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. The protective layer composition includes a polyetherimide and an organic solvent, the polyetherimide including ether imide repeat units derived from a diamine and an aromatic diether anhydride; the content of metal ions in the protective layer composition is 10 ppb or less. The protective layer composition can reduce 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 patterning processes. Among them, the patterning compositions used to form patterned films mainly include chemically amplified organic resin patterning compositions and patterning compositions containing metal elements, and the latter has shown obvious advantages in forming patterns with small feature sizes.

[0003] However, during the coating process on a substrate (such as a wafer), a metal-based patterned composition containing metal elements or its supporting layer material (such as a metal hard mask material that improves the pattern resolution formed by the metal-based patterned composition) will flow toward the edge of the substrate, causing the edge of the substrate to be easily contaminated by the metal elements, thereby affecting the yield and reliability of the manufactured electronic devices.

[0004] In order to reduce the above-mentioned metal contamination problem, the industry mainly adopts the following strategies: coating a certain thickness of protective material on the edge of the substrate, then spin-coating a metal-based patterned composition on one side of the substrate, and then using an edge cleaner to remove at least a portion of the metal-based patterned composition or its supporting layer material in contact with the protective material, and then removing the above-mentioned protective material after the metal-based patterned material or its supporting layer material is exposed and developed to be converted into a patterned film. In theory, the above-mentioned protective material needs to meet many requirements, such as good tolerance to solvents and developers in the metal-based patterned composition, no significant dissolution in the edge cleaner, and rapid removal by specific solvents. However, the substrate edge protection materials actually used rarely meet the above requirements at the same time, resulting in low or even ineffective ability to protect against metal contamination. Summary of the invention

[0005] In view of this, the embodiments of the present application provide a protective layer composition and its application, an electronic device and a manufacturing method thereof, which can effectively reduce metal contamination of a substrate during the manufacturing process of an electronic device.

[0006] Specifically, the first aspect of an embodiment of the present application provides a protective layer composition, which includes polyetherimide and an organic solvent, wherein the polyetherimide includes etherimide repeating units derived from diamine and aromatic diether anhydride; the metal ion content in the protective layer composition is less than or equal to 10 ppb.

[0007] The protective layer composition contains the above-mentioned polyetherimide, so that the protective layer composition has a high selective chemical etching rate, has no obvious solubility characteristics in the solvent, edge washing agent, and developer in the metal-based patterned composition, and can be quickly removed by a specific solvent, so that the protective layer composition can be set at the edge of the substrate, and can stably exist at the edge of the substrate during the coating and development process of the metal-based patterned composition, reducing / preventing the metal ions in the metal-based patterned composition from contaminating the edge of the substrate, and will not damage the metal-based patterned film during its removal process, thereby ensuring the yield and performance reliability of the prepared electronic device. In addition, the metal ion content of the above-mentioned protective layer composition is less than or equal to 10ppb, which can ensure that it can be effectively used for anti-metal pollution protection at the edge of the substrate. Similarly, the protective layer composition can also reduce the metal pollution caused by the supporting layer material of the metal-based patterned composition.

[0008] In the embodiment of the present application, the etherimide repeating unit includes at least one structure as shown in formula (I):

[0009]

[0010] Wherein, T is -O- or -OZO-, Z is selected from a divalent group containing at least one aromatic ring, and R is selected from a C 2-20 The polyetherimide having the etherimide repeating unit shown in formula (I) has a high solubility in aromatic solvents and good chemical corrosion resistance in aliphatic solvents, so that the degree of dissolution of the protective layer material containing the polyetherimide during the coating, edge washing and development of the metal-based patterned composition is extremely low, and can better play the role of reducing metal contamination of the substrate.

[0011] Furthermore, in some embodiments of the present application, Z comprises a structure represented by formula (1):

[0012]

[0013] wherein a, b, and c are independently selected from integers of 0 to 4, and R 1 , R 2 are independently selected from halogen atoms, halogenated or unhalogenated C 1-10 Alkyl, halogenated or unhalogenated C 1-10 One or more of alkoxy; X is selected from a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, C with or without heteroatoms 1-18 One of the divalent hydrocarbon groups; the position marked with * is the connection position.

[0014] In some embodiments of the present application, a=0, b=0, c=1; the X is selected from -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, halogenated or unhalogenated C 1-5 In this case, the polyetherimide having the etherimide repeating unit represented by formula (I) is easier to synthesize.

[0015] In some embodiments of the present application, the R in formula (I) includes the structure shown in formula (2):

[0016]

[0017] Wherein, d and e are independently selected from integers of 0-4, f is 0 or 1; L1 and L2 are independently selected from single bonds or C 1-6 Alkylene; R 3 , R 4 Each occurrence is independently selected from a halogen atom, a halogenated or unhalogenated C 1-10 Alkyl, halogenated or unhalogenated C 1-10 one or more of alkoxy; Q is selected from a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, halogenated or unhalogenated C 1-5 One of the alkylene groups; the position marked with * is the connection position.

[0018] In some embodiments of the present application, the polyetherimide further comprises an imide repeating unit derived from a diamine and an aromatic dianhydride without an ether oxygen bond. The introduction of other repeating units can adjust the solubility of the polyetherimide in different solvents.

[0019] In some possible embodiments of the present application, the imide repeating unit independently includes one or more structures represented by formula (II), formula (III), and formula (IV):

[0020]

[0021] Wherein, R is selected from one or more of an alkylene group containing or not containing heteroatoms, a cycloalkylene group containing or not containing heteroatoms, and an arylene group containing or not containing heteroatoms; and W does not contain an ether oxygen bond.

[0022] In the embodiment of the present application, the polyetherimide satisfies at least one of the following (a) to (c):

[0023] (a) the polyetherimide has a melt index of 0.1-10 g / min measured at 340° C.-370° C.;

[0024] (b) the intrinsic viscosity of the m-cresol solution of the polyetherimide at 25° C. is greater than 0.2 dL / g;

[0025] (c) The glass transition temperature of the polyetherimide is in the range of 200-280°C.

[0026] In the embodiment of the present application, the weight average molecular weight of the polyetherimide is in the range of 1000-150000. The weight average molecular weight of the polyetherimide is in an appropriate range, which is conducive to regulating the solubility of the protective layer containing it in different solvents.

[0027] In some embodiments of the present application, the polyetherimide includes a first polyetherimide with a weight average molecular weight of 1000-10000, and a second polyetherimide with a weight average molecular weight greater than 10000 to 150000. With the combination of two large and small molecular weight polyetherimides, the dry film of the protective layer composition has better solubility resistance in aliphatic ketone solvents (such as cyclohexanone), aliphatic alcohol solvents (such as methyl isobutyl alcohol), ester solvents (such as PGMEA) or acidic solutions thereof, and can be quickly removed by solvents such as anisole.

[0028] In some embodiments of the present application, the solubility of the first film formed by the first polyetherimide and the second film formed by the second polyetherimide in different solvents satisfies: at 25° C., the thickness loss rate of the first film immersed in cyclohexanone is greater than and less than The thickness loss rate after immersion in methyl isobutyl carbinol is less than The thickness loss rate after immersion in anisole is greater than At 25°C, the thickness loss rate of the second film immersed in cyclohexanone is less than The thickness loss rate after immersion in methyl isobutyl carbinol is less than The thickness loss rate after immersion in anisole is greater than

[0029] The film thickness loss rates of the low molecular weight first polyetherimide film and the high molecular weight second polyetherimide film in different solvents are regulated to meet the above requirements, which can better ensure that the dry film of the above protective layer composition containing such first polyetherimide and second polyetherimide has better tolerance to fatty ketone solvents, fatty alcohol solvents, etc., and can be quickly removed by anisole.

[0030] In some embodiments of the present application, in the protective layer composition, the mass ratio of the second polyetherimide to the first polyetherimide is 1 to 20. In this case, the protective layer composition has good tolerance to fatty ketone solvents, fatty alcohol solvents, etc., and the protective layer formed by it can be quickly removed by anisole.

[0031] 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.

[0032] The protective layer composition is arranged at the edge of the substrate to be patterned. 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.

[0033] A third aspect of the embodiments of the present application provides a method for manufacturing an electronic device, comprising:

[0034] 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;

[0035] 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;

[0036] removing at least a portion of the metal-based patterned material film layer in contact with the protective layer;

[0037] 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;

[0038] After the developing, the protective layer is removed.

[0039] 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.

[0040] 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

[0041] 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.

[0042] Figure 1 An exemplary flow chart of a patterning process is shown. DETAILED DESCRIPTION

[0043] The embodiments of the present application will be described below in conjunction with the drawings in the embodiments of the present application.

[0044] 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.

[0045] In order to form a patterned film with a small 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). 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 side and even the back of the substrate), 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.

[0046] 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 the surface of one side of the wafer and the protective layer material. A5 shows the edge washing process of the metal-based patterned material. A5 specifically shows the washing away of the metal-based patterned material located at the edge of the wafer, and exposing the EPL material (dark gray part) 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, resulting in differences in their 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.

[0047] In theory, the EPL material used to reduce metal pollution 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, especially when the thickness of the EPL is small, which makes it difficult to effectively play the role of anti-metal pollution in practice. For example, with the continuous reduction in the requirements for pattern feature size in the electronic device manufacturing process, the thickness of the EPL material should be close to the coating thickness of the metal-based patterned material, and the thickness of the EPL material is getting smaller and smaller, which requires that the thinner EPL material can still not be significantly dissolved by the solvent, developer, and edge washing agent in the metal-based patterned material, otherwise its ability to resist metal pollution will be greatly reduced. In view of this, the present application provides a protective layer composition and its application that can effectively reduce metal contamination in non-pattern areas during the manufacturing process of electronic devices.

[0048] An embodiment of the present application provides a protective layer composition for reducing metal contamination at the edge of a substrate, the protective layer composition comprising polyetherimide and an organic solvent, the polyetherimide comprising etherimide repeating units derived from diamine and aromatic diether anhydride; the metal ion content in the protective layer composition is less than or equal to 10 ppb.

[0049] The protective layer composition contains polyetherimide with etherimide repeating units. The applicant has found through a series of studies that it has no obvious solubility characteristics in the solvent, edge washer, and developer of the metal-based patterned composition, especially in ketones, esters, and their acidic solutions. It has excellent corrosion resistance, so the protective layer composition can be set at the edge of the substrate, and the protective layer material formed can be stably present at the edge of the substrate during the coating and development process of the metal-based patterned composition. Even if the metal ions in the metal-based patterned composition flow to the side and back of the substrate during its coating and development process, due to the presence of the protective layer material on the edge of the substrate, it can be ensured that the metal ions will not contaminate the side and back of the substrate, and the protective layer material can be quickly removed by a specific solvent (such as an aromatic ether solvent) without damaging the pattern of the metal-based patterned film, thereby effectively ensuring that the electronic device has a high yield and stable performance. Similarly, the protective layer composition can also reduce the metal pollution caused by the supporting layer material of the metal-based patterned composition.

[0050] In addition, the polyetherimide prepared by the reaction of diamine and aromatic diether anhydride generally contains metal ions at the ppm level (the metal ions generally originate from raw materials such as diamine and diether anhydride, or the ambient atmosphere when synthesizing the polyetherimide), and the present application controls the metal ion content of the above-mentioned protective layer composition containing the polyetherimide to be less than or equal to 10 ppb, which can ensure that the protective layer composition can be effectively used for anti-metal pollution protection at the edge of the substrate.

[0051] In the present application, in the infrared spectrum of the above polyetherimide, at 1779 cm -1 、1722cm -1 The carbonyl (-C(=O)) stretching vibration peak at wave number 720cm -1 The bending vibration peak of carbonyl group is shown at 1604cm -1 The characteristic peak of CNC stretching vibration in the imide ring is shown at 1340 cm -1 The stretching vibration peak of CN is shown at 1225 cm -1 and 1097cm -1 The characteristic absorption peak of ether bond (-O-) is shown at

[0052] In the embodiment of the present application, the etherimide repeating unit may include at least one structure as shown in formula (I):

[0053]

[0054] Wherein, T is -O- or -OZO-, Z is independently selected from a divalent group containing at least one aromatic ring each time, and R is independently selected from a C group containing or not containing heteroatoms each time. 2-20 One or more divalent hydrocarbon groups.

[0055] In this case, the etherimide repeating unit represented by formula (I) may be derived from a diamine (NH2-R-NH2) and an aromatic diether anhydride represented by formula (i)

[0056] In the present application, the polyether amide may include only one etherimide repeating unit as shown in formula (I) (in this case, the polyether amide is a homopolymer); or include two or more etherimide repeating units of different structures as shown in formula (I) (in this case, the polyether amide is a copolymer).

[0057] In the present application, the main chain of the etherimide repeating unit contains at least one ether oxygen bond (-O-). When T is -O-, the main chain of the etherimide repeating unit contains one ether oxygen bond (-O-); when T is -OZO-, the main chain of the etherimide repeating unit contains at least two ether oxygen bonds. The etherimide repeating unit shown in formula (I) can ensure that the polyetherimide has good tolerance to solvents, edge washers, and developers (such as fatty ketones, fatty alcohols, ester solvents, etc.) in commonly used metal-based patterning compositions, and thus the protective layer material containing the polyetherimide has a very low degree of dissolution during the coating, edge washing, and development processes of the metal-based patterning composition, and can effectively play the role of reducing metal contamination of the substrate.

[0058] In formula (I), the bonding position of T can be at the 3,3', 4,4', 3,4', or 4,3' position of the two benzene rings. Exemplarily, formula (I) can be any of the following structures:

[0059]

[0060] In the present application, the Z group has two bonding positions, and its two ends are respectively connected to the ether oxygen atom, so it is called a divalent group. Among them, Z can be a divalent aromatic group (i.e., arylene) containing or not containing heteroatoms, and the number of carbon atoms can be 6-24. The divalent aromatic group containing or not containing heteroatoms can be monocyclic or polycyclic. Among them, the monocyclic divalent aromatic group can specifically be a substituted or unsubstituted phenylene group. The polycyclic divalent aromatic group containing or not containing heteroatoms can be a condensed ring type or a non-condensed ring type; wherein the non-condensed ring polycyclic divalent aromatic group has a bridging group between the two aromatic rings; the bridging group can be a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, C containing or not containing heteroatoms, 1-18 divalent hydrocarbon group, etc.; each aromatic ring may or may not have a substituent.

[0061] In some embodiments of the present application, Z is selected from the structure shown in formula (1):

[0062]

[0063] wherein a, b, and c are independently selected from integers of 0 to 4, and R 1 , R 2 are independently selected from halogen atoms, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 1-10 One or more of the alkoxy groups; X is independently selected from a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, C with or without heteroatoms at each occurrence 1-18 One of the divalent hydrocarbon groups; the position marked with * is the connection position.

[0064] It can be understood that when Z is a structure represented by formula (1), the aforementioned formula (I) is specifically a structure represented by the following formula (I-a):

[0065]

[0066] In this case, the etherimide repeating unit represented by formula (I-a) is derived from a diamine (NH2-R-NH2) and an aromatic diether anhydride.

[0067]

[0068] In formula (1), R 1 , R 2 Respectively represent the substituents on each phenylene group; when a=0, it means that there is no substituent on the left benzene ring in formula (1); when b=0, it means that there is no substituent on the right benzene ring in formula (1). When a and b are non-zero integers, they can be 1, 2, 3 or 4. When c=0, formula (1) is specifically: That is, Z is a substituted or unsubstituted phenylene group. When c is any integer from 1 to 4, Z shown in formula (1) is a non-condensed polycyclic divalent aromatic group, and two adjacent substituted or unsubstituted phenylene groups are connected by a bridging group X. In some embodiments, when c=1, formula (1) is specifically:

[0069] R 1 , R 2 In, the halogen atom can be selected from one or more of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). Unsubstituted alkyl or alkoxy can be linear or branched. Alkoxy can be understood as an alkyl containing an ether bond (-O-) connecting group. Among them, the substituents in the substituted alkyl and substituted alkoxy can include halogen atoms, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, etc. In some embodiments, the substituted alkyl can be a haloalkyl, specifically a perhaloalkyl, or a partially haloalkyl. Similarly, the substituted alkoxy can be a haloalkoxy.

[0070] Wherein, the carbon number of the substituted or unsubstituted alkyl group and the substituted or unsubstituted alkoxy group can be independently 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. In some embodiments, the carbon number of the substituted or unsubstituted alkyl group and the substituted or unsubstituted alkoxy group is independently selected from an integer of 1-8, and further can be an integer of 1-6 or 1-4. Exemplarily, the alkyl group can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, etc. The alkoxy group can be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, etc.

[0071] In some embodiments of the present application, X is C with or without heteroatoms. 1-18 Divalent hydrocarbon group. Wherein, "divalent hydrocarbon group" refers to a group formed by removing two hydrogen atoms bound to a carbon atom in a hydrocarbon substance; it may be saturated or unsaturated; it may be straight-chain, branched or cyclic. Specifically, the divalent hydrocarbon group may include one or more of a straight-chain or branched alkylene group, a cycloalkylene group, a chain or cyclic alkenylene group, a chain or cyclic alkynylene group, and an arylene group; these divalent hydrocarbon groups may be unsubstituted or substituted; they may contain heteroatoms or not. Wherein, "heteroatoms" refers to atoms other than carbon and hydrogen, for example, it may be one or more of an oxygen atom (O), a sulfur atom (S), a nitrogen atom (N), a phosphorus atom (P), a boron atom (B), a silicon atom (Si), a halogen atom (such as F, Cl, Br, I), etc. Among them, the carbon number of the alkylene group containing or not containing heteroatoms can be 1-18; the carbon number of the cycloalkylene group containing or not containing heteroatoms can be 2-18, preferably 3-18; the carbon number of the chain alkenylene group and chain alkynylene group containing or not containing heteroatoms can be 2-18; the carbon number of the cyclic alkenylene group and cyclic alkynylene group containing or not containing heteroatoms can be 3-18; the carbon number of the arylene group can be 3-18, preferably 6-18.

[0072] When the divalent hydrocarbon group contains heteroatoms, specifically, at least some of the hydrogen atoms in the divalent hydrocarbon group may be replaced by one or more heteroatoms or heteroatom-containing groups, and / or some of these carbon atoms may be replaced by one or more heteroatoms or heteroatom-containing groups. The hydrogen atoms in the divalent hydrocarbon group may be replaced by halogen atoms, and monovalent polar groups containing heteroatoms such as nitro (-NO2), cyano (-CN), amino (such as -NH2, secondary amino (such as alkylamino), tertiary amino (such as dialkylamino)), hydroxyl (-OH), carboxyl (-COOH), sulfonic acid (-SO3H), etc.; and / or, bivalent connecting groups containing heteroatoms are inserted between at least some of the carbon atoms in the divalent hydrocarbon group. Exemplarily, the heteroatom-containing linking group may be an ether bond (-O-), a thioether bond (-S-), a carbonyl group (-C(=O)-), -C(=O)-O-, a sulfonyl bond (-S(=O)2-), a sulfinyl bond (-S(=O)-), a substituted or unsubstituted imino group (such as -NH-, -N(CH3)-), an amide bond (-NHCO-), etc. Thus, the aforementioned divalent hydrocarbon group containing or not containing heteroatoms may be a substituted or unsubstituted divalent hydrocarbon group containing or not containing the aforementioned heteroatom-containing linking group.

[0073] In some embodiments of the present application, a=0, b=0, c=1. In this case, Z is specifically a structure shown in formula (1a):

[0074]

[0075] wherein X is selected from -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, substituted or unsubstituted C 1-5 One of the alkylene groups.

[0076] In this case, the etherimide repeating unit represented by formula (I-a) is relatively easy to synthesize, and the polyetherimide with the etherimide repeating unit has high solubility in aromatic ethers (such as anisole) and good chemical corrosion resistance in fatty ketones, fatty alcohols, alkyl ester solvents, etc. 1-5 The alkylene group may 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 a halogen atom, an alkoxy group, and an aryl group. 1-5 The alkylene group is -C(CF3)2- or -C(Ph)2-. Ph represents a phenyl group. In some embodiments, Z shown in formula (1a) is specifically 2,2-(4-phenylene)isopropylidene

[0077]

[0078] In the above formula (I), R is derived from diamine NH2-R-NH2. Each occurrence of R is independently selected from C 2-20 In some embodiments of the present application, R can be selected from a linear or branched C 2-20 Alkylene, C with or without heteroatoms 3-20 Cycloalkylene, C with or without heteroatoms 6-20 One or more of arylene groups. Wherein, the carbon number of the alkylene group is specifically 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19. The carbon number of the cycloalkylene group can be specifically 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19, and can further be 3-12 or 3-8. The carbon number of the arylene group can further be 6-18, 6-12, etc. The distribution form and distribution position of heteroatoms in divalent hydrocarbon groups such as alkylene, cycloalkylene, and arylene groups can refer to the description of the previous text of this application, that is, at least some hydrogen atoms and / or carbon atoms in these hydrocarbon groups can be replaced by one or more heteroatoms or heteroatom-containing groups.

[0079] In some embodiments of the present application, each occurrence of R is independently selected from substituted or unsubstituted alkylene, and the main chain contains -O-, -S-, -NH-, -N(R 5 )-, one or more of substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene. 5 It can be a substituted or unsubstituted alkyl. The substituents in the substituted alkylene and substituted cycloalkylene may include halogen atoms, substituted or unsubstituted C 1-6 One or more of alkoxy, etc.

[0080] Exemplarily, R is -(CH2) 2～20 -、-(CH2) m -NH-(CH2) n -、-(CH2) m -N(CH3)-(CH2) n -、-(CH2) m -S-(CH2) n -、-(CH2) m -O-(CH2) n -、-(CH2) m -O-(CH2) n -O-(CH2) p -、-(CH2) m -NH-(CH2) n -NH-(CH2) p -、 Each occurrence of m, n, and p is independently selected from integers of 1-6.

[0081] In some other embodiments of the present application, R in formula (I) is selected from C containing or not containing heteroatoms 6-20 Arylene. In this case, the polyetherimide has better tolerance to solvents, edge washers, and developers (such as fatty ketones, fatty alcohols, alkyl ester solvents, etc.) in common metal-based patterning compositions. The degree of dissolution of the protective layer material containing the polyetherimide during the coating, edge washing, and development of the metal-based patterning composition is very low, which can effectively reduce the effect of metal contamination of the substrate, and the protective layer material of the polyetherimide can be easily removed by aromatic ether solvents. As described above in relation to T in this application, R can be selected from monocyclic or polycyclic C containing or not containing heteroatoms. 6-20 Arylene. The polycyclic arylene group may be a condensed ring arylene group (such as substituted or unsubstituted naphthylene) or a non-condensed ring polycyclic arylene group, wherein adjacent aromatic rings are connected by a bridging group.

[0082] Furthermore, in some embodiments of the present application, R comprises a structure shown in formula (2):

[0083]

[0084] wherein d and e are independently selected from integers of 0-4, f is 0 or 1; each occurrence of L1 and L2 is independently selected from a single bond or C 1-6 Alkylene; 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 one or more of alkoxy; Q is independently 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; the position marked with * is the connection position.

[0085] Among them, L1 and L2 are selected from C 1-6 In the case of an alkylene group, specific examples include methylene (-CH2-), ethylene (-CH2CH2-), n-propylene (-CH2CH2CH2-), n-butylene (-CH2CH2CH2CH2-), n-pentylene (-(CH2)5-), n-hexylene (-(CH2)6-), and the like.

[0086] About R 3 , R 4 , please refer to the previous description of R in formula (1) in this application 1 , R 2 In some embodiments, R 3 , R 4 are independently selected from halogen atoms, halogenated or unhalogenated C 1-6 Alkyl, halogenated or unhalogenated C 1-6 One or more of the alkoxy groups are further selected from halogen atoms, halogenated or unhalogenated C 1-4 Alkyl, halogenated or unhalogenated C 1-4 When d and e are non-zero integers, they can be 1, 2, 3 or 4.

[0087] In some embodiments, in formula (2), L1 and L2 are both single bonds, and f=1. In this case, formula (2) is specifically: In some other embodiments, f=0, and in this case, formula (2) is specifically: Furthermore, f=0 and L1 and L2 are both single bonds. In this case, formula (2) is specifically:

[0088] In some embodiments of the present application, each occurrence of R is independently selected from any of the following structures:

[0089] Wherein, each d and e are integers of 0-4, L1 and L2 are independently selected from a single bond or C 1-6 Alkylene; R 3 , R 4 are independently selected from halogen atoms, C 1-4 Alkyl, C 1-4 One or more of the alkoxy groups; Q is selected from a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, C 1-5 One of the alkylene groups.

[0090] Exemplarily, each occurrence of the above R is independently selected from any one of the structures shown in the following formula (2a) to formula (21):

[0091]

[0092] The definition of Q in formula (2h) is the same as that in formula (2) above. 1-5 Alkylene, which can be specifically -(CH2) 1～5 -、-C(CH3)2-、 wait.

[0093] When R in formula (I) is selected from the structures shown in formula (2a) to formula (2l), the diamine NH2-R-NH2 corresponding to R is easier to obtain, has a higher reactivity in reacting with aromatic diether anhydride to form polyetherimide, and can make the polyetherimide having repeating units of formula (I) have a higher solubility in aromatic solvents such as anisole.

[0094] In some embodiments of the present application, among all the etherimide repeating units shown in formula (I), the molar proportion of the etherimide repeating unit (which can be referred to as etherimide repeating unit A) when R is selected from the structures shown in formula (2a) to (2l) is more than 50%. This helps to ensure that the aforementioned polyetherimide has a high solubility in aromatic solvents such as anisole, and has better corrosion resistance to common metal-based patterning composition solvents, edge washers, and developers (such as fatty ketones, fatty alcohols, and alkyl ester solvents). Furthermore, when R in formula (I) is selected from the structures shown in formula (2a) to (2l), Z is 2,2-(4-phenylene)isopropylidene.

[0095] In the embodiment of the present application, the molar proportion of the etherimide repeating unit shown in formula (I) in all the repeating units of the polyetherimide is 90%-100%. The polyetherimide contains a relatively high molar proportion of etherimide repeating units, which is conducive to ensuring that the polyetherimide has no obvious solubility characteristics in solvents, edge washers, and developers in common metal-based patterned compositions, especially has excellent corrosion resistance in ketones, esters and their acidic solutions, so that it can stably exist at the edge of the substrate during the coating and development process of the metal-based patterned composition, and can ensure that the metal ions from the metal-based patterned material will not contaminate the side and back of the substrate.

[0096] It is understood that when the molar proportion of the etherimide repeating unit is 100%, it means that the polyetherimide does not contain other repeating units. When the molar proportion of the etherimide repeating unit is less than 100%, it means that the polyetherimide also includes repeating units of other structures. In this case, the polyetherimide is a copolymer. Among them, the molar proportion of the etherimide repeating unit in all the repeating units of the polyetherimide can be 95%-100%, or 98%-100%.

[0097] In some embodiments of the present application, the polyetherimide also includes an imide repeating unit derived from a diamine and an aromatic dianhydride. The main chain of the imide repeating unit does not contain an ether oxygen bond (-O-). The introduction of repeating units of other structures can adjust the solubility of the polyetherimide in different solvents. Among them, in all repeating units of polyetherimide, the molar proportion of the above-mentioned imide repeating unit can be 0-10%, further can be 0-5%, or 0-2%, etc. Exemplarily, the molar proportion of the imide repeating unit can be specifically 0.1%, 0.2%, 0.5%, 1%, 1.5%, 2%, 3%, 4%, 4.5%, 5%, etc.

[0098] In the embodiment of the present application, the imide repeating unit may include one or more structures shown in formula (II), formula (III), and formula (IV):

[0099]

[0100]

[0101] Wherein, each occurrence of R is independently selected from one or more of an alkylene group containing or not containing heteroatoms, a cycloalkylene group containing or not containing heteroatoms, and an arylene group containing or not containing heteroatoms, and W is different from the aforementioned T. W does not contain an ether oxygen bond (—O).

[0102] Wherein, each occurrence of W can be independently selected from one or more of a single bond, -S-, -S(=O)2-, -S(=O)-, -C(=O)-, a halogenated or unhalogenated alkylene group, a halogenated or unhalogenated arylene group. In some embodiments, W can be a halogenated or unhalogenated arylene group, or a halogenated or unhalogenated arylene group whose main chain contains at least one of -S-, -S(=O)2-, -S(=O)-, and -C(=O)-. In some embodiments, in formula (II), W is -S-, -S(=O)2-, -C(=O)-, -Ph-S-Ph-, or -Ph-C(=O)-Ph-; wherein, -Ph- represents a phenylene group.

[0103] That is, the aromatic dianhydride may include one or more of the substances represented by the following formula (ii), formula (iii), and formula (iv):

[0104]

[0105] wherein W is as defined in the above formula (II).

[0106] For example, the aromatic dianhydride represented by formula (ii) may include one or more of the following substances:

[0107]

[0108] In the present application, the polyetherimide can be synthesized from reaction raw materials including diamine and aromatic diether anhydride. In some embodiments of the present application, the polyetherimide can be synthesized from aromatic diether anhydride represented by formula (i) and diamine of the general formula NH2-R-NH2:

[0109] Wherein, T and R are as defined in formula (I) of the present application.

[0110] For example, the aromatic diether anhydride represented by formula (i) may include any one or more of the substances represented by the following formulae (i-1) to (i-16).

[0111]

[0112] Among them, the substance shown in formula (i-1) can be called bisphenol A type diether dianhydride, or 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride. The substance shown in formula (i-2) can be called 3,3-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride. The substance shown in formula (i-3) can be called 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride. The substance shown in formula (i-4) can be called 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride. The substance shown in formula (i-5) can be called 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride. The substance shown in formula (i-6) can be called 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride. The substance represented by formula (i-7) can be called 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride. The substance represented by formula (i-8) can be called 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride. The substance represented by formula (i-9) can be called 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride. The substance represented by formula (i-10) can be called 4,4'-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride. The substance represented by formula (i-11) can be called 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfone dianhydride. The substance represented by formula (i-12) can be called 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride. The substance represented by formula (i-13) can be called 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride. The substance represented by formula (i-14) can be called 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride. The substance represented by formula (i-15) can be called 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)benzophenone dianhydride. The substance represented by formula (i-16) can be called 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride.

[0113] Exemplarily, the diamine with the general formula NH2-R-NH2 may include one or more of the following substances: ethylenediamine, 1,2-propylenediamine (chemical formula NH2CH2CH(NH2)CH3), trimethylenediamine (chemical formula NH2-(CH2)3-NH2, also known as 1,3-propylenediamine), hexamethylenediamine (chemical formula NH2-(CH2)6-NH2), heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylenediamine (chemical formula NH2-(CH2)2-CH(CH3)-(CH2)4-NH2), 4,4-dimethylheptamethylenediamine (chemical formula NH2-(CH2)3-C(CH3)2-(CH2)3-NH2), 4-methyl nonamethylenediamine (chemical formula NH2-(CH2)3-CH(CH3)-(CH2)5-NH2), 5-methylnonamethylenediamine (chemical formula NH2-(CH2)4-CH(CH3)-(CH2)4-NH2), 2,5-dimethylhexamethylenediamine (chemical formula NH2-CH2-CH(CH3)-(CH2)2-CH(CH3)-CH2-NH2), 2,5-dimethylheptamethylenediamine (chemical formula NH2-CH2-CH(CH3)-(CH2)2-CH(CH3)-(CH2)2-NH2), 3-methoxyhexamethylenediamine Methylenediamine (chemical formula is NH2-(CH2)3-CH(OCH3)-(CH2)3-NH2), 2,2-dimethylpropylenediamine (chemical formula is NH2-CH2-C(CH3)2-CH2-NH2), diethylenetriamine (chemical formula is shown in formula (A)), triethylenetetramine (chemical formula is shown in formula (B)), N-methyl-bis(3-aminopropyl)amine (chemical formula is shown in formula (C)), 1,2-bis(3-aminopropoxy)ethane (chemical formula is shown in formula (D)), bis(3-aminopropyl)sulfide (chemical formula is NH2-(CH2)3-S-(CH2)3-NH2), 1,4-cyclohexanediamine, bis-(4-aminocyclohexyl)methane (chemical formula is shown in formula (C)), (chemical formula shown in formula (E)), m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, m-xylene diamine, p-xylene diamine, 2-methyl-4,6-diethyl-1,3-phenylene diamine (chemical formula shown in formula (F)), 5-methyl-4,6-diethyl-1,3-phenylene diamine (chemical formula shown in formula (G)), benzidine, 3,3'-dimethylbenzidine (chemical formula shown in formula (H)), 3,3'-dimethoxybenzidine (chemical formula shown in formula (I')), 1,5-diaminonaphthalene, bis(4-aminophenyl)methane (chemical formula shown in formula (J)), bis(2-chloro-4-amino-3,5-diethylphenyl)methane (chemical formula shown in formula (K)), 2,2-bis(4-aminophenyl)propane (chemical formula as shown in formula (L)), 1,3-diamino-4-isopropylbenzene (chemical formula as shown in formula (M)), bis(4-aminophenyl)ether (chemical formula as shown in formula (N)), bis(4-aminophenyl)sulfide (chemical formula as shown in formula (O)), bis-(4-aminophenyl)sulfone (chemical formula as shown in formula (P), also known as sulfonyl diphenylamine). In some embodiments, the organic diamine includes one or more of m-phenylenediamine, p-phenylenediamine, 2,2-bis(4-aminophenyl)propane, and sulfonyl diphenylamine. ,

[0114]

[0115] The polyetherimide can be prepared by different methods, and the specific preparation method is not limited. In some embodiments of the present application, the polyetherimide can be prepared according to the following method:

[0116] (1) under a protective atmosphere, adding a diamine of the general formula NH2-R-NH2 and an aromatic diether anhydride to an aprotic solvent to react to obtain a reaction solution;

[0117] (2) coating the reaction solution on a substrate and baking it to form a film, and then performing heat treatment to complete the imidization of the film, and then peeling it from the substrate to obtain a polyetherimide film.

[0118] Wherein, in step (1), the protective atmosphere may be nitrogen, etc. The aprotic solvent may include N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), γ-butyrolactone (GBL), dimethyl sulfoxide (DMSO), etc. The reaction solution includes a polyamic acid having an ether oxygen bond in the main chain (i.e., polyetheramic acid).

[0119] In step (2), the substrate may be a clean glass substrate, etc. The baking may be performed under a vacuum environment at a temperature of 50°C-120°C (for example, 60°C, 70°C, 80°C, 90°C, etc.). The baking time may be 0.5h-12h, for example, 1h, 2h, 3h, 4h, 5h, 6h, 8h, 10h, 11h, etc. The baking is to remove most of the solvent in the reaction solution to obtain a polyetheramic acid dry film, and to reduce the temperature and duration of the subsequent imidization reaction.

[0120] The heat treatment may be carried out in an oven under vacuum or protective atmosphere. The protective atmosphere may be a mixed atmosphere of hydrogen and argon, a mixed atmosphere of hydrogen and nitrogen, an argon atmosphere or a nitrogen atmosphere, etc. In some embodiments of the present application, the heat treatment is a gradient heat treatment, which may specifically include: first heating to 100°C-130°C and keeping warm for a first time, then heating to 140°C-200°C and keeping warm for a second time, and finally heating to 200°C-250°C and keeping warm for a third time. Each first time, second time, and third time are independently within the range of 0.25h-2h, for example, specifically 0.5h, 0.75h, 1h, 1.25h, 1.5h, etc.

[0121] In the present application, after the heat treatment is completed, the substrate with the polyetherimide film can be naturally cooled to room temperature, and then the polyetherimide film thereon can be peeled off. The polyetherimide film includes polyetherimide, and the polyetherimide includes repeating units derived from aromatic diether anhydride and diamine NH2-R-NH2.

[0122] In some embodiments of the present application, the raw materials for synthesizing the polyetherimide further include an aromatic dianhydride whose main chain does not contain an ether oxygen bond. Thus, the polyetherimide has repeating units derived from the aromatic dianhydride and the diamine NH2-R-NH2.

[0123] In the present application, the polyetherimide used for the above-mentioned protective layer composition may have a low level of residual volatile species. The residual volatile species may be derived from one or more of residual solvents, residual reaction raw materials (such as excess diamines or dianhydrides), water, etc. In some embodiments, the concentration of residual volatile species of the polyetherimide is less than 1000ppm, further less than 500ppm, preferably less than 300ppm, or even less than 100ppm. Among them, the residual volatile species in the final polymer product can be achieved at a lower level by known methods (such as devolatilization or distillation). Among them, devolatilization or distillation can be carried out at normal pressure, or under reduced pressure. Suitable devolatilization devices can be wiped film evaporators, devolatilization extruders, etc.

[0124] In the embodiment of the present application, the glass transition temperature (T g ) is in the range of 200°C to 280°C. The T g It can be known from the polymer curve measured by differential scanning calorimetry (DSC). g To some extent, it is related to the relative molecular weight of polyetherimide.

[0125] In some embodiments of the present application, the prepared polyetherimide can be heated to a molten state using known melt filtration techniques and then filtered to remove foreign matter, carbonized particles, cross-linked resins or similar impurities therein. Melt filtration can be performed immediately after the polyetherimide material is synthesized, or subsequently (for example, before the polyetherimide is used to prepare the above-mentioned protective layer composition). The polyetherimide can be melt filtered during the extrusion operation. A filter having a pore size sufficient to remove particles with a size of 40 microns or more can be used for melt filtration. Further, the filter used for melt filtration has a pore size sufficient to remove particles with a size of 100 microns or more.

[0126] In the embodiment of the present application, the melt index of the polyetherimide measured at 340°C-370°C is 0.1-10g / min. The melt index can be measured according to the American Society for Testing Materials (ASTM) D1238. The testing instrument is a melt index testing instrument. The test method of the melt index generally includes: first melting the polymer material into a melt, and then measuring the mass of the polymer melt passing through a standard die capillary (such as) at a specified temperature (such as 340°C-370°C) and pressure for a certain period of time (usually 10 minutes). The larger the value of the melt index, the smaller the viscosity of the polymer, the smaller the molecular weight, and the better the processing fluidity; conversely, the smaller the value of the melt index, the greater the viscosity of the polymer, the greater the molecular weight, and the worse the processing fluidity.

[0127] The polyetherimide has a suitable melt index, which reflects that it has a suitable relative molecular mass, and the chemical etching rate of the protective layer material containing the polyetherimide in different solvents can be adjusted accordingly. Exemplarily, the melt index of the polyetherimide can be specifically 0.2g / min, 0.5g / min, 1.0g / min, 2.0g / min, 1.0g / min, 2.0g / min, 3.0g / min, 4.0g / min, 5.0g / min, 6.0g / min, 7.0g / min, 8.0g / min, 9.0g / min, etc.

[0128] In the embodiment of the present application, the intrinsic viscosity of the meta-cresol solution of the polyetherimide at 25°C is greater than 0.2dL / g, for example, 0.35-0.7dL / g. The intrinsic viscosity, which can also be referred to as "characteristic viscosity", refers to the reduced viscosity when the concentration of the polymer solution tends to zero, and its value does not change with the concentration of the polymer solution. The above-mentioned intrinsic viscosity can be measured by testing the meta-cresol solution of polyetherimide at 25°C using an Ubbelohde viscometer or a capillary viscometer. When the test temperature and solvent are constant, the intrinsic viscosity of the same polymer is only related to its relative molecular weight. Exemplarily, the above-mentioned intrinsic viscosity can be specifically 0.4dL / g, 0.45dL / g, 0.5dL / g, 0.55dL / g, 0.6dL / g, 0.65dL / g, etc.

[0129] In the embodiment of the present application, the weight average molecular weight M of the polyetherimide is w In the range of 1000-150000. w It can be measured by gel permeation chromatography (GPC) using polystyrene as a standard. w In an appropriate range, it is beneficial to ensure that the protective layer containing it has good solubility resistance in aliphatic solvents and can be quickly dissolved by aromatic solvents. w is 2000, 5000, 6000, 7000, 8000, 10,000, 11,000, 12,000, 15,000, 18,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, 60,000, 70,000, 80,000, 90,000, 100,000, 120,000, 140,000, etc. In some embodiments, the M of the polyetherimide is w In the range of 5000-80000.

[0130] In some embodiments of the present application, the polyetherimide includes a first polyetherimide and a second polyetherimide, wherein the weight average molecular weight of the first polyetherimide is less than the weight average molecular weight of the second polyetherimide. The first polyetherimide and the second polyetherimide may have repeating units of the same or different structures. Further, the weight average molecular weight M of the first polyetherimide is w The weight average molecular weight M of the second polyetherimide is 1000-10000. wIn the range of greater than 10,000 to less than or equal to 150,000. In this way, under the synergistic cooperation of the low molecular weight polyetherimide and the high molecular weight polyetherimide, it is more favorable that the thickness of the protective layer material containing them does not change significantly after being soaked in aliphatic ketone solvents, aliphatic alcohol solvents, ester solvents or their acidic solutions (such as no significant increase or decrease in thickness), the corrosion resistance of these solvents is good, and it is ensured that the removal time of the protective layer material containing them when being removed by solvents such as anisole is not too long and it is easier to remove. In some embodiments, the M of the first polyetherimide is w The M of the second polyetherimide is 5000-10000, and can further be 6000-9500, 8000-10000, 8000-9500, etc. w It can be 10,000-80,000, for example, 12,000-50,000, 15,000-30,000, etc.

[0131] In some embodiments of the present invention, the solubility of the first film formed by the first polyetherimide and the second film formed by the second polyetherimide in different solvents satisfies: at 25° C., the thickness loss rate of the first film immersed in cyclohexanone is greater than and less than The thickness loss rate after immersion in methyl isobutyl carbinol is less than The thickness loss rate after immersion in anisole is greater than At 25°C, the thickness loss rate of the second film immersed in cyclohexanone is less than The thickness loss rate after immersion in methyl isobutyl carbinol is less than The thickness loss rate after immersion in anisole is greater than

[0132] Controlling the solubility of the low molecular weight first polyetherimide film and the high molecular weight second polyetherimide film in different solvents to meet the above requirements can better ensure that the dry film of the protective layer composition containing both the first polyetherimide and the second polyetherimide has better tolerance to fatty ketone solvents, fatty alcohol solvents, etc., and can be quickly removed by anisole. It can be understood that in some embodiments of the present application, at 25°C, the thickness loss of the first film after immersion in cyclohexanone for 60 seconds is greater than and less than The thickness loss after immersion in methyl isobutyl methanol for 60 seconds is less than The thickness loss after immersion in anisole for 10 seconds is greater than At 25°C, the thickness loss of the second film after being immersed in cyclohexanone for 60 seconds is less than The thickness loss after immersion in methyl isobutyl methanol for 60 seconds is less than The thickness loss after immersion in anisole for 10 seconds is greater than

[0133] It should be noted that the first film is formed by coating a solution containing only the first polyetherimide and an organic solvent and then baking it. The second film is formed by coating a solution containing only the second polyetherimide and an organic solvent and then baking it.

[0134] In some embodiments of the present application, in the above-mentioned protective layer composition, the mass ratio of the second polyetherimide to the first polyetherimide is greater than or equal to 1, for example, the mass ratio is 1-20. This is more conducive to the above-mentioned protective layer composition having better corrosion resistance to fatty ketone solvents, fatty alcohol solvents, etc., and ensures 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. Specifically, the mass ratio can be 1.5:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, etc. In some embodiments, the mass ratio is (1-10):1.

[0135] In the embodiment of the present application, in the above-mentioned protective layer composition, the total mass percentage of polyetherimide is 0.1wt%-20wt%. The mass percentage of the polyetherimide in the above-mentioned protective layer composition can be adjusted according to the required protective layer film thickness. Generally, the higher the solution concentration, the thicker the corresponding film layer. Exemplarily, the mass percentage of the polyetherimide 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 polyetherimide is above 3wt%. In other ways, the mass percentage of polyetherimide is below 15wt%. In some embodiments, the mass percentage of polyetherimide is 1wt%-10wt%. In this case, the protective layer composition is not prone to excessive flow, and the film thickness formed by coating is relatively low, so as to better match the patterning process with small pattern feature size.

[0136] In the embodiment of the present application, the organic solvent used in the above-mentioned protective layer composition may include one or more of anisole, gamma-butyrolactone, N-methyl-2-pyrrolidone, and aromatic hydrocarbons. Further, the organic solvent may also include one or more of cyclohexanone, cyclopentanone, 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 above-mentioned organic solvent includes at least one of the above-mentioned anisole, gamma-butyrolactone (GBL), N-methyl-2-pyrrolidone, and aromatic hydrocarbons, an appropriate amount of aliphatic solvents may be further included. 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. Exemplary aromatic hydrocarbon solvents may include one or more of benzene, toluene, xylene, and the like.

[0137] In some embodiments of the present application, the protective layer composition further includes an auxiliary agent. Among them, the auxiliary agent may include but is not limited to one or more of ultraviolet absorbers, stabilizers, lubricants, plasticizers, pigments, dyes, colorants, antistatic agents, metal passivators, release agents, etc. These auxiliary agents can be added according to actual needs. The total mass percentage of the auxiliary agent in the protective layer composition may be less than 3wt%, for example, in the range of 0.01wt%-3wt%, and further in the range of 0.01-1wt%.

[0138] Wherein, the stabilizer may include one or more of a light stabilizer (such as a UV stabilizer) and a voltage stabilizer. Exemplarily, the stabilizer may include one or more of a phosphorus-containing stabilizer, a hindered phenol stabilizer, etc. Wherein, the phosphorus-containing stabilizer may include, but is not limited to, a phosphorous (phosphonic) ester (such as triaryl phosphite), a phosphorous (phosphonic) ester (such as aryl phosphate), etc. In order to reduce the loss of the stabilizer, the relative molecular weight of the phosphorus-containing stabilizer may be in the range of 300-5000, and the relative molecular weight of the hindered phenol stabilizer may be above 500.

[0139] Generally, polyetherimide obtained by reacting diamine and diether anhydride substances generally contains metal ions at the ppm level, and the metal ion content in the protective layer composition obtained by directly mixing it with an organic solvent is also at the ppm level, or even higher. The present application controls the metal ion content in the above-mentioned protective layer composition to be less than or equal to 10ppb. This ensures that the protective layer composition can be used at the edge of the substrate for anti-metal pollution protection. Among them, the metal ion content therein can be reduced before the protective layer composition is coated on the edge of the substrate. For example, the protective layer composition can be subjected to ion exchange treatment to reduce the metal ion content therein, and / or the metal ion content can be reduced by extraction in an acidic solution. Exemplarily, the metal ion content in the protective layer composition can be specifically 10ppb, 9ppb, 8ppb, 7ppb, 6ppb, 5ppb, 4ppb, 3ppb, 2ppb, 1ppb, etc. In some embodiments of the present application, the metal ion content in the above-mentioned protective layer composition is less than or equal to 5ppb, and further less than or equal to 4ppb.

[0140] The embodiments of the present application also provide an application of the protective layer composition to reduce metal contamination in non-pattern areas during a patterning process.

[0141] The application is to reduce the contamination of non-patterned areas by metal-based patterned materials or their supporting layer materials. The "non-patterned areas" refer to non-predetermined areas where metal-based patterned materials or their supporting layer materials are not intended to be set, such as the edge of a substrate, or the edge of an electronic device.

[0142] Accordingly, the embodiments of the present application also provide the use of polyetherimide to reduce metal contamination in non-pattern areas during a patterning process; the polyetherimide includes etherimide repeating units derived from diamine and aromatic diether anhydride.

[0143] The protective layer composition containing polyetherimide, or the polyetherimide can be arranged at the edge of the substrate to act as an edge protection material. In the semiconductor patterning process, it can 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 while not 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. Among them, the specific structure / physical and chemical properties of the polyetherimide can be referred to the description of the previous text of this application.

[0144] This embodiment also provides a method for manufacturing an electronic device, comprising:

[0145] 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;

[0146] 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;

[0147] Step S03, removing at least a portion of the metal-based patterned material film layer in contact with the protective layer;

[0148] Step S04, 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;

[0149] Step S05, after the development, removing the protective layer.

[0150] In step S01, the substrate can be selected according to specific needs, for example, it can be a silicon wafer (such as Figure 1 As 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, 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.

[0151] In some embodiments of the present application, the protective layer composition is disposed on the peripheral area of ​​one side surface of the substrate (the surface is the surface to be coated with the metal-based patterned material), such as Figure 1 The peripheral area of ​​the upper surface of the substrate shown in A2 (see the dark gray part). In this case, the edge of the substrate includes the peripheral area of ​​the surface of one side of the substrate. The peripheral area is also the non-patterned area of ​​the surface of the substrate. The other area surrounded by the peripheral area is the patterned area on the upper surface of the substrate (see the area indicated by the arrow in A2), which is an ideal retention area for the patterned material. During exposure, only the patterned material is retained on the patterned area. In some other embodiments of the present application, the protective layer composition is disposed on the peripheral area of ​​the surface of one side of the substrate (such as the upper surface or the front side) and covers the side of the substrate. The side is adjacent to the upper surface. In this case, the edge of the substrate includes the peripheral area and the side of the surface of one side of the substrate. In other embodiments of the present application, the protective layer composition is disposed on the peripheral areas of the two side surfaces of the substrate disposed opposite to each other, and covers the side of the substrate (such as the upper surface or the front side). Figure 1 The side surface is located between the two oppositely disposed surfaces of the substrate. For example, the protective layer covers the peripheral area of ​​the upper surface (or front surface) of the substrate, the peripheral area of ​​the lower surface (or back surface) of the substrate, and the side surface of the substrate. In this case, the edge of the substrate includes the peripheral area and the side surface of the two oppositely disposed surfaces of the substrate.

[0152] 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 film 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 film 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 surface of one side of the substrate, in Figure 1 A2 is specifically the width of the dark grey ring.

[0153] In some embodiments of the present application, the protective layer composition can be directly spin-coated to form a film without heating. During the spin-coating process, the organic solvent in the protective layer composition is volatilized. No additional heating is performed after coating the protective layer composition, which can simplify the process steps and does not affect the corrosion resistance of the protective layer containing a small amount of organic solvent to the solvent, edge cleaning agent, etc. in the metal-based patterning composition. In other embodiments of the present application, after coating the protective layer composition, a heating treatment (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.).

[0154] In step S02, the metal-based patterned composition refers to a patterned composition containing a metal element. In some embodiments, the patterned composition containing a metal element can be a metal oxide photoresist (MOR), a photoresist containing a metal complex, etc. The metal-based patterned material can include but is not limited to those mentioned in the following patents: U.S. Patent No. 9,315,636; No. 8,568,958; No. 9,201,305; No. 9,296,922; No. 9,409,793 and No. 9,499,698 and U.S. Patent Application No. 62 / 437,449 (filed on December 21, 2016) and No. 14 / 978,232 (filed on December 22, 2015), which are hereby incorporated herein in their entirety.

[0155] In some embodiments of the present application, the above-mentioned metal-based patterned composition can be disposed on the substrate by coating. Among them, the specific coating method can be spin coating. When spin coating is used, 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. Among them, the solvent in the metal-based patterned composition includes but is not limited to one or more of aliphatic ketone solvents, aliphatic alcohol solvents, ester solvents, etc. Exemplarily, aliphatic ketone solvents may include one or more of cyclohexanone, 4-methyl-2-pentanone, etc. 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 carbinol, etc. Ester solvents may include PGMEA (propylene glycol methyl ether acetate), ethyl lactate, etc.

[0156] 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.

[0157] 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.

[0158] 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.

[0159] 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, etc. 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 harmful effects on the protective layer of the embodiment of the present application. Exemplarily, the side-washing agent includes, but is not limited to, one or more of PGMEA, PGME, ethyl lactate, methoxyethanol, ethoxypropanol, ethoxyethanol, 1-pentanol, 4-methyl-2-pentanol, cyclohexanone, etc. In some embodiments, the side-washing agent is a mixed solvent in which the volume ratio of PGMEA to PGME is 7:3.

[0160] 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.

[0161] 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.

[0162] 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.

[0163] The developer used for development can be selected according to the properties of the metal-based patterned material used. Common developers include one or more of aliphatic ketone solvents (such as cyclohexanone), aliphatic alcohol solvents, aliphatic ether solvents, ester solvents, and the like.

[0164] In step S05, after removing the protective layer, the remaining patterned film is separated from the edge of the substrate (eg Figure 1 (as shown in A8 in FIG. 1 ).

[0165] 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, gamma-butyrolactone, N-methyl-2-pyrrolidone, etc. can be used to remove the protective layer. In some embodiments, anisole is specifically used to remove the protective layer. The removal rate of the protective layer is fast and does not damage the metal-based patterned film.

[0166] 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.

[0167] It is understandable that, after the above step S05, other functional layers may be manufactured on the substrate.

[0168] The manufacturing method of the above-mentioned electronic device provided in the embodiment of the present application, before coating the metal-based patterned composition on the substrate, uses the protective layer composition of the embodiment of the present application to protect the edge of the substrate, which can stably exist during the formation process of the metal-based patterned film (including coating, edge removal, development, etc.), reducing 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 addition, when a metal-based patterned film with a small characteristic 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.

[0169] 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.

[0170] The electronic device may include a semiconductor device (such as a chip), an integrated circuit, 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 electronic device, there is usually no metal-based patterned film.

[0171] The embodiments of the present application are further described below with reference to a plurality of embodiments.

[0172] Synthesis Example 1

[0173] Under nitrogen protection, 120 g of N,N-dimethylacetamide (DMAc) and 0.048 mol of 2,2-bis(4-aminophenyl)propane were added to a 500 mL flask equipped with a magnetic stirrer, and the mixture was stirred thoroughly to obtain a diamine solution; 0.05 mol of bisphenol A diether dianhydride was then added to the diamine solution, and DMAc was added to adjust the solid content of the solution to 10%, and the mixture was stirred at room temperature for 12 h to obtain a reaction solution containing polyether amide acid;

[0174] The above reaction solution was slowly poured onto a clean horizontal glass plate and evenly spread with a glass rod, then placed in a blast oven and baked at 80°C for 10 hours to remove most of the DMAc solvent to obtain a pre-dried polyetheramic acid film, which was then heated to complete imidization. The specific heating procedure was: 120°C-1h, 180°C-1h, 220°C-1h. After cooling to room temperature, the polyetherimide was peeled off from the glass plate and recorded as PEI1.

[0175] The reaction process of this synthetic example 1 is as follows:

[0176]

[0177] The weight average molecular weight M of PEI1 was measured by gel permeation chromatography using polystyrene as a standard. w is 8432, the M w is the number average molecular weight M n The ratio is 1.87.

[0178] Synthesis Example 2

[0179] The difference between Synthesis Example 2 and Synthesis Example 1 is that 2,2-bis(4-aminophenyl)propane is replaced by the same molar amount (i.e., 0.048 mol) of p-phenylenediamine. The polyetherimide prepared in Synthesis Example 2 is denoted as PEI2. The weight average molecular weight M of PEI2 is measured by gel permeation chromatography. w is 8859, M w / M n =2.12.

[0180] Synthesis Example 3

[0181] The difference between Synthesis Example 3 and Synthesis Example 2 is that the molar amount of p-phenylenediamine used in Synthesis Example 2 is changed to 0.049 mol. The polyetherimide prepared in Synthesis Example 3 is recorded as PEI3. The weight average molecular weight M of PEI3 is measured by gel permeation chromatography. w is 16859, M w / M n =1.93.

[0182] Synthesis Example 4

[0183] The difference between Synthesis Example 4 and Synthesis Example 2 is that the molar amount of p-phenylenediamine used in Synthesis Example 2 is changed to 0.047 mol. The polyetherimide prepared in Synthesis Example 4 is recorded as PEI4. The weight average molecular weight M of PEI4 is measured by gel permeation chromatography. w is 6368, M w / M n =2.18.

[0184] Synthesis Example 5

[0185] The difference between Synthesis Example 5 and Synthesis Example 2 is that the molar amount of p-phenylenediamine used in Synthesis Example 2 is changed to 0.045 mol. The polyetherimide prepared in Synthesis Example 5 is recorded as PEI5. The weight average molecular weight M of PEI5 is measured by gel permeation chromatography. w is 4559, M w / M n =2.53.

[0186] Among them, the reaction formulas for synthesizing PEI2, PEI3, PEI4 and PEI5 include:

[0187]

[0188] Comparative Synthesis Example 1

[0189] 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 DMAc and 15 mL of toluene were added, and the mixture was stirred at room temperature for 10 minutes.

[0190] The mixture was reacted at 150°C for 5 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. After mixing for 30 minutes, it was allowed to settle overnight, and 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 3 liters of hexane and mixed for 1 hour and then the solid was allowed to settle, and the polymer polysulfone, recorded as PSU1, was precipitated.

[0191] Among them, the reaction formulas involved in the synthesis of PSU1 include:

[0192]

[0193] The weight average molecular weight M of PSU1 was measured by gel permeation chromatography. w 16783, M w / M n =2.13.

[0194] Comparative Synthesis Example 2

[0195] The difference between Comparative Synthesis Example 2 and Comparative Synthesis Example 1 is that the reaction time at 150° C. is 10 hours. The polysulfone obtained in Comparative Synthesis Example 2 is denoted as PSU2.

[0196] The weight average molecular weight of PSU2 was measured by gel permeation chromatography. w is 54384, M w / M n =1.89.

[0197] Different protective layer composition materials were prepared according to the formula shown in Table 1 below. Metal ion impurity (abbreviated as metal impurity) filter and particle filter were used to filter and remove metal impurities and particles in the composition. The following is the series order of the filters: (1) adsorption type metal impurity filter, (2) chelate type metal impurity filter, (3) ultra-high molecular weight polyethylene (UPE) particle filter with an average pore size of 10nm and (4) UPE particle filter with an average pore size of 1nm. Among them, the filtration pressure is 0.20MPa, and the number of cycles is 5-15 times, until the protective layer composition is measured by a laser particle counter (Laser Particle Counter, LPC) to have no particles with a particle size ≥0.15μm. The metal ion impurities in the composition were analyzed by inductively coupled plasma mass spectrometry (ICP-MS). The particles in the composition were detected by a laser particle counter (LPC).

[0198] Subsequently, each of the filtered protective layer compositions was spin-coated on the edge of the wafer and baked at 250°C for 60 seconds, and the thickness of the obtained protective layer was tested and summarized in Table 1 below. Then, the wafer with the protective layer was immersed in a cyclohexanone solvent at 25°C for 60 seconds, and then the wafer was taken out and dried, and the thickness of the remaining protective layer was tested. The results are shown in Table 1.

[0199] Table 1

[0200]

[0201]

[0202] It can be seen from Table 1 that the protective layer materials of Comparative Examples 1-3 using polysulfone have poor solubility in cyclohexanone solvent, and the film thickness loss ratio after immersion in cyclohexanone for 60 seconds is greater than 95%. When the polymer content in the protective layer material is the same, the protective layer material of the present application example using polyetherimide has much higher tolerance to cyclohexanone than Comparative Examples 1-3.

[0203] Among them, when the protective layer material contains one or two of low molecular weight polyetherimide PEI1, PEI2, PEI4, and PEI5 (Examples 1-2, 7, and 10), there is a small amount of dissolution in cyclohexanone. The protective layer material of Example 4 using high molecular weight polyetherimide PEI3 has good solubility resistance in cyclohexanone, and mainly a small amount of swelling occurs. Compared with Example 2 using only low molecular weight PEI2 or Example 4 using only high molecular weight PEI3, the protective layer materials of Examples 5-6 use high molecular weight polyetherimide PEI3 and low molecular weight polyetherimide PEI2 at the same time, and the film thickness after being soaked in cyclohexanone for 60s does not change much, and has better solvent resistance.

[0204] Similarly, the film thickness loss of the protective layer materials of Examples 8-11 using both high molecular weight PEI3 and low molecular weight PEI4 after immersion in cyclohexanone is also significantly lower than that of Example 7 using only low molecular weight PEI4. The protective layer materials of Examples 13-14 using both high molecular weight PEI3 and low molecular weight PEI5 have better solubility resistance to cyclohexanone than the protective layer material of Example 12 using only low molecular weight PEI5.

[0205] The applicant also tested the solubility of the film layers of some of the above protective layer compositions in cyclohexanone mixed with 10% formic acid and cyclohexanone mixed with 10% acetic acid. The test results are shown in Table 2 below.

[0206] Table 2

[0207]

[0208] Combining Table 1 and Table 2, it can be seen that the film layers formed by the protective layer compositions of Examples 5, 6, 8, 9 and 13 not only have good solvent resistance in cyclohexanone, but also have good dissolution resistance in its acidic solution. However, the protective layer material of Comparative Example 2 using polysulfone has poor tolerance to cyclohexanone and its acidic solvent.

[0209] The protective film composition shown in the following Table 3 is used as a representative to test the removal effect of anisole on the protective layer material provided in the examples of the present application.

[0210] Specifically, several sets of protective film compositions are provided according to the formulations shown in Table 3 below. Each protective layer composition is spin-coated on the edge of the wafer (eg Figure 1The wafer was then immersed in anisole for 10 seconds, and then the wafer was taken out and dried. The remaining thickness of the protective film was tested and compared with the thickness before immersion to calculate the thickness loss. The test results are shown in Table 3.

[0211] Table 3

[0212]

[0213] It can be seen from Table 1 and Table 3 that the protective layer using high and low molecular weight PEI in the present application can maintain good solvent resistance in cyclohexanone solvent while achieving a faster removal rate in anisole. In addition, the protective layer materials of other embodiments in Table 1 can also be removed faster in anisole, and the data are not attached here one by one.

[0214] The protective layer composition provided in the above Example 13 (the mass ratio of anisole, PEI3 and PEI5 is 99:0.8:0.2) is spin-coated on the edge of the wafer, and baked at 250°C or not after coating according to the process shown in Table 4, and then solubility tests are carried out in 10wt% formic acid solution of 4-methyl-2-pentanone, methyl isobutyl carbinol, 10% acetic acid solution of cyclohexanone, and anisole, respectively. The test results are summarized in Table 4 below.

[0215] Table 4

[0216]

[0217] It can be seen from Table 4 that the protective layer material formed by coating the protective layer composition of Example 13 of the present application has good tolerance to the acidic solution of 4-methyl-2-pentanone, the acidic solution of cyclohexanone, and methyl isobutyl carbinol, regardless of whether it is baked after coating; and the anisole solvent can be easily removed.

[0218] 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.

[0219] Application Example 1

[0220] (1) Figure 1 As shown in A2, the edge of the wafer is coated with the protective layer composition of Example 5.

[0221] (2) Figure 1 As shown in A4, a metal anti-etching agent containing Sn element is coated on the wafer (the Example 2 disclosed by Zhang Lei et al. in CN115220300A is synthesized: based on radiation-sensitive tin oxide cluster material, dissolved in cyclohexanone, with a solid content of 1.5wt%).

[0222] (3) Figure 1 As shown in A5, cyclohexanone is used to wash away the anti-etching agent material located on the edge of the wafer.

[0223] (4) The anti-etching agent layer is exposed using electron beam etching technology.

[0224] (5) Figure 1 As shown in A7, 2-heptanone is used as a developer to develop the exposed resist layer for 60 seconds.

[0225] (6) Anisole is used to remove the protective layer material located on the edge of the wafer.

[0226] (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 the following Table 5.

[0227] 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 5.

[0228] The difference between Application Example 2 and Application Example 1 is that the protective layer composition of Example 15 is used to coat the edge of the wafer.

[0229] The only difference between Comparative Application Example 1 and Application Example 1 is that the protective layer composition of Comparative Example 1 is used to coat the edge of the wafer.

[0230] The only difference between Comparative Application Example 2 and Application Example 1 is that the edge of the wafer is coated with a protective layer composition having the same formulation as that of Example 5, but the protective layer composition is not filtered for gold impurities, and the total gold impurity detection result of the composition is 235 ppb.

[0231] Table 5

[0232]

[0233] It can be seen from Table 5 that in Application Example 1-2, the total amount of metal atom contamination on the back and side of the wafer was less than 10 10 / cm 2 , meeting the requirements of the semiconductor industry. In comparative application example 1, PSU material is used as the wafer edge protection material, but because the edge protection material dissolves more in the cyclohexanone solvent (refer to the data in Table 1), it does not effectively protect the wafer, resulting in excessive detection of metal ion impurities on the back and sides of the wafer. In comparative application example 2, since the metal element impurities in the protective layer composition used exceed 10ppb, metal impurities will remain on the edge of the wafer, which will also cause the detection result of metal ion impurities to exceed the standard.

[0234] It can be seen that the protective layer composition provided in the embodiment of the present application can have a good anti-metal contamination effect, and can reduce the metal contamination caused by the metal-based patterned material and its supporting layer materials in unnecessary areas of the wafer.

[0235] 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.

[0236] 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.

[0237] 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.

[0238] 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.

[0239] 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, characterized in that: The protective layer composition comprises polyetherimide and an organic solvent, wherein the polyetherimide comprises an etherimide repeating unit derived from a diamine and an aromatic diether anhydride; and the metal ion content in the protective layer composition is less than or equal to 10 ppb.

2. The protective layer composition according to claim 1, characterized in that The etherimide repeating unit comprises at least one structure as shown in formula (I): Wherein, T is -O- or -OZO-, Z is selected from a divalent group containing at least one aromatic ring, and R is selected from a C 2-20 A divalent hydrocarbon group.

3. The protective layer composition according to claim 2, characterized in that: The Z comprises a structure shown in formula (1): wherein a, b, and c are independently selected from integers of 0 to 4, and R 1 , R 2 are independently selected from halogen atoms, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 1-10 One or more of alkoxy; X is selected from a single bond, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, C with or without heteroatoms 1-18 One of the divalent hydrocarbon groups; the position marked with * is the connection position.

4. The protective layer composition according to claim 3, characterized in that a=0,b=0,c=1;wherein X is selected from —O—, —S—, —S(=O)—, —S(=O)2—, —C(=O)—, halogenated or unhalogenated C 1-5 One of the alkylene groups.

5. The protective layer composition according to any one of claims 2 to 4, characterized in that: The R comprises the structure shown in formula (2): Wherein, d and e are independently selected from integers of 0-4, f is 0 or 1; L1 and L2 are independently selected from single bonds or C 1-6 Alkylene; 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 one or more of alkoxy; 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; the position marked with * is the connection position.

6. The protective layer composition according to any one of claims 1 to 5, characterized in that: The molar proportion of the etherimide repeating units in all the repeating units of the polyetherimide is 90%-100%.

7. The protective layer composition according to any one of claims 1 to 6, characterized in that: The polyetherimide also includes imide repeating units derived from a diamine and an aromatic dianhydride that does not contain an ether oxygen bond.

8. The protective layer composition according to claim 7, characterized in that The imide repeating units independently include one or more structures represented by formula (II), formula (III), and formula (IV): Wherein, R is selected from one or more of an alkylene group containing or not containing heteroatoms, a cycloalkylene group containing or not containing heteroatoms, and an arylene group containing or not containing heteroatoms; and W does not contain an ether oxygen bond.

9. The protective layer composition according to any one of claims 1 to 8, characterized in that: The polyetherimide satisfies at least one of the following (a) to (c): (a) the polyetherimide has a melt index of 0.1-10 g / min measured at 340° C.-370° C.; (b) the intrinsic viscosity of the m-cresol solution of the polyetherimide at 25° C. is greater than 0.2 dL / g; (c) The glass transition temperature of the polyetherimide is in the range of 200-280°C.

10. The protective layer composition according to any one of claims 1 to 9, characterized in that: The weight average molecular weight of the polyetherimide is in the range of 1,000-150,000.

11. The protective layer composition according to any one of claims 1 to 10, characterized in that: The polyetherimide comprises a first polyetherimide with a weight average molecular weight of 1,000-10,000 and a second polyetherimide with a weight average molecular weight of greater than 10,000 to 150,000.

12. The protective layer composition according to claim 11, characterized in that: The solubility of the first film formed by the first polyetherimide and the second film formed by the second polyetherimide in different solvents satisfies: At 25°C, the thickness loss rate of the first film immersed in cyclohexanone is greater than and less than The thickness loss rate after immersion in methyl isobutyl carbinol is less than The thickness loss rate after immersion in anisole is greater than At 25°C, the thickness loss rate of the second film immersed in cyclohexanone is less than The thickness loss rate after immersion in methyl isobutyl carbinol is less than The thickness loss rate after immersion in anisole is greater than 13. The protective layer composition according to claim 11 or 12, characterized in that: In the protective layer composition, the mass ratio of the second polyetherimide to the first polyetherimide is 1-20.

14. The protective layer composition according to any one of claims 1 to 13, characterized in that: In the protective layer composition, the mass percentage of the polyetherimide is 0.1wt%-20wt%.

15. The protective layer composition according to any one of claims 1 to 14, characterized in that: The organic solvent includes one or more of anisole, gamma-butyrolactone, N-methyl-2-pyrrolidone, and aromatic hydrocarbons.

16. The protective layer composition according to any one of claims 1 to 15, characterized in that: The protective layer composition further comprises one or more of an ultraviolet absorber, a stabilizer, a lubricant, a plasticizer, a pigment, a dye, a colorant, an antistatic agent, a metal passivator, and a release agent.

17. Use of the protective layer composition according to any one of claims 1 to 16 to reduce metal contamination in non-pattern areas in a patterning process.

18. A method for manufacturing an electronic device, characterized in that: include: Applying the protective layer composition according to any one of claims 1 to 16 on the edge of the substrate to form a protective layer; 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; 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.

19. The manufacturing method according to claim 18, characterized in that: 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.

20. An electronic device, characterized in that: The method is prepared by the manufacturing method described in any one of claims 18 to 19.

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