DNQ-containing double-photosensitive photoresist material as well as preparation method and application thereof

Abstract

The invention discloses a DNQ-containing double-photosensitive functional photoresist material and a preparation method and application thereof, and belongs to the technical field of photoetching materials, and the preparation method comprises the following steps: taking sulfonyl chloride and vinyl ethyl ether as modified materials, taking di-tert-butyl dicarbonate as a chemical amplifying agent, and modifying resin through free radical solution polymerization. The invention also discloses the DNQ-containing dual-photosensitive functional photoresist material prepared by the preparation method and application of the DNQ-containing dual-photosensitive functional photoresist material in a photoresist system. The DNQ-containing double-photosensitive photoresist material shows excellent resolution, has good acid resistance and coating uniformity, maintains the performance characteristics of a monomer sensitizer, also improves the dissolution characteristics and thermal stability of a resist, has excellent photochemical properties in the industrial production aspect of products in the fields of G lines and I lines, and has wide application prospects. And the method can be widely applied to the processes of circuit packaging, manufacturing of printed circuits and integrated circuits, micro-machining of discrete semiconductor devices and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of photolithography materials, and in particular relates to a dual-photosensitive photoresist material containing DNQ and a preparation method and application thereof. Background Art

[0002] Photoresist materials are key basic materials for integrated circuit manufacturing and the most critical functional chemical materials involved in photolithography technology. They can be widely used in the manufacture of printed circuits and integrated circuits, as well as in the micro-processing of discrete semiconductor devices. With the advancement of integrated circuit technology nodes, the design of raw resins corresponding to different application processes of photoresists plays a key role. Among them, polymer resins are the main components of photoresist materials. Resin raw materials determine the performance characteristics of photoresists to a certain extent, so the design of raw resins in the development of photoresists has always been an indispensable key research topic. At present, the resin raw materials in market application demand are still mainly traditional I-line resists of phenolic resins and diazonaphthoquinone (DNQ) sulfonates, which occupy a huge market share in the application of integrated circuit manufacturing, so high requirements are placed on the performance of DNQ series resins for photoresists.

[0003] Phenolic resin-diazo naphthoquinone UV positive photoresist is the most widely used and relatively mature system in G-line and I-line. Most of the commercial positive thick film photoresists belong to diazonaphthoquinone positive photoresists. The characteristics of this type of photoresist are that there is no swelling problem of the film when developing with a diluted alkaline developer, and the imaging film is easy to fall off in a concentrated alkaline solution. The PAC contained is a photosensitive composition widely used in integrated circuits (ICs), especially for liquid crystal displays (LCDs) and positive PS boards (including CTP boards). Conventional phenolic resin / diazo naphthoquinone photoactive compound (DNQ-PAC) type photoresists have slow UV sensitivity and poor resolution accuracy compared to standard chemically amplified (CA) positive photoresists. Chemically amplified (CA) positive photoresists are widely used at short wavelengths and have the characteristics of high resolution in IC manufacturing. However, CA photoresists need to undergo a post-baking process after acid generation during exposure, which is time-consuming. The large time interval between exposure and post-baking will also have a certain impact on the performance of the photoresist. This is because CA photoresist is highly sensitive to the alkali content in the air. The photoresist is baked too long after exposure, resulting in a low degree of surface deprotection of the protective groups. The photoresist surface presents a T-shape (T-Top). The manufacturing defects caused by this shape directly affect the yield and performance.

[0004] At present, a large number of literatures have reported the preparation and modification results of DNQ series photoresists in the existing field. For example, the prior art discloses a non-chemically amplified positive-tone I-line photoresist, in which poly(p-hydroxystyrene) is functionalized with the photosensitizer 2-diazo-1-naphthoquinone-4-sulfonyl chloride to obtain a new photoactive compound PHS-DNQ. The single-component non-chemically amplified positive-tone photoresist prepared by the surface plasma lithography technology is studied, and it is found that the non-chemically amplified positive-tone I-line photoresist has high sensitivity and high resolution (Wang L, Wei Q, Zhang CA non-chemically amplified positive-tone I-line photoresist for high resolution patterning [C] / / Semiconductor Technology International Conference. IEEE, 2016. DOI: 10.1109 / CSTIC.2016.7463972.). In addition, the prior art also discloses a novel one-component positive-tone chemically amplified I-line molecular glass photoresist based on tannic acid, which is prepared by an esterification reaction of tannic acid with 2-diazo-1-naphthoquinone-4-sulfonyl chloride and dibutyl dicarbonate. The compound mainly utilizes chemical modification of tannic acid to improve the solubility of the compound in various organic solvents (Qi W, Liyuan W. Novel One-component Positive-tone Chemically Amplified I-Line Molecular Glass Photoresist Based on Tannic Acid [J]. Chemical Research in Chinese Universities, 2015, 31 (004): 585-589. DOI: 10.1007 / s40242-015-5016-3.). There are also many patent literature reports on the preparation and modification of DNQ series photoresists. For example, CN114730131A discloses a diazo naphthoquinone (DNQ) type photoresist composition containing an alkali-soluble acrylic resin, which has repeating units of various structures and exhibits a development speed of 50 angstroms / second in 0.26N TMAH. CN112166378 A discloses a chemically amplified photoresist based on phenolic varnish / DNQ. The polymer component is a phenolic resin derivative, which contains a phenolic resin repeating unit with a free phenolic hydroxyl portion and a phenolic resin repeating unit with a phenolic hydroxyl portion protected by an acid-cleavable acetal portion. However, the above prior art has problems such as low resin exposure sensitivity, complex polymerization method and low resolution.

[0005] At present, the commonly used "novolac / DNQ" glue with phenolic resin monomer and diazinoquinone as the main components is widely used in G-line (436nm) and I-line (365nm) photoresists. The research on phenolic resin for photoresist mainly focuses on the modification of phenolic resin in diazo compounds, azide compounds and epoxy resins. The photoresist prepared by using a single DNQ group as a modifier has relatively poor photosensitive performance, relatively high exposure dose requirements, and the lines do not have high resolution. In a large number of research reports, physical mixing methods are used to mix additives with synthetic resins to prepare modified materials, but incompatible systems are prone to occur during the modification process, uneven dispersion and phase separation occur in the mixture, and high solubility requirements are placed on the designed solvent, which limits the subsequent application in different performance fields.

[0006] Therefore, how to modify and modify the molecular structure of phenolic resin and para-hydroxystyrene resin based on novolac / DNQ glue to provide a new modified DNQ dual-photosensitive functional photoresist resin material with high sensitivity and high resolution is a technical problem that technical personnel in this field urgently need to solve. Summary of the invention

[0007] To solve the above technical problems, the present invention proposes a synthesis and lithographic characterization of a chemically amplified, DNQ-functionalized dual-photoresist for high-resolution lithography.

[0008] To achieve the above object, the present invention provides the following technical solutions:

[0009] A method for preparing a dual-photosensitive functional photoresist material containing DNQ, using sulfonyl chloride and vinyl ethyl ether as modification materials and di-tert-butyl dicarbonate as a chemical amplifier, and modifying the resin through free radical solution polymerization.

[0010] Beneficial effects: The present invention modifies and modifies the molecular structure of the resin on the basis of novolac / DNQ glue, proposes a new synthesis method of chemically amplified glue, and prepares a dual-photosensitive photoresist material containing DNQ. The sulfonyl chloride and di-tert-butyl dicarbonate therein can produce a certain synergistic effect. Compared with the photoresist material prepared by the traditional resin only grafted with tert-butyl groups or sulfonyl chloride groups, the pattern developing ability is poor or the dissolution rate changes greatly after the photolithography process. In addition, the resin selected in the present invention has the characteristics of low cost, simple process, excellent mechanical and electrical properties, etc., so the prepared dual-photosensitive photoresist material containing DNQ has high stability.

[0011] Preferably, the resin is phenolic resin and / or p-hydroxystyrene resin;

[0012] More preferably, the phenolic resin is a condensate of phenol, methylphenol or dimethylphenol and formaldehyde, the methylphenol is one or a combination of two or more of o-methylphenol, m-methylphenol or p-methylphenol, and the dimethylphenol is one or any combination of 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol and 3,5-dimethylphenol;

[0013] The weight average molecular weight of the phenolic resin is 3000-50000, and the developing speed ADR ranges from 10-300 nm / s.

[0014] The p-hydroxystyrene resin is a reactant of nucleophilic addition of malonic acid and aldehydes and ketones, and the aldehydes and ketones are one or any combination of benzaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde and p-hydroxybenzaldehyde;

[0015] The weight average molecular weight of the p-hydroxystyrene resin is 1,000 to 50,000.

[0016] Preferably, the method specifically comprises the following steps:

[0017] The vinyl ether solution and the resin / sulfonyl chloride reaction solution are mixed and reacted to obtain a resin / sulfonyl chloride / vinyl ether reaction solution, and then di-tert-butyl dicarbonate solution is added to continue the reaction to obtain the DNQ-containing dual-photosensitive functional photoresist material.

[0018] Among them, the use of vinyl ethyl ether and sulfonyl chloride has the advantages of simple operation and easy chemical modification.

[0019] Preferably, the resin / sulfonyl chloride reaction solution is obtained by mixing sulfonyl chloride and resin in an organic solvent.

[0020] Preferably, the mass ratio of the organic solvent to the resin is (2-5):1;

[0021] The molar ratio of the sulfonyl chloride to the hydroxyl group in the resin is 1:(1.7-100), preferably 1:(2.5-50).

[0022] Preferably, the organic solvent includes one of propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), dioxane, N,N-dimethylformamide or N,N-dimethylacetamide, preferably propylene glycol methyl ether acetate.

[0023] Beneficial effects: PGMEA as a solvent has a good promoting effect on the coating of the membrane in the subsequent process, and PGMEA is more environmentally friendly and economical.

[0024] Preferably, the temperature of the mixed reaction is 20-30° C. and the time is 6-20 hours.

[0025] Preferably, the solvent in the vinyl ether solution is one of propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), dioxane, N,N-dimethylformamide or N,N-dimethylacetamide, preferably propylene glycol methyl ether acetate.

[0026] The mass ratio of the solvent of the vinyl ethyl ether solution to vinyl ethyl ether (EVE) is (2-4):1.

[0027] Preferably, the solvent in the di-tert-butyl dicarbonate solution is one of propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), dioxane, N,N-dimethylformamide or N,N-dimethylacetamide, more preferably propylene glycol methyl ether acetate (PGMEA);

[0028] The mass ratio of the solvent to di-tert-butyl dicarbonate in the di-tert-butyl dicarbonate solution is (2-4):1.

[0029] Preferably, the molar ratio of the vinyl ether to the hydroxyl group in the resin is 1:(1.7-10);

[0030] The molar ratio of the di-tert-butyl dicarbonate to the hydroxyl group in the resin is 1:(4-34).

[0031] Beneficial effects: The addition of vinyl ethyl ether and di-tert-butyl dicarbonate (BOC) in the present invention can protect the phenolic hydroxyl groups of the resin to a certain extent, and also reduce the deprotection effect of BOC, effectively improving the solubility and pattern development effects in terms of photolithography performance. In addition, the ratio of sulfonyl chloride, vinyl ethyl ether and di-tert-butyl dicarbonate (BOC) needs to be controlled within the above range. If the ratio of raw material addition is too high or too low, the performance of the obtained photoresist will be reduced. For example, when the molar ratio of the raw material BOC addition ratio to the hydroxyl group in the para-hydroxystyrene resin is 1:35, the corresponding photoresist cannot have imaging capability, as shown in SEM. Figure 5 .

[0032] Preferably, the reaction temperature is 20-30°C and the reaction time is 4-8h;

[0033] The temperature of the continued reaction is 20-30°C and the time is 4-8h.

[0034] A method for preparing a DNQ-containing dual-photosensitive functional photoresist material provides a DNQ-containing dual-photosensitive functional photoresist material.

[0035] Application of a dual-photosensitive functional photoresist material containing DNQ in a photoresist system.

[0036] A photoresist system comprises a photoacid generator and the DNQ-containing dual-photosensitive photoresist material described in the above technical solution.

[0037] Preferably, the mass ratio of the photoacid generator to the dual-photosensitive functional photoresist material containing DNQ is (0.001-0.1):1, and more preferably (0.01-0.05):1.

[0038] Preferably, the photoacid generator is a compound that can be decomposed into a strong acid under the exposure wavelength, and can be an ionic or esterified compound, and can be any commonly used type in the art, such as a sulfonium salt, an iodonium salt, etc.;

[0039] More preferably, the photoacid generator is tert-butylphenyl iodonium salt perfluorooctane sulfonic acid, triphenyl sulfonium perfluorobutyl alkane sulfonic acid, triphenyl sulfonium trifluorosulfonic acid, HG108, NIT or HG103;

[0040] Among them, the structural formulas of HG108, NIT or HG103 are as follows:

[0041]

[0042]

[0043] More preferably, an amine compound and a solvent may be added to the photoresist system as required;

[0044] Wherein, the amine compound includes tetrabutylammonium hydroxide, triethylamine or triethanolamine, but is not limited to such compounds;

[0045] The mass of the amine compound is 0.1-10% of the mass of the dual-photosensitive photoresist material containing DNQ;

[0046] The solvent is propylene glycol methyl ether acetate, and the mass ratio of the solvent to the dual-photosensitive photoresist material containing DNQ is adjusted according to actual film thickness requirements.

[0047] The photoresist material of the present invention can be deprotected by non-chemical amplification of sulfonyl chloride, which avoids the influence of acid diffusion to a certain extent. At the same time, a photoacid generator is used as a catalyst to cause the acid-labile groups hanging from the molecular chains of the polymer resin to fall off, thereby changing the polarity of the polymer. The exposure time during the chemical amplification reaction is short, and the post-baking process also promotes the reaction of the glue.

[0048] Compared with the prior art, the present invention has the following advantages and technical effects:

[0049] 1. The present invention adopts a chemical method, selects sulfonyl chloride and vinyl ethyl ether as modification materials according to the physical and chemical properties of phenolic resin and para-hydroxystyrene resin, and uses di-tert-butyl dicarbonate (BOC) as a chemical amplifier to achieve the modification of the resin by free radical solution polymerization. The dual-photosensitive photoresist material containing DNQ provided by the present invention shows excellent resolution, good acid resistance and coating uniformity, and has good adhesion to the surface of silicon substrate. The control of the ratio of vinyl ethyl ether and BOC can adjust the pattern imaging degree and film thickness of the glue. The material has excellent photochemical properties in the industrial production of products in the G-line and I-line fields;

[0050] 2. The dual-photosensitive photoresist material containing DNQ of the present invention has physical properties such as improved hardness, glossiness, adhesion and weather resistance of the coating. Compared with the traditional DNQ photoresist, the resist of the present invention exhibits higher photosensitivity due to the combined effect of photolysis and chemical amplification of the DNQ group, achieving higher sensitivity, higher resolution, less resist profile, reducing the standing wave effect, improving the photosensitivity of the chemical amplified glue, making the structure more stable, and achieving low-dose (40mJ / cm 2 ) can achieve the effect of exposing the entire area with high contrast;

[0051] 3. The dual-photosensitive photoresist material containing DNQ of the present invention protects the phenolic hydroxyl group of the resin to a certain extent, and reduces the deprotection effect of BOC, effectively improves the solubility of the glue in terms of photolithography performance, and the addition of vinyl ethyl ether improves the resolution of the photoresist, reducing the requirement for high-temperature baking. The photoresist material of the present invention has excellent resolution and coating uniformity in the field of G-line (436nm) and I-line (365nm) photoresist industry, has good adhesion to the surface of silicon substrate, realizes the synergistic effect of excellent performance after grafting of multiple single-type materials, meets the needs of multiple industries for photoresist synthetic resin materials, and can be applied to semiconductor devices that need to regulate the solubility of synthetic resins in developer, such as communication products (mobile phones), computers (notebooks), portable electronic products, consumer electronics, network hardware (servers, etc.), medical instruments, household electronic products and other electronic equipment, and can also be applied to electronics, machinery, construction and circuit packaging and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] The drawings constituting a part of the present application are used to provide a further understanding of the present application. The illustrative embodiments and descriptions of the present application are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings:

[0053] Figure 1 is a SEM image of a film prepared using the dual-photosensitive photoresist material containing DNQ prepared in Example 1;

[0054] Among them, the line size is the pattern under the 1μm mask;

[0055] Figure 2 is a SEM image of a film prepared using the dual-photosensitive photoresist material containing DNQ prepared in Example 2 under a 1 μm mask;

[0056] Figure 3 is a SEM image of a film prepared using the dual-photosensitive photoresist material containing DNQ prepared in Comparative Example 1 under a 1 μm mask;

[0057] Figure 4 is a SEM image of a film prepared using the dual-photosensitive photoresist material containing DNQ prepared in Comparative Example 2 under a 1 μm mask;

[0058] Figure 5 This is a SEM image of a film prepared using the photoresist material prepared in Comparative Example 6 (the molar ratio of the added raw material BOC to the hydroxyl group in the p-hydroxystyrene resin is 1:35) under a 1 μm mask. DETAILED DESCRIPTION

[0059] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0060] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the present invention is further described in detail below with reference to the accompanying drawings and specific embodiments.

[0061] The embodiment of the present invention provides a method for preparing a dual-photosensitive functional photoresist material containing DNQ, characterized in that sulfonyl chloride and vinyl ethyl ether are used as modifying materials, and di-tert-butyl dicarbonate is used as a chemical amplifier, and the resin is modified by free radical solution polymerization.

[0062] In a preferred embodiment, the resin is a phenolic resin and / or a p-hydroxystyrene resin;

[0063] In a more preferred embodiment, the phenolic resin is a condensate of phenol, methylphenol or dimethylphenol and formaldehyde, the methylphenol is one or a combination of two or more of o-methylphenol, m-methylphenol or p-methylphenol, and the dimethylphenol can be one or any combination of 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol and 3,5-dimethylphenol;

[0064] The weight average molecular weight of the phenolic resin is 3000-50000, and the developing speed ADR ranges from 10-300 nm / s. If it exceeds the above range, it will cause large film loss, affecting the photolithography process and the stability of the photoresist.

[0065] The p-hydroxystyrene resin is a reactant of nucleophilic addition of malonic acid and aldehydes and ketones, and the aldehydes and ketones are one or any combination of benzaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde and p-hydroxybenzaldehyde;

[0066] The weight average molecular weight of the p-hydroxystyrene resin is 1000 to 50000. If it exceeds the above range, it will increase the difficulty of chemical group modification, inaccurate modification ratio, and affect the solubility of the photoresist in the developer.

[0067] In a preferred embodiment, the method specifically comprises the following steps:

[0068] The vinyl ether solution and the resin / sulfonyl chloride reaction solution are mixed and reacted to obtain a resin / sulfonyl chloride / vinyl ether reaction solution, and then di-tert-butyl dicarbonate solution is added to continue the reaction to obtain the DNQ-containing dual-photosensitive functional photoresist material.

[0069] In a preferred embodiment, the resin / sulfonyl chloride reaction solution is obtained by mixing sulfonyl chloride and resin in an organic solvent.

[0070] In a preferred embodiment, the mass ratio of the organic solvent to the resin is 2 to 5:1;

[0071] The molar ratio of the sulfonyl chloride to the hydroxyl group in the resin is 1:(1.7-100), preferably 1:(2.5-50). If it is lower than the above range, the photoresist sensitivity will decrease, and if it is higher than the above range, the photoresist film retention efficiency will be low.

[0072] In a preferred embodiment, the organic solvent includes one of propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), dioxane, N,N-dimethylformamide or N,N-dimethylacetamide, preferably propylene glycol methyl ether acetate.

[0073] In a preferred embodiment, the temperature of the mixing reaction is 20-30°C and the time is 6-20 hours. If it is lower than the above range, the synthetic resin will be unevenly distributed and the synthesis efficiency will be low. If it is higher than the above range, the performance of the monomer will change at high temperature, affecting the stability of the experiment.

[0074] In a preferred embodiment, the solvent in the vinyl ether solution is one of propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), dioxane, N,N-dimethylformamide or N,N-dimethylacetamide, preferably propylene glycol methyl ether acetate.

[0075] The mass ratio of the solvent to the vinyl ethyl ether (EVE) of the vinyl ethyl ether solution is 2 to 4: 1. If it is lower than the above range, the sensitivity of the photoresist will be affected, and if it is higher than the above range, the process stability of the photoresist will be reduced.

[0076] In a preferred embodiment, the solvent in the di-tert-butyl dicarbonate solution is one of propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), dioxane, N,N-dimethylformamide or N,N-dimethylacetamide, more preferably propylene glycol methyl ether acetate (PGMEA);

[0077] The mass ratio of the solvent to di-tert-butyl dicarbonate in the di-tert-butyl dicarbonate solution is 2 to 4:1.

[0078] In a preferred embodiment, the molar ratio of the vinyl ether to the hydroxyl group in the resin is 1:(1.7-10);

[0079] The molar ratio of di-tert-butyl dicarbonate to the hydroxyl group in the resin is 1:(4-34). If it is lower than the above range, the film retention performance of the photoresist will deteriorate, and if it is higher than the above range, the imaging ability of the photoresist will be reduced.

[0080] In a preferred embodiment, the reaction temperature is 20-30°C and the reaction time is 4-8h;

[0081] The temperature of the continued reaction is 20-30°C and the time is 4-8 hours. If it is lower than the above range, the chemical group modification efficiency will be reduced and the alkali resistance will be reduced. If it is higher than the above range, the photoresist group will be over-protected, the lithography imaging ability will be reduced, and the sensitivity will be reduced.

[0082] The embodiment of the present invention also provides a method for preparing a dual-photosensitive functional photoresist material containing DNQ, and obtains a dual-photosensitive functional photoresist material containing DNQ.

[0083] The embodiment of the present invention also provides an application of a dual-photosensitive functional photoresist material containing DNQ in a photoresist system.

[0084] The embodiment of the present invention further provides a photoresist system, comprising a photoacid generator and the DNQ-containing dual-photosensitive photoresist material according to claim 8.

[0085] In a preferred embodiment, the mass ratio of the photoacid generator to the dual-photosensitive functional photoresist material containing DNQ is 0.001 to 0.1: 1, and more preferably 0.01 to 0.05: 1. If it is lower than the above range, the sensitivity and contrast of the photoresist will be reduced, and if it is higher than the above range, the alkali resistance of the photoresist will be reduced.

[0086] In a preferred embodiment, the photoacid generator is a compound that can be decomposed into a strong acid under the exposure wavelength, and can be an ionic or esterified compound, and can be any commonly used type in the art, such as a sulfonium salt, an iodonium salt, etc.;

[0087] In a more preferred embodiment, the photoacid generator is tert-butylphenyl iodonium salt perfluorooctane sulfonic acid, triphenyl sulfonium perfluorobutyl alkane sulfonic acid or triphenyl sulfonium trifluorosulfonic acid, HG108, NIT or HG103;

[0088] Among them, the structural formulas of HG108, NIT or HG103 are as follows:

[0089]

[0090] In a more preferred embodiment, an amine compound and a solvent may be added to the photoresist system as required;

[0091] Wherein, the amine compound includes tetrabutylammonium hydroxide, triethylamine or triethanolamine, but is not limited to such compounds;

[0092] The mass of the amine compound is 0.1-10% of the mass of the dual-photosensitive photoresist material containing DNQ;

[0093] The solvent is propylene glycol methyl ether acetate, and the mass ratio of the solvent to the dual-photosensitive photoresist material containing DNQ is adjusted according to actual film thickness requirements.

[0094] The phenolic resin, p-hydroxystyrene resin, 2-diazo-1-naphthol-4-sulfonyl chloride and 2-diazo-1-naphthol-5-sulfonyl chloride used in the examples of the present invention were purchased from Beijing New Materials (Shandong) Co., Ltd.

[0095] The phenolic resin is a condensate of p-methylphenol and formaldehyde, and has a weight average molecular weight of 4466. The molar number of hydroxyl groups is calculated as follows: the mass of the phenolic resin / 121.

[0096] The p-hydroxystyrene resin is a nucleophilic addition reaction product of malonic acid and benzaldehyde, and has a weight average molecular weight of 5949. The molar number of hydroxyl groups is calculated according to the following method: mass of the p-hydroxystyrene resin / 120.

[0097] The vinyl ethyl ether, propylene glycol methyl ether acetate, and di-tert-butyl dicarbonate used were purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0098] Unless otherwise specified, the room temperature in the embodiments of the present invention refers to 25±3°C.

[0099] Example 1

[0100] A method for preparing a dual-photosensitive functional photoresist material containing DNQ, comprising the following steps:

[0101] (1) Preparation of resin / sulfonyl chloride: 24.5 g of phenolic resin was added to a round-bottom flask containing 136 g of propylene glycol methyl ether acetate, and magnetic stirring was performed at a speed of 25 rpm. Then 3.1 g of 2-diazo-1-naphthol-5-sulfonyl chloride was added, and the mixture was mixed evenly. The mixture was reacted at room temperature for 10 h to obtain a phenolic resin / sulfonyl chloride reaction solution.

[0102] (2) Preparation of resin / sulfonyl chloride / vinyl ethyl ether: 2.5 g of vinyl ethyl ether was added to a beaker containing 2 g of propylene glycol methyl ether acetate and ultrasonically mixed. The resulting mixture was added to the reaction solution obtained in step (1), and the mixture was reacted at 25° C. with magnetic stirring for 5 h to obtain a phenolic resin / sulfonyl chloride / vinyl ethyl ether reaction solution.

[0103] (3) Preparation of dual-photosensitive functional photoresist material of DNQ: Take 3.8g of di-tert-butyl dicarbonate and add it into a beaker containing 4g of propylene glycol methyl ether acetate and mix it evenly by ultrasonic. Add the obtained mixed solution to the reaction solution obtained in step (2), and react with magnetic stirring at 25°C for 5h. The obtained reaction system is the dual-photosensitive functional photoresist material containing DNQ.

[0104] Example 2

[0105] A method for preparing a dual-photosensitive functional photoresist material containing DNQ, comprising the following steps:

[0106] (1) Preparation of resin / sulfonyl chloride: 26.8 g of p-hydroxystyrene resin was added to a round-bottom flask containing 134.5 g of propylene glycol methyl ether acetate, and magnetic stirring was performed at a speed of 25 rpm. Then 3.1 g of 2-diazo-1-naphthol-5-sulfonyl chloride was added, and the mixture was mixed evenly. The mixture was reacted at room temperature for 10 h to obtain a phenolic resin / sulfonyl chloride reaction solution.

[0107] (2) Preparation of resin / sulfonyl chloride / vinyl ethyl ether: 2.5 g of vinyl ethyl ether was added to a beaker containing 2 g of propylene glycol methyl ether acetate and ultrasonically mixed. The resulting mixture was added to the reaction solution obtained in step (1), and the mixture was reacted at 25° C. with magnetic stirring for 5 h to obtain a phenolic resin / sulfonyl chloride / vinyl ethyl ether reaction solution.

[0108] (3) Preparation of dual-photosensitive functional photoresist material of DNQ: Take 3.8g of di-tert-butyl dicarbonate and add it into a beaker containing 4g of propylene glycol methyl ether acetate and mix it evenly by ultrasonic. Add the obtained mixed solution to the reaction solution obtained in step (2), and react with magnetic stirring at 25°C for 5h. The obtained reaction system is the dual-photosensitive functional photoresist material containing DNQ.

[0109] Example 3

[0110] A method for preparing a dual-photosensitive functional photoresist material containing DNQ, comprising the following steps:

[0111] (1) Preparation of resin / sulfonyl chloride: 96.5 g of p-hydroxystyrene resin was added to a round-bottom flask containing 484.2 g of propylene glycol methyl ether acetate, and magnetic stirring was performed at a speed of 25 rpm. Then, 11.6 g of 2-diazo-1-naphthol-5-sulfonyl chloride was added, and the mixture was mixed evenly and reacted at room temperature for 10 h to obtain a phenolic resin / sulfonyl chloride reaction solution.

[0112] (2) Preparation of resin / sulfonyl chloride / vinyl ethyl ether: 10 g of vinyl ethyl ether was added into a beaker containing 6 g of propylene glycol methyl ether acetate and ultrasonically mixed. The resulting mixture was added into the reaction solution obtained in step (1), and the mixture was reacted at 25° C. with magnetic stirring for 5 h to obtain a phenolic resin / sulfonyl chloride / vinyl ethyl ether reaction solution.

[0113] (3) Preparation of dual-photosensitive functional photoresist material of DNQ: Take 135.8g of di-tert-butyl dicarbonate and add it into a beaker containing 36g of propylene glycol methyl ether acetate and mix it evenly by ultrasonic. Add the obtained mixed solution into the reaction solution obtained in step (2), and react with magnetic stirring at 25°C for 5h. The obtained reaction system is the dual-photosensitive functional photoresist material containing DNQ.

[0114] Comparative Example 1

[0115] A method for preparing a phenolic resin / sulfonyl chloride photoresist material comprises the following steps:

[0116] 24.5 g of phenolic resin was added to a round-bottom flask containing 136 g of propylene glycol methyl ether acetate, and magnetic stirring was performed at a speed of 25 rpm. Then 3.1 g of 2-diazo-1-naphthol-5-sulfonyl chloride was added, and after mixing evenly, the mixture was reacted at room temperature for 10 hours to obtain a phenolic resin / sulfonyl chloride photoresist material.

[0117] Comparative Example 2

[0118] A method for preparing a resin / sulfonyl chloride photoresist material comprises the following steps:

[0119] Preparation of resin / sulfonyl chloride: Add 26.8 g of p-hydroxystyrene resin into a round-bottom flask containing 134.5 g of propylene glycol methyl ether acetate, stir magnetically at 25 rpm, then add 3.1 g of 2-diazo-1-naphthol-5-sulfonyl chloride, mix well, and react at room temperature for 10 h to obtain a resin / sulfonyl chloride photoresist material.

[0120] Comparative Example 3

[0121] A method for preparing a resin / sulfonyl chloride / di-tert-butyl dicarbonate photoresist material comprises the following steps:

[0122] (1) Preparation of resin / sulfonyl chloride: 24.5 g of phenolic resin was added to a round-bottom flask containing 136 g of propylene glycol methyl ether acetate, and magnetic stirring was performed at a speed of 25 rpm. Then 3.1 g of 2-diazo-1-naphthol-5-sulfonyl chloride was added, and the mixture was mixed evenly. The mixture was reacted at room temperature for 10 h to obtain a phenolic resin / sulfonyl chloride reaction solution.

[0123] (2) Preparation of resin / sulfonyl chloride / di-tert-butyl dicarbonate photoresist material: 3.8 g of di-tert-butyl dicarbonate was added to a beaker containing 4 g of propylene glycol methyl ether acetate and ultrasonically mixed. The resulting mixture was added to the reaction solution obtained in step (1), and the mixture was reacted at 25° C. with magnetic stirring for 5 h. The resulting reaction system was the resin / sulfonyl chloride / di-tert-butyl dicarbonate photoresist material.

[0124] Comparative Example 4

[0125] A method for preparing a resin / sulfonyl chloride / vinyl ether photoresist material comprises the following steps:

[0126] (1) Preparation of resin / sulfonyl chloride: 24.5 g of phenolic resin was added to a round-bottom flask containing 136 g of propylene glycol methyl ether acetate, and magnetic stirring was performed at a speed of 25 rpm. Then 3.1 g of 2-diazo-1-naphthol-5-sulfonyl chloride was added, and the mixture was mixed evenly. The mixture was reacted at room temperature for 10 h to obtain a phenolic resin / sulfonyl chloride reaction solution.

[0127] (2) Preparation of resin / sulfonyl chloride / vinyl ethyl ether: 2.5 g of vinyl ethyl ether was added into a beaker containing 2 g of propylene glycol methyl ether acetate and ultrasonically mixed. The resulting mixture was added to the reaction solution obtained in step (1), and the mixture was reacted at 25° C. with magnetic stirring for 5 h to obtain a phenolic resin / sulfonyl chloride / vinyl ethyl ether photoresist material.

[0128] Comparative Example 5

[0129] A method for preparing a photoresist material, which is different from Example 1 only in that the addition ratio of sulfonyl chloride, vinyl ethyl ether and di-tert-butyl dicarbonate is changed, and specifically comprises the following steps:

[0130] (1) Preparation of resin / sulfonyl chloride: 24.5 g of phenolic resin was added to a round-bottom flask containing 136 g of propylene glycol methyl ether acetate, and magnetic stirring was performed at a speed of 25 rpm / min. Then, 2.9 g of 2-diazo-1-naphthol-5-sulfonyl chloride was added, and the mixture was mixed evenly. The mixture was reacted at room temperature for 10 h to obtain a phenolic resin / sulfonyl chloride reaction solution.

[0131] (2) Preparation of resin / sulfonyl chloride / vinyl ethyl ether: 2.3 g of vinyl ethyl ether was added to a beaker containing 2 g of propylene glycol methyl ether acetate and ultrasonically mixed. The resulting mixture was added to the reaction solution obtained in step (1), and the mixture was reacted at 25° C. with magnetic stirring for 5 h to obtain a phenolic resin / sulfonyl chloride / vinyl ethyl ether reaction solution.

[0132] (3) Preparation of dual-photosensitive functional photoresist material of DNQ: Take 3.5g of di-tert-butyl dicarbonate and add it into a beaker containing 4g of propylene glycol methyl ether acetate and mix it evenly by ultrasonic. Add the obtained mixed solution into the reaction solution obtained in step (2), and react with magnetic stirring at 25°C for 5h. The obtained reaction system is the dual-photosensitive functional photoresist material containing DNQ.

[0133] Comparative Example 6

[0134] A method for preparing a p-hydroxystyrene / di-tert-butyl dicarbonate photoresist material, which is different from Example 2 only in that only di-tert-butyl dicarbonate is modified and its addition ratio is changed, specifically comprising the following steps:

[0135] Add 24.5 g of p-hydroxy resin into a round-bottom flask containing 136 g of propylene glycol methyl ether acetate, and stir magnetically at a speed of 25 rpm / min. Add 15.3 g of di-tert-butyl dicarbonate into the obtained reaction solution, and react with magnetic stirring at 25°C for 5 hours. The obtained reaction system is p-hydroxystyrene / di-tert-butyl dicarbonate photoresist material.

[0136] Technical effects:

[0137] The photoresist materials of Examples 1-3 and Comparative Examples 1-5 were subjected to performance tests, and the film thickness was tested using an optical measurement method. The test results are shown in Table 1. The photolithography performance test was carried out according to the following process conditions, as follows:

[0138] Add 2% of the mass of the photoresist material to the obtained photoresist material, and filter the solution through a 0.2μm filter. Then use static spraying to spray on the silicon substrate. After spraying, set the speed to 300rpm, rotate for 3s so that the glue can cover the entire wafer, increase the speed to 500rpm and keep it for 5s, then accelerate to 1200rpm and keep it for 60s, and finally reduce the speed at 300rpm for 10s to complete the spraying. After coating, bake on a heating plate at 110°C for 5min. After cooling, use 2.38% tetramethylammonium hydroxide aqueous solution (TMAH) to develop for 90s. Finally, rinse with deionized water for 10s and dry, and use optical measurement to test the film thickness before and after development and calculate the difference.

[0139] Table 1 Test results

[0140] Test items Film thickness loss value (nm) Example 1 0.6 Example 2 0.2 Example 3 1.5 Comparative Example 1 659.8 Comparative Example 2 555.5 Comparative Example 3 44 Comparative Example 4 69 Comparative Example 5 24

[0141] From the test results of Examples 1-3 and Comparative Examples 1-2, it can be seen that the film loss of the product of Comparative Example 1 and the product of Comparative Example 2 is 659.8nm and 555.5nm respectively. Compared with the film thickness loss in Examples 1-3, Examples 1-3 obviously have a high film retention effect. Example 2 is within the most preferred range of the present invention, and compared with the film thickness loss in Examples 1 and 3, Example 2 has a high film retention effect.

[0142] The thin films prepared by using the photoresist materials of Example 1-2 and Comparative Example 1-2 were exposed by using a laser direct writing machine at a UV wavelength of 405 nm, and the performance was tested by using a scanning electron microscope. The results are as follows: Figure 1-4 As shown. Figure 1-4 It can be seen from the results of the test under a scanning electron microscope that the film prepared by the dual-photosensitive functional photoresist material containing DNQ of the present invention has clear resolution, good film-forming performance, and uniform coating distribution. The present invention has excellent optical properties under exposure conditions of G line (436nm) and I line (365nm). Compared with the film prepared by the photoresist material of comparative example 1-2 and example 1-2, example 1-2 obviously has higher resolution and better pattern development performance. Figure 5 The mask lines after photolithography do not appear clearly, indicating that the patterning ability of the photoresist obtained by chemical modification of the single chemical amplifier BOC is insufficient, and the amount of chemical modification also has a great influence on the photolithography performance, which further proves that Example 1-2 has excellent photolithography ability.

[0143] The above are only preferred specific implementations of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed in the present application should be included in the protection scope of the present application. Therefore, the protection scope of the present application should be based on the protection scope of the claims.

Claims

1. A method for preparing a dual-photosensitive functional photoresist material containing DNQ, characterized in that: The resin is modified by free radical solution polymerization using sulfonyl chloride and vinyl ethyl ether as modification materials and di-tert-butyl dicarbonate as a chemical amplifier.

2. The method for preparing a dual-photosensitive functional photoresist material containing DNQ according to claim 1, characterized in that: The specific steps include: The vinyl ether solution and the resin / sulfonyl chloride reaction solution are mixed and reacted to obtain a resin / sulfonyl chloride / vinyl ether reaction solution, and then di-tert-butyl dicarbonate solution is added to continue the reaction to obtain the DNQ-containing dual-photosensitive functional photoresist material.

3. The method for preparing a dual-photosensitive functional photoresist material containing DNQ according to claim 2, characterized in that: The resin / sulfonyl chloride reaction solution is obtained by dissolving sulfonyl chloride and resin in an organic solvent and mixing them for reaction.

4. The method for preparing a dual-photosensitive functional photoresist material containing DNQ according to claim 3, characterized in that: The mass ratio of the organic solvent to the resin is (2-5):1; The molar ratio of the sulfonyl chloride to the hydroxyl group in the resin is 1:(1.7-100).

5. The method for preparing a dual-photosensitive functional photoresist material containing DNQ according to claim 2, characterized in that: The temperature of the mixed reaction is 20-30° C. and the time is 6-20 hours.

6. The method for preparing a dual-photosensitive functional photoresist material containing DNQ according to claim 2, characterized in that: The molar ratio of the vinyl ether to the hydroxyl group in the resin is 1:(1.7-10); The molar ratio of the di-tert-butyl dicarbonate to the hydroxyl group in the resin is 1:(4-34).

7. The method for preparing a dual-photosensitive functional photoresist material containing DNQ according to claim 2, characterized in that: The temperature of the continued reaction is 20-30°C and the time is 4-8h.

8. The dual-photosensitive functional photoresist material containing DNQ prepared by the method for preparing the dual-photosensitive functional photoresist material containing DNQ as claimed in any one of claims 1 to 7.

9. Use of the dual-photosensitive functional photoresist material containing DNQ as claimed in claim 8 in a photoresist system.

10. A photoresist system, characterized in that: The invention comprises a photoacid generator and the dual-sensitive photoresist material containing DNQ as claimed in claim 8.

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