A fluorine-containing diazonium naphthoquinone photosensitive compound, a preparation method and application thereof

Abstract

The application discloses a fluorine-containing diazonium naphthoquinone photosensitive compound and a preparation method and application thereof, and belongs to the technical field of photoetching materials.The fluorine-containing polyphenol compound is used as a grafting matrix, and is subjected to esterification reaction with diazonium naphthoquinone sulfonyl chloride, so that the fluorine-containing diazonium naphthoquinone sulfonate photosensitizer with high resolution, high heat resistance and low metal ions is obtained.Compared with the same photosensitizer without fluorine, the fluorine-containing photosensitive compound has a thermal decomposition temperature increased by about 15 DEG C, the photoresist contrast can be up to 2.03, the sensitivity is 240 mJ / cm 2 , and a 5-micron fine line pattern can be developed.The photosensitive compound provided by the application significantly improves the thermal stability, resolution and contrast of the i-line photoresist, and is suitable for photoetching processes in the fields of integrated circuit manufacturing, display panel processing and advanced packaging.

Description

Technical Field

[0001] This invention belongs to the field of photolithography materials technology, specifically relating to a fluorinated diazonium naphthoquinone-based photosensitive compound, its preparation method, and its application. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] As photolithography technology continues to advance towards extreme ultraviolet (EUV), traditional ultraviolet photoresists, represented by i-line (365 nm), have maintained an irreplaceable position due to their mature process system and significant cost advantages. G-line (436 nm) and I-line (365 nm) photoresists are core materials for mature semiconductor processes, display panels, and advanced packaging. Their mainstream system is a photosensitizer composed of phenolic resin and diazonaphthoquinone (DNQ).

[0004] Traditional diazonaphthoquinone (DNQ) photosensitizers generally use a fluorine-free polyphenol skeleton, which has the following key defects: (1) poor thermal stability, the diazo group is easily decomposed by heat; (2) low photosensitivity and slow exposure response; (3) weak solubility inhibition and insufficient contrast; (4) resolution is difficult to further improve; (5) poor compatibility with resin, which affects the image quality.

[0005] Currently, there is no mature technology that uses fluorine to introduce modified diazonaphthoquinone photosensitizers to achieve high thermal stability, high contrast, and high resolution. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a fluorinated diazonoquinone-based photosensitive compound, its preparation method, and its applications.

[0007] To achieve the above objectives, the technical solution of the present invention is as follows: In a first aspect, the present invention provides a fluorinated diazononaphthoquinone photosensitizer, which is obtained by esterification reaction of a fluorinated polyphenol grafted parent with diazononaphthoquinone sulfonyl chloride; The fluorinated polyphenol graft parent has fluorine atoms, trifluoromethyl or trifluoroethyl substituents; The diazonoquinone group includes 1,2-naphthoquinone-2-azido-5-sulfonyl.

[0008] Secondly, the present invention provides a method for preparing the above-mentioned fluorinated diazonoquinone photosensitizer, comprising the following steps: The fluorinated polyphenol graft parent compound and diazonoquinone sulfonyl chloride were dissolved in an organic solvent and stirred together. Then, an alkaline catalyst was added and the reaction continued. The pH of the resulting reaction solution was adjusted to ≤5, and a solid was precipitated. The solid was then filtered, washed, and dried to obtain the final product.

[0009] Thirdly, the present invention provides a photosensitizer composition comprising the above-described fluorinated diazonoquinone photosensitizer or the fluorinated diazonoquinone photosensitizer prepared by the above-described preparation method.

[0010] Fourthly, the present invention provides the application of the above-mentioned fluorinated diazononaphthoquinone photosensitizer or the fluorinated diazononaphthoquinone photosensitizer or the above-mentioned photosensitizer composition in G / I photoresist.

[0011] Fifthly, the present invention provides a G / I line positive photoresist, comprising, by weight: 100 parts of phenolic resin; 1-50 parts of the above-mentioned fluorinated diazonoquinone photosensitizer; and 70-1900 parts of organic solvent; It also includes a silane coupling agent (KH560), with a mass-to-volume ratio of phenolic resin to silane coupling agent of (0.1~1):(40~100), expressed in g / μL.

[0012] In a sixth aspect, the present invention provides an application of the above-mentioned G / I line positive photoresist in semiconductor I-line lithography, OLED / liquid crystal display panel lithography, advanced packaging lithography, and LED lithography.

[0013] One or more of the above technical solutions have the following advantages or beneficial effects: This invention uses fluorinated polyphenol compounds as grafting matrix and performs esterification reaction with diazononaphthoquinone sulfonyl chloride to obtain high-resolution, high-heat-resistant, low-metal-ion fluorinated diazononaphthoquinone sulfonate photosensitizers.

[0014] The photosensitive compound was prepared by esterification of a fluorinated grafted parent compound with 2-diazo-1-naphthoquinone-5-sulfonyl chloride. The fluorinated grafted parent compound was selected from fluorinated monobenzene ring polyphenol structures such as 1-(2,4-dihydroxyphenyl)-2,2,2-trifluoroethane-1-one and 2,2,2-trifluoro-1-(2,3,4-trihydroxyphenyl)ethane-1-one. The fluorinated grafted parent compound was prepared via Friedel-Crafts acylation, a short synthetic route with readily available starting materials.

[0015] Compared to fluorine-free photosensitizers of the same type, the fluorine-containing photosensitive compound of this invention has a thermal decomposition temperature that is increased by approximately 15°C, a photoresist contrast ratio that can reach up to 2.03, and a sensitivity of 240 mJ / cm². 2 It can develop fine line patterns of 5 μm.

[0016] The photosensitive compound provided by this invention significantly improves the thermal stability, resolution, and contrast of i-line photoresists, making it suitable for photolithography processes in integrated circuit manufacturing, display panel processing, and advanced packaging. Attached Figure Description

[0017] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0018] Figure 1 Infrared spectra of 14 fluorinated diazonoquinone photosensitizers (A-DNQ~N-DNQ).

[0019] Figure 2 The UV-Vis absorption spectra of 14 fluorinated diazonoquinone photosensitizers (A-DNQ~N-DNQ) are shown.

[0020] Figure 3 TGA curves for 14 fluorinated diazonoquinone photosensitizers (A-DNQ~N-DNQ).

[0021] Figure 4 The effect of diazonaphthoquinone photosensitizers (A-DNQ~F-DNQ) on photolithography at different solid contents and exposure doses; (a) solid content of 10 wt% (corresponding to an exposure dose of 240 mJ / cm²) 2 (a) Optical image at the corresponding exposure dose, (b) Solid content of 15 wt% (corresponding to an exposure dose of 300 mJ / cm²) 2 (c) Optical image at the corresponding exposure dose, and (d) photoresist with a solid content of 20 wt% (corresponding to an exposure dose of 360 mJ / cm). 2 Optical image at the corresponding exposure dose. The gray areas in the image represent the background color of the silicon wafer. Scale bar: 100 μm.

[0022] Figure 5 The effect of diazonaphthoquinone photosensitizers (G-DNQ~L-DNQ) on photolithography at different solid contents and exposure doses was investigated; among which, (a) a solid content of 10 wt% (corresponding to an exposure dose of 240 mJ / cm) was used. 2 (a) Optical image at the corresponding exposure dose, (b) Solid content of 15 wt% (corresponding to an exposure dose of 300 mJ / cm²) 2 (c) Optical image at the corresponding exposure dose, and (d) photoresist with a solid content of 20 wt% (corresponding to an exposure dose of 360 mJ / cm). 2 Optical image at the corresponding exposure dose. The gray areas in the image represent the background color of the silicon wafer. Scale bar: 100 μm.

[0023] Figure 6The effect of different solid contents and exposure doses on the photolithography effect of diazononaphthoquinone photosensitizers (M-DNQ~N-DNQ); among which, (a) solid content of 10 wt% (corresponding to an exposure dose of 240 mJ / cm) 2 (a) Optical image at the corresponding exposure dose, (b) Solid content of 15 wt% (corresponding to an exposure dose of 300 mJ / cm²) 2 (c) Optical image at the corresponding exposure dose, and (d) photoresist with a solid content of 20 wt% (corresponding to an exposure dose of 360 mJ / cm). 2 Optical image at the corresponding exposure dose. The gray areas in the image represent the background color of the silicon wafer. Scale bar: 100 μm.

[0024] Figure 7 shows the E-DNQ photoresist with a solid content of 15 wt% at 300 mJ / cm². 2 Photolithographic pattern under exposure. Scale bar: 100 μm.

[0025] Figure 8 Contrast curves showing the normalized film thickness as a function of exposure dose for D-DNQ, E-DNQ, F-DNQ, and G-DNQ. Detailed Implementation

[0026] This invention addresses the problems of low resolution and contrast, and insufficient thermal stability of i-line photoresists in existing technologies by introducing fluorine atoms or trifluoromethyl (–CF3) at specific sites in the grafting matrix, achieving three core improvements: (1) Fluorine improves thermal stability The C–F bond energy is extremely high (≈485 kJ / mol), much higher than that of CH and CC bonds. The steric hindrance and electronic effects of fluorine atoms inhibit the thermal decomposition of the diazo group, increasing the thermal decomposition temperature by 10–20℃.

[0027] (2) Fluorine enhances photosensitivity (faster light response) The strong electron-withdrawing effect of fluorine reduces the electron cloud density of diazo groups, promotes the photolysis Wolff rearrangement, and makes the photosensitizer easier to decompose at the I line (365 nm), thus improving photosensitivity.

[0028] (3) Fluorine enhances contrast and resolution Fluorine enhances intermolecular hydrogen bonding and polar interactions, significantly improving the ability to inhibit dissolution in unexposed areas; after exposure, carboxylic acids are generated, resulting in a larger abrupt change in solubility, a significant increase in contrast γ, and steeper image edges with higher resolution.

[0029] In one typical embodiment, the present invention provides a fluorinated diazononaphthoquinone photosensitizer, which is obtained by esterification reaction of a fluorinated polyphenol grafted parent with diazononaphthoquinone sulfonyl chloride; The fluorinated polyphenol graft parent has fluorine atoms, trifluoromethyl or trifluoroethyl substituents; The diazonoquinone group is selected from one of 1,2-naphthoquinone-2-diazo-5-sulfonyl groups.

[0030] In some embodiments of this implementation, the fluorinated polyphenol grafting parent material is selected from one of the following structures: (1) 1-(2,4-dihydroxyphenyl)-2,2,2-trifluoroethane-1-one; (2) 2,2,2-trifluoro-1-(2,3,4-trihydroxyphenyl)ethane-1-one; (3) difluorosubstituted resorcinol derivatives; (4) fluorinated tribenzodiol compounds.

[0031] The structural formula of the graft parent includes any one or more of the following AN: .

[0032] The fluorine-grafted parent skeleton is selected from a single benzene ring structure containing at least two phenolic hydroxyl groups, and one or more fluorine-containing substituents are attached to the benzene ring; Fluorine-containing grafting parent E: 2,2,2-trifluoro-1-(2,3,4-trihydroxyphenyl)ethane-1-one.

[0033] The fluorine-containing grafted parent materials (D, E, F, G) are prepared through the following steps: Resorcinol or pyrogallol was reacted with trifluoroacetic anhydride under aluminum trichloride catalysis by Friedel-Crafts acylation to obtain a fluorinated ketone intermediate. The preparation process of the fluorinated grafted parent compound D or E includes: resorcinol or pyrogallol and trifluoroacetic anhydride undergoing a Friedel-Crafts acylation reaction under aluminum trichloride catalysis to obtain a fluorinated ketone intermediate. Specific steps include: dissolving resorcinol in an organic solvent, then adding aluminum trichloride; adding trifluoroacetic anhydride in an ice bath under a protective atmosphere, maintaining the reaction at 0°C for 20–40 min, then heating to 30–50°C and refluxing for 7–9 h; finally, extraction, concentration, and purification to obtain the final product.

[0034] Furthermore, the molar ratio of resorcinol or pyrogallol, trifluoroacetic anhydride and aluminum trichloride is (10~30):(10~30):(30~50), preferably (15~25):(15~25):(35~45).

[0035] The specific preparation process of the fluorinated photosensitizer structure (fluorine-introduced DNQ system) is shown below:

[0036] The mechanisms of action of fluorine include: electron-withdrawing effect to improve photosensitivity; high bond energy to improve thermal stability; strong hydrogen bonding to improve solubility contrast; and low polarity / high hydrophobicity to improve film uniformity.

[0037] In one typical embodiment, the present invention provides a method for preparing the above-mentioned fluorinated diazonoquinone photosensitizer, comprising the following steps: The fluorinated polyphenol graft parent compound and diazonoquinone sulfonyl chloride were dissolved in an organic solvent and stirred together. Then, an alkaline catalyst was added and the reaction continued. The pH of the resulting reaction solution was adjusted to ≤5, and a solid was precipitated. The solid was then filtered, washed, and dried to obtain the final product.

[0038] Adjusting the pH to ≤5 is to ensure the esterification rate of the phenolic hydroxyl groups.

[0039] Preferably, the preparation method includes the following steps: Step S1: Dissolve the fluorine-containing grafted parent material in the organic solvent acetone, add 2-diazo-1-naphthoquinone-5-sulfonyl chloride, and stir and mix at a temperature of 20~40℃; Step S2: Add the alkaline catalyst triethylamine dropwise, and continue the reaction for 2-4 hours, monitoring the reaction by TLC until it is complete; Step S3: Pour the reaction solution into deionized water, adjust the pH to about 5, precipitate the solid, filter, wash, and vacuum dry to obtain the fluorinated diazonoquinone photosensitive compound.

[0040] In some embodiments of this implementation, when the fluorinated polyphenol graft parent and diazonoquinone sulfonyl chloride are dissolved in an organic solvent, they are stirred in a water bath at 20~60℃ (specifically 20℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, etc., preferably 30~50℃) for 10~60 min (specifically 10 min, 20 min, 30 min, 40 min, 50 min, 60 min, etc., preferably 20~40 min).

[0041] In some embodiments of this implementation, the molar ratio of the fluorinated polyphenol graft parent to diazonoquinone sulfonyl chloride is 1:(0.1~5), specifically 1:0.1, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, or 1:5. The organic solvent includes acetone.

[0042] Basic catalysts include one or more of triethylamine, pyridine, and diisopropylethylamine.

[0043] The molar ratio of diazonoquinone sulfonyl chloride to alkaline catalyst is (0.8~1.2):(0.8~1.2), preferably 1:1. Generally, it is in equal amounts with sulfonyl chloride, as it acts as an acid-binding agent, reacting with an equal amount of HCl released during the reaction; therefore, an equal amount with Cl atoms is sufficient.

[0044] The mass-volume ratio of the grafting parent material to the organic solvent is (0.5~2):(10~30), preferably (1~1.1):(15~25), in g / mL.

[0045] In some embodiments of this implementation, the alkaline catalyst is added dropwise at a rate of 17.5 mol / (0.5h~2h) for a duration of 0.5~2h. After the addition is complete, the reaction continues at 20~60℃ for 1~4h, specifically 1h, 2h, 2.5h, 3h, 3.5h, 4h, etc.

[0046] It should be noted that the alkaline catalyst should be added dropwise. If it is added all at once, the reaction will be too fast, the system will be too messy, and the esterification rate of the subsequent products cannot be guaranteed.

[0047] In some embodiments of this implementation, water is added to the obtained reaction solution, the pH is adjusted to ≤5 with acid, and the mixture is stirred at room temperature for 0.5~5h, preferably 0.5~1.5h.

[0048] In some embodiments of this implementation, the drying includes vacuum drying, with drying conditions of 40~50℃ for 5~10 h.

[0049] Preferably, a method for preparing a fluorinated diazononaphthoquinone photosensitizer includes the following steps: dissolving a fluorinated polyphenol graft matrix and diazononaphthoquinone sulfonyl chloride in an organic solvent; adding an organic base as a dehydrohalogenation reagent and reacting at 20-60°C for 1-4 h; quenching the reaction system with acid until pH < 5; adding pure water to crystallize, filtering, washing, and vacuum drying to obtain the fluorinated diazononaphthoquinone photosensitizer.

[0050] In one typical embodiment, the present invention provides a photosensitizer composition comprising the above-described fluorinated diazonoquinone photosensitizer or the fluorinated diazonoquinone photosensitizer prepared by the above-described preparation method.

[0051] In one typical embodiment, the present invention provides the application of the above-mentioned fluorinated diazononaphthoquinone photosensitizer or the fluorinated diazononaphthoquinone photosensitizer prepared by the above preparation method or the above photosensitizer composition in G / I photoresist.

[0052] Esterification rate of photoresist ( 1 The content of H NMR (integrated method) is ≥65%, preferably ≥68.7%, and more preferably ≥80%.

[0053] The thermal decomposition temperature of the photoresist (TGA first stage) is ≥150℃, preferably ≥155℃, and more preferably ≥160℃.

[0054] In one typical embodiment, the present invention provides a G / I line positive photoresist, comprising, by weight: 100 parts of phenolic resin; 1-50 parts of the above-mentioned fluorinated diazonoquinone photosensitizer; and 70-1900 parts of organic solvent.

[0055] The photoresist has a solid content of 10 wt% to 20 wt%, preferably 14 wt% to 16 wt%, and optimally 15 wt%. Different solid contents require different exposure doses. The exposure dose corresponding to a 10 wt% solid content photoresist is 240 mJ / cm². 2 15wt% and 20wt% solid content photoresists correspond to 300mJ / cm². 2 and 360mJ / cm 2 The exposure metering is determined by the amount of solids. Lower solids content corresponds to a lower amount of photosensitizer, thus reducing the required exposure metering.

[0056] It also includes a silane coupling agent (KH560), and the mass-volume ratio of phenolic resin to silane coupling agent is (0.1~1):(40~100), preferably (0.4~0.6):(40~60), in g / μL.

[0057] The preparation method of G / I line positive photoresist includes: mixing phenolic resin, the above-mentioned fluorinated diazonoquinone photosensitizer, organic solvent and silane coupling agent, magnetically stirring until completely dissolved, filtering, and allowing to stand to remove bubbles to obtain positive photoresist. Preferably, magnetic stirring is performed for 2-5 hours until completely dissolved.

[0058] In some embodiments of this implementation, the organic solvent is selected from at least one of propylene glycol methyl ether acetate (PGMEA) and ethyl lactate (EL).

[0059] In some embodiments of this implementation, the photoresist is spin-coated onto a substrate (such as a silicon wafer), pre-baked at 90-110°C for 50-70 seconds, and exposed using a 365 nm G / I line exposure machine with an exposure dose of 200-400 mJ / cm². 2 Develop with 2-3% TMAH developer for 60 seconds, rinse with deionized water for 20-40 seconds, and spin dry.

[0060] The spin coating speed is 2000~3000 rpm, preferably 2500 rpm; the photoresist resolution is ≥5μm, the contrast ratio γ is ≥1, preferably ≥1.2, more preferably ≥1.8, even more preferably ≥2, which can be 1.2~2.1. The sensitivity E0 is 200~300mJ / cm. 2 The lines have sharp edges, no residual glue, and no bridging.

[0061] In one typical embodiment, the present invention provides the application of the above-mentioned G / I line positive photoresist in semiconductor I-line photolithography, OLED / liquid crystal display panel photolithography, advanced packaging photolithography, and LED photolithography.

[0062] In this invention, unless otherwise specified, all other test materials and instruments are conventional test materials in the field and can be purchased through commercial channels.

[0063] To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments.

[0064] Example 1: Preparation of fluorine-containing grafted parent material D In a 250 mL two-necked flask, 2.200 g (20 mmol) of resorcinol was dissolved in 40 mL of anhydrous dichloromethane, and 5.400 g (40 mmol) of aluminum trichloride was added. Under nitrogen protection, 3.00 mL (20 mmol) of trifluoroacetic anhydride was slowly added dropwise in an ice bath at 0 °C, and the reaction was maintained at 0 °C for 30 min, followed by reflux and stirring at 40 °C for 8 h. After the reaction was complete, the mixture was extracted with dichloromethane / water, and the organic layer was concentrated by rotary evaporation. Column chromatography (dichloromethane:methanol = 60:1) was used to purify the compound D 3.586 g, with a yield of 87%.

[0065] 1 H NMR (400 MHz, DMSO-d6): δ 11.18 (s, 1H), 11.06 (s, 1H), 7.61 (dt, J=9.1,1.8 Hz, 1H), 6.48 (dd, J=9.0,2.3 Hz, 1H), 6.40 (d, J=2.3 Hz, 1 H).

[0066] 19 F NMR (376 MHz, DMSO-d6): δ -70.37.

[0067] HRMS (ESI) m / z: [MH] - Calculated value of C8H5F3O3: 205.0113, measured value: 205.0088.

[0068] Example 2: Preparation of Fluorine-Containing Grafted Parent Material E By replacing resorcinol with 2.520 g (20 mmol) of pyrogallol, and with the rest the same as in Example 1, compound E3.314 g was obtained, with a yield of 74.6%.

[0069] 1H NMR (400 MHz, DMSO-d6): δ 10.74 (s, 2H), 9.07 (s, 1H), 7.21 (dq, J=9.0,2.1 Hz, 1H), 6.56 (d, J=9.0 Hz, 1H).

[0070] 19 F NMR (376 MHz, DMSO-d6): δ -69.31, -69.33.

[0071] HRMS (ESI) m / z: [MH] - Calculated value of C8H5F3O4: 221.0062, measured value: 221.0060.

[0072] Example 3: Synthesis of the fluorinated photosensitizer E-DNQ 1.111 g (5 mmol) of graft parent E was dissolved in 20 mL of acetone, and 4.702 g (17.5 mmol) of 2-diazo-1-naphthoquinone-5-sulfonyl chloride was added. The mixture was stirred in a water bath at 40 °C for 30 min. 2.44 mL (17.5 mmol) of triethylamine was added dropwise over half an hour at a rate of 17.5 mol / h, completing the addition in 0.5–1 h. The reaction mixture was then continued for 3 h. The reaction solution was poured into 800 mL of deionized water, and 3.5 g of 35% hydrochloric acid was added dropwise to adjust the pH to approximately 5. The mixture was stirred at room temperature for 1 h. After filtration, the solution was washed three times with 200 mL of deionized water and dried under vacuum at 40–50 °C for 8 h to obtain a yellow powder, E-DNQ.

[0073] 1 The structure was confirmed by 1H NMR and FT-IR characterization, and the esterification rate was ( 1 The H NMR integral method yielded 80.3%, and the thermal decomposition temperature (TGA first stage) was approximately 163℃.

[0074] Example 4: Synthesis of fluorinated photosensitizers F-DNQ and G-DNQ E was replaced by grafted parent compounds F and G, respectively. The amount of 2-diazo-1-naphthoquinone-5-sulfonyl chloride was calculated as 3.5 times the molar number of hydroxyl groups in the grafted parent compound. The amount of triethylamine was the same as that of sulfonyl chloride, and the rest was the same as in Example 3. F-DNQ and G-DNQ were obtained, with esterification rates of 88.8% and 70.5%, respectively, and thermal decomposition temperatures of approximately 161°C and 158°C, respectively.

[0075] The synthesis, preparation steps, and feed ratios of fluorinated photosensitizers A-DNQ, B-DNQ, C-DNQ, D-DNQ, H-DNQ, I-DNQ, and J-DNQ are all the same as those for the synthesis of F-DNQ, except for the different grafting parent materials.

[0076] Example 5: Preparation of i-line positive photoresist To prepare a photoresist with a total mass of 5 g and a solid content of 15 wt%, accurately weigh 0.5 g of phenolic resin and 0.25 g of E-DNQ photosensitizer prepared in Example 3, add 4.25 g of PGMEA solvent, add 50 μL of silane coupling agent KH560, stir magnetically for 2-5 h until completely dissolved, filter twice through a 0.22 μm polytetrafluoroethylene filter membrane, and allow to stand to remove bubbles to obtain i-line positive photoresist.

[0077] Example 6: Photolithography and Patterning The photoresist from Example 5 was spin-coated onto a 1-inch silicon wafer at 2500 rpm and pre-baked at 100°C for 60 s. A 365 nm i-line exposure machine was used with an exposure dose of 300 mJ / cm². 2 Develop with 2.38% TMAH developer for 60 seconds, rinse with deionized water for 30 seconds, and spin dry. Optical microscopy showed that clear line patterns and circular patterns of 5 μm and 10 μm were successfully obtained, with smooth lines, steep edges, and no bridging or breakage.

[0078] Example 7: Sensitivity and Contrast Test The D-DNQ, E-DNQ, F-DNQ, and G-DNQ photoresists were subjected to gradient exposure (30~480 mJ / cm²) according to the process in Example 6. 2 After development, the remaining film thickness in each exposed area is measured. According to the contrast formula γ = [log(E0 / E_p)] -1 Calculate: D-DNQγ=1.28, E-DNQγ=2.03, F-DNQγ=1.64, G-DNQγ=1.86. Sensitivity E0 is: D-DNQ 210mJ / cm² 2 E-DNQ 240 mJ / cm 2 F-DNQ 230 mJ / cm 2 G-DNQ 280 mJ / cm 2 .

[0079] Comparative Example 1: Synthesis and Photolithographic Properties of Fluorine-Free Photosensitizers M-DNQ and N-DNQ Using fluorine-free grafted parent materials M and N as raw materials, M-DNQ and N-DNQ were synthesized according to the method in Example 4. Photoresists were prepared and photolithography was performed according to Examples 5-6. The results showed that the first-stage thermal decomposition temperature of the fluorine-free photosensitizer was below 148℃, the edge roughness of the pattern was significantly greater than that of E-DNQ, and the resolution was below 5 μm. This indicates that the introduction of fluorine effectively improved thermal stability and pattern quality.

[0080] Comparative Example 2 The synthesis of K-DNQ, M-DNQ, and N-DNQ followed the same preparation steps and feed ratios as Comparative Example 1, except for the different grafting parent materials.

[0081] Figure 1 Infrared spectroscopy tests confirmed that the diazonoquinone unit was successfully esterified into the grafted parent skeleton.

[0082] like Figure 2 As shown, all photosensitizers have a maximum absorption peak at 355 nm, so a 365 nm UV exposure machine can be selected to expose the X-DNQ photoresist.

[0083] like Figure 3 As shown, all samples exhibited the first stage of weight loss at 128-163°C. Furthermore, the fluorine-containing D, E, F, and G-DNQ photosensitizers showed a higher thermal decomposition temperature (163°C), which was approximately 15°C higher than the other samples (148°C).

[0084] like Figures 4-6 As shown, the analysis of 10 μm line patterns of photoresists with solid contents of 10 wt%, 15 wt%, and 20 wt% under different exposure doses revealed that the pattern formed by the 15 wt% photoresist had steeper edges, exhibiting better film retention and pattern fidelity.

[0085] like Figure 7 As shown in the comparison, E-DNQ, F-DNQ, and G-DNQ photoresists exhibited the best pattern quality, developing vertical and intersecting lines of 10 μm with clear intersections, as well as complete, smooth-edged circular structures with a diameter of 10 μm. Among them, E-DNQ showed the best pattern quality, further developing fine lines of 5 μm.

[0086] D-DNQ and G-DNQ photoresists have more microscopic 'jagged' or 'burr' defects at the edges of the patterned lines compared to E-DNQ photoresist. The contrast (γ) is obtained by fitting a linear equation to the slope of the linear region of the descending segment of the contrast curve.

[0087] like Figure 8 As shown in the contrast curves of normalized film thickness as a function of exposure dose, different photoresists exhibit significant differences. The E-DNQ photoresist showed the highest contrast ratio (2.03), consistent with the results from the solid content experiment. The E-DNQ photoresist also exhibited the steepest line edges. The sensitivity was 240 mJ / cm². 2 .

[0088] 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 fluorinated diazonoquinone photosensitizer, characterized in that, It is obtained by esterification of a fluorinated polyphenol grafted parent with diazonoquinone sulfonyl chloride; The fluorinated polyphenol graft parent has fluorine atoms, trifluoromethyl or trifluoroethyl substituents; The diazonoquinone group includes 1,2-naphthoquinone-2-azido-5-sulfonyl.

2. The fluorinated diazonoquinone photosensitizer according to claim 1, characterized in that, The fluorinated polyphenol graft matrix is ​​selected from one of the following structures: ； Preferably, the fluorinated grafting parent is selected from a single benzene ring structure containing at least two phenolic hydroxyl groups, and one or more fluorinated substituents are attached to the benzene ring, preferably any one or more of the fluorinated grafting parent D, E, F, and G; Preferably, the fluorinated grafted parent compound is prepared by the following steps: resorcinol or pyrogallol is reacted with trifluoroacetic anhydride under aluminum trichloride catalysis by Friedel-Crafts acylation to obtain a fluorinated ketone intermediate.

3. A method for preparing the fluorinated diazonoquinone photosensitizer according to claim 1 or 2, characterized in that, Includes the following steps: The fluorinated polyphenol graft parent compound and diazonoquinone sulfonyl chloride were dissolved in an organic solvent and stirred together. Then, an alkaline catalyst was added and the reaction continued. The pH of the resulting reaction solution was adjusted to ≤5, and a solid was precipitated. The solid was then filtered, washed, and dried to obtain the final product.

4. The preparation method according to claim 3, characterized in that, When the fluorinated polyphenol graft parent compound and diazonium naphthoquinone sulfonyl chloride are dissolved in an organic solvent, they are stirred in a water bath at 20-60°C for 10-60 minutes. Preferably, the molar ratio of the fluorinated polyphenol graft parent to diazonoquinone sulfonyl chloride is 1:(0.1~5); Preferably, the basic catalyst includes one or more of triethylamine, pyridine, and diisopropylethylamine; Preferably, the molar ratio of diazonoquinone sulfonyl chloride to the basic catalyst is (0.8~1.2):(0.8~1.2); Preferably, the alkaline catalyst is added dropwise over a period of 0.5 to 2 hours. Preferably, after the addition is completed, the reaction continues at 20~60℃ for 1~4 hours.

5. A photosensitizer composition, characterized in that, Includes the fluorinated diazononaphthoquinone photosensitizer according to claim 1 or 2, or the fluorinated diazononaphthoquinone photosensitizer prepared by the preparation method according to claim 3 or 4.

6. The use of a fluorinated diazononaphthoquinone photosensitizer according to claim 1 or 2, or a fluorinated diazononaphthoquinone photosensitizer prepared by the preparation method according to claim 3 or 4, or a photosensitizer composition according to claim 5, in G / I photoresist.

7. The application according to claim 6, characterized in that, by 1 According to the H NMR integration method, the esterification rate of the photoresist is ≥65%, preferably ≥68.7%, and more preferably ≥80%; Preferably, in the first stage of TGA, the thermal decomposition temperature of the photoresist is ≥150℃, more preferably ≥155℃, and even more preferably ≥160℃.

8. A G / I line positive photoresist, characterized in that, The product comprises, by weight, 100 parts of phenolic resin; 1-50 parts of the fluorinated diazonoquinone photosensitizer as described in claim 1 or 2; and 70-1900 parts of organic solvent. It also includes silane coupling agents, with a mass-to-volume ratio of phenolic resin and silane coupling agent of (0.1~1):(40~100), expressed in g / μL.

9. The G / I line positive photoresist according to claim 8, characterized in that, The photoresist has a solid content of 10 wt% to 20 wt%, preferably 14 wt% to 16 wt%. The preparation method of G / I line positive photoresist includes: mixing phenolic resin, fluorinated diazonoquinone photosensitizer, organic solvent and silane coupling agent, stirring magnetically until completely dissolved, filtering, and allowing to stand to remove bubbles to obtain positive photoresist; Preferably, the organic solvent is selected from at least one of propylene glycol methyl ether acetate and ethyl lactate.

10. The application of the G / I line positive photoresist as described in claim 8 or 9 in semiconductor photolithography, display panel photolithography, advanced packaging photolithography, and LED photolithography.

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