Patterning composition, patterning film, patterning substrate, semiconductor device and manufacturing method thereof

Abstract

The embodiment of the invention provides a patterning composition, a patterning film, a patterning substrate, a semiconductor device and a manufacturing method of the semiconductor device. The patterned composition comprises fluorine-containing matrix resin, a photoacid generator and a fluorine-containing additive, the fluorine-containing matrix resin comprises an acid-unstable repetitive unit, a repetitive unit with a lactone structure and a repetitive unit with a hexafluoroisopropanol structure, and the repetitive units of the fluorine-containing matrix resin have an aliphatic ring structure; the fluorine-containing additive comprises a repeating unit derived from a fluorine-containing monomer A with a hexafluoroisopropanol structure and a repeating unit derived from a fluorine-containing monomer B with an alicyclic ring structure. The film layer of the patterning composition can resist dissolution of the photoacid generator during immersion exposure, and a patterning film with the shape and the resolution ratio meeting the requirements can be finally formed.

Description

Technical Field

[0001] The present application relates to the field of patterning technology, and in particular to a patterning composition, a patterned film, a patterned substrate, a semiconductor device, and a method for manufacturing the same. Background Art

[0002] The manufacturing process of semiconductor integrated circuits typically involves a patterning process. The patterning material used in this process is generally a chemically amplified patterning composition comprising a host resin with acid-labile groups and a light-sensitive photoacid generator (PAG). In the mainstream immersion patterning process, it is necessary to avoid direct contact between the patterning material and liquids such as water to prevent the PAG from dissolving and thus failing to obtain a pattern with the desired shape and / or resolution. To this end, the industry typically spin-coats a waterproof topcoat on the patterned material film layer to prevent contact with liquids such as water, but this adds a step to the patterning process.

[0003] To reduce the number of steps in the patterning process and improve efficiency, the industry has proposed introducing a small amount of fluorinated polymers as additives into the patterning composition to form a barrier layer similar to a topcoat. The principle is that the fluorinated polymers can float to the surface of the film during the film formation process, acting as a barrier to liquids such as water. However, this solution is generally only suitable for patterning compositions whose main resin does not contain fluorine. Adding conventional fluorinated additives to patterning compositions containing a fluorinated main resin presents certain technical challenges. This is mainly due to the interaction between the fluorinated additives and the fluorinated repeating units in the main resin, resulting in the risk of incomplete floating. As a result, the patterned material film performs poorly in terms of water barrier and PAG dissolution resistance. Summary of the Invention

[0004] In view of this, the embodiments of the present application provide a patterned composition and its application. By introducing a fluorine-containing additive of a specific structure into a patterned composition containing a fluorine-containing main resin, the topcoat process is avoided, so that the patterned composition can be smoothly and conveniently used in an immersion patterning process, ensuring that the components of the components are evenly distributed, and the contact angle of the film layer with water is large, and the amount of dissolved matter during immersion exposure is small, ultimately obtaining a patterned film with a shape and resolution that meet the requirements.

[0005] Specifically, the first aspect of the embodiment of the present application provides a patterned 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 the hexafluoroisopropanol structure also includes an aliphatic ring structure connected to the hexafluoroisopropanol structure; wherein the fluorine-containing additive is a polymer comprising repeating units derived from a fluorine-containing monomer A and repeating units derived from a fluorine-containing monomer B, wherein the fluorine-containing monomer A includes a hexafluoroisopropanol structure, the fluorine-containing monomer B includes 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 includes 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 that the fluorine-containing additive has good compatibility with the above-mentioned fluorine-containing main resin, and the two will not phase separate to cause uneven coating of the composition containing them or defects in the film layer. At the same time, the fluorine and the fluorine-containing repeating unit A in the latter can enable the fluorine-containing additive to float smoothly to the surface of the film layer during the coating and film formation process of the patterned composition. During immersion exposure, it can play a hydrophobic role and prevent PAG from dissolving. 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 patterned composition can be used to form a patterned film with a shape and resolution that meets the requirements.

[0007] In the embodiment of the present application, the fluorinated monomer A comprises a structure represented by formula (A), and the fluorinated monomer B comprises a structure represented by formula (B): Formula (A) Formula (B) Wherein, R, R' are independently selected from hydrogen atom, fluorine atom, methyl, or trifluoromethyl, L1 is a divalent linking group, R1 includes 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 carries a fluorine atom, but -L2-R2 does not include the hexafluoroisopropanol structure.

[0008] Among them, the fluorinated monomer A with a hexafluoroisopropanol structure may or may not include an aliphatic ring structure, and the fluorinated monomer B includes a hexafluoroisopropanol structure but does not include a hexafluoroisopropanol structure. The fluorinated additive formed by the polymerization of these two fluorinated monomers can effectively exert the above-mentioned hydrophobic and PAG dissolution-blocking effects.

[0009] In some embodiments of the present application, the L1 is selected from one or more of a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, and a lactone ring containing or not containing a heteroatom linking group; wherein the heteroatom linking group includes -C(=O)-O- # and -OC(=O)- # At least one of them, the # end is close to the R1.

[0010] L1 is selected from the above groups, so that a monomer with a hexafluoroisopropanol structure connected to L1 is easier to obtain, and the above fluorine-containing additive can be made to have essentially no absorption in the ultraviolet region without affecting the photosensitivity of the patterned material film layer, and has good solubility in an alkaline developer.

[0011] In some embodiments of the present application, in R2, the substituents in the substituted aliphatic ring structure include one or more of a fluorine atom, a fluoroalkyl ester group, and a fluoroalkyl group.

[0012] In this case, the substituted aliphatic ring structure containing fluorine atoms in R2 is more conducive to the complete floating of the fluorine-containing additive in the patterned composition containing the fluorine-containing main resin, thereby achieving good hydrophobicity and preventing PAG from dissolving.

[0013] In some embodiments of the present application, the fluorinated monomer A includes one or more of the following substances:

[0014] .

[0015] In some embodiments of the present application, the fluorinated monomer B includes one or more of the following substances:

[0016] .

[0017] In some embodiments of the present application, the repeating unit derived from the fluorine-containing monomer B accounts for 10% to 70% by mole in the fluorine-containing additive.

[0018] In this case, it is more conducive to the good compatibility between the fluorine-containing additive and the fluorine-containing main resin, and there will be no phase separation to cause uneven coating of the above-mentioned patterned composition. It is also conducive to ensuring that the fluorine-containing additive and the fluorine-containing main resin have certain differences, which is conducive to the fluorine-containing additive being able to float smoothly to the surface of the film layer during the coating and film-forming process of the above-mentioned patterned composition, and exerting its hydrophobicity, blocking PAG dissolution and reducing pattern watermark defects.

[0019] 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 within an appropriate range ensures that the fluorine-containing additive can fully exert its hydrophobic effect and prevent PAG dissolution during immersion exposure, while also preventing excessive use, which may cause development defects in the film layer of the patterned composition after exposure.

[0020] In some embodiments of the present application, the molar proportion of the acid-labile repeating units in the fluorine-containing main resin may be 10-70%, the molar proportion of the repeating units with a lactone structure may be 5-80%, and the molar proportion of the repeating units with a hexafluoroisopropanol structure may be 1%-20%. Fluorine-containing main resins that meet these conditions are commonly used in patterning compositions.

[0021] In some embodiments of the present application, the patterning composition further comprises an acid quencher, which can help quench excess photoacid generated by the fluorine-containing host resin during exposure, thereby preventing the pattern formed using the patterning composition from having too low a resolution.

[0022] In some embodiments of the present application, the patterning 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.

[0023] A second aspect of the present invention provides a patterned film, which is formed using the patterned composition described in the first aspect of the present invention. The patterned film can be converted into a patterned film having a specific pattern by a patterning process including exposure, baking, and development after the patterned composition is applied.

[0024] A third aspect of the present invention provides a patterned substrate, wherein the pattern on the patterned substrate is formed using the patterned composition described in the first aspect of the present invention. The pattern on the patterned substrate may be formed by transferring the pattern of a patterned thin film formed using the patterned composition onto a substrate. The patterned substrate can be used in the manufacture of semiconductor devices, such as chips, to improve the fabrication precision and quality of the devices.

[0025] A fourth aspect of the present application provides a semiconductor device, which utilizes the patterned film described in the second aspect of the present application, or utilizes the patterned substrate described in the third aspect of the present application. The semiconductor device may include a patterned substrate and a device structure formed on the patterned substrate.

[0026] The present invention also provides a method for manufacturing a semiconductor device, comprising: Applying the patterned composition described in the first aspect of the embodiment of the present application on a substrate to form a patterned material film layer on the substrate; The patterned material film layer is exposed and baked in sequence, and then developed with a developer to form a patterned thin film on the substrate.

[0027] In some embodiments of the present application, after forming the patterned film, the method further includes: transferring the pattern of the patterned film to a substrate to obtain a patterned substrate.

[0028] Furthermore, after obtaining the patterned substrate, the method may further include: forming a structure required for the semiconductor device on the patterned substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 A schematic flow chart of a patterning process provided in an embodiment of the present application.

[0030] Figure 2 SEM images of patterned films formed by the patterned compositions of Example 1 and Comparative Example 1 through a patterning process of immersion exposure using a mask plate Dense having a periodic line pattern are summarized; Figure 2 (a) is a SEM photo of the patterned film of Example 1. Figure 2 (b) is a SEM photograph of the patterned film of Comparative Example 1.

[0031] Figure 3 SEM images of patterned films formed by the patterned compositions of Example 1 and Comparative Example 1 through a patterning process of immersion exposure using a mask Semi having a periodic line pattern are summarized; Figure 3 (a) is a SEM photo of the patterned film of Example 1. Figure 3 (b) is a SEM photograph of the patterned film of Comparative Example 1.

[0032] Figure 4 SEM images of patterned films formed by the patterned compositions of Example 1 and Comparative Example 1 through a patterning process of immersion exposure using a mask Iso having a periodic line pattern are summarized; Figure 4 (a) is a SEM photo of the patterned film of Example 1. Figure 4 (b) is a SEM photograph of the patterned film of Comparative Example 1. DETAILED DESCRIPTION

[0033] The embodiments of the present application will be described below with reference to the accompanying drawings.

[0034] In the manufacturing process of semiconductor integrated circuits, patterning is an important process. The patterning process generally includes the following steps: (1) coating a patterning composition (such as a chemically amplified patterning composition comprising a main 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 having a predetermined pattern, i.e., performing selective exposure, causing the photoacid generator in the irradiated area (i.e., the exposed area) to generate photoacid; in the baking process after exposure, the photoacid can catalyze the deprotection of the acid-labile groups in the main resin of the exposed area, thereby increasing the polarity of the base resin in the exposed area, thereby producing a difference in the solubility of the developer between the exposed area and the unexposed area; (3) after exposure and baking, the patterned material film layer is developed with a developer to selectively dissolve the film structure of the exposed area or the unexposed area, leaving a patterned film having the same or opposite pattern as the mask on the substrate; (4) in the etching process, the remaining patterned film selectively protects the underlying material from being etched or slowly etches, thereby realizing the transfer of the pattern to the underlying material, and finally realizing the desired pattern on the substrate material.

[0035] Immersion patterning refers to a patterning process in which a liquid medium with a high refractive index, such as pure water or a fluorine-based inert liquid, is present between the lens of the exposure device and the patterned material film on the substrate during exposure. The introduction of this liquid medium can improve the resolution of the resulting pattern. Because the patterned material film directly comes into contact with the immersion exposure liquid, such as water, during exposure, it can easily lead to the dissolution of photoacid generators (PAGs) and other substances from the patterned material film. The greater the amount of these substances, the more severe the damage to the lens, or the inability to achieve the desired pattern shape or sufficient resolution.

[0036] To this end, the industry usually spin-coats a waterproof top coating (topcoat) on the patterned material film layer to prevent it from contacting liquids such as water, but this increases the number of steps in the patterning process and reduces efficiency. The industry has also proposed directly introducing fluorine-containing polymer additives into the patterned composition, hoping that it can float to the surface of the film layer during the film formation process of the composition and play a role in blocking liquids such as water, but this solution is generally only suitable for patterned compositions whose main resin does not contain fluorine, because conventional fluorine-containing additives interact with the fluorine-containing repeating units in the main resin and cannot achieve complete floating, affecting their topcoat-like role. Based on this, the present application introduces a fluorine-containing additive with a specific structure into the patterned composition containing a fluorine-containing main resin to avoid adding an additional topcoat formation step after the patterned material film layer is formed, and the fluorine-containing additive can be well dispersed in the composition and can smoothly float to the surface of the film layer during the film formation process of the composition to play a role in blocking liquids such as water and preventing PAG from dissolving.

[0037] The present invention provides a patterned composition comprising a fluorine-containing main resin, a photoacid generator and a fluorine-containing additive. 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 fluorinated additive is a polymer comprising repeating units derived from a fluorinated monomer A and repeating units derived from a fluorinated monomer B, wherein the fluorinated monomer A comprises a hexafluoroisopropanol structure and the fluorinated monomer B comprises an aliphatic ring structure.

[0038] In the above-mentioned patterned composition, the above-mentioned three types of repeating units of the fluorine-containing main resin all include 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 also includes a fluorine-containing repeating unit with a hexafluoroisopropanol structure (referred to as fluorine-containing repeating unit A) and a fluorine-containing repeating unit with an aliphatic ring structure (referred to as fluorine-containing repeating unit B). Among them, the aliphatic ring structure and the fluorine-containing repeating unit A in the fluorine-containing repeating unit B can ensure that the fluorine-containing additive has good compatibility with the fluorine-containing main resin, and the two will not phase separate, resulting in uneven coating of the composition containing them or defects in the film layer; at the same time, the above-mentioned fluorine-containing repeating unit B with an aliphatic ring structure in the fluorine-containing additive also contains fluorine, which ensures that the fluorine-containing additive has certain differences from the fluorine-containing main resin, which is conducive to the fluorine-containing additive being able to float smoothly to the surface of the film layer during the coating and film formation process of the patterned composition, thereby successfully performing its hydrophobic function and preventing PAG from dissolving during immersion exposure; the presence of the fluorine-containing repeating unit A also helps to improve the hydrophobicity and enhance the floating effect. Furthermore, when water is used as the immersion exposure liquid, the patterned material film layer formed by the patterning composition exhibits large static and advancing contact angles with water, demonstrating excellent hydrophobicity. This facilitates subsequent evaporation of water and reduces pattern defects caused by residual watermarks. The hexafluoroisopropanol structure within the fluorinated repeating unit A facilitates the removal of the fluorinated additive by an alkaline developer during subsequent development, enabling the formation of patterned films with the desired shape and resolution using the patterning composition.

[0039] As a result, the patterned material film formed from the patterned composition exhibits a large contact angle with water and exhibits minimal leachables during immersion exposure, ultimately yielding a patterned film with satisfactory shape and resolution. Furthermore, because the present embodiment directly adds a fluorine-containing additive with a specific structure to the patterned composition, there is no need for a separate topcoat formation step prior to immersion exposure or after the patterned material film, simplifying the patterning process and improving efficiency.

[0040] It is understood that the above-mentioned fluorine-containing additive can be a copolymer formed by polymerizing monomer raw materials including a fluorine-containing monomer A with a hexafluoroisopropanol structure and a fluorine-containing monomer B with an aliphatic ring structure. Wherein, the fluorine-containing monomer B does not contain a hexafluoroisopropanol structure. Similarly, the above-mentioned fluorine-containing main resin can be a polymer formed by polymerizing monomer raw materials including a monomer with an acid-labile aliphatic ring structure, a monomer with a lactone structure, and a monomer with a hexafluoroisopropanol structure connected to the aliphatic ring structure. The biggest difference in structure between the fluorine-containing additive and the above-mentioned fluorine-containing main resin is that the fluorine-containing additive does not include a repeating unit with an acid-labile group. Although the fluorine-containing monomer B of the fluorine-containing additive includes an aliphatic ring structure, the aliphatic ring structure is not acid-labile. In addition, the fluorine-containing additive is used as an additive. It is understood that in the above-mentioned patterned composition, the mass of the fluorine-containing additive is less than that of the fluorine-containing main resin.

[0041] In some embodiments of the present application, the fluorinated monomer A may include a structure represented by formula (A), and the fluorinated monomer B may include a structure represented by formula (B): Formula (A) Formula (B) Among them, R a 、R b Independently selected from hydrogen atom (H), fluorine atom (F), methyl (-CH3), or trifluoromethyl (-CF3); L1 is a divalent linking group, R1 includes 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 carries a fluorine atom, but -L2-R2 does not include the hexafluoroisopropanol structure.

[0042] Among them, when at least one of L2 and R2 contains a fluorine atom, it is limited that -L2-R2 does not include a hexafluoroisopropanol structure, which can ensure that the structure represented by formula (B) does not overlap with the structure represented by formula (A), especially when L1 in formula A includes an aliphatic ring structure.

[0043] Accordingly, the structure of the repeating unit derived from the fluorinated monomer A (which may be referred to as the fluorinated repeating unit A) is shown in formula (A'), and the structure of the repeating unit derived from the fluorinated monomer B (which may be referred to as the fluorinated repeating unit B) is shown in formula (B'): Formula (A') Formula (B').

[0044] In Formula (A) or Formula (A'), L1 is a divalent linking group, which may be a divalent hydrocarbon group containing or not containing a heteroatom linking group. Specifically, L1 can 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, and an arylene group. The aforementioned groups may or may not contain a heteroatom linking group, and the aforementioned hydrocarbon group may be substituted or unsubstituted. "Chain" can mean straight or branched. The number of carbon atoms in an alkylene group may be 1-20, and further may be 1-10; the number of carbon atoms in a cycloalkylene group may be 3-20, and further may be 4-10. The number of carbon atoms in a chain alkenylene group or a chain alkynylene group may be 2-20, and the number of carbon atoms in a cyclic alkenylene group or a cyclic alkynylene group may be 4-20.

[0045] Among them, the divalent hydrocarbon group containing no heteroatoms can be exemplified by methylene (-CH2-), ethylene (-CH2CH2-), -CH(CH3)-, n-propylene (-(CH2)3-), -C(CH3)2-, -CH(CH3)-CH2-, -CH( t -Bu)-CH2-( t -Bu represents tert-butyl), -CH(CH2CH(CH3)2)-CH2-, -CH(CH2CH(CH3)2)-, -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, Saturated chain alkylene groups such as 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 and octadecane; monocyclic cycloalkylene groups such as cyclobutylene, cyclopentylene, cyclohexylene and cyclooctylene; divalent polycyclic cycloalkylene groups such as norbornylene and adamantylene; arylene groups such as phenylene, naphthylene and phenanthrenyl.

[0046] The above-mentioned divalent hydrocarbon group may contain a heteroatom linking group, and the heteroatom linking group may be located between some carbon atoms in the divalent hydrocarbon group or at its end. Exemplary heteroatom linking groups may include, but are not limited to, one or more of an ether bond (-O-), a thioether bond (-S-), a carbonyl group (-C(=O)-), -C(=O)-O-, -OC(=O)-, an imine bond (-NH-), an amide bond (-NHCO-), a carbamate bond (-NH-COO-), a sulfonyl bond (-SO2-), a sulfonate bond (-OS(=O)2-), -OC(=O)-O-, and -C(=O)-OC(=O)-. Among them, a cyclic divalent hydrocarbon group containing a heteroatom linking group -C(=O)-O- in the ring skeleton may be referred to as a lactone ring, and such a lactone ring may also serve as a divalent linking group. Exemplary lactone rings may include a γ-butyrolactone ring, a norbornyl lactone ring, and an adamantane lactone ring. A cyclic divalent hydrocarbon group containing a heteroatom linking group -OS(=O)2- in the ring backbone may be referred to as a sultone ring or as a divalent linking group. A cyclic divalent hydrocarbon group containing -O- in the ring backbone may be referred to as a divalent internal ether ring, and an aliphatic ring structure containing a sulfide bond -S- in the ring backbone may be referred to as an internal sulfide ring. A cyclic divalent hydrocarbon group containing a -OC(=O)-O- group in the ring backbone may be referred to as a cyclic carbonate ring. A cyclic divalent hydrocarbon group containing a heteroatom linking group -NHCO- in the ring backbone may be referred to as a lactam ring.

[0047] In some embodiments of the present application, L1 can be selected from one or more of substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, and lactone ring with or without heteroatom linking groups. # and -OC(=O)- # At least one of the following, with the # end close to R1. That is, L1 can be selected from one or more of a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a lactone ring, a substituted or unsubstituted alkylene group containing at least one of -C(=O)-O- and -OC(=O)-, a substituted or unsubstituted cycloalkylene group connected to at least one of C(=O)-O- and -OC(=O)-, and a lactone ring connected to at least one of C(=O)-O- and -OC(=O)-. As described above, the heteroatom linking group herein is located between or at the end of some carbon atoms in these divalent hydrocarbon groups.

[0048] L1 is selected from the above groups, so that a monomer with a hexafluoroisopropanol structure connected to L1 is easier to obtain, and the above fluorine-containing additive can be made to have essentially no absorption in the ultraviolet region without affecting the photosensitivity of the patterned material film layer, and has good solubility in an alkaline developer.

[0049] The substituents in the substituted alkylene group may 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, and the like. The substituents in the substituted cycloalkylene group may 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 (for substituents in a substituted alkyl group, see Substituents in a Substituted Alkylene Group), an alkoxy group, and the like. It will be appreciated that in some cases, a substituted or unsubstituted alkylene / cycloalkylene group containing at least one of C(=O)-O- and -OC(=O)- may also include other heteroatom-containing linking groups.

[0050] In some possible embodiments of the present application, the fluorinated monomer A comprises one or more of the following substances: (A1) (A2) (A3) (A4) (A5) (A6) (A7) (A8) (A9) (A10).

[0051] In formula (B) or formula (B'), if L2 is a single bond, then R2 is a substituted alicyclic structure containing a fluorine atom (i.e., an alicyclic structure containing a fluorine-containing substituent). If L2 is a divalent linking group, then R2 is a substituted or unsubstituted alicyclic 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 alicyclic structure containing a fluorine atom. The substituents on the substituted alicyclic structure containing a fluorine atom may specifically include fluorine-containing substituents (e.g., one or more of a fluorine atom, a fluoroalkyl group, a fluoroalkyl ester group, etc.), and in some cases, may also include other substituents. A fluoroalkyl ester group may be represented as -OC(=O)-R''- or -C(=O)-O-R'', where R'' is a fluoroalkyl group.

[0052] For L2, which is a divalent linking group, see the explanation of L1 above in this application. In some embodiments, L2 is a single bond, or one or more substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, containing or not containing a heteroatom linking group. The heteroatom linking group includes, but is not limited to, one or more of -O-, -S-, -OS(=O)2-, -C(=O)-O-, -OC(=O)-O-, -C(=O)-OC(=O)-, etc. If L2 contains a fluorine atom, it is understood that the fluorine atom can be located in a substituted alkylene or a substituted cycloalkylene.

[0053] For R2 in formula (B) or formula (B'), the substituted or unsubstituted aliphatic ring structure can specifically be a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group containing or not containing a heteroatom linking group. Heteroatom linking groups include, for example, one or more of -O-, -S-, -OS(=O)2-, -C(=O)-O-, -OC(=O)-O-, and -C(=O)-OC(=O)-.

[0054] Wherein, the substituents in the substituted aliphatic ring structure may be one or more, and the substituents may include but are not limited to halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, ester groups (-OC(=O)-R''- or -C(=O)-O-R'', R'' includes alkyl groups, fluoroalkyl groups or cycloalkyl groups, etc.), substituted or unsubstituted alkyl groups (such as the substituents of the substituted alkyl groups include one or more of halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, alkoxy groups, etc.), substituted or unsubstituted alkoxy groups (the substituents in the substituted alkoxy groups can refer to the substituents in the substituted alkyl groups), substituted or unsubstituted cycloalkyl groups (such as the substituents include halogen atoms, substituted or unsubstituted alkyl groups, etc.), etc.

[0055] In some embodiments, the substituents in the substituted aliphatic ring structure in R2 include one or more of a fluorine atom, a fluoroalkyl ester group, and a fluoroalkyl group. These fluorine-containing substituted aliphatic ring structures further facilitate the complete floating of the fluorine-containing additive in the patterning composition containing the fluorine-containing host resin, thereby providing a good hydrophobic effect and preventing the dissolution of the PAG.

[0056] In some embodiments of the present application, R2 may comprise one or more of the following substituted or unsubstituted groups: adamantane ring, norbornyl ring, norbornyl lactone ring, or adamantane lactone ring. In this case, such an R2 can ensure good compatibility between the fluorinated additive and the fluorinated host resin with an aliphatic ring structure. Furthermore, the R2 group can provide a certain hydrophobic effect, increasing the surface contact angle of the film formed by the patterned composition and regulating the dissolution rate of the fluorinated additive in an alkaline developer.

[0057] In some possible embodiments of the present application, the fluorinated monomer B may include one or more of the following substances:

[0058] .

[0059] It is understood that in some embodiments of the present application, the fluorine-containing additive may further include other repeating units in addition to the above repeating units A and B. In the examples of the present application, the structures of other repeating units in the fluorine-containing additive are not limited.

[0060] In some embodiments of the present application, the molar proportion of the fluorinated repeating unit B derived from the fluorinated monomer B with an aliphatic ring structure in all the repeating units of the fluorinated additive can be 10%-70%. This effectively ensures that the fluorinated additive has certain differences from the fluorinated host resin, which is beneficial for the fluorinated additive to smoothly float to the surface of the film layer during the coating and film formation process of the above-mentioned patterned composition, so that it can smoothly play its role of hydrophobicity and blocking PAG dissolution during immersion exposure. Specifically, the molar proportion can be 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, etc.

[0061] In some possible embodiments of the present application, the molar proportion of the fluorinated repeating unit B in the fluorinated additive is 30%-60%. This facilitates good compatibility between the fluorinated additive and the fluorinated host resin, preventing phase separation that would otherwise result in uneven coating of the patterned composition and pattern defects. Furthermore, the fluorinated additive is more likely to float smoothly to the film surface during the coating process of the patterned composition containing the fluorinated host resin, thereby exerting its hydrophobic properties, preventing PAG dissolution, and reducing pattern watermark defects.

[0062] In some embodiments of the present application, the molar proportion of the fluorinated repeating unit A with a hexafluoroisopropanol structure in the fluorinated additive may be less than 90%, for example, 20%-90%, and specifically 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, or 85%. In some embodiments, the molar proportion of the fluorinated repeating unit A in the fluorinated additive is 30%-90%. In this case, the fluorinated additive comprising the fluorinated repeating unit A and the fluorinated repeating unit B with an aliphatic ring structure can better exert its hydrophobicity, block PAG dissolution, and reduce pattern watermark defects.

[0063] Illustratively, the above-mentioned fluorine-containing additive can be prepared by the following method: in the presence of an initiator, a monomer raw material for synthesizing the fluorine-containing additive is subjected to a polymerization reaction in a solvent to obtain the fluorine-containing additive; wherein the monomer raw material includes a fluorine-containing monomer A with a hexafluoroisopropanol structure and a fluorine-containing monomer B with an aliphatic ring structure.

[0064] The initiator may be a free radical polymerization initiator such as a hydroperoxide, a dialkyl peroxide, a diacyl peroxide, or an azo compound. The polymerization reaction temperature may be 40-150°C, for example, 60°C, 70°C, 80°C, 100°C, 110°C, 120°C, or 130°C. The polymerization reaction time may be 1-48 hours, which may be adjusted based on the desired molecular weight of the fluorinated additive.

[0065] In addition, after the polymerization reaction is completed, the reaction material containing the fluorine-containing additive can be placed in a sedimentation agent (such as methanol, ethanol, isopropanol, etc.) for sedimentation to precipitate the fluorine-containing additive.

[0066] In the embodiments of the present application, the mass of the fluorine-containing additive in the patterned composition is less than that of the fluorine-containing main resin. 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, for example, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 9.5%. Controlling the amount of the fluorine-containing additive relative to the fluorine-containing main resin within an appropriate range can ensure that it can fully exert its hydrophobic effect and prevent PAG dissolution during immersion exposure, while preventing development defects in the film layer of the patterned composition after exposure due to excessive use.

[0067] In the embodiments of the present application, the acid-labile repeating units with acid-labile groups in the above-mentioned fluorine-containing main resin ensure that the acid-labile groups can undergo bond cleavage under photoacid catalysis during the baking process after exposure, thereby changing the polarity of the resin (for example, the acid-labile groups can be converted into carboxyl groups, making the resin alkali-soluble).

[0068] In some embodiments of the present application, the acid-labile repeating unit may have a structure shown in formula (I): Formula (I) Among them, R c Including hydrogen atoms, methyl (-CH3) or trifluoromethyl (-CF3), AL includes an acid-labile group, and the acid-labile group includes an aliphatic ring structure. That is, the aliphatic 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 3-20 Cycloalkyl, any two R3 can be bonded to each other to form a ring.

[0069] Here, "any two R3's bonded together to form a ring" means that any two R3's bonded together, together with the carbon atoms to which they are bonded, form a divalent alicyclic hydrocarbon group. The acid-labile group AL includes an alicyclic structure, specifically 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). Under photoacid catalysis accompanied by heat treatment, the AL group in formula (I) can undergo bond cleavage, resulting in the conversion of -COO-AL in formula (I) to the polar group -COOH.

[0070] In some embodiments of the present application, the acid-labile repeating unit may include a repeating unit derived from at least one of the following monomers: .

[0071] The repeating unit with a lactone structure in the fluorine-containing main resin can help enhance the adhesion between the dried film layer of the patterned composition and the attached substrate, and improve the dry etching resistance of the film layer.

[0072] As described above in this application, an aliphatic ring structure containing a -C(=O)-O- group in the ring backbone can be referred to as a lactone structure. The aliphatic ring structure may or may not have a substituent (i.e., the lactone structure may or may not have a substituent). For substituents on the aliphatic ring structure, reference can be made to the description of substituents in the substituted aliphatic ring structure in R2 above in this application. Furthermore, it should be noted that, in addition to the -C(=O)-O- group, the ring backbone of the lactone structure may also contain one or more of -O-, -S-, etc.

[0073] Exemplarily, the repeating unit of the lactone structure can be selected from one or more of the following structures:

[0074]

[0075] .

[0076] In the above repeating units, R d are independently selected from a hydrogen atom, a methyl group or a trifluoromethyl group.

[0077] In the above-mentioned fluorine-containing main resin, the repeating unit with the hexafluoroisopropanol structure helps to enhance the solubility of the fluorine-containing main resin in the developer, and accordingly also enhances the developing effect of the above-mentioned patterning composition.

[0078] In some embodiments of the present application, in the fluorine-containing main resin, the structure of the repeating unit with a hexafluoroisopropanol structure can be as shown in formula (II): Formula (II) Wherein, L1' is a divalent linking group including an aliphatic ring structure.

[0079] Regarding this divalent linking group, please refer 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 contain an aliphatic ring structure, while L1 may or may not contain an aliphatic ring structure.

[0080] In formula (II), the aliphatic ring structure can be a divalent substituted or unsubstituted cycloalkylene group (on the same chain as the -COO- group in formula (II)), or a monovalent substituted or unsubstituted cycloalkyl group (i.e., it is not on the same chain as the -COO- group in formula (II) and serves as a substituent on a carbon atom in the main chain of L1').

[0081] Exemplarily, the repeating unit represented by formula (II) can be derived from one or more of the following monomers: .

[0082] It is understood that in some embodiments of the present application, the fluorinated main resin may further include other repeating units that are different from the acid-labile repeating units, repeating units with lactone structures, and repeating units with hexafluoroisopropanol structures. In the examples of the present application, the structures of the other repeating units in the fluorinated main resin are not limited.

[0083] In some embodiments of the present application, in the fluorine-containing main resin, in addition to the repeating units with a hexafluoroisopropanol structure containing fluorine atoms, one or more of the acid-labile repeating units, repeating units with polar groups, or other repeating units may also contain fluorine atoms, but not all repeating units containing fluorine main atoms contain fluorine.

[0084] In some embodiments of the present application, in the fluorinated main resin, the molar proportion of the acid-labile repeating unit may be 10-70%, the molar proportion of the repeating unit with a polar group may be 5-80%, and the molar proportion of the repeating unit with a hexafluoroisopropanol structure may be 1%-20%. The molar proportion of each of the above repeating units specifically refers to its molar proportion in all the repeating units in the fluorinated main resin.

[0085] In some embodiments, the molar proportion of the acid-labile repeating units in the fluorine-containing main resin can be 30-65%, for example, 35%, 40%, 45%, 48%, 50%, 52%, 55%, 58%, or 60%. The molar proportion of the repeating units with polar groups in the fluorine-containing main resin can be 30-60%, for example, 32%, 35%, 40%, 42%, 45%, 47%, 48%, 50%, 52%, or 55%. The molar proportion of the repeating units with hexafluoroisopropanol structures in the fluorine-containing main resin can be 2%-15%, for example, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or 12%.

[0086] Similar to the synthesis of the above-mentioned fluorine-containing additive, the above-mentioned fluorine-containing main resin can also be obtained by polymerizing the corresponding monomer raw materials in a solvent in the presence of an initiator.

[0087] In some embodiments of the present application, in the above-mentioned fluorine-containing main resin, the monomer corresponding to the acid-labile repeating unit includes and , the monomers corresponding to the repeating units with polar groups include , the monomers corresponding to the repeating units with hexafluoroisopropanol structure include .

[0088] In the embodiments of this application, the photoacid generator (PAG) is a substance that generates photoacid when exposed to an exposure source. There are no specific requirements for the PAG in this application. In some embodiments, the PAG may include a small molecule onium salt, such as a sulfonium salt, an iodonium salt, or a diazonium salt. For example, a sulfonium salt may include a sulfonium cation and an anion containing an acidic group.

[0089] In some embodiments of the present application, the sulfonium salt used as the photoacid generator may have a structure represented by the following formula (III): Formula (III) Wherein, R4, R5, and R6 are independently selected from substituted or unsubstituted monovalent hydrocarbon groups containing or not containing heteroatom linking groups, and any two of R4, R5, and R6 can be bonded to each other to form a ring, and X - is an anion containing an acidic group, wherein the acidic group may include one or more of a sulfonate group, a sulfate group, a carbonate group, a fluorosulfonamide group, and the like.

[0090] The monovalent hydrocarbon group may include one or more of an alkyl group, a cycloalkyl group, a chain or cyclic alkenyl group, a chain or cyclic alkynyl group, and an aryl group, and these hydrocarbon groups may be unsubstituted or substituted. As for the heteroatom linking group, as described above, it may include one or more of an ether bond (-O-), a thioether bond (-S-), a carbonyl group (-C(=O)-), -C(=O)-O-, -OCO-, an imine bond (-NH-), an amide bond (-NHCO-), a carbamate bond (-NH-COO-), a sulfonyl bond (-SO2-), a sulfonate bond (-OS(=O)2-), a carbonate bond (-OC(=O)-O-), and -C(=O)-OC(=O)-.

[0091] In some possible embodiments, the sulfonium cation in the sulfonium salt may include any of the following structures.

[0092]

[0093] In some possible embodiments, X in formula (III) - Can be R e -CF2-SO3 - , where R e is a substituted or unsubstituted monovalent hydrocarbon group containing or not containing a heteroatom linking group. In some cases, R e is a fluorine atom, a fluoroalkyl group, R'-OC(=O)-, or R'-C(=O)-O-, wherein R' is a substituted or unsubstituted aliphatic saturated hydrocarbon group. The substituent in the substituted aliphatic saturated hydrocarbon group may include, but is not limited to, one or more of a halogen atom, a hydroxyl group, a cyano group, an ester group, an alkyl group, a cycloalkyl group, and the like.

[0094] Exemplary photoacid generators include, but are not limited to, one or more of the following: P1 P2

[0095] P3 P4

[0096] In an embodiment of the present application, the mass of the photoacid generator is 0.5%-20% of the mass of the fluorine-containing main resin. Controlling the mass ratio of the photoacid generator to the fluorine-containing main resin within an appropriate range can ensure that the acid-labile groups of the fluorine-containing main resin are fully broken during the post-exposure baking process, while not increasing the degree of acid diffusion of the patterned composition film layer during the post-exposure baking process due to an excessive proportion of the mass of the photoacid generator, thereby reducing the pattern resolution. Exemplarily, the mass of the photoacid generator is 1%, 2%, 5%, 6%, 8%, 10%, 15%, 18%, 20%, etc., of the mass of the base resin.

[0097] In some embodiments of the present application, the patterning composition further comprises an acid quencher. The presence of the acid quencher can help quench excess photoacid generated by the fluorine-containing host resin during exposure, thereby inhibiting photoacid diffusion and preventing a reduction in the resolution of a pattern formed using the patterning composition.

[0098] There is no special requirement for the structure of the acid quencher in this application. For example, the acid quencher may include one or more of the following substances: Q1: Q2: .

[0099] In the embodiment of the present application, the mass of the acid quencher does not exceed 10% of the mass of the above-mentioned fluorine-containing base resin, for example, specifically 0.2%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, and 8%.

[0100] In an embodiment of the present application, the patterned composition further comprises an organic solvent. The organic solvent comprises one or more of a ketone solvent, an ester solvent, an ether solvent, and an alcohol solvent. The organic solvent can effectively dissolve the components of the patterned composition. In particular, the fluorine-containing additive can be effectively dissolved in the organic solvent without precipitation and affecting the stability of the patterned composition.

[0101] For example, ketone solvents may include, but are not limited to, one or more of 2-heptanone, methyl-2-n-pentanone, cyclohexanone, and cyclopentanone. Ester solvents may include, but are not limited to, one or more of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, butyl acetate, methyl 3-methoxypropionate, γ-butyrolactone (GBL), and methyl 2-hydroxyisobutyrate (HBM). Ether solvents may include, but are not limited to, one or more of propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether. Alcohol solvents may include, but are not limited to, one or more of isopropyl alcohol and 3-methoxybutanol. In some embodiments, the organic solvent may include PGMEA and GBL in a volume ratio of 8:2.

[0102] In addition, other additives may be added to the patterning composition as needed, such as one or more of a defoaming agent, a sensitizer, an anti-halation agent, etc.

[0103] In embodiments of the present application, the solid content of the patterned composition may be 2 wt% to 10 wt%. Controlling the solid content of the patterned composition within an appropriate range can help ensure that the patterned composition has a suitable viscosity and coating thickness. The solid content refers to the sum of the weight percentages of all components in the patterned composition, excluding the organic solvent.

[0104] The above-mentioned patterned composition in the embodiment of the present application has good coating performance, is easy to coat and form a film, the surface of the formed coating film layer is smooth, the film thickness is easy to adjust, and the development conditions meet the requirements of the patterning process, which is convenient for application in the field of semiconductor patterning.

[0105] The present application also provides a patterning method, such as Figure 1 As shown, the patterning process includes: S01, coating the patterned composition of the embodiment of the present application on a substrate to form a patterned material film layer on the substrate; S02, exposing and baking the patterned material film layer in sequence, and then developing it with a developer to form a patterned thin film on the substrate.

[0106] In step S01, the substrate to be coated with the patterned composition can be selected based on specific needs. For example, it can be a silicon wafer or a silicon wafer covered with other layers. Other layers can include, but are not limited to, one or more of a bottom anti-reflective coating (BARC), an epitaxial layer, a metal layer, and a dielectric layer (such as SiO2 or Si3N4). These other layers are typically obtained by pre-treating the substrate. These pre-treatment methods include: surface hydrophilization with an O2 plasma; cleaning in a Piranha solution (H2O: 30% ammonia: 30% H2O2 = 5:1:1) for 15-20 minutes, followed by a deionized water rinse and an isopropyl alcohol rinse to achieve hydrophilic treatment; or coating the substrate with hexamethyldisilazane (HMDS) by evaporation or spin coating to render the substrate hydrophobic.

[0107] The patterning composition may be applied by methods including, but not limited to, spin coating, dip coating, brush coating, spray coating, and roller coating. In some possible embodiments, the coating method may be spin coating. Depending on the size of the substrate, an appropriate volume of the patterning composition may be spin-coated onto the substrate to form a patterned material film layer of a predetermined thickness. Exemplarily, the coating thickness of the patterning composition may be in the range of 5 nm to 2 μm.

[0108] As previously described in this application, the structure of the aforementioned fluorine-containing additive is highly compatible with the other components of the patterning composition (e.g., the fluorine-containing main resin, PAG, etc.). Therefore, during the coating process of the patterning composition containing the aforementioned fluorine-containing additive, uneven component extraction / distribution, film formation defects, etc. are less likely to occur. Furthermore, during the coating and film formation process of the patterning composition, the aforementioned fluorine-containing additive can float to the surface of the film layer, resulting in a patterned material film layer comprising a top and bottom layer structure. The bottom layer (closer to the coated substrate) primarily comprises the fluorine-containing main resin, PAG, and an optional acid quencher, while the top layer (farther from the coated substrate) primarily comprises the fluorine-containing additive, which provides hydrophobic protection for the bottom layer. Consequently, it is unnecessary to form an additional topcoat layer on the surface of the patterned material film layer.

[0109] In some embodiments of the present application, a post-apply bake (PAB) is performed after applying the patterning composition to minimize the solvent content in the patterning composition. The pre-bake can be performed on a hot plate or in an oven. Typical pre-bake temperatures range from 60°C to 150°C, and durations range from 10 seconds to 30 minutes. In one embodiment, the pre-bake temperature ranges from 90°C to 120°C, and durations range from 30 seconds to 10 minutes, and further ranges from 30 seconds to 90 seconds.

[0110] In step S02, the exposure source used for exposure can be a light source with a wavelength below 400 nm, X-rays, or an electron beam. Exemplary exposure sources can include deep ultraviolet light with a wavelength of 193 nm or 248 nm. During immersion exposure, a mask with a predetermined pattern can be placed above the patterned material film layer, and an immersion exposure device can illuminate the patterned material film layer through the mask to achieve selective exposure (i.e., patterned exposure). During exposure, a liquid medium, such as pure water, is present between the surface of the patterned material film layer and the lens of the immersion exposure device.

[0111] Among them, during the immersion exposure process, the fluorine-containing additive located on the upper part of the patterned material film layer has a hydrophobic effect and can prevent the liquid medium for immersion exposure, such as water, from invading the lower part of the patterned material film layer, thereby preventing the dissolution of PAG components in the film layer, and thus facilitating the shape of the subsequently formed patterned film to be closer to the mask plate used and have a higher resolution.

[0112] After selective exposure of the patterned material film, the PAG in the exposed areas decomposes to produce acid. Post-exposure baking (PEB) is performed after exposure to ensure that the acid generated during the exposure process catalyzes the deprotection of the acid-labile groups of the fluorine-containing host resin in the exposed areas of the patterned material film, thereby achieving polarity reversal of the resin. This in turn creates a difference in solubility in the developer between the exposed and non-exposed areas of the film. The PEB is typically performed at a temperature of 60-200°C and for a duration of 10 seconds to 30 minutes. In some embodiments, the PEB temperature is 100-130°C and the duration is 30 seconds to 10 minutes, or even 30-90 seconds.

[0113] Since the chemical properties of the exposed portion of the patterned material film layer change, its solubility in the developer is different from that of the unexposed portion. Therefore, the patterned material film layer that has been exposed and baked is treated with a developer to achieve selective dissolution and patterning of the patterned material film layer. The development process can select a suitable developer according to the properties of the patterned material. In some embodiments of the present application, the developer includes an alkaline aqueous solution. After being treated with the alkaline developer, the exposed area of the patterned material film layer will dissolve in the alkaline developer and be removed, and the unexposed area is almost insoluble in the alkaline developer, thereby forming a target positive pattern (such as Figure 1 ), which is basically the same as the pattern of the exposure mask.

[0114] Since the above-mentioned fluorine-containing additive contains a repeating unit with a hexafluoroisopropanol structure, the additive has good solubility in the alkaline developer. Even if it is located above the film layer whose main components are the fluorine-containing main resin and PAG, it will not affect the removal of the exposed area of the patterned material film layer during the development process.

[0115] The alkaline substance in the alkaline aqueous solution includes one or more of sodium hydroxide, potassium hydroxide, ammonia water, sodium carbonate, triethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), etc.

[0116] In some embodiments of the present application, the developer containing the alkaline aqueous solution may further contain an organic solvent. The organic solvent used for development should be miscible with water and may include, but is not limited to, one or more of ketone solvents, alcohol solvents, ether solvents, and ester solvents. For examples of these organic solvents, please refer to the list of organic solvents in the patterning composition above in this application.

[0117] Common development methods such as dipping or spraying can be used. Specifically, the exposed and baked patterned material film layer can be immersed in a developer, or the developer can be sprayed onto the surface of the exposed and baked patterned material film layer. The contact time between the developer and the patterned material film layer (i.e., the development time) can range from 3 seconds to 180 seconds, and further from 5 seconds to 120 seconds.

[0118] After development, a water rinse can be optionally added for 20-120 seconds to clean the film. A baking process (i.e., post-bake) can also be added. This hardens the pattern structure, making it more stable and less prone to collapse. The post-bake temperature can range from 60-200°C, and the time can range from 20-120 seconds. In some embodiments, the post-bake is performed at 90°C for 60 seconds.

[0119] After development, the obtained patterned film can be observed using an electron microscope or an atomic force microscope to observe whether there are pattern defects and to obtain parameters such as pattern resolution and line width roughness.

[0120] In some embodiments of the present application, after the above step S02, the following step S03 is further included: using the above patterned film as a mask, etching the substrate to transfer the pattern of the patterned film to the substrate to obtain a patterned substrate.

[0121] The patterned film has excellent etch resistance during the etching step and can selectively protect the underlying substrate material. Under certain etching conditions, the substrate material not protected by the patterned film can be etched away, while the substrate material protected by the patterned film can be retained, ultimately forming a pattern on the substrate material, i.e., transferring the pattern of the patterned film to the substrate. Exemplarily, the etching medium used in the etching process can be a fluorine-containing gas. Generally, the patterned film is subsequently removed (e.g., by ashing) to allow the fabrication of other functional layers on the patterned substrate.

[0122] The patterning method provided in the embodiment of the present application can be applied to the patterning process of the semiconductor integrated circuit manufacturing process by adopting the patterning composition of the embodiment of the present application to obtain a pattern structure with good pattern shape and high resolution, which is conducive to the development of semiconductor devices towards high integration and high precision.

[0123] The present invention also provides a patterned film formed using the patterning composition described above or obtained using the patterning method described above. The patterned film can be used to fabricate high-precision masks used in integrated circuit patterning processes. The pattern of the patterned film can be transferred to a substrate, such as a silicon wafer, by etching to form a predetermined pattern on the substrate.

[0124] Since the patterned composition contains a specific fluorine-containing additive, the film layer thereof can have good hydrophobicity and low resistance to PAG dissolution during immersion exposure, thereby obtaining a patterned film with a satisfactory pattern shape and good depth of focus (DOF) after baking and development.

[0125] The present invention also provides a patterned substrate. The pattern on the patterned substrate is formed using the patterned composition described in the present invention or obtained using the patterning method described above. The patterned substrate can be used in the manufacture of semiconductor devices (such as chips), improving the fabrication precision and quality of the devices, thereby enhancing the performance of the semiconductor devices.

[0126] In some embodiments of the present application, a method for preparing a patterned substrate includes: The patterned film is formed on a substrate; and the pattern of the patterned film is transferred to the substrate to obtain a patterned substrate.

[0127] Among them, the process of forming a patterned film can refer to the description in the previous part of this application, and will not be repeated here. "Transferring the pattern of the patterned film to the substrate" can be achieved by selectively etching the substrate material under the action of the mask of the patterned film. Among them, etching can specifically be etching with a fluorine-containing gas, or ion etching, etc. The substrate material that is not protected by it is etched, and the etching speed of the protected part is slower than that of the unprotected part, and finally a pattern is formed on the substrate material, that is, 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 below it to achieve patterning of other film layers, and the substrate also has the pattern of other film layers accordingly; it can also be directly etched on the basis of the patterned other film layers to achieve patterning of the substrate.

[0128] The present invention also provides a semiconductor device that uses the patterned substrate of the present invention, or a method for preparing the semiconductor device includes the patterning method of the present invention. The semiconductor device has a high manufacturing yield, high precision, and stable performance.

[0129] The semiconductor device may include a chip, etc. During the preparation of the chip, other functional layers may be prepared after the above patterning process is completed.

[0130] Specifically, the semiconductor device provided in the embodiments of the present application can be used in terminal devices, such as tablet computers, laptop computers, mobile phones, digital cameras, wearable electronic devices, virtual reality devices, etc.

[0131] The present invention also provides a method for manufacturing a semiconductor device, comprising: A patterned substrate is prepared by the aforementioned patterning method; The structure required for the semiconductor device is formed on the patterned substrate to obtain the semiconductor device.

[0132] The structure required for the semiconductor device may also be formed on the basis of the patterned thin film provided in the embodiment of the present application.

[0133] The embodiments of the present application are further described below with reference to a number of embodiments.

[0134] Example 1 (1) Preparation of fluorine-containing main resin: The fluorine-containing main resin used in Example 1 of the present application is obtained by acid-unstable monomer 1 , acid-labile monomer 2 , monomer 3 with lactone skeleton and monomer 4 with hexafluoroisopropanol structure The fluorine-containing main resin is obtained by polymerization reaction in the presence of an initiator in a molar ratio of 45:10:30:15. w It is 10.1k.

[0135] (2) Preparation of fluorine-containing additives: Under a nitrogen atmosphere, the fluorinated monomer A represented by formula (A6) and the fluorinated monomer B represented by formula (B1) were mixed in a solvent (specifically, isopropyl acetate) at a molar ratio of 40:60. After stirring, a certain amount of initiator, azobisisobutyronitrile (AIBN), was added and polymerization was carried out at 85°C for 6 hours. After the reaction, the resulting reaction solution was added to methanol for precipitation to obtain the desired fluorinated additive, designated as F1.

[0136] The M of the fluorinated additive was determined by gel permeation chromatography using polystyrene as a standard. w 4500, M w / M n is 1.03.

[0137] A6: B1: .

[0138] (III) Preparation of Patterned Composition 100 parts by mass of the aforementioned fluorinated host resin, 5 parts by mass of the aforementioned fluorinated additive, 15 parts by mass of a photoacid generator (PAG), and 1 part by mass of a quencher were mixed in a mixed solvent consisting of PGMEA and GBL in a mass ratio of 8:2. After thorough stirring, a patterned composition having a solid content of 6.5% was obtained. Specifically, the PAG used in Example 1 was 10 parts by mass of the substance represented by Formula (P1) and 5 parts by mass of the substance represented by Formula (P2); the quencher was the substance represented by Formula (Q1).

[0139] P1: P2: Q1:

[0140] The patterned composition provided in Example 1 was subjected to the following tests, and the test results are summarized in Table 1.

[0141] Hydrophobicity test of patterned composite film layer: Each patterned composition was spin-coated onto a silicon wafer and baked at 110°C for 60 seconds to form a patterned material film. Pure water was then dropped onto the patterned material film, and the static contact angle of water on the film surface was measured using a contact angle meter.

[0142] Dissolution test of patterned composition film layer: Each patterning composition was spin-coated onto a silicon wafer and baked at 110°C for 60 seconds to form a patterned material film layer approximately 160 nm thick. The silicon wafer was then bonded to a silicone rubber sheet with a central hollow (the hollowed-out portion was filled with 10 mL of ultrapure water), ensuring contact between the patterned material film surface and the ultrapure water for 10 seconds without leaking from the silicone rubber sheet. The silicon wafer was then removed, and the ultrapure water was recovered using a glass syringe to prepare the analysis sample. The peak intensity of the photoacid generator (PAG) anion in the recovered ultrapure water sample was then measured using liquid chromatography-mass spectrometry (LC-MS) at 35°C, using a mixture of 0.1 wt% formic acid in a 3:7 volume ratio of water and methanol as the mobile phase. Under the same test conditions, the peak intensities of 1 ppb, 10 ppb, and 100 ppb aqueous solutions of PAG were measured to create a standard curve. The dissolved amount was calculated from the peak intensities measured above using the standard curve. The unit is 10 -12 mol / cm 2 / s.

[0143] Patterning compositions are used in patterning processes: First, HMDS was evenly coated on the surface of a silicon wafer using vapor deposition (evaporation temperature: 120°C, time: 60 seconds) to render the surface hydrophobic. Next, a bottom anti-reflective coating (BARC) with a thickness of approximately 90 nm was formed on the HMDS-deposited silicon wafer.

[0144] Next, each patterned composition was spin-coated onto the BARC coating surface of the silicon wafer, and PAB baking was performed (110° C., 60 seconds) to form a patterned material film layer with a thickness of about 160 nm.

[0145] The patterned material film was then selectively exposed using an ArF excimer laser immersion lithography system through a mask with a periodic line pattern (Dense S68P128, with a line pitch of 68nm, a period of 128nm, and a line width of 60nm). During exposure, pure water was used as the immersion solvent between the film and the immersion lithography lens. A PEB bake (90°C, 60 seconds) was performed immediately after exposure.

[0146] Finally, the patterned material film layer after the above treatment was immersed in a 2.38wt% tetramethylammonium hydroxide (TMAH) aqueous solution at 25°C for 60 seconds, and then washed with water and dried to form a positive patterned film with a periodic line pattern on the BARC coating of the silicon wafer.

[0147] The exposure when the critical dimension (CD) of the patterned film reaches the target value (specifically, the line spacing is close to the mask used) is taken as the optimal exposure. This optimal exposure is the sensitivity. The test results are summarized in Table 1.

[0148] In addition, the cross-sectional shape of the pattern of the patterned film obtained after exposure and development using the above-mentioned mask plate Dense S68P128 was observed using a scanning electron microscope (SEM), and the line width L in the middle of the pattern was measured. b and the line width L at the top of the film a , will be in the range of 0.9≤(L a -L b ) / L b The results are summarized in Table 1.

[0149] According to the formulations shown in Table 1 below, patterned compositions required for other examples or comparative examples were prepared, and the differences from Example 1 are listed in Table 1 below. Relevant test results of these patterned compositions are also summarized in Table 1.

[0150] Table 1

[0151] In Table 1 above, the fluorine-containing additive F2 used in Examples 4-6 is a polymer formed by copolymerizing the fluorine-containing monomer A6 and the fluorine-containing monomer B1 in a molar ratio of 50:50.

[0152] The fluorine-containing additive F3 used in Example 9 is a polymer formed by copolymerizing a fluorine-containing monomer A6 with a hexafluoroisopropanol structure and a fluorine-containing monomer B1 with an aliphatic ring structure in a molar ratio of 92:8.

[0153] The fluorine-containing additive F4 used in Example 10 is a polymer formed by copolymerizing a fluorine-containing monomer A6 with a hexafluoroisopropanol structure and a fluorine-containing monomer B1 with an aliphatic ring structure in a molar ratio of 20:80.

[0154] The fluorine-containing additive DF1 used in Comparative Example 2 was obtained by polymerizing only the fluorine-containing monomer A represented by formula (A6) having a hexafluoroisopropanol structure.

[0155] As shown in Table 1 above, a comparison between each embodiment and Comparative Example 1, which does not include a fluorine-containing additive, indicates that when a fluorine-containing additive meeting the requirements of the present application is added to a patterned composition containing a fluorine-containing host resin, the fluorine-containing additive can float to the surface during the film formation process of the patterned composition. This improves the hydrophobicity of the patterned composition film (as demonstrated by a larger static water contact angle) and reduces the dissolution of the PAG beneath the film during immersion exposure. This does not affect the exposure sensitivity of the overall patterned material film, resulting in a good patterned film shape after exposure, baking, and development. Furthermore, a comparison between Example 8 and Comparative Example 2 in Table 1 indicates that when a fluorine-containing additive is included in the patterned composition, but the structure of the fluorine-containing additive does not meet the requirements of the embodiments of the present application, its effect in improving the hydrophobicity of the patterned material film and preventing PAG dissolution is less pronounced.

[0156] In addition, from the comparison between Examples 1 and 4 and Examples 9-10 in Table 1, it can be seen that when the mass proportions of the fluorine-containing additives used in the composition are similar, when the molar proportion of the fluorine-containing monomer B derived from the aliphatic ring structure in the fluorine-containing additive is greater than 8% and less than 80% (for example, 10-70%), the fluorine-containing additive has a more obvious effect of improving the hydrophobicity of the patterned material film layer and preventing the dissolution of PAG.

[0157] Figure 2 SEM images of patterned films formed by the patterned compositions of Example 1 and Comparative Example 1 through a patterning process of immersion exposure using the above-mentioned mask Dense having a periodic line pattern are also summarized. Figure 3 SEM images of patterned films formed by the patterned compositions of Example 1 and Comparative Example 1 through immersion exposure using a mask Semi (S85P210, i.e., line spacing of 85 nm and period size of 210 nm) having a periodic line pattern are also summarized. Figure 4 SEM images of patterned films formed by the patterned compositions of Example 1 and Comparative Example 1 through immersion exposure using a mask plate Iso (S110P1500, i.e., line spacing of 110 nm and period size of 1500 nm) having a periodic pattern are also summarized.

[0158] from Figures 2 to 4The obtained depth of focus data and line width roughness (LWR) of each patterned film at the optimal exposure are summarized in Table 2 below.

[0159] Table 2

[0160] As can be seen from Table 2, when the same mask is used for immersion exposure, the patterned film formed using the patterning composition of Example 1 with the addition of a specific fluorine-containing additive can have a smaller or constant depth of focus (a smaller depth of focus can reflect a higher pattern resolution) and / or a lower low edge roughness (LWR), resulting in higher overall pattern quality.

[0161] The foregoing merely represents exemplary embodiments of the present application, and while the description is relatively specific and detailed, it should not be construed as limiting the scope of the present invention. It should be noted that a person of ordinary skill in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.

[0162] It should be understood that the first, second, and various numerical references used herein are merely distinctions for ease of description and are not intended to limit the scope of this application. In this application, "and / or" describes the relationship between associated objects, indicating that three possible relationships exist. For example, "A and / or B" can represent: A alone, A and B simultaneously, and B alone, where A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0163] In the description of this application, unless otherwise specified, "multiple" means greater than or equal to two. "At least one" means one or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single or plural items. For example, "at least one of a, b, or c" or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or plural.

[0164] In addition, the numerical range indicated by "-" in this application refers to the range that includes the numerical values recorded before and after the "-" as the minimum and maximum values, respectively. In this application, expressions about parameter ranges, such as "greater than or equal to (≥)", "less than or equal to (≤)", "above...", and "below..." all include the number itself. The numerical values and numerical ranges involved in the embodiments of this application are approximate values. Due to the influence of manufacturing processes / testing methods, etc., there may be a certain range of errors. Those skilled in the art can consider this part of the error to be negligible.

Claims

1. A patterned composition, characterized in that The invention 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; The fluorine-containing additive is a polymer including repeating units derived from a fluorine-containing monomer A and repeating units derived from a fluorine-containing monomer B, wherein the fluorine-containing monomer A includes a hexafluoroisopropanol structure, and the fluorine-containing monomer B includes an aliphatic ring structure.

2. The patterned composition according to claim 1, wherein The fluorinated monomer A comprises a structure represented by formula (A), and the fluorinated monomer B comprises a structure represented by formula (B): Formula (A) Formula (B) Wherein, R, R' are independently selected from hydrogen atom, fluorine atom, methyl, or trifluoromethyl, L1 is a divalent linking group, R1 includes 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 carries a fluorine atom, but -L2-R2 does not include the hexafluoroisopropanol structure.

3. The patterned composition according to claim 2, wherein The L1 is selected from one or more of a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, and a lactone ring containing or not containing a heteroatom linking group; wherein the heteroatom linking group includes -C(=O)-O- # and -OC(=O)- # At least one of them, the # end is close to the R1.

4. The patterned composition according to claim 2, wherein In R2, the substituents in the substituted aliphatic ring structure include one or more of a fluorine atom, a fluoroalkyl ester group, and a fluoroalkyl group.

5. The patterned composition according to any one of claims 1 to 4, wherein The repeating units derived from the fluorine-containing monomer B account for 10% to 70% by mole in the fluorine-containing additive.

6. The patterned composition according to any one of claims 1 to 4, wherein The mass of the fluorine-containing additive is 0.5%-10% of the mass of the fluorine-containing main resin.

7. A patterned film, characterized in that: The patterned thin film is formed by the patterned composition according to any one of claims 1 to 6.

8. A patterned substrate, characterized in that The pattern on the patterned substrate is formed using the patterning composition according to any one of claims 1 to 6.

9. A semiconductor device, characterized in that: The method is to use the patterned film as claimed in claim 7, or to use the patterned substrate as claimed in claim 8.

10. A method for manufacturing a semiconductor device, characterized in that: include: coating the patterning composition according to any one of claims 1 to 6 on a substrate to form a patterned material film layer on the substrate; The patterned material film layer is sequentially exposed and baked, and then developed with a developer to form a patterned thin film on the substrate.

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