Patterned compositions and their use

Abstract

The present application provides a kind of patterning composition and its application.The patterning composition includes fluorine-containing main body resin, photoacid generator and fluorine-containing additive, fluorine-containing main body resin includes acid-labile repeating unit, lactone structure bearing repeating unit and hexafluoroisopropanol structure bearing repeating unit, and the repeating unit of fluorine-containing main body resin has aliphatic ring structure;Fluorine-containing additive includes repeating unit derived from fluorine-containing monomer A with hexafluoroisopropanol structure and repeating unit derived from fluorine-containing monomer B with aliphatic ring structure.The film layer of the above-mentioned patterning composition can resist the dissolution of photoacid generator when immersed exposure, and can finally form the patterned film with required shape and resolution.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of patterning technology, in particular to a patterning composition and application thereof. BACKGROUND

[0002] The manufacturing process of semiconductor integrated circuits usually involves a patterning process. The patterning material used in the patterning process is generally a chemical amplification type patterning composition including a main resin having an acid-labile group and a photosensitive photo acid generator (PAG). In the mainstream immersion patterning process, it is necessary to avoid direct contact of the patterning material with water and the like, so as to prevent the PAG from dissolving out and thus failing to obtain a pattern with a required shape and / or resolution. For this purpose, the industry usually applies a waterproof topcoat on the patterning material film layer to prevent the patterning material film layer from contacting water and the like, but this increases the process steps of the patterning process.

[0003] To reduce the steps of the patterning process and improve efficiency, the industry proposes to introduce a small amount of fluorine-containing polymer as an additive into the patterning composition to form a barrier layer similar to the function of the topcoat. The principle is that the fluorine-containing polymer can float to the surface of the film layer during the film formation of the patterning composition and thus play a role in blocking water and the like. However, this scheme is generally only suitable for patterning compositions with a main resin not containing fluorine. Adding a conventional fluorine-containing additive to a patterning composition containing a fluorine-containing main resin presents certain technical challenges, mainly because the fluorine-containing additive interacts with the fluorine-containing repeating units in the main resin and thus there is a risk that it cannot completely float, so that the patterning material film layer performs poorly in terms of water blocking and PAG dissolution resistance. SUMMARY

[0004] In view of this, the present application provides a patterning composition and application thereof. By introducing a fluorine-containing additive with a specific structure into a patterning composition containing a fluorine-containing main resin, the topcoat process is avoided, so that the patterning composition containing the same can be successfully and conveniently used in an immersion patterning process, ensuring uniform distribution of the components, a large contact angle of the film layer with water, a small amount of dissolubles during immersion exposure, and finally obtaining a patterned film with a required shape and resolution.

[0005] Specifically, the first aspect of the embodiments of the present application provides a patterning composition, comprising a fluorine-containing main resin, a photoacid generator and a fluorine-containing additive, wherein the fluorine-containing main resin comprises an acid-labile repeating unit with an acid-labile aliphatic ring structure, a repeating unit with a lactone structure and a repeating unit with a hexafluoroisopropanol structure; the repeating unit with a hexafluoroisopropanol structure further comprises an aliphatic ring structure connected with a hexafluoroisopropanol structure; wherein the fluorine-containing additive is a polymer comprising a repeating unit derived from a fluorine-containing monomer A and a repeating unit derived from a fluorine-containing monomer B, wherein the fluorine-containing monomer A comprises a hexafluoroisopropanol structure, the fluorine-containing monomer B comprises an aliphatic ring structure, and the molar proportion of the repeating unit derived from the fluorine-containing monomer B in the fluorine-containing additive is 10%-70%.

[0006] The above-mentioned fluorine-containing additive simultaneously comprises a fluorine-containing repeating unit A with a hexafluoroisopropanol structure and a fluorine-containing repeating unit B with an aliphatic ring structure, the aliphatic ring structure in the latter and the former can ensure good compatibility between the fluorine-containing additive and the above-mentioned fluorine-containing main resin, and the two will not separate to cause uneven coating film or film defects of the composition containing them, meanwhile, the fluorine and the fluorine-containing repeating unit A in the latter can make the fluorine-containing additive smoothly float to the surface of the film layer during the coating and film forming process of the patterning composition, and it can play the functions of hydrophobicity and blocking PAG dissolution during immersion exposure, and the hexafluoroisopropanol structure in the fluorine-containing repeating unit A can facilitate the fluorine-containing additive to be washed away by the alkaline developer in the subsequent development process, so that the patterning film with required shape and resolution can be formed by using the patterning composition.

[0007] In the embodiments of the present application, the above-mentioned fluorine-containing monomer A comprises a structure represented by formula (A), and the fluorine-containing monomer B comprises a structure represented by formula (B):

[0008] Formula (A) Formula (B)

[0009] wherein, R a , R b are independently selected from a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, L1 is a divalent linking group, R1 comprises a hexafluoroisopropanol structure ; L2 is a single bond or a divalent linking group, R2 is a substituted or unsubstituted aliphatic ring structure, and at least one of L2 and R2 has a fluorine atom, but -L2-R2 does not comprise the hexafluoroisopropanol structure.

[0010] wherein, the fluorine-containing monomer A with a hexafluoroisopropanol structure can or can not comprise an aliphatic ring structure, the fluorine-containing monomer B comprises a hexafluoroisopropanol structure but does not comprise a hexafluoroisopropanol structure, and the fluorine-containing additive formed by polymerization of the two kinds of fluorine-containing monomers can effectively play the above-mentioned hydrophobicity and PAG dissolution blocking effect.

[0011] In some embodiments of the present application, L1is selected from one or more of substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, and lactone ring, with or without a heteroatom linking group; wherein the heteroatom linking group comprises at least one of -C(=O)-O- # and -O-C(=O)- # , and the # end is adjacent to R1.

[0012] L1is selected from the above groups, so that the monomer with the structure of hexafluoroisopropanol connected with L1is easy to obtain, and can make the above-mentioned fluorine-containing additive have substantially no absorption in the ultraviolet region without affecting the photosensitivity of the patterning material film layer, and has good solubility in alkaline developer.

[0013] In some embodiments of the present application, in R2, the substituents in the substituted aliphatic ring structure include one or more of fluorine atoms, fluorinated alkyl ester groups, and fluorinated alkyl groups.

[0014] In this case, the substituted aliphatic ring structure containing fluorine atoms in R2is more helpful for the above-mentioned fluorine-containing additive to be completely floated in the patterning composition containing the fluorine-containing main resin, thereby playing a good hydrophobic and PAG dissolution prevention effect.

[0015] In some embodiments of the present application, the fluorine-containing monomer A includes one or more of the following substances:

[0016]

[0017] .

[0018] In some embodiments of the present application, the fluorine-containing monomer B includes one or more of the following substances:

[0019]

[0020] .

[0021] In some embodiments of the present application, the mole ratio of the repeating unit derived from the fluorine-containing monomer B in the fluorine-containing additive is 10%-70%.

[0022] In this case, the fluorine-containing additive and the fluorine-containing main resin have good compatibility and do not separate, so that the coating film of the patterned composition is uniform, and the fluorine-containing additive and the fluorine-containing main resin have certain difference, so that the fluorine-containing additive can float to the surface of the film during the coating process of the patterned composition, and the functions of hydrophobicity, PAG dissolution resistance and reduction of pattern watermark defects can be played.

[0023] In some embodiments of the present application, the mass of the fluorine-containing additive is 0.5%-10% of the mass of the fluorine-containing main resin. Controlling the amount of the fluorine-containing additive relative to the fluorine-containing main resin in an appropriate range can ensure that the fluorine-containing additive can fully play the role of hydrophobicity and PAG dissolution resistance during immersion exposure, and can also prevent the film from developing defects after exposure of the patterned composition.

[0024] In some embodiments of the present application, the mole fraction of the acid-labile repeating unit in the fluorine-containing main resin can be 10-70%, the mole fraction of the lactone-containing repeating unit can be 5-80%, and the mole fraction of the hexafluoroisopropanol-containing repeating unit can be 1%-20%. The fluorine-containing main resin meeting the condition is a commonly used fluorine-containing resin in the patterned composition.

[0025] In some embodiments of the present application, the patterned composition further comprises an acid quencher. The presence of the acid quencher can help quench the excessive photoacid generated in the exposure process of the fluorine-containing main resin, and avoid the pattern resolution formed by using the patterned composition being too low.

[0026] In some embodiments of the present application, the patterned composition further comprises an organic solvent, and the organic solvent comprises one or more of a ketone solvent, an ester solvent, an ether solvent and an alcohol solvent.

[0027] The second aspect of the embodiments of the present application provides a patterned film formed by the patterned composition of the first aspect of the embodiments of the present application. The patterned film can be formed by a patterned process comprising exposure, baking, development and the like after coating the patterned composition.

[0028] The third aspect of the embodiments of the present application provides a patterned substrate, and the pattern on the patterned substrate is formed by the patterned composition of the first aspect of the embodiments of the present application. The pattern on the patterned substrate can be transferred from the patterned film formed by the patterned composition to the substrate. The patterned substrate can be used for the preparation of semiconductor devices such as chips, and the manufacturing precision and quality of the devices can be improved.

[0029] The fourth aspect of the embodiments of the present application provides a semiconductor device, which adopts the patterned film according to the second aspect of the embodiments of the present application, or adopts the patterned substrate according to the third aspect of the embodiments of the present application. The semiconductor device can include a patterned substrate, and a device structure formed on the patterned substrate.

[0030] The embodiments of the present application also provide a method for preparing a semiconductor device, which includes:

[0031] The patterned composition according to the first aspect of the embodiments of the present application is coated on a substrate to form a patterned material film layer on the substrate;

[0032] The patterned material film layer is subjected to exposure, baking and developing with a developer in sequence to form a patterned film on the substrate.

[0033] In some embodiments of the present application, after the patterned film is formed, the method further includes transferring the pattern of the patterned film to a substrate to obtain a patterned substrate.

[0034] Further, after the patterned substrate is obtained, the method can further include forming a structure required by a semiconductor device on the patterned substrate. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 A flowchart of a patterned process provided by the embodiments of the present application is shown.

[0036] Figure 2 SEM photos of the patterned films formed by the patterned process of the patterned composition of Example 1 and Comparative Example 1 subjected to immersion exposure with the mask plate Dense having a periodic line pattern are shown in Table 1; Figure 2 Table 1 (a) is the SEM photo of the patterned film of Example 1, Figure 2 Table 1 (b) is the SEM photo of the patterned film of Comparative Example 1.

[0037] Figure 3 SEM photos of the patterned films formed by the patterned process of the patterned composition of Example 1 and Comparative Example 1 subjected to immersion exposure with the mask plate Semi having a periodic line pattern are shown in Table 2; Figure 3 Table 2 (a) is the SEM photo of the patterned film of Example 1, Figure 3 Table 2 (b) is the SEM photo of the patterned film of Comparative Example 1.

[0038] Figure 4 SEM photos of the patterned films formed by the patterned process of the patterned composition of Example 1 and Comparative Example 1 subjected to immersion exposure with the mask plate Iso having a periodic line pattern are shown in Table 3; Figure 4Fig. 2 (a) is an SEM photograph of the patterned film of Example 1, Figure 4 Fig. 2 (b) is an SEM photograph of the patterned film of Comparative Example 1. DETAILED DESCRIPTION

[0039] The embodiments of the present application will be described below with reference to the accompanying drawings.

[0040] In the manufacturing process of semiconductor integrated circuits, a patterning process is an important process. The patterning process generally includes the following steps: (1) applying a patterning composition (such as a chemical amplification type patterning composition including a base resin having an acid-labile group and a photoacid generator) on a substrate to form a patterned material film layer; (2) irradiating the patterned material film layer with an exposure source through a mask plate having a predetermined pattern, i.e., performing selective exposure, to cause the photoacid generator in the irradiated area (i.e., the exposed area) to generate photoacid; during the post-exposure baking process, the photoacid can catalyze the deprotection of the acid-labile group in the base resin of the exposed area, so that the polarity of the base resin in the exposed area is increased, thereby causing the difference in solubility of the exposed area and the unexposed area to the developer; (3) after the exposure and baking, the patterned material film layer is subjected to a developer treatment, so as to selectively dissolve the film layer structure of the exposed area or the unexposed area, and leave a patterned film on the substrate having the same or opposite pattern as the mask; (4) in the etching process, the patterned film left is used to selectively protect the underlying material from being etched or slowly etched, so as to realize the transfer of the pattern to the underlying material, and finally realize the desired pattern on the substrate material.

[0041] Among them, the immersion type patterning process refers to a patterning process in which a liquid high refractive index medium such as pure water or a fluorine-based inert liquid is present between the lens of the exposure device and the patterned material film layer on the substrate during exposure. The introduction of the liquid medium can improve the resolution of the formed pattern. Since the patterned material film layer is in direct contact with the immersion exposure liquid such as water during exposure, the photoacid generator (PAG) and the like are easily dissolved out of the patterned material film layer. The more the amount of the dissolved-out substance, the more serious the damage to the lens, or the pattern shape cannot be obtained as required, and the resolution cannot be fully obtained.

[0042] To this end, the industry usually spin-coats a layer of water-resistant topcoat on the patterned material film to prevent it from contacting with liquid such as water, which increases the process of the patterning process and reduces the efficiency. The industry also proposes to directly introduce fluorine-containing polymer additives into the patterning composition, hoping that it can float to the surface of the film during the film-forming process of the composition and play a role in blocking liquid such as water, but this scheme is generally only suitable for the patterning composition whose main resin does not contain fluorine, because the conventional fluorine-containing additives interact with the fluorine-containing repeating units in the main resin and cannot achieve complete floating, affecting its role similar to topcoat. Based on this, the present application introduces a fluorine-containing additive with a specific structure into the patterning composition containing a fluorine-containing main resin to avoid the additional formation process of topcoat after forming the patterned material film, and the fluorine-containing additive can be well dispersed in the composition and can smoothly float to the surface of the film during the film-forming process of the composition and play a role in blocking liquid such as water, blocking PAG dissolution.

[0043] The embodiment of the present application provides a kind of patterning composition, including fluorine-containing main resin, photoacid generator and fluorine-containing additive.Therein, fluorine-containing main resin includes acid-labile repeating unit with acid-labile aliphatic ring structure, repeating unit with lactone structure and repeating unit with hexafluoroisopropanol structure The repeating unit with hexafluoroisopropanol structure also includes aliphatic ring structure connected with hexafluoroisopropanol structure. Wherein, fluorine-containing additive is polymer including repeating unit derived from fluorine-containing monomer A and repeating unit derived from fluorine-containing monomer B, fluorine-containing monomer A includes hexafluoroisopropanol structure, and fluorine-containing monomer B includes aliphatic ring structure.

[0044] In the above-mentioned patterning composition, the fluorine-containing main body resin includes the above-mentioned three types of repeating units each including an aliphatic ring structure (the lactone structure can be understood as a cyclic hydrocarbon group with an ester bond in the ring), and the above-mentioned fluorine-containing additive includes both a fluorine-containing repeating unit with a hexafluoroisopropanol structure (denoted as fluorine-containing repeating unit A) and a fluorine-containing repeating unit with an aliphatic ring structure (denoted as fluorine-containing repeating unit B). The aliphatic ring structure in the fluorine-containing repeating unit B and the fluorine-containing repeating unit A can ensure good compatibility between the fluorine-containing additive and the fluorine-containing main body resin, and the two will not separate to cause uneven coating or defects in the film of the composition containing them. At the same time, the above-mentioned fluorine-containing repeating unit B with an aliphatic ring structure also contains fluorine, which ensures that the fluorine-containing additive and the fluorine-containing main body resin are also different to some extent, which is beneficial to the fluorine-containing additive to float smoothly to the surface of the film during the coating and film forming process of the patterning composition, so that it can smoothly play the function of hydrophobicity and blocking PAG dissolution during immersion exposure. The presence of the fluorine-containing repeating unit A also helps to improve the hydrophobicity and improve the floating effect. In addition, in the case of using water as the immersion exposure liquid, the surface of the patterning material film formed by the above-mentioned patterning composition has a large static contact angle / advancing contact angle with water and good hydrophobicity, which is beneficial to the subsequent evaporation of water and reduces the pattern defects caused by water marks. The hexafluoroisopropanol structure in the fluorine-containing repeating unit A can facilitate the removal of the fluorine-containing additive by alkaline developer in the subsequent development process, so that the patterning composition can be used to form a patterned film with required shape and resolution.

[0045] Therefore, the patterning material film formed by the above-mentioned patterning composition has a large contact angle with water and a small amount of dissolved substances during immersion exposure, and finally a patterned film with required shape and resolution can be obtained. In addition, because the embodiment of the present application directly adds a fluorine-containing additive with a specific structure in the above-mentioned patterning composition, there is no need to add a topcoat forming process after the patterning material film before immersion exposure, which is beneficial to the simplification and efficiency improvement of the patterning process.

[0046] It is understood that the above-mentioned fluorine-containing additive can be a copolymer formed by polymerization of monomer raw materials including the fluorine-containing monomer A having a hexafluoroisopropyl alcohol structure and the fluorine-containing monomer B having a fatty ring structure. Among them, the fluorine-containing monomer B does not contain a hexafluoroisopropyl alcohol structure. Similarly, the above-mentioned fluorine-containing main body resin can be a polymer formed by polymerization of monomer raw materials including a monomer having an acid-labile fatty ring structure, a monomer having a lactone structure, and a monomer having a hexafluoroisopropyl alcohol structure connected to a fatty ring structure. The biggest difference between the fluorine-containing additive and the above-mentioned fluorine-containing main body resin in structure is that the fluorine-containing additive does not include a repeating unit having an acid-labile group. Although the fluorine-containing monomer B of the fluorine-containing additive includes a fatty ring structure, the fatty ring structure is not acid-labile. In addition, the fluorine-containing additive is used as an additive, and it is understood that the mass of the fluorine-containing additive is less than that of the fluorine-containing main body resin in the above-mentioned patterning composition.

[0047] In some embodiments of the present application, the above-mentioned fluorine-containing monomer A can include a structure represented by formula (A), and the above-mentioned fluorine-containing monomer B can include a structure represented by formula (B):

[0048] Formula (A) Formula (B)

[0049] wherein R a , R b are independently selected from a hydrogen atom (H), a fluorine atom (F), a methyl group (-CH3), or a trifluoromethyl group (-CF3); L1 is a divalent linking group, and R1 includes a hexafluoroisopropyl alcohol structure ; L2 is a single bond or a divalent linking group, R2 is a substituted or unsubstituted fatty ring structure, and at least one of L2 and R2 has a fluorine atom, but -L2-R2 does not include the hexafluoroisopropyl alcohol structure.

[0050] When at least one of L2 and R2 has a fluorine atom, the limitation that -L2-R2 does not include a hexafluoroisopropyl alcohol structure can ensure that the structure represented by formula (B) does not range-cross with the structure represented by formula (A), especially when L1 in formula A includes a fatty ring structure.

[0051] Correspondingly, the structure of the repeating unit derived from the fluorine-containing monomer A (which can be referred to as fluorine-containing repeating unit A) is represented by formula (A'), and the structure of the repeating unit derived from the fluorine-containing monomer B (which can be referred to as fluorine-containing repeating unit B) is represented by formula (B'):

[0052] Formula (A') Formula (B').

[0053] In formula (A) or formula (A'), L1is a divalent linking group, which can specifically be a divalent hydrocarbon group with or without a heteroatom-containing linking group. Specifically, L1may be selected from one or more of an alkylene group, a cyclic alkylene group (i.e., a cycloalkylene group), a chain or cyclic alkenylene group, a chain or cyclic alkynylene group, an arylene group, the aforementioned groups can or can not contain a heteroatom-containing linking group, and the aforementioned hydrocarbon groups can be substituted or unsubstituted. Among them, "chain" can be linear or branched. The number of carbon atoms of the alkylene group can be 1-20, further can be 1-10; the number of carbon atoms of the cycloalkylene group can be 3-20, further can be 4-10. The number of carbon atoms of the chain alkenylene group or the chain alkynylene group can be 2-20, and the number of carbon atoms of the cyclic alkenylene group or the cyclic alkynylene group can be 4-20.

[0054] Among them, the divalent hydrocarbon group without a heteroatom can be listed as methylene (-CH2-), ethylene (-CH2CH2-), -CH(CH3)-, n-propylene (-(CH2)3-), -C(CH3)2-, -CH(CH3)-CH2-, -CH(CH2CH3)-, -CH(CH2CH2CH3)-, -CH(CH2CH(CH3)2)-, -CH(CH2CH(CH3)2)-CH2-, -CH(CH(CH3)2)-, -CH(Cy)-CH2- (Cy represents cyclohexyl), butane-1,4-diyl (-(CH2)4-), pentane-1,5-diyl (-(CH2)5-), hexane-1,6-diyl (-(CH2)6-), heptane-1,7-diyl (-(CH2)7-), octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl, octadecylene, and the like saturated chain alkylene; cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, and the like monocyclic cycloalkylene, spirobicyclopentane-1,1'-diyl, spirobicyclohexane-1,1'-diyl, and the like divalent polycyclic cycloalkylene; phenylene, naphthylene, phenanthrylene, and the like arylene. t t Among them, the divalent hydrocarbon group without a heteroatom can be listed as methylene (-CH2-), ethylene (-CH2CH2-), -CH(CH3)-, n-propylene (-(CH2)3-), -C(CH3)2-, -CH(CH3)-CH2-, -CH(CH2CH3)-, -CH(CH2CH2CH3)-, -CH(CH2CH(CH3)2)-, -CH(CH2CH(CH3)2)-CH2-, -CH(CH(CH3)2)-, -CH(Cy)-CH2- (Cy represents cyclohexyl), butane-1,4-diyl (-(CH2)4-), pentane-1,5-diyl (-(CH2)5-), hexane-1,6-diyl (-(CH2)6-), heptane-1,7-diyl (-(CH2)7-), octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl, octadecylene, and the like saturated chain alkylene; cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, and the like monocyclic cycloalkylene, spirobicyclopentane-1,1'-diyl, spirobicyclohexane-1,1'-diyl, and the like divalent polycyclic cycloalkylene; phenylene, naphthylene, phenanthrylene, and the like arylene.

[0055] ​wherein the divalent hydrocarbon group can contain a heteroatom linking group, which can be located between some carbon atoms in the divalent hydrocarbon group or at the end thereof. Exemplary heteroatom linking groups can include, but are not limited to, one or more of an ether bond (-0-), a sulfide bond (-S-), a carbonyl group (-C(=0)-), -C(=0)-0-, -0-C(=0)-, an imine bond (-NH-), an amide bond (-NHCO-), a carbamate bond (-NH-COO-), a sulfonyl bond (-S02-), a sulfonate bond (-0-S(=0)2-), -0-C(=0)-0-, -C(=0)-0-C(=0)-, and the like. Among them, a cyclic divalent hydrocarbon group containing the heteroatom linking group -C(=0)-0- in the ring skeleton can be referred to as a lactone ring, and such a lactone ring can also serve as a 2-valent linking group. Exemplary lactone rings can be a gamma-butyrolactone ring, a norbornene lactone ring, an adamantane lactone ring, and the like. A cyclic divalent hydrocarbon group containing the heteroatom linking group -0-S(=0)2- in the ring skeleton can be referred to as a sulfolactone ring, and can also serve as a 2-valent linking group. A cyclic divalent hydrocarbon group containing -0- in the ring skeleton can be referred to as a divalent internal ether ring, and a fatty ring structure containing a sulfide bond -S- in the ring skeleton can be referred to as an internal sulfide ring. A cyclic divalent hydrocarbon group containing the -0-C(=0)-0- group in the ring skeleton can be referred to as a cyclic carbonate ring. A cyclic divalent hydrocarbon group containing the heteroatom linking group -NHCO- in the ring skeleton can be referred to as a lactam ring.

[0056] In some embodiments of the present application, L1may be selected from one or more of substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, lactone ring, which can or can not contain a heteroatom linking group. Among them, the heteroatom linking group at least includes at least one of -C(=0)-0- and -0-C(=0)-, and the # end is close to R1. That is, L1may be selected from one or more of substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, lactone ring, substituted or unsubstituted alkylene containing at least one of -C(=0)-0- and -0-C(=0)-, substituted or unsubstituted cycloalkylene linked with at least one of -C(=0)-0- and -0-C(=0)-, and lactone ring linked with at least one of -C(=0)-0- and -0-C(=0)-. As described previously, the heteroatom linking group here is located between some carbon atoms or at the end of these divalent hydrocarbon groups. # and -0-C(=0)- # Among them, the heteroatom linking group at least includes at least one of -C(=0)-0- and -0-C(=0)-, and the # end is close to R1. That is, L1may be selected from one or more of substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, lactone ring, substituted or unsubstituted alkylene containing at least one of -C(=0)-0- and -0-C(=0)-, substituted or unsubstituted cycloalkylene linked with at least one of -C(=0)-0- and -0-C(=0)-, and lactone ring linked with at least one of -C(=0)-0- and -0-C(=0)-. As described previously, the heteroatom linking group here is located between some carbon atoms or at the end of these divalent hydrocarbon groups.

[0057] L1is selected from the above-mentioned groups, so that the monomer with the structure of hexafluoroisopropanol connected with L1is relatively easy to obtain, and can make the above-mentioned fluorine-containing additive have substantially no absorption in the ultraviolet region without affecting the photosensitivity of the patterned material film layer, and have good solubility in alkaline developer.

[0058] The substituents in the substituted alkylene group can include, but are not limited to, one or more of a halogen atom, a hydroxyl group (-OH), a cyano group (-CN), a carboxyl group (-COOH), an alkoxy group, a substituted or unsubstituted cycloalkyl group, etc. The substituents in the substituted cycloalkylene group can include, but are not limited to, one or more of a halogen atom, a hydroxyl group, a cyano group, a carboxyl group, a substituted or unsubstituted alkyl group (the substituents in the substituted alkyl group can refer to the substituents in the substituted alkylene group), an alkoxy group, etc. It can be understood that, in some cases, the substituted or unsubstituted alkylene / cycloalkylene group containing at least one of C(=O)-O- and -O-C(=O)- can also include other heteroatom-containing linking groups.

[0059] In some possible embodiments of the present application, the above-mentioned fluorine-containing monomer A includes one or more of the following:

[0060] (A1) (A2) (A3) (A4) (A5) (A6) (A7)

[0061] (A8) (A9) (A10).

[0062] In the above-mentioned formula (B) or formula (B'), if L2 is a single bond, R2 is a substituted aliphatic ring structure containing a fluorine atom (i.e., an aliphatic ring structure containing a fluorine-containing substituent). If L2 is a divalent linking group, R2 is a substituted or unsubstituted aliphatic ring structure, and at least one of L2 and R2 contains a fluorine atom. In this case, L2 is a divalent linking group containing a fluorine atom, and / or R2 is a substituted aliphatic ring structure containing a fluorine atom. The substituents in the substituted aliphatic ring structure containing a fluorine atom can specifically include a fluorine-containing substituent (e.g., one or more of a fluorine atom, a fluoroalkyl group, a fluoroalkyl ester group, etc.), and in some cases, can also include other substituents. The fluoroalkyl ester group can be represented as -O-C(=O)-R''- or -C(=O)-O-R'', and R'' is a fluoroalkyl group.

[0063] For L2, which is a divalent linking group herein, reference is made to the foregoing explanation of L1. In some embodiments, L2 is a single bond, or one or more of a substituted or unsubstituted alkylene group, with or without heteroatom linking groups, a substituted or unsubstituted cycloalkylene group, with or without heteroatom linking groups. Heteroatom linking groups include, but are not limited to, one or more of -0-, -S-, -0-S(=0)2-, -C(=0)-0-, -0-C(=0)-0-, -C(=0)-0-C(=0)-, and the like. If L2 contains a fluorine atom, it is to be understood that the fluorine atom can be in a substituted alkylene group, or in a substituted cycloalkylene group.

[0064] For R2in Formula (B) or Formula (B'), the substituted or unsubstituted aliphatic cyclic structure can be a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group, with or without heteroatom linking groups. Heteroatom linking groups include, for example, one or more of -0-, -S-, -0-S(=0)2-, -C(=0)-0-, -0-C(=0)-0-, -C(=0)-0-C(=0)-, and the like.

[0065] wherein the substituents in the substituted aliphatic cyclic structure can be one or more, and can include, but are not limited to, one or more of a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, an ester group (-0-C(=0)-R" or -C(=0)-0-R", R" including an alkyl group, a fluoroalkyl group, or a cycloalkyl group, and the like), a substituted or unsubstituted alkyl group (e.g., the substituents of the substituted alkyl group include one or more of a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, an alkoxy group, and the like), a substituted or unsubstituted alkoxy group (the substituents of the substituted alkoxy group can be referred to the substituents of the substituted alkyl group), a substituted or unsubstituted cycloalkyl group (e.g., the substituents include a halogen atom, a substituted or unsubstituted alkyl group, and the like), and the like.

[0066] In some embodiments, the substituents in the substituted aliphatic cyclic structure in R2include one or more of a fluorine atom, a fluoroalkyl ester group, a fluoroalkyl group. These substituted aliphatic cyclic structures containing fluorine atoms are more helpful for the above-mentioned fluorine-containing additives to float up completely in the above-mentioned patterning composition containing the fluorine-containing host resin, and to play a good hydrophobic effect and prevent PAG from dissolving out.

[0067] In some embodiments of the present application, R2may include one or more of the following substituted or unsubstituted groups: adamantane ring, norbornane ring, norbornane lactone ring, adamantane lactone ring. In such a case, such R2can ensure good compatibility between the fluorine-containing additive and the fluorine-containing host resin with aliphatic cyclic structure. In addition, the R2group can also provide a certain hydrophobic effect, increase the surface contact angle of the film layer formed by the above-mentioned patterning composition, and adjust the dissolution rate of the fluorine-containing additive in the alkaline developer.

[0068] In some possible embodiments of the present application, the fluorine-containing monomer B described above can include one or more of the following:

[0069]

[0070] .

[0071] It can be understood that, in some embodiments of the present application, the fluorine-containing additive described above can further include other repeating units in addition to the repeating unit A and the repeating unit B described above. In the embodiments of the present application, the structure of the other repeating units in the fluorine-containing additive is not limited.

[0072] In some embodiments of the present application, the mole ratio of the fluorine-containing repeating unit B derived from the fluorine-containing monomer B with a fatty ring structure in all repeating units of the fluorine-containing additive can be 10%-70%. This effectively ensures that the fluorine-containing additive has certain differences from the fluorine-containing main resin, which is beneficial for the fluorine-containing additive to float to the surface of the film layer during the coating and film forming process of the patterned composition described above, so that it can play the role of hydrophobicity and blocking PAG dissolution during immersion exposure. Specifically, the mole ratio can be 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, etc.

[0073] In some possible embodiments of the present application, the mole ratio of the fluorine-containing repeating unit B in the fluorine-containing additive is 30%-60%. In this case, it is more beneficial for the fluorine-containing additive to have good compatibility with the fluorine-containing main resin, so that it will not separate to cause uneven coating and pattern defects of the patterned composition described above, and it is also more beneficial for the fluorine-containing additive to float to the surface of the film layer during the coating and film forming process of the patterned composition containing the fluorine-containing main resin, so that it can play the functions of hydrophobicity, blocking PAG dissolution and reducing pattern watermark defects.

[0074] In some embodiments of the present application, the mole ratio of the fluorine-containing repeating unit A with a hexafluoroisopropanol structure in the fluorine-containing additive can be 90% or less, for example, 20%-90%, and specifically can be 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, or 85%, etc. In some embodiments, the mole ratio of the fluorine-containing repeating unit A in the fluorine-containing additive is 30%-90%. In this case, the fluorine-containing additive including the fluorine-containing repeating unit A and the fluorine-containing repeating unit B with a fatty ring structure can better play the roles of hydrophobicity, blocking PAG dissolution and reducing pattern watermark defects.

[0075] For example, the fluorine-containing additive described above can be prepared by the following method: in the presence of an initiator, polymerizing monomer raw materials for synthesizing the fluorine-containing additive in a solvent to obtain the fluorine-containing additive; wherein the monomer raw materials include a fluorine-containing monomer A with a hexafluoroisopropanol structure and a fluorine-containing monomer B with a fatty ring structure.

[0076] The initiator described above can be a hydroperoxide, a dialkyl peroxide, a diacyl peroxide, an azo compound, or the like radical polymerization initiator. The temperature of the polymerization reaction described above can be 40-150°C, for example, specifically 60°C, 70°C, 80°C, 100°C, 110°C, 120°C, 130°C, or the like. The time of the polymerization reaction can be 1-48 hours, which can be adjusted according to the molecular weight of the fluorine-containing additive required.

[0077] In addition, after the polymerization reaction described above is completed, the reaction material containing the fluorine-containing additive can be placed in a settling agent (such as methanol, ethanol, isopropanol, or the like) for settling to precipitate the fluorine-containing additive.

[0078] In the embodiments of the present application, the mass of the fluorine-containing additive in the patterning composition described above is less than that of the fluorine-containing main resin. In some embodiments of the present application, the mass of the fluorine-containing additive described above is 0.5%-10% of the mass of the fluorine-containing main resin, for example, specifically 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 9.5%, or the like. Controlling the amount of the fluorine-containing additive relative to the fluorine-containing main resin within an appropriate range can not only ensure that it can fully play a role in hydrophobicity and PAG dissolution blocking during immersion exposure, but also can prevent the film layer of the patterning composition after exposure from developing defects due to excessive use.

[0079] In the embodiments of the present application, the acid-labile repeating unit with an acid-labile group in the fluorine-containing main resin described above ensures that the resin can undergo bond cleavage of the acid-labile group during the baking process after exposure through photoacid catalysis, so that the polarity of the resin changes (for example, the acid-labile group can be converted into a carboxyl group, so that the resin becomes alkali-soluble).

[0080] In some embodiments of the present application, the acid-labile repeating unit can have a structure shown in formula (I):

[0081] Formula (I)

[0082] wherein, R c includes a hydrogen atom, a methyl group (-CH3), or a trifluoromethyl group (-CF3), and AL includes an acid-labile group, which includes a fatty ring structure. That is, the fatty ring structure is acid-labile. In some embodiments, AL can be -C(R3)3, each R3 is independently selected from C 1-20 alkyl or C 3-20cycloalkyl, and any two R3may be bonded to each other to form a ring.

[0083] Here, "any two R3are bonded to each other to form a ring" means that any two R3may be bonded to each other, and together with the carbon atom to which each is bonded, form a divalent alicyclic hydrocarbon group. The alicyclic structure included in the acid-labile group AL can be a monocyclic alicyclic structure (e.g., a cyclopentane ring, a cyclohexane ring), or a polycyclic alicyclic structure (e.g., an adamantane ring, a norbornane ring), etc. Under photoacid catalysis with heat treatment, the AL group in formula (I) can undergo bond cleavage, resulting in the conversion of -COO-AL in formula (I) to a polar group -COOH.

[0084] In some embodiments of the present application, the acid-labile repeating unit described above can include a repeating unit derived from at least one monomer selected from the group consisting of:

[0085] .

[0086] The repeating unit having a lactone structure in the fluorine-containing base resin described above can help to enhance the adhesion between the dried film layer of the patterning composition described above and the adherend, and to improve the dry-etch resistance of the film layer.

[0087] As described previously in the present application, the alicyclic structure in the ring skeleton containing a -C(=O)-O- group can be referred to as a lactone structure. The alicyclic structure can or can not have a substituent group (i.e., the lactone structure can or can not have a substituent group). The substituent group on the alicyclic structure can be as described previously in the present application with respect to the substituent group in the substituted alicyclic structure in R2. In addition, it should be noted that the ring skeleton of the lactone structure can contain one or more of -O-, -S-, etc. in addition to the -C(=O)-O- group.

[0088] For example, the repeating unit of the lactone structure described above can be selected from one or more of the following structures:

[0089]

[0090]

[0091] .

[0092] In the repeating units described above, R d is independently selected from a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0093] The repeating unit with the hexafluoroisopropanol structure helps to enhance the solubility of the fluorine-containing base resin in the developing solution, and accordingly increases the developing effect of the above-mentioned patterning composition.

[0094] In some embodiments of the present application, the repeating unit with the hexafluoroisopropanol structure in the fluorine-containing base resin can be shown as formula (II):

[0095] Formula (II)

[0096] In formula (II), L1' is a divalent linking group comprising a cycloaliphatic structure.

[0097] For the divalent linking group, reference can be made to the explanation of L1 in formula (A') in the application. The difference between L1' in formula (II) and L1 in formula (A') is that L1' must comprise a cycloaliphatic structure. L1 may or may not comprise a cycloaliphatic structure.

[0098] In formula (II), the cycloaliphatic structure can be a divalent substituted or unsubstituted cycloalkylene group (in the same chain as the -COO- group in formula (II)), or a monovalent substituted or unsubstituted cycloalkyl group (i.e., it is not in the same chain as the -COO- group in formula (II), and it is a substituent on a carbon atom in the main chain of L1').

[0099] For example, the repeating unit shown in formula (II) can be derived from one or more of the following monomers:

[0100] .

[0101] It can be understood that in some embodiments of the present application, the above-mentioned fluorine-containing base resin further comprises other repeating units, which are different from the above-mentioned acid-labile repeating unit, the repeating unit with the lactone structure, and the repeating unit with the hexafluoroisopropanol structure. In the embodiments of the present application, the structure of the other repeating units in the fluorine-containing base resin is not limited.

[0102] In some embodiments of the present application, in addition to the repeating unit with the hexafluoroisopropanol structure containing fluorine atoms, one or more of the acid-labile repeating unit, the repeating unit with the lactone structure, or the other repeating unit can also contain fluorine atoms, but all the repeating units of the fluorine-containing base resin do not contain fluorine.

[0103] In some embodiments of the present application, the acid-labile repeating unit in the fluorine-containing main resin can account for 10-70% by mole, the lactone-containing repeating unit can account for 5-80% by mole, and the hexafluoroisopropanol-containing repeating unit can account for 1-20% by mole. The mole percentage of each of the repeating units refers to the mole percentage of the repeating unit in all repeating units in the fluorine-containing main resin.

[0104] In some embodiments, the acid-labile repeating unit in the fluorine-containing main resin can account for 30-65% by mole, for example, specifically 35%, 40%, 45%, 48%, 50%, 52%, 55%, 58%, or 60%, etc. The lactone-containing repeating unit in the fluorine-containing main resin can account for 30-60% by mole, for example, specifically 32%, 35%, 40%, 42%, 45%, 47%, 48%, 50%, 52%, or 55%, etc. The hexafluoroisopropanol-containing repeating unit in the fluorine-containing main resin can account for 2-15% by mole, for example, specifically 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or 12%, etc.

[0105] Similar to the synthesis of the fluorine-containing additive described above, the fluorine-containing main resin described above can also be obtained by polymerization of corresponding monomer raw materials in a solvent in the presence of an initiator.

[0106] In some embodiments of the present application, the acid-labile repeating unit in the fluorine-containing main resin described above corresponds to a monomer comprising and The lactone-containing repeating unit corresponds to a monomer comprising The hexafluoroisopropanol-containing repeating unit corresponds to a monomer comprising .

[0107] In embodiments of the present application, the photoacid generator (PAG) described above is a substance that can generate a photoacid under irradiation of an exposure source. In the present application, there is no special requirement for the photoacid generator. In some embodiments, the photoacid generator can include a small molecule onium salt, for example, a sulfonium salt, an iodonium salt, a diazonium salt, etc. Taking the sulfonium salt as an example, it can include a sulfonium cation and an anion containing an acidic group.

[0108] In some embodiments of the present application, the sulfonium salt as the photoacid generator can have a structure shown in the following formula (III):

[0109] Formula (III)

[0110] wherein R4, R5, and R6 are independently selected from substituted or unsubstituted monovalent hydrocarbon groups with or without a heteroatom-containing linking group, any two of R4, R5, and R6 can be bonded to each other to form a ring, X -are anions containing an acidic group. Among others, the acidic group can include one or more of sulfonate, sulfate group, carbonate group, fluorosulfonyl amide group, etc.

[0111] wherein the monovalent hydrocarbon group can include one or more of alkyl, cycloalkyl, chain or cyclic alkenyl, chain or cyclic alkynyl, aryl, which can be unsubstituted or substituted. With respect to the heteroatom linking group, as described previously, can include one or more of ether linkage (-0-), thioether linkage (-S-), carbonyl (-C(=0)-), -C(=0)-0-, -OCO-, imine linkage (-NH-), amide linkage (-NHCO-), carbamate linkage (-NH-COO-), sulfonyl linkage (-S02-), sulfonate linkage (-0-S(=0)2-), carbonate linkage (-0-C(=0)-0-), -C(=0)-0-C(=0)-, etc.

[0112] In some possible embodiments, the sulfonium cation in the sulfonium salt can include any of the following structures.

[0113]

[0114] In some possible embodiments, X in formula (III) - may be R e -CF2-SO3 - wherein R e is a substituted or unsubstituted monovalent hydrocarbon group with or without a heteroatom linking group. In some cases, R e is a fluorine atom, a fluoroalkyl group, R’-0-C(=0)-, or R’-C(=0)-0-, wherein R’ is a substituted or unsubstituted aliphatic saturated hydrocarbon group. The substituents in the substituted aliphatic saturated hydrocarbon group can include, but are not limited to, one or more of halogen atom, hydroxyl group, cyano group, ester group, alkyl group, cycloalkyl group, etc.

[0115] Exemplary photo-acid generators include, but are not limited to, one or more of the following:

[0116] P1 P2

[0117] P3 P4

[0118] In some embodiments of the present application, the photoacid generator has a mass of 0.5% to 20% of the mass of the fluorine-containing base resin. Controlling the mass ratio of the photoacid generator to the fluorine-containing base resin within an appropriate range can ensure that the acid-labile groups of the fluorine-containing base resin are fully broken during the post-exposure bake process, and also prevent the mass ratio of the photoacid generator from being too high, which would increase the acid diffusion of the patterned composition film during the post-exposure bake process and reduce the pattern resolution. For example, the photoacid generator has a mass of 1%, 2%, 5%, 6%, 8%, 10%, 15%, 18%, 20%, or the like, of the mass of the base resin.

[0119] In some embodiments of the present application, the patterned composition further comprises an acid quencher. The presence of the acid quencher can help quench the excess photoacid generated by the fluorine-containing base resin during the exposure process, so as to inhibit the diffusion of the photoacid and avoid a reduction in the pattern resolution formed using the patterned composition.

[0120] The structure of the acid quencher is not particularly limited in the present application. For example, the acid quencher can include one or more of the following:

[0121] Q1: Q2: .

[0122] In some embodiments of the present application, the mass of the acid quencher is not more than 10% of the mass of the fluorine-containing base resin, for example, specifically 0.2%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 8%.

[0123] In some embodiments of the present application, the patterned composition further comprises an organic solvent. The organic solvent includes one or more of a ketone solvent, an ester solvent, an ether solvent, and an alcohol solvent. The organic solvent can enable good dissolution of the components in the patterned composition, and in particular, the fluorine-containing additive can be well dissolved in the organic solvent and will not precipitate to affect the stability of the patterned composition.

[0124] For example, the ketone solvent can include, but is not limited to, one or more of 2-heptanone, methyl-2-n-pentanone, cyclohexanone, cyclopentanone, and the like. The ester solvent can include one or more of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, butyl acetate, 3-methoxypropyl acetate, gamma-butyrolactone (GBL), methyl 2-hydroxyisobutyrate (HBM), and the like. The ether solvent can include, but is not limited to, one or more of propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and the like. The alcohol solvent can include, but is not limited to, one or more of isopropyl alcohol, 3-methoxybutanol, and the like. In some embodiments, the organic solvent can include PGMEA and GBL in a volume ratio of 8:2.

[0125] In addition, other additives such as one or more of defoaming agent, sensitizer, anti-halo agent, etc. can also be added to the above-mentioned patterning composition as needed.

[0126] In the present application, the solid content in the above-mentioned patterning composition can be 2wt%-10wt%. Controlling the solid content in the patterning composition within an appropriate range can help to ensure that the above-mentioned patterning composition has a suitable viscosity and coating thickness. The solid content refers to the sum of the mass percentage of other components in the above-mentioned patterning composition except for the organic solvent.

[0127] The above-mentioned patterning composition of the present application has good coating performance, is convenient to coat into a film, forms a coating film layer with a smooth surface, the film thickness is easy to adjust, the development conditions meet the requirements of the patterning process, and is convenient for application in the field of semiconductor patterning.

[0128] The present application also provides a patterning method, as shown in Figure 1 The patterning process includes:

[0129] S01, coating the above-mentioned patterning composition of the present application on a substrate to form a patterning material film layer on the substrate;

[0130] S02, sequentially exposing and baking the patterning material film layer, and then developing with a developer to form a patterned film on the substrate.

[0131] In step S01, the substrate to be coated with the patterning composition can be selected according to specific needs, for example, it can be a silicon wafer, or a silicon wafer covered with other film layers. The other film layers can include but are not limited to one or more of bottom anti-reflective coating (BARC), epitaxial layer, metal layer, dielectric layer (such as SiO2 or Si3N4), etc. Generally, the other film layers can be obtained by pretreating the substrate, and the pretreatment method can be: performing O2 plasma surface hydrophilic activation on the silicon wafer substrate; or washing in Piranha solution (H2O: 30% ammonia water: 30% H2O2= 5:1:1) for 15-20 mins, and then washing with deionized water and isopropanol to complete the hydrophilic treatment; or using evaporation or spin coating to cover hexamethyldisilazane (HMDS) on the substrate to perform surface hydrophobic treatment on the substrate.

[0132] The coating method of the above-mentioned patterning composition includes, but is not limited to, spin coating, dip coating, brushing, spraying, rolling, and the like. In some possible embodiments, the coating method can be spin coating. According to the size of the substrate, an appropriate volume of the above-mentioned patterning composition can be taken and spin coated on the substrate to form a film layer of the patterning material with a certain thickness. Exemplarily, the coating thickness of the patterning composition can be in the range of 5 nm to 2 μm.

[0133] As described above, the above-mentioned fluorine-containing additive has good compatibility with other components of the patterning composition (e.g., the fluorine-containing main resin, the PAG, and the like), and thus, during the coating process of the patterning composition containing the fluorine-containing additive, the patterning composition is less likely to separate / distribute unevenly, and generate film defects, and during the coating and film formation of the patterning composition, the fluorine-containing additive can float to the surface of the film layer, so that the obtained film layer of the patterning material can include a two-layer structure, wherein the lower layer (close to the coated substrate) mainly contains the fluorine-containing main resin, the PAG, and optionally the acid quencher, and the upper layer (far from the coated substrate) mainly contains the fluorine-containing additive, which can protect the lower layer of the film from being hydrophobic. Therefore, it is not necessary to form a topcoat layer on the surface of the film layer of the patterning material.

[0134] In some embodiments of the present application, after the above-mentioned patterning composition is coated, a pre-baking (PAB, Post-Apply Bake) is further performed to minimize the solvent content in the patterning composition. The pre-baking can be performed on a hot plate or in an oven. The typical temperature of the pre-baking can be 60-150 °C, and the time can be 10 seconds to 30 minutes. In an embodiment, the pre-baking temperature is 90-120 °C, and the time is 30 seconds to 10 minutes, and further can be 30-90 seconds.

[0135] In step S02, the exposure source used for exposure can be a light source with a wavelength of less than 400 nm, X-ray, or electron beam. Exemplarily, the exposure source can be deep ultraviolet light with a wavelength of 193 nm or 248 nm, and the like. In the immersion exposure, a mask plate with a predetermined pattern can be placed above the film layer of the patterning material, and the liquid immersion exposure device can irradiate the film layer of the patterning material through the mask plate to achieve selective exposure (i.e., patterned exposure). During exposure, a liquid medium such as pure water exists between the surface of the film layer of the patterning material and the lens of the liquid immersion exposure device.

[0136] In the immersion exposure process, the fluorine-containing additive on the upper part of the film layer of the patterning material has a hydrophobic effect and can prevent the liquid immersion exposure liquid medium such as water from invading the lower part of the film layer of the patterning material, thereby preventing the PAG component and the like in the film layer from dissolving out, and further facilitating the shape of the subsequently formed patterned film to be closer to the mask plate used and the resolution to be higher.

[0137] After the selective exposure of the patterned material film layer, the PAG in the exposed area is decomposed to generate acid. After exposure, post exposure bake (PEB) is performed to ensure that the acid generated during the exposure process catalyzes the deprotection of the acid-labile repeating units of the fluorine-containing main resin in the exposed area of the patterned material film layer to achieve the polarity inversion of the resin, and then the exposed area and the non-exposed area of the film layer have a difference in solubility to the developer. The typical temperature of the PEB can be 60-200°C, and the time can be 10 seconds to 30 minutes. In some embodiments, the temperature of the PEB is 100-130°C, and the time is 30 seconds to 10 minutes, and further can be 30-90 seconds.

[0138] Because the chemical properties of the exposed part of the patterned material film layer are changed, its solubility to the developer is different from that of the unexposed part, therefore, the patterned material film layer after exposure and baking is treated with a developer, which can achieve selective dissolution and pattern formation of the patterned material film layer. The developing process can select a suitable developing solution according to the properties of the patterned material. In some embodiments of the present application, the developer includes an alkaline aqueous solution. After treatment with the alkaline developer, the exposed area of the patterned material film layer is dissolved in the alkaline developer and removed, and the unexposed area is almost insoluble in the alkaline developer, thereby forming a target positive pattern (such as shown in FIG. 2) on the substrate, which is basically the same as the pattern of the exposure mask plate. Figure 1

[0139] Because the above-mentioned fluorine-containing additive contains repeating units with hexafluoroisopropanol structure, the additive has good solubility in the alkaline developing solution, and even if it is located above the film layer whose main components are fluorine-containing main resin and PAG, it will not affect the removal of the exposed area of the patterned material film layer during the developing process.

[0140] The alkaline substance in the alkaline aqueous solution includes one or more of sodium hydroxide, potassium hydroxide, aqueous ammonia, sodium carbonate, triethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), etc.

[0141] In some embodiments of the present application, the developer containing the alkaline aqueous solution can also be added with an organic solvent. The organic solvent used for developing should be miscible with water, and the organic solvent can include but is not limited to one or more of ketone solvents, alcohol solvents, ether solvents, ester solvents, etc. For examples of these organic solvents, please refer to the previous enumeration of organic solvents in the patterned composition.

[0142] ​The developing can be performed by using a common method such as immersion or spraying. That is, the patterned material film after exposure and baking can be immersed in a developing agent or the developing agent can be sprayed on the surface of the patterned material film after exposure and baking. The contact time (i.e., developing time) of the developing agent with the patterned material film can be 3 seconds to 180 seconds, and further can be 5 seconds to 120 seconds.

[0143] In addition, a water rinsing process can be selectively added after development. The rinsing time can be 20 seconds to 120 seconds. The rinsing can make the film cleaner. A baking process (i.e., post-baking) can also be selectively added. The post-baking can harden the pattern structure and make the structure more stable and less likely to collapse. The post-baking temperature can be 60-200°C, and the time can be 20-120 seconds. In some embodiments, the post-baking is performed at 90°C for 60 seconds.

[0144] After development, the obtained patterned film can be observed by using an electron microscope or an atomic force microscope to observe whether there are pattern defects and to obtain the pattern resolution and line width roughness.

[0145] In some embodiments of the present application, after the step S02, the following step S03 is further included: using the above patterned film as a mask to etch the substrate, so as to transfer the pattern of the patterned film to the substrate to obtain a patterned substrate.

[0146] The patterned film has good etching resistance in the etching step, can selectively protect the substrate material thereunder, and after etching under certain conditions, the substrate material not protected by the patterned film can be etched away, and the substrate material protected by the patterned film can be retained, so as to finally form a pattern on the substrate material, that is, to transfer the pattern of the patterned film to the substrate. For example, the etching medium used in the etching process can be a fluorine-containing gas. Generally, the patterned film is also usually removed (for example, by ashing) to make other functional layers on the patterned substrate.

[0147] The patterned method provided by the embodiments of the present application can be applied to the patterning process of the semiconductor integrated circuit preparation process by using the patterned composition of the embodiments of the present application, so as to obtain a pattern structure with good pattern shape and high resolution, which is beneficial to the development of semiconductor devices in the direction of high integration and high precision.

[0148] The embodiments of the present application also provide a patterned film formed by using the patterned composition described above or obtained by using the patterned method described above. The patterned film can be used to make a high-precision mask plate in the integrated circuit patterning process. The pattern of the patterned film can be transferred to a substrate such as a silicon wafer by etching, so as to form a preset pattern on the substrate.

[0149] Due to the addition of the specific fluorine-containing additive in the above-mentioned patterning composition, the film layer thereof has good hydrophobicity and low PAG dissolution resistance in the immersion exposure process, so that a patterned film with a required pattern shape and good depth of focus (DOF) can be obtained after baking and development.

[0150] The embodiment of the present application also provides a patterned substrate, a pattern on the patterned substrate being formed by using the above-mentioned patterning composition or obtained by using the above-mentioned patterning method. The patterned substrate can be used in the preparation of a semiconductor device (such as a chip), so as to improve the manufacturing precision and quality of the device, and further improve the performance of the semiconductor device.

[0151] In some embodiments of the present application, the method for preparing the patterned substrate comprises:

[0152] forming the above-mentioned patterned film on the substrate; and transferring the pattern of the patterned film to the substrate to obtain a patterned substrate.

[0153] The process for forming the patterned film can refer to the description in the foregoing of the present application, and will not be described here again. The pattern of the patterned film can be transferred to the substrate by performing selective etching on the substrate material under the mask effect of the patterned film. The etching can be, for example, etching by using a fluorine-containing gas or ion etching. The substrate material not protected by the patterned film is etched, and the etching speed of the protected part is slower than that of the unprotected part, so that a pattern is finally formed on the substrate material, i.e., the pattern is transferred to the substrate. For example, the patterned film can be used as a mask to etch other film layers on the substrate thereunder, so as to realize the patterning of the other film layers, and the substrate also has the pattern of the other film layers correspondingly; or the substrate can be etched directly on the basis of the patterned other film layers, so as to realize the patterning of the substrate.

[0154] The embodiment of the present application also provides a semiconductor device, which uses the above-mentioned patterned substrate or the preparation method of which comprises the above-mentioned patterning method. The semiconductor device has a high manufacturing yield, high precision and stable performance.

[0155] The semiconductor device can be, for example, a chip. In the preparation process of the chip, other functional layers can be prepared after the above-mentioned patterning process is completed.

[0156] Specifically, the semiconductor device provided by the embodiment of the present application can be applied in a terminal device, for example, a tablet computer, a notebook computer, a mobile phone, a digital camera, a wearable electronic device, a virtual reality device, etc.

[0157] The embodiment of the present application also provides a method for preparing a semiconductor device, comprising:

[0158] The patterned substrate is prepared by the aforementioned patterning method.

[0159] The structure required by the semiconductor device is formed on the patterned substrate, and the semiconductor device is obtained.

[0160] The formation of the structure required by the semiconductor device can also be based on the patterned film provided in the embodiments of the present application.

[0161] The embodiments of the present application are further described in the following embodiments.

[0162] Embodiment 1

[0163] (I) Preparation of the fluorine-containing main resin:

[0164] The fluorine-containing main resin used in Embodiment 1 of the present application is obtained by polymerization of acid-labile monomer 1 , acid-labile monomer 2 , monomer 3 with lactone skeleton , and monomer 4 with hexafluoroisopropanol structure in a molar ratio of 45:10:30:15 in the presence of an initiator. The weight average molecular weight M w of the fluorine-containing main resin is 10.1k.

[0165] (II) Preparation of the fluorine-containing additive:

[0166] The fluorine-containing monomer A represented by the aforementioned formula (A6) and the fluorine-containing monomer B represented by formula (B1) are mixed in a molar ratio of 40:60 in a solvent (specifically, isopropyl acetate) under a nitrogen atmosphere, stirred uniformly, and then a certain amount of initiator - azobisisobutyronitrile (AIBN) is added. Polymerization is carried out at 85°C for 6 hours. After the reaction is completed, the obtained reaction solution is added to methanol for sedimentation, and the desired fluorine-containing additive is obtained, which is denoted as F1.

[0167] The M w of the fluorine-containing additive is 4500, the M w / M n is 1.03, which is tested by gel permeation chromatography using polystyrene as a standard.

[0168] A6: B1: .

[0169] (III) Preparation of the patterned composition

[0170] A patternable composition having a solid content of 6.5% was obtained by mixing 100 parts by mass of the above-mentioned fluorine-containing base resin, 5 parts by mass of the above-mentioned fluorine-containing additive, 15 parts by mass of a photoacid generator (PAG), and 1 part by mass of a quencher in a mixed solvent composed of PGMEA and GBL in a mass ratio of 8:2, and then sufficiently stirring. In this case, the PAG used in Example 1 was specifically 10 parts by mass of a substance represented by formula (P1) and 5 parts by mass of a substance represented by formula (P2); and the quencher was a substance represented by formula (Q1).

[0171] P1: P2: Q1:

[0172] The patternable composition provided in Example 1 was subjected to the following various tests, and the test results are summarized in Table 1.

[0173] Hydrophobicity test of the patternable composition film layer:

[0174] Each of the patternable compositions was spin-coated onto the surface of a silicon wafer, and baked at 110°C for 60 seconds to form a patternable material film layer. Then, pure water was dropped onto the surface of the patternable material film layer, and a contact angle meter was used to test the static contact angle of the water on the surface of the film layer.

[0175] Dissolution amount test of the patternable composition film layer:

[0176] Each of the patternable compositions was spin-coated onto the surface of a silicon wafer, and baked at 110°C for 60 seconds to form a patternable material film layer having a thickness of about 160 nm. Then, the silicon wafer was attached to a centrally hollowed-out piece of silicone rubber (the hollowed-out part of which was filled with 10 mL of ultrapure water) so that the surface of the patternable material film layer was in contact with the ultrapure water for 10 seconds, and the ultrapure water did not leak out of the silicone rubber piece. Thereafter, the silicon wafer was removed, and a glass syringe was used to recover the ultrapure water as an analysis sample. Next, a liquid chromatograph-mass spectrometer (LC-MS) was used to test the peak intensity of the anion of the photoacid generator (PAG) in the recovered ultrapure water sample (the test temperature was 35°C, and the chromatographic mobile phase was a mixture of water and methanol in a volume ratio of 3:7 to which 0.1 wt% of formic acid was added). The peak intensities of 1 ppb, 10 ppb, and 100 ppb aqueous solutions of the PAG were also measured under the same test conditions to prepare a standard curve, and the dissolution amount was calculated from the above-mentioned peak intensity using the standard curve, with the unit being 10 -12 mol / cm 2 / s.

[0177] Use of the patternable composition in a patterning process:

[0178] First, HMDS is uniformly deposited onto the surface of a silicon wafer using a vapor deposition method (vapor deposition temperature of 120°C and time of 60 seconds) to achieve surface hydrophobicity treatment of the silicon wafer; then, a bottom anti-reflective coating (BARC) with a thickness of about 90 nm is formed on the surface of the silicon wafer with HMDS deposited.

[0179] Next, each patterned composition is spin-coated onto the BARC coating surface of the silicon wafer and then PAB baked (110°C, 60 seconds) to form a patterned material film layer with a thickness of about 160 nm.

[0180] Then, using an ArF excimer laser immersion exposure apparatus, the patterned material film was selectively exposed through a Dense mask (S68P128, i.e., line spacing of 68 nm, period size of 128 nm, and linewidth of 60 nm) with a periodic line pattern. During exposure, pure water was used as the immersion solvent between the film and the lens of the immersion exposure apparatus. Immediately after exposure, PEB baking (90°C, 60 seconds) was performed.

[0181] Finally, the patterned material film after the above treatment was immersed and developed for 60 seconds at 25°C using a 2.38 wt% tetramethylamine hydroxide (TMAH) aqueous solution, followed by water washing and drying, to form a positive patterned thin film with periodic line patterns on the BARC coating of the silicon wafer.

[0182] Among them, the exposure amount when the critical dimension (CD) of the patterned film reaches the target value (specifically, the line spacing is close to that of the mask used) is taken as the optimal exposure amount, which is the sensitivity. The test results are summarized in Table 1.

[0183] Furthermore, the cross-sectional shape of the patterned thin film obtained after exposure and development using the aforementioned mask Dense S68P128 was observed using a scanning electron microscope (SEM), and the linewidth L in the middle of the pattern was measured. b and the linewidth L at the top of the membrane a , will be in the range of 0.9≤(L a -L b ) / L b Situations within the range of ≤1.1 are rated as "good," while those outside this range are rated as "poor." The relevant results are summarized in Table 1.

[0184] Prepare patterned compositions for other examples or comparative examples according to the formulations shown in Table 1 below, and list the differences between them and Example 1 in Table 1 below. Also, summarize the relevant test results of these patterned compositions in Table 1.

[0185] Table 1

[0186]

[0187] In Table 1 above, the fluorine-containing additive F2 used in Example 4-6 is a polymer formed by copolymerization of the fluorine-containing monomer A6 and the fluorine-containing monomer B1 at a molar ratio of 50:50.

[0188] The fluorine-containing additive F3 used in Example 9 is a polymer formed by copolymerization of the fluorine-containing monomer A6 with a hexafluoroisopropanol structure and the fluorine-containing monomer B1 with a fatty ring structure at a molar ratio of 92:8.

[0189] The fluorine-containing additive F4 used in Example 10 is a polymer formed by copolymerization of the fluorine-containing monomer A6 with a hexafluoroisopropanol structure and the fluorine-containing monomer B1 with a fatty ring structure at a molar ratio of 20:80.

[0190] The fluorine-containing additive DF1 used in Comparative Example 2 is obtained by polymerization of only the fluorine-containing monomer A represented by formula (A6) with a hexafluoroisopropanol structure.

[0191] From the comparison between each of the examples and Comparative Example 1 in which no fluorine-containing additive is added in Table 1 above, it can be seen that when a fluorine-containing main resin-containing patterning composition is further added with a fluorine-containing additive meeting the requirements of the present application, the fluorine-containing additive can float to the surface during the film formation process of the patterning composition, which is conducive to improving the hydrophobicity of the film layer of the patterning composition (reflected by a larger water static contact angle), reducing the dissolution of PAG below the film layer during immersion exposure, and not affecting the exposure sensitivity of the overall patterning material film layer, and the shape of the resulting patterned film after exposure, baking and development is good. In addition, from the comparison between Example 8 and Comparative Example 2 in Table 1, it can be seen that when a fluorine-containing additive is contained in the patterning composition, but the structure of the fluorine-containing additive does not meet the requirements of the examples of the present application, the effect of improving the hydrophobicity of the patterning material film layer and blocking the dissolution of PAG is not obvious.

[0192] In addition, from the comparison between Example 1, 4 and Examples 9-10 in Table 1, it can be seen that when the mass proportion of the fluorine-containing additive used in the composition is close, and the molar proportion of the fluorine-containing monomer B derived from the fluorine-containing monomer B with a fatty ring structure in the fluorine-containing additive is greater than 8% to less than 80% (for example, 10-70%), the effect of the fluorine-containing additive on improving the hydrophobicity of the patterning material film layer and blocking the dissolution of PAG is more obvious.

[0193] Figure 2 SEM photos of the patterned films formed by the patterning process of the patterning compositions of Example 1 and Comparative Example 1 using the above mask plate Dense with a periodic line pattern for immersion exposure are also summarized. Figure 3The SEM photos of the patterned films formed by the patterning process of the patterning compositions of Example 1 and Comparative Example 1 using a mask plate Semi (S85P210, i.e. line space is 85 nm, period size is 210 nm) with a periodic line pattern for immersion exposure are also summarized. Figure 4 The SEM photos of the patterned films formed by the patterning process of the patterning compositions of Example 1 and Comparative Example 1 using a mask plate Iso (S110P1500, i.e. line space is 110 nm, period size is 1500 nm) with a periodic pattern for immersion exposure are also summarized.

[0194] From Figures 2 to 4 The depth of focus data, line width roughness (LWR) of each patterned film at the optimum exposure dose are summarized in Table 2 below.

[0195] Table 2

[0196]

[0197] From Table 2, it can be known that, under the condition of using the same mask plate for immersion exposure, the patterned film formed by the patterning composition of Example 1 with the addition of specific fluorine-containing additives can have smaller or unchanged depth of focus (smaller depth of focus can reflect higher pattern resolution), and / or lower low edge roughness (LWR), and the overall pattern quality is higher.

[0198] The above description is merely illustrative of the exemplary embodiments of the present application, and is not intended to limit the scope of the present application. It should be pointed out that, for those skilled in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which all belong to the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the appended claims.

[0199] It should be understood that the first, second and various numerical numbers involved herein are only for the convenience of differentiation, and do not limit the scope of the present application. In the present application, the association relationship of "and / or" describing the associated objects indicates that there can be three kinds of relationships, for example, A and / or B can represent the cases of A alone, A and B together, and B alone, where A and B can be singular or plural. The character " / " generally represents an "or" relationship between the associated objects before and after it.

[0200] In the description of the present application, unless otherwise specified, the meaning of "a plurality of" is greater than or equal to two. "At least one" means one or more. "At least one of the following" or the like means any combination of these items, including any combination of single item or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can represent: a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple.

[0201] In addition, the numerical range indicated by "-" in the present application means a range including the minimum value and the maximum value indicated by the numerical value before and after the "-" respectively. In the present application, the expressions such as "greater than or equal to (≥)", "less than or equal to (≤)", "above", "below" with respect to the range of parameters include the present number. The numerical values and numerical ranges involved in the embodiments of the present application are approximate values, and there may be a certain range of error due to the influence of manufacturing process / testing method, etc., which can be considered negligible by those skilled in the art.

Claims

1. A patterning composition characterized in that, The composition comprises a fluorine-containing main resin, a photoacid generator and a fluorine-containing additive, wherein the fluorine-containing main resin comprises an acid-labile repeating unit with an acid-labile aliphatic ring structure, a repeating unit with a lactone structure and a repeating unit with a hexafluoroisopropanol structure; the repeating unit with the hexafluoroisopropanol structure further comprises an aliphatic ring structure connected to the hexafluoroisopropanol structure; and the mole percentage of the repeating unit with the hexafluoroisopropanol structure in the fluorine-containing main resin is 10%-20%; The fluorine-containing additive is a polymer comprising a repeating unit derived from a fluorine-containing monomer A and a repeating unit derived from a fluorine-containing monomer B, wherein the fluorine-containing monomer A comprises a hexafluoroisopropanol structure, the fluorine-containing monomer B comprises an aliphatic ring structure, the aliphatic ring structure in the fluorine-containing monomer B is not acid-labile, and the fluorine-containing monomer A comprises a structure represented by formula (A): Formula (A) wherein R is selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, R1comprises a hexafluoroisopropanol structure a , L1is a divalent linking group; the L1is selected from one or more of a substituted or unsubstituted alkylene, a substituted or unsubstituted cycloalkylene, an internal ester ring containing a heteroatom linking group, and the heteroatom linking group comprises at least one of -C(=O)-O- # and -O-C(=O) # , the # end is proximate to R1 ​ The mole percentage of the repeating unit derived from the fluorine-containing monomer B in the fluorine-containing additive is 45%-70%.

2. The patterning composition of claim 1, wherein, The fluorine-containing monomer B comprises a structure represented by formula (B): Formula (B) wherein R b selected from a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, L2is a single bond or a divalent linking group, R2is a substituted or unsubstituted aliphatic ring structure, and at least one of said L2and said R2bears a fluorine atom, but -L2-R2does not include the hexafluoroisopropanol structure.

3. The patterning composition of claim 2, wherein The fluorine-containing monomer B comprises one or more of the following substances: 。 4. The patterning composition of claim 1, wherein The fluorine-containing monomer A comprises one or more of the following substances: 。 5. The patterning composition of any one of claims 1-4, wherein The mass of the fluorine-containing additive is 0.5%-10% of the mass of the fluorine-containing main resin.

6. A patterned film, characterized by, The patterned film is formed by the patterned composition according to any one of claims 1-5.

7. A patterned substrate, characterized in that, The pattern on the patterned substrate is formed by the patterned composition according to any one of claims 1-5.

8. A semiconductor device, characterized by, The patterned film is formed by the patterned composition according to claim 6, or the patterned substrate is formed by the patterned composition according to claim 7.

9. A method of manufacturing a semiconductor device, characterized by The composition comprises: The patterned composition according to any one of claims 1-5 is coated on a substrate to form a patterned material film layer on the substrate; The patterned material film layer is subjected to exposure, baking and then developing with a developer in sequence to form a patterned film on the substrate.

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