Protective layer compositions and their applications, electronic devices and their manufacturing methods

Abstract

This application provides a protective layer composition and its application, as well as an electronic device and its manufacturing method. The protective layer composition includes a resin and an organic solvent. The resin comprises a structured polyaryl ester and a second polymer, with the polyaryl ester and the second polymer comprising 80%-99% and 1%-20% of the resin by mass, respectively. The second polymer comprises polycarbonate with repeating units and / or a polymer with repeating units. This protective layer composition can reduce metal contamination of the non-patterned areas of the substrate caused by metal-based patterned materials or their associated layer materials during the formation of patterned thin films. Furthermore, the contaminant can be easily removed subsequently, improving the fabrication yield and performance reliability of the electronic device.

Description

Technical Field

[0001] This application relates to the field of patterning technology, specifically to a protective layer composition and its application, electronic devices and their manufacturing methods. Background Technology

[0002] The fabrication process of electronic devices typically involves patterning. Among these processes, metal-based patterning compositions containing metal elements exhibit significant advantages in forming patterns with small feature sizes. However, during the coating process of the metal-based patterning composition or its supporting layer materials (such as metal-based hard mask materials to improve pattern resolution) onto a substrate (such as a wafer), the metal can flow towards the edges of the substrate, making the substrate edges susceptible to contamination by metal elements. This can negatively impact the fabrication yield and reliability of electronic devices.

[0003] Applying an edge protection material to the substrate edge can reduce the aforementioned metal contamination problem to some extent. Theoretically, the edge protection material must simultaneously meet several requirements, such as good resistance to solvents, edge cleaners, and developers in the metal-based patterning composition, and rapid removal by specific solvents. However, practically used substrate edge protection materials rarely meet all these requirements simultaneously, hindering their widespread application. Summary of the Invention

[0004] In view of this, embodiments of this application provide a protective layer composition and its application, an electronic device and its manufacturing method. The protective layer formed by using this protective layer composition can take into account both good chemical resistance and easy removal, so as to effectively reduce the metal contamination of the substrate edge by the metal base material during the manufacturing process of electronic devices, and the removal of the metal does not affect the quality of the formed pattern.

[0005] Specifically, the first aspect of this application provides a protective layer composition comprising a resin and an organic solvent. The resin comprises 80%-99% by mass of a polyarylate and 1%-20% by mass of a second polymer. The polyarylate has the structure shown in formula (I). The second polymer comprises one or more of a polycarbonate having repeating units shown in formula (II) and a polymer having repeating units shown in formula (III).

[0006]

[0007] Where m and p are both greater than 0, Ar1 is selected from divalent groups including at least two connected aromatic rings, and Ar2 is a divalent group containing at least one aromatic ring; X is selected from -S(=O)-, -S(=O)2-, and -C(=O)-; L is selected from single bonds, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, substituted or unsubstituted C 1-5 One of the alkylene groups;

[0008] R, R 1 R 2 R 3 R 4 Each occurrence is independently selected from one of the following: halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkyl carbonyl group, substituted or unsubstituted aryl group, where n, a, b, c, d are independently integers from 0 to 4, and e is 0 or 1.

[0009] The aforementioned protective layer composition can be used to reduce metal contamination at the edges of substrates. This protective layer composition contains two types of polymers. The polyarylate with the specific structure described above has no significant solubility in chain aliphatic solvents and exhibits good solubility in aromatic solvents such as anisole. The second polymer primarily helps improve the removal efficiency of the film layer from aromatic solvents. When these two types of polymers are mixed in a specific mass ratio to form the resin of the protective layer composition, the film layer of this protective layer composition can be guaranteed to have good resistance to solvents, edge washers, developers, etc. (such as linear fatty ketones, fatty alcohols, or their acidic solutions) in common metal-based patterned compositions or their supporting layer materials, and can be rapidly removed by solvents such as aromatic ethers (such as anisole). Therefore, the film layer of this protective layer composition can stably exist at the substrate edge during the coating, edge washing, and development processes of metal-based patterned materials or their supporting layer materials, reducing / preventing metal element contamination of the substrate edge in these materials, and its removal process does not damage the metal-based pattern, thereby ensuring the yield and performance reliability of the manufactured electronic devices.

[0010] In some embodiments of this application, Ar1 and Ar2 independently have the structure shown in formula (IV):

[0011]

[0012] Where Q is selected from single bonds, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, substituted or unsubstituted C. 1-5 One of the alkylene groups; R 5 R 6 Each occurrence is independently selected from one of the following: halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryl group; s and t are independently selected from integers from 0 to 4; * indicates the linking position.

[0013] Polycarbonates or polyarylates with Ar1 selected from repeating units of the structure shown in formula (IV) have high solubility in aromatic ether solvents (such as anisole) and exhibit certain chemical resistance in fatty alcohols.

[0014] In some embodiments of this application, the R is independently selected each time it appears from a halogen atom, a substituted or unsubstituted C atom. 1-12 Alkyl, substituted or unsubstituted C 1-12 Alkoxy, substituted or unsubstituted C 6-24 One of the aryl groups; the R 1 R 2 R 3 R 4 R 5 R 6 Each occurrence is independently selected from halogen atoms, substituted or unsubstituted C atoms. 1-10 Alkyl, substituted or unsubstituted C 1-10 One of the alkoxy groups.

[0015] In other embodiments of this application, n, a, b, c, and d are all 0. In equation (IV), s and t are both 0. That is, R does not exist in equation (I), and R does not exist in equation (III). 1 To R 4 R does not exist in equation (IV). 5 and R 6 In this case, polyarylates, polycarbonates, and the polymers having repeating units as shown in formula (Ⅲ) are easier to prepare.

[0016] In the embodiments of this application, the ratio of m to p in formula (Ⅰ) is in the range of 7:3 to 3:7. In this case, the above-mentioned polyarylate has good solubility in aromatic solvents such as anisole, which facilitates the preparation of the above-mentioned protective layer composition with good dispersibility.

[0017] In some embodiments of this application, the polyarylate comprises 80-95% by mass in the resin, and the second polymer comprises 5%-20% by mass in the resin. This is more conducive to the film layer of the above protective layer composition having better resistance to dissolution by linear fatty ketone solvents, linear fatty alcohol solvents, etc., and being easier to remove by solvents such as anisole.

[0018] In some embodiments of this application, the weight-average molecular weight of the polyarylate is 20,000-50,000; the weight-average molecular weight of the polycarbonate or the polymer having repeating units as shown in formula (III) is 5,000-50,000. The molecular weights of these two types of polymers fall within such ranges, and their synergistic effect makes it more advantageous that the thickness of the protective layer material containing them does not change significantly after immersion in linear fatty ketone solvents, linear fatty alcohol solvents, linear ester solvents, or their acidic solutions, and that the removal time using solvents such as anisole is shorter.

[0019] In some embodiments of this application, the film thickness loss rate of the polyarylate film immersed in 2-heptanone at 25°C is less than... The film thickness loss rate after immersion in anisole at 25°C is greater than The film thickness loss of the polycarbonate film or the polymer film having repeating units as shown in formula (III) when immersed in 2-heptanone at 25°C is greater than The film thickness loss rate when immersed in anisole at 25°C is greater than By controlling the solubility of the films of the two types of polymers in different solvents to meet the above requirements, it is possible to better ensure that the film of the above protective layer composition containing both types of polymers has better resistance to linear fatty ketone solvents, linear fatty alcohol solvents, etc., and can be quickly removed by aromatic ether solvents such as anisole.

[0020] In this embodiment, the organic solvent includes one or more of anisole, cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, γ-butyrolactone, and aromatic hydrocarbons. Both of these polymers exhibit good solubility in these organic solvents.

[0021] The second aspect of this application provides the application of the protective layer composition as described in the first aspect of this application in reducing metal contamination in non-patterned areas during a patterning process.

[0022] The protective layer composition is applied to the edge of the substrate to be patterned, wherein the protective layer material formed after the solvent evaporates can prevent the metal-based patterning material or its matching layer material from flowing to the edge of the substrate and directly contacting the edge of the substrate, thereby achieving the effect of resisting metal contamination.

[0023] A third aspect of this application provides a method for manufacturing an electronic device, comprising:

[0024] The protective layer composition described in the first aspect of this application is applied to the edge of the substrate to form a protective layer;

[0025] A metal-based patterned material is coated on one side surface of the substrate to form a metal-based patterned material film on the substrate and the protective layer;

[0026] Remove at least a portion of the metal-based patterned material film that is in contact with the protective layer;

[0027] The metal-based patterned material film layer left on the substrate is sequentially exposed and developed to form a metal-based patterned thin film on the substrate;

[0028] After development, the protective layer is removed.

[0029] In the above-mentioned manufacturing method of electronic devices, the protective layer composition of the present application is used to protect the edge of the substrate. It can exist stably during the formation of the metal-based patterned thin film, which can reduce the metal contamination of the non-patterned area of ​​the substrate (such as the edge of the substrate) caused by the metal-based patterned material. It can also be easily removed after the metal-based patterned thin film is formed, thereby improving the preparation yield and performance reliability of electronic devices.

[0030] The fourth aspect of this application also provides an electronic device manufactured using the manufacturing method described in the third aspect of this application. Attached Figure Description

[0031] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0032] Figure 1 An exemplary flowchart of the patterning process is shown. Detailed Implementation

[0033] The embodiments of this application will now be described in conjunction with the accompanying drawings.

[0034] Patterning processes typically include the following steps: (1) coating a patterning composition onto a substrate and heating it to form a patterned material film; (2) selectively exposing the patterned material film through an exposure source via a mask with a predetermined pattern, so that the solubility of the developer varies between the exposed and unexposed areas; (3) developing the exposed patterned material film with a developer to leave a patterned film on the substrate with the same or opposite pattern as the mask, and selectively etching the substrate using this patterned film as a mask to finally achieve the desired pattern on the substrate.

[0035] To form patterned thin films with small feature sizes, the patterning compositions currently used in patterning processes are mostly metal-based patterning compositions containing metal elements, such as metal oxide resists (MOR). However, after coating a predetermined area on one side of the substrate with this metal-based patterning composition, it typically flows to the edges of the substrate (including non-determined areas on the front, sides, and even the back). This causes non-determined areas of the substrate to be contaminated by metal ions from the metal-based patterning composition, thereby affecting the yield and reliability of electronic devices manufactured using this substrate.

[0036] To reduce the aforementioned metal contamination problems caused by metal-based patterned materials. Figure 1 An exemplary flowchart of a current patterning process is shown. Figure 1 A1 illustrates a commonly used substrate-wafer structure. A2 shows a schematic diagram of coating a wafer protective layer (EPL) material (dark gray portion) onto the wafer edge using an edge-applied sizing method. A3 shows a method for further removing residual solvent from the EPL material through heat treatment. A4 shows a metal-based patterned composition spin-coated onto one side surface of the wafer to form a metal-based patterned material film. Figure 1 In Figure A4, the metal-based patterned material (light gray area) covers one side surface of the wafer and the EPL material on the wafer edge. Figure A5 shows the edge washing process of the metal-based patterned material. This edge washing process specifically removes the metal-based patterned material located at the wafer edge, exposing the EPL material at the wafer edge. Figure A6 shows the exposure process of the metal-based patterned material left on the wafer. After selective exposure using a mask, the exposed and unexposed areas of the metal-based patterned material develop structural differences, resulting in differences in their solubility in the developer. After development with the developer, a metal-based patterned film is left on the wafer surface (as shown in Figure A7). Finally, the aforementioned EPL material is removed using a specific solvent.

[0037] Theoretically, the EPL material used to reduce metal contamination should not significantly dissolve in the solvent of the metal-based patterning composition; nor should it significantly dissolve in the edge-washing agent used in the edge-washing process of the metal-based patterning material; nor should it significantly dissolve in the developer used in the development process. After the metal-based patterned film is obtained through development, the EPL material should also be easily removed without damaging the pattern of the patterned film. However, currently used EPL materials rarely meet the above requirements simultaneously, resulting in poor actual ability to reduce metal contamination, or difficulty in removal that affects the pattern quality. Therefore, this application provides a protective layer composition that balances good chemical resistance and easy removal, so as to effectively reduce metal contamination in the non-patterned areas of the substrate during the manufacturing process of electronic devices without affecting the quality of the formed pattern.

[0038] This application provides a protective layer composition comprising a resin and an organic solvent. The resin comprises 80%-99% by mass of a polyarylate and 1%-20% by mass of a second polymer. The polyarylate has the structure shown in Formula (I). The second polymer comprises one or more of a polycarbonate having repeating units shown in Formula (II) and a polymer having repeating units shown in Formula (III).

[0039]

[0040] Where m and p are both greater than 0, Ar1 is selected from divalent groups including at least two connected aromatic rings, and Ar2 is a divalent group containing at least one aromatic ring; X is selected from -S(=O)-, -S(=O)2-, and -C(=O)-; L is selected from single bonds, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, substituted or unsubstituted C 1-5 One of the alkylene groups;

[0041] R, R 1 R 2 R 3 R 4 Each occurrence is independently selected from one of the following: halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryl group, n, a, b, c, d are independently integers from 0 to 4, and e is 0 or 1.

[0042] The above-described protective layer composition can be used to reduce metal contamination at substrate edges. The protective layer composition contains a polyarylate with the specific structure described above. This polyarylate exhibits no significant solubility in chain aliphatic solvents, particularly showing good solubility in linear fatty ketones, linear fatty alcohols, and their acidic solutions. It also exhibits some solubility in aromatic solvents (such as anisole), forming a homogeneous solution. The polycarbonate having repeating units as shown in Formula (II) or the polymer having repeating units as shown in Formula (III) (collectively referred to as the second polymer) primarily helps improve the wet removal efficiency of aromatic solvents (such as anisole) on the protective layer composition film.

[0043] Simultaneously employing the two types of polymers mentioned above, and controlling the mass ratio of the polyarylate in the resin system to 80%-99%, ensures that the protective layer composition exhibits good resistance to common metal-based patterning compositions' solvents, edge-washing agents, and developers (such as linear fatty ketone solvents (e.g., 2-heptanone, methyl isopentyl ketone), linear fatty alcohol solvents (e.g., methyl isobutyl methanol), linear fatty ester solvents (e.g., propylene glycol methyl ether acetate (PGMEA)) or their acidic solutions). During the coating, edge-washing, and development processes of the metal-based patterning composition, it remains stably present at the substrate edge (e.g., the outer periphery, side, and back of the substrate's front side), reducing / preventing metal ion contamination of the substrate's edge from the metal-based patterning composition. Furthermore, the protective layer composition can be rapidly removed by solvents such as aromatic ethers (e.g., anisole) and alicyclic ketones (e.g., cyclohexanone) without damaging the pattern of the metal-based patterned film, thereby effectively ensuring a high yield and stable performance of the manufactured electronic devices. Similarly, this protective layer composition can also reduce the metal contamination problem caused by the matching layer materials of the metal-based patterned composition.

[0044] In this application, the molecular structural characteristics of the above polymers can be obtained by combining infrared spectroscopy, nuclear magnetic resonance spectroscopy, and other methods.

[0045] In this application, both groups Ar1 and Ar2 contain aromatic rings. These aromatic rings can be pure aromatic rings or heterocyclic aromatic rings containing cyclic heteroatoms (such as oxygen (O), sulfur (S), nitrogen (N), phosphorus (P), boron (B), etc.). Each aromatic ring can be substituted or unsubstituted. Each aromatic ring can be a monocyclic aromatic ring (such as a benzene ring) or a fused-ring polycyclic aromatic ring (such as a naphthalene ring). When Ar1 and Ar2 contain two or more aromatic rings, adjacent aromatic rings are connected by a linking group. The linking group can be selected from one or more of single bonds, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, substituted or unsubstituted alkylene groups, and substituted or unsubstituted arylene groups, but is not limited thereto. The substituents in the substituted alkylene groups can include one or more of halogen atoms, substituted or unsubstituted alkoxy groups, and substituted or unsubstituted aryl groups. The substituents in the substituted aryl group may include one or more of the following: a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, etc. Exemplarily, the linking group may be -CH2-, -C(CH3)2-, -C(CF3)2-, -OC(=O)-, -O-CH2-, or -O-Ph, etc. Ph represents phenyl.

[0046] In some embodiments of this application, Ar2 is a divalent group comprising at least two connected aromatic rings. These aromatic rings are the main chain of the repeating unit in formula (II). In this case, the aforementioned polycarbonate exhibits good resistance to solvents, edge cleaners, and developers (such as fatty ketones, fatty alcohols, alkyl ester solvents, etc.) commonly found in metal-based patterning compositions.

[0047] In some embodiments of this application, Ar1 and Ar2 independently have the structure shown in formula (IV):

[0048]

[0049] Where Q is selected from single bonds, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, substituted or unsubstituted C. 1-5 One of the alkylene groups; R 5 R 6 Each occurrence is independently selected from one of the following: halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryl group; s and t are independently selected from integers from 0 to 4; * indicates the linking position.

[0050] Ar1, as shown in formula (IV), is a biphenyl divalent aryl group, with adjacent substituted or unsubstituted benzene rings linked by a linking group Q. Polycarbonates or polyarylates with Ar1 selected from repeating units of the structure shown in formula (IV) have high solubility in aryl ether solvents (such as anisole) and exhibit some chemical resistance in fatty alcohols. Wherein, R... 5 R 6 These represent the substituents on each benzene ring. When s = 0, it represents the benzene ring on the left side of formula (IV) without any substituent R. 5 When t = 0, the right-hand benzene ring in formula (IV) has no substituent R. 6 When s and t are non-zero integers, they can be 1, 2, 3, or 4.

[0051] In Q, C is either substituted or unsubstituted. 1-5 The alkylene group can be, for example, any of the following groups, substituted or unsubstituted: methylene (-CH2-), ethylene (-CH2CH2-), n-propylene (-CH2CH2CH2-), 2,2-isopropylidene (-C(CH3)2-), etc. Among them, the substituted C... 1-5 The substituents in the alkylene group include one or more of halogen atoms, alkoxy groups, and aryl groups, specifically -C(CF3)2- or -C(Ph)2-.

[0052] The halogen atoms involved in the embodiments of this application may include one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

[0053] The substituents in the substituted alkyl and substituted alkoxy groups involved in the embodiments of this application may include one or more of halogen atoms, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, etc., but are not limited thereto. The substituents in the substituted aryl groups may include one or more of halogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, etc., but are not limited thereto.

[0054] The aforementioned substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, and substituted or unsubstituted aryl groups may contain or not contain heteroatom-containing linking groups. Heteroatom-containing linking groups may be inserted between some carbon atoms of the aforementioned groups or directly connected to one end of them. Heteroatoms may include one or more of O, N, S, P, or Si. Exemplary heteroatom-containing linking groups may include one or more of ether bonds (-O-), thioether bonds (-S-), carbonyl groups (-C(=O)-), -C(=O)-O-, -OC(=O)-, sulfonyl bonds (-S(=O)2-), sulfinyl bonds (-S(=O)-), substituted or unsubstituted imino groups (such as -NH-, -N(CH3)-, etc.), and amide bonds (-NHCO-). For example, a substituted or unsubstituted alkoxy group can be considered as a substituted or unsubstituted alkyl group connected to an ether oxygen atom. A substituted or unsubstituted alkyl carbonyl group can be understood as an alkyl group connected to a carbonyl group, and it is also considered within the scope of alkyl groups as defined in this application.

[0055] In some embodiments of this application, the substituted alkyl group may be a haloalkyl group, the substituted alkoxy group may be a haloalkoxy group, and the substituted aryl group may be an aryl group substituted with at least one of a halogen atom, alkyl group, haloalkyl group, alkoxy group, and haloalkoxy group. Specifically, the haloalkyl group may be a fully haloalkyl group or a partially haloalkyl group. The haloalkoxy group may be a fully haloalkoxy group or a partially haloalkoxy group.

[0056] In this application, the number of carbon atoms in the substituted or unsubstituted alkyl group and the substituted or unsubstituted alkoxy group can independently range from 1 to 20. That is, the substituted or unsubstituted alkyl group is a substituted or unsubstituted C1 to C2 group. 20 Alkyl group. The carbon number refers to unsubstituted alkyl groups. Substituted or unsubstituted alkoxy groups are those with substituted or unsubstituted C1-C2 atoms. 20 Alkoxy group. The number of carbon atoms refers to an unsubstituted alkoxy group. The unsubstituted alkyl or alkoxy group can be linear or branched. In some embodiments, the number of carbon atoms in the substituted or unsubstituted alkyl group and the substituted or unsubstituted alkoxy group is independently 1-18, and more specifically 1-12, 1-10, 1-8, 1-6, or 1-4, etc. Exemplarily, the unsubstituted alkyl group can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, etc. The unsubstituted alkoxy group can be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, etc.

[0057] The number of carbon atoms in a substituted or unsubstituted cycloalkyl group can be 3-20, and more specifically 3-15, 3-12, or 5-20. Substituents in a substituted cycloalkyl group can include halogen atoms, alkyl groups, alkoxy groups, etc. Examples of unsubstituted epoxy groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc.

[0058] The number of carbon atoms in a substituted or unsubstituted aryl group can range from 6 to 30. That is, the substituted or unsubstituted aryl group has substituted or unsubstituted C6 to C3 carbon atoms. 30 Aryl group. In some embodiments, the carbon atoms of the substituted or unsubstituted aryl group are 6-24, 6-20, or 6-10, etc. Examples of unsubstituted aryl groups can be phenyl, naphthyl, biphenyl, etc.

[0059] In some embodiments of this application, in formula (I), R is independently selected each time it appears from a halogen atom, a substituted or unsubstituted C atom. 1-12 Alkyl, substituted or unsubstituted C 1-12 Alkoxy, substituted or unsubstituted C 6-24 One of the aryl groups. Further, the substituted C 1-12 Alkyl, substituted C 1-12 The substituent in the alkoxy group is a halogen atom. The substituted C 6-24 Substituents in aryl groups include halogen atoms or C atoms. 1-6 Alkyl groups, etc. In some other embodiments of this application, n in formula (I) is 0.

[0060] In some embodiments of this application, in formula (IV), R 5 R 6 Each occurrence is independently selected from halogen atoms, substituted or unsubstituted C atoms. 1-10 Alkyl, substituted or unsubstituted C 1-10 One of the alkoxy groups. Further, the substituted C... 1-10 Alkyl, substituted C 1-10 The substituents in the alkoxy group are halogen atoms, such as fluorine atoms.

[0061] In some other embodiments of this application, s and t in formula (IV) are both 0. In this case, Ar1 or Ar2 represented by the structure in formula (IV) is specifically... Q can be -CH2-, -C(CH3)2-, -C(CF3)2-, -C(=O)-, -S(=O)-, -S(=O)2-, etc. For example, in this case, the repeating unit shown in equation (II) can include any of the following structures:

[0062]

[0063] In some embodiments of this application, in formula (Ⅲ), R 1R 2 R 3 R 4 Each occurrence is independently selected from halogen atoms, substituted or unsubstituted C atoms. 1-10 Alkyl, substituted or unsubstituted C 1-10 One of the alkoxy groups. Further, the substituted C... 1-10 Alkyl, substituted C 1-10 The substituent in the alkoxy group is a halogen atom, such as a fluorine atom. In some other embodiments of this application, a, b, c, and d in formula (III) are all 0. In this case, it means that there are no substituents on any of the benzene rings in formula (III).

[0064] In the aforementioned formula (Ⅲ), for L and X, please refer to the explanation of Q above in this application.

[0065] When e = 0, it means that the structure enclosed in parentheses does not exist. In this case, equation (Ⅲ) has the following structure: For example, the repeating unit shown in equation (Ⅲ) can be wait.

[0066] When e = 1, the repeating unit shown in equation (Ⅲ) is specifically: This repeating unit can be derived from diphenols. and In this case, if a, b, c, and d are all 0, then the repeating unit shown in equation (Ⅲ) can include any of the following exemplary structures:

[0067]

[0068] It should be noted that the aforementioned polycarbonate may include one repeating unit as shown in Formula (II); or it may include two or more repeating units with different structures as shown in Formula (II). The polycarbonate repeating unit shown in Formula (II) may be derived from the dihydroxy monomer HO-Ar1-OH and the diester R'-OC(=O)OR'. It is understood that in some cases, the polycarbonate may also include other repeating units with structures different from those in Formula (II). Similarly, in some cases, the aforementioned polyarylate may include repeating units with structures other than those corresponding to subscript m and subscript p in Formula (I). This application does not limit the structure of other repeating units.

[0069] The polymer having the repeating unit shown in formula (III) (referred to as "polymer 2.2" for ease of description) may include one repeating unit as shown in formula (III); or may include two or more repeating units with different structures as shown in formula (III). It is understood that polymer 2.2 may include repeating units with other structures besides the repeating unit shown in formula (III). Generally, the molar percentage of the repeating unit shown in formula (III) in all repeating units of polymer 2.2 may be 80%-100%. This ensures that polymer 2.2 has excellent solubility in aromatic solvents such as aryl ethers and alicyclic solvents.

[0070] In some embodiments of this application, the ratio of m to p in the aforementioned formula (I) is in the range of 7:3 to 3:7. That is, m / p is in the range of 0.43 to 2.33. In this case, the above-mentioned polyarylate exhibits good resistance to solvents such as linear fatty ketones and linear fatty alcohols, while also showing better solubility in aromatic solvents such as anisole, making it easier to obtain the above-mentioned protective layer composition with good dispersibility. Exemplarily, m / p can specifically be 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.5, 1.6, 1.8, 2.0, 2.1, or 2.2, etc. Optionally, m is in the range of 3 to 150, and p is in the range of 2 to 100.

[0071] In some embodiments of this application, the weight-average molecular weight M of the aforementioned polyimide is... w The value is 20,000-50,000; the polycarbonate or the polymer having repeating units as shown in formula (Ⅲ) (polymer 2.2) has an M w The value is 5000-50000. The M of the polyimide and the second polymer (polycarbonate and / or polymer 2.2) that meet the aforementioned structural requirements. w Within this range, and through their synergistic effect, it is more advantageous for the protective layer material containing them to maintain essentially no significant change in thickness after immersion in linear fatty ketone solvents, linear fatty alcohol solvents, linear ester solvents, or their acidic solutions, and for the removal time required by solvents such as anisole to be shorter. For example, the M of polyimide... w It can be in the range of 20,000-40,000. Polycarbonate, polymer 2.2 M w It can be in the range of 10,000-40,000, and further in the range of 15,000-4,000.

[0072] In this embodiment, the molecular weight distribution index (PDI) of the polyarylate, the polycarbonate, and the polymer having repeating units as shown in formula (Ⅲ) is less than 3.5, for example, 1.1-3.5. The PDI is equal to the weight-average molecular weight M of each polymer.w Number-average molecular weight M n The dispersibility and viscosity of the above-mentioned protective layer compositions made from two types of polymers within an appropriate range using PDI are not significantly different between different batches, which helps to ensure that the protective layer compositions perform similarly in various application scenarios.

[0073] Among them, M of each polymer w PDI can be determined by gel permeation chromatography (GPC) using polystyrene as a standard.

[0074] In this embodiment of the application, the film thickness loss rate of the polyarylate film immersed in 2-heptanone at 25°C is less than... The film thickness loss rate after immersion in anisole at 25°C is greater than The film thickness loss of the polycarbonate film or the polymer film having the repeating unit shown in formula (III) when immersed in 2-heptanone at 25°C is greater than The film thickness loss rate when immersed in anisole at 25°C is greater than

[0075] By controlling the solubility of the films of the two types of polymers in different solvents to meet the above requirements, it is possible to better ensure that the films of the above-mentioned protective layer compositions containing both types of polymers have better resistance to linear fatty ketone solvents, linear fatty alcohol solvents, etc., and can be rapidly removed by aromatic ether solvents such as anisole. Here, the films of each polymer mentioned above refer to films formed by coating a solution containing the polymer and an organic solvent and then baking.

[0076] It should be noted that the solubility of the films of the above polymers in other linear aliphatic ketones (e.g., methyl isopentyl ketone) besides 2-heptanone also meets the above requirements. The solubility of the films of the above polymers in other aromatic ethers besides anisole also meets the above requirements.

[0077] In this application, the polyarylate comprises 80%-99% by mass in the resin, and more preferably 80%-95%. Correspondingly, the second polymer (polycarbonate and / or polymer having repeating units as shown in formula (III)) comprises 1%-20% by mass in the resin, and more preferably 5%-20%. Controlling the mass percentage of the polyarylate in the resin constituting the above-mentioned protective layer composition to a suitable high range is beneficial for the film layer of the above-mentioned protective layer composition to have good resistance to dissolution by linear fatty ketone solvents, linear fatty alcohol solvents, etc., and ensures that the protective layer material containing them does not take too long to remove when removed by solvents such as anisole and is easier to remove.

[0078] For example, the mass percentage of the polyarylate in the resin can be 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99%, etc. The mass percentage of the second polymer in the resin can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20%, etc.

[0079] In some embodiments of this application, the second polymer comprises a polycarbonate having repeating units as shown in formula (II). Further, the second polymer also includes a polymer having repeating units as shown in formula (III).

[0080] In other embodiments of this application, the second polymer comprises a polymer having repeating units as shown in formula (Ⅲ). Further, the second polymer also includes polycarbonate having repeating units as shown in formula (Ⅱ).

[0081] In this embodiment, the total mass percentage of the resin in the protective layer composition is 0.1 wt% to 20 wt%. The total mass percentage of the resin in the protective layer composition can be adjusted according to the desired film thickness of the protective layer; generally, a higher solution concentration corresponds to a thicker film. Exemplarily, the mass percentage of the resin can be 0.2 wt%, 0.5 wt%, 1 wt%, 2 wt%, 2.5 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 8 wt%, 9 wt%, 10 wt%, 12 wt%, 15 wt%, 16 wt%, 18 wt%, or 19 wt%, etc. In some embodiments, the mass percentage of the resin is 3 wt% or more. In other embodiments, the mass percentage of polyetherimide is 15 wt% or less. In some embodiments, the mass percentage of the resin is 1 wt% to 10 wt%. In this case, the protective layer composition is less prone to excessive flow, and the resulting film thickness is lower, better matching the patterning process with small pattern feature sizes.

[0082] In this embodiment of the application, the organic solvent in the above-described protective layer composition may include one or more of anisole, cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, γ-butyrolactone (GBL), and aromatic hydrocarbons. The aforementioned polyarylates, polycarbonates, and polymers 2.2 can all achieve good solubility in these organic solvents. Exemplary aromatic hydrocarbon solvents may include one or more of benzene, toluene, xylene, etc.

[0083] In some embodiments of this application, the organic solvent may further include one or more of dialkyl ketones (alkyl groups having 1-6 carbon atoms) and alkyl acetates (alkyl groups having 1-6 carbon atoms). When the organic solvent includes at least one of the following: anisole, cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, GBL, and aromatic hydrocarbons, a suitable amount of linear aliphatic solvent may also be included to ensure the dissolution of the aforementioned polymers. Exemplary dialkyl ketones may include, but are not limited to, one or more of butanone, ethyl isopropyl ketone, 2-hexanone, methyl isobutyl ketone, methyl isopropyl ketone, 3-methyl-2-pentanone, 2-pentanone, and 3-pentanone. Exemplary alkyl acetates may include, but are not limited to, one or more of methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, and isobutyl acetate.

[0084] In some embodiments of this application, the protective layer composition further includes additives. These additives may include, but are not limited to, one or more of the following: ultraviolet absorbers, stabilizers, lubricants, plasticizers, pigments, dyes, colorants, antistatic agents, metal passivators, and release agents. These additives may be added as needed.

[0085] This application also provides the application of the above-described protective layer composition in resisting metal contamination in non-patterned areas during patterning processes.

[0086] Specifically, this application aims to reduce or prevent contamination of non-patterned areas by metal-based patterned materials or their associated layer materials. "Non-patterned areas" refer to unplanned areas where metal-based patterned materials or their associated layer materials are not intended to be applied, such as the edges of a substrate.

[0087] The aforementioned protective layer composition can be disposed at the edge of the substrate, acting as an edge protection material. During the patterning process, it can reduce or prevent the flow of the metal-based patterning material or its associated layer material to the substrate edge and direct contact with it, thereby achieving an anti-metal contamination effect. This allows for the formation of a high-quality patterned thin film on the substrate without causing metal contamination to the non-patterned areas of the electronic device substrate, improving the fabrication yield and performance reliability of the electronic device.

[0088] This embodiment also provides a method for manufacturing an electronic device, including the following steps S01 to S05.

[0089] Step S01: Apply the above-described protective layer composition of the present application embodiment to the edge of the substrate to form a protective layer.

[0090] The substrate can be selected according to specific needs; for example, it can be a silicon wafer (such as...). Figure 1As shown in A1, the surface of the silicon wafer may or may not have other coatings. Other coatings may be one or more of the following: anti-reflective coating, hard mask layer, epitaxial layer, metal layer, dielectric layer, and decorative layer. Of course, in other embodiments, the substrate may also be non-circular, such as a rectangular sheet.

[0091] In this embodiment, the edge of the substrate includes the peripheral region of the surface of the substrate to be coated with the patterned metal-based composition (which may be referred to as the upper surface or front side), the side surface of the substrate, and the back surface. This peripheral region is also the non-patterned / non-predetermined region of the front side of the substrate. The other regions of the front side surrounded by this peripheral region are the patterned regions of the front side of the substrate (see...). Figure 1 The area indicated by the arrow in A2 is the ideal area for retaining patterned material. During exposure, the patterned material is retained only on this patterned area. Figure 1 In A2, the dark gray area represents the coating area of ​​the protective layer composition, which is also the edge of the substrate. The edge of the substrate belongs to the unpatterned area of ​​the substrate.

[0092] The protective layer composition can be coated onto the edge of the substrate using techniques known in the art. For example, the protective layer composition can be coated onto the substrate by spin coating. In embodiments of this application, the coating thickness of the protective layer composition is 10 nm-1000 nm; and / or, the coating width of the protective layer composition is 0.5 mm-1.5 mm. In some embodiments, the protective layer composition is coated with a thickness of at least 10 nm, at least 50 nm, at least 100 nm, at least 200 nm, or at least 300 nm. Additionally, the protective layer composition is coated with a thickness of up to 900 nm or up to 800 nm. In some embodiments, the protective layer composition is coated with a width of at least 0.6 mm, at least 0.7 mm, or at least 0.75 mm. Additionally, the protective layer composition is coated with a width of up to 1.2 mm or up to 1.0 mm. The coating width of the protective layer composition specifically refers to the coating width of the protective layer composition located in the peripheral area on the front side of the substrate. Figure 1 In the middle, A2 specifically refers to the width of the dark gray ring.

[0093] In some embodiments of this application, after coating the protective layer composition, a heat treatment (as described above) can be performed. Figure 1 As shown in Figure A3), the heat treatment is performed to further remove residual organic solvents from the protective layer. In some embodiments, the temperature of the heat treatment can be in the range of 150-350°C (e.g., 180°C, 200°C, 220°C, 250°C, 280°C, 300°C, etc.), and the time can be 30-120s (e.g., 45s, 60s, 90s, etc.).

[0094] Step S02: A metal-based patterned composition is coated on one side surface of the substrate to form a metal-based patterned material film on the substrate and the protective layer.

[0095] The metal-based patterning composition refers to a patterning composition containing a metal element. In some embodiments, the metal-based patterning composition may include a metal oxide photoresist (MOR) or a photoresist containing a metal complex. This application does not limit the specific composition of the metal-based patterning composition.

[0096] The specific coating method for the above-mentioned metal-based patterned composition can be spin coating. The solvent used in the metal-based patterned composition should not have a detrimental effect on the protective layer material of the embodiments of this application. The solvent in the metal-based patterned composition includes, but is not limited to, one or more of linear fatty ketone solvents, linear fatty alcohol solvents, and linear ester solvents. For example, linear fatty ketone solvents may include one or more of 2-heptanone, 4-methyl-2-pentanone, etc. Linear fatty alcohol solvents may include one or more of PGME (propylene glycol ethyl ether), methoxyethanol, ethoxypropanol, ethoxyethanol, 1-pentanol, 4-methyl-2-pentanol, methyl isobutyl methanol (MIBC), etc. Linear ester solvents may include PGMEA (propylene glycol methyl ether acetate), ethyl lactate, etc.

[0097] Furthermore, during the spin-coating of a metal-based patterned composition onto one side of the substrate, it may flow to unpatterned areas of the substrate (such as the peripheral area of ​​the front side of the substrate, the side side of the substrate, the back side of the substrate, etc.), covering the substrate and its protective layer (such as...). Figure 1 (As shown in A4). However, due to the presence of the aforementioned protective layer, the metal-based patterned composition will not directly contact the non-patterned areas of the substrate, thus preventing metal contamination.

[0098] In this embodiment of the application, after coating the metal-based patterned composition, a baking process can be performed to remove the solvent remaining in the metal-based patterned material film. Exemplarily, this baking process can be performed at a temperature of 150°C-450°C for 60-120 seconds.

[0099] Step S03: Remove at least a portion of the metal-based patterned material film that is in contact with the protective layer.

[0100] Step S03 primarily involves removing the metal-based patterned material located at the edge of the substrate. This process can be referred to as edge removal. Various techniques can be used to remove at least a portion (not necessarily all) of the metal-based patterned material film layer in contact with the protective layer. During this edge removal process, no harmful effects should be caused to the metal-based patterned material film layer not in contact with the protective layer. Even after edge removal, some metal-based patterned material in contact with the protective layer material may still be retained, as long as the retained portion does not significantly reduce the protective layer's resistance to metal contamination. For example, after edge removal, up to 5% of the metal-based patterned material in contact with the protective film layer may be retained. Figure 1 A5 specifically illustrates the removal of the metal-based patterned material located on the protective layer material at the edge of the wafer.

[0101] Suitable techniques for removing at least a portion of the metal-based patterned material film in contact with the protective layer include, but are not limited to, chemical mechanical polishing (CMP), plasma etching, or wet etching. In some embodiments of this application, when using wet etching, an edge-cleaning agent can be used to remove at least a portion of the metal-based patterned material film in contact with the protective layer. This edge-cleaning agent will not have a detrimental effect on the protective layer of the embodiments of this application. Exemplarily, the edge-cleaning agent includes, but is not limited to, one or more of PGMEA, PGME, ethyl lactate, methoxyethanol, ethoxypropanol, ethoxyethanol, 1-pentanol, and 4-methyl-2-pentanol.

[0102] Step S04, the patterned metal-based material film layer left on the substrate is sequentially exposed (e.g., Figure 1 As shown in A7), development (as shown in Figure 1) Figure 1 As shown in A8, a metal-based patterned thin film is formed on the substrate.

[0103] In step S04, the exposure can be selective exposure, where an exposure source is passed through a mask with a predetermined pattern to irradiate the metal-based patterned material film layer left on the substrate. The exposure source can be a light source with a wavelength below 400 nm, X-rays, or an electron beam, etc. After selective exposure, the exposed portion of the metal-based patterned material film layer undergoes a chemical reaction, resulting in a difference in solubility of the developer compared to the unexposed portion.

[0104] In some embodiments of this application, a post-baking process can be performed after exposure and before development to promote the further completion of incomplete chemical reactions in the exposed metal-based patterned material film.

[0105] Because the exposed and unexposed areas of a metal-based patterned material film have different solubilities for the developer, developing the exposed patterned material film with the developer can reveal a patterned thin film on the substrate. After developer treatment, the exposed portion of the patterned material film is washed away, resulting in positive development, leaving a positive pattern on the substrate identical to the exposure mask; after developer treatment, the exposed portion of the patterned material film is not washed away, resulting in negative development, leaving a negative pattern on the substrate complementary to the exposure mask.

[0106] The developing agent used can be selected based on the properties of the metal-based patterning material used. Common developing agents include one or more of the following: linear fatty ketone solvents (such as 2-heptanone, 4-methyl-2-pentanone), linear fatty alcohol solvents (such as MIBC), linear ester solvents, and fatty ether solvents.

[0107] Step S05: After development, the protective layer is removed.

[0108] After removing the aforementioned protective layer, the remaining patterned metal-based film is spaced apart from the edge of the substrate (e.g., Figure 1 (As shown in A8).

[0109] In this application, suitable techniques for removing the protective layer include, but are not limited to, plasma etching or wet etching. When wet etching is used, the solvent employed must not have a detrimental effect on the patterned thin film. In some embodiments of this application, the protective layer can be removed using the organic solvent used to formulate the protective layer composition. For example, one or more of anisole, cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, γ-butyrolactone, etc., can be used to remove the protective layer. This results in a faster removal rate of the protective layer without damaging the metal-based patterned thin film.

[0110] Following step S05 above, a patterned substrate is obtained, comprising a substrate and a metal-based patterned thin film disposed on the substrate. This patterned thin film can serve as a high-precision mask for etching the substrate. The pattern of the metal-based patterned thin film can be transferred to a substrate such as a silicon wafer through etching, thereby forming a preset pattern on the substrate.

[0111] It is understandable that after step S05 above, other functional layers can be fabricated on the substrate.

[0112] In the manufacturing method of the electronic device provided in this application embodiment, before coating the substrate with the metal-based patterned composition, the protective layer composition of this application embodiment is used to protect the edge of the substrate. This protective layer composition can stably exist during the formation process of the metal-based patterned thin film (including coating, edge removal, development, etc.), reducing or avoiding metal contamination of the non-patterned areas (such as the substrate edge) of the substrate by the metal-based patterned material. Furthermore, after the metal-based patterned thin film is formed, the protective layer material can be easily removed without damaging the patterned thin film, thereby improving the fabrication yield and performance reliability of the electronic device. In particular, when a metal-based patterned thin film with small feature dimensions is formed on the substrate, the thickness of the protective layer is relatively thin, but due to its good corrosion resistance to solvents, edge-washing agents, developers, etc., used in metal-based patterned materials, it can still effectively resist metal contamination.

[0113] In some embodiments of this application, the substrate in step S01 is a substrate with a metal-based patterned hard mask on its surface. This metal-based patterned hard mask helps improve the resolution of the pattern formed by the metal-based patterned composition in step S02. In this case, the substrate can be prepared using the following method:

[0114] (1) The protective layer composition described in the present application is applied to the edge of the substrate to form a protective layer;

[0115] (2) A metal-based hard mask composition is coated on one side surface of the substrate to form a metal-based hard mask layer on the substrate and the protective layer;

[0116] (3) Remove at least a portion of the metal-based hard mask layer that is in contact with the protective layer;

[0117] (4) Expose and develop the metal-based hard mask layer left on the substrate in sequence to form a metal-based patterned hard mask on the substrate;

[0118] (5) Remove the protective layer to obtain a substrate with a metal-based patterned hard mask formed on its surface.

[0119] After step (5), a metal-based patterned thin film can be formed on the substrate on which a metal-based patterned hard mask is formed, according to the aforementioned electron manufacturing method. Steps (1) to (5) here are similar to the aforementioned steps S01 to S05, the main difference being that the metal-based patterned composition involved is replaced with a metal-based hard mask composition, so they will not be described again.

[0120] Before coating the metal-based patterned hard mask onto the substrate, the protective layer composition of the present application embodiment is used to protect the edge of the substrate. It can be stably maintained during the formation process of the metal-based patterned hard mask (including coating, edge removal, development, etc.), reducing or avoiding metal contamination of the non-patterned areas of the substrate (such as the substrate edge) by the metal-based hard mask material. After the metal-based patterned hard mask is formed, the protective layer material can be easily removed without damaging the patterned hard mask, thereby improving the fabrication yield and performance reliability of electronic devices.

[0121] This application also provides an electronic device, which is manufactured using the above-described manufacturing method of the electronic device in this application.

[0122] The electronic device may include, but is not limited to, a semiconductor device. An exemplary semiconductor device may be a chip, etc. After the preparation of the aforementioned metal patterned thin film is completed, other functional layers can be prepared. The final electronic device typically does not contain a metal-based patterned thin film.

[0123] The technical solutions of the embodiments of this application will be further described below through multiple examples.

[0124] Table 1 below summarizes the structure of the polymers involved in this application, as well as their weight-average molecular weight (Mw) and molecular weight distribution index (PDI) information.

[0125] Table 1 Polymer Raw Material List

[0126]

[0127] In Table 1 above, PC-1 was purchased from Aladdin Company. PAR-1, PAR-2, PSU-1, etc., were synthesized by the applicant.

[0128] The reaction formulas for synthesizing PAR-1 and PAR-2 ​​include:

[0129]

[0130] The specific steps for synthesizing PAR-1 are as follows:

[0131] In a three-necked flask containing 200 mL of deionized water, 220 mmol of NaOH, 100 mmol of bisphenol A (BPA), 2 mmol of BTEAC (benzyltriethylammonium chloride), and 5 mmol of NaHSO3 were added and stirred for 30 min. In a beaker containing 400 mL of CH2Cl2, 50 mmol of IPC (isophthaloyl chloride) and 50 mmol of TPC (terephthaloyl chloride) were added and stirred for 30 min to obtain an organic phase solution. The organic phase solution was added dropwise to the above three-necked flask, and the reaction was carried out at 0 °C for 1 h, then at room temperature for 4 h. Then, 1 mmol of PTBT (p-tert-butylphenol) was added, and the reaction was terminated after 2 h. The resulting reaction material was precipitated with methanol, washed repeatedly with ethanol and deionized water, and dried under vacuum at 80 °C for 2 h to obtain a white polymer with a yield greater than 90%.

[0132] The synthetic route for PAR-2 ​​is as follows:

[0133] In a three-necked flask containing 200 mL of deionized water, 220 mmol of NaOH, 100 mmol of bisphenol A (BPA), 2 mmol of BTEAC (benzyltriethylammonium chloride), and 5 mmol of NaHSO3 were added and stirred for 30 min. In a beaker containing 400 mL of CH2Cl2, 70 mmol of IPC (isophthaloyl chloride) and 30 mmol of TPC (terephthaloyl chloride) were added and stirred for 30 min to obtain an organic phase solution. The organic phase solution was added dropwise to the above three-necked flask, and the reaction was carried out at 0 °C for 1 h, then at room temperature for 4 h. Then, 1 mmol of PTBT (p-tert-butylphenol) was added, and the reaction was terminated after 2 h. The resulting reaction material was precipitated with methanol, washed repeatedly with ethanol and deionized water, and dried under vacuum at 80 °C for 2 h to obtain a white polymer with a yield greater than 90%.

[0134] The synthesis of PSU-1 includes the following steps:

[0135] (1) In a 500 ml round-bottom flask equipped with a condenser, nitrogen purging, Dean Stark trap (filled with toluene) and a top-mounted mechanical stirrer, add bisphenol A (0.05 mol), bis(p-chlorophenyl) sulfone (0.05 mol), dry potassium carbonate (0.10 mol), 100 mL of DMF and 15 mL of toluene, and stir the mixture at room temperature for 10 minutes.

[0136] (2) The mixture was reacted at 150°C for 10 hours, and then the resulting reaction mixture was cooled to below 50°C and filtered through filter paper. The filtered solution (pH 9-10) was neutralized to pH 6-7 with 10 wt% HCl aqueous solution, and then poured into a 1 L flask containing 500 mL of deionized water to form a precipitate. After mixing for 30 minutes, the precipitate was allowed to settle overnight, and then the water (500 mL) was decanted and 1 L of tetrahydrofuran (THF) was added to the remaining viscous solid. The above THF solution was immersed in 3 L of hexane and mixed for 1 hour, and then the solid was allowed to settle. Polymer polysulfone, denoted as PSU1, was precipitated.

[0137] The reactions involved in the synthesis of PSU-1 include:

[0138]

[0139] Preparation of protective layer composition and solvent resistance test

[0140] According to the formulations shown in Table 2 below, each polymer was dissolved in anisole at a certain mass ratio, and after ultrasonic vibration, a protective layer composition was obtained. Subsequently, each protective layer composition was spin-coated onto the edge of the wafer (e.g., ...). Figure 1 As shown in Figure A2), and baked at 250°C for 60 seconds to form a protective layer, with an initial thickness of [missing information]. Within the specified range. Afterwards, the wafers with the protective layer were immersed in different solvents at room temperature for a certain period of time. The wafers were then removed and dried. The residual thickness of the protective layer was tested, and the residual film rate was calculated. The test results are summarized in Table 2. Wherein, residual film rate = residual thickness / initial thickness.

[0141] In Table 2, Solvent 1 and Solvent 2 are commonly used solvents for metal oxide resists (MOR). Solvent 1 is a mixed solvent of methyl isoamyl ketone (MIAK) and formic acid (FA), with FA comprising 10 wt% of the mixed solvent. Solvent 2 is methyl isobutyl methanol (MIBC). The developer is a commonly used developer for MOR, specifically a mixed solvent of 2-heptanone and FA, with FA comprising 10 wt% of the mixed solvent.

[0142] The meanings of the symbols in Table 2 are as follows: ++++: residual film rate [90%, 100%]; +++: residual film rate [75%, 90%]; ++: residual film rate [60%, 75%]; +: residual film rate [10%, 60%]; O: residual film rate (0, 10%).

[0143] Table 2

[0144]

[0145]

[0146] In Table 2, the protective layer compositions of Comparative Examples 1-2 used only PSU-1 or PC-1 resins. While their solvent resistance to MIBC was acceptable, their resistance to acidic solvents such as linear aliphatic ketones MIAK or 2-heptanone was poor, with a residue rate of less than 10%. The protective layer composition of Comparative Example 3 used only polyarylate PAR-1, which showed good resistance to MOR solvents and developers, and a low film thickness loss rate. However, some residue remained in the removal agents—anisole or cyclohexanone.

[0147] Furthermore, based on the formula: thickness loss = initial film thickness × (1 - residual film rate), the thickness loss of the PSU-1 film (i.e., the protective layer of Comparative Example 1) after immersion in the acidic solvent of 2-heptanone for 90 seconds can be calculated as follows: The thickness loss after immersion in anisole for 1 second is The thickness loss of the PC-1 film (i.e., the protective layer of Comparative Example 2) after immersion in the acidic solvent of 2-heptanone for 90 seconds was [missing information]. The thickness loss after immersion in anisole for 1 second is The thickness loss of the PAR-1 film (i.e., the protective layer of Comparative Example 3) after immersion in the acidic solvent of 2-heptanone for 90 seconds was [missing information]. The thickness loss after immersion in anisole for 5 seconds is

[0148] The protective layer compositions of Examples 1-9 combine the polymers mentioned in Comparative Examples 1 and / or 2 with polymers PAR-1 or PAR-2 ​​in appropriate proportions, balancing the physical properties of various polymers. This ensures that the protective layer can be quickly removed by anisole or cyclohexanone removers without affecting its solvent resistance. In particular, Example 4 exhibits superior solvent resistance and the ability to be removed by removers.

[0149] Furthermore, a comparison between Comparative Examples 4-7 and Examples 1-7 reveals that, when polyarylate PAR-1 is used, excessive introduction of PC-1 or PSU-1 leads to a decrease in the protective layer's resistance to linear fatty ketones or their acidic solvents, affecting the protective layer's long-term stability in protecting the wafer edges.

[0150] To demonstrate that the protective layer material provided in this application embodiment can reduce metal contamination, the following application embodiment 1 is provided.

[0151] Application Examples

[0152] (1) As Figure 1 As shown in A2, the protective layer composition of Example 3 is applied to the edge of the wafer, and as... Figure 1 As shown in A3, a dry protective layer is formed after baking.

[0153] (2) Figure 1 As shown in A4, a Sn-containing MOR was coated on the wafer (the radiation-sensitive tin oxide cluster compound 2 disclosed by Zhang Lei et al. in Example 2-1 of CN115220300A was synthesized, dissolved in a mixed solvent of MIAK and 10% FA, with a solid content of 1.5 wt%).

[0154] (3) Figure 1 As shown in A5, MIAK is used as an edge cleaning agent to remove the anti-etching material located on the edge of the wafer.

[0155] (4) The above-mentioned anti-etching layer is exposed using electron beam etching technology.

[0156] (5) Figure 1 As shown in A7, 2-heptanone mixed with 10% FA was used as the developer to develop the above-exposed resist layer for 60 seconds.

[0157] (6) Use anisole to remove the protective layer material located on the edge of the wafer.

[0158] (7) The total metal contamination on the back and sides of the wafer was analyzed using ICP-MS technology, expressed in cm³. 2 The test results are summarized in Table 3 below, based on the number of metal atoms on the surface.

[0159] Based on the method described in Application Example 1, the following application examples are provided, and the results of metal contamination tests are also summarized in Table 3 below.

[0160] Table 3

[0161]

[0162] As can be seen from Table 3, in Application Examples 1-2, because the protective layer material of Example 3 or 4 was used to protect the wafer edges, after removing the protective material, the total metal atom contamination on the back and sides of the wafer was found to be less than 10. 10 / cm 2 This meets the requirements of the electronics industry. In contrast, Application Example 1 uses PSU-1 as the wafer edge protection material, and Application Example 2 uses PC-1. However, because these edge protection materials dissolve significantly in linear fatty ketone solvents (refer to data in Table 2), they fail to provide effective protection for the wafer, resulting in excessive metal ion impurities on the back and sides of the wafer. Application Example 3 uses only PAR-1 as the wafer edge protection material. Although it has good resistance to common solvents, it is difficult to remove, and metal elements derived from MOR remain on the protective layer, resulting in a still significant amount of metal contamination on the wafer with this protective layer.

[0163] The protective layer formed by the protective layer composition provided in this application embodiment has good resistance to MOR solvents, edge cleaning agents and developers. It can exist stably during the coating, edge removal and development of MOR, and can be easily removed afterwards without leaving residue on the substrate, thus effectively resisting metal contamination of the substrate edge.

[0164] The above description merely illustrates exemplary embodiments of this application, and while the description is specific and detailed, it should not be construed as limiting the scope of this patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

[0165] It should be understood that the use of the terms "first," "second," and various numerical designations in this document is merely for descriptive convenience and is not intended to limit the scope of this application.

[0166] In this application, "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone, where A and B can be singular or plural. The character " / " generally indicates that the related objects before and after it are in an "or" relationship.

[0167] In the description of this application, unless otherwise stated, "multiple" means two or more. "At least one" means one or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0168] Furthermore, the numerical range indicated by "-" in this application refers to the range including the values ​​before and after "-", which are respectively taken as the minimum and maximum values. In this application, expressions regarding parameter ranges, such as "greater than or equal to (≥)", "less than or equal to (≤)", "above", and "below", all include the stated number. The numerical values ​​and ranges involved in the embodiments of this application are approximate values, and may have a certain range of errors due to the influence of manufacturing processes / testing methods, etc. These errors are negligible to those skilled in the art.

Claims

1. A protective layer composition for reducing metal contamination at substrate edges, characterized in that, The protective layer composition includes a resin and an organic solvent. The resin includes 80%-99% by weight of a polyarylate and 1%-20% by weight of a second polymer. The polyarylate has the structure shown in Formula (I). The second polymer includes one or more of a polycarbonate having repeating units shown in Formula (II) and a polymer having repeating units shown in Formula (III). Where m and p are both greater than 0, Ar1 is selected from divalent groups including at least two connected aromatic rings, and Ar2 is a divalent group containing at least one aromatic ring; X is selected from -S(=O)-, -S(=O)2-, and -C(=O)-; L is selected from single bonds, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, substituted or unsubstituted C 1-5 One of the alkylene groups; R, R 1 R 2 R 3 R 4 Each occurrence is independently selected from one of the following: halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryl group, n, a, b, c, d are independently integers from 0 to 4, and e is 0 or 1.

2. The protective layer composition as claimed in claim 1, characterized in that, Ar1 and Ar2 independently have the structure shown in formula (IV): Where Q is selected from single bonds, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, substituted or unsubstituted C. 1-5 One of the alkylene groups; R 5 R 6 Each occurrence is independently selected from one of the following: halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryl group; s and t are independently selected from integers from 0 to 4; * indicates the linking position.

3. The protective layer composition as described in claim 1 or 2, characterized in that, Each occurrence of R is independently selected from halogen atoms, substituted or unsubstituted C atoms. 1-12 Alkyl, substituted or unsubstituted C 1-12 Alkoxy, substituted or unsubstituted C 6-24 One of the aryl groups; The R 1 R 2 R 3 R 4 R 5 R 6 Each occurrence is independently selected from halogen atoms, substituted or unsubstituted C atoms. 1-10 Alkyl, substituted or unsubstituted C 1-10 One of the alkoxy groups.

4. The protective layer composition according to any one of claims 1-3, characterized in that, In the formula (Ⅰ), the ratio of m to p is in the range of 7:3 to 3:

7.

5. The protective layer composition according to any one of claims 1-4, characterized in that, In equation (Ⅲ), e is 1, and a, b, c, and d are 0.

6. The protective layer composition according to any one of claims 1-5, characterized in that, The polyarylate comprises 80-95% by mass in the resin, and the second polymer comprises 5%-20% by mass in the resin.

7. The protective layer composition as claimed in claim 6, characterized in that, The weight-average molecular weight of the polyarylate is 20,000-50,000; the weight-average molecular weight of the polycarbonate or the polymer having the repeating unit shown in formula (Ⅲ) is 5,000-50,000.

8. The protective layer composition according to any one of claims 1-7, characterized in that, The film thickness loss rate of the polyarylate film immersed in 2-heptanone at 25°C is less than The film thickness loss rate after immersion in anisole at 25°C is greater than The film thickness loss of the polycarbonate film or the polymer film having repeating units as shown in formula (III) when immersed in 2-heptanone at 25°C is greater than The film thickness loss rate when immersed in anisole at 25°C is greater than 9. The protective layer composition according to any one of claims 1-8, characterized in that, The organic solvent includes one or more of anisole, cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, γ-butyrolactone, and aromatic hydrocarbons.

10. The application of the protective layer composition according to any one of claims 1-9 in resisting metal contamination in non-patterned areas during a patterning process.

11. A method for manufacturing an electronic device, characterized in that, include: The protective layer composition as described in any one of claims 1-9 is applied to the edge of the substrate to form a protective layer; A metal-based patterned composition is coated on one side surface of the substrate to form a metal-based patterned material film on the substrate and the protective layer; Remove at least a portion of the metal-based patterned material film that is in contact with the protective layer; The metal-based patterned material film layer left on the substrate is sequentially exposed and developed to form a metal-based patterned thin film on the substrate; After development, the protective layer is removed.

12. An electronic device, characterized in that, It is prepared by the manufacturing method described in claim 11.

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