Monodisperse partially protected molecules, methods of making and use in lithography

Abstract

The application discloses a monodisperse partially-protected compound shown in the following formula (I) and a preparation method and application thereof. The compound is used as a molecular glass photoresist. Compared with a polydisperse partially-protected molecular glass photoresist, the compound has high synthesis repeatability and uniform components. The exposure area has a consistent dissolution rate in a developing solution, which is beneficial to improving line edge and line width roughness. Compared with a fully-protected molecular glass photoresist, the exposed hydroxyl groups are increased, a smaller exposure dose can realize the solubility difference between the exposure area and the non-exposure area, and the sensitivity of the photoresist is further improved.

Description

Technical Field

[0001] This invention belongs to the field of materials technology, specifically relating to a class of monodisperse partially protected molecules, their preparation methods, and their application in photolithography. Background Technology

[0002] Photoresist is a type of photon- or electron-sensitive thin-film material. After irradiation, a significant difference in solubility occurs between exposed and unexposed areas, which is then further developed to obtain a photolithographic pattern. The photoresist film acts as a barrier layer, and its properties determine the quality of the photolithographic pattern, thus affecting subsequent etching processes and the quality of the substrate pattern.

[0003] The performance of photoresists is generally evaluated based on factors such as resolution, sensitivity, line edge roughness (LER) / line width roughness (LWR), contrast, etching durability, and outgassing. To meet the increasing demands of the semiconductor industry for chip integration, excellent photoresists must simultaneously possess high resolution, high sensitivity, low line edge roughness, high etching durability, and low outgassing. Therefore, the development of high-performance photoresists is of paramount importance.

[0004] Traditional chemically amplified photoresists typically use polymer resins with molecular weights of 5000–15000 Daltons as the host material. Their lithographic resolution is limited by molecular size and the inhomogeneity of acid distribution. Furthermore, the large molecular size, polydispersity of molecular weight, and molecular chain entanglement of polymers easily lead to significant line edge roughness, making them unsuitable as host materials for next-generation extreme ultraviolet (EUV) lithography. Currently, research on EUV photoresists focuses on molecular glasses. These small-molecule compounds possess well-defined molecular structures, stable amorphous states, and high glass transition temperatures, while also exhibiting the thermal stability and film-forming properties of polymers, making them suitable as host materials for high-resolution photoresists. According to relevant literature, using molecular glasses as host materials has yielded very promising results; some molecular glass photoresists, with the aid of EUV lithography, have achieved lithographic stripe resolutions below 20 nm (Performance of EUV molecular resists based on fullerenederivatives--Proc. SPIE 7972(2011)797209). However, the host materials of current molecular glass photoresists are primarily partially protected structures with polydisperse acid-sensitive groups. This polydisperse partially protected structure is a mixture, and the resulting molecular structures are not entirely identical; the positions and numbers of protecting groups are uncertain. Furthermore, in more precise photolithography processes, even subtle differences in molecular structure can significantly impact the lithography results. Summary of the Invention

[0005] To overcome the shortcomings of existing technologies, this invention provides a class of monodisperse partially protected molecular glass compounds, their preparation methods, and applications. The monodisperse partially protected molecular glasses of this invention have a defined structure and are obtained through precise chemical synthesis and control of the partially protected ratio. This allows for higher resolution and better photolithography results.

[0006] This invention first provides a compound represented by Formula I:

[0007]

[0008] Wherein, A is selected from -S-, -S(O)-, -S(O)2-, -C(CH3)2- or adamantyl alkyl;

[0009] R1 is the same, R2 is the same, R3 is the same, R1, R2 and R3 are the same or different, and are independently selected from H and OR. a Or C 1-12 Alkyl, the R a It is an acid-sensitive group; and one of R1, R2 and R3 is an OR a .

[0010] According to an embodiment of the present invention, the protection ratio is denoted as the number of acid-sensitive groups / (number of acid-sensitive groups + number of OH groups) in the compound of formula (I), and the protection ratio is approximately 67%, expressed as two-thirds.

[0011] According to an embodiment of the present invention, the acid-sensitive group refers to a group that can be removed from the host material under acid catalysis conditions.

[0012] According to an embodiment of the present invention, the R a Selected from the following groups:

[0013]

[0014] in, Indicates a connection key.

[0015] According to an embodiment of the present invention, the compound shown in formula (I) has the structure shown in formula (IA):

[0016]

[0017] Among them, R2 is selected from OR a A, R a As defined above.

[0018] According to an embodiment of the present invention, the compound represented by formula (I) is selected from the following structures:

[0019]

[0020]

[0021] Among them, R1, R2, and R3 independently have the definitions described above.

[0022] According to an embodiment of the present invention, the compound shown in formula (I) has the following structure:

[0023]

[0024] The present invention also provides a method for preparing the compound shown in formula (I), comprising the following steps:

[0025]

[0026] Where A, R1, R2, and R3 are as defined above, R b For oxygen protecting groups, such as unsubstituted or C-protected groups. 1-6 Alkyl, C 1-6 Alkoxy-substituted benzyl groups;

[0027] A1) The compound of formula (I-3) is combined with Rb The -X reaction yields a compound of formula (I-2), where X is a halogen;

[0028] A2) The compound of formula (I-2) is then reacted with the compound of formula (I-4) or its ester (e.g., pinacol ester) to obtain the compound of formula (I-1).

[0029]

[0030] Wherein, R1, R2, and R3 are as defined above.

[0031] A3) Then, the compound of formula (I-1) is subjected to a deprotection reaction to obtain the compound of formula (I).

[0032] The present invention also provides the application of the above-mentioned compound as a photoresist host material.

[0033] The present invention further provides a positive photoresist composition comprising the above-mentioned compounds.

[0034] According to the present invention, the photoresist composition comprises the above-mentioned compound, a photoacid generator, and a photoresist solvent.

[0035] According to the present invention, in the photoresist composition, the compound accounts for 1 to 10 wt% of the total mass of the positive photoresist composition, the photoacid generator accounts for 0.01 to 1 wt% of the total mass of the positive photoresist composition, and the remainder is photoresist solvent.

[0036] According to the present invention, the photoacid generator is selected from ionic or nonionic photoacid generators, including one or more of triphenylthionium trifluoromethanesulfonate, triphenylthionium perfluorobutylsulfonate, di(4-tert-butylphenyl)iodomonium p-toluenesulfonate, or N-hydroxynaphthalimide trifluoromethanesulfonate.

[0037] According to the present invention, the photoresist solvent is selected from one or more of propylene glycol monomethyl ether acetate, ethyl lactate, ethylene glycol monomethyl ether, or cyclohexanone.

[0038] The present invention also provides a positive photoresist film comprising the compound.

[0039] The present invention also provides a method for preparing a positive photoresist film, comprising applying the positive photoresist composition onto a substrate to form a film to obtain the positive photoresist film.

[0040] In one embodiment, the application method is spin coating.

[0041] In one embodiment, the substrate may be a silicon wafer.

[0042] The present invention also provides the application of the positive photoresist composition and positive photoresist film as described above in photolithography.

[0043] In one embodiment, the positive photoresist composition and positive photoresist film are used in photolithography technologies such as 248nm photolithography, 193nm photolithography, extreme ultraviolet (EUV) photolithography, nanoimprint lithography, or electron beam lithography; they are particularly suitable for electron beam lithography and extreme ultraviolet lithography technologies.

[0044] Beneficial effects

[0045] 1. This invention provides a compound represented by Formula I, with a protection ratio of approximately 67%. When used as a photoresist substrate, it is a partially protected monodisperse molecular glass photoresist. Compared to polydisperse partially protected molecular glass photoresists, it exhibits high reproducibility in synthesis and uniform composition. The exposure areas dissolve at a consistent rate in the developer, which is beneficial for improving line edge and linewidth roughness.

[0046] 2. Compared to fully protected molecular glass photoresists, partially protected monodisperse molecular glass photoresists have more exposed hydroxyl groups, allowing for the achievement of solubility differences between exposed and unexposed areas with a smaller exposure dose, thus further improving the sensitivity of the photoresist.

[0047] 3. Microelectronic devices typically use high-purity silicon wafers as substrates, which are highly hydrophilic and generally require hydrophobic treatment before coating. Monodisperse partially protected molecular glasses contain phenolic hydroxyl groups, which improve adhesion to the substrate. Simultaneously, hydrogen bonds between molecules increase intermolecular forces, making the film more rigid, raising its glass transition temperature, and preventing the exposure pattern from collapsing.

[0048] 4. Compared to fully protected molecular glass photoresists, monodisperse partially protected molecular glass photoresists have higher sensitivity due to the presence of some phenolic hydroxyl groups in the molecules. Furthermore, the reduced proportion of acid-sensitive groups and the increased hydrocarbon ratio in partially protected molecular glass photoresists further enhance the photoresist's etching resistance.

[0049] 5. The selected core framework is a halogenated polyphenol, which, after palladium-catalyzed coupling, forms a branched polyphenyl structure that easily forms a stable amorphous state, which is beneficial for spin coating film formation.

[0050] 6. Monodisperse-protected molecular glass allows for denser molecular packing, enhancing the film's etching resistance. Furthermore, the reduced proportion of acid-sensitive groups within the entire molecule further contributes to improved etching resistance. Monodisperse molecular glass photoresists contain exposed phenolic hydroxyl groups, allowing for further modification as needed. For example, silicon-containing units can be introduced to increase etching resistance, while sulfur-containing units can be introduced to increase the refractive index. Attached Figure Description

[0051] Figure 1 Thermogravimetric and differential scanning calorimetric (DSC) plots of bis-((4-hydroxy-3,5-bis(4-tert-butylcarbonyl)phenyl)phenyl)sulfoxide in Example 5 are shown.

[0052] Figure 2 The photolithographic pattern obtained in Example 6 using di-((4-hydroxy-3,5-di(4-tert-butylcarbonyl)phenyl)phenyl) sulfoxide as the photoresist substrate and electron beam exposure.

[0053] Figure 3 Using monodisperse partially protected compound bis-((4-hydroxy-3,5-bis(4-tert-butylcarbonyl)phenyl)phenyl)adamantane, fully protected compound bis-((4-tert-butylcarbonyl)phenyl)phenyl)adamantane, and a polydisperse bis-((4-hydroxy-3,5-bis(4-hydroxy)phenyl)phenyl)adamantane derivative with a protection ratio of 67% as the main photoresist materials, the photolithographic patterns obtained by electron beam lithography were obtained.

[0054] Figure 4 Differential scanning calorimetry (DSC) curves of the monodisperse partially protected compound di-((4-hydroxy-3,5-di(4-tert-butylcarbonyl)phenyl)phenyl)propane, the fully protected compound di-((4-tert-butylcarbonyl)phenyl)phenyl)propane, and a polydisperse di-((4-hydroxy-3,5-di(4-hydroxy)phenyl)phenyl)propane derivative with a protection ratio of 67%.

[0055] Figure 5 Using monodisperse partially protected compounds bis-((4-hydroxy-3,5-bis(4-tert-butylcarbonyl)phenyl)phenyl)propane, fully protected compounds bis-((4-tert-butylcarbonyl)phenyl)phenyl)propane, and polydisperse bis-((4-hydroxy-3,5-bis(4-hydroxy)phenyl)phenyl)propane derivatives with a protection ratio of 67% as the main photoresist materials, the photolithographic patterns obtained by extreme ultraviolet lithography were obtained.

[0056] Terminology Definitions and Explanations

[0057] Unless otherwise stated, the definitions of groups and terms recorded in this application specification and claims, including definitions as examples, exemplary definitions, preferred definitions, definitions recorded in tables, and definitions of specific compounds in the examples, can be arbitrarily combined and combined with each other. Such combinations and combinations of group definitions and compound structures should be understood as being within the scope of this application specification and / or claims.

[0058] Unless otherwise stated, the numerical ranges described in this specification and claims are equivalent to describing at least each specific integer value therein. For example, the numerical range "1-12" is equivalent to describing each integer value in the numerical range "1-12", namely 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12. Furthermore, when certain numerical ranges are defined as "numbers", it should be understood that they describe the two endpoints of the range, each integer within the range, and each decimal within the range. For example, "numbers from 0 to 10" should be understood to describe not only each integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10, but also at least the sum of each of these integers with 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, and 0.9.

[0059] Term "C" 1-12 "Alkyl" should be understood as representing a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 12 carbon atoms. For example, "C 1-10 "Alkyl" refers to straight-chain and branched alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. 1-8 "Alkyl" refers to straight-chain and branched alkyl groups having 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms. 1-6 "Alkyl" means a straight-chain or branched alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, or 1,2-dimethylbutyl, or their isomers. Detailed Implementation

[0060] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0061] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0062] Example 1

[0063]

[0064] Step 1, Preparation of tert-butyl 2-(4-bromophenoxy)acetic acid:

[0065] The specific operating steps are as follows: In a 100 mL single-necked reaction flask, add p-bromophenol (1.73 g, 10.0 mmol, 1.0 eq), tert-butyl chloroacetate (1.65 g, 11 mmol, 1.1 eq), potassium carbonate (1.65 g, 12 mmol, 1.2 eq), tetrabutylammonium bromide catalyst (128 mg, 0.4 mmol, 0.04 eq), and 30 mL of N-methylpyrrolidone solvent. Heat the reaction system to 80 °C and react for 6 h. Cool the reaction system to room temperature, pour the reaction solution into 100 mL of water to terminate the reaction, extract the aqueous phase multiple times with dichloromethane, combine the organic phases, wash once with water and once with saturated brine, and dry with anhydrous sodium sulfate. Reduce the solvent by rotary evaporation to obtain 2.64 g of a colorless, transparent oil, with a yield of 92%. 1 ¹H NMR (400MHz, CDCl₃): δ (ppm) 7.48 (d, 2H, benzene), 6.98 (d, 2H, benzene), 4.88 (s, 2H, -CH₂), 1.52 (s, 9H, -CH₃). MS (MALDI-TOF): m / z = 287.1, calculated (C₂... 12 H 15 BrO3)m / z=287.2(M+).

[0066] The second step is the preparation of 2-(4-(pinacolborate)phenoxy)tert-butyl acetate:

[0067] The specific operating steps are as follows: 2-(4-bromophenoxy)tert-butyl acetate (2.87 g, 10.0 mmol, 1.0 eq), pinacol diborate (2.79 g, 11 mmol, 1.1 eq), catalyst [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride (73 mg, 0.1 mmol, 0.01 eq), and 30 ml of dry dioxane were placed in a 100 ml Schlenk flask. The reaction was repeated three times with vacuum and nitrogen purging. The apparatus was placed in an oil bath at 100 °C and refluxed for 7 h. After the reaction was completed, the reaction solution was poured into 100 ml of water, and the aqueous phase was extracted multiple times with dichloromethane. The organic phases were combined and washed once with water and once with saturated brine, respectively, and dried over anhydrous sodium sulfate. The solvent was evaporated to dryness, yielding 3.2 g of a light yellow oily substance, with a yield of 96%. 1¹H NMR (400MHz, CDCl₃): δ (ppm) 7.48 (d, 2H, benzene), 6.98 (d, 2H, benzene), 4.88 (s, 2H, -CH₂), 1.52 (s, 9H, -CH₃), 1.21 (s, 12H, -CH₃). MS (MALDI-TOF): m / z = 334.2, calculated values ​​(C₂, 2H, -CH₃). 18 H 27 BO5) m / z=334.3(M+).

[0068] Example 2

[0069] The core skeleton is diphenyl sulfoxide, the acid-sensitive group is tert-butyloxycarbonyl, the protection ratio is about 67%, which is expressed as two-thirds;

[0070]

[0071] Step 1, Preparation of di-((4-benzyloxy-3,5-dibromo)phenyl)sulfoxide:

[0072] The specific operating steps are as follows: In a 250 mL single-necked reaction flask, add 5.49 g ((4-hydroxy-3,5-dibromo)phenyl) sulfoxide (10 mmol, 1.0 eq), benzyl bromide (3.59 g, 21 mmol, 2.1 eq), potassium carbonate (3.3 g, 24 mmol, 2.4 eq), 18-crown-6 (528 mg, 2 mmol, 0.2 eq), and 100 mL of dry acetone. Heat the reaction system to 70 °C and react for 6 h. Cool the reaction system to room temperature, evaporate the reaction solution to dryness, dissolve the solid in 200 mL of dichloromethane, wash twice with water, wash once with saturated brine, and dry with anhydrous sodium sulfate. Evaporate the solvent to dryness to obtain 7 g of a white solid, yield 95.8%. 1 ¹H NMR (400MHz, CDCl₃): δ (ppm) 7.74 (s, 4H, benzene), 7.32–7.48 (m, 10H, benzene), 5.26 (s, 4H, -CH₂). MS (MALDI-TOF): m / z = 729.7, calculated (C₂) 26 H 18 Br4O3S)m / z=729.9(M+).

[0073] The second step is the preparation of di-((4-benzyloxy-3,5-di(4-tert-butylcarbonyl)phenyl)phenyl)sulfoxide:

[0074] The specific operating steps are as follows: In a 50 mL Schlenk reaction flask, add di-((3,5-dibromo-4-benzyloxy)phenyl) sulfoxide (0.73 g, 1.0 mmol, 1.0 eq), pinacol 4-tert-butyl carbonate phenylboronic acid (1.92 g, 6.0 mmol, 6.0 eq), potassium carbonate (0.828 g, 6.0 mmol, 6.0 eq), and tetrakis(triphenylphosphine)palladium (11.6 mg, 0.01 mmol, 0.01 eq). Under a nitrogen atmosphere, add 8 mL of a mixed solvent of dioxane and 8 mL of water to the reaction flask using a syringe. Place the reaction apparatus in a 100 °C oil bath and reflux for 8 h. After the reaction is complete, cool the reaction solution to room temperature, add 100 mL of dichloromethane, wash twice with water, wash once with saturated brine, and dry with anhydrous sodium sulfate. Remove the solvent to obtain a yellow oily substance. The solid was dissolved in 5 ml of dichloromethane, and then added dropwise to 100 ml of ethanol to precipitate, yielding 1.1 g of a white solid with a yield of 93.2%. 1 HNMR (400MHz, CDCl3): δ (ppm) 7.74 (s, 4H, benzene), 7.68 (d, 8H, benzene), 7.32-7.48 (m, 10H, benzene) 7.12 (d, 8H, benzene), 5.26 (s, 4H, -CH2), 1.34 (s, 36H, -CH3). MS (MALDI-TOF): m / z=1182.3, calculated value (C 70 H 70 O 15 S) m / z = 1182.9(M+).

[0075] The third step is the preparation of di-((4-hydroxy-3,5-di(4-tert-butylcarbonyl)phenyl)phenyl)sulfoxide:

[0076] The specific operating steps are as follows: Di-((4-benzyloxy-3,5-bis(4-tert-butylcarbonyl)phenyl)phenyl) sulfoxide (1.18 g, 1 mmol, 1.0 eq) was dissolved in ethyl acetate, and Pd / C (60 mg, 0.05 mmol, 0.05 eq) was weighed as a catalyst. The reaction was carried out under a hydrogen atmosphere at a temperature of 60 °C. After approximately 48 h, the catalyst was removed by filtration, and the filtrate was evaporated to dryness to obtain the target product, yielding 0.9 g of a white solid, with a yield of 90%. 1H NMR (400MHz, CDCl3): δ (ppm) 10.2 (s, 2H, -OH), 7.74 (s, 4H, benzene), 7.68 (d, 8H, benzene), 7.12 (d, 8H, benzene), 1.34 (s, 36H, -CH3). MS (MALDI-TOF): m / z=1002.3, calculated value (C 56 H 58 O 15 S)m / z=1002.6(M+).

[0077] Example 3

[0078] The core skeleton is diphenyladamantane, the acid-sensitive group is tert-butyloxycarbonyl, the protection ratio is 67%, which is expressed as two-thirds;

[0079]

[0080] Step 1, Preparation of di-((4-benzyloxy-3,5-dibromo)phenyl)adamantane:

[0081] The specific operating steps are as follows: In a 250 mL single-necked reaction flask, add 6.51 g ((4-hydroxy-3,5-dibromo)phenyl)adamantane (10 mmol, 1.0 eq), benzyl bromide (3.59 g, 21 mmol, 2.1 eq), potassium carbonate (3.3 g, 24 mmol, 2.4 eq), 18-crown-6 (528 mg, 2 mmol, 0.2 eq), and 120 mL of dry acetone. Heat the reaction system to 70 °C and react for 8 h. Cool the reaction system to room temperature, evaporate the reaction solution to dryness, dissolve the solid in 250 mL of dichloromethane, wash twice with water, wash once with saturated brine, and dry with anhydrous sodium sulfate. Evaporate the solvent to dryness to obtain 7.6 g of a white solid, yield 93.3%. 1 H NMR (400MHz, CDCl3): δ (ppm) 7.73 (s, 4H, benzene) 7.31-7.45 (m, 10H, benzene) 5.26 (s, 4H, -CH2), 2.33 (s, 2H,adamantane),1.91–1.84(m,10H,adamantane),1.76(s,2H,adamantane). MS (MALDI-TOF): m / z=815.9, calculated value (C 36 H 32 Br4O2)m / z=815.9(M+).

[0082] The second step is the preparation of di-((4-benzyloxy-3,5-bis(4-tert-butylcarbonyl)phenyl)phenyl)adamantane:

[0083] The specific operating steps are as follows: In a 50 mL L Schlenk reaction flask, add di-((3,5-dibromo-4-benzyloxy)phenyl)adamantane (0.81 g, 1.0 mmol, 1.0 eq), pinacol 4-tert-butyl carbonate phenylboronic acid (1.92 g, 6.0 mmol, 6.0 eq), potassium carbonate (0.828 g, 6.0 mmol, 6.0 eq), and tetrakis(triphenylphosphine)palladium (11.6 mg, 0.01 mmol, 0.01 eq). Under a nitrogen atmosphere, add 10 mL of a mixed solvent of dioxane and 10 mL of water to the reaction flask using a syringe. Place the reaction apparatus in a 100 °C oil bath and reflux for 8 h. After the reaction is complete, cool the reaction solution to room temperature, add 100 mL of dichloromethane, wash twice with water, wash once with saturated brine, and dry with anhydrous sodium sulfate. Remove the solvent to obtain a yellow oily substance. The solid was dissolved in 5 ml of dichloromethane, and then added dropwise to 100 ml of ethanol to precipitate, yielding 1.1 g of a white solid with a yield of 87.3%. 1 H NMR (400MHz, CDCl3): δ (ppm) 7.74 (s, 4H, benzene), 7.67 (d, 8H, benzene), 7.33-7.47 (m, 10H, benzene) 7.13 (d, 8H, benzene), 5.24 (s, 4H, -CH2), 2.34(s,2H,adamantane),1.92–1.83(m,10H,adamantane),1.76(s,2H,adamantane),1.34(s,36H,-CH3). MS (MALDI-TOF): m / z=1268.6, calculated value (C 80 H 84 O 14 )m / z=1268.6(M+).

[0084] The third step is the preparation of di-((4-hydroxy-3,5-di(4-tert-butylcarbonyl)phenyl)phenyl)adamantane:

[0085] The specific operating steps are as follows: Di-((4-benzyloxy-3,5-bis(4-tert-butylcarbonyl)phenyl)phenyl)adamantane (1.27 g, 1 mmol, 1.0 eq) was dissolved in ethyl acetate, and Pd / C (60 mg, 0.05 mmol, 0.05 eq) was weighed as a catalyst. The reaction was carried out under a hydrogen atmosphere at a temperature of 60 °C. After approximately 48 h, the catalyst was removed by filtration, and the filtrate was evaporated to dryness to obtain the target product, yielding 1.0 g of a white solid, with a yield of 91.8%. 1H NMR (400MHz, CDCl3): δ (ppm) 10.0 (s, 2H, -OH), 7.74 (s, 4H, benzene), 7.68 (d, 8H, benzene), 7.12 (d, 8H, benzene), 2.34(s,2H,adamantane),1.92–1.83(m,10H,adamantane),1.75(s,2H,adamantane),1.34(s,36H,-CH3). MS (MALDI-TOF): m / z=1088.5, calculated value (C 66 H 72 O 14 )m / z=1088.5(M+).

[0086] Example 4

[0087] The core skeleton is bisphenol A, the acid-sensitive group is tert-butyloxycarbonyl, the protection ratio is 67%, which is expressed as two-thirds;

[0088]

[0089] Step 1, Preparation of di-((4-benzyloxy-3,5-dibromo)phenyl)propane:

[0090] The specific operating steps are as follows: In a 250 mL single-necked reaction flask, add 5.4 g ((4-hydroxy-3,5-dibromo)phenyl)propane (10 mmol, 1.0 eq), benzyl bromide (3.59 g, 21 mmol, 2.1 eq), potassium carbonate (3.3 g, 24 mmol, 2.4 eq), 18-crown-6 (528 mg, 2 mmol, 0.2 eq), and 80 mL of dry acetone. Heat the reaction system to 70 °C and react for 6 h. Cool the reaction system to room temperature, evaporate the reaction solution to dryness, dissolve the solid in 150 mL of dichloromethane, wash twice with water, wash once with saturated brine, and dry with anhydrous sodium sulfate. Evaporate the solvent to dryness to obtain 6.9 g of a white solid, yield 95.4%. 1 ¹H NMR (400MHz, CDCl₃): δ (ppm) 7.72 (s, 4H, benzene), 7.32–7.46 (m, 10H, benzene), 5.24 (s, 4H, -CH₂), 1.56 (s, 6H, -CH₃). MS (MALDI-TOF): m / z = 723.8, calculated (C 29 H 24 Br4O2)m / z=723.8(M+).

[0091] The second step is the preparation of di-((4-benzyloxy-3,5-bis(4-tert-butylcarbonyl)phenyl)phenyl)propane:

[0092] The specific operating steps are as follows: In a 50 mL L Schlenk reaction flask, add di-((3,5-dibromo-4-benzyloxy)phenyl)propane (0.72 g, 1.0 mmol, 1.0 eq), pinacol 4-tert-butyl carbonate phenylboronic acid (1.92 g, 6.0 mmol, 6.0 eq), potassium carbonate (0.828 g, 6.0 mmol, 6.0 eq), and tetrakis(triphenylphosphine)palladium (11.6 mg, 0.01 mmol, 0.01 eq). Under a nitrogen atmosphere, add 10 mL of a mixed solvent of dioxane and 10 mL of water to the reaction flask using a syringe. Place the reaction apparatus in a 100 °C oil bath and reflux for 8 h. After the reaction is complete, cool the reaction solution to room temperature, add 100 mL of dichloromethane, wash twice with water, wash once with saturated brine, and dry with anhydrous sodium sulfate. Remove the solvent to obtain a yellow oily substance. The solid was dissolved in 5 ml of dichloromethane, and then added dropwise to 100 ml of ethanol to precipitate, yielding 1.0 g of a white solid with a yield of 85.5%. 1 H NMR (400MHz, CDCl3): δ (ppm) 7.73 (s, 4H, benzene), 7.67 (d, 8H, benzene), 7.32-7.45 (m, 10H, benzene) 7.11 (d, 8H, benzene), 5.26 (s, 4H, -CH2), 1.58(s, 6H, -CH3), 1.34(s, 36H, -CH3). MS (MALDI-TOF): m / z=1176.5, calculated value (C 73 H 76 O 14 )m / z=1176.5(M+).

[0093] The third step is the preparation of di-((4-hydroxy-3,5-bis(4-tert-butylcarbonyl)phenyl)phenyl)propane:

[0094] The specific operating steps are as follows: Di-((4-benzyloxy-3,5-bis(4-tert-butylcarbonyl)phenyl)phenyl)propane (1.18 g, 1 mmol, 1.0 eq) was dissolved in ethyl acetate, and Pd / C (60 mg, 0.05 mmol, 0.05 eq) was weighed as a catalyst. The reaction was carried out under a hydrogen atmosphere at a temperature of 60 °C. After approximately 48 h, the catalyst was removed by filtration, and the filtrate was evaporated to dryness to obtain the target product, yielding 0.9 g of a white solid, with a yield of 90%. 1H NMR (400MHz, CDCl3): δ (ppm) 10.4 (s, 2H, -OH), 7.78 (s, 4H, benzene), 7.68 (d, 8H, benzene), 7.14 (d, 8H, benzene), 1.56 (s, 6H, -CH3), 1.34 (s, 36H, -CH3). MS (MALDI-TOF): m / z=996.4, calculated value (C 59 H 64 O 14 m / z = 996.4 (M+).

[0095] Example 5

[0096] The thermal stability and glass transition temperature of the molecular glass di-((4-hydroxy-3,5-bis(4-tert-butylcarbonyl)phenyl)phenyl)sulfoxide in Example 2 were determined using a thermogravimetric analyzer and a differential scanning calorimeter. The results were obtained from the thermogravimetric and differential scanning calorimetric curves of this compound (see attached figure). Figure 1 As can be seen, its thermal decomposition temperature is greater than 150℃ and its glass transition temperature is above 100℃, which meets the requirements of photolithography for heat treatment temperature.

[0097] Example 6

[0098] A positive photoresist composition comprises di-((4-hydroxy-3,5-di(4-tert-butylcarbonyl)phenyl)phenyl) sulfoxide, propylene glycol monomethyl ether acetate, and triphenylsulfonium perfluorobutyl sulfonate obtained in Example 2. The specific method is as follows: Di-((4-hydroxy-3,5-di(4-tert-butylcarbonyl)phenyl)phenyl) sulfoxide prepared in Example 2 is dissolved in propylene glycol monomethyl ether acetate (PGMEA) to obtain a 5% (w / w) solution. 0.5 wt% of triphenylsulfonium perfluorobutyl sulfonate is added as a photoacid generator. The solution is filtered through a 0.1 μm microporous filter to obtain a spin-coating solution. Spin-coating is performed on a silicon wafer substrate, and the film is baked at 100°C for 2 minutes. The prepared film is then subjected to electron beam lithography experiments at the National Center for Nanoscience and Technology with an exposure period of 80 nm, resulting in very uniform lithographic stripes with a linewidth of 30 nm. The lithography results are shown in the attached figure. Figure 2 .

[0099] Example 7

[0100] Substances A, B, and C are respectively a monodisperse partially protected compound bis-((4-hydroxy-3,5-bis(4-tert-butylcarbonyl)phenyl)phenyl)adamantane, a fully protected compound bis-((4-tert-butylcarbonyl)phenyl)phenyl)adamantane, and a polydisperse bis-((4-hydroxy-3,5-bis(4-hydroxy)phenyl)phenyl)adamantane derivative with a protection ratio of 67%. Compound A is derived from Example 3, and the synthesis of B and C is based on an existing patent (patent application number: CN201710578509.8). Substances A, B, and C are used as the main photoresist materials, and a positive photoresist is composed of triphenylthionium perfluorobutylsulfonate and propylene glycol monomethyl ether acetate. The specific method is as follows: Taking substance A as an example, substance A is dissolved in propylene glycol monomethyl ether acetate to prepare a 5% (w / w) solution. 0.5 wt% of triphenylthionium perfluorobutylsulfonate is added as a photoacid generator. The solution is filtered through a 0.1 μm microporous filter to obtain a spin-coating solution. An appropriate amount of the spin-coating solution is dropped onto a silicon wafer substrate, spin-coated into a film, and baked at 100°C for 2 minutes to remove the photoresist solvent. The prepared photoresist film is subjected to electron beam lithography experiments at the National Center for Nanoscience and Technology, with an electron beam lithography pattern of 30 nm L / s. Substances B and C are prepared in the same manner to obtain photoresist films and subjected to electron beam lithography. After exposure, the films are developed with 2.38 wt% TMAH alkaline solution, rinsed with ultrapure water for 60 s, and dried with nitrogen. (Appendix) Figure 3 (a), (b), and (c) are photolithographic patterns obtained by electron beam exposure using substances A, B, and C as the main materials, respectively. Judging from the quality and contrast of the photolithographic patterns, the attached... Figure 3 (a) is significantly better than (b) and (c). (See appendix) Figure 3 (b) The grooves were not completely cleaned, and there were obvious bridgings between the photolithographic stripes. This was because the surface of the fully protected substrate material was too hydrophobic, making it difficult for the hydrophilic developer to penetrate the grooves, resulting in incomplete development and numerous defects in the photolithographic pattern, thus affecting its resolution. (See attached image.) Figure 3(c) Not only is the contrast poor, but the lithographic stripes also exhibit breakage. This is because the substrate material in the exposed areas is polydisperse, resulting in uneven deprotection ratios of acid-sensitive groups and inconsistent dissolution rates in the developer. This leads to inconsistent development across different areas, causing stripe breakage. Compared to substrate materials B and C, compound A has a more defined molecular structure, resulting in a more uniform deprotection ratio in the exposed areas and a more consistent dissolution rate in the developer, thus avoiding lithographic pattern breakage and blurring. Furthermore, the exposed phenolic hydroxyl groups in compound A help adjust the hydrophilicity / hydrophobicity of the film surface, facilitating the spread of the developer on the film surface and promoting its entry into the trenches for a cleaner cleaning. In addition, using a monodisperse partially protected compound as the substrate material results in the highest lithographic sensitivity because the substrate material itself contains some exposed phenolic hydroxyl groups, requiring only a small amount of exposure to dissolve in the developer.

[0101] Example 8

[0102] Substances E, F, and G are, respectively, the monodisperse partially protected compound di-((4-hydroxy-3,5-bis(4-tert-butylcarbonyl)phenyl)phenyl)propane, the fully protected compound di-((4-tert-butylcarbonyl)phenyl)phenyl)propane, and a polydisperse di-((4-hydroxy-3,5-bis(4-hydroxy)phenyl)phenyl)propane derivative with a protection ratio of 67%. Compound E is derived from Example 4, and the synthesis of F and G is based on a prior patent (patent application number: CN201210156675.6). Their glass transition temperatures were measured using differential scanning calorimetry, and the results are shown in the attached figure. Figure 4 As shown in the figure, through analysis and calculation, the glass transition temperatures from highest to lowest are E (143℃) > F (127℃) > G (102℃). G is a polydisperse mixture, resulting in the lowest glass transition temperature. E is a monodisperse partially protected compound, where exposed hydroxyl groups enhance intermolecular forces through hydrogen bonding, leading to the highest glass transition temperature. According to relevant literature (DOI: 10.1016 / j.mee.2007.01.052), strong intermolecular forces and high glass transition temperatures are beneficial in suppressing lithographic pattern collapse and enhancing the resolution and contrast of the lithographic pattern.

[0103] Example 9

[0104] Substances E, F, and G from Example 8 were used as the main photoresist materials, and combined with triphenylthionium trifluoromethanesulfonate and propylene glycol monomethyl ether acetate to form a positive photoresist. The specific method is as follows: Taking substance E as an example, substance E was dissolved in propylene glycol monomethyl ether acetate to obtain a 5% (w / w) solution, and 0.5 wt% of triphenylthionium trifluoromethanesulfonate was added as a photoacid generator. The solution was filtered through a 0.1 μm microporous filter to obtain a spin-coating solution. An appropriate amount of the spin-coating solution was dropped onto a silicon wafer substrate, spin-coated into a film, and baked at 100°C for 2 minutes to remove the photoresist solvent. The prepared photoresist film was subjected to extreme ultraviolet (EUV) lithography at the Shanghai Synchrotron Radiation Facility soft X-ray beamline, with a grating period of 100 nm. Substances F and G were prepared in the same manner to obtain photoresist films and subjected to EUV lithography. After exposure, develop with 2.38 wt% TMAH alkaline solution, rinse with ultrapure water for 60 seconds, and dry with nitrogen. (See attached image) Figure 5 (e), (f), and (g) are photolithographic patterns obtained by extreme ultraviolet (EUV) exposure using substances E, F, and G as the main materials, respectively. Judging from the quality and contrast of the photolithographic patterns, the attached... Figure 5 (e) is significantly better than Figures (f) and (g). Appendix Figure 5 The grooves in (f) were not completely cleaned because the surface of the fully protective substrate material was too hydrophobic, making it difficult for the hydrophilic developer to penetrate the grooves, resulting in incomplete development and affecting the resolution of the photolithographic pattern. (See attached image) Figure 5 (g) Not only is the pattern contrast poor, but the lithographic stripes also exhibit collapse. This is because substance G is polydisperse, has a relatively low glass transition temperature, and therefore weak mechanical strength of the lithographic stripes. When the aspect ratio is too large, pattern collapse easily occurs. Compared to the host materials F and G, compound E has a defined molecular structure and contains exposed phenolic hydroxyl groups. These enhance the intermolecular forces through hydrogen bonding, improving the mechanical strength of the photoresist film and making it less prone to collapse. Simultaneously, the exposed phenolic hydroxyl groups in compound E reduce the hydrophobicity of the film surface, facilitating the spread of the developer on the film surface and promoting the developer's entry into the trenches, resulting in cleaner cleaning and improved resolution of the lithographic pattern. Similar to Example 7, using a monodisperse-protected compound as the host material results in the highest lithographic sensitivity, for the same reasons as in Example 7.

[0105] The embodiments of the technical solution of the present invention have been described above by way of example. It should be understood that the protection scope of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the protection scope of the claims of this application.

Claims

1. A compound represented by Formula I: in, A is selected from -C(CH3)2- or adamantyl alkyl; R1 is the same, R2 is the same, R3 is the same, R1, R2 and R3 are the same or different, and are independently selected from H and OR. a The R a It is an acid-sensitive group; and one of R1, R2 and R3 is an OR a ; R a Selected from the following groups: in, Indicates a connection key.

2. The compound according to claim 1, characterized in that, The compound shown in formula (I) has the structure shown in formula (II): R2 is selected from OR a A, R a It has the definition as described in claim 1.

3. The compound according to claim 1, characterized in that, The compound shown in formula (I) is selected from the following structures: ； ； R1, R2, and R3 each have the definition described in claim 1 independently.

4. The compound according to claim 1, characterized in that, The compound shown in formula (I) is selected from the following structures: 、 。 5. A method for preparing the compound according to any one of claims 1-4, characterized in that, Includes the following steps: Wherein A, R1, R2, and R3 independently have the definitions of any one of claims 1-4, R b For no substitute or by C 1-6 Alkyl, C 1-6 Alkoxy-substituted benzyl groups; A1) The compound of formula (I-3) is combined with R b The -X reaction yields a compound of formula (I-2), where X is a halogen; A2) The compound of formula (I-2) is then reacted with the compound of formula (I-4) or its ester to obtain the compound of formula (I-1). Wherein, R1, R2, and R3 independently have the definitions of any one of claims 1-4. A3) Then, the compound of formula (I-1) is subjected to a deprotection reaction to obtain the compound of formula (I).

6. The use of the compound according to any one of claims 1-4 as a photoresist host material.

7. A positive photoresist composition comprising the compound according to any one of claims 1-4.

8. The photoresist composition according to claim 7, characterized in that, The photoresist composition also includes a photoacid generator and a photoresist solvent.

9. The photoresist composition according to claim 8, characterized in that, In the photoresist composition, by mass fraction, the compound accounts for 1 to 10 wt% of the total mass of the positive photoresist composition, the photoacid generator accounts for 0.01 to 1 wt% of the total mass of the positive photoresist composition, and the remainder is photoresist solvent.

10. The photoresist composition according to claim 8, characterized in that, The photo-induced acid-producing agent is selected from one or more of the following: triphenylthionium trifluoromethanesulfonate, triphenylthionium perfluorobutyl sulfonate, di(4-tert-butylphenyl)iodomonium p-toluenesulfonate, or N-hydroxynaphthalimide trifluoromethanesulfonate.

11. The photoresist composition according to claim 8, characterized in that, The photoresist solvent is selected from one or more of propylene glycol monomethyl ether acetate, ethyl lactate, ethylene glycol monomethyl ether, or cyclohexanone.

12. A positive photoresist film comprising the compound according to any one of claims 1-4.

13. The use of the positive photoresist composition of claim 7 and / or the positive photoresist film of claim 12 in photolithography.

14. The application according to claim 13, characterized in that, The lithography is 248 nm lithography, 193 nm lithography, extreme ultraviolet lithography, nanoimprint lithography, or electron beam lithography.

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