Compound, photosensitive composition and use thereof

Abstract

The application provides a compound, a photosensitive composition and application thereof. The compound comprises a cation and an anion, and the structure of the cation is shown in formula (I): (I); wherein R1 is a halogen atom or a group containing an ethynylene group; R2, R3, R4, R5 and R6 are independently selected from any one of a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-C20 alkyl group and the like, and R2, R3, R4, R5 and R6 are not all hydrogen atoms; and the anion is X ‑ The application provides a compound which can be used in a photosensitive composition. When the compound is applied to the photosensitive composition, the photosensitive composition has high absorption efficiency to an exposure light source and can effectively inhibit acid diffusion, so that the exposure performance of the photosensitive composition is improved, the precision of a prepared pattern is improved, and the performance of an electronic device is improved.

Description

Technical Field

[0001] This application relates to the field of electronic device fabrication technology, specifically to a compound, a photosensitive composition, and their applications. Background Technology

[0002] Patterning processes generally involve coating a photosensitive composition onto a substrate to form a photosensitive film layer, exposing the photosensitive film layer through a mask with a specific pattern, and then transforming the photosensitive film layer into a patterned film through development and other processes. Finally, the substrate with the patterned film is etched to obtain a patterned substrate with the predetermined pattern. During exposure, the photoacid generator (PAG) in the photosensitive composition catalyzes the deprotection reaction of acid-insecure groups by generating acid, resulting in a change in solubility, thereby achieving pattern transfer and formation. Since each photon can trigger multiple deprotection reactions, a chemical amplification effect is achieved. This chemical amplification effect enables the patterning composition to complete the patterning process with extremely low exposure doses, significantly improving patterning efficiency, reducing production costs, and making high-precision patterning possible.

[0003] However, with the continuous development of electronic devices (such as semiconductor devices) and the shrinking of critical dimensions, the requirements for patterning processes in electronic device fabrication are becoming increasingly stringent. The acid diffusion problem that occurs during the baking process after exposure of the patterned composition is becoming increasingly prominent, which increases line width roughness, leads to poor line width uniformity, and severely affects the accuracy and consistency of the pattern, thereby impacting the performance of semiconductor devices. Therefore, there is an urgent need to provide a photoacid-generating compound that can effectively suppress acid diffusion and has good absorption efficiency for the exposure light source. Summary of the Invention

[0004] In view of this, this application provides a compound, a photosensitive composition and its application. The compound can be applied to the photosensitive composition. Applying the compound to the photosensitive composition can effectively suppress acid diffusion while having high absorption efficiency for the exposure light source, thereby improving the exposure performance of the photosensitive composition, improving the accuracy of the obtained pattern, and thus improving the performance of the semiconductor device.

[0005] The first aspect of this application provides a compound comprising a cation and an anion, wherein the structure of the cation is shown in formula (I): (Ⅰ); Wherein, R1 is a halogen atom or a group containing an ethynyl group; R2, R3, R4, R5, and R6 are independently selected from hydrogen atoms, halogen atoms, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, C1-C20 alkoxy groups, aryloxy groups, and -SO2R groups. A -OSO2R B -COR C -COOR D -CONR E R F –PO(OR) G )2、-SR H R is any one of mercapto, substituted or unsubstituted amino, hydroxy, nitro and cyano groups, wherein R A R B R C R D R E R F R G R H The alkyl groups are each independently selected from any one of substituted or unsubstituted alkyl groups and aryl groups, and R2, R3, R4, R5, and R6 are not all hydrogen atoms; The anion is X. - The X - The structure is shown in equation (Ⅱ): (II); R7 is selected from one or more of hydrogen atoms, substituted or unsubstituted C1-C30 alkyl groups, substituted or unsubstituted alicyclic groups, and substituted or unsubstituted aromatic cyclic groups; R8 is a substituted or unsubstituted alkylene group. The cations with the aforementioned special structure in this compound can significantly improve the absorption efficiency of the photosensitive composition to the exposure light source by specifically selecting the groups R1, R2, R3, R4, R5, and R6. By selecting the aforementioned special anions as the anions in the compound, the anions and cations in the compound synergistically work together to effectively inhibit acid diffusion during the post-exposure baking stage, thereby improving its exposure performance, optimizing the exposure process window, and thus improving the precision and consistency of the obtained patterns, ultimately increasing the yield and precision of electronic devices.

[0006] In some embodiments of this application, R1 is selected from Cl, Br, I, or any group shown in formulas (Ⅲ-1)-(Ⅲ-5): (Ⅲ-1); (Ⅲ-2); (Ⅲ-3); (Ⅲ-4); (Ⅲ-5) Compounds containing the above-mentioned groups have high absorption efficiency for exposure light sources, especially for certain light sources such as i-line light (wavelength 365 nm), electron beams, and light with wavelengths less than 15 nm.

[0007] In some embodiments of this application, at least one of R2, R3, R4, R5, and R6 is a C1-C3 alkyl group; and / or, R4 is not a hydrogen atom.

[0008] In some embodiments of this application, the anion is selected from any one of the groups shown as formulas (II-1)-(II-15): (Ⅱ-1); (Ⅱ-2); (Ⅱ-3); (Ⅱ-4); (Ⅱ-5); (Ⅱ-6); (Ⅱ-7); (Ⅱ-8); (Ⅱ-9); (Ⅱ-10); (Ⅱ-11); (Ⅱ-12); (Ⅱ-13); (Ⅱ-14); (Ⅱ-15). The compounds provided in this application, through special selection and combination of anionic and cationic moieties, can be applied to photosensitive compositions to achieve high absorption efficiency for exposure light sources while also exhibiting excellent acid diffusion suppression effects. This improves the overall exposure performance of the photosensitive composition, thereby enhancing the precision of the resulting patterns and ultimately improving the performance of semiconductor devices.

[0009] A second aspect of this application provides a photosensitive composition comprising the compound, polymer, and solvent provided in the first aspect. This photosensitive composition, comprising the aforementioned compound, exhibits high absorption efficiency to the exposure light source while effectively suppressing acid diffusion, thereby providing excellent exposure performance.

[0010] In some embodiments of this application, the mass percentage of the compound in the photosensitive composition is 0.05%-4%. By controlling the content of the compound within a suitable range, the chemical reactions within the system can be further regulated, especially the rate and efficiency of the deprotection reaction, thereby further improving the imaging quality of the micro-patterns obtained.

[0011] In some embodiments of this application, the polymer comprises one or more repeating structural units as shown in formulas (Ⅳ-1)-(Ⅳ-4): (Ⅳ-1); (Ⅳ-2); (Ⅳ-3); (Ⅳ-4). By selecting polymers including repeating structural units derived from monomers containing acid-deprotected groups, these polymers exhibit high acid sensitivity. Under the influence of acid or acid and high temperature, their acid-deprotected groups are easily removed from the polymer backbone, resulting in significant solubility reversal and a fast response speed.

[0012] In some embodiments of this application, the mass ratio of the compound to the polymer in the photosensitive composition is (5-40):100. By controlling the mass ratio of the compound and polymer components within a suitable range, the rate and efficiency of the chemical reaction within the system can be further controlled, thereby further improving the precision and consistency of the obtained micropatterns.

[0013] In some embodiments of this application, the photosensitive composition further includes an alkaline neutralizing agent, which comprises one or more of nitrogen-containing compounds containing primary amine groups, secondary amine groups, and tertiary amine groups. Introducing an alkaline neutralizing agent into the photosensitive composition can further control acid diffusion in the system, extend the post-exposure baking delay time, and enhance the formulation stability of the photosensitive composition.

[0014] In some embodiments of this application, the mass ratio of the alkaline neutralizing agent to the polymer is (0.1-15):100. By controlling the mass ratio of the alkaline neutralizing agent to the polymer within the above range, the acid-base balance of the system during the exposure process can be further controlled, the diffusion of acid can be further effectively suppressed, and the quality and precision of the micro-patterns obtained can be further improved.

[0015] A third aspect of this application provides a patterned film formed using the photosensitive composition provided in the second aspect. The photosensitive composition provided above exhibits excellent suppression of acid diffusion in the system, thereby improving the exposure performance of the photosensitive composition and effectively enhancing the precision and quality of the patterns obtained during the patterning process in semiconductor device fabrication.

[0016] A fourth aspect of this application also provides an electronic device comprising a patterned substrate and a functional layer disposed on the patterned substrate; the patterned substrate is obtained by etching a substrate having a patterned film provided in the third aspect on its surface. The compounds provided in this application enable photosensitive compositions to have good exposure properties and can form patterned films on the surface of electronic devices to obtain high-quality micropatterns, thereby enabling the electronic devices to have excellent overall performance.

[0017] The fifth aspect of this application also provides a method for fabricating an electronic device, comprising: The photosensitive composition provided in the second aspect is coated onto a substrate to form a film layer on the substrate; The film layer is exposed and developed using a photomask to form a patterned film on the substrate; Etching yields a patterned substrate; The functional layer is fabricated to obtain the electronic device. Attached Figure Description

[0018] Figure 1 The 1H NMR spectrum of compound (A)-1 in Example 1 of this application; Figure 2 The 1H NMR spectrum of polymer (B)-2 in Example 4 of this application; Figure 3 This is the absorption spectrum of the photosensitive composition of Example 1 of this application; Figure 4 This is the pattern morphology of the photosensitive composition of Example 1 of this application after exposure. Detailed Implementation

[0019] The present application will be further described in detail below with reference to preferred embodiments, but the scope of protection of the present application is not limited to the following specific embodiments.

[0020] In this application, all technical terms have the same meaning as commonly understood by those skilled in the art. The technical terms used herein are for the purpose of describing specific embodiments only and are not intended to limit the scope of protection of this application.

[0021] Patterning processes generally involve coating a photosensitive composition onto a substrate to form a photosensitive film layer, exposing the photosensitive film layer through a mask with a specific pattern, and then transforming the photosensitive film layer into a patterned film through development and other processes. Finally, the substrate with the patterned film is etched to obtain a patterned substrate with the predetermined pattern. During the exposure process, the solubility of the film material in the exposed area changes. Specifically, the photoacid generator (PAG) in the photosensitive composition catalyzes the deprotection reaction of acid-unstable groups in the polymer by generating acid, resulting in a change in solubility, thereby achieving pattern transfer and formation. Since each photon can trigger multiple deprotection reactions, a chemical amplification effect is achieved. This chemical amplification effect enables the patterning composition to complete the patterning process with extremely low exposure doses, significantly improving patterning efficiency, reducing production costs, and making high-precision patterning possible.

[0022] However, with the continuous development of electronic devices (such as semiconductor devices) and the shrinking of critical dimensions, the requirements for patterning processes in electronic device fabrication are becoming increasingly stringent. Acid diffusion during the post-exposure baking process of patterned compositions is becoming increasingly prominent, increasing linewidth roughness and leading to poor linewidth uniformity, severely affecting the accuracy and consistency of the pattern, and consequently impacting the performance of semiconductor devices. Furthermore, acid diffusion also narrows the exposure energy window, meaning that the control of the patterning process in actual production will be significantly more difficult. Even slight deviations can lead to pattern defects or process failures, greatly reducing the stability and reliability of the patterning process. Therefore, there is an urgent need to provide a photoacid-generating compound that can effectively suppress acid diffusion and has good absorption efficiency for the exposure light source.

[0023] To address the aforementioned technical problems, this application provides a compound that, in a photosensitive composition system, can effectively suppress acid diffusion while exhibiting high absorption efficiency for the exposure light source. Specifically, the compound comprises a cation and anion, the structure of which is shown in formula (I): (Ⅰ); Wherein, R1 is a halogen atom or a group containing an ethynyl group; R2, R3, R4, R5, and R6 are independently selected from hydrogen atoms, halogen atoms, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, C1-C20 alkoxy groups, aryloxy groups, and -SO2R groups. A -OSO2R B -COR C -COOR D -CONR E R F–PO(OR) G )2、-SR H R is any one of mercapto, substituted or unsubstituted amino, hydroxy, nitro and cyano groups, wherein R A R B R C R D R E R F R G R H The alkyl groups are each independently selected from any one of substituted or unsubstituted alkyl groups and aryl groups, and R2, R3, R4, R5, and R6 are not all hydrogen atoms; The anion is X - X - The structure is shown in equation (Ⅱ): (II); Wherein, R7 is selected from one or more of hydrogen atoms, substituted or unsubstituted C1-C30 alkyl groups, substituted or unsubstituted aliphatic cyclic groups, and substituted or unsubstituted aromatic cyclic groups; R8 is a substituted or unsubstituted alkylene group. Specifically, the compounds provided in this application can be used as photoacid-generating agents in photosensitive compositions. These photoacid-generating agents catalyze the deprotection reaction of acid-unstable groups in the polymer of the photosensitive composition by generating acid, resulting in a change in solubility, thereby achieving pattern transfer and formation. The cations with the above-mentioned special structure in this compound can significantly improve the absorption efficiency of the photosensitive composition to the exposure light source by specifically selecting the groups R1, R2, R3, R4, R5, and R6. By selecting the aforementioned special anions as the anions in the compound, the anions and cations in the compound work synergistically to effectively suppress acid diffusion during the baking stage after exposure, thereby improving its exposure performance and optimizing the exposure process window. For example, it reduces line width roughness, improves line width uniformity, reduces the degree of local fluctuation at the edge of the patterned film, and improves the smoothness of the line edges. To a certain extent, it avoids blurry or irregular shapes at the edge of the pattern, thereby improving the accuracy and consistency of the pattern, and ultimately improving the yield and precision of electronic devices.

[0024] In this embodiment, R1 is a halogen atom or a group containing an ethynyl group. By selecting a suitable R1, the volume of the anionic portion can be further increased, and the rigidity can be further enhanced, thereby making it more conducive to the suppression of acid diffusion. Compounds containing the above-mentioned groups have high absorption efficiency for exposure light sources, especially for certain light sources such as i-line light (wavelength 365 nm), electron beams, and light with wavelengths less than 15 nm, which have more outstanding absorption effects.

[0025] In some embodiments of this application, the halogen atom can be, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. When R1 is a halogen atom, the compound has a high absorption efficiency for the exposure light source. Furthermore, when R1 is one of the aforementioned halogen atoms, the raw materials for preparing the compound are simpler and more readily available, which can further reduce the synthesis difficulty and preparation cost of the compound, and is beneficial for large-scale industrial production.

[0026] In this application, the ethynylene group specifically refers to "-C≡C-", that is, a divalent unsaturated group formed by removing two hydrogen atoms from an acetylene molecule. In some embodiments of this application, the group containing the ethynylene group can be any one of the groups shown in formulas (Ⅲ-1)-(Ⅲ-5): (Ⅲ-1); (Ⅲ-2); (Ⅲ-3); (Ⅲ-4); (Ⅲ-5) When R1 is a group containing an ethynyl group, the volume of the anionic portion can be further increased, and the rigidity can be further enhanced, which is more conducive to the inhibition of acid diffusion.

[0027] In the embodiments of this application, R2, R3, R4, R5, and R6 are independently selected from hydrogen atoms, halogen atoms, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, C1-C20 alkoxy groups, aryloxy groups, and -SO2R groups. A -OSO2R B -COR C -COOR D -CONR E R F –PO(OR) G )2、-SR H R is any one of mercapto, substituted or unsubstituted amino, hydroxy, nitro and cyano groups, wherein R A R B R C R D R E R F R G R HThe alkyl groups are independently selected from any one of substituted or unsubstituted alkyl or aryl groups, and R2, R3, R4, R5, and R6 are not all hydrogen atoms. By making the above-mentioned special group selections for R2, R3, R4, R5, and R6, and ensuring that R2, R3, R4, R5, and R6 are not all hydrogen atoms, and by modifying different sites in the benzene ring structure attached to the iodide ion in the cation with different groups, the absorbance of the compound can be adjusted to match different photosensitive composition systems and different types of exposure light sources, thereby obtaining an ideal photosensitive composition.

[0028] In the embodiments of this application, the halogen atom includes, but is not limited to, one or more of fluorine, chlorine, bromine, and iodine atoms.

[0029] In this application, the alkyl group can be either a chain alkyl group or a cycloalkyl group. A chain alkyl group is a saturated hydrocarbon group formed by removing one hydrogen atom from a chain alkane molecule, and can include straight-chain alkyl groups and branched-chain alkyl groups. Specifically, the alkyl group can include, but is not limited to, at least one of methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, 2-methylbutyl, 3-methylbutyl, 4-methylbutyl, 2,2-dimethylpropyl, n-hexyl, cyclohexyl, 2-methylhexyl, 3-methylhexyl, 4-methylpentyl, 5-methylpentyl, 2-ethylbutyl, and 3-ethylbutyl. In this application, the alkyl group has 1-20 carbon atoms. In some specific embodiments, the alkyl group has, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 16, 18, or 20 carbon atoms. In other embodiments of this application, the alkyl group has 1-3 carbon atoms.

[0030] In this application, the alkenyl group can be a chain alkenyl group. A chain alkenyl group is a chain-like unsaturated hydrocarbon group containing at least one carbon-carbon double bond, and can include straight-chain alkenyl groups and branched alkenyl groups. Specifically, the alkenyl group can include, but is not limited to, at least one of vinyl, propenyl, allyl, isopropenyl, butenyl, butadienyl, and hexenyl groups. In this application, the alkenyl group has 2-20 carbon atoms. In some specific embodiments, the alkenyl group can have, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 16, 18, or 20 carbon atoms.

[0031] In this application, the alkynyl group is an unsaturated hydrocarbon group containing at least one carbon-carbon triple bond, and may include, but is not limited to, straight-chain alkynyl groups and branched-chain alkynyl groups. Specifically, the alkynyl group may include, but is not limited to, at least one of ethynyl, 1-propynyl, and 2-propynyl. In this application, the number of carbon atoms in the alkynyl group is 2-20. In some specific embodiments, the number of carbon atoms in the alkynyl group may be, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 16, 18, or 20.

[0032] In the embodiments of this application, aryl refers to the group remaining after removing one hydrogen atom from an aromatic hydrocarbon molecule. In some specific embodiments of this application, aryl includes, but is not limited to, phenyl, benzyl, naphthyl, and biphenyl.

[0033] In this application, an alkoxy group refers to a functional group formed by an alkyl group bonded to the rest of the molecule via an oxygen atom. In some specific embodiments, the alkoxy group may include, but is not limited to, at least one of methoxy, ethoxy, isopropoxy, and tert-butoxy. In this application, the alkoxy group has 1-20 carbon atoms. In some specific embodiments, the alkoxy group may have, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 16, 18, or 20 carbon atoms.

[0034] In this application, an aryloxy group refers to a functional group formed by an aryl group being bonded to the rest of the molecule via a peroxide atom. In some specific embodiments, the aryloxy group may include, but is not limited to, at least one of phenoxy and 1-naphthoxy. In this application, the number of carbon atoms in the aryloxy group is 6-20. In some specific embodiments, the number of carbon atoms in the aryloxy group may be, for example, 6, 7, 8, 9, 10, 12, 14, 15, 16, 18, or 20.

[0035] In this embodiment of the application, the substituted amino group can be -NHR. I It can also be -NR J R K , where R I R J R K Each alkyl group is independently selected from substituted or unsubstituted alkyl or aryl groups. In some specific embodiments, the alkyl group may be, for example, methyl, and the substituted alkyl group may be, for example, a haloalkyl group.

[0036] In the embodiments of this application, R A R B R C R D R E R F R G R H Each alkyl group is independently selected from substituted or unsubstituted alkyl or aryl groups. In some specific embodiments, the alkyl group may be, for example, methyl, and the substituted alkyl group may be, for example, a haloalkyl group.

[0037] In the embodiments of this application, substitution refers to the replacement of at least one hydrogen atom in alkyl, alkenyl, alkynyl, or other groups by a substituent group. In the embodiments of this application, when multiple hydrogen atoms in alkyl, alkenyl, alkynyl, or other groups are replaced by substituent groups, the substituent groups may be the same or different. In some embodiments of this application, the substituent group may be one or more of halogen atoms, mercapto, amino, hydroxyl, nitro, and cyano groups.

[0038] In the embodiments of this application, R2, R3, R4, R5, and R6 are not all hydrogen atoms. In some embodiments of this application, the number of hydrogen atoms in R2, R3, R4, R5, and R6 can be, for example, 0, 1, 2, 3, or 4. By specifically selecting at least one group in the cation, the absorption efficiency of the photosensitive composition to the exposure light source can be significantly improved.

[0039] In some embodiments of this application, at least one of R2, R3, R4, R5, and R6 is a C1-C3 alkyl group. In some embodiments of this application, the C1-C3 alkyl group can be, for example, methyl, ethyl, n-propyl, or isopropyl. In some embodiments of this application, only one of R2, R3, R4, R5, and R6 may be a C1-C3 alkyl group, or two or more may be C1-C3 alkyl groups. In some embodiments of this application, R4 is not a hydrogen atom. In some specific embodiments of this application, R4 is a C1-C3 alkyl group, and R2, R3, R5, and R6 are all hydrogen atoms. By selecting specific groups at the para position of the iodide ion attachment site in the benzene ring structure, the light absorption effect of the compound on the exposure light source can be further improved.

[0040] In this embodiment, the anion has the structure shown in formula (II): (II); R7 is selected from one or more of hydrogen atoms, substituted or unsubstituted C1-C30 alkyl groups, substituted or unsubstituted aliphatic cyclic groups, and substituted or unsubstituted aromatic cyclic groups; R8 is a substituted or unsubstituted alkylene group. By selecting the above-mentioned suitable anions, they can synergistically cooperate with the cations to enable the photosensitive composition to have a good inhibitory effect on acid diffusion during the baking stage after exposure, thereby improving its exposure performance, optimizing the exposure process window, improving the accuracy and consistency of the pattern, and ultimately improving the yield and precision of electronic devices.

[0041] In the embodiments of this application, R7 is selected from one or more of hydrogen atoms, substituted or unsubstituted C1-C30 alkyl groups, substituted or unsubstituted alicyclic groups, and substituted or unsubstituted aromatic cyclic groups.

[0042] In this application, the alkyl group can be either a chain alkyl group or a cycloalkyl group. A chain alkyl group is a saturated hydrocarbon group formed by removing one hydrogen atom from a chain alkane molecule, and can include straight-chain alkyl groups and branched-chain alkyl groups. Specifically, the alkyl group can include, but is not limited to, at least one of methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, 2-methylbutyl, 3-methylbutyl, 4-methylbutyl, 2,2-dimethylpropyl, n-hexyl, cyclohexyl, 2-methylhexyl, 3-methylhexyl, 4-methylpentyl, 5-methylpentyl, 2-ethylbutyl, and 3-ethylbutyl. In this application, the alkyl group has 1-30 carbon atoms. In some specific embodiments, the number of carbon atoms in the alkyl group can be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 16, 18, 20, 22, 24, 25, 26, 28, or 30. In other embodiments of this application, the number of carbon atoms in the alkyl group is 1-3.

[0043] In this application, a substituted alkyl group refers to an alkyl group in which at least one hydrogen atom is replaced by a substituent group. In this application, when multiple hydrogen atoms in an alkyl group are replaced by substituent groups, the substituent groups may be the same or different. In some embodiments of this application, the substituent group may be one or more of the following: halogen atom, mercapto, amino, hydroxyl, nitro, and cyano.

[0044] In this application, the alicyclic group, also called an alicyclic group, refers to a monovalent or polyvalent group formed by removing one or more hydrogen atoms from an alicyclic compound (alicyclic compound). In this application, the alicyclic group can be a saturated alicyclic group or an unsaturated alicyclic group. In some embodiments of this application, the alicyclic group includes one or more of saturated cyclic groups, unsaturated cyclic groups, polycyclic groups, and alicyclic derivative groups with functional groups. In some specific embodiments, the alicyclic group can be, for example, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, adamantyl, 2-adamantanone, norbornyl, and derivative groups of the above groups with functional groups. In some embodiments of this application, the alicyclic derivative group with functional groups may also have one or more -CH2- replaced by -O- or -C=O-.

[0045] In some embodiments of this application, the substituted aliphatic cyclic group may be one or more hydrogen atoms replaced by a hydroxyl group, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C3-C12 aliphatic hydrocarbon group, or a C6-C20 aromatic hydrocarbon group.

[0046] In the embodiments of this application, an aromatic cyclic group refers to a monovalent or polyvalent group with aromaticity formed by removing one or more hydrogen atoms from an aromatic compound. In some embodiments of this application, the aromatic cyclic group includes one or more of monocyclic aromatic groups, fused-ring aromatic groups, and heterocyclic aromatic groups. In some specific embodiments, the aromatic cyclic group may be, for example, phenyl, benzyl, 1-naphthyl (α-naphthyl), 2-naphthyl (β-naphthyl), 9-anthrayl, 2-pyridyl (α-pyridyl), or 2-furanyl.

[0047] In some embodiments of this application, R7 may be selected from methyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, substituted or unsubstituted phenyladamantyl, 2-adamantanone, substituted or unsubstituted phenyl, and groups as shown in formulas (V-1) to (V-3): (V-1); (V-2); (V-3). The aforementioned R7 can further enhance the synergistic effect of anions and cations, thereby further improving the light absorption and exposure performance of the compound.

[0048] In this application, R8 is a substituted or unsubstituted alkylene group. In some embodiments of this application, when R8 is a substituted alkylene group, the substituent group can be a halogen atom, specifically, for example, one or more of fluorine, chlorine, bromine, and iodine atoms. In some embodiments, R8 is a C1-C5 fluoroalkylene group. In some specific embodiments, R8 can be, for example, one or more of -CHCF3-, -CH2CH2CF2-, and -CH2CH2CHF-.

[0049] In some embodiments of this application, the anion is any one of the groups shown in formulas (II-1)-(II-15): (Ⅱ-1); (Ⅱ-2); (Ⅱ-3); (Ⅱ-4); (Ⅱ-5); (Ⅱ-6); (Ⅱ-7); (Ⅱ-8); (Ⅱ-9); (Ⅱ-10); (Ⅱ-11); (Ⅱ-12); (Ⅱ-13); (Ⅱ-14); (Ⅱ-15). By selecting the aforementioned anions, the inhibitory effect of the compound on acid diffusion can be further enhanced.

[0050] The compounds provided in this application employ a specific combination of anions and cations, with particular selection of their respective functional groups, to achieve synergistic effects. This controls the rate and efficiency of the deprotection reaction, allowing for more precise acid release during exposure. The resulting compounds possess both excellent light absorption efficiency and acid diffusion suppression. When applied to photosensitive compositions, these compounds act as photoacid-generating agents, exhibiting high absorption efficiency against the exposure light source while effectively suppressing acid diffusion. This improves the resolution and edge sharpness of the resulting patterns, thereby enhancing the overall performance of the photosensitive composition and ultimately improving the performance of semiconductor devices.

[0051] In some embodiments of this application, the compounds provided above can be prepared via the following synthetic route:

[0052] In some embodiments of this application, in the above synthetic route, AX includes cation A. + and anion X - In some embodiments of this application, cation A + It could be Na + Ammonium salt cations; anions X - See above. In some specific embodiments, the ammonium salt cation may be one or more of the following: trimethylbenzylammonium cation, triethylmethylammonium cation, and tetraethylammonium cation.

[0053] In this embodiment, step ③ of the above synthetic route is an ion exchange reaction. In some embodiments, the reaction system for the ion exchange reaction is a mixed solution of dichloromethane and water, specifically, for example, a mixed solution of dichloromethane and water with a volume ratio of 1:1. In some embodiments, the ion exchange reaction includes a stirred reaction at room temperature for 2-4 hours.

[0054] This application also provides a photosensitive composition comprising the compounds and polymer solvents provided above. The photosensitive composition, comprising the compounds provided above, exhibits high absorption efficiency to the exposure light source while effectively suppressing acid diffusion, thereby giving the photosensitive composition excellent exposure performance.

[0055] The photosensitive compositions provided in this application are suitable for light sources including, but not limited to, i-line light (wavelength 365 nm), g-line light (wavelength 436 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), electron beams, and light with wavelengths less than 15 nm (e.g., EUV). In some specific embodiments, the photosensitive compositions exhibit more pronounced absorption effects and better exposure performance for i-line light (wavelength 365 nm), electron beams, and light with wavelengths less than 15 nm.

[0056] In some embodiments of this application, the photosensitive composition may include one or more of the compounds shown in Formula (I) provided above. In other embodiments of this application, the photosensitive composition may include one of the compounds shown in Formula (I) provided above. In still other embodiments of this application, the photosensitive composition may include two or more of the compounds shown in Formula (I) provided above. The types of compounds in the photosensitive composition of this application can be selected according to actual usage requirements, specifically according to the types of polymers in the photosensitive composition. These compounds can act as photoacid-generating agents in the photosensitive composition, catalyzing the deprotection reaction of acid-unstable groups in the polymer of the photosensitive composition by generating acid, resulting in a change in solubility, thereby achieving pattern transfer and formation.

[0057] In some embodiments of this application, the mass percentage of the compound in the photosensitive composition is 0.05%-4%. In some specific embodiments, the mass percentage of the compound in the photosensitive composition may be, for example, 0.05%, 0.06%, 0.08%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.2%, 1.4%, 1.5%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.5%, 2.6%, 2.8%, 3%, 3.2%, 3.4%, 3.5%, 3.6%, 3.8%, or 4%. By controlling the content of the compound within a suitable range, the chemical reactions within the system can be further regulated, especially the rate and efficiency of the deprotection reaction, thereby further improving the imaging quality of the micropatterns obtained. In this application, the mass percentage of the compound in the photosensitive composition can be determined by, but is not limited to, nuclear magnetic resonance spectroscopy. Specifically, for example, it can be determined by characterizing the characteristic peaks of the compound using nuclear magnetic resonance spectroscopy, and the mass percentage of the compound in the photosensitive composition can be obtained based on the integral ratio of the characteristic peaks.

[0058] In this application, the polymer is an important component of the patterned composition. The polymer provides the photosensitive composition with corrosion resistance and structural reliability, and undergoes a solubility transformation under the action of acid. In some embodiments of this application, the polymer includes one or more repeating structural units as shown in formulas (VI-1)-(VI-3): (VI-1); (VI-2); (VI-3); In equations (VI-1) to (VI-3), R 1 R 3 R 5 Each alkyl group is independently selected from any one of hydrogen atoms, halogen atoms, and substituted or unsubstituted C1-C3 alkyl groups. In some embodiments, the halogen atom may be, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. In some embodiments, it may be, for example, methyl, ethyl, n-propyl, or isopropyl. In some embodiments, the substituent group of the substituted C1-C3 alkyl group may be a halogen atom, specifically, for example, one or more of fluorine, chlorine, bromine, and iodine atoms. In some embodiments, the substituent group of the substituted C1-C3 alkyl group may be one or more. In some embodiments of this application, R... 1 R 3 R 5 Each atom is independently selected from hydrogen, fluorine, methyl, or trifluoromethyl.

[0059] In some embodiments of this application, in formula (VI-1), R 2 Selected from any one of substituted or unsubstituted 4- to 15-membered lactone groups, 2-(4-fluorophenyl)-2-propyl, hydroxyadamantyl, and hydroxyphenyl. In some specific embodiments of this application, R... 2 For example, it can be any of the groups shown in formulas (1-1) to (1-14): (1-1); (1-2); (1-3); (1-4); (1-5); (1-6); (1-7); (1-8); (1-9); (1-10); (1-11); (1-12); (1-13); (1-14); among which, This indicates that the connection site can be any connectable site in the structure.

[0060] In some embodiments of this application, in formula (VI-2), R 4 It can be -(C=O)OR 0 , where R 0 Selected from any one of the groups shown in formulas (2-1) to (2-24): (2-1); (2-2); (2-3); (2-4); (2-5); (2-6); (2-7); (2-8); (2-9); (2-10); (2-11); (2-12); (2-13); (2-14); (2-15); (2-16); (2-17); (2-18); (2-19); (2-20); (2-21); (2-22); (2-23); among which, This indicates that the connection site can be any connectable site in the structure.

[0061] In some embodiments of this application, R6 is at least one selected from substituted or unsubstituted C10-C30 aryl groups, substituted or unsubstituted 8- to 30-membered heteroaryl groups, such as naphthyl, anthracene, tetraphenyl, perylene, phenanthrene, pyrene, indolyl, quinolinyl, benzopyranyl, xanthonyl, carbazoyl, or anthraquinoneyl.

[0062] In some embodiments of this application, the polymer in the photosensitive composition comprises repeating structural units as shown in formulas (V-1)-(V-3). By selecting polymers containing all three structural units described above, the polymer can possess excellent support, acid deprotection, and photosensitivity. In some embodiments of this application, the polymer in the photosensitive composition comprises one or more of the repeating structural units as shown in formulas (Ⅳ-1)-(Ⅳ-4): (Ⅳ-1); (Ⅳ-2); (Ⅳ-3); (Ⅳ-4).

[0063] In some embodiments of this application, the polymer may include one of the repeating structural units shown in formulas (Ⅳ-1)-(Ⅳ-4). In other embodiments of this application, the polymer may include two or more of the repeating structural units shown in formulas (Ⅳ-1)-(Ⅳ-4). In some specific embodiments of this application, the polymer in the photosensitive composition includes repeating structural units shown in formulas (Ⅳ-1)-(Ⅳ-4). By selecting a combination containing these four specific repeating structural units, the polymer can be better adapted to the system containing the compound (PAG) provided above in this application, further improving the uniformity and stability of the system. In some specific embodiments of this application, the polymer in the photosensitive composition includes repeating structural units shown in formulas (Ⅳ-1)-(Ⅳ-4), specifically, the molar ratio of the repeating structural units shown in formula (Ⅳ-1), (Ⅳ-2), (Ⅳ-3), and (Ⅳ-4) is 50:35:10:5.

[0064] This application utilizes polymers comprising repeating structural units derived from monomers containing acid-deprotected groups. These polymers exhibit high acid sensitivity; under acidic conditions or in the presence of acid and high temperatures, their acid-deprotected groups readily detach from the polymer backbone, resulting in significant solubility reversal and a rapid response. In the embodiments of this application, the polymer may further comprise repeating structural units derived from other monomers. In the embodiments of this application, the polymer may be obtained through free radical polymerization of one or more monomers.

[0065] In some embodiments of this application, the weight-average molecular weight (Mw) of the polymer is 3000 g / mol to 10000 g / mol. In some specific embodiments, the weight-average molecular weight of the polymer can be, for example, 3000 g / mol, 3500 g / mol, 4000 g / mol, 4500 g / mol, 5000 g / mol, 5500 g / mol, 6000 g / mol, 6500 g / mol, 7000 g / mol, 7500 g / mol, 8000 g / mol, 8500 g / mol, 9000 g / mol, 9500 g / mol, or 10000 g / mol. Controlling the weight-average molecular weight of the polymer within the above range ensures high etching tolerance while allowing for a certain difference in dissolution rate before and after exposure. In this application, the weight-average molecular weight of the polymer can be, but is not limited to, measured by GPC (Gel Permeation Chromatography).

[0066] In some embodiments of this application, the polymer's PDI (Polymer Dispersity Index) is 1-1.5. Specifically, the polymer's PDI in this application is Mw / Mn (weight-average molecular weight / number-average molecular weight). The PDI in this application is a parameter used to describe the width of the polymer's molecular weight distribution. A larger PDI (greater than 1) indicates a more uneven and wider molecular weight distribution; a smaller PDI (closer to 1) indicates a more uniform and narrower molecular weight distribution. When the PDI equals 1, it means that all polymer molecular chains have the same molecular weight. In some specific embodiments of this application, the polymer's PDI can be, for example, 1, 1.05, 1.1, 1.156, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, or 1.5. By controlling the polymer's PDI within the aforementioned suitable range, this application can further improve the system uniformity and stability of the photosensitive composition, thereby further reducing the risk of defects in the patterned film. In this application, the PDI of the polymer can be measured, but is not limited to, by GPC (Gel Permeation Chromatography).

[0067] In some embodiments of this application, the polymer content in the photosensitive composition is 0.5%-10% by mass. In some specific embodiments, the polymer content in the photosensitive composition can be, for example, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, or 10%. By controlling the polymer content in the photosensitive composition within a suitable range, this application can improve the coating effect of the photosensitive composition, thereby improving its film-forming properties and the uniformity of the formed film layer. Furthermore, it can effectively control the production cost of the patterned composition. In some embodiments, the polymer content in the photosensitive composition can be 70%-85% by mass. Further controlling the polymer content in the photosensitive composition can further improve the film-forming properties of the photosensitive composition and the uniformity and photosensitivity of the formed photosensitive film layer. In some embodiments of this application, the photosensitive composition can be freeze-dried first, and then the obtained solid can be tested using NMR to calculate the polymer mass percentage in the photosensitive composition.

[0068] In this application, the photosensitive composition may include only one polymer, or it may include two or more different polymers. In this application, the same polymer may include only one structural unit, or it may include multiple different structural units.

[0069] In some embodiments of this application, the mass ratio of the compound to the polymer in the photosensitive composition is (5-40):100. In some specific embodiments, the mass ratio of the compound to the polymer in the photosensitive composition can be, for example, 5:100, 6:100, 8:100, 10:100, 12:100, 14:100, 15:100, 16:100, 18:100, 20:100, 22:100, 24:100, 25:100, 26:100, 28:100, 30:100, 32:100, 34:100, 35:100, 36:100, 38:100, or 40:100. By controlling the mass ratio of the two components in the photosensitive composition system within a suitable range, the rate and efficiency of the chemical reaction within the system can be further controlled, thereby further improving the precision and consistency of the obtained micropatterns. In some embodiments of this application, the mass ratio of the compound to the polymer in the photosensitive composition can be (20-30):100. Further controlling the ratio can further improve the film-forming properties and exposure performance of the photosensitive composition, thereby further improving the overall performance of the patterned film.

[0070] In this application, the solvent in the photosensitive composition can be any solvent known in the art capable of dissolving and dispersing the aforementioned polymers, compounds, and other components. In some specific embodiments, the solvent in the photosensitive composition includes, but is not limited to, propylene glycol methyl ether acetate (PGMEA), n-butyl acetate, ethyl acetate, and γ-ethyl acetate. One or more of butyrolactone and propylene glycol methyl ether. In some embodiments of this application, the solvent in the photosensitive composition may be a single solvent system containing only one solvent, or a mixed solvent system containing two or more of the solvents mentioned above.

[0071] In some embodiments of this application, the solvent content in the photosensitive composition is 90%-99.5% by mass. In some specific embodiments, the solvent content in the photosensitive composition may be, for example, 90%, 90.5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99%, or 99.5%. By further limiting the solvent content, the coating performance of the photosensitive composition can be improved, while the various components in the photosensitive composition can be more uniformly and stably dispersed, further improving the uniformity, stability, and film-forming properties of the photosensitive composition. Furthermore, when the photosensitive composition is used to prepare a patterned film, the solvent can completely evaporate during the pretreatment process before irradiation of the coating, thus not affecting the formation of the patterned film or the precision and quality of the patterned film. In some embodiments of this application, the solvent content in the photosensitive composition may be 97%-99.5% by mass. Photosensitive compositions with solvent mass percentages within this range can further improve stability and film-forming properties.

[0072] In some embodiments of this application, the photosensitive composition further includes an alkaline neutralizing agent, which includes one or more of hexylamine, heptylamine, octylamine, nonylamine, aniline, 2-methylaniline, 4-methylaniline, 4-nitroaniline, 1-naphthylamine, 2-naphthylamine, 1,2-ethylenediamine, 1,4-butanediamine, 1,6-hexanediamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, methyl dibutylamine, methyl dioctylamine, triheptylamine, and tris(3,6-dioxaheptyl)amine. In other embodiments of this application, the alkaline neutralizing agent in the photosensitive composition may also include a photodegradable base (PDB). Introducing photodegradable bases into the photosensitive composition can further control the acid diffusion problem in the system. Photodegradable bases have the characteristic of maintaining alkalinity in non-exposed areas and decomposing into neutral or weakly acidic substances in exposed areas, enabling them to dynamically regulate the acid-base balance during exposure and effectively inhibit acid diffusion. At the same time, photodegradable bases can also extend the baking delay time after exposure and enhance the formulation stability of the photosensitive composition.

[0073] In some embodiments of this application, the mass percentage of the alkaline neutralizing agent in the photosensitive composition is 0.001%-2%. In some specific embodiments, the mass percentage of the alkaline neutralizing agent in the photosensitive composition may be, for example, 0.001%, 0.002%, 0.005%, 0.008%, 0.01%, 0.02%, 0.05%, 0.08%, 0.1%, 0.2%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.5%, 1.6%, 1.8%, or 2%. By controlling the content of the alkaline neutralizing agent in the photosensitive composition within a suitable range, this application can, to a certain extent, avoid excessive alkalinity leading to a narrowing of the developing window and reduced sensitivity, and avoid insufficient alkalinity control leading to ineffective suppression of acid diffusion. Thus, while ensuring high sensitivity and high resolution, sufficient developing window and excellent linewidth roughness are obtained.

[0074] In some embodiments of this application, the mass ratio of the alkaline neutralizing agent to the polymer in the photosensitive composition is (0.1-15):100. In some specific embodiments, the mass ratio of the alkaline neutralizing agent to the polymer in the photosensitive composition can be, for example, 0.1:100, 0.2:100, 0.4:100, 0.5:100, 0.6:100, 0.8:100, 1:100, 2:100, 3:100, 4:100, 5:100, 6:100, 7:100, 8:100, 9:100, 10:100, 11:100, 12:100, 13:100, 14:100, or 15:100. By controlling the mass ratio of the alkaline neutralizing agent to the polymer within the above range, the acid-base balance of the system during exposure can be further controlled, acid diffusion can be further effectively suppressed, and the quality and precision of the obtained micro-patterns can be further improved.

[0075] In some embodiments of this application, to improve the overall performance of the photosensitive composition, the photosensitive composition may further include additives, such as leveling agents and surfactants, or one or more of these. The addition of leveling agents and surfactants can improve the uniformity of the coated film. The type and amount of leveling agents and surfactants can be added according to actual usage requirements.

[0076] In some embodiments of this application, the resolution of the photosensitive composition after electron beam exposure and development is less than or equal to 50 nm. In some specific embodiments, the resolution of the photosensitive composition after electron beam exposure and development may be, for example, 50 nm, 45 nm, 40 nm, 35 nm, or 30 nm.

[0077] In the embodiments of this application, the photosensitive composition can be a positive photosensitive composition, that is, the photoacid generated by exposure will cause the polymer to detach acid de-groups, so that the polymer can be dissolved in alkaline developing solution, and the resulting pattern is the same as that of the photomask.

[0078] In one embodiment of this application, the method for preparing the photosensitive composition includes: mixing a polymer, a compound, and a solvent to obtain the photosensitive composition. The method for preparing the photosensitive composition provided by this application is simple, has low preparation cost, uses readily available raw materials, and yields a photosensitive composition with good stability and exposure performance, which is beneficial for commercial application.

[0079] In the embodiments of this application, nuclear magnetic resonance (NMR) can be used to characterize the types and contents of each component in the photosensitive composition. In some embodiments, the photosensitive composition can be subjected to freeze-drying or other treatments to remove the solvent, the solid substance obtained after freeze-drying is dissolved in a quantitative amount of deuterated reagent and subjected to NMR testing, the NMR test results are peaked according to the internal standard results, and then the mass of each component is calculated and determined.

[0080] This application also provides a patterned film formed using the photosensitive composition described above. This patterned film can be used as a high-precision mask in integrated circuit patterning processes. The pattern of the patterned film can be transferred to a substrate such as a silicon wafer by etching, thereby forming a designed pattern on the substrate. Because the photosensitive composition described above has good stability, the patterned film obtained using it exhibits high patterning quality.

[0081] In some embodiments of this application, the method for preparing a patterned film includes: coating a photosensitive composition onto a substrate to form a film layer; exposing and developing the film layer using a photomask to form a patterned film on the substrate surface. In some specific embodiments, the coating method includes, but is not limited to, spin coating, a high-speed film formation method that can obtain a more uniform patterned film. In some embodiments of this application, a pre-baking treatment is included after coating the photosensitive composition to form the film layer and before exposing the film layer; a post-baking treatment is also included after exposure and before development.

[0082] This application provides an electronic device fabricated using the patterned film described in any of the above embodiments. The electronic device provided by this application has high precision, which is beneficial for improving the overall performance of the electronic device. In some embodiments of this application, the semiconductor device includes a structure obtained by etching a film layer (i.e., a patterned film) formed by coating a structure to be patterned (such as a substrate to be patterned) with the above-described photosensitive composition, followed by exposure and development.

[0083] In some embodiments, the electronic device may specifically be a semiconductor device. This application does not limit the specific type of semiconductor device. In one embodiment of this application, the semiconductor device may be an integrated circuit device, including a chip. During chip fabrication, other functional layers can be fabricated after the aforementioned patterning process is completed.

[0084] This application also provides a method for fabricating an electronic device, comprising: S101. Coat the photosensitive composition described in any of the above embodiments onto a substrate to form a photosensitive film layer on the substrate. S102. Coating the photosensitive composition with a photomask, or exposing the film layer to an exposure light source; S103. Using a developer to develop the exposed photosensitive film layer, or the film layer, to form a patterned film on the substrate.

[0085] The preparation method provided in this application is simple, and the resulting semiconductor device has excellent overall performance, which is conducive to its commercial application.

[0086] In step S101, the substrate can be selected according to actual needs. Specifically, the substrate can be, but is not limited to, a silicon wafer or a silicon wafer with a coating. For example, the coating can be an anti-reflective coating, an anti-etching coating, an epitaxial layer, a metal layer, a dielectric layer, a modification layer, or a matching layer. Other coatings can usually be obtained by pre-treating the substrate. Pre-treatment methods can be: hydrophilic activation of the silicon wafer substrate with O2 plasma; or cleaning in Piranha solution (H2O:30% ammonia:30% H2O2=5:1:1) for 15-20 minutes, followed by rinsing with deionized water and isopropanol to complete the hydrophilic treatment; or using vapor deposition or spin coating to coat the substrate with hexamethyldisilazane (HMDS) to perform surface hydrophobic treatment; the hydrophobic treatment can be performed after the hydrophilic treatment; or adding an underlying anti-reflective layer, an underlying carbon-containing coating, or an underlying silicon-containing coating.

[0087] In this embodiment, a suitable volume of photosensitive composition is taken according to the size of the substrate and coated onto the substrate by spin coating to form a photosensitive composition coating.

[0088] In some embodiments of this application, the substrate can be cleaned before coating to remove impurities and dust from its surface. Specifically, the cleaning method can be, but is not limited to, using solvents, acids, ultrasonic cleaning, or jet cleaning. In some embodiments of this application, the cleaning method can be ultrasonic cleaning.

[0089] In some embodiments of this application, in step S102, the exposure light source can be, but is not limited to, light with a wavelength of 13 nm-380 nm, an electron beam, soft X-rays, etc. In some specific embodiments, the exposure light source can be, for example, i-line light (wavelength 365 nm), g-line light (wavelength 436 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), an electron beam, and light with a wavelength less than 15 nm. The exposure conditions, such as the exposure amount, can be appropriately adjusted according to the exposure light source, formulation composition, type of additives, etc. Furthermore, the above exposure can also be immersion exposure.

[0090] In step S102, a baking process (pre-baking) can be performed after coating and before exposure to remove excess solvent from the film layer and improve the structural reliability of the patterned composition; a baking process (post-baking) can also be performed after exposure and before development to promote the removal of acid-protected groups from the resin in the coating. The baking temperature is 70℃-160℃, and the baking time is 20s-120s. Specifically, the baking temperature can be, but is not limited to, 70℃, 80℃, 100℃, 120℃, 140℃, 160℃, etc., and the baking time can be, but is not limited to, 20s, 40s, 60s, 80s, 100s, or 120s. In one embodiment of this application, the baking temperature can be 60℃-150℃, and the baking time can be 20s-80s. In some specific embodiments of this application, the baking temperature can be 100℃-200℃, and the baking time can be 70s-120s.

[0091] In step S103, a developing solution is used for developing to obtain a patterned film. In this embodiment, the cleaning time is 10 s-300 s, and the cleaning can be divided into single-step cleaning and multi-step cleaning.

[0092] In some embodiments of this application, the developing solution includes a developer, which can be selected and used in combination according to the properties of the patterning composition to improve the etching effect. The developing time is 10 s-120 s. Specifically, the developing solution can be selected from organic solutions, inorganic solutions, pure solvents, mixed solvents, solvents containing other additives, etc. Specifically, in some embodiments of this application, the developing solution can be a 0.5-5% aqueous solution of tetramethylammonium hydroxide (TMAH), or it can be an organic solvent such as ketones, alcohols, ethers, esters, lactones, high-boiling-point alcohols, etc. Among them, ketones can be, for example, cyclohexanone and methyl-2-n-pentyl ketone; alcohols can be, for example, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; ethers can be, for example, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethylene glycol monoethyl ether. The solvents used include propylene glycol dimethyl ether and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate; lactones such as γ-butyrolactone; and high-boiling-point alcohol solvents such as diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, and 1,3-butanediol. The developer may be a mixture of one or more of the above solvents. In some embodiments, the process after development includes rinsing and baking to remove impurities from the surface of the patterned film and improve the structural reliability of the patterned film.

[0093] In some embodiments of this application, a patterned substrate can be obtained by etching or electron implantation of a film layer (i.e., a patterned film) formed by coating the substrate to be patterned with the above-described patterning composition and then exposing and developing it.

[0094] In some embodiments of this application, after forming a patterned thin film on the substrate, the method for fabricating the above-mentioned electronic device further includes: S104. The patterned substrate is etched or electron-injected to form a patterned substrate, thereby obtaining an electronic device.

[0095] The technical solution of this application will be described in detail below with reference to several embodiments.

[0096] Example 1 2.77 g of 4-bromo-1,8-naphthalenedicarboxylic anhydride (1.0 eq, 10 mmol), 6.57 g of 4-iodoaniline (3.0 eq, 30 mmol), and 3.44 g of imidazole (5.0 eq, 50 mmol) were dissolved in 150 mL of chloroform. The mixture was then refluxed for 12 hours. After cooling, the chloroform was removed by vacuum distillation to give the first intermediate, IM1. ; 4.78 g of the first intermediate IM1 (1.0 eq, 10 mmol)), 1.84 g of toluene (2.0 eq, 20 mmol) and 2.07 g of m-chloroperbenzoic acid were added. m -CPBA (1.2 eq, 12 mmol) was dissolved in 150 mL of dichloromethane, and then 7.5 g of the ionizing agent trifluoromethanesulfonic acid TfOH (5.0 eq, 50 mmol) was added dropwise to the resulting mixture at room temperature. After the addition was complete, the reaction was stirred for 3 hours. The dichloromethane was removed by vacuum distillation to give the second intermediate IM2. ; 7.18 g of the second intermediate IM2 (1.0 eq, 10 mmol) and 4.10 g of sodium 4-(adamantane-1-carboxyloxy)-1,1,2,2-tetrafluorobutane-1-sulfonate (1.0 eq, 10 mmol) were dissolved in 200 mL of a mixed solution of dichloromethane and water (volume ratio 1:1). The mixture was stirred at room temperature for 3 hours for ion exchange. The dichloromethane phase was collected, and 100 mL of water was added three times for extraction and separation. The dichloromethane phase was collected again, and the dichloromethane was removed by vacuum distillation. After drying, compound (A)-1 and sodium trifluoromethanesulfonate were obtained. The sodium trifluoromethanesulfonate was removed by washing with water. The 1H NMR spectrum of compound (A)-1 is shown below. Figure 1 As shown;

[0097] The obtained compound (A)-1 (25 phr) was dissolved in propylene glycol methyl ether acetate (PGMEA) to prepare a compound solution with a mass concentration of 5%; then the compound solution was mixed and dissolved with polymer (B)-1 (100 phr) and alkaline neutralizer (C)-1 (3 phr), and the solvent PGMEA was added to bring the solid content to 1.4 wt% to obtain the photosensitive composition; 10 g of polymer (B)-1 was dissolved in PGMEA to prepare a 10% (w / w) resin solution. 2 g of the photosensitive composition was dissolved in γ-butyrolactone (GBL) to prepare a 5% (w / w) solution. 0.2 g of the alkaline neutralizer (C)-1 was dissolved in GBL to prepare a 1% (w / w) solution. The pre-dissolved solutions were prepared with a polymer mass of 100 parts, a photoacid-producing agent mass fraction of 25 parts relative to the polymer mass, and an alkaline compound mass fraction of 3 parts relative to the polymer mass. The excess GBL and PGMEA in the pre-dissolved solvent were added at a mass ratio of 1:5 to obtain a solution with a 14% solids content, thus yielding the photosensitive composition. Polymer (B)-1 has a Mw of 4317 and a PDI of 1.37; polymer (B)-1 comprises structural units with the following molar percentages: (35 mol%) (10 mol%) (50 mol%) (5 mol%) The structural formula of alkaline neutralizer (C)-1 is shown below: ; The photosensitive composition is coated onto the substrate by spin coating, and after pre-baking, electron beam exposure, post-baking, and development, a patterned film is formed on the substrate.

[0098] Take 1 mL of spin-coated carbon (SOC) and spin-coat it onto the surface of a silicon wafer to form a 200 nm substrate film. Take 0.5 mL of the prepared photosensitive composition and spin-coat it onto the above-mentioned base film to form a 20 nm photosensitive film. Then, the photosensitive film layer was pre-baked at 80℃ for 1 min to obtain the pre-baked photosensitive film layer; the surface roughness of the pre-baked photosensitive film layer was tested, and the results are shown in Table 2. The photosensitive film layer after pre-baking was exposed using an i-line exposure device. After exposure, it was post-baked at 80°C for 1 min to obtain a patterned film.

[0099] Example 2 The only difference from Example 1 is that compound (A)-1 is replaced with compound (A)-2: .

[0100] (A)-2 Example 3 The only difference from Example 1 is that compound (A)-1 is replaced with compound (A)-3: .

[0101] (A)-3 Example 4 The only difference from Example 1 is that polymer (B)-1 is replaced with polymer (B)-2, which has a Mw of 4625 and a PDI of 1.32; polymer (B)-2 comprises structural units with the following molar percentages: (50 mol%) (37 mol%) (10 mol%) (3mol%); the 1H NMR spectrum of polymer (B)-2 is as follows: Figure 2 As shown.

[0102] Example 5 The only difference from Example 1 is that compound (A)-1 is replaced with compound (A)-4: .

[0103] (A)-4 Comparative Example 1 The only difference from Example 1 is that compound (A)-1 is replaced with compound (D)-1: .

[0104] (D)-1 Comparative Example 2 The only difference from Example 1 is that compound (A)-1 is replaced with compound (D)-2: .

[0105] (D)-2 Comparative Example 3 The only difference from Example 1 is that compound (A)-1 is replaced with compound (D)-3: .

[0106] (D)-3 The types and contents of each component in the photosensitive compositions of Examples 1-5 and Comparative Examples 1-3 are shown in Table 1.

[0107] Table 1

[0108] In Table 1, phr (Parts Per Hundred of Resin) refers to the number of parts by mass of each component in the photosensitive composition relative to the polymer in 100 parts by mass; PGMEA is propylene glycol methyl ether acetate.

[0109] Performance testing Film thickness: The film thickness of the patterned films prepared by the photosensitive compositions of Examples 1-5 and Comparative Examples 1-3 were tested according to the elliptic polarization method specified in GB / T 30867-2014. The results are shown in Table 2.

[0110] Roughness (Ra): The roughness of the patterned films prepared by the photosensitive compositions of Examples 1-5 and Comparative Examples 1-3 were tested according to the method specified in GB / T 3505-2009. The results are shown in Table 2.

[0111] Film loss after 60s development: The difference in film thickness before and after development of the photosensitive films prepared by the photosensitive compositions of Examples 1-5 and Comparative Examples 1-3 was measured according to the method specified in GB / T 30791-2014. The results are shown in Table 2. (Development conditions: 23°C, using 2.38wt% tetramethylammonium hydroxide (TMAH), development for 60s).

[0112] Resolution: The photosensitive film layers prepared by the photosensitive compositions of Examples 1-5 and Comparative Examples 1-3 were exposed using a 365 nm i-line exposure machine according to the method specified in GB / T 32120-2015. The patterned film obtained after exposure was tested according to the method specified in Appendix B (Near Field Mask Lattice Method) of GB / T 30904-2014. The smallest resolvable circular aperture diameter was reported. Specifically, CD-SEM was used for observation. The measured resolution is shown in Table 2.

[0113] The absorption spectrum of the photosensitive composition of Example 1 is shown below. Figure 3 As shown, from Figure 3 It can be seen that the photosensitive composition has extremely high absorbance at a wavelength of 365 nm. The pattern morphology after exposure in Example 1 is shown below. Figure 4 The pattern has a linewidth of 40 nm and a pitch of 100 nm. Figure 4 It can be seen that the patterned film prepared by the photosensitive composition of Example 1 has a small line width roughness (LWR) and a good line width uniformity (CDU).

[0114] Table 2

[0115] As can be seen from Table 2, Examples 1-5 of this application, by adding compounds with special structures to the photosensitive composition, enable the photosensitive composition to effectively suppress acid diffusion while having high absorption efficiency for the exposure light source, thereby improving its exposure performance and the accuracy of the obtained pattern. It has low surface roughness and small film loss, while having good resolution, thereby improving the performance of semiconductor devices.

[0116] The anionic moiety in the compound provided in Comparative Example 1 differs from that in Example 1 of this application, and the cationic moiety in the compounds provided in Comparative Examples 2 and 3 differs from that in Example 1 of this application. Compared with Comparative Examples 1-3, the embodiments of this application can significantly improve their exposure performance by selecting suitable anions and cations and choosing special groups for specific sites. The pattern morphology after exposure in Example 1 is shown below. Figure 4 ,from Figure 4 It can be seen that the patterned film prepared by the photosensitive composition of Example 1 has a small line width roughness (LWR) and a good line width uniformity (CDU).

[0117] It should be understood that the use of the terms "first," "second," and various numerical designations in this document is merely for descriptive convenience and is not intended to limit the scope of this application.

[0118] In this application, "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone, where A and B can be singular or plural. The character " / " generally indicates that the related objects before and after it are in an "or" relationship.

[0119] In this application, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b or c", or "at least one of a, b and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc or abc, where a, b, and c can be single or multiple.

[0120] In this application, "-" indicates a range value, including the endpoint values ​​at both ends. For example, the value of a can be 0.5-15, meaning that the value of a can be between 0.5 and 15, and includes the endpoint values ​​of 0.5 and 15.

[0121] It should be understood that in the various embodiments of this application, the order of the above processes does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.

[0122] The above description represents the preferred embodiments of this application, but should not be construed as limiting the scope of this application. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of this application, and these improvements and modifications are also considered to be within the scope of protection of this application.

Claims

1. A compound, characterized in that, The compound comprises a cation and an anion, and the structure of the cation is shown in formula (I): (Ⅰ)； Wherein, R1 is a halogen atom or a group containing an ethynyl group; R2, R3, R4, R5, and R6 are independently selected from hydrogen atoms, halogen atoms, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, C1-C20 alkoxy groups, aryloxy groups, and -SO2R groups. A -OSO2R B -COR C -COOR D -CONR E R F –PO(OR) G )2、-SR H R is any one of mercapto, substituted or unsubstituted amino, hydroxy, nitro and cyano groups, wherein R A R B R C R D R E R F R G R H The alkyl groups are each independently selected from any one of substituted or unsubstituted alkyl groups and aryl groups, and R2, R3, R4, R5, and R6 are not all hydrogen atoms; The anion is X. - The X - The structure is shown in equation (Ⅱ): (Ⅱ)； R7 is selected from one or more of hydrogen atoms, substituted or unsubstituted C1-C30 alkyl groups, substituted or unsubstituted alicyclic groups, and substituted or unsubstituted aromatic cyclic groups; R8 is a substituted or unsubstituted alkylene group.

2. The compound according to claim 1, characterized in that, The R1 is selected from any one of Cl, Br, I, or groups as shown in formulas (Ⅲ-1)-(Ⅲ-5): (Ⅲ-1)； (Ⅲ-2)； (Ⅲ-3)； (Ⅲ-4)； (Ⅲ-5)。 3. The compound according to claim 1, characterized in that, At least one of R2, R3, R4, R5, and R6 is a C1-C3 alkyl group; and / or, R4 is not a hydrogen atom.

4. The compound according to claim 1, characterized in that, The anion is selected from any one of the groups shown in formulas (II-1)-(II-15): (Ⅱ-1)； (Ⅱ-2)； (Ⅱ-3)； (Ⅱ-4)； (Ⅱ-5)； (Ⅱ-6)； (Ⅱ-7)； (Ⅱ-8)； (Ⅱ-9)； (Ⅱ-10)； (Ⅱ-11)； (Ⅱ-12)； (Ⅱ-13)； (Ⅱ-14)； (Ⅱ-15)。 5. A photosensitive composition, characterized in that, The photosensitive composition comprises the compound, polymer, and solvent as described in any one of claims 1-4.

6. The photosensitive composition according to claim 5, characterized in that, In the photosensitive composition, the mass percentage of the compound is 0.05%-4%.

7. The photosensitive composition according to claim 5, characterized in that, The polymer comprises one or more repeating structural units as shown in formulas (Ⅳ-1)-(Ⅳ-4): (Ⅳ-1)； (Ⅳ-2)； (Ⅳ-3)； (Ⅳ-4)。 8. The photosensitive composition according to claim 6, characterized in that, In the photosensitive composition, the mass ratio of the compound to the polymer is (5-40):

100.

9. The photosensitive composition according to claim 5, characterized in that, The photosensitive composition further includes an alkaline neutralizing agent, which includes one or more of a nitrogen-containing compound containing a primary amine group, a nitrogen-containing compound containing a secondary amine group, and a nitrogen-containing compound containing a tertiary amine group.

10. The photosensitive composition according to claim 5, characterized in that, In the photosensitive composition, the mass ratio of the alkaline neutralizer to the polymer is (0.1-15):

100.

11. A patterned film, characterized in that, The patterned film is formed using the photosensitive composition as described in any one of claims 5-10.

12. An electronic device, characterized in that, The electronic device includes a patterned substrate and a functional layer disposed on the patterned substrate; the patterned substrate is obtained by etching a substrate having a patterned film as described in claim 11 on its surface.

13. A method for fabricating an electronic device, characterized in that, include: The photosensitive composition as described in any one of claims 5-10 is coated onto a substrate to form a film layer on the substrate; The film layer is exposed and developed using a photomask to form a patterned film on the substrate; Etching yields a patterned substrate; The functional layer is fabricated to obtain the electronic device.

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