Protective layer composition, application of protective layer composition, electronic device and manufacturing method of electronic device

Abstract

The embodiment of the invention provides a protective layer composition and application thereof, an electronic device and a manufacturing method of the electronic device. The protective layer composition comprises resin and an organic solvent, the resin comprises polyarylester with a # imgabs0 # structure and a second polymer, and the mass ratios of the polyarylester and the second polymer in the resin are 80%-99% and 1%-20% respectively; the second polymer includes a polycarbonate having a # imgabs 1 # repeating unit and / or a polymer having a # imgabs 2 # repeating unit. The protective layer composition can reduce the problem of metal pollution to a non-pattern area of a substrate in the process of forming a patterned film from a metal-based patterned material or a matched layer material thereof, and can be easily removed subsequently, so that the preparation yield and the performance reliability of an electronic device are improved.

Description

Technical Field

[0001] The present application relates to the field of patterning technology, and in particular to a protective layer composition and application thereof, an electronic device and a manufacturing method thereof. Background Art

[0002] The preparation process of electronic devices usually involves a patterning process. Among them, metal-based patterned compositions containing metal elements show obvious advantages in forming patterns with small feature sizes. However, during the coating process of the metal-based patterned composition or its supporting layer materials (such as metal-based hard mask materials that improve pattern resolution) on a substrate (such as a wafer), it will flow to the edge of the substrate, causing the edge of the substrate to be easily contaminated by metal elements, affecting the preparation yield and reliability of electronic devices.

[0003] Among them, coating the edge protection material on the edge of the substrate can reduce the above-mentioned metal contamination problem to a certain extent. In theory, the edge protection material needs to meet many requirements at the same time, such as good tolerance to solvents, edge washers, and developers in the metal-based patterned composition, and can be quickly removed by specific solvents. However, the substrate edge protection materials actually used rarely meet the above requirements at the same time, which hinders their widespread application. Summary of the invention

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

[0005] Specifically, in a first aspect, an embodiment of the present application provides a protective layer composition, the protective layer composition comprising a resin and an organic solvent, the resin comprising 80%-99% by weight of a polyarylate and 1%-20% by weight of a second polymer, the polyarylate having a structure represented by formula (I), and the second polymer comprising one or more of a polycarbonate having a repeating unit represented by formula (II) and a polymer having a repeating unit represented by formula (III);

[0006]

[0007] Among them, m and p are both greater than 0, Ar 1 is selected from a divalent group comprising at least two aromatic rings connected together, Ar 2 is a divalent group containing at least one aromatic ring; X is selected from -S(=O)-, -S(=O) 2 -, -C(=O)-, L is selected from a single bond, -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 a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylcarbonyl group, and a substituted or unsubstituted aryl group; n, a, b, c, and d are independently integers of 0 to 4; and e is 0 or 1.

[0009] The protective layer composition can be used to reduce metal contamination of the edge of the substrate. The protective layer composition contains two types of polymers at the same time, wherein the polyarylate of the specific structure has no obvious solubility characteristics for chain aliphatic solvents and has good solubility in aromatic solvents such as anisole; the second polymer mainly helps to improve the removal efficiency of the film layer of the composition by aromatic solvents. When these two types of polymers are mixed in a specific mass ratio to form the resin of the protective layer composition, it can be ensured that the film layer of the protective layer composition has good tolerance to solvents, edge washers, developers, etc. (such as linear fatty ketones, fatty alcohols or their acidic solutions, etc.) in common metal-based patterned compositions or their supporting layer materials, and can be quickly removed by solvents such as aromatic ethers (such as anisole). Thus, the film layer of the protective layer composition can stably exist at the edge of the substrate during the coating, edge washing and development process of the metal-based patterned material or its supporting layer material, reduce / prevent the metal elements in these materials from contaminating the edge of the substrate, and the metal-based pattern will not be destroyed during its removal process, thereby ensuring the yield and performance reliability of the electronic device obtained.

[0010] In some embodiments of the present application, the Ar 1 ,Ar 2 Independently have the structure shown in formula (IV):

[0011]

[0012] wherein Q is selected from a single bond, -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 halogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, and substituted or unsubstituted aryl groups; s and t are independently selected from integers of 0-4; the position marked with * is the connection position.

[0013] With Ar 1The polycarbonate or polyarylate having a repeating unit selected from the structure represented by formula (IV) has a high solubility in aromatic ether solvents (such as anisole) and has a certain chemical corrosion resistance in fatty alcohols.

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

[0015] In some other embodiments of the present application, n, a, b, c, and d are all 0. In formula (IV), s and t are both 0. That is, R does not exist in formula (I), and R does not exist in formula (III). 1 To R 4 In formula (IV), R is absent. 5 and R 6 In this case, polyarylate, polycarbonate, and the polymer having the repeating unit represented by formula (III) are easier to prepare.

[0016] In the embodiment of the present application, in the formula (I), the ratio of m to p is in the range of 7:3-3:7. In this case, the polyarylate has good solubility in aromatic solvents such as anisole, so that the protective layer composition with good dispersibility can be obtained.

[0017] In some embodiments of the present application, the mass proportion of the polyarylate in the resin is 80-95%, and the mass proportion of the second polymer in the resin is 5%-20%. This is more conducive to the film layer of the protective layer composition having better solubility resistance to linear aliphatic ketone solvents, linear aliphatic alcohol solvents, etc., and is easier to remove with solvents such as anisole.

[0018] In some embodiments of the present application, the weight average molecular weight of the polyarylate is 20000-50000; the weight average molecular weight of the polycarbonate or the polymer having the repeating unit represented by formula (III) is 5000-50000. The molecular weights of these two types of polymers are respectively in such a range, and their synergistic cooperation is more conducive to the thickness of the protective layer material containing them not being significantly changed after being soaked in linear aliphatic ketone solvents, linear aliphatic alcohol solvents, linear ester solvents or their acidic solutions, and the removal time used for removal by solvents such as anisole is relatively short.

[0019] In some embodiments of the present 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 represented by 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 Controlling the solubility of the films of the above two types of polymers in different solvents to meet the above requirements respectively can better ensure that the film layer of the above protective layer composition containing such two types of polymers has better tolerance to linear aliphatic ketone solvents, linear aliphatic alcohol solvents, etc., and can be quickly removed by aromatic ether solvents such as anisole.

[0020] In the embodiment of the present application, the organic solvent includes one or more of anisole, cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, γ-butyrolactone, and aromatic hydrocarbons. The above two types of polymers can be well dissolved in these organic solvents.

[0021] The second aspect of the embodiment of the present application provides the use of the protective layer composition as described in the first aspect of the present application to reduce metal contamination in non-pattern areas in a patterning process.

[0022] The protective layer composition is arranged at the edge of the substrate to be patterned, wherein the protective layer material formed after the solvent evaporates can prevent the metal-based patterned material or its supporting 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 pollution.

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

[0024] Coating the protective layer composition described in the first aspect of the present application on the edge of the substrate to form a protective layer;

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

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

[0027] sequentially exposing and developing the metal-based patterned material film layer left on the substrate to form a metal-based patterned thin film on the substrate;

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

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

[0030] The fourth aspect of the embodiments of the present application also provides an electronic device manufactured using the manufacturing method described in the third aspect of the embodiments of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0032] Figure 1 An exemplary flow chart of a patterning process is shown. DETAILED DESCRIPTION

[0033] The embodiments of the present application will be described below in conjunction with the drawings in the embodiments of the present application.

[0034] The patterning process generally includes the following steps: (1) coating a patterning composition on a substrate and forming a patterned material film layer by heating; (2) selectively exposing the patterned material film layer through an exposure source through a mask with a predetermined pattern, so that the solubility of the developer in the exposed area and the unexposed area is different; (3) developing the exposed patterned material film layer with a developer to leave a patterned film with the same or opposite pattern as the mask on the substrate, and selectively etching the substrate using the patterned film as a mask, thereby finally realizing the desired pattern on the substrate.

[0035] In order to form a patterned film with a small pattern feature size, the patterning composition currently used in the patterning process is mostly a metal-based patterning composition containing metal elements, such as a metal oxide resist (Metal Oxide Resist, referred to as MOR). Among them, after the metal-based patterning composition is coated on a predetermined area on the surface of one side of the substrate, it usually flows to the edge of the substrate (including the non-predetermined area on the front side of the substrate, the side and even the back side, etc.), which will cause the non-predetermined area of ​​the substrate to be contaminated by the metal ions in the metal-based patterning composition, thereby affecting the product yield and performance reliability of the electronic device made using the substrate.

[0036] In order to reduce the above metal contamination problems caused by metal-based patterned materials, Figure 1 An exemplary flow chart of a current patterning process is shown. Figure 1 A1 shows a commonly used substrate-wafer structure. A2 shows a schematic diagram of coating the edge of the wafer to form a wafer protective layer (Wafer protective layer, referred to as EPL) material (dark gray part) by edge gluing. A3 shows further removal of residual solvent in the EPL material by heating treatment. A4 shows spin coating a metal-based patterned composition on one side of the wafer to form a metal-based patterned material film layer. Figure 1 In A4, the metal-based patterned material (light gray part) covers one side surface of the wafer and the EPL material on the edge of the wafer. A5 shows the edge washing process of the metal-based patterned material. The edge washing process specifically washes away the metal-based patterned material located at the edge of the wafer and exposes the EPL material at the edge of the wafer. A6 shows the exposure process of the metal-based patterned material left on the wafer. After selective exposure using a mask, the exposed area and the unexposed area of ​​the metal-based patterned material produce structural differences, which makes them different in solubility in the developer. After development with the developer, a metal-based patterned film is left on the surface of the wafer (as shown in A7). Finally, a specific solvent is used to remove the aforementioned EPL material.

[0037] In theory, the above-mentioned EPL material used to reduce metal contamination should not be significantly dissolved in the solvent in the metal-based patterned composition; it should not be significantly dissolved in the edge washing agent used in the edge washing process of the metal-based patterned material; it should not be significantly dissolved in the developer used in the development process; after the metal-based patterned film is obtained by development, the EPL material should be easy to remove and not damage the pattern of the patterned film. However, the EPL materials currently used in the field rarely meet the above requirements at the same time, resulting in poor ability to actually reduce metal contamination, or it is difficult to remove and affect the pattern quality. For this reason, the present application provides a protective layer composition that can take into account good chemical resistance and easy removability, so as to effectively reduce metal contamination in the non-pattern area of ​​the substrate during the manufacturing process of electronic devices without affecting the quality of the formed pattern.

[0038] The embodiment of the present application provides a protective layer composition, which comprises a resin and an organic solvent, wherein the resin comprises 80% to 99% by weight of a polyarylate and 1% to 20% by weight of a second polymer, wherein the polyarylate has a structure represented by formula (I), and the second polymer comprises one or more of a polycarbonate having a repeating unit represented by formula (II) and a polymer having a repeating unit represented by formula (III);

[0039]

[0040] Among them, m and p are both greater than 0, Ar 1 is selected from a divalent group comprising at least two aromatic rings connected together, Ar 2 is a divalent group containing at least one aromatic ring; X is selected from -S(=O)-, -S(=O) 2 -, -C(=O)-, L is selected from a single bond, -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 a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryl group; n, a, b, c, and d are independently integers of 0 to 4; and e is 0 or 1.

[0042] The above-mentioned protective layer composition can be used to reduce metal contamination at the edge of the substrate. The above-mentioned protective layer composition contains the above-mentioned polyarylate with a specific structure, which has no obvious solubility characteristics for chain aliphatic solvents, especially has good solubility resistance in linear aliphatic ketones, linear aliphatic alcohols and their acidic solutions, and has a certain solubility in aromatic solvents (such as anisole), and can form a uniform solution. The above-mentioned polycarbonate having a repeating unit shown in formula (II) or a polymer having a repeating unit shown in formula (III) (collectively referred to as the second polymer) mainly helps to improve the wet removal efficiency of aromatic solvents (such as anisole) on the above-mentioned protective layer composition film layer.

[0043] By using the above two types of polymers at the same time and controlling the mass proportion of the above polyarylate in the resin system to be 80%-99%, it can be ensured that the film layer of the protective layer composition has good tolerance to solvents, edge washers, developers, etc. in common metal-based patterned compositions (such as linear aliphatic ketone solvents (such as 2-heptanone, methyl isoamyl ketone), linear aliphatic alcohol solvents (such as methyl isobutyl carbinol), linear aliphatic ester solvents (such as propylene glycol methyl ether acetate (PGMEA)) or its acidic solution). It can stably exist on the edge of the substrate (such as the peripheral area, side, and back of the front side of the substrate) during the coating, edge removal and development process of the metal-based patterned composition, reducing / preventing the metal ions from the metal-based patterned composition from contaminating the edge of the substrate, etc.; at the same time, the film layer of the above protective layer composition can be quickly removed by solvents such as aromatic ethers (such as anisole) and alicyclic ketones (such as cyclohexanone) without damaging the pattern of the metal-based patterned film, thereby effectively ensuring a high yield and stable performance of the prepared electronic devices. Similarly, the protective layer composition can also reduce the metal contamination problem caused by the supporting layer material of the metal-based patterning composition.

[0044] In the present application, the molecular structure characteristics of the above-mentioned polymers can be obtained by combining infrared spectroscopy testing, nuclear magnetic resonance spectroscopy testing, etc.

[0045] In this application, the group Ar 1 ,Ar 2 The aromatic rings may be pure aromatic rings or heteroaromatic rings containing heteroatoms (such as oxygen atom (O), sulfur atom (S), nitrogen atom (N), phosphorus atom (P), boron atom (B), etc.). Each aromatic ring may be substituted or unsubstituted. Each aromatic ring may be a monocyclic aromatic ring (such as a benzene ring) or a condensed polycyclic aromatic ring (such as a naphthalene ring). 1 ,Ar 2 When there are two or more aromatic rings, adjacent aromatic rings are connected by a connecting group. The connecting group can be selected from a single bond, -O-, -S-, -S(=O)-, -S(=O) 2-, -C(=O)-, substituted or unsubstituted alkylene, substituted or unsubstituted arylene, but not limited thereto. The substituents in the substituted alkylene may include one or more of halogen atoms, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, etc. The substituents in the substituted arylene may include one or more of halogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, etc. Exemplarily, the linking group may be -CH 2 -、-C(CH 3 ) 2 -、-C(CF 3 ) 2 -, -OC(=O)-, -O-CH 2 -, or -O-Ph, etc. Ph represents phenyl.

[0046] In some embodiments of the present application, Ar 2 It is a divalent group including at least two aromatic rings connected to each other. The aromatic ring is the main chain of the repeating unit in formula (II). In this case, the polycarbonate has good tolerance to solvents, edge washers, and developers (such as fatty ketones, fatty alcohols, alkyl ester solvents, etc.) in common metal-based patterning compositions.

[0047] In some embodiments of the present application, the Ar 1 ,Ar 2 Independently have the structure shown in formula (IV):

[0048]

[0049] wherein Q is selected from a single bond, -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 halogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, and substituted or unsubstituted aryl groups; s and t are independently selected from integers of 0-4; the position marked with * is the connection position.

[0050] Ar represented by formula (IV) 1 It is a biphenyl type divalent aromatic group, and two adjacent substituted or unsubstituted benzene rings are connected by a connecting group Q. 1 The polycarbonate or polyarylate having a repeating unit selected from the structure shown in formula (IV) has a high solubility in aromatic ether solvents (such as anisole) and has a certain chemical corrosion resistance in fatty alcohols. 5 , R 6When s=0, it means that there is no substituent R on the left benzene ring in formula (IV). 5 When t = 0, it means that there is no substituent R on the right benzene ring in formula (IV) 6 When s and t are non-zero integers, they can be 1, 2, 3 or 4.

[0051] In Q, substituted or unsubstituted C 1-5 For example, the alkylene group may be any of the following groups, substituted or unsubstituted: methylene (-CH 2 -), ethylene (-CH 2 CH 2 -), n-propylene (-CH 2 CH 2 CH 2 -), 2,2-isopropylidene (-C(CH 3 ) 2 -) etc. Among them, the substituted C 1-5 The substituents in the alkylene group include one or more of a halogen atom, an alkoxy group, and an aryl group, for example, -C(CF 3 ) 2 -, or -C(Ph) 2 -wait.

[0052] The halogen atoms involved in the embodiments of the present 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 the present 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 above-mentioned substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl may contain a heteroatom-containing linking group or not. The heteroatom-containing linking group may be inserted between some carbon atoms of the aforementioned groups, or directly connected to one end of them. The heteroatom may include one or more of O, N, S, P, or Si. Exemplary heteroatom-containing linking groups may include ether bonds (-O-), thioether bonds (-S-), carbonyl (-C(=O)-), -C(=O)-O-, -OC(=O)-, sulfonyl bonds (-S(=O) 2 -), sulfenyl bonds (-S(=O)-), substituted or unsubstituted imino groups (such as -NH-, -N(CH 3)-, etc.), amide bond (-NHCO-), etc. For example, a substituted or unsubstituted alkoxy group can be regarded as a substituted or unsubstituted alkyl group connected to an ether oxygen atom. A substituted or unsubstituted alkylcarbonyl group can be understood as an alkyl group connected to a carbonyl group, which is also regarded as within the scope of the alkyl group defined in this application.

[0055] In some embodiments of the present 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 by at least one of a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, and a haloalkoxy group. Specifically, the haloalkyl group may be a perhaloalkyl group or a partially haloalkyl group. The haloalkoxy group may be a perhaloalkoxy group or a partially haloalkoxy group.

[0056] In the present application, the number of carbon atoms in the substituted or unsubstituted alkyl group and the substituted or unsubstituted alkoxy group can be independently in the range of 1 to 20. 1 ~C 20 The carbon number is for unsubstituted alkyl. Substituted or unsubstituted alkoxy is substituted or unsubstituted C 1 ~C 20 Alkoxy. The number of carbon atoms is for unsubstituted alkoxy. Unsubstituted alkyl or alkoxy can be straight chain or branched. In some embodiments, the number of carbon atoms of substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy is independently 1-18, and can further be 1-12, 1-10, 1-8, 1-6 or 1-4, etc. Exemplarily, unsubstituted alkyl can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, etc. Unsubstituted alkoxy can be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, etc.

[0057] The number of carbon atoms of the substituted or unsubstituted cycloalkyl group may be 3-20, further 3-15, 3-12 or 5-20, etc. The substituents in the substituted cycloalkyl group may include halogen atoms, alkyl groups, alkoxy groups, etc. Examples of unsubstituted epoxy groups may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc.

[0058] The number of carbon atoms in the substituted or unsubstituted aryl group may be 6 to 30. 6 ~C 30 Aryl. 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 may be phenyl, naphthyl, biphenyl, etc.

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

[0060] In some embodiments of the present application, in formula (IV), R 5 , R 6 Each occurrence is independently selected from halogen atoms, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 1-10 Further, the substituted C 1-10 Alkyl, substituted C 1-10 The substituent in the alkoxy group is a halogen atom, for example, a fluorine atom.

[0061] In some other embodiments of the present application, s and t in formula (IV) are both 0. In this case, Ar shown in the structure of formula (IV) 1 or Ar 2 Specifically Q can be -CH 2 -、-C(CH 3 ) 2 -、-C(CF 3 ) 2 -, -C(=O)-, -S(=O)-, -S(=O) 2 - etc. Exemplarily, in this case, the repeating unit represented by formula (II) may include any of the following structures:

[0062]

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

[0064] In the aforementioned formula (III), regarding L and X, reference may be made to the explanation of Q in the previous text of this application.

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

[0066] When e=1, the repeating unit represented by formula (III) is specifically: The repeating unit may be derived from a diphenolic substance and In this case, if a, b, c, and d are all 0, the repeating unit represented by formula (III) may include any of the following exemplary structures:

[0067]

[0068] It should be noted that the above polycarbonate may include a repeating unit as shown in formula (II); or may include two or more repeating units with different structures as shown in formula (II). The repeating unit of the polycarbonate shown in formula (II) may be derived from a dihydroxy monomer HO-Ar 1 -OH and carbonic acid diester R'-OC(=O)OR'. It is understood that, in some cases, the polycarbonate may also include other repeating units different from the structure of formula (II). Similarly, in some cases, the above polyarylate may include repeating units of other structures in addition to the repeating units corresponding to the subscript m and the repeating units corresponding to the subscript p in formula (I). This application does not limit the structure of other repeating units.

[0069] The above-mentioned polymer having a repeating unit represented by formula (III) (referred to as "polymer 2.2" for ease of description) may include a repeating unit represented by formula (III); or may include repeating units of two or more different structures represented by formula (III). It is understood that, in addition to the repeating unit represented by the aforementioned formula (III), the above-mentioned polymer 2.2 may also include repeating units of other structures. Generally, the molar proportion of the repeating unit represented by the above-mentioned formula (III) in all the repeating units of the polymer 2.2 may be 80%-100%. This can ensure that the polymer 2.2 has excellent solubility in aromatic solvents such as aromatic ethers and alicyclic solvents.

[0070] In some embodiments of the present application, in the aforementioned formula (I), the ratio of m to p is in the range of 7:3-3:7. That is, m / p is in the range of 0.43-2.33. In this case, the above-mentioned polyarylate has good tolerance to solvents such as linear fatty ketones and linear fatty alcohols, and its solubility in aromatic solvents such as anisole is better, so as to facilitate the above-mentioned protective layer composition with good dispersibility. Exemplarily, m / p can be specifically 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 3-150, and p is in the range of 2-100.

[0071] In some embodiments of the present application, the weight average molecular weight M of the polyimide is w The polycarbonate or the polymer (polymer 2.2) having a repeating unit represented by formula (III) has an M w The M of the polyimide and the second polymer (polycarbonate and / or polymer 2.2) meeting the above structural requirements is 5000-50000. w Within this range, under their synergistic cooperation, it is more favorable that the thickness of the protective layer material containing them does not change significantly after being soaked in linear fatty ketone solvents, linear fatty alcohol solvents, linear ester solvents or their acidic solutions, and the removal time taken by solvents such as anisole is relatively short. w It can be in the range of 20000-40000. Polycarbonate, polymer 2.2 M w It may be in the range of 10000-40000, and further may be in the range of 15000-4000.

[0072] In the embodiment of the present application, the molecular weight distribution index (PDI) of the polyarylate, the polycarbonate, and the polymer having the repeating unit represented by formula (III) is less than 3.5, for example, 1.1-3.5. PDI is equal to the weight average molecular weight M of each polymer. w and number average molecular weight M n The dispersibility and viscosity of different batches of the protective layer composition made of two types of polymers with PDI in an appropriate range are not much different, which helps to ensure that the effects of the protective layer composition in various application scenarios are not much different.

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

[0074] In the embodiment of the present 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 film formed by the polycarbonate or the film formed by the polymer having the repeating unit represented by 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 above two types of polymer films in different solvents to meet the above requirements, it can be better ensured that the film layer of the above protective layer composition containing both of these two types of polymers has better tolerance to linear aliphatic ketone solvents, linear aliphatic alcohol solvents, etc., and can be quickly removed by aromatic ether solvents such as anisole. Among them, the above-mentioned films of each polymer refer to films formed by coating a solution containing the polymer and an organic solvent and then baking it.

[0076] It should be noted that the solubility of the films of the above polymers in other linear aliphatic ketones (such as methyl isoamyl ketone) except 2-heptanone also meets the above requirements. The solubility of the films of the above polymers in other aromatic ethers except anisole also meets the above requirements.

[0077] In the present application, the mass proportion of the polyarylate in the resin is 80%-99%, and can further be 80%-95%. Correspondingly, the mass proportion of the second polymer (polycarbonate and / or a polymer having a repeating unit shown in formula (III)) in the resin is 1%-20%, and can further be 5%-20%. Controlling the mass proportion of the polyarylate in the resin constituting the protective layer composition within an appropriately high range is conducive to the film layer of the protective layer composition having good solubility resistance to linear aliphatic ketone solvents, linear aliphatic alcohol solvents, etc., and ensuring that the protective layer material containing them will not take too long to remove when removed by solvents such as anisole and is easier to remove.

[0078] For example, the mass proportion of the polyarylate in the resin may be 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99%, etc. The mass proportion of the second polymer in the resin may 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 the present application, the second polymer includes a polycarbonate having a repeating unit represented by formula (II). Further, the second polymer also includes a polymer having a repeating unit represented by formula (III).

[0080] In some other embodiments of the present application, the second polymer includes a polymer having a repeating unit represented by formula (III). Further, the second polymer also includes a polycarbonate having a repeating unit represented by formula (II).

[0081] In the embodiment of the present application, in the protective layer composition, the total mass percentage of the resin is 0.1wt%-20wt%. 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, the higher the solution concentration, the thicker the corresponding film layer. Exemplarily, the mass percentage of the resin can be 0.2wt%, 0.5wt%, 1wt%, 2wt%, 2.5wt%, 3wt%, 4wt%, 5wt%, 6wt%, 8wt%, 9wt%, 10wt%, 12wt%, 15wt%, 16wt%, 18wt%, or 19wt%, etc. In some embodiments, the mass percentage of the resin is above 3wt%. In other embodiments, the mass percentage of polyetherimide is below 15wt%. In some embodiments, the mass percentage of the resin is 1wt%-10wt%. In this case, the protective layer composition is not easy to flow excessively, and the film thickness formed by coating is low, so as to better match the patterning process with small pattern feature size.

[0082] In the embodiment of the present application, the organic solvent in the protective layer composition may include one or more of anisole, cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, gamma-butyrolactone (GBL), and aromatic hydrocarbons. The polyarylate, polycarbonate, and polymer 2.2 of the aforementioned structure can be well dissolved in these organic solvents. Exemplary aromatic hydrocarbon solvents may include one or more of benzene, toluene, and xylene.

[0083] In some embodiments of the present application, the organic solvent may also include one or more of dialkyl ketones (the carbon number of the alkyl group is 1-6) and alkyl acetates (the carbon number of the alkyl group is 1-6). In the case where the organic solvent includes at least one of the above-mentioned anisole, cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, GBL, and aromatic hydrocarbons, an appropriate amount of linear aliphatic solvents may be further included to ensure the dissolution of the aforementioned polymers. Among them, 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, 3-pentanone, etc. 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, isobutyl acetate, etc.

[0084] In some embodiments of the present application, the protective layer composition further comprises an auxiliary agent. The auxiliary agent may include but is not limited to one or more of a UV absorber, a stabilizer, a lubricant, a plasticizer, a pigment, a dye, a colorant, an antistatic agent, a metal passivator, a release agent, etc. These auxiliary agents may be added according to actual needs.

[0085] The embodiments of the present application also provide the use of the protective layer composition to prevent metal contamination in non-pattern areas during a patterning process.

[0086] The application is to reduce or prevent the metal-based patterned material or its supporting layer material from contaminating the non-patterned area. The "non-patterned area" refers to a non-predetermined area where the metal-based patterned material or its supporting layer material is not intended to be disposed, such as the edge of the substrate.

[0087] The protective layer composition can be arranged at the edge of the substrate to act as an edge protection material. In the patterning process, it can reduce or prevent the metal-based patterning material or its supporting layer material from flowing to the edge of the substrate and directly contacting the edge of the substrate, thereby playing an anti-metal contamination effect. Thus, a high-quality patterned film can be formed on the substrate without causing metal contamination to the non-patterned area of ​​the electronic device substrate, thereby improving the preparation 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 : coating the protective layer composition of the embodiment of the present application on the edge of the substrate to form a protective layer.

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

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

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

[0093] In some embodiments of the present application, after coating the protective layer composition, a heating treatment may be performed (such as the aforementioned Figure 1 In some embodiments, the temperature of the heat treatment may 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 may be 30-120 s (e.g., 45 s, 60 s, 90 s, etc.).

[0094] Step S02, coating a metal-based patterned composition on one surface of the substrate to form a metal-based patterned material film layer on the substrate and the protective layer.

[0095] Among them, the metal-based patterned composition refers to a patterned composition containing metal elements. In some embodiments, the metal-based patterned composition may include a metal oxide photoresist (MOR), or a photoresist containing a metal complex, etc. The present application does not limit the specific composition of the metal-based patterned composition.

[0096] The specific coating method of the above-mentioned metal-based patterned composition can be spin coating. Wherein, the solvent used in the metal-based patterned composition should not cause harmful effects on the protective layer material of the embodiment of the present application. Wherein, the solvent in the metal-based patterned composition includes but is not limited to one or more of linear aliphatic ketone solvents, linear aliphatic alcohol solvents, linear ester solvents, etc. Exemplarily, linear aliphatic ketone solvents may include one or more of 2-heptanone, 4-methyl-2-pentanone, etc. Linear aliphatic alcohol solvents may include one or more of PGME (propylene glycol ethyl ether), methoxyethanol, ethoxypropanol, ethoxyethanol, 1-pentanol, 4-methyl-2-pentanol, methyl isobutyl carbinol (MIBC), etc. Linear ester solvents may include PGMEA (propylene glycol methyl ether acetate), ethyl lactate, etc.

[0097] In addition, during the process of spin coating the metal-based patterned composition on one side of the substrate, the metal-based patterned composition may flow to the non-patterned area of ​​the substrate (such as the peripheral area of ​​the front side of the substrate, the side of the substrate, the back side of the substrate, etc.), covering the substrate and the protective layer thereon (such as Figure 1 However, due to the presence of the protective layer, the metal-based patterned composition will not directly contact the non-patterned area of ​​the substrate to cause metal contamination.

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

[0099] Step S03, removing at least a portion of the metal-based patterned material film layer in contact with the protective layer.

[0100] Step S03 is mainly to remove the metal-based patterned material located at the edge of the substrate. This process can be called 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. In the edge removal process, no harmful effects should be caused to the metal-based patterned material film layer that is not in contact with the protective layer. Even after edge removal, some metal-based patterned materials in contact with the protective layer material are still retained, as long as the retained portion does not significantly reduce the anti-metal contamination effect of the protective layer. For example, after edge removal, at most 5% of the metal-based patterned material in contact with the protective film layer can be retained. Figure 1 A5 specifically shows the removal of the metal-based patterned material located on the wafer edge protection layer material.

[0101] Suitable techniques for removing at least a portion of the metal-based patterned material film layer 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 the present application, when wet etching is used, a side-washing agent can be used to remove at least a portion of the metal-based patterned material film layer in contact with the protective layer. Wherein, the side-washing agent will not cause a harmful effect on the protective layer of the embodiment of the present application. Exemplarily, the side-washing agent is, but is not limited to, one or more of PGMEA, PGME, ethyl lactate, methoxyethanol, ethoxypropanol, ethoxyethanol, 1-pentanol, 4-methyl-2-pentanol, etc.

[0102] Step S04, sequentially exposing the metal-based patterned material film layer left on the substrate (eg Figure 1 A7 in the figure), developing (as shown in Figure 1 ), to form a metal-based patterned film on the substrate.

[0103] In step S04, the exposure may be selective exposure, and the exposure source may be irradiated to the metal-based patterned material film layer left on the substrate through a mask having a predetermined pattern. The exposure source may be a light source with a wavelength below 400nm, or an X-ray, or an electron beam, etc. After the metal-based patterned material film layer is selectively exposed, a chemical reaction occurs in the exposed portion, and the solubility of the exposed portion in the developer differs from that of the unexposed portion.

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

[0105] Since the exposed area and the unexposed area of ​​the metal-based patterned material film layer have different solubility in the developer, the exposed patterned material film layer is developed with the developer to reveal a patterned film on the substrate. After being treated with the developer, the exposed part of the patterned material film layer is washed away, which is positive development, leaving a positive pattern identical to the exposure mask on the substrate; after being treated with the developer, the exposed part of the patterned material film layer is not washed away, which is negative development, leaving a negative pattern complementary to the exposure mask on the substrate.

[0106] The developer used for development can be selected according to the properties of the metal-based patterning material used. Common developers include one or more of linear aliphatic ketone solvents (such as 2-heptanone, 4-methyl-2-pentanone), linear aliphatic alcohol solvents (such as MIBC), linear ester solvents, aliphatic ether solvents, etc.

[0107] Step S05, after the development, removing the protective layer.

[0108] After removing the protective layer, the remaining metal-based patterned film is separated from the edge of the substrate (eg Figure 1 (as shown in A8 in FIG. 1 ).

[0109] In the embodiments of the present 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 used must have no harmful effects on the patterned film. In some embodiments of the present application, the protective layer can be removed by using an organic solvent used to prepare the protective layer composition. For example, one or more of anisole, cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, gamma-butyrolactone, etc. can be used to remove the protective layer. In this way, the removal rate of the protective layer is faster and does not damage the metal-based patterned film.

[0110] After the above step S05, a patterned substrate is obtained, which includes a substrate and a metal-based patterned film disposed on the substrate. The patterned film can be used as a high-precision mask for etching the substrate, and the pattern of the metal-based patterned film can be transferred to a substrate such as a silicon wafer by etching to form a preset pattern on the substrate.

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

[0112] In the manufacturing method of the above-mentioned electronic device provided by the embodiment of the present application, before coating the metal-based patterned composition on the substrate, the protective layer composition of the embodiment of the present application is used to protect the edge of the substrate, which can be stably present during the formation process of the metal-based patterned film (including coating, edge removal, development, etc.), reducing or avoiding the metal contamination caused by the metal-based patterned material to the non-patterned area of ​​the substrate (such as the edge of the substrate), and after the metal-based patterned film is formed, the protective layer material can be easily removed without damaging the patterned film, thereby improving the preparation yield and performance reliability of the electronic device. In particular, when a metal-based patterned film with a small feature size is formed on the substrate, the thickness of the protective layer is relatively thin, but due to its good corrosion resistance to solvents, edge washers, developers, etc. for metal-based patterned materials, it can still effectively play an anti-metal pollution role.

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

[0114] (1) coating the protective layer composition of the embodiment of the present application on the edge of the substrate to form a protective layer;

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

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

[0117] (4) sequentially exposing and developing the metal-based hard mask layer left on the substrate to form a metal-based patterned hard mask on the substrate;

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

[0119] After step (5), a metal-based patterned thin film can be formed on the substrate having a metal-based patterned hard mask formed on the surface according to the aforementioned electronic 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 by a metal-based hard mask composition, so they will not be described in detail.

[0120] Before coating a metal-based patterned hard mask on a substrate, the protective layer composition of an embodiment of the present application is used to protect the edge of the substrate. The protective layer composition can stably exist 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 area of ​​the substrate (such as the edge of the substrate) caused 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 preparation yield and performance reliability of electronic devices.

[0121] The embodiment of the present application also provides an electronic device, which is manufactured using the manufacturing method of the above-mentioned electronic device in the embodiment of the present 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 above-mentioned metal patterned film is completed, the preparation of other functional layers may be performed. In the final product of the electronic device, there is usually no metal-based patterned film.

[0123] The technical solution of the embodiment of the present application is further explained below with multiple embodiments.

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

[0125] Table 1 Polymer raw materials

[0126]

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

[0128] Among them, the reaction formula for synthesizing PAR-1 and PAR-2 ​​includes:

[0129]

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

[0131] In a three-necked flask filled with 200 mL of deionized water, add 220 mmol of NaOH, 100 mmol of bisphenol A (BPA), 2 mmol of BTEAC (benzyltriethylammonium chloride), and 5 mmol of NaHSO 3 , stirred for 30 min; in a 400 mL CH 2 Cl 2Add 50 mmol of IPC (isophthaloyl chloride) and 50 mmol of TPC (terephthaloyl chloride) into a beaker and stir for 30 min to obtain an organic phase solution; add the organic phase solution dropwise into the above three-necked flask, first react at 0°C for 1 h, then react at room temperature for 4 h, then add 1 mmol of PTBT (p-tert-butylphenol), terminate the reaction after 2 h, precipitate the obtained reaction material with methanol, then repeatedly wash with ethanol and deionized water, and vacuum dry at 80°C for 2 h to obtain a white polymer with a yield greater than 90%.

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

[0133] In a three-necked flask filled with 200 mL of deionized water, add 220 mmol of NaOH, 100 mmol of bisphenol A (BPA), 2 mmol of BTEAC (benzyltriethylammonium chloride), and 5 mmol of NaHSO 3 , stirred for 30 min; in a 400 mL CH 2 Cl 2 Add 70 mmol of IPC (isophthaloyl chloride) and 30 mmol of TPC (terephthaloyl chloride) into a beaker and stir for 30 min to obtain an organic phase solution; add the organic phase solution dropwise into the above three-necked flask, first react at 0°C for 1 h, then react at room temperature for 4 h, then add 1 mmol of PTBT (p-tert-butylphenol), terminate the reaction after 2 h, precipitate the obtained reaction material with methanol, then repeatedly wash with ethanol and deionized water, and vacuum dry 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 purge, Dean Stark trap (filled with toluene) and an overhead mechanical stirrer, 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 were added, and the mixture was stirred 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 less than 50°C and filtered through filter paper. The filtered solution (pH 9-10) was neutralized with a 10 wt% aqueous HCl solution to a pH of 6-7, and then poured into a 1L flask filled with 500 mL of deionized water to form a precipitate, mixed for 30 minutes, and allowed to settle overnight, then the water (500 mL) was decanted and 1L of tetrahydrofuran (THF) was added to the remaining sticky solid. The above THF solution was immersed in 3L of hexane and mixed for 1 hour and then the solid was allowed to settle, and the polymer polysulfone, recorded as PSU1, was precipitated.

[0137] Among them, the reaction formula involved in the synthesis of PSU-1 includes:

[0138]

[0139] Configuration of protective layer composition and solubility resistance test

[0140] According to the formula shown in Table 2 below, each polymer was dissolved in anisole at a certain mass ratio, and ultrasonic vibration was performed to obtain a protective layer composition. Subsequently, each protective layer composition was spin-coated on the edge of the wafer (such as Figure 1 A2 in the figure) and baked at 250°C for 60s to form a protective layer with an initial thickness of Afterwards, the wafers with protective layers were immersed in different solvents at room temperature for a certain period of time, the wafers were taken out and dried, the residual thickness of the protective layer was tested, and the residual film rate was calculated. The test results are also summarized in Table 2. Among them, residual film rate = residual thickness / initial thickness.

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

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

[0143] Table 2

[0144]

[0145]

[0146] In Table 2, the protective layer composition of Comparative Example 1-2 uses only PSU-1 or PC-1 as resin, and except for the acceptable solvent resistance to MIBC, its resistance to the acidic solvent of linear aliphatic ketone MIAK or 2-heptanone is poor, and the residual rate is less than 10%. The protective layer composition of Comparative Example 3 uses only polyarylate PAR-1, which has good resistance to MOR solvents and developer, and a low film thickness loss rate, but there is some residue in the remover-anisole or cyclohexanone.

[0147] In addition, according to thickness loss = initial film thickness × (1-residual film rate), it can be calculated that the thickness loss of the PSU-1 film (i.e., the protective layer of comparative example 1) after being immersed in the acidic solvent of 2-heptanone for 90 seconds is 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 being immersed in the acidic solvent of 2-heptanone for 90 seconds is 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 being immersed in the acidic solvent of 2-heptanone for 90 seconds is The thickness loss after immersion in anisole for 5 seconds is

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

[0149] In addition, the comparison between Comparative Examples 4-7 and Examples 1-7 shows that when polyarylate PAR-1 is used, excessive introduction of PC-1 or PSU-1 causes the protective layer to have poor tolerance to linear aliphatic ketones or their acidic solvents, thereby affecting the protective layer's ability to play a long-term and stable role in protecting the wafer edge.

[0150] In order to prove that the protective layer material provided in the embodiment of the present application can reduce metal pollution, the following application example 1 is provided.

[0151] Application Examples

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

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

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

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

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

[0157] (6) Anisole is used 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 is analyzed by ICP-MS technology, with the amount per cm 2 The test results are summarized in Table 3 below.

[0159] According to the method described in Application Example 1, the following application examples are provided, and the metal contamination test results are also summarized in the following Table 3.

[0160] Table 3

[0161]

[0162] It can be seen from Table 3 that in Example 1-2, the edge of the wafer is protected by the protective layer material of Example 3 or 4. After removing the protective material, it is found that the total amount of metal atom contamination on the back and side of the wafer is less than 10 10 / cm 2 , meeting the requirements of the electronics industry. In comparative application example 1, PSU-1 material is used as the wafer edge protection material, and in comparative application example 2, PC-1 material is used as the wafer edge protection material. However, because the edge protection material is more soluble in linear fatty ketone solvents (refer to the data in Table 2), it does not effectively protect the wafer, resulting in excessive metal ion impurities on the back and sides of the wafer. In comparative application example 3, only PAR-1 is used as the wafer edge protection material. Although it has good tolerance to common solvents, it is difficult to remove. The metal elements from MOR will remain on the protective layer, so that the amount of metal contamination on the wafer with the protective layer is still large.

[0163] The protective layer formed by the protective layer composition provided in the embodiment of the present application has good tolerance to MOR solvents, edge cleaning agents, and developers, and can stably exist during the coating, edge removal, and development processes of MOR, and can be easily removed later without remaining on the substrate, thereby effectively preventing the substrate edge from being contaminated by metal.

[0164] The above only expresses the exemplary embodiments of the present application, and the description is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent of the present application. It should be pointed out that for ordinary technicians in this field, several modifications and improvements can be made without departing from the concept of the present application, which all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application shall be based on the attached claims.

[0165] It should be understood that the first, second and various numerical numbers involved in this document are only distinguished for the convenience of description and are not used to limit the scope of the present application.

[0166] In this application, "and / or" describes the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone, where A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0167] In the description of this application, unless otherwise specified, the meaning of "multiple (kinds)" refers to greater than or equal to two (kinds). "At least one (kind)" refers to one (kind) or more (kinds). "At least one of the following (kinds)" or similar expressions refers to any combination of these items, including any combination of single (kinds) or plural (kinds). For example, "at least one (kind) of a, b, or c", or "at least one (kind) of a, b, and c", can all represent: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple, respectively.

[0168] In addition, the numerical range represented by "-" in the present application refers to the range including the numerical values ​​recorded before and after "-" as the minimum and maximum values, respectively. In the present application, expressions about parameter ranges, such as "greater than or equal to (≥)", "less than or equal to (≤)", "above...", "below..." all include this number. The numerical values ​​and numerical ranges involved in the embodiments of the present application are approximate values, which may be affected by the manufacturing process / test method, etc., and there may be a certain range of errors, which can be considered negligible by those skilled in the art.

Claims

1. A protective layer composition for reducing metal contamination at the edge of a substrate, characterized in that: The protective layer composition comprises a resin and an organic solvent, wherein the resin comprises 80% to 99% by weight of a polyarylate and 1% to 20% by weight of a second polymer, wherein the polyarylate has a structure represented by formula (I), and the second polymer comprises one or more of a polycarbonate having a repeating unit represented by formula (II) and a polymer having a repeating unit represented by formula (III); wherein m and p are both greater than 0, Ar1 is selected from a divalent group including at least two aromatic rings connected to each other, Ar2 is a divalent group containing at least one aromatic ring; X is selected from one of -S(=O)-, -S(=O)2-, and -C(=O)-; L is selected from a single bond, -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 a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryl group; n, a, b, c, and d are independently integers of 0 to 4; and e is 0 or 1.

2. The protective layer composition according to claim 1, characterized in that The Ar1 and Ar2 independently have the structure shown in formula (IV): wherein Q is selected from a single bond, -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 halogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, and substituted or unsubstituted aryl groups; s and t are independently selected from integers of 0-4; the position marked with * is the connection position.

3. The protective layer composition according to claim 1 or 2, characterized in that: Each occurrence of R is independently selected from halogen atoms, substituted or unsubstituted C 1-12 Alkyl, substituted or unsubstituted C 1-12 Alkoxy, substituted or unsubstituted C 6-24 One of the aromatic 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 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 to 3, characterized in that: In the formula (I), the ratio of m to p is in the range of 7:3-3:

7.

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

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

7. The protective layer composition according to 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 represented by formula (III) is 5,000-50,000.

8. The protective layer composition according to any one of claims 1 to 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 the repeating unit represented by 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 to 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. Use of the protective layer composition according to any one of claims 1 to 9 to prevent metal contamination in non-pattern areas in a patterning process.

11. A method for manufacturing an electronic device, characterized in that: include: Coating the protective layer composition according to any one of claims 1 to 9 on the edge of the substrate to form a protective layer; Coating a metal-based patterned composition on one surface of the substrate to form a metal-based patterned material film layer on the substrate and the protective layer; removing at least a portion of the metal-based patterned material film layer in contact with the protective layer; sequentially exposing and developing the metal-based patterned material film layer left on the substrate to form a metal-based patterned thin film on the substrate; After the developing, the protective layer is removed.

12. An electronic device, characterized in that: The method according to claim 11 is used to prepare the present invention.

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