Photosensitive molecule containing o-nitrobenzyl ether and diazonaphthoquinone double photosensitive groups, photoresist composition, preparation method and photoetching method

Abstract

The invention provides a photosensitive molecule containing o-nitrobenzyl ether and diazo naphthoquinone double photosensitive groups, a photoresist composition, a photosensitive molecule preparation method, a photoresist preparation method and a photoetching method, and relates to the technical field of photoresists. The photosensitive molecule containing the o-nitrobenzyl ether and diazo naphthoquinone double photosensitive groups has a structural general formula shown in a formula I, wherein the formula I is shown in the description; wherein A is molecular glass or a polymer containing a phenolic hydroxyl group, Ra is an o-nitrobenzyl group, and Rb is a diazonaphthoquinone group.

Description

Technical Field

[0001] The present disclosure relates to the field of photoresist technology, and more specifically, to a photosensitive molecule containing o-nitrobenzyl ether and diazonaphthoquinone dual photosensitive groups, a photoresist composition, a preparation method, and a photolithography method. Background Art

[0002] With the continuous advancement of semiconductor technology, Moore's Law has faced numerous challenges. Especially since the advent of ultra-large-scale integration (VLSI), the demand for finer and more precise circuits has led to a significant decline in the yield rate of the semiconductor industry. The reduction in transistor size has also led to increased leakage current, making further transistor shrinkage increasingly difficult. While Moore's Law has been temporarily extended through the introduction of technological innovations such as fin-gate transistors and extreme ultraviolet lithography, the high cost and technical complexity of these technologies have limited their widespread application. Therefore, it is necessary to explore new lithography technologies that can break the diffraction limit to achieve high-resolution, low-cost nanopatterning.

[0003] Near-field lithography utilizes near-field light, a localized light present on the surface of the illuminated material. This light is more concentrated within a smaller volume than the light generated by traditional lithography. This characteristic enables near-field lithography to overcome the limitations of traditional lithography, which relies on reducing the wavelength of the light source to improve lithography precision, and reduces the problem of light diffraction caused by the gap between the mask and the etch layer. However, due to the characteristics of the evanescent wave, the working distance of near-field lithography is subject to certain limitations. In recent years, the development of lithography technology based on surface plasmons (SP) has effectively expanded the working distance of near-field lithography, allowing the transmission depth of the evanescent wave carrying high-frequency light field information to cover the thickness range of the photoresist film layer, with a resolution of tens to hundreds of nanometers, demonstrating its practical application value.

[0004] To achieve high-resolution patterning at I-line wavelengths, SP lithography requires the use of a specific type of photoresist. While traditional chemically amplified resists have performed well in projection-type deep-UV and extreme-UV lithography, their application is limited by inherent issues such as phase separation of the photoacid generator from the resin and diffusion of the generated acid into non-exposed areas, which limits resolution. Non-chemically amplified resists based on o-nitrobenzyl ether have demonstrated high-resolution potential in near-field lithography, but their sensitivity is poor, typically requiring energy densities exceeding 300 mJ / cm².

[0005] Therefore, how to improve the sensitivity of o-nitrobenzyl ether-based photoresist is crucial to promoting its application in lithography technologies such as near-field lithography and SP lithography. Summary of the Invention

[0006] In view of this, the present disclosure provides a photosensitive molecule containing o-nitrobenzyl ether and diazonaphthoquinone dual photosensitive groups, a photoresist composition, a preparation method and a photolithography method, which can at least partially solve the above technical problems.

[0007] In a first aspect, the present disclosure provides a photosensitive molecule containing o-nitrobenzyl ether and diazonaphthoquinone dual photosensitive groups, wherein the photosensitive molecule has the general structural formula shown in Formula I:

[0008] Formula I; wherein A is a molecular glass or polymer containing a phenolic hydroxyl group, Ra is an o-nitrobenzyl group, and Rb is a diazonaphthoquinone group.

[0009] According to an embodiment of the present disclosure, A is polyhydroxystyrene, phenolic resin, calixarene, spirofluorene structure or trisphenol A.

[0010] According to an embodiment of the present disclosure, the structure of the photosensitive molecule is Formula II, Formula III, Formula IV, Formula V or Formula VI;

[0011] Wherein, formula II is Formula III is Formula IV is Formula V is Formula VI is wherein the weight average molecular weight in the structures of formula II and formula III is ≤20,000, x / (x+y+z) ≥40%, 10%≤y / (x+y+z)≤30%, 20%≤z / (x+y+z)≤30%; R5 in the structures of formula IV, formula V and formula VI is hydroxyl, Ra or Rb, and R5 in formula IV, formula V and formula VI is partially Ra and Rb; R6 is -H, -C 10 H 13 、-C n H 2n+1 or -C n H 2n OH, 1≤n≤10.

[0012] According to the embodiments of the present disclosure, in the structures of Formula IV and Formula V, the hydroxyl group is ≤62.5%, 12.5%≤Ra≤37.5%, and 12.5%≤Rb≤37.5%; in the structure of Formula VI, the hydroxyl group is ≤60%, 10%≤Ra≤40%, and 10%≤Rb≤40%.

[0013] According to the embodiments of the present disclosure, the grafting rate of the o-nitrobenzyl group in the structure of Formula I is 10% to 40%; the grafting rate of the diazonaphthoquinone group in the structure of Formula I is 10% to 40%.

[0014] According to an embodiment of the present disclosure, the structure of the o-nitrobenzyl group is Formula VII, Formula VII is ; Wherein, R1 is -NO2 or -H, R2, R3, R4 are hydrogen atom, alkyl, alkoxy, nitrogen methyl, phenyl or alkylphenyl.

[0015] A second aspect of the present disclosure provides a photoresist composition containing o-nitrobenzyl ether and diazonaphthoquinone dual photosensitive groups, comprising: the above-mentioned photosensitive molecules and an organic solvent.

[0016] According to an embodiment of the present disclosure, the organic solvent is one of propylene glycol methyl ether acetate, ethylene glycol methyl ether acetate, propylene glycol methyl ether, butyl lactate, butyl acetate and methyl isobutyl ketone, or a mixture of two thereof.

[0017] A third aspect of the present disclosure provides a method for preparing a photosensitive molecule containing o-nitrobenzyl ether and diazonaphthoquinone dual photosensitive groups, comprising: dissolving a molecular glass or polymer containing a phenolic hydroxyl group in a solvent, adding a basic catalyst and / or 18-crown ether-6, dropwise adding a reactant containing an o-nitrobenzyl group, and reacting and purifying to obtain a first product; dissolving the first product in a solvent, dropwise adding a weak basic catalyst, and then adding a reactant containing a diazonaphthoquinone group, and reacting and purifying to obtain a photosensitive molecule containing an o-nitrobenzyl ether group and a diazonaphthoquinone group, wherein the photosensitive molecule has the general structural formula shown in Formula I:

[0018] Formula I;

[0019] A is a molecular glass or polymer containing a phenolic hydroxyl group, Ra is an o-nitrobenzyl group, and Rb is a diazonaphthoquinone group.

[0020] The fourth aspect of the present disclosure provides a method for preparing a photoresist composition containing o-nitrobenzyl ether and diazonaphthoquinone dual photosensitive groups, wherein the photosensitive molecules or the photosensitive molecules prepared by the above method are dissolved in an organic solvent and filtered to obtain the photoresist composition.

[0021] A fifth aspect of the present disclosure discloses a photolithography method, which uses the above-mentioned photoresist composition or the photoresist composition prepared by the above-mentioned method to perform photolithography.

[0022] According to an embodiment of the present disclosure, the lithography method is one of i-line projection lithography, i-line interference lithography, i-line near-field lithography, and SP lithography.

[0023] The photoresist containing o-nitrobenzyl ether and diazonaphthoquinone groups provided in the embodiments of the present disclosure has at least the following beneficial effects:

[0024] By introducing a diazonaphthoquinone photosensitive group into an o-nitrobenzyl ether-based photoresist, the low sensitivity of conventional o-nitrobenzyl ether-based photoresists can be effectively addressed. The disclosed embodiments innovatively graft the diazonaphthoquinone photosensitive group onto a photosensitive molecule, leveraging its excellent photoacid generation capacity to significantly enhance the photoresist's sensitivity. Furthermore, because the o-nitrobenzyl ether and diazonaphthoquinone photosensitive groups act synergistically in the photochemical reaction, the material not only retains the high-resolution properties of o-nitrobenzyl ether but also enhances the overall photoresponse performance, resulting in a photoresist with higher exposure sensitivity while maintaining nanometer-scale resolution. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The above and other objects, features and advantages of the present disclosure will become more apparent through the following description of the embodiments of the present disclosure with reference to the accompanying drawings, in which:

[0026] Figure 1 Schematically shows a scanning pattern of a photoresist film layer according to Embodiment 1 of the present disclosure;

[0027] Figure 2 The SP photolithography pattern of the photoresist according to the first embodiment of the present disclosure is schematically shown.

[0028] Figure 3 The SP lithography pattern of the photoresist according to Comparative Example 2 of the present disclosure is schematically shown. DETAILED DESCRIPTION

[0029] Hereinafter, embodiments of the present disclosure will be described with reference to the accompanying drawings. However, it should be understood that these descriptions are merely exemplary and are not intended to limit the scope of the present disclosure. In the detailed description below, for ease of explanation, many specific details are set forth to provide a comprehensive understanding of the embodiments of the present disclosure. However, it is apparent that one or more embodiments may be implemented without these specific details. In addition, in the following description, descriptions of well-known systems and technologies are omitted to avoid unnecessary confusion of the concepts of the present disclosure.

[0030] The terms used herein are only for describing specific embodiments and are not intended to limit the present disclosure. The terms "comprise," "include," etc. used herein indicate the presence of features, steps, operations, and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, or components.

[0031] All terms used herein (including technical and scientific terms) have the meanings commonly understood by those skilled in the art unless otherwise defined. It should be noted that the terms used herein should be interpreted as having a meaning consistent with the context of this specification and should not be interpreted in an idealized or overly rigid manner.

[0032] The present disclosure provides a photosensitive molecule containing o-nitrobenzyl ether and diazonaphthoquinone dual photosensitive groups, wherein the photosensitive molecule has the general structural formula shown in Formula I:

[0033] Formula I;

[0034] Wherein, A is a molecular glass or polymer containing a phenolic hydroxyl group, Ra is an o-nitrobenzyl group, and Rb is a diazonaphthoquinone group.

[0035] In the embodiments disclosed herein, o-nitrobenzyl and diazonaphthoquinone groups are grafted onto molecular glass or polymers containing phenolic hydroxyl groups. The o-nitrobenzyl group undergoes a cleavage reaction under ultraviolet light to produce aldehydes and phenols, while the diazonaphthoquinone decomposes under light of specific wavelengths to form products such as carboxylic acids. This combination makes the photosensitive material sensitive to light of different wavelengths, expanding its application range and improving its photosensitivity.

[0036] Furthermore, the naphthoquinonediazide group Rb is:

[0037] 、 、 or .

[0038] In the embodiments disclosed herein, while conventional o-nitrobenzyl ether-based photoresists exhibit excellent resolution in near-field lithography, they suffer from low sensitivity and typically require higher exposure energies (>300mJ / cm²). This embodiment introduces a diazonaphthoquinone group, which efficiently generates acid under light, promoting chemical reactions in the photoresist. This reduces the required exposure dose, significantly improves the photosensitivity of the photoresist, and enhances overall process efficiency.

[0039] Furthermore, A is polyhydroxystyrene, phenolic resin, calixarene, spirofluorene structure or triphenol A.

[0040] Based on the above embodiments, the structure of the photosensitive molecule is Formula II, Formula III, Formula IV, Formula V or Formula VI;

[0041] Wherein, formula II is ;

[0042] Formula III is ;

[0043] Formula IV is ;

[0044] Formula V is ;

[0045] Formula VI is .

[0046] Wherein, the weight average molecular weight in the structure of formula II and the structure of formula III is ≤20,000, x / (x+y+z) ≥40%, 10%≤y / (x+y+z)≤30%, 20%≤z / (x+y+z)≤30%; R5 in the structure of formula IV, the structure of formula V and the structure of formula VI is hydroxyl, Ra or Rb, and R5 in the structure of formula IV, the structure of formula V and the structure of formula VI is partially Ra and Rb; R6 is -H, -C 10 H 13 、-C n H 2n+1 or -C n H 2n OH, 1≤n≤10.

[0047] Based on the above embodiments, the hydroxyl group in the structures of Formula IV and Formula V is ≤62.5%, 12.5%≤Ra≤37.5%, and 12.5%≤Rb≤37.5%; the hydroxyl group in the structure of Formula VI is ≤60%, 10%≤Ra≤40%, and 10%≤Rb≤40%.

[0048] In the embodiments of the present disclosure, A is preferably polyhydroxystyrene, phenolic resin, calixarene, spirofluorene structure or triphenol A as the base material of the photoresist, which can effectively improve the film-forming property and thermal stability of the photoresist. At the same time, it contains rich hydroxyl groups that can form effective chemical bonds with o-nitrobenzyl ether and diazonaphthoquinone groups, further enhancing the comprehensive photolithographic performance of the material.

[0049] According to the embodiments of the present disclosure, the grafting rate of the o-nitrobenzyl group in the structure of Formula I is 10% to 40%; the grafting rate of the diazonaphthoquinone group in the structure of Formula I is 10% to 40%.

[0050] In the embodiments disclosed herein, controlling the grafting ratio of o-nitrobenzyl and diazonaphthoquinone groups can significantly improve the sensitivity of the photoresist while maintaining high resolution. Furthermore, rationally adjusting the grafting ratio of the two photosensitive groups helps optimize the chemical stability of the photoresist and its compatibility with other process steps. For example, during the development process, a suitable grafting ratio can ensure that the photoresist layer undergoes effective chemical transformation upon exposure to light, thereby forming a clear and stable pattern structure.

[0051] Based on the above examples, the structure of the o-nitrobenzyl group is Formula VII, which is ;

[0052] Wherein, R1 is -NO2 or -H, and R2, R3, and R4 are hydrogen atom, alkyl, alkoxy, nitrogen methyl, phenyl, or alkylphenyl.

[0053] The present disclosure provides a photoresist composition containing o-nitrobenzyl ether and diazonaphthoquinone dual photosensitive groups, including the above-mentioned photosensitive molecules, with the mass percentage of the photosensitive molecules being 1% to 30%; wherein, the principle of the photosensitive molecules has been described in detail above and will not be repeated here.

[0054] It also includes an organic solvent, and the mass percentage of the organic solvent is 70% to 99%.

[0055] In the embodiments of the present disclosure, by controlling the mass percentage of the organic solvent, the film thickness of the photoresist can be regulated, and photoresist films of different thicknesses can be provided for different applications.

[0056] Furthermore, the organic solvent is one of propylene glycol methyl ether acetate, ethylene glycol methyl ether acetate, propylene glycol methyl ether, butyl lactate, butyl acetate and methyl isobutyl ketone, or a mixture of two of them.

[0057] Furthermore, the photoresist composition further comprises: at least one of an adhesion promoter and a leveling agent.

[0058] The viscosity enhancer is a thiol or thiophenol material, and the added amount is 2% to 10% of the mass of the photosensitive molecule. The leveling agent is a fluorinated polyester or polyether-modified siloxane material, and the added amount is 0.02% to 0.2% of the solvent mass.

[0059] The present disclosure provides a method for preparing a photosensitive molecule containing o-nitrobenzyl ether and diazonaphthoquinone dual photosensitive groups, comprising:

[0060] Step 1: dissolving a molecular glass or polymer containing a phenolic hydroxyl group in a solvent, adding a basic catalyst and / or 18-crown ether-6, and dropwise adding a reactant containing an o-nitrobenzyl group, and reacting and purifying to obtain a first product.

[0061] Step 2: Dissolve the first product in a solvent, add a weakly basic catalyst dropwise, and then add a reactant containing a diazonaphthoquinone group, and react and purify to obtain a photosensitive molecule containing an o-nitrobenzyl ether group and a diazonaphthoquinone group. The photosensitive molecule has the general structural formula shown in Formula I:

[0062] ; A is a molecular glass or polymer containing a phenolic hydroxyl group, Ra is an o-nitrobenzyl group, and Rb is a diazonaphthoquinone group.

[0063] In some possible embodiments, a method for preparing a photosensitive molecule is provided, comprising:

[0064] In step S1, under a nitrogen or argon atmosphere, A is dissolved in a dry solvent, and a basic catalyst and / or 18-crown ether-6 is added at a temperature of 40° C. to 100° C. for 0 to 3 hours to obtain a first reaction solution.

[0065] Furthermore, the drying solvent in S1 can be at least one of dimethylformamide and acetone, and the solid content of the drying solvent can be 5% to 25%, preferably 8% to 12%. The alkaline catalyst can be sodium hydride or potassium carbonate. The reaction time is preferably 1 hour to 1.5 hours.

[0066] In step S2, a reactant containing an o-nitrobenzyl group dissolved in a solvent is added dropwise to the first reaction solution. After reacting for 1 to 12 hours, a second reaction solution is obtained. The reaction formula is shown below:

[0067]

[0068] Furthermore, the solid content of the reactant containing o-nitrobenzyl groups dissolved in the solvent in S2 may be 5% to 25%; and the reaction time is preferably 4 h to 8 h.

[0069] In step S3, the second reaction solution is precipitated into an aqueous solution, and filtered, washed, impurity-removed, and dried to obtain a first product.

[0070] Furthermore, the aqueous solution in S3 can be pure water or an aqueous ammonium chloride solution; and the impurity removal method can be column chromatography or sedimentation.

[0071] In step S4, the first product is dissolved in a dry solvent with a solid content of 30% to 60%, and a weakly alkaline catalyst is slowly added dropwise at a temperature of -20°C to 0°C to obtain a third reaction solution.

[0072] Furthermore, the drying solvent in S4 can be a mixture of dimethylformamide and acetone, and its solid content is preferably 35% to 50%; the dropwise addition time can be 2 min to 20 min; and the weakly basic catalyst can be triethylamine.

[0073] Step S5: The reactant containing the diazonaphthoquinone group dissolved in the solvent is added dropwise to the third reaction solution. After the addition is complete, the reaction solution is placed at a temperature of 20°C to 40°C and the reaction is continued for 12 to 48 hours. After the reaction is complete, the resulting reaction liquid is precipitated into an aqueous solution, filtered, washed, impurity-removed, and dried to obtain a photosensitive molecule containing an o-nitrobenzyl ether group and a diazonaphthoquinone group. The reaction formula is as follows:

[0074]

[0075] Furthermore, the dropwise addition time in S5 may be 0.5 h to 1.5 h.

[0076] The present disclosure provides a method for preparing a photoresist composition containing o-nitrobenzyl ether and diazonaphthoquinone dual photosensitive groups, comprising: dissolving the photosensitive molecules in an organic solvent, and filtering to obtain the photoresist composition.

[0077] The present disclosure discloses a photolithography method, which uses the above-mentioned photoresist composition or the photoresist composition prepared by the above-mentioned method to perform photolithography.

[0078] Furthermore, the above-mentioned photoresist can be one of I-line projection lithography, interference lithography, near-field lithography and SP lithography.

[0079] The present disclosure is further described below through specific implementation methods.

[0080] Example 1:

[0081] The structure of the polyhydroxystyrene resin derivative containing 4,5-dimethoxy-o-nitrobenzyl ether and 2,1,5-naphthoquinone diazide structure is as follows:

[0082]

[0083] The preparation method of the polyhydroxystyrene resin derivative containing 4,5-dimethoxy-o-nitrobenzyl ether and 2,1,5-diazonaphthoquinone structure is as follows:

[0084] Under a nitrogen atmosphere, 50 g of polyhydroxystyrene (weight-average molecular weight of 4000, PDI of 1.05) was dissolved in 500 mL of dimethylformamide. 2.4 g of sodium hydride was added at 50°C and allowed to react for 1.5 hours. Subsequently, 23 g of 4,5-dimethoxy-o-nitrobenzyl bromide was dissolved in 230 mL of dimethylformamide and added dropwise to the reaction system. The reaction continued for 4 hours.

[0085] After the reaction is completed, the reaction solution is cooled to room temperature and precipitated into an aqueous solution of ammonium chloride to precipitate solid matter. The solid matter is filtered to obtain the solid matter, which is washed with water three times to remove residual inorganic salts. The washed solid is redissolved in dimethylformamide and precipitated into water again, and the reaction is repeated three times for further purification. Subsequently, the obtained solid matter is dissolved in ethyl acetate and precipitated into petroleum ether, and the reaction is repeated three times. The solid matter is dried to obtain a yellow powder of a polymer intermediate grafted with o-nitrobenzyl ether. The grafting rate of o-nitrobenzyl ether calculated by nuclear magnetic resonance is 10%.

[0086] Under a nitrogen atmosphere, 30g of the yellow powder obtained above was dissolved in a mixed solution of 20mL of anhydrous dimethylformamide and 10mL of anhydrous acetone, and 6g of triethylamine was slowly added dropwise at 0°C for 10min. Next, 14g of 2,1,5-diazonaphthoquinonesulfonyl chloride was dissolved in a mixed solution of 10mL of anhydrous dimethylformamide and 5mL of anhydrous acetone and slowly added dropwise to the above reaction system within 1h. After the addition was completed, the reaction temperature was raised to 25°C and the reaction was continued for 24h. After the reaction was completed, the reaction solution was precipitated into an aqueous solution to precipitate solid matter. After filtration, the solid was dissolved in acetone and precipitated into water again, and this was repeated 3 times to remove by-products and solvent residues. The resulting yellow solid was dried, and the grafting rate of diazonaphthoquinone was calculated to be 20% by nuclear magnetic resonance.

[0087] Example 2:

[0088] The structure of the polyhydroxystyrene resin derivative containing 4,5-dimethoxy-o-nitrobenzyl ether and 2,1,5-naphthoquinone diazide structure is as follows:

[0089]

[0090] The preparation method of the polyhydroxystyrene resin derivative containing 4,5-dimethoxy-o-nitrobenzyl ether and 2,1,5-diazonaphthoquinone structure is as follows:

[0091] Under a nitrogen atmosphere, 50 g of polyhydroxystyrene (weight-average molecular weight of 4000, PDI of 1.05) was dissolved in 500 mL of dimethylformamide. 7.2 g of sodium hydride was added at 50°C and allowed to react for 1.5 hours. Subsequently, 69 g of 4,5-dimethoxy-o-nitrobenzyl bromide was dissolved in 500 mL of dimethylformamide and added dropwise to the reaction system. The reaction continued for 4 hours.

[0092] After the reaction is completed, the reaction solution is cooled to room temperature and precipitated into an aqueous solution of ammonium chloride to precipitate solid matter. The solid matter is filtered to obtain the solid matter and washed with water three times to remove residual inorganic salts. The washed solid is redissolved in dimethylformamide and precipitated into water again, and repeated three times for further purification. Subsequently, the obtained solid matter is dissolved in ethyl acetate and precipitated into petroleum ether, and repeated three times. The solid matter is dried to obtain a yellow powder of a polymer intermediate grafted with o-nitrobenzyl ether. The grafting rate of o-nitrobenzyl ether calculated by nuclear magnetic resonance is 30%.

[0093] Under a nitrogen atmosphere, 30g of the yellow powder obtained above was dissolved in a mixed solution of 20mL of anhydrous dimethylformamide and 10mL of anhydrous acetone, and 10g of triethylamine was slowly added dropwise at 0°C for 10min. Next, 25g of 2,1,5-naphthoquinone diazonium sulfonyl chloride was dissolved in a mixed solution of 15mL of anhydrous dimethylformamide and 8mL of anhydrous acetone and slowly added dropwise to the above reaction system within 1h. After the addition was completed, the reaction temperature was raised to 25°C and the reaction was continued for 24h. After the reaction was completed, the reaction solution was precipitated into an aqueous solution to precipitate solid matter. After filtration, the solid was dissolved in acetone and precipitated into water again, and this was repeated 3 times to remove by-products and solvent residues. The resulting yellow solid was dried, and the grafting rate of naphthoquinone diazonium was calculated to be 30% by nuclear magnetic resonance.

[0094] Example 3:

[0095] The structure of the phenolic resin derivative containing 1,3-dinitrobenzyl ether and 2,1,4-diazonaphthoquinone structure is as follows:

[0096]

[0097] The preparation method of the phenolic resin derivative containing 1,3-dinitrobenzyl ether and 2,1,4-diazonaphthoquinone structure is as follows:

[0098] Under a nitrogen atmosphere, 50 g of phenolic resin (weight-average molecular weight of 11,000, PDI of 5.6) was dissolved in 200 mL of dimethylformamide. 3.9 g of sodium hydride was added at 80°C and allowed to react for 3 hours. Subsequently, 32 g of 3-nitrobenzyl bromide was dissolved in 130 mL of dimethylformamide and added dropwise to the reaction system. The reaction continued for 12 hours.

[0099] After the reaction is completed, the reaction solution is cooled to room temperature and precipitated into an aqueous solution of ammonium chloride to separate out solid matter. The solid matter is filtered and washed with water three times to remove residual inorganic salts. The washed solid is dissolved in dimethylformamide and precipitated into water, and repeated three times for further purification. Subsequently, the obtained solid matter is dissolved in ethyl acetate and precipitated into petroleum ether, and repeated three times. The solid matter is dried to obtain a yellow powder, and the grafting rate of o-nitrobenzyl ether calculated by nuclear magnetic resonance is 20%.

[0100] Under a nitrogen atmosphere, 30g of the yellow powder obtained above was dissolved in a mixed solution of 30mL of anhydrous dimethylformamide and 20mL of anhydrous acetone, and 6g of triethylamine was slowly added dropwise at 0°C for 15min. Next, 13.7g of 2,1,4-diazonaphthoquinonesulfonyl chloride was dissolved in a mixed solution of 15mL of anhydrous dimethylformamide and 10mL of anhydrous acetone, and slowly added dropwise to the above reaction system within 0.7h. After the addition was completed, the reaction temperature was raised to 30°C and the reaction was continued for 18h. After the reaction was completed, the reaction solution was precipitated into an aqueous solution to precipitate solid matter. After filtration, the solid was dissolved in acetone and then precipitated into water, and repeated 3 times. The obtained yellow solid was dried, and the grafting rate of diazonaphthoquinone was calculated to be 20% by nuclear magnetic resonance.

[0101] Example 4:

[0102] The structure of the calixarene derivative containing 4-methyl-o-nitrobenzyl ether and 1,2,5-naphthoquinone diazide structure is as follows:

[0103]

[0104] The preparation method of the calixarene derivative containing 4-methyl-o-nitrobenzyl ether and 1,2,5-naphthoquinone diazide structure is as follows:

[0105] Under a nitrogen atmosphere, 50 g of a calixarene derivative was dissolved in 280 mL of dimethylformamide. 10 g of sodium hydride was added at 60°C and the reaction was allowed to proceed for 2 h. Subsequently, 38 g of 4-methyl-o-nitrobenzyl bromide was dissolved in 215 mL of dimethylformamide and added dropwise to the reaction system. The reaction was continued for 8 h.

[0106] After the reaction, the reaction solution was cooled to room temperature and precipitated into an aqueous solution of ammonium chloride to precipitate a solid. The solid was filtered and washed three times with water to remove residual inorganic salts. Column chromatography was used for purification, using ethyl acetate and petroleum ether in a volume ratio of 1:2 as the developing solvent. The collected liquid was rotary evaporated to obtain a yellow solid powder. Nuclear magnetic resonance calculation showed that the grafting rate of o-nitrobenzyl ether was 25%.

[0107] Under a nitrogen atmosphere, 30g of the yellow powder obtained above was dissolved in a mixed solution of 25mL of anhydrous dimethylformamide and 15mL of anhydrous acetone, and 8g of triethylamine was slowly added dropwise at -10°C for 20min. Next, 17g of 1,2,5-diazonaphthoquinonesulfonyl chloride was dissolved in a mixed solution of 10mL of anhydrous dimethylformamide and 10mL of anhydrous acetone and slowly added dropwise to the above reaction system within 1.5h. After the addition was completed, the reaction temperature was raised to 40°C and the reaction was continued for 12h. After the reaction was completed, the reaction solution was precipitated into an aqueous solution to precipitate solid matter. After filtration, the solid was dissolved in acetone and precipitated into water again, and repeated 3 times. The obtained yellow solid was dried, and the grafting rate of diazonaphthoquinone was calculated to be 25% by nuclear magnetic resonance.

[0108] Example 5:

[0109] The structure of the spirofluorene derivative containing 5-(4-methoxyvinylphenyl) o-nitrobenzyl ether and 1,2,4-naphthoquinone diazide structure is as follows:

[0110]

[0111] The preparation method of the spirofluorene derivative containing 5-(4-methoxyvinylphenyl) o-nitrobenzyl ether and 1,2,4-naphthoquinone diazide structure is as follows:

[0112] Under a nitrogen atmosphere, 50 g of the spirofluorene derivative was dissolved in 400 mL of acetone, and 14.8 g of potassium carbonate and 1.5 g of 18-crown-6 were added at 60°C. 37 g of 5-(4-methoxyvinylphenyl)-o-nitrobenzyl bromide was dissolved in 120 mL of dimethylformamide and added dropwise to the reaction system. The reaction was continued for 12 hours.

[0113] After the reaction was completed, the reaction solution was cooled to room temperature and precipitated into an aqueous solution to separate out solid matter. The solid matter was filtered and washed three times with water to remove residual inorganic salts. Column chromatography was used for purification, and the developing solvent was ethyl acetate and petroleum ether in a volume ratio of 1:3. The collected liquid was rotary evaporated to obtain a yellow solid powder. The grafting rate of o-nitrobenzyl ether was calculated by nuclear magnetic resonance to be 12.5%.

[0114] Under a nitrogen atmosphere, 30g of the yellow powder obtained above was dissolved in a mixed solution of 15mL of anhydrous dimethylformamide and 5mL of anhydrous acetone, and 9.5g of triethylamine was slowly added dropwise at -20°C for 20min. Next, 21g of 1,2,4-diazonaphthoquinonesulfonyl chloride was dissolved in a mixed solution of 30mL of anhydrous dimethylformamide and 20mL of anhydrous acetone and slowly added dropwise to the above reaction system within 1.2h. After the addition was completed, the reaction temperature was raised to 30°C and the reaction was continued for 48h. After the reaction was completed, the reaction solution was precipitated into an aqueous solution to precipitate solid matter. After filtration, the solid was dissolved in acetone and precipitated into water again, and repeated 3 times. The obtained yellow solid was dried, and the grafting rate of diazonaphthoquinone was calculated to be 25% by nuclear magnetic resonance.

[0115] Example 6:

[0116] The structure of the spirofluorene derivative containing 5-(4-methoxyvinylphenyl) o-nitrobenzyl ether and 1,2,4-naphthoquinone diazide structure is as follows:

[0117]

[0118] The preparation method of the spirofluorene derivative containing 5-(4-methoxyvinylphenyl) o-nitrobenzyl ether and 1,2,4-naphthoquinone diazide structure is as follows:

[0119] Under a nitrogen atmosphere, 50 g of the spirofluorene derivative was dissolved in 400 mL of acetone, and 14.8 g of potassium carbonate and 1.5 g of 18-crown-6 were added at 60°C. 37 g of 5-(4-methoxyvinylphenyl)-o-nitrobenzyl bromide was dissolved in 120 mL of dimethylformamide and added dropwise to the reaction system. The reaction was continued for 12 hours.

[0120] After the reaction was completed, the reaction solution was cooled to room temperature and precipitated into an aqueous solution to separate out solid matter. The solid matter was filtered and washed three times with water to remove residual inorganic salts. Column chromatography was used for purification, and the developing solvent was ethyl acetate and petroleum ether in a volume ratio of 1:3. The collected liquid was rotary evaporated to obtain a yellow solid powder. The grafting rate of o-nitrobenzyl ether was calculated by nuclear magnetic resonance to be 12.5%.

[0121] Under a nitrogen atmosphere, 30g of the yellow powder obtained above was dissolved in a mixed solution of 15mL of anhydrous dimethylformamide and 5mL of anhydrous acetone, and 17g of triethylamine was slowly added dropwise at -20°C for 20min. Next, 37g of 1,2,4-diazonaphthoquinonesulfonyl chloride was dissolved in a mixed solution of 45mL of anhydrous dimethylformamide and 30mL of anhydrous acetone and slowly added dropwise to the above reaction system within 1.2h. After the addition was completed, the reaction temperature was raised to 30°C and the reaction was continued for 48h. After the reaction was completed, the reaction solution was precipitated into an aqueous solution to precipitate solid matter. After filtration, the solid was dissolved in acetone and precipitated into water again, and repeated 3 times. The resulting yellow solid was dried, and the grafting rate of diazonaphthoquinone was calculated to be 37.5% by nuclear magnetic resonance.

[0122] Example 7:

[0123] The structure of the triphenol A derivative containing 4,5-dimethoxy-o-nitrobenzyl ether and 2,1,4-diazonaphthoquinone structure is as follows:

[0124]

[0125] The preparation method of the triphenol A derivative containing 4,5-dimethoxy-o-nitrobenzyl ether and 2,1,4-diazonaphthoquinone structure is as follows:

[0126] Under a nitrogen atmosphere, 50 g of the spirofluorene derivative was dissolved in 800 mL of acetone, and 31 g of potassium carbonate and 3 g of 18-crown-6 were added at 60°C. Subsequently, 63 g of 4,5-dimethoxy-o-nitrobenzyl bromide was dissolved in 190 mL of acetone and added dropwise to the reaction system for 12 h.

[0127] After the reaction is completed, the reaction solution is cooled to room temperature and precipitated into an aqueous solution to separate out solid matter. The solid matter is filtered to obtain the solid matter and washed 3 times with water to remove residual inorganic salts. The washed solid is purified using column chromatography using a developing solvent of ethyl acetate and petroleum ether in a volume ratio of 1:4. The collected liquid is rotary evaporated to obtain a yellow solid powder, and the grafting rate of o-nitrobenzyl ether calculated by nuclear magnetic resonance is 20%.

[0128] Under a nitrogen atmosphere, 30g of the yellow powder obtained above was dissolved in a mixed solution of 50mL of anhydrous dimethylformamide and 20mL of anhydrous acetone, and 8g of triethylamine was slowly added dropwise at 0°C for 5min. Next, 20g of 2,1,4-diazonaphthoquinonesulfonyl chloride was dissolved in a mixed solution of 10mL of anhydrous dimethylformamide and 10mL of anhydrous acetone and slowly added dropwise to the above reaction system within 1h. After the addition was completed, the reaction temperature was raised to 25°C and the reaction was continued for 16h. After the reaction was completed, the reaction solution was precipitated into an aqueous solution to precipitate solid matter. After filtration, the solid was dissolved in acetone and precipitated into water again, and repeated 3 times. The obtained yellow solid was dried, and the grafting rate of diazonaphthoquinone was calculated to be 20% by nuclear magnetic resonance.

[0129] Example 8:

[0130] The structure of the triphenol A derivative containing 4,5-dimethoxy-o-nitrobenzyl ether and 2,1,4-diazonaphthoquinone structure is as follows:

[0131]

[0132] The preparation method of the triphenol A derivative containing 4,5-dimethoxy-o-nitrobenzyl ether and 2,1,4-diazonaphthoquinone structure is as follows:

[0133] Under a nitrogen atmosphere, 50 g of the spirofluorene derivative was dissolved in 800 mL of acetone, and 15 g of potassium carbonate and 1.5 g of 18-crown-6 were added at 60°C. Subsequently, 32 g of 4,5-dimethoxy-o-nitrobenzyl bromide was dissolved in 100 mL of acetone and added dropwise to the reaction system for 12 h.

[0134] After the reaction is completed, the reaction solution is cooled to room temperature and precipitated into an aqueous solution to separate out solid matter. The solid matter is filtered and washed 3 times with water to remove residual inorganic salts. The washed solid is purified using column chromatography using ethyl acetate and petroleum ether in a volume ratio of 1:4 as a developing solvent. The collected liquid is rotary evaporated to obtain a yellow solid powder, and the grafting rate of o-nitrobenzyl ether calculated by nuclear magnetic resonance is 10%.

[0135] Under a nitrogen atmosphere, 30g of the yellow powder obtained above was dissolved in a mixed solution of 50mL of anhydrous dimethylformamide and 20mL of anhydrous acetone, and 18g of triethylamine was slowly added dropwise at 0°C for 5min. Next, 50g of 2,1,4-diazonaphthoquinonesulfonyl chloride was dissolved in a mixed solution of 20mL of anhydrous dimethylformamide and 20mL of anhydrous acetone and slowly added dropwise to the above reaction system within 1h. After the addition was completed, the reaction temperature was raised to 25°C and the reaction was continued for 16h. After the reaction was completed, the reaction solution was precipitated into an aqueous solution to precipitate solid matter. After filtration, the solid was dissolved in acetone and precipitated into water again, and repeated 3 times. The resulting yellow solid was dried, and the grafting rate of diazonaphthoquinone was calculated to be 40% by nuclear magnetic resonance.

[0136] Example 9:

[0137] The structure of the triphenol A derivative containing 4,5-dimethoxy-o-nitrobenzyl ether and 2,1,4-diazonaphthoquinone structure is as follows:

[0138]

[0139] The preparation method of the triphenol A derivative containing 4,5-dimethoxy-o-nitrobenzyl ether and 2,1,4-diazonaphthoquinone structure is as follows:

[0140] Under a nitrogen atmosphere, 50 g of the spirofluorene derivative was dissolved in 800 mL of acetone, and 70 g of potassium carbonate and 7 g of 18-crown-6 were added at 60°C. Subsequently, 140 g of 4,5-dimethoxy-o-nitrobenzyl bromide was dissolved in 380 mL of acetone and added dropwise to the reaction system for 12 h.

[0141] After the reaction is completed, the reaction solution is cooled to room temperature and precipitated into an aqueous solution to separate out solid matter. The solid matter is filtered to obtain the solid matter and washed with water 3 times to remove residual inorganic salts. The washed solid is purified using column chromatography using ethyl acetate and petroleum ether in a volume ratio of 1:4 as the developing solvent. The collected liquid is rotary evaporated to obtain a yellow solid powder, and the grafting rate of o-nitrobenzyl ether calculated by nuclear magnetic resonance is 40%.

[0142] Under a nitrogen atmosphere, 30g of the yellow powder obtained above was dissolved in a mixed solution of 50mL of anhydrous dimethylformamide and 20mL of anhydrous acetone, and 4g of triethylamine was slowly added dropwise at 0°C for 5min. Next, 10g of 2,1,4-diazonaphthoquinonesulfonyl chloride was dissolved in a mixed solution of 5mL of anhydrous dimethylformamide and 5mL of anhydrous acetone and slowly added dropwise to the above reaction system within 1h. After the addition was completed, the reaction temperature was raised to 25°C and the reaction was continued for 16h. After the reaction was completed, the reaction solution was precipitated into an aqueous solution to precipitate solid matter. After filtration, the solid was dissolved in acetone and precipitated into water again, and repeated 3 times. The obtained yellow solid was dried, and the grafting rate of diazonaphthoquinone was calculated to be 10% by nuclear magnetic resonance.

[0143] Example 10:

[0144] Based on Example 1, a polyhydroxystyrene resin derivative containing o-nitrobenzyl ether groups and diazonaphthoquinone groups was prepared, wherein the grafting rate of the diazonaphthoquinone groups was 23%.

[0145] Comparative Example 1:

[0146] The structure of the polyhydroxystyrene derivative containing 4,5-dimethoxy-o-nitrobenzyl ether structure is as follows:

[0147]

[0148] The preparation method of the polyhydroxystyrene derivative containing 4,5-dimethoxy-o-nitrobenzyl ether structure is as follows:

[0149] Under a nitrogen atmosphere, 50 g of polyhydroxystyrene (weight-average molecular weight 4000, PDI 1.05) was dissolved in 500 mL of dimethylformamide. 7.2 g of sodium hydride was added and the mixture was reacted at 50°C for 1.5 h. 69 g of 4,5-dimethoxy-o-nitrobenzyl bromide was dissolved in 300 mL of dimethylformamide and added dropwise to the reaction solution for 4 h. After the reaction, the mixture was cooled to room temperature. The reaction mixture was precipitated into an aqueous solution of ammonium chloride and filtered to obtain a solid. The solid was then washed three times with water to remove inorganic salts. The solid was then dissolved in dimethylformamide and precipitated into water, and this process was repeated three times. The resulting solid was then dissolved in ethyl acetate and precipitated into petroleum ether, and this process was repeated three times. The solid was dried to obtain a yellow powder. Nuclear magnetic resonance analysis indicated a grafting yield of 30% for o-nitrobenzyl ether.

[0150] Comparative Example 2: The structure of the polyhydroxystyrene resin derivative containing 2,1,5-naphthoquinone diazide structure is as follows:

[0151]

[0152] The preparation method of the polyhydroxystyrene resin derivative containing 2,1,5-diazonaphthoquinone structure is as follows:

[0153] Under a nitrogen atmosphere, 30 g of polyhydroxystyrene (weight-average molecular weight 4000, PDI 1.05) was dissolved in a mixture of 20 mL of anhydrous dimethylformamide and 10 mL of anhydrous acetone. 10 g of triethylamine was slowly added dropwise at 0°C over 10 minutes. Next, 27 g of 2,1,5-naphthoquinonediazosulfonyl chloride was dissolved in a mixture of 15 mL of anhydrous dimethylformamide and 9 mL of anhydrous acetone and slowly added dropwise to the reaction system over 1 hour. After the addition was complete, the reaction temperature was raised to 25°C and the reaction was continued for 24 hours. After the reaction, the reaction solution was precipitated into aqueous solution to precipitate a solid. After filtration, the solid was dissolved in acetone and reprecipitated into water three times to remove byproducts and residual solvent. The resulting yellow solid was dried, and nuclear magnetic resonance analysis revealed a 30% grafting yield of naphthoquinonediazo.

[0154] Photoresists were prepared using the photosensitive molecules of Examples 1-10 and Comparative Examples 1-2, and the prepared photoresists were subjected to the following performance tests.

[0155] Figure 1 The scanning pattern of the photoresist film layer according to the first embodiment of the present disclosure is schematically shown.

[0156] (1) Photoresist film uniformity test:

[0157] The photosensitive molecules prepared in Example 1 were dissolved in propylene glycol methyl ether acetate to form a 25 mg / mL solution. After complete dissolution, the solution was filtered through a filter membrane with a pore size of 0.22 μm to prepare a photoresist. The prepared photoresist composition was spin-coated on a silicon wafer and baked at 100°C for 2 minutes to prepare a photoresist film layer. The surface of the photoresist film was scanned with an atomic force microscope to analyze the film uniformity. Figure 1 As shown, the photoresist prepared in Example 1 has good film forming properties and uniformity, with Rq=0.26nm.

[0158] (2) Film retention rate test:

[0159] The photosensitive molecules prepared in Examples 1-10 and Comparative Examples 1-2 were dissolved in propylene glycol methyl ether acetate to prepare a 25 mg / mL solution. After complete dissolution, the solution was filtered through a filter membrane with a pore size of 0.22 μm to prepare a photoresist composition.

[0160] The prepared photoresist compositions were spin-coated on silicon wafers to form films, and baked at 100° C. for 2 minutes to prepare photoresist film layers.

[0161] The photoresist film layers were developed with a 2.38% tetramethylammonium hydroxide solution for 30 seconds and then fixed with deionized water for 15 seconds. The thickness of the film layers before and after development was measured using an ellipsometer. The film retention test results are shown in Table 1.

[0162] Table 1

[0163]

[0164] As can be seen from Table 1, the film retention rate of the photoresist prepared in the embodiment of the present disclosure is 100%, indicating that the photoresist containing o-nitrobenzyl ether and diazonaphthoquinone groups has excellent development resistance and film stability.

[0165] (3) Sensitivity test:

[0166] The photosensitive molecules obtained in Examples 1-10 and Comparative Examples 1-2 were dissolved in propylene glycol methyl ether acetate to prepare a 25 mg / mL solution. After complete dissolution, the solution was filtered with a filter membrane with a pore size of 0.22 μm to prepare a photoresist composition. The photoresist composition was spin-coated on a silicon wafer, baked at 100°C for 2 minutes, and then exposed at an I-line wavelength (exposure area: a circle with a diameter of 1 cm), and then baked at 100°C for 1 minute. Developed with a 2.38% tetramethylammonium hydroxide solution for 30 seconds, then fixed with deionized water for 15 seconds, the thickness difference between the exposed area and the non-exposed area was tested using a step profiler. The exposure dose when the thickness difference is the film thickness is defined as the sensitivity. The test results are shown in Table 2.

[0167] Table 2

[0168]

[0169] As shown in Table 2, the sensitivity of the photoresist composition containing o-nitrobenzyl ether group and diazonaphthoquinone group in the embodiment of the present disclosure is ≤195 mJ / cm 2 , which are all lower than the sensitivity of the photoresist composition containing only o-nitrobenzyl ether group in Comparative Example 1, which is 300 mJ / cm 2 Among them, the sensitivity of Example 1 is the best, reaching 80mJ / cm 2 ; The sensitivity of Example 2 and Example 9 is slightly worse, which is because the grafting ratio of the photosensitive group in Example 2 and Example 9 is relatively high. The higher the grafting ratio of the photosensitive group, the worse the sensitivity, which is a normal performance of the photoresist. When the grafting ratio of the photosensitive group in Example 2 and Example 9 is reduced, the sensitivity can achieve the same excellent effect as that of Example 1. The results in Table 2 demonstrate the feasibility of the disclosed strategy of improving photosensitivity by grafting two photosensitive components.

[0170] Figure 2 The SP lithography pattern of the photoresist according to the embodiment 1 of the present disclosure is schematically shown. Figure 3 The SP lithography pattern of the photoresist according to Comparative Example 2 of the present disclosure is schematically shown.

[0171] (4) Resolution test:

[0172] The materials obtained in Example 1 and Comparative Example 2 were respectively dissolved in PGMEA to prepare a 25 mg / mL solution. After complete dissolution, the solution was filtered through a filter membrane with a pore size of 0.22 μm to prepare a photoresist composition.

[0173] The photoresist composition was spin-coated onto the SP photoresist layer and baked at 100°C for 2 minutes before SP exposure. The film was then baked at 100°C for 1 minute. Development was performed using a 2.38% tetramethylammonium hydroxide solution for 30 seconds, followed by fixing with deionized water for 15 seconds. After drying, the pattern was examined using a scanning electron microscope, resulting in a 64nm resolution pattern.

[0174] Although the sensitivity of the photoresist based on Comparative Example 2 is excellent, Figure 3 It can be seen that it does not have the ability to form 64nm high-resolution patterns. At 64nm resolution, the lines stick together and cannot adhere to the substrate. However, the photoresist based on Example 1 can obtain good patterns at 64nm resolution while taking into account both sensitivity and resolution performance, proving the feasibility of this embodiment.

[0175] Those skilled in the art will appreciate that various combinations and / or combinations of features described in the various embodiments and / or claims of this disclosure may be made, even if such combinations or combinations are not explicitly described in this disclosure. In particular, various combinations and / or combinations of features described in the various embodiments and / or claims of this disclosure may be made, without departing from the spirit and teachings of this disclosure. All such combinations and / or combinations fall within the scope of this disclosure.

[0176] The embodiments of the present disclosure are described above. However, these embodiments are for illustrative purposes only and are not intended to limit the scope of the present disclosure. Although each embodiment has been described separately above, this does not mean that the measures in each embodiment cannot be used in combination to advantage. The scope of the present disclosure is defined by the appended claims and their equivalents. Without departing from the scope of the present disclosure, those skilled in the art may make various substitutions and modifications, which should all fall within the scope of the present disclosure.

Claims

1. A photosensitive molecule containing o-nitrobenzyl ether and diazonaphthoquinone dual photosensitive groups, characterized in that: The photosensitive molecule has the general structural formula shown in Formula I: Formula I; Wherein, A is a molecular glass or polymer containing a phenolic hydroxyl group, Ra is an o-nitrobenzyl group, and Rb is a diazonaphthoquinone group.

2. The photosensitive molecule according to claim 1, wherein The A is polyhydroxystyrene, phenolic resin, calixarene, spirofluorene structure or triphenol A.

3. The photosensitive molecule according to claim 2, characterized in that The structure of the photosensitive molecule is Formula II, Formula III, Formula IV, Formula V or Formula VI; Wherein, formula II is ; Formula III is ; Formula IV is ; Formula V is ; Formula VI is ; The weight average molecular weight of the structure of Formula II and the structure of Formula III is ≤20,000, x / (x+y+z) ≥40%, 10% ≤ y / (x+y+z) ≤30%, and 20% ≤ z / (x+y+z) ≤30%; R5 in the structure of formula IV, the structure of formula V and the structure of formula VI is hydroxyl, Ra or Rb, and R5 in the structure of formula IV, the structure of formula V and the structure of formula VI is Ra and Rb; R6 is -H, -C 10 H 13 、-C n H 2n+1 or -C n H 2n OH, 1≤n≤10.

4. The photosensitive molecule according to claim 3, characterized in that In the structure of formula IV and the structure of formula V, the hydroxyl group is ≤ 62.5%, 12.5% ​​≤ Ra ≤ 37.5%, and 12.5% ​​≤ Rb ≤ 37.5%; The hydroxyl group in the structure of formula VI is ≤60%, 10%≤Ra≤40%, and 10%≤Rb≤40%.

5. The photosensitive molecule according to claim 1, characterized in that The grafting rate of the o-nitrobenzyl group in the structure of formula I is 10% to 40%; The grafting rate of the diazonaphthoquinone group in the structure of formula I is 10% to 40%.

6. The photosensitive molecule according to claim 1, wherein The structure of the o-nitrobenzyl group is Formula VII, wherein Formula VII is ; Wherein, R1 is -NO2 or -H, and R2, R3, and R4 are hydrogen atom, alkyl, alkoxy, nitrogen methyl, phenyl, or alkylphenyl.

7. A photoresist composition containing o-nitrobenzyl ether and diazonaphthoquinone dual photosensitive groups, characterized in that: include: The photosensitive molecule and organic solvent according to any one of claims 1 to 6.

8. The photoresist composition according to claim 7, wherein The organic solvent is one of propylene glycol methyl ether acetate, ethylene glycol methyl ether acetate, propylene glycol methyl ether, butyl lactate, butyl acetate and methyl isobutyl ketone, or a mixture of two of them.

9. A method for preparing a photosensitive molecule containing o-nitrobenzyl ether and diazonaphthoquinone dual photosensitive groups, characterized in that: include: Dissolving a molecular glass or polymer containing a phenolic hydroxyl group in a solvent, adding a basic catalyst and / or 18-crown ether-6, and dropwise adding a reactant containing an o-nitrobenzyl group, reacting and purifying to obtain a first product; The first product is dissolved in a solvent, a weakly basic catalyst is added dropwise, and a reactant containing a diazonaphthoquinone group is added, and the reaction is purified to obtain a photosensitive molecule containing an o-nitrobenzyl ether group and a diazonaphthoquinone group; Wherein, the photosensitive molecule has the general structural formula shown in Formula I: Formula I; A is a molecular glass or polymer containing a phenolic hydroxyl group, Ra is an o-nitrobenzyl group, and Rb is a diazonaphthoquinone group.

10. A method for preparing a photoresist composition containing o-nitrobenzyl ether and naphthoquinone diazide dual photosensitive groups, characterized in that: include: The photosensitive molecule according to any one of claims 1 to 6 or the photosensitive molecule prepared according to claim 9 is dissolved in an organic solvent and filtered to obtain the photoresist composition.

11. A photolithography method, characterized in that: Photolithography is performed using the photoresist composition according to claim 7 or 8 or the photoresist composition prepared by the method according to claim 10.

12. The photolithography method according to claim 11, wherein: The photolithography method is one of i-line projection lithography, i-line interference lithography, i-line near-field lithography and SP lithography.

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