Triptycene, triptycene derivative, synthesis method of triptycene derivative, photoresist composition and application of photoresist composition

Abstract

The invention provides a synthesis method of triptycene, which can be applied to the technical field of organic photoelectric materials. The synthesis method comprises the following steps: performing in-situ generation of benzyne by using 2-(trimethylsilyl) phenyl trifluoromethane sulfonate and cesium fluoride, and performing [4 + 2] cycloaddition reaction on the benzyne and methoxyl-substituted anthracene to generate a bridging structure, thereby obtaining the triptycene. The invention also provides a triptycene derivative, a synthesis method, a photoresist composition and application. The triptycene derivative is used as a single component to form a photoresist composition, and a 128 nm periodic photoetching pattern is successfully prepared through exposure under an i line. Compared with a traditional i-line photoresist composition, the photoresist composition provided by the invention has a higher resolution ratio.

Description

Technical Field

[0001] The present disclosure relates to the technical field of organic optoelectronic materials, and more specifically to triptycene, triptycene derivatives and synthesis methods, photoresist compositions and applications. Background Art

[0002] Triptylene is an aromatic hydrocarbon with a unique three-dimensional rigid structure. Its molecular structure consists of three benzene rings cleverly connected by bridge bonds, forming a cage-like structure similar to a butterfly. This unique spatial configuration endows triptycene and its derivatives with unique electronic properties, giving them great application potential in multiple cutting-edge fields.

[0003] In the field of supramolecular chemistry, triptycene's three-dimensional rigid structure provides an ideal template for constructing supramolecular systems with specific spatial arrangements and functions. Its unique cavity structure enables it to form stable supramolecular assemblies with a variety of molecules through non-covalent interactions (such as hydrogen bonds, van der Waals forces, and π-π stacking), laying the foundation for molecular recognition, the construction of molecular devices, and the development of new functional materials.

[0004] In materials science, the exceptional properties of triptycene and its derivatives offer broad application prospects in high-performance polymers, optoelectronic materials, and energy storage materials. For example, incorporating triptycene structures into polymer backbones or side chains can significantly improve the thermal stability, mechanical properties, and optical properties of polymers, providing a new approach for the development of high-performance engineering plastics and functional films. Furthermore, triptycene derivatives are attracting significant attention for their application in photoelectric conversion materials. Their unique electronic structure helps improve photoelectric conversion efficiency, offering new insights into the development of optoelectronic devices such as solar cells and light-emitting diodes.

[0005] In the biomedical field, triptycene's three-dimensional rigid structure and unique electronic properties offer potential applications in drug delivery, bioimaging, and biosensing. For example, rationally designing the structure of triptycene derivatives can achieve targeted drug delivery and controlled release, improving drug efficacy and reducing side effects. Furthermore, triptycene derivatives can serve as bioimaging probes for cell and tissue imaging studies, providing powerful tools for early diagnosis and treatment of diseases.

[0006] However, current methods for synthesizing triptycene have certain limitations. The traditional method for synthesizing the triptycene skeleton is to use benzylene and anthracene to undergo a Diels-Alder reaction (the Diels-Alder reaction, also known as the diene synthesis reaction, is a reaction in which a conjugated diene and a dienophile (generally known as a substituted olefin) undergo a [4+2] cycloaddition reaction to produce a six-membered cycloolefin). Among the commonly used methods for generating benzylene, the in situ generation of benzylene using o-dibromobenzene at high temperature and high pressure has extremely harsh reaction conditions. Not only does it require an extreme environment of high temperature and high pressure, increasing equipment cost and operational difficulty, but the yield is also low, making it difficult to meet the needs of large-scale production. Another method for generating benzylene using o-aminobenzoic acid under milder conditions is relatively mild, but the high cost and limited supply of o-aminobenzoic acid also limit the large-scale synthesis of triptycene.

[0007] In addition, the traditional functionalization method of triptycene is mainly to introduce functional groups on the benzene ring through substitution reaction or coupling reaction, such as -NO2, -Br, -COOH, etc. This method has obvious shortcomings. On the one hand, it is difficult to introduce more hydroxyl groups, and hydroxyl groups have important functions in many applications. For example, they can act as donors or acceptors of hydrogen bonds in supramolecular self-assembly, and can be used to improve the hydrophilicity and biocompatibility of materials in materials science; on the other hand, the reaction sites have certain limitations, and it is impossible to achieve precise modification and functionalization of the triptycene molecular structure, which limits the performance optimization and application expansion of triptycene derivatives. The traditional formula for the synthesis and functionalization of triptycene is as follows:

[0008] (1) Summary of the Invention

[0009] (1) Technical issues to be resolved

[0010] To address the above-mentioned issues, the present disclosure provides triptycene, triptycene derivatives, synthesis methods, photoresist compositions, and applications. These methods address the harsh reaction conditions and low yields associated with conventional triptycene synthesis methods. Furthermore, the triptycene derivatives obtained in the embodiments of the present disclosure can be used as a single component in photoresist formulations, successfully fabricating 128nm periodic lithographic patterns using i-line exposure. Compared to conventional i-line photoresists, these photoresists have the potential for higher resolution.

[0011] (2) Technical solution

[0012] In response to the above technical problems, the embodiments of the present disclosure provide triptycene, triptycene derivatives and synthesis methods, photoresist compositions and applications.

[0013] According to a first aspect of the present disclosure, a method for synthesizing triptycene is provided, comprising: S1. in situ generating benzyne using 2-(trimethylsilyl)phenyl trifluoromethanesulfonate and cesium fluoride, and performing a [4+2] cycloaddition reaction between the benzyne and methoxy-substituted anthracene to form a bridged structure to obtain triptycene, wherein the structural formula of triptycene is: ; wherein R1, R2, and R3 are the same or different and are independently selected from H, alcoholic hydroxyl, carboxyl, epoxy, ether, thioether, ester, amide, halogen, nitro, cyano, heterocyclic group, alkane group, or aromatic group in which hydrogen on the benzene ring is partially substituted by alkyl, hydroxyl, amino or carboxyl; x, y, and z are the corresponding number of substitutions of R1, R2, and R3 groups, and x, y, and z are all integers, wherein 0≤x≤2, 0≤y≤2, and 0≤z≤4.

[0014] In some exemplary embodiments, before step S1, the method further comprises: S1-1, compound The hydroxyl group of the compound is protected under alkaline conditions to obtain compound b. ; S1-2, using a reducing agent to treat the compound obtained in step S1-1 The carbonyl group of the anthracene is reduced to obtain an anthracene substituted with a methoxy group, wherein the structural formula of the anthracene substituted with a methoxy group is: .

[0015] In some exemplary embodiments, the base used in the alkaline conditions in step S1-1 includes sodium carbonate, potassium carbonate, or triethylamine; the protecting group in step S1-1 is iodomethane; the reducing agent in step S1-2 is zinc powder or copper powder; and the reduction reaction in step S1-2 is carried out in an aqueous solution of sodium hydroxide or potassium hydroxide.

[0016] According to a second aspect of the present disclosure, a triptycene derivative is provided, and the structural formula of the triptycene derivative is: , wherein R1, R2, R3, and R4 are the same or different and are independently selected from H, alcoholic hydroxyl, carboxyl, epoxy, ether, thioether, ester, amide, halogen, nitro, cyano, heterocyclic group, alkane group, or aromatic group in which hydrogen on the benzene ring is partially substituted by alkyl, hydroxyl, amino, or carboxyl; R5 is selected from H, naphthoquinone diazide group, or hydroxyl, and at least part of R5 is naphthoquinone diazide group; x, y, z, and m are the corresponding substitution numbers of R1, R2, R3, and R4 groups, and x, y, z, and m are all integers, wherein 0≤x≤2, 0≤y≤2, 0≤z≤4, and 0≤m≤3.

[0017] In some exemplary embodiments, the diazonaphthoquinone group is a diazonaphthoquinone sulfonate group, and the grafting rate of the diazonaphthoquinone group in the triptycene derivative is 45-65%.

[0018] In some exemplary embodiments, the structural formula of the triptycene derivative is preferably: .

[0019] According to a third aspect of the present disclosure, a method for synthesizing a triptycene derivative is provided, comprising: S2-1. reducing the methoxy group in the triptycene obtained according to any one of claims 1 to 3 using boron tribromide under low temperature conditions to obtain a hydroxylated compound b ; S2-2 p-toluenesulfonic acid as a catalyst, the use of paraformaldehyde and step S2-1 obtained in the compound b ortho-hydroxyl condensation reaction, followed by the addition of potassium carbonate to continue the reaction to obtain a compound ; S2-3 using p-toluenesulfonic acid as a catalyst, using the R4 group substituted phenol and the compound obtained in step S2-2 The condensation reaction continues to produce phenol structure compounds derived from both ends. ; S2-4. Under alkaline conditions, using 2-diazo-1-naphthol-4-sulfonyl chloride or 2-diazo-1-naphthol-5-sulfonyl chloride to the compound obtained in step S2-3 The four hydroxyl groups in the formula (I) are functionally substituted to obtain a triptycene derivative; wherein R1, R2, R3, and R4 are the same or different and are independently selected from H, an alcoholic hydroxyl group, a carboxyl group, an epoxy group, an ether, a thioether group, an ester group, an amide group, a halogen group, a nitro group, a cyano group, a heterocyclic group, an alkane group, or an aromatic group in which hydrogen on the benzene ring is partially substituted by an alkyl group, a hydroxyl group, an amino group, or a carboxyl group; x, y, z, and m are the corresponding numbers of substitutions of the R1, R2, R3, and R4 groups, and x, y, z, and m are all integers, wherein 0≤x≤2, 0≤y≤2, 0≤z≤4, and 0≤m≤3.

[0020] According to a fourth aspect of the present disclosure, an i-line single-component photoresist composition is provided, characterized in that it comprises the above-mentioned triptycene derivative or the triptycene derivative synthesized by the above-mentioned method and an organic solvent; wherein the triptycene derivative is dissolved in the organic solvent as the sole photosensitive component to form the i-line single-component photoresist composition; the organic solvent is selected from the group consisting of n-butyl acetate, ethyl acetate, propylene glycol methyl ether acetate, propylene glycol methyl ether, ethyl lactate, and mixtures thereof; and the weight percentage of the organic solvent in the photoresist composition is 85-98%.

[0021] In some exemplary embodiments, the i-line single-component photoresist composition further includes other additives, wherein the mass fraction of the other additives is not greater than 0.1%; and the other additives include one or more of a leveling agent, a surfactant, a stabilizer, and a tackifier.

[0022] According to the fifth aspect of the present disclosure, an application of the above-mentioned i-line single-component photoresist composition is provided. The i-line single-component photoresist composition is suitable for interference lithography, near-field lithography, and SP lithography with a feature size less than 100 nm and a photoresist film thickness less than 50 nm.

[0023] (3) Beneficial effects

[0024] It can be seen from the above technical solutions that the triptycene, triptycene derivatives, synthesis methods, photoresist compositions, and applications provided by the embodiments of the present disclosure have at least the following beneficial effects:

[0025] (1) Benzene is generated in situ from 2-(trimethylsilyl)phenyl trifluoromethanesulfonate, which then reacts with methoxy-substituted anthracene to undergo a Diels-Alder reaction under mild conditions to give triptycene in high yield (greater than 70%).

[0026] (2) After multiple steps of reaction, a triptycene derivative that is sensitive to i-rays is obtained, which has a high glass transition temperature (greater than 120°C) and good thermal stability; it has a definite molecular structure, a single molecular weight distribution, and a small molecular size.

[0027] (3) Due to the unique spatial structure of the molecular skeleton of the main component, the derivative is not easy to crystallize when used as a single component to configure photoresist, has good film-forming properties, and can successfully expose 128nm periodic high-resolution patterns, expanding the application of this series of molecules in the field of photoresist. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The above contents 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:

[0029] Figure 1 A flow chart schematically illustrates a method for synthesizing triptycene according to an embodiment of the present disclosure;

[0030] Figure 2 Schematically shows a flow chart of another method for synthesizing triptycene according to an embodiment of the present disclosure;

[0031] Figure 3 A flow chart schematically illustrates a method for synthesizing a triptycene derivative according to an embodiment of the present disclosure;

[0032] Figure 4 The following schematically shows a synthesis route of a triptycene derivative according to an embodiment of the present disclosure;

[0033] Figure 5 A schematic diagram schematically illustrates the working mechanism of the photoresist composition according to an embodiment of the present disclosure;

[0034] Figure 6 A schematic diagram showing the roughness test results of a photoresist film layer prepared according to the method of Example 5 of the present disclosure is shown; and

[0035] Figure 7 The following schematically shows the exposure pattern results of the photoresist film layer prepared according to Example 6 of the present disclosure. DETAILED DESCRIPTION

[0036] In order to make the objectives, technical solutions and advantages of the present disclosure more clearly understood, the present disclosure is further described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings.

[0037] 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.

[0038] 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.

[0039] Figure 1 The figure schematically shows a flow chart of a method for synthesizing triptycene according to an embodiment of the present disclosure.

[0040] like Figure 1 As shown, a method for synthesizing triptycene according to an embodiment of the present disclosure includes step S1.

[0041] In step S1, 2-(trimethylsilyl)phenyl trifluoromethanesulfonate and cesium fluoride are used to generate benzylene in situ. The benzylene and methoxy-substituted anthracene undergo a [4+2] cycloaddition reaction to form a bridged structure to obtain triptycene (compound d). The structural formula of triptycene is: ; Among them, R 1 、R 2 、R 3 The same or different groups are independently selected from H, alcoholic hydroxyl, carboxyl, epoxy, ether, thioether, ester, amide, halogen, nitro, cyano, heterocyclic group, alkane group or aromatic group in which hydrogen on the benzene ring is partially replaced by alkyl, hydroxyl, amino or carboxyl groups; x, y, z are the corresponding R 1 、R 2 、R 3 The number of group substitutions, x, y, and z are all integers, where 0≤x≤2, 0≤y≤2, and 0≤z≤4.

[0042] In step S1, the reaction mechanism for generating benzyne is as follows: 2-(trimethylsilyl)phenyl trifluoromethanesulfonate, under the action of cesium fluoride, the trifluoromethanesulfonate ion leaves as a leaving group, and at the same time, the trimethylsilyl group is attacked by the nucleophilic fluoride ion, and an elimination reaction occurs to generate benzyne. This method of generating benzyne in situ avoids the disadvantages of traditional high temperature and high pressure or the use of controlled drugs, and the reaction conditions are relatively mild and easy to control. Compared with the high temperature and high pressure generation of benzyne by o-dibromobenzene, this method reduces the risk of the reaction and the equipment requirements; compared with the generation of benzyne by o-aminobenzoic acid, the raw material cost is reduced and the supply is not restricted by regulation, which is more suitable for large-scale production.

[0043] In step S1, the [4+2] cycloaddition reaction mechanism is as follows: the generated benzyne acts as a dienophile, undergoing a [4+2] cycloaddition reaction with the methoxy-substituted anthracene (a conjugated diene). The π-electron cloud of the benzyne interacts with the π-electron cloud of the anthracene, forming a new carbon-carbon bond through a six-membered ring transition state, yielding a bridged triptycene. This reaction is highly regio- and stereoselective, capable of yielding triptycene products with specific structures. Furthermore, by varying the substituents and position of the methoxy-substituted anthracene, the structure and properties of the triptycene can be manipulated.

[0044] Figure 2 A flow chart of another method for synthesizing triptycene according to an embodiment of the present disclosure is schematically shown.

[0045] like Figure 2 As shown, another method for synthesizing triptycene according to an embodiment of the present disclosure is Figure 1 The method shown further includes steps S1-1 and S1-2 before step S1.

[0046] In step S1-1, compound a ( ) is protected under alkaline conditions to obtain compound b ( ).

[0047] Preferably, the base used in the alkaline condition in step S1-1 includes sodium carbonate, potassium carbonate or triethylamine, etc.; the protecting group in step S1-1 is iodomethane.

[0048] Under alkaline conditions, the hydroxyl oxygen atom in compound a possesses a lone pair of electrons, exhibiting a certain degree of nucleophilicity. Methyl iodide is a good methylating agent, as its carbon atom carries a partial positive charge, making it susceptible to attack by nucleophiles. The addition of a base such as sodium carbonate, potassium carbonate, or triethylamine neutralizes any protons present in the reaction system, further enhancing the nucleophilicity of the hydroxyl oxygen atom. This reaction then undergoes a nucleophilic substitution reaction with methyl iodide, yielding a methyl ether structure, compound b. The methylation reaction is relatively simple to perform and requires mild reaction conditions. Furthermore, the methyl group, as a protecting group, is relatively stable in subsequent reactions, making it less susceptible to side reactions. Furthermore, when deprotection is necessary, the methyl protecting group can usually be removed using relatively mild conditions (such as treatment with a reducing agent such as sodium borohydride under acidic conditions), restoring the hydroxyl group.

[0049] In step S1-2, the carbonyl group of compound a obtained in step S1-1 is reduced with a reducing agent to obtain methoxy-substituted anthracene (compound c), wherein the structural formula of methoxy-substituted anthracene is: .

[0050] Preferably, the reducing agent in step S1-2 is zinc powder or copper powder; and the reduction reaction in step S1-2 is carried out in an aqueous solution of sodium hydroxide or potassium hydroxide. Zinc powder has strong reducing properties and can effectively reduce carbonyl groups under alkaline conditions. The price of zinc powder is relatively low, and the zinc oxide generated after the reaction is easy to handle. The aqueous solution of sodium hydroxide or potassium hydroxide is used to provide an alkaline environment, which is conducive to the carbonyl reduction reaction. Alkaline conditions can increase the electron cloud density on the carbonyl oxygen atom and reduce the positive charge of the carbonyl carbon, but at the same time can promote the generation of reducing agent active species and the progress of the reaction. In addition, alkaline conditions also contribute to the subsequent conversion of alcoholic hydroxyl groups into methoxy groups.

[0051] The methoxy-substituted anthracene (Compound C) obtained in Steps S1-1 and S1-2 is then used as a reactant in the [4+2] cycloaddition reaction in Step S1. This synthetic strategy of first protecting the hydroxyl group and reducing the carbonyl group before the cycloaddition reaction improves reaction selectivity and yield while minimizing side reactions. By controlling the reaction conditions in each step, triptycene products with specific structures and properties can be precisely synthesized.

[0052] based on Figure 1 or Figure 2 The triptycene product obtained by the method can be further used to generate triptycene derivatives.

[0053] Figure 3 The flowchart of the synthesis method of triptycene derivatives according to an embodiment of the present disclosure is schematically shown.

[0054] like Figure 3As shown, the synthesis method of the triptycene derivative according to the embodiment of the present disclosure includes steps S2-1 to S2-4.

[0055] In step S2-1, boron tribromide is used to react with Figure 1 or Figure 2 The methoxy group in the obtained triptycene is reduced to obtain the hydroxylated compound e ( ).

[0056] Boron tribromide (BBr3) is a commonly used demethylation reagent. Under low-temperature conditions, BBr3 reacts with the methoxy group in triptycene. The boron atom in BBr3 has strong electrophilicity and can form a coordination bond with the oxygen atom in the methoxy group. The methyl group in the methoxy group then leaves in the form of bromomethane, reducing the methoxy group to a hydroxyl group, yielding product e.

[0057] In step S2-2, paraformaldehyde is used as a catalyst to carry out a condensation reaction with the ortho position of the hydroxyl group in the compound e obtained in step S2-1, and then potassium carbonate is added to continue the reaction to obtain compound f ( ).

[0058] p-Toluenesulfonic acid, as an acidic catalyst, activates the hydroxyl groups, making them more susceptible to nucleophilic addition-elimination reactions with paraformaldehyde, forming methylene bridged structures. Potassium carbonate is then added to continue the reaction. Potassium carbonate neutralizes the acid generated in the reaction system, driving the reaction forward and potentially stabilizing the intermediates or products, ultimately yielding compound f.

[0059] In step S2-3, p-toluenesulfonic acid is used as a catalyst and R 4 The phenol substituted with the group is further condensed with the compound f obtained in step S2-2 to obtain a phenol structure compound g ( ).

[0060] R 4 The phenolic hydroxyl group in the group-substituted phenol is activated under acidic conditions and undergoes a nucleophilic substitution or addition reaction with the active site in compound f to form a new covalent bond, thereby introducing a derived phenol structure at both ends of triptycene to obtain compound g.

[0061] In step S2-4, the four hydroxyl groups in compound g, obtained in step S2-3, are functionalized using 2-diazo-1-naphthol-4-sulfonyl chloride or 2-diazo-1-naphthol-5-sulfonyl chloride under alkaline conditions to yield a triptycene derivative (h). The alkaline conditions impart a negative charge to the oxygen atoms of the hydroxyl groups, enhancing their nucleophilicity. This allows for nucleophilic substitution with the electrophilic center in diazonaphthoquinonesulfonyl chloride, introducing the diazonaphthoquinone group into the triptycene derivative to yield the final triptycene derivative h.

[0062] In the embodiments of the present disclosure, the structural formula of the triptycene derivative is:

[0063] ;

[0064] Among them, R 1 、R 2 、R 3 、R 4 are the same or different and are independently selected from H, alcoholic hydroxyl, carboxyl, epoxy, ether, thioether, ester, amide, halogen, nitro, cyano, heterocyclic group, alkane group or aromatic group in which hydrogen on the benzene ring is partially replaced by alkyl, hydroxyl, amino or carboxyl; R 5 is selected from H, a diazonaphthoquinone group or a hydroxyl group, and R 5 At least part of the group is a diazonaphthoquinone group; x, y, z, m are the corresponding R 1 、R 2 、R 3 、R 4 The number of group substitutions, x, y, z, and m are all integers, where 0≤x≤2, 0≤y≤2, 0≤Z≤4, and 0≤m≤3.

[0065] The triptycene derivative has a unique three-dimensional rigid structure, with a triptycene skeleton at the center, phenol structures at both ends, and four hydroxyl groups functionalized by diazonaphthoquinone groups. 1 、R 2 、R 3 、R 4 A variety of functional groups can be introduced at different positions of the benzene ring, such as alcohol hydroxyl, carboxyl, epoxy, etc., which increases the diversity and modifiability of the structure. 5 It can be different types of diazonaphthoquinone groups or hydroxyl groups, further enriching the structure of the product.

[0066] Preferably, the diazonaphthoquinone group is a diazonaphthoquinone sulfonate group, and the grafting rate of the diazonaphthoquinone group in the triptycene derivative is 45-65%. Alternatively, the structure of the diazonaphthoquinone group is 、 .

[0067] Preferably, the structural formula of the triptycene derivative is: .

[0068] Combine Figures 1 to 3 , the synthetic route of triptycene derivatives can be found in Figure 4 ,Depend on Figure 4 As can be seen, the reagents used in each step of the synthesis of triptycene derivatives in the disclosed examples are common, and reaction conditions such as temperature and pressure are easily controlled. For example, the reaction conditions for hydroxyl protection and carbonyl reduction are mild, while the low-temperature conditions for methoxyl reduction are highly controllable, which helps reduce side reactions and improve yield and purity. The seven-step reaction yield is greater than 11%.

[0069] The functionalized triptycene derivative h, obtained according to the disclosed embodiments, exhibits photolithographic properties due to the incorporation of photosensitive groups such as 2-diazo-1-naphthol-4-sulfonyl chloride and 2-diazo-1-naphthol-5-sulfonyl chloride. During photolithography, this derivative undergoes a photochemical reaction under illumination, causing a change in its solubility, enabling patterning of specific areas. This is expected to be applied to photolithography processes in integrated circuits, microelectronics, and other fields.

[0070] The disclosed embodiments also provide an i-line single-component photoresist composition, comprising a triptycene derivative synthesized by the above method and an organic solvent; wherein the triptycene derivative is dissolved in the organic solvent as the sole photosensitive component to form an i-line single-component photoresist composition; the organic solvent is selected from the group consisting of n-butyl acetate, ethyl acetate, propylene glycol methyl ether acetate, propylene glycol methyl ether, ethyl lactate, and mixtures thereof; the weight percentage of the organic solvent in the photoresist composition is 85-98%. Optionally, the i-line single-component photoresist composition may also include other additives. The mass fraction of the other additives is not greater than 0.1%; and the other additives may include one or more of a leveling agent, a surfactant, a stabilizer, and a tackifier. The other additives may specifically include any one or more of small molecule amines, siloxanes, ethylene oxide / propane, and fluorinated alkane molecules.

[0071] The i-line single-component photoresist composition according to the embodiment of the present disclosure is particularly suitable for high-tech node lithography fields with strict requirements on film thickness, such as interference lithography, near-field lithography, and SP lithography, where the feature size is less than 100 nm and the photoresist film thickness is less than 50 nm.

[0072] Figure 5 A schematic diagram schematically illustrates the working mechanism of a photoresist composition according to an embodiment of the present disclosure.

[0073] like Figure 5As shown, according to the photoresist of the embodiment of the present disclosure, the DNQ in the exposed area will undergo Wolff rearrangement under 365nm i-line light, and then generate hydrophilic indene carboxylic acid with the participation of a molecule of water. After development with an alkaline developer, the exposed area will be partially dissolved, leaving a positive pattern. Figure 5 R is a triptycene skeleton.

[0074] The present disclosure provides a positive photoresist film, comprising Figure 3 The film is prepared by applying an i-line single-component photoresist on a substrate to form a film having a thickness of 20-100 nm. Preferably, the substrate is a silicon substrate and the application method is spin coating.

[0075] According to the above-mentioned triptycene synthesis steps S1-1, S1-2 and S1-3 and triptycene derivative synthesis steps S2-1 to S2-4, 7 specific examples and 1 comparative example are provided below.

[0076] Example 1:

[0077] In the synthesis of the main component B1 of the triptycene derivative, the ratio of diazonaphthoquinone in R6 is 50%, and the remaining positions are H. The structure of B1 is:

[0078]

[0079] The specific steps are as follows:

[0080] Step S1-1, synthesis of compound b1:

[0081]

[0082] Raw material a1 (5.0 g, 20.8 mmol) and potassium carbonate (17.0 g, 125 mmol) were dissolved in DMF (200 mL). Methyl iodide (5.18 mL, 83.3 mmol) was added and the mixture was reacted at 60°C for 8-12 hours. After the reaction, the mixture was poured into water, extracted with ethyl acetate, washed with water, and then with saturated brine. The solvent was then dried to obtain a dark brown crude product. Recrystallization gave 5.3 g of solid b1 with a calculated yield of 94%.

[0083] 1 H NMR(600MHz, CDCl3) δ7.83(dd,J=7.6,1.1Hz,2H),7.65-7.62(m,2H), 7.30(dd,J=8.4,1.1Hz,2H),4.01(s,6H)ppm.

[0084] Step S1-2, synthesis of compound c1:

[0085]

[0086] Raw material b1 (400 mg, 1.49 mmol) and Zn powder (585 mg, 8.95 mmol) were dissolved in a 10% NaOH solution (15 mL) and heated under reflux until the raw materials disappeared. After the reaction was completed, the mixture was cooled to room temperature. Ethyl acetate was added to the above solution and extracted three times. The organic layers were combined, washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed by vacuum rotary evaporation to obtain a crude product. Recrystallization gave a yellow solid c1 with a mass of 298 mg and a yield of 84%.

[0087] 1 H NMR (600 MHz, CDCl3) δ 9.28 (s, 1H), 8.35 (s, 1H), 7.59 (d, J =8.5 Hz, 2H), 7.40 (dd, J = 8.5, 7.4 Hz, 2H), 6.76 (d, J = 7.4 Hz, 2H), 4.11(s, 6H) ppm.

[0088] Step S1, synthesis of compound d1:

[0089]

[0090] The raw materials c1 (5 g, 20.8 mmol) and CsF (9 g, 62.4 mmol) were dissolved in acetonitrile (40 mL) and stirred at 30 ° C until the raw materials dissolved. 2-(Trimethylsilyl)phenyl trifluoromethanesulfonate (6 mL, 24.9 mmol) was added and the temperature was raised to 80 ° C. The reaction was allowed to proceed and monitored by TLC until the raw materials disappeared. The above solution was poured into water and extracted with DCM three times. The organic phases were combined and washed with saturated brine. The solvent was removed by vacuum rotary evaporation to obtain a crude product, which was purified by ethyl acetate slurrying to obtain a white solid d1 with a mass of 4.62 g and a yield of 70%.

[0091] 1 H NMR (600 MHz, CDCl3) δ 7.47 (dd, 1H), 7.39 (dd, 1H), 7.06 (d, J =7.3 Hz, 2H), 7.01 – 6.99 (m, 2H), 7.00 – 6.98 (m, 2H), 6.96 (dd, J = 8.2, 0.9Hz, 2H), 6.62 (d, J = 8.1 Hz, 1H), 6.40 (s, 1H), 5.44 (s, 1H), 3.88 (s, 6H)ppm.

[0092] Step S2-1, synthesis of compound e1:

[0093]

[0094] Under argon, raw material d1 (4 g, 12.7 mmol) was dissolved in anhydrous DCM (120 mL). BBr3 (3 mL, 31.8 mmol) was added at -78°C and stirred for 30 min. The temperature was then raised to 0°C and allowed to react for 8-12 h. After the reaction was complete and the starting material disappeared by TLC, the mixture was poured into ice water and filtered to obtain a filter cake. Recrystallization afforded a gray solid e1 with a mass of 3.38 g and a yield of 93%.

[0095] 1 H NMR (600 MHz, DMSO-d6) δ 8.65 (s, 2H), 6.48 – 6.44 (m, 2H), 6.06 –6.03 (m, 2H), 5.97 (d, J = 6.3 Hz, 2H), 5.86 – 5.83 (m, 2H), 5.62 (d, J = 7.0Hz, 2H), 5.28 (s, 2H), 4.54 (s, 1H) ppm.

[0096] Step S2-2, synthesis of compound f1:

[0097]

[0098] Raw material e1 (572 mg, 2 mmol), paraformaldehyde (1.2 g, 40 mmol), and p-toluenesulfonic acid (19 mg, 0.1 mmol) were dissolved in toluene (40 mL). The mixture was reacted at 50°C for 48 h, then the temperature was raised to 65°C and the reaction continued for 24 h. After TLC analysis, potassium carbonate was added to neutralize the p-toluenesulfonic acid. The filtrate was filtered and the solvent removed under reduced pressure. After dissolution in 50 mL of DCM, 3 mL of propylene glycol was added and stirred at room temperature overnight. Column chromatography (DCM:acetone = 4:1) afforded f1 as a white solid (324 mg, 47% yield).

[0099] 1H NMR (600 MHz, DMSO-d6) δ 8.77 (s, 2H), 7.38 (ddd, J = 6.4, 4.3,2.2 Hz, 2H), 6.98 – 6.94 (m, 2H), 6.90 (d, J = 7.4 Hz, 2H), 6.84 (d, J = 7.4Hz, 2H), 6.36 (s, 1H), 5.42 (s, 1H), 5.10 (s, 2H), 4.46 (s, 4H) ppm.

[0100] Step S2-3, synthesis of compound g1:

[0101]

[0102] Under N2 protection, p-cresol (187 μL, 1.73 mmol) and p-toluenesulfonic acid (13 mg, 0.07 mmol) were dissolved in toluene (2 mL). Benzyl alcohol (120 mg, 0.35 mmol) was added at 30°C and refluxed for 4 h. The mixture was cooled to room temperature until solid precipitation was complete. The solid was collected by filtration and purified by DCM / PE slurry to obtain g1, a white solid (113 mg, 62% yield).

[0103] 1H NMR (600 MHz, DMSO-d6) δ9.25 (s, 2H), 8.72 (s, 2H), 7.36 (dd, J =25.8, 6.8 Hz, 2H), 6.95 (p, J = 7.4 Hz, 2H), 6.80 (d, J = 7.5 Hz, 2H), 6.77(s, 4H), 6.66 (d, J = 8.2 Hz, 2H), 6.55 (d, J = 7.4 Hz, 2H), 6.35 (s, 1H), 5.33 (s, 1H), 3.70 (d, J = 3.2 Hz, 4H), 2.08 (s, 6H) ppm.

[0104] Step S2-3, synthesis of main component B1:

[0105]

[0106] Under N2 protection, compound g (526 mg, 1 mmol) was dissolved in 15 mL of DMF. The reaction mixture was cooled to 0°C, and triethylamine (280 μL, 2 mmol) was added dropwise. 2-diazo-1-naphthol-4-sulfonyl chloride (536 mg, 2 mmol) was dissolved in 15 mL of DMF and slowly added to the reaction mixture. The temperature was raised to 25°C and the reaction was allowed to proceed for 12 hours. Extraction with DCM and purification by column chromatography afforded B1 in 80% yield.

[0107] 1 H NMR (400 MHz, DMSO-d6) δ 8.97 (s, 2H), 8.56 (d, J = 7.9 Hz, 2H), 8.17 (d, J = 7.6 Hz, 2H), 8.01 (s, 1H), 7.64 (d, J = 9.7 Hz, 2H), 7.56 (t, J= 7.9 Hz, 2H), 7.42 (S, 1H) 7.33 (d, J = 9.9 Hz, 2H), 7.04 – 6.98 (m, 2H), 6.94 (d, J = 7.9 Hz, 4H), 6.87 (d, J = 7.4 Hz, 2H), 6.63 (d, J = 8.2 Hz, 2H),6.49 – 6.40 (m, 3H), 5.42 (d, J = 10.8 Hz, 1H), 3.75 (d, J = 12.5 Hz, 4H), 2.98 (s, 3H), 2.79 (s, 3H).

[0108] 13 C NMR (400 MHz, DMSO-d6) δ 177.03, 162.83, 149.65, 145.85, 137.20,135.28, 134.81, 134.36, 132.45, 132.30, 131.62, 131.51, 131.05, 128.46,126.57, 125.13, 124.05, 121.68, 119.57,116.2, 115.78, 110.64, 80.95, 36.27,31.25, 30.08, 20.83.

[0109] Comparative Example 1:

[0110] In the synthesis of the main component B2, the ratio of naphthoquinone diazide in R5 is 25%, and the remaining positions are H. The structural formula of B2 is:

[0111]

[0112] The synthesis steps are similar to those of B1, except that the ratio of 2-diazo-1-naphthol-4-sulfonyl chloride and triethylamine to hydroxyl group added in step S2-4 is adjusted to 1:4.

[0113] Example 2:

[0114] In the synthesis of the main component B3, R5 is 2-diazo-1-naphthol-5-sulfonyl chloride, the ratio is 50%, and the remaining positions are H. The structural formula of B3 is:

[0115]

[0116] The synthesis steps are similar to those of B1, except that the grafting group added in step S2-4 is 2-diazo-1-naphthol-5-sulfonyl chloride, and the ratio of 2-diazo-1-naphthol-5-sulfonyl chloride to the hydroxyl group is 1:2.

[0117] Comparative Example 2:

[0118] In the synthesis of the main component B4, R5 is 2-diazo-1-naphthol-5-sulfonyl chloride, the ratio is 25%, and the remaining positions are H. The structural formula of B4 is:

[0119]

[0120] The synthesis steps are similar to those of B1, except that the grafted group added in step S2-4 is 2-diazo-1-naphthol-5-sulfonyl chloride, and the ratio of 2-diazo-1-naphthol-5-sulfonyl chloride to the hydroxyl group is 1 to 4.

[0121] Example 3:

[0122] A photoresist film is prepared by dissolving 50 mg of each of the above-synthesized photoresist components (including B1, B2, B3, and B4) in 2 mL of propylene glycol methyl ether acetate, shaking thoroughly to dissolve, and then filtering through a filter to obtain a photoresist product. The solid content of the photoresist can be adjusted to meet different thickness requirements.

[0123] The dissolved photoresist material is spin-coated on a silicon wafer to form a film, and then baked at 100° C. for 2 minutes to obtain a photoresist film layer.

[0124] Example 4: Photoresist film forming performance test

[0125] A photoresist film layer was prepared using the method of Example 3 on B1, and then its roughness was tested using AFM. Figure 6 As shown, RMS = 0.286, indicating that the photoresist film forming property of this system is good.

[0126] Example 5: Film retention performance test

[0127] B1, B2, B3, and B4 were prepared using the method of Example 3 to obtain a photoresist film layer with a thickness of 50 nm. The film was developed in 2.83% TMAH for 30 seconds. The ratio of the retained film thickness to the original film thickness was the film retention rate. The film retention rates of these four materials are shown in Table 1. Among them, the film retention rates tested with materials B1 and B3 were good, and the next step of photolithography performance verification can be carried out. The grafting rate in Comparative Examples 1 and 2 was 25%, which is outside the preferred range. Therefore, the film retention rates of B2 and B4 are poor, less than 10%. The film retention performance test results are shown in Table 1.

[0128] Table 1 Film retention performance test

[0129]

[0130] Example 6: Lithography Performance Test

[0131] Prepare a photoresist film layer on B1 using the method of Example 3, then use SP photolithography to expose, develop in 2.83% TMAH for 30 seconds, and bake at 100°C for 1 minute. The exposure pattern with a period of 128nm is obtained as shown below. Figure 7 As shown. Figure 7 It can be seen that the exposed pattern presents a regularly arranged structure with a period of 128nm, and the marked line width reaches 123nm, which has extremely high dimensional accuracy and can achieve fine pattern construction at the microscopic level; the lines in the pattern are arranged regularly and the spacing is uniform, and the line width and spacing at different positions are highly consistent, with good uniformity; at the same time, the line edges are steep and clear, without obvious blur or deformation, which fully demonstrates that the photoresist film layer is extremely accurate in defining the pattern during the photolithography process.

[0132] Those skilled in the art will appreciate that the features described in the various embodiments of the present disclosure may be combined and / or coupled in various ways, even if such combinations or couplings are not explicitly described in the present disclosure. In particular, the features described in the various embodiments of the present disclosure may be combined and / or coupled in various ways without departing from the spirit and teachings of the present disclosure. All such combinations and / or couplings fall within the scope of the present disclosure.

Claims

1. A method for synthesizing triptycene, characterized in that: include: S1. Benzyne is generated in situ using 2-(trimethylsilyl)phenyl trifluoromethanesulfonate and cesium fluoride, and the benzyne undergoes a [4+2] cycloaddition reaction with methoxy-substituted anthracene to form a bridged structure to obtain triptycene, wherein the structural formula of the triptycene is: ； Among them, R 1 、R 2 、R 3 the same or different, independently selected from H, alcoholic hydroxyl group, carboxyl group, epoxy group, ether, thioether, ester group, amide group, halogen, nitro group, cyano group, heterocyclic group, alkane group or aromatic group in which hydrogen on the benzene ring is partially replaced by alkyl, hydroxyl, amino or carboxyl group; x, y, z are the corresponding R 1 、R 2 、R 3 The number of group substitutions, x, y, and z are all integers, where 0≤x≤2, 0≤y≤2, and 0≤z≤4.

2. The method according to claim 1, characterized in that Before step S1, the method further includes: S1-1, compound The hydroxyl group of is protected under alkaline conditions to obtain compound b: ; S1-2, reducing the carbonyl group in the compound b obtained in step S1-1 with a reducing agent to obtain the methoxy-substituted anthracene, wherein the structural formula of the methoxy-substituted anthracene is: .

3. The method according to claim 2, characterized in that The base used in the alkaline conditions in step S1-1 includes sodium carbonate, potassium carbonate or triethylamine; The protecting group in step S1-1 is iodomethane; The reducing agent in step S1-2 is zinc powder or copper powder; and The reduction reaction in step S1-2 is carried out in an aqueous solution of sodium hydroxide or potassium hydroxide.

4. A triptycene derivative, characterized in that: The structural formula of the triptycene derivative is: Among them, R 1 、R 2 、R 3 、R 4 the same or different, independently selected from H, alcoholic hydroxyl group, carboxyl group, epoxy group, ether, thioether, ester group, amide group, halogen, nitro group, cyano group, heterocyclic group, alkane group or aromatic group in which hydrogen on the benzene ring is partially replaced by alkyl, hydroxyl, amino or carboxyl group; R 5 is selected from H, a diazonaphthoquinone group or a hydroxyl group, and R 5 at least partly diazonaphthoquinone groups; x, y, z, m are the corresponding R 1 、R 2 、R 3 、R 4 The number of group substitutions, x, y, z, and m are all integers, where 0≤x≤2, 0≤y≤2, 0≤Z≤4, and 0≤m≤3.

5. The triptycene derivative according to claim 4, characterized in that The diazonaphthoquinone group is a diazonaphthoquinone sulfonate group, and the grafting rate of the diazonaphthoquinone group in the triptycene derivative is 45-65%.

6. The triptycene derivative according to claim 4, characterized in that The structural formula of the triptycene derivative is preferably: .

7. A method for synthesizing a triptycene derivative, characterized in that: include: S2-1. Using boron tribromide under low temperature conditions to reduce the methoxy group in the triptycene obtained by the method according to any one of claims 1 to 3 to obtain a hydroxylated compound. ; S2-2. Using p-toluenesulfonic acid as a catalyst, using paraformaldehyde and the compound obtained in step S2-1 The hydroxyl group in the condensation reaction is carried out at the adjacent position, and then potassium carbonate is added to continue the reaction to obtain the compound ; S2-3. Using p-toluenesulfonic acid as catalyst, using R 4 The phenol substituted with the compound obtained in step S2-2 The condensation reaction continues to produce phenol structure compounds derived from both ends. ; S2-4. Under alkaline conditions, the compound obtained in step S2-3 is treated with 2-diazo-1-naphthol-4-sulfonyl chloride or 2-diazo-1-naphthol-5-sulfonyl chloride. The four hydroxyl groups in the olefins are functionalized to obtain triptycene derivatives; Among them, R 1 、R 2 、R 3 、R 4 the same or different, independently selected from H, alcoholic hydroxyl group, carboxyl group, epoxy group, ether, thioether, ester group, amide group, halogen, nitro group, cyano group, heterocyclic group, alkane group or aromatic group in which hydrogen on the benzene ring is partially replaced by alkyl, hydroxyl, amino or carboxyl group; x, y, z, m are the corresponding R 1 、R 2 、R 3 、R 4 The number of group substitutions, x, y, z, and m are all integers, where 0≤x≤2, 0≤y≤2, 0≤Z≤4, and 0≤m≤3.

8. An i-line single-component photoresist composition, characterized in that The invention comprises a triptycene derivative according to any one of claims 4 to 6 or a triptycene derivative synthesized according to claim 7 and an organic solvent; wherein the triptycene derivative is dissolved in the organic solvent as the sole photosensitive component to form the i-line single-component photoresist composition; The organic solvent is selected from the group consisting of n-butyl acetate, ethyl acetate, propylene glycol methyl ether acetate, propylene glycol methyl ether, ethyl lactate and mixtures thereof; The weight percentage of the organic solvent in the photoresist composition is 85-98%.

9. The i-line single-component photoresist composition according to claim 8, wherein: Other additives are also included. Wherein, the mass fraction of the other additives is not greater than 0.1%; and The other additives include one or more of a leveling agent, a surfactant, a stabilizer, and a tackifier.

10. Use of the i-line single-component photoresist composition according to claim 8 or 9, characterized in that: The i-line single-component photoresist composition is suitable for interference lithography, near-field lithography, and SP lithography with a feature size of less than 100 nm and a photoresist film thickness of less than 50 nm.

Images