwise 50 mL of anhydrous tetrahydrofuran solution dissolved with trimethyl borate (10.4 g, 0.1 mol) into the above reaction system under ice bath conditions, and continue to react at room temperature for 10 hours after the dropwise addition; After the reaction is completed, pour the reaction solution into 200mL of 0.5M dilute hydrochloric acid, evaporate THF under reduced pressure, and then add sodium bicarbonate to the remaining solution to adjust the pH to >7, that is, a large amount of white solid is formed; for the solution containing white solid Suction filtration was carried out to obtain white solid and filtrate respectively; the obtained filtrate was extracted with dichloromethane, and the obtained organic phase was dried over anhydrous sodium sulfate and concentrated to obtain a large amount of white solid; the two parts obtained after the above suction filtration and concentration were The white solids were combined, washed with water and dried in vacuo to obtain 2.9 g of compound 1c as a white solid with a yield of 35.3%.

(3) Preparation of compound A

Add compound 1d (314.8mg, 1mmol), compound 1c (825mg, 5mmol) prepared in step (2), tetrakistriphenylphosphine palladium (173mg, 0.15mmol), anhydrous potassium carbonate (1.38 g, 10mmol), 5mL of water and 50mL of tetrahydrofuran, under nitrogen protection, heated and refluxed for 5 hours; The phases were separated by silica gel chromatography (eluent: V _{petroleum ether} : V _{ethyl acetate} : V _{triethylamine} = 10:1:0.001) to obtain 196 mg of compound A as a colorless solid with a yield of 45%. ¹ H NMR (400MHz, CDCl ₃ ): δ=7.63(s,3H),7.62–7.58(m,6H),6.83(d,6H,J=8.8Hz),3.00(s,18H)ppm. Melting point is 179-181°C, and the thermogravity temperature is 360°C.

According to the above method, replace N,N'-dimethylaniline with N,N'-diethylaniline to prepare 1,3,5-tris(4-N,N'-diethylaniline)benzene compound.

Claims (4)

1. A 1,3,5-tris(4-N,N'-dialkylaniline) benzene organic compound, characterized in that: the 1,3,5-tris(4-N,N' -dialkylaniline) benzene organic compounds have the following general structure:

Wherein, R is a C ₁ -C ₂ alkyl group. 2. A method for synthesizing 1,3,5-tris(4-N,N'-dialkylaniline) benzene-based organic compounds according to claim 1, characterized in that: the synthesis method comprises sequentially The following steps: (1) Dissolve N,N'-dialkylaniline, tetrabutylammonium bromide, and methanol in dichloromethane at a molar ratio of 1:0.1:0.5; There is a dichloromethane solution of liquid bromine in an amount 1 times the number of moles of N,N'-dialkylaniline for reaction; after the reaction is completed, the solution obtained by the reaction is washed with water and saturated aqueous sodium bicarbonate solution, and then the washed solution is After concentration, add it to the mixed solution of ethanol and water to precipitate the solid, filter the solution containing the solid with suction and wash the obtained solid with the mixed solution of ethanol and water, and dry it in vacuum to obtain 4-bromo-N,N'-dialkylaniline ; (2) Dissolve the 4-bromo-N,N'-dialkylaniline obtained in step (1) and metal magnesium in anhydrous tetrahydrofuran at a molar ratio of 1:1.2, and react at room temperature under nitrogen protection; then Under bath conditions, add dropwise anhydrous tetrahydrofuran solution of trimethyl borate dissolved with 2 times the molar number of 4-bromo-N,N'-dialkylaniline into the solution obtained from the reaction; Carry out the reaction, after the reaction is completed, pour the reaction solution into 0.5M dilute hydrochloric acid, remove tetrahydrofuran under reduced pressure, then add sodium bicarbonate to the remaining solution to adjust the pH of the solution>7 to form a white solid, and suction filter the solution containing the white solid , to obtain a white solid and a filtrate respectively; the obtained filtrate was extracted with dichloromethane, the obtained organic phase was dried over anhydrous sodium sulfate, and concentrated to obtain a white solid; the two parts of the white solid obtained after the above suction filtration and concentration were combined and dried in vacuo , to obtain 4-boronic acid-N,N'-dialkylaniline; (3) 4-boronic acid-N,N'-dialkylaniline obtained in step (2) is mixed with 1,3,5-tribromobenzene, anhydrous potassium carbonate, and tetrakistriphenylphosphine palladium in a molar ratio of 5 :1:10:0.15 is dissolved in the mixed solution of water and tetrahydrofuran, and heated to reflux reaction under the condition of nitrogen protection; After the phase is separated by silica gel chromatography column, 1,3,5-tri(4-N,N'-dialkylaniline) benzene organic compound with the following structure is obtained;

Wherein, R is a C ₁ -C ₂ alkyl group. 3. The synthesis method according to claim 2, characterized in that: the mixed solution of ethanol and water is a mixed solution of ethanol and water with a volume ratio of 1:1. 4. The synthesis method according to claim 2, characterized in that: the mixed solution of water and tetrahydrofuran is a mixed solution of water and tetrahydrofuran with a volume ratio of 1:10.

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