Polyhydroxy phenolic compounds and methods for their preparation, diazonium naphthoquinone sulfonic acid esters and methods for their preparation, and photoresist compositions

Abstract

The application provides a polyhydroxy phenolic compound, a preparation method thereof, a diazonium naphthoquinone sulfonate, a preparation method thereof and a photoresist composition. The polyhydroxy phenolic compound has the following structure shown in formula (I). The diazonium naphthoquinone sulfonate prepared by using the polyhydroxy phenolic compound provided by the application as an intermediate is applied to the photoresist composition as a photosensitive agent, and the obtained photoresist not only has clear resolution and high photosensitivity, but also has excellent thermal stability and etching resistance, and has a wide application prospect in the field of semiconductors.

Description

Technical Field

[0001] This invention relates to the field of photosensitizer technology, and more specifically, to a polyhydroxyphenol compound and its preparation method, a diazonaphthoquinone sulfonate and its preparation method, and a photoresist composition. Background Technology

[0002] Positive photoresist compositions used in integrated circuit manufacturing typically contain an alkali-soluble resin, such as linear phenolic resin, and a photosensitizer containing a diazonoquinone compound. The positive photoresist composition can be spin-coated or roll-coated onto a substrate, such as a semiconductor wafer, glass, ceramic, or metal, at a thickness of 0.5–3 μm. The coating is then heated and dried, and ultraviolet light is irradiated onto the coating through a mask to complete the exposure process. The exposed photoresist coating is then developed to form a positive pattern on the substrate. Alternatively, a positive image can be used as a mask to etch the substrate, thereby forming the desired pattern on the substrate. After development, the coating needs to be subjected to high-temperature treatment again; this process is called hardening. In most cases, after exposure, development, and hardening, the substrate is treated with an etchant solution or plasma; these processes are called wet etching or dry etching.

[0003] Among methods for forming fine photoresist patterns, the most efficient approach is to utilize high-resolution, high-contrast photoresists, which can be introduced through an exposure apparatus and a development process to obtain the aforementioned fine photoresist patterns. Positive photoresists are frequently used in integrated circuit manufacturing due to their ability to produce high-resolution and highly etch-resistant patterns. Positive photoresist compositions typically contain alkali-soluble phenolic resins and diazonaquinone-type photosensitizers. On one hand, phenolic resins are soluble in alkaline developing solutions and do not swell in the developing solution. On the other hand, the diazonaquinone photosensitizer is converted to indene carboxylic acid upon exposure, thereby increasing the solubility of the phenolic resin, while in non-exposed areas it undergoes a cross-linking reaction with the phenolic resin, thus acting as a dissolution inhibitor. The phenolic resin / diazonaphthoquinone system is widely used due to these advantages.

[0004] Some US patents disclose positive photoresist compositions containing diazonaphthoquinone sulfonate of 2,3,4-trihydroxybenzophenone and phenolic resin components, which can be used to manufacture semiconductor devices. However, photoresists containing this type of photosensitizer have problems with resolution and pattern shape (outline).

[0005] Some Japanese patents disclose positive photoresist compositions containing 2,3,4,4'-tetrahydroxybenzophenone diazonaquinone sulfonate and a phenolic resin prepared from a mixture of p-cresol and 2,5-xylenol. However, 2,3,4,4'-tetrahydroxybenzophenone diazonaquinone sulfonate has very low solubility in photoresist formulations, failing to achieve the goal of improving photoresist sensitivity. Other Japanese patents disclose positive photoresist compositions containing 2-hydroxyphenyl-2-trihydroxyphenylpropane diazonaquinone ester, but these photoresists have significant defects in thermal stability and etching resistance, making them unsuitable for dry etching processes.

[0006] In view of this, the present invention is hereby proposed. Summary of the Invention

[0007] The main objective of this invention is to provide a polyhydroxyphenol compound and its preparation method, a diazonium naphthoquinone ester and its preparation method, and a photoresist composition, in order to solve the technical problem that photoresists containing diazonium naphthoquinone structural photosensitizers in the prior art cannot simultaneously possess high resolution, high sensitivity, thermal stability, and etching resistance.

[0008] To achieve the above objectives, according to one aspect of the present invention, a polyhydroxyphenol compound is provided having the structure shown in formula (I):

[0009]

[0010] Wherein, R1, R2, and R3 independently represent hydrogen, halogen, C1-C18 straight-chain or branched alkyl, C6-C12 aryl, C1-C8 alkoxy, C1-C8 alkylthio, C2-C10 unsaturated hydrocarbon, C3-C12 cycloalkyl, C4-C12 cycloalkylalkyl, C1-C9 alkylacyl, C7-C13 aromatic acyl, C3-C6 heterocyclic group whose carbon or hydrogen atom may be selectively replaced by O, S, or N atoms, and C1-C18 alkylamino or aromatic amino; a, b, and c independently represent integers between 0 and 2; x, y, and z independently represent integers between 0 and 3, where x+y+z≥2.

[0011] Furthermore, R1, R2, and R3 each independently represent hydrogen, C1-C6 straight-chain or branched alkyl, C6-C12 aryl, and C1-C6 alkoxy.

[0012] Furthermore, the polyhydroxyphenol compound is selected from at least one of the following structural compounds:

[0013]

[0014]

[0015] To achieve the above objectives, according to another aspect of the present invention, a method for preparing a polyhydroxyphenol compound is also provided, the method comprising: step S1, mixing raw material a and raw material b in a first organic solvent and reacting them under the action of a catalyst to obtain a polyhydroxyphenol compound product system; step S2, purifying the polyhydroxyphenol compound product system to obtain a polyhydroxyphenol compound; wherein, raw material a has the structure of formula (a) and raw material b has the structure of formula (b):

[0016]

[0017] R1, R2, R3, x, y, z, a, b, c, and polyhydroxyphenolic compounds all have the same meaning as described in the first aspect above.

[0018] Further, in step S1, the molar ratio of raw material a to raw material b is 1:2 to 20, preferably 1:3 to 15, and more preferably 1:4 to 10.

[0019] Furthermore, the reaction is carried out under an inert gas atmosphere, at a temperature of 25–120°C, preferably 40–105°C, and for a reaction time of 0.5–72 h, preferably 1–24 h.

[0020] Furthermore, the catalyst includes a main catalyst and a co-catalyst. The main catalyst includes at least one of concentrated hydrochloric acid, concentrated sulfuric acid, nitric acid, perchloric acid, hydroiodic acid, hydrobromic acid, acetic acid, benzenehexacarboxylic acid, trichloroacetic acid, trifluoromethanesulfonic acid, trinitrobenzenesulfonic acid, Amberlyst 123, Amberlyst 15WET, and Amberlyst 119WET. The co-catalyst includes at least one of mercaptoacetic acid, mercaptopropionic acid, mercaptosuccinic acid, dimercaptopropanol, n-octylthiol, n-decanethiol, and n-dodecylthiol.

[0021] According to a third aspect of the invention, a diazonaphthoquinone sulfonate is also provided, which has the structure shown in formula (II):

[0022]

[0023] Formula (II), where D represents hydrogen, R1, R2, R3, x, y, z, a, b, and c all have the same meaning as in the first aspect above.

[0024] Furthermore, the diazonoquinone sulfonate is selected from at least one of the following structural compounds:

[0025]

[0026] According to a fourth aspect of the present invention, a method for preparing diazonoquinone sulfonate is also provided, the method comprising: step A1, mixing a polyhydroxyphenol compound and DNQ in a second organic solvent and reacting them under the action of an acid-binding agent to obtain a diazonoquinone sulfonate product system; step A2, purifying the diazonoquinone sulfonate product system to obtain diazonoquinone sulfonate; wherein the polyhydroxyphenol compound is any of the polyhydroxyphenol compounds provided in the first aspect above or the polyhydroxyphenol compound obtained by the preparation method provided in the second aspect above; DNQ represents at least one of the following structural compounds:

[0027]

[0028] Diazonaphthoquinone sulfonate has the structure shown in formula (II) above.

[0029] Further, in step A1, the reaction is carried out under an inert gas protective atmosphere, the reaction temperature is 20-60°C, preferably 25-40°C, and the reaction time is 0.5-6 hours, preferably 1-3 hours.

[0030] Furthermore, the acid-binding agent includes at least one of triethylamine, tripropylamine, ethylenediamine, pyridine, 4-dimethylaminopyridine, quinoline, N,N-dimethylaniline, tetramethylammonium hydroxide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, lithium diisopropylamino, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide, ammonium hydroxide, and sodium hydride, preferably at least one of triethylamine, pyridine, and sodium bicarbonate.

[0031] According to a fifth aspect of the invention, a photoresist composition is also provided, the photoresist composition comprising a resin and a photosensitizer, the photosensitizer being any of the diazonaphthoquinone sulfonates provided in the third aspect above or a diazonaphthoquinone sulfonate obtained according to any of the preparation methods provided in the fourth aspect above.

[0032] Furthermore, the diazonaphthoquinone ester accounts for 0.5% to 5.0% of the mass of the photoresist composition.

[0033] Furthermore, the resin is a phenolic resin, and preferably the phenolic resin has a weight-average molecular weight M. w The range is 2,000 to 40,000.

[0034] By applying the technical solution provided in this application, the diazonoquinone sulfonate prepared using the polyhydroxyphenol compound provided in this application as an intermediate is used as a photosensitizer in the photoresist composition. The resulting photoresist not only has clear resolution and high photosensitivity, but also excellent thermal stability and etching resistance, and has broad application prospects in the semiconductor field. Detailed Implementation

[0035] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to the embodiments.

[0036] As analyzed in the background section of this application, the photoresists containing diazonoquinone structural photosensitizers disclosed in the prior art have the technical problem that they cannot simultaneously possess high resolution, high zeta survivability, thermal stability, and etching resistance. In order to solve this technical problem, this application provides a polyhydroxyphenol compound and its preparation method, a diazonoquinone ester and its preparation method, and a photoresist composition.

[0037] In a first exemplary embodiment of this application, a polyhydroxyphenol compound is provided having the structure shown in formula (I):

[0038]

[0039] In this context, R1, R2, and R3 each independently represent hydrogen, halogen, C1-C18 straight-chain or branched alkyl, C6-C12 aryl, C1-C8 alkoxy, C1-C8 alkylthio, C2-C10 unsaturated hydrocarbon, C3-C12 cycloalkyl, C4-C12 cycloalkylalkyl, C1-C9 alkylacyl, C7-C13 aromatic acyl, C3-C6 heterocyclic group whose carbon or hydrogen atom may be selectively replaced by O, S, or N atoms, and C1-C18 alkylamino or aromatic amino; a, b, and c each independently represent an integer between 0 and 2, such as 0, 1, or 2; x, y, and z each independently represent an integer between 0 and 3, such as 0, 1, 2, or 3, where x+y+z≥2.

[0040] By applying the technical solution provided in this application, the diazonoquinone sulfonate prepared using the polyhydroxyphenol compound provided in this application as an intermediate is used as a photosensitizer in the photoresist composition. The resulting photoresist not only has clear resolution and high photosensitivity, but also excellent thermal stability and etching resistance, and has broad application prospects in the semiconductor field.

[0041] In some embodiments of this application, when R1, R2, and R3 independently represent hydrogen, C1-C6 straight-chain or branched alkyl, C6-C12 aryl, or C1-C6 alkoxy, the diazonoquinone sulfonate obtained by preparing the polyhydroxyphenol compound as an intermediate is used as a photosensitizer in the photoresist composition, and the resulting photoresist has superior resolution, photosensitivity, thermal stability, and etching resistance.

[0042] In some embodiments of this application, the polyhydroxyphenol compound is selected from at least one of the following structural compounds:

[0043]

[0044]

[0045] The diazonoquinone sulfonate prepared by using the above-mentioned polyhydroxyphenol compound as an intermediate is used as a photosensitizer in the photoresist composition, resulting in a photoresist with better performance, including better resolution, photosensitivity, thermal stability and etching resistance.

[0046] In a second typical embodiment of the above application, a method for preparing a polyhydroxyphenol compound is also provided. This method includes: step S1, mixing raw material a and raw material b in a first organic solvent and reacting them under the action of a catalyst to obtain a polyhydroxyphenol compound product system; step S2, purifying the polyhydroxyphenol compound product system to obtain a polyhydroxyphenol compound; wherein raw material a has the structure of formula (a) and raw material b has the structure of formula (b).

[0047]

[0048] The terms R1, R2, R3, x, y, z, a, b, c, and the polyhydroxyphenolic compounds all have the same meaning as in the first typical embodiment described above, and will not be repeated here.

[0049] By applying the technical solution of this application, the preparation method of polyhydroxyphenol compounds provided by this application is simple, safe to operate, low in cost, and high in yield. The solvent used can be recycled, generating less solid waste, which is environmentally friendly and easy to realize large-scale industrial production.

[0050] To further improve the yield of polyhydroxyphenol compounds, in step S1, the molar ratio of raw material a to raw material b is preferably 1:2 to 20, especially when the molar ratio is 1:3 to 15, the yield is improved, and particularly when the molar ratio is 1:4 to 10, the product yield is higher.

[0051] To further improve the preparation efficiency of polyhydroxyphenol compounds, it is preferable that the reaction in step S1 is carried out under an inert gas atmosphere, including but not limited to nitrogen and argon. The reaction temperature of raw material a and raw material b is 25–120°C, and the reaction time is 0.5–72 h, especially when the reaction temperature is 40–105°C and the reaction time is 1–24 h, which is more conducive to improving the preparation efficiency. From the perspective of energy consumption, a reaction temperature of 50–80°C is more preferred.

[0052] The catalyst is not limited to any particular substance; any substance capable of promoting the reaction of raw material a and raw material b to prepare a polyhydroxyphenol compound can be used as the catalyst of this application. From the perspective of further improving catalytic efficiency, the preferred catalyst includes a main catalyst and a co-catalyst. The co-catalyst includes, but is not limited to, one or more mixtures of concentrated hydrochloric acid (mass concentration of 20.0% to 38.0%), concentrated sulfuric acid (mass concentration of 70.0% to 98.0%), nitric acid, perchloric acid, hydroiodic acid, hydrobromic acid, acetic acid, benzenehexacarboxylic acid, trichloroacetic acid, trifluoromethanesulfonic acid, trinitrobenzenesulfonic acid, Amberlyst 123 (DuPont), Amberlyst 15WET (DuPont), and Amberlyst 119WET (DuPont). The co-catalyst includes, but is not limited to, one or more mixtures of mercaptoacetic acid, mercaptopropionic acid, mercaptosuccinic acid, dimercaptopropanol, n-octylthiol, n-decanethiol, and n-dodecylthiol.

[0053] The type of the first organic solvent is not limited; any organic solvent capable of simultaneously dispersing raw material a and raw material b is acceptable, including but not limited to one or more mixtures of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, ethylene glycol, glycerol, acetone, butanone, dichloromethane, dichloroethane, chloroform, N,N-dimethylformamide, tetrahydrofuran, 1,4-dioxane, pyridine, and N-methylpyrrolidone.

[0054] To further improve the purity of the polyhydroxyphenol compound, step S2 above preferably includes the following purification processes in sequence: crystallization, first solid-liquid separation, recrystallization, second solid-liquid separation, and drying.

[0055] To improve crystallization efficiency, crystallization is preferably carried out in hot water, with the temperature of the hot water being 30–90°C, preferably 40–80°C.

[0056] In some embodiments of this application, crystallization includes adding the polyhydroxyphenol compound product system to hot water for crystallization and washing twice to improve the purity of the product.

[0057] The methods of the first and second solid-liquid separations are not limited, including but not limited to filtration or centrifugation, with filtration being preferred.

[0058] To further improve the efficiency of recrystallization, it is preferable to carry out the above recrystallization in an organic solvent, which includes, but is not limited to, one or more of benzene, toluene, chlorobenzene, m-xylene, o-xylene, p-xylene, dichloromethane, dichloroethane, diethyl ether, ethyl acetate, petroleum ether, n-hexane, cyclohexane, n-heptane, and n-octane.

[0059] To further improve drying efficiency, vacuum drying is preferred, with a pressure of 10–500 mbar and a temperature of 40–60°C.

[0060] In some embodiments of this application, the polyhydroxyphenol compound was prepared according to the following steps:

[0061] (1) Under an inert gas protective atmosphere, the first organic solvent, raw material a, and raw material b are stirred and mixed evenly at room temperature;

[0062] (2) Add the co-catalyst and main catalyst slowly in sequence while stirring, raise the temperature to the reaction temperature, and keep the temperature for reaction.

[0063] (3) After the reaction in step (2) is completed, the resulting reaction solution is added to hot water to crystallize and washed twice, and then filtered.

[0064] (4) The solid obtained after step (3) is recrystallized with an organic solvent, filtered, and dried under reduced pressure to obtain a polyhydroxyphenol compound.

[0065] Typical, but not limiting, methods for preparing polyhydroxyphenolic compounds provided in this application may include the following molar ratios: 1:2, 1:3, 1:5, 1:6, 1:8, 1:10, 1:12, 1:15, 1:18, 1:20, or any combination of two of these ratios; 25°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 105°C, 110°C, 115°C, 120°C, or any combination of two of these ratios; and 0.5h, 1h, 2h, 5h, 8h, 12h, 16h, 24h, 36h, 48h. The values ​​are: 60h, 72h, or any two of these values; the water temperature during crystallization treatment is 30℃, 40℃, 50℃, 60℃, 70℃, 80℃, 90℃, or any two of these values; the drying pressure is 10mbar, 20mbar, 50mbar, 100mbar, 150mbar, 200mbar, 300mbar, 400mbar, 500mbar, or any two of these values; the drying temperature is 40℃, 42℃, 45℃, 48℃, 50℃, 52℃, 55℃, 58℃, 60℃, or any two of these values.

[0066] In a third typical embodiment of this application, a diazononaphthoquinone sulfonate is also provided, which has the structure shown in formula (II) below:

[0067]

[0068] Where D represents hydrogen,

[0069] R1, R2, R3, x, y, z, a, b, and c have the same meaning as in the first typical embodiment described above.

[0070] By applying the technical solution of this application, the diazonaphthoquinone sulfonate provided in this application is used as a photosensitizer in a photoresist composition. The resulting photoresist not only has clear resolution and high photosensitivity, but also excellent thermal stability and etching resistance, and has broad application prospects in the semiconductor field.

[0071] In some embodiments of this application, the diazonoquinone sulfonate is selected from at least one of the following structural compounds:

[0072]

[0073] When diazonoquinone sulfonate is selected from one or more of the above-mentioned structural compounds, the photoresist formed after its application in the photoresist composition has superior resolution, high photosensitivity, thermal stability and etching resistance.

[0074] In a fourth typical embodiment of this application, a method for preparing diazononaphthoquinone sulfonate is also provided. The method includes: step A1, mixing a polyhydroxyphenol compound and DNQ in a second organic solvent and reacting them under the action of an acid-binding agent to obtain the diazononaphthoquinone sulfonate product system; step A2, purifying the diazononaphthoquinone sulfonate product system to obtain diazononaphthoquinone sulfonate; wherein the polyhydroxyphenol compound is the polyhydroxyphenol compound provided in the first typical embodiment or the polyhydroxyphenol compound obtained according to the preparation method provided in the second typical embodiment, and the DNQ represents at least one of the following structural compounds, and the diazononaphthoquinone sulfonate has the structure shown in formula (II) above.

[0075]

[0076] The method for preparing polyhydroxyphenol compounds provided in this application is simple, safe to operate, low in cost, and has a high yield. The solvent used can be recycled, resulting in less solid waste, making it environmentally friendly and easy to scale up for industrial production.

[0077] To further improve the preparation efficiency of diazonaphthoquinone sulfonate, step A1 is preferred, in which the reaction is carried out under the protection of an inert gas, including but not limited to nitrogen or argon; the reaction temperature is 20-60℃, and the reaction time is 0.5-6h, especially when the reaction temperature is 25-40℃ and the reaction time is 1-3h, it is more conducive to improving the preparation efficiency of diazonaphthoquinone sulfonate.

[0078] The type of acid-binding agent is not limited, and any substance that can promote the reaction between polyhydroxyphenolic compounds and DNQ is acceptable, including but not limited to at least one of triethylamine, tripropylamine, ethylenediamine, pyridine, 4-dimethylaminopyridine, quinoline, N,N-dimethylaniline, tetramethylammonium hydroxide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, lithium diisopropylamino, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide, ammonium hydroxide, and sodium hydride, preferably a mixture of one or more of triethylamine, pyridine, and sodium bicarbonate.

[0079] The type of the second organic solvent is not limited; any organic solvent capable of dispersing polyhydroxyphenolic compounds and DNQ may be used, including but not limited to one or more of methanol, ethanol, benzene, toluene, dichloromethane, dichloroethane, acetone, butanone, tetrahydrofuran, o-xylene, m-xylene, N,N-dimethylformamide, tetrahydrofuran, ethyl acetate, 1,4-dioxane, pyridine, and N-methylpyrrolidone.

[0080] To further improve purification efficiency, it is preferable that in step A2 above, purification includes at least one of solid-liquid separation, crystallization, washing, and drying.

[0081] To further improve crystallization efficiency, crystallization is preferably carried out in dilute hydrochloric acid, with a preferred mass concentration of 0.1–5.0%, and more preferably 0.5–2.0%.

[0082] To further improve drying efficiency, vacuum drying is preferred, with a pressure of 10–500 mbar and a temperature of 40–60°C.

[0083] Typical, but not limiting, reactions in the preparation of diazonoquinone sulfonates include temperatures such as 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, or any range between two such values; reaction times such as 1 h, 1.5 h, 2 h, 2.5 h, 3 h, or any range between two such values; and the mass concentration of dilute hydrochloric acid used for crystallization such as 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.5%, 2%, 3%, 4%. %, 5%, or any two values ​​in the range; drying pressure such as 10mbar, 20mbar, 50mbar, 100mbar, 150mbar, 200mbar, 300mbar, 400mbar, 500mbar, or any two values ​​in the range; drying temperature such as 40℃, 42℃, 45℃, 48℃, 50℃, 52℃, 55℃, 58℃, 60℃, or any two values ​​in the range.

[0084] In some embodiments of this application, diazonoquinone sulfonate was prepared according to the following steps:

[0085] (1) Under an inert gas protective atmosphere, the second organic solvent, the polyhydroxyphenol compound and DNQ are mixed evenly;

[0086] (2) At room temperature, slowly add the acid-binding agent, raise the temperature to the reaction point, and keep the temperature to continue the reaction;

[0087] (3) After the reaction in step (2) is completed, the solid precipitated in the system is removed by filtration once. The mother liquor obtained after filtration is slowly added to dilute hydrochloric acid (mass concentration 0.5% to 2.0%), stirred to precipitate crystals, and filtered twice to obtain crude diazonium quinone sulfonate.

[0088] (4) The crude diazonoquinone sulfonate obtained in step (3) is washed three times with pure water and dried under reduced pressure to obtain diazonoquinone sulfonate.

[0089] In a fifth typical embodiment of this application, a photoresist composition is also provided, comprising a resin and a photosensitizer, wherein the photosensitizer is a diazoquinone sulfonate provided in the third typical embodiment above or a diazoquinone sulfonate obtained according to the preparation method provided in the fourth typical embodiment above.

[0090] The photoresist formed by applying the technical solution provided in this application not only has clear resolution and high photosensitivity, but also excellent thermal stability and etching resistance, and has broad application prospects in the semiconductor field.

[0091] To further improve the high photosensitivity of the photoresist, it is preferable that the mass percentage of the photosensitizer in the photoresist composition is 0.5% to 5.0%.

[0092] To further improve the mechanical strength of the photoresist, the preferred type of resin is phenolic resin, especially when the weight-average molecular weight M of the phenolic resin is M. w When the value is 2000-40000, the photoresist prepared by this photoresist composition has better mechanical properties.

[0093] Typical, but not limiting, photoresist compositions may contain a photosensitive element comprising, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, or any combination of two values; the weight-average molecular weight M of the phenolic resin is... w Such as 2000, 5000, 8000, 10000, 15000, 20000, 25000, 30000, 40000 or any two numbers in the range.

[0094] In some embodiments of this application, during the preparation of photoresist using the above-mentioned photoresist composition, phenolic resin and photosensitizer are dispersed in propylene glycol methyl ether acetate to facilitate the preparation of a photoresist with stable performance.

[0095] The beneficial effects of this application will be further illustrated below with reference to embodiments and comparative examples.

[0096] In the reaction diagrams provided in the following examples, "Cat." represents the catalyst.

[0097] Example 1

[0098] This embodiment provides a method for preparing polyhydroxyphenol compound 1(I), and the reaction diagram for its preparation is shown below:

[0099]

[0100] The specific steps include:

[0101] (1) Nitrogen gas is introduced into a 500mL four-necked flask. Under the nitrogen atmosphere, 200mL of acetone, 10.6g of raw material 1(a) and 28.2g of raw material 1(b) are added and stirred until evenly mixed. The system temperature is maintained at 25-30℃.

[0102] (2) Add 0.21g mercaptopropionic acid and 1.97g concentrated sulfuric acid (mass concentration of 98.0%) dropwise to a four-necked flask; heat to 55℃ and reflux for about 1.5 hours to complete the reaction and obtain the reaction solution;

[0103] (3) The reaction solution was added to 200 mL of pure water, and a solid precipitated out. The mixture was stirred and washed at 60 °C for 30 min, and then filtered. The filter cake was washed again with 200 mL of pure water at 60 °C for 30 min, and then filtered. The obtained solid was added to a mixed solution of toluene and methanol, and the mixture was heated to reflux under stirring until completely dissolved. The mixture was then slowly cooled to 0-5 °C using an ice-water bath. The wet filter cake was filtered and dried at 150 mbar at 60 °C to obtain a white solid. The purity was determined by HPLC to be 99.5%, and the yield was approximately 78.0%.

[0104] The structure of product 1(I) was confirmed by proton and carbon NMR spectroscopy, and the specific characterization results are as follows:

[0105] 1 H-NMR ((CD3)2SO, 400MHz): 7.97(2H,s),7.74(2H,s),7.65(2H,d),6.99(4H,d),6.86(2H,d),6.73(4H,d),6.21(2H,s);

[0106] 13 C-NMR ((CD3)2SO, 100MHz): 157.9, 153.8, 145.3, 135.7, 131.9, 129.6, 123.5, 116.1, 115.1, 113.9, 63.4.

[0107] Example 2

[0108] This embodiment provides a method for preparing polyhydroxyphenol compound 2(I), and the reaction diagram of the preparation is shown below:

[0109]

[0110] The specific steps include:

[0111] (1) Nitrogen gas is introduced into a 500mL four-necked flask. Under the nitrogen atmosphere, 200mL of methanol, 9.0g of raw material 2(a) and 32.9g of raw material 2(b) are added and stirred until homogeneous. The system temperature is maintained at 25-30℃.

[0112] (2) Add 3.25g mercaptopropionic acid and 4.93g concentrated sulfuric acid (98.0% by mass) dropwise to a four-necked flask; heat to 65℃ and reflux for about 16 hours to complete the reaction and obtain the reaction solution;

[0113] (3) The reaction solution was added to 600 mL of pure water, and a solid precipitated out. The mixture was stirred and washed at 60 °C for 30 min, and then filtered. The filter cake was then washed with 1000 mL of pure water at 60 °C for 30 min, and then filtered. The obtained solid was added to a mixed solution of toluene and methanol, and the mixture was heated to reflux under stirring until completely dissolved. The solution was then slowly cooled to 0-5 °C using an ice-water bath. The wet filter cake was filtered and dried at 150 mbar at 60 °C to obtain an off-white solid. The purity was determined by HPLC to be 99.0%, and the yield was approximately 60.5%.

[0114] The structure of product 2(I) was confirmed by proton nuclear magnetic resonance spectroscopy, and the specific characterization results are as follows:

[0115] 1H-NMR ((CD3)2SO, 400MHz): 10.28(2H,s),9.96(2H,s),7.90(2H,d),7.34-7.55(4H,t),6. 87(2H,dd),6.79(2H,s),6.68(2H,s),2.75(4H,t),1.92(4H,m),1.71(4H,m),1.19(6H,m);

[0116] Example 3

[0117] This embodiment provides a method for preparing polyhydroxyphenol compound 3(I), and the reaction diagram of the preparation is shown below:

[0118]

[0119] The preparation method differs from that in Example 2 in that raw material 2(a) is replaced with 9.8 g of raw material 3(a), and raw material 2(b) is replaced with 45.0 g of raw material 3(b). The reaction time is 12 hours, while other conditions remain unchanged. A total of 17.6 g of off-white solid product 3(I) is obtained, with a purity of 98.8% and a yield of 72.7%.

[0120] The structure of product 3(I) was confirmed by proton nuclear magnetic resonance spectroscopy, and the specific characterization results are as follows:

[0121] 1H-NMR ((CD3)2SO, 400MHz): 8.79(1H,s),8.69(2H,s),7.90(1H,d),7.70(1H,d),7.38(1H,td),7.29(1H,td),7.10(1H,dd),7.04 -7.00(2H,m),6.95(2H,dd),6.84(1H,dd),6.78(2H,d),6.23(1H,d),2.80-2.69(2H,m),1.57(4H,qdd),1.22(6H,d),0.82(6H,t);

[0122] Example 4

[0123] This embodiment provides a method for preparing polyhydroxyphenol compound 4(I), and the reaction diagram of the preparation is shown below:

[0124]

[0125] The preparation method differs from that in Example 2 in that raw material 2(a) is replaced with 10.6 g of raw material 4(a), and raw material 2(b) is replaced with 38.5 g of raw material 4(b). The reaction time is 22 hours, while other conditions remain unchanged. A total of 15.9 g of off-white solid product 5(I) is obtained, with a purity of 98.5% and a yield of 53.6%.

[0126] The structure of product 4(I) was confirmed by proton nuclear magnetic resonance spectroscopy, and the specific characterization results are as follows:

[0127] 1H-NMR ((CD3)2SO, 400MHz): 9.97(2H,s,)9.40(2H,s),8.78(2H,s,),7.65(2H,d),6.83(2H,dd),6.67 (2H,t),6.43(2H,s),6.34(2H,d),2.63(4H,td,),1.60(4H,p),1.38-1.24(12H,m),0.93-0.85(6H,m);

[0128] Example 5

[0129] This embodiment provides a method for preparing polyhydroxyphenol compound 5(I), and the reaction diagram of the preparation is shown below:

[0130]

[0131] The preparation method differs from that in Example 4 in that raw material 4(b) is replaced with 35.6 g of raw material 5(b), while other conditions remain unchanged. A total of 15.5 g of off-white solid product 5(I) was obtained, with a purity of 98.9% and a yield of 52.5%.

[0132] The structure of product 5(I) was confirmed by proton nuclear magnetic resonance spectroscopy, and the specific characterization results are as follows:

[0133] 1H-NMR ((CD3)2SO, 400MHz): 9.97(2H,s),9.40(2H,s),8.78(2H,s),7.65(2H,d),6.83(2H,dd),6.67 (2H,t),6.42(2H,s),6.34(2H,d),2.63(2H,td),1.60(4H,p),1.42-1.29(10H,m),0.94-0.85(6H,m);

[0134] Example 6

[0135] This embodiment provides a method for preparing polyhydroxyphenol compound 6(I), and the reaction diagram of the preparation is shown below:

[0136]

[0137] The preparation method differs from that in Example 4 in that raw material 4(b) is replaced with 7.4 g of raw material 6(b), while other conditions remain unchanged. A total of 17.5 g of off-white solid product 6(I) was obtained, with a purity of 99.6% and a yield of 75.0%.

[0138] The structure of product 6(I) was confirmed by proton nuclear magnetic resonance spectroscopy, and the specific characterization results are as follows:

[0139] 1H-NMR ((CD3)2SO, 400MHz): 8.79(2H,s),8.29(2H,s),7.67(2H,d),7.02(2H,dd),6.8 3(2H,dd),6.81-6.73(4H,m),6.21(2H,d),2.57(4H,td),1.65(4H,dtd),1.00(6H,t);

[0140] Example 7

[0141] This embodiment provides a method for preparing polyhydroxyphenol compound 7(I), and the reaction diagram of the preparation is shown below:

[0142]

[0143] The preparation method differs from that in Example 4 in that raw material 4(b) is replaced with 26.9 g of raw material 7(b), while other conditions remain unchanged. A total of 18.9 g of off-white solid product 7(I) was obtained, with a purity of 99.3% and a yield of 68.1%.

[0144] The structure of product 7(I) was confirmed by proton nuclear magnetic resonance spectroscopy, and the specific characterization results are as follows:

[0145] 1H-NMR ((CD3)2SO, 400MHz): 9.19(2H,s),8.79(2H,s),7.67(2H,d),6.87-6.81(4H,m),6.67(2H ,s),6.23(2H,d),2.63(4H,td),2.41(6H,s),1.60(4H,p),1.42-1.29(8H,m),0.94-0.85(6H,m);

[0146] Example 8

[0147] This embodiment provides a method for preparing polyhydroxyphenol compound 8(I), and the reaction diagram of the preparation is shown below:

[0148]

[0149] The preparation method differs from that in Example 4 in that raw material 4(b) is replaced with 41.0 g of raw material 8(b), the reaction time is 16 hours, and other conditions remain unchanged. A total of 15.1 g of off-white solid product 8(I) is obtained, with a purity of 97.3% and a yield of 48.5%.

[0150] The structure of product 8(I) was confirmed by proton nuclear magnetic resonance spectroscopy, and the specific characterization results are as follows:

[0151] 1H-NMR ((CD3)2SO, 400MHz): 8.79(2H,s),7.65(4H,d),7.03(2H,s),6.83(2H,dd),6.25(2H,s),6.21(2H,d),1.41(36H,s);

[0152] Example 9

[0153] This embodiment provides a method for preparing diazonaphthoquinone sulfonate 1(II), and the reaction diagram of the preparation is shown below, where TEA represents "triethylamine".

[0154]

[0155] The specific steps include:

[0156] (1) Nitrogen gas is introduced into a 500mL four-necked flask. Under the nitrogen atmosphere, 270mL of 1,4-dioxane, 14.0g of raw material 1(I), and 25.6g of DNQ(1) are added and stirred until homogeneous. The system temperature is maintained at 25-30℃.

[0157] (2) The system was heated to 30°C, and 10.0 g of triethylamine was added dropwise over 3.0 hours. The system temperature was maintained at 30-33°C, and the reaction was stirred for about 1.0 hour. The reaction was completed, and the diazonoquinone sulfonate 1(II) product system was obtained.

[0158] (3) The solid precipitated in the diazonaphthoquinone sulfonate 1(II) product system was filtered to remove the mother liquor. The mother liquor was slowly added to 1000 mL of 1.0 wt% dilute hydrochloric acid prepared in advance and stirred to crystallize for 1.0 h. The mixture was then filtered. The filter cake was washed three times with pure water and filtered again. The wet filter cake was dried at 150 mbar and 40 °C to obtain a total of 35.8 g of pale yellow solid product 1(II). The effective content of the esterified product was 99.1% as determined by HPLC, and the yield was about 92.0%.

[0159] Example 10

[0160] This embodiment provides a method for preparing diazonaphthoquinone sulfonate 2(II), and the reaction diagram of the preparation is shown below, where TEA represents "triethylamine".

[0161]

[0162] The preparation method differs from that in Example 9 in that raw material 1 (I) is replaced with 19.3 g of raw material 2 (I), and DNQ (1) is 31.5 g, while other conditions remain unchanged. A total of 41.7 g of pale yellow solid product 2 (II) was obtained. The effective content of the esterified product was determined by HPLC to be 99.0%, and the yield was 89.6%.

[0163] Example 11

[0164] This embodiment provides a method for preparing diazonaphthoquinone sulfonate 3(II), and the reaction diagram for its preparation is shown below, where TEA represents "triethylamine".

[0165]

[0166] The preparation method differs from that in Example 9 in that raw material 1 (I) is replaced with 17.5 g of raw material 3 (I), and DNQ (2) is 18.5 g, while other conditions remain unchanged. A total of 29.6 g of orange-yellow solid product 3 (II) was obtained. The effective content of the esterified product was determined by HPLC to be 98.9%, and the yield was 88.3%.

[0167] Example 12

[0168] This embodiment provides a method for preparing diazonaphthoquinone sulfonate 4(II), and the reaction diagram of the preparation is shown below, where TEA represents "triethylamine".

[0169]

[0170] The preparation method differs from that in Example 9 in that raw material 1(I) is replaced with 21.3g of raw material 4(I), and DNQ(1) is 39.3g, while other conditions remain unchanged. A total of 47.1g of pale yellow solid product 4(II) was obtained. The effective content of the esterified product was determined by HPLC to be 98.7%, and the yield was 85.3%.

[0171] Example 13

[0172] This embodiment provides a method for preparing diazonaphthoquinone sulfonate 5(II), and the reaction diagram of the preparation is shown below, where TEA represents "triethylamine".

[0173]

[0174] The preparation method differs from that in Example 9 in that raw material 1(I) is replaced with 20.3g of raw material 5(I), and DNQ(2) is 36.4g, while other conditions remain unchanged. A total of 57.1g of orange-yellow solid product 5(II) was obtained. The effective content of the esterified product was determined by HPLC to be 99.2%, and the yield was 91.4%.

[0175] Example 14

[0176] This embodiment provides a method for preparing diazonaphthoquinone sulfonate 6(II), and the reaction diagram for its preparation is shown below, where TEA represents "triethylamine".

[0177]

[0178] The preparation method differs from that in Example 9 in that raw material 1(I) is replaced with 17.1g of raw material 6(I), and DNQ(2) is 24.6g, while other conditions remain unchanged. A total of 59.3g of orange-yellow solid product 6(II) was obtained. The effective content of the esterified product was determined by HPLC to be 98.6%, and the yield was 90.5%.

[0179] Example 15

[0180] This embodiment provides a method for preparing diazonaphthoquinone sulfonate 7(II), and the reaction diagram for its preparation is shown below, where TEA represents "triethylamine".

[0181]

[0182] The preparation method differs from that in Example 9 in that raw material 1(I) is replaced with 20.2g of raw material 7(I), and DNQ(3) is 26.5g, while other conditions remain unchanged. A total of 39.2g of orange-yellow solid product 7(II) was obtained. The effective content of the esterified product was determined by HPLC to be 98.8%, and the yield was 90.9%.

[0183] Example 16

[0184] This embodiment provides a method for preparing diazonaphthoquinone sulfonate 8(II), and the reaction diagram for its preparation is shown below, where TEA represents "triethylamine".

[0185]

[0186] The preparation method differs from that in Example 9 in that raw material 1(I) is replaced with 22.2g of raw material 8(I), and DNQ(3) is 21.6g, while other conditions remain unchanged. A total of 36.0g of orange-yellow solid product 8(II) was obtained. The effective content of the esterified product was determined by HPLC to be 98.5%, and the yield was 88.0%.

[0187] Experimental Example 1

[0188] The solubility of compound A-2,3,4,4'-tetrahydroxybenzophenone-2,1,5-diazonaphthoquinone sulfonate (Toyo Synthetic Industries, Inc., Japan) and diazonaphthoquinone sulfonate 1(II)-8(II) provided in Examples 9-16 in propylene glycol methyl ether acetate was tested, and the results are shown in Table 1 below.

[0189] The solubility test method is as follows: At room temperature (20±0.5℃), add an appropriate amount of propylene glycol methyl ether acetate as a solvent to a 250mL glass beaker. Add 0.1g of the test sample to the solvent and stir for 30min. Visually observe whether there is any undissolved sample. If it dissolves completely, continue adding 0.1g of the test sample and stirring for 30min until insoluble matter is present. Stop adding the sample, record the data, and calculate the sample solubility according to the following formula:

[0190]

[0191] Table 1

[0192] Solubility (wt%) Compound A 1.81 1(II) 1.95 2(II) 3.25 3(II) 3.02 4(II) 8.02 5(II) 5.54 6(II) 2.97 7(II) 6.40 8(II) 4.86

[0193] As can be seen from Table 1, the novel diazonaphthoquinone sulfonate 1(II)-8(II) exhibits better solubility in propylene glycol methyl ether acetate solvent compared to the widely used 2,3,4,4'-tetrahydroxybenzophenone-2,1,5-diazonaphthoquinone sulfonate, making it more suitable for photoresist preparation.

[0194] Experimental Example 2

[0195] The diazonaphthoquinone sulfonates 1(II)-8(II) and compound A-2,3,4,4'-tetrahydroxybenzophenone-2,1,5-diazonaphthoquinone sulfonate (Toyo Synthetic Industries, Inc., Japan) provided in Examples 9-16 above were mixed with resin, surfactant, adhesion promoter and solvent to form a photoresist solution. Based on 100 parts by weight of the photoresist solution, the solvent was 86 parts, the resin was 11 parts, the surfactant was 0.5 parts, the adhesion promoter was 1.0 part and the photosensitizer was 1.5 parts. The resin was a linear phenolic resin with a weight-average molecular weight of 6000 (Sumitomo Chemical Co., Ltd., Japan); the solvent was propylene glycol methyl ether acetate (Shanghai Titan Technology Co., Ltd.); the surfactant was perfluorinated surfactant S-386 (Asahi Glass Co., Ltd., Japan); and the adhesion promoter was melamine adhesive (3M China Co., Ltd.).

[0196] The aforementioned photoresist solutions were spin-coated onto silicon wafers. After vacuum drying, they were baked on a hot plate at 110°C for 90 seconds to form a photoresist coating with a thickness of approximately 1.5 μm. The photoresist coating was then exposed using a mercury lamp as the light source, with a total exposure energy of 200–400 mJ / cm². 2 After exposure, the image was developed using a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 20 seconds. After rinsing with water for 30 seconds, it was dried to remove the exposed portion, forming the photoresist pattern. The photoresist pattern was inspected using a scanning electron microscope (SU1000, Hitachi High Technology Group, Japan) to compare the resolution of the photoresist, with the minimum achievable linewidth as the standard. The resolution test results for different photoresist patterns are shown in Table 2.

[0197] Table 2

[0198] Resolution (μm) Compound A 3.5 1(II) 1.5 2(II) 1.5 3(II) 2.0 4(II) 1.5 5(II) 1.5 6(II) 1.5 7(II) 1.5 8(II) 1.5

[0199] Compared to compound A-2,3,4,4'-tetrahydroxybenzophenone-2,1,5-diazonaphthoquinone sulfonate, the diazonaphthoquinone sulfonate 1(II)-8(II) provided in Examples 9-16 produces a higher resolution pattern after exposure and development of the photoresist prepared by applying it to the photoresist composition.

[0200] Experimental Example 3

[0201] The silicon wafers with photoresist patterns prepared in Example 2 were cut into several samples and baked on hot plates at temperatures of 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, 155℃, and 160℃ for 2 minutes each. After baking, the samples were allowed to cool naturally to room temperature, and the cross-section of each photoresist pattern was observed using an optical microscope. The angle between the photoresist sidewall and the substrate was measured. When the angle was less than 70°, this temperature was considered the deformation initiation temperature, i.e., the heat resistance temperature of the photoresist. The results are shown in Table 3.

[0202] Table 3

[0203]

[0204]

[0205] Compared to compound A-2,3,4,4'-tetrahydroxybenzophenone-2,1,5-diazonaphthoquinone sulfonate, the diazonaphthoquinone sulfonate 1(II)-8(II) provided in Examples 9-16 exhibits a higher heat resistance temperature when applied to photoresist compositions.

[0206] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A photoresist composition, characterized in that, The photoresist composition comprises a resin and a photosensitizer, wherein the photosensitizer is selected from at least one of the following diazonoquinone esters: 、 、 、 、 、 、 、 ； The preparation method of the diazonoquinone ester includes: Step A1: The polyhydroxyphenol compound and DNQ are mixed in a second organic solvent and reacted under the action of an acid-binding agent to obtain the diazonoquinone sulfonate product system. Step A2: Purify the diazonoquinone sulfonate product system to obtain diazonoquinone sulfonate; The polyhydroxyphenolic compound is selected from at least one of the following structural compounds: 、 、 、 、 、 、 、 ； The DNQ represents at least one of the following structural compounds: 。 2. The photoresist composition according to claim 1, characterized in that, The diazonaphthoquinone sulfonate is selected from at least one of the following structural compounds: 、 。 3. The photoresist composition according to claim 1, characterized in that, In step A1, the reaction is carried out under an inert gas protective atmosphere, the reaction temperature is 20~60℃, and the reaction time is 0.5~6h.

4. The photoresist composition according to claim 3, characterized in that, In step A1, the reaction temperature is 25~40℃; and / or the reaction time is 1~3h.

5. The photoresist composition according to claim 1, characterized in that, Step A1, The acid-binding agent includes at least one of triethylamine, tripropylamine, ethylenediamine, pyridine, 4-dimethylaminopyridine, quinoline, N,N-dimethylaniline, tetramethylammonium hydroxide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, lithium diisopropylamino, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide, ammonium hydroxide, and sodium hydride.

6. The photoresist composition according to claim 5, characterized in that, The acid-binding agent is at least one of triethylamine, pyridine, and sodium bicarbonate.

7. The photoresist composition according to claim 1, characterized in that, The resin is a phenolic resin.

8. The photoresist composition according to claim 1, characterized in that, The weight-average molecular weight M of phenolic resin w The range is 2,000 to 40,000.

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